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Title:
COSMETIC COMPOSITION FOR MAKEUP AND/OR KERATIN MATERIAL CARE, BASED ON A MIXTURE OF RESINS MQ AND T-PR, AND MAKEUP METHOD
Kind Code:
A1
Abstract:
The present invention relates to a composition that includes, in a physiologically acceptable medium: A) a siloxane resin containing at least 80 mol % of the following units: (i) (R′3SiO1/2)a and (ii) (SiO4/2)b where R′ is, independently, an alkyl grouping having 1 to 8 carbon atoms, an aryl grouping, a carbinol grouping, or an amino grouping with the proviso that at least 95 mol % of the R′ groups are alkyl groups; a and b have values strictly greater than 0; and the ratio of a to b is between 0.5 and 1.5; B) a propyl silsesquioxane resin containing at least 80 mol % of (R″SiC>3/2) units where R″ is, independently, an alkyl grouping having 1 to 8 carbon atoms, an aryl grouping, a carbinol grouping, or an amino grouping with the proviso that at least 80 mol % of the R″ groups are propyl groups, the weight ratio between the resins a) and b) being between 1/99 and 99/1, but particularly between 85/15 and 15/85 the resins a) and b) not being bonded to each other by covalent bonds, and the number of M units in the final mixture being strictly less than the number of (T+Q) units; and C) at least one film-forming polymer selected from among the group including: an ethylene sequential copolymer (also called an ethylene sequential polymer) containing at least one first sequence having a vitreous transition temperature (Tg) greater than or equal to 400° C. and derived, in whole or in part, from one or more first monomers, such that the homopolymer prepared from said monomers at a vitreous transition temperature less than or equal to 400° C., and from at least one second sequence having a vitreous transition temperature less than or equal to 20° C. and derived, in whole or in part, from one or more second monomers, such that the homopolymer prepared from said monomers has a vitreous transition temperature less than or equal to 200° C., said first sequence and said second sequence being bonded together by an intermediate statistical segment that contains at least one of said first monomers that constitutes the first sequence and at least one of said second monomers that constitutes the second sequence, and said copolymer sequence having a polydispersity index I greater than 2; and a vinyl polymer containing at least one pattern derived from dendrimer carboxilane, a dispersion of radical, acrylic, or vinyl homopolymer or copolymer particles being dispersed in said liquid fatty phase.


Inventors:
Barba, Claudia (Paris, FR)
Cavazzuti, Roberto (Paris, FR)
Ferrari, Veronique (Maisons Alfort, FR)
Ricard, Audrey (La Varenne, FR)
Application Number:
13/132497
Publication Date:
04/26/2012
Filing Date:
12/02/2009
Assignee:
L'OREAL (Paris, FR)
Primary Class:
Other Classes:
424/70.121, 424/64
International Classes:
A61K8/58; A61Q1/02; A61Q1/04; A61Q5/00
View Patent Images:
Foreign References:
WO2005075567A12005-08-18
Claims:
1. A composition comprising, in a physiologically acceptable medium: a siloxane resin, a silsesquioxane resin, and at least one film-forming polymer, wherein: the siloxane resin comprises at least 80 mol % of: at least one M unit, (R′3SiO1/2)a; and at least one Q unit, (SiO4/2)b; R′ independently represents an alkyl group comprising 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group; at least 95 mol % of the R′ groups are alkyl groups; a and b are greater than 0; a ratio of a/b is between 0.5 and 1.5; the silsesquioxane resin comprises at least 80 mol % of at least one T unit, (R″SiO3/2); R″ independently represents an alkyl group comprising 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group; at least 80 mol % of the R″ groups are propyl groups; a weight ratio of the siloxane resin to the silsesquioxane resin is between 1/99 and 99/1; the siloxane resin and the silsesquioxane resin are not bonded to one another by covalent bonds; the number of the at least one M unit is less than the number of the at least one T unit plus the at least one Q unit; and the at least one film-forming polymer is at least one polymeric form selected from the group consisting of: (i) a sequenced ethylene copolymer comprising: at least one first sequence with a glass transition temperature (Tg) higher than or equal to 40° C. and obtained completely or partly from at least one first monomer, wherein a homopolymer prepared from the at least one first monomer has a glass transition temperature higher than or equal to 40° C.; and at least one second sequence with a glass transition temperature lower than or equal to 20° C. and obtained completely or partly from at least one second monomer, wherein a homopolymer prepared from the at least one second monomer has a glass transition temperature lower than or equal to 20° C., wherein: the at least one first sequence and the at least one second sequence are bonded together by a statistical intermediate segment comprising at least one of the at least one first monomer and at least one of the at least one second mononer; and the sequenced ethylene copolymer has a polydispersity index I greater than 2; (ii) a vinyl polymer comprising at least one moiety derived from a carbosiloxane dendrimer; and (iii) a dispersion of particles of an acrylic or vinyl radical homopolymer or copolymer dispersed in a liquid fatty phase.

2. A composition comprising, in a physiologically acceptable medium: a siloxane resin, a film-forming silsesquioxane resin, and at least one film-forming polymer, wherein: the siloxane resin comprises at least 80 mol % of: at least one M unit, (R′3SiO1/2)a; and at least one Q unit, (SiO4/2)b; R′ independently represents an alkyl group comprising 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group; at least 95 mol % of the R′ groups are alkyl groups; a and b are greater than 0; a ratio of a/b is between 0.5 and 1.5; the film-forming silsesquioxane resin comprises at least 80 mol % of at least one T unit, (R″SiO3/2); R″ independently represents an alkyl group comprising 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group; at least 40 mol % of the R″ groups are propyl groups; a weight ratio of the siloxane resin to the film-forming silsesquioxane resin is between 1/99 and 99/1; the siloxane resin and the film-forming selsesquioxane resin are not bonded to one another by covalent bonds; the number of the at least one M unit is less than the number of the at least one T unit plus the at least one Q unit; and the at least one film-forming polymer is at least one polymeric form selected from the group consisting of: (i) a sequenced ethylene copolymer comprising: at least one first sequence with a glass transition temperature (Tg) higher than or equal to 40° C. and obtained completely or partly from at least one first monomer, wherein a homopolymer prepared from the at least one first monomer has a glass transition temperature higher than or equal to 40° C.; and at least one second sequence with a glass transition temperature lower than or equal to 20° C. and obtained completely or partly from at least one second monomer, wherein a homopolymer prepared from the at least one second monomer has a glass transition temperature lower than or equal to 20° C., wherein: the at least one first sequence and the at least one second sequence are bonded together by a statistical intermediate segment comprising at least one of the at least one first monomer and at least one of the at least one second mononer; and the sequenced ethylene copolymer has a polydispersity index I greater than 2; (ii) a vinyl polymer comprising at least one moiety derived from a carbosiloxane dendrimer; and (iii) a dispersion of particles of an acrylic or vinyl radical homopolymer or copolymer dispersed in a liquid fatty phase.

3. A composition comprising, in a physiologically acceptable medium: a siloxane resin, a silsesquioxane resin, and at least one film-forming polymer, wherein: the siloxane resin comprises at least 80 mol % of: at least one M unit, (R′3SiO1/2)a; and at least one Q unit, (SiO4/2)b; R′ independently represents an alkyl group comprising 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group; at least 95 mol % of the R′ groups are alkyl groups; a and b are greater than 0; a ratio of a/b is between 0.5 and 1.5; the silsesquioxane resin comprises at least 80 mol % of at least one T unit, (R″SiO3/2); R″ independently represents an alkyl group comprising 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group; at least 40 mol % of the R″ groups are propyl groups; a weight ratio of the siloxane resin to the silsesquioxane resin is between 1/99 and 99/1; the siloxane resin and the silsequioxane resin are not bonded to one another by covalent bonds; the number of the at least one M unit is less than the number of the at least one T unit plus the at least one Q unit; and the at least one film-forming polymer is at least one polymeric form selected from the group consisting of: (i) a sequenced ethylene copolymer comprising: at least one first sequence with a glass transition temperature (Tg) higher than or equal to 40° C. and obtained completely or partly from at least one first monomer, wherein a homopolymer prepared from the at least one first monomer has a glass transition temperature higher than or equal to 40° C.; and at least one second sequence with a glass transition temperature lower than or equal to 20° C. and obtained completely or partly from at least one second monomer, wherein a homopolymer prepared from the at least one second monomer has a glass transition temperature lower than or equal to 20° C., wherein: the at least one first sequence and the at least one second sequence are bonded together by a statistical intermediate segment comprising at least one of the at least one first monomer and at least one of the at least one second mononer; and the sequenced ethylene copolymer has a polydispersity index I greater than 2; (ii) a vinyl polymer comprising at least one moiety derived from a carbosiloxane dendrimer; and (iii) a dispersion of particles of an acrylic or vinyl radical homopolymer or copolymer dispersed in a liquid fatty phase.

4. (canceled)

5. (canceled)

6. (canceled)

7. The composition of claim 1, wherein the siloxane resin further comprises at least one residual silanol group, —SiOH, in a proportion between 2 and 10% by weight of the siloxane resin.

8. The composition of claim 1, wherein the silsesquioxane resin further comprises at least one unit selected from the group consisting of a residual silanol group, —SiOH, and an alkoxy group, wherein: the residual silanol group, —SiOH, is present in the composition in a proportion between 2 and 10% by weight of the silsesquioxane resin; and the alkoxy group is present in the composition in a proportion smaller than or equal to 20% by weight of the silsesquioxane resin.

9. The composition of claim 1, wherein R′ independently represents: an alkyl group comprising 1 to 8 carbon atoms selected from at least one group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl and octyl; an aryl group selected from at least one group consisting of phenyl, naphthyl, benzyl, tolyl, xylyl, xenyl, methylphenyl, 2-phenylethyl, 2-phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl; a carbinol group selected from at least one group consisting of: (1) formula R1OH, wherein R1 represents a bivalent hydrocarbon group comprising at least 3 carbon atoms or a bivalent hydrocarbonoxy group containing at least 3 carbon atoms; and (2) formula R2OH, wherein R2 represents: (i) an arylene group —(CH2)xC6H4—, x having a value between 0 and 10; (ii) —CH2CH(CH3)(CH2)xC6H4—, x having a value between 0 and 10; and (iii) —(CH2)xC6H4(CH2)x—, x having a value between 1 and 10; and an amino group selected from at least one group consisting of: (1) —R3NH2; and (2) —R3NHR4NH2, wherein: R3 represents a bivalent hydrocarbon comprising at least 2 carbon atoms; and R4 represents a bivalent hydrocarbon comprising at least 2 carbon atoms.

10. The composition of claim 9, wherein the R1 group is at least one moiety selected from the group consisting of: an alkylene group —(CH2)x—, x having a value between 3 and 10; —CH2CH(CH3)—; —CH2CH(CH3)CH2—; —CH2CH2CH(CH2CH3)CH2CH2CH2—; and —OCH(CH3)(CH2)x—, x having a value between 1 and 10.

11. The composition of claim 9, wherein the R3 and R4 groups are at least one moiety selected from group consisting of ethylene, propylene, —CH2CHCH3—, butylene, —CH2CH(CH3)CH2—, pentamethylene, hexamethylene, 3-ethylhexamethylene, octamethylene and decamethylene.

12. The composition of claim 9, wherein the amino group is at least one moiety selected from the group consisting of: —CH2CH2CH2NH2; —CH2(CH3)CHCH2(H)N(CH)3; —CH2CH2NHCH2CH2NH2; —CH2CH2NH2; —CH2CH2NHCH3; —CH2CH2CH2CH2NH2; —(CH2CH2NH)3H; and —CH2CH2NHCH2CH2NHC4H9.

13. The composition of claim 1, wherein R′ represents a methyl group.

14. The composition of claim 1, wherein at least 90 mol % of the R″ groups are propyl groups.

15. The composition of claim 1, wherein the sequenced ethylene copolymer comprises an intermediate sequence comprising: at least one constituent monomer of the at least one first sequence; and at least one constituent monomer of the at least one second sequence, wherein: the sequenced ethylene copolymer has a polydispersity index greater than 2; the at least one second sequence is obtained from acrylic acid and isobutyl acrylate; and the at least one first sequence is obtained from isobornyl acrylate and isobornyl methacrylate.

16. The composition of claim 1, wherein the at least one moiety derived from a carbosiloxane dendrimer comprises at least one dendritic carbosiloxane structure represented by formula (I): embedded image wherein: Z is a divalent organic group; p is 0 or 1; R1 is an aryl or alkyl group comprising 1 to 10 carbon atoms; and X1 is a silylalkyl group represented by formula (II): embedded image wherein: R1 is an aryl or alkyl group comprising 1 to 10 carbon atoms; R2 is an alkylene group comprising 1 to 10 carbon atoms; R3 is an alkyl group comprising 1 to 10 carbon atoms; and Xi+1 is a at least one moiety selected from the group consisting of: a hydrogen atom; an aryl group; an alkyl group comprising up to 10 carbon atoms; and the silylalkyl group, Xi, wherein the exponent “i” is an integer from 1 to 10, indicating the generation of the silylalkyl group beginning in each dendritic carbosiloxane structure with a value of 1 for the group Xi in formula (I); and ai is an integer from 0 to 3.

17. The composition of claim 1, wherein the particles of the acrylic or vinyl radical homopolymer or copolymer in the dispersion of particles (iii) are: acrylic polymers or copolymers; insoluble in the water-soluble alcohols.

18. The composition of claim 1, wherein the content of the at least one film-forming polymer is 0.1 to 60% by weight as dry material of the film-forming polymer.

19. The composition of claim 1, further comprising at least one additional ingredient selected from the group consisting of a pasty compound of non-animal origin, a fatty-phase thickening agent or a gelling rheological agent, a wax, a hydrophilic gelling agent, a filler, a film-forming polymer, an ionic surfactant, and a fiber, wherein: the fatty-phase thickening agent or the gelling rheological agent are not dimethicone crosspolymers; the wax is not candelilla wax, ozokerite or silicone wax; and the ionic surfactant is not lauryl ether sulfate.

20. A method for makeup and/or cosmetic care of at least one horny tissue, comprising applying the composition of claim 1 on the at least one horny tissues.

21. The composition of claim 3, wherein the siloxane resin and the silsesquioxane resin are obtained by a process comprising: (1) mixing a solution of the siloxane resin with a solution of the silsesquioxane resin; then (2) heating a resulting mixture for at least 1 hour between 90° C. and 250° C. without a catalyst for chemical condensation of the two resins.

22. The composition of claim 21, wherein a partial or complete distillation of at least one aromatic solvent is carried out during or after the mixing (1) while replacing the aromatic solvent with a cosmetically acceptable volatile solvent.

23. The composition of claim 3, wherein the siloxane resin and the silsesquioxane resin are formulated by: (1) mixing a solution of the siloxane resin with a solution of the silsesquioxane resin, then (2) heating a resulting mixture in an extruder for at least 10 minutes between 90° C. and 250° C. without a catalyst for chemical condensation of the two resins.

24. The composition of claim 23, wherein a partial or complete distillation of at least one aromatic solvent is carried out during or after the mixing (1), while discharging a mixture of resins directly in the solid state.

25. The composition of claim 1, wherein the weight ratio of the siloxane resin to the silsesquioxane resin is between 85/15 and 15/85.

26. The method of claim 20, the method applied to at least one horny tissue of the lips.

Description:

The invention relates to a cosmetic composition intended for horny tissues, especially the lips and skin, the hair and nails. The invention relates in particular to makeup compositions for the said horny tissues, comprising at least one siloxane resin and at least one film-forming polymer.

One of the objectives of the application is to provide makeup compositions intended for horny tissues (skin, mucous membranes, fiber, eyelashes and integument) permitting deposition of a totally non-transfer film with good comfort and a good level of gloss, particularly in the case of lipstick.

In the field of lipstick and of makeup in general, the formulator is on the lookout for compositions that have good staying power, so as to satisfy the expectations of the consumers. These compositions must also be of non-transfer nature, while offering good comfort properties.

The formulator is therefore on the lookout for raw materials and/or systems that make it possible to obtain compositions characterized by improved staying power and by a good level of comfort when they are deposited. By comfort there will be understood comfort upon application, or in other words a composition that is deposited easily in terms of gliding and of deposited amount, while the deposited film is not too thick and/or not too tacky. By comfort there will also be understood comfort after application, such that the user does not feel any tugging or drying out in particular.

The person skilled in the art knows to use polymers to obtain these properties of staying power in the course of the day.

These polymers have very different chemical natures and are conveyed either in a fatty phase or in an aqueous phase.

By way of examples there can be cited the silicone resins, especially of MQ type, the polyacrylates, the latexes, etc.

Although these polymers effectively impart properties of staying power, especially of non-transfer, they are most often accompanied by discomfort either during application of the product (difficult spreading, sticking, etc.) or in the course of the day (tugging, mask effect, etc.).

It is therefore necessary to seek a technical solution that makes it possible to obtain these properties of staying power while preserving comfortable use.

This objective is achieved by virtue of the compositions according to the invention.

The object of the present invention is effectively a composition comprising, in a physiologically acceptable medium:

    • a) a siloxane resin comprising at least 80 mol % of the units:
      • (i) (R′3SiO12)a (hereinafter “M” units) and
      • (ii) (SiO4/2)b (hereinafter “Q” units)
    • wherein
      • R′ independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group,
    • with the proviso that at least 95 mol % of the R′ groups are alkyl groups,
      • a and b have values strictly greater than 0;
      • and the a/b ratio ranges between 0.5 and 1.5,
    • and
    • b) a propyl silsesquioxane resin comprising at least 80 mol % of (R″SiO3/2) units (hereinafter “T” units), in which R″ independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 80 mol % of the R″ groups are propyl groups,
    • the weight ratio between resins a) and b) being between 1/99 and 99/1, particularly between 85/15 and 15/85,
    • resins a) and b) not being bonded to one another by covalent bonds,
    • and the number of M units of the final mixture being strictly smaller than the number of (T+Q) units,
    • and
    • c) at least one film-forming polymer, preferably chosen from among the group comprising:
      • a sequenced ethylene copolymer (also referred to as sequenced ethylene polymer), containing at least one first sequence having a glass transition temperature (Tg) higher than or equal to 40° C. and being obtained completely or partly from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature higher than or equal to 40° C., and at least one second sequence having a glass transition temperature lower than or equal to 20° C. and being obtained completely or partly from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature lower than or equal to 20° C., the said first sequence and the said second sequence being bonded together by a statistical intermediate segment comprising at least one of the said first constituent monomers of the first sequence and at least one of the said second constituent monomers of the second sequence, and the said sequenced copolymer having a polydispersity index I greater than 2,
      • a vinyl polymer comprising at least one moiety derived from carbosiloxane dendrimer,
      • a dispersion of particles of acrylic or vinyl radical homopolymer or copolymer dispersed in the said liquid fatty phase.

The compositions according to the invention may also comprise an additional ingredient, preferably chosen from among pasty compounds of non-animal origin, fatty-phase thickening or gelling rheological agents, waxes, hydrophilic gelling agents, fillers, ionic surfactants, fibers and mixtures thereof.

Preferably, the compositions according to the invention may comprise at least one additional ingredient, preferably chosen from among pasty compounds of non-animal origin, fatty-phase thickening or gelling rheological agents with the exception of dimethicone cross-polymers, waxes with the exception of candelilla wax, of ozokerite and of the silicone waxes, hydrophilic gelling agents, fillers, ionic surfactants with the exception of lauryl ether sulfate, fibers and mixtures thereof.

In particular, according to one embodiment, the waxes are chosen from among beeswax, lanolin wax and Chinese insect wax; rice wax, carnauba wax, ouricurry wax, esparto grass wax, cork fiber wax, sugar cane wax, Japan wax and sumac wax; montan wax, microcrystalline waxes, paraffins; polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis, waxes obtained by catalytic hydrogenation of animal or vegetable oils having fatty, linear or branched C8-C32 chains, fluoro waxes, wax obtained by hydrogenation of olive oil esterified with stearyl alcohol, waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol, and tacky waxes. Preferably, the ionic surfactants are chosen from among cationic surfactants, amphoteric surfactants, carboxylates, taurates and N-acyl N-methyltaurates, alkylsulfoacetates, polypeptides, anionic derivatives of alkyl polyglycoside, amine-derived salts of C16-C30 fatty acids, salts of polyoxyethylenated fatty acids, phosphoric acids and their salts, sulfosuccinates, alkyl sulfates, isethionates and N-acylisethionates, acylglutamates, soy derivatives, citrates, proline derivatives, lactylates, sarcosinates, sulfonates and glycinates.

Preferably, the fatty-phase thickening or gelling rheological agents are chosen from among crystalline polymers, mineral lipophilic structuring agents, lipophilic polyamides, lipophilic polyureas and polyurethanes, silicone polymers comprising, as the case may be, at least one hydrocarbon moiety composed of two groups capable of establishing hydrogen interactions chosen from among ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino, biguanidino groups and combinations thereof, organo gelling agents, block polymers, cholesteric liquid crystal agents, dimethicone/vinyldimethicone copolymers and vinyldimethicone/alkyl dimethicone copolymers, such as vinyldimethicone/lauryl dimethicone copolymers.

Another object of the present invention is a composition comprising, in a physiologically acceptable medium:

    • a) a siloxane resin comprising at least 80 mol % of the units:
      • (i) (R′3SiO1/2)a (hereinafter “M” units) and
      • (ii) (SiO4/2)b (hereinafter “Q” units)
    • wherein
      • R′ independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group,
    • with the proviso that at least 95 mol % of the R′ groups are alkyl groups,
      • a and b have values strictly greater than 0;
      • and the a/b ratio ranges between 0.5 and 1.5,
    • and
    • b) a film-forming propyl silsesquioxane resin comprising at least 80 mol % of (R″SiO3/2) units (hereinafter “T” units), in which R″ independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 40 mol % of the R″ groups are propyl groups,
    • the weight ratio between resins a) and b) being between 1/99 and 99/1, particularly between 85/15 and 15/85,
    • resins a) and b) not being bonded to one another by covalent bonds,
    • and the number of M units of the final mixture being strictly smaller than the number of (T+Q) units,
    • and
    • c) at least one film-forming polymer, preferably chosen from among the group comprising:
      • a sequenced ethylene copolymer (also referred to as sequenced ethylene polymer), containing at least one first sequence having a glass transition temperature (Tg) higher than or equal to 40° C. and being obtained completely or partly from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature higher than or equal to 40° C., and at least one second sequence having a glass transition temperature lower than or equal to 20° C. and being obtained completely or partly from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature lower than or equal to 20° C., the said first sequence and the said second sequence being bonded together by a statistical intermediate segment comprising at least one of the said first constituent monomers of the first sequence and at least one of the said second constituent monomers of the second sequence, and the said sequenced copolymer having a polydispersity index I greater than 2,
      • a vinyl polymer comprising at least one moiety derived from carbosiloxane dendrimer,
      • a dispersion of particles of acrylic or vinyl radical homopolymer or copolymer dispersed in the said liquid fatty phase.

Siloxane resin a), referred to as “MQ resin” hereinafter, preferably comprises residual silanol groups (—SiOH). In this case, the quantity of —OH groups preferably ranges between 2 and 10% by weight of the MQ resin, preferably between 2 and 5% by weight of the MQ resin. Preferably, the R′ groups of the MQ resin are methyl groups.

Resin b), referred to as “propyl T resin” hereinafter, preferably comprises residual silanol groups (—SiOH) and/or alkoxy groups. In this case, the quantity of —OH groups preferably ranges between 2 and 20% by weight of the propyl T resin, and/or the quantity of alkoxy groups is smaller than or equal to 20% by weight of the propyl T resin. Preferably, the quantity of —OH groups ranges between 6 and 8% by weight of the propyl T resin, and/or the quantity of alkoxy groups is smaller than or equal to 10% by weight of the propyl T resin.

The propyl T resin according to the invention is such that at least 40 mol % of the R″ groups are propyl groups; preferably at least 50 mol %, and more preferentially at least 90 mol %.

By covalent bond there is understood a chemical bond between at least 2 atoms (carbon, silicon, oxygen, etc.) in which each of the bonded atoms commonly contributes an electron of one of its outer layers in order to form an electron pair bonding the two atoms.

The MQ resin according to the invention comprises at least 80 mol % of the units:

    • (i) (R′3SiO1/2)a (hereinafter “M” units) and
    • (ii) (SiO4/2)b (hereinafter “Q” units)
    • wherein
      • R′ independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group,
    • with the proviso that at least 95 mol % of the R′ groups are alkyl groups,
      • a and b have values strictly greater than 0;
      • and the a/b ratio ranges between 0.5 and 1.5.

The R′ radical of the MQ resin independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group.

The alkyl groups may be chosen in particular from among the methyl, ethyl, propyl, butyl, pentyl, hexyl and octyl groups. Preferably the alkyl group is a methyl group.

The aryl groups may be chosen from among the phenyl, naphthyl, benzyl, tolyl, xylyl, xenyl, methylphenyl, 2-phenylethyl, 2-phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl groups, the aryl group preferentially being a phenyl group.

In the present invention, “carbinol group” is understood as any group containing at least one hydroxyl radical bonded to a carbon (COH). The carbinol groups may therefore contain more than one COH radical, such as, for example

embedded image

If the carbinol group is free of aryl groups, it contains at least 3 carbon atoms. If the carbinol group comprises at least one aryl group, it contains at least 6 carbon atoms.

As examples of carbinol groups free of aryl groups and containing at least 3 carbon atoms there can be cited the groups of formula R1OH, in which R1 represents a bivalent hydrocarbon radical containing at least 3 carbon atoms or a bivalent hydrocarbonoxy radical containing at least 3 carbon atoms. As examples of the R1 group there can be cited alkylene radicals such as —(CH2)x—, the value of x ranging between 3 and 10, —CH2CH(CH3)—, —CH2CH(CH3)CH2—, —CH2CH2CH(CH2CH3)CH2CH2CH2— and —OCH(CH3)(CH2)x—, the value of x ranging between 1 and 10.

As examples of carbinol groups containing aryl groups having at least 6 carbon atoms there can be cited the groups of formula R2OH, in which R2 represents an arylene radical such as —(CH2)xC6H4—, x having a value between 0 and 10, —CH2CH(CH3)(CH2)xC6H4—, x having a value between 0 and 10, —(CH2)xC6H4(CH2)x—, x having a value between 1 and 10. The carbinol groups containing aryl groups generally contain 6 to 14 atoms.

By amino group according to the invention, there is understood in particular groups of formula —R′NH2 or —R3NHR4NH2, R3 representing a bivalent hydrocarbon radical having at least 2 carbon atoms and R4 representing a bivalent hydrocarbon radical having at least 2 carbon atoms. The R3 group generally represents an alkylene radical having 2 to 20 carbon atoms. As examples of R3 groups there can be cited the ethylene, propylene, —CH2CHCH3—, butylene, —CH2CH(CH3)CH2—, pentamethylene, hexamethylene, 3-ethylhexamethylene, octamethylene and decamethylene groups. The R4 group generally represents an alkylene radical having 2 to 20 carbon atoms. As examples of R4 groups there can be cited the ethylene, propylene, —CH2CHCH3—, butylene, —CH2CH(CH3)CH2—, pentamethylene, hexamethylene, 3-ethylhexamethylene, octamethylene and decamethylene groups.

The amino groups are generally —CH2CH2CH2NH2 and —CH2(CH3)CHCH2(H)NCH)3, —CH2CH2NHCH2CH2NH2, —CH2CH2NH2, —CH2CH2NHCH3, —CH2CH2CH2CH2NH2, —(CH2CH2NH)3H and —CH2CH2NHCH2CH2NHC4H9.

MQ resins suitable for use as component a), as well as their manufacturing methods, are known in the prior art. U.S. Pat. No. 2,814,601 of Currie et al., dated 26 Nov. 1957, incorporated into the present document by reference, describes a method for manufacturing MQ resins by transformation of a water-soluble silicate into a silicic acid monomer or a silicic acid oligomer by using an acid. Once adequate polymerization has been achieved, trimethylchlorosilane terminal groups are introduced to obtain the MQ resin. Another method for preparation of MQ resins is described in U.S. Pat. No. 2,857,356 of Goodwin, dated 21 Oct. 1958, incorporated into the present document by reference. Goodwin describes a method for manufacturing an MQ resin by cohydrolysis of a mixture of an alkyl silicate and of an organopolysiloxane trialkylsilane capable of being hydrolyzed by water.

The MQ resins suitable as component a) in the present invention may contain D and T units, with the proviso that at least 80 mol %, even 90 mol % of the total siloxane units are M and Q units. The MQ resins may also contain residual hydroxy groups as mentioned hereinabove. The MQ resins may also contain additional terminal groups, in which case the residual hydroxy groups are made to react with appropriate M groups.

Propyl T resin b) according to the invention comprises at least 80 mol % of (R″SiO3/2) units, in which R″ independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 40 mol % of the R″ groups are propyl groups.

Preferably, the propyl T resin according to the invention is such that at least 50 mol % of the R″ groups are propyl groups, preferably at least 90 mol %.

Preferably, propyl T resin b) is film-forming. By “film-forming resin” there is understood a resin capable of forming, on its own or in the presence of an auxiliary filmifying agent, a macroscopically continuous film that adheres to horny tissues, and preferably a cohesive film, and even better a film whose cohesion and mechanical properties are such that the said film may be isolated and manipulated in isolation, for example when the said film is formed by casting on a non-sticking surface, such as a Teflon-coated or silicone-coated surface.

The definition of the R″ radical is the same as that of the R′ radical. The aforementioned definitions applicable to R′ are therefore applicable to R″.

Propyl T resin b) according to the invention is a silsesquioxane resin. Silsesquioxane resins are well known in the prior art and are generally obtained by hydrolysis of an organosilane containing three hydrolyzable groups, such as halogen or alkoxy groups, present in the molecule. Propyl T resin b) may therefore be obtained by hydrolysis of propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, or by cohydrolysis of the aforementioned propylalkoxysilanes with diverse alkoxysilanes. As examples of these alkoxysilanes there can be cited methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane. Propyltrichlorosilane may also be hydrolyzed alone or in the presence of alcohol. In this case, the cohydrolysis may be achieved by adding methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane or similar chlorosilanes and methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane or similar methylalkoxysilanes. As alcohols suitable for this purpose there may be cited methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butanol, methoxyethanol, ethoxyethanol or similar alcohols. As examples of solvents of hydrocarbon type that may be used simultaneously there may be cited toluene, xylene or similar aromatic hydrocarbons, hexane, heptane, isooctane or similar linear or partly branched saturated hydrocarbons; as well as cyclohexane or similar aliphatic hydrocarbons.

Propyl T resins b) according to the invention may contain M, D and Q units, with the proviso that at least 80 mol %, even 90 mol % of the total siloxane units are T units. The propyl T resins may also contain residual hydroxy and/or alkoxy groups, as mentioned in the foregoing.

The composition according to the invention also comprises a physiologically acceptable medium. By physiologically acceptable medium there is understood a medium compatible with the skin, the mucous membranes and the integument.

This medium may comprise at least one volatile silicone or organic solvent, this solvent preferably being compatible with resins a/ and b/ and compatible with a cosmetic use.

As volatile silicone solvent there may be cited the cyclic polysiloxanes, the linear polysiloxanes and mixtures thereof.

As volatile linear polysiloxanes there may be cited hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetradecamethylhexasiloxane and hexadecamethylheptasiloxane.

As volatile cyclic polysiloxanes there may be cited hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane.

The organic solvent may also be an alcohol such as ethanol, isopropanol, butanol, n-propanol; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone; an aliphatic hydrocarbon such as heptane, hexane, octane or isododecane; a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, ethylene glycol n-butyl ether.

The mixture of resins at and b/ may be obtained from each of the resins in solution in a solvent.

In general, at the end of synthesis of the MQ resin according to the invention, this resin is obtained directly in solution in xylene.

Similarly, at the end of synthesis of propyl T resin b) according to the invention, this resin is obtained directly in solution in toluene.

Each of these resins in solution is mixed with the other according to the following protocol:

    • 1) Mixing the two resin solutions under agitation, then heating, especially in a reactor or in an autoclave (in order to be able to operate under pressure if necessary, or on the other hand by establishing a partial vacuum), even in an extruder, which may or may not be equipped with a solvent “devolatilization” system, under the following specific conditions:
      • heating is carried out homogeneously: the heating temperature must be higher than 90° C. and lower than or equal to 250° C., and preferably between 90° C. and 190° C.
      • Either heating is carried out at a single temperature, between 90° C. and 250° C.,
      • Or heating may be carried out at successive temperature levels:
      • first between 90° C. and T1° C.,
      • T1° C. being a temperature value intermediate between 90° C. and
      • T2° C., which is the final temperature,
      • for a duration between 10 minutes and 2 hours, then
      • between T1° C. and T2° C., for a duration between 10 minutes and 4 hours,
      • the temperature T2° C. corresponding to the maximum temperature chosen for the reaction.
      • This value of T2° C. is variable depending on the chosen mode of operation and on the chosen reactor type: traditional reactor or autoclave or extruder, but T2° C. remains lower than or equal to 250° C. It is also possible to interpose intermediate temperature levels between T1° C. and T2° C.;
      • the duration of heating is at least one hour in the reactor or in the autoclave and at least 10 minutes in the extruder, preferably between 1 h and 5 h in the reactor or in the autoclave, and preferably between 10 minutes and 2 hours in the extruder;
      • with the proviso that these heat treatments are carried out without the presence of a catalyst for chemical condensation between the two MQ and propyl T resins. Such a catalyst is in particular a mineral base, especially NaOH, KOH or ammonia.
    • 2) Optionally, partial or complete distillation of the aromatic solvents is carried out after or even during step 1) of the heat treatment of the two resins at the indicated temperature level, while replacing them by a cosmetically acceptable volatile solvent. Such a volatile solvent may be in particular a volatile or non-volatile silicone, preferably decamethylcyclopentasiloxane, or a volatile or non-volatile organic solvent, preferably isododecane.
    • 3) Also optionally, after mixing of the two initial solutions of each resin in a volatile solvent, the mixture of the solutions is processed in a single-screw or twin-screw kneader of the “devolatilization” extruder type, in a temperature interval between 90° and 250° C., making it possible to volatilize the volatile solvents by establishing a partial vacuum, while operating continuously, and then to pass the molten, solvent-free mixture into a die. The molten mixture is then cooled at the outlet of the die and chopped into solid granules or into powder form. In this case the mixture is directly in solid form and will be redissolved in the chosen solvents when it is time for formulation.

Furthermore, another object of the present invention is a composition such as described hereinabove comprising, in a physiologically acceptable medium:

1) the mixture between a siloxane resin a) and a propyl silsesquioxane resin b), the mixture being such as described hereinabove, and

2) at least one film-forming polymer, preferably chosen from among the group comprising:

    • a sequenced ethylene copolymer (also referred to as sequenced ethylene polymer), containing at least one first sequence having a glass transition temperature (Tg) higher than or equal to 40° C. and being obtained completely or partly from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature higher than or equal to 40° C., and at least one second sequence having a glass transition temperature lower than or equal to 20° C. and being obtained completely or partly from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature lower than or equal to 20° C., the said first sequence and the said second sequence being bonded together by a statistical intermediate segment comprising at least one of the said first constituent monomers of the first sequence and at least one of the said second constituent monomers of the second sequence, and the said sequenced copolymer having a polydispersity index I greater than 2,
    • a vinyl polymer comprising at least one moiety derived from carbosiloxane dendrimer,
    • a dispersion of particles of acrylic or vinyl radical homopolymer or copolymer dispersed in the said liquid fatty phase.

the siloxane resin a) and the propyl silsesquioxane resin b) being formulated in the composition via a mixture capable of being obtained according to the following method:

    • Mixing, preferably under agitation, of a solution of siloxane resin with a solution of propyl silsesquioxane resin, the solvent present in each of the solutions preferably being volatile, then
    • Heating, especially in a reactor or in an autoclave or in an extruder, under the following specific conditions:
      • heating is carried out homogeneously at a temperature higher than 90° C. and lower than or equal to 250° C., and preferably between 90° C. and 190° C.; heating may be carried out at a single temperature, or in temperature levels, as indicated hereinabove;
      • the duration of heating is at least one hour in the reactor or in the autoclave and at least 10 minutes in the extruder, preferably between 1 h and 5 h in the reactor or in the autoclave, and preferably between 10 minutes and 2 hours in the extruder;
      • with the proviso that these heat treatments are carried out without the presence of a catalyst for chemical condensation between the two MQ and propyl T resins. Such a catalyst is in particular a mineral base, especially NaOH, KOH or ammonia.

This method may comprise, after or even during the mixing step, an additional step of partial or complete distillation of the aromatic solvents, while replacing them with a cosmetically acceptable solvent.

In the case that an extruder is used, this method may comprise, after or even during the mixing step, an additional step of partial or complete distillation of the aromatic solvents, while discharging the mixture directly in the solid state.

The final heat-treatment step, or even the heat treatment itself may be achieved in a kneader provided for agitation of very viscous media such as:

    • a kneader of “Z-arm” type (“Zigma blender”), especially a Brabender kneader,
    • a screw kneader of extruder type, particularly a single-screw or a twin-screw extruder (with or without a stage for “devolatilization” of starting volatile solvents) or in a kneader that permits devolatilization by establishing a thin film on the walls.

Resin mixtures 1) suitable for use according to the invention are especially those described in Application WO 2005/075567, the contents of which are incorporated here by reference, particularly those described in Tables 1 and 3 of the said Application. It is also possible to use resin mixtures 1) described in Application WO2007/145765, particularly those described in Examples 12 to 14 of that Application, wherein the weight ratios between resins a) and b) are respectively 50/50, 60/40 and 71/29 (70/30).

According to a particular mode, there is used resin mixture 1) described in Example 22 of the said Application WO2005/075567, wherein the weight ratio between resin a) and b) is 85/15.

According to a particular mode, there is used resin mixture 1) described in Example 13 of the said Application WO2007/145765, wherein the weight ratio between resin a) and b) is 60/40.

Preferably, the siloxane resin is present in the composition in a total content of dry resin material ranging from 1% to 80% by weight relative to the total weight of the composition, preferably ranging from 5% to 70% by weight, and better ranging from 6% to 60% by weight.

The compositions according to the invention may assume diverse forms, especially the form of powder, anhydrous dispersion, water-in-oil or water-in wax emulsion, oil-in-water emulsion, multiple emulsions or wax-in-water emulsion, or gel.

Preferably, the composition according to the invention comprises less than 3%, or better less than 1% of water by weight relative to the total weight of the composition. Even more preferably, the composition is completely anhydrous. By anhydrous there is understood in particular that preferably water is not deliberately added to the composition but may be present in the trace state in the different compounds used in the composition.

The compositions according to the invention may also comprise an additional ingredient, preferably chosen from among pasty compounds of non-animal origin, fatty-phase thickening or gelling rheological agents, waxes, hydrophilic gelling agents, fillers, ionic surfactants, fibers and mixtures thereof.

Film-Forming Polymers

The composition according to the invention comprises at least one film-forming polymer. The compositions according to the invention may therefore comprise at least one film-forming polymer and mixture 1) described hereinabove.

In the present invention, there is understood by “film-forming polymer” a polymer capable of forming, on its own or in the presence of an auxiliary filmifying agent, a macroscopically continuous film that adheres to horny tissues, and preferably a cohesive film, and even better a film whose cohesion and mechanical properties are such that the said film may be isolated and manipulated in isolation, for example when the said film is formed by casting on a non-sticking surface, such as a Teflon-coated or silicone-coated surface.

The film-forming polymer or polymers used, in association with the mixtures of MQ and propyl T resins, may be conveyed in the oil phase (fat-soluble or fat-dispersible polymers) or conveyed in an aqueous phase (water soluble polymers or latex).

Preferably, the composition according to the invention comprises at least one polymer chosen from among the group comprising:

    • a sequenced ethylene copolymer (also referred to as sequenced ethylene polymer), containing at least one first sequence having a glass transition temperature (Tg) higher than or equal to 40° C. and being obtained completely or partly from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature higher than or equal to 40° C., and at least one second sequence having a glass transition temperature lower than or equal to 20° C. and being obtained completely or partly from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature lower than or equal to 20° C., the said first sequence and the said second sequence being bonded together by a statistical intermediate segment comprising at least one of the said first constituent monomers of the first sequence and at least one of the said second constituent monomers of the second sequence, and the said sequenced copolymer having a polydispersity index I greater than 2,
    • a vinyl polymer comprising at least one moiety derived from carbosiloxane dendrimer,
    • a dispersion of particles of acrylic or vinyl radical homopolymer or copolymer dispersed in the said liquid fatty phase.

Sequenced Ethylene Polymer:

According to an exemplary embodiment of the invention, the film-forming polymer is a film-forming sequenced ethylene polymer, which preferably comprises at least one first sequence and at least one second sequence having different glass transition temperatures (Tg), the said first and second sequences being bonded together by an intermediate sequence comprising at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence.

Advantageously, the first and second sequences of the sequenced polymer are incompatible with one another.

Such polymers are described, for example, in the documents of EP 1411069 or WO04/028488. The Application EP 1411069 describes the possibility of preparing sequenced polymers from acrylate monomer or methacrylate monomer.

In particular, according to one embodiment, the composition according to the present invention contains at least one sequenced ethylene copolymer (also referred to as sequenced ethylene polymer), containing at least one first sequence having a glass transition temperature (Tg) higher than or equal to 40° C. and being obtained completely or partly from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature higher than or equal to 40° C., and at least one second sequence having a glass transition temperature lower than or equal to 20° C. and being obtained completely or partly from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature lower than or equal to 20° C., the said first sequence and the said second sequence being bonded together by a statistical intermediate segment comprising at least one of the said first constituent monomers of the first sequence and at least one of the said second constituent monomers of the second sequence, and the said sequenced copolymer having a polydispersity index I greater than 2.

The sequenced polymer used according to the invention therefore comprises at least one first sequence and at least one second sequence.

By “at least” one sequence there is understood one or more sequences.

By “sequenced” polymer there is understood a polymer comprising at least two distinct sequences, preferably at least three distinct sequences.

By “ethylene” polymer there is understood a polymer obtained by polymerization of monomers containing an ethylenic unsaturation.

The sequenced ethylene polymer used according to the invention is prepared exclusively from monofunctional monomers.

That means that the sequenced ethylene polymer used according to the present invention does not contain multifunctional monomers, which make it possible to break the linearity of a polymer in order to obtain a branched or even cross-linked polymer, according to the proportion of the multifunctional polymer. Neither does the polymer used according to the invention contain macromonomers (by “macromonomer” there is understood a monofunctional monomer having a pendant group of polymeric nature, and preferably having a molecular weight greater than 500 g/mol, or else a polymer containing, at one of its ends, a polymerizable terminal group (or an ethylenically unsaturated group)), which are used in preparation of a graft polymer.

It is emphasized that the terms “first” and “second” hereinabove and hereinafter in no way affect the order of the said sequences (or blocks) in the polymer structure.

Advantageously, the first sequence and the second sequence of the polymer used in the invention may be incompatible with one another.

By “sequences incompatible with one another” it is understood that the mixture formed by a polymer corresponding to the first sequence and by a polymer corresponding to the second sequence is not miscible in the polymerization solvent, constituting the majority by weight, of the sequenced polymer, at room temperature (20° C.) and atmospheric pressure (105 Pa), for a content of the mixture of the said polymers greater than or equal to 5% by weight relative to the total weight of the mixture of the said polymers and of the said polymerization solvent, its being understood that:

i) the said polymers are present in the mixture in a content such that the respective weight ratio ranges from 10/90 to 90/10, and that
ii) each of the polymers corresponding to the first and second sequences has a (weight or number) average molecular weight equal to that of the sequenced polymer±15%.

In the case of a mixture of polymerization solvents, and assuming two or more solvents present in identical proportions by weight, the said polymer mixture is not miscible in at least one of those.

Of course, in the case of polymerization carried out in a single solvent, this is the majority solvent.

The sequenced polymer according to the invention comprises at least one first sequence and at least one second sequence, bonded together by an intermediate segment comprising at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence. The intermediate segment (also referred to as intermediate sequence) has a glass transition temperature Tg between the glass transition temperatures of the first and second sequences.

The intermediate segment is a sequence comprising at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence is capable of making these sequences “compatible”.

Advantageously, the intermediate segment comprising at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence of the polymer is a statistical polymer.

Preferably, the intermediate sequence is obtained substantially from constituent monomers of the first sequence and of the second sequence.

By “substantially” there is understood at least 85%, preferably at least 90%, better at least 95% and even better 100%.

The sequenced polymer according to the invention is advantageously a film-forming sequenced ethylene polymer.

By “ethylene” polymer there is understood a polymer obtained by polymerization of monomers containing an ethylenic unsaturation.

By “film-forming polymer” there is understood a polymer capable of forming, on its own or in the presence of an auxiliary filmifying agent, a continuous deposit on a substrate, especially on horny tissues.

Preferentially, the polymer according to the invention does not comprise silicon atoms in its skeleton. By “skeleton” there is understood the main chain of the polymer, as opposed to pendant side chains.

Preferably, the polymer according to the invention is not water-soluble, meaning that the polymer is not soluble in water or in a mixture of water and lower linear or branched monohydric alcohols having 2 to 5 carbon atoms, such as ethanol, isopropanol or n-propanol, without modification of pH, at an active material content of at least 1% by weight, at room temperature (20° C.).

Preferably, the polymer according to the invention is not an elastomer.

By “non-elastomeric polymer” there is understood a polymer which, when it is subjected to a stress tending to stretch it (for example by 30% relative to its initial length), does not return to a length substantially identical to its initial length when the stress ceases.

More specifically, by “non-elastomeric polymer” there is denoted a polymer having an instantaneous recovery Ri<50% and a delayed recovery R2h<70% after having undergone an elongation of 30%. Preferably, Ri is <30% and R2h is <50%.

More precisely, the non-elastomeric character of the polymer is determined according to the following protocol:

A polymer film is prepared by casting a polymer solution in a Teflon-coated die then drying it for 7 days in a controlled environment at 23±5° C. and 50±10% relative humidity.

In this way there is obtained a film of approximately 100 μm thickness, from which there are cut rectangular specimens (for example, with a punch) having a width of 15 mm and a length of 80 mm.

This specimen is subjected to tensile load by means of an apparatus sold under the name Zwick, under the same temperature and humidity conditions as for drying.

The specimens are drawn at a speed of 50 mm/min, and the distance between the jaws is 50 mm, corresponding to the initial length (l0) of the specimen.

