CA2299340A1 - Preservative system for personal hygiene products - Google Patents

Abstract

The invention relates to the use of a mixture of at least one quarternary ammonium compound and at least one anionic preservative and/or at least one .alpha.-hydroxycarboxylic acid as a preservative system for personal hygiene products. The invention also relates to a preservative system containing at least one quaternary ester compound (esterquat) and at least one alkaline salicylate in a weight ratio of 1:20 to 100:1.

Description

,. CA 02299340 2000-02-04 Preservative System for Personal Hygiene Products This invention relates to the preservation of body care compositions, more particularly to the preservation of hair care compositions, using quaternary ammonium compounds and anionic preservatives and/or a-hydroxycarboxylic acids. The present invention also relates to a mixture of special quaternary ammonium compounds, so-called esterquats, and sodium salicylate and to its use as a preservative for personal care compositions.
The human body, especially the hair, is treated in various ways with cosmetic preparations (hair treatment compositions). These treatments include, for example, the cleaning of the body and the hair with shampoos and shower preparations and bleaching, coloring and shaping of hair with wave lotions, tinting compositions and styling preparations.
Hair treatment compositions formulated as conditioners or rinses are normally aqueous emulsions of various water-soluble or fat-soluble ingredients. The preservation of such emulsions to maintain performance, particularly in the event of prolonged storage, is sometimes difficult.
Quaternary ammonium compounds, which are used in many body care compositions, particularly in most hair treatment compositions, do have a certain microbicidal effect in such compositions, but this is not sufficient on its own for preservation.
It has now been found that effective preservation of body care compositions, more particularly hair care compositions, can be achieved if a combination of at least one quaternary ammonium compound and at least one anionic preservative and/or at least one a-hydroxycarboxylic acid is used as the preservative system.
These active ingredients surprisingly complement one another in such a way that a synergistic increase in effect is obtained.

Accordingly, the present invention relates to the use of a mixture of - at least one quaternary ammonium compound and - at least one anionic preservative and/or - at least one a-hydroxycarboxylic acid as a preservative system for body care compositions.
The body care composition is preferably a hair care composition. In the context of the invention, hair care compositions also include those hair treatment compositions which are merely intended to produce a decorative change in the hair, for example hair colorants or permanent wave preparations.
Suitable quaternary ammonium compounds are both polymeric and monomeric substances. The polymers suitable for use in accordance with the invention are generally cationic polymers containing an ammonium group. Preferred cationic polymers are, for example, - quaternized cellulose derivatives of the type commercially obtainable under the names of Celquat~ and Polymer JR~; the compounds Celquat~ H 100, Celquat~ L 200 and Polymer JR~ 400 are preferred quaternized cellulose derivatives;
- polysiloxanes containing quaternary groups, - polymeric dimethyl diallyl ammonium salts and copolymers thereof with esters and amides of acrylic acid and methacrylic acid; the products commercially obtainable under the names of Merquat~ 100 (poly(dimethyl diallyl ammonium chloride)) and Merquat~ 550 (dimethyl diallyl ammonium chloride/acrylamide copolymer) are examples of such cationic polymers;
- copolymers or vinyl pyrrolidone with quaternized derivatives of dialkyl-aminoacrylate and methacrylate, for example vinyl pyrrolidone/dimethyl-aminomethacrylate copolymers quaternized with diethyl sulfate;
compounds such as these are commercially obtainable under the ._ CA 02299340 2000-02-04 names of Gafquat~ 734 and Gafquat~ 755;
- vinyl pyrrolidone/methoimidazolinium chloride copolymers which are commercially obtainable under the name of Luviquat~, - quaternized polyvinyl alcohol and the polymers containing quaternary nitrogen atoms in the main polymer chain which are known by the names of - Polyquaternium 2, - Polyquaternium 17, - Polyquaternium 18 and - Polyquaternium 27.
However, it is generally of advantage to use a compound from the group of cationic surfactants as the quaternary ammonium compound.
Among the cationic surfactants, quaternary ammonium compounds are preferred. Preferred quaternary ammonium compounds are ammonium halides, more particularly chlorides and bromides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkyl methyl ammonium chlorides, for example cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, dicetyl dimethyl ammonium chloride, dicetyl dimethyl ammonium bromide, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, dilauryl dimethyl ammoni-um chloride, lauryl dimethyl benzyl ammonium chloride and tricetyl methyl ammonium chloride.
Other suitable quaternary ammonium compounds are quaternary ester compounds, so-called esterquats, which can be preferred by virtue of their ready biodegradability. In this connection, reference is made for example to WO 91101295, according to which triethanolamine is partly esterified with fatty acids in the presence of hypophosphorous acid and, after air has been passed through, the reaction mixture is quaternized with dimethyl sulfate or ethylene oxide. The following patents are cited as representative of the extensive prior art available on the subject: US
3,915,867, US 4,370,272, EP-A 0 239 910, EP-A 0 293 955 A2, EP-A 0 295 739 and EP-A 0 309 052. Overviews of this subject have been published, for example, by R. Puchta et al. in Tens. Surf. Det, 30, 186 (1993), by M. Brock in Tens. Surf. Det., 30, 394 (1993) and by R.
Lagerman et al. in J. Am. Oil. Chem. Soc., 71, 97 (1994).
