Title:
LIQUID DETERGENT COMPOSITIONS CONTAINING SURFACTANTS AND PEROXIDE BLEACHING AGENTS
United States Patent 3850831
Abstract:
Liquid detergent compositions are provided comprising a surfactant and a peroxide bleaching agent, having good storage stability by virtue of their being substantially free from liquid water, and dissolved or dispersed in a polyhydric alcohol or ether thereof which is liquid at ambient temperature.
US Patent References:
CLEANSER COMPOSITONS FOR ARTIFICIAL DENTURES AND METHODS OF PREPARING THE SAME
Hill - March 1972 - 3652420
DETERGENT COMPOSITIONS CONTAINING A SEQUESTRANT AND OPTIONALLY A BLEACHING AGENT HAVING A REDUCED TENDENCY TO ATTACK COPPER, ZINC AND ALUMINUM
Hellsten et al. - April 1972 - 3655569
CLEANSER COMPOSITONS FOR ARTIFICIAL DENTURES AND METHODS OF PREPARING THE SAME
Hill - March 1972 - 3652420
DETERGENT COMPOSITIONS CONTAINING A SEQUESTRANT AND OPTIONALLY A BLEACHING AGENT HAVING A REDUCED TENDENCY TO ATTACK COPPER, ZINC AND ALUMINUM
Hellsten et al. - April 1972 - 3655569
Inventors:
Hellsten, Karl Martin Edvin (Odsmal, SW)
Santamaki, Seppo Olavi (Lindome, SW)
Santamaki, Seppo Olavi (Lindome, SW)
Application Number:
05/270388
Publication Date:
11/26/1974
Filing Date:
07/10/1972
View Patent Images:
Export Citation:
Assignee:
Mo Och Domsjo Aktiebolag (Ornskoldsvik, SW)
Primary Class:
Other Classes:
510/505, 510/304, 510/506, 510/467, 510/108
International Classes:
C11D3/20; C11D3/39; C11D17/00; C11D7/54
Field of Search:
252/99,95,104
Primary Examiner:
Weinblatt, Mayer
Claims:
Having regard for the foregoing disclosure, the following is claimed as the inventive and patentable embodiments thereof
1. A liquid detergent composition consisting essentially of from about 5 to about 35 percent by weight of a water-soluble inorganic per compound bleaching agent which is a solid and which is stable at ambient temperature selected from the group consisting of the water-soluble alkali metal and ammonium perborates, percarbonates, persulfates and perpyrophosphates, from about 5 to about 35 percent by weight of an organic surfactant selected from the group consisting of anionic, cationic, nonionic and ampholytic surfactants, and an amount within the range from about 5 to about 30 percent by weight sufficient to form a liquid composition of a polyhydric alcohol or ether thereof which is liquid at ambient temperature and selected from the group consisting of polyhydric alcohols having from two to about three hydroxyl groups and from 2 carbon atoms to about 6 carbon atoms, and polymeric polyoxyalkylene alcohols having a molecular weight within the range from about 100 up to about 4,000, and mono- and polyethers thereof having at least one free hydroxyl group and an alkyl group having from one to about four carbon atoms, the polyoxyethylene glycols having a molecular weight within the range from about 100 to about 400, and the polyoxypropylene and polyoxybutylene glycols having a molecular weight within the range from about 100 to about 4,000, the composition being substantially free from liquid water.
2. A liquid detergent composition according to claim 1, in which the polyhydric alcohol has from 2 to about 3 hydroxyl groups and from 2 to about 6 carbon atoms.
3. A liquid detergent composition according to claim 2, in which the polyhydric alcohol is in polymeric oxyalkylene unit form.
4. A liquid detergent composition according to claim 3, in which the polyoxyalkylene polyol is a polyoxyethylene glycol having a molecular weight within the range from about 108 to about 400.
5. A liquid detergent composition according to claim 4, in which the polyoxyalkylene polyol is a polyoxy-1,2-propylene glycol having a molecular weight within the range from about 136 to about 4,000.
6. A liquid detergent composition according to claim 1, in which the polyhydric alcohol is glycerol.
7. A liquid detergent composition according to claim 1, in which the amount of polyhydric alcohol is within the range from about 10 to about 20 percent.
8. A liquid detergent compositions according to claim 1, in which the surfactant is an alpha-olefin sulfonate, the alpha-olefins having from about 15 to about 18 carbon atoms.
9. A liquid detergent composition according to claim 1, in which the surfactant has the formula: ##SPC12##
10. A liquid detergent composition according to claim 1, in which the surfactant is a polyoxyalkylene phosphate ester having the formula: ##SPC13##
11. A liquid detergent composition according to claim 1, in which the peroxide bleaching agent is a water-soluble per compound which is a solid and which is stable at ambient temperature, selected from the group consisting of the water-soluble alkali metal and ammonium perborates, percarbonates, persulfates, and perpyrophosphates.
12. A liquid detergent composition according to claim 1, in which the amount of the peroxide bleaching agent is within the range from about 10 to about 25 percent by weight.
13. A liquid detergent composition according to claim 11, in which the peroxide bleaching agent is sodium perborate.
14. A liquid detergent composition according to claim 1, including an alkaline builder salt selected from the group consisting of alkaline inorganic and organic builder salts and sequestrants in an amount within the range from about 10 to about 80 percent by weight of the total solids of the composition.
15. A liquid detergent composition according to claim 14, in which the alkaline builder salt is an alkali metal polyphosphate.
16. A liquid detergent composition according to claim 1, including a chelating or sequestering agent selected from the group consisting of alkali metal, ammonium, and organic amine salts of polyamino-carboxylic acids selected from the group consisting of ethylene diamine tetraacetic acid, nitrilotriacetic acid, hexamethylene diamine tetraacetic acid, and diethylene triamine pentaacetic acid; oxycarboxylic acids selected from the group consisting of citric and gluconic acids; and unsaturated polycarboxylic acids selected from the group consisting of polymaleic acid, polyitaconic acid and polyacrylic acid, characterized by the ability to sequester or form complexes with hardness-forming metal ions in aqueous solutions in an amount within the range from about 5 to about 40 percent.
1. A liquid detergent composition consisting essentially of from about 5 to about 35 percent by weight of a water-soluble inorganic per compound bleaching agent which is a solid and which is stable at ambient temperature selected from the group consisting of the water-soluble alkali metal and ammonium perborates, percarbonates, persulfates and perpyrophosphates, from about 5 to about 35 percent by weight of an organic surfactant selected from the group consisting of anionic, cationic, nonionic and ampholytic surfactants, and an amount within the range from about 5 to about 30 percent by weight sufficient to form a liquid composition of a polyhydric alcohol or ether thereof which is liquid at ambient temperature and selected from the group consisting of polyhydric alcohols having from two to about three hydroxyl groups and from 2 carbon atoms to about 6 carbon atoms, and polymeric polyoxyalkylene alcohols having a molecular weight within the range from about 100 up to about 4,000, and mono- and polyethers thereof having at least one free hydroxyl group and an alkyl group having from one to about four carbon atoms, the polyoxyethylene glycols having a molecular weight within the range from about 100 to about 400, and the polyoxypropylene and polyoxybutylene glycols having a molecular weight within the range from about 100 to about 4,000, the composition being substantially free from liquid water.
2. A liquid detergent composition according to claim 1, in which the polyhydric alcohol has from 2 to about 3 hydroxyl groups and from 2 to about 6 carbon atoms.
3. A liquid detergent composition according to claim 2, in which the polyhydric alcohol is in polymeric oxyalkylene unit form.
4. A liquid detergent composition according to claim 3, in which the polyoxyalkylene polyol is a polyoxyethylene glycol having a molecular weight within the range from about 108 to about 400.
5. A liquid detergent composition according to claim 4, in which the polyoxyalkylene polyol is a polyoxy-1,2-propylene glycol having a molecular weight within the range from about 136 to about 4,000.
