WO2004026269A1

WO2004026269A1 - Hair treatment agent having strengthening properties

Info

Publication number: WO2004026269A1
Application number: PCT/EP2003/009939
Authority: WO
Inventors: Konstanze Mayer; Peter Schmiedel; Michael Heyer
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2002-09-17
Filing date: 2003-09-08
Publication date: 2004-04-01
Also published as: AU2003264277A1; DE10243037A1

Abstract

The invention relates to the use of non-ionic, cross-linked polymers containing (meth)acrylate and having an average particle diameter of between 50 and 500 nm for strengthening keratin fibres, and to a hair treatment agent containing said polymers.

Description

Hair treatment agent with setting properties

The present invention relates to the use of nonionic, crosslinked (meth) acrylate-containing polymers with an average particle diameter in the range from 50 to 500 nm for strengthening keratin fibers, and to hair treatment compositions which contain these polymers.

An attractive looking hairstyle is now generally considered an indispensable part of a well-groomed exterior. Due to current fashion trends, hairstyles are always considered chic, which for many hair types can only be built up using certain setting agents or can be maintained for a longer period.

For the shaping and shaping of the hair, it is customary to use hairdressing agents such as hair fixers or hair sprays. Hair setting agents are distributed in damp hair for styling, while hair sprays are sprayed onto the finished hairstyle for fixation.

In order to achieve a sufficient hair-setting effect, agents are generally used which remain on the hair. However, this entails the risk of an undesirable strain on the hair.

The setting active ingredients, which are usually polymeric compounds, are generally used in the form of hair setting agents or hair sprays. However, it is also possible to incorporate them into conventional hair cleaners or conditioners.

For example, German patent application DE 19949517.3 describes setting hair cleansing agents in the form of an aqueous preparation which contain a synergistic combination of a water-soluble foaming surfactant and a film-forming polymer dispersed therein, which is a copolymer of quat.-ammonium-substituted acrylates. The German patent application DE 4414424.5 describes hair treatment agents with good rewashability. The compositions contain an aqueous dispersion of an insoluble polymer, the polymer having a glass transition temperature between -20 and + 70 ° C and being essentially formed from monomers which are selected from esters of acrylic acid, esters of methacrylic acid and styrene. The hair treatment compositions also contain a water-soluble polymer.

European patent application EP-A2 0288012 describes hair cosmetic compositions which contain fine particles of a crosslinked polymer. The polymer is derived from a monofunctional oil-soluble monomer, the polymerization product of which has a glass transition temperature of up to 300 ° K. The polymer is still insoluble in water and ethanol and does not form a film at normal temperature.

It is also state of the art to use film-forming polymers as hair-setting active ingredients.

The hair-setting active ingredients known from the prior art often no longer have sufficient effects in high ambient humidity. They can also strain the hair, especially when used in the form of a leave-on formulation, or change its feel or shine in an undesirable manner.

Furthermore, the applicability of the known hair-setting active ingredients is restricted by their solubilities or dispersibility in the corresponding hair treatment compositions and by their compatibility with the other formulation components contained therein. For example, the combination of the cationic polymers widely used as hair-setting active ingredients with anionic formulation components can lead to undesirable precipitation.

The present invention was based on the object of providing hair treatment compositions for strengthening keratin fibers are suitable and have advantages over the hair-setting agents known from the prior art which have a hair-setting effect.

It has now surprisingly been found that nonionic, crosslinked (meth) acrylate-containing polymers with an average particle diameter in the range from 50 to 500 nm can meet these requirements in an outstanding manner and can bring about a significant strengthening of keratin fibers.

A first subject of the invention is therefore the use of a non-ionic, cross-linked (meth) acrylate-containing polymer with an average particle diameter in the range from 50 to 500 nm for the strengthening of keratin fibers.

According to the invention, keratin fibers are to be understood as meaning furs, wool, feathers, hair and in particular human hair.

The invention further relates to a hair treatment composition which, in addition to conventional cosmetic constituents, furthermore contains a dispersion of a nonionic, crosslinked (meth) acrylate-containing polymer with an average particle diameter in the range from 50 to 500 nm.

In the context of the invention, a crosslinked (meth) acrylate-containing polymer is to be understood as a crosslinked homopolymer or copolymer which is based on two or more monomers, including the crosslinker. At least one of these monomers must be polyfunctional in order to effect crosslinking. Including the crosslinker, according to the invention at least one of the monomers must furthermore be a derivative of acrylic acid or methacrylic acid, derivative being understood to mean in particular an ester or an amide.

Monomers for the polymers used according to the invention are monounsaturated polymerizable compounds, preferably the esters and amides of acrylic acid and methacrylic acid and vinylpyrrolidone. In the sense of the Esters and amides with alcohols or amines having 1 to 6 carbon atoms are preferred, it being possible for the alcohols or amines to be additionally substituted with 1 to 3 hydroxyl groups. In addition to N-vinylpyrrolidone, the following are particularly suitable as monomers: methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, sec-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-dodecyl acrylate, 2-hydroxyl acrylate, 2-hydroxyl acrylate Isopropylacrylamide and the corresponding methacrylic acid derivatives.

Polymers which are particularly preferred for the purposes of the invention are poly-N-isopropylacrylamide and N-vinylpyrrolidone / (meth) acrylic ester copolymers.

In the event that the polymer used according to the invention consists of several different monomers, the weight ratio of the different monomers to one another is not subject to any particular restrictions.

The crosslinking of the polymer required according to the invention can be carried out by means of a polyfunctional monomer such as, for example, N, N'-methylenebisacramide or 1-vinyl-3- (E) -ethylidene pyrrolidone. Crosslinking with N, N ^' - methylenebisacrylamide is preferred for the purposes of the invention.

The polymer is about 0.5 to about 20%, but preferably about 2 to about 10% and most preferably about 4 to about 6% cross-linked. A degree of crosslinking of x% is understood to mean that for 100 parts by weight of the total monofunctional monomers on which the polymer is based, x parts by weight of the crosslinker, i.e. of the polyfunctional monomer or the mixture of polyfunctional monomers.

Nonionic crosslinked (meth) acrylate-containing polymers suitable according to the invention with an average particle diameter in the range from 50 to 500 nm are preferably obtainable by polymerizing the monomers on which the polymer is based with one another in an emulsion polymerization. The cross-linking is expediently thereby causes a suitable amount of a polyfunctional monomer or crosslinking agent to be added to the monomer or monomer mixture to be polymerized.