One example of esterquats are the quaternized fatty acid triethanol-amine ester salts corresponding to general formula I:

[R'CO(-OCHZCH2)mOCHZCHz-N+-CH2CH20(-CHZCH20)"R2~X- (I) CHZCH20(-CH2CHz0)pR3 in which R'CO is an acyl group containing a total of 6 to 22 carbon atoms, R2 and R3 independently of one another represent hydrogen or have the same meaning as R'CO, R4 is an alkyl group containing 1 to 4 carbon atoms or a (CH2CH20-)qH group, m, n and p together stand for 0 or for numbers of 1 to 12, q is a number of 1 to 12 and X- is halide, alkyl sulfate or alkyl phosphate.
Typical examples of quaternized fatty acid triethanolamine ester salts which may be used in accordance with the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and the technical mixtures thereof obtained, for example, in the pressure hydrolysis of natural fats and oils.
Technical C~2_~s cocofatty acids and, in particular, partly hydrogenated C~so~s tallow or palm oil fatty acids and high-elaidic C~6-18 fatty acid cuts are preferably used.
To produce the quaternized fatty acid triethanolamine ester salts corresponding to general formula I, the fatty acids and the triethanolamine _ CA 02299340 2000-02-04 may be used in a molar ratio of 1.1:1 to 3:1. With the performance properties of the esterquats in mind, it has proved to be of particular advantage to use the fatty acids and the triethanolamine in a molar ratio of 1.2:1 to 2.2:1 and preferably 1.5:1 to 1.9:1. The preferred quaternized fatty acid triethanolamine ester salts corresponding to general formula I are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C~6~~8 tallow or palm oil fatty acid (iodine value 0 to 40).
From the performance point of view, it has proved to be of particular advantage to use quaternized fatty acid triethanolamine ester salts corre-sponding to general formula I where R'CO is an acyl group containing 16 to 18 carbon atoms, R2 has the same meaning as R'CO, R3 is hydrogen, R4 is a methyl group, m, n and p stand for 0 and X- represents methyl sulfate.
Besides the quaternized fatty acid triethanolamine ester salts corre-sponding to general formula I, other suitable esterquats are quaternized ester salts of fatty acids with diethanolalkylamines corresponding to formula R' [R5C0(-OCHZCH2)mOCH2CH2-N+-CH2CH20(-CH2CH20)"Rs]X- (II) R$
in which R5C0 is an acyl group containing a total of 6 to 22 carbon atoms, R6 is hydrogen or has the same meaning as R5C0 and R' and Ra inde-pendently of one another represent alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or for numbers of 1 to 12 and X- is halide, alkyl sulfate or alkyl phosphate.
Finally, another group of suitable esterquats are the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkyl amines corre-.. CA 02299340 2000-02-04 sponding to formula III:
R12 O(-CH2CH20)",OCR9 [R11-N+-CHZCH-CH20(-CH2CH20)~Rlo]X_ (111) in which R9C0 is an acyl group containing a total of 6 to 22 carbon atoms, R'° represents hydrogen or has the same meaning as R9C0, R11, R12 and R13 independently of one another are alkyl groups containing 1 to 4 carbon atoms, m and n together stand for 0 or for numbers of 1 to 12 and X- is halide, alkyl sulfate or alkyl phosphate.
So far as the choice of the preferred fatty acids and the optimum degree of esterification are concerned, the examples mentioned for I also apply to the esterquats corresponding to formulae II and III. The esterquats are normally marketed in the form of 50 to 90% by weight alcoholic solutions which may readily be diluted with water as required.
The compounds corresponding to formulae I to III are of course individual compounds although, in general, mixtures of these compounds may also be used for the purposes of the invention. The technical mixtures obtainable with variable compositions through the production process may also be used. If the quaternary ammonium are not esterquats, it is preferred in accordance with the invention for the quaternary ammonium compound to be cetyl trimethyl ammonium bromide or cetyl trimethyl ammonium chloride or a mixture of these two compounds.
An alkali metal salt of an organic acid or a mixture of alkali metal salts of one or more organic acids is preferably used as anionic preservative. Salts of the organic acids which may be used as antimicro-bial preservatives, for example in the preservation of foods and/or cosmetics, are preferably used for the purposes of the present invention.
These salts include, for example, salts of formic acid, acetic acid, .. CA 02299340 2000-02-04 propionic acid, lactic acid, sorbic acid, benzoic acid, salicylic acid or laevulinic acid or mixtures of two or more of these acids.
Basically, any salts of the acids mentioned with lithium, sodium, potassium, rubidium or caesium may be used as the alkali metal salts.
However, the sodium or potassium salts of the acids mentioned are preferably used, the sodium salts being particularly preferred.
Among the anionic preservatives, the alkali metals of salicylic acid, more particularly sodium salicylate, are preferred.
Alternatively to or in addition to the at least one anionic preservative, at least one a-hydroxycarboxylic acid may be used in accordance with the invention. Preferred a-hydroxycarboxylic acids are lactic acid, tartaric acid, malic acid and citric acid; lactic acid, malic acid and tartaric acid are particularly preferred. The a-hydroxycarboxylic acids may of course also be used in the form of their physiologically compatible salts, more particularly their alkali metal, alkaline earth metal and aluminium salts.
According to the invention, it can be of advantage to use a combination of a quaternary ammonium compound, an anionic preservative and an a-hydroxycarboxylic acid as the preservative system. Where a binary mixture is used, it can be of advantage to use a quaternary ammonium compound in combination with an anionic solvent.
The ratio by weight of quaternary ammonium compound to anionic preservative or a-hydroxycarboxylic acid is generally about 1:20 to 100:1.
