EP0993298A1

EP0993298A1 - Preservative system for personal hygiene products

Info

Publication number: EP0993298A1
Application number: EP98938713A
Authority: EP
Inventors: Detlef Hollenberg; Kurt Seidel; Christian Priebe
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1997-08-04
Filing date: 1998-07-30
Publication date: 2000-04-19
Also published as: BR9811843A; PL338475A1; CA2299340A1; JP2001513488A; SK1492000A3; KR20010022607A; HUP0100333A2; TR200000270T2; DE19733684A1; CN1268047A; WO1999007331A1; AU8733198A

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 α-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

Preservative system for personal care products

The invention relates to the preservation of personal care products, in particular the preservation of hair care products using quaternary ammonium compounds and anionic preservatives and / or α-hydroxycarboxylic acids. The invention also relates to a mixture of special quaternary ammonium compounds, the so-called ester quats, and sodium salicylate and its use as a preservative for body care products.

The human body, in particular the human hair, is today treated in a variety of ways with cosmetic preparations (hair treatment agents). This includes, for example, cleaning the body and hair with shampoos and shower preparations, and bleaching, dyeing and shaping hair with waving agents, tinting agents and styling preparations.

Hair treatment agents that are formulated as a hair treatment or conditioner are usually aqueous emulsions of various water- or fat-soluble ingredients. Preserving such emulsions to maintain their usability, in particular after prolonged storage, is sometimes difficult. Quaternary ammonium compounds, which are used in many personal care products, especially in most hair treatment products, exert a certain microbicidal action in these, but this alone is not sufficient for preservation.

It has now been found that very good preservation of personal care products, in particular hair care products, is possible in that a combination of at least one quaternary ammonium compound and at least one anionic preservative and or at least one α-hydroxy carboxylic acid is used as the preservative system. Surprisingly, these active ingredients complement each other in such a way that a synergistic increase in activity occurs.

The invention therefore 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 α-hydroxycarboxylic acid as a preservative system for personal care products.

The personal care product is preferably a hair care product. The hair care products within the meaning of the invention also include those hair treatment products which only bring about a decorative change in the hair, for example hair colorants or permanent waving compositions.

Both polymeric and monomeric substances can be used as the quaternary ammonium compound. The polymers which can be used in the context of the invention are generally cationic polymers which have an ammonium group. Preferred cationic polymers are, for example

quaternized cellulose derivatives, as are commercially available under the names Celquat "and Polymer JR ^* ; the compounds Celquat ^* H 100, Celquat ^* L 200 and Polymer JR ^* 400 are preferred quaternized cellulose derivatives;

Polysiloxanes with quaternary groups, polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid; the products commercially available under the names Merquat'100 (poly (dimethyldiallylammonium chloride)) and Merquat ^* 550 (dimethyldiallyl ammonium chloride-acrylamide copolymer) are examples of such cationic polymers; Copolymers of vinyl pyrrolidone with quaternized derivatives of dial kylaminoacrylate and methacrylate, for example diethyl sulfate quaternized Vmylpyrrolidon-Dimemylaminomethacrylat copolymers; such compounds are commercially available under the names Gafquat ^* 734 and Gafquat "755;

Vmylpyrrolidone-Memoimidazoliniumchlorid-Copolymers, as they are offered under the name Luviquat ^® , quaternized polyvinyl alcohol as well as those under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and

Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain.

As a rule, however, it is advantageous if a compound from the group of the cationic surfactants is selected as the quaternary ammonium compound. Quaternary ammonium compounds are preferred among the cationic surfactants. Preferred are ammonium halides, especially chlorides and bromides, such as allyl trimethylammonium chlorides, dialkyldiethylammonium chlorides and triethyl methylammonium chlorides, e.g. Cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, dicetyldimethylammonium chloride,

Dicetyldimethylammonium bromide, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, dilauryldime ylammonium chloride, lauryldimethylthylbenzylammonium chloride and tricetylmethylammonium chloride.

Also suitable as quaternary ammonium compounds are quaternary ester compounds, so-called "ester quats", which may be preferred because of their good biodegradability.

In this connection, reference is made, for example, to WO 91/01295, according to which triethanolamine is partially esterified with fatty acids in the presence of hypophosphorous acid, air is passed through and then quaternized with dimethyl sulfate or ethylene oxide. Representing the extensive state of the At this point, technology is also referred to 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 on this topic are, for example, by R. Puchta et al. in Tens.Surf.Det. , 30, 186 (1993), M. Brock in Tens.Surf.Det. , 30, 394 (1993) and R. Lagerman et al. in J.Am.Oil.Chem.Soc, 71, 97 (1994).

An example of ester quats are the quaternized fatty acid triemanolamine ester salts of the general formula I

R ⁴

I.

