CN1268047A - 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

The preservative system that is used for personal hygiene products

The present invention relates to the anticorrosion of human body care composition, relate more specifically to the anticorrosion of agent of taking care of hair, wherein used quaternary ammonium compound and anion antiseptic and/or alpha-hydroxy carboxylic acid compounds.The mixture that the present invention also relates to specific quaternary ammonium compound (so-called esterquats) and sodium salicylate with and as the application of human body care composition antiseptic.

Nowadays human body, particularly Hair grooming cosmetic formulations (hair-treatment composition) are handled with the whole bag of tricks.These processing for example comprise cleans health and hair with shampoo and shower preparation, carries out bleaching, dyeing and the molding of hair with curly hair water, composition for hair dying and hair caring preparation.

Be mixed with the normally various water solublity of hair-treatment composition of conditioner or Rinsing or the aqueous emulsion of fat-soluble ingredient.It usually is difficult that this emulsion anticorrosion will keep its performance, the particularly performance after storing over a long time.The quaternary ammonium compound that is used for some human body care compositions has microbicidal effect really in these compositionss, be insufficient but itself be used for anticorrosion.

Have now found that, if with the combination of at least a quaternary ammonium compound and at least a anion antiseptic and/or at least a alpha-hydroxy carboxylic acid compounds as preservative system, it is very effective anticorrosion just can to finish human body care composition, the particularly agent of taking care of hair.The unexpected complementary action of these components makes it to have obtained the collaborative increase on effect.

Therefore, the present invention relates to the purposes of the mixture of following component:--at least a quaternary ammonium compound and--at least a anion antiseptic and/or--at least a alpha-hydroxy carboxylic acid compounds as the preservative system of human body care composition.

Preferred human body care composition is the hair care agent.In the context of the present invention, the hair care agent also comprises the hair-treatment composition that those just hope the change that obtains hair and decorate, for example hair-dyeing agent or long-acting curly hair preparation.

The quaternary ammonium compound that is fit to is polymeric material or monomeric substance.The polymer that is suitable for the present invention's use generally is the cationic polymer that contains ammonium.The preferred cation polymer is, for example--can obtain from the market with Celquat ^With Polymer JR ^Be the quaternized cellulose of trade name, wherein Compound C elquat ^H 100, Celquat ^L 200 and Polymer JR ^The 400th, preferred quaternized cellulose;--contain the polysiloxanes of quaternary ammonium group;--polymeric dimethyldiallylammonium salt and they and the ester of acrylic acid and methacrylic acid and the copolymer of amide; Merquat by name ^100 (PDDA) and Merquat ^550 (dimethyl diallyl ammonium chloride/acrylamide copolymers) are the examples of this cationoid polymer;--the copolymer of the quaternary ammonium derivative of vinyl pyrrolidone and dialkyl amido acrylate and methacrylate, for example use the quaternised vinyl pyrrolidone of dithyl sulfate/dimethylaminomethyl acrylate copolymer; Suchlike chemical compound has market supply, and its commodity are called Gafquat ^734 and Gafquat ^755 chemical compound;--vinyl pyrrolidone/methyl chloride imidazoline (Methoimidazoliniumchlorid) copolymer, its supply of commodities is called Luviquat ^--quaternised polyvinyl alcohol and contain the polymer of quaternary nitrogen atoms in main polymer chain, its merchant's name has--polyquaternium 2--polyquaternium 17--polyquaternium 18 Hes--, and polyquaternium 27

Yet using cationic surfactant one compounds generally is favourable as quaternary ammonium compound.In these cationic surfactants, quaternary ammonium compound is preferred.Preferred quaternary ammonium compound has ammonium halide, more especially ammonium chloride and ammonium bromide, such as alkyl trimethyl ammonium chloride, dialkyl dimethyl ammonium chloride and trialkyl methyl ammonium chloride, for example cetyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, two cetyl alkyl dimethyl ammonium chlorides, two cetyl dimethyl ammonium bromide, stearyl trimethyl ammonium chloride, VARISOFT TA100, dilauryl alkyl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and three cetyl ammonio methacrylates.

Other suitable quaternary ammonium compound has the season ester compounds, i.e. so-called " esterquats " is because they are easy to biodegradation, so be preferential the selection.Please refer to for example WO91/01295, be in the presence of hypophosphorous acid triethanolamine to be carried out partial esterification with fatty acid in this document for this reason, and behind bubbling air that mixture is quaternized with dimethyl sulfate or oxirane.Now enumerate the representative of following patent as a large amount of prior aries: US3 in this respect, 915,867, US 4,370,272, and EP-A 0 239 910, EP-A 0 293 955 A2, EP-A0 295 739 EP-A 0 309 052.The summary of relevant this content for example has been disclosed in: people such as R.Puchta, Tens.Surf.Det., 30,186 (1993); M.Brock, Tens.Surf.Det., 30,394 (1993); And R.Lagerman etc., U.S.'s oiling association can will (J.Am.Oil.Chem.Soc.) 71,97 (1994).

The example of Esterquats is the quaternary fatty acid triethanolamine ester salts corresponding to general formula I: R in the formula ¹CO contains the acyl group that adds up to 6-22 carbon atom, R ²And R ³Each represents hydrogen or and R independently of each other ¹The implication of CO is identical, R ⁴Be an alkyl or (a CH who contains 1-4 carbon atom ₂CH ₂O-) _qH base, m, n and p jointly represent 0 or the number of 1-12, and q is the number of 1-12, X ^-Be halide ion, alkyl sulfate or alkyl phosphoric acid root.