The size of the polymer particles depends on the production process used and can be influenced, for example, by the use of emulsifiers and by the choice of the concentration of the reactants during the polymerization. Through simple routine experiments, the person skilled in the art can determine the suitable production conditions for a respectively selected combination of monomers in order to obtain polymer particles of the size suitable according to the invention.

Anionic surfactants such as sodium dodecyl sulfate or alkylaryl polyglycol ether sulfate sodium salt are suitable as emulsifiers for the preparation of the polymers used according to the invention by emulsion polymerization.

The polymers used according to the invention are preferably prepared by emulsion polymerization in water as the dispersant.

Any initiator suitable for such an emulsion polymerization can be used as the polymerization initiator, but water-soluble initiators such as potassium peroxodisulfate are preferably used.

The reaction mixture obtained in the emulsion polymerization can be further purified in a manner known per se. For example, dialysis can remove residual monomers, and centrifugation, filtration, freeze-drying or spray-drying can reduce the water content to a desired level or keep the polymers in an anhydrous, unswollen state.

The crosslinked (meth) acrylate-containing polymers used according to the invention are nonionic, ie they are not anionic, cationic or zwitterionic. This means in particular that they are free of acidic groups, such as carboxylate groups, and that they are free of quaternary or basic groups such as mono-, di- or trialkylamino groups, which would give the cross-linked polymer per se or in acidic solution a cationic character.

The average particle size of the polymers suitable according to the invention is between 50 and 500 nm, the value being based on the average particle diameter in the longitudinal direction, i.e. in the direction of the greatest expansion of the particles. The particle size was determined in the context of the invention by laser diffraction using the Mastersizer-RT device from Malvern.

The polymers suitable according to the invention preferably have a glass transition temperature of more than 30 ° C. and particularly preferably of more than 50 ° C. Here, the person skilled in the art can make the necessary preselection based on the known laws that exist between the glass transition temperatures of the respective homopolymers and the corresponding copolymers.

Suitable hair treatment agents according to the invention are all agents whose application to the hair of the user primarily or among other things would like to achieve a shaping or shape-maintaining effect on the hairstyle. For example, cleaning agents such as shampoos, setting agents such as hair fixers, hair sprays and hair dryers, permanent shaping agents such as permanent wave and fixing agents, care agents such as conditioners, hair treatments and hair rinses, color-changing agents such as bleaching agents, oxidation dyes and toning agents based on direct dyes, Trade hair lotions and hair tip fluids. Accordingly, the preparations can be formulated as solutions, emulsions, gels, creams, aerosols or lotions. Furthermore, the hair treatment compositions according to the invention can be both rinse-off and products left on the hair. Rinse-off hair treatment agents are a preferred embodiment of the invention. Hair treatment compositions which are particularly preferred according to the invention are hair shampoos.

The hair treatment compositions according to the invention contain the nonionic, crosslinked (meth) acrylate-containing polymer with an average particle diameter in the range from 50 to 500 nm in amounts of preferably about 0.01 to about 10, in particular about 0.05 to about 5, and particularly preferably about 0 , 1 to about 1 wt .-%, each based on the total weight of the agent.

In a further preferred embodiment, the agents according to the invention contain at least one surfactant, particularly preferably an anionic surfactant. The term surfactants is understood to mean surface-active substances which carry an anionic or cationic charge in the molecule. Both an anionic and a cationic charge can also be present in the molecule. These zwitterionic or amphoteric surface-active substances can also be used according to the invention. Furthermore, the surface-active substances can also be non-ionic.

Suitable anionic surfactants in agents according to the invention are all anionic surface-active substances suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium and the mono-, di- and triaikanolammonium salts with 2 to 4 carbon atoms in the alkanol group,

- linear and branched fatty acids with 8 to 30 carbon atoms (soaps),

Ether carboxylic acids of the formula RO- (CH2-CH ₂ O) _χ -CH2 ~ COOH, in which R is a linear alkyl group with 8 to 30 C atoms and x = 0 or 1 to 16, Acyl sarcosides with 8 to 24 carbon atoms in the acyl group,

Acyl taurides with 8 to 24 carbon atoms in the acyl group,

Acyl isethionates with 8 to 24 carbon atoms in the acyl group,

Monosulfonic acid and dialkyl sulfosuccinates with 8 to 24 carbon atoms in the alkyl group and mono-alkyl polyoxyethyl sulfosuccinates with 8 to 24 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups,

linear alkanesulfonates with 8 to 24 carbon atoms,

- linear alpha olefin sulfonates with 8 to 24 carbon atoms,

- Alpha-sulfofatty acid methyl esters of fatty acids with 8 to 30 carbon atoms,

Alkyl sulfates and alkyl polyglycol ether sulfates of the formula R-0 (CH ₂ -CH ₂ 0) _x - OSO ₃ H, in which R is a preferably linear alkyl group with 8 to 30 C atoms and x = 0 or 1 to 12,

Mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030,

sulfated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids with 8 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms,

- Alkyl and / or alkenyl ether phosphates of the formula (I)

O

II

Rl (OCH2CH2) n— O -P - OR2 (I)

OX in R ^{1 is} preferred for an aliphatic hydrocarbon radical with 8 to 30

Carbon atoms, R ² for hydrogen, a radical (CH ₂ CH ₂ 0) _n R ¹ or X, n for

Numbers from 1 to 10 and X for hydrogen, an alkali or alkaline earth metal or

NR ³ R ⁴ R ⁵ R ⁶ , with R ³ to R ⁶ independently of one another for a C ₁ to C ₄ -

Hydrocarbon residue, stands,

sulfated fatty acid alkylene glycol esters of the formula (II) R ⁷ CO (AlkO) _n SO ₃ M (II) in which R ⁷ CO- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, Alk for CH ₂ CH ₂ , CHCH3CH2 and / or CH ₂ CHCH ₃ , n for numbers of 0, 5 to 5 and M represents a cation as described in DE-OS 197 36 906.5, - monoglyceride sulfates and monoglyceride ether sulfates of the formula (III),

CH2θ (CH2CH2θ) _χ - COR8 CHO (CH ₂ CH ₂ O) yH (in)

CH2θ (CH2CH2θ) _z - SO3X in R ⁸ CO for a linear or branched acyl radical having 6 to 22 carbon atoms, x, y and z in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and X for a Alkali or alkaline earth metal stands. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adducts or their formulated with sulfuric acid trioxide. Monoglyceride sulfates of the formula (III) are preferably used in which R ⁸ CO represents a linear acyl radical having 8 to 18 carbon atoms. Monoglyceride sulfates and monoglyceride ether sulfates are described, for example, in EP-B1 0 561 825, EP-B1 0 561 999, DE-A1 42 04 700 or by AKBiswas et al. in J.Am.Oil.Chem.Soc. 37, 171 (1960) and FUAhmed in J.Am.Oil.Chem.Soc. 67, 8 (1990).

