DE10243037A1 - Hair treatment agent contains a nonionic, crosslinked (meth)acrylate-containing polymer of average particle diameter 50-500 nm to fix the hair - Google Patents

Abstract

Use is claimed of nonionic, crosslinked (meth)acrylate-containing polymers of average particle diameter 50-500 nm in fixing keratin fibers ((meth)acrylate = ester or amide). An Independent claim is also included for a hair-treatment agent containing conventional ingredients, together with a dispersion of a nonionic, crosslinked (meth)acrylate-containing polymer of average particle diameter 50-500 nm.

Description

The present invention relates to the use of non-ionic, cross-linked (meth) acrylate Polymers with an average particle diameter in the range of 50 to 500 nm for strengthening keratin fibers, as well as hair treatment agents, that contain these polymers.

An appealing looking hairstyle is now generally regarded as an indispensable part of a well-groomed exterior. Due to current fashion trends, hairstyles always apply as chic, which can only be used with certain hair types using certain Build strengthening active ingredients or maintain them for a longer period to let.

To shape and design the Hair it is common Use hair styling products such as hair fixers or hair sprays. Hair fixers are distributed in damp hair for styling, while Hair sprays can be sprayed onto the finished hairstyle for fixation.

To provide adequate hair fixation To achieve effect, means are generally used, which remain on the hair. However, this is a danger undesirable Load on the hair associated.

The firming agents in which it is usually polymeric compounds are in usually applied in the form of hair fixatives or hair sprays. However, it is also possible them in common hair cleaners or conditioners incorporate.

This is how the German patent application describes it DE 19949517.3 Setting hair cleaners 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 products with good washability. 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.

The European patent application EP-A2 0288012 describes hair cosmetic compositions containing fine particles of a cross-linked 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.

Furthermore, it is state of the art use film-forming polymers as hair-setting active ingredients.

The known from the prior art hair-setting ingredients show at high ambient humidity often no longer sufficient effects. You can also strain the hair especially when used in the form of a leave-on formulation, or undesirably change its grip or gloss.

The applicability of the well-known hair-setting ingredients through their solubility or dispersibility in the corresponding hair treatment agents limited as well as their compatibility with the rest contained recipe components. So it can with the combination of the cationic widely used as hair fixatives Polymers with anionic formulation components to undesirable precipitations come.

The present invention was now the task of providing hair treatment agents, which for Strengthening keratin fibers are suitable and compared to the hair treatment agents known from the prior art which have a hair-setting effect Have advantages.

It has now surprisingly been found that non-ionic, cross-linked (meth) acrylate-containing polymers with a medium Particle diameters in the range from 50 to 500 nm meet these requirements fulfill in an excellent way and bring about significant strengthening of keratin fibers can.

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

According to the invention, keratin fibers include furs, To understand wool, feathers, hair and especially human hair.

Another object of the invention is a hair treatment product that, in addition to common cosmetic ingredients furthermore a dispersion of a nonionic, crosslinked (meth) acrylate Polymers with an average particle diameter in the range of Contains 50 to 500 nm.

For the purposes of the invention, a crosslinked (meth) acrylate-containing polymer is a crosslinked To understand tes homopolymer or copolymer, which is based on the inclusion of the crosslinker, two or more monomers. 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.

As monomers for those used in the invention Polymers are suitable for monounsaturated polymerizable compounds, preferably the esters and amides of acrylic acid and methacrylic acid and vinyl pyrrolidone. For the purposes of the invention, esters and amides with alcohols are preferred or amines with 1 to 6 carbon atoms, the alcohols or Amines in addition can be substituted with 1 to 3 hydroxyl groups. In addition to N-vinyl pyrrolidone 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-hydroxyethyl acrylate, N-isopropylacrylamide and the corresponding methacrylic acid derivatives.

Particularly in the sense of the invention preferred polymers are poly-N-isopropylacrylamide and N-vinyl pyrrolidone / (meth) acrylic ester copolymers.

For in the event that used according to the invention Polymer consists of several different monomers the weight ratio the different monomers to each other are not special Restrictions.

The crosslinking required according to the invention of the polymer can be by means of a polyfunctional monomer such as N, N '' - methylenebisacrylamide or 1-vinyl-3- (E) -ethylidene pyrrolidone respectively. Crosslinking with N, N'-methylenebisacrylamide is preferred in the sense of the invention.

The polymer is about 0.5 to about 20%, but preferably about 2 to about 10% and very particularly preferably about 4 to about 6% cross-linked. Under a degree of networking from x% it is understood that on 100 parts by weight of the total monofunctional on which the polymer is based Monomers x parts by weight of the crosslinker, i.e. of the polyfunctional Monomers or the mixture of polyfunctional monomers come.

Non-ionic crosslinked materials suitable according to the invention (meth) acrylate-containing polymers with an average particle diameter in the range from 50 to 500 nm are preferably obtainable by that the Monomers underlying the polymer in an emulsion polymerization polymerized together. The cross-linking is expedient by causing a suitable monomer or mixture of monomers to be polymerized Amount of a polyfunctional monomer or crosslinker admixed.

The size of the polymer particles depends on used manufacturing process and can for example by the use of emulsifiers and the choice of concentration of the reactants during the Polymerization affected become. Through simple routine experiments, the specialist can work for each elected Combination of monomers the appropriate manufacturing conditions determine in order to obtain polymer particles of the size suitable according to the invention.

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

The preparation of the used according to the invention Polymers by emulsion polymerization is preferably used in Water carried out as a dispersant.

Comes as a polymerization initiator everyone for initiator suitable for such an emulsion polymerization, however, water-soluble initiators such as potassium peroxodisulfate are preferred used.

That with emulsion polymerization reaction mixture obtained can continue in a manner known per se be cleaned up. For example, dialysis are freed of residual monomers, and by centrifugation, filtration, Freeze drying or spray drying can reduce the water content to a desired level or the polymers are kept in an anhydrous, unswollen state become.