The instantaneous recovery Ri is determined as follows:

    • the specimen is drawn by 30% (εmax), or in other words by approximately 0.3 times its initial length (la)
    • the stress is relaxed by imposing a return speed equal to the tension speed, or in other words 50 mm/min, and the residual elongation of the specimen is measured in percent, after return to zero load stress (εi).

The instantaneous recovery in % (Ri) is given by the following formula:


Ri=(εmax−εi)/εmax)×100

To determine the delayed recovery, the percentage residual elongation of the specimen after 2 hours (ε2h) is measured 2 hours after return to zero load stress.

The delayed recovery (R2h) in % is given by the following formula:


R2h=(εmax−ε2h)/εmax)×100

Purely by way of indication, a polymer according to an embodiment of the invention preferably has an instantaneous recovery Ri of 10% and a delayed recovery R2h of 30%.

The polydispersity index of the polymer of the invention is greater than 2.

Advantageously, the sequenced polymer used in the compositions according to the invention has a polydispersity index I greater than 2, for example ranging from 2 to 9, preferably greater than or equal to 2.5, for example ranging from 2.5 to 8, and better greater than or equal to 2.8, and especially ranging from 2.8 to 6.

The polydispersity index I of the polymer is equal to the ratio of weight-average molecular weight Mw to number-average molecular weight Mn.

The weight-average and number-average molecular weights (Mw and Mn respectively) are determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometer detector).

The weight-average molecular weight (Mw) of the polymer according to the invention is preferably smaller than or equal to 300,000; for example, it ranges from 35,000 to 200,000, and better from 45,000 to 150,000 g/mol.

The number-average molecular weight (Mn) of the polymer according to the invention is preferably smaller than or equal to 70,000; for example, it ranges from 10,000 to 60,000, and better from 12,000 to 50,000 g/mol.

Preferably, the polydispersity index of the polymer according to the invention is greater than 2, for example ranging from 2 to 9, preferably greater than or equal to 2.5, for example ranging from 2.5 to 8, and better greater than or equal to 2.8 and especially ranging from 2.8 to 6.

First Sequence Having a Tg Higher than or Equal to 40° C.

The sequence having a Tg higher than or equal to 40° C. has, for example, a Tg ranging from 40 to 150° C., preferably higher than or equal to 50° C., for example ranging from 50 to 120° C., and better higher than or equal to 60° C., for example ranging from 60 to 120° C.

The indicated glass transition temperatures of the first and second sequences may be theoretical Tg values determined from the theoretical Tg values of the constituent monomers of each of the sequences, as can be found in a reference manual such as Polymer Handbook, 3rd ed., 1989, John Wiley, according to the following relationship, which is known as Fox's law:

1/Tg=i(ϖi/Tgi),

where ωl is the weight fraction of monomer i in the sequence under consideration and Tgi is the glass transition temperature of the homopolymer of monomer i.

Unless otherwise indicated, the Tg values indicated for the first and second sequences in the present Application are theoretical Tg values.

The difference between the glass transition temperatures of the first and second sequences is generally larger than 10° C., preferably larger than 20° C., and better larger than 30° C.

    • In the present invention, the expression “between . . . and . . . ” is understood to denote an interval of values that excludes the indicated bounds, and “from . . . to . . . ” and “ranging from . . . to . . . ” an interval of values that includes the bounds.

The sequence having a Tg higher than or equal to 40° C. may be a homopolymer or a copolymer.

The sequence having a Tg higher than or equal to 40° C. may be obtained completely or partly from one or more monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature higher than or equal to 40° C. This sequence may also be referred to as “rigid sequence”.

In the case in which this sequence is a homopolymer, it is obtained from monomers, which are such that the homopolymers prepared from these monomers have glass transition temperatures higher than or equal to 40° C. This first sequence may be a homopolymer composed of a single type of monomer (for which the Tg of the corresponding homopolymer is higher than or equal to 40° C.).

In the case in which the first sequence is a copolymer, it may be obtained completely or partly from one or more monomers, whose nature and concentration are chosen such that the Tg of the resulting copolymer is higher than or equal to 40° C. As an example, the copolymer may comprise:

    • monomers that are such that the homopolymers prepared from these monomers have Tg values higher than or equal to 40° C., for example a Tg ranging from 40 to 150° C., preferably higher than or equal to 50° C., for example ranging from 50 to 120° C., and better higher than or equal to 60° C., for example ranging from 60 to 120° C., and
    • monomers that are such that the homopolymers prepared from these monomers have Tg values lower than 40° C., chosen from among the monomers having a Tg between 20 and 40° C. and/or the monomers having a Tg lower than or equal to 20° C., for example a Tg ranging from −100 to 20° C., preferably lower that 15° C., especially ranging from −80 to 15° C., and better lower than 10° C., for example ranging from −50 to 0° C., such as described hereinafter.

The first monomers, whose homopolymers have a glass transition temperature higher than or equal to 40° C., are preferably chosen from among the following monomers, also referred to as main monomers:

    • the methacrylates of formula CH2═C(CH3)—COOR1,
      in which R1 represents a linear or branched unsubstituted alkyl group containing 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, or R1 represents a C4 to C12 cycloalkyl group, preferably a C8 to C12 cycloalkyl group, such as isobornyl methacrylate,
    • the acrylates of formula CH2═CH—COOR1,
      in which R1 represents a C4 to C12 cycloalkyl group, such as an isobornyl group or a tert-butyl group,
    • the (meth)acrylamides of formula:

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where R7 or R8, which may be identical or different, each represent a hydrogen atom or a linear or branched C1 to C12 alkyl group, such as an n-butyl, t-butyl, isopropyl, isohexyl, isooctyl or isononyl group; or R7 represents H and R8 represents a 1,1-dimethyl-3-oxobutyl group, and R′ denotes H or methyl. As an example of monomers there may be cited N-butyl acrylamide, N-t-butyl acrylamide, N-isopropyl acrylamide, N,N-dimethyl acrylamide and N,N-dibutyl acrylamide,

    • and mixtures thereof.

The first sequence is advantageously obtained from at least one acrylate monomer of formula CH2═CH—COOR2 and from at least one methacrylate monomer of formula CH2═C(CH3)—COOR2, in which R2 represents a C4 to C12 cycloalkyl group, preferably a C8 to C12 cycloalkyl group, such as isobornyl. The monomers and their proportions are preferably chosen such that the glass transition temperature of the first sequence is higher than or equal to 40° C.

According to one embodiment, the first sequence is obtained from:

i) at least one acrylate monomer of formula CH2═CH—COOR2, in which R2 represents a C4 to C12 cycloalkyl group, preferably a C8 to C12 cycloalkyl group, such as isobornyl,
ii) and at least one methacrylate group of formula CH2═C(CH3)—COOR′2, in which R′2 represents a C4 to C12 cycloalkyl group, preferably a C8 to C12 cycloalkyl group, such as isobornyl.

According to one embodiment, the first sequence is obtained from at least one acrylate monomer of formula CH2═CH—COOR2, in which R2 represents a C8 to C12 cycloalkyl group, such as isobornyl, and from at least one methacrylate monomer of formula CH2═C(CH3)—COOR′2, in which R′2 represents a C8 to C12 cycloalkyl group, such as isobornyl.

Preferably, R2 and R′2 independently or simultaneously represent an isobornyl group.

Preferably, the sequenced polymer comprises 50 to 80% by weight of isobornyl methacrylate/acrylate, 10 to 30% by weight of isobutyl acrylate and 2 to 10% by weight of acrylic acid.

The first sequence may be obtained exclusively from the said acrylate monomer and from the said methacrylate monomer.

The acrylate monomer and the methacrylate monomer are preferably in weight propositions between 30:70 and 70:30, preferably between 40:60 and 60:40, especially on the order of 50:50.

The proportion of the first sequence will advantageously range from 20 to 90% by weight of the polymer, better from 30 to 80% and even better from 60 to 80%.

According to one embodiment, the first sequence is obtained by polymerization of isobornyl methacrylate and isobornyl acrylate.

Second Sequence Having a Glass Transition Temperature Lower than 20° C.

The second sequence advantageously has a glass transition temperature Tg lower than or equal to 20° C., for example has a Tg ranging from −100 to 20° C., preferably lower than or equal to 15° C., for example ranging from −80 to 15° C., and better lower than or equal to 10° C., for example ranging from −100° C. to 10° C., especially ranging from −30° C. to 10° C.

The second sequence is obtained completely or partly from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature lower than or equal to 20° C.

This sequence may also be referred to as “flexible sequence”.

The monomer having a Tg lower than or equal to 20° C. (referred to as second monomer) is preferably chosen from among the following monomers:

    • the acrylates of formula CH2═CHCOOR3,
      R3 representing a linear or branched unsubstituted C1 to C12 alkyl group, with the exception of the tert-butyl group, in which one or more hetero atoms chosen from among O, N, S are present, possibly intercalated,
    • the methacrylates of formula CH2═C(CH3)—COOR4,
      R4 representing a linear or branched unsubstituted C6 to C12 alkyl group, in which one or more hetero atoms chosen from among O, N, S are present, possibly intercalated;
    • the vinyl esters of formula R5—CO—O—CH═CH2
      where R5 represents a linear or branched C4 to C12 alkyl group;
    • the ethers of vinyl alcohol and C4 to C12 alcohol,
    • the N—(C4 to C12)-alkyl acrylamides, such as N-octyl acrylamide,
    • and mixtures thereof.

The preferred monomers having a Tg lower than or equal to 20° C. are isobutyl acrylate, ethyl-2-hexyl acrylate or mixtures thereof in all proportions.

Each of the first and second sequences may contain, in minority proportion, at least one constituent monomer of the other sequence.

Thus the first sequence may contain at least one constituent monomer of the second sequence and vice versa.

Each of the first and/or second sequences may comprise, in addition to the monomers indicated hereinabove, one or more other monomers, referred to as additional monomers, different from the main monomers cited in the foregoing.

The nature and quantity of this or those additional monomer or monomers are chosen such that the sequence in which they are present has the desired glass transition temperature. As an example, this additional monomer is chosen from among:

the monomers having ethylene unsaturations and comprising at least one tertiary amine function, such as 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide and the salts thereof,

    • the methacrylates of formula CH2═C(CH3)—COOR6
      in which R6 represents a linear or branched alkyl group containing 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, the said alkyl group being substituted by one or more substituents chosen from among the hydroxyl groups (such as 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate) and the halogen atoms (Cl, Br, I, F), such as trifluoroethyl methacrylate,
    • the methacrylates of formula CH2═C(CH3)—COOR9,
      R9 representing a linear or branched C6 to C12 alkyl group, in which one or more hetero atoms chosen from among O, N, S are present, possibly intercalated, the said alkyl group being substituted by one or more substituents chosen from among the hydroxyl groups and the halogen atoms (Cl, Br, I, F);
    • the acrylates of formula CH2═CHCOOR10,
      R10 representing a linear or branched C6 to C12 alkyl group substituted by one or more substituents chosen from among the hydroxyl groups and the halogen atoms (Cl, Br, I, F), such as 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate, or R10 represents a (C1 to C12)-alkyl-O-POE (polyoxyethylene) with 5 to 10 repetitions of the oxyethylene moiety, for example methoxy-POE, or R8 represents a polyoxyethylene group comprising 5 to 10 ethylene oxide moieties.

In particular, the first sequence may comprise, by way of additional monomer:

    • (meth)acrylic acid, preferably acrylic acid,
    • tert-butyl acrylate
    • the methacrylates of formula CH2═C(CH3)—COOR1
      in which R1 represents a linear or branched unsubstituted alkyl group containing 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group,
    • the (meth)acrylamides of formula:

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where R7 or R8, which may be identical or different, each represent a hydrogen atom or a linear or branched C1 to C12 alkyl group, such as an n-butyl, t-butyl, isopropyl, isohexyl, isooctyl or isononyl group; or R7 represents H and R8 represents a 1,1-dimethyl-3-oxobutyl group, and R′ denotes H or methyl. As an example of monomers there may be cited N-butyl acrylamide, N-t-butyl acrylamide, N-isopropyl acrylamide, N,N-dimethyl acrylamide and N,N-dibutyl acrylamide,

    • and mixtures thereof.

The additional monomer may represent 0.5 to 30% by weight of the polymer. According to one embodiment, the polymer of the invention does not contain additional monomer.

Preferably, the polymer of the invention comprises at least isobornyl acrylate and isobornyl methacrylate monomers in the first sequence and isobutyl acrylate and acrylic acid monomers in the second sequence.

Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in equivalent proportions by weight in the first sequence and isobutyl acrylate and acrylic acid monomers in the second sequence.

Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in equivalent proportions by weight in the first sequence and isobutyl acrylate and acrylic acid monomers in the second sequence, the first sequence representing 70% by weight of the polymer.

Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in equivalent proportions by weight in the first sequence and isobutyl acrylate and acrylic acid monomers in the second sequence. Preferably, the sequence of Tg higher than 40° C. representing 70% by weight of the polymer, and the acrylic acid representing 5% by weight of the polymer.

According to one embodiment, the first sequence does not contain additional monomer. According to a preferred embodiment, the second sequence comprises acrylic acid by way of additional monomer. In particular, the second sequence is advantageously obtained from an acrylic acid monomer and at least one other monomer having a Tg lower than or equal to 20° C.

According to a preferred embodiment, the sequenced ethylene polymer is a copolymer comprising at least one acrylate monomer of formula CH2═CH—COOR2, in which R2 represents a C8 to C12 cycloalkyl group, and/or at least one methacrylate monomer of formula CH2═C(CH3)—COOR′2, in which R′2 represents a C8 to C12 cycloalkyl group, at least one second acrylate monomer of formula CH2═CHCOOR3, in which R3 represents a linear or branched unsubstituted C1 to C12 alkyl group, with the exception of the tert-butyl group, and at least one acrylic acid monomer.

Preferably, the copolymer used in the compositions according to the invention is obtained from at least one isobornyl methacrylate monomer, at least one isobornyl acrylate monomer, at least one isobutyl acrylate monomer and at least one acrylic acid monomer.

Advantageously, the copolymer used in the invention comprises 50 to 80% by weight of isobornyl methacrylate/acrylate mixture, 10 to 30% by weight of isobutyl acrylate and 2 to 10% by weight of acrylic acid.

The sequenced copolymer may advantageously comprise more than 2% by weight of acrylic acid monomers, and especially from 2 to 15% by weight, for example from 3 to 15% by weight, in particular from 4 to 15% by weight, even from 4 to 10% by weight of acrylic acid monomers relative to the total weight of the said copolymer.

The constituent monomers of the second sequence and the proportions thereof are chosen such that the glass transition temperature of the second sequence is lower than or equal to 20° C.

Intermediate Segment

The intermediate segment (also referred to as intermediate sequence) bonds the first sequence and the second sequence of the polymer used according to the present invention. The intermediate segment results from the polymerization:

i) of the first monomer or monomers, and possibly of the additional monomer or monomers, remaining available after their polymerization to a degree of conversion of 90% at most, to form the first sequence,
ii) and of the second monomer or monomers, and possibly of the additional monomer or monomers, added to the reaction mixture.

The formation of the second sequence is initiated when the first monomers no longer react or are no longer being incorporated into the polymer chain, either because they have all been consumed or because their reactivity does not permit them to be further consumed.

Thus the intermediate segment comprises the available first monomers resulting from a degree of conversion of these first monomers smaller than or equal to 90%, during introduction of the second monomer or monomers during synthesis of the polymer.

The intermediate segment of the sequenced polymer is a statistical polymer (which may also be referred to as a statistical sequence). This means that it comprises a statistical distribution of the first monomer or monomers and of the second monomer or monomers as well as of any additional monomer or monomers that may be present.

Thus the intermediate segment is a statistical sequence, just as the first sequence and the second sequence if they are not homopolymers (or in other words if they are both formed from at least two different monomers).

Method for Preparation of the Copolymer:

The sequenced ethylene copolymer according to the invention is prepared by free radical polymerization, according to well known techniques for this type of polymerization.

The free radical polymerization is carried out in the presence of an initiator, whose nature is adapted, in known manner, according to the desired polymerization temperature and the polymerization solvent. In particular, the initiator may be chosen among the peroxide function initiators, the oxidation-reduction couples, or other radical polymerization initiators known to those skilled in the art.

In particular, by way of peroxide function initiator, the following examples may be cited:

    • a. the peroxy esters, such as tert-butyl peroxyacetate, tert-butyl perbenzoate, tert-butyl peroxy-2-ethylhexanoate (Trigonox 21S of Akzo Nobel), 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox 141 of Akzo Nobel);
    • b. the peroxydicarbonates, such as diisopropyl peroxydicarbonate;
    • c. the peroxyketones, such as methyl ethyl ketone peroxide;
    • d. hydroperoxides, such as hydrogen peroxide (H2O2), tert-butyl hydroperoxide;
    • e. the diacyl peroxides, such as acetyl peroxide, benzoyl peroxide;
    • f. the dialkyl peroxides, such as di-tert-butyl peroxide;
    • g. the inorganic peroxides, such as potassium peroxodisulfate (K2S2O8);

By way of initiator in the form of oxidation-reduction couple, there may be cited the couple potassium thiosulfate+potassium peroxodisulfate, for example.

According to a preferred embodiment, the initiator is chosen from among the organic peroxides comprising 8 to 30 carbon atoms. Preferably, the initiator used is 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane, sold under the name Trigonox® 141 by the Akzo Nobel Company.

The sequenced copolymer used according to the invention is prepared by free radical polymerization and not by controlled or living polymerization. In particular, the polymerization of the sequenced ethylene copolymer is carried out in the absence of control agents, and in particular in the absence of control agent traditionally used in living or controlled polymerization processes, such as the nitroxides, the alkoxyamines, the dithio esters, the dithiocarbamates, the dithiocarbonates or xanthates, the trithiocarbonates, the copper-based catalysts, for example.

As indicated in the foregoing, the intermediate segment is a statistical sequence, just as the first sequence and the second sequence if they are not homopolymers (or in other words if they are both formed from at least two different monomers).

The sequenced copolymer may be prepared by free radical polymerization, and in particular by a method consisting of mixing, in the same reactor, a polymerization solvent, an initiator, at least one monomer with glass transition higher than or equal to 40° C., at least one monomer of glass transition lower than or equal to 20° C., according to the following sequence:

    • part of the polymerization solvent and if necessary part of the initiator and monomers of the first charge are poured into the reactor, and the mixture is heated to a reaction temperature between 60 and 120° C.,
    • the said at least one first monomer of Tg higher than or equal to 40° C. and if necessary part of the initiator are then poured into a first charge, which is allowed to react for a duration T corresponding to a degree of conversion of the said monomers of 90% at most,
    • more polymerization initiator, the said at least one second monomer of glass transition lower than or equal to 20° C. are then poured into the reactor in a second charge, which is allowed to react for a duration T′, at the end of which the degree of conversion of the said monomers reaches a plateau,
    • the reaction mixture is returned to room temperature.

Preferably, the copolymer may be prepared by free radical polymerization, in particular by a method consisting of mixing, in the same reactor, a polymerization solvent, an initiator, an acrylic acid monomer, at least one monomer of glass transition lower than or equal to 20° C., at least one acrylate monomer of formula CH2═CH—COOR2, in which R2 represents a C4 to C12 cycloalkyl group, and at least one methacrylate monomer of formula CH2═C(CH3)—COOR′2, in which R′2 represents a C4 to C12 cycloalkyl group, according to the following step sequence:

    • part of the polymerization solvent and if necessary part of the initiator and monomers of the first charge are poured into the reactor, and the mixture is heated to a reaction temperature between 60 and 120° C.,
    • the said at least acrylate monomer of formula CH2═CH—COOR2 and the said at least methacrylate monomer of formula CH2═C(CH3)—COOR′2, in the capacity of monomers of Tg higher than or equal to 40° C., and if necessary part of the initiator are then poured into a first charge, which is allowed to react for a duration T corresponding to a degree of conversion of the said monomers of 90% at most,
    • more polymerization initiator, the acrylic acid monomer and the said at least monomer of glass transition lower than or equal to 20° C. are then poured into the reactor in a second charge, which is allowed to react for a duration T′, at the end of which the degree of conversion of the said monomers reaches a plateau,
    • the reaction mixture is returned to room temperature.

By polymerization solvent there is understood a solvent or a mixture of solvents. In particular, by way of usable polymerization solvent, there may be cited:

    • the ketones that are liquid at room temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone, acetone;
    • the propylene glycol ethers that are liquid at room temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, mono-n-butyl ether of dipropylene glycol;
    • the short-chain esters (having 3 to 8 carbon atoms in total), such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate, isopentyl acetate;
    • the ethers that are liquid at room temperature, such as diethyl ether, dimethyl ether or dichlorodiethyl ether;
    • the alkanes that are liquid at room temperature, such as decane, heptane, dodecane, isododecane, cyclohexane, isohexadecane;
    • the aromatic cyclic compounds that are liquid at room temperature, such as toluene and xylene; the aldehydes that are liquid at room temperature, such as benzaldehyde, acetaldehyde and mixtures thereof.

Traditionally, the polymerization solvent is a volatile oil with flash point below 80° C. The flash point is measured in particular according to ISO Standard 3679.

The polymerization solvent may be chosen in particular from among ethyl acetate, butyl acetate, the alcohols such as isopropanol, ethanol, the aliphatic alkanes such as isododecane and mixtures thereof. Preferably, the polymerization solvent is a mixture of butyl acetate and isopropanol or isododecane.

According to another embodiment, the copolymer may be prepared by free radical polymerization according to a method consisting of mixing, in the same reactor, a polymerization solvent, an initiator, at least one monomer with glass transition lower than or equal to 20° C., and at least one monomer of Tg higher than or equal to 40° C., according to the following step sequence:

    • part of the polymerization solvent and if necessary part of the initiator and monomers of the first charge are poured into the reactor, and the mixture is heated to a reaction temperature between 60 and 120° C.,
    • the said at least one monomer of glass transition lower than or equal to 20° C. and if necessary part of the initiator are then poured into a first charge, which is allowed to react for a duration T corresponding to a degree of conversion of the said monomers of 90% at most,
    • more polymerization initiator, the said at least one monomer of Tg higher than or equal to 40° C. are then poured into the reactor in a second charge, which is allowed to react for a duration T′, at the end of which the degree of conversion of the said monomers reaches a plateau,
    • the reaction mixture is returned to room temperature.

According to a preferred embodiment, the copolymer may be prepared by free radical polymerization according to a preparation method consisting of mixing, in the same reactor, a polymerization solvent, an initiator, an acrylic acid monomer, at least one monomer of glass transition lower than or equal to 20° C., at least one monomer of Tg higher than or equal to 40° C., and, in particular, in the capacity of monomers of Tg higher than or equal to 40° C., at least one acrylate monomer of formula CH2═CH—COOR2, in which R2 represents a C4 to C12 cycloalkyl group, and at least one methacrylate monomer of formula CH2═C(CH3)—COOR′2, in which R′2 represents a C4 to C12 cycloalkyl group, according to the following step sequence:

    • part of the polymerization solvent and if necessary part of the initiator and monomers of the first charge are poured into the reactor, and the mixture is heated to a reaction temperature between 60 and 120° C.,
    • the acrylic acid monomer and the said at least monomer of glass transition lower than or equal to 20° C. and if necessary part of the initiator are then poured into a first charge, which is allowed to react for a duration T corresponding to a degree of conversion of the said monomers of 90% at most,
    • more polymerization initiator, the said at least one acrylate monomer of formula CH2═CH—COOR2 and the said at least one methacrylate monomer of formula CH2═C(CH3)—COOR′2, in the capacity of monomer of Tg higher than or equal to 40° C., are then poured into the reactor in a second charge, which is allowed to react for a duration T′, at the end of which the degree of conversion of the said monomers reaches a plateau,
    • the reaction mixture is returned to room temperature.

The polymerization temperature is preferably on the order of 90° C.

The duration of reaction after the second charge is preferably between 3 and 6 hours.

Sequenced copolymers such as those described in the foregoing are described in particular in Patent Applications EP A 1411069 and EP A 1882709.

The film-forming polymer may be chosen from among the block or static polymers and/or copolymers composed in particular of polyurethanes, polyacrylics, silicones, fluoro polymers, butyl rubbers, ethylene copolymers, natural rubbers and polyvinyl alcohols and mixtures thereof. The monomers of the block or static copolymers comprising at least one association of monomers whose polymer results in a glass transition temperature lower than room temperature (25° C.) may be chosen in particular from among butadiene, ethylene, propylene, acrylic, methacrylic, isoprene, isobutene, a silicone and mixtures thereof.

Vinyl Polymer Grafted with a Carbosiloxane Dendrimer

According to a second embodiment, the composition according to the invention may comprise, by way of film-forming polymer, a film-forming polymer chosen from among the vinyl polymers comprising at least one moiety derived from carbosiloxane dendrimer.

The vinyl polymer may have in particular a skeleton and at least one side chain, which comprises a carbosiloxane dendrimer structure. Within the context of the present invention, the term “carbosiloxane dendrimer structure” represents a molecular structure possessing branched groups having high molecular weights, the said structure having high regularity in the radial direction starting from the bond to the skeleton. Such carbosiloxane dendrimer structures are described in the form of a highly branched siloxane-silylalkylene copolymer in Kokai 9-171 154, a Japanese Patent Application laid open to public inspection.

The vinyl polymer contains moieties derived from carbosiloxane dendrimers that can be represented by the following general formula:

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in which R1 represents an aryl group or an alkyl group possessing 1 to 10 carbon atoms, and X1 represents a silylalkyl group which, when i=1, is represented by the formula:

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in which R1 is the same as defined hereinabove, R2 represents an alkylene group possessing 2 to 10 carbon atoms, R3 represents an alkyl group possessing 1 to 10 carbon atoms, Xi+1 represents a hydrogen atom, an alkyl group possessing 1 to 10 carbon atoms, an aryl group or the silylalkyl group defined hereinabove with i=i+1; i is an integral number from 1 to 10, representing the generation of the said silylalkyl group, and ai is an integral number from 0 to 3; Y represents a radical-polymerizable organic group chosen from the group constituted by an organic group that contains a methacrylic group or an acrylic group and that is represented by the formulas:

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in which R4 represents a hydrogen atom or an alkyl group, R5 represents an alkylene group possessing 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group or a butylene group, the methylene group and the propylene group being preferred; and
an organic group that contains a styryl group and is represented by the formula:

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in which R6 represents a hydrogen atom or an alkyl group, R7 represents an alkyl group possessing 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group or a butyl group, the methyl group being preferred; R8 represents an alkylene group possessing 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, the ethylene group being preferred; b in an integral number from 0 to 4 and c is equal to 0 or 1, such that if c is equal to 0, —(R8)c— represents a bond.
R1 represents an aryl group or an alkyl group possessing 1 to 10 carbon atoms, where the alkyl group is preferably represented by a methyl group, an ethyl group, a propyl group, butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group, a cyclohexyl group, and where the aryl group is preferably represented by a phenyl group and a naphthyl group, in which the methyl and phenyl groups are particularly preferred, and the methyl group is preferred above all.

The vinyl polymer that contains a carbosiloxane dendrimer structure may be the product of polymerization of

(A) 0 to 99.9 parts by weight of a monomer of vinyl type; and

(B) 100 to 0.1 parts by weight of a carbosiloxane dendrimer that contains a group that can be polymerized by means of radicals, represented by the general formula:

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in which Y represents a radical-polymerizable organic group, R1 represents an aryl group or an alkyl group possessing 1 to 10 carbon atoms, and X1 represents a silylalkyl group which, when i=1, is represented by the formula:

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in which R1 is the same as defined hereinabove, R2 represents an alkylene group possessing 2 to 10 carbon atoms, R3 represents an alkyl group possessing 1 to 10 carbon atoms, X1+1 represents a hydrogen atom, an alkyl group possessing 1 to 10 carbon atoms, an aryl group or the silylalkyl group defined hereinabove with i=i+1; i is an integral number from 1 to 10, representing the generation of the said silylalkyl group, and a1 is an integral number from 0 to 3; where the said radical-polymerizable organic group contained in component (B) is chosen from the group constituted by an organic group that contains a methacrylic group or an acrylic group and that is represented by the formulas:

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in which R4 represents a hydrogen atom or an alkyl group, R5 represents an alkylene group possessing 1 to 10 carbon atoms; and
an organic group that contains a styryl group and is represented by the formula:

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in which R6 represents a hydrogen atom or an alkyl group, R7 represents an alkyl group possessing 1 to 10 carbon atoms, R8 represents an alkylene group possessing 1 to 10 carbon atoms, b is an integral number from 0 to 4 and c is equal to 0 or 1. In the case that c is equal to 0, —(R8)c— represents a bond.

The monomer of vinyl type that is component (A) in the vinyl polymer is a monomer of vinyl type that contains a radical-polymerizable vinyl group. There is no particular limitation as regards the type of such a monomer. What follows are examples of this monomer of vinyl type: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, or a lower analogous alkyl methacrylate; glycidyl methacrylate; n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, methacrylic acid, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl methacrylate or a higher analogous methacrylate; vinyl acetate, vinyl propionate, or a vinyl ester of lower analogous fatty acid; vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate, or an ester of higher analogous fatty acid; styrene, vinyltoluene, benzyl methacrylate, phenoxyethyl methacrylate, vinylpyrrolidone, or analogous aromatic vinyl monomers; methacrylamide, N-methylol methacrylamide, N-methoxymethyl methacrylamide, isobutoxymethoxy methacrylamide, N,N-dimethyl methacrylamide, or analogous monomers of vinyl type that contain amide groups; hydroxyethyl methacrylate, hydroxypropyl alcohol methacrylate, or analogous monomers of vinyl type that contain hydroxyl groups; methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, or analogous monomers of vinyl type that contain a carboxylic acid group; tetrahydrofurfuryl methacrylate, butoxyethyl methacrylate, ethoxydiethylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene glycol monomethacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, or an analogous monomer of vinyl type with ether bonds; methacryloxypropyltrimethoxysilane, polydimethylsiloxane having a methacrylic group on one of its molecular ends, polydimethylsiloxane having a styryl group on one of its molecular ends, or an analogous silicone compound possessing unsaturated groups; butadiene; vinyl chloride; vinylidine chloride; methacrylonitrite; dibutyl fumarate; anhydrous maleic acid; anhydrous succinic acid; methacryt glycidyl ether; an organic salt of an amine, an ammonium salt, and an alkali metal salt of methacrylic acid, of itaconic acid, of crotonic acid, of maleic acid or of fumaric acid; a radical-polymerizable unsaturated monomer possessing a sulfonic acid group, such as a styrenesulfonic acid group; a quaternary ammonium salt derived from methacrylic acid, such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride; and an ester of methacrylic acid of an alcohol possessing a tertiary amine group, such as an ester of methacrylic acid and diethylamine.

Multifunctional monomers of vinyl type may also be used. What follows represents examples of such compounds: trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trioxyethyl methacrylate, tris-(2-hydroxyethyl)isocyanurate dimethacrylate, tris-(2-hydroxyethyl)isocyanurate trimethacrylate, polydimethylsiloxane capped with styryl groups possessing divinylbenzene groups at both ends, or analogous silicone compounds possessing unsaturated groups.

The carbosiloxane dendrimer, which is component (B), is represented by the following formula:

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What follows are preferred examples of the radical-polymerizable organic group Y: an acryloxymethyl group, a 3-acryloxypropyl group, a methacryloxymethyl group, a 3-methacryloxypropyl group, a 4-vinylphenyl group, a 3-vinylphenyl group, a 4-(2-propenyl)phenyl group, a 3-(2-propenyl)phenyl group, a 2-(4-vinylphenyl)ethyl group, a 2-(3-vinylphenyl)ethyl group, a vinyl group, an allyl group, a methallyl group and a 5-hexenyl group.

R1 represents an alkyl group or an aryl group possessing 1 to 10 carbon atoms, where the alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group or a cyclohexyl group; and the aryl group may be a phenyl group or a naphthyl group. The methyl and phenyl groups are particularly preferred, the methyl group being preferred above all. X1 represents a silylalkyl group which, when i=1, is represented by the formula:

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in which R2 represents an alkylene group possessing 2 to 10 carbon atoms, such as an ethylene group, a propylene group, a butylene group, a hexylene group or an analogous linear alkylene group; a methylmethylene group, a methylethylene group, a 1-methylpentylene group, a 1,4-dimethylbutylene group or an analogous branched alkylene group. The ethylene, methylethylene, hexylene, 1-methylpentylene and 1,4-dimethylbutylene groups are preferred above all. R3 represents an alkyl group possessing 1 to 10 carbon atoms, such as the methyl, ethyl, propyl, butyl and isopropyl groups. R1 is the same as defined hereinabove. Xi+1 represents a hydrogen atom, an alkyl group possessing 1 to 10 carbon atoms, an aryl group or the silylalkyl group with i=i+1; ai is an integral number from 0 to 3 and i is an integral number from 1 to 10, indicating the generation number, which represents the number of repetitions of the silylalkyl group.

For example, when the generation number is equal to one, the carbosiloxane dendrimer may be represented by the first general formula shown below, in which Y, R1, R2 and R3 are the same as defined hereinabove, R12 represents a hydrogen atom or is identical to R1; a1 is identical to ai. Preferably, the mean total number of OR3 groups in a molecule is in the range from 0 to 7. When the generation number is equal to 2, the carbosiloxane dendrimer may be represented by the second general formula shown below, in which Y, R1, R2, R3 and R12 are the same as defined hereinabove; a1 and a2 represent the ai of the indicated generation. Preferably, the mean total number of OR3 groups in a molecule is in the range from 0 to 25. In the case that the generation number is equal to 3, the carbosiloxane dendrimer may be represented by the third general formula shown below, in which Y, R1, R2, R3 and R12 are the same as defined hereinabove; a1, a2 and a3 represent the ai of the indicated generation. Preferably, the mean total number of OR3 groups in a molecule is in the range from 0 to 79.

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A carbosiloxane dendrimer containing a radical-polymerizable organic group may be represented by the following mean structural formulas:

text missing or illegible when filed text missing or illegible when filed

The carbosiloxane dendrimer may be manufactured according to the method for manufacturing a branched siloxane silalkylene described in Japanese Patent Hei 9-171154. For example, it may be produced by subjecting to a hydrosilylation reaction an organosilicon compound that contains a hydrogen atom bonded to a silicon atom, represented by the following general formula:

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and an organosilicon compound that contains an alkenyl group. In the above formula, the organosilicon compound may be represented by 3-methacryloxypropyltris(dimethylsiloxy)silane, 3-acryloxypropyltris-(dimethylsiloxy)silane and 4-vinylphenyltris-(dimethylsiloxy)silane. The organosilicon compound that contains an alkenyl group may be represented by vinyltris-(trimethylsiloxy)silane, vinyltris-(dimethylphenylsiloxy)silane, and 5-hexenyltris-(trimethylsiloxy)silane. The hydrosilylation reaction is carried out in the presence of a chloroplatinic acid, of a complex of vinylsiloxane and platinum or of an analogous catalyst of a transition metal.

In the vinyl polymer that contains a dendrimer structure, the polymerization ratio between components (A) and (B), in terms of weight ratio between (A) and (B), may be in a range of 0/100 to 99.9/0.1, and preferably in a range of 1/99 to 99/1. A ratio of 0/100 between components (A) and (B) means that the compound becomes a homopolymer of component (B).

The vinyl polymer contains a carbosiloxane dendrimer structure and this polymer may be obtained by copolymerization of components (A) and (B) or by polymerization of component (B) alone. The polymerization may be a radical polymerization or an ionic polymerization, but radical polymerization is preferred. The polymerization may be carried out by causing a reaction between components (A) and (B) in a solution during a period of 3 to 20 hours in the presence of a radical initiator at a temperature of 50° C. to 150° C. An appropriate solvent for this purpose is hexane, octane, decane, cyclohexane or an analogous aliphatic hydrocarbon; benzene, toluene, xylene or an analogous aromatic hydrocarbon; diethyl ether, dibutyl ether, tetrahydrofuran, dioxane or analogous ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone or analogous ketones; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate or analogous esters; methanol, ethanol, isopropanol, butanol or analogous alcohols; octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane or an analogous organosiloxane oligomer. A radical initiator may be any compound known in the art for traditional radical polymerization reactions. Specific examples of such radical initiators are 2,2′-azobis(isobutyronitrile), 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile) or analogous compounds of azobis type; benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate or an analogous organic peroxide. These radical initiators may be used alone or in a combination of two or more. The radical initiators may be used in a quantity of 0.1 to 5 parts by weight per 100 parts by weight of components (A) and (B). A chain transfer agent may be added. The chain transfer agent may be 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, a polydimethylsiloxane possessing a mercaptopropyl group or an analogous compound of mercapto type; methylene chloride, chloroform, carbon tetrachloride, butyl bromide, 3-chloropropyltrimethoxysilane or an analogous halogen compound. In the manufacture of the polymer of vinyl type, the residual vinyl monomer that has not reacted may be eliminated after the polymerization under conditions of heating under vacuum.

To facilitate the preparation of the mixture of raw material for cosmetic products, the number-average molecular weight of the vinyl polymer containing a carbosiloxane dendrimer may be chosen in a range between 3,000 and 2,000,000, preferably between 5,000 and 800,000. It may be a liquid, a gum, a paste, a solid, a powder or any other form. The preferred forms are solutions constituted by dilution of a dispersion or of a powder in solvents.

The vinyl polymer may be a dispersion, in a liquid such as a silicone oil, an organic oil, an alcohol or water, of a polymer of vinyl type having a carbosiloxane dendrimer structure in its side molecular chain.

In this embodiment, the vinyl polymer having a carbosiloxane dendrimer structure in its side molecular chain is the same as that described hereinabove. The liquid may be a silicone oil, an organic oil, an alcohol or water. The silicone oil may be a dimethylpolysiloxane having the two molecular ends capped by trimethylsiloxy groups, a copolymer of methylphenylsiloxane and dimethylsiloxane having both molecular ends capped with trimethylsiloxy groups, a copolymer of methyl-3,3,3-trifluoropropylsiloxane and dimethylsiloxane having both molecular ends capped with trimethylsiloxy groups, or analogous non-reactive linear silicone oils, as well as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane or an analogous cyclic compound. In addition to non-reactive silicone oils, there may be used modified polysiloxanes possessing functional groups such as silanol groups, amino groups and polyether groups at the ends or in the interior of the side molecular chains.

The organic oils may be paraffin oil, isoparaffin, hexyl laurate, isopropyl myristate, myristyl myristate, cetyl myristate, 2-octyldodecylmyristate; isopropyl palmitate, 2-ethylhexyl palmitate, butyl stearate, decyl oleate, 2-octyldodecyl oleate, myristyl lactate, cetyl lactate, lanolin acetate, stearic alcohol, cetostearic alcohol, oleic alcohol, avocado oil, almond oil, olive oil, cocoa oil, jojoba oil, gum oil, sunflower seed oil, soy oil, camellia oil, squalane, castor oil, mink oil, cottonseed oil, coconut oil, egg yolk oil, beef suet, lard, polypropylene glycol monooleate, neopentyl glycol 2-ethylhexanoate or an analogous glycol ester oil; triglyceryl isostearate, the triglyceride of a fatty acid of coconut oil or an ester oil of an analogous polyhydric alcohol; polyoxyethylene lauryl ether, polyoxypropylene cetyl ether or an analogous polyoxyalkylene ether.

The alcohol may be any type whatsoever that is appropriate for use in conjunction with a raw material for cosmetic products. For example, it may be methanol, ethanol, butanol, isopropanol or analogous lower alcohols. A solution or a dispersion of alcohol should have a viscosity in the range of 10 to 109 mPa at 25° C. To improve the sensory properties of use in a cosmetic product, the viscosity should be in the range of 100 to 5×108 mPa·s.

The solutions and the dispersions may be easily prepared by mixing the vinyl polymer having a carbosiloxane dendrimer structure with a silicone oil, an organic oil, an alcohol or water. The liquids may be present in the step of polymerization of the polymer of vinyl type having a carbosiloxane dendrimer structure. In this case, the residual vinyl monomer that has not reacted should be completely eliminated by heat treatment of the solution or of the dispersion under atmospheric or reduced pressure. In the case of a dispersion, the dispersity of the polymer of vinyl type may be improved by adding a surfactant. Such an agent may be hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, myristylbenzenesulfonic acid, or anionic surfactants of sodium salts of these acids; octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, dioctadecyldimethylammonium hydroxide, beef suet trimethylammonium hydroxide, coconut oil trimethylammonium hydroxide or an analogous cationic surfactant; a polyoxyalkylene alkyl ether, a polyoxyalkylene alkylphenol, a polyoxyalkylene alkyl ester, polyoxyalkylene sorbitol ester, polyethylene glycol, polypropylene glycol, an ethylene oxide adduct of diethylene glycol trimethylnonanol, and nonionic surfactants of polyester type, as well as mixtures. In addition, the solvents and the dispersions may be combined with iron oxide appropriate for use with cosmetic products, or an analogous pigment, as well as zinc oxide, titanium dioxide, silicon oxide, mica, talc or analogous inorganic oxides in the form of powder. In the dispersion, a mean diameter of the particles of polymer of vinyl type may be in a range between 0.001 and 100 microns, preferably between 0.01 and 50 microns. In fact, outside the recommended range, a cosmetic product mixed in the emulsion will not have a sufficiently good sensation on the skin or to the touch, and will not have sufficient spreading properties or a pleasant sensation.

The vinyl polymer contained in the dispersion or solution may have a concentration in a range between 0.1 and 95% by weight, preferably between 5 and 85% by weight. However, to facilitate the manipulation and preparation of the mixture, the range should preferably be between 10 and 75% by weight.

The vinyl polymer may be one of the polymers described in the examples of Patent Application EP0963751 or, for example, the product TIB-4-200 sold by Dow Corning.

According to one embodiment, the vinyl polymer additionally comprises at least one fluoro organic group.

Particularly preferred are structures in which the polymerized vinyl moieties constitute the skeleton, and carbosiloxane dendritic structures as well as fluoro organic groups are fixed to the side chains.

The fluoro organic groups may be obtained by substituting, with fluorine atoms, all or part of the hydrogen atoms of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl and other alkyl groups having 1 to 20 carbon atoms, as well as of alkyloxyalkylene groups having 6 to 22 carbon atoms.

The groups represented by the formula: —(CH2)x—(CF2)y—R13 are suggested by way of example of fluoroalkyl groups, obtained by substituting fluorine atoms for hydrogen atoms of alkyl groups. In the formula, the index “x” is 0, 1, 2 or 3 and “y” is an integer from 1 to 20. R13 is an atom or a group chosen from among a hydrogen atom, a fluorine atom, —CH(CF3)2— or CF(CF3)2. Such fluorine-substituted alkyl groups are exemplified by linear or branched polyfluoroalkyl or perfluoroalkyl groups represented by the formulas presented below.

—CF3, —C2F5, -nC3F7, —CF(CF3)2, -nC4F9, CF2CF(CF3)2, -nC6F13, -nC8F17, —CH2CF3, —CH(CF3)2, CH2CH(CF3)2—CH2(CF2)2F, —CH2(CF2)3F, —CH2(CF2)4F, —CH2(CF2)6F, —CH2(CF2)8F, —CH2CH2CF3, —CH2CH2(CF2)2F, —CH2CH2(CF2)3F, —CH2CH2(CF2)4F, —CH2CH2(CF2)6F, —CH2CH2(CF2)8F, —CH2CH2(CF2)10F, —CH2CH2(CF2)12F, —CH2CH2(CF2)14F, —CH2CH2(CF2)16F, —CH2CH2CH2CF3, —CH2CH2CH2(CF2)2F, —CH2CH2CH2(CF2)2H—CH2(CF2)4H and —CH2CH2(CF2)3H. The groups represented by

—CH2CH2—(CF2)m—CFR14-[OCF2CF(CF3)]n—OC3F7 are suggested as fluoroalkyloxyfluoroalkylene groups obtained by substituting fluorine atoms for hydrogen atoms of alkyloxyalkylene groups. In the formula, the index “m” is 0 or 1, “n” is 0, 1, 2, 3, 4 or 5, and R14 is a fluorine atom or CF3. Such fluoroalkyloxyfluoroalkylene groups are exemplified by the perfluoroalkyloxyfluoroalkylene groups represented by the formulas presented below.
—CH2CH2CF(CF3)—[OCF2CF(CF3)]n—OC3F7, —CH2CH2CF2CF2—[OCF2CF(CF3)]n—OC3F7.

The number-average molecular weight of the vinyl polymer used in the present invention may be between 3,000 and 2,000,000, and more preferably between 5,000 and 800,000.

This type of fluoro vinyl polymer may be obtained by addition

    • of a vinyl monomer (B) that does not have a fluoro organic group in the molecule
    • to a vinyl monomer containing fluoro organic groups in molecule (A), and
    • a carbosiloxane dendrimer (C) containing radical-polymerizable organic groups represented by the following general formula (III):

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in which Y is a radical-polymerizable organic group and R1 and Xi are as hereinabove, and by subjecting them to copolymerization.

The vinyl monomers (A) containing fluoro organic groups in the molecule are preferably monomers represented by the general formula:—(CH2)═CR15COORf. In the formula, R15 is a hydrogen atom or a methyl group, Rf is a fluoro organic group exemplified by the fluoroalkyl and fluoroalkyloxyfluoroalkylene groups described above. The compounds represented by the formulas presented below are suggested by way of specific examples of component (A). In the formulas presented below, “z” is an integer from 1 to 4.