The quaternary ammonium compounds are generally used in a concentration of about 0.1 to about 10% by weight, based on the composition according to the invention as a whole. Quantities of about 0.5 to 7% by weight are preferred, quantities of about 0.8 to 5% by weight being particularly preferred.
The anionic preservatives are generally used in a concentration of about 0.1 to about 2% by weight and preferably in a concentration of about 0.5 to about 1 % by weight, based on the composition containing the anionic preservative as a whole.
The a-hydroxycarboxylic acids are preferably used in quantities of about 0.1 to about 0.5% by weight, based on the preparation as a whole.
In certain countries, the limits mentioned above may be restricted by legal upper limits.
In the interests of ready biodegradability of the preservative system used, it is of advantage to use a quaternary ester compound as the quaternary ammonium compound. In the context of the invention, ester-quats are understood to be the above-mentioned quaternary ammonium compounds corresponding to general formulae I, II and III.
The esterquats are preferably used in combination with the alkali metal salts of salicylic acid and, more preferably, in combination with sodium salicylate.
Accordingly, the present invention relates to a preservative system containing at least one quaternary ester compound (esterquat) and at least one alkali metal salicylate in a ratio by weight of about 1:20 to about 100:1 as active ingredients.
Sodium salicylate is preferably used as the alkali metal salicylate.
The present invention also relates to a preservative system as described above in which distearoyl ethyl hydroxyethyl ammonium methosulfate (INCI name: Distearoylethyl Hydroxyethylmoniummetho-sulfate, for example marketed as Dehyquart~ F 75 by Henkel KGaA, Dusseldorf) is used as the quaternary ester compound.
The present invention also relates to the use of a preservative system containing at least one quaternary ester compound (esterquat) and at least one alkali metal salicylate in a ratio by weight of 1:20 to 100:1 as active ingredients in body care compositions.
The above-described combination of quaternary ammonium compound and anionic preservative suitable as a preservative system may be used in a number of body care compositions, more particularly hair care compositions.
These include, for example, the following hair care compositions:
shampoos, rinses, conditioners, hair-tip fluids, colorants, hair sprays and wave lotions.
Accordingly, the final composition may contain a number of other compounds, for example with a cleaning, conditioning, coloring or shaping effect, besides the preserving combination of active ingredients.
If the preservative system according to the invention is to be used, for example, in shampoos, at least one anionic, zwitterionic, amphoteric or nonionic surfactant is generally present in addition to the preserving combination of active substances.
In principle, any anionic surfactants suitable for use on the human body may be used together with the preserving active-substance combination according to the invention, the preservative system, providing they are not incompatible with the cationic component of the preservative system. Whether such incompatibility is present for certain compounds is either known to the expert or can be established by simple tests. Anionic surfactants of the type in question are characterized by a water-solubilizing anionic group such as, for example, at least one carboxylate, sulfate, sulfonate or phosphate group and at least one hydrocarbon group, preferably at least one lipophilic alkyl group containing about 10 to about 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester groups, ether, amide and hydroxyl groups may be present in the molecule.
Examples of suitable anionic surfactants are:
- linear fatty acids containing 10 to 22 carbon atoms (soaps), - ether carboxylic acids corresponding to the formula R'4-O(-CH2-CH20)X-CH2-COOH, in which R'4 is a linear alkyl group containing 10 to 22 carbon atoms and x = 0 or 1 to 16, - amide ether carboxylates corresponding to the formula [R'5-NH(-CH2-_ CA 02299340 2000-02-04 CH2-O)~-CHZ-COO]mZ, in which R'S is a linear or branched, saturated or unsaturated acyl group containing 2 to 29 carbon atoms, n is an integer of 1 to 10, m has a value of 1 or 2 and Z is a cation from the group of alkali or alkaline earth metals, - acyl sarcosides containing 10 to 18 carbon atoms in the acyl group, acyl taurides containing 10 to 18 carbon atoms in the acyl group, - acyl isethionates containing 10 to 18 carbon atoms in the acyl group, - sulfosuccinic acid monoesters and dialkyl esters containing 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl poly oxyethyl esters containing 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, - linear alkane sulfonates containing 12 to 18 carbon atoms, - linear a-olefin sulfonates containing 12 to 18 carbon atoms, - a-sulfofatty acid methyl esters of fatty acids containing 12 to 18 carbon atoms, alkyl sulfates and alkyl polyglycol ether sulfates corresponding to the formula R'6(-CH2-CH20)X S03H, in which R'6 is a preferably linear alkyl group containing 10 to 18 carbon atoms and x = 0 or 1 to 12, - sulfated hydroxyalkyl polyethylene and/or hydroxyalkyl polypropylene glycol ethers according to DE-A 37 23 354, - sulfonates of unsaturated fatty acids containing 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A 39 26 344, - esters of tartaric acid and citric acid with alcohols which represent products of the addition of about 2 to 15 molecules of ethylene oxide and/or propylene oxide onto fatty alcohols containing 8 to 22 carbon atoms, in the form of the alkali metal, alkaline earth metal and/or ammonium salts, preferably in the form of their sodium, potassium, magnesium and/or ammonium and mono-, di- and/or trialkanolammonium salts containing 2 or 3 carbon atoms in the alkanol group.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids containing 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and sulfosuc-cinic acid monoalkyl and dialkyl esters containing 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters con-taining 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups.
Besides the anionic surfactants mentioned, nonionic surfactants may also be present in the compositions according to the invention containing the preservative system.