The representative instance of the quaternary fatty acid triethanolamine ester salts that can use in the present invention has the product based on caproic acid, sad, capric acid, lauric acid, myristic acid, Palmic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachidic acid, mountain Yu acid and erucic acid, and their cuts, for example derive from the pressurized hydrolysis product of natural oil.Industry C _12-18Fatty acid distribution of coconut oil and particularly partially hydrogenated C _16-18Adeps Bovis seu Bubali or palm oil fatty acid and the C that is rich in elaidic acid ₁₆-C ₁₈The fatty acid fraction is preferred the use.

Production is during corresponding to the quaternary fatty acid triethanolamine ester salts of general formula I, and the mol ratio of fatty acid and triethanolamine can be with 1.1: 1-3: 1.Consider the application performance of esterquats, with 1.2: 1-2.2: 1, preferred 1.5: 1-1.9: 1 fatty acid and triethanolamine mol ratio are proved to be particularly advantageous.Preferably be corresponding to the quaternary fatty acid triethanolamine ester salts of general formula I single-, two-and the cuts of three esters, average esterification degree is 1.5-1.9, and derived from industrial C _16/18Adeps Bovis seu Bubali or palm oil fatty acid (iodine number is 0-40).

From the application performance viewpoint, it is particularly advantageous using such quaternary fatty acid triethanolamine ester salts corresponding to general formula I, R wherein ¹CO is acyl group, the R that contains 16-18 carbon atom ²Implication and R ¹Identical, the R of CO ³Be hydrogen, R ⁴Be methyl, m, n and p represent O, X ^-The represent methylidene sulfate radical.

Except the quaternised fatty acid triethanolamine ester salts corresponding to general formula I, other esterquats that is fit to has corresponding to the fatty acid of general formula I I and the quaternised ester salt of diethanol alkylamine:

R in the formula ⁵CO contains the acyl group that adds up to 6-22 carbon atom, R ⁶Be hydrogen or implication and R ⁵CO is same, R ⁷And R ⁸Be the alkyl that independently contains mutually 1-4 carbon atom, m and n be common to represent 0 or the number of 1-12, X ^-Be halide ion, alkyl sulfate or alkyl phosphoric acid root.

At last, another group esterquats that is fit to has the fatty acid and 1 corresponding to formula III, the quaternized ester salt of 2-dihydroxypropyl dialkylamine:

R in the formula ⁹CO contains the acyl group that adds up to 6-22 carbon atom, R ¹⁰Be hydrogen or implication and R ⁹CO is same, R ¹¹, R ¹²And R ¹³Be the alkyl that independently contains mutually 1-4 carbon atom, m and n be common to represent 0 or the number of 1-12, X ^-Be halide ion, alkyl sulfate or alkyl phosphoric acid root.

With regard to the selection of preferred fatty acid and best esterification degree, the example that formula I is mentioned also is applicable to the esterquats corresponding to formula II and formula III.Esterquats normally sells with the alcoholic solution of 50-90% (weight), as needs dilute with water easily.

Though the chemical compound corresponding to formula I-III is independent chemical compound, the mixture of these chemical compounds also can be used for purpose of the present invention in general.The cuts that the composition that obtains by production process changes also is operable.If quaternary ammonium compound is not esterquats, according to the present invention, preferred quaternary ammonium compound should be the mixture of cetyl trimethylammonium bromide or cetyl trimethyl ammonium chloride or these two kinds of chemical compounds.

Organic acid alkali metal salt or one or more organic acid alkali metal salt mixtures preferably are used as the anion antiseptic.Can be as the preferred use of the object of the invention institute as the acylate of anti-microbial preservative (for example in food and/or cosmetics anticorrosion use).

These salt comprise the mixture of for example formates, acetate, propionate, lactate, sorbate, benzoate, Salicylate or levulinate or two or more these salt.

Any salt of described acid and lithium, sodium, potassium, rubidium or caesium can be used as alkali metal salt in principle.But the sodium salt of described acid or potassium salt are preferred, and sodium salt is particularly preferred.

In the anion antiseptic, the salicylic acid alkali metal salt, more especially salicylic acid sodium salt is preferred.

As the substituting or replenishing of at least a anion antiseptic, can use at least a alpha-hydroxy carboxylic acid compounds according to the present invention.Preferred alpha-hydroxy carboxylic acid compounds is lactic acid, tartaric acid, malic acid and citric acid.Lactic acid, malic acid and tartaric acid are preferential especially the selections.Certainly the form that alpha-hydroxy carboxylic acid compounds also can its physiology compatible salt is used, more especially their alkali metal, alkaline-earth metal and aluminum salt.

According to the present invention, using the combination of quaternary ammonium compound, anion antiseptic and alpha-hydroxy carboxylic acid compounds is favourable as preservative system.If the use binary mixture is favourable with quaternary ammonium compound and anion solvent combination.

The weight ratio of quaternary ammonium compound and anion antiseptic or alpha-hydroxy carboxylic acid compounds generally is about 1: 20-100: 1.

The general working concentration of quaternary ammonium compound is about 0.1-10% (weight), totally calculates based on the present composition.Preferred amount is about 0.5-7% (weight), preferred especially 0.8-5% (weight).

The working concentration of anion antiseptic generally is about 0.1-2% (weight), and preferred 0.5-1% totally calculates based on the compositions that contains the anion antiseptic.

The preferable amount of alpha-hydroxy carboxylic acid compounds is about 0.1-0.5% (weight), totally calculates based on preparation.

In some country, above-mentioned qualification can be limited by the legal upper limit.

In view of the easily biological-degradable of used preservative system, use season ester compounds is favourable as quaternary ammonium compound.In the context of the present invention, esterquats is interpreted as above-mentioned quaternary ammonium compound corresponding to general formula I, II and III.

It is preferred that Esterquats is used in combination with the salicylic acid alkali metal salt, more preferably is used in combination with sodium salicylate.