    • CH2═CCH3COO—CF3. CH2═CCH3COO—C2F5. CH2═CCH3COO-nC3F7.
    • CH2═CCH3COO—CF(CF3)2. CH2═CCH3COO-nC4F9.
    • CH2═CCH3COO—CF2CF(CF3)2. CH2═CCH3COO-nC5F11.
    • CH2═CCH3COO-nC6F13. CH2═CCH3COO-nC8F17. CH2═CCH3COO—CH2CF3.
    • CH2═CCH3COO—CH(CF3)2. CH2═CCH3COO—CH2CH(CF3)2.
    • CH2═CCH3COO—CH2(CF2)F.
    • CH2═CCH3COO—CH2(CF2)3F. CH2═CCH3COO—CH2(CF2)4F.
    • CH2═CH3COO—CH2(CF2)6F. CH2═CCH3COO—CH2(CF2)8F.
    • CH2═CH3COO—CH2CH2CF3. CH2═CCH3COO—CH2CH2(CF2)2F.
    • CH2═CCH3COO—CH2CH2(CF2)3F. CH2═CCH3COO—CH2CH2(CF2)4F.
    • CH2═CCH3COO—CH2CH2(CF2)6F. CH2═CCH3COO—CH2CH2(CF2)8F.
    • CH2═CCH3COO—CH2CH2(CF2)10F. CH2═CCH3COO—CH2CH2(CF2)12F.
    • CH2═CCH3COO—CH2CH2(CF2)14F. CH2CCH3COO—CH2CH2(CF2)16F.
    • CH2═CCH3COO—CH2CH2CH2CF3. CH2═CCH3COO—CH2CH2CH2(CF2)2F.
    • CH2═CCH3COO—CH2CH2CH2(CF2)H. CH2═CCH3COO—CH2(CF2)4H.
    • CH2═CCH3COO—CH2CH2(CF2)3H.
    • CH2═CCH3COO—CH2CH2CF(CF3)—[OCF2CF(CF3)]Z—OC3F7.
    • CH2═CCH3COO—CH2CH2CF2CF2—[OCF2CF(CF3)]Z—OC3F7.
    • CH2═CHCOO—CF3. CH2═CHCOO—C2F5. CH2═CHCOO-nC3F7. CH2═CHCOO—CF(CF3)2.
    • CH2—CHCOO-nC4F9. CH2═CHCOO—CF2CF(CF3)2. CH2═CHCOO-nC5F11.
    • CH2═CHCOO-nC6F13. CH2═CHCOO-nC8F17. CH2═CHCOO—CH2CF3.
    • CH2═CHCOO—CH(CF3)2. CH2—CHCOO—CH2CH(CF3)2. CH2═CHCOO—CH2(CF2)2F.
    • CH2═CHCOO—CH2(CF2)8F. CH2—CHCOO—CH2(CF2)4F. CH2═CHCOO—CH2(CF2)6F.
    • CH2═CHCOO—CH2(CF2)8F. CH2═CHCOO—CH2CH2CF3.
    • CH2═CHCOO—CH2CH2(CF2)2F.
    • CH2═CHCOO—CH2CH2(CF2)3F. CH2═CHCOO—CH2CH2(CF2)4F.
    • CH2═CHCOO—CH2CH2(CF2)6F. CH2═CHCOO—CH2CH2(CF2)8F.
    • CH2═CHCOO—CH2CH2(CF2)10F. CH2═CHCOO—CH2CH2(CF2)12F.
    • CH2═CHCOO—CH2CH2(CF2)14F. CH2═CHCOO—CH2CH2(CF2)16F.
    • CH2═CHCOO—CH2CH2CH2CF3. CH2═CHCOO—CH2CH2CH2(CF2)2F.
    • CH2═CHCOO—CH2CH2CH2(CF)2H. CH2═CHCOO—CH2(CF2)4H.
    • CH2═CHCOO—CH2CH2(CF2)3H.
    • CH2═CHCOO—CH2CH2CF(CF3)—[OCF2CF(CF3)]Z—OC3F7.
    • CH2═CHCOO—CH2CH2CF2CF2—[CF2CF(CF3)]Z—OC3F7.

Among those, the vinyl polymers represented by the formulas presented below are preferable.

    • CH2═CHCOO—CH2CH2(CF2)6F. CH2═CHCOO—CH2CH2(CF2)8F.
    • CH2═CCH3COO—CH2CH2(CF2)6F. CH2═CCH3COO—CH2CH2(CF2)8F.
    • CH2═CHCOO—CH2CF3. CH2═CCH3COO—CH2CF3

The vinyl polymers represented by the formulas presented below are particularly preferable.

    • CH2═CHCOO—CH2CF3. CH2═CCH3COO—CH2CF3.

The vinyl monomers (B) that do not contain fluoro organic groups in the molecule may be any molecules whatsoever having radical-polymerizable vinyl groups, which molecules are exemplified for example by methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and other lower alkyl acrylates or methacrylates; glycidyl acrylate, glycidyl methacrylate; n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, and other higher acrylates and methacrylates; vinyl acetate, vinyl propionate and other vinyl esters of lower fatty acids; vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate, and other esters of higher fatty acids; styrene, vinyltoluene, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, vinylpyrrolidone and other aromatic vinyl monomers; dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and other vinyl esters with amino groups, acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, isobutoxymethoxy acrylamide, isobutoxymethoxy methacrylamide, N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide, and other monomers of vinyl type that contain amide groups; hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl alcohol of acrylic acid, hydroxypropyl alcohol of methacrylic acid, and other vinyl monomers that contain hydroxy groups; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, and other vinyl monomers that contain a carboxylic acid group; tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, ethoxydiethylene glycol acrylate, ethoxydiethylene glycol methacrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and other vinyl monomers with ether bonds; acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, polydimethylsiloxanes having acryl or methacryl groups on one of the ends, polydimethylsiloxanes containing alkenaryl groups on one of the ends, and other silicone compounds containing unsaturated groups; butadiene; vinyl chloride; vinylidine chloride; acrylonitrile, methacrylonitrile; dibutyl fumarate; maleic anhydride; dodecylsuccinic anhydride; acryl glycidyl ether, methacryl glycidyl ether, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, alkali metal salts, ammonium salts and the organic amine salts of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid and other radical-polymerizable unsaturated carboxylic acids, radical-polymerizable unsaturated monomers containing sulfonic acid groups, such as styrenesulfonic acid as well as their alkali metal salts, their ammonium salts and their organic amine salts; quaternary ammonium salts derived from acrylic acid or methacrylic acid, such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride; esters of methacrylic acid of an alcohol possessing a tertiary ammonium group, such as the diethylamine ester of methacrylic acid and their quaternary ammonium salts.

In addition, it is also possible to use, by way of vinyl monomers (B), the polyfunctional vinyl monomers that are exemplified for example by trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trioxyethyl acrylate, trimethylolpropane trioxyethyl methacrylate, tris-(2-hydroxyethyl)isocyanurate diacrylate, tris-(2-hydroxyethyl)isocyanurate dimethacrylate, tris-(2-hydroxyethyl)isocyanurate triacrylate, tris-(2-hydroxyethyl)isocyanurate trimethacrylate, polydimethylsiloxane in which both ends of the molecular chain are blocked by alkenaryl groups, and other silicone compounds with unsaturated groups.

As regards the aforementioned ratio in which component (A) and component (B) are copolymerized, the weight ratio of compound (A) to compound (B) must be in the range from 0.1:99.9 to 100:0, and preferably in the range of 1:99 to 100:0.

Carbosiloxane dendrimer (C) is represented by general formula (III) indicated hereinabove. In formula (III), Y is a radical-polymerizable organic group, whose type is not subject to any special limitations whatsoever, provided it is an organic group capable of undergoing a radical addition reaction. Organic groups containing acryl and methacryl, organic groups containing alkenaryl, or alkenyl groups with 2 to 10 carbon atoms represented by the general formulas presented below are suggested by way of specific examples.

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In the formulas, R4 and R6 are hydrogen atoms or methyl groups, R5 and R8 are alkylene groups with 1 to 10 carbon atoms, and R7 is an alkyl group with 1 to 10 carbon atoms. The index “b” is an integer from 0 to 4, and “c” is 0 or 1. Acryloxymethyl, 3-acryloxypropyl, methacryloxymethyl, 3-methacryloxypropyl, 4-vinylphenyl, 3-vinylphenyl, 4-(2-propenyl)phenyl, 3-(2-propenyl)phenyl, 2-(4-vinylphenyl)ethyl, 2-(3-vinylphenyl)enyl, vinyl, allyl, methallyl and 5-hexenyl are suggested by way of examples of such radical-polymerizable organic groups. The exponent “i” in formula (II), which is an integer from 1 to 10, is the number of generations of the said silylalkyl group, or in other words the number of times that the silylalkyl group is repeated. Thus the carboxyloxane dendrimer of this component with a generation number of 1 is represented by the general formula:

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(in which Y, R1, R2 and R3 are such as hereinabove and R12 is a hydrogen atom or such as R1 described hereinabove. The index “a1” is an integer from 0 to 3, the mean total of “a1” per molecule being from 0 to 7). The carbosiloxane dendrimers of this component with a generation number of 2 are represented by the general formula:

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(in which Y, R1, R2, R3 and R12 are such as hereinabove and the indices “a1” and “a2” are integers from 0 to 3, the mean total of “a1” and of “a2” per molecule being from 0 to 25).

The carbosiloxane dendrimers of this component with a generation number of 3 are represented by the general formula:

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(in which Y, R1, R2, R3 and R12 are such as hereinabove and the indices “a1”, “a2” and “a3” are integers from 0 to 3, the mean total of “a1” of “a2” and of “a3” per molecule being from 0 to 79).

Component (C) is exemplified by carbosiloxane dendrimers represented by the formulas of mean composition represented below.

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The carbosiloxane dendrimers of component (C) may be prepared by using the method of preparation of branched siloxane/silalkylene copolymers described in the document EP1055674. For example, they may be prepared by subjecting organic silicone compounds containing alkenyl groups and silicone compounds comprising hydrogen atoms bonded to the silicon, represented by the general formula:

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(in which R1 and Y are such as hereinabove) to a hydrosilylation reaction. For example, 3-methacyloxypropyltris(dimethylsiloxy)silane, 3-acryloxypropyltris(dimethylsiloxy)silane and 4-vinylphenyltris(dimethylsiloxy)silane are used by way of silicon compounds represented by the above formula. Vinyltris(dimethylsiloxy)silane, vinyltris(dimethylphenylsiloxy)silane and 5-hexenyltris(trimethylsiloxy)silane are used as organic silicon compounds containing alkenyl groups. In addition, it is preferable to carry out the hydrosilylation reaction in the presence of a transition metal catalyst such as chloroplatinic acid and the complex of platinum/vinylsiloxane.

The copolymerization ratio of component (C), in terms of its weight ratio relative to the total of compound (A) and of compound (B), must be in the range of 0.1:99.9 to 99.9:0.1, and preferably in the range of 1:99 to 99:1, and even more preferably in the range of 5:95 to 95:5.

Amino groups may be introduced into the side chains of the vinyl polymer by using, included in component (B), vinyl monomers containing amino groups, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate, then carrying out a modification with potassium monochloroacetate, ammonium monochloroacetate, the aminomethylpropanol salt of monochloroacetic acid, the triethanolamine salt of monobromoacetic acid, sodium monochloropropionate, and other alkali metal salts of halo fatty acids; otherwise it is possible to introduce carboxylic acid groups into the side chains of the vinyl polymer by using, included in component (B), vinyl monomers containing carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid and similar compounds, then neutralizing the product with triethylamine, diethylamine, triethanolamine and other amines.

The fluoro vinyl polymer may be one of the polymers described in the examples of Patent Application WO03/045337 or, for example, the product TIB-4-100 sold by Dow Corning.

Polymer in Dispersion

According to a third embodiment of the invention, the film-forming polymer present in the composition according to the invention is a dispersion of particles of acryl or vinyl radical homopolymer or copolymer dispersed in the liquid fatty phase of the composition.

According to the invention, the polymer in the form of particles dispersed in the volatile liquid fatty phase is a solid insoluble in the liquid fatty phase of the composition even at its softening temperature, in contrast to a wax that itself is of polymeric origin which itself is soluble in the liquid organic phase (or fatty phase) at its melting temperature.

The composition according to the invention advantageously comprises at least one stable dispersion of generally spherical particles or one or more polymers in a volatile liquid fatty phase. In particular, these dispersions may have the form of polymer nanoparticles in stable dispersion in the said liquid organic phase. The nanoparticles preferably have a mean size between 5 and 800 nm, and better between 50 and 500 nm. Nevertheless, it is possible to obtain polymer particle sizes as large as 1 μm.

Preferably, the polymer particles in dispersion are insoluble in the water-soluble alcohols, such as ethanol, for example.

The polymers in dispersion that can be used in the first composition of the invention preferably have a molecular weight on the order to 2,000 to 10,000,000 g/mol, and a Tg of −100° C. to 300° C. and better of −50° C. to 100° C., preferably of −10° C. to 50° C.

It is possible to use filmifiable polymers, preferably having a low Tg, lower than or equal to skin temperature and especially lower than or equal to 40° C.

Preferably, the polymer used is filmifiable, or in other words capable of forming, on its own or in association with a plasticizing agent, an isolable film. Nevertheless, it is possible to use a non-filmifiable polymer.

By “non-filmifiable polymer” there is understood a polymer that is not capable, on its own, of forming an isolable film. This polymer makes it possible, in association with a non-volatile compound of the oil type, to form a continuous and homogeneous deposit on the skin and/or the lips.

Among the filmifiable polymers there may be cited the acrylic or vinyl radical homopolymers or copolymers, preferably having a Tg lower than or equal to 40° C. and in particular ranging from −10° to 30° C., used alone or in a mixture.

Among the non-filmifiable polymers, there may be cited vinyl or acrylic radical homopolymers or copolymers, possibly cross-linked, preferably having a Tg higher than o 40° C. and in particular ranging from −40° C. to 150° C., used alone or in a mixture.

By radical polymer there will be understood a polymer obtained by polymerization of monomers having in particular ethylenic unsaturation, each monomer being capable of homopolymerization (as opposed to the polycondensates). The radical polymers may be in particular vinyl polymers or copolymers, especially acrylic polymers.

The acrylic polymers may result from the polymerization of ethylenically unsaturated monomers having at least one acid group and/or of esters of these acid monomers and/or of amides of these acids.

As monomer carrying an acid group there may be used α,β-ethylenic unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid. Preferably there will be used (meth)acrylic acid and crotonic acid, and more preferentially (meth)acrylic acid.

The esters of acid monomers are advantageously chosen from among the esters of (meth)acrylic acids (also referred to as (meth)acrylates), such as the alkyl (meth)acrylates, in particular with C1-C20 alkyl, preferably C1-C8, the aryl (meth)acrylates, in particular with C6-C10 aryl, the hydroxyalkyl (meth)acrylates, in particular with C2-C6 hydroxyalkyl. As alkyl (meth)acrylates there may be cited methyl, ethyl, butyl, isobutyl, 2-ethylhexyl and lauryl (meth)acrylate. As hydroxyalkyl (meth)acrylates there may be cited hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate. As aryl (meth)acrylates there may be cited benzyl or phenyl acrylate.

The particularly preferred (meth)acrylic acid esters are the alkyl (meth)acrylates.

As radical polymer there are preferably used the copolymers of (meth)acrylic acid and alkyl (meth)acrylate, especially with C1-C4 alkyl. More preferentially, there may be used the methyl acrylates, copolymerized if necessary with acrylic acid.

As amides of acid monomers there may be cited the (meth)acrylamides and especially the N-alkyl (meth)acrylamides, in particular with C2-C12 alkyl, such as N-ethyl acrylamide, N-t-butyl acrylamide, N-octyl acrylamide; the N-dialkyl (C1-C4) (meth)acrylamides.

The acrylic polymers may also result from the polymerization of ethylenically unsaturated monomers having at least one amine group, in free or else partly or completely neutralized form, or else even partly or completely quaternized. Such monomers may be, for example, dimethylaminoethyl (meth)acrylate, dimethylaminoethyl methacrylamide, vinylamine, vinylpyridine, diallyldimethylammonium chloride.

The vinyl polymers may also result from the homopolymerization or copolymerization of at least one monomer chosen from among the vinyl esters and the styrene monomers. In particular, these monomers may be polymerized with acid monomers and/or their esters and/or their amides, such as those mentioned in the foregoing. As examples of vinyl esters there may be cited vinyl acetate, vinyl propionate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate. As styrene monomers there may be cited styrene and alpha-methylstyrene.

The list of monomers given is not limitative, and it is possible to use any monomer known to those skilled in the art and falling within the categories of acrylic and vinyl monomers (including the monomers modified by a silicone chain).

As other usable vinyl monomers there may also be cited:

    • N-vinylpyrrolidone, vinyl caprolactam, the vinyl N—(C1-C6)alkyl pyrroles, the vinyloxazoles, the vinylthiazoles, the vinylpyrimidines, the vinylimidazoles.
    • the olefins such as ethylene, propylene, butylene, isoprene, butadiene.

The vinyl polymer may be cross-linked by means of one or more difunctional monomers, especially comprising at least two ethylenic unsaturations, such as ethylene glycol dimethacrylate of diallyl phthalate.

The polymer or polymers in dispersion in the organic liquid phase may represent, as dry material, 5 to 40% by weight of the composition, preferably 5 to 35% and better 8 to 30%.

Preferably the choice is to use a dispersion of particles of filmifiable polymer, the particles being dispersed in a volatile oil.

According to one embodiment, the composition contains a stabilizer solid at room temperature. The polymer particles are preferably stabilized at the surface by virtue of a stabilizer, which may be a sequenced polymer, a graft polymer and/or a statistical polymer, alone or in a mixture. Stabilization may be effected by any known means, and in particular by direct addition of the sequenced polymer, graft polymer and/or statistical polymer during polymerization.

The stabilizer is preferably also present in the mixture before polymerization of the polymer. Nevertheless, it is also possible to add it continuously, especially when the monomers are also added continuously.

There may be used 2-30% by weight of stabilizer relative to the initial mixture of monomers, and preferably 5-20% by weight.

Among the graft polymers there may be cited the silicone polymers grafted with a hydrocarbon chain; the hydrocarbon polymers grafted with a silicone chain.

Thus there may be used grafted or sequenced block copolymers comprising at least one block of polyorganosiloxane type and at least one block of a radical polymer, such as the graft copolymers of acrylic/silicone type, which may be employed in particular when the non-aqueous medium is a silicone.

There may also be used grafted or sequenced block copolymers comprising at least one block of polyorganosiloxane type and at least one polyether. The polyorganopolysiloxane block may be in particular a polydimethylsiloxane or else even a poly (C2-C18) alkyl methylsiloxane; the polyether block may be a poly (C2-C18) alkylene, particularly polyoxyethylene and/or polyoxypropylene. In particular, there may be used copolyol dimethicones or copolyol (C2-C18) alkyl dimethicones, such as those sold under the name “Dow Corning 3225C” by the Dow Corning Company, the lauryl dimethicones, such as those sold under the name “Dow Corning Q2-5200” by the Dow Corning Company.

As grafted or sequenced block copolymers there may also be cited those comprising at least one block resulting from the polymerization of at least one ethylenic monomer having one or more ethylenic bonds, which may be conjugated, such as ethylene or the dienes such as butadiene and isoprene, and at least one block of a vinyl and better styrene polymer. When the ethylenic monomer contains several ethylenic bonds, which may be conjugated, the residual ethylenic unsaturations after polymerization are generally hydrogenated. Thus, in known manner, the polymerization of isoprene leads, after hydrogenation, to the formation of ethylene-propylene block, and the polymerization of butadiene leads, after hydrogenation, to the formation of ethylene-butylene block. Among these polymers there may be cited the sequenced copolymers, especially of “diblock” or “triblock” type of the polystyrene/polyisoprene (SI), polystyrene/polybutadiene (SB) type, such as those sold under the name of ‘LUVITOL HSB’ by BASF, of the polystyrene/copoly(ethylene-propylene) (SEP) type, such as those sold under the name of ‘Kraton’ by Shell Chemical Co or even of the polystyrene/copoly(ethylene-butylene) (SEB) type. In particular, there may be used Kraton G1650 (SEBS), Kraton G1651 (SEBS), Kraton G1652 (SEBS), Kraton G1657X (SEBS), Kraton G1701X (SEP), Kraton G1702X (SEP), Kraton G1726X (SEB), Kraton D-1101 (SBS), Kraton D-1102 (SBS), Kraton D-1107 (SIS). The polymers are generally referred to as hydrogenated or non-hydrogenated diene copolymers.

There may also be used Gelled Permethyl 99A-750, 99A-753-59 and 99A-753-58 (mixture of triblock and star polymer), Versagel 5960 of Penreco (triblock+star polymer); OS129880, OS129881 and OS84383 of Lubrizol (styrene/methacrylate copolymer).

As grafted or sequenced block copolymers comprising at least one block resulting from the polymerization of at least one ethylenic monomer having one or more ethylenic bonds and at least one block of an acrylic polymer there may be cited the poly(methyl methacrylate)/polyisobutylene bisequenced or trisequenced copolymers or the graft copolymers with poly(methyl methacrylate) skeleton and polyisobutylene grafts.

As grafted or sequenced block copolymers comprising at least one block resulting from the polymerization of at least one ethylenic monomer having one or more ethylenic bonds and at least one block of a polyether such as a C2-C18 polyalkylene (especially containing polyethylene and/or polyoxypropylene) there may be cited the polyoxyethylene/polybutadiene or polyoxyethylene/polyisobutylene bisequenced or trisequenced copolymers.

Thus there may be employed copolymers based on alkyl acrylates or methacrylates obtained from C1-C4 alcohols and on alkyl acrylates or methacrylates obtained from C8-C30 alcohols. In particular, there may be cited the copolymer of stearyl methacrylate/methyl methacrylate.

When the liquid synthesis solvent comprises at least one silicone oil, the stabilizing agent is preferably chosen from among the group consisting of the grafted or sequenced block copolymers comprising at least one block of polyorganosiloxane type and at least one block of a radical polymer or of a polyether or of a polyester, such as the polyoxypropylene and/or oxyethylene blocks.

When the liquid fatty phase does not comprise silicone oil, the stabilizing agent is preferably chosen from among the group consisting of:

    • (a) the grafted or sequenced block copolymers comprising at least one block of polyorganosiloxane type and at least one block of a radical polymer or of a polyether or of a polyester,
    • (b) copolymers based on alkyl acrylates or methacrylates obtained from C1-C4 alcohols and on alkyl acrylates or methacrylates obtained from C8-C30 alcohols,
    • (c) the grafted or sequenced block copolymers comprising at least one block resulting from the polymerization of at least one ethylenic monomer with conjugated ethylenic bonds and at least one block of a vinyl or acrylic polymer or of a polyether or polyester or mixtures thereof.

Preferably diblock polymers are used as stabilizing agent.

When the polymer has a glass transition temperature too high for the desired application, there may be associated therewith a plasticizer so as to lower this temperature of the mixture used. The plasticizer may be chosen from among the plasticizers usually used in the field of application and especially from among the compounds capable of being polymer solvents. There may also be used coalescence agents in order to help the polymer to form a continuous and homogeneous deposit.

The coalescence agents or plasticizers that can be used in the invention are especially those cited in the document FR A 2782917.

The composition may contain a polymer plasticizer, so as to lower the Tg of the polymer film and to improve the adherence of the polymer film on its substrate, in particular the horny tissues. The plasticizing compound lowers especially the glass transition temperature of the polymer by at least 2, 3 or 4° C., preferably by 5° C. to 20° C. In a preferred embodiment, the plasticizing compound lowers especially the glass transition temperature of the polymer by at least 2, 3 or 4° C., preferably by 5° C. to 20° C., when the plasticizing compound represents at most 10% by weight of the polymer.

According to one embodiment, the compound may be chosen from among the esters with at least one carboxylic acid group comprising 1 to 7 carbon atoms and one polyol comprising at least 4 hydroxyl groups.

The polyol according to the invention may be an ose or a polyol derived from an ose, such as erythritol, xylitol or sorbitol. The polyol may be a mono or polysaccharide comprising one to 10 oses, preferably from one to 4, even more preferably one or two oses. The polyol may be chosen from among erythritol, xylitol, sorbitol, glucose and sucrose.

The polyol according to the invention is preferably a disaccharide. Among the disaccharides, there may be cited sucrose (alpha-D-glucopyranosyl-(1-2)-beta-D-fructofuranose), lactose (beta-D-galactopyranosyl-(1-4)-beta-D-glucopyranose) and maltose (alpha-D-glucopyranosyl-(1-4)-beta-D-glucopyranose).

The plasticizer may be composed of a polyol substituted by at least two different monocarboxylic acids or by at least three different monocarboxylic acids. The acid is preferably a monocarboxylic acid chosen in particular from among the acids comprising 1 to 7 carbon atoms, preferably 1 to 5 carbon atoms, for example acetic, n-propanoic, isopropanoic, n-butanoic, isobutanoic, tert-butanoic, n-pentanoic and benzoic acids.

According to a preferred embodiment, the ester is sucrose di-acetate-hexa-(2-methylpropanoate).

Solvent for Synthesis of Polymer Particles

The polymer dispersion may be manufactured as described in the document of EP A 749747.

A mixture comprising the initial monomers as well as a radical initiator is prepared. This mixture is dissolved in a solvent referred to hereinafter in the present description as “synthesis solvent”. When the fatty acid is a non-volatile oil, the polymerization may be carried out in an apolar organic solvent (synthesis solvent) then the non-volatile oil (which must be miscible with the said synthesis solvent) may be added and the synthesis solvent selectively distilled.

The synthesis solvent is chosen such that the initial monomers and the radical initiator are soluble therein and the obtained polymer particles are insoluble therein, in order that they precipitate during their formation. In particular, the synthesis solvent may be chosen from among the alkanes such as heptane, isododecane or cyclohexane.

When the chosen fatty phase is a volatile oil, the polymerization may be carried out directly in the said oil, which therefore also has the function of synthesis solvent. The monomers must also be soluble therein, and also the radical initiator and the polymer obtained must be soluble therein.

Before polymerization, the monomers are preferably present in the synthesis solvent in a concentration of 5-20% by weight of the reaction mixture. The totality of the monomers may be present in the solvent before the start of the reaction, or part of the monomers may be added at a rate commensurate with the evolution of the polymerization reaction.

The radical initiator may be in particular azo-bis-isobutyronitrile or tert-butylperoxy-2-ethyl hexanoate.

The volatile phase of the composition may be constituted by or may comprise the solvent for synthesis of the dispersed polymer particles.

As examples of non-aqueous dispersions of fat-dispersible film-forming polymer in the form of non-aqueous dispersions of polymer particles in one or more silicone and/or hydrocarbon oils and capable of being stabilized at their surface by at least one stabilizing agent, especially a sequenced, grafted or statistical polymer, there may be cited the acrylic dispersions in isododecane, such as Mexomere PAP® of the CHIMEX Co., the dispersions of particles of a graft ethylene, preferably acrylic polymer in a liquid fatty phase, the ethylene polymer being advantageously dispersed in the absence of additional surface stabilizer of the particles such as described in particular in the document WO 04/055081.

Reactive Silicones

According to another embodiment, the composition according to the invention may comprise, by way of film-forming polymer, two-component systems such as the compounds X and Y defined hereinafter, capable of polymerizing in situ, at atmospheric pressure and room temperature, and of forming films advantageously biocompatible, non-sticking, slightly opalescent and even peelable. Such systems are especially described in part in Patents WO 01/96450 and GB 2407496 of Dow Corning.

According to a particular embodiment, the compounds X and the compounds Y are silicones.

The compounds X and Y may or may not be amines.

According to another embodiment, at least one of the compounds X and Y is a polymer whose main chain is formed predominantly by organosiloxane units.

Among the silicone compounds cited hereinafter, some may exhibit both film-forming and adhesive properties, depending, for example, on their proportion of silicone or depending on whether they are used in a mixture with a particular additive. Consequently, it is possible to modulate the film-forming properties or the adhesive properties of such compounds depending on the envisioned use, and this is the case in particular for the reactive elastomeric silicones referred to as “room temperature vulcanization”.

The compounds X and Y may react together at a temperature varying between room temperature and 180° C. Advantageously, the compounds X and Y are capable of reacting together at room temperature (20±5° C.) and atmospheric pressure, or advantageously in the presence of a catalyst, via a hydrosilylation reaction or a condensation reaction, or a cross-linking reaction in the presence of a peroxide.

According to a particular embodiment, the compounds X and Y react by hydrosilylation in the presence of a catalyst.

Advantageously, the compounds X and Y are chosen from among the silicone compounds capable of reacting by hydrosilylation in the presence of a catalyst; in particular, the compound X is chosen from among the polyorganosiloxanes comprising units of formula (I) described below and the compound Y is chosen from among the organosiloxanes comprising alkylhydrogenosiloxanes of formula (III) described below.

According to a particular embodiment, the compound X is a polydimethylsiloxane containing terminal vinyl groups, and the compound Y is a polymethylhydrogenosiloxane.

The compound X is therefore advantageously chosen from among the polyorganosiloxanes comprising siloxane units of formula:

RmRSiO(3-m)2(I)

    • in which:
      • R represents a linear or cyclic monovalent hydrocarbon group comprising 1 to 30 carbon atoms, preferably 1 to 20 and better 1 to 10 carbon atoms, such as, for example, a short-chain alkyl radical comprising, for example, 1 to 10 carbon atoms, in particular a methyl radical or else a phenyl group, preferably a methyl radical,
      • m is equal to 1 or 2 and
      • R′ represents:
        • an unsaturated aliphatic hydrocarbon group comprising 2 to 10, preferably 3 to 5 carbon atoms, such as, for example, a vinyl group or a —R″—CH═CHR′″ group, in which R″ is a divalent aliphatic hydrocarbon chain, comprising 1 to 8 carbon atoms, bonded to the silicon atom, and R′″ is a hydrogen atom or an alkyl radical comprising 1 to 4 carbon atoms, preferably a hydrogen atom; as the R′ group there may be cited the vinyl and allyl groups and mixtures thereof; or
        • an unsaturated cyclic hydrocarbon group comprising 5 to 8 carbon atoms, such as, for example, a cyclohexenyl group.

Preferably, R′ is an unsaturated aliphatic hydrocarbon group, preferably a vinyl group.

According to one embodiment, R represents an alkyl radical comprising 1 to 10 carbon atoms or else a phenyl group, and preferably a methyl radical, and R′ is a vinyl group.

The compound Y may be advantageously chosen from among the polyorganosiloxanes comprising at least one alkylhydrogenosiloxane unit of the following formula:

RpHSiO(3-p)2(III)

    • in which:
    • R represents a linear or cyclic monovalent hydrocarbon group comprising 1 to 30 carbon atoms such as, for example an alkyl radical having 1 to 30 carbon atoms, preferably 1 to 20 and better 1 to 10 carbon atoms, in particular a methyl radical, or else a phenyl group, and p is equal to 1 or 2. Preferably, R is a hydrocarbon group, preferably methyl.

According to one embodiment, the compositions comprising the component X and/or Y may also comprise an additional reactive compound such as:

      • the organic or mineral particles comprising at least 2 unsaturated aliphatic groups at their surface; for example there may be cited the silicas surface-treated for example by silicone compounds containing vinyl groups, such as, for example, silica treated with cyclotetramethyltetravinylsiloxane,
      • silazane compounds such as hexamethyldisilazane.

The hydrosilylation reaction is carried out in the presence of a catalyst, which may be present with one or the other of the compounds X or Y or may be present in isolated manner. For example, this catalyst may be present in the composition in an encapsulated form, if the two components X and Y, whose interaction it must bring about, are present in this same composition in a non-encapsulated form or, conversely, it may be present in the composition in a non-encapsulated form if at least one of the compounds X and Y is present in the composition in an encapsulated form. The catalyst is preferably based on platinum or tin.

The catalyst may be present in a content ranging from 0.0001% to 20% by weight relative to the total weight of the composition comprising it.

The compounds X and/or Y may be associated with polymerization inhibitors or retarders, and more particularly with catalyst inhibitors. Without imposing any limitation, there may be cited the cyclic polymethylvinylsiloxanes, and in particular tetravinyl tetramethyl cyclotetrasiloxane, the acetylenic alcohols, preferably volatile, such as methylisobutynol.

The presence of ionic salts, such as sodium acetate, may have an influence on the rate of polymerization of the compounds.

By way of example of a combination of compounds X and Y reacting by hydrosilylation in the presence of a catalyst, there may be cited the following references proposed by the Dow Corning Company: DC 7-9800 Soft Skin Adhesive Parts A & B, as well as the combination of the following mixtures A and B prepared by Dow Corning:

MIXTURE A:
Ingredient (INCI name)CAS No.Contents (%)Function
Dimethylsiloxane,68083-19-2 55-95Polymer
dimethylvinylsiloxy terminals
Silica silylate68909-20-6 10-40Filler
1,3-Diethenyl-1,1,3,3-68478-92-2TraceCatalyst
tetramethyldisiloxane complexes
Tetramethyldivinyldisiloxane 2627-95-40.1-1 Polymer

MIXTURE B:
Ingredient (INCI name)CAS No.Contents (%)Function
Dimethylsiloxane,68083-19-255-95Polymer
dimethylvinylsiloxy terminals
Silica silylate68909-20-610-40Filler
Dimethyl, methylhydrogen siloxane,68037-59-2 1-10Polymer
trimethylsiloxy terminals

The compound X may represent from 0.1% to 95% by weight relative to the total weight of the composition containing it, preferably from 1% to 90%, and better from 5% to 80%.

The compound Y may represent from 0.1% to 95% by weight relative to the total weight of the composition containing it, preferably from 1% to 90%, and better from 5% to 80%.

The composition according to the invention may comprise a plasticizing agent favoring the formation of a film with the film-forming polymer. Such a plasticizing agent may be chosen from among all the compounds known to those skilled in the art as being capable of fulfilling the sought function.

Other Film-Forming Polymers:

Polymer in Dispersion or in Solution in an Oil Phase:

According to another embodiment, the composition according to the invention may also comprise, by way of film-forming polymers, a film-forming polymer in dispersion or in solution different from those cited in the foregoing. It must be verified that none of these are doubles of those cited in the foregoing

Among the film-forming polymers that can be used in the composition of the present invention, there may be cited the synthetic polymers of radical type or polycondensate type, the polymers of natural origin, and mixtures thereof.

By radical film-forming polymer there is understood a polymer obtained by polymerization of monomers having unsaturation, especially ethylenic, each monomer being capable of homopolymerization (unlike the polycondensates).

The film-forming polymers of radical type may be in particular vinyl polymers or copolymers, especially acrylic polymers.

The vinyl film-forming polymers may result from the polymerization of ethylenically unsaturated monomers having at least one acid group and/or esters of these acid monomers and/or amides of these acid monomers.

As monomer carrying acid groups there may be used α,β-ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid. Preferably there are used (meth)acrylic acid and crotonic acid, and more preferably (meth)acrylic acid.

The esters of acid monomers are advantageously chosen from among the esters of (meth)acrylic acid (also referred to as the (meth)acrylates), especially alkyl (meth)acrylates, in particular C1-C30 alkyl, preferably C1-C20, aryl (meth)acrylates, in particular C6-C10 aryl, hydroxyalkyl (meth)acrylates), in particular C2-C6 hydroxyalkyl.

Among the alkyl (meth)acrylates there may be cited methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate.

Among the hydroxyalkyl (meth)acrylates there may be cited hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate.

Among the aryl (meth)acrylates there may be cited benzyl acrylate and phenyl acrylate.

The particularly preferred esters of (meth)acrylic acid are the alkyl (meth)acrylates.

According to the present invention, the alkyl group of the esters may be either fluorinated or pefluorinated, meaning that part or all of the hydrogen atoms of the alkyl group have been substituted by fluorine atoms.

As amides of acid monomers there may be cited, for example, the (meth)acrylamides, and especially the N-alkyl (meth)acrylamides, in particular C2-C12 alkyl. Among the N-alkyl (meth)acrylamides there may be cited N-ethyl acrylamide, N-t-butyl acrylamide, N-t-octyl acrylamide and N-undecyl acrylamide.

The vinyl film-forming polymers may also result from the homopolymerization or the copolymerization of monomers chosen from among the vinyl esters and the styrene monomers. In particular, these monomers may be polymerized with acid monomers and/or their esters and/or their amides, such as those mentioned in the foregoing.

As examples of vinyl esters there may be cited vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butylbenzoate.

As styrene monomers, there may be cited styrene and alpha-methylstyrene.

Among the film-forming polycondensates there may be cited the polyurethanes, the polyesters, the amide polyesters, the polyamides and the epoxy ester resins, the polyureas.

The polyurethanes may be chosen among the anionic, cationic, non-ionic or amphoteric polyurethanes, the polyurethane acrylics, the polyurethane polyvinylpyrrolidones, the polyester polyurethanes, the polyether polyurethanes, the polyureas, the polyurea polyurethanes and mixtures thereof.

The polyesters may be obtained in known manner by polycondensation of dicarboxylic acids with polyols, especially diols.

The dicarboxylic acid may be aliphatic, alicyclic or aromatic. As examples of such acids there may be cited: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norbornane dicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid. These dicarboxylic acid monomers may be used alone or in combination of at least two dicarboxylic acid monomers. Among these monomers, phthalic acid, isophthalic acid and terephthalic acid preferentially are chosen.

The diol may be chosen from among the aliphatic, alicyclic, aromatic diols. Preferably there is used a dial chosen from among: ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, cyclohexane dimethanol, 4-butanediol. As other polyols there may be used glycerol, pentaerythritol, sorbitol, trimethylol propane.

The amide polyesters may be obtained in a manner analogous to that for the polyesters, by polycondensation of diacids with diamines or amino alcohols. As diamine there may be used ethylenediamine, hexamethylenediamine, meta- or para-phenylenediamine. As amino alcohol there may be used monoethanolamine.

According to an example of composition according to the invention, the film-forming polymer may be a polymer solubilized in a liquid fatty phase comprising organic oils or solvents (it is then said that the film-forming polymer is a fat-soluble polymer). Preferably the liquid fatty phase comprises a volatile oil, if necessary in a mixture with a non-volatile oil.

By way of example of fat-soluble polymer there may be cited the copolymers of vinyl ester (the vinyl group being bonded directly to the oxygen atom of the ester group and the vinyl ester having a linear or branched, saturated hydrocarbon radical with 1 to 19 carbon atoms, bonded to the carbonyl of the ester group) and of at least one other monomer, which may be a vinyl ester (different from the already present vinyl ester), an α-olefin (having 8 to 28 carbon atoms), an alkyl vinyl ether (whose alkyl group contains 2 to 18 carbon atoms), or an allyl or methallyl ester (having a linear or branched, saturated hydrocarbon radical with 1 to 19 carbon atoms, bonded to the carbonyl of the ester group).

These copolymers may be cross-linked by means of cross-linking agents, which may be either of the vinyl type or of the allyl or methallyl type, such as tetrallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate and divinyl octadecanedioate.

As examples of these copolymers there may be cited the following copolymers: vinyl acetate/allyl stearate, vinyl acetate//vinyl laurate, vinyl acetate/vinyl stearate, vinyl acetate/octadecene, vinyl acetate/octadecyl vinyl ether, vinyl propionate/allyl laurate, vinyl propionate/vinyl laurate, vinyl stearate/octadecene-1, vinyl acetate/dodecene-1, vinyl stearate/ethyl vinyl ether, vinyl propionate/cetyl vinyl ether, vinyl stearate/allyl acetate, vinyl 2,2-dimethyl octanoate/vinyl laurate, allyl 2,2-dimethyl pentanoate/vinyl laurate, vinyl dimethyl propionate/vinyl stearate, allyl dimethyl propionate/vinyl stearate, vinyl propionate/vinyl stearate, cross-linked with 0.2% divinylbenzene, vinyl dimethyl propionate/vinyl laurate cross-linked with 0.2% divinylbenzene, vinyl acetate/octadecyl vinyl ether, cross-linked with 0.2% tetraallyloxyethane, vinyl acetate/allyl stearate, cross-linked with 0.2% divinylbenzene, vinyl acetate/1-octadecene, cross-linked with 0.2% divinylbenzene; and allyl propionate/allyl stearate cross-linked with 0.2% divinylbenzene.

As supplementary examples of fat-soluble film-forming polymers there may be cited the copolymers of vinyl ester and at least one other monomer, which may be a vinyl ester, especially vinyl neodecanoate, vinyl benzoate and vinyl t-butylbenzoate, an α-olefin, an alkyl vinyl ether, or an allyl or a methallyl ester.

As fat-soluble film-forming polymers there may also be cited fat-soluble copolymers, and in particular those resulting from copolymerization of vinyl esters having 9 to 22 carbon atoms or acrylates or alkyl methacrylates, the alkyl radicals having 10 to 20 carbon atoms.

Such fat-soluble copolymers may be chosen from among the copolymers of: vinyl polystearate, vinyl polystearate cross-linked by means of divinylbenzene, diallyl ether, or diallyl phthalate, the copolymers of stearyl poly(meth)acrylate, vinyl polylaurate, lauryl poly(meth)acrylate, these poly(meth)acrylates being capable of being cross-linked by means of ethylene glycol dimethacrylate or tetraethylene glycol.

The fat-soluble polymers defined in the foregoing are known and are described especially in the Application FR A 2232303; they may have a weight-average molecular weight ranging from 2,000 to 500,000, and preferably from 4,000 to 200,000.

As fat-soluble film-forming polymers that can be used in the invention there may also be cited polyalkylenes and especially C2-C20 alkene copolymers such as polybutene, the alkyl celluloses with a C1 to C8 saturated or unsaturated, linear or branched alkyl radical such as ethyl cellulose and propyl cellulose, the copolymers of vinylpyrrolidone (VP) and especially the copolymers of vinylpyrrolidone and C2 to C40 alkene, and better C3 to C20. By way of examples of VP copolymers that can be used in the invention there may be cited the copolymer of VP/vinyl acetate, VP/ethyl methacrylate, butylated polyvinylpyrrolidone (PVP); VP/ethyl methacrylate/methacrylic acid, VP/eicosene, VP/hexadecene, VP/triacontene, VP/styrene, VP/acrylic acid/lauryl methacrylate.

There may also be cited the silicone resins, generally soluble or swellable in silicone oils, that are cross-linked polyorganosiloxane polymers.

By way of examples of commercially available polymethylsilsesquioxane resins there may be cited those sold by the Wacker Company under the reference Resin MK, such as Belsil PMS MK, or by the SHIN-ETSU Company under the references KR-220L.

By way of examples of commercially available polypropylsilsesquioxane resins there may be cited those sold under the reference DC670 by the Dow Corning Company.

As siloxysilicate resins there may be cited the trimethylsiloxysilicate resins (TMS), such as those sold under the reference SR1000 by the General Electric Company or under the reference TMS 803 by the Wacker Company. There may also be cited the trimethylsiloxysilicate resins sold in a solvent such as cyclomethicone, sold under the trade name KF-7312J by the Shin-Etsu Company, or “DC 749”, “DC 593” by the Dow Corning Company.

There may also be cited copolymers of silicone resins such as those cited hereinabove with polydimethylsiloxanes, such as the pressure-sensitive adhesive copolymers sold by the Dow Corning Company under the reference BIO-PSA and described in the document U.S. Pat. No. 5,162,410, or else the silicone copolymers obtained by the reaction of a silicone resin, such as those described hereinabove, and a diorganosiloxane such as those described in the document WO 2004/073626.

There may also be cited the acrylic/silicone graft copolymers having a vinyl, methacrylic or acrylic polymeric skeleton and organosiloxane or polyorganoxilane pendant grafts. Such polymers are described in particular in U.S. Pat. Nos. 4,693,935, 4,981,903 and 4,981,902.

Preferably, these polymers comprise monomers A, C and optionally B, for which:

    • A is at least one vinyl, methacrylate or acrylate monomer that can undergo free radical polymerization;
    • B, when present, is at least one rigidifying monomer that can be copolymerized with A;
    • C is a monomer of the following formula:


X(Y)nSi(R)3-mZm

Where

    • X is a vinyl group that can be copolymerized with monomers A and B;
    • Y is a divalent linker;
    • n is 0 or 1;
    • m is an integer between 1 and 3;
    • R is a hydrogen atom, an alkyl radical having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl radical, an alkoxy radical having 1 to 10 carbon atoms;
    • Z is a monovalent polymeric siloxane group.

Examples of monomers A are lower to intermediate esters of methacrylic acid and C1-12 alcohols with linear or branched chain, of styrene, vinyl esters, vinyl chloride, vinylidine chloride or acryloyl monomers.

Examples of monomers B are polar acrylic or methacrylic monomers having at least one hydroxy, amino, ester or ionic group (such as the quaternary ammoniums, the carboxylate salt or the acids such as the carboxylic acids, the acrylic acids, sulfonic acid or salts thereof).

Monomer C is defined above.

As examples of acrylic/silicone graft copolymers there may be cited those sold by 3M under the reference 3M Silicones “Plus” VS70 Dry Polymer®, with the INCI name: Polysilicone-6, or else KP-561® sold by SHIN-ETSU with the INCI name: Acrylates/Stearyl Acrylate/Dimethicone Methacrylate Copolymer, KP-56210 sold by SHIN-ETSU with the INCI name: Acrylates/Behenyl Acrylate/Dimethicone Acrylate Copolymer.

Polymer in Aqueous Dispersion (Latex) or Water-Soluble Polymer

The composition may contain an aqueous phase, and the film-forming polymer may be present in this aqueous phase. In this case it will preferably be a polymer in aqueous dispersion or a water-soluble polymer.

Among the film-forming polymers that can be used in the composition of the present invention there may be cited the synthetic polymers of radical type or of polycondensate type, the polymers of natural origin and mixtures thereof.

As examples of water-soluble film-forming polymers there may be cited:

    • the proteins, such as the proteins of vegetable origin, such as the proteins of wheat, of soy; the proteins of animal origin, such as the keratins, for example the hydrolyzates of keratin and the sulfonic keratins;
    • the polymers of cellulose, such as hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethylhydroxyethyl cellulose, carboxymethyl cellulose, as well as the quaternized derivatives of cellulose;
    • the acrylic polymers or copolymers, such as the polyacrylates or the polymethacrylates;
    • the vinyl polymers, such as the polyvinylpyrrolidones, the copolymers of methyl vinyl ether and malic anhydride, the copolymer of vinyl acetate and crotonic acid, the copolymers of vinylpyrrolidone and vinyl acetate; the copolymers of vinylpyrrolidone and caprolactam; polyvinyl alcohol;
    • the polymers of anionic, cationic, amphoteric or non-ionic chitin or chitosan,
    • the gums arabic, guar gum, the xanthan derivatives, karaya gum;
    • the alginates and the carragenanes;
    • the glycoaminoglycanes, hyaluronic acid and its derivatives;
    • shellac resin, sandarac gum, the dammars, the elemis, the copals;
    • deoxyribonucleic acid;
    • the mucopolysaccharides, such as the chondroitin sulfates,
    • and mixtures thereof.

The film-forming polymer may also be present in the composition in the form of particles in dispersion in an aqueous phase, known generally under the name of latex or pseudolatex. The techniques for preparation of these dispersions are well known to those skilled in the art.

