Bolich Jr., Raymond Edward (Montgomery, OH)
Aylor, Robert Benson (Blue Ash, OH)

05/313908

12/23/1975

12/11/1972

Download PDF 3928251       PDF help

Click for automatic bibliography generation

The Procter & Gamble Company (Cincinnati, OH)

510/125

510/424, 424/70.310, 424/70.220, 510/425, 424/70.210, 510/494, 510/506, 424/70.190

C11D1/94; C11D17/00; C11D1/12; C11D1/29; C11D1/66; C11D1/72; C11D1/722; C11D1/74; C11D1/88; C11D1/02; C11D1/92

252/545,549,554,526,546,DIG.13,DIG.14,DIG.7

3562170		February 1971	Gorayan et al.
3649543		March 1972	Cahn et al.
3666671	DETERGENT COMPOSITION AND PROCESS OF SHAMPOOING HAIR THEREWITH	May 1972	Kalopissis et al.
3755559		August 1973	Hewitt

Lovering, Richard D.

Aylor, Robert Hemingway Ronald Allen George B. L. W.

What is claimed is

1. A mild shampoo composition comprising surfactants and water, said surfactants consisting of a mixture of:

2. The composition of claim 1 wherein the anionic surfactant is present in an amount of from about 2% to about 15% by weight of the composition.

3. The composition of claim 2 wherein the molecular ratio of the anionic surfactant to the zwitterionic surfactant is from about 1:1 to about 3:1.

4. The composition of claim 2 wherein the molecular ratio of the anionic surfactant to the zwitterionic surfactant is from about 1:1 to about 2:1.

5. The composition of claim 1 having a pH of about 7.0.

6. The composition of claim 1 wherein the zwitterionic surfactant has the formula

7. The composition of claim 6 wherein Y is a carboxylate group.

8. The composition of claim 6 wherein Y is a sulfonate group.

9. The composition of claim 1 wherein the zwitterionic surfactant has the formula

10. The composition of claim 1 wherein the anionic surfactant is a sodium salt of a fatty alcohol polyethoxy ether sulfate containing a fatty alkyl group containing from about 10 to about 14 carbon atoms and about 3 ethoxy moieties per molecule.

11. The composition of claim 1 wherein R is a fatty acid amido group containing from about 10 to about 14 carbon atoms and n is about 3.

12. The composition of claim 1 wherein the nonionic surfactant is a polyethoxylataed mono fatty acid ester of sorbitol wherein the fatty acid contains from about 10 to about 16 carbon atoms and wherein there are from about 15 to about 40 ethoxy moieties per molecule.

13. The composition of claim 12 wherein the fatty acid is lauric acid.

14. The composition of claim 1 wherein the non-ionic surfactant is a polyethoxylated alkyl alcohol wherein said alkyl alcohol contains from about 10 to about 14 carbon atoms and wherein there are from about 15 to about 40 ethoxy moieties per molecule.

15. The composition of claim 1 wherein the nonionic surfactant is a polyethoxylated polypropylene glycol wherein said polypropylene glycol has a molecular weight of from about 8,000 to about 12,000 and said polyethoxylated polypropylene glycol contains from about 20 to about 100 ethoxy moieties per molecule.

16. The composition of claim 1 wherein the anionic surfactant is a sodium salt of a polyethoxylated fatty alcohol sulfosuccinate monoester, wherein said fatty alcohol contains from about 10 to about 14 carbon atoms and said polyethoxylated fatty alcohol contains about 3 ethoxy moieties per molecule.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to shampoo compositions, particularly those which are very mild and have a minimal tendency to sting the eyes.

2. Prior Art

Compositions containing the reaction products of ethoxylated anionic surfactants and certain specific amphoteric surfactants and polyethoxylated nonionic surfactants have been disclosed in U.S. Pat. Nos. 2,999,069 and 3,055,836, Masci and Poirier. Similar disclosures are contained in the corresponding foreign patent applications such as British Pat. Nos. 850,514, 850,515, and 921,122; and Canadian Pat. No. 595,532. In each of these patents, the disclosure is of a reaction product formed between the anionic surfactant and the amphoteric surfactant which contains ternary nitrogen groups.

