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Publication numberUS3156656 A
Publication typeGrant
Publication dateNov 10, 1964
Filing dateJan 6, 1958
Priority dateJan 6, 1958
Also published asDE1113792B
Publication numberUS 3156656 A, US 3156656A, US-A-3156656, US3156656 A, US3156656A
InventorsLouis H Libby
Original AssigneeGillette Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Aqueous shampoo composition
US 3156656 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United, States Patent 3,156,656 AQUEOUS SHAMPOO COMPOSITION Louis H. Libby, Highland Park,- Ill., assignor to The Gillette Company, Chicago, 111., a corporation of Delaware No Drawing. Filed Jan. 6, 1958, Ser. No. 707,150 13 Claims. (Cl. 252152) This invention relates to a shampoo composition and pertains more specifically to such a composition comprising in combination a cationic surface active agent, a non-ionic polyoxyalkylene surface active agent, and certain cycloimidine derivatives.

It is known that cationic surface active agents are desirable for use in shampoos because they not only are effective in hard water as well as in soft, but in addition their use leaves the hair in a desirable condition in that it is readily combed either wet or dry with a minimum of snarling and possesses a desirable glossy appearance. However, these surface active agents are generallypoor foamers and are deficient in cleansing efiectiveness. Moreover, high concentrations result in undue irritation of the skin and thus these agents have not achieved widespread use in shampoos. It is also well known that nonionic polyoxyalkylene surface active agents possess the desired cleansing effectiveness in both hard and soft water, although they are poor foamers and lack the property of leaving the air in good condition. It therefore would be expected that a combination of cationic and non-ionic polyoxyalkylene surface active agents would provide a highly effective shampoo composition. However, the combination of these two agents exhibits high ophthalmic irritancy characteristics as shown, for example, by applying such a shampoo composition to the eyes of rabbits, and this is true even though each surface active agent of the combination by itself displays very little irritancy.

It has now been discovered that by adding to the foregoing mixed composition certain cycloimidine derivatives, the ophthalmic irritancy of the combination is greatly reduced, as shown by the standard Draize Rabbit Eye Irritation Test, without impairing the desirable characteristics imparted to the combination by its several components and while improving the foaming character istics thereof. The pH of the compositions of the invention may vary widely, from 3 to 75, although it is preferably from 4.5 to 6.5.

Any cationic surface active agent may be employed in the present invention, quaternary ammonium chlorides which contain at least one alkyl group having from 12 to 20 carbon atoms being preferred. Among the numerous cationic surface active agents which may be used are distearyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, stearyl trimethyl ammonium chloride, coco dimethyl benzyl ammonium chloride, dicoco dimethyl ammonium chloride, cetyl pyridinium chloride, cetyl trimethyl ammonium bromide, stearyl amine salts that are soluble in water such as stearyl amine acetate and stearyl amine hydrochloride, stearyl dimethyl amine hydrochloride, distearyl amine hydrochloride, alkyl phenoxyethoxyethyl dimethyl ammonium chloride, decyl pyridinium bromide, pyridinium chloride derivative of the acetyl amino ethyl esters of lauric acid, lauryl trimethyl ammonium chloride, decyl amine acetate, lauryl dimethyl ethyl ammonium chloride, the lactic acid and citric acid and other acid salts of stearyl-l-amidoethyl-Z-heptad'ecyl-Z-imidazoline, quaternaries of such imizadoline with methyl chloride, benzyl chloride, chloroacetic acid and similar compounds, mixtures of the foregoing, and the like. Particularly preferred are stearyl trimethyl ammonium chloride, the lactic or the citric acid salt of stearyl-l-amidoethyl-Z-heptadecyl-2-imidazoline, or mixtures thereof.