Therefore, the present invention relates to contain weight ratio and be about 1: 20-100: 1 at least a season ester compounds (esterquat) and at least a salicylic acid alkali metal salt are as the preservative system of active component.

What be preferably used as the salicylic acid alkali metal salt is salicylic acid sodium salt.

The present invention also relates to above-mentioned preservative system, wherein is that (INCI name: DistearoylethylHydroxyethylmoniummethosulfate is for example with Dehyquart with distearyl acyl group ethyl-hydroxyethyl ammonium methyl sulfate ^F 75 trade names are sold, and manufacturer is Henkel KGaA, D ü sseldorf) as the season ester compounds.

The present invention also relates to contain weight ratio is 1: 20-100: 1 at least a season ester compounds (esterquat) and at least a salicylic acid alkali metal salt are as the application of preservative system in the human body care composition of active component.

Above-mentionedly be suitable as the quaternary ammonium compound of preservative system and the combination of anion antiseptic can be used in many human body care compositions the agent of more especially taking care of hair.

Hair care agent below they for example comprise: shampoo, Rinsing, liquid (Haarspitzenfluids) sent out sharp by regulator, hair dye, hair jelly and wave set.

Therefore, last preparation also contains other some chemical compounds except antiseptical active component combination, and the chemical compound of cleaning, adjusting, painted or molding effect is for example arranged.

When if preservative system of the present invention is used for for example shampoo, except the antiseptical active substance combination, generally also have at least a anion, amphion, both sexes or non-ionic surface active agent.

Be suitable for any anion surfactant that human body uses and can use with antiseptic actives matter combination of the present invention (preservative system) in principle, if they be not with preservative system in cationic components inconsistent.Whether this incompatibility of some chemical compound exists the professional and technical personnel is known, or can be determined by simple test.The anion surfactant of said type be with give water-soluble anionic group such as at least one carboxylate radical, sulfate radical, sulfonate radical or phosphate groups and at least one alkyl, preferably at least one oleophylic alkyl that contains about 10-22 carbon atom is a feature.In addition, in molecule, can there be ethylene glycol, Polyethylene Glycol ether, ester group, ether, amide and hydroxyl.

The anion surfactant that is fit to for example has:--contain the straight chain fatty acid (soap) of 10-22 carbon atom,--corresponding to formula R ¹⁴O (CH ₂CH ₂O) _xCH ₂COOH (R wherein ¹⁴Be the straight chained alkyl that contains 10-22 carbon atom, x=0 or 1-16) the ether carboxylic acid,--corresponding to formula [R ¹⁵NH (CH ₂CH ₂O) _nCH ₂COO] _mZ (R in the formula ¹⁵Be to contain the straight chain of 2-29 carbon atom or the saturated or unsaturated acyl group of branching; n is the integer of 1-10; m is 1 or 2 number; Z is alkali metal or alkaline earth metal cation) the amide ether carboxylate;--contain the acyl group sarcosine chemical compound of 10-18 carbon atom in the acyl group; the acyl taurine salt that contains 10-18 carbon atom in the acyl group;--contain the acyl-hydroxyethyl sulfonate of 10-18 carbon atom in the acyl group;--contain the 2-Sulfosuccinic acid monoalkyl polyoxy ethyl ester that contains 8-18 carbon atom in the sulfosuccinic acid monoesters of 8-18 carbon atom and diester and the alkyl and contain 1-6 ethyoxyl in the alkyl;--contain the straight chain alkyl sulfonate of 12-18 carbon atom;--contain the linear alpha-olefin sulfonate of 12-18 carbon atom;--contain the alpha-sulfo-fatty acid methyl of the fatty acid of 12-18 carbon atom, corresponding to formula R ¹⁶(CH ₂CH ₂O) _xSO ₃H (R in the formula ¹⁶The straight chained alkyl that preferably contains 10-18 carbon atom, x=0 or 1-12) alkyl sulfate and alkyl polyglycol ether sulfate,--sulphation hydroxyalkyl polyglycol ether and/or hydroxyalkyl polypropylene glycol ether among the DE-A 37 23 354,--the sulfonate of the unsaturated fatty acid that contains 12-24 carbon atom and 1-6 two keys among the DE-A 39 26 344,--the ester of tartaric acid and citric acid and alcohol, the oxirane and/or the adduction product of expoxy propane on the aliphatic alcohol of 8-22 carbon atom of the about 2-15 molecule of this alcohol representative, respectively with alkali metal, the form of alkaline-earth metal and/or ammonium salt, preferably their sodium, potassium, contain in magnesium salt and/or ammonium salt and the silane alcohol base list of 2 or 3 carbon atoms-, two-and/or three alkanol ammonium salts.

The preferred anionic surfactants surfactant has alkyl sulfate, alkyl polyglycol ether sulfate and alkyl to contain to contain in 10-18 carbon atom and the molecule 2-Sulfosuccinic acid monoalkyl polyethoxy ester that contains 8-18 carbon atom in the 2-Sulfosuccinic acid mono alkyl ester that contains 8-18 carbon atom in the ether carboxylic acid of 12 ethylene glycol ethers at the most and the alkyl and dialkyl and the alkyl and contain 1-6 ethyoxyl.

Except that described anion surfactant, non-ionic surface active agent also can be present in the compositions that the present invention contains preservative system.

Non-ionic surface active agent contains the hydrophilic group of the combination of for example polynary alcohol radical, polyalkylene glycol ethers base or polyhydric alcohol and polyglycols ether as them.Corresponding compounds for example has:--2-30 moles of ethylene oxide and/or 0-5 mole expoxy propane the straight-chain fatty alcohol that contains 8-22 carbon atom contain the fatty acid of 12-22 carbon atom or alkyl in contain adduction product on the alkylphenol of 8-15 carbon atom,--the C of 1-30 moles of ethylene oxide and glycerol adduct _12-22Fatty-acid monoester and diester,--C _8-22The alkyl list-and the analog of oligomeric glycosides and its ethoxylation,--the adduction product of 5-60 moles of ethylene oxide on Oleum Ricini and/or castor oil hydrogenated.

