EP1830797A1 - Hair conditioner comprising corneocyte proteins or corneocyte polypeptides - Google Patents

Abstract

Disclosed is a hair conditioner that has advantageous properties and contains 0.05 to 5 percent by weight of at least one corneocyte protein or corneocyte polypeptide having a relative molar mass ranging between 10 and 40 kDa.

Description

"Hair treatment agent with corneocyte proteins or polypeptides"

The invention relates to hair treatment compositions containing corneocyte proteins or proteins with comparable structures or polypeptides and the use of these agents for the cleaning and / or care of skin and hair.

The cosmetic treatment of skin and hair is an important part of human body care. For example, human hair is today treated in a variety of ways with hair cosmetic preparations. These include, for example, the cleansing of hair with shampoos, the care and regeneration with rinses and cures and the bleaching, dyeing and shaping of the hair with dyes, tinting agents, waving agents and styling preparations. In this case, means for changing or nuancing the color of the head hair play a prominent role. Apart from the bleaching agents that cause an oxidative lightening of the hair by degradation of the natural hair dyes, so in the field of hair coloring essentially three types of hair dye are of importance:

For permanent, intensive colorations with corresponding fastness properties, so-called oxidation colorants are used. Such colorants usually contain oxidation dye precursors, so-called developer components and coupler components. The developer components form the actual dyes under the influence of oxidizing agents or of atmospheric oxygen with one another or with coupling with one or more coupler components. The oxidation stains are characterized by excellent, long lasting staining results. For naturally acting dyeings, however, it is usually necessary to use a mixture of a larger number of oxidation dye precursors; In many cases, direct dyes are still used for shading. If the dyes formed or used directly in the course of color formation have significantly different fastnesses (eg UV stability, perspiration fastness, wash fastness, etc.), this may increase with time a noticeable and therefore undesirable color shift come. This phenomenon occurs more frequently when the hairstyle has hair or hair zones of different degrees of damage. An example of this is long hair, in which the hair tips exposed for a long time to all sorts of environmental influences are usually much more damaged than the relatively newly regrown hair zones.

For temporary dyeings usually dyeing or tinting agents are used which contain so-called direct drawers as a coloring component. These are dye molecules that grow directly on the hair and do not require an oxidative process to form the color. These dyes include, for example, the henna already known from antiquity for coloring body and hair. These dyeings are generally much more sensitive to shampooing than the oxidative dyeings, so that a much more undesirable nuance shift or even a visible "discoloration" occurs much more quickly.

Finally, recently, a novel dyeing process has received much attention. In this method, precursors of the natural hair dye melanin are applied to the hair; These then form naturally-analogous dyes in the course of oxidative processes in the hair. In such processes, for example, 5,6-dihydroxyindoline is used as the dye precursor. In particular, multiple use of agents with 5,6-dihydroxyindoline, it is possible to reproduce natural hair color to people with graying hair. The dyeing can be done with atmospheric oxygen as the sole oxidant, so that no further oxidizing agent must be used. In individuals with originally medium blond to brown hair, the indoline can be used as the sole dye precursor. On the other hand, satisfactory results can often only be achieved for use in persons with originally red and, in particular, dark to black hair color, by using other dye components, in particular special oxidation dye precursors.

Not least due to the heavy use of hair, for example by dyeing or perming, as well as by the cleaning of the hair with shampoos and by environmental pollution, the importance of care products with the longest possible effect increases. Such care products affect the natural structure and properties of the hair. So, after that, you can go to such treatments For example, the wet and dry combability of the hair, the hold and the fullness of the hair to be optimized or the hair to be protected from increased splitting.

It has therefore long been customary to subject the hair to a special aftertreatment. In this case, the hair is treated with special active ingredients, for example quaternary ammonium salts or special polymers, usually in the form of a rinse. Depending on the formulation, this treatment improves the combability, the hold and the fullness of the hair and reduces the splitting rate.

Furthermore, so-called combination preparations have recently been developed in order to reduce the expense of the usual multi-stage process, especially in the direct application by consumers.

These preparations contain, in addition to the usual components, for example for the cleaning of the hair, in addition to active ingredients which were formerly reserved for the hair aftertreatment agents. The consumer thus saves an application step; At the same time, packaging costs are reduced because one product is less needed.

The available active ingredients both for separate aftertreatment agents and for combination preparations generally have a preferential effect on the hair surface. Thus, active ingredients are known which give the hair shine, hold, fullness, better wet or dry combabilities or prevent splitting. Just as important as the external appearance of the hair, however, is the internal structural cohesion of the hair fibers, which can be greatly influenced, in particular, by oxidative and reductive processes such as dyeing and perming.

However, the known active ingredients can not cover all needs sufficiently. There is therefore still a need for active ingredients or combinations of active substances for cosmetic products with good care properties and good biodegradability. In particular in dye-containing and / or electrolyte-containing formulations, there is a need for additional skin-care active ingredients which can be incorporated without problems into known formulations.

It has now been found that particularly advantageous results can be achieved when one korneozyt proteins or polypeptides of molecular weight in Hair treatment center! incorporated.

A first object of the present invention are hair treatment compositions containing 0.05 to 5 wt .-% of at least one corneocyte protein or polypeptide having a molecular weight of 10 to 40 kDa.

According to the invention, the hair treatment compositions contain at least one Komeozyt- protein or polypeptide with a molecular weight of 10,000 to 40,000 daltons. In the context of the present invention, the term "Komeozyt protein or polypeptide" is understood as meaning a protein or polypeptide which, in addition to the hair, also occurs in the stratum corneum.

The stratum corneum (SC), also called the horny layer, forms the outer layer of the epidermis and serves primarily as a permeability barrier. This protective layer consists of 14 to 27 layers of tightly packed, platelet-like, coreless, keratin-rich and continuously chelating komeocytes (homocells). The thickness of the stratum corneum varies between 6 and 15 microns, where it is pronounced on the palm and sole much more pronounced than other parts of the body.

Fundamentally, the structure of the SC can be described as a two-compartment model: dedifferentiated, protein-containing cells are embedded in a matrix according to the brick-mortar principle, which can also be regarded as an interstitial lipid phase. The cells are responsible for the physical and chemical stability, while the intercellular, non-polar lipids as a putty substance prevent the penetration of water and dissolved substances, thus controlling water retention and water evaporation. Insoluble keratin, a hydratable and swellable substance, water and lipids are the main constituents of the horny layer. Of these, keratin and lipids are found in the intracellular space. Keratin accounts for approximately 80% of the total mass of the komeocytes. The dense packing of the components in the cell results in high stability, strength and elasticity. The cell interior is additionally surrounded by a cornified envelope, loricrin, small proline-rich proteins, filaggrin, elafin, involucrin and cystatin, and in the intercellular space are ceramides (sphingolipids), fatty acids and cholesterol in equimolar proportions Concentrations include cholesterol esters, triglycerides, glycosphingolipids and cholesterol sulfate in the Cell spaces available. The presence of the lipids in the appropriate composition and their specific structural organization may be considered essential for the expression of an intact barrier function (eg, protection against water loss).

Preferred corneocyte proteins or polypeptides are in particular loricrin and involucrin. In addition, cornifin, trichohyalin, scielline, profilggrin and keratolinin are also preferred, so that preferred hair treatment compositions according to the invention are characterized in that the corneocyte protein (s) or polypeptide (s) is / are selected from the group Involucrin, Loricrin , Cornifin, trichohyalin, scielline, profilaggrin and keratolinine.

According to the invention, corneocyte proteins or polypeptides of a certain molecular mass range are used. Proteins of corresponding molar masses can be obtained by known methods from the stratum corneum, polypeptides having the corresponding molar masses can be obtained, for example, by decomposition of higher molecular weight proteins or polypeptides.

