US 3849348 A
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United States Patent US. Cl. 252-547 1 Claim ABSTRACT OF THE DISCLOSURE This disclosure relates to an aqueous foaming detergent comprising three essential ingredients, a higher alkyl betaine, sulfobetaine, amidobetaine or amido sulfobetaine; a tertiary amine oxide; and a higher alkyl quaternary nitrogen compound.
This is a continuation of application Ser. No. 816,027, filed Apr. 14, 1969, now abandoned.
The present invention relates to an aqueous, foaming detergent formulation useful as a shampoo, skin cleansing liquid and as a fabric washing and conditioning composition.
Cationic surface active agents, well known in the art have been employed as anti-microbial and/or anti-static constituents of hair conditioning and fabric treating compositions. When these agents are combined with anionic surface active agents in proportions to give homogeneous solutions, the cationic agents generally do not become adsorbed on the hair or fabric to an appreciable extent, and the compositions do not foam well. By combining the cationic agents with compatible amphoteric detergents, compositions are obtained which foam well but do not deposit very much cationic agent on the animate or inanimate substrate at alkaline pHs; or deposit cationic agent on the treated substrate but do not foam well at acid pHs.
Hence, it is apparent that the need exists for a composition which both cleans and conditions in a single step under both acid and alkaline conditions.
Accordingly, it is an object of this invention to provide foaming fabric washing compositions capable of simultaneously cleansing and depositing cationic softeners and bacteriostats on the washed fabric.
Another object is to provide a shampoo composition which will both foam profusely and deposit appreciable amounts of cationic surfactant on the hair and skin.
It has now been found that cationic surface active agents can be combined with a higher alkyl betaine and a tertiary amine oxide over a wide pH range to yield a foaming detergent composition capable of washing, softening and sanitizing in a single operation.
The cationic surface active agents employed in this invention are quaternary ammonium salts having a long chain hydrophobic radical. Especially effective are such compounds as oleyl or stearyl dimethyl benzyl ammonium salts. The oleyl or stearyl radicals may be replaced by other long chain alkyl radicals such as undecylenyl, lauryl, myristyl or cetyl, or by long chain radicals having other groups (e.g. aryloxethyl groups as in diisobutyl phenoxyethoxyethyl dimethyl benzyl ammonium chloride); the benzyl radical may be replaced by a substituted benzyl radical such as 3,4-dimethyl-benzyl, ethylbenzyl, etc., or by an alkyl radical such as methyl, ethyl, lauryl or stearyl (e.g. in di-long chain alkyl dimethyl ammonium chlorides, cetyl trimethyl ammonium bromide, oleyl dimethyl ethyl ammonium bromide, myristyl dimethyl 3,4-dichlorobenzyl ammonium chloride). The quaternary ammonium salt may have the nitrogen in a ring, e.g. in
an N-oleyl N-ethyl morpholinium or N-pyridinium salt or N-(lauroyl colamino formylmethyl) pyridinium chloride, or in an alkyl isoquinolinium salt (e.g. lauryl isoquinolinium bromide) or in an imidazolinium compound such as a l-methyl-l-alkylamidoethyl-Z alkylimidazolinium salt in which the alkyl groups have an average chain length of 17 carbon atoms.
In the preferred compounds there is a quaternary nitrogen atom directly linked to a carbon atoms of a hydrophobic radical of at least ten carbon atoms (such as a long chain alkyl radical or an alkylaryl radical, in which there are l0-20 carbon atoms, for example), three valences of the nitrogen atom being also directly linked to the other carbon atoms which may be in separate radicals (such as alkyl, particularly low alkyl, or aralkyl radicals) or in a cyclic structure including the quaternary nitrogen atom (as in a morpholine, pyridine, quinoline or imidazoline ring). While the hydrophobic radical may be a simple hydrocarbon or hydrocarbon ether radical, it may also contain substituents such as halogen, and may even contain intermediate linkages, such as the amide and ester linkages of the higher alkanoyl colamino formylmethyl radical RCOOCH CH NHCOCH although, as will be seen from the following examples, the presence of such amide or ester linkages is not at all essential in the practice of this invention.
The anion of the quaternary ammonium salt is most usually a chloride or methosulfate (OSO OCH ion, but other ions may be used as is Well known in the art, e.g. bromide, phosphate, dialkyl phosphate, 0r acetate ions.
The cationic surfactants can be selected to either produce primarily antistatic effects when deposited on the substrate or be productive of antimicrobial efiects, or blended to do both.