In another preferred specific embodiments of the present invention, corresponding to general formula R ¹⁷O (Z) _XAlkylpolyglycosides be used as non-ionic surface active agent.R in these chemical compounds ¹⁷Contain 6-22 carbon atom, and can be straight chain or branching.The alkyl of linear primary alkyl or 2-position methyl-branched is preferred.Alkyl R ¹⁷For example be 1-octyl group, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl.1-octyl group, 1-decyl, 1-lauryl and 1-myristyl are particularly preferred.When with so-called oxo alcohol during as raw material, the chemical compound that contains odd numbers of carbon atoms in the alkyl chain is dominant.

Useful alkylpolyglycosides can contain for example only a kind of specific alkyl R in the present composition ¹⁷But alkylpolyglycosides normally prepares with natural oil, fat or mineral oil.In this case, R ¹⁷It is mixture corresponding to the special processing of the mixture of starting compound or those chemical compounds.Particularly preferred alkylpolyglycosides is R wherein ¹⁷Mainly be those alkylpolyglycosides of representing following groups:--C ₈And C ₁₀Alkyl,--C ₁₂And C ₁₄Alkyl,--C ₈-C ₁₆Alkyl,--C ₁₂-C ₁₆Alkyl.

Any monosaccharide or oligosaccharide all can be used as sugar unit Z.Normally used is sugar and the corresponding oligosaccharide that contains 5 or 6 carbon atoms.Such sugar has for example glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose.Preferred sugar unit is glucose, fructose, galactose, arabinose and sucrose.Particularly preferably be glucose.

The alkylpolyglycosides that is suitable for the present invention's use contains an average 1.1-5 sugar unit.Wherein the x value is preferred for the alkylpolyglycosides of 1.1-1.6.The x value is the most particularly preferred for the alkylpolyglycosides of 1.1-1.4.

The alkoxylate homologue of described alkylpolyglycosides also can be used by the present invention.Each alkylglycoside unit in these homologues can contain and on average be up to 10 oxirane and/or propylene oxide units.

The chemical compound that contains alkyl as surfactant can be a pure material.But general preferably produce these chemical compounds from natural plants or animal material, what therefore obtain is the mixture that contains different carbon numbers in alkyl chain that is decided by this concrete raw material.

The surfactant of the adduct of oxirane and/or expoxy propane and aliphatic alcohol or the derivant of these adducts can be the product that has " normally " homologue to distribute, and also can be the product that has narrow homologue to distribute.The product that has " normally " homologue to distribute is considered to make the homologue mixture that catalyst obtains with alkali metal, alkali metal hydroxide or alkali metal alcoholates in the reaction of aliphatic alcohol and alkylene oxide.It is with for example alkali salt, alkaline earth oxide, hydroxide or the alkoxide of brucite, ether carboxylic acid obtain as catalyst that contrast with it, narrow homologue distribute.The product that use has narrow homologue distribution is favourable.

The amount that preferably contains amphion, anion and/or non-ionic surface active agent with the compositions of preservative system of the present invention preparation is 0.5-40% (weight), more preferably 0.5-20% (weight); In a preferred especially specific embodiments, its amount is totally calculated based on compositions for 1-5% (weight).

The compositions that contains preservative system of the present invention normally exists with form moisture or water/alcoholic solution or dispersion liquid.Water-based formulation or calculate based on prescription is overall that to contain the alcohol, the particularly alcoholic acid prescription that are lower than 15% (weight) be preferred.But pure based formulas, more especially the prescription of ethanol based to use for special type also can be preferred.

Except that the combination that must have antiseptic actives matter, compositions can contain vitamin and/or vitamin derivative substituting or replenishing as listed one or more other chemical compounds.Natural in principle, synthetic, water miscible or oil-soluble vitamin and vitamin derivative are fit to.

Particularly suitable vitamin and vitamin derivative have for example vitamin A, vitamin E, vitamin e acetate, vitamin E-nicotinate, vitaminF, vitamin B ₃, vitamin B ₆, nicotiamide, biotin, vitamin C, vitamin B ₅With their derivant, more especially panthenol, pantothenic acid, calcium pantothenate, general benzyl ethyl ether, panthenyl hydroxypropylsteardimonium chloride (Panthequat ^, Innovachem), pantethin and panthenyltriacetate.Saturated or the unsaturated homologue for example general basic propyl ether of similar derivative thing, general basic butyl ether and other branching or straight chain also is operable certainly.This is equally applicable to the salt of pantothenic acid, and its possible counter ion counterionsl gegenions are not limited to calcium ion, but comprises that all physiology can accept metal cation, for example alkali metal and alkaline-earth metal ions, more especially magnesium, sodium or potassium ion.The present invention also comprises use various vitamin, particularly vitamin B ₅With all possible stereoisomer of its derivant, D-type and L-type and the mixture of the two all can be used according to the invention.

In general, being used for the vitamin of the present composition or the amount of vitamin derivative is 0.01-30% (weight), totally calculates based on compositions.0.02-15% (weight), more especially the amount of 0.02-8% (weight) is normally particularly advantageous for the production of aqueous standby preparation.In many cases, the amount of 0.05-5% (weight) is enough.For concentrate, use 0.05-30% (weight), 1-25% (weight) more especially, and vitamin and/or the vitamin derivative of preferred especially 3-20% (weight) are favourable.