Hair treatment compositions which are preferred according to the invention are characterized in that the corneocyte protein or polypeptide has a molar mass of from 12.5 to 37.5 kDa, preferably from 15 to 35 kDa and in particular from 20 to 30 kDa.

Corneocyte proteins or polypeptides, which can preferably be used according to the invention, comprising - as already mentioned - involucrin, loricrin, cornifin, trichohyalin, scielline, profilaggrin and keratolinin and / or polypeptide fragments of these proteins. The proteins or polypeptides may be derived from natural sources or produced recombinantly. The proteins or polypeptides may optionally be branched, e.g. by a chemical branching agent or by an enzyme which forms bonds between adjacent polypeptides.

The proteins or polypeptides can be modified if desired. Such modifications include, for example, chemical derivatization of one or more amino acids or modification of the amino acid sequence of the protein or polypeptide. These modifications can be used to identify the proteins or polypeptides to impart certain properties, such as higher water solubility, greater stability against exposure to chemicals, atmospheric or enzymatic influences, etc ..

Depending on the molecular weight of the amino acids contained in the corneocyte proteins or polypeptides, these proteins or polypeptides may contain from a few hundred to a thousand amino acids. Preferred hair treatment agents according to the invention are characterized in that the komeocyte protein or polypeptide comprises 200 to 500 amino acids, preferably 250 to 450 amino acids, more preferably 275 to 400 amino acids and in particular 300 to 350 amino acids.

With particular preference, the corneocyte proteins or polypeptides contained in the hair treatment compositions according to the invention contain the amino acid glycine. Particularly preferred is a content of the protein or polypeptide of glycine of 1 to 40%, preferably from 1, 5 to 35% and in particular from 2 to 30% glycine. In the context of the present invention, the term "1% glycine" means that of 100 amino acids contained in the protein or polypeptide molecule, one amino acid is glycine, analogously, the term "30% glycine" in the context of the present invention means that of 100 amino acids contained in the protein or polypeptide molecule are 30 amino acids glycine.

A content of the corneocyte proteins or polypeptides contained in the hair treatment compositions according to the invention at the amino acid serine is also preferred. Particularly preferred is a content of the protein or polypeptide on serine of 1 to 30%, preferably from 1.5 to 25% and in particular from 2 to 20% serine.

In further preferred hair treatment compositions according to the invention, the corneocyte proteins and comparable prostines or polypeptides have the amino acid sequence "glycine-serine." Particularly preferred are proteins or polypeptides which are rich in this amino acid sequence / the Komeozyt- protein (s) or - polypeptide (s) having the amino acid sequence glycine-serine, wherein preferred proteins are characterized in that the amino acids in the amino acid sequence glycine-serine bound at least 5%, preferably at least 10% and in particular at least 15 % of all contained in the protein or polypeptide Make up amino acids. In other words, in the protein, the amino acid sequence "glycine-serine" per 200 amino acids is contained at least five times (5%), preferably at least 10 times (10%) and especially at least 15 times (15%).

Also, a content of Komeozyt proteins or polypeptides contained in the hair treatment compositions according to the invention at the amino acid cysteine is preferred. Particularly preferred is a content of the protein or polypeptide to cysteine of 1 to 20%, preferably from 1.5 to 15% and in particular from 2 to 10% cysteine.

In further preferred hair treatment compositions according to the invention, the corneocyte protein or polypeptide has the amino acid sequence "glycine-serine-cysteine." Particular preference is given to proteins or polypeptides which are rich in this amino acid sequence. the corneocyte protein (s) or polypeptide (s) have the amino acid sequence glycine-serine-cysteine, preferred proteins being characterized in that the amino acids linked in the amino acid sequence glycine-serine cysteine at least 5%, preferably at least 10% and In particular, in the protein, the amino acid sequence "glycine-serine-cysteine" per 300 amino acids is at least five times (5%), preferably at least 10 times (10%) and especially at least 15 times (15%) included.

The agents according to the invention may contain further active ingredients and adjuvants. These are described below.

The use of surfactants (E) in the compositions according to the invention has proved to be particularly advantageous. In a further preferred embodiment, the agents according to the invention therefore contain surfactants. The term "surfactants" is understood as meaning surface-active substances which form adsorption layers on the upper and boundary surfaces or which can aggregate in volume phases to give micelle colloids or lyotropic mesophases. A distinction is made between anionic surfactants consisting of a hydrophobic radical and a negatively charged hydrophilic head group, amphoteric surfactants which carry both a negative and a compensating positive charge, cationic surfactants which, in addition to a hydrophobic radical, have a positively charged hydrophilic group, and nonionic Surfactants which have no charges but strong dipole moments and are highly hydrated in aqueous solution.

Suitable anionic surfactants (E1) in preparations according to the invention are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such as. As a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present 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 having 2 to 4 C atoms in the alkanol group,

- linear and branched fatty acids having 8 to 30 C 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 having 8 to 30 C atoms and x = 0 or 1 to 16,

Acylsarcosides having 8 to 24 C atoms in the acyl group,

Acyltaurides having 8 to 24 carbon atoms in the acyl group,

Acyl isethionates having 8 to 24 C atoms in the acyl group,

Sulfosuccinic acid mono- and dialkyl esters having 8 to 24 C atoms in the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl esters having 8 to 24 C atoms in the alkyl group and 1 to 6 oxyethyl groups,

linear alkanesulfonates having 8 to 24 carbon atoms, linear alpha-olefin sulfonates having 8 to 24 carbon atoms,

Alpha-sulfofatty acid methyl esters of fatty acids having 8 to 30 C 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 having 8 to 30 C atoms and x = 0 or 1 to 12,

- Sulfated Hydroxyalkylpolyethylen- and / or Hydroxyalkylenpropylenglykolether

- Sulfonates of unsaturated fatty acids having 8 to 24 carbon atoms and 1 to 6 double bonds

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 containing 8 to 22 carbon atoms,

Alkyl and / or alkenyl ether phosphates of the formula (E 1-1), R ¹ (OCH ₂ CH ₂ ) _n -OP (O) (OX) -OR ² (E1-l)

in the 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 ² or X, n is from 1 to 10 and X is hydrogen, an alkali metal radical or alkaline earth metal or NR ³ R ⁴ R ⁵ R ⁶ , where R ³ to R ⁶ independently of one another represent hydrogen or a C ₁ to C ₄ hydrocarbon radical, is a sulfated fatty acid alkylene glycol ester of the formula (E1-II) R ⁷ CO (AlkO) _n SO ₃ M (EI-II) in the R ⁷ CO- for a linear or branched, aliphatic, saturated and / or unsaturated acyl radical having 6 to 22 C atoms, Alk for CH ₂ CH ₂ , CHCH ₃ CH ₂ and / or CH ₂ CHCH ₃ , n is from 0.5 to 5 and M is a cation, monoglyceride sulfates and monoglyceride ether sulfates of the formula (E1-III)

CH ₂ O (CH ₂ CH ₂ O) _x -COR ⁸

I

CHO (CH ₂ CH ₂ O) _y H (E1-III)

I CH ₂ O (CH ₂ CH ₂ O) ₂ SO ₃ X

in which R ⁸ CO is a linear or branched acyl radical having 6 to 22 carbon atoms, x, y and z in total for O 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 and their ethylene oxide adducts with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. Monoglyceride sulfates of the formula (E1-III) in which R ⁸ CO is a linear acyl radical having 8 to 18 carbon atoms are preferably used,

amide ether carboxylic acids,

Condensation products of C ₈ - C ₃₀ - fatty alcohols with protein hydrolysates and / or amino acids and their Derivaten.welche are known to the skilled person as protein fatty acid condensates, such as Lamepon ^® - types Gluadin ^® - types Hostapon ^® KCG or Amisoft ^® - types. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 C atoms in the alkyl group and up to 12 glycol ether groups in the molecule, sulfosuccinic acid mono- and dialkyl esters having 8 to 18 C atoms in the alkyl group and sulfosuccinic acid monoalkylpolyoxyethylester with 8 to 18 C atoms in the alkyl group and 1 to 6 oxyethyl groups, Monoglycerdisulfate, alkyl and Alkenyletherphosphate and protein fatty acid condensates.