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

Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and carry at least one -COO ^(_) - or -Sθ ₃ ^(_) group. Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylammonium glycinate, N-acyl-aminopropyl-N, N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate, and 2 -Alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known under the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants are surface-active compounds which, in addition to a C - C ₂₄ - alkyl or acyl group in the molecule at least one free amino group and at least one -COOH or -SO ₃ H group and are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N- alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-

Alkylaminopropionic acids and alkylaminoacetic acids, each with about 8 to 24 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C12 C ₁₈ - sarcosine.

Nonionic surfactants contain z as a hydrophilic group. B. a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether group. Such connections are, for example

- Adducts of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide with linear and branched fatty alcohols with 8 to 30 C atoms, with fatty acids with 8 to 30 C atoms and with alkylphenols with 8 to 15 C atoms in the alkyl group,

- Addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide end-capped with a methyl or C ₆ -C ₆ alkyl radical to linear and branched fatty alcohols having 8 to 30 C atoms Fatty acids with 8 to 30 carbon atoms and alkylphenols with 8 to 15 carbon atoms in the alkyl group, such as those under the sales names

Dehydol ^® LS, Dehydol ^® LT (Cognis) available types,

Ci2-C ₃₀ fatty acid monoesters and diesters of addition products from 1 to 30

Mole of ethylene oxide to glycerol,

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil,

Polyol fatty acid esters, such as the commercial product Hydagen ^® HSP

(Cognis) or Sovermol types (Cognis), alkoxylated triglycerides, alkoxylated fatty acid alkyl esters of the formula R ⁹ CO- (OCH ₂ CHR ¹⁰ ) _W OR ¹¹ , in which R ⁹ CO for a linear or branched, saturated and / or unsaturated acyl radical 6 to 22 carbon atoms, R ¹⁰ for hydrogen or methyl, R ¹¹ for linear or branched alkyl radicals with 1 to 4

Carbon atoms and w represents numbers from 1 to 20,

Amine oxides,

Hydroxy mixed ethers as described, for example, in DE-OS 19738866,

Sorbitan fatty acid esters and addition products of ethylene oxide

Sorbitan fatty acid esters such as the polysorbates,

Sugar fatty acid esters and addition products of ethylene oxide

Zuckerfettsäureester,

Addition products of ethylene oxide with fatty acid alkanolamides and

Fatty amines,

Fatty acid N-alkyl glucamides,

Alkyl polygycosides according to the general formula RO- (Z) _x where R is

Alkyl, Z stands for sugar and x for the number of sugar units. The alkyl polyglycosides which can be used according to the invention can contain only one specific alkyl radical R. Usually, however, these compounds are made from natural fats and oils or mineral oils.

In this case, the alkyl radicals R are mixtures corresponding to

Starting compounds or according to the respective processing of these

Connections before. Alkylpolyglycosides in which R

- essentially from C ₈ - and C-io-alkyl groups,

- essentially from C ₁₂ - and C-ι alkyl groups,

- essentially from C ₈ - to Ci ₆ -alkyl groups or

- essentially from C12 to Ciβ alkyl groups or

- essentially from C1. ₆ to cis alkyl groups.

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

The alkyl polyglycosides which can be used according to the invention contain on average 1.1 to 5 sugar units. Alkyl polyglycosides with x values of 1.1 to 2.0 are preferred. Alkyl glycosides in which x is 1.1 to 1.8 are very particularly preferred.

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

The alkylene oxide adducts with saturated linear fatty alcohols and fatty acids, each with 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid, have proven to be preferred nonionic surfactants. Preparations with excellent properties are also obtained if they contain fatty acid esters of ethoxylated glycerol as nonionic surfactants. These connections are characterized by the following parameters. The alkyl radical R contains 6 to 22 carbon atoms and can be either linear or branched. Primary linear and methyl-branched aliphatic radicals in the 2-position are preferred. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl are particularly preferred. When using so-called "oxo alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The compounds with alkyl groups used as surfactant can each be uniform substances. However, it is generally preferred to start from natural vegetable or animal raw materials in the production of these substances, so that substance mixtures with different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants, which are addition products of ethylene and / or propylene oxide onto fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrowed homolog distribution can be used. “Normal” homolog distribution is understood to mean mixtures of homologs which are obtained as catalysts from the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates. On the other hand, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with a narrow homolog distribution can be preferred.

In a preferred embodiment, nonionic, zwitterionic and / or amphoteric surfactants and mixtures thereof can be preferred.

Cationic surfactants of the type of the quaternary ammonium compounds, the esterquats and the amidoamines can also be used according to the invention. Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, and the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms.

Ester quats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are sold, for example, under the trademarks Stepantex ^® , Dehyquart ^® and Armocare ^® . The products Armocare ^® VGH-70, an N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75, Dehyquart ^® C-4046, Dehyquart ^® L80 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually produced by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group is that available under the name Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine.

In a preferred embodiment of the invention, a hair treatment composition according to the invention contains an alkyl sulfate or alkyl polyglycol ether sulfate as the anionic surfactant, the sodium salt of double or triple ethoxylated lauryl or myristyl alcohol being particularly preferred as the alkyl polyglycol ether sulfate. Depending on the type of hair treatment agent and the surfactant, the preferably anionic surfactants can be used in amounts of about 0.1 to about 30% by weight, preferably about 1 to about 20% by weight and very particularly preferably from about 5 to about 15% by weight. based on the total agent.

Furthermore, the agents according to the invention can also contain a natural emulsifier. Preferred natural emulsifiers are phospholipids, in particular lecithin, saponins, bile acids and their derivatives, in particular cholic acid, deoxycholic acid, lithocholic acid and taurocholic acid, tannic acid and abientic acid. Phospholipids and saponins are preferred natural emulsifiers.

The hair treatment compositions according to the invention can furthermore contain at least one fatty substance or a wax.