Except that component A and B, compositions of the present invention also can contain protein hydrolysate (individually or with one or more row components).Protein hydrolysate is interpreted as the mixture of aminoacid, oligopeptide and polypeptide and their derivant in the context of the present invention.

Being fit to by the aminoacid that the present invention uses is for example arginine, lysine, cysteine, glutamine, agedoite and valine.The ispol that animal or plant protein obtains with alkali, acid or enzyme hydrolysis basically fully also proves suitable.

Being fit to the oligopeptide that uses by the present invention and polypeptide has (part) hydrolyzate that obtains with sour, alkali or enzyme hydrolysis of animal or plant albumen for example or they.The protein that is fit to has for example keratin, collagen protein, elastin laminin, soybean protein, lactoprotein, casein, fibroin, sericin, wheat protein, fibroin and almond protein.According to the present invention, keratin and vegetable protein are preferred.Hydrolytic process obtains mean molecule quantity and is about 400-50,000 daltonian mixture.Typical mean molecule quantity is at about 500-8,000 dalton's scope.According to the present invention, the hydrolysate of keratin, fibroin and vegetable protein is preferred.

In the context of the present invention, the derivant of aminoacid, oligopeptide and polypeptide is interpreted as their cationic derivative and the condensation substance of they and fatty acid.

Cationic derivative is to react and quaternized subsequently obtaining with the chemical compound reaction that contains quaternary ammonium group usually or with corresponding amine.

Many such season protolysates obtain from market, and they for example comprise:--cation collagen hydrolysate, for example commercially available prod Lamequat ^L (INCI name: Lauryldimonium Hydroxypropyl Hydrolyzed Collagen; ChemischeFabrik Gr ü nau),--cation keratin hydrolyzate, for example commercially available prod Croquat ^(CTFA name: Cocodimonium Hydroxypropyl Hydrolyzed Keratin; Croda),--with Hydrotriticum ^The cation Semen Tritici aestivi hydrolyzate that QL obtains (CTFA name: Lauryldimonium Hydroxypropyl Hydrolyzed Wheat Protein; Croda),--with Crotein ^The product that Q obtains (INCI name: HydroxypropyltrimoniumHydrolyzed Collagen; Croda) and--with Lexein ^The quaternized protein hydrolysate that Q X 3000 (Inolex) obtains.

In the production of protein hydrolysate/fatty acid condensation product, be preferred as acid constituents with oleic acid, myristic acid, 9-undecylenic acid, fatty acid distribution of coconut oil and rosin acid.Condensation substance also can exist with the form of salt, more especially sodium, potassium and triethanolamine salt.

Condensation substance based on collagen hydrolysate also has the CTFA name: the oleoyl hydrolytic collagen, the myristoyl hydrolytic collagen, oleoyl hydrolysis of animal collagen protein, potassium cocos nucifera oil hydrolyzed animal protein, TEA Colophonium acyl hydrolytic collagen, potassium endecatylene acyl hydrolytic collagen and TEA cocos nucifera oil hydrolytic collagen.The commercially available prod for example has: Lamepon ^LPO, Lamepon ^4 SK, Lamepon ^UD, Lamepon ^460, Lamepon ^PA TR, Lamepon ^ST 40 and Lamepon ^S (Gr ü nau) and Lexein ^A 240, Lexein ^S 620 and Lexein ^A 520 (Inolex).

The condensation product of elastin laminin hydrolyzate and fatty acid (for example lauric acid) (CTFA name: also be operable the lauroyl elastin hydrolysis).Its corresponding commodity are Crolastin ^AS (Croda).

The potassium cocoyl hydrolyzed wheat protein that supply of commodities is arranged is Promois EGCP (Seiwa).

Other is suitable for by the commodity that the present invention uses Lexein being arranged ^A 200 (Inolex), Lamepon ^PO-TR, Lamepon ^PA-K, Lamepon ^S-MV and Lamepon ^S-TR (Gr ü nau) and Crotein ^CCT (Croda).

The active substance combination of quaternary ammonium compound of the present invention and anion antiseptic not only can be used for the hair restoration compositions, also can be used for making hair to produce the product that pure decoration changes, and for example is used for the hair-dyeing agent.As be used for the hair-dyeing agent, except at least a quaternary ammonium compound and at least a anion antiseptic, at least a dyestuff or dyestuff former also need be arranged with to dyeing keratinous fibres.Obtain Color, oxidative staining agent generally will contain two groups of chemical compounds that are known as developer (Entwickler) and colour coupler (Kuppler).

According to the present invention, preferred developer has p-phenylenediamine (PPD), to methylene phenyl diamidogen, para-aminophenol, o-aminophenol, 1-(2 '-ethoxy)-2, the 5-diaminobenzene, N, two (2-ethoxy) p-phenylenediamine (PPD) of N-, 2-(2, the 5-diamino phenoxy) ethanol, 1-phenyl-3-carboxamido-4-amino-5-pyrazolone, 4-amino-3-methylphenol, 2,4,5, the 6-tetraminopyrimidine, 2-hydroxyl-4,5, the 6-Triaminopyrimidine, 4-hydroxyl-2,5, the 6-Triaminopyrimidine, 2,4-dihydroxy-5, the 6-di-amino-pyrimidine, 2-dimethylamino-4,5, the 6-Triaminopyrimidine, 2-hydroxyethylamino methyl-4-amino-phenol, 4,4 '-diamino-diphenylamine, 4-amino-3-fluorophenol, 2-amino methyl-4-amino-phenol, 2-hydroxymethyl-4-amino-phenol, two (2-hydroxyl-5-aminophenyl) methane, 1, two (4-aminophenyl) Diazesuberanes of 4-, 1, two (N-(2-ethoxy)-N-(4-aminophenyl amino))-2-propanol of 3-, 4-amino-2-(2-hydroxy ethoxy) phenol and according to EP 0 740 741 or according to the 5-diamino-pyrazole derivative of WO 94/089704, for example 4,5-diaminostilbene-(2 '-ethoxy) pyrazoles.