The non-ionic polyoxyalkylene surface active agent may be any of the numerous surface active agents prepared, for example, by condensation of ethylene oxide with a variety of other compounds, of which many are known. The polyoxyalkylene chain in such agents may contain from 5 to 20 alkylenoxy units, preferably from 10 to 15, each alkylene group containing from 2 to 3 carbon atoms. Among those which are suitable are ethylene oxide condensates with alkyl phenols such as nonyl phenyl polyoxyethylene ether, the condensation products of ethylene oxide with fatty alcohols such as tridecyl polyoxyethylene ether, the condensation products of ethylene oxide with long chain alkyl mercaptans such as dodecyl polyoxyethylene thioether, the condensation products of ethylene oxide with long chain fatty acids such as the polyoxyethylene ester of lauric acid, the condensation products of ethylene oxide with long chain fatty acid amides or the condensation products of ethylene oxide with partial fatty acid esters of a polyhydroxy compound such as sorbitol, for example, the lauric ester of sorbitan polyoxyethylene ether, the condensation products of ethylene oxide with a hydrophobic base formed by condensing propylene oxide with propylene glycol, the condensation products of ethylene oxide with lanolin, the condensation products of ethylene oxide itself. It will be understood, of course, that propylene oxide may be used in place of ethylene oxide in many of these compounds with much the same results. The lower alkyl phenyl polyethylene glycol ethers are preferred.

The cycloimidine derivatives which have been found effective to reduce the ophthalmic irritancy of the combinations of the present invention are those having the following structures:

' in which R is a hydrocarbon group having from 4 to 18 carbon atoms, R R and R are selected from the group consisting of (a) aliphatic hydrocarbon groups of 1 to 4 carbon atoms, (b) hydroxy-substituted aliphatic hydrocarbon groups of 1 to 4 carbon atoms, (c) aliphatic hydrocarbon groups having a single ether linkage and of 2 to 4 carbon atoms, (d) hydroxy-substituted aliphatic hydrocarbon groups having a single ether linkage and of 2 to 4 carbon atoms, (e) aliphatic keto groups containing only a single keto linkage and otherwise being hydrocarbon of 2 to 4 carbon atoms, (f) aliphatic keto groups containing only a single keto linkage and otherwise being hydroxy-substituted hydrocarbon of 2 to 4 carbon atoms, and M is an alkali metal. In the foregoing structure R represents an organic radical which if connected to a carboxyl group provides a monocarboxylic acid; i.e., a fatty acid such as n-valeric, caproic, caprylic, pelargonic, lauric, palmitic, stearic, and the like.

It will be understood that R R and R may be the same or different in any particular compound within this class; for example, R R and R may be such groups as CH2, C2H4-', -'C3H6, and -C4H8, 01' any of these groups in which any one or more of the hydrogen atoms has been replaced by a hydroxy group, as for example, in -CH CHOHCH or CH CHOHCHOHCH In addition, any of these groups, including those containing hydroxy groups, may contain a single oxygen ether or keto linkage, as for example -C H OC H In each compound both of the alkali metal atoms represented by the letter M may be identical or may be different; preferably, the alkali metal atom is either sodium or potassium.

The cycloimidine derivatives are well known and may be prepared as described in Mannheimer US. Patents 2,528,378, granted October 31, 1950, and 2,773,068, granted December 4, 1956.

The shampoo compositions of the present invention are aqueous compositions which may contain in addition to water, if desired, small quantities of an alcohol solvent such as ethyl or propyl alcohol. The cationic surface active agent is present in an amount from 0.4% to 7% by weight of the total composition, while the non-ionic polyoxyalkylene surface active agent is present in an amount from 2% to 20% by weight of the total composition, the relative proportions of these two ingredients with respect to each other not being critical. The cycloimidine derivative in order to be elfective must be present in an amount from 8% to 20% by weight of the total composition and must be at least equal to the amount of the non-ionic polyoxyalkylene surface active agent present in the composition.

