DE3044754A1 - Hair treatment compsn. contg. an anionic polymer - contg. carboxylic or sulphonic gps., and an amphoteric polymer contg. basic nitrogen and acid gps., gives good conditioning - Google Patents

Abstract

Hair treatment compsn. is made comprising (a) at least one anionic polymer contg. one or more carboxylic or sulphonic gps., and (b) at least one amphoteric polymer with units A and B distributed statistically in the polymer chain, where A is a gp. derived from a monomer contg. at least one basic N atom and B is a gp. derived from an acid monomer contg. one or more carboxyl or sulphonic acid gps., or A and B may represent a cationic polymer chain contg. sec., tert. or quat. amine gps. (excepting piperazinyl), at least one of the amine gps. carrying a carboxyl or sulphonic gp. bound via a hydrocarbon gp., or A and B may form part of a polymer chain with ethylene alpha, beta-dicarboxylic gps., one of the carboxyl gps. having been reacted with a polyamine contg. one or more prim., sec. or tert. amine gps., with the proviso that when A and B represent a cationic polymer chain with polyaminoamide gps. in which at least one of the amine gps. carries a carboxyl or sulphonic gp. bound via a hydrocarbon gp., the anionic polymer is not a vinyl acetate/crotonic acid copolymer. The compsns. give a good conditioning and cosmetic effect to hair, e.g. during shampooing, bleaching, dyeing, permanent waving, etc. The treated hair has good softness, body and resistance to entanglement.

Description

The invention relates to new preparations, in particular cosmetic

Table means for treating keratin fibers, preferably hair. The main aim of the invention is the combined use of an anionic polymer with an amphoteric polymer.

It is already known to use anionic polymers in agents for treatment of hair to achieve certain properties, e.g. a Hardening of the keratin fibers or good hold or shine of the hair. They mostly will applied without subsequent rinsing of the hair.

However, anionic polymers have the disadvantage of being poor Fixation on the keratin fibers so that they can be easily removed during rinsing or without Rinsing can be easily atomized, causing great fragility and poor substantivity has the consequence. In order to remedy this disadvantage, the applicant has already proposed to use cationic polymers together with the anionic polymers; see e.g.

FR-PS 2 383 660. Although this combination of anionic and cationic Polymerizate gives the hair good cosmetic properties, it has been shown that successive treatments with this combination especially in the case from sensitized hair to brittle and heavily coated hair. This brittle or enveloped character of the hair after several treatments is presumably based on the selective elimination of the anionic polymer after several treatments the deposition of several layers of cationic polymers results.

It has now been found that when using an amphoteric polymer treated several times with these agents instead of the cationic polymer itself Keratin fibers have a good hold and are pliable, soft and shiny. Particularly interesting results are obtained with treatments that are usually performed by a Rinsing, e.g. shampooing, as well as treatments with the help of Lotions or creams that are applied to the hair before or after coloring, Decolorize, shampoo or condition the perm.

It has been shown that when using certain amphoteric polymers in combination with anionic polymers, the hair is given good hold, without the cosmetic disadvantages of selective elimination occurring.

The aim of the invention is therefore to provide means for treating keratin fibers provide the at least one anionic and at least one amphoteric polymer contain. The aim of the invention is also a method for treating keratin fibers, in which an anionic and an amphoteric polymer are used. goal of Finally, the invention is also a process for fixing anionic polymers on keratin fibers with the help of an amphoteric polymer.

The agents according to the invention are essentially characterized by that they are in a suitable medium that allows the application of polymers to keratinous fibers allows a) at least one anionic polymer with one or more carboxylic acid or sulfonic acid groups and b) at least one amphoteric polymer, which contains units A and B in a randomly distributed manner in the polymer chain, where A is a unit that is different from a monomer having at least one basic nitrogen atom and B is a unit that differs from an acidic monomer with an or derived from several carboxylic acid or sulfonic acid groups, or A and B also groups can be derived from zwitterionic carboxy betaine monomers, A and B can also be a cationic polymer chain, the secondary, tertiary (with Except for piperazinyl) or quaternary amine groups, with at least one of the amine groups a carboxylic acid or bonded via a hydrocarbon radical Sulfonic acid group, or A and B part of a polymer chain of ethylene-a, l3-dicarboxylic acid units are, in which one of the carboxylic acid groups with a polyamine, the one or more carries primary, secondary or tertiary amine groups, has been converted, contains, provided that when A and B are a cationic polymer chain, the polyaminoamide units containing at least one of the amine groups via a hydrocarbon radical Bound carboxylic acid or sulfonic acid group carries the anionic polymer is not a vinyl acetate-crotonic acid bipolymer.