Zwitterionic surfactants (E2) are those surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^W or -SO ₃ ^ group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyl dimethylammonium glycinate, N-acylaminopropyl N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and Alkyl-3-carboxymethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxymethylglycinat. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Ampholytic surfactants (E3) are understood as meaning those surface-active compounds which contain, in addition to a C ₈ -C ₂₄ -alkyl or -acyl group, at least one free amino group and at least one -COOH or -SO ₃ H group in the molecule and for forming internal Salts are capable. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-Aikylaminobuttersäuren, N-Alkyliminodipropionsäuren, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-Alkylaminopropionsäuren and Alkylaminoessigsäuren each having about 8 to 24 C. Atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C 12 -C ₁₈ -acylsarcosine.

Nonionic surfactants (E4) contain, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups as the hydrophilic group. Such compounds are, for example Addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group, with a methyl or C ₂ - C ₆ - alkyl radical end-capped addition products of 2 to 50 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear and branched fatty alcohols having 8 to 30 carbon atoms, to fatty acids having 8 to 30 C-atoms and to alkylphenols containing 8 to 15 carbon atoms in the alkyl group, such as the type available under the commercial names Dehydol ^® LS, Dehydol ^® LT (Cognis),

C ₂ -C ₃₀ -fatty acid mono- and diesters of addition products of 1 to 30 mol of ethylene oxide with glycerol,

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

Polyol fatty acid esters, such as the commercially available product ^® Hydagen HSP (Cognis) or Sovermol - types (Cognis), alkoxylated triglycerides, alkoxylated fatty acid alkyl esters of formula (E4-I)

R ¹ CO- (OCH ₂ CHR ² ) _W OR ³ (E4-I)

in the R ¹ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or methyl, R ^{3 is a} linear or branched alkyl radical having 1 to 4 carbon atoms and w is a number from 1 to 20 stands, amine oxides, hydroxy mixed ethers,

Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,

Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters,

Addition products of ethylene oxide onto fatty acid alkanolamides and fatty amines, sugar surfactants of the alkyl and alkenyl oligoglycoside type according to formula (E4-II),

R ⁴ O- [G] _P (E4-II) in which R ^{4 is} an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry.

The alkyl and alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (E4-II) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in the individual molecule must always be an integer, and Here, especially the values p = 1 to 6 can assume, the value p for a certain alkyloligoglycoside is an analytically determined arithmetical variable, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred. The alkyl or alkenyl radical R ⁴ can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. Preference is given to alkyl oligoglucosides of the chain length C ₈ -C ₁₀ (DP = 1 to 3), which are obtained as a feedstock in the distillative separation of technical C ₈ -C ₁₈ coconut fatty alcohol and having a fraction of less than 6% by weight C 1 - Alcohol can be contaminated and alkyl oligoglucosides based on technical Cg _/ n-oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹⁵ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and technical mixtures thereof which can be obtained as described above. Alkyl oligoglucosides based on hydrogenated _{C12 /} i ₄ coconut alcohol with a DP of 1 to 3 Sugar surfactants of the fatty acid N-alkyl polyhydroxyalkylamide type, a nonionic surfactant of the formula (E4-III),

R ⁵ CO-NR ⁶ - [Z] (E4-III)

in which R ^{5 is} CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{6 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Zj is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups , The fatty acid N-alkylpolyhydroxyalkylamides are known substances which are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. Preferably, the fatty acid N-alkylpolyhydroxyalkylamides are derived from reducing sugars having 5 or 6 carbon atoms, especially glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (E4-IV):

R ⁷ CO-NR ⁸ -CH ₂ - (CHOH) ₄ -CH ₂ OH (E4-IV)

The fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (E4-IV) in which R ^{8 is} hydrogen or an alkyl group and R ^{7 is} CO for the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitic acid, Stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Particular preference is given to fatty acid N-alkylglucamides of the formula (E4-IV) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C 12/14 coconut fatty acid or a corresponding derivative. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.

The preferred nonionic surfactants are the alkylene oxide addition products of saturated linear fatty alcohols and fatty acids having in each case 2 to 30 moles of ethylene oxide per mole of fatty alcohol or fatty acid. Preparations with excellent properties Shafts are also obtained when they contain fatty acid esters of ethoxylated glycerol as nonionic surfactants.

These connections are identified by the following parameters. The alkyl radical R contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When using so-called "oxo-alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

Furthermore, very particularly preferred nonionic surfactants are the sugar surfactants. These may preferably be present in the agents used according to the invention in amounts of from 0.1 to 20% by weight, based on the total agent. Amounts of 0.5-15% by weight are preferred, and most preferred are amounts of 0.5-7.5% by weight.

The compounds with alkyl groups used as surfactant can each be uniform substances. However, it is usually preferred to start from the production of these substances from native plant or animal raw materials, so as to obtain substance mixtures with different, depending on the particular raw material alkyl chain lengths.

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. By "normal" homolog distribution are meant mixtures of homologs which are obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions, on the other hand, are obtained when, 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 narrow homolog distribution may be preferred. Cationic surfactants of the quaternary ammonium compound type, the esterquats and the amidoamines can 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. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as 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.

According to the invention, preference is given to using QAV with behenyl radicals, in particular those known as behentrimonium chloride or bromide

(Docosanyltrimethylammonium chloride or bromide) known substances. Other preferred QAV's have at least two behenyl residues, with QAV being particularly preferred, which are two behenyl residues on an imidazolinium backbone. Commercially available, these substances are, for example, under the names Genamin ^® KDMP (Clariant) and Crodazosoft ^® DBQ (Crodauza).

Esterquats 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 marketed under the trade names Stepantex® ^{®, ®} and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-Palmitoyloxy- ethyl) dimethyl ammonium 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 prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group of substances that available under the name Tegoamid ^® S 18 commercially stearamidopropyldimethylamine is dimethylamine. The cationic surfactants are contained in the agents according to the invention preferably in amounts of 0.05 to 10 wt .-%, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred. "Based on the total agent" means in the context of the present invention "based on the mixture of the preparation of oxidation dye precursors (A) and the Oxidationsmittei preparation (B).

The surfactants (E) are used in amounts of 0.1-45% by weight, preferably 0.5-30% by weight and very particularly preferably 0.5-25% by weight, based on the total agent used according to the invention ,

Anionic, nonionic, zwitterionic and / or amphoteric surfactants and mixtures thereof may be preferred according to the invention.

In summary, hair-treatment compositions according to the invention are preferred which, based on their weight, contain from 0.5 to 70% by weight, preferably from 1 to 60% by weight and in particular from 5 to 25% by weight of anionic and / or nonionic (cf. ), and / or cationic and / or amphoteric surfactant (s).

Another preferred group of ingredients of the hair treatment compositions according to the invention are vitamins, provitamins or vitamin precursors. These are described below:

The group of substances called vitamin A includes retinol (vitamin A ₁ ) and 3,4-didehydroretinol (vitamin A ₂ ). The ß-carotene is the provitamin of retinol. As vitamin A component according to the invention, for example, vitamin A acid and its esters, vitamin A aldehyde and vitamin A alcohol and its esters such as the palmitate and the acetate into consideration. The agents according to the invention preferably contain the vitamin A component in amounts of 0.05-1% by weight, based on the total preparation.

The vitamin B group or the vitamin B complex include u. a.

