|Publication number||US3755559 A|
|Publication date||Aug 28, 1973|
|Filing date||Aug 23, 1971|
|Priority date||Aug 23, 1971|
|Publication number||US 3755559 A, US 3755559A, US-A-3755559, US3755559 A, US3755559A|
|Original Assignee||Colgate Palmolive Co|
|Export Citation||BiBTeX, EndNote, RefMan|
|Referenced by (29), Classifications (25)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent 3,755,559 HIGH-LATHERING CONDITIONING SHAMPOO COMPOSITION Gordon Trent Hewitt, Upper Montclair, N.J., assignor to Colgate-Palmolive Company, New York, N.Y.
No Drawing. Continuation of abandoned application Ser. No. 816,395, Apr. 15, 1969. This application Aug. 23, 1971, Ser. No. 174,192
The portion of the term of the patent subsequent to Jan. 16, 1990 has been disclaimed Int. Cl. A61k 7/08; Clld 1 84 US. Cl. 424--70 7 Claims ABSTRACT OF THE DISCLOSURE This disclosure relates to a stable, creamy-foam shampoo comprising a tertiary amine oxide, a higher alkyl betaine or sulphobetaine and a soap in the ratio of 2:1:1, respectively.
of 11 to 18 carbon atoms. Soaps of dicarboxylic acids may also be used such as the soaps of dimerized linoleic acid. Soaps of such other higher molecular weight acids such as rosin or tall oil acids, e.g. abietic acid, may also be employed. Specific examples include triethanolamine myristrate, triethanolamine cocoate, potassium isostearate, potassium myristate and the like. The soap functions as an opacifier and thickener and contributes some conditioning properties to the instant composition. Since fatty acids are a natural ingredient of the skin, the usefulness of soap for cosmetic purposes as an ingredient of a shampoo is desirable.
The water-solu-ble tertiary amine oxide which constitutes the major ingredient of this composition may be represented by the general formula: R R R N O wherein R is a higher alkyl radical having from 10 to 18 carbon atoms, such as lauryl, decyl, cetyl, oleyl, stearyl, hexadecyl or an amide substituted group, such as RCONH(CH where RC0 is a long chain alkanoyl radical and n is a small whole number; R and R are each lower alkyl diminishing the natural lustre of the hair. Soap-containing shampoos in the past have had the disadvantage of dulling the hair due to the precipitation thereon of lime and magnesium soap or the like, especially in hard water which also reduces the foaming action of the shampoo. This has largely been overcome by the substitution of synthetic organic detergents for the soap. However, many synthetic detergents tend to remove the natural oils from the hair, leaving it'dy and diflicult to manage. A variety of conditioning agents have been added in an attempt to overcome the detrimental effects of natural oil loss and to improve manageability of the hair. The presence of said conditioning agents have had the disadvantage of adversely affecting the foaming action of the shampoo, whereby the foam volume and/ or foam stability were insufiicient to effect adequate cleansing of the hair. In addition, the conditioning action of aforesaid agents were in many instances inadequate and it was necessary to utilize the additional step of rinsing with a conditioning composition. a Accordngly, it is an object of the invention to provide a high-lathering shampoo with stable, creamy foam in the presence of hair soil.
Another object is to provide a shampoo which leaves the hair conditioned, i.e. lustrous, smooth and manageable. It has now been found that so ap can be combined with a tertiary amine oxide and a higher alkyl betaine or sulfobetaine in an alkaline aqueous medium to yield a cleansing and conditioning shampoo having high and stable foaming capabilities.