Particularly preferred amphoteric polymers are: (1) Polymers obtained by copolymerizing a monomer which is derived from a vinyl compound with a carboxylic acid group, for example acrylic, methacrylic, maleic or α-chloroacrylic acid, with a basic monomer which is derived from a substituted vinyl compound with at least one basic nitrogen atom, for example a dialkylaminoalkyl methacrylate or acrylate or dialkylaminoalkyl methacrylamide or acrylamide; See, for example, U.S. Patent 3,836,537; (2) Polymers with units derived from (a) at least one monomer from the group of acrylamides or methacrylamides which are substituted on the nitrogen by an alkyl radical, (b) at least one acidic comonomer which contains one or more reactive carboxylic acid groups, and (c) at least one basic comonomer, for example an acrylic or methacrylic acid ester with primary, secondary, tertiary or quaternary amine substituents or the quaternization product of dimethylaminoethyl methacrylates with dimethyl or diethyl sulfate; N-substituted acrylamides or methacrylamides which are particularly preferred according to the invention are groups whose alkyl radicals contain 2 to 12 carbon atoms, in particular N-ethyl acrylamide, N-tert-butyl acrylamide, N-tert-octyl acrylamide, N-octyl acrylamide, N-decyl acrylamide and N-dodecyl acrylamide and the corresponding methacrylamides. Preferred acidic comonomers are acrylic, methacrylic, crotonic, itaconic, maleic and fumaric acid and the C14 monoalkyl esters of maleic or fumaric acid. Preferred basic comonomers are aminoethyl, butylaminoethyl, N, N-dimethylaminoethyl and N-tert-butylaminoethyl methacrylate; (3) crosslinked and wholly or partially alkylated polyaminoamides, which are different from polyaminoamides of the general formula (I) derive, in which R is a divalent radical which is derived from a saturated dicarboxylic acid, an aliphatic mono- or dicarboxylic acid with an ethylenic double bond or an ester of a lower alkanol with 1 to 6 carbon atoms of these acids, or a radical which means the addition of a of the acids mentioned with a bis-primary or bis-secondary amine, and Z represents the radical of a bis-primary, mono- or bis-secondary polyalkylenepolyamine, preferably 1) in proportions of 60 to 100 mol percent the radical where X = 2 and n = 2 or 3 or x = 3 and n = 2; which is derived from diethylenetriamine, triethylenetetramine or dipropylenetriamine, 2) in proportions of 0 to 40 mol percent the above remainder (II), where x = 2 and n = 1, which is derived from ethylenediamine, or the remainder which is derived from piperazine; 3) in proportions of 0 to 20 mol percent the remainder - NH - (CH2) 6 - NH -, which is derived from hexamethylenediamine, these polyaminoamides by adding a bifunctional crosslinking agent from the group of epihalohydrins, diepoxides, dianhydrides and bis-unsaturated derivatives have been crosslinked with an average of 0.025 to 0.35 mol percent crosslinking agent per amino group of the polyaminoamide and have been alkylated with acrylic acid, chloroacetic acid or an alkane sultone or their salts.

Preferred saturated carboxylic acids are acids with 6 to 10 carbon atoms, such as adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, terephthalic acid, acids with an ethylenic double bond, for example acrylic, methacrylic and itaconic acid. Alkane sultones preferred for the alkylation are propane and butane sultone and the salts of the alkylating agents are preferably sodium and potassium salts; 4) Polymers with zwitterionic units of the formula in which R1 is a polymerizable unsaturated group, e.g.

B. an acrylate, methacrylate, acrylamide or methyl acrylamide group means, x and y are integers from 1 to 3, R2 and R3 are hydrogen, methyl, Mean ethyl or propyl, R4 and R5 represent hydrogen or an alkyl radical, where the sum of the carbon atoms in R4 and R5 is not greater than 10.

The polymers with these units can also have units which are derived from non-zwitterionic monomers, for example from vinylpyrrolidone, dimethyl or diethylaminoethyl acrylate or methacrylate, alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate, 5) polymers derived from Derive chitosan and contain monomer units of the following formulas: where the unit A is present in proportions from 0 to 30%, B in proportions from 5 to 50% and C in proportions from 30 to 90 z and R in the formula C is a radical of the formula is, where in the case of n = O R6, R7 and R8 are identical or different hydrogen, methyl, hydroxyl, acetoxy or amino, a monoalkylamine or dialkylamine radical, which is optionally interrupted by one or more nitrogen atoms and / or optionally by one or more amines -, hydroxyl, carboxyl, alkylthio or sulfonic acid groups, or an alkylthio radical whose alkyl group bears an amino radical, at least one of the radicals R6, R7 and R8 in this case being a hydrogen atom, or in the case of n = 1 R6, R7 and R8 are each hydrogen atoms, and the salts of these compounds with bases or acids; 6) Polymers of the general formula IV (FR-PS 1 400 366): in which R is hydrogen, CH30, CH3CH20 or phenyl, R1 is hydrogen or a lower alkyl radical, e.g. methyl or ethyl, R2 is hydrogen or a lower alkyl radical, e.g. methyl or ethyl, R3 is a lower alkyl radical, e.g. methyl or ethyl , or a radical of the formula R4-N (R2) 2 and R4 is the group -CH2-CH2-, -CH2 -CH2 -CH2-, as well as higher homologues of these radicals and contains up to 6 carbon atoms.

The amphoteric polymers used according to the invention have a Molecular weight from 500 to 2 million. Preferred polymers are those of Groups (2), (4), (5) and (6).

Particularly preferred anionic polymers are water-soluble polymers, by neutralizing the acid groups with an alkali base, e.g. sodium or Potassium hydroxide, or an amine such as triethanolamine, 2-amino-2-methylpropan-1-ol or 2-amino-2-methylpropane-1,3-diol can be obtained. These polymers have a molecular weight of 500 to 5,000,000.

The carboxylic acid groups are carried by unsaturated mono- or dicarboxylic acids, for example those of the formula in which n is an integer from 0 to 10, A denotes a methylene group which is optionally connected via a heteroatom, such as oxygen or sulfur, to the carbon atom of the unsaturated group or the adjacent methylene group, if n is greater than 1, R1 Is hydrogen, phenyl or benzyl, R2 is hydrogen, carboxyl or a lower alkyl radical and R3 is hydrogen, -CH2-COOH, phenyl, benzyl or a lower alkyl radical. In the above formula, the lower alkyl group preferably contains 1 to 4 carbon atoms, such as

Methyl or ethyl.