The cross-linked used according to the invention (Meth) acrylate-containing polymers are nonionic, i. H. they are not anionic, cationic or zwitterionic. This means in particular that she are free of acidic groups, e.g. Carboxylate groups, and that they are free are of quaternary or basic groups such as Mono-, di- or trialkylamino groups, which unites the cross-linked polymer per se or in acidic solution would give cationic character.

The average particle size of those suitable according to the invention Polymers 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 the particle relates. The particle size was within the scope of the invention via laser diffraction with the device Mastersizer-RT 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, based on the known laws, between the glass transition temperatures of the respective homopolymers and the corresponding copolymers, make the necessary preselection.

Come as a hair treatment product all means according to the invention in question, with their application to the hair of the user mainly or among other things, a shaping or shape-maintaining effect want to achieve the hairstyle. For example, it can be cleaning agents such as shampoos, firming agents such as hair fixers, hair sprays and blow dryer shafts, permanent shaping agents such as permanent waving and fixing agents, care agents such as conditioning agents, Hair treatments and conditioners, color-changing Agents such as bleaching agents, oxidation dyes and tinting agents based on direct dyes, hair lotions and hair tip fluids act. Can accordingly the preparations as solutions, Emulsions, gels, creams, aerosols or lotions can be formulated. It can also be the case with the hair treatment compositions according to the invention both to rinse off (rinse-often) as well as products left on the hair (leaveon) act. Rinse-off hair treatment agents are a preferred embodiment of the invention.

Hair treatment agents particularly preferred according to the invention are hair shampoos.

The hair treatment compositions according to the invention contain the non-ionic, cross-linked (meth) acrylate-containing polymer an average particle diameter in the range from 50 to 500 nm in amounts of preferably about 0.01 to about 10, especially about 0.05 to about 5, and particularly preferably about 0.1 to about 1% by weight, each based on the total weight of the agent.

In a further preferred embodiment contain the agents according to the invention 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. Also in the molecule both an anionic and a cationic charge are present. These zwitterionic or amphoteric surface-active substances can also be used according to the invention be used. Can continue the surface active Substances can also be non-ionic.

in der R¹ bevorzugt für einen aliphatischen Kohlenwasserstoffrest mit 8 bis 30 Kohlenstoffatomen, R² für Wasserstoff, einen Rest (CH₂CH₂O)_nR¹ oder X, n für Zahlen von 1 bis 10 und X für Wasserstoff, ein Alkali- oder Erdalkalimetall oder NR³R⁴R⁵R⁶, mit R³ bis R⁶ unabhängig voneinander stehend für einen C₁ bis C₄- Kohlenwasserstoffrest, steht,

• – lineare und verzweigte Fettsäuren mit 8 bis 30 C-Atomen (Seifen),
• – Ethercarbonsäuren der Formel R-O-(CH₂-CH₂O)_X-CH₂-COOH, in der R eine lineare Alkylgruppe mit 8 bis 30 C-Atomen und x = 0 oder 1 bis 16 ist,
• – Acylsarcoside mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Acyltauride mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Acylisethionate mit 8 bis 24 C-Atomen in der Acylgruppe,
• – Sulfobernsteinsäuremono- und -dialkylester mit 8 bis 24 C-Atomen in der Alkylgruppe und Sulfobernsteinsäuremono-alkylpolyoxyethylester mit 8 bis 24 C-Atomen in der Alkylgruppe und 1 bis 6 Oxyethylgruppen,
• – lineare Alkansulfonate mit 8 bis 24 C-Atomen,
• – lineare Alpha-Olefinsulfonate mit 8 bis 24 C-Atomen,
• – Alpha-Sulfofettsäuremethylester von Fettsäuren mit 8 bis 30 C-Atomen,
• – Alkylsulfate und Alkylpolyglykolethersulfate der Formel R-O(CH₂-CH₂O)_x-OSO₃H, in der R eine bevorzugt lineare Alkylgruppe mit 8 bis 30 C-Atomen und x = 0 oder 1 bis 12 ist,
• – Gemische oberflächenaktiver Hydroxysulfonate gemäß DE-A-37 25 030 ,
• – sulfatierte Hydroxyalkylpolyethylen- und/oder Hydroxyalkylenpropylenglykolether gemäß DE-A-37 23 354 ,
• – Sulfonate ungesättigter Fettsäuren mit 8 bis 24 C-Atomen und 1 bis 6 Doppelbindungen gemäß DE-A-39 26 344 ,
• – Ester der Weinsäure und Zitronensäure mit Alkoholen, die Anlagerungsprodukte von etwa 2–15 Molekülen Ethylenoxid und/oder Propylenoxid an Fettalkohole mit 8 bis 22 C-Atomen darstellen,
• – Alkyl- und/oder Alkenyletherphosphate der Formel (I)
• – sulfatierte Fettsäurealkylenglykolester der Formel (II) R⁷CO(AlkO)_nSO₃M (II) in der R⁷CO- für einen linearen oder verzweigten, aliphatischen, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 C-Atomen, Alk für CH₂CH₂, CHCH₃CH₂ und/oder CH₂CHCH₃, n für Zahlen von 0,5 bis 5 und M für ein Kation steht, wie sie in der DE-OS 197 36 906.5 beschrieben sind,
• – Monoglyceridsulfate und Monoglyceridethersulfate der Formel (III),
  
  in der R⁸CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen, x, y und z in Summe für 0 oder für Zahlen von 1 bis 30, vorzugsweise 2 bis 10, und X für ein Alkali- oder Erdalkalimetall steht. Typische Beispiele für im Sinne der Erfindung geeignete Monoglycerid(ether)sulfate sind die Umsetzungsprodukte von Laurinsäuremonoglycerid, Kokosfettsäuremonoglycerid, Palmitinsäuremonoglycerid, Stearinsäuremonoglycerid, Ölsäuremonoglycerid und Talgfettsäuremonoglycerid sowie deren Ethylenoxidaddukte mit Schwefeltrioxid oder Chlorsulfonsäure in Form ihrer Natriumsalze. Vorzugsweise werden Monoglyceridsulfate der Formel (III) eingesetzt, in der R⁸CO für einen linearen Acylrest mit 8 bis 18 Kohlenstoffatomen steht. Monoglyceridsulfate und Monoglyceridethersulfate werden beispielsweise in der EP-B1 0 561 825 , der EP-B1 0 561 999 , der DE-A1 42 04 700 oder von A.K.Biswas et al. in J.Am.Oil.Chem.Soc. 37, 171 (1960) und F.U.Ahmed in J.Am.Oil.Chem.Soc. 67, 8 (1990) beschrieben.