The compositions of this invention are all extremely mild and have minimum or no eye sting. This is a very desirable combination of characteristics. For example, children cannot keep shampoo out of their eyes and the resulting pain can be extremely damaging to good relations between the parent and child. Yet, one would not want to have a shampoo which didn't sting, but which caused serious damage, since then one needs the pain to encourage a thorough rinsing of the eye. Thus, the combination of mildness and lack of eye sting is extremely desirable.

The prior art compositions discussed hereinbefore do sting the eyes, but less than conventional shampoos. The compositions of this invention are as mild and in many instances milder than the prior art compositions and in many instances sting the eyes less. It is surprising that zwitterionic compounds, of the type disclosed herein, are as mild or milder than the "reaction product" compositions of the prior art, when used in combination with the anionic and nonionic surfactants of this invention. Although, betaines and sultaines are well known in the art, the ability of applicants' three-component compositions to be used as shampoos without stinging eyes was unknown.

THE INVENTION

This invention relates to the discovery of a mild shampoo composition comprising:

A. a polyethoxylated anionic surfactant selected from the group consisting of (1) a surfactant having the formula R(OC ₂ H ₄ ) _n OSO ₃ M, wherein R is a hydrophobic group selected from the group consisting of alkyl groups containing from about 8 to about 16 carbon atoms, alkylphenyl groups wherein the alkyl group contains from about 6 to about 15 carbon atoms, and fatty acid amido groups wherein the fatty acid contains from about 8 to about 16 carbon atoms, wherein n is a number from about 1 to about 10 (preferably 1 to 5) and M is a non-toxic cation which makes the surfactant water-soluble, preferably a cation selected from the group consisting of sodium, potassium, ammonium and triethanolammonium cations, and (2) a water-soluble (e.g., sodium, potassium, ammonium or triethanolammonium) polyethoxylated fatty alcohol sulfosuccinate monoester wherein said fatty alcohol contains from about 8 to about 16 carbon atoms, preferably from about 10 to about 14 carbon atoms, and said polyethoxylated fatty alcohol contains from about 1 to about 10 ethoxy moieties per molecule, preferably from about 1 to 5;

B. a zwitterionic surfactant having the formula

wherein A, B, and C are each selected from the group consisting of 0 and 1, wherein A is 0 when B is 1 and A is 1 when B is 0, wherein C can only be 1 when Y is a sulfonate group, wherein each R ² is selected from the group consisting of alkyl groups containing from about 8 to about 16 carbon atoms and a moiety having the formula R ⁵ -- C(O)NH -- R ⁶ -- wherein R ⁵ is an alkyl group containing from about 8 to about 16 carbon atoms and R ⁶ is an alkylene group containing from 1 to about 5 carbon atoms (preferably 2-4 carbon atoms and most preferably 3 carbon atoms), wherein each R ³ is selected from the group consisting of alkyl, hydroxyalkyl and alkoxyalkyl groups which can be connected to form a ring and each of which contains from 1 to about 3 carbon atoms, wherein Y is selected from the group consisting of sulfonate and carboxylate groups, and wherein R ⁴ is an alkylene group containing from 1 to about 5 carbon atoms when Y is a carboxylate group and is selected from the group consisting of alkylene and hydroxyalkylene groups containing from about 2 to about 5 carbon atoms when Y is a sulfonate group and wherein the hydroxy group is on a secondary carbon atom;