[R'COt-OCHzCHjJ ^ CHjCH ^ N ^ CHjCHjO ^ CHjCHjOJ ^ lX (I),

CH ₂ CH ₂ 0 (-CH ₂ CH ₂ 0) _p R ³

in the R'CO for an acyl radical with a total of 6 to 22 carbon atoms, R ² and R ³ independently of one another for hydrogen or R'CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O-) _q H group, m, n and p in total stands for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X ^" for halide, alkyl sulfate or alkyl phosphate.

Typical examples of quaternized fatty acid triethanolamine ester salts which can be used in the context of 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, arachidic acid, behenic acid and erucic acid and also technical mixtures thereof as they occur, for example, in the pressure splitting of natural fats and oils. Technical C ₁₂ . _lg coconut fatty acids and especially partially hardened C _I6 . ₁₈ tallow or palm fatty acids and high elaidic acid C ₁₆ . _Ig fatty acid cuts used.

For the production of the quaternized fatty acid triethanolamine ester salts of the According to general formula I, the fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1. With regard to the application properties of the ester quats, an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred quaternized fatty acid triethanolamine ester salts of the 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 _16/18 tallow or palm fatty acid (Iodine number 0 to 40).

From an application point of view, quaternized fatty acid triethanolamine ester salts of the general formula I have proven to be particularly advantageous if R'CO for an acyl radical with 16 to 18 carbon atoms, R ² for R'CO, R ³ for hydrogen, R ⁴ for a methyl group, m , n and p is 0 and X ^"is methyl sulfate.

In addition to the quaternized fatty acid triethanolamine ester salts of the general formula I, quaternized ester salts of fatty acids with diethanolalkylamines of the formula II are also suitable as esterquats,

R ⁷ [R ⁵ CO (-OCH ₂ CH ₂ ) _m OCH ₂ CH ₂ -N ⁺ -CH ₂ CH ₂ 0 (-CH ₂ CH ₂ 0) _n R ⁶ ] X (ID,

R ⁸

in which R ⁵ CO for an acyl radical with a total of 6 to 22 carbon atoms, R ⁶ for hydrogen or R ⁵ CO, and R ⁷ and R ⁸ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X ^"represents halide, alkyl sulfate or alkyl phosphate.

Finally, the quaternized ones are a further group of suitable ester quats To name ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula HI,

R ' ² 0 (-CH ₂ CH ₂ 0) _m OCR ⁹ [R "-N ⁺ -CH ₂ CH-CH ₂ O (-CH ₂ CH ₂ O) _n R ¹⁰ ] X (III),

in which R ⁹ CO represents an acyl radical with a total of 6 to 22 carbon atoms, R ^{10 represents} hydrogen or R ⁹ CO, R ¹¹ , R ¹² and R ¹³ independently of one another for alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X ^"represents halide, alkyl sulfate or alkyl phosphate.

With regard to the selection of the preferred fatty acids and the optimal degree of esterification, the examples given for I also apply to the esterquats of the formulas π and DI. The esterquats usually come on the market in the form of 50 to 90% strength by weight alcoholic solutions, which can be diluted with water if required.

The substances described with the formulas I to IQ are naturally individual substances, and mixtures of these substances can generally also be considered for the use according to the invention. It is also possible to use the technical mixtures of substances that are available in changing compositions due to the manufacturing process.

If the quaternary ammonium compounds are not esterquats, it is preferred in the sense according to the invention if the quaternary ammonium compound is cetyltrimethylammonium bromide or cetyltrimethylammonium chloride, or if it is a mixture of the two compounds mentioned.

An alkali metal salt is preferably used as the anionic preservative an organic acid or a mixture of alkali metal salts of one or more organic acids. In the use according to the invention, preference is given to using salts of organic acids of the type which can be used, for example, for preserving foods and / or cosmetics as antimicrobial preservatives.

These include, for example, salts of formic acid, acetic acid, propionic acid, lactic acid, sorbic acid, benzoic acid, salicylic acid or laevulinic acid or mixtures of two or more of the acids mentioned.

In principle, all salts of the acids mentioned with lithium, sodium, potassium, rubidium or cesium are suitable as alkali metal salts. However, the sodium or potassium salts of the acids mentioned are preferably used, particularly preferably the sodium salts.

Preferred among the anionic preservatives are the alkali metal salts of salicylic acid, in particular sodium salicylate.

As an alternative or in addition to the at least one anionic preservative, at least one α-hydroxycarboxylic acid can be used according to the invention. Preferred α-hydroxycarboxylic acids are lactic acid, tartaric acid, malic acid and citric acid; Lactic acid, malic acid and tartaric acid are particularly preferred. Of course, the α-hydroxy carboxylic acids can also be used in the form of their physiologically tolerable salts, in particular the alkali metal, alkaline earth metal and aluminum salts.