Nonionic surfactants contain, for example, a polyol group, a poly-alkylene glycol ether group or a combination of polyol and polyglycol ether groups as their hydrophilic group. Corresponding compounds are, for example, - products of the addition of 2 to 30 moles of ethylene oxide and/or 0 to 5 moles of propylene oxide onto linear fatty alcohols containing 8 to 22 carbon atoms or onto fatty acids containing 12 to 22 carbon atoms or onto alkylphenols containing 8 to 15 carbon atoms in the alkyl group, - 02_22 fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol, - C$_22 alkyl mono- and oligoglycosides and ethoxylated analogs thereof and - products of the addition of 5 to 60 moles of ethylene oxide onto castor oil and/or hydrogenated castor oil.
In another preferred embodiment of the invention, alkyl polyglyco-sides corresponding to the general formula R"O(-Z)X are used as the nonionic surfactants. In these compounds, the alkyl group R" contains 6 to 22 carbon atoms and may be both linear and branched. Primary linear or 2-methyl-branched alkyl groups are preferred. Corresponding alkyl groups R" are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl groups. 1-Octyl, 1-decyl, 1-lauryl and 1-myristyl groups are particularly preferred. Where so-called "oxoalcohols" are used as starting materials, compounds containing an odd number of carbon atoms in the alkyl chain predominate.
The alkyl polyglycosides usable in the compositions according to the invention may contain, for example, only one particular alkyl group R'a.
However, the alkyl polyglycosides are normally prepared from natural fats and oils or mineral oils. In this case, the alkyl groups R" are mixtures corresponding to the starting compounds or to the particular working-up of those compounds.
Particularly preferred alkyl polyglycosides are those in which R"
stands - essentially for C8 and Coo alkyl groups, - essentially for C~2 and C~4 alkyl groups, - essentially for C8 to C~6 alkyl groups or - essentially for C~z to C~6 alkyl groups.
Any monosaccharides or oligosaccharides may be used as the sugar unit Z. Sugars containing 5 or 6 carbon atoms and the correspond-ing oligosaccharides are normally used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar units are glucose, fructose, galactose, arabinose and sucrose; glucose is particularly preferred.
The alkyl polyglycosides suitable for use in accordance with the invention contain on average 1.1 to 5 sugar units. Alkyl polyglycosides where x has a value of 1.1 to 1.6 are preferred. Alkyl polyglycosides where x has a value of 1.1 to 1.4 are most particularly preferred.

The alkoxylated homologs of the alkyl polyglycosides mentioned may also be used in accordance with the invention. These homologs may contain on average up to 10 ethylene oxide and/or propylene oxide units per alkyl glycoside unit.
The compounds containing alkyl groups used as surfactants may be pure substances. However, it is generally preferred to produce these compounds from native vegetable or animal raw materials so that mixtures containing a different number of carbon atoms in the alkyl chain, depending on the particular raw material, are obtained.
The surfactants which are adducts of ethylene oxide and/or propylene oxide with fatty alcohols or derivatives of these adducts may be both products with a "normal" homolog distribution and products with a narrow homolog distribution. Products with a "normal" homolog distribution are understood to be mixtures of homologs which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. By contrast, narrow homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. It can be of advantage to use so-called narrow-range products.
The compositions prepared using the preservative system according to the invention preferably contain the zwitterionic, anionic and/or nonionic surfactants in quantities of 0.05 to 40% by weight, more preferably in quantities of 0.5 to 20% by weight and, in one particularly preferred embodiment, in quantities of 1 to 5% by weight, based on the composition as a whole.
The compositions containing the preservative system according to the invention are normally present in the form of aqueous or aqueous/alco-holic solutions or dispersions. Water-based formulations and formulations containing less than 15% by weight, based on the formulation as a whole, _ CA 02299340 2000-02-04 of alcohol, particularly ethanol, are preferred. However, alcohol-based, more particularly ethanol-based, formulations may also be preferred for special applications.
Besides the preserving active-substance combination compulsorily present, the compositions may contain a vitamin and/or a vitamin derivative in addition to or instead of one or more of the other compounds already listed. Basically, natural, synthetic, water-soluble or oil-soluble vitamins and vitamin derivatives are suitable.
Particularly suitable vitamins and vitamin derivatives are, for example, vitamin A, vitamin E acetate, vitamin E nicotinate, vitamin F, vitamin B3, vitamin B6, nicotinic acid amide, vitamin H, vitamin C, vitamin B5 and derivatives thereof, more particularly panthenol, pantothenic acid, calcium pantothenate, pantothenyl ethyl ether, panthenyl hydroxypropyl steardimonium chloride (Panthequat~, Innovachem), pantethines and panthenyltriacetate. Corresponding derivatives, for example panthotenyl ether, panthotenyl butyl ether and other branched or linear, saturated or unsaturated homologs may of course also be used. The same applies to the salts of panthotenic acid of which the possible counterions are not confined to calcium, but also encompass all physiologically acceptable metal cations, for example the alkali and alkaline earth metals, more particularly magnesium, sodium or potassium. The invention also encom-passes the use of all possible stereoisomers of the various vitamins; in the particular case of vitamin B5 and its derivatives, both the D-form and the L-form and mixtures of the two forms may be used in accordance with the invention.