Preferred anionic polymers are: homo- and copolymers of acrylic or methacrylic acid and their salts, especially commercial products VERSICOL E or K from Allied Colloid, ULTRAHOLD 8 from Ciba Geigy, DARVAN No. 7 from Van der Bilt; Copolymers of acrylic acid and acrylamide in the form of their sodium salt are sold by HERCULES under the names RETEN 421, 423 or 425, Copolymers of acrylic or methacrylic acid and vinyl alcohol, e.g. HYDAGEN F from HANDLE; - Copolymers of the above acids with a monoethylenically unsaturated one Monomers, such as ethylene, vinylbenzene, vinyl or allyl esters, acrylic or methacrylic acid esters, which optionally on a polyalkylene glycol, such as polyethylene glycol, grafted and are possibly networked.

Such polymers are, for example, in FR-PS 1 222 944 and DE-OS 2,330,956; Copolymers of the type the one in the chain contains an optionally N-alkylated and / or hydroxyalkylated acrylamide unit, as described in LU-PS 75 370 and 75 371 and by American Cyanamid sold as QUADRAMER 5; Copolymers of crotonic acid1 e.g. those those in the chain vinyl acetate or propionate units and optionally others Monomers, e.g. allyl or methallyl esters, vinyl ethers or vinyl esters of saturated long chain fatty acids having, for example, at least 5 carbon atoms; these Polymers can optionally be grafted and crosslinked. Polymers of this Art are e.g. in FR-PS 1 222 944, 1 580 545, 2 265 782, 2 265 781 and 1 564 110 described. Resins 28-29-30 and 26-13-14 are commercial products in this class from National Starch; Polymers of maleic, fumaric or itaconic acid or anhydride with vinyl esters, vinyl ethers, vinyl halides, phenyl vinyl derivatives, acrylic acid and their esters. These polymers can be esterified. Polymers of this Art are, for example, in U.S. Patents 2,047,398, 2,723,248 and 2,102,113, and GB 839 805 and are described as GANTREZ AN or ES by General Aniline or as EMA 1325 distributed by MONSANTO. Polymers of this class are also copolymers of maleic, citraconic or itaconic anhydride with allyl or methallyl esters, which optionally contain an acrylamide or methacrylamide group in the chain and are monoesterified or monoamidated; see FR-OS 76 13929 and 76 20917 of the applicant; Salts of polystyrene sulfonic acid, e.g. the sodium salts FLEXAN 500 with a molecular weight of about 500,000 or FLEXAN 130 with a molecular weight of about 100,000 of the National Starch. These compounds are described, for example, in FR-PS 2 198 729; - Alkali or alkaline earth metal salts of lignosulfonic acids, especially calcium and sodium lignosulfonate, e.g.

MARASPERSE C-21 from the American Can Co. or the C10-C14 products from Avplane; - polymers with alkylnaphthalenesulfonic acid units in the salt form, e.g. the sodium salt DARVAN No. 1 from Van der Bilt.

The amphoteric polymers of group (3) are used together with anionic Polymers used that differ from vinyl acetate-crotonic acid bipolymers are, in particular polymers with acrylic or methacrylic acid units, terpolymers with crotonic acid units, polymers of maleic, fumaric or itaconic acid or anhydride and polymers derived from sulfonic acid.

According to the invention, combinations of the amphoteric are particularly preferred Polymers of groups (2) or (5) with the following anionic polymers - Homo- or copolymers of acrylic or methacrylic acid or their salts; - Polymers of maleic acid or anhydride; - salts of polystyrene sulfonic acid.

Combinations of the Commercial product AMPHOMER and the anionic polymers GANTREZ ES 425, HYDAGEN F, VERSICOL E5, VERSICOL K11 and FLEXAN.

The agents preferably contain no further polymers and in particular no cationic polymer. The polymers used according to the invention may be present in amounts from 0.01 to 10, preferably 0.5 to 5 weight percent be. The pH of the agents is usually from 2 to 11, preferably from 3 to 10 and especially 4 to 8.5.

The agents are preferably used to treat human hair used and can be in various forms, e.g. as a liquid, cream, Emulsion or gel.

You can also use water or any cosmetically acceptable Contain solvents, especially monoalcohols, e.g. alkanols with 1 to 8 carbon atoms, such as ethanol, isopropanol, benzyl alcohol, phenylethyl alcohol, polyalcohols, e.g. Alkylene glycols, such as ethylene glycol or propylene glycol, glycol ethers, e.g. mono-, Di- or triethylene glycol monoalkyl ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or diethylene glycol monoethyl ether, and mixtures thereof. These solvents can in amounts less than equal to 70 percent by weight based on the weight of the Total means, can be used.

The agents can also contain electrolytes, preferably salts of Alkali metals such as sodium, potassium or lithium.

These salts are preferably halides, e.g. chlorides or bromides, Sulphates or salts of organic acids, preferably acetates or lactates.

The funds can be in the form of a powder that is diluted before use will. Agents which, when used normally, are subsequently rinsed, are preferred and enable particularly good results. They can be used in particular as shampoos, Rinsing lotions, creams or treatment preparations that are used before or after coloring, before or after shampooing, before or after the perm, or as coloring agents, water wave lotions, brush lotions, decolorizing, permanent wave or de-curling preparations.