The use of a combination of a quaternary ammonium compound, an anionic preservative and an α-hydroxycarboxylic acid as the preservative system can be used according to the invention be preferred. When using a binary mixture, it may be preferred to use a quaternary ammonium compound in combination with an anionic solvent.

The weight ratio of quaternary ammonium compound to anionic preservative or α-hydroxycarboxylic acid is usually 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 total agent according to the invention. Amounts of approximately 0.5 to 7, particularly preferably of approximately 0.8 to 5% by weight are particularly preferred.

The anionic preservatives are generally used in a concentration of about 0.1 to about 2% by weight, preferably about 0.5 to about 1% by weight, based on the total preparation containing the anionic preservative.

The α-hydroxycarboxylic acids are preferably used in amounts of about 0.1 to about 0.5% by weight, based on the preparation as a whole.

The above Limits can be limited by legal upper limits in individual countries.

In terms of good biodegradability of the preservative system used, it is advantageous if a quaternary ester compound is used as the quaternary ammonium compound. Ester quats in the sense of the invention are understood to mean the abovementioned quaternary ammonium compounds having the general formulas I, II and HI.

The combination of the ester quats with the alkali metal is particularly preferred. tall salts of salicylic acid, particularly preferred is the combination with sodium salicylate.

The invention thus relates to a preservative system comprising at least one quaternary ester compound (ester quat) and at least one alkali metal salicylate in a weight ratio of about 1:20 to about 100: 1 as active substances.

Sodium salicylate is preferably used as the alkali salicylate.

Another object of the invention is a preservative system as described above, wherein emylammmoniummethosulfat as quaternary Esterverbindung Distearoylethylhydroxy- (INCI name: Distearoylethyl hydroxy ethylmoniummethosulfate, for example marketed as Dehyquart ^® F 75, manufacturer: Henkel KGaA, Dusseldorf) is used.

The invention also relates to the use of a preservative system containing, as active substances, at least one quaternary ester compound (ester quat) and at least one alkali metal salicylate in a weight ratio of 1:20 to 100: 1 in personal care products.

The active ingredient combination of quaternary ammonium compound and anionic preservative described above, which is suitable as a preservative system, can be used in a large number of preparations for body care, in particular for hair care.

These include, for example, the following hair care products such as shampoos, hair rinses, hair treatments, hair tip fluids, colorants, hair sprays or waving agents.

In addition to the preservative combination of active ingredients, a number can further compounds are present in the final preparation, which have, for example, a cleaning, finishing, coloring or shaping effect.

If the preservative system according to the invention is to be used, for example, in shampoos, there is generally at least one anionic, zwitterionic, amphoteric or nonionic surfactant in addition to the preservative active ingredient combination.

All anionic, surface-active substances suitable for use on the human body are in principle suitable for use together with the preservative active ingredient combination according to the invention, the preservative system, provided that they are not incompatible with the cationic component of the preservative system. Whether such intolerance is present for certain compounds is either known to the person skilled in the art or can be determined by simple experiments. Such anionic, surface-active substances are characterized by a water-solubilizing anionic group such as. B. at least one carboxylate, sulfate, sulfonate or phosphate group and at least one hydrocarbon group, preferably at least one lipophilic alkyl group with about 10 to about 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester groups, ether, amide and hydroxyl groups can be contained in the molecule. Examples of suitable anionic surfactants are:

linear fatty acids with 10 to 22 carbon atoms (soaps),

Ether carboxylic acids of the formula R ¹⁴ -O (-CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R ^{14 is} a linear alkyl group with 10 to 22 C atoms and x = 0 or 1 to 16,

Amide ether carboxylates of the formula [R ¹⁵ -NH (-CH ₂ -CH ₂ -O) _n -CH ₂ -COO] _m Z, in which R ^{15 represents} a linear or branched, saturated or unsaturated

Acyl radical with 2 to 29 carbon atoms, n for integers from 1 to 10, m for the Numbers 1 or 2 and Z represents a cation from the group of the alkali or alkaline earth metals,

Acyl sarcosides with 10 to 18 carbon atoms in the acyl group, acyl taurides with 10 to 18 carbon atoms in the acyl group, acyl isothionates with 10 to 18 carbon atoms in the acyl group, sulfosuccinic acid and dialkyl esters with 8 to 18 carbon atoms in the Alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl ester with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkane sulfonates with 12 to 18 carbon atoms, linear alpha-olefin sulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl ester of fatty acids with 12 to 18 C atoms, alkyl sulfates and alkyl polyglycol ether sulfates of the formula R ¹⁶ (-CH ₂ -CH ₂ O) _x - SO ₃ H, in which R ^{16 is} a, preferably linear, alkyl group having 10 to 18 C 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 with 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 are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols with 8 to 22 carbon atoms,

in each case in the form of the alkali, alkaline earth and / or ammonium salts, preferably in the form of their sodium, potassium, magnesium and / or ammonium salts and the mono-, di- and / or trialkanolammomium salts with 2 or 3 carbon atoms in the alkanol group.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfoberstein Acid monoalkyl polyoxyethyl ester with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups.