In general, the vitamins or vitamin derivatives are used in the com-positions according to the invention in quantities of 0.01 to 30% by weight, based on the composition as a whole. Quantities of 0.02 to 15% by weight and, more particularly, 0.02 to 8% by weight are normally of particular advantage for the production of aqueous ready-to-use preparations. In many cases, quantities of 0.05 to 5% by weight are sufficient. For concentrates, it can be of advantage to use vitamins and/or vitamin deriva-tives in quantities of 0.05 to 30% by weight, more particularly 1 to 25% by weight and, in one particularly preferred embodiment, 3 to 20% by weight.
Besides components A and B, the compositions according to the invention may also contain protein hydrolyzates either individually or together with one or more of the ingredients already listed. Protein hydro-lyzates in the context of the invention are understood to be a mixture of amino acids, oligopeptides and polypeptides and derivatives thereof.
Amino acids suitable for use in accordance with the invention are, for example, arginine, lysine, cysteine, glutamine, asparagine and valine.
Amino acid mixtures obtainable by substantially complete basic, acidic or enzymatic hydrolysis of animal or vegetable proteins have also proved to be suitable.
Oligopeptides and polypeptides suitable for use in accordance with the invention are, for example, animal or vegetable proteins or their (partial) hydrolyzates obtained by acidic, basic or enzymatic hydrolysis. Suitable proteins are, for example, keratin, collagen, elastin, soya protein, milk protein, casein, fibroins, sericin, wheat protein, silk protein and almond protein. According to the invention, keratin and the vegetable proteins can be preferred. The hydrolysis process gives mixtures with average molecular weights of about 400 to about 50,000 dalton. Typical average molecular weights are in the range from about 500 to about 8000 dalton.
According to the invention, hydrolyzates of keratin, silk protein and vegetable proteins are preferred.
Derivatives of the amino acids, oligopeptides and polypeptides in the context of the invention are understood to be cationic derivatives thereof and condensates thereof with fatty acids.
Cationic derivatives are obtained by reaction with compounds which normally contain quaternary ammonium groups or by reaction with corre-sponding amines and subsequent quaternization.
A number of such quaternary protein hydrolyzates are commercially obtainable, including for example:
- cationic collagen hydrolyzate, for example the product marketed as Lamequat~ L (INCI name: Lauryldimonium Hydroxypropyl Hydrolyzed Collagen; Chemische Fabrik Griinau), - cationic keratin hydrolyzate, for example the product marketed as Croquat~ (CTFA name: Cocodimonium Hydroxypropyl Hydrolyzed Keratin; Croda) - cationic wheat hydrolyzate obtainable as Hydrotriticum~ QL (CTFA
name: Lauryldimonium Hydroxypropyl Hydrolyzed Wheat Protein;
Croda) - the product obtainable as Crotein~ Q (INCI name: Hydroxypropyl-trimonium Hydrolyzed Collagen; Croda) and - the quaternized protein hydrolyzate obtainable as Lexein~ QX 3000 (Inolex).
Oleic acid, myristic acid, undecylenic acid, cocofatty acid and abietic acid are preferably used as the acid component in the production of the protein hydrolyzate/fatty acid condensates. The condensates may also be present in the form of salts, more particularly sodium, potassium and triethanolamine salts.
The condensates based on collagen hydrolyzate also bear the CTFA
names Oleoyl Hydrolyzed Collagen, Myristoyl Hydrolyzed Collagen, Oleoyl Hydrolyzed Animal Collagen, Potassium Coco Hydrolyzed Animal Protein, TEA Abietoyl Hydrolyzed Collagen, Potassium Undecylenoyl Hydrolyzed Collagen and TEA Coco Hydrolyzed Collagen. Commercial products are, for example, Lamepon~ LPO, Lamepon~ 4 SK, Lamepon~ UD, Lamepon~
460, Lamepon~ PA TR, Lamepon~ ST 40 and Lamepon~ S (Grunau) and _ CA 02299340 2000-02-04 Lexein~ A 240, Lexein~ S 620 and Lexein~ A 520 (Inolex).
Condensation products of elastin hydrolyzates with fatty acids, for example lauric acid (CTFA name: Lauroyl Hydrolyzed Elastin) may also be used. Crolastin~ AS (Croda) is a corresponding commercial product.
A potassium cocoyl hydrolyzed wheat protein is commercially available as Promois EGCP (Seiwa).
Other commercial products suitable for use in accordance with the invention are Lexein~ A 200 (Inolex), Lamepon~ PO-TR, Lamepon~ PA-K, Lamepon~ S-MV and Lamepon~ S-TR (Grunau) and Crotein~ CCT
(Croda).
The combination of quaternary ammonium compound and anionic preservative according to the invention may be used not only in hair-regenerating compositions, but also in products which produce a purely decorative change in the hair, for example in hair colorants. If the combination according to the invention is used in hair colorants, at least one dye or dye precursor for coloring keratin fibers is present in addition to the at least one quaternary ammonium compound and the at least one anionic preservative. To obtain the coloring effect, oxidation colorants generally contain two groups of compounds known as primary and second-ary intermediates.