Preferred fatty substances are linear and branched, saturated and unsaturated fatty alcohols or fatty alcohol mixtures based on natural raw materials with 8 to 22 carbon atoms in the alkyl chain, such as, for example, decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleyl alcohol, eruco alcohol, ricinol alcohol , stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, caprylic alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol, and their Guerbet alcohols, as well as fatty alcohol cuts the naturally occurring by reducing triglycerides such as beef tallow, palm oil, peanut oil, rapeseed oil, cottonseed oil, soybean oil, sunflower oil, and Linseed oil or fatty acid esters formed from their transesterification products with corresponding alcohols and thus represent a mixture of different fatty alcohols. Monoesters of fatty acids with alcohols with 6 to 24 carbon atoms and triglycerides of natural origin can also be used as fatty substances. Paraffin oils and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil, peach seed oil, henna oil from Lawsonia inermis and oil from Cassia auriculata can also be used as fatty substances.

Fatty substances for the purposes of the invention are also silicone oils, in particular dialkyl and alkylarylsiloxanes, such as, for example, dimethylpolysiloxane and methylphenylpolysiloxane, and their alkoxylated and quaternized analogs. Examples of such silicones are the products sold by Dow Corning under the names DC 190, DC 200, DC 344, DC 345 and DC 1401.

By definition, waxes are esters of long-chain fatty acids with long-chain fatty alcohols. According to the invention, both natural waxes, chemically modified waxes and synthetic waxes can be used. Examples of such waxes are

Vegetable waxes, such as candelilla wax, camauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax and montan wax,

Animal waxes such as beeswax, shellac wax, walrus, lanolin and pretzel fat,

• Mineral waxes such as ceresin and ozokerite

Petrochemical waxes such as petrolatum, paraffin waxes and micro waxes,

• Hard waxes such as Montanester waxes, Sasol waxes and hydrogenated jojoba waxes, as well

• Polyalkylene waxes and polyethylene glycol waxes.

Waxes preferred according to the invention are vegetable waxes such as candelilla wax, camamauba wax and Japanese wax and beeswax.

The fatty substances or waxes are usually present in amounts of from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight and particularly preferably from 0.3 to 6% by weight, based on the total composition, used. For special agents, however, the amount of fat can also be up to 90% by weight. Furthermore, the hair treatment compositions according to the invention can contain at least one protein hydrolyzate or a derivative thereof. Protein hydrolyzates are product mixtures that are obtained by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins).

According to the invention, protein hydrolyzates of both vegetable and animal origin can be used.

Animal protein hydrolyzates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolyzates, which can also be in the form of salts. Such products are, for example, under the trademarks Dehylan ^® (Cognis), Promois ^® (Interorgana), Collapuron ^® (Cognis), Nutrilan ^® (Cognis), Gelita-Sol ^® (Deutsche Gelatine Fabriken Stoess & Co), Lexein ^® (Inolex) and Kerasol ^® (Croda) sold.

According to the invention, the use of protein hydrolysates of plant origin, e.g. B. soy, almond, rice, pea, potato and wheat protein hydrolyzates. Such products are available, for example, under the trademarks Gluadin ^® (Cognis), DiaMin ^® (Diamalt), Lexein ^® (Inolex) and Crotein ^® (Croda).

Although the use of the protein hydrolyzates as such is preferred, amino acid mixtures or individual amino acids, such as arginine, lysine, histidine or pyrroglutamic acid, which have otherwise been obtained, can optionally be used in their place. It is also possible to use derivatives of the protein hydrolyzates, for example in the form of their fatty acid condensation products. Such products are sold for example under the names Lamepon ^® (Cognis), Gluadin ^® (Cognis), Lexein ^® (Inolex), Crolastin ^® (Croda) or Crotein ^® (Croda).

Cationized protein hydrolyzates can also be used according to the invention, the underlying protein hydrolyzate being derived from animals, for example from collagen, milk or keratin, from the plant, for example from wheat, corn, rice, potatoes, soy or almonds, from marine life forms, for example from fish collagen or algae, or from biotechnologically obtained protein hydrolyzates. The protein hydrolysates on which the cationic derivatives according to the invention are based can be obtained from the corresponding proteins by chemical, in particular alkaline or acidic hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. The hydrolysis of proteins usually results in a protein hydrolyzate with a molecular weight distribution of approximately 100 daltons up to several thousand daltons. Preferred cationic protein hydrolyzates are those whose underlying protein content has a molecular weight of 100 to 25,000 Daltons, preferably 250 to 5000 Daltons. Cationic protein hydrolyzates also include quaternized amino acids and their mixtures. The quaternization of the protein hydrolyzates or the amino acids is often carried out using quaternary ammonium salts such as, for example, N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides. Furthermore, the cationic protein hydrolyzates can also be further derivatized. As typical examples of the inventive cationic protein hydrolysates and derivatives are under the INCI - ^th names in the "International Cosmetic Ingredient Dictionary and Handbook" (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 Street, NW, Suite 300 , Washington, DC 20036-4702) and commercially available products: Cocodimonium hydroxypropyl hydrolyzed collagen, Cocodimonium hydroxypropyl hydrolyzed casein, Cocodimonium hydroxypropyl hydrolyzed collagen, Cocodimonium hydroxypropyl hydrolyzed hair keratin, Cocodimonium hydroxypropyl hydrolyzed keratin, Cocodimonium hydroxypropyl hydrolyzed Rice Hydrolyzed Silk, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Cocodimonium Hydroxypropyl Silk Amino Acids, Hydroxypropyl Arginine Lauryl / Myristyl Ether HCI, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Casei n, hydroxypropyltrimonium hydrolyzed collagen, hydroxypropyltrimonium hydrolyzed conchiolin protein, hydroxypropyltrimonium hydrolyzed keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxyproypltrimonium Hydrolyzed Silk, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyl Hydrolyzed Vegetable Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein / Siloxysilicate, Laurdimonium Hydroxypropyl Hydrolyzed Soy Protein, Laurdimonium Hydroxypropyl Hydrolyzed Soy Protein, Laurdimonium Siloxysilicates, lauryldimonium hydroxypropyl hydrolyzed casein, lauryldimonium hydroxypropyl hydrolyzed collagen, lauryldimonium hydroxypropyl hydrolyzed keratin, lauryldimonium hydroxypropyl hydrolyzed silk, lauryldimonium hydroxypropyl hydrolyzed soy protein, steardimonium hydroxypropyl hydrolyzed casein, steardimonium hydroxypropyl, steardimonium hydroxypropyl Hydroxypropyl Hydrolyzed Silk, Steardimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Vegetable Protein, Steardimonium Hydroxypropyl Hydrolyzed Wheat Protein, Steartrimonium Hydroxyethyl Hydrolyzed Collagen, Quaternium-76 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Collagen, Quatemium-79 Hydrolyzed Keratin, Quaternium-79 Hydrolyzed Milk Protein, Quatemium Quaternium-79 Hydrolyzed Soy Protein, Quatemium-79 Hydrolyzed Wheat Protein. The plant-based cationic protein hydrolyzates and derivatives are very particularly preferred.