In order to increase the lubricity of the composition still further and to provide a shampoo having high foaming characteristics, it is preferred to include in the composition, in addition to the foregoing ingredients, from 0.4% to 7% by weight of a lower alkylolamide of a fatty acid having from to 20 carbon atoms in the chain; for example, the monoor di-ethanolamide or monoor di-isopropanolamide of lauric acid, coconut oil fatty acid, palrnitic acid, stearic acid, and the like.

These characteristics may be further improved by including also from 0.4% to 7% by weight of a compound having the structure in which R and R is each a lower alkyl group containing up to four carbon atoms, and R is one of the radicals having the structure in which R and R is each a lower alkyl group containing up to 4 carbon atoms, among which are 3,6-dimethyl- 4-octyne-3,6-diol; 2,5-dimethyl-3-hexyne-2,S-diol; 3,6-diethyl-4-octyne-3,6-diol; 3,6-dimethyloctane-3,6-diol; and the like.

Any of the usual additives such as opacifiers, perfumes, coloring agents, stabilizers, preservatives, and the like may also be included in the composition if desired.

The following specific examples are intended to illustrate more clearly the nature of the invention, but are not intended as a limitation upon the scope of the claims.

Example 1 An aqueous solution was prepared containing 2.4% by Weight of the condensation product of ethylene oxide with an alkyl phenol sold under'the name Triton X-lOO and 1.5% by weight of alkyl dimethyl benzyl ammonium chloride sold under the name BTC. Citric acid was added to adjust the pH of the solution to pH 5, and it was then em ployed in the standard Draize Rabbit Eye Test procedure. Out of five eyes tested, four showed moderate to severe lesions.

There was added to the foregoing solution 9.6% by weight of a cycloimidine derivative sold under the name Miranol C2M and having the structure in which R is the residue of coconut oil fatty acid. When employed in the same test only a single negligible reaction was observed out of five eyes tested.

Example 2 An aqueous solution was prepared containing 1.5 by weight of distearyl dimethyl ammonium chloride. When tested as described in Example 1, one moderate to severe lesion was observed in six eyes tested. The addition of Triton X- increased considerably the irritancy of the composition until when as much as 12% by weight of Triton X-lOO was present (pH 5), four severe lesions and three moderate to severe lesions were observed in seven eyes tested.

However, the irritancy was eliminated by the introduction into the mixture of a cycloimidine derivative known as Miranol CM having the structure in which R is the residue of coconut fatty acid.

A composition containing 6% by weight of Triton X-lOO, 1.5 of distearyl dimethyl ammonium chloride, 6% by Weight of Miranol CM, and sufiicient acid to provide pH 5, when tested as above, showed negative results for all six eyes tested.

Example 3 An aqueous solution was prepared containing 4% by weight of Triton X-100, 15% of distearyl dimethyl ammonium chloride, 16% of Miranol CM, and sufiicient lactic acid to provide pH 5. All negative results were obtained out of five eyes tested.

Example 4 An aqueous solution was prepared containing 2.4% by weight of Triton X-lOO, 1.5% distearyl dimethyl ammonium chloride, 9.6% Miranol 02M, and sufficient tartaric acid to provide neutral pH. All negative results were obtained in six eyes tested.

All of the mixed compositions described in Examples 1 to 4 inclusive possessed the desired cleansing properties of the non-ionic surface active agent as well as the hairconditioning properties of the cationic surface active agent. Similar results were obtained with other similar materials within the scope of the invention.

Example 5 The following compositions were prepared, in which the parts are by weight, the pH in each case being 5:

Each of the foregoing compositions possessed a Inbricity even better than that of the compositions of Examples 1 to 4 inclusive and in addition possessed markedly superior foaming characteristics without any loss of cleans- 5 ing power or hair-conditioning properties. When tested for ophthalmic irritancy by the standard Draize test, only a single negligible reaction was observed in fifteen eyes tested.