Soaps utilized in the composition include the water solu-' ble salts of higher fatty acids of naturally occurring vege'table or animal fats and oils. Examples are sodium, potassium, ammonium, monoethanolamine, diethanol amine, triethanolamine salts, morpholine, diglycolamine, etc. of fatty acids occurring in coconut oil, soy bean oil, castor oil, tallow, or synthetically produced fatty acids. The acid portion of the soap is advantageously that of-a fatty acid such as lauric, myristic, stearic, oleic, elaidic, isostearic, palmiti'c, undecylenic, tridecylenic, pentadecylenic or other saturated or unsaturated fatty acid radical such as methyl, ethyl, propyl or a substituted lower alkyl radical such as hydroxyethyl, hydroxyethoxyethyl, hydroxy polyethoxyethyl etc. Examples of suitable tertiary amine oxides include lauryl dimethyl amine oxide, coconut dimethylamine oxide, dodecyl dimethyl amine oxide,
and the like. The tertiary nitrogen may also be in the form of a cyclic compound such as cocyl morpholine oxide, cocyl imidazoline oxide, etc. The higher alkyl betaine or sulfobetaine utilized in the instant invention renders the soap and tertiary amine oxide compatible and is per se mildly antibacterial. The betaines may be represented by the following structural formula:
x B ut-Rorwherein R is a high molecular alkyl radical having from 10-18 carbon atoms or the amide radical RCONH(CH wherein R is a higher alkyl. radical, R and R are each alkyl radicals having from about 1 to 3 carbon atoms, R, is an alkylene or hydroxyalkyleneradical having from 1 to 4 carbon atoms, and X is an anion selected from the group consisting of SO =ai1d COO= radicals..R and R may be a mixture of a high molecular. alkyl radical and may contain one or more intermediate linkages such as ether or polyether linkages or non-functional substituents such as hydroxyl or halogen radicals which do not affect the hydrophobic characterof the radical..The ionic neutrality of the betaines over awide pH range permits both foaming and adsorption' thereof from the washing solu tion. Examples .of betaines useful herein include the high alkyl betaines, .such as coco dimethyl carboxymethyl betaine, lauryl dimethyl carbox'ym'ethyl betaine, lauryl dimethyl alpha-carb'oxy-ethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2 hydroxyethyl) carboxy methyl betaine, stearyl bis-(2 hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gamma-carboxy-propyl betaine, lauryl bis-(2 hydroxypropyl) alphacarboxyethyl betaine, etc. The sulfobetaines may-be represented by coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl bis-(2 hydroxyethyl) sulfopropyl betaine and the like, amido betaines and amidosulfobetaines, wherein the RCQNH(CI -I radical is attached to the nitrogenatom of the betaine are also useful in this invention. It is sometimes preferable to use the sulfobetaine because of their better solubility and compatability with synthetic detergents, wherein the betaines are desirable in the preparations of an opaque composition because of their thickening properties.
The mixture of higher alkyl betaine, soap and tertiary amine oxide should be suitably proportioned at proper pH values in an aqueous solution to yield foaming cleansing compositions which yield a strong adsorption onto hair, scalp and skin. By suitably selecting the ingredients, clear aqueous solutions with low cloud points are obtainable at alkaline pH, preferably at pH 8-9. Although the proportions of ingredients can be varied over a wide range, it is desirable that the sum of amine oxide plus betaine should be greater than the amount of soap, and the preferred ratio is 2 parts amine oxide: 1 part betaine: 1 part soap. In general, the tertiary amine oxide ingredient constitutes the major detergent in the composition in amounts ranging from 5% to 40% and preferably to 20% by weight of the total. The amount of the betaine ingredient should be sufficient to effect compatability between the tertiary amine oxide and the soap, usually about 6% and preferably about one half the amine oxide content, and more specifically about 5% to 10% by weight of the total composition. The amount of soap is less than the sum of the amine oxide and the betaine, usually about 6% and preferably one half of the amine oxide content, and more specifically about 5% to 10% by weight of the total product.
Formulations embraced by this invention are stable, homogeneous aqueous shampoos which lather properly. These compositions have the dual function of washing and conditioning the hair, leaving the hair soft and more manageable after shampooing. The need for frequent combing is minimized and the act of combing the hair is accomplished with greater facility due to the elimination of tangled hair. The hair is rendered signficantly antistatic and exhibits good sheen or luster and curl retention. Other important advantages include a desirable modification of the foaming power so that there is achieved superior foam volume and stability in the presence of fatty acid soaps.