The protein hydrolyzates and their derivatives can be contained in the agents according to the invention in amounts of 0.01 to 10% by weight, based on the total agent. Amounts of 0.1 to 5% by weight, in particular 0.1 to 3% by weight, are very particularly preferred.

Furthermore, the hair treatment compositions according to the invention can contain a conditioning agent selected from the group formed by cationic surfactants, cationic polymers, alkylamidoamines and synthetic oils. Cationic polymers can be preferred as conditioning agents. These are usually polymers that have a quaternary nitrogen atom, for example in

Form of an ammonium group.

Preferred cationic polymers are, for example, quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives. polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products commercially available under the names Merquat ^® 100 (poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers. Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as, for example, vinylpyrrolidone-dimethyfaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755.

Vinylpyrrolidone-methoimidazolinium chloride copolymers, such as are offered under the name Luviquat ^® , quaternized polyvinyl alcohol and those under the names Polyquatemium 2, Polyquaternium 17, Polyquatemium 18 and

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

Cationic polymers of the first four groups are particularly preferred.

Preferred cationic surfactants are those of the quaternary ammonium compound type, for example ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and triaikylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride,

Lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, behenyltrimethylammonium methosulfate, as well as the imidazolium compounds known under the INCI names Quatemium-27 and Quaternium-83.

In particular, for environmental reasons these quaternary ammonium compounds can also be so-called esterquats such as N obtainable under the name Armocare® ^® VGH-70 commercially, N-bis (2-palmitoyloxyethyl) dimethyl be used instead.

Another group of conditioning active substances, which is also of particular interest for ecological reasons, is alkylamidoamines such as that commercially available under the name Tegoamid ^® S 18

Stearamidopropyl.

Also suitable as conditioning agents are silicone oils, in particular dialkyl and alkylarylsiloxanes, such as dimethylpolysiloxane and methylphenylpolysiloxane, and their alkoxylated and quaternized analogs. Examples of such silicones are the Dow Corning under the names DC 190, DC 200, DC 344, DC 345 and DC 1401 products sold and the commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicon), Dow Corning ^® 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer. Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary polydimethylsiloxanes, Quatemium-80).

Paraffin oils and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil can also be used as conditioning agents. Likewise suitable hair-conditioning compounds are phospholipids, for example soy lecithin, egg lecithin and cephalins.

The conditioning agents can be present in the agents according to the invention in amounts of about 0.01 to about 10% by weight, based on the total agent. Amounts from about 0.1 to about 5% by weight, in particular about 0.1 to about 3% by weight, are very particularly preferred.

Hair treatment agents according to the invention, which are hair coloring or tinting agents, can contain at least one oxidation dye precursor of the developer type, if appropriate in combination with oxidation dye precursors of the coupler type, and / or a substantive dye and / or a dye which occurs naturally.

In a further embodiment, the hair treatment compositions according to the invention can, if necessary additionally, serve for the permanent shaping of human hair.

Permanent hair shaping is carried out according to the known permanent wave method in such a way that the hair is mechanically deformed and the deformation z. B. by winding on hair rollers or papillots. Before and / or after this shaping, the hair is treated with the aqueous preparation of a keratin-reducing substance and rinsed with water or an aqueous solution after an exposure time. In a second step, the hair is then treated with the aqueous preparation of an oxidizing agent. After an exposure time, this is also rinsed out of the hair and the hair is freed from the mechanical shaping aids (curlers, papillots).

The aqueous preparation of the keratin reducing agent is usually made alkaline so that the hair swells and in this way a deep penetration of the keratin-reducing substance into the hair is made possible. The keratin-reducing substance cleaves part of the disulfide bonds of the Keratins to -SH groups, so that there is a loosening of the peptide crosslinking and due to the tension in the hair due to the mechanical deformation to a new orientation of the keratin structure. Under the influence of the oxidizing agent, disulfide bonds are again formed, and in this way the keratin structure is re-fixed in the predetermined deformation.

The nonionic crosslinked (meth) acrylate-containing polymers according to the invention can be incorporated both in the keratin-reducing (waving agent) and in the keratin-oxidizing agent (fixing solution) of the permanent waving treatment. The use of the polymers according to the invention in fixing solutions is particularly preferred.

Almost exclusively alkaline (pH values from 8.5 to 9.5) solutions of thioglycolic acid or its salts or esters as well as thiolactic acid, cysteamine, thio malic acid or a-

Mercaptoethanesoulfonic acid used.

Mandatory component of the fixative are oxidizing agents, e.g. As sodium bromate, potassium bromate, hydrogen peroxide, and the usual stabilizers for stabilizing aqueous hydrogen peroxide preparations. The pH of such aqueous H ₂ θ ₂ preparations, which usually contain about 0.5 to 3.0% by weight of H2O2, is preferably 2 to 4; it is adjusted by inorganic acids, preferably phosphoric acid. Bromate-based fixatives usually contain the bromates in concentrations of 1 to 10% by weight and the pH of the solutions is adjusted to 4 to 7. Fixing agents based on enzymes (peroxidases) which contain no or only small amounts of oxidizing agents, in particular H ₂ O ₂ , are also suitable.

In principle, the pH of the agents according to the invention can be between 2-11, the person skilled in the art knowing the preferred pH ranges for the different agents. The pH of the agents according to the invention, provided they are hair care agents, is preferably between 2 and 7, with values from 3 to 5 being particularly preferred. Setting this pH can be convenient any acid used for cosmetic purposes can be used. Eating acids are usually used. Edible acids are understood to mean those acids that are ingested as part of normal food intake and have positive effects on the human organism. Edible acids are, for example, acetic acid, lactic acid, tartaric acid, citric acid, malic acid, ascorbic acid and gluconic acid. In the context of the invention, the use of citric acid and lactic acid is particularly preferred. Hair colorants are preferably formulated in a pH range of about 7 to 11.