A particularly preferred embodiment is the use as a shampoo. In this case, contain the invention Means next to the named polymers at least one anionic, nonionic, cationic or amphoteric surfactant or mixtures thereof. Suitable anionic surfactants are e.g. the following compounds and their mixtures: alkali, ammonium, amine or amino alcohol salts of the following compounds: - alkyl sulfates, alkyl ether sulfates, alkyl amide sulfates and ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates; - alkyl sulfonates, Alkyl amide sulfonates, alkyl aryl sulfonates, α-olefin sulfonates, - alkyl sulfosuccinates, Alkyl ether sulfosuccinates, alkyl amide sulfosuccinates; - alkyl sulfosuccinamates; - alkyl sulfoacetates, Alkyl polyglycerol carboxylates; - alkyl phosphates, alkyl ether phosphates; - alkyl sarcosinates, Alkyl polypeptidates, alkyl amido polypeptidates, alkyl isethionates, alkyl taurates.

(The alkyl radical of these compounds is a linear chain from 12 to 18 carbon atoms).

- Fatty acids, e.g. oleic, castor, palmitic and stearic acids, acids of coconut oil or hydrogenated coconut oil, carboxylic acids of polyglycol ethers of the formula: Alk - (OCH2 - CH2) n - OCH2 2 where Alk is a linear chain with 12 to 18 carbon atoms and n is an integer from 5 to 15.

Particularly preferred anionic surfactants are: sodium, ammonium and triethanolamine lauryl sulfate, with 2.2 moles of ethylene oxide ethoxylated sodium lauryl ether sulfate, the triethanolamine salt of lauroyl keratinic acid, the triethanolamine salt of the condensation product of coconut acids with animal protein hydrolysates, products of the formula: R - (OCH2 - CH2) x - OCH2 - COOH in which R is an alkyl radical with usually 12 to 14 carbon atoms and x has a value of 6 to 10.

Nonionic surfactants which can optionally be used in a mixture with the anionic surfactants mentioned are, for example, the condensation products of monoalcohols, α-diols, alkylphenols, amides or diglycolamides with glycide, for example compounds of the formula in which R4 is an aliphatic, cycloaliphatic or arylaliphatic radical with preferably 7 to 21 carbon atoms or a mixture thereof, whereby the aliphatic chains can contain ether, thioether or hydroxymethylene groups, and p has a statistical mean value of 1 to 10 (cf.e.g. FR- PS 2,091,516); Compounds of the formula in which R5 denotes an alkyl, alkenyl or alkylaryl radical and q has a statistical mean value of 1 to 10 (cf., for example, FR-PS 1 477 048); Compounds of the formula: in which R6 denotes an aliphatic, straight-chain or branched, saturated or unsaturated radical with 8 to 30 carbon atoms, of natural or synthetic origin, which optionally carries one or more hydroxyl groups, or a mixture of these, r is an integer or decimal number from 1 to 5 and represents the mean degree of condensation (see, for example, FR-PS 2 328 763).

Other compounds in this class are alcohols, alkylphenols and Fatty acids with linear fat chains that are 8 to 18 carbon atoms and are polyethoxylated or polyglycerated. Are also suitable Copolymers of ethylene oxide and propylene oxide, condensates of ethylene oxide and Propylene oxide with fatty alcohols, polyethoxylated fatty amides, polyethoxylated fatty amines, Ethanolamides, fatty acid glycol esters, fatty acid sorbitol esters and fatty acid sucrose esters.

Particularly preferred nonionic surfactants have the formula in which R4 is a mixture of alkyl radicals having 9 to 12 carbon atoms and p has a statistical value of 3.5; in which R5 is C12 H25 and q has a statistical value of 4 to 5; in which R6 denotes a mixture of residues which are derived from lauric, myristic, oleic and coconut fatty acids, and r has a statistical value of 3 to 4.

Preferred polyethoxylated or polyglycerated fatty alcohols are Oleyl alcohol, ethoxylated with 10 moles of ethylene oxide, lauryl alcohol, ethoxylated with 12 moles of ethylene oxide, nonylphenol, ethoxylated with 9 moles of ethylene oxide, oleyl alcohol, polyglycerized with 4 moles of glycerine, and sorbitan monolaurate, polyethoxylated with 20 Moles of ethylene oxide.

Suitable cationic surfactants, used alone or in admixture are in particular fatty amine salts, e.g., alkylamine acetates, quaternary Ammonium salts, such as alkyldimethylbenzylammonium, alkyltrimethylammonium, alkyldimethylhydroxyäthylammonium and dimethyldistearylammonium chloride and bromide, alkylaminoethyltrimethylammonium methanesulfate, Alkyl pyridinium salts and imidazoline derivatives. The alkyl radical of these compounds preferably contains 1 up to 22 carbon atoms. Compounds of a cationic nature are also suitable, e.g. amine oxides such as alkyldimethylamine or alkylaminoethyldimethylamine oxides.

Suitable amphoteric surfactants are e.g. alkylamino mono- and dipropionates, Betaines, such as N-alkyl betaines, N-alkylsulfobetaines and N-alkylamino betaines, cycloimidinium derivatives, such as alkylimidazolines, and asparagine derivatives. The alkyl radical of these surfactants contains preferably 1 to 22 carbon atoms.

The surfactant concentration in the shampoos is usually 3 to 50, preferably 3 to 20% by weight, and the pH is usually 3 to 10.

Another preferred embodiment are rinse lotions that are before or after shampooing. These lotions can be aqueous or aqueous-alcoholic solutions, emulsions, thickened lotions or gels. in the In the case of emulsions, these can be nonionic or anionic. The non-ionic Emulsions mainly consist of a mixture of bl and / or fatty alcohol and a polyethoxylated alcohol such as polyethoxylated stearyl or cetyl stearyl alcohol. Cationic surfactants can also be added to these preparations, such as those used, for.