Foam tests on prototype hair conditioning shampoos have indicated that the foam stabilization contribution of alkanolamide so clearly beneficial in anionic-based shampoos, is not needed in the betaine-amine oxide-fatty acid soap compositions. Both foam volumes and foam consistencies of these novel compositions are superior to prior art formulations as evidenced by a higher volume of foam which was more stable, and slower to break down or drain out of the hair and scalp. In addition, other soap-containing shampoos are more susceptible to the eifects of hard water, rendering the instant products more versatile under myriad conditions. The unusual foam stability of the amine oxide and betaine in the presence of soap renders these ternary formulations useful as soap bars and as bubble bath compositions with foam which is not destroyed by the use of conventional bath soap.
The compatability exhibited by the betaine, soap and amine oxide ingredients, and the excellent protein adsorption of the betaine-amine oxide-soap complex at alkaline pH render these formulations particularly useful as conditioning shampoos. This is unexpected since prior art formulations containing anionic surfactants including soap and alkanolamides do not leave the hair conditioned and do not give evidence of any deposition and residual conditioning surfactants as is shown by the instant compositions, as demonstrated by the substantive deposition of Rubine W. S. dye by the shampooed and rinsed hair. Normally, substrate such as hair will not retain Rubine W. S. dye, a water-soluble anionic dye, unless first treated with cationic surfactants. However, it has now been found that untreated hair shampooed with the instant composition does retain the Rubine dye; illustrating the effective deposition of conditioning surfactants thereon. This substantivity can be exploited in the formulation of hair coloring shampoos by the addition of direct dyes and polyethylen imine to the instant compositions.
Various adjuvant materials may be added to these foaming, aqueous, detergent compositions such as small amounts of viscosity builders and conditioning agents inclusive of gums, hydroxypropyl methyl cellulose and alkanola'mides such as lauric myristic diethanolamide, monoalkanolamides, isopropanolamides. Other ingre dients may include alkaline or acid buffers to aid in the adjustment and maintenance of the desired pH of the finished product such as borax, various inorganic watersoluble phosphates, sodium hydroxide, citric acid, etc. Other additions include optical brighteners, bleaches, germicides, fungicides, bactericides, colorants, perfumes, etc. in minor amounts which do not interfere With the conditioning properties of the composition.
In the manufacture of the shampoo in aqueous forms, the soap component may be prepared in advance or in situ by dissolving the soap fatty acid in warm amine oxide plus betaine or sullfobetaine. The neutrailizing base such as triethanolamine, potassium hydroxide or the like is added until the pH is sufficiently alkaline, preferably 8-9. The resultant solutions are clear, moderately viscous shampoos and retain their clarity when cooled to 34 F. at pHs above 8.3. At pHs below 8.5 it has been found that the amine oxide and the soap are particularly inclined to precipitate, but the precipitation is definitely retarded by the presence of the betaine or sulfobetaine component.
The following specific examples are further illustrative of the nature of the present invention, and it is to be understood that the invention is not limited thereto. All parts are by Weight unless otherwise indicated.
The above ingredients are mixed together with agitation yielding a clear moderately viscous solution particularly useful as a high foaming shampoo.
EXAMPLE II In lieu of the triethanolamine myristate ingredient of Example I, 4% isostearic acid is added to a warm solution of the amine oxide and sulfobetaine and sufficient triethanolamine is used to obtain a pH of 8.6. This composition remains clear when cooled to 34 F. The resultant product is a superior, clear, foaming, conditioning shampoo.
EXAMPLE III To the composition of Example II is added 3.0% lauric myristic diethanolamide. This composition is more viscous than the solutions of Examples I and II, and remains clear when cooled to 34 F. This shampoo product is found to lather profusely and to wash and condition hair.
In addition to the usual and conventional soaps, as described above, there may also be employed other types of fatty carboxylates such as the (l) N-alkanoyl sarcosinates e.g.
wherein R is e.g. C to C (decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, etc.); R is hydrogen, alkyl or cycloalkyl e.g. methyl, ethyl, propyl, hexyl, octyl, cyclohexyl, cyclopentyl substituted cyclohexyls, etc.; x is 1 to 4 and M is a conventional cation, e.g., Na+, K and NHJ; (2) compounds of the type wherein R is alkyl or alkaryl of eg C to C in is 2 or 3, n is 1 to 50 and preferably 1 to 10 and t is 1, 2 or 3; M is a conventional cation e.g. Na+, K+ NH NHQCHZCHZOH,
NH (CH CH OH) N(CH CH OH) etc.