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 as well as the mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group,

in which R ^{1 is} preferably an aliphatic hydrocarbon radical having 8 to 30 carbon atoms, R ^{2 is} hydrogen, a radical (CH ₂ CH ₂ O) _n R ¹ or X, n is a number from 1 to 10 and X is 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 representing a C ₁ to C ₄ hydrocarbon radical,

• - linear and branched fatty acids with 8 to 30 carbon atoms (soaps),
• Ether carboxylic acids of the formula RO- (CH ₂ -CH ₂ O) _X -CH ₂ -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 RO (CH ₂ -CH ₂ O) _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 .
• - Sulphated hydroxyalkyl polyethylene and / or hydroxyalkylene propylene glycol ether 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 with 8 to 22 carbon atoms,
• - Alkyl and / or alkenyl ether phosphates of the formula (I)
• Sulfated fatty acid alkylene glycol esters of the formula (II) R ⁷ CO (AlkO) _n SO ₃ M (II) in the 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 , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ , n for numbers from 0.5 to 5 and M stands for a cation, as in the DE-OS 197 36 906.5 are described
• Monoglyceride sulfates and monoglyceride ether sulfates of the formula (III),
  
  in which R ⁸ CO stands for a linear or branched acyl radical with 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 stands for an alkali or alkaline earth metal. 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, for example, in the EP-B1 0 561 825 , the EP-B1 0 561 999 , the 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 mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl ester with 8 to 18 carbon 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 at least one -COO ^(-) - or -SO ₃ ^(-) group in the molecule. 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 ₈ -C ₂₄ -alkyl or -acyl group, contain at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and are capable of forming internal 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-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 24 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acyl sarcosine.

• – Anlagerungsprodukte von 2 bis 50 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare und verzweigte Fettalkohole mit 8 bis 30 C-Atomen, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe,
• – mit einem Methyl- oder C₂-C₆-Alkylrest endgruppenverschlossene Anlagerungsprodukte von 2 bis 50 Mol Ethylenoxid und/oder 0 bis 5 Mol Propylenoxid an lineare und verzweigte Fettalkohole mit 8 bis 30 C-Atomen, an Fettsäuren mit 8 bis 30 C-Atomen und an Alkylphenole mit 8 bis 15 C-Atomen in der Alkylgruppe, wie beispielsweise die unter den Verkaufsbezeichnungen Dehydol^® LS, Dehydol^® LT (Cognis) erhältlichen Typen,
• – C₁₂-C₃₀-Fettsäuremono- und -diester von Anlagerungsprodukten von 1 bis 30 Mol Ethylenoxid an Glycerin,
• – Anlagerungsprodukte von 5 bis 60 Mol Ethylenoxid an Rizinusöl und gehärtetes Rizinusöl,
• – Polyolfettsäureester, wie beispielsweise das Handelsprodukt Hydagen^® HSP (Cognis) oder Sovermol – Typen (Cognis),
• – alkoxilierte Triglyceride,
• – alkoxilierte Fettsäurealkylester der Formel R⁹CO-(OCH₂CHR¹⁰)_wOR¹¹, in der R⁹CO für einen linearen oder verzweigten, gesättigten und/oder ungesättigten Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹⁰ für Wasserstoff oder Methyl, R¹¹ für lineare oder verzweigte Alkylreste mit 1 bis 4 Kohlenstoffatomen und w für Zahlen von 1 bis 20 steht,
• – Aminoxide,
• – Hydroxymischether, wie sie beipielsweise in der DE-OS 19738866 beschrieben sind,
• – Sorbitanfettsäureester und Anlagerungeprodukte von Ethylenoxid an Sorbitanfettsäureester wie beispielsweise die Polysorbate,
• – Zuckerfettsäureester und Anlagerungsprodukte von Ethylenoxid an Zuckerfettsäureester,
• – Anlagerungsprodukte von Ethylenoxid an Fettsäurealkanolamide und Fettamine,
• – Fettsäure-N-alkylglucamide,
• – Alkylpolygykoside entsprechend der allgemeinen Formel RO-(Z)_x wobei R für Alkyl, Z für Zucker sowie x für die Anzahl der Zuckereinheiten steht. Die erfindungsgemäß verwendbaren Alkylpolyglykoside können lediglich einen bestimmten Alkylrest R enthalten. Üblicherweise werden diese Verbindungen aber ausgehend von natürlichen Fetten und Ölen oder Mineralölen hergestellt. In diesem Fall liegen als Alkylreste R Mischungen entsprechend den Ausgangsverbindungen bzw. entsprechend der jeweiligen Aufarbeitung dieser Verbindungen vor.

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 ₂ -C ₆ -alkyl radical to linear and branched fatty alcohols having 8 to 30 C atoms, to fatty acids having 8 to 30 C atoms atoms and onto alkylphenols having 8 to 15 carbon atoms in the alkyl group, such as the type available under the commercial names Dehydol ^® LS, Dehydol ^® LT (Cognis),
• C ₁₂ -C ₃₀ fatty acid monoesters and diesters of adducts of 1 to 30 moles of ethylene oxide with glycerol,
• - adducts of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil,
• - polyol, such as the commercially available 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 is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{10 is} hydrogen or methyl, R ^{11 represents} linear or branched alkyl radicals having 1 to 4 carbon atoms and w represents numbers from 1 to 20,
• Amine oxides,
• - Hydroxy mixed ethers, such as those in the DE-OS 19738866 are described
• Sorbitan fatty acid esters and addition products of ethylene oxide with sorbitan fatty acid esters such as, for example, the polysorbates,
• - sugar fatty acid esters and adducts of ethylene oxide with sugar fatty acid esters,
• - adducts of ethylene oxide with fatty acid alkanolamides and fatty amines,
• Fatty acid N-alkylglucamides,
• - Alkyl polygycosides according to the general formula RO- (Z) _x where R is alkyl, Z is sugar and x is 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 the starting compounds or corresponding to the respective working up of these compounds.