In addition to the specified anionic surfactants, nonionic surfactants can also be present in the preparations according to the invention containing the preservative system.

These contain z as a hydrophilic group. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Examples of such connections are:

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear fatty alcohols with 8 to 22 C atoms or with fatty acids with 12 to 22 C atoms or with alkylphenols with 8 to 15 C atoms in the alkyl group,

C ₁₂ -C ₂₂ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,

C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogues as well

Addition products of 5 to 60 moles of ethylene oxide with castor oil and / or hardened castor oil.

In a further embodiment, it is preferred to select alkyl polyglycosides of the general formula R ¹⁷ O (-Z) _x as nonionic surfactants. In the compounds thus designated, the alkyl radical R ^{17 contains} 6 to 22 carbon atoms and can be either linear or branched. Primary linear or methyl branched methyl in the 2-position are preferred. Such alkyl radicals R ¹⁷ are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl radicals. 1-Octyl, 1-decyl, 1-lauryl or 1-myristyl radicals are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in predominate the alkyl chain.

The alkyl polyglycosides which can be used in the preparations according to the invention can contain, for example, only one specific alkyl radical R ¹⁷ . Usually, however, the alkyl polyglycosides are produced from natural fats and oils or mineral oils. In this case, alkyl radicals R ^{17 are} mixtures corresponding to the starting compounds or corresponding to the respective working up of these compounds.

Alkylpolyglycosides in which R ¹⁷

stands essentially for C ₈ and C ₁₀ alkyl groups, essentially for C ₁₂ and C _{] 4} alkyl groups, essentially for C ₈ to C ₁₆ alkyl groups or essentially for C ₁₂ to C ₁₆ alkyl groups.

Any mono- or oligosaccharides can be used as sugar building block Z. Sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides are usually used. Examples of such sugars are glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, gulose, idose, talose and sucrose. Preferred sugar units are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain an average of 1.1 to 5 sugar units. Alkyl polyglycosides in which x is from 1.1 to 1.6 are preferred. Alkyl polyglycosides in which x is 1.1 to 1.4 are very particularly preferred.

The alkoxylated homologs of the alkyl polyglycosides mentioned can also be used according to the invention. These homologues can contain an average of up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

The compounds with alkyl groups used as surfactants can each be pure substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with a different number of carbon atoms in the alkyl chain, depending on the respective raw material, are obtained. In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologues which are obtained as catalysts when fatty alcohol and alkylene oxide are reacted using alkali metals, alkali metal hydroxides or alkali metal alcoholates. In contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.

The preparations produced using the preservative system according to the invention preferably contain the zwitterionic, anionic and / or nonionic surfactants in amounts of 0.5 to 40% by weight, in particular 0.5 to 20% by weight and particularly preferably 1 to 5% by weight .%, based on the entire preparation.

The preparations containing the preservative system according to the invention are usually in the form of aqueous or aqueous-alcoholic solutions or dispersions. Preferred are water-based formulations and formulations which contain less than 15% by weight, based on the preparation as a whole, of alcohol, in particular ethanol. However, formulations based on alcohol, in particular based on ethanol, may also be preferred for special applications.

In addition to the mandatory active ingredient combination, the preparations can contain a vitamin and / or a vitamin derivative in addition to or instead of one or more of the other compounds already listed contain. In principle, 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, vitamin E acetate, vitamin E nicotinate, vitamin F, vitamin B ₃ , vitamin B ₆ , nicotinamide, vitamin H, vitamin C, vitamin B ₅ and its derivatives , in particular panthenol, panthotenic acid, calcium panthotenate, panthotenyl ethyl ether, panmenyl hydroxypropyl steardimonium chloride

(Panthequat ^® , Innovachem), panthetine and panthenyl triacetate. Analog derivatives, for example panthotenylpropyl ether, panthotenyl butyl ether and further branched or linear, saturated or unsaturated homologs, can of course also be used. The same applies to the salts of pantothenic acid, the possible counterions of which are not only limited to calcium, but also include all physiologically acceptable metal cations, for example the alkali and alkaline earth metals, in particular magnesium, sodium or potassium. The invention also encompasses the use of all possible stereoisomers of the different vitamins, it being possible in particular for vitamin B ₅ and its derivatives to use both the D and L forms and all mixtures of the two forms according to the invention.

As a rule, the vitamins or vitamin derivatives are used in the preparations according to the invention in amounts of 0.01 to 30% by weight, based on the entire preparation. Usually 0.02 to 15, in particular 0.02 to 8% by weight are particularly advantageous for the production of aqueous, ready-to-use preparations. In many cases, amounts between 0.05 and 5% by weight are sufficient. For concentrates, it can be advantageous to use vitamins and / or vitamin derivatives in amounts of 0.05 to 30% by weight, in particular 1 to 25% by weight and particularly preferably 3 to 20% by weight.