6. A liquid detergent composition according to claim 1, in which the polyhydric alcohol is glycerol.
7. A liquid detergent composition according to claim 1, in which the amount of polyhydric alcohol is within the range from about 10 to about 20 percent.
8. A liquid detergent compositions according to claim 1, in which the surfactant is an alpha-olefin sulfonate, the alpha-olefins having from about 15 to about 18 carbon atoms.
9. A liquid detergent composition according to claim 1, in which the surfactant has the formula: ##SPC12##
10. A liquid detergent composition according to claim 1, in which the surfactant is a polyoxyalkylene phosphate ester having the formula: ##SPC13##
11. A liquid detergent composition according to claim 1, in which the peroxide bleaching agent is a water-soluble per compound which is a solid and which is stable at ambient temperature, selected from the group consisting of the water-soluble alkali metal and ammonium perborates, percarbonates, persulfates, and perpyrophosphates.
12. A liquid detergent composition according to claim 1, in which the amount of the peroxide bleaching agent is within the range from about 10 to about 25 percent by weight.
13. A liquid detergent composition according to claim 11, in which the peroxide bleaching agent is sodium perborate.
14. A liquid detergent composition according to claim 1, including an alkaline builder salt selected from the group consisting of alkaline inorganic and organic builder salts and sequestrants in an amount within the range from about 10 to about 80 percent by weight of the total solids of the composition.
15. A liquid detergent composition according to claim 14, in which the alkaline builder salt is an alkali metal polyphosphate.
16. A liquid detergent composition according to claim 1, including a chelating or sequestering agent selected from the group consisting of alkali metal, ammonium, and organic amine salts of polyamino-carboxylic acids selected from the group consisting of ethylene diamine tetraacetic acid, nitrilotriacetic acid, hexamethylene diamine tetraacetic acid, and diethylene triamine pentaacetic acid; oxycarboxylic acids selected from the group consisting of citric and gluconic acids; and unsaturated polycarboxylic acids selected from the group consisting of polymaleic acid, polyitaconic acid and polyacrylic acid, characterized by the ability to sequester or form complexes with hardness-forming metal ions in aqueous solutions in an amount within the range from about 5 to about 40 percent.
Description:
Synthetic detergent compositions containing a surfactant and a peroxide bleaching agent have become very popular for household use. However, peroxide bleaching agents have a poor stability in aqueous solutions, and for this reason detergent compositions containing them have had to be marketed in solid form. Stabilizers have been incorporated in such compositions to improve the stability of the peroxide bleaching agent in aqueous solution, but such stabilizers have been found not to be very effective.
However, the particulate detergent compositions containing peroxide bleaching agents are difficult to dissolve, especially in cold or lukewarm water. Moreover, in order to formulate such compositions in solid form, it is necessary first to mix the ingredients with the addition of a liquid, to obtain a good admixture, and then dry the resulting slurry before the peroxide bleaching agent can decompose, which increases handling and production costs. The particulate detergent compositions when thoroughly dried have a tendency to dust, which makes them difficult to handle, and unpleasant to measure out in the dosing capsule of automatic washing machines.
In order to avoid these difficulties, it has been proposed that such compositions be provided in liquid form, dissolved or dispersed in an anhydrous liquid detergent as the liquid suspending or dispersing medium. However, in order to form a uniform slurry or solution in this case, an unusually high amount of the liquid detergent must be employed. According to the amount of peroxide bleaching agent and other builders required, the amount of liquid anhydrous surfactant has to be within the range from about 20 to about 90 percent by weight of the composition. In addition, for 0.1 to about 10 percent by weight of a finely divided carrier, such as silica or alumina, is usually needed, to aid in dispersing the peroxide bleaching agent through the liquid detergent, where it is not soluble therein. Solid carriers of this sort are disadvantageous, however, because they are water-insoluble, and tend to become deposited on the wash, after which they are difficult to remove. Moreover, the amount of liquid surfactant is normally in excess of what is required, or what can be advantageously or efficiently utilized in conjunction with other active ingredients, such as builders and soil-suspending agents, as a result of which the detergent power of the surfactant is to a considerable extent wasted, the detergent serving merely as a suspending medium. Moreover, the peroxide bleaching agent and other inorganic solid ingredients are poorly dissolved or dispersed in most liquid surfactants, as a result of which solubilizing or hydrotropic agents, such as sodium xylene sulfonate, have to be included, to increase the solubility of the solid ingredients in the liquid. Also, the viscosity may be unduly high and has to be lowered by addition of solvents, such as ethanol and benzene.
In accordance with the invention, it has been determined that it is possible to formulate a liquid substantially anhydrous detergent composition containing a peroxide bleaching agent and a surfactant in normal amounts, without the addition of carriers, such as silica or alumina, if there is combined with the peroxide bleaching agent surfactant and any other solid ingredients present an amount within the range from about 5 to about 30 percent by weight of the composition of a polyhydric alcohol or ether thereof which is liquid at ambient temperature. The composition is substantially free from liquid water, although water can be present in the form of water of crystallization with, for example, the peroxide bleaching agent, or the builder, or other ingredients.
Any polyhydric alcohol having from two to about three hydroxyl groups and from two carbon atoms to about six carbons can be used. The polyhydric alcohols can also be combined in polymeric oxyalkylene unit forms, having a molecular weight from about 100 up to a molecular weight of approximately 4,000, as well as mono and poly ethers thereof having at least one free hydroxyl group.
The polyoxyalkylene glycols also can be employed. The polyoxyethylene glycols have a molecular weight within the range from about 108 to about 400, and the polyoxypropylene glycols (of 1,2-oxypropylene units) have a molecular weight within the range from about 136 to about 4,000. Monoalkyl ethers of these polyhydric alcohols can be used, in which the alkyl group has from one to about four carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, and secondary butyl. Exemplary monoalkyl ethers are ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, tripropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dibutylene glycol monobutyl ether, polyoxyethylene glycol monoethyl ether, and polyoxypropylene glycol monopropyl ether.
The tri and tetrahydric polyols also can be used. Glycerol, butylenetriol-1,2,3, pentylenetriol-2,3,4, and hexylenetriol-2,3,5 are exemplary. The mono and dialkyl ethers of the trihydric alcohols, wherein the alkyl group has from about one to about four carbon atoms, also can be used.
If desired, a combination of two or more different polyhydric alcohols, or polyhydric alcohols and monohydric ethers thereof, or polyhydric alcohol monohydric ethers, can be used. Such mixtures facilitate adjustment of the viscosity of the resulting composition.
The amount of polyhydric alcohol or monohydric ether thereof that is required depends upon the polyhydric alcohol or ether employed, as well as the other ingredients of the detergent composition. Enough polyhydric alcohol or monohydric ether thereof is employed to form a liquid detergent composition in which the solid ingredients are either dissolved or dispersed, that is, substantially free from liquid water. In general, such compositions can be obtained using an amount of polyhydric alcohol or monohydric ether thereof within the range from about 5 to about 30 percent by weight of the composition. In most instances, an amount within the range from about 10 to about 20 percent is preferred.
The polyhydric alcohols and ethers thereof act as solvents in the compositions of the invention, and the resulting liquid compositions have a high storage stability, due to the absence of water. The presence of the polyhydric alcohol or ether is also desirable and advantageous when the composition is diluted with water to form a washing solution, since the polyhydric alcohol brings about a more rapid dissolution of the composition. In addition, polyoxypropylene glycols impart a foam-moderating action to the composition, which renders the composition particularly suitable for use in automatic washing machines, particularly those which have a tendency to produce foam in use.
As the surfactant in the compositions of the invention, any anionic, cationic, nonionic, or ampholytic surfactant can be used, separately or in combinations, both of the same and of different types. The surfactant should be either a liquid at ambient temperature, or should form a liquid phase (either a solution or a dispersion) with the polyhydric alcohol or ether. The amount of the surfactant is within the range from about 5 to about 30 percent, preferably from about 10 to about 20 percent, by weight of the detergent composition.