As aqueous dispersion of film-forming polymer there may be used the acrylic dispersions sold under the trade names: Neocryl XK-90®, Neocryl A-10708, Neocryl A-10908, Neocryl BT-62®, Neocryl A-1079®, and Neocryl A-523® by the AVECIA-NEORESINS Company; Dow Latex 432® by the DOW CHEMICAL Company; Daitosol 5000 AD® or Daitosol 5000 SJ® by the DAITO KASEY KOGYO Company; Syntran 5760® by the Interpolymer Allianz Company, Opt® by the Rohm and Haas Company, the aqueous dispersions of acrylic or styrene/acrylic polymers sold under the trade name JONCRYL® by the JOHNSON POLYMER Company or else the aqueous dispersions of polyurethane sold under the trade names Neorez R-981® and Neorez R-974® by the AVECIA-NEORESINS Company, Avalure UR-405®, Avalure UR-410®, Avalure UR-425®, Avalure UR-450®, Sancure 875®, Avalure UR-445® and Sancure 2060® by the NOVEON Company, Impranil 85® by the BAYER Company, Aquamere H-1511® by the HYDROMER Company, the sulfopolyesters sold under the brand Eastman AQ® by the EASTMAN CHEMICAL PRODUCTS Company, the vinyl dispersions such as Mexomere PAM® of the CHIMEX Company, the aqueous dispersions of polyvinyl acetate such as “Vinybran®” of the Nisshin Chemical Company or those sold by the UNION CARBIDE Company, the aqueous dispersions of vinylpyrrolidone, dimethylaminopropyl methacrylamide and lauryldimethylpropylmethylacrylamidoammonium chloride terpolymer such as Styleze W of ISP, the aqueous dispersions of polyurethane/polyacrylic hybrid polymers such as those sold under the references “Hybridur®” by the AIR PRODUCTS Company or “Duromer®” of NATIONAL STARCH, the dispersions of core/shell type: for example, those sold by the ATOFINA Company under the reference Kynar (core:fluoro-shell:acrylic) or else those described in the document U.S. Pat. No. 5,188,899 (core:silica-shell:silicone) and mixtures thereof.

According to a particular embodiment, the composition according to the invention comprises, by way of hydrophilic film-forming polymers, at least the association of a cationic polymer and an anionic polymer.

The cationic polymer may be chosen from among the ether derivatives of quaternary cellulose, the copolymers of cellulose with a water-soluble monomer of quaternary ammonium, the cyclopolymers, the cationic polysaccharides, the silicone-containing cationic polymers, the quaternized or non-quaternized copolymers of vinylpyrrolidone and dialkylaminoalkyl acrylate or methacrylate, the quaternary polymers of vinylpyrrolidone and vinylimidazole, the polyamidoamines and mixtures thereof.

Preferably, the cationic polymer is a hydroxy(C1-C4)alkyl cellulose containing quaternary ammonium groups.

The anionic polymer is advantageously chosen from among:

A) the acrylic or methacrylic acid homopolymers or copolymers or their salts, the copolymers of acrylic acid and acrylamide and their salts, the sodium salts of polyhydroxycarboxylic acids such as the copolymers of acrylic acid and acrylamide sold in the form of their sodium salt under the trade names RETEN® by the HERCULES Company, the sodium polymethacrylate sold under the trade name DARVAN No. 7® by the VANDERBILT Company, the sodium salts of polyhydroxycarboxylic acids sold under the trade name HYDAGEN F® by the HENKEL Company.
B) the copolymers of acrylic or methacrylic acids with a monoethylene monomer such as ethylene, styrene, the vinyl esters, the esters of acrylic or methacrylic acid, possibly grafted onto a polyalkylene glycol such as polyethylene glycol; the copolymers of this type containing, in their chain, an acrylamide moiety, which may be N-alkylated and/or hydroxyalkylated, the copolymers of acrylic acid and C1-C4 alkyl methacrylate and the terpolymers of vinylpyrrolidone, acrylic acid and C1-C20 alkyl methacrylate;
C) the copolymers derived from crotonic acid, such as those containing, in their chain, vinyl acetate or propionate moieties and possibly other monomers such as allyl or methallyl esters, vinyl ether or vinyl ester of a linear or branched, saturated carboxylic acid having a long-chain hydrocarbon, such as those containing at least 5 carbon atoms, these polymers possibly being able to be grafted;
D) the polymers derived from maleic, fumaric, itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters; the copolymers of maleic, citraconic, itaconic anhydrides and an allyl or methallyl ester, possibly containing an acrylamide, methacrylamide group, an α-olefin, acrylic or methacrylic esters, acrylic or methacrylic acids or vinylpyrrolidone in their chain, the anhydride functions being monoesterified or monoamidified;
E) the polyacrylamides containing carboxylate groups,
F) deoxyribonucleic acid;
G) the copolymers of at least one carboxylic diacid, of at least one diol and of at least one bifunctional aromatic monomer carrying a —SO3M group with M representing a hydrogen atom, an ammonium ion NH4+ or a metal ion;

    • and mixtures thereof.

The most particularly preferred anionic polymers are chosen from among the non-cross-linked anionic polymers such as the methyl vinyl ether/monoesterified maleic anhydride copolymers sold under the trade name GANTREZ ES 425 by the ISP Company, the acrylic acid/ethyl acrylate/N-tert-butyl acrylamide terpolymers sold under the trade name ULTRAHOLD STRONG by the BASF Company, the copolymers of methacrylic acid and methyl methacrylate sold under the trade name EUDRAGIT L by the ROHM PHARMA Company, the vinyl acetate/vinyl tert-butyl benzoate/crotonic acid terpolymers and the crotonic acid/vinyl acetate/vinyl neododecanoate terpolymers sold under the trade name Resin 28-29-30 by the NATIONAL STARCH Company, the copolymers of methacrylic acid and ethyl acrylate sold under the trade name LUVIMER MAEX or MAE by the BASF Company, the vinylpyrrolidone/acrylic acid/lauryl methacrylate terpolymers sold under the trade name ACRYLIDONE LM by the ISP Company and the homopolymers of acrylic or methacrylic acid sold, for example, under the trade name VERSICOL E 5 or the sodium polymethacrylate sold under the trade name DARVAN 7 by the VANDERBILT Company, and mixtures thereof.

Preferably, the anionic polymer is a sodium polymethacrylate.

Pastes of Non-Animal Origin

The compositions according to the invention may comprise at least one paste of non-animal origin.

The compositions according to the invention may therefore comprise at least one paste of non-animal origin and the mixture 1) described hereinabove.

By “pasty compound” within the meaning of the present invention there is understood a lipophilic fatty compound capable of reversible change of state from solid to liquid and containing, at the temperature of 23° C., a liquid fraction and a solid fraction.

At the temperature of 23° C., a pasty compound is in the form of a liquid fraction and a solid fraction. In other words, the starting melting temperature of the pasty compound is lower than 23° C. The liquid fraction of the pasty compound, measured at 23° C., represents 20 to 97% by weight of the pasty compound. More preferentially, at 23° C., this liquid fraction represents 25 to 85% and better 30 to 60% by weight of the pasty compound.

The liquid fraction by weight of the pasty compound at 23° C. is equal to the ratio of the enthalpy of melting consumed at 23° C. to the enthalpy of melting of the pasty compound.

The enthalpy of melting consumed at 23° C. is the quantity of energy absorbed by the sample for transition from the solid state to the state in which it exists at 23° C., consisting of a liquid fraction and a solid fraction.

The enthalpy of melting of the pasty compound is the enthalpy consumed by the compound in changing from the solid state to the liquid state. The pasty compound is said to be in the solid state when the entirety of its mass is in solid form. The pasty compound is said to be in the liquid state when the entirety of its mass is in liquid form.

The enthalpy of melting of the pasty compound is equal to the area under the curve of the thermogram obtained by means of a differential scanning calorimeter (D. S. C.), such as the calorimeter sold under the trade name MDSC 2920 by the TA Instrument Company, with a temperature rise of 5 or 10° C. per minute, according to ISO standard 11357-3:1999. The enthalpy of melting of the pasty compound is the quantity of energy necessary to make the compound change from the solid state to the liquid state. It is expressed in J/g.

The liquid fraction of the pasty compound, measured at 32° C., preferably represents 40 to 100% by weight of the pasty compound, even better 50 to 100% by weight of the pasty compound. When the liquid fraction of the pasty compound measured at 32° C. is equal to 100%, the temperature of the end of the melting range of the pasty compound is lower than or equal to 32° C. The liquid fraction of the pasty compound, measured at 32° C., is equal to the ratio of the enthalpy of melting consumed at 32° C. to the enthalpy of melting of the pasty compound. The enthalpy of melting consumed at 32° C. is calculated in the same way as the enthalpy of melting consumed at 23° C.

By “non-animal origin” there is understood a pasty compound chosen from among the pasty compounds of synthetic and vegetable origin (produced or derived from plants).

The pasty compound preferably has a hardness at 20° C. ranging from 0.001 to 0.5 MPa, preferably from 0.002 to 0.4 MPa.

The hardness is measured according to the method of penetration of an indenter into a sample of the compound, and in particular by means of a texture analyzer (for example the TA-TX2i of Rheo), equipped with a stainless steel cylinder with a diameter of 2 mm. The hardness measurement is carried out at 20° C. at the center of 5 specimens. The cylinder is introduced into each specimen, the penetration depth being 0.3 mm. The value recorded as the hardness is that of the maximum peak.

The pasty compound of non-animal origin is chosen from among the synthetic compounds and the compounds of vegetable origin. A pasty compound of non-animal origin may be obtained by synthesis from starting products of vegetable origin.

The pasty compound is advantageously chosen from among:

    • the polymeric or non-polymeric silicone compounds, such as the polydimethylsiloxanes of high molecular weights, the polydimethylsiloxanes with side and/or terminal chains of alkyl or alkoxy type having 8 to 24 carbon atoms, especially the stearyl dimethicones,
    • the polymeric or non-polymeric fluoro compounds,
    • the vinyl polymers, especially
      • the olefin homopolymers,
      • the olefin copolymers,
      • the homopolymers and copolymers of hydrogenated dienes,
      • the linear or branched homopolymeric or copolymeric oligomers of alkyl (meth)acrylates, preferably having C8-C30 alkyl groups,
      • the homopolymeric and copolymeric oligomers of vinyl esters having C8-C30 alkyl groups,
      • the homopolymeric and copolymeric oligomers of vinyl ethers having C8-C30 alkyl groups,
    • the fat-soluble polyethers resulting from the polyetherification between one or more C2-C100 diols, preferably C2-C50,
    • the esters and the polyesters,
    • and mixtures thereof.

The pasty compound may be a polymer, especially of hydrocarbon type.

A preferred pasty silicone and fluoro compound is polymethyl-trifluoropropyl-methylalkyl-dimethylsiloxane, manufactured under the trade name X22-1088 by SHIN-ETSU.

When the pasty compound is a silicone and/or fluoro polymer, the composition advantageously comprises a compatibilizing agent, such as the short-chain esters, such as isodecyl neopentanoate.

Among the fat-soluble polyethers there may be cited in particular the copolymers of ethylene oxide and/or propylene oxide with C6-C30 alkylene oxides. Preferably, the weight ratio of the ethylene oxide and/or of the propylene oxide to the alkylene oxides in the copolymer is 5:95 to 70:30. In this family, there will be cited in particular the block copolymers comprising C6-C30 alkylene oxide blocks having a molecular weight ranging from 1,000 to 10,000, for example, a polyoxyethylene/polydodecylene glycol block copolymer such as the ethers of dodecanediol (22 mol) and of polyethylene glycol (45 oxyethylene moieties or OE) sold under the brand ELFACOS ST9 by Akzo Nobel.

Among the esters, there are especially preferred:

    • the esters of a glycerol oligomer, especially the esters of diglycerol, in particular the condensates of adipic acid and glycerol for which part of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids such as stearic acid, capric acid, stearic acid, isostearic acid and 12-hydroxystearic acid, such as those sold in particular under the brand Softisan 649 by the Sasol Company;
    • the esters of phytosterol;
    • the esters of pentaerythritol;
    • the esters formed from:
      • at least one C16-40 alcohol, at least one of the alcohols being a Guerbet alcohol and
      • a diacid dimer formed from at least one C18-40 unsaturated fatty acid, such as the ester of fatty acid dimer of tall oil comprising 36 carbon atoms and of a mixture i) of Guerbet alcohols comprising 32 carbon atoms and ii) behenyl alcohol; the ester of linoleic acid dimer and of a mixture of two Guerbet alcohols, 2-tetradecyloctadecanol (32 carbon atoms) and 2-hexadecyleicosanol (36 carbon atoms);
    • the non-cross-linked polyesters resulting from the polycondensation between a dicarboxylic acid or a C4-C50 linear or branched polycarboxylic acid and a C2-C50 diol or polyol;
    • the polyesters that result from the esterification between a polycarboxylic acid and an ester of aliphatic hydroxylated carboxylic acid such as Risocast DA-L and Risocast DA-H sold by the Japanese company KOKYU ALCOHOL KOGYO, which are esters resulting from the esterification reaction of hydrogenated castor oil with dilinoleic acid or isostearic acid; and
    • the aliphatic esters of ester resulting from esterification between an ester of aliphatic hydroxylated carboxylic acid and an aliphatic carboxylic acid, for example that sold under the trade name Salacos HCIS (V)-L by the Nishing Oil Company.

A Guerbet alcohol is the reaction product of the Guerbet reaction, well known to those skilled in the art. It is a reaction in which a primary aliphatic alcohol is transformed into its alkylated dimer alcohol with loss of one equivalent of water.

The aliphatic carboxylic acids described above generally comprise 4 to 30 and preferably 8 to 30 carbon atoms. They are preferably chosen from among hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, hexyldecanoic acid, heptadecanoic acid, octadecanoic acid, isostearic acid, nonadecanoic acid, eicosanoic acid, isoarachidic acid, octyldodecanoic acid, heneicosanoic acid, docosanoic acid and mixtures thereof.

The aliphatic carboxylic acids are preferably branched.

The esters of hydroxylated aliphatic carboxylic acid are advantageously obtained from a hydroxylated aliphatic carboxylic acid containing 2 to 40 carbon atoms, preferably 10 to 34 carbon atoms and better 12 to 28 carbon atoms, and 1 to 20 hydroxyl groups, preferably 1 to 10 hydroxyl groups and better 1 to 6 hydroxyl groups. The esters of hydroxylated aliphatic carboxylic acid are chosen especially from among:

a) the partial or total esters of saturated linear monohydroxylated aliphatic monocarboxylic acids;
b) the partial or total esters of unsaturated monohydroxylated aliphatic monocarboxylic acids;
c) the partial or total esters of saturated monohydroxylated aliphatic carboxylic polyacids;
d) the partial or total esters of saturated polyhydroxylated aliphatic carboxylic polyacids;
e) the partial or total esters of C2 to C16 aliphatic polyols that have been reacted with a mono or polyhydroxylated aliphatic mono or polycarboxylic acid;
f) and mixtures thereof.

The aliphatic esters of ester are advantageously chosen from among:

    • the ester resulting from the esterification reaction of hydrogenated castor oil with isostearic acid in proportions of 1 to 1 (1/1), which is referred to as hydrogenated castor oil monoisostearate,
    • the ester resulting from the esterification reaction of hydrogenated castor oil with isostearic acid in proportions of 1 to 2 (1/2), which is referred to as hydrogenated castor oil diisostearate,
    • the ester resulting from the esterification reaction of hydrogenated castor oil with isostearic acid in proportions of 1 to 3 (1/3), which is referred to as hydrogenated castor oil triisostearate,
      and mixtures thereof.

Preferably, the pasty compound is chosen from among the compounds of vegetable origin.

Among those there may be cited in particular isomerized jojoba oil, such as the trans isomerized partly hydrogenated jojoba oil manufactured or sold by the Desert Whale Company under the commercial reference Iso-Jojoba-50®, orange wax such as, for example, that sold under the reference Orange Peel Wax by the Koster Keunen Company, shea butter, partly hydrogenated olive oil such as, for example, the compound sold under the reference Beurrolive by the Soliance Company, cocoa butter, mango oil such as, for example, Lipex 302 of the Aarhuskarlshamm Company.

The pasty compound or compounds are preferably present in a quantity greater than or equal to 1% by weight relative to the total weight of the composition, for example 1 to 15% by weight, better in a quantity greater than or equal to 2% by weight, ranging for example from 2 to 10% by weight, and even more preferentially from 3 to 8% by weight relative to the total weight of the composition.

Fatty-Phase Thickening or Gelling Rheological Agent

The composition according to the invention may comprise a fatty-phase thickening or gelling rheological agent.

The compositions according to the invention may therefore comprise at least one fatty-phase thickening or gelling rheological agent and the mixture of MQ and propyl T resins described hereinabove.

By “fatty-phase thickening or gelling rheological agent” there is understood a compound capable of increasing the viscosity of the fatty phase of the composition. The fatty-phase thickening or gelling rheological agent makes it possible in particular to obtain a composition that may have a texture ranging from fluid to solid textures.

The fatty-phase thickening or gelling rheological agent may be chosen from among:

    • the crystalline polymers, preferably chosen from among the semi-crystalline polymers, the esters of dextrin and fatty acid, the hydrophobic modified polysaccharides, the crystalline olefin copolymers and the crystalline polycondensates;
    • the mineral lipophilic structuring agents, such as the lipophilic clays and the hydrophobic silicas, such as hydrophobic treated pyrogenic silica,
    • the lipophilic polymers of polyamide type,
    • the lipophilic polyureas and polyurethanes,
    • the silicone polymers containing, as the case may be, at least one hydrocarbon moiety containing two groups capable of establishing hydrogen interactions chosen from among the ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino, biguanidino groups and combinations thereof, preferably amide groups,
    • the organo gelling agents;
    • the block polymers;
    • the cholesteric liquid crystal agents;
    • the silicone elastomers;
    • and mixtures thereof.

Preferably the fatty-phase rheological agent is chosen from among the semi-crystalline polymers, the block polymers, the lipophilic polymers of polyamide type and the silicone polymers comprising at least one hydrocarbon moiety containing two groups capable of establishing hydrogen interactions chosen from among the amide groups, the mineral lipophilic structuring agents, in particular the lipophilic clays and the hydrophobic silicas, and the silicone elastomers.

It is pointed out that, according to the invention, in the case of associations of a fatty-phase rheological agent with an oil, there is understood by “oil” a fatty substance that is liquid at room temperature.

It is also pointed out that, by “volatile compound”, for example “volatile oil”, there is understood, within the meaning of the invention, any compound (or non-aqueous medium) capable of evaporating on contact with the skin or the horny fiber in less than one hour, at room temperature and atmospheric pressure. The volatile compound is a volatile cosmetic compound, liquid at room temperature, having in particular a non-zero vapor pressure at room temperature and atmospheric pressure, especially having a vapor pressure ranging from 0.13 Pa to 40,000 Pa (10−3 to 300 mm Hg), in particular ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mm Hg), and more particularly ranging from 1.3 Pa to 1,300 Pa (0.01 to 10 mm Hg).

In contrast, by “non-volatile compound”, for example “non-volatile oil”, there is understood a compound that remains on the skin or horny fiber at room temperature and atmospheric pressure for at least several hours, and having in particular a vapor pressure lower than 104 mm Hg (0.13 Pa).

The oil may be chosen from among the volatile and non-volatile hydrocarbon and/or silicone and/or fluoro oils and their mixtures. These oils may be of animal, vegetable, mineral or synthetic origin. By “hydrocarbon oil” there is understood an oil containing mainly carbon and hydrogen atoms and possibly one or more functions chosen from among the hydroxyl, ester, ether, carboxylic functions. By way of example of oil that can be used in the invention, there may be cited:

    • the hydrocarbon oils of animal origin, such as perhydrosqualene;
    • the vegetable hydrocarbon oils, such as the liquid triglycerides of fatty acids with 4 to 24 carbon atoms, such as the triglycerides of heptanoic or octanoic acids or else sunflower seed, corn, soy, gourd, grape seed, sesame, hazelnut, apricot, macadamia, castor, avocado oils, the triglycerides of caprylic/capric acids such as those sold by the Stearineries Dubois Company or those sold under the trade names Miglyol 810, 812 and 818 by the Dynamit Nobel Company, jojoba oil, shea butter;
    • the linear or branched hydrocarbons of mineral or synthetic origin, such as the paraffin oils and their derivatives, vaseline, the polydecenes, the polybutenes, hydrogenated polyisobutene such as Parleam;
    • the synthetic esters and ethers especially of fatty acids, such as the oils of formula R1COOR2, in which R1 represents the residue of a higher fatty acid containing 1 to 40 carbon atoms and R2 represents a hydrocarbon chain containing 1 to 40 carbon atoms, with R1+R2≧10, such as, for example, Purcellin oil, isononyl isononanoate, isopropyl myristate, ethyl 2-hexyl palmitate, octyl 2-dodecyl stearate, octyl 2-dodecyl erucate, isostearyl isostearate, tridecyl trimellitate; the hydroxylated esters such as isostearyl lactate, octyl hydroxy stearate, octyl dodecyl hydroxy stearate, diisostearyl malate, triisocetyl citrate, heptanoates, octanoates, decanoates of fatty alcohols; polyol esters, such as propylene glycol dioctanoate, neopentyl glycol diheptanoate, diethylene glycol diisononanoate; and the pentaerythritol esters, such as pentaerythrityl tetraisostearate;
    • fatty alcohols having 12 to 26 carbon atoms, such as octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleic alcohol;
    • the fluoro, possibly partly hydrocarbon and/or silicone oils;
    • the silicone oils, such as the linear or cyclic volatile or non-volatile polydimethylsiloxanes (PDMS); the polydimethylsiloxanes containing alkyl, alkoxy or phenyl groups pendant from or at the end of the silicone chain, groups having 2 to 24 carbon atoms; the phenyl silicones, such as the phenyl trimethicones, the phenyl dimethicones, the phenyl trimethylsiloxy diphenyl siloxanes, the diphenyl dimethicones, the diphenyl methyldiphenyl trisiloxanes, the 2-phenyl ethyl trimethyl-siloxy silicates;
    • mixtures thereof.

Preferably, the oil has a molecular weight greater than or equal to 250 g/mol, especially between 250 and 10,000 g/mol, preferably greater than or equal to 300 g/mol, especially between 300 and 8,000 g/mol and better, greater than or equal to 400 g/mol, especially between 400 and 5,000 g/mol.

In general, in the fatty phase, the ratio of the oil or oils to the particular compound or compounds is from 10/90 to 90/10, preferably from 20/80 to 80/20 and more preferably from 30/70 to 70/30.

This oil may be chosen from among:

    • the polybutylenes, such as INDOPOL H-100 (of molecular weight or MW=965 g/mol), INDOPOL H-300 (MW=1340 g/mol), INDOPOL H-1500 (MW=2160 g/mol) sold or manufactured by the AMOCO Company;
    • the hydrogenated polyisobutylenes, such as PANALANE H-300 E sold or manufactured by the AMOCO Company (M=1340 g/mol), VISEAL 20000 sold or manufactured by the SYNTEAL Company (MW=6,000 g/mol), REWOPAL PIB 1000 sold or manufactured by the WITCO Company (MW=1,000 g/mol);
    • the polydecenes and the hydrogenated polydecenes, such as: PURESYN 10 (MW=723 g/mol), PURESYN 150 (MW=9,200 g/mol) sold or manufactured by the MOBIL CHEMICALS Company,
    • the esters such as
    • the esters of linear fatty acids having a total carbon number ranging from 30 to 70, such as pentaerythrityl tetrapelargonate (MW=697.05 g/mol),
    • the hydroxylated esters, such as diisostearyl malate (MW=639 g/mol),
    • the aromatic esters such as tridecyl trimellitate (MW=757.19 g/mol),
    • the esters of fatty alcohol or of C24-C28 branched fatty acids, such as those described in Application EP A 0955039, and especially triisocetyl citrate (MW=865 g/mol), pentaerythrityl tetraisononanoate (MW=697.05 g/mol), glyceryl triisostearate (MW=891.51 g/mol), glyceryl tridecyl-2 tetradecanoate (MW=1143.98 g/mol), pentaerythrityl tetraisostearate (MW=1202.02 g/mol), polyglyceryl-2 tetraisostearate (MW=1232.04 g/mol) or else pentaerythrityl tetradecyl-2 tetradecanoate (MW=1538.66 g/mol),
    • the oils of vegetable origin, such as sesame oil (820.6 g/mol),
    • and mixtures thereof.

Crystalline Polymers

a) Semi-Crystalline Polymers

It is pointed out that, according to the invention, in the case of the aforementioned associations, there is understood by “semi-crystalline polymer” polymers containing a crystallizable part, crystallizable pendant and/or terminal chain or crystallizable sequence in the skeleton and/or at the ends, and an amorphous part in the skeleton and having a first-order reversible phase-change temperature, particularly of melting (solid-liquid transition). When the crystallizable part is in the form of a crystallizable sequence of the polymer skeleton, the amorphous part of the polymer is in the form of an amorphous sequence; in this case the semi-crystalline polymer is a sequenced copolymer, for example of the diblock, triblock or multiblock type, containing at least one crystalline sequence and at least one amorphous sequence. By “sequence” there is generally understood at least 5 identical repeating moieties. The crystallizable sequence or sequences are then of chemical nature different from that of the amorphous sequence or sequences.

The semi-crystalline polymer according to the invention has a melting temperature higher than or equal to 30° C. (especially ranging from 30° C. to 80° C.), preferably ranging from 30° C. to 60° C. This melting temperature is a first-order state-change temperature.

This melting temperature may be measured by any known method and in particular by means of a differential scanning calorimeter (D.S.C.).

Advantageously, the semi-crystalline polymer or polymers to which the invention applies have a number-average molecular weight greater than or equal to 1,000.

Advantageously, the semi-crystalline polymer or polymers of the composition of the invention have a number-average molecular weight Mn ranging from 2,000 to 800,000, preferably from 3,000 to 500,000, better from 4,000 to 150,000, especially lower than 100,000 and better from 4,000 to 99,000. Preferably, they have a number-average molecular weight greater than 5,600, ranging for example from 5,700 to 99,000.

By “crystallizable chain or sequence” within the meaning of the invention there is understood a chain or sequence that, if it were alone, would change reversibly from the amorphous state to the crystalline state depending on whether it was above or below the melting temperature. A chain within the meaning of the invention is a group of atoms in pendant or side position relative to the polymer skeleton. A sequence is a group of atoms belonging to the skeleton, this group constituting one of the repetitive moieties of the polymer. Advantageously, the “crystallizable pendant chain” may be a chain containing at least 6 carbon atoms.

Preferably, the crystallizable sequence or sequences or chains of semi-crystalline polymers represent at least 30% of the total weight of each polymer and better at least 40%. The semi-crystalline polymers of the invention with crystallizable sequences are sequenced or multisequenced polymers. They may be obtained by polymerization of monomers with reactive double (or ethylenic) bonds or by polycondensation. When the polymers of the invention are polymers with crystallizable side chains, the latter are advantageously in random or statistical form.

Preferably, the semi-crystalline polymers of the invention are of synthetic origin. In addition, they do not contain any polysaccharide skeleton. In general, the crystallizable moieties (chains or sequences) of semi-crystalline polymers according to the invention are derived from monomers with a crystallizable sequence or sequences or chain or chains used for the manufacture of semi-crystalline polymers.

According to the invention, the semi-crystalline polymer may be chosen from among the sequenced copolymers containing at least one crystallizable sequence and at least one amorphous sequence, the homopolymers and the copolymers carrying at least one crystallizable side chain per repetitive moiety, and mixtures thereof.

The semi-crystalline polymers that can be used in the invention are in particular:

    • the sequenced copolymers of polyolefins with controlled crystallization, especially those whose monomers are described in EP A 0951897,
    • the polycondensates, and especially of aliphatic or aromatic polyester or aliphatic/aromatic copolyester type.
    • the homopolyers or copolymers carrying at least one crystallizable side chain and the homopolymers or copolymers carrying at least one crystallizable sequence in the skeleton, such as those described in the document U.S. Pat. No. 5,156,911,
    • the homopolyers or copolymers carrying at least one crystallizable side chain, in particular with a fluoro group or groups, such as described in the document WO A 01/19333,
    • and mixtures thereof.

In the two latter cases, the crystallizable side chain or chains or sequence or sequences are hydrophobic.

A) Semi-Crystalline Polymers with Crystallizable Side Chains:

There may be cited in particular those defined in the documents U.S. Pat. No. 5,156,911 and WO A 01/19333. These are homopolymers or copolymers containing 50 to 100% by weight of moieties resulting from the polymerization of one or more monomers carrying crystallizable hydrophobic side chains.

    • These homopolymers or copolymers are of any nature, provided they exhibit the conditions indicated in the foregoing.

They may result:

    • from the polymerization, especially radical, of one or more monomers with double or ethylenic bonds that are reactive with respect to polymerization, or in other words with vinyl, (meth)acrylic or allyl groups.
    • from the polycondensation of one or more monomers carrying co-reactive groups (carboxylic or sulfonic acid, alcohol, amine or isocyanate), such as, for example, the polyesters, the polyurethanes, the polyethers, the polyureas, the polyamides.

In general, these polymers are chosen in particular from among the homopolymers and copolymers resulting from the polymerization of at least one monomer with crystallizable chain or chains that may be represented by the formula X:

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with M representing an atom of the polymer skeleton, S representing a spacer, C representing a crystallizable group.

The crystallizable “S—C” chains may be aliphatic or aromatic, possibly fluorinated or perfluorinated. “S” represents in particular a linear or branched or cyclic (CH2)n group or (CH2CH2O)n or (CH2O), where n is an integer ranging from 0 to 22. Preferably, “S” is a linear group. Preferably, “S” and “C” are different.

When the crystallizable “S—C” chains are aliphatic hydrocarbon chains, they contain alkyl hydrocarbon chains with at least 11 carbon atoms and at most 40 carbon atoms and better at most 24 carbon atoms. In particular, they are aliphatic chains or alkyl chains possessing at least 12 carbon atoms and preferably they are C14-C24 alkyl chains. When they are fluorinated or perfluorinated alkyl chains, they contain at least 6 fluorinated carbon atoms and especially at least 11 carbon atoms, of which at least 6 carbon atoms are fluorinated.

As examples of semi-crystalline polymers or copolymers with a crystallizable chain or chains there may be cited those resulting from the polymerization of one or more of the following monomers: the saturated alkyl (meth)acrylates with the C14-C24 alkyl group, the perfluoroalkyl (meth)acrylates with a C11-C15 perfluoroalkyl group, the N-alkyl (meth)acrylamides with the C14 to C24 alkyl group with or without fluorine atoms, the vinyl esters with alkyl or perfluoro (alkyl) chains with the C14 to C24 alkyl group (with at least 6 fluorine atoms for a perfluoro alkyl chain), the vinyl ethers with alkyl or perfluoro (alkyl) chains with the C14 to C24 alkyl group and at least 6 fluorine atoms for a perfluoroalkyl chain, the C14 to C24 alpha-olefins, such as, for example, octadecene, the para-alkylstyrenes with an alkyl group containing 12 to 24 carbon atoms, mixtures thereof.

When the polymers result from a polycondensation, the hydrocarbon and/or fluoro crystallizable chains such as defined hereinabove are carried by a monomer, which may be a diacid, a diol, a diamine, a diisocyanate.

When the polymers comprising objects of the invention are copolymers, they additionally contain 0 to 50% of groups Y or Z resulting from the copolymerization:

α) of Y, which is a polar or non-polar monomer or a mixture of both:

    • When Y is a polar monomer, it is either a monomer carrying polyoxyalkylene groups (especially oxyethylene and/or oxypropylene), a hydroxyalkyl (meth)acrylate such as hydroxyethyl acrylate, (meth)acrylamide, an N-alkyl (meth)acrylamide, an N,N-dialkyl (meth)acrylamide such as, for example, N,N-diisopropyl acrylamide or N-vinylpyrrolidone (NVP), N-vinyl caprolactam, a monomer carrying at least one carboxylic acid group such as (meth)acrylic, crotonic, itaconic, maleic, fumaric acids, or carrying a carboxylic acid anhydride group such as maleic anhydride, and mixtures thereof.
    • When Y is a non-polar monomer, it may be an ester of the linear, branched or cyclic alkyl (meth)acrylate type, a vinyl ester, an alkyl vinyl ether, an alpha-olefin, styrene or styrene substituted by a C1 to C10 alkyl group, such as α-methylstyrene, a macromonomer of the polyorganosiloxane type with vinyl unsaturation.

By “alkyl” there is understood within the meaning within the meaning of the invention a saturated group, especially with C8 to C24 unless otherwise expressly mentioned, and better with C14 to C24.

β) of Z, which is a polar monomer or a mixture of polar monomers. In this case, Z has the same definition as “polar Y” defined above.

Preferably, the semi-crystalline polymers with crystallizable side chain are homopolymers of alkyl (meth)acrylate or alkyl (meth)acrylamide with an alkyl group such as defined above, and especially with C14 to C24, copolymers of these monomers with a hydrophilic monomer, preferably of different nature from that of (meth)acrylic acid, such as N-vinylpyrrolidone or hydroxyethyl (meth)acrylate and mixtures thereof.

B) The polymers carrying at least one crystallizable sequence in the skeleton:

These polymers are especially sequenced copolymers composed of at least 2 sequences of different chemical nature, one of which is crystallizable.

    • There may be used the sequenced polymers defined in U.S. Pat. No. 5,156,911;
    • The sequenced copolymers of olefin or cycloolefin with a crystallizable chain, such as those obtained from the sequenced polymerization of:
      • cyclobutene, cyclohexene, cyclooctene, norbornene (or in other words bicyclo(2,2,1)heptene-2), 5-methylnorbornene, 5-ethylnorbornene, 5,6-dimethylnorbornene, 5,5,6-trimethylnorbornene, 5-ethylidene-norbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a,5,8a-octahydronaphthalene, dicyclopentadiene or mixtures thereof,
      • with ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-eicosene or mixtures thereof.
      • and in particular the block copoly(ethylene/norbornene)s and the block (ethylene/propylene/ethylidene-norbornene) terpolymers. There may also be used those resulting from the sequenced copolymerization of at least two C2-C16 α-olefins and better C2-C12 and even better C4-C12, such as those cited in the foregoing, and in particular the sequenced bipolymers of ethylene and 1-octene.
    • The copolymers may be copolymers having at least one crystallizable sequence, the rest of the copolymer being amorphous (at room temperature). These copolymers may additionally have two crystallizable sequences of different chemical nature. The preferred copolymers are those that possess, at room temperature, sequentially distributed, both a crystallizable sequence and an amorphous sequence that are both hydrophobic and lipophilic; for example, there may be cited the polymers possessing crystallizable sequences and one of the following amorphous sequences:
      • Naturally crystallizable sequence: a) polyester such as the poly(alkylene terephthalate), b) polyolefin such as the polyethylenes or polypropylenes.
      • Amorphous and lipophilic sequence such as the amorphous polyolefins or copoly(olefin)s, such as poly(isobutylene), hydrogenated polybutadiene, hydrogenated poly(isoprene).

As examples of such copolymers with separate crystallizable sequence and amorphous sequence there may be cited:

α) the sequenced poly(ε-caprolactone)-b-poly(butadiene) copolymers, used preferably in hydrogenated form, such as those described in the article “Melting behavior of poly(e-caprolactone)-block-polybutadiene copolymers” of S. Nojima, Macromolecules, 32, 3727-3734 (1999).

β) the sequenced or multisequenced hydrogenated sequenced poly(butylene terephthalate)-b-poly(isoprene) sequenced copolymers cited in the article “Study of morphological and mechanical properties of PP/PBT” of B. Boutevin et al., Polymer Bulletin, 34, 117-123 (1995).

γ) the sequenced poly(ethylene)-b-copoly(ethylene/propylene) copolymers cited in the articles “Morphology of semi-crystalline block copolymers of ethylene-(ethylene-alt-propylene)” of P. Rangarajan et al., Macromolecules, 26, 4640-4645 (1993) and “Polymer aggregates with crystalline cores: the system poly(ethylene)-poly(ethylene-propylene)” of P. Richter et al., Macromolecules, 30, 1053-1068 (1997).

δ) the sequenced poly(ethylene)-b-poly(ethylethylene) copolymers cited in the general article “Crystallization in block copolymers” of I. W. Hamley, Advances in Polymer Science, vol. 148, 113-137 (1999).

The semi-crystalline polymers of the composition of the invention may or may not be partly cross-linked, since the degree of cross-linking does not impair their dissolution or dispersion in the liquid fatty phase by heating above their melting point. They may then be chemically cross-linked, by reaction with a multifunctional monomer during polymerization. They may also be physically cross-linked, which may then be due either to the establishment of bonds of hydrogen or dipole type between groups carried by the polymer, such as, for example, the dipole interactions between carboxylate ionomers, these interactions being of small quantity and carried by the polymer skeleton; or to phase separation between the crystallizable sequences and the amorphous sequences carried by the polymer.

Preferably, the semi-crystalline polymers of the composition according to the invention are non-cross-linked.

According to a particular embodiment of the invention, the polymer is chosen from among the copolymers resulting from the polymerization of at least one monomer with crystallizable chain chosen from among the saturated C14 to C24 alkyl (meth)acrylates, the C11 to C15 perfluoroalkyl (meth)acrylates, the N—(C14 to C24)alkyl (meth)acrylamides with or without fluorine atoms, the vinyl esters with C14 to C24 alkyl or perfluoroalkyl chains, the vinyl ethers with C14 to C24 alkyl or perfluoroalkyl chains, the C14 to C24 alpha-olefins, the para-alkylstyrenes with an alkyl group containing 12 to 24 carbon atoms, with at least one ester or amide of C1 to C10 monocarboxylic acid, possibly fluorinated, which may be represented by the following formula:

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in which R1 is H or CH3, R represents a C1-C10 alkyl group, which may be fluorinated, and X represents O, NH or NR2, where R2 represents a C1-C10 alkyl group, which may be fluorinated.

According to a more particular embodiment of the invention, the polymer is obtained from a monomer with crystallizable chain chosen from among the saturated C14 to C22 alkyl (meth)acrylates.

By way of particular example of structuring semi-crystalline polymer that can be used in the composition according to the invention there may be cited the products Intelimer® of the Landec Company described in the brochure “Intelimer® polymers”, Landec IP22 (Rev. 4-97). These polymers are in solid form at room temperature (25° C.). They carry crystallizable side chains and have the foregoing formula X.

The semi-crystalline polymers may be especially:

those described in Examples 3, 4, 5, 7, 9, 13 of U.S. Pat. No. 5,156,911, with —COHO group, resulting from the copolymerization of acrylic acid and C5 to C16 alkyl (meth)acrylate and more particularly from the copolymerization:

    • of acrylic acid, hexadecyl acrylate and isodecyl acrylate in a weight ratio of 1/16/3,
    • of acrylic acid and pentadecyl acrylate in a weight ratio of 1/19,
    • of acrylic acid, hexadecyl acrylate, ethyl acrylate in a weight ratio of 2.5/76.5/20,
    • of acrylic acid, hexadecyl acrylate and methyl acrylate in a weight ratio of 5/85/10,
    • of acrylic acid and octadecyl methacrylate in a weight ratio of 2.5/97.5,
    • of hexadecyl acrylate, monomethyl ether of polyethylene glycol methacrylate with 8 ethylene glycol moieties, and acrylic acid in a weight ratio of 8.5/1/0.5.

There may also be used the polymer of structure “O” of National Starch, such as that described in the document U.S. Pat. No. 5,736,125 of melting point 44° C. as well as the semi-crystalline polymers with crystallizable pendant chains containing fluoro groups such as described in Examples 1, 4, 6, 7 and 8 of the document of WO A 01/19333.

There may also be used the semi-crystalline polymers obtained by copolymerization of stearyl acetate and acrylic acid or NVP such as described in the documents U.S. Pat. No. 5,519,063 or EP A 550745, with melting temperatures of 40° C. and 38° C. respectively.

There may also be used the semi-crystalline polymers obtained by copolymerization of behenyl acrylate and acrylic acid or NVP, such as described in the documents U.S. Pat. No. 5,519,063 and EP A 550745, with melting temperatures of 60° C. and 58° C. respectively.

Preferably, the semi-crystalline polymers do not contain any carboxylic group.

Waxy Polymer Obtained by Metallocene Catalysis:

Finally, the semi-crystalline polymers according to the invention may also be chosen from among the waxy polymers obtained by metallocene catalysis, such as those described in US Application 2007/0031361.

These polymers are homopolymers or copolymers of ethylene and/or propylene prepared by metallocene catalysis, or in other words by polymerization at low pressure and in the presence of a metallocene catalyst.

The weight-average molecular weight (Mw) of the waxes obtained by metallocene catalysis described in that document is smaller than or equal to 25,000 g/mol; for example, it ranges from 2,000 to 22,000 g/mol and better from 4,000 to 20,000 g/mol.

The number-average molecular weight (Mn) of the waxes obtained by metallocene catalysis described in that document is preferably smaller than or equal to 15,000 g/mol; for example, it ranges from 1,000 to 12,000 g/mol and better from 2,000 to 10,000 g/mol.

The polydispersity index I of the polymer is equal to the ratio of the weight-average molecular weight Mw to the number-average molecular weight Mn. Preferably, the polydispersity index of the waxy polymers is between 1.5 and 10, preferably between 1.5 and 5, preferably between 1.5 and 3 and even better between 2 and 2.5.

The waxy homopolymers and copolymers may be obtained in known manner from ethylene and/or propylene monomers, for example by metallocene catalysis according to the method described in the document EP 571882.

The homopolymers and copolymers of ethylene and/or propylene prepared by metallocene catalysis may or may not be modified “polarly” (polar modified waxes, or in other words waxes modified so that they exhibit the properties of a polar wax). The polar-modified waxy homopolymers and copolymers may be prepared in known manner from the non-modified waxy homopolymers and copolymers such as those described in the foregoing by oxidation with oxygen-containing gases, such as air, or by grafting with polar monomers such as maleic acid or acrylic acid or else with derivatives of these acids. These two routes making it possible to achieve polar modification of the polyolefins obtained by metallocene catalysis are described respectively in the documents EP 890583 and U.S. Pat. No. 5,998,547 for example, the content of these two documents being incorporated by way of reference.

According to the present invention, the polar modified homopolymers and copolymers of ethylene and/or propylene prepared by metallocene catalysis and particularly preferred are polymers modified so that they exhibit hydrophilic properties. By way of example, there may be cited homopolymers or copolymers of ethylene and/or propylene modified by the presence of hydrophilic groups, such as maleic anhydride, acrylate, methacrylate, polyvinylpyrrolidone (PVP), etc.

The waxy homopolymers or copolymers of ethylene and/or propylene modified by the presence of hydrophilic groups such as maleic anhydride or acrylate are particularly preferred.

By way of example there may be cited:

    • the polypropylene waxes modified by maleic anhydride (PPMA) sold by the Clariant Company or the polypropylene-ethylene-maleic anhydride copolymers, such as those sold by the Clariant Company under the name of LicoCare, such as LicoCare PP207 LP3349, LicoCare CM401 LP3345, LicoCare CA301 LP 3346 and LicoCare CA302 LP 3347, or else
    • the non-modified polyethylene waxes sold by the Clariant Company, such as the product LicoCare PE 102 LP3329.

Within the scope of a composition for the lips, there will be preferred a polar-modified waxy polymer having a low degree of crystallinity, preferably of less than 40%.

The use of these waxy polymers makes it possible in particular to limit the loss of gloss of lipstick compositions.

b) Esters of Dextrin and Fatty Acid:

The esters of dextrin and fatty acids may be chosen especially from among the mono or poly esters of dextrin and at least one fatty acid, and the compounds represented by formula (C):

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in which:

    • n is an integer ranging from 3 to 200, especially ranging from 20 to 150, and in particular ranging from 25 to 50,
    • the radicals R1, R2 and R3, identical or different, are chosen from among hydrogen or an acyl group (R—CO—), in which the R radical is a saturated or unsaturated, linear or branched hydrocarbon group possessing 7 to 29, in particular 7 to 21, especially 11 to 19, more particularly 13 to 17, even 15 carbon atoms, with the proviso that at least one of the said radicals R1, R2 or R3 is different from hydrogen.

In particular, R1, R2 and R3 may represent hydrogen or an acyl group (R—CO—), in which R is a hydrocarbon radical such as defined in the foregoing, with the proviso that at least two of the said radicals R1, R2 or R3 are different from hydrogen.

All radicals R1, R2 and R3 may represent an identical or different acyl group (R—CO), and especially identical.

In particular, n advantageously varies from 25 to 50, and especially it is equal to 38 in general formula (C) of the ester according to the invention.

Especially when the radicals R1, R2 and/or R3, identical or different, represent an acyl group (R—CO), they may be chosen from among the caprylic, capric, lauric, myristic, palmitic, stearic, arachic, behenic, isobutyric, isovaleric, ethyl-2-butyric, ethylmethylacetic, isoheptanoic, ethyl-2-hexanoic, isononanoic, isodecanoic, isotridecanolc, isomyristic, isopalmitic, isostearic, isoarachic, isohexanoic, decenoic, dodecenoic, tetradecenoic, myristoleic, hexadecenoic, palmitoleic, oleic, elaidic, asclepinic, gondoleic, eicosenoic, sorbic, linoleic, linolenic, punicic, stearidonic, arachidonic, stearolic radicals and mixtures thereof.

Preferably, there are used by way of ester of dextrin and fatty acid or acids at least one dextrin palmitate, This may be used alone or in a mixture with other esters.

Advantageously, the ester of dextrin and fatty acid has a degree of substitution smaller than or equal to 2.5 on the basis of one glucose unit, especially varying from 1.5 to 2.5, preferably from 2 to 2.5. The weight-average molecular weight of the dextrin ester may be in particular 10,000 to 150,000, especially 12,000 to 100,000 and even 15,000 to 80,000.

Dextrin esters, in particular dextrin palmitates, are commercially available under the trade name RHEOPEARL TL or RHEOPEARL KL of the Chiba Flour Company.

c) Hydrophobic Modified Polysaccharides

The polysaccharide used in the present invention is preferably chosen from among the fructans.

The fructans or fructosans are oligosaccharides or polysaccharides comprising a chain of anhydrofructose units, possibly associated with one more different saccharidic residues of fructose. The fructans may be linear or branched. The fructans may be products obtained directly from a vegetable or microbial source or else products whose chain length has been modified (increased or decreased) by fractionation, synthesis or hydrolysis, especially enzymatically. The fructans generally have a degree of polymerization of 2 to approximately 1000 and preferably of 2 to approximately 60.