According to the present invention, preferred couplers has the 1-naphthols, 1,2, the 3-benzenetriol, 1,5-, 2,7-and 1, the 7-dihydroxy naphthlene, o-aminophenol, 5-amino-2-methyl phenol, m-aminophenol, resorcinol, the resorcinol monomethyl ether, m-diaminobenzene., 1-phenyl-3-methyl-5-pyrazolone, 2,4-two chloro-3-amino-phenols, 1,3-two (2, the 4-diamino phenoxy) propane, the 4-chloro resorcinol, 2-chloro-6-methyl-3-amino-phenol, the 2-methylresorcinol, the oreinol diphenol, 2,5-dimethyl resorcinol, 2, the 6-dihydroxy-pyridine, 2, the 6-diamino-pyridine, 2-amino-3-pyridone, 2,6-dihydroxy-3, the 4-diamino-pyridine, 3-amino-2-methylamino-6-methoxypyridine, 4-amino-2-hydroxy-methylbenzene, 2, two (2-hydroxyethylamino) toluene of 6-, 2,4-diamino phenoxy ethanol, 1-methoxyl group-2-amino-4-(2-hydroxyethylamino) benzene, 2-methyl-4-chloro-5-amino-phenol, the 6-methyl isophthalic acid, 2,3, the 4-tetrahydroquinoxaline, 3,4-methylene-dioxy phenol, 3, the 4-methylene dioxo group aniline, 2,6-dimethyl-3-amino-phenol, 3-amino-6-methoxyl group-2-methylamino phenol, 2-hydroxyl-4-amino-benzene oxygen ethanol, 2-methyl-5-(2-hydroxyethylamino) phenol and 2,6-dihydroxy-3, the 4-lutidines.

These developers and colour coupler often use with free form, but then preferably use the form of its salt, more especially its hydrochlorate and sulphate form when they contain amino.

The hair-dyeing agent contains the preferred 0.005-20% of amount (weight) of developer and colour coupler, and more preferably 0.1-5% (weight) totally calculates based on oxide hair dye respectively.The consumption of developer and colour coupler generally is equimolar basically.Though use equimolar amounts basically to be proved to be to be fit to, use excessive a certain oxidation dye precursors not have harm, so the mol ratio of developer and colour coupler can be 1: 0.5-1: 3, more especially 1: 1-1: 2.

In another embodiment, hair dye also can contain direct dyes as the unique dyeing component that further changes tone except oxidation dye precursors.

Typical direct dyes has nitrophenylene diamine, nitro amino phenol, azo dye, anthraquinone or indophenols.Preferred direct dyes is international name or the following chemical compound of trade name: HC Huang 2, HC Huang 4, HC Huang 5, HC Huang 6, basic yellow 57, disperse orange 3, HC red 3, the red BN of HC, alkalescence red 76, HC orchid 2, HC orchid 12, disperse blue 3, alkalescence blue 99, HC purple 1, disperse violet 1, disperse violet 4, disperse black 9, bismarck brown 16 and bismarck brown 17 and 4-amino-2-nitrodiphenylamine-2 '-carboxylic acid, 6-nitro-1,2,3, the 4-tetrahydroquinoxaline, ethoxy-2-nitrotoluidine, 4,6-dinitro-2-aminophenol., 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxyl-4-Nitrobenzol.The amount that preparation of the present invention in this specific embodiments contains direct dyes is preferably 0.01-20% (weight), totally calculates based on stain.

In addition, compositions of the present invention also can contain natural dye, and is red such as mignonettetree, mignonettetree is grey, mignonettetree is black, Chamomile, sandalwood, postfermented tea, black alder, Salvia japonica Thunb., Lignum Sappan, Radix Rubiae, catechu, sedre and faggot.

Other dye component that exists in hair dye of the present invention can be indole and indoline and their physiology compatible salt.Preferred example is 5,6-dihydroxy indole, N-methyl-5,6-dihydroxy indole, N-ethyl-5,6-dihydroxy indole, N-propyl group-5,6-dihydroxy indole, N-butyl-5,6-dihydroxy indole, 5,6-dihydroxy indole-2-carboxylic acid, 6-oxyindole, 6-amino indole and 4-amino indole.Preferred also have 5,6-dihydroxy indoline, N-methyl-5,6-dihydroxy indoline, N-ethyl-5,6-dihydroxy indoline, N-propyl group-5,6-dihydroxy indoline, N-butyl-5,6-dihydroxy indoline, 5,6-dihydroxy indoline-2-carboxylic acid, 6-hydroxyl indoline, the amino indoline of 6-and the amino indoline of 4-.

About the dyestuff that is adapted at using in hair-dyeing of the present invention and the toning prescription, also please be concrete with reference to following document: Ch.Zviak, hair nursing science (The Science of Hair Care), the 7th chapter, (PP.248-250; Direct dyes) and the 8th chapter, PP.264-267; Oxidation dye precursors rolls out version (editor: Ch.Culnan and H.Maibach), Marcel Dekker Inc., New York/Basel, (1986) as the 7th of dermatological (" Dermatology ") book series; And European cosmetic material catalogue (" Europaeische Inventar derKosmetik-Rohstoffe "), Europaeische Gemeinschaft publishes.By Bundesverband Deutscher Industrie-und Hundelsunternehmenfuer Arzneimittel, Reformwaren und Koerperpflegemittel e.V., Mannheim, Germany provides disk.

Oxidation dye precursors or optional direct dyes need not to be single chemical compound.Hair dye of the present invention in contrast (since produce single dyestuff used method caused) can contain a spot of other component, as long as they do not play detrimental effect to coloration result or must be removed because of other reason (for example toxic).