The anionic sulfate or sulfonate ester surfactants constitute a well known class of anionic surfactants. The alkyl aryl sulfonates are defined by the formula ##SPC1##
where R is alkyl having from eight to about eighteen carbons, n is a number from 1 to 3, and M is hydrogen on an alkali metal, ammonium or organic amine cation. One example thereof is sodium dodecyl benzene sulfonate.
Another example are the sulfonated phenyl polypropylene alkanes, characterized by the branched chain structure of polypropylene and tertiary alkyl carbon at the benzene ring, and having the following general structure: ##SPC2##
where M is hydrogen, an alkali metal, ammonium, or an organic amine cation, R 1 and R 2 are alkyl, of the type formula C n H 2n +1 , and at least one R is a polypropylene group, the whole alkyl group containing preferably 12 to 15 carbon atoms. These are known compounds, whose preparation and properties are set forth in U.S. Pat. No. 2,477,383, to Lewis, issued July 26, 1949; they are available in commerce under the trade names "Oronite," "Ultrawet," and "Neolene."
Other water-soluble alkyl aromatic sulfonic acids include those prepared by alkylating benzene or naphthalene with a kerosene fraction, followed by sulfonation to aromatic sulfonic acids, such as sodium keryl benzene sulfonate.
Another class of useful surfactants are the aminoalkane sulfonates, which are characterized by the following structure: ##SPC3##
where A is hydrogen or an alkali metal, i.e., ammonium, sodium or potassium, n is a small whole number from 1 to about 5, preferably 2 or 3, R is hydrogen or an alkyl, aryl, or cycloaliphatic group, such as methyl, and R' is an alkyl or alkylene radical, such as myristyl, palmityl, oleyl and stearyl. Sodium palmitic tauride, sodium palmitic methyl tauride, sodium myristic methyl tauride, sodium palmitic stearic methyl tauride, and sodium palmitic methyl amidopropane sulfonate are typical examples thereof.
These compounds are prepared by interacting the corresponding aliphatic acid anhydride or halide with an organic aliphatic aminosulfonic acid, such as taurine, NH 2 CH 2 CH 2 SO 3 H, and various N-substituted taurines, such as N-methyl taurine or aminopropane sulfonic acid, NH 2 (CH 2 ) 3 SO 3 H.
Other anionic surfactants include esters of sulfuric acid with aliphatic alcohols of ten to eighteen carbon atoms, particularly oleic acid, tall oil, turkey red oil, and acids derived by the reduction of the fatty acids derived from coconut oil, palm oil, sperm oil and the like long-chain fatty acids, sulfonated castor oil, esters and ethers of isethionic acid, long-chain fatty acid esters and long-chain alkyl ethers of 2,3-dihydroxy-propane sulfonic acid and sulfuric acid esters of monoglycerides and glycerol monoethers.
The nonionic polyoxyalkylene ether, ester and glycol surfactants have the following general formula: ##SPC4##
where R is hydrogen or a straight or branched chain saturated or unsaturated hydrocarbon group having from 8 to 26 carbon atoms or an aralkyl group having a straight or branched chain saturated or unsaturated hydrocarbon group of from 6 to 24 carbon atoms attached to the aryl nucleus, and attached to A through the aryl nucleus, A is selected from the group consisting of ethereal oxygen and sulfur, carboxylic ester and thiocarboxylic ester groups, R 3 and R 4 are hydrogen or methyl, and x is a number from 2 to 50. R can, for example, be a straight or branched chain alkyl group, such as octyl, nonyl, decyl, lauryl, myristyl, cetyl, or stearyl, or an alkylaryl group such as octylphenyl, nonylphenyl, decylphenyl, stearylphenyl, etc. In this formula, OH could also be replaced by the group --O(C 3 H 6 O) m H, where m is a number ranging from 1 to 10. Examples of such nonionic surfactants are such as have been obtained by adding ethylene oxide, propylene oxide or butylene oxide to the above mentioned alcohols or phenols.
The sulfated alkoxylated derivatives of the above also are useful anionic surfactants: ##SPC5##
where M is hydrogen or an alkali metal or an organic amine cation and x, R 3 , R 4 , A and R are as above.
Where R is alkyl it will be evident that the wetting agent can be regarded as derived from an alcohol, mercaptan, oxy or thio fatty acid of high molecular weight, by condensation with ethylene oxide, propylene oxide or butylene oxide. Typical of this type of alkyl product are the condensation products of oleyl or lauryl (dodecyl) alcohol, or mercaptan, or oleic or lauric acid, with from 8 to 17 moles of ethylene oxide, such as "Emulfor ON." Typical alkyl esters are "Renex" (polyoxyethylene ester of tall oil acids) and "Neutronyl 331" (higher fatty acid ester of polyethylene glycol).
Where R is aralkyl, the wetting agent can be derived from an alkyl phenol or thiophenol.
Another class of anionic surfactants are the polyoxyalkylene phosphate esters described by the following formula: ##SPC6##
R 1 and R 2 can be the same or different. One or both of R 1 and R 2 is a radical containing polyoxyalkylene ether and no more than one of R 1 and R 2 is hydrogen. The radical containing polyoxyalkylene ether is of the form ##SPC7##
in which n has a value greater than zero, up to about 30, and preferably is within the range from about 1 to about 10, and denotes the average number of oxyalkylene units in the chain. It will be understood that there will be present in admixture species having n values both higher and lower than the average value for n. R 4 and R 5 are hydrogen or methyl.
R 3 is a primary or secondary straight or branched chain saturated or unsaturated aliphatic radical having from about 10 to about 24 carbon atoms, preferably from about 12 to about 22 carbon atoms, or a mono, di, or trialkyl-substituted phenyl radical having from about 6 to about 24 carbon atoms, and preferably from about 8 to about 18 carbon atoms in the alkyl portion.
M is hydrogen or a water-soluble salt-forming cation such as an alkali metal, such as, for instance, sodium or potassium; ammonia; or an organic amine, such as an alkanolamine or an alkylamine radical, for example, monoethanolamine, diethanolamine, triethanolamine, butylamine, octylamine, or hexylamine.
These polyoxyalkylene phosphate esters are known compounds, and are described in U.S. Pat. Nos. 3,294,693 and 3,235,627 and the disclosure thereof in these patents is hereby incorporated by reference. Additional polyoxyalkylene phosphate esters are described in U.S. Pat. No. 3,400,148, at column 17, and in the Mahew & Krupin article in Soap and Sanitary Chemicals, referred to above. The disclosures thereof in these publications are also incorporated by reference.
Additional polyoxyalkylene phosphate ester surfactants are described in U.S. Pat. No. 3,122,508 to Grifo, Mayhew, Stefcik and Woodward, dated Feb. 25, 1964, and in U.S. Pat. Nos. 3,004,056 and 3,004,057 to Nunn and Hesse, dated Oct. 10, 1961.
In general, the polyoxyalkylene ether phosphates are prepared by reaction of phosphorous pentoxide, orthophosphoric acid, pyrophosphoric acid, or a polyphosphoric acid with a suitable nonionic surfactant base.
In the course of the esterification, monoesters and diesters may both be formed, but one may be obtained in preference to the other, according to the reaction conditions and the molar proportions of the reactants. Phosphate esters composed of the mixtures of the mono and di esters in any proportion can be employed, but it is generally preferred that the major proportion, if not all, of the phosphate ester be composed of mono esters.
It may also be noted that the oxypropylene phosphate esters have a lesser foaming tendency than the oxyethylene phosphate esters, and may be preferred for low foaming compositions. Moreover, the lower the value of n and the higher the number of carbon atoms in the R substituent of the oxyalkylene group, the less the foaming tendency of the phosphate ester.