The higher alkyl betaine utilized as the major detergent in the instant invention is compatible with the aforedefined cationic agent and are themselves mildly antibacterial. Bacteriological tests on betaines in combination with cationics show a potentiation of the antibacterial activity of the cationic due to the presence of an excess of betaine. The betaines may be represented by the following structural formula:
wherein R is a high molecular alkyl radical having from 10-18 carbon atoms or the amido radical RCONH (CH 3 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 hydroxy-alkylene radical having from 1 to 4 carbon atoms, and X is an anion selected from the group consisting of S0 and COO: radicals. R and R may be a mixture of high molecular alkyl radicals 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 affeet the hydrophobic character of the radical. The ionic neutrality of the betaines over a wide pH range permits both foaming and adsorption of the cationic agent from the washing solution. Examples of betaines useful herein include the high alkyl betaines such as coco dimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxy-ethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(Z-hydroxyethyl) carboxy methyl betaine, stearyl bis-(2 hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gammacarboxypropyl betaine, lauryl bis-(2 hydroxypropyl) alpha-carboxyethyl betaine, etc. The sulfobetaines may be represented by coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2 hydroxyethyl) sulfopropyl betaine and the like; amido betaines and amidosulfobetaines, wherein the RCONH(CH radical is attached to the nitrogen atom of the betaine are also useful in this invention.
Another essential ingredient of the present invention is a tertiary amine oxide which may be represented by the general formula: R R R 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 wherein RC is a long chain alkanoyl radical and n is a small whole number; R and R are each lower alykl radicals 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 mixture of a higher alkyl betaine, a higher alkyl quaternary nitrogen compound and a tertiary amine oxide should be suitably proportionated at proper pH values in an aqueous solution to yield foaming, cleansing compositions which yield a strong adsorption onto substrates such as cotton, hair, wool, skin, etc. By suitably selecting the ingredients, clear aqueous solution with low cloud points are obtainable over a wide range of pH without the need for the incorporation of alcohol or glycols as cosolvents. Although the pH can range from 3 to 10, the preferred range is 7.5 to 10, since at alkaline pHs adsorption of cationic active material is strongest. By selecting the molecular weights of the ingredients, the viscosity of the final product can be varied from very thin to moderately viscous. In general, the betaine ingredient constitutes the major detergent in the composition in amounts ranging from to 30% and preferably 13 to 20% by weight of the total. The proportion of cationic agent is usually less than 5% and preferably 2.0% by weight of the total composition but may range from 0.5 to 5%. The proportion of tertiary amine oxide is advantageously less than 15.0% and preferably 3 to by weight of the total detergent composition but may range from 1 to 15%. The amount of amine oxide can be increased if the molecular weights of the betaine compound and the cationic agent are increased.
Formulations embraced by this invention are stable, homogeneous aqueous compositions which lather profusely. Foam tests on prototype conditioning and anti-dandrulf formulations have indicated that the foam stabilization contribution of alkanolamides, so clearly beneficial in anionic-based shampoos, is not needed in the betaineamine oxide-cationic compositions. Apparently the alkaline amine oxide and cationic-betaine complex are already providing fatty nonionic components. Both foam volumes and foam consistencies of these novel compositions are superior to prior art formulations. These products are slow rinsing and feel quite diiferent than conventional shampoos. The feel is more like that of a conditioning creme rinse in that the squeaky-clean feel of rinsed anionic-washed substrates (including soap) is not encountered. These products also exhibit anti-static effects, desirable in both shampoos and fabric washing.
The compatibility exhibited by the betaine, cationic surfactant and amine oxide ingredients, and the excellent protein adsorption of the betaines and cationics over a wide pH range render these formulations particularly useful as conditioning shampoos and fabric treating compositions. By selecting the antibacterial cationic surfactant, products are formulated which can be used as surgical scrub soaps and as antidandruif rinses or shampoos.
Various adjuvant materials may be added to these foaming aqueous detergent compositions such as small amounts of viscosity builders and conditioning agents inelusive of gums, hydroxy-propyl methyl cellulose and alkanolatmides such as lauric myristic diethanolamide, monoalkanolamides, isopropanolamides. Other ingredients 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 water-soluble 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 and sanitizing properties of the composition.
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. 1
EXAMPLE I Ingredients Percent Cocosulphobetaine 15. 0
C Ha coc0I IC H2CH2CH2SO3' Cocobctaine 5. 0
C Ha cocoI I+CHzC O O" Stearyl dim t liyl benzyl ammonium chloride 2. 0 Lauryl dimethyl amine oxide 5. 0 Water q.s
The above ingredients are mixed together with agitation. The resultant liquid has a pH of 7.5 and a cloud point below 34 F. This product is a homogenous, stable, foaming detergent useful either as a conditioning shampoo or fabric washing composition.