• – im wesentlichen aus C₈- und C₁₀-Alkylgruppen,
• – im wesentlichen aus C₁₂- und C₁₄-Alkylgruppen,
• – im wesentlichen aus C₈- bis C_{1 6}-Alkylgruppen oder
• – im wesentlichen aus C₁₂- bis C₁₆-Alkylgruppen oder
• – im wesentlichen aus C₁₆ bis C₁₈-Alkylgruppen besteht.

Alkylpolyglycosides in which R

• Essentially from C ₈ and C ₁₀ alkyl groups,
• Essentially from C ₁₂ and C ₁₄ alkyl groups,
• - essentially from C ₈ - to C _{1 6} -alkyl groups or
• - essentially from C ₁₂ - to C ₁₆ alkyl groups or
• - consists essentially of C ₁₆ to C ₁₈ alkyl groups.

Any sugar block Z can be used Mono- or oligosaccharides can be used. Usually sugar with 5 or 6 carbon atoms and the corresponding oligosaccharides used. Examples of such sugars are glucose, fructose, Galactose, arabinose, ribose, xylose, lyxose, allose, old rose, mannose, Gulose, Idose, Talose and Sucrose. Preferred sugar building blocks are Glucose, fructose, galactose, arabinose and sucrose; Is glucose particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain an average of 1.1 to 5 sugar units. Alkylpolyglykoside with x values from 1.1 to 2.0 are preferred. Very particularly preferred are alkyl glycosides where x is 1.1 to 1.8.

Even the alkoxylated homologues of the alkyl polyglycosides mentioned can be used according to the invention become. These homologues can on average up to 10 ethylene oxide and / or propylene oxide units included per alkyl glycoside unit.

As preferred nonionic surfactants the alkylene oxide addition products have become saturated linear Fatty alcohols and fatty acids with 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations with excellent properties are also used obtained when used as nonionic surfactants fatty acid esters of ethoxylated glycerin.

These connections are through the marked the following parameters. The alkyl radical R contains 6 to 22 Carbon atoms and can be both linear and branched. Primary are preferred linear and 2-methyl branched aliphatic radicals. Such Examples of alkyl radicals are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. 1-Octyl, 1-decyl, 1-lauryl, 1-myristyl. When using so-called "oxo alcohols" predominate as starting materials Compounds with an odd number of carbon atoms in the alkyl chain.

For the compounds used as surfactants alkyl groups can be uniform substances act. However, it is usually preferred in manufacturing of these substances from native vegetable or animal raw materials going out so that one Mixtures of substances with different raw materials dependent alkyl chain lengths receives.

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. In contrast, narrow homolog distributions are obtained if, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alcoholates are used as catalysts. The use of products with restricted homologs distribution can be preferred.

In a preferred embodiment can non-ionic, zwitterionic and / or amphoteric surfactants and their mixtures may be preferred.

Can also be used according to the invention cationic surfactants of the quaternary ammonium compound type, the Esterquats and the Amidoamine. Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as Alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and Tricetylmethylammoniumchlorid, as well as those under the INCI names Quaternium-27 and quaternium-83 known imidazolium compounds. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms on.

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 an alkyl sulfate or alkyl polyglycol ether sulfate as anionic surfactant, where as the alkyl polyglycol ether sulfate the sodium salt of two or triple ethoxylated lauryl or myristyl alcohol is particularly preferred is.

Depending on the type of hair treatment product and the surfactant can the preferably anionic surfactants in amounts of about 0.1 to about 30% by weight, preferably about 1 to about 20% by weight, and most preferably from about 5 to about 15% by weight based on the total agent his.

Furthermore, the agents according to the invention another natural one Emulsifier included. Preferred natural emulsifiers are phospholipids, in particular lecithin, saponins, bile acids and their derivatives, in particular cholic, deoxycholic, lithocholic and taurocholic acid, tannic acid and abientic acid. Phospholipids and saponins are preferred natural emulsifiers.

The hair treatment compositions according to the invention can also contain at least one fat or 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 Decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, Decadienol, oleyl alcohol, eruca 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, as well as their Guerbet alcohols and fatty alcohol cuts, through reduction of course occurring triglycerides such as beef tallow, palm oil, peanut oil, turnip oil, cottonseed oil, soybean oil, sunflower oil and linseed oil or from whose transesterification products arise with appropriate alcohols Fettsäureestern are generated and thus a mixture of different fatty alcohols represent. Monoesters can also be used as fatty substances of fatty acids with alcohols with 6 to 24 carbon atoms and natural triglycerides Origin.

Can also be used as fatty substances are paraffin oils as well as vegetable oils like jojoba oil, Sunflower oil, Orange oil, Almond oil, Wheat germ oil, Peach kernel oil, Henna oil from Lawsonia inermis and oil from Cassia auriculata.

Fat substances in the sense of the invention are still silicone oils, especially dialkyl and alkylarylsiloxanes, such as Dimethylpolysiloxane and methylphenylpolysiloxane, as well as their alkoxylated and quaternized analogues. Examples of such silicones are by Dow Corning under the designations DC 190, DC 200, DC 344, DC 345 and DC 1401 products.