Exemplary organic compounds having an active hydrogen atom that can be employed to produce alkylene oxide adducts for the radical of the oxyalkylene phosphate esters (R 3 in the formula ##SPC8##
are the primary alcohols such as octanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, eicosanol, docosanol, tetracosanol, straight or branched, primary or secondary OXO-alcohols, i.e., alcohols prepared by the OXO process, having from 12 to 26 carbon atoms, such as the essentially straight chain alcohols produced from Fischer-Tropsch olefins by the OXO-process, and multi-branched chain alcohols produced from olefins having at least 7 carbon atoms and two side chains, such as tripropylene, tetrapropylene, pentapropylene, diisobutylene and triisobutylene by the OXO process, mono, di and trialkyl phenols, such as octyl phenol, isooctyl phenol, nonyl phenol, dodecyl phenol, dioctyl phenol, dinonyl phenol, didodecyl phenol, trioctyl phenol, trihexyl phenol, tridodecyl phenol, methyloctyl phenol, and ethylisononyl phenol, tri-primary, secondary, and tertiary butyl phenol, 3-methyl-4,6-dibutyl phenol, octadecyl phenol, dioctadecyl phenol, trioctadecyl phenol, mono, di and tributyl cresol, mono, di and trinonyl cresol.
The polyoxyalkylene base ##SPC9##
can be polyoxy-1,2-propylene; polyoxyethylene; polyoxy-1,2-butylene; polyoxy-2,3-butylene; the so-called Pluronic type of nonionic surfactants, generally block copolymers of a polyoxyethylene chain and a polymerized alkylene oxide of at least three carbon atoms, preferably 1,2-propylene oxide, ranging in molecular weight from about 300 to about 10,000. Thus, the alkylene oxide condensate may consist entirely of one alkylene oxide, or of a condensed mixture of two or more alkylene oxides, such as a mixture of ethylene oxide and propylene oxide, in blocks, or heterogeneously distributed in the oxyalkylene chain.
Among the nonionic surfactants, a preferred class are the alkoxylated alkyl phenols and thiophenols, which have the following general formula: ##SPC10##
where R is a straight or branched chain saturated or unsaturated hydrocarbon group having at least 6 carbon atoms up to approximately 24 carbon atoms, A is oxygen or sulfur, R 4 and R 5 are hydrogen or methyl, and x is a number from 8 to 50. R can, for example, be a straight or branched chain octyl, nonyl, decyl, lauryl, cetyl, myristyl or stearyl group. Typical are the condensation products of octyl and nonyl phenol and thiophenol with from 8 to 17 moles of ethylene oxide, available commercially under the trade name "Igepal CA."
Also useful are the poly-1,2-alkylene oxide wetting agents described and claimed in U.S. Pat. Nos. 2,674,619 to Lundsted, dated Apr. 6, 1954, and 2,677,700 to Jackson et al., dated May 4, 1954. These are condensates of 1,2-alkylene oxides, such as 1,2-propylene oxide or 1,2-butylene oxide, alone or in admixture, and such mixtures can also include ethylene oxide, such as the polyoxypropyleneoxyethylene condensates, the ethylene oxide residues constituting from 20 to 90 percent of the resulting condensate.
These condensates conform to one of the following two type formulae:
Y [ (C 3 H 6 O) n -- E -- H ] x
where Y is the residue of an organic compound containing therein x active hydrogen atoms, n is an integer, x is an integer greater than 1; the values of n and x are such that the molecular weight of the compound, exclusive of E, is at least 900, as determined by hydroxyl number; E is a polyoxyalkylene chain wherein the oxygen/carbon atom ratio is at least 0.5, and E constitutes 20-90 percent, by weight, of the compound: ##SPC11##
wherein Y is the residue of an organic compound containing therein a single hydrogen atom capable of reacting with a 1,2-alkylene oxide; R 1 , R 2 , R 3 and R 4 are selected from the group consisting of hydrogen, aliphatic radicals and aromatic radicals, at least one such substituent being a radical other than hydrogen; m is greater than 6.4 as determined by hydroxyl number, and X is a water-solubilizing group.
Further suitable nonionic surfactants have the general formula:
H(OC 2 H 4 ) n1 -- (OC 3 H 6 ) m1 -- OC 2 to 3 H 4 to 6 -- O(C 3 H 6 O) m2 -- (C 2 H 4 O) n2 --H wherein m 1 and m 2 are numbers ranging from 10 to 50, and n 1 and n 2 are numbers ranging from 1 to 50. Examples of surfactants according to this formula are block copolymers of ethylene oxide and propylene oxide based on propylene glycol and having added to them propylene oxide up to a molecular weight of 1,000 to 3,000, after which ethylene oxide has been added to cause the proportion of ethylene oxide to constitute 5 to 80 percent of the molecular weight of the compound.
As the peroxide bleaching agent, any water-soluble per compound which is a solid and which is stable at ambient temperature can be employed, such as the water-soluble alkali metal and ammonium perborates, percarbonates, persulfates, and perpyrophosphates. The amount of the peroxide bleaching agent is within the range from about 5 to about 35 percent, preferably from about 10 to about 25 percent by weight of the composition. The peroxide salts should be water-soluble at least at the bleaching and/or washing concentration.
Exemplary are sodium perborate, NaBO 3 . 4H 2 O, and NaBO 3 . H 2 O, potassium perborate, ammonium perborate, magnesium perborate, sodium percarbonate, potassium percarbonate, ammonium percarbonate, sodium perpyrophosphate, potassium perpyrophosphate, and ammonium perpyrophosphate, sodium persulfate, potassium persulfate, and ammonium persulfate.
In addition to the soap and/or nonsoap surfactants, and persalt, the detergent compositions can include other components which are customary in synthetic surfactant formulations, such as alkaline builder salts, neutral builder salts, soil suspending agents, optical brightening agents, coloring agents and pigments, and perfumes.
Alkaline inorganic and organic builder salts or sequestrants are added in order to improve soil-removal power, particularly for heavily soiled articles. The amount of the alkaline builder salt is usually within the range from about 10 to about 80 percent by weight of the total solids of the composition, preferably from 20 to 60 percent by weight. The alkali metal polyphosphates are particularly advantageous in contributing heavy duty performance and in improving detergent properties in hard water. Such polyphosphates include pentasodium tripolyphosphate, sodium acid tripolyphosphate, pentapotassium tripolyphosphate, tetrasodium and tetrapotassium pyrophosphate, sodium tetraphosphate, sodium hexametaphosphate, and pentaammonium tripolyphosphate.
The alkali metal silicates, borates, and carbonates also can be employed, alone or in admixture with polyphosphates as alkaline builder salts. Examples are the sodium silicates, borax, and sodium carbonate.
Also useful are chelating or sequestering agents. These include the alkali metal, ammonium, and organic amine salts of polyamino-carboxylic acids, for example, the mono, di, tri and tetrasodium salts of ethylene diamine tetraacetic acid, the mono, di and trisodium salts of nitrilo-triacetic acid, and the sodium salts of hexamethylene diamine tetraacetic acid and diethylene triamine pentaacetic acid; salts of oxycarboxylic acids, such as citric acid and gluconic acid; and salts of unsaturated polycarboxylic acids, such as polymaleic acid, polyitaconic acid and polyacrylic acid. These compounds are characterized by the ability to sequester or form complexes with hardness-forming metal ions in aqueous solutions, and therefore are particularly useful when the detergent composition is to be employed in water of medium or heavy hardness. The amount of chelating agent or sequestrant is generally within the range from about 5 to about 40 percent, but preferably from about 10 to about 30 percent by weight of the composition.
Neutral builder salts such as sodium sulfate and potassium sulfate are formed in the neutralization of the sulfate or sulfonate ester detergents and are usually present in admixture with such detergents. Additional amounts of such sulfates can be added, if desired, to build or extend the composition.
Soil-suspending agents also can be added, particularly for heavy duty formulations. Suitable soil-suspending agents are sodium carboxymethyl cellulose, sodium cellulose sulfate, lower alkyl and hydroxy alkyl cellulose ethers, such as ethyl hydroxyethyl cellulose, ethyl hydroxypropyl cellulose, hydroxyethyl cellulose, as well as polyvinyl alcohol and polyvinylpyrrollidone. Soil-suspending agents are usually used, if at all, in amounts of from about 0.05 to about 5 percent, preferably from 0.1 to 2 percent, by weight of the total solids.