Furthermore, the hair treatment compositions according to the invention can contain all the additives customary for the respective intended use. In particular, these can be cosmetic additives which have a cleaning, nourishing or other effect on the external appearance of the hair. Such additives which do not have a direct effect on the hair, but otherwise have a positive effect on the scalp or, for example, the hair follicles, can also be present in the preparation according to the invention.

Other customary constituents of the preparations according to the invention can be: anionic, zwitterionic, amphoteric and nonionic polymers such as, for example, vinyl acetate / crotonic acid copolymers, polydimethylsiloxanes, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers and maleinic acid copolymers, methyl vinyl ether thereof, methyl vinyl ether Esters, uncrosslinked and crosslinked with polyols, acrylic amidopropyl-trimethylammonium chloride / acrylate copolymers, octylacrylamide / - methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone,

Vinyl pyrrolidone / vinyl acetate copolymers, vinyl pyrrolidone / dimethylaminoethyl methacrylate / vinyl caprolactam terpolymers and optionally derivatized cellulose ethers. symmetrical and asymmetrical, linear and branched dialkyl ethers with a total of between 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, for example di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n- undecyl ether and di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl-n-undecyl ether, n-undecyl-n-dodecyl ether and n-hexyl-n-undecyl ether as well as di- tert-butyl ether, di-iso-pentyl ether, di-3-ethyldecyl ether, tert-butyl-n-octyl ether, iso-pentyl-n-octyl ether and 2-methyl-pentyl-n-octyl ether, petroleum jelly

Defoamers like silicones,

Thickeners such as gelatin or vegetable gums, for example agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays and layered silicates such as. B. bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol, the Ca, Mg or Zn soaps,

Refatting agents such as fatty acid alkanolamides, fatty acids, fatty acid esters such as isopropyl myristate, palmitate, oleate and stearate, optionally ethoxylated partial glycerides, wool wax derivatives, lecithin, perhydrosqualene,

Isopropyl adipate or the fatty substances described above, structurants such as maleic acid, mono-, di- and oligosaccharides, perfume oils, dimethyl isosorbide and cyclodextrins,

Solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, dyes for coloring the agent,

Antidandruff active ingredients such as piroctone olamine, zinc omadine and climbazole, other substances for adjusting the pH, vitamins and vitamin precursors such as panthenol, its derivatives and biotin, plant and honey extracts, such as in particular extracts from oak bark, nettle, witch hazel, hops, chamomile, Burdock root, horsetail, linden flowers, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, cuckoo flower, quendel, yarrow, squirrel, meristem, ginseng and ginger ginger Other active ingredients such as ceramides, allantoin, pyrrolidone carboxylic acids, and bisabolol, light stabilizers,

Consistency agents such as sugar esters, polyol esters or polyol alkyl ethers, fatty acid alkanolamides, physiologically compatible inorganic or organic acids, swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Humectants such as sorbitol, lactic acid salts, glycerol or polysaccharide opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers, pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate, complexing agents such as EDTA, NTA, ß-alanine diacetic acid and phosphonic acid Reducing agents such as thioglycolic acid and its derivatives, thiolactic acid, cysteamine, thio malic acid and α-mercaptoethanesulfonic acid, oxidizing agents such as hydrogen peroxide, potassium bromate and sodium bromate, blowing agents such as propane-butane mixtures, N ₂ 0, dimethyl ether, CO ₂ , N ₂ and air and antioxidants.

With regard to further components and quantity ranges for the individual ingredients, reference is made to the manuals known to the person skilled in the art, e.g. K. Schrader, Fundamentals and Recipes for Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

In one embodiment of the invention, the agents can be packaged in the form of foam aerosols. Both the formulation with a liquefied gas as a blowing agent and in the form of so-called pump sprays are possible, in which the pressure required for spraying is built up by mechanical pumping. Nitrogen, air, carbon dioxide, propane, butane, isobutane, pentane and dimethyl ether are preferred blowing agents. Although chlorofluorocarbons and chlorinated hydrocarbons are excellent propellants with regard to the aerosol properties achieved, their use as propellants is in the Agents according to the invention are less preferred due to the known ozone problem.

Another object of the present invention is a method for setting hair, in which an inventive hair treatment agent, as described in the preceding text, is applied to the hair in an effective amount. The agent can then be rinsed out again after a contact time or left on the hair until the next hair wash. In a preferred embodiment of the method, the agent is rinsed out again after an exposure time.

It has been found within the scope of the invention that the use of nonionic, crosslinked (meth) acrylate-containing polymers with an average particle diameter in the range from 50 to 500 nm in the hair treatment compositions described in the preceding text has advantages for both the manufacturer and the user of such compositions connected is.

For the formulation of such agents, there are advantages above all with regard to freedom from formulation, since the polymers used according to the invention are extremely compatible with the customary formulation components and, in particular, there are no incompatibilities, e.g. show a precipitation, with anionic components. Although the particles in the hair treatment compositions according to the invention are undissolved, i.e. Being in the form of a dispersion, its small size allows for easy incorporation and the production of transparent formulations.

The advantages in use are particularly evident in the increased wet and, above all, dry combing of the hair, which means improved formability and stylability of the hair. These effects desired for the user are achieved without the problems known from the prior art of impairing hair gloss or volume being observed. Also, the use of the polymers does not result in an undesirable strain on the hair or a sticky handle. After the apprenticeship In particular, improved hair fixation and styling shampoos and shampoos for fine hair can be formulated in the present invention.

The invention enables the formulation of combination preparations which, in addition to a first effect, such as, for example, hair cleaning or hair coloring, have hair fixation as a further effect. Separate post-treatment is no longer necessary for hair fixation, and the user saves one application step. At the same time, the packaging effort is reduced because one product is used less.

The following examples are intended to explain the subject matter of the invention in more detail.

Unless otherwise stated, all quantities are to be understood as% by weight.

Examples

Example 1: Preparation of a polymer starting from N-isopropylacrylamide ("P-N-IPAAm")

470 ml of deionized water (fully demineralized water), 7 g of N-isopropylacrylamide, 0.35 g of N, N-methylenebisacrylamide and 0.094 g of sodium dodecyl sulfate were weighed into a 1 liter four-necked flask and brought to 70 under N2 atmosphere and reflux at 200 rpm ° C warmed. After 30 minutes, 0.28 g of potassium peroxodisulfate in 30 ml of demineralized water was added, and the reaction was ended after a further 4 hours. A milky, cloudy dispersion was obtained, the viscosity of which was 70 MPas (20 ° C., 20 rpm).