B. are mentioned above. Anionic emulsions mainly exist from soap base.

Agents in the form of thickened lotions or gels contain thickeners and optionally solvents.

Usable thickeners are, for example, sodium alginate, gum arabic and cellulose derivatives, such as methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, Hydroxy propyl cellulose and hydroxypropyl methyl cellulose. One thickening the lotions can also be made with a mixture of polyethylene glycol and polyethylene glycol stearate or distearate or with a mixture of phosphoric acid ester and amide will. The concentration of the thickener can be 0.5 to 30, preferably 0.5 up to 15 percent by weight. The pH of the rinse lotions is usually in the range from 3 to 9.

When the agents according to the invention are used as hairdressing lotions, shaping lotions or water wave lotions are present, they contain the above-mentioned ingredients the combination and optionally non-ionic polymers and antifoam agents in aqueous, alcoholic or aqueous-alcoholic solution.

When the agents according to the invention dye preparations for keratin fibers represent, they contain in addition to the amphoteric and anionic polymer (s) at least one precursor of an oxidation dye and / or a direct dye and, if necessary, various adjuvants that make up a formulation as a cream, Enable gel or solution.

They can also contain antioxidants, or sequestrants contain any other additives commonly used in agents of this type will.

The precursors of oxidation dyes are aromatic compounds of the diaminobenzene, diaminopyridine, aminophenol or phenol type. With these preliminary stages On the one hand, a distinction is made between dye precursors of the para type and dye precursors of the ortho type, selected from diaminobenzenes, diaminopyridines and aminophenols and diphenylamines, as well as, on the other hand, couplers, i.e. met a derivatives among m-diaminobenzenes, m-diaminopyridines, m-aminophenols, m-diphenols, phenols and naphthols. Azo and anthraquinone dyes are suitable as direct dyes, Nitro derivatives of the benzene series, indamines, indophenols and indoanilines. Of the The pH of these colorants is usually 7 to 11 and can be adjusted by adding a base, such as ammonia, alkali hydroxides, alkali or ammonium carbonates, alkylamines, alkanolamines or their mixtures can be adjusted to the desired value.

The combination according to the invention can also be formulated into preparations that are suitable for curling or curling hair. These preparations contain in addition to or

the amphoteric and anionic polymers one or more reducing agents and optionally other adjuvants commonly used in agents of this type and they are used in conjunction with a neutralizing agent. Suitable Reducing agents are sulfites, mercaptans, and especially thioglycolates and thiolactates or their mixtures. The neutralizing agent contains as oxidizing agent e.g. Hydrogen peroxide or alkali bromates or perborates.

The above agents can also be formulated as aerosols, with e.g. carbon dioxide, nitrogen, nitrous oxide, volatile propellants Hydrocarbons, such as butane, isobutane or propane, or preferably chlorinated ones or fluorinated hydrocarbons can be used.

The agents according to the invention can also be any other cosmetic Contain ingredients, e.g. perfumes, coloring agents that color the agent itself, Preservatives, electrolytes, sequestrants, thickeners, plasticizers, Synergists, foam stabilizers, sun filters and peptizers, depending on the intended application.

The method according to the invention for treating keratin fibers can consist of an agent containing the amphoteric and the anionic polymer, Apply directly to the hair by scraping the hair using the agent e.g. shampooed, colored or conditioned.

The combination according to the invention can also be formed in situ on the hair by using a product e.g. in the form of a pre-lotion the first time, which contains the amphoteric polymer, and the second time an agent, e.g. in the form a shampoo or coloring agent that contains the anionic polymer. According to another embodiment, the first time you can use a shampoo that has the contains amphoteric polymer, and the second time use an agent, e.g. a Lotion containing the anionic polymer. It can also be done one after the other at the first One time a shampoo that contains the amphoteric polymer, and the second time one second shampoo are used, which contains the anionic polymer, wherein the pH of the two agents used is set differently so that at the application of the agent containing the anionic polymer, conditions exist, which enable the combination according to the invention to be deposited well on the hair.

The invention also relates to a method of crimping or uncrimping of hair, which the first time you use a reducing preparation that is the combination of anionic and amphoteric polymer and the second time a neutralizing one Applying the preparation. One can also use a reducing preparation the first time contains the amphoteric polymer or polymers, and the second time a neutralizing one Use a preparation containing the anionic polymer (s).

The invention also relates to a method for fixing anionic Polymer on keratin fibers, in which the fixation of the anionic polymer caused by combining with an amphoteric polymer, either in the same Agent is included or has been previously applied to the keratin fibers.

The following examples illustrate the invention. In the examples All quantitative data relate to the weight of the active substance.

Example 1 The following composition is prepared: AMPHOMER 1 g Anionic polymer 28-29-30 0.6 g Non-ionic surfactant TA-1 8 g Sandopan DTC-AC 2 g hydrochloric acid q.s.p pH 6.7 water to q.s.p. 100 g This product is called Used shampoo. The damp hair is easy to comb; after drying are they are full and fine and give the hairstyle good hold. Repeated shampooing one after the other does not entail any disadvantage in terms of brittleness or cladding.

Similar results are obtained with means 2 to 8 of Table I.