Optical brightening agents that may be used include stilbines, diamino-stilbines, acylated cyanuric and triazalyl derivatives of stilbines, diphenyl derivatives, dibenzothiophene derivatives, aminocoumarone salts, derivatives of azotized aminocontaining benzoxazoles, benzothiazoles, and benzimidazoles. A number of such agents are disclosed in U.S. Pat. No. 3,122,508.
The compositions of the invention can be used for washing and cleaning a variety of materials, such as textiles, metals, plastics, leather, wood, stone, glass, porcelain, painted surfaces, tile, both in household and industrial applications.
The following Examples in the opinion of the inventors represent preferred embodiments of the invention:
EXAMPLE 1
A liquid detergent composition was prepared having the following formulation:
Parts by Ingredients Weight ______________________________________ Tallow fatty alcohol ethylene oxide adduct 1 17.5 Cetyl alcohol propylene glycol ether phosphate 2 2.5 Propylene glycol 10.0 Sodium perborate, NaBO 3 .4H 2 O 30.0 Sodium nitrilotriacetic acid, Na 3 NTA.H 2 O 25.0 Sodium carboxymethylcellulose 2.0 Optical whitener for cellulose 0.4 Sodium carbonate 7.6 Water glass Na 2 O.3.3SiO 2 5.0 ______________________________________ 1 Condensation product of tallow fatty alcohols with eight moles of ethylene oxide. 2 Phosphate ester of cetyl alcohol condensed with two moles of 1,2-propylene oxide.
The ingredients listed were mixed by hand, and the resulting liquid paste was homogenized using a colloid mill. The composition obtained was in the form of a viscous cloudy liquid, having a viscosity of 65,000 cp at 25°C. The composition was packed in jars, and stored for two months at room temperature. The jars were then opened, and the product examined. The product showed no signs of phase separation. Analysis of the peroxide content showed an average loss of only 4.1 percent of peroxide value. It is thus apparent that the detergent composition is stable to storage for at least two months at room temperature.
The liquid detergent composition was readily dissolved in water to form a dilute washing solution which had excellent washing properties.
EXAMPLE 2
A liquid detergent composition was preparing having the following formulation:
Parts by Ingredients Weight ______________________________________ Sodium mixed alpha-olefins sulfonates, the mixed olefins having from 15 to 18 carbon atoms 17.5 Glycerol 35.0 Sodium perborate, NaBO 3 .4H 2 O 30.0 Sodium nitrilotriacetic acid, Na 3 NTA.H 2 O 25.0 Sodium carboxymethylcellulose 2.0 Optical whitener for cellulose 0.4 Sodium carbonate 7.6 Water glass Na 2 O.3.3SiO 2 5.0 ______________________________________
The ingredients were mixed by hand, and the resulting liquid paste was homogenized in a colloid mill. A yellow-white viscous liquid was obtained, having a viscosity of 65,000 cp at 25°C. The detergent composition was packed in jars, and stored at room temperature for 2 months. The jars were then opened and the composition examined. The composition had not separated into two phases, and an analysis of the peroxide content showed a loss of only 4.4 percent. Thus, it is clear that this composition is quite storage-stable for at least 2 months.
The composition was readily dissolved in water when diluted to a washing concentration, and gave a washing solution having excellent washing properties.
EXAMPLE 3
A liquid detergent composition was prepared having the following formulation:
Parts by Ingredients Weight ______________________________________ Dinonyl phenol hexadecaethylene glycol ether 25 Polypropylene glycol, molecular weight 1800 10 Pentasodium tripolyphosphate 35 Sodium perborate 20 Sodium silicate 8 Sodium carboxymethylcellulose, Na CMC 1.5 Optical whitener 0.1 ______________________________________
The ingredients were mixed by hand, and the resulting liquid paste was homogenized in a colloid mill. A viscous liquid was obtained, having the viscosity of about 60,000 cp at 25°C. The composition was packed in jars and stored at room temperature for 2 months. The jars were then opened. The composition had not separated into separate phases. Analysis of the peroxide content showed a loss of only 4.0 percent, evidencing good storage stability.
The composition could be readily diluted with water to form a washing solution which had good washing properties.
EXAMPLE 4
A liquid detergent composition was prepared having the following formulation:
Parts by Ingredients Weight ______________________________________ Polypropylene glycol polyethylene glycol ether corresponding to the formula HO(C 3 H 7 O) 21 (C 2 H 4 O) 5 H 20 Hexylene glycol 15 Sodium citrate 20 Sodium percarbonate 15 Sodium silicate 5 Sodium carboxymethylcellulose 1 Sodium carbonate 24 ______________________________________
The ingredients were mixed by hand, and the resulting liquid paste was then homogenized using a colloid mill. A viscous liquid was obtained having a viscosity of about 60,000 cp at 25°C. This composition was stored in jars at room temperature for 2 months, and the jars then opened. The composition had not separated into two phases. Analysis of the peroxide content showed a loss of only 4.1 percent, evidencing good storage stability under these conditions.
The liquid composition was readily diluted with water to a washing concentration, and the resulting solution had excellent washing properties.
However, the particulate detergent compositions containing peroxide bleaching agents are difficult to dissolve, especially in cold or lukewarm water. Moreover, in order to formulate such compositions in solid form, it is necessary first to mix the ingredients with the addition of a liquid, to obtain a good admixture, and then dry the resulting slurry before the peroxide bleaching agent can decompose, which increases handling and production costs. The particulate detergent compositions when thoroughly dried have a tendency to dust, which makes them difficult to handle, and unpleasant to measure out in the dosing capsule of automatic washing machines.
In order to avoid these difficulties, it has been proposed that such compositions be provided in liquid form, dissolved or dispersed in an anhydrous liquid detergent as the liquid suspending or dispersing medium. However, in order to form a uniform slurry or solution in this case, an unusually high amount of the liquid detergent must be employed. According to the amount of peroxide bleaching agent and other builders required, the amount of liquid anhydrous surfactant has to be within the range from about 20 to about 90 percent by weight of the composition. In addition, for 0.1 to about 10 percent by weight of a finely divided carrier, such as silica or alumina, is usually needed, to aid in dispersing the peroxide bleaching agent through the liquid detergent, where it is not soluble therein. Solid carriers of this sort are disadvantageous, however, because they are water-insoluble, and tend to become deposited on the wash, after which they are difficult to remove. Moreover, the amount of liquid surfactant is normally in excess of what is required, or what can be advantageously or efficiently utilized in conjunction with other active ingredients, such as builders and soil-suspending agents, as a result of which the detergent power of the surfactant is to a considerable extent wasted, the detergent serving merely as a suspending medium. Moreover, the peroxide bleaching agent and other inorganic solid ingredients are poorly dissolved or dispersed in most liquid surfactants, as a result of which solubilizing or hydrotropic agents, such as sodium xylene sulfonate, have to be included, to increase the solubility of the solid ingredients in the liquid. Also, the viscosity may be unduly high and has to be lowered by addition of solvents, such as ethanol and benzene.
In accordance with the invention, it has been determined that it is possible to formulate a liquid substantially anhydrous detergent composition containing a peroxide bleaching agent and a surfactant in normal amounts, without the addition of carriers, such as silica or alumina, if there is combined with the peroxide bleaching agent surfactant and any other solid ingredients present an amount within the range from about 5 to about 30 percent by weight of the composition of a polyhydric alcohol or ether thereof which is liquid at ambient temperature. The composition is substantially free from liquid water, although water can be present in the form of water of crystallization with, for example, the peroxide bleaching agent, or the builder, or other ingredients.
Any polyhydric alcohol having from two to about three hydroxyl groups and from two carbon atoms to about six carbons can be used. The polyhydric alcohols can also be combined in polymeric oxyalkylene unit forms, having a molecular weight from about 100 up to a molecular weight of approximately 4,000, as well as mono and poly ethers thereof having at least one free hydroxyl group.