In addition to components A and B, the preparations according to the invention can be used alone or together with one or more of those already listed Ingredients, including protein hydrolyzates. Protein hydrolyzates are understood to be a mixture of amino acids, oligopeptides and polypeptides and their derivatives.

Amino acids which can be used according to the invention are, for example, arginine, lysine, cysteine, glutamine, asparagine and valine. Amino acid mixtures which can be obtained by largely completely basic, acidic or enzymatic hydrolysis of animal or vegetable proteins have also proven suitable.

Oligopeptides and polypeptides which can be used according to the invention are, for example, animal or vegetable proteins or their (partial) hydrolysates obtained by acidic, basic or enzymatic means. Suitable proteins are, for example, keratin, collagen, elastin, soy protein, milk protein, casein, fibroine, sericin, wheat protein, silk protein and almond protein. Keratin and the vegetable proteins can be preferred according to the invention. The hydrolysis produces mixtures of substances with average molecular weights in the range from approximately 400 to approximately 50,000 Daltons. Usual average molecular weights are in the range from about 500 to about 8000 daltons. Hydrolysates of keratin, silk protein and vegetable proteins are preferred according to the invention.

Derivatives of amino acids, oligopeptides and polypeptides are understood according to the invention to mean their cationic derivatives and their condensation products with fatty acids.

Cationic derivatives are obtained by reaction with compounds which usually carry quaternary ammonium groups or by reaction with corresponding amines and subsequent quaternization.

A number of such quaternary protein hydrolyzates are available as commercial products, for example: cationic collagen hydrolyzate, for example that under the name

Lamequat ^® L product on the market (INCI name:

Lauryldimonium hydroxypropyl hydrolyzed collagen; Chemical factory

Grünau), cationic keratin hydrolyzate, for example that under the name

Croquat ^® product on the market (CTFA name:

Cocodimonium Hydroxypropyl Hydrolyzed Keratin; Croda) cationic wheat hydrolyzate, available under the name Hydrotriti- cum ^® QL (CTFA name: Lauryldimonium Hydroxypropyl Hydrolyzed

Wheat protein; Croda) the product available under the name Crotein ^® Q, according to INCI

"Hydroxypropyltrimonium Hydrolyzed Collagen" (Croda) and the quaternized protein hydrolyzate available as Lexein ^® QX 3000 (Inolex).

To produce the condensation products of protein hydrolyzates with fatty acids, oleic acid, myristic acid, undecylenic acid, coconut fatty acid and abietic acid are preferably used as the acid component. These condensation products can also be in the form of salts, in particular sodium, potassium and triethanolamine salts.

The condensation products based on collagen hydrolyzate also carry 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 include Lamepon ^® LPO, Lamepon ^® 4 SK, Lamepon ^® UD, Lamepon ^® 460, Lamepon ^® PA TR, Lamepon ^® ST 40 and Lamepon ^® S (Grünau) as well as 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) can also be used. Crolastin ^® AS (Croda) is a corresponding market product.

A Potassium Cocoyl Hydrolyzed Wheat Protein (Seiwa) is available under the name Promois EGCP.

Further according to the invention are commercial products Lexein ^® A 200 (Inolex), Lamepon ^® PO-TR, Lamepon ^® PA-K, Lamepon ^® S-MV and Lamepon S ^® TR (Grunau) and Crotein CCT ^® (Croda).

The active ingredient combination of quaternary ammonium compound and anionic preservative according to the invention can be used not only in preparations for hair regeneration but also in products which bring about a purely decorative change in the hair, for example in hair colorants. If the active ingredient combination according to the invention is used in hair colorants, then in addition to the at least one quaternary ammonium compound and the at least one anionic preservative there is also at least one dye or dye precursor for dyeing keratin fibers. In order to achieve the coloring effect, oxidation coloring agents usually contain two groups of substances, which are called developers and couplers.

Preferred developer components according to the invention are p-phenylenediamine, p-toluenediamine, p-aminophenol, o-aminophenol, 1- (2'-hydroxyethyl) -2,5-diaminobenzene, N, N-bis (2-hydroxyethyl) -p -phenylenediamine, 2- (2.5-

Diaminophenoxy) ethanol, l-phenyl-3-carboxyamido-4-aminopyrazolone-5, 4-amino-3-methylphenol, 2,4,5, 6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine , 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2-

Hydroxyethylaminomethy 1-4-amino-phenol, 4,4'-diaminodiphenylamine, 4-amino-3-fluoro-phenol, 2-aminomethyl-4-amino-phenol, 2-hydroxymethyl-4-aminophenol, bis- (2-hydroxy-5 aminophenyl) methane, 1,4-bis (4-aminophenyl) diazacycloheptane, 1,3-bis (N (2-hydroxyethyl) -N (4-aminophenylamino)) -2-propanol, 4-amino-2- (2-hydroxyethoxy) phenol and 4,5-diaminopyrazole derivatives according to EP 0 740 741 or WO 94/08970 such as 4,5-diamino-l- (2'-hydroxyethyl) pyrazole.