When producing hair dye is that oxidation dye precursors is mixed in the present composition that contains component A and B component at least.For being used to the purpose of having hair dyed, compositions of the present invention can be mixed with example emulsion, aerosol, emulsion, gel, perhaps or even contain the frothing solution of surfactant, for example shampoo, foamed aerosol or other dosage form that is adapted at using on the hair.

In principle, can carry out oxidative color-developing with aerial oxygen.But preferred use is chemical oxidizing agent, particularly not only need have dyeing also to need the last light time at Crinis Carbonisatus.Particularly suitable oxidant is persulfate, chlorite and at first is the adduction product of hydrogen peroxide or they and urea, tripolycyanamide or sodium borate.Oxidation also can be carried out with enzyme.In this case, available enzyme is transferred to air oxygen on the developer or the oxidant in effect of a small amount of existence is improved.It is the measure that the effect of a small amount of (for example 1% or lower, calculate based on prescription is overall) hydrogen peroxide is improved by peroxidase that enzyme is urged an example of method.

The oxidant preparation preferably directly just mixed with the oxidation dye precursors preparation before hair dyeing.The preferred pH value of formed thus standby hair dye should be in the scope of 6-10.It is particularly advantageous that hair dye uses in a weak alkaline medium.Temperature during use can be 15-40 ℃ of scope.Carry out rinsing after about 30 minutes with from being removed hair dye in contact by dyeing hair.When using the high surface agent carrier for example to dye shampoo, hair need not reuse shampoo washing.

Preservative system of the present invention also can be used for the perming production of preparation.In the context of the present invention, the curly hair preparation is interpreted as being used for the preparation of the permanent shaped of keratin fiber.As this class molding is to make mechanical texturing and will be out of shape fixing with the auxiliary agent that is fit to.Before or after distortion, fiber is handled with the aqueous compositions of kerateine material (wave set), and water or aqueous solution rinsing after contact a period of time.Second step was to handle fiber with the aqueous compositions of oxidant (fixative).Behind the contact certain hour, rinsing goes out fixative and remove the mechanical-moulded device (curler, steamed roll) that helps from fiber.

The curly hair preparation contains reducible keratic material mercaptan, for example TGA, thiolactic acid, thiomalic acid, sulfydryl ethyl sulfonic acid and their salt and ester, half light amine, cysteine, Bunte salt and alkali sulfite slaine.The alkali metal of TGA and/or thiolactic acid or ammonium salt and free acid are preferred.The preferred concentration that they are used for setting lotion is 0.5-1.0 mole/kilogram, totally calculates based on the curly hair preparation, and be 5-10 at pH value, more especially during 7-8.5.

Oxidant for example sodium bromate, Potassium bromate. or hydrogen peroxide is used as fixative with the stabilizing agent that typically is used for stable aqueous hydrogen peroxide preparation.The preferred pH value of this aqueous hydrogen peroxide preparation (often containing about 0.5-3.0% (weight) hydrogen peroxide) is to regulate with mineral acid, preferably phosphoric acid in the 2-4 scope.

The concentration that contains bromate based on the fixative of bromate often is 1-10, and the pH value of solution is transferred to 4-7.The fixative based on enzyme (peroxidase) that does not contain or only contain small amounts agent, particularly hydrogen peroxide also is fit to.

Setting lotion and fixative all can be mixed with Emulsion, gel or liquid.Compositions also can be mixed with foamed aerosol, with liquid gas (such as propane/butane mix, nitrogen, CO ₂, air, N ₂O, dimethyl ether, Chlorofluorocarbons (CFCs) propellant or their mixture) be packaged together in the aerosol container of foam valve.Fixative also can be mixed with solid, and wherein contained oxidant is a solid form, and for example Potassium bromate. or sodium only just add water in these reagent before application.It also is favourable that oxidant is mixed with two components system.One of these two kinds of components are preferably the aqueous solution of hydrogenperoxide steam generator or another oxidant, and another component contains remaining batching, and they also are to face with before mixing.

Hair-treatment composition of the present invention can be the product that can fall from hair rinse after contact certain hour (generally about 1-45 minute), also can be the product that is retained on the hair.

Preservative system of the present invention can use under different pH value.For example the preferred pH value of shampoo, Rinsing and wave set is 2.5-7.0, more especially in the 4.0-6.0 scope.Contrast with it, the pH value of oxide hair dye generally is the 6.0-10.0 scope, more especially the 7.0-9.0 scope.

In fact, any acid or the alkali that is used for cosmetics all can be used to regulate pH value.As use acid for adjusting pH value, it is favourable using food-grade acid such as acetic acid, ascorbic acid and gluconic acid.But alpha-hydroxy carboxylic acid compounds (such as lactic acid, tartaric acid, citric acid and malic acid) is except also can be used to regulate pH value as the component of preservative system.

According to the application of imagination and the kind of preparation, preparation of the present invention can contain any cosmetics additive of using always for various application.