The polyoxyalkylene glycols also can be employed. The polyoxyethylene glycols have a molecular weight within the range from about 108 to about 400, and the polyoxypropylene glycols (of 1,2-oxypropylene units) have a molecular weight within the range from about 136 to about 4,000. Monoalkyl ethers of these polyhydric alcohols can be used, in which the alkyl group has from one to about four carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, and secondary butyl. Exemplary monoalkyl ethers are ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, tripropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dibutylene glycol monobutyl ether, polyoxyethylene glycol monoethyl ether, and polyoxypropylene glycol monopropyl ether.
The tri and tetrahydric polyols also can be used. Glycerol, butylenetriol-1,2,3, pentylenetriol-2,3,4, and hexylenetriol-2,3,5 are exemplary. The mono and dialkyl ethers of the trihydric alcohols, wherein the alkyl group has from about one to about four carbon atoms, also can be used.
If desired, a combination of two or more different polyhydric alcohols, or polyhydric alcohols and monohydric ethers thereof, or polyhydric alcohol monohydric ethers, can be used. Such mixtures facilitate adjustment of the viscosity of the resulting composition.
The amount of polyhydric alcohol or monohydric ether thereof that is required depends upon the polyhydric alcohol or ether employed, as well as the other ingredients of the detergent composition. Enough polyhydric alcohol or monohydric ether thereof is employed to form a liquid detergent composition in which the solid ingredients are either dissolved or dispersed, that is, substantially free from liquid water. In general, such compositions can be obtained using an amount of polyhydric alcohol or monohydric ether thereof within the range from about 5 to about 30 percent by weight of the composition. In most instances, an amount within the range from about 10 to about 20 percent is preferred.
The polyhydric alcohols and ethers thereof act as solvents in the compositions of the invention, and the resulting liquid compositions have a high storage stability, due to the absence of water. The presence of the polyhydric alcohol or ether is also desirable and advantageous when the composition is diluted with water to form a washing solution, since the polyhydric alcohol brings about a more rapid dissolution of the composition. In addition, polyoxypropylene glycols impart a foam-moderating action to the composition, which renders the composition particularly suitable for use in automatic washing machines, particularly those which have a tendency to produce foam in use.
As the surfactant in the compositions of the invention, any anionic, cationic, nonionic, or ampholytic surfactant can be used, separately or in combinations, both of the same and of different types. The surfactant should be either a liquid at ambient temperature, or should form a liquid phase (either a solution or a dispersion) with the polyhydric alcohol or ether. The amount of the surfactant is within the range from about 5 to about 30 percent, preferably from about 10 to about 20 percent, by weight of the detergent composition.
The anionic sulfate or sulfonate ester surfactants constitute a well known class of anionic surfactants. The alkyl aryl sulfonates are defined by the formula ##SPC1##
where R is alkyl having from eight to about eighteen carbons, n is a number from 1 to 3, and M is hydrogen on an alkali metal, ammonium or organic amine cation. One example thereof is sodium dodecyl benzene sulfonate.
Another example are the sulfonated phenyl polypropylene alkanes, characterized by the branched chain structure of polypropylene and tertiary alkyl carbon at the benzene ring, and having the following general structure: ##SPC2##
where M is hydrogen, an alkali metal, ammonium, or an organic amine cation, R 1 and R 2 are alkyl, of the type formula C n H 2n +1 , and at least one R is a polypropylene group, the whole alkyl group containing preferably 12 to 15 carbon atoms. These are known compounds, whose preparation and properties are set forth in U.S. Pat. No. 2,477,383, to Lewis, issued July 26, 1949; they are available in commerce under the trade names "Oronite," "Ultrawet," and "Neolene."
Other water-soluble alkyl aromatic sulfonic acids include those prepared by alkylating benzene or naphthalene with a kerosene fraction, followed by sulfonation to aromatic sulfonic acids, such as sodium keryl benzene sulfonate.
Another class of useful surfactants are the aminoalkane sulfonates, which are characterized by the following structure: ##SPC3##
where A is hydrogen or an alkali metal, i.e., ammonium, sodium or potassium, n is a small whole number from 1 to about 5, preferably 2 or 3, R is hydrogen or an alkyl, aryl, or cycloaliphatic group, such as methyl, and R' is an alkyl or alkylene radical, such as myristyl, palmityl, oleyl and stearyl. Sodium palmitic tauride, sodium palmitic methyl tauride, sodium myristic methyl tauride, sodium palmitic stearic methyl tauride, and sodium palmitic methyl amidopropane sulfonate are typical examples thereof.
These compounds are prepared by interacting the corresponding aliphatic acid anhydride or halide with an organic aliphatic aminosulfonic acid, such as taurine, NH 2 CH 2 CH 2 SO 3 H, and various N-substituted taurines, such as N-methyl taurine or aminopropane sulfonic acid, NH 2 (CH 2 ) 3 SO 3 H.
Other anionic surfactants include esters of sulfuric acid with aliphatic alcohols of ten to eighteen carbon atoms, particularly oleic acid, tall oil, turkey red oil, and acids derived by the reduction of the fatty acids derived from coconut oil, palm oil, sperm oil and the like long-chain fatty acids, sulfonated castor oil, esters and ethers of isethionic acid, long-chain fatty acid esters and long-chain alkyl ethers of 2,3-dihydroxy-propane sulfonic acid and sulfuric acid esters of monoglycerides and glycerol monoethers.
The nonionic polyoxyalkylene ether, ester and glycol surfactants have the following general formula: ##SPC4##
where R is hydrogen or a straight or branched chain saturated or unsaturated hydrocarbon group having from 8 to 26 carbon atoms or an aralkyl group having a straight or branched chain saturated or unsaturated hydrocarbon group of from 6 to 24 carbon atoms attached to the aryl nucleus, and attached to A through the aryl nucleus, A is selected from the group consisting of ethereal oxygen and sulfur, carboxylic ester and thiocarboxylic ester groups, R 3 and R 4 are hydrogen or methyl, and x is a number from 2 to 50. R can, for example, be a straight or branched chain alkyl group, such as octyl, nonyl, decyl, lauryl, myristyl, cetyl, or stearyl, or an alkylaryl group such as octylphenyl, nonylphenyl, decylphenyl, stearylphenyl, etc. In this formula, OH could also be replaced by the group --O(C 3 H 6 O) m H, where m is a number ranging from 1 to 10. Examples of such nonionic surfactants are such as have been obtained by adding ethylene oxide, propylene oxide or butylene oxide to the above mentioned alcohols or phenols.
The sulfated alkoxylated derivatives of the above also are useful anionic surfactants: ##SPC5##
where M is hydrogen or an alkali metal or an organic amine cation and x, R 3 , R 4 , A and R are as above.
Where R is alkyl it will be evident that the wetting agent can be regarded as derived from an alcohol, mercaptan, oxy or thio fatty acid of high molecular weight, by condensation with ethylene oxide, propylene oxide or butylene oxide. Typical of this type of alkyl product are the condensation products of oleyl or lauryl (dodecyl) alcohol, or mercaptan, or oleic or lauric acid, with from 8 to 17 moles of ethylene oxide, such as "Emulfor ON." Typical alkyl esters are "Renex" (polyoxyethylene ester of tall oil acids) and "Neutronyl 331" (higher fatty acid ester of polyethylene glycol).
Where R is aralkyl, the wetting agent can be derived from an alkyl phenol or thiophenol.
Another class of anionic surfactants are the polyoxyalkylene phosphate esters described by the following formula: ##SPC6##
R 1 and R 2 can be the same or different. One or both of R 1 and R 2 is a radical containing polyoxyalkylene ether and no more than one of R 1 and R 2 is hydrogen. The radical containing polyoxyalkylene ether is of the form ##SPC7##
in which n has a value greater than zero, up to about 30, and preferably is within the range from about 1 to about 10, and denotes the average number of oxyalkylene units in the chain. It will be understood that there will be present in admixture species having n values both higher and lower than the average value for n. R 4 and R 5 are hydrogen or methyl.