- Vitamin B ₁ (thiamine)

- Vitamin B ₂ (riboflavin) - Vitamin B ₃ . Under this name, the compounds nicotinic acid and nicotinamide (niacinamide) are often performed. Preferred according to the invention is the nicotinic acid amide, which is preferably contained in the agents according to the invention in amounts of from 0.05 to 1% by weight, based on the total agent. .

- Vitamin B ₅ (pantothenic acid, panthenol and pantolactone). Panthenol and / or pantolactone are preferably used in the context of this group. Derivatives of panthenol which can be used according to the invention are, in particular, the esters and ethers of panthenol and also cationically derivatized panthenols. Individual representatives are, for example, the panthenol triacetate, the panthenol monoethyl ether and its monoacetate and also the cationic panthenol derivatives disclosed in WO 92/13829. The said compounds of the vitamin B ₅ type are preferably contained in the agents according to the invention in amounts of 0.05-10% by weight, based on the total agent. Amounts of 0.1-5 wt .-% are particularly preferred.

- Vitamin B ₆ (pyridoxine and pyridoxamine and pyridoxal).

Vitamin C (ascorbic acid). Vitamin C is used in the agents according to the invention preferably in amounts of 0.1 to 3 wt .-%, based on the total agent. Use in the form of palmitic acid ester, glucosides or phosphates may be preferred. The use in combination with tocopherols may also be preferred.

Vitamin E (tocopherols, especially α-tocopherol). Tocopherol and its derivatives, which include in particular the esters such as the acetate, the nicotinate, the phosphate and the succinate, are preferably present in the agents according to the invention in amounts of 0.05-1% by weight, based on the total agent.

Vitamin F. The term "vitamin F" is usually understood as meaning essential fatty acids, in particular linoleic acid, linolenic acid and arachidonic acid.

Vitamin H. Vitamin H is the compound (3aS, 4S, 6aft) -2-oxohexahydrothienp [3,4-c (] - imidazole-4-valeric acid, for which, however, the trivial name biotin has become established the agents according to the invention preferably in amounts of 0.0001 to 1, 0 wt .-%, in particular in amounts of 0.001 to 0.01% by weight. In summary, hair treatment compositions according to the invention are preferred which contain vitamins, pro-vitamins and vitamin precursors, which are assigned to the groups A, B, C, E, F and H, preferred compositions of said compounds in amounts of from 0.1 to 5 wt. -%, preferably from 0.25 to 4% by weight and in particular from 0.5 to 2.5 wt .-%, each based on the total agent included.

Hair treatment agents which are particularly preferred according to the invention additionally contain silicone (e). Here, particularly preferred hair treatment compositions according to the invention are characterized in that they additionally silicone (s), preferably in amounts of 0.1 to 10 wt .-%, preferably from 0.25 to 7 wt .-% and in particular from 0.5 to 5 Wt .-%, each based on the total agent included.

Particularly preferred hair treatment compositions according to the invention which contain at least one silicone selected from:

(i) polyalkyl siloxanes, polyaryl siloxanes, polyalkylaryl siloxanes which are volatile or nonvolatile, straight chain, branched or cyclic, crosslinked or uncrosslinked;

(ii) polysiloxanes containing in their general structure one or more organofunctional groups selected from: a) substituted or unsubstituted aminated groups; b) (perforated groups; c) thiol groups; d) carboxylate groups; e) hydroxylated groups; T) alkoxylated groups; g) acyloxyalkyl groups; h) amphoteric groups; i) bisulfite groups; j) hydroxyacylamino groups; k) carboxy groups;

I) sulfonic acid groups; and m) sulfate or thiosulfate groups; (iii) linear polysiloxane (A) - polyoxyalkylene (B) - block copolymers of the type (A-B) _n with n>3;

(iv) grafted silicone polymers having a non-silicone organic backbone consisting of an organic backbone formed from organic monomers containing no silicone to which at least one polysiloxane macromer has been grafted in the chain and optionally at least one chain end;

(v) grafted polysiloxane backbone silicone polymers to which have been grafted non-silicone organic monomers having a polysiloxane backbone onto which at least one organic macromer not containing silicone has been grafted in the chain, and optionally at least at one of its ends ;

(vi) or mixtures thereof.

Particularly preferred hair treatment compositions according to the invention are characterized in that they contain at least one silicone of the formula I.

(CH ₃ ) ₃ Si - [O-Si (CH ₃ ) 2] _x -O-Si (CH ₃ ) 3 (I), in which x is a number from 0 to 100, preferably from 0 to 50, more preferred from 0 to 20 and especially 0 to 10.

The hair treatment agents preferred according to the invention comprise a silicone of the above formula I. These silicones are designated according to the INCI nomenclature as DIMETHICONE. In the context of the present invention, as the silicone of the formula I, the compounds are preferably:

(CH ₃ ) ₃ Si-O- (CH ₃ ) ₂ Si-O-Si (CH ₃ ) 3

(CH ₃ ) ₃ SHO- (CH ₃ ) ₂ Si] ₂ -O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si - [O- (CH ₃ ) ₂ Si] ₃ -O-Si (CH ₃ ) 3

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₄ -O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₅ -O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₆ -O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₇ -O-Si (CH ₃ ) ₃ (CH ₃ ) ₃ Si - [O- (CH ₃ ) ₂ Si] ₈ -O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si - [O - (CH ₃ ) ₂ Si] _g - O - Si (CH ₃ ) 3

(CH3) 3 Si- [O- (CH _{3) 2} Si] ₁₀ -O-Si (CH3) 3

(CH ₃ ) ₃ Si - [O- (CH ₃ ) ₂ Si] ₁₁ -O-Si (CH ₃ ) 3

(CH _{3) 3} Si- [O- (CH _{3) 2} Si] _t2 -O-Si (CH _{3) 3}

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₃ -O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₄ -O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₅ -O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₆ -O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₇ -O-Si (CH ₃ ) ₃

(CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₁₈ -O-Si (CH ₃ ) 3

(CH _{3) 3} Si- [O- (CH _{3) 2} Si] _1g -O-Si (CH ₃₎ 3

(CH ₃ ) ₃ Si [0- (CH ₃ ) ₂ Si] ₂ o-0-Si (CH ₃ ) ₃

where (CH ₃ ) ₃ Si-O-Si (CH ₃ ) ₃ , (CH ₃ ) ₃ Si-O- (CH ₃ ) ₂ Si-O-Si (CH ₃ ) ₃ and / or (CH ₃ ) ₃ Si [O- (CH ₃ ) ₂ Si] ₂ -O-Si (CH ₃ ) 3 are particularly preferred.

Of course, mixtures of o.g. Silicones may be included in the compositions of the invention.

Preferred silicones which can be used according to the invention have viscosities of from 0.2 to 2 mm ² s ^-1 at 20 ^° C., with silicones having viscosities of from 0.5 to 1 mm ^{2 being} particularly preferred.