Examples 6 to 11 Aqueous solutions were prepared having the following compositions in which the parts are by weight, the solution in each case being adjusted to pH 5 by addition of citric acid:

Tergitol NPX 8. Diethanolamide of laurie acid.-- 3. 0 Lactic acid salt of stearyl amido -eithyl-2-heptadecyl irnidazoine Citric acid salt of stearyl amide ethyl-Z-heptadecyl imidazo- Tl P Stefiryl trimethyl ammonium c r e Ethoxylated lanolin derivative sold as Ethoxylan 50 (50% active Condensate of ethylene oxide with hydrophobic base formed by condensing propylene oxide with propylene glycol sold as Pluronic I 68 Miranol 02M 3,6-Dimethyl-4-octyne-3,6- Water, perfume, etc., to

H Heisman cacao Each of the foregoing compositions possessed a very satisfactory lubricity and exhibited hair conditioning properties along with cleansing properties. All of the compositions were satisfactory when tested for ophthalmic irritancy by the Draize test.

Similar results are obtained using other specific surface active agents as described above.

Although specific embodiments of the invention have been described herein, it is not intended to limit the invention solely thereto, but to include all of the obvious variations and modifications within the spirit and scope of the appended claims.

What is claimed is:

1. An aqueous shampoo composition consisting essentially of water in combination with (A) a cationic surface active agent in an amount from 0.4% to 7% by weight, (B) a non-ionic polyoxyalkylene surface active agent containing from to 20 alkylenoxy units, each said unit having from 2 to 3 carbon atoms, said non-ionic agent being present in an amount from 2% to 20% by weight, and (C) an amount, at least equal to the amount of said non-ionic agent and from 8% to 20% by weight, of a member of the class consisting of compounds having the structures in which R is a hydrocarbon group having from 4 to 18 carbon atoms, R R and R are selected from the group consisting of (a) aliphatic hydrocarbon groups of 1 to 4 carbon atoms, (b) hydroXy-substituted aliphatic hydrocarbon groups of 1 to 4 carbon atoms, (0) aliphatic hydrocarbon groups having a single ether linkage and of 2 to 4 carbon atoms, (d) hydroXy-substituted aliphatic hydrocarbon groups having a single ether linkage and of 2 to 4 carbon atoms, (e) aliphatic keto groups containing only a single keto linkage and otherwise being hydrocarbon of 2 to 4 carbon atoms, (7) aliphatic keto groups containing only a single keto linkage and otherwise being 6 hydroxy-substituted hydrocarbon of 2 to 4 carbon atoms, and M is an alkali metal.

2. An aqueous shampoo composition as defined in claim 1 consisting essentially of in addition from 0.4% to 7% by weight of a lower alkylolamide of a fatty acid having from 10 to .20 carbon atoms.

3. An aqueous shampoo composition as defined in claim 1 consisting essentially of in addition from 0.4% to 7% by weight of a compound having the structure Ra R (i3-Ro in which R; and R is each a lower alkyl group and R is a member of the class consisting of R10 R10 45045-111. and -on, ong-c au in which R and R is each a lower alkyl group.

4. An aqueous shampoo composition as defined in claim 1 consisting essentially of in addition from 0.4% to 7% by weight of a lower alkylolamide of a fatty acid having from 10 to 20 carbon atoms, and from 0.4% to 7% by weight of a compound having the structure in which R, and R is each a lower alkyl group, and R is a member of the class consisting of in which R and R is each a lower alkyl group.

5. An aqueous shampoo composition as defined in claim 1 in which said cationic surface active agent consists essentially of a quaternary ammonum chloride con taining at least one alkyl group having 12 to 20 carbon atoms and said non-ionic polyoxyalkylene surface active agent consists essentially of a lower alkyl phenyl polyethylene glycol ether.

6. An aqueous shampoo composition consisting essentially of Water in combination with a cationic surface active agent in an amount from 0.4% to 7% by weight, a non-ionic polyoxyalkylene surface active agent containing from 5 to 20 alkylenoxy units, each said unit having from 2 to 3 carbon atoms, said non-ionic agent being present in an amount from 2% to 20% by weight, and a compound having the structure I l R-d ---N-cn,cn,oNa

on 011,00 ONa m which R is an aliphatic hydrocarbon group having from 4 to 18 carbon atoms, the last said compound being present in an amount from 8% to 20% by weight at least equal to the amount of said non-ionic agent.