Coupler components preferred according to the invention 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-Phe - nylenediamine, l-phenyl-3-methyl-pyrazolon-5, 2,4-dichloro-3-aminophenol, 1,3-bis (2,4-diaminophenoxy) propane, 4-chlororesorcinol, 2-chloro-6 -methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2,6-dihydroxypyridine, 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-

Diaminophenoxyethanol, 1-methoxy-2-amino-4- (2-hydroxyethylamino) -benzene, 2-methyl-4-chloro-5-aminophenol, 6-methyl-l, 2,3,4-tetrahydro- quinoxaline, 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-dimethylpyridine.

These developers and couplers are usually used in free form. For substances with amino groups, however, it can be preferred to use them in salt form, in particular in the form of the hydrochlorides and sulfates.

The hair colorants contain both the developers and the couplers preferably in an amount of 0.005 to 20% by weight, preferably 0.1 to 5% by weight, in each case based on the total oxidation colorant. Developers and couplers are generally used in approximately molar amounts to one another. If the molar use has also proven to be expedient, it is a certain excess of individual oxidation dye precursors is not disadvantageous, so that developers and couplers can be present in a molar ratio of 1: 0.5 to 1: 3, in particular 1: 1 to 1: 2.

In a further embodiment, the hair colorants can contain direct dyes either as the sole coloring component for further modification of the color shades in addition to the oxidation dye precursors.

Direct dyes are usually nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred direct dyes are those with the international names or trade names 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 known compounds and 4-amino-2-nitrodiphenylamine-2 ' -carboxylic acid, 6-nitro-l, 2,3,4-tetrahydroquinoxaline, hydroxyethyl-2-nitro-toluidine, picramic acid, 2-amino-6-chloro-4-nitrophenol 4-ethylamino-3-nitrobenzoic acid and 2-chloro 6-ethylamino-1-hydroxy-4-nitrobenzene. The agents according to the invention in this embodiment preferably contain the substantive dyes in an amount of 0.01 to 20% by weight, based on the total colorant.

Furthermore, the preparations according to the invention can also contain naturally occurring dyes such as, for example, henna red, henna neutral, henna black, chamomile flowers, sandalwood, black tea, rotten bark, sage, blue wood, madder root, catechu, sedre and alkanna root.

Further dye components contained in the colorants according to the invention can also be indoles and indolines, and also their physiologically tolerable salts. Preferred examples are 5,6- Dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propy 1-5, 6-dihydroxy indole, N-butyl-5, 6-dihydroxy indole, 5, 6-dihydroxy indole-2-carboxylic acid, 6-hydroxy indole, 6-aminoindole and 4-aminoindole. Also preferred are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, 5 , 6-dihydroxyindoline-2-carboxylic acid, 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

With regard to the dyes which can be used in the hair dyeing and tinting agents according to the invention, reference is also expressly made to the monograph Ch. Zviak, The Science of Hair Care, chapter 7 (pages 248-250; direct dyes) and chapter 8, pages 264-267; Oxidation dye precursors), published as Volume 7 of the "Dermatology" series (ed .: Ch., Culnan and H. Maibach), Marcel Dekker Inc., New York, Basel, 1986, and the "European Inventory of Cosmetic Raw Materials", published by the European Community, available in diskette form from the Federal Association of German Industry and Commerce for Medicines, Reformed Products and Personal Care Products, Mannheim.

It is not necessary that the oxidation dye precursors or the optional direct dyes each represent uniform compounds. Rather, in the hair colorants according to the invention, due to the production processes for the individual dyes, further components may also be present in minor amounts, provided that these do not adversely affect the coloring result or for other reasons, e.g. toxicological, must be excluded.

To produce the colorants, the oxidation dye precursors are incorporated into the preparation according to the invention, at least containing component A and component B. For the purpose of hair coloring, the preparations according to the invention are, for example, as a cream, aerosol, emulsion, gel or else formulated as a surfactant-containing, foaming solution, for example as a shampoo, aerosol foam or in some other way, which are suitable for use on the hair.