R 3 is a primary or secondary straight or branched chain saturated or unsaturated aliphatic radical having from about 10 to about 24 carbon atoms, preferably from about 12 to about 22 carbon atoms, or a mono, di, or trialkyl-substituted phenyl radical having from about 6 to about 24 carbon atoms, and preferably from about 8 to about 18 carbon atoms in the alkyl portion.
M is hydrogen or a water-soluble salt-forming cation such as an alkali metal, such as, for instance, sodium or potassium; ammonia; or an organic amine, such as an alkanolamine or an alkylamine radical, for example, monoethanolamine, diethanolamine, triethanolamine, butylamine, octylamine, or hexylamine.
These polyoxyalkylene phosphate esters are known compounds, and are described in U.S. Pat. Nos. 3,294,693 and 3,235,627 and the disclosure thereof in these patents is hereby incorporated by reference. Additional polyoxyalkylene phosphate esters are described in U.S. Pat. No. 3,400,148, at column 17, and in the Mahew & Krupin article in Soap and Sanitary Chemicals, referred to above. The disclosures thereof in these publications are also incorporated by reference.
Additional polyoxyalkylene phosphate ester surfactants are described in U.S. Pat. No. 3,122,508 to Grifo, Mayhew, Stefcik and Woodward, dated Feb. 25, 1964, and in U.S. Pat. Nos. 3,004,056 and 3,004,057 to Nunn and Hesse, dated Oct. 10, 1961.
In general, the polyoxyalkylene ether phosphates are prepared by reaction of phosphorous pentoxide, orthophosphoric acid, pyrophosphoric acid, or a polyphosphoric acid with a suitable nonionic surfactant base.
In the course of the esterification, monoesters and diesters may both be formed, but one may be obtained in preference to the other, according to the reaction conditions and the molar proportions of the reactants. Phosphate esters composed of the mixtures of the mono and di esters in any proportion can be employed, but it is generally preferred that the major proportion, if not all, of the phosphate ester be composed of mono esters.
It may also be noted that the oxypropylene phosphate esters have a lesser foaming tendency than the oxyethylene phosphate esters, and may be preferred for low foaming compositions. Moreover, the lower the value of n and the higher the number of carbon atoms in the R substituent of the oxyalkylene group, the less the foaming tendency of the phosphate ester.
Exemplary organic compounds having an active hydrogen atom that can be employed to produce alkylene oxide adducts for the radical of the oxyalkylene phosphate esters (R 3 in the formula ##SPC8##
are the primary alcohols such as octanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, eicosanol, docosanol, tetracosanol, straight or branched, primary or secondary OXO-alcohols, i.e., alcohols prepared by the OXO process, having from 12 to 26 carbon atoms, such as the essentially straight chain alcohols produced from Fischer-Tropsch olefins by the OXO-process, and multi-branched chain alcohols produced from olefins having at least 7 carbon atoms and two side chains, such as tripropylene, tetrapropylene, pentapropylene, diisobutylene and triisobutylene by the OXO process, mono, di and trialkyl phenols, such as octyl phenol, isooctyl phenol, nonyl phenol, dodecyl phenol, dioctyl phenol, dinonyl phenol, didodecyl phenol, trioctyl phenol, trihexyl phenol, tridodecyl phenol, methyloctyl phenol, and ethylisononyl phenol, tri-primary, secondary, and tertiary butyl phenol, 3-methyl-4,6-dibutyl phenol, octadecyl phenol, dioctadecyl phenol, trioctadecyl phenol, mono, di and tributyl cresol, mono, di and trinonyl cresol.
The polyoxyalkylene base ##SPC9##
can be polyoxy-1,2-propylene; polyoxyethylene; polyoxy-1,2-butylene; polyoxy-2,3-butylene; the so-called Pluronic type of nonionic surfactants, generally block copolymers of a polyoxyethylene chain and a polymerized alkylene oxide of at least three carbon atoms, preferably 1,2-propylene oxide, ranging in molecular weight from about 300 to about 10,000. Thus, the alkylene oxide condensate may consist entirely of one alkylene oxide, or of a condensed mixture of two or more alkylene oxides, such as a mixture of ethylene oxide and propylene oxide, in blocks, or heterogeneously distributed in the oxyalkylene chain.
Among the nonionic surfactants, a preferred class are the alkoxylated alkyl phenols and thiophenols, which have the following general formula: ##SPC10##
where R is a straight or branched chain saturated or unsaturated hydrocarbon group having at least 6 carbon atoms up to approximately 24 carbon atoms, A is oxygen or sulfur, R 4 and R 5 are hydrogen or methyl, and x is a number from 8 to 50. R can, for example, be a straight or branched chain octyl, nonyl, decyl, lauryl, cetyl, myristyl or stearyl group. Typical are the condensation products of octyl and nonyl phenol and thiophenol with from 8 to 17 moles of ethylene oxide, available commercially under the trade name "Igepal CA."
Also useful are the poly-1,2-alkylene oxide wetting agents described and claimed in U.S. Pat. Nos. 2,674,619 to Lundsted, dated Apr. 6, 1954, and 2,677,700 to Jackson et al., dated May 4, 1954. These are condensates of 1,2-alkylene oxides, such as 1,2-propylene oxide or 1,2-butylene oxide, alone or in admixture, and such mixtures can also include ethylene oxide, such as the polyoxypropyleneoxyethylene condensates, the ethylene oxide residues constituting from 20 to 90 percent of the resulting condensate.
These condensates conform to one of the following two type formulae:
Y [ (C 3 H 6 O) n -- E -- H ] x
where Y is the residue of an organic compound containing therein x active hydrogen atoms, n is an integer, x is an integer greater than 1; the values of n and x are such that the molecular weight of the compound, exclusive of E, is at least 900, as determined by hydroxyl number; E is a polyoxyalkylene chain wherein the oxygen/carbon atom ratio is at least 0.5, and E constitutes 20-90 percent, by weight, of the compound: ##SPC11##
wherein Y is the residue of an organic compound containing therein a single hydrogen atom capable of reacting with a 1,2-alkylene oxide; R 1 , R 2 , R 3 and R 4 are selected from the group consisting of hydrogen, aliphatic radicals and aromatic radicals, at least one such substituent being a radical other than hydrogen; m is greater than 6.4 as determined by hydroxyl number, and X is a water-solubilizing group.
Further suitable nonionic surfactants have the general formula:
H(OC 2 H 4 ) n1 -- (OC 3 H 6 ) m1 -- OC 2 to 3 H 4 to 6 -- O(C 3 H 6 O) m2 -- (C 2 H 4 O) n2 --H wherein m 1 and m 2 are numbers ranging from 10 to 50, and n 1 and n 2 are numbers ranging from 1 to 50. Examples of surfactants according to this formula are block copolymers of ethylene oxide and propylene oxide based on propylene glycol and having added to them propylene oxide up to a molecular weight of 1,000 to 3,000, after which ethylene oxide has been added to cause the proportion of ethylene oxide to constitute 5 to 80 percent of the molecular weight of the compound.
As the peroxide bleaching agent, any water-soluble per compound which is a solid and which is stable at ambient temperature can be employed, such as the water-soluble alkali metal and ammonium perborates, percarbonates, persulfates, and perpyrophosphates. The amount of the peroxide bleaching agent is within the range from about 5 to about 35 percent, preferably from about 10 to about 25 percent by weight of the composition. The peroxide salts should be water-soluble at least at the bleaching and/or washing concentration.
Exemplary are sodium perborate, NaBO 3 . 4H 2 O, and NaBO 3 . H 2 O, potassium perborate, ammonium perborate, magnesium perborate, sodium percarbonate, potassium percarbonate, ammonium percarbonate, sodium perpyrophosphate, potassium perpyrophosphate, and ammonium perpyrophosphate, sodium persulfate, potassium persulfate, and ammonium persulfate.