C. a polyethoxylated nonionic surfactant selected from the group consisting of: (1) polyethoxylated alcohols, said alcohols containing an alkyl group, either primary or secondary, and either straight or branched chain, containing from about 8 to about 16 carbon atoms and said polyethoxylated alcohols containing from about 10 to about 45 ethoxy moieties per molecule, (2) polyethoxylated alkylphenols wherein the alkyl group contains from about 6 to about 15 carbon atoms and wherein the polyethoxylated alkylphenol contains from about 10 to about 45 ethoxy moieties per molecule, (3) polyethoxylated mono fatty acid esters of sorbitol wherein said fatty acids contain from about 8 to about 18 carbon atoms and said polyethoxylated mono fatty acid ester of sorbitol contains from about 10 to about 45 ethoxy moieties per molecule, (4) polyethoxylated polypropylene glycol, said polypropylene glycol having a molecular weight of from about 1,000 to about 15,000 and said polyethoxylated polypropylene glycol containing from about 15 to about 300 ethoxy moieties per molecule, and (5) polyethoxylated fatty acids wherein said fatty acid contains from about 8 to about 16 carbon atoms and said polyethoxylated fatty acid contains from about 10 to about 45 ethoxy moieties per molecule; and

D. water,

the molecular ratio of (A) to (B) being from about 1:1 to about 4:1; the weight ratio of (A) + (B) to (C) being from about 2:1 to about 1:2; and the pH of the composition being from about 6.0 to about 8.0.

DESCRIPTION OF THE INVENTION

1. The polyethoxylated anionic surfactant

The polyethoxylated anionic surfactants of this invention are very mild. It is essential that the anionic surfactant be mild since it is normally used in a molar excess over the amount of zwitterionic surfactant present so as to minimize the amount of cationic species present. The anionic surfactant provides good lather properties. Typically the composition will contain from about 2 to about 15% of the anionic surfactant, preferably from about 4 to about 8 % for a liquid shampoo, and from about 3 to about 10% for a paste shampoo. The sodium salts of the polyethoxylated anionic surfactants are preferred, but any non-toxic, water-soluble salt can be used, including potassium, triethanolammonium, and ammonium salts.

The preferred polyethoxylated anionic surfactants are the sodium salt of C ₁₀ -C ₁₄ fatty alcohol polyethoxy( 3) ether sulfate, the sodium salt of polyethoxylated( 3) C ₁₀ -C ₁₄ mono fatty alcohol sulfosuccinate, and the sodium salt of C ₁₀ -C ₁₄ fatty acyl amido polyethoxy( 4) ether sulfate. Other suitable polyethoxylated anionic surfactants are disclosed hereinafter in the examples.

2. The zwitterionic surfactants

The zwitterionic surfactant provides major lather benefits while modifying the nature of the composition so that it is less strongly anionic. The molecular ratio of the anionic to zwitterionic surfactant is from about 1:1 to about 4:1, preferably from about 1:1 to about 3:1, most preferably from about 1:1 to about 2:1.

Preferred zwitterionic surfactants are propylamido betaines derived from C ₁₀ -C ₁₆ fatty acids, and the corresponding propylamido sultaines, and C ₁₀ -C ₁₆ alkyl sultaines wherein the cationic and sulfonate anionic groups are separated by a propylene group and the remaining groups are methyl groups. Specifically, preferred zwitterionic surfactants are (a) those having the formula

wherein R ⁷ is an alkyl group containing from about 9 to about 15 carbon atoms, wherein each R ⁸ is selected from the group consisting of methyl, ethyl, and 2-hydroxyethyl groups, wherein Y is selected from the group consisting of sulfonate and carboxylate groups, and wherein R ⁹ is a methylene group when Y is a carboxylate group and is selected from the group consisting of propylene and 2-hydroxypropylene groups when Y is a sulfonate group; and (b) those having the formula

wherein R ¹⁰ contains from about 10 to about 16 carbon atoms, wherein each R ¹¹ is selected from the group consisting of methyl, ethyl, and 2-hydroxyethyl groups, and wherein X is selected from the group consisting of hydrogen and hydroxyl groups. Examples of other zwitterionic surfactants are given in the examples hereinafter.

3. The polyethoxylated nonionic surfactant

The polyethoxylated nonionic surfactant provides a mildness benefit. It also contributes to the character of the lather, although in general, the nonionic surfactant tends to control and diminish the amount of the lather. The ratio of the polyethoxylated anionic surfactant and zwitterionic surfactant to the polyethoxylated nonionic surfactant is from about 2:1 to about 1:2, preferably from about 1:1 to about 1:2, and most preferably from about 1:1 to about 1:1.2.