Three groups of fructans are distinguished. The first group corresponds to products whose fructose units are for the most part bonded by β-2-1 bonds. These are substantially linear fructans such as the inulins. The second group also corresponds to linear fructoses, but the fructose units are substantially bonded by β-3-2-6 bonds. These products are levans. The third group corresponds to mixed fructans, or in other words having β-2-6-1 and β-2-1 chains. These are substantially branched fructans such as the graminans.

The fructans used in the compositions according to the invention are inulins. Inulin may be obtained, for example, from chicory, dahlia or Jerusalem artichoke. Preferably, the inulin used in the composition according to the invention is obtained, for example, from chicory.

The polysaccharides, in particular the inulins, used in the composition according to the invention are hydrophobically modified. In particular, they are obtained by grafting hydrophobic chains onto the hydrophilic skeleton of the fructan.

The hydrophobic chains capable of being grafted onto the main chain of the fructan may be especially saturated or unsaturated, linear or branched hydrocarbon chains having 1 to 50 carbon atoms, such as the alkyl, arylalkyl, alkylaryl, alkoylene groups; divalent cycloaliphatic groups or organopolysiloxane chains. These hydrocarbon or organopolysiloxane chains may comprise in particular one or more ester, amide, urethane, carbamate, thiocarbamate, urea, thiourea and/or sulfonamide functions such as especially methylenedicyclohexyl and isophorone; or divalent aromatic groups such as phenylene.

In particular, the polysaccharide, especially inulin, has a degree of polymerization of 2 to approximately 1,000 and preferably of 2 to approximately 60, and a degree of substitution smaller than 2 on the basis of one fructose unit.

According to a preferred embodiment, the hydrophobic chains have at least one alkyl carbamate group of formula R—NH—CO—, in which R is an alkyl group having 1 to 22 carbon atoms.

According to a more preferred embodiment, the hydrophobic chains are lauryl carbamate groups.

In particular, by way of non-limitative illustration of hydrophobically modified inulins that may be used in the compositions according to the invention, there may be cited stearoyl inulin such as those sold under the trade names Lifidrem INST by the Engelhard Company and Rheopearl INS by the Chiba Company; palmitoyl inulin; undecylenoyl inulin, such as those sold under the trade names Lifidrem INUK and Lifidrem INUM by the Engelhard Company; and inulin lauryl carbamate, such as that sold under the name INUTEC SP1 by the ORAFTI Company.

In particular, the hydrophobically modified polysaccharide is an inulin grafted with lauryl carbamate, especially resulting from the reaction of lauryl isocyanate with an inulin, in particular resulting from chicory. By way of examples of these compounds there may be cited in particular the product sold under the name INUTEC SP1 by the ORAFTI Company.

d) Copolymers of Crystalline Olefins:

The copolymer of crystalline olefins used in the compositions of the present application may be any olefin copolymer, or in other words a copolymer containing only olefinic moieties, having a controlled and moderate crystalline character, or in other words a degree of crystallinity at most equal to 50%, preferably between 5 and 40%, and better between 10 and 35%.

These copolymers are generally elastomers or plastomers and may be synthesized by any known method, in particular by radical reaction, by Ziegler-Natta catalysis or by metallocene catalysis, preferably by metallocene catalysis.

A first class of crystalline olefin copolymers that can be used in the compositions according to the invention are copolymers of α-olefin, in particular of C2-C16 and better C2-C12 α-olefin. Preferably, these copolymers are bipolymers or terpolymers and most particularly bipolymers.

Among the bipolymers recommended for the compositions of the invention there may be cited the bipolymers of ethylene and C4-C16, preferably C4-C12 α-olefin and the bipolymers of propylene and C4-C16, preferably C4-C12 α-olefin. Even more preferably, the α-olefin is chosen from among butene-1, pentene-1, hexene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1,3,5,5-trimethylhexene-1,3-methylpentene-1 and 4-methylpentene-1.

Among these monomers, butene-1 and octene-1 are particularly preferred.

The proportion of α-olefin in the bipolymer is generally between 2 and 40 mol %, preferably 3 to 30 mol %, and better 4 to 20 mol %.

The recommended ethylene-octene bipolymers are the plastomers having an octene content between 5.2 and 6.2 mol %, a degree of crystallinity between 28% and 38% and the elastomers having an octene content between 8 and 14 mol % and a degree of crystallinity between 10 and 28%.

These bipolymers are synthesized by metallocene catalysis.

Such bipolymers are sold by the DOW CHEMICAL Company under the trade names AFFINITY (plastomers) and ENGAGE (elastomers).

Ethylene-butene bipolymers are sold by the EXXON Company under the commercial name EXACT RESINS.

Among the terpolymers there may be cited the terpolymers of ethylene, propylene and C4-C16 preferably C4-C12-olefin.

In these terpolymers, the contents of C4-C16-olefin are as indicated in the foregoing, and the preferred α-olefins are butene, hexene and octene.

A second class of olefin copolymers suitable for the compositions according to the invention are copolymers of ethylene or propylene and a cycloolefin, in particular the bipolymers.

In general, the cycloolefin content of the copolymers is smaller than 20 mol %.

Among the usable cycloolefins, there may be cited cyclobutene, cyclohexene, cyclooctadiene, norbornene, dimethano-octahydronaphthalene (DMON), ethylidene norbornene, vinyl norbornene and 4-vinylcyclohexene.

The recommended copolymers of this class are the copolymers of ethylene and norbornene. The norbornene content of these copolymers is generally smaller than 18 mol % in order to exhibit the required crystalline character, and these copolymers are synthesized by metallocene catalysis.

Appropriate ethylene/norbornene copolymers are sold by the MITSUI PETROCHEMICAL or MITSUI-SEKKA Company under the trade name APEL and by the HOECHST-CELANESE Company under the trade name TOPAS.

Other recommended ethylene/cycloolefin copolymers are the ethylene/cyclobutene and ethylene/cyclohexene bipolymers with low cycloolefin content, generally lower than 20 mol %.

A third class of appropriate olefin copolymers is constituted by the olefin copolymers of controlled tacticity, or in other words copolymers containing moieties of different tacticity.

Among these copolymers of controlled tacticity there may be cited the isotactic propylene/atactic propylene and syndiotactic propylene/atactic propylene copolymers.

The isotactic or syndiotactic moieties or sequences confer the crystalline character on the copolymer, while the amorphous atactic moieties or sequences prevent excessive crystallinity of the copolymer and regulate the degree of crystallinity as well as the morphology and size of the crystallites.

The content of isotactic or syndiotactic moieties, the moieties conferring the crystalline character on the copolymer, is therefore determined so as to obtain the desired percentage crystallinity (≦50%) in the copolymer.

The content of tactic moieties is generally between 10 and 80 mol %. Nevertheless, the content of atactic moieties is preferably smaller than 30 mol %.

These copolymers are synthesized by metallocene catalysis.

A fourth class of olefin copolymers suitable for the present invention is constituted by the copolymers of monoolefin and diene, for example the ethylene/butadiene, propylene/butadiene, ethylene/isoprene and propylene/isoprene bipolymers and the ethylene/propylene/diene terpolymers, also obtained by metallocene synthesis.

The proportion of diene moieties in the controlled crystallization copolymer is generally between 3 and 20 mol %.

To improve the regulation of the crystallinity of the polymer, there may be added if necessary to the composition according to the invention additives that impair crystallization and favor formation of small crystals. These additives, although used in small proportion, constitute numerous and small nucleation “sites” distributed uniformly in the mass. These additives are typically crystals of an organic or mineral substance.

In the case of an organic additive that must crystallize, this must have a melting point higher than the melting zone of the copolymer and preferably must form small crystals.

At a temperature above its melting point, this substance is preferably soluble in the mixture of liquid fatty phase and molten polymer. Thus, during cooling, the initially dissolved additive recrystallizes in the form of numerous small crystals, thoroughly distributed in the mixture, then the polymer recrystallizes by forming small crystalline domains due to the presence of the additive crystals. This technique for recrystallization of polymers is traditional.

The degree of crystallization, the size and the morphology of the olefin copolymers according to the invention may also be adjusted by mixing a first olefin copolymer according to the invention with a second crystalline polymer or copolymer, partly compatible with the first olefin copolymer. The second polymer or copolymer may be an olefin copolymer according to the invention, but with a degree of crystallinity different from that of the first copolymer, including a higher degree of crystallinity than the degree of crystallinity of the olefin copolymers according to the invention.

The second crystallizable polymer may also be a polymer of different nature, for example a copolyethylene/vinyl acetate obtained by radical copolymerization or even a crystallizable polyethylene such as those commonly used in the cosmetic field.

For more details as to this method for adjusting the degree of crystallinity, reference is made to the articles entitled “Elastomeric blends of homogeneous ethylene-octene copolymers (Elastomeric mixtures of homogeneous ethylene-octene copolymers)” S. Bensason et al., Polymer, Volume 38, No. 15, 1997, pages 3913-19, and “Blends of homogeneous ethylene-octene copolymers (Mixtures of homogeneous ethylene-octene copolymers)” S. Bensason et al., Polymer, Volume 38, No. 14, 1997, pages 3513-20.

d) Crystalline Polycondensates:

The usable polycondensate may be capable of being obtained by reaction:

    • of 10 to 30% by weight, relative to the total weight of the polycondensate, of at least one polyol comprising 3 to 6 hydroxyl groups;
    • of 30 to 80% by weight, relative to the total weight of the polycondensate, of at least one linear, branched and/or cyclic, saturated or unsaturated non-aromatic monocarboxylic acid comprising 6 to 32 carbon atoms;
    • of 0.1 to 10% by weight, relative to the total weight of the polycondensate, of at least one aromatic monocarboxylic acid comprising 7 to 11 carbon atoms, possibly substituted in addition by 1 to 3 linear, branched and/or cyclic, saturated or unsaturated alkyl radicals comprising 1 to 32 carbon atoms;
    • of 5 to 40% by weight, relative to the total weight of the polycondensate, of at least one linear, branched and/or cyclic, saturated or unsaturated, even aromatic polycarboxylic acid comprising at least 2 carboxylic groups COOH, especially 2 to 4 COOH groups; and/or a cyclic anhydride of such a polycarboxylic acid.

Preferably, the polycondensate is capable of being obtained by reaction:

    • of 10% by weight of at least one aromatic monocarboxylic acid comprising 7 to 11 carbon atoms, possibly additionally substituted by 1 to 3 linear, branched and/or cyclic, saturated or unsaturated alkyl radicals comprising 1 to 32 carbon atoms; and
    • of 15 to 30% by weight, relative to the total weight of the polycondensate, of at least one polyol comprising 3 to 6 hydroxyl groups; and
    • of 30 to 40% by weight, relative to the total weight of the polycondensate, of at least one linear, branched and/or cyclic, saturated or unsaturated non-aromatic monocarboxylic acid comprising 6 to 32 carbon atoms;
    • of 10 to 25% by weight, relative to the total weight of the polycondensate, of at least one linear, branched and/or cyclic, saturated or unsaturated, even aromatic polycarboxylic acid comprising at least 2 carboxylic groups COOH, especially 2 to 4 COOH groups; and/or a cyclic anhydride of such a polycarboxylic acid;
      these conditions being cumulative,
      then the ratio between the number of moles of aromatic monocarboxylic acid and the number of moles of non-aromatic monocarboxylic acid is between 0.08 and 0.70.

The polycondensate may also be capable of being obtained by reaction:

    • of 10 to 30% by weight, relative to the total weight of the polycondensate, of at least one polyol comprising 3 to 6 hydroxyl groups;
    • of 45 to 80% by weight, relative to the total weight of the polycondensate, of at least one linear, branched and/or cyclic, saturated non-aromatic monocarboxylic acid comprising 6 to 32 carbon atoms;
    • of 0.1 to 10% by weight, relative to the total weight of the polycondensate, of at least one aromatic monocarboxylic acid comprising 7 to 11 carbon atoms, possibly substituted in addition by 1 to 3 linear, branched and/or cyclic, saturated or unsaturated alkyl radicals comprising 1 to 32 carbon atoms;
    • of 5 to 40% by weight, relative to the total weight of the polycondensate, of at least one linear, branched and/or cyclic, saturated or unsaturated, even aromatic polycarboxylic acid comprising at least 2 carboxylic groups COOH, especially 2 to 4 COOH groups; and/or a cyclic anhydride of such a polycarboxylic acid.

One of the constituents necessary for the preparation of polycondensates according to the invention is a compound comprising 3 to 6 hydroxyl groups (polyol), especially 3 to 4 hydroxyl groups. Quite obviously, a mixture of such polyols may be used. The said polyol may be in particular a carbon compound, especially a saturated or unsaturated, linear, branched and/or cyclic hydrocarbon compound comprising 3 to 18 carbon atoms, especially 3 to 12, even 4 to 10 carbon atoms, and 3 to 6 hydroxy (OH) groups, and being able to comprise additionally one or more oxygen atoms intercalated in the chain (ether function). The said polyol is preferably a linear or branched, saturated hydrocarbon compound comprising 3 to 18 carbon atoms, especially 3 to 12, even 4 to 10 carbon atoms, and 3 to 6 hydroxy (OH) groups. It may be chosen from among the following compounds, alone or in a mixture:

    • the triols, such as 1,2,4-butanetriol, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, glycerol;
    • the tetraols, such as pentaerythritol (tetramethylolmethane), erythritol, diglycerol or ditrimethylolpropane;
    • the pentols such as xylitol,
    • the hexyls such as sorbitol and mannitol; or else dipentaerythritol or triglycerol.

Preferably, the polyol is chosen from among glycerol, pentaerythritol, diglycerol, sorbitol and mixtures thereof; and pentaerythritol is even better. The polyol or the polyol mixture preferably represents 10 to 30% by weight, especially 12 to 25% by weight, and better 14 to 22% by weight of the total weight of the final polycondensate.

Another constituent necessary for the preparation of the polycondensates according to the invention is a linear, branched and/or cyclic, saturated or unsaturated non-aromatic monocarboxylic acid comprising 6 to 32 carbon atoms, especially 8 to 28 carbon atoms and still better 10 to 24, even 12 to 20 carbon atoms. Quite obviously a mixture of such non-aromatic monocarboxylic acids may be used. By non-aromatic monocarboxylic acid there is understood a compound of formula RCOOH, in which R is a linear, branched and/or cyclic, saturated or unsaturated hydrocarbon radical comprising 5 to 31 carbon atoms, especially 7 to 27 carbon atoms, and still better 9 to 23 carbon atoms, even 11 to 19 carbon atoms. Preferably, the R radical is saturated. Still better, the said R radical is linear or branched, and preferentially with C5-C31, even C11-C21.

In one particular embodiment of the invention, the non-aromatic monocarboxylic acid has a melting point higher than or equal to 25° C., especially higher than or equal to 28° C., even to 30° C.; in fact it has been observed that, when such an acid is employed, in particular in large quantity, it is possible on the one hand to obtain good gloss and staying power of the said gloss and, on the other hand, to reduce the quantity of waxes usually present in the envisioned composition.

Among the non-aromatic monocarboxylic acids capable of being employed there may be cited, alone or in mixtures:

    • the saturated monocarboxylic acids such as caproic acid, caprylic acid, isoheptanoic acid, 4-ethylpentanoic acid, ethyl-2-hexanoic acid, 4,5-dimethylhexanoic acid, 2-heptylheptanoic acid, 3,5,5-trimethylhexanoic acid, octanoic acid, isooctanoic acid, nonanoic acid, decanoic acid, isononanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, cerotic acid (hexacosanoic acid); cyclopentanecarboxylic acid, cyclopentaneacetic acid, 3-cyclopentylpropionic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, 4-cyclohexylbutyric acid;
    • the unsaturated but non-aromatic monocarboxylic acids, such as caproleic acid, obtusilic acid, undecylenic acid, dodecylenic acid, linderic acid, myristoleic acid, physeteric acid, tsuzuic acid, palmitoleic acid, oleic acid, petroselinic acid, vaccenic acid, elaidic acid, gondoic acid, gadoleic acid, erucic acid, cetoleic acid, nervonic acid, linoleic acid, linolenic acid, arachidonic acid.

Among the non-aromatic monocarboxylic acids having a melting temperature higher than or equal to 25° C. there may be cited, alone or in mixtures:

    • among the saturated monocarboxylic acids: decanoic (capric) acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, cerotic (hexacosanoic) acid;
    • among the unsaturated but non-aromatic monocarboxylic acids: petroselinic acid, vaccenic acid, elaidic acid, gondoic acid, gadoleic acid, erucic acid, nervonic acid.

Preferably there may be used 2-ethylhexanoic acid, isooctanoic acid, lauric acid, myristic acid, isoheptanoic acid, isononanoic acid, nonanoic acid, palmitic acid, isostearic acid, stearic acid, behenic acid and mixtures thereof, and even better isostearic acid alone or stearic acid alone.

The said non-aromatic monocarboxylic acid or the mixture of the said acids preferably represents 30 to 80% by weight, especially 40 to 75% by weight, even 45 to 70% by weight, and better 50 to 65% by weight of the total weight of the final polycondensate.

Another constituent necessary for the preparation of the polycondensates according to the invention is an aromatic monocarboxylic acid comprising 7 to 11 carbon atoms, possibly substituted in addition by 1 to 3 linear, branched and/or cyclic, saturated or unsaturated alkyl radicals comprising 1 to 32 carbon atoms, especially 2 to 12, even 3 to 8 carbon atoms. Quite obviously a mixture of such aromatic monocarboxylic acids may be used.

By aromatic monocarboxylic acid there is understood a compound of formula R′COOH, in which R′ is an aromatic hydrocarbon radical comprising 6 to 10 carbon atoms, and in particular the benzoic and naphthoic radicals. The said R′ radical may be substituted additionally by 1 to 3 linear, branched and/or cyclic, saturated or unsaturated alkyl radicals comprising 1 to 32 carbon atoms, especially 2 to 12, even 3 to 8 carbon atoms; and especially chosen from among methyl, ethyl, propyl, isopropyl, butyl, isobutyl, terbutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, isoheptyl, octyl or isooctyl. Among the aromatic monocarboxylic acids capable of being employed there may be cited, alone or in mixtures, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, 1-naphthoic acid, 2-naphthoic acid, 4-tert-butylbenzoic acid, 1-methyl-2-naphthoic acid, 2-isopropyl-1-napthoic acid. Preferably there may be used benzoic acid, 4-tert-butylbenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, 1-naphthoic acid, alone or in mixtures; and even better benzoic acid alone. The said aromatic monocarboxylic acid or the mixture of the said acids preferably represents 0.1 to 10% by weight, especially 0.5 to 9.95% by weight, still better 1 to 9.5% by weight, even 1.5 to 8% by weight of the total weight of the final polycondensate.

Another constituent necessary for the preparation of the polycondensates according to the invention is a linear, branched and/or cyclic, saturated or unsaturated, even aromatic polycarboxylic acid comprising at least 2 carboxylic groups COOH, especially 2 to 4 COOH groups; and/or a cyclic anhydride of such a polycarboxylic acid. Quite obviously a mixture of such polycarboxylic acids and/or anhydrides may be used. The said polycarboxylic acid may be especially chosen from among the linear, branched and/or cyclic, saturated or unsaturated, even aromatic polycarboxylic acids comprising 2 to 50, especially 2 to 40 carbon atoms, in particular 3 to 36, even 3 to 18, and still better 4 to 12 carbon atoms, even 4 to 10 carbon atoms; the said acid comprises at least two carboxylic groups COOH, preferably 2 to 4 COOH groups.

Preferably, the said polycarboxylic acid is linear, saturated, aliphatic and comprises 2 to 36 carbon atoms, especially 3 to 18 carbon atoms, even 4 to 12 carbon atoms; or else it is aromatic and comprises 8 to 12 carbon atoms. Preferably it comprises 2 to 4 COOH groups. The said cyclic anhydride of such a polycarboxylic acid may be represented in particular by one of the following formulas:

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in which the groups A and B are, independently of one another:

    • a hydrogen atom,
    • a linear, branched and/or cyclic, saturated or unsaturated, aliphatic or else aromatic carbon radical; comprising 1 to 16 carbon atoms, especially 2 to 10 carbon atoms, even 4 to 8 carbon atoms, especially methyl or ethyl;
    • or else A and B taken together form a saturated or unsaturated, even aromatic ring comprising in total 5 to 7, especially 6 carbon atoms.

Preferably, A and B represent a hydrogen atom or together form an aromatic ring comprising in total 6 carbon atoms.

Among the polycarboxylic acids or their anhydrides capable of being employed there may be cited, alone or in mixtures.

    • the dicarboxylic acids, such as decanedioic acid, dodecanedioic acid, cyclopropanedicarboxylic acid, cyclohexanedicarboxylic acid, cyclobutanedicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, suberic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pimelic acid, sebacic acid, azelaic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, itaconic acid, the dimers of fatty acids (especially with C36), such as the products sold under the trade names Pripol 1006, 1009, 1013 and 1017 by Uniqema;
    • the tricarboxylic acids such as cyclohexanetricarboxylic acid, trimellitic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid;
    • the tetracarboxylic acids, such as butanetetracarboxylic acid and pyromellitic acid,
    • the cyclic anhydrides of these acids and especially phthalic anhydride, trimellitic anhydride, maleic anhydride and succinic anhydride.

Preferably there may be used adipic acid, phthalic anhydride and/or isophthalic acid, and even better isophthalic acid alone.

The said polycarboxylic acid and/or its cyclic anhydride preferably represents 5 to 40% by weight, especially 10 to 30% by weight, and better 14 to 25% by weight of the total weight of the final polycondensate.

The polycondensate according to the invention may additionally comprise a silicone with hydroxyl (OH) and/or carboxylic (COOH) function.

It may comprise 1 to 3 hydroxyl and/or carboxylic functions and it preferably comprises two hydroxyl functions or else two carboxylic functions.

These functions may be situated at the end of the chain or in the chain, but advantageously at the end of the chain.

Preferably there are employed silicones having a weight-average molecular weight (Mw) between 300 and 20,000, especially 400 and 10,000, even 800 and 4,000.

This silicone may have the formula:

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in which:

    • W and W′ are, independently of one another, OH or COOH; preferably W═W′;
    • p and q are, independently of one another, equal to 0 or 1,
    • R and R′ are, independently of one another, a divalent linear, branched and/or cyclic, saturated or unsaturated, even aromatic carbon, especially hydrocarbon radical; comprising 1 to 12 carbon atoms, especially 2 to 8 carbon atoms, and possibly additionally comprising 1 or more heteroatoms chosen from among O, S and N, especially 0 (ether);
      in particular, R and/or R′ may have the formula —(CH2)a— with a=1-12, and especially methylene, ethylene, propylene, phenylene;
      or else the formula —[(CH2)XO]z— with x=1, 2 or 3 and z=1-10; in particular, x=2 or 3 and z=1-4; and better x=3 and z=1.
    • R1 to R6 are, independently of one another, a linear, branched and/or cyclic, saturated or unsaturated, even aromatic carbon radical comprising 1 to 20 carbon atoms, especially 2 to 12 carbon atoms; preferably R1 to R6 are saturated or else aromatic, and they may be chosen in particular from among the alkyl radicals, in particular the methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl and octadecyl radicals, the cycloalkyl radicals, in particular the cyclohexyl radical, the aryl radicals, especially phenyl and naphthyl, the arylalkyl radicals, especially benzyl and phenylethyl, as well as the tolyl and xylyl radicals.
    • m and n are, independently of one another, integers between 1 and 140 and are such that the weight-average molecular weight (Mw) of the silicone is between 300 and 20,000, especially between 400 and 10,000, even between 800 and 4,000.

There may be cited in particular the α,ω-diol or α,ω-dicarboxylic polyalkylsiloxanes, and especially the α,ω-diol polydimethylsiloxanes and the α,ω-dicarboxylic polydimethylsiloxanes; the α,ω-diol or am-dicarboxylic polyarylsiloxanes, and especially the α,ω-diol or α,ω-dicarboxylic polyphenylsiloxanes; the polyarylsiloxanes with silanol functions, such as polyphenylsiloxane; the polyalkylsiloxanes with silanol functions such as polydimethylsiloxane; the polyaryl/alkylsiloxanes with silanol functions such as polyphenyl/methylsiloxane or else polyphenyl/propylsiloxane.

More particularly, there will be used the α,ω-diol polydimethylsiloxanes of weight-average molecular weight (Mw) between 400 and 10,000, even between 500 and 5,000, and especially between 800 and 4,000.

When it is present, the said silicone may preferably represent 0.1 to 15% by weight, especially 1 to 10% by weight, even 2 to 8% by weight of the weight of the polycondensate.

In a preferred embodiment of the invention, the aromatic monocarboxylic acid is present in molar quantity smaller than or equal to that of the non-aromatic monocarboxylic acid; in particular the ratio between the number of moles of aromatic monocarboxylic acid and the number of moles of non-aromatic monocarboxylic acid is preferably between 0.08 and 0.70, especially between 0.10 and 0.60, in particular between 0.12 and 0.40.

Preferentially, the polycondensate according to the invention is capable of being obtained by reaction:

    • of at least one polyol chosen from among, alone or in mixtures, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, glycerol; pentaerythritol, erythritol, diglycerol, dimethylolpropane; xylitol, sorbitol, mannitol, dipentaerythritol and/or triglycerol;
      present preferably in a proportion of 10 to 30% by weight, especially 12 to 25% by weight, and better 14 to 22% by weight, relative to the total weight of the final polycondensate;
    • of at least one non-aromatic monocarboxylic acid chosen from among, alone or in mixtures, caproic acid, caprylic acid, isoheptanoic acid, 4-ethylpentanoic acid, 2-ethylhexanoic acid, 4,5-dimethylhexanoic acid, 2-heptylheptanoic acid, 3,5,5-trimethylhexanoic acid, octanoic acid, isooctanoic acid, nonanoic acid, decanoic acid, isononanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, cerotic (hexacosanoic) acid; cyclopentanecarboxylic acid, cyclopentaneacetic acid, 3-cyclopentylpropionic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, 4-cyclohexylbutyric acid;
      present preferably in a proportion of 30 to 80% by weight, especially 40 to 75% by weight, and better 45 to 70% by weight, relative to the total weight of the final polycondensate;
    • of at least one aromatic monocarboxylic acid chosen from among, alone or in mixtures, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, 1-naphthoic acid, 2-naphthoic acid, 4-tert-butylbenzoic acid, 1-methyl-2-naphthoic acid, 2-isopropyl-1-napthoic acid;
      present preferably in a proportion of 0.1 to 10% by weight, especially 1 to 9.5% by weight, even 1.5 to 8% by weight, relative to the total weight of the final polycondensate; and
    • of at least one polycarboxylic acid or one of its anhydrides chosen from among, alone or in mixtures, decanedioic acid, dodecanedioic acid, cyclopropanedicarboxylic acid, cyclohexanedicarboxylic acid, cyclobutanedicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, suberic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, terephthalic acid, isophthalic acid, pimelic acid, sebacic acid, azelaic acid, glutaric acid, adipic acid, fumaric acid, maleic acid;
      cyclohexanetricarboxylic acid, trimellitic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid; butanetetracarboxylic acid, pyromellitic acid, phthalic anhydride, trimellitic anhydride, maleic anhydride and succinic anhydride;
      present preferably in a proportion of 5 to 40% by weight, especially 10 to 30% by weight, and better 14 to 25% by weight, relative to the total weight of the final polycondensate.

Preferably, the polycondensate according to the invention is capable of being obtained by reaction:

    • of at least one polyol chosen from among, alone or in mixtures, glycerol; pentaerythritol, sorbitol and mixtures thereof, and still better pentaerythritol alone; present in a proportion of 10 to 30% by weight, especially 12 to 25% by weight, and better 14 to 22% by weight, relative to the total weight of the final polycondensate;
    • of at least one non-aromatic monocarboxylic acid chosen from among, alone or in mixtures, 2-ethylhexanoic acid, isooctanoic acid, lauric acid, myristic acid, palmitic acid, isostearic acid, isononanoic acid, stearic acid, behenic acid and mixtures thereof, and even better isostearic acid alone or stearic acid alone;
      present in a proportion of 30 to 80% by weight, especially 40 to 75% by weight, and better 45 to 70% by weight, relative to the total weight of the final polycondensate;
    • of at least one aromatic monocarboxylic acid chosen from among, alone or in mixtures, benzoic acid, o-toluic acid, m-toluic acid, 1-naphthoic acid, and even better benzoic acid alone;
      present in a proportion of 0.1 to 10% by weight, especially 1 to 9.5% by weight, even 1.5 to 8% by weight relative to the total weight of the final polycondensate; and
    • of at least one polycarboxylic acid or one of its anhydrides chosen from among, alone or in mixtures, phthalic anhydride and isophthalic acid, and even better isophthalic acid alone;
      present in a proportion of 5 to 40% by weight, especially 10 to 30% by weight, and better 14 to 25% by weight, relative to the total weight of the final polycondensate.

The polycondensate according to the invention may be prepared by esterification/polycondensation methods usually employed by those skilled in the art. By way of illustration, a general preparation method consists in:

    • mixing the polyol and the aromatic and non-aromatic monocarboxylic acids,
    • heating the mixture under an inert atmosphere, at first up to the melting point (generally 100-130° C.) and then to a temperature between 150 and 220° C. until complete consumption of the monocarboxylic acids (attained when the acid index is smaller than or equal to 1), preferably by distilling off water at the same rate as it is formed, then
    • if necessary cooling the mixture to a temperature between 90 and 150° C.,
    • adding polycarboxylic acid and/or cyclic anhydride, and optionally the silicone with hydroxyl or carboxylic functions, all at once or in sequenced manner, then
    • once again heating to a temperature lower than or equal to 220° C., especially between 170 and 220° C., preferably continuing to eliminate the water formed, until there are obtained the required characteristics in terms of acid index, viscosity, hydroxyl index and solubility.

It is possible to add conventional esterification catalysts, for example of sulfonic acid type (especially in a concentration between 1 and 10% by weight) or of titanate type (especially in a concentration between 5 and 100 ppm by weight).

It is also possible to carry out the reaction in its entirety or in part in an inert solvent such as xylene and/or under reduced pressure, to facilitate the elimination of water.

Advantageously neither catalyst nor solvent is used.

The said preparation method may also comprise a step of addition of at least one antioxidant agent into the reaction mixture, especially in a concentration between 0.01 and 1% by weight relative to the total weight of monomers, so as to limit possible degradation associated with prolonged heating.

The antioxidant agent may be of primary type or of secondary type, and may be chosen from among the hindered phenols, the secondary aromatic amines, the organophosphorus compounds, the sulfur compounds, the lactones, the acryl bisphenols; and mixtures thereof.

Mineral Lipophilic Structuring Agents

The fatty-phase thickening or gelling rheological agent may be a mineral structuring lipophilic agent.

There may be cited especially the lipophilic clays, such as the clays that have been modified if necessary, such as the hectorites modified by a C10 to C22 fatty acid ammonium chloride, such as hectorite modified by distearyldimethylammonium chloride.

There may also be cited the hydrophobic silicas, such as pyrogenic silica, which has been hydrophobically surface-treated if necessary, whose particle size is smaller than 1 μM. It is in fact possible to modify the surface of the silica chemically, by chemical reaction causing a decrease in the number of silanol groups present at the surface of the silica. In particular, silanol groups may be substituted by hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups may be:

    • trimethylsiloxyl groups, which are obtained in particular by treatment of pyrogenic silica in the presence of hexamethyldisilazane. Silicas treated in this way are known as “silica silylate” according to the CTFA (6th Edition, 1995). For example, they are sold under the references “AEROSIL R812®” by the Degussa Company, “CAB-O-SIL TS-530®” by the Cabot Company.
    • dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained in particular by treatment of pyrogenic silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas treated in this way are known as “silica dimethyl silylate” according to the CTFA (6th Edition, 1995). For example, they are sold under the references “AEROSIL R972®”, “AEROSIL R974®” by the Degussa Company, “CAB-O-SIL TS-6100”, “CAB-O-SIL TS 720®” by the Cabot Company.

The hydrophobic pyrogenic silica preferably has a particle size that may be nanometric to micrometric, for example ranging approximately from 5 to 200 nm.

Lipophilic Polyamide Polymers

By polymer within the meaning of the invention there is understood a compound having at least 2 repeating moieties, preferably at least 3 repeating moieties and still better 10 repeating moieties.

As preferred lipophilic structuring polyamides that can be used in the invention, there may be cited the polyamides branched by pendant fatty chains and/or terminal fatty chains having 12 to 120 carbon atoms and especially 12 to 68 carbon atoms, the terminal fatty chains being bonded to the polyamide skeleton by ester groups. These polymers are more specially those described in the document U.S. Pat. No. 5,783,657 of the Union Camp Company. Each of these polymers satisfies especially the following formula (I):

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in which n denotes an integral number of amide moieties such that the number of ester groups represents 10% to 50% of the total number of ester and amide groups; R1, independently in each occurrence, is an alkyl or alkenyl group having at least 4 carbon atoms; R2, independently in each occurrence, represents a C4 to C42 group, with the proviso that 50% of the R2 groups represent a C30 to C42 hydrocarbon group; R3, independently in each occurrence, represents an organic group provided with at least 2 carbon atoms, hydrogen atoms and optionally one or more oxygen or nitrogen atoms; and R4, independently in each occurrence, represents a hydrogen atom, a C1 to C10 alkyl group or a direct bond to R3 or to another R4, so that the nitrogen atom to which both R3 and R4 are bonded is part of a heterocyclic structure defined by R4—N—R3, with at least 50% of the R4 groups representing a hydrogen atom.

In particular, the ester groups of formula (I), which make up part of the terminal and/or pendant fatty chains within the meaning of the invention, represent 15 to 40% of the total number of ester and amide groups and better 20 to 35%. In addition, n advantageously represents an integral number ranging from 1 to 5. Preferably, R1 is a C12 to C22 alkyl group, and preferably C16 to C22. Advantageously, R2 may be a C10 to C42 hydrocarbon group (especially alkyl or alkenyl) having a polymerized fatty acid structure or a dimer structure whose carboxylic acid groups have been removed (these groups being used to form the amide). Preferably, at least 50% and better 75% of the R groups are groups having 30 to 42 carbon atoms. The other R2 groups are C4 to C19 and even C4 to C12 hydrogenated groups. Preferably, R3 represents a C2 to C36 hydrocarbon group or a polyoxyalkylene group and R4 represents a hydrogen atom. Preferably, R3 represents a C2 to C12 hydrocarbon group. The hydrocarbon groups may be saturated or unsaturated, linear, cyclic or branched groups. Furthermore, the alkyl and alkenyl groups may be linear or branched groups.

Advantageously, the polymer of the composition of the invention comprises a weight-average molecular weight ranging from 2,000 to 20,000 and better from 2,000 to 10,000.

According to the invention, structuring of the oil is achieved by means of one or more polymers of formula (I). In general, the polymers of formula (I) have the form of mixtures of polymers, these mixtures additionally being able to contain a synthetic product such that n is equal to 0, or in other words a diester.

By way of example of structuring polymers that can be used in the composition according to the invention there may be cited the commercial products sold by the Bush Boake Allen Company under the names Uniclear 80, Uniclear 100, Uniclear 80 V, Uniclear 100 V and Uniclear 100 VG. They are sold respectively in the form of an 80% gel (in terms of active material) in a mineral oil and a 100% gel (in terms of active material). They have a softening point of 88 to 94° C. These commercial products are a mixture of copolymer of a C36 diacid condensed on ethylenediamine, with an average molecular weight of approximately 6,000. In addition, the remaining terminal acid groups are esterified by cetylstearyl alcohol.

As structuring polymer that can be used in the invention there may also be cited the polyamide resins resulting from the condensation of an aliphatic dicarboxylic acid and a diamine (including compounds having more than 2 carbonyl groups and more than 2 amine groups), the carbonyl and amine groups of adjacent unitary moieties being condensed via an amide bond. These polyamide resins are especially those sold under the brand Versamid® by General Mills, Inc. and the Henkel Corp. (Versamid 930, 744 or 1655) or by Olin Mathieson Chemical Corp. under the brand Onamid®, especially Onamid S or C. These resins have a weight-average molecular weight ranging from 6,000 to 9,000. For more information about these polyamides, reference may be made to the documents U.S. Pat. No. 3,645,705 and U.S. Pat. No. 3,148,125. More especially, Versamid® 930 or 744 is used.

There may also be used the polyamides sold by Union Camp Corp. under the references Uni-Rez (2658, 2931, 2970, 2621, 2613, 2624, 2665, 1554, 2623, 2662) and the product sold under the reference Macromelt 6212 by the Henkel Company. For more information about these polyamides, reference may be made to the document U.S. Pat. No. 5,500,209.

The structuring polymers in the composition of the invention advantageously have a softening temperature higher than 70° C. and possibly ranging up to 190° C. Preferably, it has a softening temperature ranging from 80 to 130°. These polymers are in particular non-waxy polymers.

Lipophilic Polyurea or Polyurethane Polymers

As fatty-phase rheological agent there may also be cited the polyurethanes and the polyureas soluble or dispersible in the hydrocarbon oil or oils, and containing:

    • at least two urethane groups or at least two urea groups or at least one urethane group and one urea group in the chain,
    • at least one hydrocarbon sequence or graft or aliphatic polyester with a long hydrocarbon chain, preferably branched.

By long hydrocarbon chain there is understood a linear or branched hydrocarbon chain containing at least 8 carbon atoms and preferably 10 to 500 carbon atoms.

The polymers preferred according to the invention are defined by one of the following three formulas:

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in which
n denotes an integral number from 1 to 10,000, and preferably from 1 to 1,000,
x represents, separately or together, —O— or —NH—,
R is a divalent radical chosen from among the alkylene, cycloalkylene, aromatic radicals and mixtures thereof, if necessary functionalized,
A1 and A2, be identical or different, denote monovalent linear, branched or cyclic hydrocarbon radicals, which may be saturated or contain unsaturations, containing 1 to 80 carbon atoms,

D is

1) a divalent saturated or unsaturated aliphatic and/or cycloaliphatic hydrocarbon sequence, and/or aliphatic polyester with long hydrocarbon chain, or
2) a graft

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in which Z is a trivalent hydrocarbon radical that may contain one or more hetero atoms, and φ is a linear, branched or cyclic aliphatic chain,

3) mixtures of sequences 1) and grafts 2).

Monovalent hydrocarbon radicals A1 and A2 are preferably chosen from among the saturated or unsaturated aliphatic, cycloaliphatic and aromatic radicals. Radicals A1 and A2 are derived from monoalcohols and/or monoamines, used if necessary to consume the residual isocyanate groups at the end of polymerization.

In the case that D is a saturated or unsaturated aliphatic and/or cycloaliphatic hydrocarbon sequence, it is derived:

    • from a natural or synthetic oil, or
    • from the addition product (dimer, trimer or polymer) of at least two unsaturated aliphatic chains, such as the aliphatic radicals derived from “dimeric” fatty acids, such as, for example, the addition products between oleic chains, or
    • from polyenes, preferably hydrogenated, such as polybutadiene, hydrogenated polyisoprene, or the polyolefins or copolyolefins.

In the case that D is an aliphatic polyester sequence with a long hydrocarbon chain, it is preferably derived from branched polyesters with long hydrocarbon chains, such as, for example, poly(12-hydroxystearate).

In the case that D is a graft, φ is a saturated or unsaturated, linear, branched or cyclic aliphatic chain containing 8 to 40 carbon atoms. The possible hetero atoms of trivalent radical Z are preferably —O—, —N—, and —S—.

The structuring polyurethanes and/or polyureas according to the invention result from the polymerization reaction between:

1) at least one aliphatic, cycloaliphatic and/or aromatic diisocyanate of the general formula O═C═N—R—N═C═O, where R is such as defined in the foregoing,
2) at least one difunctional derivative HX-D-XH having two active hydrogens, each of which is capable of reacting with an isocyanate group, where

    • X denotes —O— or —NH—, and
    • D is such as defined in the foregoing, and
      3) possibly a monofunctional derivative A1-XH, or two monofunctional derivatives A1-XH and A2-XH having a single active hydrogen that is capable of reacting with an isocyanate group, to consume the residual isocyanate groups that may not have reacted entirely with the difunctional reagents H—X-D-X—H, which monofunctional derivatives A1-XH and A2-XH may be identical or different, and A1 and A2 being such as defined in the foregoing.

The isocyanates used in the polymerization reaction may be aliphatic, cycloaliphatic or aromatic. Advantageously there will be used hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate.

The difunctional derivatives H—X-D-X—H may be chosen from among the dimer diols and their derivatives, the alkane diols, the polydienes with hydroxyl ends, preferably hydrogenated, the polyolefins with hydroxyl ends, the branched polyesters with long alkyl chain carrying at least two reactive groups, the natural or synthetic oils carrying two to three hydroxyl groups, and finally the dimer diamines and the diamines with long aliphatic chain.

The dimer diols are C36 branched aliphatic and/or alicyclic diols and/or a mixture of the said dimers. These diols are prepared from “corresponding dimeric fatty acids”.

By “corresponding dimeric fatty acids” there is understood the dimeric fatty acids that have the same structure as these diols but which possess two carboxylic acid ends instead of the diol ends. The transformation of dimeric fatty acids into dimer diols may be achieved either by hydrogenation of methyl esters of the dimeric fatty acids or by direct dimerization of oleic alcohol. In particular, there will be cited the dimer diols sold by the COGNIS Company under the commercial names of SOVERMOL 908 (97% purity) and SOVERMOL 650 NS (68% purity).

There may also be used the polyether-diol and the polycarbonate-diol oligomers prepared by subsequent etherification or esterification of these same C36 branched dimer diols. These oligomers generally have a number-average molecular weight on the order of 500 to 2,000 and possess two hydroxyl functions.

The polydienes with hydroxyl ends are, for example, those defined in French Patent FR 2782723. They are chosen in the group comprising the homopolymers and copolymers of polybutadiene, polyisoprene and poly(1,3-pentadiene). These oligomers have a number-average molecular weight smaller than 7,000, and preferably 1,000 to 5,000. They have a functionality of 1.8 to 3 and preferably close to 2 at the end of the chain.

These polydienes with hydroxyl ends are, for example, the hydroxylated polybutadienes sold by the ELF ATOCHEM Company under the brands POLY BD-45H® and POLY BD R-20 LM®. These products are preferably used in hydrogenated form.

There may also be used homopolymeric or copolymeric polyolefins with α,ω hydroxyl ends, such as, for example:

    • the oligomers of polyisobutylene with α,ω hydroxyl ends, or
    • the copolymers sold by the MITSUBISHI Company under the brand POLYTAIL®, especially those of the following structure:

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having a melting point of 60 to 70° C.

As difunctional derivative H—X-D-X—H it is possible to use a branched polyester having a long alkyl chain and containing at least two reactive groups, such as, for example, poly(12-hydroxystearate) with hydroxyl ends. This polyester is obtained by auto-condensation of 1,2-hydroxystearic acid on itself, then reaction with a polyol to consume the residual acid groups. This oligomer has the structure

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where the sum m+n is such that the oligomer has a number-average molecular weight on the order of 2,000 and a hydroxyl functionality on the order of 1.8.

There may also be used as difunctional derivative H—X-D-X—H natural or synthetic oils carrying two to three hydroxyl groups.

In a particular embodiment of the invention, there will be used the oils carrying two hydroxyl groups per chain, and preferably the monoglycerides of the structure:

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R1 being a C8 to C30 linear or branched alkyl chain, such as, for example, glycerol monostearate.

Such glycerol monoesters correspond, for example, to the difunctional derivatives H—X-D-X—H, where:

    • D represents

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    • X represents —O—, and

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represents

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where R1 is defined as in the foregoing.

When these glycerol monoesters are reacted with a diisocyanate, a solubilizing graft and not a sequence is introduced into the polymer chain, as was the case with the difunctional derivatives cited in the foregoing.

In a variant, there will be used a difunctional derivative H—X-D-X—H chosen from among the oils carrying three hydroxyl groups per chain, such as, for example, hydrogenated or non-hydrogenated castor oil.

In this case, the polymerization reaction is carried out with a deficit of diisocyanate compared with the stoichiometry of the reaction, to avoid cross-linking of the polymer and to preserve good solubility thereof.

There may also be used diols with long aliphatic chains. Advantageously, there will be used the diols of structure HO-D-OH, where D is a linear or branched alkyl chain containing 8 to 40 carbon atoms. These diols are sold by the ATOCHEM Company under the trade name VIKINOL®. There will also be cited 1,12-dodecanediol and 1,10-decanediol, the latter being sold by the COGNIS Company under the commercial name of SOVERMOL 110®.

There may also be used the diols of the structure

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where R2 is an alkyl chain containing 8 to 40 carbon atoms.

These diols with long aliphatic chains are preferably used with one or the other of the H—X-D-X—H derivatives cited in the foregoing, to be used as chain couplers during synthesis of polyurethanes and/or polyureas.

Finally, there may be used as difunctional H—X-D-X—H derivative the dimer diamines or the diamines with long aliphatic chain.

The use of such reagents in the polymerization reaction makes it possible to introduce urea groups instead of urethane groups into the polymer.

According to a particular embodiment of the invention, there will be used dimer diamines having the same structure as the dimer diols described in the foregoing, or in other words dimer diamines containing two primary amine functions instead of hydroxyl groups.

These dimer diamines may be obtained from the transformation of dimeric fatty acids, such as the dimer diols.

In a variant, there may be used diamines of structure H2N-D-NH2, where D is a linear or branched alkyl chain containing 8 to 40 carbon atoms. These diamines are preferably used in mixtures with a difunctional derivative H—X-D-X—H chosen from among the dimer diols and their derivatives, the polydienes and polyolefins with hydroxyl ends, the branched polyesters with long alkyl chains, and the oils carrying 2 to 3 hydroxyl groups, cited in the foregoing.

Among these diamines there may be cited:

    • 1,10-diaminodecane and 1,12-diaminododecane, and
    • the following diamino oils sold by the AKZO NOBEL Company: cocopropylene diamine (distilled or non-distilled) DUOMEEN® C or CD, hydrogenated Tallowpropylene diamine DUOMEEN® HT, C16-22 alkylpropylene diamine DUOMEEN® M, oleylpropylene diamine DUOMEEN® O, Tallowpropylene diamine DUOMEEN® T.

As regards the monofunctional derivatives A1-XH and A2-XH, they are advantageously chosen from among the monoalcohols or monoamines having linear or branched alkyl chains containing 1 to 80 carbon atoms, the natural or synthetic oils carrying a single hydroxyl group per chain, such as, for example, the diesters of glycerols or the triesters of citric acid and fatty alcohol.