Suchlike additive comprises:--amphoteric surfactant, the sweet ammonia carboxylic of N-alkyl that for example contains 8-18 carbon atom in the alkyl respectively, N-alkyl propanoic acid, N-alkyl amino butanoic acid, N-alkyl imino dipropionic acid, the sweet ammonia carboxylic of N-ethoxy-N-alkyl amido propyl group, the N-alkyl taurine, N-alkyl sarcosine, 2-alkyl aminopropionic acid and p dialkylaminobenzoic acid,--zwitterionic surfactant, for example so-called betanin and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazole quinoline,--anionic polymer, for example polyacrylic acid and polymethylacrylic acid, their salt, they and acrylic acid-and methacrylic acid-ester and-copolymer of amide and they and the crosslinked derivant that obtains of multifunctional reagent; This compounds for example can obtain with following merchant's name, for example Carbopol ^934, Carbopol ^934P, Carbopol ^940, Carbopol ^950, Carbopol ^980 and Carbopol ^EDT type (production firm is BF Goodrich) and PNC ^400 (production firms: 3V Sigma);--non-ionic polymers, vinyl pyrrolidone/vinyl acrylate copolymer for example, polyvinylpyrrolidone and vinyl pyrrolidone/vinyl acetate copolymer,--thickening agent, such as agar, guar gum, alginate, cellulose ether, gelatin, pectin and/or cover xanthan with mat,--structural agent, such as glucose and maleic acid,--hair is regulated chemical compound, such as phospholipid, soybean lecithin for example, egg lecithin and cephalin, and silicone oil,--essential oil, Isosorbide dimethyl ether and cyclodextrin,--solubilizing agent, such as ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,--dyestuff,--anti-dandruff agent, such as Climbazol, Piroctone Olamine and Zinc Omadine,--other regulates the material of pH value,--active substance, such as bisabolol, allantoin, and plant extract,--the UV filters agent,--fat and wax, such as spermaceti, Cera Flava, montan wax, paraffin, ester, glyceride and aliphatic alcohol,--fatty acid alkanol amides,--expand and penetrating agent, such as PCA, glycerol, propylene glycol list ethylether, carbonate, bicarbonate, guanidine, a urea and a generation-, secondary-, tertiary phosphate,--opacifier, such as latex and styrene/acrylamide copolymer,--pearling agent, such as glycol monomethyl-and distearate and PEG-3-distearate,--propellant, such as propane/butane mix, N ₂O, dimethyl ether, CO ₂And air, and--antioxidant.

Now the present invention will be described with embodiment.

Embodiment

Antiseptic effect for test active substance combination of the present invention has prepared two prescriptions that following component is arranged: an amount of citric acid suitable quantity of water prescription 2 of prescription 1:2.5% Stenol 1618 (Cetearyl Alcohol) Henkel0.5% Cutina GMS (tristerin) Henkel0.4% Eumulgin B1 (Ceteareth-12) Henkel0.1% Cetiol OE (dioctyl ether) Henkel2.4% Dehyquart A (Cetrimomium Chloride) Henkel2.0% glucose:

Identical with prescription 1, but add 0.57% sodium salicylate in addition.

PH value (two prescriptions): about 2.8

The antiseptic effect test of prescription 1 and 2 is as follows:

The test microorganism:

The bacterial cultures that is used to test contains following microorganism:

-staphylococcus aureus ATCC 6538

-Enterococcus?faecium ATCC 6057

-escherichia coli ATCC 11229

-clostridium perfringen DSM 30053

-bacillus pyocyaneus ATCC 15442

The fungal cultures that is used to test contains following microorganism:

-candida albicans ATCC 10231

-aspergillus niger ATCC 6275

-penicillium rubrum CMI 113729

-Trichoderma viride BAM T 21

Respectively contain 10 with above-mentioned microorganism preparation ⁸CBU/ milliliter antibacterial and 10 ⁷The standard microorganism suspension of CBU/ milliliter fungus.Prescription 1 with 10 gram amounts is tested with 2 and 0.1 milliliters of bacterial suspensions of prescription and 0.1 milliliter of fungus suspension respectively in disinfectant vessel.In the glass homogenizer, mix at least 10 homogenizer strokes to mix microbial suspension.The prescription that will add microorganism with two inoculation circles directly imposes on THL standard I Nutrient agar, THL wort agar, THL standard I nutrient broth and THL beerwort soup.

Observed sterilization time (my god) as follows:

Antibacterial (2.510 ⁶) fungus (610 ⁵)

Prescription 1:＞21＞35

Prescription 2:1 1

Claims (13)

1. the mixture of following component is as the application of the preservative system of human body care composition,--at least a quaternary ammonium compound and--at least a anion antiseptic and/or--at least a alpha-hydroxy carboxylic acid compounds.

2. the described application of claim 1 is characterized in that the human body care composition is the hair care agent.

3. claim 1 or 2 described application is characterized in that quaternary ammonium compound is cetyl trimethylammonium bromide and/or cetyl trimethyl ammonium chloride.

4. the application of aforementioned each claim is characterized in that quaternary ammonium compound is at least a season ester compounds.

5. the application of aforementioned each claim is characterized in that the anion antiseptic is an organic acid alkali metal salt.

6. the described application of claim 5 is characterized in that organic acid alkali metal salt is the salt of formic acid, acetic acid, propanoic acid, lactic acid, sorbic acid, benzoic acid, salicylic acid and levulic acid.

7. the application of aforementioned each claim is characterized in that sodium salicylate is used as at least a anion antiseptic.

8. the application of aforementioned each claim is characterized in that alpha-hydroxy carboxylic acid compounds is selected from lactic acid, tartaric acid, malic acid and citric acid.

9. the application of aforementioned each claim, it is characterized in that at least a quaternary ammonium compound and at least a anion antiseptic and/or alpha-hydroxy carboxylic acid compounds are with weight ratio 1: 20-100: 1 exists.

10. the application of aforementioned each claim is characterized in that the cetyl trimethyl ammonium chloride is used as at least a quaternary ammonium compound.

11. one kind contains weight ratio is 1: 20-100: at least a season of 1 ester compounds and at least a salicylic acid alkali metal salt as the preservative system of active substance.

12. the described preservative system of claim 11 is characterized in that distearyl acyl group ethyl-hydroxyethyl ammonium methyl sulfate is used as at least a season ester compounds.

13. claim 11 or 12 described preservative systems is characterized in that sodium salicylate is used as at least a anion antiseptic.