Preferred nonionic surfactants include polyethoxylated (15-40) sorbitan monoacylate (C ₁₀ -C ₁₆ ; preferably monolaurate), polyethoxylated (20-100) polypropylene glycol (M.W. 8,000-12,000), and polyethoxylated (15-40) fatty alcohols (C ₁₀ -C ₁₄ ). Other examples of nonionic surfactants are disclosed hereinafter in the examples.

4. Water

Water is used to make up the shampoo compositions to the desired physical form. For liquid shampoos, there will normally be from about 50 to about 85% of water present, preferably from about 65 to about 80%. For a paste shampoo, there will normally be from about 30 to about 60% water present, preferably from about 35 to about 55%.

5. Other ingredients

In addition to the ingredients described hereinbefore, the shampoo compositions of this invention can also contain other conventional shampoo components, including dyes, preservatives such as ethanol, perfumes, thickeners, opacifiers, antibacterial agents, antidandruff agents, buffering agents, conditioning agents, etc. Desirably, only ingredients which are not irritating to the eye are added.

It is especially desirable and preferred to have buffering agents present to maintain the pH of the composition within the range from about 6.0 to about 8.0, preferably from about 6.5 to about 7.5, and most preferably, about 7. Such buffering agents include NaOH, NCl, NaHPO ₄ , boric acid, etc. It is also very desirable to include antidandruff agents such as zinc pyridinethiol N-oxide.

The choice of a proper thickener is complicated by the fact that the ingredients react with many anionic thickeners and many nonionic thickeners fail to thicken the compositions. Suitable thickening agents include carragenan, hydroxyethyl cellulose (e.g., one with a D.S. of about 2,5 whose 1% solution has a viscosity of 3-4,000 centipoises at 25°C.), and the compounds disclosed in U.S. Pat. No. 3,472,840, F. W. Stone and J. M. Rutherford, Jr., as set forth in the application of Roger Clarence Birkofer, Ser. No. 313,907, entitled "MILD THICKENED SHAMPOO COMPOSITIONS WITH CONDITIONING PROPERTIES," filed concurrently herewith, and now abondoned. These thickeners are desirable in that they tend to provide clear, single-phase compositions. All patents and applications referred to herein are specifically incorporated herein by reference. All percentages, ratios, and parts herein are by weight unless otherwise specified.

EXAMPLE I

Ingredient % by Weight ______________________________________ 3-(N,N-dimethyl-N-laurylamino)propane 4.9 sulfonate (sultaine) Sodium salt of sulfated polyethoxylated (3) 6.6 coconut fatty alcohol (AE ₃ S) Polyethoxylated (20) sorbitan mono- 14.0 laurate (Tween 20) Ethanol 7.0 Water balance Adjusted to a pH of 7.0 with HCl. ______________________________________

EXAMPLE II

Ingredient % by Weight ______________________________________ N-(3-coconutacylamidopropyl)-N,N- 5.0 dimethyl-2-aminoacetate (amidobetaine) AE ₃ S 7.2 Polyethoxylated (206 moles) polypropylene 14.0 glycol, molecular weight 10,800. (PPG) Water balance Adjusted to pH of 7.0 with HCl. ______________________________________

EXAMPLE III

Ingredient % by Weight ______________________________________ Amido Betaine 4.0 Sodium polyethoxylated(3)lauryl sulfosucci- 8.2 nate monoester (Ethoxylated sulfosuccinate) PPG 14.0 Ethanol 7.0 NaH ₂ PO ₄ .H ₂ O 1.0 Water balance pH adjusted to 7.0 with NaOH. ______________________________________

EXAMPLE IV

Ingredient % by Weight ______________________________________ Sultaine 4.5 AE ₃ S 7.0 Polyethoxylated(20)tridecyl alcohol (β- 14.0 methyl dodecanol) (PTA) Ethanol 7.0 Cationic thickener -2 [cationic cellulose 1.25 ether of Claim 7 of U.S. Pat. No. 3,472,840, wherein a is 2, b is 2, q is 0, m + p is about 1.5, the degree of substitution of the cationic group (and m) are about 0.2, and the viscosity of a 1% aqueous solution is 125-1500 centipoises at 25°C.] Water balance pH adjusted to 7.0 with HCl. ______________________________________