The above aqueous detergent composition has a cloud point below 34 F. at pH 7.5.
EXAMPLE III Ingredients Percent Cocoamidosulphobetaine 12.
0 1 CH3 coco-C-N-(CHDa-N -(CHQa-S O;-
H" CH3 Cnpnamiflnhatnlnn 5. 0
O CH: coco-O-N-(CHM-N-ClL-C O O H CH:
Lauryl myristyl dimethyl 3,4-diehloro henzyl ammonium chloride. 1. 0 Oleyl dimethyl benzyl ammonium chloride 1. Cocoamidopropyl dimethyl amine oxide. 5. 0 Laurie myristic diethanolamide (70:30) 3. 0 Perfume 0. 4 Water q.s
The above aqueous detergent composition has a cloud point below 34 F. at pH 7.5.
This aqueous detergent product has a cloud point of 40 F. and a clear point of 42 F. at pH 7.5.
EXAMPLES V AND VI Percent ngredients 5 6 Laurie myristic diethannlamirla 3. 0 3. O Cocoamldosupphohnmine 11. 5 23. 0
0 CH3 cocoC-N(CHz)aN+-(CH:) SOr H CH3 Cocoamidopropyl dimethyl amine oxide 3. 5 7. 0 Shtearyl dimethylbenzyl ammonium chloride. 2.0 9. l
The above ingredients when mixed in an aqueous medium yield a pH of 8.0. The addition of a soluble polythionate or polythionic acid compound hereto results in antidandruii shampoos.
The above ingredients are mixed together and stirred with slight warming. A clear yellow liquid at pH 7.45 is obtained which is particularly suitable as a shampoo.
6 EXAMPLE VIII To the ingredients of Example VII are added 0.7% hydroxypropyl methyl cellulose, 0.4% spice perfume and an amount or organic blue dye sufficient to color the solution (FDC Blue #1), and the water content is reduced to 47.2%. This shampoo has a pH of 7.9 and is a superior conditioning shampoo.
EXAMPLE IX Ingredients Percent Cocoamidosulphobetaine (50% aqueous solution) Cocoamidopropyl dimethyl amine oxide (50% aqueous solution) Cocoamidobetaine (60% aqueous solution) Laurie myristic die de Oleyl dimethyl benzyl ammonium chloride (55% aqueous solution) Deionized water.-
All the ingredients are stirred together with slight warming. The resultant solution has a pH of 7.95. This shampoo is clear at room temperature between a pH of 5 and 9.4.
EXAMPLE X The shampoo of Example IX can be further thickened by adding 1% lauric myristic diethanolamide.
'l-methyl-l-alkyl aminoethyl-2-alkyl imidazolinium methosuliat where alkyl-stearyl, palmityl or hydrogenated tallowyl.
The brightener is dispersed in the alcohol and 2% water, and added to the clear aqueous solution of the other ingredients. The resultant pH is 6.95 which is adjusted to 9.3 with any suitable alkalizing agent. This composition is particularly useful as a laundry detergent containing both softener and brightener. For washing and conditioning such polyamide fabrics as wool, silk and nylon, the use of a nonionic oxazole optical bleach and/or one of the coumarin-derived optical bleaches provides excellent whitening for light colored fabrics.
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 the equivalents can be substituted therefor without departing from the principles and true spirit of the invention.
What is claimed is:
1. A foaming aqueous detergent composition effective in simultaneously cleansing and conditioning in a single operation consisting essentially of (a) 13% to 20% by weight of a compound of the formula Br I. R2NR4X- 3,849,348 7 8 wherein References Cited R is a C to C alkyl or RCONH(CH where I UNITED STATES PATENTS R is a higher alkyl radical;
R2 and R3 are each C1 to 03 alkyl; 3,697,452 10/1972 Olson et a1. 252 s4s R4 is C1 to c4 alkylene or hydroxyalkylene; 5 3,496,110 2/1970 Shumway et a1 252-546 and X is sulfo or carboxy ion; 3,507,796 4/1970 V958 252106 (b) 3% to 10% by weight of a mono C to C alk l, 3,296,145 1/1967 Fmdlan et a1 252-106 d'- t C k l h 1k 1 t t aggge gxidsej Y Y Y C1 to C3 3 Y er lary LEON D. ROSDOL, Primary Examiner (c) 0.5% to 5% by weight of a C to C quaternary 10 E. L. ROLLINS, Assistant Examiner nitrogen compound;
((1) and the balance primarily water, said composition US. Cl. X.R.
having a pH in the range of 7.5 to 10. 13 546 548 528