Particularly preferred agents according to the invention contain one or more amino-functional silicones. Such silicones may e.g. through the formula

M (RaQbSiO ₍ 4.ab) / ₂ ) x (RcS10 ₍ 4-c) / ₂ ) yM

Will be described, wherein in the above formula R is a hydrocarbon or a hydrocarbon radical having from 1 to about 6 carbon atoms, Q is a polar radical of the general formula -R ¹ HZ, wherein R ^{1 is} a divalent connecting group attached to hydrogen and the Z is an organic, amino-functional radical is bound, composed of carbon and hydrogen atoms, carbon, hydrogen and oxygen atoms or carbon, hydrogen and nitrogen atoms, and Z is an organic, amino-functional radical, which contains at least one amino-functional group; "a" assumes values in the range of about 0 to about 2, "b" assumes values in the range of about 1 to about 3, "a" + "b" is less than or equal to 3, and "c" is a number in the range from about 1 to about 3, and x is a number ranging from 1 to about 2,000, preferably from about 3 to about 50, and most preferably from about 3 to about 25, and y is a number ranging from about 20 to about 10,000, preferably from about 125 to about 10,000, and most preferably from about 150 to about 1,000, and M is a suitable silicone end group as known in the art, preferably trimethylsiloxy. Non-limiting examples of the groups represented by R include alkyl groups such as methyl, ethyl, propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, isohexyl and the like; Alkenyl radicals such as vinyl, halovinyl, alkylvinyl, allyl, haloallyl, alkylallyl; Cycloalkyl radicals such as cyclobutyl, cyclopentyl, cyclohexyl and the like; Phenyl radicals, benzyl radicals, halohydrocarbon radicals such as 3-chloropropyl, 4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl, chlorophenyl and the like, and sulfur containing radicals such as mercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and the like; preferably R is an alkyl radical containing from 1 to about 6 carbon atoms, and most preferably R is methyl. Examples of R ¹ include methylene, ethylene, propylene, hexamethylene, decamethylene, CH ₂ CH (CH ₃ ) CH ₂ -, phenylene, naphthylene, -CH ₂ CH ₂ SCH ₂ CH ₂ -, -CH ₂ CH ₂ OCH ₂ -, - OCH ₂ CH ₂ -, -OCH ₂ CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) C (O) OCH ₂ -, - (CH ₂ ) ₃ CC (O) OCH ₂ CH ₂ -, -C ₆ H ₄ C ₆ H ₄ -, -C ₆ H ₄ CH ₂ C ₆ H ₄ -; and - (CH ₂ J ₃ C (O) SCH ₂ CH ₂ -.

Z is an organic, amino-functional radical containing at least one functional amino group. A possible formula for Z is NH (CH ₂ ) _Z NH ₂ , wherein z is 1 or more. Another possible formula for Z is -NH (CH ₂ ) _Z (CH ₂ ) zzNH, wherein both z and zz are independently 1 or more, this structure comprising diamino ring structures, such as piperazinyl. Z is most preferably a -NHCH ₂ CH ₂ NH ₂ radical. Another possible formula for Z is - N (CH ₂ J ₂ (CH ₂ ) _ZZ NX ₂ or -NX ₂ , wherein each X of X _{2 is} independently selected from the group consisting of hydrogen and alkyl groups of 1 to 12 carbon atoms, and zz is 0.

Q is most preferably a polar, amine functional group of the formula - CH ₂ CH ₂ CH ₂ NH ₂ CH ₂ CH ₂ NH ₂ . In the formulas, "a" assumes values in the range of about 0 to about 2, "b" assumes values in the range of about 2 to about 3, "a" + "b" is less than or equal to 3, and "c "is a number in the range of about 1 to about 3. The molar Ratio of the R ₃ Q _b SiO ₍₄ _a- _{b ) / 2} units to the R _c Si0 _(4-c) / ₂ units is in the range of about 1: 2 to 1:65, preferably about 1: 5 to about 1:65, and most preferably from about 1:15 to about 1:20. When one or more silicones of the above formula are employed, then the various variable substituents in the above formula may be for the various silicone components present in the silicone blend , to be different.

Preferred hair treatment compositions according to the invention are characterized in that they contain an amino-functional silicone of the formula (II)

RV ₃ G _3-8 -Si (OSiG ₂ ) _n - (OSiG _b R ' _{2- b} ) _m -O-SiG ₃ . _a -R _'a (II),

contain, in which means:

G is -H, a phenyl group, -OH, -O-CH ₃ , -CH ₃ , -O-CH ₂ CH ₃ , -CH ₂ CH ₃ , -O-

CH ₂ CH ₂ CH ₃₁ -CH ₂ CH ₂ CH ₃ , -O-CH (CH ₃ ) ₂ , -CH (CH ₃ ) ₂ , -O-CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₂ CH ₃ , -O-CH ₂ CH (CHs) ₂ , -CH ₂ CH (CH ₃ ) ₂ , -O-CH (CH ₃ ) CH ₂ CH ₃ , -CH (CH ₃ ) CH ₂ CH ₃ , - OC (CH ₃ ) ₃ , -C (CH ₃ ) ₃ ;

a is a number between O and 3, in particular O;

b is a number between 0 and 1, in particular 1,

m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n is preferably values from 0 to 1999 and in particular from 49 to 149 and m preferably values from 1 to 2000, in particular from 1 to 10,

R 'is a monovalent radical selected from O -QN (R ") - CH ₂ -CH ₂ -N (R ⁿ ) ₂ o -QN (R") ₂ O -QN ⁺ (R ¹¹ J ₃ A- o -QN ⁺ H (R ") ₂ A- o -QN ⁺ H ₂ (R") A- o -QN (R ") - CH ₂ -CH ₂ -N ⁺ RΗ ₂ A-, where each Q is a chemical bond, -CH ₂ -, -CH ₂ -CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -C (CH ₃ ) ₂ -, - CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ C (CHs) ₂ -, -CH (CH ₃ ) CH ₂ CH ₂ -,

R "is identical or different radicals from the group -H, -phenyl, -benzyl, -CH ₂ - CH (CH ₃ ) Ph, the C _1-2 o-alkyl radicals, preferably -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ H ₃ , -CH ₂ CH (CHa) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ , and A is an anion which is preferably selected from chloride, bromide, iodide or methosulfate.

Particularly preferred hair treatment compositions according to the invention are characterized in that they contain at least one amino-functional silicone of the formula (IIa)

(CH ₃ ) ₃ Si- [O-Si (CH ₃ ) ₂ ] π [OSi (CH 3)] _m -OSi (CH 3) 3 (IIa),

I CH ₂ CH (CH ₃ ) CH ₂ NH (CH ₂ ) ₂ NH ₂

in which m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n preferably values of 0 to 1999 and in particular of 49 to 149 and m preferably values of 1 to 2000 , in particular from 1 to 10 assumes.

These silicones are referred to as trimethylsilylamodimethicones according to the INCI declaration.

Also particularly preferred are hair treatment compositions according to the invention which contain at least one amino-functional silicone of the formula (IIb)

R- [Si (CH3) ₂ -O] _n1 tSi (R) -O] _m - [Si (CH ₃₎ 2] _n2 -R (IIb),

I (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH ₂

in which R is -OH, -O-CH ₃ or a ~CH ₃ group and m, n1 and n2 are numbers whose sum (m + n1 + n2) is between 1 and 2,000, preferably between 50 and 150 , where the sum (n1 + n2) preferably assumes values from 0 to 1999 and in particular from 49 to 149 and m preferably values from 1 to 2000, in particular from 1 to 10.

These silicones are referred to as amodimethicones according to the INCI declaration.

Regardless of which amino-functional silicones are used, preference is given to hair-treatment compositions according to the invention which are an amino-functional silicone contain the amine number above 0.25 meq / g, preferably above 0.3 meq / g and in particular above 0.4 meq / g. The amine number stands for the milliequivalents of amine per gram of amino-functional silicone. It can be determined by titration and also expressed in mg KOH / g.

Hair treatment compositions which are preferred according to the invention are characterized in that, based on their weight, they contain 0.01 to 10% by weight, preferably 0.1 to 8% by weight, particularly preferably 0.25 to 7.5% by weight and in particular 0, 5 to 5 wt.% Amino-functional silicone (s) included.

The INCI CYCLOMETHICONE designated cyclic dimethicones are inventively used with preference. Here, hair treatment compositions according to the invention are preferred, the at least one silicone of the formula III

J-ΓO-SHCHIW _* - (Hl)

in which x is a number from 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and in particular 0, 1, 2, 3, 4, 5 or 6 stands.

The silicones described above have a backbone composed of -Si-O-Si units. Of course, these Si-O-Si units may also be interrupted by carbon chains. Appropriate molecules are accessible by chain extension reactions and are preferably used in the form of silicone-in-water emulsions.

The silicone-in-water emulsions which can be used according to the invention can be prepared by known processes, as disclosed, for example, in US Pat. No. 5,998,537 and EP 0 874 017 A1.