• – pflanzliche Wachse, wie Candelillawachs, Carnaubawachs, Japanwachs, Espartograswachs, Korkwachs, Guarumawachs, Reiskeimölwachs, Zuckerrohrwachs, Ouricurywachs und Montanwachs,
• – tierische Wachse wie Bienenwachs, Schellackwachs, Walrat, Lanolin und Bürzelfett,
• – Mineralwachse wie Ceresin und Ozokerit
• – Petrochemische Wachse wie Petrolatum, Paraffinwachse und Mikrowachse,
• – Hartwachse wie Montanesterwachse, Sasolwachse und hydrierte Jojobawachse, sowie
• – Polyalkylenwachse und Polyethylenglykolwachse.

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, carnauba wax, Japanese 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, carnauba wax and Japanese wax as well as beeswax.

The fatty substances or waxes are common in amounts 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 Means used. For special means can increase the amount of fat but also up to 90 % By weight.

Furthermore, the hair treatment compositions according to the invention contain at least one protein hydrolyzate or a derivative thereof. Protein hydrolyzates are product mixes that are acidic, basic or enzymatically catalyzed breakdown of proteins (proteins) become.

According to the invention, protein hydrolyzates can both of vegetable as well as animal origin.

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 plants, 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 HCl, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed C asein, 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 protein, hydroxypropyltrimonium hydrolyzed protein Soy Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein / Siloxysilicate, Lauryldi monium 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 hydrolyzedylated hydroxyl Silk, Steardimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Vegetable Protein, Steardimonium Hydroxypropyl Hydrolyzed Wheat Protein, Stearidimonium Hydroxyethyl Hydrolyzed Collagen, Quaternium-76 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Milk Protein, 79 Quaternium-79 Hydrolyzed Silk, Quaternium-79 Hydrolyzed Soy Protein, Quaternium-79 Hydrolyzed Wheat Protein.

Those are very particularly preferred Cationic protein hydrolysates and derivatives based on plants.

In the agents according to the invention can the protein hydrolyzates and their derivatives in amounts from 0.01 to 10 wt .-% based on the total agent. amounts from 0.1 to 5% by weight, in particular 0.1 to 3% by weight, are very special prefers.

Furthermore, the hair treatment compositions according to the invention a conditioning agent selected from the group consisting of cationic surfactants, cationic polymers, alkylamidoamines and synthetic oils is formed.

As conditioning agents, cationic Polymers may be preferred. These are usually polymers that are a quaternary Contain nitrogen atom, for example in the form of an ammonium group.

• – quaternisierte Cellulose-Derivate, wie sie unter den Bezeichnungen Celquat^® und Polymer JR^® im Handel erhältlich sind. Die Verbindungen Celquat^® H 100, Celquat^® L 200 und Polymer JR^®400 sind bevorzugte quaternierte Cellulose-Derivate.
• – polymere Dimethyldiallylammoniumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat^®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat^®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere.
• – Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats- und -methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminomethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat^®734 und Gafquat^®755 im Handel erhältlich.
• – Vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, wie sie unter der Bezeichnung Luviquat^® angeboten werden.
• – quaternierter Polyvinylalkohol sowie die unter den Bezeichnungen
• – Polyquaternium 2,
• – Polyquaternium 17,
• – Polyquaternium 18 und
• – Polyquaternium 27 bekannten Polymeren mit quartären Stickstoffatomen in der Polymerhauptkette.

Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® . The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives.
• - 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 vinyl pyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as, for example, vinyl pyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755.
• - Vinylpyrrolidone-methoimidazolinium chloride copolymers, as are offered under the name Luviquat ^® .
• - Quaternized polyvinyl alcohol and those under the names
• - polyquaternium 2,
• - polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain.

Cationic ones are particularly preferred Polymers of the first four groups.

Preferred cationic surfactants are quaternary type Ammonium compounds, e.g. Ammonium halides, especially chlorides and bromides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, Stearyltrimethylammonium chloride, distearyldimethylammonium chloride, Lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, behenyltrimethylammonium methosulfate, and those under the INCI names Quaternium-27 and Quaternium-83 known imidazolium compounds.

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 agents which is also of particular interest for ecological reasons are alkylamidoamines such as stearamidopropyldimethylamine, which is commercially available under the name Tegoamid ^® S 18.

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 products sold by Dow Corning under the names DC 190, DC 200, DC 344, DC 345 and DC 1401 and the commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow ^Corning® 929 emulsion (contained tend a hydroxyl-amino-modified silicone, which is also called amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes , Quaternium-80).

Can also be used as conditioning Active ingredients are paraffin oils as well as vegetable oils like jojoba oil, Sunflower oil, Orange oil, Almond oil, Wheat germ oil and peach seed oil.

Also suitable hair conditioning Compounds are phospholipids, for example soy lecithin, egg lecithin and cephaline.

In the agents according to the invention can the conditioning agents in amounts from about 0.01 to about 10 wt .-% based on the total agent. amounts from about 0.1 to about 5% by weight, especially from about 0.1 to about 3 % By weight are very particularly preferred.

Hair treatment compositions according to the invention, the hair coloring or tinting agents can represent at least an oxidation dye intermediate of the developer type, if necessary in combination with oxidation dye precursors of the coupler type, and / or one direct dye and / or one found in nature Contain dye.

In another embodiment can the hair treatment compositions according to the invention, if necessary additionally, serve to permanently deform human hair.

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

The aqueous preparation of the keratin reducing agent is common set alkaline so that the hair swells and in this way a deep penetration of the keratin-reducing substance into the hair allows becomes. The keratin-reducing substance cleaves part of the disulfide bonds of keratin to -SH groups, so that there is a loosening of the Peptide crosslinking and due to the tension of the hair by the mechanical Deformation leads to a reorientation of the keratin structure. Under the influence of the Oxidizing agent, disulfide bonds are again formed, and in this way the keratin structure is in the predetermined deformation newly fixed.

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

As a waving agent today almost exclusively alkaline solutions (pH values from 8.5 to 9.5) of thioglycolic or their salts or esters as well as thiolactic acid, cysteamine, thio malic acid or α-mercaptoethanesoulfonic acid.