Although the present invention has been described with reference to particular embodiments and examples it will be apparent to those skilled in the art that variations and modifications of this invention can be made and that equivalents can be substituted therefor without departing from the principles and true spirit of the invention.
1. A clear, aqueous, high-lathering shampoo composition for simultaneously cleansing and conditioning hair in a single operation which consists essentially of 5% to 20% by weight of a higher alkyl betaine having the structural formula wherein R is C -C alkyl or C -C alkyl amidopropyl, R and R are each alkyl or hydroxyalkyl radicals having from about 1 to 3 carbon atoms, R, is an alkylene or hydroxyalkylene radical having from 1 to 4 carbons, and X is an anion selected from the group consisting of SO and CO to by weight of a higher alkyl amine oxide having the general formula R R R N- O wherein R is C -C alkyl or C -C alkyl amidopropyl and R and R are each selected from the group consisting of C -C alkyl, C -C hydroxyalkyl and C -C hydroxyalkyloxyalkyl or R and R together with the amino nitrogen form a morpholino or imidazole group; from 5% to 20% by weight of a water-soluble soap selected from the group consisting of salts of a saturated C -C fatty acid; said salt being selected from the group consisting of sodium, potassium, ammonium, monoethanolamine, diethanolamine, triethanolamine, diglycolamine, and morpholine; and the balance being water; said shampoo having a pH of from 8 to 8.6.
2. A composition in accordance with claim 1 wherein the amine oxide is lauryl dimethylamine oxide.
3. A composition in accordance with claim 1 wherein the soap is a triethanolamine soap.
4. A composition in accordance with claim 1 wherein said higher alkyl betaine is present in an amount of 5% to 10% by weight, said soap is present in an amount of 5% to 10% by weight, and the sum of said betaine and said amine oxide being greater than the amount of soap.
5. The composition in accordance with claim 4 wherein the ratio of amine oxidezbetainezsoap is 221:1.
6. A composition in accordance with claim 1 wherein the betaine ingredient is cocosulfobetaine.
7. A composition in accordance with claim 6 wherein the amine oxide is lauryl dimethylamine oxide and the soap is a triethanolamine soap.
References Cited UNITED STATES PATENTS OTHER REFERENCES The Sulfobetaine Technical Bulletin, printed by Texi- Lana Corporation, 1966.
Fatty Amine Oxides by E. Jungermann and M. E.
Ginn, Soap & Chemical Specialties, September 1964, pp. 59-62.
Recent Advances in Fatty Amine Oxides by T. P. Matson, Journal American Oil Chemists Society, vol. 40, November 1963, pp. 640-642.
LEON D. ROSDOL, Primary Examiner D. L ALBRECHT, Assistant Examiner US. Cl. X.R.