In summary, this preparation process comprises the emulsifying mixture of components, one of which contains at least one polysiloxane, the other of which contains at least one organosilicone material which reacts with the polysiloxane in a chain extension reaction, wherein at least one metal ion-containing Catalyst for the chain extension reaction, at least one surfactant and water are present.

Chain extension reactions with polysiloxanes are known and may include, for example, the hydrosilylation reaction in which an Si-H group having an aliphatically unsaturated group in the presence of a platinum / rhodium catalyst to form polysiloxanes having some Si (C) _P- Si bonds (p = 1-6), the polysiloxanes also being referred to as polysiloxanes-polysilalkylenes copolymers.

The chain extension reaction may also include the reaction of an Si-OH group (e.g., a hydroxy-terminated polysiloxane) with an alkoxy group (e.g., alkoxysilanes, silicates, or alkoxysiloxanes) in the presence of a metal-containing catalyst to form polysiloxanes.

The polysiloxanes used in the chain extension reaction include a ss-linear polymer of the following structure:

R-Si (R ₂ MO-Si (R ₂ H _n -O-SiR ₃

In this structure, each R independently represents a hydrocarbon radical having up to 20 carbon atoms, preferably having 1 to 6 carbon atoms, such as an alkyl group (for example, methyl, ethyl, propyl or butyl), an aryl group (for example, phenyl), or group required for the chain extension reaction ("reactive group", for example Si-bonded H atoms, aliphatically unsaturated groups such as vinyl, allyl or hexenyl, hydroxy, alkoxy, such as methoxy, ethoxy or propoxy, alkoxy-alkoxy, acetoxy, amino, etc.), with the proviso that on average one to two reactive groups are present per polymer, n is a positive number> 1. Preferably, a plurality of the reactive groups, more preferably> 90%, and especially> 98% of the reactive groups, on the terminal Si -Atomen bound in siloxane. Preferably, n is numbers describing polysiloxanes having viscosities between 1 and 1,000,000 mm ² / s, more preferably viscosities between 1,000 and 100,000 mm ² / s.

The polysiloxanes may be branched to a low degree (for example, <2 mol% of the siloxane units), but the polymers are substantially linear, especially preferably completely linear. In addition, the substituents R may in turn be substituted, for example with N-containing groups (for example amino groups), epoxy groups, S-containing groups, Si-containing groups, O-containing groups, etc. Preferably, at least 80% of the radicals R are alkyl radicals, especially preferably methyl groups.

The organosilicone material that reacts with the polysiloxane in the chain extension reaction may be either a second polysiloxane or a molecule that acts as a chain extender. When the organosilicone material is a polysiloxane, it has the above-mentioned general structure. In these cases, one polysiloxane in the reaction has (at least) one reactive group, and a second polysiloxane has (at least) a second reactive group that reacts with the first.

If the organosilicone material comprises a chain-extending agent, it may be a material such as a silane, a siloxane (e.g. disiloxane or trisiloxane) or a silazane. For example, a composition comprising a polysiloxane according to the above-described general structure having at least one Si-OH group can be chain extended by reacting with an alkoxysilane (for example, a dialkoxysilane or trialkoxysilane) in the presence of tin or titanium-containing catalysts is reacted.

The metal-containing catalysts in the chain extension reaction are usually specific for a particular reaction. Such catalysts are known in the art and include, for example, metals such as platinum, rhodium, tin, titanium, copper, lead, etc. In a preferred chain extension reaction, a polysiloxane having at least one aliphatically unsaturated group, preferably an end group, is reacted with an organosilicone material Presence of a hydrosysylation catalyst which is a siloxane or polysiloxane having at least one (preferably terminal) Si-H group. The polysiloxane has at least one aliphatically unsaturated group and satisfies the general formula given above in which R and n are as defined above, with an average of between 1 and 2 groups R having one aliphatic unsaturated group per polymer. Representative aliphatic unsaturated groups are, for example, vinyl, allyl, hexenyl and cyclohexenyl or a group R ² CH = CHR ³ in which R ^{2 is} a divalent aliphatic silicon-bonded chain and R ^{3 is} a hydrogen atom or an alkyl group. The organosilicone material having at least one Si-H group preferably has the above called structure in which R and n are as defined above and wherein on average between 1 and 2 groups R is a hydrogen and n is 0 or a positive integer

This material may be a polymer or a low molecular weight material such as a siloxane (for example, a disiloxane or a trisiloxane).

The polysiloxane having at least one aliphatic unsaturated group and the organosilicone material having at least one Si-H group react in the presence of a hydrosilylation catalyst. Such catalysts are known in the art and include, for example, platinum and rhodium-containing materials. The catalysts may take any known form, for example platinum or rhodium supported on support materials (such as silica gel or activated carbon) or other suitable compounds such as platinum chloride, salts of platinum or chloroplatinic acids. Chloroplatinic acid, either as a commercially available hexahydrate or in anhydrous form, is a preferred catalyst because of its good dispersibility in organosilicone systems and low color changes.

In a further preferred chain extension reaction, a polysiloxane having at least one Si-OH group, preferably an end group, is reacted with an organosilicone material having at least one alkoxy group, preferably a siloxane having at least one Si-OR group or an alkoxysilane having at least two alkoxy groups , In this case, the catalyst used is again a metal-containing catalyst.

For the reaction of an Si-OH group with an Si-OR group, there are many catalysts known from the literature, for example organometallic compounds such as organotin salts, titanates or titanium chelates or complexes. Examples include tin octoate, dibutyltin dilaurate, dibutyltin diacetate, dimethyltin dineodecanoate, dibutyltin dimethoxide, isobutyltin triceroate, dimethyltin dibutyrate, dimethyltin dineodecanoate, triethyltin tartrate, tin oleate, tin naphthenate, tin butyrate, tin acetate, tin benzoate, tin sebacate, Tin succinate, tetrabutyl titanate, tetraisopropyl titanate, tetraphenyltitant, tetraoctadecyl titanate, titanium naphthanate, ethyltriethanolamine titanate, titanium diisopropyl diethyl acetoacetate, titanium diisopropoxy diacetyl acetonate, and titanitetra alkoxides in which the alkoxide is butoxy or propoxy. In addition, the silicone-in-water emulsions preferably contain at least one surfactant. These have been described in detail above.

Hair treatment compositions which are likewise preferred according to the invention are characterized in that they contain at least one silicone of the formula IV

RaSKO-SiRzlHCHaJn-lO-SiRdyO-SiRa (IV),

in which R is identical or different radicals from the group -H, -phenyl, -benzyl, -CH ₂ -CH (CH ₃ ) Ph _{1 of} the C _1-20 -alkyl radicals, preferably -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , - C (CH ₃ J ₃ , x and y stand for a number from 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and especially 0, 1, 2, 3, 4, 5 or 6 and n is a number from 0 to 10, preferably from 1 to 8 and in particular from 2, 3, 4, 5, 6.

The silicones are preferably water-soluble. Hair treatment compositions which are preferred according to the invention are therefore characterized in that they can additionally contain a water-soluble silicone.