In principle, the oxidative development of the coloring can take place with atmospheric oxygen. However, a chemical oxidizing agent is preferably used, especially if, in addition to the coloring, a lightening effect on human hair is desired. Persulfates, chlorites and in particular hydrogen peroxide or its adducts with urea, melamine and sodium borate are suitable as oxidizing agents. It is also possible to carry out the oxidation with the aid of enzymes. The enzymes can be used to transfer atmospheric oxygen to the developer or to enhance the effect of small amounts of oxidizing agents present. An example of an enzymatic process is the procedure to increase the effect of small amounts (e.g. 1% and less, based on the total agent) of hydrogen peroxide by peroxidases.

The preparation of the oxidizing agent is expediently mixed with the preparation from the oxidation dye precursors immediately before hair coloring. The resulting ready-to-use hair dye should preferably have a pH in the range from 6 to 10. It is particularly preferred to use the hair dye in a weakly alkaline environment. The application temperatures can range between 15 and 40 ° C. After an exposure time of approx. 30 minutes, the hair dye is removed from the hair to be colored by rinsing. Washing with a shampoo is not necessary if a carrier with a high tenside content, e.g. a coloring shampoo was used.

The preservative system according to the invention can also be used in the production of corrugating agents. Waving agents are understood to mean agents which serve the permanent deformation of keratin fibers. A Such deformation is usually achieved by mechanically deforming the fiber and fixing the deformation using suitable aids. Before and / or after this deformation, the fiber is treated with the aqueous preparation of a keratin-reducing substance (waving agent) and rinsed with water or an aqueous solution after an exposure time. In a second step, the fiber is then treated with the aqueous preparation of an oxidizing agent (fixing agent). After an exposure time, this is also rinsed out and the fiber is freed of the mechanical deformation aids (curlers, papillots).

As keratin-reducing substances, the waving agents contain mercaptans, for example thioglycolic acid, thiolactic acid, thio malic acid, mercaptoethanesulfonic acid and their salts and esters, cysteamine, cysteine, multicolored 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. These are preferably used in the waving agents in concentrations of 0.5 to 1.0 mol / kg, based on the entire waving agent, at a pH of 5 to 10, in particular 7 to 8.5.

Oxidizing agents, e.g. As sodium bromate, potassium bromate, or hydrogen peroxide, together with stabilizers customary for stabilizing aqueous hydrogen peroxide preparations, are used. The pH of such aqueous H ₂ O ₂ preparations, which usually contain about 0.5 to 3.0% by weight of H ₂ O ₂ , is preferably 2 to 4; it is adjusted by inorganic acids, preferably phosphoric acid.

Bromate-based fixatives usually contain the bromates in concentrations of 1 to 10 and the pH of the solutions is adjusted to 4 to 7. Fixing agents based on enzymes (peroxidases) which contain no or only small amounts of oxidizing agents, in particular H ₂ O ₂ , are also suitable. Both the waving agent and the fixing agent can be formulated as a cream, gel or liquid. Furthermore, it is possible to assemble the agent in the form of foam aerosols, which are mixed with a liquefied gas such. B. propane-butane mixtures, nitrogen, CO ₂ , air, N ₂ O, dimethyl ether, chlorofluorocarbon blowing agents or mixtures thereof are filled in aerosol containers with a foam valve. The fixatives can also be formulated as solids. They then contain the oxidizing agent in the form of a solid, for example potassium or sodium bromate. Only shortly before use, these agents are then mixed with water. It may also be preferred to formulate the oxidizing agent as a two-component system. The two components, one of which is preferably a hydrogen peroxide solution or an aqueous solution of another oxidizing agent and the other of which contains the other constituents, are likewise only mixed shortly before use.

The hair treatment compositions according to the invention can be both products which are rinsed out of the hair after a certain contact time, generally about 1 to 45 minutes, and products which remain on the hair.

The preservative system according to the invention can be used at different pH values. Hair shampoos and conditioners as well as waving lotions preferably have a pH of 2.5 to 7.0, in particular 4.0 to 6.0. In contrast, the pH value of oxidation colorants is usually 6.0 to 10.0, in particular 7.0 to 9.0.

To adjust this pH value, practically any acid or base that can be used for cosmetic purposes can be replaced. In the event that an acid is used to adjust the pH, it may be preferred to use an acid from the group of the edible acids, for example acetic acid, ascorbic acid and gluconic acid. If necessary, the α- Hydroxy carboxylic acids such as lactic acid, tartaric acid, citric acid and malic acid, in addition to their property as part of the preservative system, serve to adjust the pH.

Depending on the intended use and the type of formulation, the preparations according to the invention can contain all the cosmetic additives customary for the particular intended use.