Table I Shampoos Example Polymer Solvent Acid play amphoteric % cationic% surfactant% and / or% pH or adjuvants Base 2 PAM-1 0.3 Darvan No. 7 1 Akypo RLM 100 4 7.8 NaOH AST 12-14 8 3 CHIT 0.4 Darvan # 1 0.7 TA-1 8 6.7 HCl AES 4 PAM-2 0.05 Flexan 130 0.2 Triethanolamine Lauryl Sulphate 2.5 8 NaOH Aromax DMMCD / W 5 5 PAM-2 0.1 Hydagen F 0.3 TA-1 10 8 NaOH Akypo RLM 100 5 6 PAM-3 0.2 Versicol E.5. 0.4 Mirand C.2M 7.6 NaCl 7.6 HCl TA-3 2.4 3 7 Amphomer 1.5 Versicol K.11 4 AES 2 8 NaOH AST 12.14 10 8 Amphomer 2 Goodrite 3 Aromox DM14D / W 10 8.8 NaOH K.752 AST 12.14 25 Example 9 The following composition is prepared: Amphoteric polymer amphomer 0.8 g anionic polymer Hydagen F 1.2 g surfactant ACS 15 OE 3g surfactant ACS PO 1.5 g Polawax GP 200 2.0 g polyethylene glycol distearate 6000 0.5 g Cellosize QP 4400 H 0.8 g Ammonyx 4002 2 g Lexein A 510 1.4 g lactic acid q.s.p. pH 5.6 water q.s.p. 100 g of this remedy is washed on and toweled Applied hair, left on for a few minutes and rinsed out.

The damp hair is soft and easy to comb. The dry hair can be easily styled and have a good hold.

Similar results are obtained with the means of Examples 10-20 from Table II.

Table II rinsing lotions by-polymer solvent acid or amphoteric% cationic% surfactant% and / or% pH base adjuvants 10 amphomer 1 28.29.30 0.9 ACS PO 2 Polawax GP200 3.5 6 HCl Ammonyx 4002 2 Lexein X.250 0.85 11 CHIT 0.7 Darvan No. 7 1.2 7.5 HCl 12 Amphomer 0.6 Hydagen F 1 Lexein S.620 1.6 7 Lactic acid 13 Amphomer 0.35 28.29.30 0.4 Lexein X.250 0.85 7 Lactic acid 14 PAM-2 0.8 Hydagen P 0.7 ACS PO 1.5 Ammonyx 4002 3 HCl ACS 15 OE 2 Lexein S.620 0.7 5.7 15 PAM-2 0.9 Darvan # 1 1 Lexein X.250 0.5 5 HCl 16 PAM-2 0.7 Goodrite K.722 0.3 Lexein S.620 0.29 5.9 HCl 17 PAM-2 0.6 Hydagen F 1.2 Lexein S.620 1 6 HCl Lexein X.250 0.5 18 AM 0.4 Darvan No. 7 0.7 6.6 HCl 19 AM 1 28.19.30 0.6 ACS PO 2 Cellosize QP 5.5 HCl - CO H 0.8 ACS 15 OE 3 Ammonyx 4002 2 Lexein X.250 0.8 20 CHIT 0.09 Versicol E. 5 0.02 7.1 HCl When using the means of the examples 11, 18 and 20 observed in the form of water wave lotions without a final rinse a good hold of the hair and easy combability.

Example 1 21 The first time a shampoo with the following composition is used: PAM-2 0.7 g surfactant TA-2 15 g surfactant TA-1 3 g water qsp 100 g HCl pH 6.4 The second time an aqueous lotion is used The following composition is used: VERSICOL E5 -0.65 g NATROSOL 250 HHR 0.3 g water qsp 100 g HCl pH 6 In the above examples, the trade names and abbreviations refer to the following products: PAM-1: polymer obtained by reacting PAA-1 with propane sultone in proportions of 50%; PAA-1: polyaminoamide obtained by condensation of adipic acid and diethylenetriamine in equimolar amounts and crosslinking with epichlorohydrin in a ratio of 11 moles of crosslinking agent per 100 amine groups of the polyaminoamide; PAM-2: polymer obtained by reacting PAA-1. with sodium chloroacetate; AMPHOMER: Octylacrylamide-acrylate-butylaminoethyl methacrylate copolymer; National Starch product; AM: polymer of the formula: PAM-3: polymer obtained by reacting PAA-1 with propane sultone; CHIT: polymer with the units in proportions of about 50/50; 28.29.30: vinyl acetate-crotonic acid-vinyl neodecanoate terpolymer; National Starch product; HYDAGEN F: sodium salt of polyhydroxycarboxylic acid; Product from Henkel; DARVAN No. 7: Sodium Polymethacrylate; Van der Bilt product; DARVAN No. 1: sodium salt of polymerized alkylnaphthalenesulfonic acid; Van der Bilt product; GANTREZ ES 425: poly (methyl vinyl ether / maleic acid) monobutyl ester; General Aniline product; FLEXAN 130: sodium salt of polystyrene sulfonate (molecular weight about 100,000); National Starch product; VERSICOL E.5 .: Mixture of acrylic acid homo- and copolymers; Viscosity as a 25 percent solution 16 cp, molecular weight about 3500; Product of Allied Colloids; VERSICOL K.11: polymer of methacrylic acid, molecular weight 10,000, viscosity as a 25 percent solution 1,000 cP; Product of Allied Colloids; GOODRITE K.752: polyacrylic acid with a molecular weight of 1800; Goodrich product; GOODRITE K.722: polyacrylic acid with a molecular weight of 45,000; Goodrich product; AES: sodium alkyl (C12-C14) ether sulfate, ethoxylated with 2.2 mol of ethylene oxide; TA-1: Non-ionic surfactant of the formula: R = C12-alkyl n = 3.5 (statistical mean value) TA-2: Non-ionic surfactant of the formula: n = 4.2 (statistical mean); TA-3: Mixture of polyglycerated diglycol fatty amides of the formula: n = 3.5 (statistical mean) R = mixture of residues derived from natural C12-C18 fatty acids; MIRANOL C-2M: Cycloimidazoline derivative of coconut oil: Product from Miranol: SANDOPAN DTC.AC: 7-tridecethcarboxylic acid of the formula: CH3 (CH211 CH2 - (OCH2-CH2) 60CH2-COOH; product from Sandoz; POLAWAX GP 200: mixture of fatty alcohols and ethoxylated products; product from Croda; CELLOSIZE QP 4400 H: hydroxyethyl cellulose with a viscosity of 4400 cP as a 2 percent aqueous solution at 250C with a Brookfield module 4; AMMONYX 4002: stearyldimethylbenzylammonium chloride; product from Franconyx; LEXEIN A 510: condensation product of abietic acid with a -CollagenEIN hydrolyzate; LEX from Inolex; 250: hydrolyzate of collagen proteins; product of Wilson; LEXEIN S 620: potassium salt of a condensate of collagen proteins and coconut fatty acid with a molecular weight of 700 to 800; product of Inolex; ACS 15 OE: cetostearyl alcohol, ethoxylated with 15 mol of ethylene oxide; AKYPO RLM-100: Surfactant of the formula: R- (OCH2CH2) 100CH2C00H, R = mixture of C12-C1 4-alkyl radicals; product of Chem. Y .; AST 12-14: triethanolamine alkyl (C12-C14) sulfate; AROMOX DM-14 DW: Compound of the formula: C14-H29.N (CH3) 2 product of AKZO CHEMIE; NATROSOL 250 HHR: hydroxyethyl cellulose; Product from HERCULES; ACS PO: mixture of cetostearyl alcohol and cetyl stearyl alcohol, ethoxylated with 15 mol of ethylene oxide; AROMOX DM MCD / W: alkyldimethylamine oxide (alkyl = derived from coconut oil); Product from AKZO Chemie.