The hydrogel particles thus synthesized had a diameter of approx. 200 to 300 nm in the swollen state at room temperature, ie. H. in the state of dispersion. The particle size was determined by laser diffraction using the Malvern Mastersizer-RT. The N-isopropylacrylamide was no longer detectable in the dispersion by means of HPLC (<1ppm).

The polymer dispersion thus prepared was then freeze-dried, the polymer being obtained in a non-swollen form as a white powder in a yield of 95%. It had a glass transition temperature of 152 ° C (measurement using modulated dynamic differential calorimetry, MDSC). For further use the polymer can e.g. redisperse with water to a desired concentration. For example 4, the freeze-dried polymer was redispersed with water to a final concentration of 0.04% by weight, based on the total weight of the aqueous dispersion, corresponding to a concentration of 0.4 g / l of dispersion.

Alternatively, the polymer dispersion obtained in the aforementioned synthesis reaction can be separated from the main amount of the salts and water used in the preparation by centrifugation. In this case the polymer is obtained in a swollen state. Example 2: Preparation of a polymer based on ethyl methacrylate and N-vinylpyrrolidone ("EMA-VP")

480 ml of deionized water, 4.1 g of ethyl methacrylate, 15.9 g of N-vinylpyrrolidone, 5.4 g of alkylarylpolyglycol ether sulfate sodium salt and 1 g of N, N-methylenebisacrylamide were weighed into a 2-liter four-necked flask and under a N ₂ atmosphere and heated to reflux with stirring at 200 rpm to 70 ° C. After 30 minutes, 0.8 g of potassium peroxodisulfate in 30 ml of demineralized water was added, and the reaction was ended after a further 4 hours. A dispersion was obtained, the viscosity of which was 5 MPas (20 ° C., 20 rpm). The aqueous dispersion was then dialyzed to reduce the level of residual monomers, which is desirable for use in cosmetics. After dialysis, the residual content of N-vinylpyrrolidone was 9 ppm and that of ethyl methacrylate was 16 ppm. The hydrogel particles synthesized in this way had an average particle diameter of approximately 100 to 300 nm at room temperature. They showed no glass temperature below 90 ° C (measurement by MDSC).

The reaction product was worked up and an aqueous dispersion with a concentration of 0.4 g polymer / l dispersion was prepared analogously to Example 1.

Examples 3.1-3.23: Preparation of further polymers The crosslinked polymers 3.1 to 3.23 were prepared in a manner analogous to that in Example 2 (cf. Table 1), 5 parts by weight of N, N-methylene bisacrylamide being added to 100 parts by weight of the monomers listed in Table 1 were used for the polymerization reaction. Table 1

Example 4: Investigation of the effectiveness of the polymers according to the invention on hair from an aqueous dispersion

a) Carrying out the measurements

a.1) Wet combability measurements

When determining the combability, the work for combing wet strands of hair was measured. Before the zero measurement, the hair was medium-blonded and then combed in the wet state, the combing forces required thereby being recorded. After the zero measurement, the strands of hair were treated once with the respective formulation (10 minutes, 0.5 g Formulation per g of hair) and then rinsed for 1 minute with a total of 1 liter of water at 38 ° C. Each measurement was made with 20 strands of hair. In each case, 10 comb values of a strand of hair were determined and compared before application and after application of the formulations in the wet state.

a.2) Dry combability measurements and measurement of the electrostatic charge

The measurements were carried out in a constant climate (25% relative humidity, 30 ° C); the hair strands were conditioned for 24 hours. When determining the combability, the work for combing dry strands of hair was measured. The hair was medium-blonded before the zero measurement and then combed in the dry and conditioned state, the combing forces required being recorded. After the zero measurement, the strands of hair were treated once with the respective formulation (10 minutes, 0.5 g of formulation per g of hair) and then rinsed for 1 minute with a total of 1 liter of water at 38 ° C. and then dried. Each measurement was made with 20 strands of hair. 10 comb values of a strand of hair were determined and compared before and after the application of the formulations in the dry and conditioned state. The electrostatic charge was examined in parallel with the dry combing work with the approval of the electrostatic charge. The actual measurement was carried out using the charge tapping on a double Faraday cage after performing the 10 combs.

a.3) Sensory assessment

The sensory assessment was determined using an expert panel. The strands of hair used were initially 30 min. pre-cleaned with a 12% Texapon NSO solution (pH 6.5) and 5 min. rinsed with water. The strands were then treated with the respective formulations (0.5 g formulation per g hair, 5 min exposure time, 1 min rinsing time) and at 20% rel. Humidity in the climate box dried overnight. To a defined one To ensure the environment, the tests were carried out in a climate room at 22 ° C and approx. 45% relative humidity with standard daylight lighting. Each subject received new strands of hair. The recipe was assigned to the individual attributes and evaluated against the corresponding reference.

The parameters are assessed on the following scale:

The tested attribute lies in the property tested in each case.

-1 = significantly worse than standard

- 0.5 = slightly worse than standard

0 = exactly like standard

+ 0.5 = slightly better than standard

+ 1 = significantly better than standard

The determination was made by comparing the hair treated with the respective basic formulation against the hair treated with the corresponding formulation according to the invention. The panel consisted of 11 experts whose judgments were averaged.

b) application of the polymer dispersion to hair

The application on strands of hair was standardized using a dipping process. Standard European hair was used, which had been pre-cleaned, rinsed and dried. The hair was then immersed in the aqueous polymer dispersions prepared according to Examples 1 and 2 at a concentration of 0.4 g / l. Depending on the application as rinse-off or leave-on products, the strands of hair were then rinsed off if necessary. The samples were then at 25% rel. Humidity and 30 ° C in the air.

c) Determination of dry combability

When determining the combability of dry hair, the work for combing dry strands of hair on 20 strands of hair pretreated in accordance with b) carried out. The values of 10 combs on strands of hair were determined and compared before or after application of the polymers, if necessary rinsing and drying. The room climate was 25% rel. Humidity and 30 ° C. The hair strands were conditioned for 24 hours.