In a further preferred embodiment, the agents according to the invention may contain emulsifiers (F). Emulators cause at the phase interface the formation of water- or oil-stable adsorption layers, which protect the dispersed droplets against coalescence and thus stabilize the emulsion. Emulsifiers are therefore constructed like surfactants from a hydrophobic and a hydrophilic part of the molecule. Hydrophilic emulsifiers preferably form O / W emulsions and hydrophobic emulsifiers preferably form W / O emulsions. An emulsion is to be understood as meaning a droplet-like distribution (dispersion) of a liquid in another liquid under the expense of energy in order to create stabilizing phase interfaces by means of surfactants. The selection of these emulsifying surfactants or emulsifiers depends on the substances to be dispersed and the respective outer phase and the fineness of the emulsion. Emulsifiers which can be used according to the invention are, for example

- Addition products of 4 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group, C ₁₂ -C ₂₂ -fatty acid mono- and diesters of addition products of from 1 to 30 mol of ethylene oxide onto polyols having from 3 to 6 carbon atoms, in particular to glycerol,

Ethylene oxide and polyglycerol addition products to methyl glucoside fatty acid esters, fatty acid alkanolamides and fatty acid glycamides,

C ₈ -C ₂₂ -alcohols and oligoglycosides and their ethoxylated analogs, with degrees of oligomerization of from 1.1 to 5, in particular 1.2 to 2.0, and glucose as sugar component being preferred,

Mixtures of alkyl (oligo) glucosides and fatty alcohols, for example, the commercially available product ^® Montanov 68,

Adducts of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil,

Partial esters of polyols having 3-6 carbon atoms with saturated fatty acids having 8 to 22 C atoms,

- sterols. Sterols are understood to mean a group of steroids which have a hydroxyl group on C-atom 3 of the steroid skeleton and are isolated both from animal tissue (zoosterols) and from vegetable fats (phytosterols). Examples of zoosterols are cholesterol and lanosterol. Examples of suitable phytosterols are ergosterol, stigmasterol and sitosterol. Mushrooms and yeasts are also used to isolate sterols, the so-called mycosterols.

- Phospholipids. Of these, especially the glucose phospholipids, e.g. as lecithins or phosphatidylcholines from e.g. Egg yolk or plant seeds (e.g., soybeans) are understood.

Fatty acid esters of sugars and sugar alcohols, such as sorbitol,

- polyglycerols and polyglycerol derivatives such as polyglycerol poly-12-hy- droxystearat (Dehymuls ^® PGPH commercial product) ₁

- Linear and branched fatty acids with 8 to 30 C atoms and their Na, K, ammonium, Ca, Mg and Zn salts.

The agents according to the invention preferably contain the emulsifiers in amounts of 0.1-25% by weight, in particular 0.5-15% by weight, based on the total agent.

The compositions according to the invention may preferably contain at least one nonionic emulsifier having an HLB value of 8 to 18. Nonionic emulsifiers having an HLB value of 10 to 15 may be particularly preferred according to the invention. As further advantageous, it has been shown that polymers (G) are included in the inventive compositions. In a preferred embodiment, therefore, polymers are added to the compositions used according to the invention, both cationic, anionic, amphoteric and nonionic polymers having proven effective.

Cationic or amphoteric polymers are preferably usable according to the invention. Cationic or amphoteric polymers are to be understood as meaning polymers which have a group in the main and / or side chain which may be "temporary" or "permanent" cationic. According to the invention, "permanently cationic" refers to those polymers which have a cationic group, irrespective of the pH of the agent. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group. Preferred cationic groups are quaternary ammonium groups. In particular, those polymers in which the quaternary ammonium group is bonded via a C 1-4 hydrocarbon group to a polymer main chain constructed from acrylic acid, methacrylic acid or derivatives thereof have proven to be particularly suitable.

Homopolymers of the general formula (G1-I),

R ¹

I - [CH ₂ -C-] _n X- (G1-I)

I

CO-O- (CHa) _1T1 -N ⁺ R ² R ³ R ⁴

in which R ¹ = -H or -CH ₃ , R ² , R ³ and R ^{4 are} independently selected from C 1-4 -alkyl, -alkenyl or -hydroxyalkyl groups, m = 1, 2, 3 or 4, n is a natural number and X- is a physiologically acceptable organic or inorganic anion, as well as copolymers consisting essentially of the monomer units listed in formula (G1-I) and nonionic monomer units, are particularly preferred cationic polymers. In the context of these polymers, preference is given to those according to the invention for which at least one of the following conditions applies: - R ¹ is a methyl group

- R ² , R ³ and R ⁴ are methyl groups

- m has the value 2.

Suitable physiologically tolerated counterions X ^" are, for example, halide ions, sulfate ions, phosphate ions, methosulfate ions and organic ions such as lactate, citrate, tartrate and acetate ions, preference being given to halide ions, in particular chloride.

A particularly suitable homopolymer is, if desired crosslinked, PolyCmethacryloyloxyethyltrimethylammoniumchlorid) with the INCI name Polyquatemium-37. Such products are available, for example under the names Rheocare ^® CTH (Cosmetic Rheologies) and Synthalen® ^® CR (Ethnichem) in trade. If desired, the crosslinking can be carried out with the aid of poly olefinically unsaturated compounds, for example divinylbenzene, tetraallyloxyethane, methylenebisacrylamide, diallyl ether, polyallylpolyglyceryl ethers, or allyl ethers of sugars or sugar derivatives such as erythritol, pentaerythritol, arabitol, mannitol, sorbitol, sucrose or glucose. Methylenebisacrylamide is a preferred crosslinking agent.

The homopolymer is preferably used in the form of a nonaqueous polymer dispersion which should not have a polymer content of less than 30% by weight. Such polymer dispersions are available under the names Salcare ^® SC 95 (about 50% polymer content, additional components: mineral oil (INCI name: Mineral Oil) and tridecyl polyoxypropylene-polyoxyethylene-ether (INCI name: PPG-1-Trideceth- 6)), and Salcare ^® SC 96 (about 50% polymer content, additional components: mixture of diesters of propylene glycol with a mixture of caprylic and capric acid (INCI name: propylene glycol Dicaprylate / Dicaprate) and tridecyl poiyoxypropylen-polyoxyethylene ether (INCI name: PPG-1-Trideceth-6)) commercially available.

Copolymers containing monomer units according to formula (G 1-1) as non-ionic monomer, preferably acrylamide, methacrylamide, acrylic acid-C ^ alkyl ester and methacrylic acid-C _M alkyl esters. Among these nonionic monomers, the acrylamide is particularly preferred. These copolymers can also be crosslinked, as described above in the case of the homopolymers. A preferred copolymer according to the invention is the crosslinked actylamide-methaciyloyloxyethyltrimethylammonium chloride copolymer. Such copolymers in which the monomers are present in a weight ratio of about 20:80, commercially available as about 50% non-aqueous polymer dispersion under the name Salcare ^® SC 92nd

Further preferred cationic polymers are, for example

- Quaternized cellulose derivatives, such as those under the names Celquat ^® and Polymer JR ^® commercially available. The compounds Celquat ^® H 100, Celquat L 200 and Polymer JR ^{® ®} 400 are preferred quaternized cellulose derivatives

cationic alkyl polyglycosides according to DE-PS 44 13 686,

- cationized honey, for example the commercial product Honeyquat ^® 50,

- cationic guar derivatives, such as in particular the products sold under the trade names Cosme- dia ^® Guar and Jaguar ^®,

polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (Dimethyldiallylammoni- trimethylammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers,

- Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoalkyl acrylate and methacrylate, such as with diethyl sulfate quaternized vinylpyrrolidone-dimethylaminoethyl methacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially,

- vinylpyrrolidone vinylimidazoliummethochloride copolymers, such as those offered under the names Luviquat.RTM ^® FC 370, FC 550, FC 905 and HM 552,

- quaternized polyvinyl alcohol,

- as well as the polymers known under the names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 with quaternary nitrogen atoms in the polymer main chain.

Can be used as cationic polymers (. B. commercial product, Quatrisoft ^® LM 200) under the designations Polyquaternium-24, known polymers. Also usable in the invention are the copolymers of vinylpyrrolidone, such as the commercial products Copolymer 845 (manufactured by ISP), Gaffix ^® VC 713 (manufacturer: ISP), Gafquat ^® ASCP 1011, Gafquat ^® HS 110 Luviquat.RTM ^® 8155 and Luviquat.RTM ^® MS 370..