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 N ₂ O ₂ preparations, which usually contain about 0.5 to 3.0% by weight of H ₂ O ₂ , is preferably 2 to 4; it is adjusted by inorganic acids, preferably phosphoric acid. Bromate-based fixatives usually contain the bromates in concentrations of 1 to 10% 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.

The pH of the agents according to the invention can generally be between 2 - 11 lie, the expert the preferred pH ranges for the different Means knows. The pH of the agents according to the invention, if it is hair care products is preferably between 2 and 7, wherein Values from 3 to 5 are particularly preferred. To set this pH can be practically any for Acid usable for cosmetic purposes be used. Usually edible acids are used. Are under pleasure acids such acids understood that under the usual Food intake and positive effects have the human organism. Edible acids are, for example, acetic acid, lactic acid, tartaric acid, citric acid, malic acid, ascorbic acid and Gluconic. The use of citric acid and lactic acid particularly preferred. Hair Dye 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 used in the preparation according to the invention be included.

• – Anionische, zwitterionische, amphotere und nichtionische Polymere wie beispielsweise Vinylacetat/Crotonsäure-Copolymere, Polydimethylsiloxane, Vinylpyrrolidon/Vinylacrylat-Copolymere, Vinylacetat/Butylmaleat/Isobornyl-acrylat-Copolymere, Methylvinylether/Maleinsäureanhydrid-Copolymere und deren Ester, unvernetzte und mit Polyolen vernetzte Polyacrylsäuren, Acrylamidopropyl-trimethylammoniumchlorid/Acrylat-Copolymere, Octylacrylamid/-Methyl-methacrylat/tert.Butylaminoethylmethacrylat/2-Hydroxypropylmethacrylat-Copolymere, Polyvinylpyrrolidon, Vinylpyrrolidon/Vinylacetat-Copolymere, Vinylpyrrolidon/Dimethylaminoethylmethacrylat/Vinylcaprolactam-Terpolymere sowie gegebenfalls derivatisierte Celluloseether.
• – symmetrische und unsymmetrische, lineare und verzweigte Dialkylether mit insgesamt zwischen 12 bis 36 C-Atomen, insbesondere 12 bis 24 C-Atomen, beispielsweise Di-n-octylether, Di-n-decylether, Di-n-nonylether, Di-n-undecylether und Di-n-dodecylether, n-Hexyl-n-octylether, n-Octyl-n-decylether, n-Decyl-n-undecylether, n-Undecyl-n-dodecylether und n-Hexyl-n-Undecylether sowie Di-tert-butylether, Di-iso-pentylether, Di-3-ethyldecylether, tert.-Butyl-n-octylether, iso-Pentyl-n-octylether und 2-Methyl-pentyl-n-octylether,
• – Vaseline
• – Entschäumer wie Silikone,
• – Verdickungsmittel wie Gelatine oder Pflanzengumme, beispielsweise Agar-Agar, Guar-Gum, Alginate, Xanthan-Gum, Gummi arabicum, Karaya-Gummi, Johannisbrotkernmehl, Leinsamengummen, Dextrane, Cellulose-Derivate, z. B. Methylcellulose, Hydroxyalkylcellulose und Carboxymethylcellulose, Stärke-Fraktionen und Derivate wie Amylose, Amylopektin und Dextrine, Tone und Schichtsilikate wie z. B. Bentonit oder vollsynthetische Hydrokolloide wie z. B. Polyvinylalkohol, die Ca-, Mg- oder Zn- Seifen,
• – Rückfettungsmittel wie Fettsäurealkanolamide, Fettsäuren, Fettsäureester wie Isopropylmyristat, -palmitat, -oleat und -stearat, gegebenenfalls ethoxylierte Partialglyceride, Wollwachsderivate, Lecithin, Perhydrosqualen, Isopropyladipat oder die voranstehend beschriebenen Fettstoffe
• – Strukturanten wie Maleinsäure, Mono-, Di- und Oligosaccharide,
• – Parfümöle, Dimethylisosorbid und Cyclodextrine,
• – Lösungsvermittler, wie Ethanol, Isopropanol, Ethylenglykol, Propylenglykol, Glycerin und Diethylenglykol,
• – Farbstoffe zum Anfärben des Mittels,
• – Antischuppenwirkstoffe wie Piroctone Olamine, Zink Omadine und Climbazol,
• – weitere Substanzen zur Einstellung des pH-Wertes,
• – Vitamine und Vitaminvorstufen, wie Panthenol, dessen Derivate und Biotin,
• – Pflanzen- und Honigextrakte, wie insbesondere Extrakte aus Eichenrinden, Brennessel, Hamamelis, Hopfen, Kamille, Klettenwurzel, Schachtelhalm, Lindenblüten, Mandel, Aloe Vera, Kokosnuß, Mango, Aprikose, Limone, Weizen, Kiwi, Melone, Orange, Grapefruit, Salbei, Rosmarin, Birke, Wiesenschaumkraut, Quendel, Schafgarbe, Hauhechel, Meristem, Ginseng und Ingwerwurzel,
• – Weitere Wirkstoffe wie Ceramide, Allantoin, Pyrrolidoncarbonsäuren, und Bisabolol,
• – Lichtschutzmittel,
• – Konsistenzgeber wie Zuckerester, Polyolester oder Polyolalkylether,
• – Fettsäurealkanolamide,
• – physiologisch verträgliche anorganische oder organische Säuren,
• – Quell- und Penetrationsstofte wie Glycerin, Propylenglykolmonoethylether, Carbonate, Hydrogencarbonate, Guanidine, Harnstoffe sowie primäre, sekundäre und tertiäre Phosphate,
• – Feuchthaltemittel wie Sorbit, Milchsäuresalze, Glycerin oder Polysaccharide
• – Trübungsmittel wie Latex, Styrol/PVP- und Styrol/Acrylamid-Copolymere,
• – Perlglanzmittel wie Ethylenglykolmono- und -distearat sowie PEG-3-distearat,
• – Komplexbildner wie EDTA, NTA, β-Alanindiessigsäure und Phosphonsäuren,
• – Reduktionsmittel wie z.B. Thioglykolsäure und deren Derivate, Thiomilchsäure, Cysteamin, Thioäpfelsäure und α-Mercaptoethansulfonsäure,
• – Oxidationsmittel wie Wasserstoffperoxid, Kaliumbromat und Natriumbromat,
• – Treibmittel wie Propan-Butan-Gemische, N₂O, Dimethylether, CO₂, N₂ und Luft sowie
• – Antioxidantien.