Such common additives are: amphoteric surfactants, for example N-alkylglycines, N-alkylpropionic acids,

N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl

N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaaminopropionic acid and alkylaminoacetic acid, each with about 8 to 18 C-

Atoms in the alkyl group, zwitterionic surfactants, for example the so-called betaines and 2-

AJ ^ l-3-carboxymemyl-3-hydroxyethyl-imidazolines, anionic polymers, for example polyacrylic and polymethacrylic acids, their salts, their copolymers with acrylic and methacrylic acid esters and amides and their derivatives, which are obtained by crosslinking with polyfunctional agents ; Compounds of this type are, for example, under the names Carbopof934, Carbopol ^* 934P,

Carbopof940, Carbopol ^* 950, Carbopo 980 and as CarbopofEDT types

(Manufacturer: all BF Goodrich) and PNC'400 (manufacturer: 3V Sigma) available; nonionic polymers, for example vinylpyrrolidone / vinyl acrylate copolymers, polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers,

Thickeners such as agar agar, guar gum, alginates, cellulose ethers,

Gelatin, pectins and / or xanthan gum,

Structurands such as glucose and maleic acid, hair-conditioning compounds such as phospholipids, for example

Soy lecithin, egg lecithin and cephaline, as well as silicone oils, Perfume oils, dimethyl isosorbitol and cyclodextrins,

Solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin and diethylene glycol,

Dyes,

Anti-dandruff active ingredients such as climbazole, piroctone oliana and zinc omadine, other substances for adjusting the pH value,

Active ingredients such as bisabolol, allantoin and plant extracts,

Light stabilizers,

Fats and waxes, such as walrus, beeswax, montan wax, paraffins,

Esters, glycerides and fatty alcohols,

Fatty acid alkanolamides,

Swelling and penetration substances such as PCA, glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex or styrene / acrylamide copolymers,

Pearlescent agents such as ethylene glycol mono- and distearate or PEG-3 distearate,

Blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air as well

Antioxidants.

The invention is explained below using examples.

Example 1:

In order to check the preservative effect of the active ingredient combination according to the invention, two formulations of the following composition were formulated:

Recipe 1:

2.5% Stenol 1618 (Cetearyl Alcohol) Henkel

0.5% Cutina GMS (Glyceryl Stearate) handle

0.4% Eumulgin Bl (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

Recipe 2:

As recipe 1, additional 0.57% Na salicylate

pH value (both formulations): approx. 2.8

The preservative effect of example formulations 1 and 2 was then investigated.

Test microorganisms:

The bacterial cultures used for the investigation 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 investigation contained the following microorganisms:

Candida albicans ATCC 10231 Aspergillus niger ATCC 6275 Penicillium rubrum CMI 113729 Trichoderma viride BAM T 21

Standard microbial suspensions with 10 ⁸ CFU / ml bacteria and 10 ⁷ CFU / ml fungi were prepared from the above-mentioned microorganisms. Each 10 g of sample formulations 1 and 2 were then loaded in a sterile vessel with 0.1 ml of the bacterial and 0.1 ml of the fungal suspension. The germ suspensions were mixed in a glass homogemsator with at least 10 homogemsator strokes. Direct smears of 2 inoculation loops each on THL Standard I nutrient agar, THL wort agar, THL Standard I nutrient broth and THL wort broth were carried out from the sample formulations so loaded.

The following kill times were found (in days):

Bacteria (2.5 • 10 ⁶ ) Fungi (6 • 10 ⁵ )

Recipe 1:> 21> 35

Recipe 2: 1 1

Claims

PATENT CLAIMS

1. Use of a mixture of at least one quaternary ammonium compound and at least one anionic preservative and / or at least one α-hydroxycarboxylic acid as a preservative system for body care agents.

2. Use according to claim 1, characterized in that the Köφer- care product is a hair care product.

3. Use according to claim 1 or 2, characterized in that the quaternary ammonium compound is cetyltrimethylammonium bromide and / or cetyltrimethylammonium chloride.

4. Use according to any one of the preceding claims, characterized in that the quaternary ammonium compound is at least one quaternary ester compound.

5. Use according to one of the preceding claims, characterized in that the anionic preservative is an alkali metal salt of an organic acid.

6. Use according to 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. Use according to one of the preceding claims, characterized in that sodium salicylate is used as at least one anionic preservative.

8. Use according to one of the preceding claims, characterized in that the α-hydroxycarboxylic acid is selected from the group formed by lactic acid, tartaric acid, malic acid and citric acid.

9. Use according to one of the preceding claims, characterized in that the at least one quaternary ammonium compound and the at least one anionic preservative and / or the α-hydroxycarboxylic acid are contained in a weight ratio of 1:20 to 100: 1.

10. Use according to one of the preceding claims, characterized in that cetyltrimethylammonium chloride is used as at least one quaternary ammonium compound.

11. Preservative system containing as active substance at least one quaternary ester compound and at least one alkali salicylate in a weight ratio of 1:20 to 100: 1.

12. Preservative system according to claim 11, characterized in that distearoylethylhydroxyethylammonium methosulfate is used as at least one quaternary ester compound.

13. Preservative system according to claim 11 or 12, characterized in that sodium salicylate is used as at least one anionic preservative.