According to the invention, preferred primary intermediates are p-phenylenediamine, p-toluylenediamine, p-aminophenol, o-aminophenol, 1-(2'-hydroxyethyl)-2,5-diaminobenzene, N,N-bis-(2-hydroxyethyl)-p-phenylenediamine, 2-(2,5-diaminophenoxy)-ethanol, 1-phenyl-3-carboxy-amido-4-amino-5-pyrazolone, 4-amino-3-methylphenol, 2,4,5,6-tetraamino-pyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triamino-pyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2-hydroxyethylaminomethyl-4-aminophenol, 4,4'-diaminodiphenylamine, 4-amino-3-fluorophenol, 2-aminomethyl-4-amino-phenol, 2-hydroxymethyl-4-aminophenol, bis-(2-hydroxy-5-aminophenyl)-' WO 99/07331 18 PCT/EP98/04762 methane, 1,4-bis-(4-aminophenyl)-diazacycloheptane, 1,3-bis-(N-(2-hydroxyethyl)-N-(4-aminophenylamino))-2-propanol, 4-amino-2-(2-hydroxy-ethoxy)-phenol and 4,5-diaminopyrazole derivatives according to EP 0 740 741 or WO 94108970, for example 4,5-diamino-1-(2'-hydroxyethyl)-pyrazole.
According to the invention, preferred secondary intermediates are 1-naphthol, pyrogallol, 1,5-, 2,7- and 1,7-dihydroxynaphthalene, o-aminophenol, 5-amino-2-methylphenol, m-aminophenol, resorcinol, resorcinol monomethyl ether, m-phenylenediamine, 1-phenyl-3-methyl-5-pyrazolone, 2,4-dichloro-3-aminophenol, 1,3-bis-(2,4-diaminophenoxy)-propane, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol, 2,6-dihydroxypyri-dine, 2,6-diaminopyridine, 2-amino-3-hydroxypyridine, 2,6-dihydroxy-3,4-diaminopyridine, 3-amino-2-methylamino-6-methoxypyridine, 4-amino-2-hydroxytoluene, 2,6-bis-(2-hydroxyethylamino)-toluene, 2,4-diamino-phenoxyethanol, 1-methoxy-2-amino-4-(2-hydroxyethylamino)-benzene, 2-methyl-4-chloro-5-aminophenol, 6-methyl-1,2,3,4-tetrahydroquinoxaline, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 2,6-dimethyl-3-aminophenol, 3-amino-6-methoxy-2-methylaminophenol, 2-hydroxy-4-aminophenoxyethanol, 2-methyl-5-(2-hydroxyethylamino)-phenol and 2,6-dihydroxy-3,4-dimethyl pyridine.
These primary and secondary intermediates are normally used in free form. Where they contain amino groups, however, they are preferably used in salt form, more especially in the form of the hydrochlorides and sulfates.
The hair colorants contain both the primary intermediates and the secondary intermediates in a quantity of preferably 0.005 to 20% by weight and more preferably 0.1 to 5% by weight, based on the oxidation colorant as a whole. The primary and secondary intermediates are generally used in substantially equimolar quantities. Although the use of substantially equimolar quantities has proved to be appropriate, there is no disadvan-tage in using a certain excess of individual oxidation dye precursors, so that primary and secondary intermediates may be present in a molar ratio of 1:0.5 to 1:3 and, more particularly, 1:1 to 1:2.
In another embodiment, the hair colorants may contain substantive dyes in addition to the oxidation dye precursors either as sole coloring component for further modifying the color tones.
Substantive dyes are typically nitrophenylenediamines, nitroamino-phenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are the compounds known under the International names or commercial names of HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, Basic Yellow 57, Disperse Orange 3, HC Red 3, HC Red BN, Basic Red 76, HC Blue 2, HC Blue 12, Disperse Blue 3, Basic Blue 99, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Basic Brown 16 and Basic Brown 17 and also 4-amino-2-nitrodiphenylamine-2'-carboxylic acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitrotoluidine, picram-ic acid, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene. The preparations according to the invention in this embodiment contain the substantive dyes in a quantity of, preferably, 0.01 to 20% by weight, based on the colorant as a whole.
In addition, the compositions according to the invention may also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, black alder bark, sage, logwood, madder root, catechu, sedre and alkanet.
Other dye components present in the colorants according to the invention may be indoles and indolines and physiologically compatible salts thereof. Preferred examples are 5,6-dihydroxyindole, N-methyl-5,6-di-hydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole. Also preferred are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxy-indoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.
With regard to the dyes suitable for use in the hair coloring and tinting formulations according to the invention, reference is also specifically made to Ch. Zviak's work The Science of Hair Care, Chapter 7 (pages 248-250; Substantive Dyes) and Chapter 8, pages 264-267; Oxidation Dye Precursors), published as Vol. 7 of the Series "Dermatology" (Editors: Ch.
Culnan and H. Maibach), Marcel Dekker Inc., New York/Basel, 1986 and to the "Europaische Inventar der Kosmetik-Rohstoffe" published by the Europaische Gemeinschaft and available in diskette form from the Bundesverband Deutscher Industrie- and Handelsunternehmen fur Arzneimittel, Reformwaren and Korperpflegemittel e.V., Mannheim, Germany.
The oxidation dye precursors or the substantive dyes present, if any, do not have to be single compounds. Instead, the hair colorants according to the invention - due to the processes used for producing the individual dyes - may contain small quantities of other components providing they do not adversely affect the coloring result or have to be ruled out for other reasons, for example toxicological reasons.
To produce the colorants, the oxidation dye precursors are incorporated in the composition according to the invention containing at least component A and component B. For coloring hair, the compositions according to the invention may be formulated, for example, as cremes, aerosols, emulsions, gels or even surfactant-containing foaming solutions, for example shampoos, foam aerosols or other formulations suitable for application to the hair.
Basically, the color may be oxidatively developed with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, particularly when human hair is to be not only colored, but also lightened.
Particularly suitable oxidizing agents are persulfates, chlorites and above all hydrogen peroxide or addition products thereof with urea, melamine or sodium borate. Oxidation may also be carried out with enzymes. In this case, the enzymes may be used both to produce oxidizing per compounds and to enhance the effect of an oxidizing agent present in small quantities.