The envisioned polycondensation reactions are traditionally carried out in an organic solvent capable of dissolving the reagents and the formed polymer. This solvent is preferably easy to eliminate at the end of the reaction, especially by distillation, and it does not react with the isocyanate groups.

In general, each of the reagents is dissolved in a portion of the organic solvent prior to the polymerization reaction.

It is often desired to use a catalyst to activate the polymerization. This will generally be chosen from among the catalysts commonly used in the chemistry of polyurethanes and polyureas, such as, for example, tin 2-ethyl hexanoate.

The molar proportion between the main reagents of the polymerization reaction depends on the chemical structure and molecular weight of the polymers (polyurethanes and/or polyureas) that are desired to be obtained, as is traditionally the case in the chemistry of polyurethanes and polyureas. Similarly, the order of introduction of the reagents will be adapted to this chemistry.

Thus the reaction of two moles of functional derivative H—X-D-X—H with one mole of isocyanate yields, after complete consumption of the reagents, a polymer defined by formula I:

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This reaction will be advantageously carried out in the following manner:

    • the initial medium is a solution comprising two moles of derivative H—X-D-X—H, for example two moles of dimer diol, in a solvent, for example tetrahydrofuran,
    • to this initial solution there is added dropwise a solution comprising one mole of diisocyanate dissolved in the same solvent, such as, for example, toluene diisocyanate dissolved in tetrahydrofuran.

Furthermore, the equimolar reaction of a difunctional derivative H—X-D-X—H with a diisocyanate, with consumption of the residual isocyanates by a monofunctional compound A1-XH, yields a polymer defined by formula III:

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Preferably, this reaction will then be carried out by simultaneous addition, into a reactor, of an organic solution of one mole of H—X-D-X—H, such as, for example, a POLYTAIL® described in the foregoing, and an organic solution of one mole of diisocyanate, such as, for example, 4,4′-dicyclohexylmethane diisocyanate. The simultaneous addition of these two organic solutions is also known as “double decantation”. At the end of double decantation, the reaction mixture is heated to 60° C. for 5 hours. Then a sample of the reaction medium is withdrawn to determine the residual isocyanates by using a method known to those skilled in the art. Finally there is added to the reaction medium a solution of a chosen monofunctional compound A1-X—H, in quantity sufficient to consume the residual isocyanates, this quantity having been estimated on the basis of the determination of the residual isocyanates. Advantageously, 1-decanol will be used as monofunctional derivative A1-X—H.

Finally, the reaction between

    • one mole of compound H—X-D-X—H, such as, for example, a dimer diol,
    • there moles of diisocyanate, such as, for example, 4,4′-dicyclohexyl methane diisocyanate, and
    • two moles of structure coupler

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where φ is a linear, branched or cyclic aliphatic chain containing 8 to 20 carbon atoms, leads to the formation of a polymer, both sequenced and grafted, of the structure:

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Any residual isocyanates being able to be consumed by addition of an appropriate quantity of monofunctional reagent A1-X—H.

Such a polymer is obtained in the following manner:

    • the initial reaction medium is composed of a solution comprising one mole of a difunctional derivative H—X-D-X—H,
    • a solution of three moles of diisocyanate is added dropwise to this medium,
    • it is then allowed to react for 3 hours at 60° C.;
    • then there is decanted into this medium an organic solution comprising two moles of a coupler defined by the formula

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any residual isocyanates will be able to be consumed by addition of an appropriate quantity of monofunctional reagent A1-XH.

Lipophilic Silicone Polymers:

The lipophilic silicone polymer structuring agents are, for example, polymers of the polyorganosiloxane type, such as those described in the documents U.S. Pat. No. 5,874,069, U.S. Pat. No. 5,919,441, U.S. Pat. No. 6,051,216 and U.S. Pat. No. 5,981,680. According to the invention, the polymers used as structuring agent may belong to the following two families:

    • 1) polyorganosiloxanes containing at least two groups capable of establishing hydrogen interactions, these two groups being situated in the polymer chain, and/or
    • 2) polyorganosiloxanes containing at least two groups capable of establishing hydrogen interactions, these two groups being situated on grafts or branches.

The groups capable of establishing hydrogen interactions may be chosen from among the ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino, biguanidino groups and combinations thereof.

According to a first variant, the silicone polymers are polyorganosiloxanes such as defined above and whose moieties capable of hydrogen interactions are disposed in the polymer chain.

The silicone polymers may be more particularly polymers comprising at least one moiety according to the general formula I:

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in which

1) R4, R5, R6 and R7, identical or different, represent a group chosen from among:

    • the saturated or unsaturated, linear, branched or cyclic C1 to Co hydrocarbon groups, which may contain one or more oxygen, sulfur and/or nitrogen atoms in their chain and which may be substituted partly or completely by fluorine atoms,
    • the C6 to C10 aryl groups, possibly substituted by one or more C1 to C4 alkyl groups,
    • the polyorganosiloxane chains, which may or may not contain one or more oxygen, sulfur and/or nitrogen atoms,

2) the groups X, identical or different, represent a linear or branched C1 to C30 di-yl alkylene group, which may contain one or more oxygen and/or nitrogen atoms in its chain,

3) Y is a saturated or unsaturated, linear or branched divalent C1 to C50 alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene group. which may contain one or more oxygen, sulfur and/or nitrogen atoms and/or carry as substituent one of the following atoms or groups of atoms: fluorine, hydroxy, C3 to Cg cycloalkyl, C1 to C40 alkyl, C5 to C10 aryl, phenyl, possibly substituted by 1 to 3 C1 to C3 alkyl groups, C1 to C3 hydroxyalkyl and C1 to Cg aminoalkyl, or

4) Y represents a group according to the formula:

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in which

    • T represents a saturated or unsaturated, linear or branched trivalent or tetravalent O3 to C24 hydrocarbon group, possibly substituted by a polyorganosiloxane chain, which may contain one or more atoms chosen from among O, N and S, or T represents a trivalent atom chosen from among N, P and Al, and
    • R8 represents a linear or branched C1 to C50 alkyl group, or a polyorganosiloxane chain, which may contain one or more ester, amide, urethane, thiocarbamate, urea, thiourea and/or sulfonamide groups, which may or may not be bonded to another chain of the polymer,

5) the groups G, identical or different, represent the divalent groups chosen from among:

text missing or illegible when filed

where R9 represents a hydrogen atom or a linear or branched C1 to C20 alkyl group, with the proviso that at least 50% of the R9 groups of the polymer represent a hydrogen atom and that at least two of the groups G of the polymer are another group such as:

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6) n is an integral number ranging from 2 to 500, preferably 2 to 200, and m is an integral number ranging from 1 to 1,000, preferably 1 to 700 and still better from 6 to 200. According to the invention, 80% of the R4, R5, R6 and R7 of the polymer are preferably chosen from among the methyl, ethyl, phenyl and 3,3,3-trifluoropropyl groups.

According to the invention, Y may represent diverse divalent groups, possibly containing one or two free valences to establish bonds with other moieties of the polymer or copolymer. Preferably, Y represents a group chosen from among:

a) the linear C1 to C20 alkylene groups, preferably C1 to C10,

b) the branched C30 to C56 alkylene groups that may contain rings and unconjugated unsaturations,

c) the C5-C6 cycloalkylene groups,

d) the phenylene groups, possibly substituted by one or more C1 to C40 alkyl groups,

e) the C1 to C20 alkylene groups containing 1 to 5 amide groups,

f) the C1 to C20 alkylene groups containing one or more substituents chosen from among the hydroxyl, C3 to C8 cycloalkane, C1 to C3 hydroxyalkyl and C1 to C6 alkylamine groups,

g) the polyorganosiloxane chains of formula:

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in which R4, R5, R6, R7, T and m are such as defined hereinabove, and

h) the polyorganosiloxane chains of formula:

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According to the second variant, the polyorganosiloxanes may be polymers comprising at least one moiety according to formula (II):

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in which

R4 and R6, identical or different, are such as defined hereinabove for formula (I),

R10 represents a group such as defined hereinabove for R4 and R6, or represents the group of formula —X-G-R12, in which X and G are as defined hereinabove for formula (I) and R12 represents a hydrogen atom or a saturated or unsaturated, linear, branched or cyclic C1 to C50 hydrocarbon group, possibly containing one or more atoms chosen from among O, S and N in its chain, possibly substituted by one or more fluorine atoms and/or one or more hydroxyl groups, or a phenyl group, possibly substituted by one or more C1 to C4 alkyl groups,

R11 represents the group of formula —X-G-R12, in which X, G and R12 are such as defined hereinabove,

    • m1 is an integral number ranging from 1 to 998, and
    • m2 is an integral number ranging from 2 to 500.

According to the invention, the silicone polymer used as structuring agent may be a homopolymer, or in other words a copolymer containing several identical moieties, in particular moieties of formula (I) or formula (II).

According to the invention, there may also be used a silicone polymer constituted by a copolymer containing several different moieties of formula (I), or in other words a polymer in which at least one of R4, R5, R6, R7, X, G, Y, m and n is different in one of the moieties. The copolymer may also be formed from several moieties of formula (II), in which at least one of R4, R6, R15, R11, m1 and m2 is different in at least one of the moieties.

There may also be used a polymer containing at least one moiety of formula (I) and at least one moiety of formula (II), wherein the moieties of formula (I) and the moieties of formula (II) may be identical to or different from one another.

According to a variant of the invention, there may also be used a polymer comprising at least one hydrocarbon moiety containing two groups capable of establishing hydrogen interactions, chosen from among the ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino, biguanidino groups and combinations thereof. These copolymers may be block polymers, sequenced polymers or graft polymers.

According to an advantageous embodiment of the invention, the groups capable of establishing hydrogen interactions are amide groups of formula —C(O)NH— and —HN—C(O)—. In this case, the structuring agent may be a polymer comprising at least one moiety of formula (III) or (IV):

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in which R4, R5, R6, R7, X, Y, m and n are such as defined hereinabove.

Such a moiety may be obtained:

    • either by a condensation reaction between a silicone with α,ω-carboxylic acid ends and one or more diamines, according to the following reaction scheme:

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    • or by reaction of two molecules of α-unsaturated carboxylic acid with a diamine according to the following reaction scheme:


CH2═CH—X′—COOH+H2N—Y—NH2—CH2—CH—X1—CO—NH—Y—NH—CO—X1—CH═CH2

followed by addition of a siloxane onto the ethylene unsaturations, according to the following scheme:

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in which X1—(CH2)2— corresponds to X defined hereinabove and Y, R4, R5, R6, R7 and m are such as defined hereinabove,

    • or by reaction of a silicone with α,ω-NH2 ends and a diacid of formula HOOC—Y—COOH according to the following reaction scheme:

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In these polyamides of formula (III) or (IV), m ranges from 1 to 700, in particular from 15 to 500 and especially from 50 to 200, and n ranges in particular from 1 to 500, preferably from 1 to 100 and still better from 4 to 25,

    • X is preferably a linear or branched alkylene chain having 1 to 30 carbon atoms, in particular 1 to 20 carbon atoms, especially 5 to 15 carbon atoms and more particularly 10 carbon atoms, and
    • Y is preferably a linear or branched alkylene chain or may contain rings and/or unsaturations, having 1 to 40 carbon atoms, in particular 1 to 20 carbon atoms, and still better 2 to 6 carbon atoms, in particular 6 carbon atoms.

In formulas (III) and (IV), the alkylene group representing X or Y may possibly contain, in its alkylene part, at least one of the following elements:

1) 1 to 5 amide, urea, urethane or carbamate groups,

2) a C5 or Cg cycloalkyl group, and

3) a phenylene group, possibly substituted by 1 to 3 identical or different C1 to C3 alkyl groups.

In formulas (III) and (IV), the alkylene groups may also be substituted by at least one element chosen in the group constituted by:

    • a hydroxy group,
    • a C3 to C8 cycloalkyl group,
    • one to three C1 to C40 alkyl groups,
    • a phenyl group, possibly substituted by one to three C1 to C3 alkyl groups,
    • a C1 to C3 hydroxyalkyl group, and
    • a C1 to C6 aminoalkyl group.

In these formulas (III) and (IV), Y may also represent:

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where R8 represents a polyorganosiloxane chain and T represents a group of the following formula:

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in which a, b and c are, independently, integral numbers ranging from 1 to 10, and R13 is a hydrogen atom or a group such as those defined for R4, R5, R6 and R7.

In formulas (III) and (IV), R4, R5, R6 and R7 preferably represent, independently, a linear or branched C1 to C40 alkyl group, preferably a CH3, C2H5, n-C3H7 or isopropyl group, a polyorganosiloxane chain or a phenyl group, possibly substituted by one to three methyl or ethyl groups.

As has been seen in the foregoing, the polymer may comprise identical or different moieties of formula (III) or (IV).

Thus the polymer may be a polyamide containing several moieties of formula (III) or (IV) of different lengths, or in other words a polyamide according to formula (V):

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in which X, Y, n, R4 to R7 have the meanings given hereinabove, ml and m2, which are different, are chosen in the interval ranging from 1 to 1,000, and p is an integral number ranging from 2 to 300.

In this formula, the moieties may be structured so as to form either a block copolymer or a random copolymer or an alternating copolymer. In this copolymer, the moieties may be not only of different lengths but also of different chemical structures, for example having different Y groups. In this case, the polymer may be represented by formula VI:

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in which R4 to R7, X, Y, m1, m2, n and p have the meanings given hereinabove and Y1 is different from Y but is chosen from among the groups defined for Y. As in the foregoing, the different moieties may be structured so as to form either a block copolymer or a random copolymer or an alternating copolymer.

In this first embodiment of the invention, the structuring agent may also be constituted by a graft copolymer. Thus the polyamide containing silicone units may be grafted and possibly cross-linked by silicone chains containing amide groups. Such polymers may be synthesized with trifunctional amines.

In this case, the polymer may comprise at least one moiety of formula (VII):

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in which X1 and X2, which are identical or different, have the meaning given for X in formula (I), n is such as defined in formula (I), Y and T are such as defined in formula (I), R14 to R21 are groups chosen in the same group as R4 to R7, m1 and m2 are numbers in the interval ranging from 1 to 1,000, and p is an integral number ranging from 2 to 500.

In formula (VII), it is preferred that

    • p range from 1 to 25, still better from 1 to 7,
    • R14 to R21 be methyl groups,
    • T be represented by one of the following formulas:

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in which R22 is a hydrogen atom or a group chosen from among the groups defined for R4 to R7, and R23, R24 and R25 are, independently, linear or branched alkylene groups, more preferably, with the formula:

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in particular with R23, R24 and R25 representing —CH2—CH2—,

    • m1 and m2 range from 15 to 500, and still better from 15 to 45,
    • X1 and X2 represent —(CH2)10—, and
    • Y represents —CH2—.

These polyamides with grafted silicone moiety of formula (VII) may be copolymerized with silicone polyamides of formula (II) to form block copolymers, alternating copolymers or random copolymers. The percentage by weight of grafted silicone moieties (VII) in the copolymer may range from 0.5 to 30% by weight.

According to the invention, as has been seen in the foregoing, the siloxane units may be in the main chain or skeleton of the polymer, but they may also be present in grafted or pendant chains. In the main chain, the siloxane units may be in the form of segments as described hereinabove. In the pendant or grafted chains, the siloxane units may be present individually or in segments.

According to an embodiment variant of the invention, there may be used a copolymer of silicone polyamide and hydrocarbon polyamide, or a copolymer containing moieties of formula (III) or (IV) and hydrocarbon polyamide moieties. In this case, the silicone polyamide moieties may be disposed at the ends of the hydrocarbon polyamide.

Preferably, the preferred compounds are those of formula III, whose INCI name is Nylon 611/dimethicone copolymers. According to this embodiment, the groups R4, R5, R6 and R7 represent methyl groups, one of X and Y represents an alkylene group with 6 carbon atoms and the other an alkylene group groups of 11 carbon atoms.

By way of example there may be cited the compounds sold by the Dow Corning Company under the name DC 2-8179 (DP 100) and DC 2-8178 (DP 15). The degree of polymerization DP of these compounds corresponds to n in formula III.

Advantageously, the composition according to the invention comprises at least one polydimethylsiloxane block polymer of general formula (I) possessing an index m whose value is approximately 15.

More preferably, the composition according to the invention comprises at least one polymer comprising at least one moiety of formula (III), where m ranges from 5 to 100, in particular from 10 to 75 and more particularly is on the order of 15; more preferably, R4, R5, R6 and R7 represent, independently, a linear or branched C1 to C40 alkyl group, preferably a CH3, C2H5, n-C3H7 or isopropyl group in formula (III).

By way of example of a usable silicone polymer there may be cited one of the silicone polyamides obtained in conformity with Examples 1 to 3 of the document U.S. Pat. No. 5,981,680.

According to an embodiment variant of the invention, the polymer is constituted by a homopolymer or copolymer containing urethane or urea groups. These polymers are described in detail in Application WO 2003/106614, published 24 Dec. 2003.

As in the foregoing, such a polymer may contain polyorganosiloxane moieties containing two or more urethane and/or urea groups, either in the polymer skeleton or on side chains or as pendant groups. The polymers containing at least two urethane and/or urea groups in the skeleton may be polymers comprising at least one moiety according to the following formula (VIII):

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in which R4, R5, R8, R7, X, Y, m and n have the meanings given hereinabove for formula (I), and U represents —O— or —NH—, in order that:

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corresponds to a urethane or urea group.

In this formula (VIII), Y may be a linear or branched C1 to C40 alkylene group, possibly substituted by a C1 to C15 alkyl group or a C5 to C10 aryl group. Preferably there will be used a —(CH2)6— group.

Y may also represent a C5 to C12 cycloaliphatic or aromatic group, which may be substituted by a C1 to C15 alkyl group or a C5 to C10 aryl group, for example a radical chosen from among the methylene-4-4-biscyclohexyl radical, the radical derived from isophorone diisocyanate, 2,4 and 2,6-tolylenes, 1,5-naphthylene, p-phenylene and 4,4′-biphenylene methane. In general, Y preferably represents a linear or branched C1 to C40 alkylene radical, or a C4 to C12 cycloalkylene radical.

Y may also represent a polyurethane or polyurea sequence corresponding to the condensation of several diisocyanate molecules with one or more coupler molecules or the diol or diamine type. In this case, Y comprises several urethane or urea groups in the alkylene chain.

It may be represented by formula (IX):

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in which B1 is a group chosen from among the groups given hereinabove for Y, U is —O— or —NH—, and B2 is chosen from among:

    • the linear or branched C1 to C40 alkylene groups,
    • the C5 to C12 cycloalkylene groups, possibly carrying alkyl substituents, for example one to three methyl or ethyl groups, or alkylene, for example the diol radical: cyclohexane dimethanol,
    • the phenylene groups, which may possibly carry C1 to C3 alkyl substituents, and
    • the groups of formula:

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in which T is a trivalent hydrocarbon radical, which may contain one or more hetero atoms such as oxygen, sulfur and nitrogen, and R8 is a polyorganosiloxane chain or a linear or branched C1 to C50 alkyl chain.

As an example, T may represent:

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where w is an integral number ranging from 1 to 10 and R8 is a polyorganosiloxane chain.

When Y is a linear or branched C1 to C40 alkylene group, the —(CH2)2— and —(CH2)6— groups are preferred.

In the formula given above for Y, d may be an integer ranging from 0 to 5, preferably from 0 to 3, more preferably equal to 1 or 2.

Preferably, B2 is a linear or branched C1 to C40 alkylene, in particular —(CH2)2— or —(CH2)6—, or the group:

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where R8 is a polyorganosiloxane chain.

As in the foregoing, the polymer constituting the texturizing copolymer may be formed from urethane silicone and/or urea silicone moieties of different length and/or constitution, and may have the form of block, sequenced or statistical (random) copolymers.

The polymers of formula (VIII) containing urea or urethane groups in the silicone polymer chain may be obtained by reaction between a silicone with α,ω-NH2 or OH terminal groups, of formula:

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in which m, R4, R5, R6, R7 and X are such as defined for formula (I), and a diisocyanate OCN—Y—NCO, where Y has the meaning given in formula (I); and possibly a diol or diamine coupler of formula H2N—B2—NH2 or HO—B2—OH, where B2 is such as defined in formula (IX).

Depending on the stoichiometric proportions between the two reagents, diisocyanate and coupler, Y will be able to have formula (IX) with d equal to 0 or d equal to 1 to 5.

As in the case of the silicone polyamides of formula (IV), (II) or (III), there may be used in the invention silicone polyurethanes or polyureas having moieties of different length and structure, in particular moieties of different lengths due to the number of silicone units. In this case, the copolymer may be represented, for example, by the formula:

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in which R4, R5, R6, R7, X, Y and U are such as defined for formula (VIII) and m1, m2, n and p are such as defined for formula (V).

According to the invention, the silicone may also contain urethane and/or urea groups no longer in the skeleton but in side branches. In this case, the polymer may comprise at least one moiety of the following formula:

text missing or illegible when filed

in which R4, R6, R5, m1 and m2 have the meanings given hereinabove for formula (II) and R5 for formula (I),

    • U represents O or NH,
    • R26 represents a C1 to C40 alkylene group, possibly containing one or more hetero atoms chosen from among O and N, or a phenylene group, and
    • R27 is chosen from among the saturated or unsaturated, linear, branched or cyclic C1 to C50 alkyl groups, and the phenyl groups, possibly substituted by one to three C1 to C3 alkyl groups.

The polymers containing at least one moiety of formula (X) contain siloxane units and urea or urethane groups, and they may be used as texturizing copolymer in the compositions of the invention.

The siloxane polymers may have a single urea or urethane group per branch or may have branches with two urea or urethane groups, or even contain a mixture of branches with one urea or urethane group and branches with two urea or urethane groups.

They may be obtained from branched polysiloxanes, containing one or two amino groups per branch, by reacting these polysiloxanes with monoisocyanates.

By way of examples of starting polymers of this type having amino and diamino branches there may be cited the polymers according to the following formulas:

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In these formulas, the “/” symbol indicates that the segments may be of different lengths and in a random order, and R represents a linear aliphatic group having preferably 1 to 6 carbon atoms and still better 1 to 3 carbon atoms.

Such branched polymers may be formed by reacting a siloxane polymer having at least three amino groups per polymer molecule with a compound having a single monofunctional group (for example, an acid, an isocyanate or isothiocyanate), thus causing this monofunctional group to react with one of the amino groups and to form the groups capable of establishing hydrogen interactions. The amino groups may be on side chains extending from the main chain of the siloxane polymer such that the groups capable of establishing hydrogen interactions are formed on these side chains, or else the amino groups may be at the ends of the main chain such that the groups capable of hydrogen interaction will be terminal groups of the polymer.

As a mode of operation for forming a polymer containing siloxane units and groups capable of establishing hydrogen interactions there may be cited the reaction of a diamine siloxane and of a diisocyanate in a silicone solvent so as to produce a gel directly. The reaction may be carried out in a silicone fluid, the resulting product being dissolved in the silicone fluid at elevated temperature, the temperature of the system then being lowered to form the gel.

The polymers preferred for incorporation into the compositions according to the present invention are urea-siloxane copolymers that are linear and that contain urea groups as groups capable of establishing hydrogen interactions in the skeleton of the polymer.

By way of illustration of a polysiloxane terminated by four urea groups there may be cited the polymer of formula:

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where Ph is a phenyl group and n is a number from 0 to 300, in particular from 0 to 100, for example 50.

This polymer is obtained by reacting the following polysiloxane having amino groups:

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with phenyl isocyanate.

Branched silicone polyurethanes or polyureas may also be obtained by using, instead of the diisocyanate OCN—Y—NCO, a triisocyanate of the following formula:

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In this way there is obtained a silicone polyurethane or polyurea having branches containing an organosiloxane chain with groups capable of establishing hydrogen interactions. Such a polymer comprises, for example, a moiety according to the formula:

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in which X1 and X2, which are identical or different, have the meaning given for X in formula (I), n is such as defined in formula (I), Y and T are such as defined in formula (I), R14 to R21 are groups chosen in the same group as R4 to R7, m1 and m2 are numbers in the interval ranging from 1 to 1,000, and p is an integral number ranging from 2 to 500.

As in the case of polyamides, silicone polyurethane or polyurea or hydrocarbon polyurethane or polyurea copolymers may be used in the invention by carrying out the reaction of synthesis of the polymer in the presence of a difunctional α,ω sequence of non-silicone nature, for example a polyester, a polyether or a polyolefin.

As has been seen in the foregoing, the copolymers of the invention may have siloxane moieties in the main chain of the polymer and groups capable of establishing hydrogen interactions either in the main chain of the polymer or at the ends thereof, or on side chains or branches of the main chain. This may correspond to the following five arrangements:

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in which the continuous line is the main chain of the siloxane polymer and the squares represent the groups capable of establishing hydrogen interactions.

In case (1), the groups capable of establishing hydrogen interactions are disposed at the ends of the main chain. In case (2), two groups capable of establishing hydrogen interactions are disposed at each of the ends of the main chain.

In case (3), the groups capable of establishing hydrogen interactions are disposed in the interior of the main chain, in repetitive moieties.

Cases (4) and (5) correspond to copolymers in which the groups capable of establishing hydrogen interactions are disposed on branches of the main chain of a first series of moieties that are copolymerized with moieties not containing groups capable of establishing hydrogen interactions.

The polymers and copolymers used in the composition of the invention advantageously have a solid-liquid transition temperature of 45° C. to 190° C. Preferably they have a solid-liquid transition temperature ranging from 70° C. to 130° C. and better from 80° C. to 105° C.

Organo Gelling Agents:

The oil-type structuring agent may also be chosen from among the non-polymeric molecular organic gelling agents, also referred to as organo gelling agents, which are compounds whose molecules are capable of establishing physical interactions between one another, leading to auto-aggregation of the molecules with formation of a supra-molecular 3D network, which is responsible for the gelling of the oil or oils (also referred to as liquid fatty phase).

The supra-molecular network may result from the formation of a network of fibrils (due to stacks or aggregations of molecules of organo gelling agent), immobilizing the molecules of the liquid fatty phase.

The ability to form this network of fibrils, and therefore to gelify, depends on the nature (or chemical class) of the organo gelling agent, on the nature of the substituents carried by its molecules for a given chemical class, and on the nature of the liquid fatty phase.

The physical interactions are diverse but exclude co-crystallization. These physical interactions are in particular interactions of the auto-complementary hydrogen interaction type, π interactions between unsaturated rings, dipole interactions, coordination bonds with organometallic derivatives and their associations. In general, each molecule of an organo gelling agent may establish several types of physical interactions with a neighboring molecule. Thus the molecules of organo gelling agents according to the invention advantageously contain at least one group capable of establishing hydrogen bonds and better at least two groups capable of establishing hydrogen bonds, at least one aromatic ring and better at least two aromatic rings, at least one or more ethylenically unsaturated bonds and/or at least one or more asymmetric carbons. Preferably, the groups capable of forming hydrogen bonds are chosen from among the hydroxyl, carbonyl, amine, carboxylic acid, amide, urea, benzyl groups and associations thereof.

The organo gelling agent or agents according to the invention are soluble in the liquid fatty phase after heating until a transparent homogeneous liquid phase is obtained. They may be solid or liquid at room temperature and atmospheric pressure.

The molecular organo gelling agent or agents that can be used in the composition according to the invention are in particular those described in the document “Specialist Surfactants”, edited by D. Robb, 1997, pp. 209-263, Chapter 8 by P. Terech, European Applications EP A 1068854 and EP A 1086945, or else in Application WO A 02/47031.

Among these organo gelling agents there may be cited in particular the amides of carboxylic acids, particularly the tricarboxylic acids, such as the cyclohexanetricarboxamides (see European Patent Application EP A 1068854), the diamides having hydrocarbon chains that each contain 1 to 22 carbon atoms, for example 6 to 18 carbon atoms, the said chains being non-substituted or substituted with at least one substituent chosen from among the ester, urea and fluoro groups (see Application EP A 1086945) and especially the diamides resulting from the reaction of diaminocyclohexane, in particular of diaminocyclohexane in trans form, and of an acid chloride such as, for example, N,N′-bis(dodecanoyl)-1,2-diaminocyclohexane, the amides of N-acylamino acids, such as the diamides resulting from the action of an N-acylamino acid with amines containing 1 to 22 carbon atoms, such as, for example, those described in the document WO-93/23008, and especially the amides of N-acyl glutamic acid, in which the acyl group represents a C8 to C22 alkyl chain, such as the dibutylamide of N-lauroyl-L-glutamic acid, manufactured or sold by the Ajinomoto Company under the trade name GP-1, and mixtures thereof.

As organo gelling agents there may also be used compounds of bis-urea type of the following general formula:

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in which

    • A is a group of formula (II)

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where R1 is a linear or branched C1 to C4 alkyl radical and the * symbolize the points of attachment of group A to each of the two nitrogen atoms of the rest of the compound of general formula (I), and

    • R and R′, identical or different, are chosen from among:
    • i) the radicals of formula (III):

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in which:

    • L is a single bond or a divalent carbon radical, especially a saturated or unsaturated, linear, branched and/or cyclic hydrocarbon (alkylene), comprising 1 to 18 carbon atoms, which may comprise 1 to 4 hetero atoms chosen from among N, O and S;
    • Ra is
      a) a carbon radical, especially a saturated or unsaturated, linear, branched and/or cyclic hydrocarbon (alkyl), comprising 1 to 18 carbon atoms, which may comprise 1 to 8 hetero atoms chosen from among N, O, Si and S; or else
      b) a silicone radical of formula:

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where n is between 0 and 100, especially between 1 and 80, even 2 to 20; and R2 and R6 are, independently of one another, carbon radicals, especially linear or branched hydrocarbons (alkyl), having 1 to 12, especially 1 to 6 carbon atoms, which may comprise 1 to 4 hetero atoms, especially 0;

    • Rb and Rc are, independently of one another, chosen from among:
      a) the carbon radicals, especially saturated or unsaturated, linear, branched and/or cyclic hydrocarbons (alkyl), comprising 1 to 18 carbon atoms, which may comprise 1 to 4 hetero atoms chosen from among N, O, Si and S;
      b) the radicals of formula:

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where n is between 0 and 100, especially between 1 and 80, even 2 to 20;
and R′2 and R′6 are, independently of one another, carbon radicals, especially linear or branched hydrocarbons (alkyl), having 1 to 12, especially 1 to 6 carbon atoms, which may comprise 1 to 4 hetero atoms, especially O.
and

    • ii) the saturated or unsaturated, linear, branched and/or cyclic C1 to C30 alkyl radicals, possibly comprising 1 to 3 hetero atoms chosen from among O, S, F and N;
      its being understood that at least one of the radicals R and/or R′ is of formula (III).

In particular, group A may be of formula:

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where R1 and the * are as defined in the foregoing.
In particular, R1 may be a methyl group, thus leading to a group A of formula:

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in which the * are as defined in the foregoing.
In particular, the compounds according to the invention may be in the form of a mixture associated with the fact that A may be a mixture of 2,4-tolylene and 2,6-tolylene, especially in proportions of (2,4 isomer)/2,6 isomer) varying from 95/5 to 80/20.

According to the invention, at least one of the radicals R and/or R′ must be of formula (III):

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In this formula, L is preferably a divalent carbon radical, especially a saturated or unsaturated, linear, branched and/or cyclic hydrocarbon (alkylene), comprising 1 to 18 carbon atoms, which may comprise 1 to 4 hetero atoms chosen from among N, O and S.

In the radical L, the carbon chain may be interrupted by the hetero atom or atoms and/or may comprise a substituent comprising the said hetero atom or atoms.

In particular, L may be of —(CH2)n— structure, where n=1 to 18, especially 2 to 12, even 3 to 8.

Preferably, L is chosen from among the methylene, ethylene, propylene, butylene radicals and especially n-butylene or octylene.

The radical L may also be branched, for example of the —CH2—CH(CH3)— type, which leads to the following radical of formula III):

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The radical Ra may be a carbon radical, especially a saturated or unsaturated, linear, branched and/or cyclic hydrocarbon (alkyl), comprising 1 to 18 carbon atoms, which may comprise 1 to 8 hetero atoms chosen from among N, O, Si and S. The carbon chain may be interrupted by the hetero atom or atoms and/or may comprise a substituent comprising the said hetero atom or atoms; in particular the hetero atoms may form one or more —SiO— (or —OSi)— groups.

Thus the radical Ra may be of —(CH2)n′-CH3 structure, where n′=0 to 17, especially 1 to 12, even 1 to 6. In particular, Ra may be methyl, ethyl, propyl or butyl.

It may also be of —(CH2)x-O—(CH2)z-CH3 or else —(CH2)x-O—(CH2)y-O—(CH2)z-CH3 structure, where x=1 to 10, preferably 2; y=1 to 10, preferably 2, and z=1 to 10, preferably 0 or 1.

The radical Ra may also be of —SiR4R5R6 structure (case where n=0), in which R4, R5 and R6 are, independently of one another, preferably alkyl radicals having 1 to 12 carbon atoms, especially 1 to 6 carbon atoms; in particular, R4, R5 and/or R6 may be chosen from among methyl, ethyl, propyl, butyl.

The radical Ra may also be a silicone radical of formula:

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in which R2 to R6 are, independently of one another, preferably alkyl radicals having 1 to 12 carbon atoms, especially 1 to 6 carbon atoms; in particular, R2 to R6 may be chosen from among methyl, ethyl, propyl, butyl;
and in particular a radical:

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where n=1 to 100; and even more particularly a radical:

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The radicals Rb and Rc, identical or different, may be carbon radicals, especially saturated or unsaturated, linear, branched and/or cyclic hydrocarbons (alkyl), comprising 1 to 18 carbon atoms, which may comprise 1 to 8 hetero atoms chosen from among N, O, Si and S. In these radicals, the carbon chain may be interrupted by the hetero atom or atoms and/or may comprise a substituent comprising the said hetero atom or atoms; in particular the hetero atoms may form one or more —SiO— (or —OSi)— groups.

Thus they may be of —(CH2)m-CH3 structure, where m=0 to 17, especially 1 to 12, even 2 to 5. In particular, Rb and/or Rc may be methyl, ethyl, propyl or butyl;

They may also be of —O—(CH2)m′-CH3 structure, where m′=0 to 5, especially 1 to 4, and in particular methoxy or ethoxy.

They may also be of —(CH2)x-O—(CH2)z-CH3 or else —(CH2)x-O—(CH2)y-O—(CH2)z-CH3 structure, where x=1 to 10, preferably 2; y=1 to 10, preferably 2, and z=1 to 10, preferably 0 or 1.

They may also be of structure:

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where n is between 0 and 100, especially between 1 and 80, even 2 to 20;
and R′2 to R′6 are, independently of one another, preferably alkyl radicals having 1 to 12 carbon atoms, especially 1 to 6 carbon atoms; in particular, R′2 to R′6 may be chosen from among methyl, ethyl, propyl, butyl.

When they are of formula (III), the radicals R and/or R′ are preferably chosen from among the following radicals:

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and also those of formula:

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where n varies from 0 to 100 and in particular

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and

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or else

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in which x=1 to 10, preferably 2; and y=1 to 10, preferably 2;
and L is such as defined hereinabove.

In these formulas, L is preferably a linear or branched C1-C8 alkylene radical, especially methylene, ethylene, propylene, butylene and especially n-butylene, octylene or of formula —CH2—CH(CH3)—.

In a particular embodiment, R and R′, identical or different, are both of formula (III).

In another embodiment, one of the radicals R or R′ represents a saturated or unsaturated, linear, branched and/or cyclic C1 to C30 alkyl radical, possibly comprising 1 to 3 hetero atoms chosen from among O, S, F and N.

This proves particularly advantageous for conferring a universal character on the compounds of formula (I), or in other words permitting them to texturize, equally well, polar or apolar carbon media, linear or cyclic silicone media, mixed oils, or in other words carbon media that are part silicone, as well as mixtures thereof.

The carbon chain may be interrupted by the hetero atom or atoms and/or may comprise a substituent comprising the said hetero atom or atoms, especially in the form of carbonyl groups (—CO—), of one or more hydroxy radicals (—OH), and/or of an ester radical —COOR″, where R″=linear or branched alkyl radical having 1 to 8 carbon atoms.

Thus the said radical R or R′ may be a group chosen from among:

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where * has the definition given hereinabove.

In a preferred embodiment, R or R′ represents a saturated or unsaturated, preferably non-cyclic, branched, especially singly branched alkyl radical comprising 3 to 16 carbon atoms, especially 4 to 12, even 4 to 8 carbon atoms, and possibly comprising 1 to 3 hetero atoms chosen from among O, S, F and/or N, preferably O and/or N.

In particular, R or R′ may be tert-butyl or 2-ethylhexyl radicals or of formula:

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When the compound of formula (I) comprises a radical R that is an alkyl radical, and therefore a radical R′ that is of formula (III), the ratio between nR and nR′ is preferably between 5/95 and 95/5, for example between 10/90 and 90/10, in particular between 40/60 and 85/15, especially between 50/50 and 80/20, even between 60/40 and 75/25;

where nR is the number of moles of NH2—R amine and nR′ is the number of moles of NH2—R′ amine used to prepare the compound of formula (I).

The compounds according to the invention may have the form of salts and/or isomers of compounds of formula (I).

In general, the compounds of general formula (I) according to the invention may be prepared as described in Application FR 2910809.

The compounds of silicone bis-urea type described in the foregoing may be in a mixture with other non-silicone bis-urea compounds. According to a first aspect, the non-silicone bis-urea compounds may correspond to the following general formula (II):

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in which:

    • A is a group of formula:

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where R′ is a linear or branched C1 to C4 alkyl radical and the * symbolize the points of attachment of the group A to each of the two nitrogen atoms of the rest of the compound of general formula (II), and

    • R is a saturated or unsaturated, singly branched, non-cyclic, C6 to C15 alkyl radical, whose hydrocarbon chain is possibly interrupted by 1 to 3 hetero atoms chosen from among O, S and N, or
      one of the salts or isomers thereof.

According to a preferred embodiment of the invention, the group represented by A is a group of formula:

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where R′ and the * are such as defined in the foregoing.

In particular, R′ may be a methyl group, and the group A is then more particularly a group of formula:

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where the * are such as defined in the foregoing.

According to a first embodiment of the invention, R may be chosen from among the singly branched radicals of general formula CnH2n+1, where n is an integer varying from 6 to 15, particularly from 7 to 9, even equal to 8.

Thus the two groups R of the compound of formula (II) may respectively represent a group:

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where * symbolizes the point of attachment of each of the groups R to each of the nitrogen atoms of the rest of the compound of general formula (II).

According to a second embodiment of the invention, R may be chosen from among the singly branched radicals of general formula Cm−pH2m+1−2pXp, where p is equal to 1, 2 or 3, preferably equal to 1, m is an integer varying from 6 to 15, preferably from 10 to 14, in particular from 10 to 12, even equal to 11, and X represents sulfur and/or oxygen atoms, in particular oxygen atoms.

More particularly, R may be a radical of formula Cm′H2m′X—(Cp′H2p′X′)r—CxH2x+1, in which X and X′ are, independently of one another, an oxygen or sulfur atom, preferably oxygen, r is equal to 0 or 1, m′, p′ and x are integers such that their sum varies from 6 to 15, in particular from 10 to 12, is even equal to 11, and its being understood that at least one of the carbon chains Cm′H2m′, Cp′H2p′ or CxH2x+1 is branched.

Preferably the CxH2x+1 chain is branched, preferably r is equal to 0, preferably m′ is an integer varying from 1 to 10, especially from 2 to 6, in particular equal to 3, and/or preferably x is an integer varying from 4 to 16, especially from 6 to 12, in particular equal to 8.

Thus the two groups R of the compound of formula (I) may respectively represent a group:

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where * symbolizes the point of attachment of each of the groups R to each of the nitrogen atoms of the rest of the compound of general formula (I).

Such compounds may be present in the compositions according to the invention in mixtures with isomers, especially position isomers on group A, especially in proportions of 95/5 or 80/20.

As becomes evident from the examples hereinafter, the presence of one or the other of its radicals in the molecule of general formula (II) proves particularly advantageous for conferring universal character within the meaning of the invention upon the corresponding non-silicone bis-urea derivatives.

As representative and non-limitative compounds that are quite particularly suitable for the invention there may be cited more particularly the following compounds, used in pure or mixed form:

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and the salts thereof.

According to another aspect of the invention, the non-silicone bis-urea derivatives following formula (III):

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in which:

    • A is a group of formula:

text missing or illegible when filed

where

    • R3 is a hydrogen atom or a linear or branched C1 to C4 alkyl radical,
    • n and m are, independently of one another, equal to 0 or 1, and
    • * symbolize the point of attachment of the group A to the two nitrogen atoms of the rest of the compound of general formula (III),
    • R1 is a saturated or unsaturated, branched, non-cyclic C3 to C15 carbon radical, possibly containing 1 to 3 hetero atoms chosen from among O, S, F and N and/or a carbonyl, and combinations thereof,
    • R2 is different from R1 and is chosen from among the linear, branched or cyclic, saturated or unsaturated C1-C24 alkyl radicals, possibly containing 1 to 3 hetero atoms chosen from among O, S, F and N, and possibly substituted by:
      • 1, 2 or 3 hydroxy radicals,
      • an ester radical (—COOR4), where R is a linear or branched alkyl radical having 1 to 8, especially 1 to 6, even 2 to 4 carbon atoms;
      • a saturated, unsaturated cyclic or aromatic radical having 5 to 12 carbon atoms, in particular a phenyl radical, possibly substituted by one or more identical or different radicals chosen from among the C1-C4 alkyl radicals, trifluoromethyl, or a morpholine derivative, and/or
      • one or more linear or branched C1-C4 alkyl radicals or one of the salts or isomers thereof.

In particular, n and m are equal, and more particularly are equal to zero, and R3 is a radical R′3 such as defined below. Thus A preferably represents a group

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where R3′ is a linear or branched C1 to C4 alkyl radical and * symbolize the point of attachment of the group A to the two nitrogen atoms of the rest of the compound of general formula (III).

According to a variant of the invention, the compound of general formula (III) comprises, by way of A, at least one group chosen from among:

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where R3′ and * are such as defined in the foregoing.

In particular R3′ may be a methyl group, and in this case group A represents a group

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where * are defined as in the foregoing.

In particular, the compounds are such that A is a mixture of 2,4-tolylene and 2,6-tolylene, especially in proportions of (2,4 isomer)/2,6 isomer) varying from 95/5 to 80/20.

According to one embodiment of the invention, the compound of general formula (III) comprises, by way of R1, a branched C6-C15 radical.

According to one embodiment of the invention, the compound of general formula (III) comprises, by way of R1, a compound chosen from among:

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where * symbolize the point of attachment of the group R1 to the nitrogen of the rest of the compound of general formula (III).

As becomes evident from the examples hereinafter, the presence of one and/or the other of its two radicals in the molecule of general formula (III) proves particularly advantageous for conferring universal character within the meaning of the invention upon the corresponding asymmetric bis-urea derivatives.

As regards R2, which is different from R1, it may be advantageously chosen from among the following groups:

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where * symbolize the point of attachment of the group R1 to the nitrogen of the rest of the compound of general formula (III).

In general, the described compounds may be prepared as described in Application FR 2910809.

Fatty-Phase Gelling Silicone Elastomers

By “elastomer” there is understood a deformable, flexible solid material having viscoelastic properties, and especially the consistency of a sponge. This elastomer is formed from polymeric chains of high molecular weight, whose mobility is limited by a uniform network of cross-linking points.

The elastomeric organopolysiloxanes used in the composition according to the invention are preferably partly or completely cross-linked. They have the form of particles.

In particular, the elastomeric organopolysiloxane particles have a size ranging from 0.1 to 500 μm preferably from 3 to 200 μm and better from 3 to 50 μm. These particles may have any shape and for example may be spherical, flat or amorphous.

When they are included in an oil phase, these elastomeric organopolysiloxanes become transformed, depending on the proportion of the oil phase used, into a product of spongy appearance when they are used in the presence of low contents of oil phase, or into a homogeneous gel in the presence of higher quantities of oil phase. The gelling of the oil phase by these elastomers may be total or partial.

Thus the elastomers of the invention may be conveyed in the form of anhydrous gel composed of an elastomeric organopolysiloxane and of an oil phase. The oil phase used during the manufacture of the anhydrous elastomeric organopolysiloxane gel contains one or more oils that are liquid at room temperature (25° C.), chosen from among the hydrocarbon oils and/or the silicone oils. Advantageously, the oil phase is a silicone liquid phase containing one or more oils chosen from among the linear chain or cyclic polydimethylsiloxanes that are liquid at room temperature, possibly containing an alkyl or aryl chain of pendant type or at the end of the chain, the alkyl chain having 1 to 6 carbon atoms.

According to one embodiment, the elastomeric organopolysiloxanes used according to the invention may be obtained by addition and cross-linking reaction, in the presence of a catalyst, preferably a catalyst of platinum type, of at least:

    • (i) an organopolysiloxane having two vinyl groups in α-ω position of the silicone chain per molecule; and
    • (ii) an organopolysiloxane having at least two hydrogen atoms bonded to one silicon atom per molecule.

The first organopolysiloxane (i) is chosen from among the polydimethylsiloxanes; it is preferably an α-ω-dimethylvinyl polydimethylsiloxane.

The organopolysiloxane is preferably in a gel obtained according to the following steps:

    • (a) mixing of the first and second organopolysiloxanes (i) and (ii);
    • (b) addition of an oil phase to the mixture of step (a);
    • (c) polymerization of the first and second organopolysiloxanes (i) and (ii) in the oil phase in the presence of a catalyst, preferably a platinum catalyst.

According to one embodiment, the cross-linked organopolysiloxane may be obtained by a polymeric addition reaction of an organohydrogenopolysiloxane of formula (I) with an organopolysiloxane of formula (II) and/or an unsaturated hydrogen chain of formula (III).

According to one variant, the cross-linked organopolysiloxane is obtained by a polymeric reaction of an organohydrogenopolysiloxane of formula (I) with an organopolysiloxane of formula (II).

Organohydrogenopolysiloxane of Formula (I)

The organohydrogenopolysiloxane of formula (I) comprises at least one structural unit chosen in the group composed of an SiO2 unit, an HSiO1.5 unit, an RSiO1.5 unit, an RHSiO unit, an R2SiO unit, an R3SiO0.5 unit and an R2HSiO0.5 unit, wherein the group R in these units is a monovalent hydrocarbon chain containing 1 to 16 carbon atoms and may or may not be substituted, but is different from an unsaturated aliphatic group and possesses on average at least 1.5 hydrogen atoms bonded to a silicon atom.