Claims (18)

Means and method for treating keratin fibers Patent claims 1. Agents for treating keratin fibers, especially hair, d a d u r c h g It is not noted that they are in a medium that allows the application of polymers allows on keratin fibers, a) at least one anionic polymer with a or more carboxylic acid or sulfonic acid groups and b) at least one amphoteric Polymer containing units A and B in a randomly distributed manner in the polymer chain, where A is a unit that differs from a monomer with at least one basic Nitrogen atom and B is a unit different from an acidic monomer with one or more carboxylic acid or sulfonic acid groups, or A and B are groups derived from zwitterionic carboxybetaine monomers, A and B can also be a cationic polymer chain, the secondary, tertiary (with the exception of piperazinyl) or quaternary amine groups, where at least one of the amine groups one bound via a hydrocarbon residue Carboxylic acid or sulfonic acid group, or A and B part of a polymer chain of ethylene-a, B-dicarboxylic acid units, in which one of the carboxylic acid groups with a polyamine with one or more primary, secondary or tertiary amine groups has been implemented, but in this case the anionic polymer is not Vinyl acetate-crotonic acid bipolymer is included. 2. Composition according to claim 1, characterized in that the amphoteric polymer is selected from (1) copolymers of a monomer which is derived from a vinyl compound having a carboxylic acid group, preferably acrylic, methacrylic, maleic or α-chloroacetic acid, with a basic monomer derived from a substituted vinyl compound having at least one basic nitrogen atom, preferably a dialkylaminoalkyl methacrylate or acrylate or dialkylaminoalkyl methacrylamide or acrylamide; (2) Polymers with units derived from (a) at least one monomer from the group of acrylamides and methacrylamides which are substituted on the nitrogen by an alkyl radical, (b) at least one acidic comonomer with one or more reactive carboxylic acid groups and (c ) at least one basic comonomer, for example acrylic or methacrylic acid esters with primary, secondary, tertiary or quaternary amine substituents or the quaternization product of dimethylaminoethyl methacrylates with dimethyl or diethyl sulfate; (3) crosslinked and fully or partially alkylated polyaminoamides which are derived from a polyaminoamide of the general formula: in which R is a divalent radical which is derived from a saturated dicarboxylic acid, an aliphatic mono- or dicarboxylic acid with an ethylenic double bond or an ester of a lower alkanol having 1 to 6 carbon atoms with these acids, or is a radical which, when added, is a bis-primary or bis-secondary amine is formed with these acids, and Z represents a radical of a bis-primary, mono- or bis-secondary polyalkylene polyamine, these polyaminoamides by adding a bifunctional crosslinking agent from the group of epihalohydrins, diepoxides, dianhydrides and bis-unsaturated Derivatives in a ratio of 0.025 to 0.35 mol of crosslinking agent per amine group of the polyaminoamide has been crosslinked and alkylated by reaction with acrylic acid, chloroacetic acid or an alkane sultone or their salts, the anionic polymer in this case being different from vinyl acetate-crotonic acid bipolymers ; (4) Polymers with zwitterionic units of the formula in which R1 is a polymerizable unsaturated group, for example an acrylate, methacrylate, acrylamide or methacrylamide group, x and y are integers from 1 to 3, R2 and R3 are hydrogen, methyl, ethyl or propyl, R4 and R5 are hydrogen or Are alkyl radicals, the sum of the carbon atoms in R4 and R5 not being greater than 10; (5) Polymers derived from chitosan and containing monomer units of the following formulas: wherein the unit (A) is present in a proportion of 0 to 30%, (B) in a proportion of 5 to 50% and (C) in a proportion of 30 to 90% and R in the formula (C) is a residue the formula means, where in the case of n = 0 R6, R7 and R8 are identical or different hydrogen, methyl, hydroxyl, acetoxy or amino, a monoalkylamine or dialkylamine radical, which is optionally interrupted by one or more nitrogen atoms and / or optionally by one or more amines -, hydroxyl, carboxyl, alkylthio or sulfonic acid groups, or an alkylthio radical whose alkyl group bears an amino radical, at least one of the radicals R6, R7 and R8 in this case being hydrogen, or in the case of n = 1 R6 , R7 and R8 are each hydrogen atoms, and salts of these compounds with bases or acids; (6) Polymers of the general formula in which RH, CH30, CH3CH2 0 or phenyl, R1 is H or a lower alkyl radical, for example methyl or ethyl, R2 is H or a lower alkyl radical, for example methyl or ethyl, R3 is a lower alkyl radical, for example Methyl or ethyl, or a radical of the formula R4-N (R2) 2 and R4 the group -CH2-CH2-, -CH2-CH, -CH2, -CH2-CH- and the higher homologues these radicals represent -CH3 and contain up to 6 carbon atoms. 