One example of an enzymatic process is the procedure whereby the effect of small quantities (for example 1 % and less, based on the formulation as a whole) of hydrogen peroxide is enhanced by peroxidases.
The preparation of the oxidizing agent is preferably mixed with the preparation of the oxidation dye precursors immediately before coloring of the hair. The ready-to-use hair colorant formed should preferably have a pH value in the range from 6 to 10. The hair colorants are used with particular advantage in a mildly alkaline medium. The temperatures at which they are applied may be in the range from 15 to 40°C. After a contact time of about 30 minutes, the hair colorant is removed from the hair to be colored by rinsing. There is no need to wash the hair with a shampoo where a high-surfactant carrier, for example a coloring shampoo, has been used.
The preservative system according to the invention may also be used in the production of wave preparations. Wave preparations in the context of the invention are understood to be preparations which are used for permanently shaping keratin fibers. Shaping such as this is generally achieved by mechanically deforming the fibers and setting the deformation with suitable auxiliaries. Before and/or after their deformation, the fibers are treated with the aqueous preparation of a keratin-reducing substance (wave lotion) and, after a contact time, are rinsed with water or an aqueous solution. In a second step, the fibers are treated with an aqueous preparation of an oxidizing agent (fixing agent). After a certain contact time, the fixing agent is also rinsed out and the mechanical shaping aids (curlers, rollers) are removed from the fibers.
The wave preparations contain as the keratin-reducing substances mercaptans, for example thioglycolic acid, thiolactic acid, thiomalic acid, mercaptoethane sulfonic acid and salts and esters thereof, cysteamine, cysteine, Bunte salts and alkali metal salts of sulfurous acid. The alkali metal or ammonium salts of thioglycolic acid and/or thiolactic acid and the free acids are preferred. They are used in the wave preparations in concentrations of preferably 0.5 to 1.0 mole/kg, based on the wave preparation as a whole, at a pH value of 5 to 10 and, more particularly, 7 to 8.5.
Oxidizing agents, for example sodium bromate, potassium bromate or hydrogen peroxide, are used together with typical stabilizers for stabilizing aqueous hydrogen peroxide preparations as the fixing agents.
The pH value of such aqueous H202 preparations, which normally contain about 0.5 to 3.0% by weight of H~02, is preferably in the range from 2 to 4 and is adjusted with inorganic acids, preferably phosphoric acid.
Bromate-based fixing agents contain the bromates in concentrations of normally 1 to 10 and the pH of the solutions is adjusted to a value of 4 to 7. Enzyme-based fixing agents (peroxidases), which contain only small quantities, if any, of oxidizing agents, more particularly Hz02, are also suitable.
Both the wave preparation and the fixing agent may be formulated as a cream, gel or liquid. The compositions may also be formulated as foam aerosols which are packed in aerosol containers with a foam valve together with a liquefied gas such as, for example, propane/butane mixtures, nitrogen, C02, air, NZO, dimethyl ether, chlorofluorocarbon propellants or mixtures thereof. The fixing agents may also be formulated as solids, in which case they contain the oxidizing agent in the form of a solid, for example potassium or sodium bromate. Water is then added to these agents just before application. It can also be of advantage to formulate the oxidizing agent as a two-component system. The two components, of which one is preferably a hydrogen peroxide solution or an aqueous solution of another oxidizing agent and the other contains the remaining ingredients, are also mixed just before application.
The hair treatment compositions according to the invention may be both products which are rinsed out from the hair after a certain contact time, generally about 1 to 45 minutes, and products which are left on the hair.
The preservative system according to the invention may be used at different pH values. For example, shampoos and rinses and wave lotions preferably have a pH value of 2.5 to 7.0 and, more particularly, in the range from 4.0 to 6Ø By contrast, the pH value of oxidation colorants is generally in the range from 6.0 to 10.0 and, more particularly, in the range from 7.0 to 9Ø
Virtually any acid or base usable for cosmetic purposes may be used to adjust this pH value. Where an acid is used for pH adjustment, it can be of advantage to use an acid from the group of food-grade acids, for example acetic acid, ascorbic acid and gluconic acid. However, the a-hydroxycarboxylic acids (such as lactic acid, tartaric acid, citric acid and malic acid), besides being part of the preservative system, may also be used for pH adjustment.
In accordance with the application envisaged and the particular formulation, the preparations according to the invention may contain any of the cosmetic additives normally used for the particular application envisaged.