The group R in the organohydrogenopolysiloxane of formula (I) may be an alkyl group containing 1 to 16, preferably 10 to 16 carbon atoms. This group R may be, for example, a methyl group, an ethyl group, a propyl group, a lauryl group, a myristyl group and a palmityl group.

The group R in the organohydrogenopolysiloxane of formula (I) may also be an aryl group such as a phenyl or tolyl group.

The group R, still in the organohydrogenopolysiloxane of formula (I), may also be a monovalent hydrocarbon chain comprising a cycloalkyl group such as cyclohexyl or else a hydrocarbon chain substituted by one, two or more groups chosen from among a halogen atom such as chlorine, bromine, fluorine and a cyano group, for example an α-trifluoropropyl or chloromethyl group.

In particular, the group R preferably represents at least 30 mol % of methyl groups and from 5 to 50 mol %, preferably from 10 to 40 mol % of hydrocarbon chains containing 10 to 16 carbon atoms.

The hydrocarbon chain may then advantageously contain at least one lauryl group, and even the majority of the groups R may be lauryl groups.

The organohydrogenopolysiloxane of formula (I) may be linear, branched or cyclic.

The organohydrogenopolysiloxane of formula (I) preferably contains 2 to 50 and even more preferably 2 to 10 hydrogen atoms bonded to a silicon atom (Si—H). The content of hydrogen atoms bonded to a silicon atom in this compound of formula (I) traditionally varies from 0.5 to 50 mol %, and even more preferably from 1 to 20 mol % relative to the total sum of the hydrogen atoms and of all the organic groups bonded to a silicon atom.

Organopolysiloxane of Formula (II)

The organopolysiloxane of formula (II) comprises at least one structural unit chosen in the group composed of an SiO2 unit, a (CH2═CH)SiO1.5 unit, an RSiO1.5 unit, an R(CH2═CH)SiO unit, an R2SiO unit, an R3SiO0.5 unit and an R2(CH2═CH)SiO0.5 unit, wherein the group R is such as defined in formula (I) and possesses on average at least 1.5 vinyl groups bonded to a silicon atom.

This compound preferably contains 2 to 50 vinyl groups bonded to a silicon atom.

The mean number of vinyl groups bonded to a silicon atom preferably varies from 2 to 10 and even more preferably from 2 to 5.

Preferably, at least 30 mol % of the groups R are methyl groups and 5 to 50 mol %, preferably from 10 to 40 mol % of the groups R are a hydrocarbon chain containing 10 to 16 carbon atoms.

The organopolysiloxane of formula (II) may be linear, branched or cyclic.

The content of vinyl groups in the compound of formula (II) preferably varies between 0.5 and 50 mol %, and even more preferably from 1 to 20 mol % relative to all the organic groups bonded to a silicon atom.

Optional Unsaturated Hydrocarbon Chain of Formula (III)

The unsaturated hydrocarbon chain of formula (III) corresponds to the following formula:


CmH2m-1(CH2)xCmH2m-1

in which
m is an integer varying from 2 to 6 and
x is an integer equal to at least 1.
x is preferably an integer varying from 1 to 20.

By way of example of this compound of formula (III) there may be cited pentadiene, hexadiene, heptadiene, octadiene, pentadecadiene, heptadecadiene and pentatriacontadiene.

The polymeric addition reactions are described in detail in the document US 2004/0234477.

Among the cross-linked organopolysiloxanes there are preferred the cross-linked polyalkyl dimethylsiloxanes. By polyalkyl dimethylsiloxane there is understood a linear organopolysiloxane of formula (IV)

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containing grafts, bonded in monovalent or divalent manner, of formula (V)

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in which:
Ra is an alkyl group containing 10 to 16 carbon atoms, and preferably it may be a lauryl group,
ya is an integer from 1 to 100;
za is an integer from 1 to 100,
yb is an integer from 1 to 100,
zb is an integer from 1 to 100.

By “bonded in divalent manner” there is understood bonded to two separate organopolysiloxanes of formula (IV). In other words, this means a bridge between two linear chains such as defined in formula (IV).

As non-emulsifying elastomers that can be used according to the invention there are preferably used the dimethicone/vinyl dimethicone copolymers (INCI name: Dimethicone/Vinyldimethicone crosspolymer), and the vinyl dimethicone/alkyl dimethicone copolymers, such as the vinyl dimethicone/lauryl dimethicone copolymers (INCI name: Vinyl Dimethicone/Lauryl Dimethicone Crosspolymer).

As non-emulsifying elastomers that can be used according to the invention there may be cited:

    • those of INCI name Dimethicone/Vinyldimethicone Crosspolymer (and) C12-14 Pareth-12: such as those sold under the name “DC 9509” by the Dow Corning Company,
    • those of INCI name Dimethicone/Vinyldimethicone Crosspolymer: such as those sold under the name “DC9505”, or “DC 9506” by the Dow Corning Company, those of INCI name Cyclomethicone (and) Dimethicone/Vinyldimethicone Crosspolymer: such as those sold under KSG-15® by Shin-Etsu, Methyl Trimethicone (and) Dimethicone/Vinyldimethicone Crosspolymer: such as those sold by Shin-Etsu under KSG-1610®,
    • those of INCI name Dimethicone (and) Dimethicone/Vinyldimethicone Crosspolymer: such as those sold under KSG-16® by Shin-Etsu, Isododecane (and) Dimethicone/Vinyldimethicone Crosspolymer: such as those sold under USG-106® by Shin-Etsu,
    • those of INCI name: Vinyl Dimethicone/Lauryl Dimethicone Crosspolymer: KSG-41® (in a mineral oil), KSG-42® (in isododecane), KSG-43® (in triethylhexanoin) and KSG-44® (in squalane), sold by Shin-Etsu.

As non-emulsifying elastomer there may also be cited spherical non-emulsifying silicone elastomers in the form of elastomeric cross-linked organopolysiloxane powder coated with silicone resin, especially silsesquioxane resin, such as described, for example, in U.S. Pat. No. 5,538,793. Such elastomers are sold under the trade names ‘KSP-100”, KSP-101”, “KSP-102”, “KSP-103”, “KSP-104”, “KSP-105” by the Shin Etsu Company.

Other elastomeric cross-linked organopolysiloxanes in the form of spherical powders may be hybrid silicone powders functionalized by fluoroalkyl groups, especially sold under the trade name “KSP-200” by the Shin Etsu Company; hybrid silicone powders functionalized by phenyl groups, especially sold under the trade name “KSP-300” by the Shin Etsu Company.

There may also be used, in the compositions according to the invention, silicone elastomers with MQ groups, such as those sold by the Wacker Company under the trade names Belsil RG100, Belsil RPG33 and preferably RG80. These particular elastomers, when they are in association with the resins according to the invention, may make it possible to improve the non-transfer properties of compositions comprising them.

Cholesteric Liquid Crystal Agents:

By liquid crystal agents there is understood compounds generating a mesomorphic state, or in other words a state for which melting of the crystals makes it possible to obtain liquids possessing optical properties comparable to those of certain crystals. These compounds are defined more precisely in the Liquid Crystals chapter of Ullmann's Encyclopedia.

These liquid crystal agents are described in particular in the patents or patent applications EP 545409, WO 94109086, EP 709445, GB 2282145, GB 2276883, WO 95132247, WO 95132248, EP 686674, EP 711780.

These liquid crystal agents may react in response to vibrations by a change in viscosity and/or by a change of color. More particularly, the compounds generating a mesomorphic state are compounds with cholesteric function, whose structure is the following:

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R is an alkyl, alkylcarbonyl group comprising 1 to 30 carbon atoms, which may or may not be substituted by cyclic, aromatic, halogen groups, which may or may not be branched.

On a non-limitative basis there may be cited as liquid crystals satisfying this definition: cholesterol erucyl carbonate, cholesterol methyl carbonate, cholesterol oleyl carbonate, cholesterol para-nonylphenyl carbonate, cholesterol phenyl carbonate, cholesterol acetate, cholesterol benzoate, cholesterol butyrate, cholesterol isobutyrate, cholesterol chloride, cholesterol chloroacetate, cholesterol cinnamate, cholesterol crotanoate, cholesterol decanoate, cholesterol erucate, cholesterol heptanoate, cholesterol hexanoate, cholesterol myristate, cholesterol nonanoate, cholesterol octanoate, cholesterol oleate, cholesterol propionate, cholesterol valerate, dicholesteryl carbonate.

The composition according to the invention may contain a continuous aqueous phase or a continuous oil phase.

By composition of continuous aqueous phase there is understood that the composition has a conductivity, measured at 25° C., greater than or equal to 23 S/cm (microSiemens/cm), the conductivity being measured, for example, by means of an MPC227 conductimeter of Mettler Toledo and an Inlab730 conductivity measuring cell. The measuring cell is immersed in the composition, in such a way as to eliminate the air bubbles that tend to form between the 2 electrodes of the cell. The conductivity reading is taken as soon as the value of the conductimeter has stabilized. A mean is established over at least 3 successive measurements.

By composition of continuous oil phase there is understood that the composition has a conductivity, measured at 25° C., greater than or equal to 23 μS/cm (microSiemens/cm), the conductivity being measured, for example, by means of an MPC227 conductimeter of Mettler Toledo and an Inlab730 conductivity measuring cell. The measuring cell is immersed in the composition, in such a way as to eliminate the air bubbles that tend to form between the 2 electrodes of the cell. The conductivity reading is taken as soon as the value of the conductimeter has stabilized. A mean is established over at least 3 successive measurements.

The compositions may contain 1 to 60% of fatty-phase rheological agent. Preferably, the composition contains 2% to 50% by weight, better 5% to 40% of fatty-phase rheological agent.

In the case that the composition comprises a fatty-phase rheological agent, it contains a continuous oil phase.

Waxes

The composition according to the invention may comprise at least one wax.

The compositions according to the invention may therefore comprise at least one wax, and mixture 1) described hereinabove.

By wax within the meaning of the present invention there is understood a lipophilic compound, solid at room temperature (25° C.), with reversible change of state between solid and liquid, having a melting point higher than or equal to 30° C. and possibly up to 120° C.

The melting point of the wax may be measured by means of a differential scanning calorimeter (D.S.C.), for example the calorimeter sold under the trade name DSC 30 by the METTLER Company.

The waxes may be hydrocarbon, fluoro and/or silicone and be of vegetable, mineral, animal and/or synthetic origin. In particular, the waxes have a melting temperature higher than 25° C. and better higher than 45° C.

The wax or the mixture of waxes is present in a content at least equal to 7% by weight. Preferably, it is present in a content ranging from 10 to 40% by weight relative to the total weight of the composition, better from 15 to 35% and even better from 16 to 30% by weight.

In particular, there may be used hydrocarbon waxes such as beeswax, lanolin wax, and Chinese insect waxes; rice wax, carnauba wax, ouricurry wax, esparto grass wax, cork fiber wax, sugar cane wax, Japan wax and sumac wax; montan wax, microcrystalline waxes, paraffins; polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis and the waxy copolymers as well as the esters thereof.

There may also be cited the waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C8-C32 fatty chains.

Among those, there may be cited in particular hydrogenated jojoba oil, hydrogenated sunflower seed oil, hydrogenated castor oil, hydrogenated copra oil and hydrogenated lanolin oil, di-(trimethylol-1,1,1-propane) tetrastearate sold under the trade name “HEST 2T-4S” by the HETERENE Company, di-(trimethylol-1,1,1-propane) tetrabehenate sold under the trade name HEST 2T-4B by the HETERENE Company.

There may also be cited the fluoro waxes.

There may also be used the wax obtained by hydrogenation of olive oil esterified with stearyl alcohol sold under the trade name “PHYTOWAX Olive 18 L 57” or else the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol sold under the trade name “PHYTOWAX ricin 16L64 and 22L73” by the SOPHIM Company. Such waxes are described in Application FR A 2792190.

According to a particular embodiment, the compositions according to the invention may comprise at least one wax referred to as tacky wax, or in other words possessing a tack greater than or equal to 0.7 N·s and a hardness smaller than or equal to 3.5 MPa.

The use of a tacky wax especially may make it possible to obtain a cosmetic composition that is applied easily on the eyelashes, clings well to the eyelashes and leads to the formation of a smooth, homogeneous and thickening makeup.

The tacky wax used may possess especially a tack ranging from 0.7 N·s to 30 N·s, in particular greater than or equal to 1 N·s, especially ranging from 1 N·s to 20 N·s, in particular greater than or equal to 2 N·s, especially ranging from 2 N·s to 10 N·s and in particular ranging from 2 N·s to

5N·s.

The tack of the wax is determined by measuring the evolution of force (compression force or stretching force) as a function of time at 20° C. by means of the texturometer sold under the trade name “TA-TX2i®” by the RHEO Company, equipped with an acrylic polymer traveler in the form of a cone having an angle of 45°.

The measurement protocol is the following:

The wax is melted at a temperature equal to the melting point of the wax+10° C. The molten wax is cast in a receptacle of 25 mm diameter and 20 mm depth. The wax is recrystallized at room temperature (25° C.) for 24 hours, in such a way that the surface of the wax is plane and smooth, then the wax is kept for at least 1 hour at 20° C. before the measurement of the tack is carried out.

The traveler of the texturometer is displaced at a speed of 0.5 mm/s, then penetrates into the wax as far as a penetration depth of 2 mm. When the traveler has penetrated to a depth of 2 mm into the wax, the traveler is maintained in fixed position for 1 second (corresponding to the relaxation time) then is withdrawn at a speed of 0.5 mm/s.

During the relaxation time, the force (compression force) decreases rapidly to zero, then during withdrawal of the traveler, the force (stretching force) becomes negative then increases again to the value 0. The tack corresponds to the integral of the curve of force as a function of time for the part of the curve corresponding to the negative values of force (stretching force). The value of the tack is expressed in N·s.

The tacky wax that may be used generally has a hardness of smaller than or equal to 3.5 MPa, in particular ranging from 0.01 MPa to 3.5 MPa, especially ranging from 0.05 MPa to 3 MPa, even better ranging from 0.1 MPa to 2.5 MPa.

The hardness is measured according to the protocol described in the foregoing.

As tacky wax there may be used a C20-C40 alkyl (hydroxystearyloxy) stearate (the alkyl group comprising 20 to 40 carbon atoms) alone or in a mixture, in particular a C20-C40 alkyl 12-(12′-hydroxystearyloxy) stearate of formula (II):

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in which m is an integer ranging from 18 to 38, or a mixture of compounds of formula (II).

Such a wax is sold in particular under the trade names “Kester Wax K 82 P®” and “Kester Wax K 80 P®” by the KOSTER KEUNEN Company.

The waxes cited above generally have a starting melting point lower than 45° C.

There may also be used the microcrystalline wax sold under the reference SP18 by the STRAHL and PITSCH Company, which wax has a hardness of approximately 0.46 MPa and a tack value of approximately 1 N·s.

The wax or waxes may be present in the form of an aqueous microdispersion of wax. By aqueous microdispersion of wax there is understood an aqueous dispersion of wax particles in which the size of the said wax particles is smaller than or equal to approximately 1 μm.

The microdispersions of wax are stable dispersions of colloidal particles of wax, and are described in particular in “Microemulsions Theory and Practice”, L. M. Prince Ed., Academic Press (1977) pages 21-32.

In particular, these wax microdispersions may be obtained by melting the wax in the presence of a surfactant and possibly a portion of water, then progressively adding hot water with agitation.

There is observed the intermediate formation of an emulsion of water-in-oil type, followed by a phase inversion that finally yields a microemulsion of the oil-in-water type. Upon cooling, there is obtained a stable microdispersion of solid colloidal particles of wax.

The wax microdispersions may also be obtained by agitation of the mixture of wax, surfactant and water using agitation means such as ultrasound, high-pressure homogenizer, turbines.

The particles of the wax microdispersion preferably have mean dimensions smaller than 1 μm (in particular ranging from 0.02 μm to 0.99 μm), preferably smaller than 0.5 μm (in particular ranging from 0.06 μm to 0.5 μm).

These particles are composed substantially of a wax or of a mixture of waxes. Nevertheless, they may comprise a minority proportion of fatty oil and/or paste additives, a surfactant and/or a common fat-soluble additive/active substance.

Hydrophilic Gelling Agents:

The composition according to the invention may comprise at least one hydrophilic gelling agent, also referred to as hydrophilic thickening agent hereinafter.

These thickening agents may be used alone or in association. These thickening agents may be chosen in particular from among the gums and the cellulose polymers.

By hydrophilic thickening agent there is understood a thickening agent that is soluble or dispersible in water.

As hydrophilic thickening agents there may be cited in particular the water-soluble or water-dispersible thickening polymers. These may be chosen in particular from among:

    • polyvinylpyrrolidone,
    • polyvinyl alcohol,
    • the modified or non-modified carboxyvinyl polymers, such as the products sold under the trade names Carbopol (CFTA name: carbomer) by the Goodrich Company;
    • the acrylic or methacrylic homopolymers or copolymers or their salts and their esters, and in particular the products sold under the trade names VERSICOL F® or VERSICOL K® or Salcare SC95 by the ALLIED COLLOID Company, ULTRAHOLD 8® by the CIBA-GEIGY Company, the polyacrylates and polymethacrylates such as the products sold under the trade names of Lubragel and Norgel by the GUARDIAN Company or under the trade name Hispagel by the HISPANO CHIMICA Company, the polyacrylic acids of SYNTHALEN K type;
    • the polyacrylamides;
    • the copolymers of acrylic acid and acrylamide sold in the form of their sodium salt under the trade names RETEN® by the HERCULES Company, the sodium polymethacrylate sold under the trade name DARVAN No. 7® by the VANDERBILT Company, the sodium salts of polyhydroxycarboxylic acids sold under the trade name HYDAGEN F® by the HENKEL Company;
    • the polymers and copolymers of 2-acrylamido-2-methylpropanesulfonic acid, possibly cross-linked and/or neutralized, such as the poly(2-acrylamido-2-methylpropanesulfonic acid) sold by the CLARIANT Company under the trade name “Hostacerin AMPS” (CTFA name: ammonium polyacryldimethyltauramide);
    • the cross-linked anionic copolymers of acrylamide and AMPS, having the form of a water-in-oil emulsion, such as those sold under the name of SEPIGEL 305 (C.T.F.A. name: Polyacrylamide/C13-14 isoparaffin/Laureth-7) and under the name of SIMULGEL 600 (C.T.F.A. name: Acrylamide/Sodium acryloyldimethyl taurate copolymer/Isohexadecane/Polysorbate 80) by the SEPPIC Company;
    • the polyacrylic acid/alkyl acrylate copolymers of PEMULEN type;
    • the polysaccharide biopolymers such as xanthan gum, guar gum, gum arabic, carob gum, acacia gum, the scleroglucans, the derivatives of chitin and chitosan, the carrageenans, the gellans, the alginates, the celluloses such as microcrystalline cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose;
    • the hydrophilic pyrogenic silicas obtained by hydrolysis at high temperature of a volatile silicon compound in an oxyhydrogen flame, producing a finely divided silica. The hydrophilic silicas have a large number of silanol groups at their surface. Such hydrophilic silicas are sold, for example, under the trade names “AEROSIL 130®”, “AEROSIL 200®”, “AEROSIL 255®”, “AEROSIL 300®”, “AEROSIL 380®” by the Degussa Company, “CAB-O-SIL HS-5®”, “CAB-O-SIL EH-5®”, “CAB-O-SIL LM-130®”, “CAB-O-SIL MS-55®”, “CAB-O-SIL M-5®” by the Cabot Company. They preferably have a particle size that may be nanometric to micrometric, for example ranging approximately from 5 to 200 nm;
    • the hydrophilic clays;
    • the associative polymers such as PEG-150/STEARYL ALCOHOL/SMDI COPOLYMER sold under the name Aculyn 46 by Rohm & Haas, or STEARETH-100/PEG-136/HDI COPOLYMER sold under the name Rheolate FX 1100 by Elementis);
    • and mixtures thereof.

The hydrophilic thickening agent may be chosen from among the associative polymers. By “associative polymer” within the meaning of the present invention there is understood any amphiphilic polymer containing in its structure at least one fatty chain and at least one hydrophilic portion. The associative polymers according to the present invention may be anionic, cationic, non-ionic or amphoteric.

Among the associative anionic polymers there may be cited those containing at least one hydrophilic moiety and at least one fatty-chain allyl ether moiety, more particularly from among those whose hydrophilic moiety is composed of an ethylenically unsaturated anionic monomer, more particularly of a vinyl carboxylic acid and very particularly of an acrylic acid, a methacrylic acid or mixtures thereof, and whose fatty-chain allyl ether moiety corresponds to the monomer of the following formula (I):


CH2═C(R)CH2OBnR (I)

in which R′ denotes H or CH3, B denotes the ethyleneoxy radical, n is zero or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon radical chosen from among the alkyl, arylalkyl, aryl, alkylaryl, cycloalkyl radicals comprising 8 to 30 carbon atoms, preferably 10 to 24, and still more particularly 12 to 18 carbon atoms.

Anionic amphiphilic polymers of this type are described and prepared according to an emulsion polymerization method in EP Patent 0216479.

As associative anionic polymers there may also be cited the anionic polymers containing at least one hydrophilic moiety of olefinically unsaturated carboxylic acid type, and at least one hydrophobic moiety exclusively of the type (C10-C30) alkyl ester of unsaturated carboxylic acid. By way of example there may be cited the anionic polymers described and prepared according to U.S. Pat. Nos. 3,915,921 and 4,509,949.

As cationic associative polymers there may be cited the quaternized cellulose derivatives and the polyacrylates with amino side groups.

The non-ionic associative polymers may be chosen from among:

    • the celluloses modified by groups containing at least one fatty chain, such as, for example, the hydroxyethyl celluloses modified by groups containing at least one fatty chain, such as alkyl groups, especially with C8-C22, arylalkyl, alkylaryl groups, such as NATROSOL PLUS GRADE 330 CS(C16 alkyl) sold by the AQUALON Company,
    • the celluloses modified by polyalkylene glycol alkylphenol ether groups,
    • the guars such as hydroxypropyl guar, modified by groups containing at least one fatty chain, such as an alkyl chain
    • the copolymers of vinylpyrrolidone and fatty-chain hydrophobic monomers;
    • the copolymers of C1-C6 alkyl methacrylates or acrylates and amphiphilic monomers containing at least one fatty chain,
    • the copolymers of hydrophilic methacrylates or acrylates and hydrophobic monomers containing at least one fatty chain, such as, for example, the polyethylene glycol methacrylate/lauryl methacrylate copolymer,
    • the associative polyurethanes,
    • mixtures thereof.

Preferably, the associative polymer is chosen from among the associative polyurethanes. The associative polyurethanes are non-ionic sequenced copolymers containing, in the chain, both hydrophilic sequences, most often of polyoxyethylene nature, and hydrophobic sequences, which may be aliphatic chains alone and/or cycloaliphatic and/or aromatic chains.

In particular, these polymers contain at least two lipophilic hydrocarbon chains having C6 to C30 carbon atoms, separated by a hydrophilic sequence, wherein the hydrocarbon chains may be pendant chains or chains at the end of the hydrophilic sequence. In particular, it is possible to provide one or more pendant chains. In addition, the polymer may contain a hydrocarbon chain at one end or at both ends of a hydrophilic sequence. The associative polyurethanes may be sequenced in triblock or multiblock form. The hydrophobic sequences may therefore be at each end of the chain (for example: triblock copolymer with hydrophilic central sequence) or distributed both at the ends and in the chain (multisequenced copolymer, for example). These polymers may also be grafts or star polymers. Preferably, the associative polyurethanes are triblock copolymers whose hydrophilic sequence is a polyoxyethylene chain containing 50 to 1,000 oxyethylene groups. In general, the associative polyurethanes contain a urethane bond between the hydrophilic sequences, thus explaining the origin of the name.

By way of example of associative polymers that can be used in the invention there may be cited the polymer C16—OC120—C16 of the SERVO DELDEN Company (under the name SER AD FX1100, a molecule with urethane function and weight-average molecular weight of 1300), OE being one oxyethylene moiety. As an associative polymer there may also be used Rheolate 205 with urea function sold by the RHEOX Company or else Rheolate 208 or 204 or even Rheolate FX 1100 by Elementis. These associative polyurethanes are sold in pure form. The product DW 1206B of ROHM & HAAS with C20 alkyl chain and urethane bond, sold as 20% dry material in water, may also be used.

There may also be used solutions or dispersions of these polymers, especially in water or in aqueous alcohol media. By way of examples of such polymers there may be cited SER AD FX1010, SER AD FX1035 and SER AD 1070 of the SERVO DELDEN Company, Rheolate 255, Rheolate 278 and Rheolate 244 sold by the RHEOX Company. There may also be used the product Aculyn 46, DW 1206F and DW 1206J, as well as Acrysol RM 184 or Acrysol 44 of the ROHM & HAAS Company, or else Borchigel LW 44 of the BORCHERS Company.

Fillers:

The composition according to the invention may comprise at least one filler.

The filler or fillers may be present in a content ranging from 0.01% to 50% by weight relative to the total weight of the composition, preferably ranging from 0.01 to 30% by weight.

By fillers there must be understood particles of any shape, colorless or white, mineral or synthetic, insoluble in the medium of the composition regardless of the temperature at which the composition is manufactured. These fillers are used in particular to modify the rheology or the texture of the composition.

The fillers may be mineral or organic of any platelet, spherical or oblong shape, regardless of the crystallographic form (for example layered, cubic, hexagonal, orthorhombic, etc.). There may be cited talc, mica, silica, kaolin, polyamide powders (Nylon®) (Orgasol® of Atochem), the powders of polymethyl methacrylate, the powders of acrylic polymers, poly-β-alanine and polyethylene, the powders of tetrafluoroethylene polymers (Teflon®), lauroyl lysine powders, starch powders, the powders of cellulose, boron nitride, the hollow microspheres of organic polymers, especially the polymeric hollow microspheres of polyvinylidine chloride/acrylonitrile, such as Expancel® (Nobel Industrie), of acrylic acid copolymers (Polytrap of the Dow Corning Company) and the microbeads of silicone resin (Tospearls® of Toshiba, for example), the particles of elastomeric polyorganosiloxanes, precipitated calcium carbonate, magnesium carbonate and bicarbonate, hydroxyapatite, the microspheres of hollow silica (Silica Beads® of Maprecos), the microcapsules of glass or ceramic, clay, quartz, the powder of natural diamond, the metal soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate.

As mineral fillers there may be cited in particular talc, mica, silica, kaolin, boron nitride, precipitated calcium carbonate, magnesium carbonate and bicarbonate, hydroxyapatite, the microspheres of hollow silica (Silica Beads® of Maprecos), the microcapsules of glass or ceramic, clay, quartz, the powder of natural diamond or mixtures thereof.

As silica powder there may be cited:

    • the microspheres of porous silica sold under the trade name SILICA BEADS SB-700 by the MYOSHI Company; “SUNSPHERE® H51”, “SUNSPHERE® H33” by the ASAHI GLASS Company;
    • the microspheres of amorphous silica coated with polydimethylsiloxane sold under the trade name “SA SUNSPHERE® H 33”, “SA SUNSPHERE® H53” by the ASAHI GLASS Company.

Preferably, the mineral filler is silica, talc or a mixture thereof.

Among the spherical fillers there are preferred the silicas, such as the hollow silica microspheres, in particular the SB700® of Miyoshi Kasei.

According to a preferred embodiment. the composition according to the invention additionally comprises at least one other filler. The said at least one other filler may be mineral or organic. It may therefore be a mixture of mineral and organic fillers.

According to one alternative, the composition according to the invention may contain a mineral filler and one other mineral filler, the said mineral fillers being such as defined hereinabove, and possibly at least one organic filler such as defined below.

According to another alternative, the composition according to the invention may contain one mineral filler and one organic filler.

As organic fillers there may be cited in particular the polyamide powders (Nylon® or Orgasol® of Arkema), the powders of acrylic polymers, especially the powders of polymethyl methacrylate, polymethyl methacrylate/ethylene glycol dimethacrylate, allyl polymethacrylate/ethylene glycol dimethacrylate, ethylene glycol dimethacrylate/lauryl methacrylate copolymer, the powders of cellulose, poly-β-alanine and polyethylene, the powders of tetrafluoroethylene polymers (Teflon®), lauroyl lysine, starch, the polymeric hollow microspheres such as those of polyvinylidine chloride/acrylonitrile, such as Expancel® (Nobel Industrie), of acrylic acid copolymers (Polytrap of the Dow Corning Company) and the microbeads of silicone resin (Tospearls® of Toshiba, for example), the particles of elastomeric polyorganosiloxanes, especially obtained by polymerization of organopolysiloxane having at least two hydrogen atoms each bonded to a silicon atom and of an organopolysiloxane comprising at least two groups with ethylenic unsaturation (especially two vinyl groups) in the presence of a platinum catalyst, or also the metal soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate.

Ionic Surfactants

The composition according to the invention may comprise at least one ionic surfactant.

The compositions according to the invention may therefore comprise at least one ionic surfactant and mixture 1) described hereinabove.

The surfactant may be lipophilic and/or hydrophilic, used alone or in combination. The surfactant may be chosen from among the anionic, cationic, amphoteric surfactants.

The surfactant may be present in the composition according to the invention and in a content ranging from 0.1% to 10% by weight relative to the total weight of the composition, and preferably ranging from 0.5% to 8% by weight, and preferentially ranging from 0.5% to 7% by weight.

When the ionic surfactant is an anionic surfactant, it is chosen from among:

    • the carboxylates, such as sodium 2-(2-hydroxyalkyloxy)acetate;
    • the taurates and N-acyl N-methyltaurates;
    • the alkylsulfoacetates;
    • the polypeptides;
    • the anionic derivatives of alkyl polyglycoside (acyl-D-galactoside uronate);
    • the salts of C16-C30 fatty acids, especially those derived from amines, such as triethanolamine stearate and/or 2-amino-2-methylpropane-1,3-diol stearate;
    • the salts of polyoxyethylenated fatty acids, especially those derived from amines or the alkaline salts, and mixtures thereof;
    • the phosphoric esters and their salts such as “DEA oleth-10 phosphate” (Crodafos N 10N of the CRODA Company) or monopotassium monocetyl phosphate (Amphisol K of Givaudan);
    • the sulfosuccinates such as “Disodium PEG-5 citrate lauryl sulfosuccinate” and “Disodium ricinoleamido MEA sulfosuccinate”;
    • the alkyl sulfates;
    • the isethionates and N-acryl isethionates;
    • the acyl glutamates such as “Disodium hydrogenated tallow glutamate” (AMISOFT HS-21 R® sold by the AJINOMOTO Company) and sodium stearyl glutamate (AMISOFT HS-11 PF® sold by the AJINOMOTO Company) and mixtures thereof;
    • the soy derivatives such as potassium soyate;
    • the citrates, such as glyceryl stearate citrate (Axol C 62 Pellets of Degussa);
    • the proline derivatives, such as sodium palmitoyl proline (Sepicalm VG of Seppic), or the mixture of sodium palmitoyl sarcosinate, magnesium palmitoyl glutamate, palmitic acid and palmitoyl proline (Sepifeel One of Seppic);
    • the lactylates, such as sodium stearoyl lactylate (Akoline SL of Karlshamns AB);
    • the sarcosinates, such as sodium palmitoyl sarcosinate (Nikkol sarcosinate PN) or the 75/25 mixture of stearoyl sarcosine and myristoyl sarcosine (Crodasin SM of Croda);
    • the sulfonates, such as Sodium C14-17 alkyl sec sulfonate (Hostapur SAS 60 of Clariant);
    • the glycinates, such as sodium cocoyl glycinate (Amilite GCS-12 of Ajinomoto).

The compositions according to the invention may also contain one or more amphoteric surfactants such as the N-acyl amino acids, such as the N-alkyl aminoacetates and disodium cocoamphodiacetate and the amine oxides such as stearamine oxide, the betaines, the N-alkylamido betaines and their derivatives, the sultaines, the alkyl polyaminocarboxylates, the alkylamphoacetates, or even the silicone surfactants such as the dimethicone copolyol phosphates such as that sold under the trade name PECOSIL PS 100® by the PHOENIX CHEMICAL Company and mixtures thereof.

Preferably, the compositions according to the invention also comprise an elastomer of amphiphilic silicone containing polyalkylene, in particular polyoxyethylene and/or polyoxypropylene hydrophilic groups, sequences or grafts, or polyglycerol hydrophilic groups, sequences or grafts, which are capable in addition of possessing alkyl side groups, in particular lauryl side groups, especially an elastomer of polyglycerol silicone. By way of example, there is used an elastomeric cross-linked organopolysiloxane that may be obtained by cross-linking addition reaction of diorganopolysiloxane containing at least one hydrogen bonded to silicon and polyglycerol compounds having ethylenically unsaturated groups, especially in the presence of platinum catalyst.

As polyglycerol silicone elastomers there may be used those sold under the trade names “KSG-710,” “KSG-810,” “KSG-820,” “KSG-830,” “KSG-840” by the Shin-Etsu Company.

Fibers

The composition may comprise fibers.

By “fiber” there is to be understood an object of length L and of diameter D such that L is greater than D, D being the diameter of the circle in which the cross section of the fiber is inscribed. In particular, the L/D ratio (or form factor) is chosen in the interval ranging from 3.5 to 2,500, preferably from 5 to 500, and better from 5 to 150.

The fibers that can be used in the composition of the invention may be fibers of synthetic or natural, mineral or organic origin. They may be short or long, individual or organized, for example, in braids, hollow or solid. They may have any shape and in particular be of circular or polygonal (square, hexagonal or octagonal) cross section depending on the specific application envisioned. In particular, their ends are blunted or polished to avoid causing injury.

In particular, the fibers have a length ranging from 1 μm to 10 mm, preferably from 0.1 mm to 5 mm and better from 0.3 mm to 3 mm. Their cross section may be contained in a circle of diameter ranging from 2 nm to 500 μl, preferably ranging from 100 nm to 100 μm and better from 1 μm to 50 μm. The weight or titer of the fibers is often expressed in denier or decitex and represents the weight in grams for 9 km of filament. Preferably, the fibers according to the invention have a titer chosen in the interval ranging from 0.01 to 10 denier, preferably from 0.1 to 2 denier and better from 0.3 to 0.7 denier.

Such fibers are described in particular in Applications FR A 2844710, EP A 1201221, the contents of which are incorporated by reference.

The fibers may be present in the composition in a content ranging from 0.1% to 30% by weight relative to the total weight of the composition, preferably ranging from 0.1% to 20% by weight, and preferentially ranging from 0.1% to 10% by weight.

Other Ingredients and/or Additives

The ingredients described below may be used alone or in association with the resins of the invention or as additives to supplement other aforementioned ingredients in association with the said resins according to the invention.

Silicone Elastomers

The compositions according to the invention may additionally comprise an amphiphilic silicone elastomer, preferably chosen from among the polyoxyalkylene and polyglycerol silicone elastomers.

As polyoxyalkylene silicone elastomers there may be cited those described in U.S. Pat. Nos. 5,236,986, 5,412,004, 5,837,793, 5,811,487.

As polyoxyalkylene silicone elastomers there may be used:

    • those of INCI name PEG-10 Dimethicone/Vinyl dimethicone crosspolymer: such as those sold under the trade names “KSG-21”, “KSG-20” by Shin-Etsu;
    • those of INCI name Lauryl PEG-15 Dimethicone/Vinyldimethicone

Crosspolymer: such as those sold under the trade names “KSG-30” and “KSG-31”, “KSG-32” (in isododecane), “KSG-33” (in trioctanoin), “KSG-210”, “KSG-310” (in a mineral oil), “KSG-320” (in isododecane), “KSG-330”, “KSG-340” by the Shin-Etsu Company.

As elastomers of polyglycerol silicones there may be used:

    • those of INCI name Dimethicone (and) Dimethicone/Polyglycerin-3 crosspolymer: such as those sold under the trade names “KSG-710” by Shin-Etsu;
    • those of INCI name Lauryl Dimethicone/Polyglycerin-3 crosspolymer: such as those sold under the trade names “KSG-840” (in squalene) by the Shin-Etsu Company.

These particular elastomers, when they are in association with the resins according to the invention, may make it possible to improve the non-transfer and comfort (flexibility) properties of compositions containing them.

Oils

The composition according to the invention may comprise at least one oil.

The oil may be chosen from among the hydrocarbon oils, the silicone oils, the fluoro oils.

The oil may be chosen from among the volatile oils, the non-volatile oils, and mixtures thereof.

By hydrocarbon oil there is understood an oil formed substantially, even constituted of carbon and hydrogen atoms, and possibly of oxygen, nitrogen atoms, and not containing silicon or fluorine atoms; it may contain ester, ether, amine, amide groups.

By silicone oil there is understood an oil containing at least one silicon atom, and especially containing Si—O groups.

By fluoro oil there is understood an oil containing at least one fluorine atom.

The composition according to the invention may comprise at least one volatile oil.

By “volatile oil” there is understood an oil (or non-aqueous medium) capable of evaporating on contact with the skin in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a volatile cosmetic oil, liquid at room temperature, having especially a non-zero vapor pressure at room temperature and atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40,000 Pa (10−3 to 300 mm Hg), in particular ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mm Hg), and preferentially ranging from 1.3 Pa to 1,300 Pa (0.01 to 10 mm Hg).

In addition, the volatile oil generally has a boiling point, measured at atmospheric pressure, ranging from 150° C. to 260° C., and preferably ranging from 170° C. to 250° C.

The composition according to the invention may comprise a volatile hydrocarbon oil, in particular chosen from among the hydrocarbon oils having a flash point ranging from 40° C. to 102° C., preferably ranging from 40° C. to 55° C., and preferentially ranging from 40° C. to 50° C.

As volatile hydrocarbon oil there may be cited the volatile hydrocarbon oils having 8 to 16 carbon atoms and mixtures thereof, and in particular the C8-C16 branched alkanes such as the C8-C16 iso-alkanes (also referred to as isoparaffins), isododecane, isodecane, isohexadecane and, for example the oils sold under the commercial names of Isopars or Permethyls, the C8-C16 branched esters such as isohexyl neopentanoate, and mixtures thereof. Preferably, the volatile hydrocarbon oil is chosen from among the volatile hydrocarbon oils having 8 to 16 carbon atoms and mixtures thereof, in particular from among isododecane, isodecane, isohexadecane, and in particular is isododecane.

For good properties of color staying power while preserving a matt and comfortable deposit for coloring applications there will be preferred volatile hydrocarbon solvents with 8 to 16 carbon atoms, in particular from 9 to 13 carbon atoms. As C8 to C16 volatile hydrocarbon solvent there may be cited in particular the linear or branched, in particular branched alkanes, such as the C8-C16 iso-alkanes (also referred to as isoparaffins), isododecane, isodecane, isohexadecane, and, for example, the oils sold under the commercial names of Isopars or Permethyls, and mixtures thereof. Preferably, the volatile hydrocarbon solvent having 8 to 16 carbon atoms is chosen from among isododecane, isodecane, isohexadecane, and mixtures thereof. According to a particular embodiment, the volatile solvent is isododecane.

According to another particular embodiment the volatile hydrocarbon solvent is a volatile linear alkane having a flash point in the interval ranging from 70° C. to 120° C., and more particularly from 80° C. to 100° C., and especially being around 89° C.

A volatile linear alkane suitable for the invention is liquid at room temperature (approximately 25° C.).

According to one embodiment, an alkane suitable for the invention may be a volatile linear alkane comprising 8 to 16 carbon atoms in particular 10 to 15 carbon atoms, and more particularly 11 to 13 carbon atoms.

A volatile linear alkane suitable for the invention may advantageously be of vegetable origin.

Such an alkane may be obtained directly or in several steps from a vegetable raw material such as an oil, a butter, a wax, etc.

By way of example of alkane suitable for the invention, there may be mentioned the alkanes described in Patent Application WO 2007/068371 of the Cognis Company.

These alkanes are obtained from fatty alcohols, themselves obtained from copra or palm oil.

By way of example of linear alkane suitable for the invention there may be cited n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13), n-tetradecane (C14), n-pentadecane (C15), n-hexadecane (C16) and n-heptadecane (C17), and mixtures thereof, and in particular the mixture of n-undecane (C11) and n-tridecane (C13) sold under the reference CETIOL UT by the Cognis Company.

According to a particular embodiment, a volatile linear alkane suitable for the invention may be chosen from among n-nonane, n-undecane, n-dodecane, n-tridecane, n-heptadecane, and mixtures thereof.

More particularly, a volatile linear alkane suitable for the invention may be employed in the form of an n-undecane/n-tridecane mixture.

Preferably, in such a mixture, the n-undecane:n-tridecane weight ratio may be 50:50 to 90:10, preferably varying from 60:40: to 80:20, preferably varying from 65:35 to 75:25.

In particular, a composition according to the invention may comprise an n-undecane:n-tridecane mixture in a weight ratio of 70:30. Such a mixture is sold under the trade name CETIOL UT by the COGNIS Company.

For skin makeup products, especially foundations and lipsticks, there will advantageously be used volatile linear hydrocarbon oils having 8 to 16 carbon atoms.

As volatile silicone oil there may be cited the linear or cyclic silicones having 2 to 7 silicon atoms, these silicones possibly containing alkyl or alkoxy groups having 1 to 10 carbon atoms. As volatile silicone oil that can be used in the invention there may be cited in particular octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and mixtures thereof.

The volatile oil may be present in the composition according to the invention in a content ranging from 0.1% to 90% by weight relative to the total weight of the composition, preferably ranging from 1% to 70% by weight, and preferentially ranging from 5% to 50% by weight.

The composition according to the invention may comprise at least one non-volatile oil.

By “non-volatile oil”, there is understood an oil that remains on the horny tissues at room temperature and atmospheric pressure for at least several hours, and having in particular a vapor pressure lower than 10−3 mm Hg (0.13 Pa). A non-volatile oil may also be defined as having an evaporation rate such that, under the conditions defined in the foregoing, the quantity evaporated at the end of 30 minutes is smaller than 0.07 mg/cm2.

As non-volatile hydrocarbon oil there may be used paraffin oil (or vaseline), squalane, hydrogenated polyisobutylene (Parleam oil), perhydrosqualene, mink, turtle, soy oil, sweet almond oil, calophyllum, palm, grapeseed, sesame, corn, arara, colza, sunflower seed, cotton, apricot, castor, avocado, jojoba, olive or cereal germ oil; esters of lanolic acid, oleic acid, lauric acid, stearic acid; the fatty esters, especially with C12-C36, such as isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate or lactate, di(2-ethylhexyl) succinate, diisostearyl malate, glycerine or diglycerine triisostearate; behenic acid, oleic acid, linoleic acid, linolenic acid or isostearic acid; the higher fatty alcohols, especially with C16-C22, such as cetanol, oleic alcohol, linoleic or linolenic alcohol, isostearic alcohol or octyldodecanol; and mixtures thereof.

In particular, to obtain a makeup for achieving matt colors, while preserving comfortable use, both during application and after makeup, there will be used non-volatile C6-C22 hydrocarbon oils, which may be chosen from among:

    • the carbonates of the following formula (1): R1-O—C(═O)—O—R′1, where R1 and R′1, identical or different, represent a saturated or unsaturated (preferably saturated), linear or branched, C4 to C12, and preferentially C5 to C10 alkyl chain, possibly having at least one saturated or unsaturated (preferably saturated) ring;
    • which oils of formula (I) may be dicaprylyl carbonate, sold under the trade name Cetiol CC® by the COGNIS Company, di(2-ethylhexyl) carbonate, sold under the trade name TEGOSOFT DEC® by the Goldschmidt Company, di-isobutyryl carbonate; di-neopentyl carbonate; dipentyl carbonate, di-neoheptyl carbonate; di-heptyl carbonate; di-isononyl carbonate; or di-nonyl carbonate;
    • the monoesters of formula (II): R2-O—C(═O)—R′2, where R2 and R′2, identical or different, represent a saturated or unsaturated (preferably saturated), linear or branched, C4 to C12, and preferentially C5 to C10 alkyl chain, possibly having at least one saturated or unsaturated, preferably saturated ring;
    • which oils of formula (II) may be 2-ethylhexyl isobutyrate, 2-ethylhexyl butyrate, caprylyl butyrate, isononyl isobutyrate, 2-ethylhexyl hexanoate, isononyl hexanoate, neopentyl hexanoate, caprylyl heptanoate, octyl octanoate, sold under the trade name DRAGOXAT EH® by the SYMRISE Company, isononyl isononanoate,
    • the di-esters of the following formula (III): R3-O—C(═O)—R′3-C(═O)—O—R″3, where R3 and R″3, identical or different, represent a saturated or unsaturated (preferably saturated), linear or branched C4 to C12 and preferentially C5 to C10 alkyl chain, possibly having at least one saturated or unsaturated, preferably saturated ring, and R′3 represents a saturated or unsaturated C1 to C4, preferably C2 to C4 alkylene chain, such as, for example, an alkylene chain derived from succinate (in this case R′3 is a saturated C2 alkylene chain), maleate (in this case R′3 is an unsaturated C2 alkylene chain), glutarate (in this case R′3 is a saturated C3 alkylene chain), or adipate (in this case R′3 is a saturated C4 alkylene chain); in particular, R3 and R″3 are chosen from among isobutyl, pentyl, neopentyl, hexyl, heptyl, neoheptyl, 2-ethylhexyl, octyl, nonyl, isononyl; there may be cited preferentially dicaprylyl maleate, especially sold by the ALZO Company; di(2-ethylhexyl) succinate;
    • the ethers of the following formula (IV): R4-O—R4′, where R4 and R′4, identical or different, represent a saturated or unsaturated (preferably saturated), linear or branched C4 to C12 and preferentially C5 to C10 alkyl chain, possibly having at least one saturated or unsaturated, preferably saturated ring; in particular, R4 and R′4 are chosen from among isobutyl, pentyl, neopentyl, hexyl, heptyl, neoheptyl, 2-ethylhexyl, octyl, nonyl, isononyl; among the compounds of formula (IV) there may be cited preferentially dicaprylyl ether, sold under the name of Cetiol OE® by the COGNIS Company;
    • the alkyl tri-esters of formula (V): R5-O—C(O):CH2-CH[—O—C(O)—R′5]-CH2-O—C(O)—R″5, where R5, R′5 and R″5, identical or different, represent a saturated or unsaturated (preferably saturated), linear or branched C4-C10, preferably C5-C8 alkyl chain, in particular, R5, R′5 and R″5 are identical; preferably, R5, R′5 and R″5 (in particular identical) are alkyl radicals of the following fatty acids: caprylic, 2-ethylhexylic, neopentanoic, or neoheptanoic acid; as compound of formula (V) there may be cited preferentially caprylic capric triglyceride, sold in particular under the name MYRITOL 318® by the COGNIS Company;
    • and mixtures thereof.