EXAMPLE V

Ingredient % by Weight ______________________________________ Amido Betaine 4.0 Ethoxylated sulfosuccinate 8.2 PTA 14.0 Ethanol 7.0 Water balance pH adjusted to 7.0 with NaOH. ______________________________________

EXAMPLE VI

Ingredient % by Weight ______________________________________ N-(3-coconutacylamidopropyl)-N,N- 5.0 di(2-hydroxyethyl)-3-aminopropane- sulfonate Sodium salt of sulfated polyethoxylated(4) 8.0 lauroylamide (ethoxylated amido sulfate) Tween 20 13.0 Natrosol 250 HH [A hydroxyethyl cellulose 1.5 (D.P. - 2.5) having a viscosity at 1% in water at 25)C. of 3-4,000 centipoises] Ethanol 7.0 Water balance Adjusted to pH of 7.0 with NaH ₂ BO ₃ . ______________________________________

EXAMPLE VII

Ingredient % by Weight ______________________________________ 3-(N-laurylmorpholino)-2-hydroxypropane- 4.0 sulfonate Sodium nonylphenol polyethoxy(6) 7.0 ether sulfate Polyethoxylated(25) undecylphenol 16.0 Natrosol 250 HH 1.8 Ethanol 6.0 Water balance Adjusted to pH 7.0 with NaOH. ______________________________________

EXAMPLE VIII

Ingredient % by Weight ______________________________________ 3-[N-undecyl-N-ethyl-N-(2-hydroxyethyl) 4.5 ammonio]-butyrate Potassium polyethoxylated(3) 6.6 tridecanolether sulfate Polyethoxylated(30) sorbitan 17.0 monococonutacylate Ethanol 6.0 Cationic thickener, -1 (same as thickener 1.0 of Example IV except having a D.S. of the cationic group of 0.4) Water balance Adjust pH to 7.0 with HCl. ______________________________________

EXAMPLE IX

Concentrated Shampoo Ingredient % by Weight ______________________________________ 3-(N,N-dimethyl-N-coconutalkylammonio)- 10.0 2-hydroxypropane sulfonate Ethoxylated amidosulfate 15.0 Tween 20 30.0 Natrosol 250 HH 2.0 Ethanol 5.0 Water balance pH adjusted to 7.0 with NaOH. ______________________________________

EXAMPLE X

Ingredient % by Weight ______________________________________ Amido betaine 4.00 Ethoxylated sulfosuccinate 9.00 PTA 12.00 Na carrageenan 1.00 2-bromo-2-nitro-1,3-propanediol .02 (a bactericide) Distilled water balance Adjusted pH to 7.0 with NaOH. ______________________________________

EXAMPLE XI

Ingredient % by Weight ______________________________________ C-cetyl betaine 5.00 AE ₃ S 8.00 Polyethyleneglycol(20)monolaurate 14.00 Distilled water balance Adjusted pH to 7.0 with HCl. ______________________________________

EXAMPLE XII

Ingredient % by Weight ______________________________________ Sultaine 4.00 AE ₃ S 5.50 PPG (molecular weight 3,000) 14.00 Cationic thickener .60 Ethanol 7.00 Perfume 0.25 Distilled water balance Adjusted pH to 7.0 with HCl. ______________________________________

EXAMPLE XIII

Ingredient % by Weight ______________________________________ Amido betaine 3.00 Ethoxylated sulfosuccinate 7.00 Tween 20 14.00 Cationic thickener, -2 0.50 Ethanol 7.00 Distilled water balance Adjusted pH to 7.0 with NaOH. ______________________________________

When in the above Examples I-XIII the following zwitterionic surfactants, either totally or in part (e.g., a 1:1 ratio), substantially equivalent results are obtained in that the shampoos are exceptionally mild to the eyes.