7. An aqueous shampoo composition consisting essentially of water in combination with a cationic surface active agent in an amount from 0.4% to 7% by Weight, a non-ionic polyoxyalkylene surface active agent containing from 5 to 20 alkylenoxy units, each said unit having from 2 to 3 carbon atoms, said non-ionic agent being present in an amount from 2% to 20% by weight, and a compound having the structure in which R is an aliphatic hydrocarbon group having from 4 to 18 carbon atoms, the last said compound being present in an amount from 8% to 20% by weight at least equal to the amount of said non-ionic agent.

8. An aqueous shampoo composition consisting essentially of water in combination with a quaternary ammonium chloride containing at least one alkyl group having 12 to 20 carbon atoms as a surface active agent in an amount from 0.4% to 7% by weight, a lower alkyl phenyl polyethylene glycol ether surface active agent containing from 5 to 20 ethylenoxy units, the last-said surface active agent being present in an amount from 2% to 20% by weight, and a compound having the structure OH CHzCOONa in which R is an alpihatic hydrocarbon group having from 4 to 18 carbon atoms, the last said compound being present in an amount from 8% to 20% by weight at least equal to the amount of said non-ionic agent.

9. An aqueous shampoo composition as defined in claim 8 consisting essentially of in addition from 0.4% to 7% by weight of a compound having the structure in which R; and R is each a lower alkyl group, and R is a member of the class consisting of R10 llho CEC'(ER11 and --CH1-CH C-Rn in which R is an aliphatic hydrocarbon group having from 4 to 18 carbon atoms, the last said compound being present in an amount from 8% to 20% by Weight at least equal to the amount of said non-ionic agent.

11. An aqueous shampoo composition as defined in claim 10 consisting essentially of in adition from 0.4% to 7% by weight of a compound having the structure in which R and R is each a lower alkyl group, and R is a member of the class consisting of in which R and R is each a lower alkyl group.

12. An aqueous shampoo composition consisting essentially of water in combination with (A) a member of the class consisting of stearyl trimethyl ammonium chloride, the lactic acid salt of stearyl-1-amidoethyl-2-heptadecyl-2- imidazoline and the citric acid salt of stearyl-l-amidoethyl-2-heptadecyl-2-imidazoline in an amount from 0.4% to 7% by weight, (B) a non-ionic polyoxyethylene surface active agent containing from 5 to 20 ethylenoxy units, said non-ionic agent being present in an amount from 2% to 20% by weight, and a compound having the structure in which R is an aliphatic hydrocarbon group having from 4 to 18 carbon atoms, the last said compound being present in an amount from 8% to 20% by weight at least equal to the amount of said non-ionic agent.

13. An aqueous shampoo composition consisting essentially of water in combination with (A) a member of the class consisting of stearyl trimethyl ammonium chloride, the lactic acid salt of stearyl-1-amidoethyl-2-heptadecyI-Z-imidazoline and the citric acid salt of stearyl-1- amidoethyl-2-heptadecyl-Z-imidazoline in an amount from 0.4% to 7% by weight, (B) a non-ionic polyoxyethylene surface active agent containing from 5 to 20 ethylenoxy units, said non-ionic agent being present in an amount from 2% to 20% by weight, and a compound having the structure in which R is an aliphatic hydrocarbon group having from 4 to 18 carbon atoms, the last said compound being present in an amount from 8% to 20% by weight at least equal to the amount of said non-ionic agent.