The C6-C22 non-volatile hydrocarbon oil advantageously used in the said makeup and/or care compositions intended to impart matt quality to the color is dicaprylyl carbonate, in particular sold under the name of CETIOL CC by the COGNIS Company.

Advantageously, when the composition is intended for makeup and/or care of the lips and comprises a non-volatile oil, this oil is chosen from among the phenyl silicone oils. Such an oil is also referred to as phenyl silicone.

By phenyl silicone there is understood an organopolysiloxane substituted by at least one phenyl group.

The phenyl silicone is preferably non-volatile. By “non-volatile” there is understood an oil whose vapor pressure at room temperature and atmospheric pressure is non-zero and lower than 0.13 Pa.

Preferably, the weight-average molecular weight of the phenyl silicone oil is between 500 and 10,000 g/mol.

The silicone oil may be chosen from among the phenyl trimethicones, the phenyl dimethicones, the phenyl trimethylsiloxy diphenylsiloxanes, the diphenyl dimethicones, the diphenyl methyldiphenyl trisiloxanes, the 2-phenylethyl trimethylsiloxysilicates.

The silicone oil may be represented by the formula:

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in which the groups R, independently of one another, represent a methyl or a phenyl. In this formula, the silicone oil preferably comprises at least three phenyl groups, for example at least four, at least five or at least six.

According to another embodiment, the silicone oil is represented by the formula

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in which the groups R, independently of one another, represent a methyl or a phenyl, In this formula, the said organopolysiloxane preferably comprises at least three phenyl groups, for example at least four or at least five.

Mixtures of the phenyl organopolysiloxanes described in the foregoing may be used.

As examples there may be cited mixtures of triphenyl, tetraphenyl or pentaphenyl organopolysiloxanes.

According to another embodiment, the silicone oil is represented by the formula

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in which Me represents methyl, Ph represents phenyl. Such a phenyl silicone is manufactured in particular by Dow Corning under the reference Dow Corning 555 Cosmetic Fluid (INCI name: trimethyl pentaphenyl trisiloxane). The reference Dow Corning 554 Cosmetic Fluid may also be used.

According to another embodiment, the silicone oil is represented by the formula

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in which Me represents methyl, y is between 1 and 1,000, and X represents —CH2-CH(CH3)(Ph).

According to another embodiment, the silicone oil is represented by the formula

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in which —OR′ represents —O—SiMe3, y is between 1 and 1,000 and z is between 1 and 1,000.

The phenyl silicone oil may be chosen from among the phenyl silicones of the following formula (VI):

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in which

    • R1 to R10, independently of one another, are saturated or unsaturated, linear, cyclic or branched C1-C30 hydrocarbon radicals,
    • m, n, p and q are, independently of one another, integral numbers between 0 and 900, with the proviso that the sum of ‘m+n+q’ is different from 0.

Preferably, the sum of ‘m+n+q’ is between 1 and 100. Preferably, the sum of ‘m+n+p+q’ is between 1 and 900, still better between 1 and 800. Preferably, q is equal to 0.

The phenyl silicone oil may be chosen from among the phenyl silicones of the following formula (VII):

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in which

    • R1 to R6, independently of one another, are saturated or unsaturated, linear, cyclic or branched C1-C30 hydrocarbon radicals,
    • m, n and p are, independently of one another, integral numbers between 0 and 100, with the proviso that the sum of ‘n+m’ is between 1 and 100.

Preferably, R1 to R6, independently of one another, represent a saturated, linear or branched C1-C30 hydrocarbon radical, especially C1-C12, and in particular a methyl, ethyl, propyl or butyl radical.

In particular, R1 to R6 may be identical, and in addition may be a methyl radical.

Preferably, formula (VII) may be such that m=1, 2 or 3, and/or n=0 and/or p=0 or 1.

There may be used a phenyl silicone oil of formula (VI) having a viscosity at 25° C. between 5 and 1,500 mm2/s (or 5 to 1500 cSt), preferably having a viscosity between 5 and 1,000 mm2/s (or 5 to 1,000 cSt).

As phenyl silicone oil of formula (VII) there may be used in particular the phenyltrimethicones such as DC556 of Dow Corning (22.5 cSt), Silbione oil 70663V30 of Rhone Poulenc (28 cSt), or the diphenyldimethicones such as the Belsil oils, especially Belsil PDM1000 (1,000 cSt), Belsil PDM 200 (200 cSt) and Belsil PDM 20 (20 cSt) of Wacker. The values in parentheses represent the viscosities at 25° C.

The non-volatile silicone oil may be chosen from among the silicones of formula:

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in which R1, R2, R5 and R6 are, together or separately, an alkyl radical having 1 to 6 carbon atoms, R3 and R4 are, together or separately, an alkyl radical having 1 to 6 carbon atoms or an aryl radical,

X is an alkyl radical having 1 to 6 carbon atoms, a hydroxyl radical or a vinyl radical,

n and p are chosen so as to confer on the oil a weight-average molecular weight smaller than 200,000 g/mol, preferably smaller that 150,000 g/mol and more preferably smaller than 100,000 g/mol.

The non-volatile oil may be present in a content ranging from 0.1% to 70% by weight relative to the total weight of the non-volatile liquid fatty phase, preferably ranging from 0.5% to 60% by weight, and preferentially ranging from 1% to 50% by weight.

For skin makeup products, especially foundations and lipsticks, there will be used advantageously volatile or non-volatile linear silicone oils. The association of resins according to the invention and of a linear silicone oil may make it possible in particular to improve the non-transfer property.

For skin makeup products, especially lipsticks, there will be advantageously used phenyl silicone oils. The association of resins according to the invention and of a phenyl silicone oil may make it possible in particular to improve the gloss and comfort and to reduce the tacky sensation.

Non-Ionic Surfactants

The composition according to the invention may comprise at least one non-ionic surfactant.

In particular, there may be used an emulsifier possessing, at 25° C., an HLB balance (hydrophilic-lipophilic balance) within the meaning of GRIFFIN that is specific to the composition being sought.

The HLB value according to GRIFFIN is defined in J. Soc. Cosm. Chem. 1954 (volume 5), pages 249-256.

The document “Encyclopedia of Chemical Technology, KIRK-OTHMER, volume 22, p. 333-432, 3rd edition, 1979, WILEY, may be consulted for the definition of properties and functions (emulsifying) of surfactants, in particular pp. 347-377 of this reference, for non-ionic surfactants.

The non-ionic surfactants used preferentially in the composition according to the invention are chosen from among:

    • a) the non-ionic surfactants of HLB higher than or equal to 8 to 25° C., used alone or in mixtures; there may be cited in particular:
      • the esters and ethers of oses such as the mixture of cetylstearyl glucoside and of cetyl and stearyl alcohols such as Montanov 68 of Seppic;
      • the methylene and/or oxypropylene ethers (which may contain 1 to 150 oxyethylene and/or oxypropylene groups) of glycerol;
      • the oxyethylene and/or oxypropylene ethers (which may contain 1 to 150 oxyethylene and/or oxypropylene groups) of fatty alcohols (especially of C8-C24 and preferably C12-C18 alcohol) such as the oxyethylene ether of cetearylic alcohol with 30 oxyethylene groups (CTFA name “Ceteareth-30”), the oxyethylene ether of stearyl alcohol with 20 oxyethylene groups (CTFA name “Steareth-20”), and the oxyethylene ether of the mixture of C12-C15 fatty alcohols containing 7 oxyethylene groups (CTFA name “C12-15 Pareth-7”) sold under the trade name NEODOL 25-7® by SHELL CHEMICALS,
      • the esters of fatty acid (especially C8-C24, and preferably C16-C22 acid) and of polyethylene glycol (which may contain 1 to 150 ethylene glycol moieties), such as PEG-50 stearate and PEG-40 monostearate sold under the name MYRJ 52P® by the ICI UNIQUEMA Company,
      • the esters of fatty acid (especially C8-C24, and preferably C16-C22 acid) and of oxyethylene and/or oxypropylene glycerol ethers (which may contain 1 to 150 oxyethylene and/or oxypropylene groups), such as PEG-200 glyceryl monostearate sold under the trade name Simulsol 220 ™® by the SEPPIC Company; polyethoxyl glyceryl stearate with 30 ethylene oxide groups such as the product TAGAT S® sold by the GOLDSCHMIDT Company, polyethoxyl glyceryl oleate with 30 ethylene oxide groups such as the product TAGAT O® sold by the GOLDSCHMIDT Company, polyethoxyl glyceryl cocoate with 30 ethylene oxide groups such as the product VARIONIC LI 13® sold by the SHEREX Company, polyethoxyl glyceryl isostearate with 30 ethylene oxide groups such as the product TAGAT L® sold by the GOLDSCHMIDT Company and polyethoxyl glyceryl laurate with 30 ethylene oxide groups such as the product TAGAT I® of the GOLDSCHMIDT Company,
      • the esters of fatty acid (especially C8-C24, and preferably C16-C22 acid) and of oxyethylene and/or oxypropylene sorbitol ethers (which may contain 1 to 150 oxyethylene and/or oxypropylene groups), such as polysorbate 20 sold under the trade name Tween 20® by the CRODA Company, polysorbate 60 sold under the trade name Tween 60® by the CRODA Company,
      • dimethicone copolyol, such as that sold under the trade name Q2-5220® by the DOW CORNING Company,
      • dimethicone copolyol benzoate (FINSOLV SLB 101® and 201® of the FINTEX Company),
      • the copolymers of propylene oxide and ethylene oxide, also referred to as OE/OP polycondensates,
      • and mixtures thereof.

The OE/OP polycondensates are more particularly copolymers consisting of polyethylene glycol and polypropylene glycol blocks, such as, for example, the polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensates. These triblock polycondensates have, for example, the following chemical structure:


H—(O—CH2—CH2)a—(O—CH(CH3)—CH2)b—(O—CH2—CH2)a—OH,

in which formula a ranges from 2 to 120, and b ranges from 1 to 100.

The OE/OP polycondensate preferably has a weight-average molecular weight ranging from 1,000 to 15,000, and better ranging from 2,000 to 13,000. Advantageously, the said OE/OP polycondensate has a cloud point, at 10 g/L in distilled water, higher than or equal to 20° C., preferably higher than or equal to 60° C. The cloud point is measured according to the ISO 1065 standard. As OE/OP polycondensate that can be used according to the invention there may be cited the polyethylene glycol/polypropylene glycol/polyethylene glycol triblock polycondensates sold under the trade names SYNPERONIC® such as SYNPERONIC PE/L44® and SYNPERONIC PE/F127® by the ICI Company.

b) the non-ionic surfactants of HLB lower than 8 to 25° C., possibly associated with one or more non-ionic surfactants of HLB higher than 8 to 25° C., such as those cited above, such as:

    • the esters and ethers of oses such as sucrose stearate, sucrose cocoate, sorbitan stearate and mixtures thereof such as Arlatone 2121® sold by the ICI Company;
    • the oxyethylene and/or oxypropylene ethers (which may contain 1 to 150 oxyethylene and/or oxypropylene groups) of fatty alcohols (especially of C8-C24 and preferably C12-C18 alcohol) such as the oxyethylene ether of stearyl alcohol with 2 oxyethylene groups (CTFA name “Steareth-2”);
    • the esters of fatty acid (especially C8-C24, and preferably C16-C22 acid) and of polyol, especially of glycerol or sorbitol, such as glyceryl stearate, glyceryl stearate such as the product sold under the trade name TEGIN M® by the GOLDSCHMIDT Company, glyceryl laurate such as the product sold under the trade name IMWITOR312® by the HULS Company, polyglyceryl-2 stearate, sorbitan tristearate, glyceryl ricinoleate;
    • the lecithins, such as the soy lecithins (such as Emulmetik 100 J of Cargill, or Biophilic H of Lucas Meyer);
    • the cyclomethicone/dimethicone copolyol mixture sold under the trade name Q2-3225C® by the DOW CORNING Company.

The non-ionic surfactant may also be chosen from among a C8-C22 alkyl dimethicone polyol, or in other words an oxypropylene and/or oxyethylene polymethyl (C8-C22)alkyl dimethyl methyl siloxane.

The C8-C22 dimethicone copolyol is advantageously a compound of the following formula (I):

embedded image

in which

    • PE represents (—C2H4O)x-(C3H6O)y-R, where R is chosen from among a hydrogen atom and an alkyl radical with 1 to 4 carbon atoms, where x ranges from 1 to 100 and y ranges from 0 to 80, x and y not being simultaneously 0
    • m ranges from 1 to 40
    • n ranges from 10 to 200
    • o ranges from 1 to 100
    • p ranges from 7 to 21
    • q ranges from 0 to 4
      and preferably:

R=H

m=1 to 10
n=10 to 100
o=1 to 30
p=15
q=3

As C8-C22 alkyl dimethicone copolyol there may be cited cetyl dimethicone copolyol such as the product sold under the trade name Abil EM-90 by the Goldschmidt Company.

According to a particular embodiment intended for formulation of stable emulsions, having low viscosity permitting easy application, while conferring on the makeup product staying power of the makeup over time once it has been applied, there will be used advantageously at least one non-ionic silicone surfactant, possibly associated with at least one hydrocarbon surfactant and possibly also at least one wax:

As non-ionic silicone surfactant there may be cited, for example:

a) the polydialkyl silicones with hydrophilic polyoxyalkylene (polyoxyethylene (or POE) and/or polyoxypropylene (or PPO)) side and/or terminal groups. In addition, these silicone surfactants preferably contain linear or branched C1 to C20 alkyl side groups, preferably linear alkyl groups, such as lauryl or cetyl. These surfactants may also carry organosiloxane side groups.

In particular, in this category there may be cited:

    • the polydimethyl siloxanes with POE side groups, such as, in particular, KF-6011, KF-6012, KF-6013, KF-6015, KF-6016 and KF-6017 of the Shin Etsu Company;
    • the polydimethyl siloxanes with POE side groups and alkyl side groups, such as, in particular, Cetyl PEG-PPG 10/1 dimethicone, sold under the trade name ABIL EM90 by the Evonik GOLDSCHMIDT Company;
    • the branched polydimethylsiloxanes with POE side groups, such as, in particular, PEG-9 polydimethyl siloxyethyl dimethicone, sold under the trade name KF-6028 by the Shin Etsu Company;
    • the branched polydimethyl siloxanes with alkyl side groups, such as, in particular, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, sold under the trade name KF-6038 by the Shin Etsu Company;
      b) the polydialkyl silicones with polyglycerol or glycerol side groups. These silicone surfactants additionally contain preferably linear or branched C1 to C20 alkyl side groups, and preferably also linear alkyl groups, such as lauryl or cetyl. Similarly, these silicone and glycerol surfactants may also carry organosiloxane side groups.

In particular, in this category there may be cited:

    • the polydimethyl siloxanes with polyglycerol side groups, such as polyglyceryl-3 disiloxane dimethicone, sold under the trade name KF-6100 by the Shin Etsu Company;
    • the branched polydimethyl siloxanes that also have polyglycerol side groups, such as polyglyceryl-3 polydimethylsiloxyethyl dimethicone, sold under the trade name KF-6104 by the Shin Etsu Company;
    • the branched polydimethyl siloxanes, with polyglycerol side groups and with alkyl side groups, such as lauryl polyglyceryl-3 polydimethyl siloxyethyl dimethicone, sold under the trade name KF-6105 by the Shin Etsu Company;

Among the non-ionic silicone surfactants there is preferred Cetyl PEG/PPG-10/1 dimethicone, sold under the trade name ABIL EM90 by the EVONIK GOLDSCHMIDT Company.

The non-ionic silicone surfactant is advantageously in association with at least one non-ionic organic surfactant.

As non-ionic organic surfactant there may be cited the polyol esters of fatty acids, such as the mono-, di-, tri- or sesqui-oleates or stearates of sorbitol or glycerol, the laurates of glycerol or polyethylene glycol; the polyethylene glycol esters of fatty acids (polyethylene glycol monostearate or monolaurate); the polyoxyethylene sorbitol esters of fatty acids (stearate, oleate); the polyoxyethylene alkyl (lauryl, cetyl, stearyl, octyl)ethers.

Among the non-ionic organic surfactants there are preferred:

    • the polyglycerol esters of fatty acids containing at least three glycerol ether moieties, such as polyglyceryl 3;
    • the polyoxyalkylene (polyoxyethylene and/or polyoxypropylene) esters of fatty acids, preferably containing at least 3 oxyethylene groups;
    • the ethers of fatty alcohols and polyglycerols with at least 3 glyceryl ether moieties;
    • the ethers of fatty alcohols and polyoxyalkylene (POE and/or POE/PPO) with at least 3 POE groups.

Among the non-ionic organic surfactants there is preferred the polyglyceryl-4 isostearate sold under the trade name ISOLAN GI348® by the EVONIK GOLDSCHMIDT Company.

In association with the non-ionic silicone surfactant and the non-ionic organic surfactant there may be advantageously used at least one wax.

Among the waxes there is preferred the mixture of acetyl ethylene glycol stearate/glyceryl tri-stearate, in particular sold under the trade name UNITWIX by the UNITED GUARDIAN Company.

Coloring Materials

The composition according to the invention may comprise at least one coloring material.

The coloring material may be chosen from among the pulverulent coloring materials (especially the pigments and the nacres), the water-soluble or fat-soluble coloring materials.

By pigments there is to be understood particles of any shape, white or colored, mineral or organic, insoluble in the physiological medium, intended to color the composition.

By nacre there will be understood iridescent particles of any iridescent form, especially produced by certain mollusks in their shell, or else synthesized.

The pigments may be white or colored, mineral and/or organic. Among the mineral pigments there may be cited titanium dioxide, possibly surface-treated, the oxides of zirconium or cerium, as well as the oxides of zinc, of iron (black, yellow or red) or of chromium, manganese violet, ultramarine, chromium hydrate and ferric blue, the metal powders such as aluminum powder, copper powder.

Among the organic pigments there may be cited carbon black, the pigments of D & C type, and the lakes based on cochineal carmine, barium, strontium, calcium, aluminum.

There may also be cited the effect pigments such as the particles containing an organic or mineral, natural or synthetic substrate, for example glass, the acrylic resins, polyester, polyurethane, polyethylene terephthalate, the ceramics or the aluminas, wherein the said substrate may or may not be covered with metallic substances, such as aluminum, gold, silver, platinum, copper, bronze, or metal oxides such as titanium dioxide, iron oxide, chromium oxide and mixtures thereof.

The nacreous pigments may be chosen from among the white nacreous pigments such as mica covered with titanium, or bismuth oxychloride, the colored nacreous pigments such as titanium mica covered with iron oxides, titanium mica covered with especially ferric blue or with chromium oxide, titanium mica covered with an organic pigment of the aforesaid type as well as nacreous pigments based on bismuth oxychloride. There may also be used interference pigments, especially with liquid crystals or multilayers.

The term alkyl mentioned in the compounds cited in the foregoing denotes in particular an alkyl group having 1 to 30 carbon atoms, preferably having 5 to 16 carbon atoms. Hydrophobic-treated pigments are described in particular in Application EP A 1086683.

The pulverulent coloring materials such as described in the foregoing may be completely or partly surface-treated with a hydrophobic agent, in particular a compound of silicone nature, a compound of fluoro nature, a compound of fluorosilicone nature, a fatty acid or amino acid or one of the mixtures thereof.

By silicone compound there is understood a compound comprising at least one silicon atom.

By fluoro compound there is understood a compound comprising at least one fluorine atom.

By fluorosilicone compound there is understood a compound comprising at least one fluorine atom and at least one silicon atom.

By way of example, the hydrophobic treatment agent may be chosen from among the silicones such as the methicones, the dimethicones, the perfluoroalkylsilanes, the perfluoroalkyl silazanes, triethoxy caprylylsilane, triethoxysilylethyl polydimethylsiloxyethyl hexyl dimethicone; the fatty acids such as stearic acid, the metal soaps such as aluminum dimyristate, the aluminum salt of hydrogenated suet glutamate; the perfluoroalkyl phosphates, the polyoxides of hexafluoropropylene, the polyorganosiloxanes comprising perfluoroalkyl perfluoro polyether groups, the silicone-grafted acrylic polymers (especially described in Application JP A 05-339125, the contents of which are incorporated by reference); the amino acids; the N-acyl amino acids or their salts; lecithin, isopropyl trisostearyl titanate, isostearyl sebacate, and mixtures thereof.

The surface-treated pulverulent coloring materials may be prepared according to surface-treatment techniques of chemical, electronic, mechano-chemical or mechanical nature that are well known to those skilled in the art. Commercial products may also be used.

The surface agent may be absorbed or adsorbed on the pulverulent coloring materials by solvent evaporation, chemical reaction and creation of a covalent bond.

According to one variant, the surface treatment consists in coating the pulverulent coloring materials.

The coating may represent 1 to 300% by weight of the weight of the untreated pulverulent coloring materials, for example 5 to 200%, in particular 10 to 100% by weight of the weight of the untreated pulverulent coloring materials.

The coating may represent 0.1 to 10% by weight, and in particular 1 to 5% by weight of the total weight of the coated pulverulent coloring material.

The coating may be applied, for example, by adsorption of a liquid surface agent on the surface of the pulverulent coloring materials by simply mixing the pulverulent coloring materials and the said surface agent under agitation, possibly in the hot, prior to incorporating the particles in the other ingredients of the makeup or care composition.

The coating may be applied, for example, by chemical reaction of a surface agent with the surface of the pulverulent coloring materials and creation of a covalent bond between the surface agent and the pulverulent coloring materials. This method is described in particular in U.S. Pat. No. 4,578,266.

The chemical surface treatment may consist in diluting the surface agent in a volatile solvent, dispersing the pulverulent coloring materials in this mixture, then slowly evaporating the volatile solvent, so that the surface agent is deposited on the surface of the pulverulent coloring materials.

Fluoro Surface Went

The solid particles may be completely or partly surface-treated with a compound of fluoro nature.

The fluoro surface agents may be chosen from among the perfluoroalkyl phosphates, the perfluoro polyethers, polytetrafluopolyethylene (PTFE) and the perfluoroalkanes.

The perfluoro polyethers are described in particular in Patent Application EP A 486135, and are sold under the trade names FOMBLIN by the MONTEFLUOS Company.

Perfluoroalkyl phosphates are described in particular in Application JP H05-86984. The perfluoroalkyl diethanolamine phosphate sold by Asahi Glass under the reference AsahiGuard AG530 may be used.

The perfluoroalkanes may be linear or cyclic perfluoroalkanes. Among the linear perfluoroalkanes there may be cited the series of linear alkanes, such as perfluorooctane, perfluorononane or perfluorodecane. Among the cyclic perfluoroalkanes there may be cited the perfluorocycloalkanes, the perfluoro(alkylcycloalkanes), the perfluoropolycycloalkanes, the perfluoro aromatic hydrocarbons (the perfluoroarenes). Among the perfluoroalkanes there may also be cited the perfluoro organohydrocarbon compounds containing at least one hetero atom.

Among the perfluorocycloalkanes and the perfluoro(alkylcycloalcanes) there may be cited perfluorodecalin sold under the trade name of “FLUTEC PP5 GMP” by the RHODIA Company, perfluoro(methyldecalin), the perfluoro(C3-C5 alkyl-cyclohexanes) such as perfluoro(butylcyclohexane).

Among the perfluoropolycycloalkanes there may be cited the derivatives of bicyclo [3.3.1] nonane such as perfluorotrimethylbicyclo [3.3.1] nonane, the derivatives of adamantane, such as perfluorodimethyladamantane, and the perfluoro derivatives of hydrogenated phenanthrene, such as tetracosafluoro-tetradecahydrophenanthrene.

Among the perfluorearenes there may be cited the perfluoro derivatives of naphthalene such as perfluoronaphthalene and perfluoromethyl-1-naphthalene.

By way of example of commercial references of pigments treated with a fluoro compound there may be cited:

    • Yellow iron oxide/perfluoroalkyl phosphate, sold in particular under the reference PF 5 Yellow 601 by the Daito Kasei Company,
    • Red iron oxide/perfluoroalkyl phosphate, sold in particular under the reference PF 5 Red R 516L by the Daito Kasei Company,
    • Black iron oxide/perfluoroalkyl phosphate, sold in particular under the reference PF 5 Black BL 100 by the Daito Kasei Company,
    • Titanium dioxide/perfluoroalkyl phosphate, sold in particular under the reference PF 5 TiO2 CR 50 by the Daito Kasei Company,
    • Yellow iron oxide/perfluoropolymethyl isopropyl ether, sold in particular under the reference iron oxide yellow BF-25-3 by the Toshiki Company,
    • DC Red 7/perfluoropolymethyl isopropyl ether, sold in particular under the reference D&C Red 7 FHC by Cardre Inc.,
    • DC Red 6/PTFE, sold in particular under the reference T 9506 by the Warner-Jenkinson Company,

Fatty Acid or Amino Acid Treatment Agent

The hydrophobic treatment agent may be chosen from among the fatty acids, such as stearic acid; the metal soaps, such as aluminum dimyristate, the aluminum salt of hydrogenated suet glutamate; the amino acids; the N-acyl amino acids or their salts; lecithin, isopropyl trisostearyl titanate (or also referred to as ITT), and mixtures thereof.

The N-acyl amino acids may comprise an acyl group having 8 to 22 carbon atoms, such as, for example, a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl, cocoyl group. The salts of these compounds may be the aluminum, magnesium, calcium, zirconium, zinc, sodium, potassium salts. The amino acid may be, for example, lysine, glutamic acid, alanine.

The fatty acids in the present invention are in particular acids with hydrocarbon chains having 1 to 30 carbon atoms, preferably having 5 to 18 carbon atoms. The hydrocarbon chain may be saturated, monounsaturated or polyunsaturated.

By way of example of pigments coated with fatty acids there may be cited those sold under the commercial reference NAI-TAO-77891, NAI-C33-8073-10, NAI-C33-8075, NAI-C47-051-10, NAI-C33-115, NAI-C33-134, NAI-C33-8001-10, NAI-C33-7001-10, NAI-C33-9001-10 of the MIYOSHI KASEI Company.

The water-soluble coloring agents are, for example beet juice, Methylene Blue.

The synthetic or natural fat-soluble coloring agents are, for example, DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet 2, DC Orange 5, Sudan Red, the carotenes (β-carotene, lycopene), the xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan Brown, Quinoline Yellow, annatto, curcumin.

The coloring materials, in particular the pigments treated with a hydrophobic agent, may be present in the composition in a content ranging from 0.1% to 50% by weight relative to the total weight of the composition, preferably ranging from 0.5% to 30% by weight and preferentially ranging from 1% to 20% by weight.

The composition according to the invention may also contain ingredients commonly used in cosmetics, such as vitamins, oligo elements, softening agents, sequestering agents, fragrances, alkalinizing or acidifying agents, preservatives, sunscreens, anti-oxidants, anti-hair loss agents, anti-hair loss agents, propellants, or mixtures thereof.

Of course, the person skilled in the art will take care to choose this or these possible supplementary compounds and/or the quantity thereof so that the advantageous properties of the corresponding composition according to the invention are not or substantially not altered by the envisioned addition.

According to a preferred embodiment, the composition according to the invention is a lipstick.

According to a preferred embodiment, the composition according to the invention is in liquid form at 25° C.

According to another embodiment, the composition is in solid form at 25° C. In the case of a lipstick, it may be shaped as a stick or cast in a small tub, for example.

According to another aspect, the invention also relates to a method for makeup or cosmetic care of horny tissues comprising a step of application of a composition according to the invention on the said tissues.

According to another aspect, the invention also relates to a cosmetic set comprising:

    • i) a container defining at least one compartment, the said container being closed by a closure element; and
    • ii) a composition disposed in the interior of the said compartment, the composition being in conformity with the invention.

The container may be in any appropriate form. In particular, it may be in the form of a bottle, tube, jar, case, box, sachet or casing.

The closure element may be in the form of a removable stopper, cover, lid, tear-off strip, or capsule, especially of the type containing a body fixed to the container and a cap hinged on the body. It may also be in the form of an element assuring selective closure of the container, especially a pump, a valve, or a flap.

The container may be associated with an applicator, especially in the form of a brush containing an arrangement of bristles held by a twisted wire. Such a twisted brush is described in particular in U.S. Pat. No. 4,887,622. It may also be in the form of a comb containing a plurality of application elements, obtained in particular by molding. Such combs are described, for example, in French Patent 2796529. The applicator may be in the form of a makeup brush, such as described, for example, in French Patent 2722380. The applicator may be in the form of a block of foam or elastomer, of a felt, or of a spatula. The applicator may be unattached (puff or sponge) or integral with a rod carried by the closure element, such as described, for example, in U.S. Pat. No. 5,492,426. The applicator may be integral with the container, such as described, for example, in French Patent FR 2761959.

The product may be contained directly in the container, or indirectly. By way of example, the product may be disposed on an impregnated substrate, especially in the form of a wipe or pad, and disposed (as single or multiple pieces) in a box or in a sachet. Such a substrate incorporating the product is described, for example, in Application WO 01/03538.

The closure element may be coupled with the container by a threaded connection. Alternatively, the coupling between the closure element and the container is established by other than a threaded connection, especially via a bayonet mechanism, by snap fastening, clamping, welding, adhesive bonding, or by magnetic attraction. By “snap fastening” there is understood in particular any system in which one portion, especially the closure element, is elastically deformed involving passage over a strip or rib of material, then the said portion returns elastically to the non-restrained position after passing over the strip or rib.

The container may be made at least partly of thermoplastic material. By way of examples of thermoplastic materials there may be cited polypropylene or polyethylene. Alternatively, the container is made of non-thermoplastic material, especially of glass or metal (or alloy).

The container may have rigid walls or deformable walls, especially in the form of a tube or tubular bottle.

The container may comprise means intended to bring about or facilitate distribution of the composition. By way of example, the container may have deformable walls, so as to cause discharge of the composition in response to overpressure in the interior of the container, which overpressure is caused by elastic (or non-elastic) squeezing of the walls of the container. Alternatively, especially when the product is in the form of a stick, it may be entrained by a piston mechanism. Also in the case of a stick, especially of makeup product (lipstick, foundation, etc.), the container may comprise a mechanism, especially with a rack, or with a threaded rod, or with a helical ramp, and capable of displacing a stick in the direction of the said opening. Such a mechanism is described, for example, in French Patent 2806273 or in French Patent 2775566. Such a mechanism for a liquid product is described in French Patent 2727609.

The container may consist of a casing with a bottom defining at least one housing containing the composition, and a cover, especially hinged on the bottom, and capable of covering the said bottom at least partly. Such a casing is described, for example, in Application WO 03/018423 or in French Patent 2791042.

The container may be equipped with a wiper arranged in the vicinity of the opening of the container. Such a wiper makes it possible to wipe the applicator and possibly the rod with which it may be integral. Such a wiper is described, for example, in French Patent 2792618.

The composition may be at atmospheric pressure inside the container (at room temperature) or may be pressurized, especially by means of a propellant gas (aerosol). In the latter case, the container is equipped with a valve (of the type of those used for aerosols).

    • Another object of the present invention is a method for makeup of the lips, comprising application of a composition according to the invention on the said lips.

Protocol for Measuring the Staving Power:

The staying power index of the deposit obtained with the composition according to the invention is determined according to the measurement protocol described below.

There is prepared a substrate (rectangle of 40 mm×70 mm) composed of an acrylic lining (hypoallergenic acrylic adhesive on polyethylene film sold under the trade name BLENDERME ref FH5000-55113 by the 3M Santé Company) adhesively bonded onto a layer of adhesive polyethylene foam on the face opposite to that on which there is fixed the adhesive plaster (layer of foam sold under the trade name RE40X70EP3 by the JOINT TECHNIQUE LYONNAIS IND Company).

The color L*0a*0b*0 of the substrate on the side of the acrylic-lined face is measured by means of a MINOLTA CR 300 colorimeter.

The substrate prepared in this way is preheated on a hot plate maintained at a temperature of 40° C., so that the surface of the substrate is maintained at a temperature of 33° C.±1° C. While the substrate is left on the hot plate, the composition is applied over the entire non-adhesive surface of the substrate (or in other words over the acrylic-lined surface) by spreading by means of a brush to obtain a deposit of the composition of approximately 15 μm, then it is left to dry for 10 minutes.

After drying, the color L*a*b of the film obtained in this way is measured.

The color difference ΔE1 between the color of the film relative to the color of the uncoated substrate is then determined by the following relationship.


ΔE1=√{square root over ((L*−Lo*)2+(a*−ao*)2+(b*−bo*)2)}{square root over ((L*−Lo*)2+(a*−ao*)2+(b*−bo*)2)}{square root over ((L*−Lo*)2+(a*−ao*)2+(b*−bo*)2)}

The substrate is then bonded via its adhesive face (adhesive face of the foam layer) onto an anvil with a diameter of 20 mm, equipped with a screw thread. A specimen of the substrate/deposit assembly is then cut out by means of a hollow punch with a diameter of 18 mm. The anvil is then screwed onto a press (STATIF MANUEL IMADA SV-2 of the SOMECO Company) equipped with a dynamometer (IMADA DPS-20 of the SOMECO Company).

On a white photocopier paper sheet of weight 80 g/m2 there is drawn a strip of 33 mm width and 29.7 cm length, a first line is traced at 2 cm from the edge of the sheet, then a second line at 5 cm from the edge of the sheet, the first and second lines thus defining a box on the strip; then a first mark and a second mark are made in the strip at coordinates of 8 cm and 16 cm respectively from the second line. 20 μL water is place on the first mark and 10 μL refined sunflower seed oil (sold by the LESIEUR Company) on the second mark.

The white paper is placed on the base of the press then the specimen placed on the box of the strip of paper is pressed at a pressure of approximately 300 g/cm2 exerted for 30 seconds. Then the press is relaxed and the specimen is replaced just after the second line (therefore at the side of the box), a pressure of approximately 300 g/cm2 is applied once again and, as soon as contact is established, the paper is displaced in a straight line at a speed of 1 cm/s over the entire length of the strip, in such a way that the specimen traverses the deposits of water and oil.

After withdrawal of the specimen, part of the deposit has transferred onto the paper. The color L*′, a*′, b*′ of the deposit remaining on the specimen is then measured.

The color difference ΔE2 between the color of the deposit remaining of the specimen relative to the color of the uncoated substrate is then determined by the following relationship.


ΔE2=√{square root over ((L*′−Lo*)2+(a*′−ao*)2+(b*′−bo*)2)}{square root over ((L*′−Lo*)2+(a*′−ao*)2+(b*′−bo*)2)}{square root over ((L*′−Lo*)2+(a*′−ao*)2+(b*′−bo*)2)}

The staying power index of the composition, expressed as a percentage, is equal to the ratio:


100×ΔE2/ΔE1

The measurement is carried out on 6 substrates in succession and the value of the staying power corresponds to the mean of the 6 measurements obtained with the 6 substrates.

In the Application, the contents are expressed in weight relative to the total weight of the composition, unless otherwise explicitly indicated.

The purpose of the following examples is to illustrate the compositions and methods according to this invention, but in no case are they limitative of the scope of the invention. All the parts and percentages in the examples are by weight, and all the measurements were obtained at approximately 23° C., unless otherwise indicated.

EXAMPLE NO. 1

Obtaining the Mixture of MQ and Propyl T Resins According to the Invention

Materials

MQ resin=an MQ resin of formula M0.43Q0.57 and of Mn=3,230 dissolved in xylene with 70.8% by weight of solids. The MQ resin was manufactured according to the techniques described by Daudt in U.S. Pat. No. 2,676,182.

T-Propyl resin=a propyl silsesquioxane resin at 74.8% by weight in toluene. The propyl silsesquioxane resin was obtained by hydrolysis of propyl trichlorosilane.

Different solutions of MQ resin and propyl T resin are mixed in a three-necked flask equipped with an agitator. Aliquots of each mixture are placed in an aluminum cup of 2 inches diameter and heated under vacuum at a temperature of 110° C. for one hour, followed by 1 hour 25 minutes at 140° C. Visual qualitative observations are made of the clarity and hardness of the mixtures obtained (see Table 1 below):

TABLE 1
% by
Propyl TDriedweight of
Example #MQ (g)(g)Aliquot (g)aliquot (g)MQ resinClarityHardness
1-a0.0013.462.04751.53610.0ClearGummy
appearance;
soft solid
1-b1.4012.032.06431.54159.9ClearSoft solid
1-c2.8816.742.08401.551714.0ClearHarder than
1-b
1-d4.199.392.07461.541429.7ClearHarder than
1-c
1-e5.728.142.10661.560639.9ClearHarder than
1-d
1-f7.116.822.02571.496849.6ClearHarder than
1-e

The results obtained show the unexpected miscibility of the MQ and propyl T resins, based on the clarity of the mixture without solvent and the increase of hardness accompanying the increase in proportion of MQ resin.

According to an alternative denoted 1-g, there is used the mixture of resins described in Example 22 of Application WO 2005/075567, in which the weight ratio between the MQ resin and the propyl T resin is 85/15.

According to an alternative denoted 1-h, there is used the mixture described in Example 13 of Patent Application WO 2007/145765, in which the weight ratio between the MQ resin and the propyl T resin is 60/40.

EXAMPLE NO. 2

Liquid Lipstick

The following formulas of liquid lipstick were prepared.

CompositionCompositionComparative
1 according to2 according tocomposition
the inventionthe invention3 (% by
CompoundCommercial name(% by weight)(% by weight)weight)
Butyl acrylate copolymer containingDOW CORNING FA31.2531.2537.5
dendritic silicone side chains:4002 ID SILICONE
[TRI(TRIMETHYLSILOXY)ACRYLATE OF DOW
SILOXYETHYLCORNING
DIMETHYLSILOXY]
SILYLPROPYL
METHACRYLATE IN
ISODODECANE 40/60
MQ-PROPYL T (60:40) SILICONE(DOW CORNING MQ-4.20
RESIN (according to Example 1-h1603 S of DOW
hereinabove) AT 60.0% INCORNING)
ISODODECANE
MQ-PROPYL T (85:15) SILICONE(DOW CORNING MQ-4.20
RESIN (according to Example 1-g1603 H of DOW
hereinabove) AT 60.0% INCORNING)
ISODODECANE
ISODODECANEISODODECANE OF2.052.05
INEOS
SQUALANEPHYTOSQUALAN12.0212.0212.02
of SOPHIM
OCTYLDODECANOLEUTANOL G of13.6213.6213.62
COGNIS
POLYBUTENEINDOPOL H 100 of10.6510.6510.65
INEOS
ISOPROPYLPARABEN (and)LIQUAPAR OIL of0.650.650.65
ISOBUTYLPARABEN (and)ISP
BUTYLPARABEN
RED 7UNIPURE RED LC0.230.230.23
3079 OR of LCW
(SENSIENT)
IRON OXIDESSUNPURO BLACK0.050.050.05
IRON OXIDE C33-7001
of SUN
MICA (and) TITANIUM CLOISONNE SPARKLE1.001.001.00
DIOXIDE (and) GOLD 222 J of
IRON OXIDESENGELHARD
CALCIUM ALUMINUMMETASHINE ME 20402.502.502.50
BOROSILICATE (and) SILVERPS of NIPPON SHEET
GLASS
TRIMETHYLSILOXYPHENYLWACKER-BELSIL PDM15.9815.9815.98
DIMETHICONE1000 of WACKER
SILICA DIMETHYL SILYLATEAEROSIL R 972 of5.005.005.00
EVONIK DEGUSSA
SILICAAEROSIL 200 of0.500.500.50
EVONIK DEGUSSA
FRAGRANCEGOURMANDISE P1060.300.300.30
347 of ROBERTET
TOTAL:100100100

Mode of Operation:

    • a. The fillers and pigments that may possibly be present are ground in a part of the oil phase.
    • b. The rest of the fat-soluble ingredients are then mixed at a temperature on the order of 100° C. The ground mixture is then added to the oil phase.
    • c. The mixture is subjected to RAYNERI agitation for 45 minutes and the siloxane resin is added at room temperature.
    • d. The formula is poured into sealed boiling vessels containing isododecane.

Comparative composition 3 contains substantially the same proportion of dry material of film-forming polymer as compositions 1 and 2 according to the invention (siloxane resin+vinyl polymer with moiety derived from carbosiloxane dendrimer).

For composition 1 according to the invention containing a vinyl polymer comprising at least one moiety derived from carbosiloxane dendrimer and an MQ-T propyl siloxane resin, a value of 27.28±3.17 is measured for the holding power.

For composition 2 according to the invention containing a vinyl polymer comprising at least one moiety derived from carbosiloxane dendrimer and an MQ-T propyl siloxane resin, a value of 24.75±2.24 is measured for the holding power.

For comparative composition 3, which does not contain siloxane resin, a value of 18.32±0.56 is measured for the holding, power.

Thus a better holding power is obtained with the compositions according to the invention.

Example 3

Preparation of a Poly(Isobornyl Acrylate/Isobornyl Methacrylate/Isobutyl Acrylate/Acrylic Acid) Polymer

300 g isododecane is introduced into a 1-liter reactor, then the temperature is raised so as to change from room temperature (25° C.) to 90° C. in 1 hour.

There is then added, at 90° C. and in 1 hour, 105 g isobornyl methacrylate (manufactured by Arkema), 105 g isobornyl acrylate (manufactured by Arkema) and 1.8 g 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (Trigonox® D 141 of Akzo Nobel).

The mixture is maintained at 90° C. for 1 hour 30 minutes.

To the preceding mixture there is then added, again at 90° C. and in 30 minutes, 75 g isobutyl acrylate (manufactured by Fluka), 15 g acrylic acid and 1.2 g 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane.

The mixture is maintained at 90° C. for 3 hours, then the whole is cooled.

There is obtained a solution of 50% of polymer active material in isododecane.

There is obtained a polymer comprising a rigid first sequence of poly(isobornyl acrylate/isobornyl methacrylate) having a Tg of 110° C., a flexible second sequence of poly(isobutyl acrylate/acrylic acid) having a Tg of −9° C. and an intermediate sequence, which is a statistical polymer of isobornyl acrylate/isobornyl methacrylate/isobutyl acrylate/acrylic acid.

EXAMPLE NO. 4

Liquid Lipsticks

The following compositions 3 and 4 are prepared:

Composition 3Composition 4
according to theaccording to the
inventioninvention
Percentages in %Percentages in %
Compoundsby weightby weight
2-OCTYL DODECANOL9.439.43
REFINED VEGETABLE PERHYDROSQUALENE5.055.05
(PHYTOSQUALAN of SOPHIM)
ALUMINUM LAKE OF BRILLIANT YELLOW FCF2.582.58
ON ALUMINA (42/58) (CI: 15985:1 + 77002
ALUMINUM LAKE OF BRILLIANT BLUE FCF0.160.16
ON ALUMINA (12/88) (CI: 42090:2 + 77002)
CALCIUM SALT OF LITHOL RED B0.590.59
RUTILE TITANIUM OXIDE TREATED WITH2.742.74
ALUMINA/SILICA/TRI-METHYLOLPROPANE (CI:
77891)
BLACK IRON OXIDE (CI: 77499)0.320.32
MIXTURE OF (40/30/30) ISO-PROPYL, ISO-BUTYL,0.650.65
N-BUTYL P-HYDROXYBENZOATES
(LIQUAPAR OIL OF ISP)
POLY PHENYLTRIMETHYLSILOXY25.0325.03
DIMETHYLSILOXANE (VISCOSITY: 1000 CST-
MW: 3000-G/MOL) (BELSIL PDM 1000 of
WACKER)
MICA-TITANIUM DIOXIDE-BROWN IRON OXIDE22
(77/21/4) (SIZE: 16-128 MICRONS)
FRAGRANCE0.30.3
POLYBUTENE (MONOOLEFINS/ISOPARAFFINS(10.6510.65
(MW: 920) (INDOPOL H 100 of INEOS)
POLY(ISOBORNYL METHACRYLATE-CO-3030
ISOBORNYL ACRYLATE-CO-ISOBUTYL
ACRYLATE-CO-ACRYLIC ACID such as prepared in
Example 2 hereinabove (50% polymer in 50%
isododecane)
MQ-PROPYL T (60:40) SILICONE RESIN (according5.1
to Example 1-h hereinabove) AT 60.0% IN
ISODODECANE (DOW CORNING MQ-1603 S OF
DOW CORNING)
MQ-PROPYL T (85:15) SILICONE RESIN (according5.1
to Example 1-g hereinabove) AT 60.0% IN
ISODODECANE (DOW CORNING MQ-1603 H OF
DOW CORNING)
HYDROPHILIC PYROGENIC SILICA0.50.5
(AEROSIL 200 OF EVONIK DEGUSSA)
HYDROPHOBIC PYROGENIC SILICA, SURFACE-55
TREATED BY DI-METHYLSILANE
(AEROSIL R 972 OF EVONIK DEGUSSA)
Total:100100

Mode of Operation:

    • e. The fillers and pigments that may possibly be present are ground in a part of the oil phase.
    • b. The rest of the fat-soluble ingredients is then mixed at a temperature on the order of 100° C. The ground mixture is then added to the oil phase.
    • c. The mixture is subjected to RAYNERI agitation for 45 minutes and the siloxane resin is added at room temperature.
    • d. The formula is poured into sealed boiling vessels containing isododecane.

Composition 3 according to the invention contains 15% polymer (weight as dry extract) prepared according to Example 2 and 3.5% (weight as dry extract) of siloxane resin prepared according to Example 1-C), or in other words a total of 18.5% of film-forming polymer.

Comparative composition 4 contains 18.5% polymer (weight as dry extract) prepared according to Example 2.

Comparative composition 4 is very viscous and tacky and is very thick during application. It is uncomfortable on the lips, because the film formed is very thick and tacky.

Composition 3 according to the invention is much more agreeable (gliding) during application, and it forms a very much thinner and more comfortable deposit.

The foregoing example is reproduced by replacing the 60:40 weight/weight MQ:T resin in the composition by the MQ:T resin such as prepared in Example 1-f (which corresponds to a (51:49) MQ:T resin), also solubilized in 60% isododecane. A result similar to that obtained with the (60:40) MQ:T resin is obtained.