Other common constituents of the preparations according to the invention can be:

• - Anionic, zwitterionic, amphoteric and non-ionic polymers such as, for example, vinyl acetate / crotonic acid copolymers, polydimethylsiloxanes, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic acid and non-crosslinked polyacrylate copolymers with non-acrylate copolymers , Acrylamidopropyl-trimethylammonium chloride / acrylate copolymers, octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / dimethylaminoethylrolactamate ether / derivative-given vinylphenylpolymer-vinyl methacrylate / derivates.
• 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-ethyl decyl ether, tert-butyl-n-octyl ether, iso-pentyl-n-octyl ether and 2-methyl-pentyl-n-octyl ether,
• - Vaseline
• - 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,
• - anti-dandruff agents such as piroctone olamine, zinc omadine and climbazol,
• - other substances for adjusting the pH value,
• Vitamins and 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, harrow, meristem, ginseng and ginger root,
• Further active substances such as ceramides, allantoin, pyrrolidone carboxylic acids and bisabolol,
• - light stabilizers,
• - consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers,
• - fatty acid alkanolamides,
• - physiologically acceptable 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, glycerin or polysaccharides
• 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, β-alaninediacetic acid and phosphonic acids,
• 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 O, dimethyl ether, CO ₂ , N ₂ and air and
• - antioxidants.

Regarding other ingredients as well as quantity ranges for the individual ingredients are based on those known to the person skilled in the art manuals, e.g. K. Schrader, Basics and Formulations of Cosmetics, 2nd Edition, Hüthig Book 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 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 in the agents according to the invention is less preferred due to the known ozone problem.

Another subject of the present Invention is a method for setting hair, in which a hair treatment composition according to the invention, as described in the previous text, in an effective Amount is applied to the hair. Subsequently, the remedy after a Rinse time again or until the next one shampooing to be left on the hair. In a preferred embodiment of the process, the agent is rinsed out again after a contact time.

It was within the scope of the invention found that the Use of non-ionic, cross-linked (meth) acrylate-containing Polymers with an average particle diameter in the range of 50 to 500 nm in the hair treatment agents described in the preceding text as well as the manufacturer as well as the user of such agents with advantages connected is.

For the formulation of such funds results in advantages above all with regard to the freedom of formulation, since those used according to the invention Polymers excellent with the usual ones Recipe components compatible and in particular there are no incompatibilities, e.g. a Precipitation formation, with anionic components show. Even though the particles in the hair treatment compositions according to the invention unresolved, i.e. are in the form of a dispersion, their small size makes it possible easy incorporation and the production of transparent Formulations.

Show the advantages in use especially in an elevated Wet and especially dry combing work of the hair, resulting in improved formability and stylability of the Hair means. This for the Users desired Effects are achieved without the means of the state problems known in the art of impairing hair gloss or Hair volume can be observed. It also comes through use The polymers do not cause an undesirable strain on the hair or a sticky grip. According to the teaching of the present invention improved hair fixation and styling shampoos as well as shampoos for Formulate fine hair.

Through the invention, the formulation of combination products allows the additional for a first effect, such as a hair cleaning or hair coloring, have a hair fixation as a further effect. For hair fixation separate post-treatment is no longer necessary and the user saves an application step. At the same time, the packaging effort reduced because one product is used less.

The following examples are intended to Object of the invention closer explain. Unless otherwise stated, all quantities are in% by weight. to understand.

Example 1: Production of a polymer based on N-isopropylacrylamide ("P-N-IPAAm")

In a 1 liter four-necked flask, 470 ml of demineralized water (demineralized water), 7 g of N-isopropylacrylamide, 0.35 g of N, N-methylenebisacrylamide and 0.094 g of sodium dodecyl sulfate were weighed in and under N ₂ atmosphere and reflux at 200 rpm Heated to 70 ° C. After 30 minutes, 0.28 g of potassium peroxodisulfate in 30 ml of demineralized water was added, and the reaction was terminated 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 synthesized in this way had a diameter of approx. 200 to 300 at room temperature nm in the swollen state, d. H. in the state of dispersion. The Particle size was determined by laser diffraction with the device Malvern Mastersizer-RT determined. The N-isopropylacrylamide was in the dispersion can no longer be detected using HPLC (<1 ppm).

The polymer dispersion thus produced was subsequently freeze-dried, the polymer being in a non-swollen form white Powder was obtained in a yield of 95%. It had a glass transition temperature of 152 ° C on (measurement using modulated dynamic differential calorimetry, MDSC). For the further use can be the polymer e.g. redisperse with water to a desired concentration. For example 4, the freeze-dried polymer 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 dispersion, redispersed.

Alternatively, the above Polymer dispersion obtained by centrifugation of the bulk of the salts used in the manufacture and be separated from the water. In this case you get that Polymer in the swollen state.

Example 2: Production of a polymer based on ethyl methacrylate and N-vinyl pyrrolidone ("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).

Working up the reaction product and the preparation of an aqueous dispersion with a concentration of 0.4 g polymer / l dispersion analogous to example 1.

Examples 3.1 - 3.23: Production of other polymers

In the same way as in the example 2, the cross-linked polymers 3.1 to 3.23 were produced (see table 1), used for 100 parts by weight of those listed in Table 1 Monomers each additionally 5 parts by weight of N, N-methylene bisacrylamide for the Polymerization reaction were used.