In addition to the soap and/or nonsoap surfactants, and persalt, the detergent compositions can include other components which are customary in synthetic surfactant formulations, such as alkaline builder salts, neutral builder salts, soil suspending agents, optical brightening agents, coloring agents and pigments, and perfumes.
Alkaline inorganic and organic builder salts or sequestrants are added in order to improve soil-removal power, particularly for heavily soiled articles. The amount of the alkaline builder salt is usually within the range from about 10 to about 80 percent by weight of the total solids of the composition, preferably from 20 to 60 percent by weight. The alkali metal polyphosphates are particularly advantageous in contributing heavy duty performance and in improving detergent properties in hard water. Such polyphosphates include pentasodium tripolyphosphate, sodium acid tripolyphosphate, pentapotassium tripolyphosphate, tetrasodium and tetrapotassium pyrophosphate, sodium tetraphosphate, sodium hexametaphosphate, and pentaammonium tripolyphosphate.
The alkali metal silicates, borates, and carbonates also can be employed, alone or in admixture with polyphosphates as alkaline builder salts. Examples are the sodium silicates, borax, and sodium carbonate.
Also useful are chelating or sequestering agents. These include the alkali metal, ammonium, and organic amine salts of polyamino-carboxylic acids, for example, the mono, di, tri and tetrasodium salts of ethylene diamine tetraacetic acid, the mono, di and trisodium salts of nitrilo-triacetic acid, and the sodium salts of hexamethylene diamine tetraacetic acid and diethylene triamine pentaacetic acid; salts of oxycarboxylic acids, such as citric acid and gluconic acid; and salts of unsaturated polycarboxylic acids, such as polymaleic acid, polyitaconic acid and polyacrylic acid. These compounds are characterized by the ability to sequester or form complexes with hardness-forming metal ions in aqueous solutions, and therefore are particularly useful when the detergent composition is to be employed in water of medium or heavy hardness. The amount of chelating agent or sequestrant is generally within the range from about 5 to about 40 percent, but preferably from about 10 to about 30 percent by weight of the composition.
Neutral builder salts such as sodium sulfate and potassium sulfate are formed in the neutralization of the sulfate or sulfonate ester detergents and are usually present in admixture with such detergents. Additional amounts of such sulfates can be added, if desired, to build or extend the composition.
Soil-suspending agents also can be added, particularly for heavy duty formulations. Suitable soil-suspending agents are sodium carboxymethyl cellulose, sodium cellulose sulfate, lower alkyl and hydroxy alkyl cellulose ethers, such as ethyl hydroxyethyl cellulose, ethyl hydroxypropyl cellulose, hydroxyethyl cellulose, as well as polyvinyl alcohol and polyvinylpyrrollidone. Soil-suspending agents are usually used, if at all, in amounts of from about 0.05 to about 5 percent, preferably from 0.1 to 2 percent, by weight of the total solids.
Optical brightening agents that may be used include stilbines, diamino-stilbines, acylated cyanuric and triazalyl derivatives of stilbines, diphenyl derivatives, dibenzothiophene derivatives, aminocoumarone salts, derivatives of azotized aminocontaining benzoxazoles, benzothiazoles, and benzimidazoles. A number of such agents are disclosed in U.S. Pat. No. 3,122,508.
The compositions of the invention can be used for washing and cleaning a variety of materials, such as textiles, metals, plastics, leather, wood, stone, glass, porcelain, painted surfaces, tile, both in household and industrial applications.
The following Examples in the opinion of the inventors represent preferred embodiments of the invention:
EXAMPLE 1
A liquid detergent composition was prepared having the following formulation:
Parts by Ingredients Weight ______________________________________ Tallow fatty alcohol ethylene oxide adduct 1 17.5 Cetyl alcohol propylene glycol ether phosphate 2 2.5 Propylene glycol 10.0 Sodium perborate, NaBO 3 .4H 2 O 30.0 Sodium nitrilotriacetic acid, Na 3 NTA.H 2 O 25.0 Sodium carboxymethylcellulose 2.0 Optical whitener for cellulose 0.4 Sodium carbonate 7.6 Water glass Na 2 O.3.3SiO 2 5.0 ______________________________________ 1 Condensation product of tallow fatty alcohols with eight moles of ethylene oxide. 2 Phosphate ester of cetyl alcohol condensed with two moles of 1,2-propylene oxide.
The ingredients listed were mixed by hand, and the resulting liquid paste was homogenized using a colloid mill. The composition obtained was in the form of a viscous cloudy liquid, having a viscosity of 65,000 cp at 25°C. The composition was packed in jars, and stored for two months at room temperature. The jars were then opened, and the product examined. The product showed no signs of phase separation. Analysis of the peroxide content showed an average loss of only 4.1 percent of peroxide value. It is thus apparent that the detergent composition is stable to storage for at least two months at room temperature.
The liquid detergent composition was readily dissolved in water to form a dilute washing solution which had excellent washing properties.
EXAMPLE 2
A liquid detergent composition was preparing having the following formulation:
Parts by Ingredients Weight ______________________________________ Sodium mixed alpha-olefins sulfonates, the mixed olefins having from 15 to 18 carbon atoms 17.5 Glycerol 35.0 Sodium perborate, NaBO 3 .4H 2 O 30.0 Sodium nitrilotriacetic acid, Na 3 NTA.H 2 O 25.0 Sodium carboxymethylcellulose 2.0 Optical whitener for cellulose 0.4 Sodium carbonate 7.6 Water glass Na 2 O.3.3SiO 2 5.0 ______________________________________
The ingredients were mixed by hand, and the resulting liquid paste was homogenized in a colloid mill. A yellow-white viscous liquid was obtained, having a viscosity of 65,000 cp at 25°C. The detergent composition was packed in jars, and stored at room temperature for 2 months. The jars were then opened and the composition examined. The composition had not separated into two phases, and an analysis of the peroxide content showed a loss of only 4.4 percent. Thus, it is clear that this composition is quite storage-stable for at least 2 months.
The composition was readily dissolved in water when diluted to a washing concentration, and gave a washing solution having excellent washing properties.
EXAMPLE 3
A liquid detergent composition was prepared having the following formulation:
Parts by Ingredients Weight ______________________________________ Dinonyl phenol hexadecaethylene glycol ether 25 Polypropylene glycol, molecular weight 1800 10 Pentasodium tripolyphosphate 35 Sodium perborate 20 Sodium silicate 8 Sodium carboxymethylcellulose, Na CMC 1.5 Optical whitener 0.1 ______________________________________
The ingredients were mixed by hand, and the resulting liquid paste was homogenized in a colloid mill. A viscous liquid was obtained, having the viscosity of about 60,000 cp at 25°C. The composition was packed in jars and stored at room temperature for 2 months. The jars were then opened. The composition had not separated into separate phases. Analysis of the peroxide content showed a loss of only 4.0 percent, evidencing good storage stability.
The composition could be readily diluted with water to form a washing solution which had good washing properties.
EXAMPLE 4
A liquid detergent composition was prepared having the following formulation:
Parts by Ingredients Weight ______________________________________ Polypropylene glycol polyethylene glycol ether corresponding to the formula HO(C 3 H 7 O) 21 (C 2 H 4 O) 5 H 20 Hexylene glycol 15 Sodium citrate 20 Sodium percarbonate 15 Sodium silicate 5 Sodium carboxymethylcellulose 1 Sodium carbonate 24 ______________________________________
The ingredients were mixed by hand, and the resulting liquid paste was then homogenized using a colloid mill. A viscous liquid was obtained having a viscosity of about 60,000 cp at 25°C. This composition was stored in jars at room temperature for 2 months, and the jars then opened. The composition had not separated into two phases. Analysis of the peroxide content showed a loss of only 4.1 percent, evidencing good storage stability under these conditions.
The liquid composition was readily diluted with water to a washing concentration, and the resulting solution had excellent washing properties.