The following values of dry work [mJ] were determined:

Leave-on:

Hair untreated: 86.2 mJ

Hair treated with polymer from Example 1:> 300 mJ

Hair untreated: 87.1 mJ

Hair treated with polymer from Example 2:> 300 mJ

In both cases, there was a significantly significant increase in dry combing, an indication of hair fixation.

Rinse-off:

Hair untreated: 86.2 mJ

Hair treated with polymer from Example 1: 159.5 mJ (+ 85%)

Hair untreated: 87.1 mJ

Hair treated with polymer from Example 2: 92.2 mJ (+ 6%)

Even after rinsing, there was a significant increase in dry combing in both cases, a prerequisite for improved hair fixation.

d) Determination of hair shine

The hair gloss was determined by means of light reflection. For this purpose, 5 strands of hair were pretreated according to b) in the form of a leave-on treatment and additionally provided with a gloss-reducing film. It became the Measure the gloss intensity of the untreated strands of hair and then the strands of hair treated with the polymers according to the invention and determine the difference. The measurements were carried out at 25 ° C and 40% rel. Moisture carried out.

The following changes in gloss intensity resulted [%]

Hair treated with gloss-reducing film and polymer from Example 1 minus hair treated only with gloss-reducing film: - 1.0% (t test. 92.7%)

Hair treated with gloss-reducing film and polymer from Example 2 minus hair treated only with gloss-reducing film: -1.2% (t-test 93.9%)

In both cases there was a statistically indistinguishable value of the gloss intensity. The polymers according to the invention showed no negative effect on the hair gloss.

e) Determination of the hair volume

The volume was determined analytically by casting shadows on the strands of hair. For this purpose, the strands of hair were pretreated in the form of a leave-on treatment. The area of 10 of the untreated and then of the treated strands of hair was determined and compared in each case.

The following values of the volume [mm ² ] resulted:

Hair untreated: 3464 mm ²

Hair treated with polymer from Example 1: 3203 mm ² (t test. 81, 66%)

Hair untreated: 3266 mm ²

Hair treated with polymer from Example 2: 3398 mm ² (t test 89.38%) In both cases there was a statistically indistinguishable value of the volume. The polymers according to the invention accordingly showed no negative effect on the hair volume.

Example 5: Investigation of the effectiveness of the polymers according to the invention on hair from a shampoo formulation

a) Carrying out the measurements

The measurements were carried out as described in Example 4, a).

b) Shampoos used

Formulation 5.0 (comparison):

40.00% Texapon NSO ¹⁾

7.00% disodium cocoamphodiacetate

0.23% Na salicylate

0.50% Na benzoate

1.00% Arlypon F ²⁾ nB citric acid nB NaCI ad 100 water pH: 4.5 - 5.2

¹⁾ Sodium lauryl ether sulfate approx. 28% active substance (INCI - name: Sodium Laureth Sulfate) (COGNIS)

²⁾ Ci2-i ₄ fatty alcohol EO adduct

Formulation 5.1a (according to the invention):

Like formulation 5.0, but additionally containing the polymer from example 1 in a concentration of 0.4 g / l, based on the entire formulation Formulation 5.2a (according to the invention):

Like formulation 5.0, but additionally containing the polymer from example 2 in a concentration of 0.4 g / l, based on the entire formulation

Formulation 5.1 b (according to the invention):

Like formulation 5.0, but additionally containing the polymer from example 1 in a concentration of 4.0 g / l, based on the entire formulation

Formulation 5.2b (according to the invention):

Like formulation 5.0, but additionally containing the polymer from example 2 in a concentration of 4.0 g / l, based on the entire formulation

c) Determination of wet combability

Result: In the shampoo formulation, the polymers according to the invention led to a significant increase in combing work, which is an indication of hair setting and improved hair styling.

Result: In the shampoo formulation, the polymers according to the invention led to a significant increase in combing forces, which is an indication of a styling effect

d) Determination of dry combability

Result: In the shampoo formulation, the polymers according to the invention likewise led to a significant increase in combing forces, which is to be understood as an increased styling effect. The polymer from Example 1 showed a stronger styling effect than the polymer from Example 2.

Overall, the addition of a larger amount of the polymers according to the invention (4.0 g / l instead of 0.4 g / l) to a shampoo formulation made it possible to achieve a more pronounced styling effect, which is noticeable both in terms of wet and dry combability made.

e) Sensory assessment

Result: Formulations 5.1a and 5.2b showed a tendency or significantly increased stylability compared to comparative formulation 5.0.

Claims

claims

1. Use of a nonionic, crosslinked (meth) acrylate-containing polymer with an average particle diameter in the range from 50 to 500 nm for strengthening keratin fibers.

2. Hair treatment composition containing conventional cosmetic ingredients, characterized in that the composition further contains a dispersion of a nonionic, crosslinked (meth) acrylate-containing polymer with an average particle diameter in the range from 50 to 500 nm.

3. Hair treatment composition according to claim 2, characterized in that the polymer is based on at least one monomer from the group formed by N-vinylpyrrolidone, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, sec-butyl acrylate, n- Hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-dodecyl acrylate, 2-hydroxyethyl acrylate, N-isopropyl acrylamide and the corresponding methacrylic acid derivatives.

4. Hair treatment composition according to claim 2 or 3, characterized in that the polymer contains poly-N-isopropylacrylamide or an N-vinylpyrrolidone / (meth) acrylic ester copolymer.

5. Hair treatment composition according to one of claims 2 to 4, characterized in that the polymer is cross-linked with N, N'-methylenebisacrylamide.

6. Hair treatment composition according to one of claims 2 to 5, characterized in that the polymer is cross-linked to 0.5 to 20%.

7. Hair treatment composition according to one of claims 2 to 6, characterized in that the polymer has a glass transition temperature of more than 30 ° C.

8. Hair treatment composition according to one of claims 2 to 7, characterized in that the polymer in an amount of 0.01 to 10 wt .-%, preferably from 0.05 to 5 wt .-%, and particularly preferably from 0.1 is up to 1 wt .-%, based on the total weight of the agent.

9. Hair treatment composition according to one of claims 2 to 8, characterized in that it contains 1 to 20 wt .-% of an anionic surfactant.

10. Hair treatment composition according to claim 9, characterized in that the anionic surfactant is selected from alkyl sulfates and alkyl polyglycol ether sulfates.

11. A method for setting hair, characterized in that an agent according to one of claims 2 to 10 is applied to the hair in an effective amount.

12. The method according to claim 11, characterized in that the agent is rinsed out after application to the hair and an exposure time.