3. Composition according to claim 1, characterized in that the amphoteric Polymer is selected from polymers of groups (2), (4), (5) and (6) according to claim 2. 4. Composition according to claim 1, characterized in that the carboxylic acid groups are carried by unsaturated mono- or dicarboxylic acids of the formula in which n is an integer from 0 to 10, A is a methylene group which is optionally linked to the carbon atom of the unsaturated group or the adjacent methylene group via a heteroatom, such as oxygen or sulfur, if n is greater than 1, R1 Is hydrogen, phenyl or benzyl, R2 is hydrogen, carboxyl or a lower alkyl radical and R3 is hydrogen, a lower alkyl radical, -CH2COOH, phenyl or benzyl. 5. Agent according to one of claims 1 to 4, characterized in that that the anionic polymers are selected from: a) homo- or copolymers of acrylic or methacrylic acid or their salts; Acrylic acid or its esters, b) Copolymers of acrylic or methacrylic acid and a monoethylenically unsaturated one Monomer; c) copolymers derived from crotonic acid; d) polymers that derived from maleic, fumaric or itaconic acid or anhydride and vinyl esters, Vinyl ethers, vinyl halides or phenyl vinyl derivatives, these polymers can be esterified; e) Copolymers of maleic or citraconic anhydride and an allyl or methallyl ester, which is optionally a monoesterified or carry monoamidated acrylamide or methacrylamide groups; f) salts of polystyrene sulfonic acid; g) salts of lignin sulfonic acids; h) salts of alkylnaphthalenesulfonic acids. 6. Composition according to claim 1, characterized in that the amphoteric Polymer selected from polymers of group (2) or (5) according to claim 2 and the anionic polymer is selected from - homo- or copolymers of acrylic or methacrylic acid and their salts, - polymers that are different from maleic acid or derive anhydride or - salts of polystyrene sulfonic acid. 7. 'Means according to claim 1, characterized in that the amphoteric Polymer is an octylacrylamide-acrylate-butylaminoethyl methacrylate copolymer is, and the anionic polymer is selected from the sodium salt of a polyhydroxycarboxylic acid, Polymethacrylic acid, a mixture of acrylic acid homo- or copolymer; to the Sodium salt of polystyrene sulfonate and the monobutyl ester of poly (methyl vinyl ether / maleic acid). 8. Agent according to one of claims 1 to 7, characterized in that that the polymers are each present in proportions of 0.01 to 10 percent by weight are. 9. Agent according to one of claims 1 to 8, characterized in that that the pH is 2-11. 10. Agent according to one of claims 1 to 9, characterized in that that they contain at least one solvent from the group of monoalcohols, polyalcohols and glycol ether. 11. Agent according to one of claims 1 to 10, characterized in that that they contain at least one anionic, cationic, nonionic or amphoteric Contain surfactant or mixtures thereof. 12. Agent according to one of claims 1 to 11, characterized in that that it thickened as an aqueous, alcoholic or aqueous-alcoholic solution, gel Lotion, emulsion, cream or powder. 13. Agent according to one of claims 1 to 12, characterized in that that they are a cosmetically acceptable component from the group of perfumes, Dyes that dye either the agent itself or the treated fibers, Preservatives, Sequestrants, thickeners, plasticizers, synergists, foam stabilizers, Contains sun filters and peptizers. 14. Agent according to one of claims 1 to 12, characterized in that that they contain at least one electrolyte. 15. Agent for the treatment of human hair, characterized in that that they contain at least one amphoteric polymer from groups (1), (2), (4), (5) and (6) according to claim 2, at least one anionic polymer with one or more Carboxylic acid or sulfonic acid groups and at least one adjuvant that is a cosmetic Application allows included. 16. A method for the treatment of keratin fibers, characterized in that that at least one agent according to one of claims 1 to 15 is applied to the fibers. 17. The method according to claim 16, characterized in that according to leaves the application long enough to soak the hair, and then rinses. 18. A method for the treatment of keratin fibers, characterized in that that one uses the first time a means that an amphoteric polymer after the claims 1, 2 or 3 contains, and the second time using an agent that an anionic polymer according to claims 1, 4 or 5 contains.