1. 4-[N-coconutacylamidopropylene-N,N-di(2-hydroxypropyl)-ammon io]butane-1-su lfonate;

2. 2[N-pentadecylamidopropylene-N-(3-hydroxypropyl)-N-propylamm onio]ethane-1- sulfonate;

3. 4(N-laurylmorpholino)2-hydroxybutanoate;

4. 3-(N-laurylmorpholino)propane-1-sulfonate;

5. 3-(N-tridecyl-N-methyl-N-propyl)-aminopropanoate;

6. 4-(N,N,N-trimethylammonio)stearate;

7. 3-[N-Methyl-N-(2-hydroxyethyl)-N-propylammonio]eicosane-1-su lfonate;

8. 5-[N,N-(3-hydroxypropyl)-N-methylammonio]-3-hydroxydocosane- 1-carboxylate;

9. N-coconutalkyl betaine;

10. C-cetyl betaine;

11. C-hexadecyl betaine;

12. 3-(N,N-dimethyl-N-coconutalkylammonio)-2-hydroxypropane-1-su lfonate;

13. 6-coconutacylamido-3-trimethylammoniohexanoate;

14. 7-coconutacylamido-4-tri(2-hydroxyethyl-heptane-1-sulfonate;

15. 3-[N-(3-coconutacylamidopropyl)-N,N-dimethylammonio]-propane -1-sulfonate;

16. 3-[N-(3-coconutacylamidopropyl)-N,N-di(2-hydroxyethyl)-ammon io]-2-hydroxyp ropane-1-sulfonate;

17. 6-(N-coconutalkyl-N,N-dimethyl)hexanoate;

18. 5-(N,N-dipropyl-N-dodecylammonio)pentane-1-sulfonate;

19. 3-(N-methylmorpholino)stearate.

When in the above Examples I-XIII, the following ethoxylated anionic surfactants are substituted for the specifically named ethoxylated anionic surfactants, either totally or in part (e.g., a 1:1 ratio), substantially equivalent results are obtained in that the shampoos are exceptionally mild to the eyes:

1. Ammonium polyethoxylated(10)octanol ether sulfate;

2. Triethanolammonium polyethoxylated(2)2-ethyltetradecanol sulfate;

3. Potassium polyethoxylated(4) octylphenol ether sulfate;

4. Sodium polyethoxylated(6)pentadecylphenol ether sulfate;

5. Diethanolammonium polyethoxylated(4)dodecane-2-ol ether sulfate;

6. Monoethanolammonium polyethoxylated(5)tetrapropylene phenol ether sulfate;

7. Sodium polyethoxylated(8)3-nonylphenol ether sulfate;

8. Potassium polyethoxylated(4)octoylamide ether sulfate;

9. Triethanolammonium polyethoxylated(5)hexadecoylamide ether sulfate;

10. Potassium polyethoxylated(2)octanol sulfosuccinate monoester;

11. Triethanolammonium polyethoxylated(10)hexadecanol sulfosuccinate monoester.

When in the above Examples I-XIII, the following ethoxylated nonionic surfactants are substituted for the specifically named ethoxylated nonionic surfactants, either totally, or in part (e.g., a 1:1 ratio), substantially equivalent results are obtained in that the shampoos are exceptionally mild to the eyes:

1. Polyethoxylated(40)octanol;

2. Polyethoxylated(10)hexadecanol;

3. Polyethoxylated(25)2-ethylnonanol;

4. Polyethoxylated(18)dodecane-2-ol;

5. Polyethoxylated(35)hexylphenol;

6. Polyethoxylated(30)pentadecylphenol;

7. Polyethoxylated(40)tetrapropylenephenol;

8. Polyethoxylated(25)3-nonylphenol;

9. Polyethoxylated(35)sorbitan monostearate;

10. Polyethoxylated(25)sorbitan monooctanoate;

11. Polyethoxylated(25)polypropylene glycol (M.W. 1000);

12. polyethoxylated(25)octanoate;

13. Polyethoxylated(30)hexadecanoate;

14. Polyethoxylated(300)polypropylene glycol (M.W. 15,000).