Additives such as these include:
- amphoteric surfactants, for example N-alkyl glycines, N-alkylpropionic acids, N-alkylaminobutyric acid, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropytglycines, N-alkyltaurines, N-alkyl-sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids containing about 8 to 18 carbon atoms in the alkyl group, - zwitterionic surfactants, for example the so-called betaines and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines, - anionic polymers, for example polyacrylic and polymethacrylic acids, salts thereof, copolymers thereof with acrylic and methacrylic acid esters and amides and derivatives thereof obtained by crosslinking with polyfunctional agents; compounds of this type are obtainable, for example, under the names of Carbopol~ 934, Carbopol~ 934P, Carbopol~ 940, Carbopol~ 950, Carbopol~ 980 and as Carbopol~
EDT types (manufacturer: all B.F. Goodrich) and PNC~ 400 (manufacturer: 3V Sigma);
nonionic polymers such as, for example, vinyl pyrrolidone/vinyl acrylate copolymers, polyvinyl pyrrolidone and vinyl pyrrolidone/vinyl acetate copolymers, - thickeners, such as agar agar, guar gum, alginates, cellulose ethers, gelatine, pectins and/or xanthan gum, - structurants, such as glucose and malefic acid, - hair-conditioning compounds, such as phospholipids, for example soya lecithin, egg lecithin and kephalins, and also silicone oils, - perfume oils, dimethyl isosorbide and cyclodextrins, - solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, - dyes, - antidandruff agents, such as Climbazol, Piroctone Olamine and Zinc Omadine, - other substances for adjusting the pH value, active substances, such as bisabolol, allantoin and plant extracts, - UV filters, - fats and waxes, such as spermaceti, beeswax, montan wax, paraffins, esters, glycerides and fatty alcohols, - fatty acid alkanolamides, - swelling and penetration agents, such as PCA, glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates, - opacifiers, such as latex and styrene/acrylamide copolymers, - pearlescers, such as ethylene glycol mono- and distearate and PEG-3-distearate, - propellents, such as propane/butane mixtures, N20, dimethyl ether, C02 and air and - antioxidants.
The invention is illustrated by the following Examples.
Example 1 In order to test the preserving effect of the combination according to the invention, two formulations with the following composition were prepared:
Formulation 1:

2.5% Stenol 1618 (Cetearyl Alcohol) Henkel 0.5% Cutina GMS (Glyceryl Stearate) Henkel 0.4% Eumulgin B1 (Ceteareth-12) Henkel 0.1 % Cetiol OE (Dicapryl Ether) Henkel 2.4% Dehyquart A (Cetrimonium Chloride)Henkel 2.0% glucose qs citric acid qs water Formulation 2:
Same as formulation 1 plus 0.57% Na salicylate.
pH value (both formulations): ca. 2.8 w WO 99/07331 26 PCT/EP98/04762 The preserving effect of formulations 1 and 2 was then tested.
Test microorganisms:
The bacterial cultures used for the test contained the following microorganisms:
- Staphylococcus aureus ATCC 6538 - Enterococcus faecium ATCC 6057 - Escherichia coli ATCC 11229 - Enterobacter aerogenes DSM 30053 - Pseudomonas aeruginosa ATCC 15442 The fungal cultures used for the test contained the following micro-organisms:
- Candida albicans ATCC 10231 - Aspergillus niger ATCC 6275 - Penicillium rubrumCMI 113729 - Trichoderma virideBAM T 21 Standard germ suspensions each containing 10$ CBU/ml bacteria and 10' CBU/ml fungi were prepared from the microorganisms mentioned above. Quantities of 10 g of formulations 1 and 2 were then challenged with 0.1 ml of the bacterial suspension and 0.1 ml of the fungal suspension in a sterile vessel. The germ suspensions were incorporated by mixing in a glass homogenizes by at least 10 homogenizes strokes. Using two inoculation loops, the formulations thus challenged were directly applied to THL standard I nutrient agar, THL wort agar, THL standard I nutrient broth and THL wort broth.
The following destruction times were observed (in days):

" WO 99/07331 27 PCT/EP98/04762 Bacteria (2.5 ~ 106) Fungi (6 ~ 105) Formulation 1: > 21 > 35 Formulation 2: 1 1

Claims (13)

1. Claim 1 The use of a mixture of - at least one quaternary ammonium compound selected from cationic polymers, cationic surfactants and esterquats and - at least one anionic preservative and/or - at least one .alpha.-hydroxycarboxylic acid as a preservative system for body care compositions.
2. 2. The use claimed in claim 1, characterized in that the body care composition is a hair care composition.
3. 3. The use claimed in claim 1 or 2, characterized in that the quaternary ammonium compound is cetyl trimethyl ammonium bromide and/or cetyl trimethyl ammonium chloride.
4. 4. The use claimed in any of the preceding claims, characterized in that the quaternary ammonium compound is at least one quaternary ester compound.
5. 5. The use claimed in any of the preceding claims, characterized in that the anionic preservative is an alkali metal salt of an organic acid.
6. 6. The use claimed in claim 5, characterized in that the alkali metal salt of the organic acid is a salt of formic acid, acetic acid, propionic acid, lactic acid, sorbic acid, benzoic acid, salicylic acid or laevulinic acid.
7. 7. The use claimed in any of the preceding claims, characterized in that sodium salicylate is used as the at least one anionic preservative.
8. 8. The use claimed in any of the preceding claims, characterized in that the .alpha.-hydroxycarboxylic acid is selected from the group consisting of lactic acid, tartaric acid, malic acid and citric acid.
9. 9. The use claimed in any of the preceding claims, characterized in that the at least one quaternary ammonium compound and the at least one anionic preservative and/or the .alpha.-hydroxycarboxylic acid are present in a ratio by weight of 1:20 to 100:1.
10. 10. The use claimed in any of the preceding claims, characterized in that cetyl trimethyl ammonium chloride is used as the at least one quaternary ammonium compound.
11. 11. A preservative system containing at least one quaternary ester compound and at least one alkali metal salicylate in a ratio by weight of 1:20 to 100:1 as active substance.
12. 12. A preservative system as claimed in claim 11, characterized in that distearoyl ethyl hydroxyethyl ammonium methosulfate is used as the at least one quaternary ester compound.
13. 13. A preservative system as claimed in claim 11 or 12, characterized in that sodium salicylate is used as the at least one anionic preservative.