252-117, 545, 546, 547, DIGEST 13, DIGEST l4
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US3928251 *||Dec 11, 1972||Dec 23, 1975||Procter & Gamble||Mild shampoo compositions|
|US3950417 *||Feb 28, 1975||Apr 13, 1976||Johnson & Johnson||High-lathering non-irritating detergent compositions|
|US4087387 *||May 10, 1976||May 2, 1978||Lever Brothers Company||Foam cleaning composition|
|US4122043 *||Oct 2, 1975||Oct 24, 1978||Polytrol Chemical Corporation||Amidobetaine containing detergent composition non-toxic to aquatic life|
|US4132679 *||Aug 4, 1977||Jan 2, 1979||Kao Soap Co., Ltd.||Low irritant shampoo composition|
|US4137191 *||Feb 14, 1977||Jan 30, 1979||Inolex Corporation||Low-irritant surfactant composition|
|US4205103 *||May 14, 1975||May 27, 1980||The Goodyear Tire & Rubber Company||Process using same stable foam latex with built-in self gel mechanism and coating|
|US4247538 *||Sep 5, 1978||Jan 27, 1981||Witco Chemical Corporation||Conditioning shampoo|
|US4367151 *||Aug 24, 1981||Jan 4, 1983||Emery Industries, Inc.||Method of treating textiles with amidoamine oxides of polymeric fatty acids|
|US4370273 *||Feb 6, 1981||Jan 25, 1983||Emery Industries, Inc.||Amidoamine oxides of polymeric fatty acids|
|US4396525 *||Sep 14, 1981||Aug 2, 1983||Lever Brothers Company||Phosphate free liquid scouring composition|
|US4486328 *||May 3, 1983||Dec 4, 1984||Colgate-Palmolive Company||Betaine-soap shampoo composition|
|US4490355 *||Mar 14, 1983||Dec 25, 1984||Miranol Chemical Company, Inc.||Betaine based cosmetic formulations|
|US4534877 *||Jun 22, 1983||Aug 13, 1985||The Procter & Gamble Company||Shampoo compositions comprising specific betaine surfactants and a quaternary compound|
|US4555360 *||Jun 22, 1984||Nov 26, 1985||The Procter & Gamble Company||Mild detergent compositions|
|US4587030 *||Jun 13, 1984||May 6, 1986||Economics Laboratory, Inc.||Foamable, acidic cleaning compositions|
|US4699728 *||May 29, 1986||Oct 13, 1987||Ecolab, Inc.||Aqueous acidic composition for cleaning fiberglass|
|US4919846 *||Sep 23, 1988||Apr 24, 1990||Shiseido Company Ltd.||Detergent composition containing a quaternary ammonium cationic surfactant and a carboxylate anionic surfactant|
|US4978526 *||Sep 26, 1988||Dec 18, 1990||Inolex Chemical Company||Hair and skin conditioning agents and methods|
|US5336445 *||Aug 11, 1992||Aug 9, 1994||The Procter & Gamble Company||Liquid hard surface detergent compositions containing beta-aminoalkanols|
|US5342549 *||Jun 7, 1993||Aug 30, 1994||The Procter & Gamble Company||Hard surface liquid detergent compositions containing hydrocarbyl-amidoalkylenebetaine|
|US5454983 *||Aug 27, 1993||Oct 3, 1995||The Procter & Gamble Company||Liquid hard surface detergent compositions containing zwitterionic and cationic detergent surfactants and monoethanolamine and/or beta-aminoalkanol|
|US5531933 *||Aug 23, 1994||Jul 2, 1996||The Procter & Gamble Company||Liquid hard surface detergent compositions containing specific polycarboxylate detergent builders|
|US5534198 *||Jan 25, 1995||Jul 9, 1996||The Procter & Gamble Company||Glass cleaner compositions having good filming/streaking characteristics and substantive modifier to provide long lasting hydrophilicity|
|US5536450 *||Apr 19, 1995||Jul 16, 1996||The Procter & Gamble Comany||Liquid hard surface detergent compositions containing amphoteric detergent surfactant and perfume|
|US5536451 *||Jan 18, 1994||Jul 16, 1996||The Procter & Gamble Company||Liquid hard surface detergent compositions containing short chain amphocarboxylate detergent surfactant|
|US5540865 *||Jan 13, 1995||Jul 30, 1996||The Procter & Gamble Company||Hard surface liquid detergent compositions containing hydrocarbylamidoalkylenebetaine|
|DE3445410A1 *||Dec 13, 1984||Jul 4, 1985||Colgate Palmolive Co||Reaktionsprodukt aus positiv geladenen kationischen polymeren und negativ geladenen anionischen polymeren|
|WO1988004315A1 *||Dec 11, 1987||Jun 16, 1988||Wickford Corp New Jersey||Composition for the removal of indelible stains from the human epidermis and the reconditioning and cleaning of processed animal skins|
|U.S. Classification||424/70.19, 510/427, 424/70.22, 510/494, 424/70.21, 510/129, 424/70.31, 510/126, 510/490, 510/125, 510/503, 510/430, 510/124|
|Cooperative Classification||A61Q5/12, A61K8/44, A61K8/361, A61Q5/02, A61K8/40, A61K2800/596|
|European Classification||A61Q5/02, A61K8/40, A61K8/36C, A61K8/44, A61Q5/12|