Table 1

Example 4: Investigation the effectiveness of the polymers of the invention on hair an aqueous dispersion out

• a) Implementation of measurements
• a.1) Wet combability measurements

When determining the combability, the work for combing wet strands of hair was done 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 of 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 electrostatic charge

The measurements were at a constant Climate (25% relative humidity, 30 ° C) carried out; the hair strands were conditioned for 24 hours. at the determination of dry combability became the work of combing of dry strands of hair measured. The hair was medium-blonded before the zero measurement and then combed in the dry and conditioned state, whereby the combing forces required are recorded were. After the zero measurement, the hair strands were once with the respective Formulation treated (10 minutes, 0.5 g formulation per g 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. It were 10 comb values each a strand of hair before application and after application of the formulations determined and compared in dry and conditioned condition.

The electrostatic charge was parallel to dry combing examined with approval of the electrostatic charge. The actual measurement took place over the charge tap on a double Faraday cage after performing the 10 combs.

a.3) Sensory assessment

The sensory assessment was sensory about a Expert panel determined. The strands of hair used were initially 30 minute pre-cleaned with a 12% Texapon NSO solution (pH 6.5) and 5 min. rinsed with water. Then were the strands 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 above Dried overnight. To ensure a defined environment, the tests were carried out in a climate room at 22 ° C and approx. 45% relative humidity carried out with standard daylight lighting. Each subject received new strands of hair. The recipe was against the corresponding reference assigned to individual attributes and evaluated.

• –1 = deutlich schlechter als Standard
• –0,5 = etwas schlechter als Standard
• 0 = genau wie Standard
• + 0,5 = etwas besser als Standard
• + 1 = deutlich besser als Standard

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 comparison of 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 on hair

The application on strands of hair was done standardized over a diving process. European standard hair was used the previously cleaned, rinsed and had been dried. After that, the hair was put in the after the Examples 1 and 2 produced aqueous polymer dispersions submerged at a concentration of 0.4 g / l. Depending on the application The strands of hair were then used as rinse-often or leave-on products rinsed if necessary. Subsequently the samples were at 25% rel. Humidity and 30 ° C in the air.

e) Determination of dry combability

When determining dry combability becomes the work of combing of dry strands of hair pretreated on 20 according to b) strands of hair carried out. The values of 10 combs on strands of hair were given in each case or after application of the polymers, rinsing and drying, if necessary, and compared. The room climate was 25% rel. Humidity and 30 ° C. The conditioning time of strands of hair was 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 often:
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 showed yourself here in both cases a significant increase dry combing work, requirement for improved hair fixation.

d) Determination of hair shine

The hair shine was achieved by means of light reflection certainly. For this purpose, 5 strands of hair each in accordance with b) in the form of a leave-on treatment pretreated and additionally provided with a gloss-reducing film. There was the luster intensity of the untreated Strands of hair, and subsequently with the polymers of the invention treated strands of hair measured and the difference determined. The measurements were taken 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 a 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 a gloss-reducing film: –1.2% (t-test 93.9%)

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

e) Determination of the hair volume

The volume was analyzed by image analysis Shadow cast of strands of hair certainly. For this purpose, the strands of hair were pretreated in the form of a leave-on treatment. It was the area determined from 10 of the untreated and then the treated strands of hair and compared.

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 statistical indistinguishable value of volume. The polymers according to the invention therefore showed no negative effect on hair volume.

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

a) Implementation of the measurements

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

b) Shampoos used

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 wording

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 wording

Formulation 5.1b (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 wording

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 wording

e) Determination of wet combability

Result: in the shampoo formulation led the polymers of the invention to a significant increase combing, what an indication of represents a hair fixation and improved hair styling.

Result: in the shampoo formulation led the polymers of the invention to a significant increase of combing what an indication of represents a styling effect

d) Determination of dry combability

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

Overall seen through the Add a larger amount of the polymers of the invention (4.0 g / l instead of 0.4 g / l) in a shampoo formulation a clearer Styling effect can be achieved, both in the wet as also in dry combability made noticeable.

e) Sensory assessment

Result: the formulations 5.1a and 5.2b showed opposite Comparative formulation 5.0 one tends to be significant increased Stylability.

Claims (12)

Use of a non-ionic, cross-linked (meth) acrylate-containing polymer with an average particle diameter in the range of 50 to 500 nm for strengthening keratin fibers. Hair treatment compositions containing customary cosmetic Components, characterized in that the agent continues to be a Dispersion of a non-ionic, cross-linked (meth) acrylate Polymers with an average particle diameter in the range of Contains 50 to 500 nm. Hair treatment composition according to claim 2, characterized in that the Polymer is based on at least one monomer from the group that is formed from 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-isopropylacrylamide and the corresponding methacrylic acid derivatives. Hair treatment composition according to claim 2 or 3, characterized characterized that as Polymer poly-N-isopropylacrylamide or an N-vinylpyrrolidone / (meth) acrylic ester copolymer is included. Hair treatment composition according to one of claims 2 to 4, characterized in that the Polymer is 0.5 to 20% cross-linked. Hair treatment composition according to claim 4, characterized in that this Polymer with N, N '' methylenebisacrylamide is cross-linked. Hair treatment composition according to one of claims 2 to 6, characterized in that the Polymer a glass transition temperature of more than 30 ° C having. 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 of 0.05 to 5% by weight, and particularly preferably 0.1 to 1% by weight is included, based on the total weight of the agent. Hair treatment composition according to one of claims 2 to 8, characterized in that it Contains 1 to 20 wt .-% of an anionic surfactant. Hair treatment composition according to claim 9, characterized in that this anionic surfactant selected is made from alkyl sulfates and alkyl polyglycol ether sulfates. Process for setting hair, characterized in that that he an agent according to one of the claims Apply 2 to 10 to the hair in an effective amount. A method according to claim 11, characterized in that he the agent after application to the hair and a contact time rinses.