References Cited in the file of this patent UNITED STATES PATENTS 2,528,378 Mannheimer Oct. 31, 1950 2,619,467 Isbell Nov. 25, 1952 2,773,068 Mannheimer Dec. 4, 1956 2,794,765 Albrecht June 4, 1957 2,820,043 Rainey Jan. 14, 1958 2,831,815 Klisch Apr. 22, 1958 2,950,255 Goff Aug. 23, 1960 OTHER REFERENCES Lesser: Shampoos Part II Soap and Sanitary Chemicals, January 1951, pp. 3841, 115, 117 and 119. Page 40.

McCutcheon: Synthetic Detergents and Emulsifiers -Up to date, Part IV of Four, in Soap and Chemical Specilaites, p. 59, vol. 31, October 1955.

Schwartz and Perry: Surface Active Agents, Interscience Publishers, Inc. (N.Y.), 1949, pp. 212, 213, 218 and 219.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2528378 *Sep 20, 1947Oct 31, 1950John J Mccabe JrMetal salts of substituted quaternary hydroxy cycloimidinic acid metal alcoholates and process for preparation of same
US2619467 *Apr 16, 1949Nov 25, 1952 Detergent mixtures containing
US2773068 *Jul 11, 1955Dec 4, 1956Hans S MannheimerSubstitution derivatives of imidazoline alkanoic quaternary ammonium hydroxide and process of preparing same
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3322676 *Jun 22, 1965May 30, 1967Ciba LtdShampoos
US3331781 *Jun 21, 1965Jul 18, 1967OrealAmphoteric surface-active agents and method of preparing them
US3431207 *Jun 28, 1965Mar 4, 1969Malmstrom Chem CorpWater-insoluble bacteriostats in soap and detergent solutions
US3549544 *Oct 3, 1966Dec 22, 1970Swift & CoLiquid synthetic detergent
US3708426 *Jun 16, 1970Jan 2, 1973Dragoco Gerberding Co GmbhHair cosmetic preparation
US3925241 *Feb 26, 1973Dec 9, 1975Basf Wyandotte CorpAmphoteric surfactant gels
US3928251 *Dec 11, 1972Dec 23, 1975Procter & GambleMild shampoo compositions
US3951878 *Nov 23, 1971Apr 20, 1976Millmaster Onyx CorporationImidazoline oxides
US3990991 *Nov 4, 1975Nov 9, 1976Revlon, Inc.Shampoo conditioner formulations
US4013576 *Nov 21, 1973Mar 22, 1977Wesley-Jessen Inc.Contact lens treating composition
US4058488 *Sep 17, 1975Nov 15, 1977Millmaster Onyx CorporationImidazoline oxides
US4154706 *Jul 7, 1977May 15, 1979Colgate-Palmolive CompanyNonionic shampoo
US4294728 *Nov 26, 1979Oct 13, 1981Societe Anonyme Dite: L'orealShampoo and/or bubble bath composition containing surfactant and 1,2 alkane diol
US4336151 *Jul 6, 1981Jun 22, 1982American Cyanamid CompanyDisinfectant/cleanser compositions exhibiting reduced eye irritancy potential
US4336152 *Jul 6, 1981Jun 22, 1982American Cyanamid CompanyDisinfectant/cleanser compositions exhibiting reduced eye irritancy potential
US4452732 *Dec 6, 1982Jun 5, 1984The Procter & Gamble CompanyShampoo compositions
US5679330 *Dec 28, 1994Oct 21, 1997Kao CorporationShampoo composition
Classifications
U.S. Classification510/124, 510/479, 424/70.19, 510/423, 510/490, 510/121, 510/505, 510/480, 424/70.31
International ClassificationA61K8/90, A61K8/49, A61K8/34, A61K8/41, A61Q5/02, C11D1/00, A61K8/92
Cooperative ClassificationA61K2800/596, A61K8/90, A61K8/925, A61K8/416, A61K8/345, A61K8/4946, A61Q5/02
European ClassificationA61K8/92F, A61K8/41L, A61K8/34D, A61K8/90, A61Q5/02, A61K8/49F1