Other cationic polymers which can be used in the agents according to the invention are the so-called "temporary cationic" polymers. These polymers usually contain an amino group which, at certain pH values, is present as quaternary ammonium group and thus cationic. Preferably, for example, are chitosan and its derivatives, such as 101 are freely available commercially, for example under the trade names Hydagen CMF ^®, Hydagen HCMF ^®, Kytamer ^® PC and Chitolam ^® NB /.

According to the invention preferred cationic polymers are cationic cellulose derivatives and chitosan and its derivatives, in particular the commercial products Polymer ^® JR 400, Hydagen ^® HCMF and Kytamer ^® PC, cationic guar derivatives, cationic honey derivatives, in particular the commercial product Honeyquat ^® 50, cationic Alkylpolyglycodside according to DE-PS 44 13 686 and polymers of the type Polyquaternium-37.

Furthermore, cationized protein hydrolyzates are to be counted among the cationic polymers, wherein the underlying protein hydrolyzate from the animal, for example from collagen, milk or keratin, from the plant, for example from wheat, corn, rice, potatoes, soy or almonds, marine life forms, for example from fish collagen or algae, or biotechnologically derived protein hydrolysates. The protein hydrolyzates on which the cationic derivatives according to the invention are based can be obtained from the corresponding proteins by chemical, in particular alkaline or acid hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. The hydrolysis of proteins usually results in a protein hydrolyzate having a molecular weight distribution of about 100 daltons up to several thousand daltons. Preference is given to those cationic protein hydrolyzates whose underlying protein content has a molecular weight of 100 to 25,000 daltons, preferably 250 to 5000 daltons. Furthermore, cationic protein hydrolyzates are to be understood as meaning quaternized amino acids and mixtures thereof. The quaternization of the protein hydrolyzates or amino acids is often carried out using quaternary ammonium salts such as N, N-dimethyl-N- (n-alkyl) N- (2-hydroxy-3-chloro-n-propyl) ammonium halides. Furthermore, the cationic protein hydrolysates may also be further derivatized. As typical examples of the cationic protein hydrolysates and derivatives of the invention are under the INCI - names in the "International Cosmetic Ingredient Dictionary and Handbook" ^(th seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 Street, NW, Suite 300, Washington, DC 20036-4702) above and in Commercially available products called: Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimopnium Hydroxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Rice Protein, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Hydroxypropyl Arginine Lauryl / Myristyl Ether HCl, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Casein, Hydroxypropyltrimonium Hydrolyzed Collagen, Hydroxypropyltrimonium Hydrolyzed Conchiolin Protein,

Hydroxypropyltrimonium Hydrolyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, 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 Wheat Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein / Siloxysilicate, Lauryldimony Hydroxypropyl Hydrolyzed Casein, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen, Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Casein, Steardimonium Hydroxypropyl Hydrolyzed Collagen, Steardimonium Hydroxypropyl Hydrolyzed Keratin, Steardimonium Hydroxypropyl Hydrolyzed Rice Protein, Steardimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Vegetable Protein, Steardimonium Hydroxy Propyl Hydrolyzed Wheat Protein, Steartrimonium Hydroxyethyl Hydrolyzed Collagen, Quatemium-76 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Collagen, Quaternium-79 Hydrolyzed Keratin, Quaternium-79 Hydrolyzed Milk Protein, Quaternium-79 Hydrolyzed Soy Protein, Quaternium-79 Hydrolyzed Wheat Protein.

Very particular preference is given to the cationic protein hydrolysates and derivatives based on plants.

In addition to cationic polymers or in their place, the agents according to the invention can also contain amphoteric polymers. These are additional at least one negatively charged group in the molecule and are also referred to as zwitterionic polymers. In the context of the present invention, preferably usable zwitterionic polymers are composed essentially together

A) monomers with quaternary ammonium groups of the general formula (Z-I),

R ¹ -CH = CR ² -CO-Z- (C _n H _2n ) -N ( ⁺ ) R ³ R ⁴ R ⁵ A <^" ) ( ^z" 0

In the R ¹ and R ² independently of one another are hydrogen or a methyl group and R ³ , R ⁴ and R ^{5 are} independently alkyl groups having 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer of 2 to 5 and A ^ 'is the anion of an organic or inorganic acid

and

B) monomeric carboxylic acids of the general formula (Z-II),

R ⁶ -CH = CR ⁷ -COOH (II)

in which R ⁶ and R ^{7 are} independently hydrogen or methyl groups.

Suitable starting monomers are, for. Dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, dimethylaminopropylacrylamide,

Dimethylaminopropylmethacrylamide and diethylaminoethylacrylamide when Z is an NH group or dimethylaminoethyl acrylate, dimethylaminoethylmethacrylate and diethylaminoethyl acrylate when Z is an oxygen atom.

The monomers containing a tertiary amino group are then quaternized in a known manner, methyl chloride, dimethyl sulfate or diethyl sulfate being particularly suitable as alkylating reagents. The quaternization reaction can be carried out in aqueous solution or in the solvent. Advantageously, those monomers of formula (ZI) are used which are derivatives of acrylamide or methacrylamide. Preference is furthermore given to those monomers which contain halide, methoxy-sulfate or ethoxy sulfate ions as counterions. Also preferred are those monomers of the formula (ZI) in which R ³ , R ⁴ and R ^{5 are} methyl groups.

The acrylamidopropyltrimethylammonium chloride is a most preferred monomer of formula (Z-I).

Suitable monomeric carboxylic acids of the formula (Z-II) are acrylic acid, methacrylic acid, crotonic acid and 2-methylcrotonic acid. Preference is given to using acrylic or methacrylic acid, in particular acrylic acid.

The zwitterionic polymers which can be used according to the invention are prepared from monomers of the formulas (Z-I) and (Z-II) by polymerization processes known per se. The polymerization can be carried out either in aqueous or aqueous-alcoholic solution. The alcohols used are alcohols having 1 to 4 carbon atoms, preferably isopropanol, which simultaneously serve as polymerization regulators. However, other components than regulators may also be added to the monomer solution, eg. For example, formic acid or mercaptans, such as thioethanol and thioglycolic acid. The initiation of the polymerization takes place with the aid of free-radical-forming substances. For this purpose, redox systems and / or thermally decomposing radical formers of the azo compound type, such. As azoisobutyronitrile, azo-bis (cyanopentanoic acid) or azo-bis (amidinopropane) dihydrochloride can be used. As redox systems are z. B. combinations of hydrogen peroxide, potassium or ammonium peroxodisulfate and tertiary butyl hydroperoxide with sodium sulfite, sodium dithionite or hydroxylamine hydrochloride as a reduction component.

The polymerization can be carried out isothermally or under adiabatic conditions, depending on the concentration ratios by the heat of polymerization released, the temperature range for the course of the reaction between 20 and 200 ⁰ C may vary, and the reaction optionally under the must be carried out adjusting overpressure. Preferably, the reaction temperature is between 20 and 100 ⁰ C.

The pH during the copolymerization may vary within a wide range. Advantageously, polymerization is carried out at low pH values; however, pH values above the neutral point are also possible. After the polymerization is treated with an aqueous base, for. As sodium hydroxide, potassium hydroxide or ammonia, to a pH between 5 and 10, preferably 6 to 8 set. Further details of the polymerization process can be found in the examples.

Be particularly effective, such polymers have been found in which the monomers of the formula (Z-I) were present in excess over the monomers of formula (Z-II). It is therefore preferred in accordance with the invention to use those polymers which are prepared from monomers of the formula (ZI) and the monomers of the formula (Z-II) in a molar ratio of 60:40 to 95: 5, in particular from .75: 25 to 95: 5, exist.

The cationic or amphoteric polymers are preferably contained in the agents according to the invention in amounts of from 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5 wt .-% are particularly preferred.

The anionic polymers (G2) are anionic polymers which have carboxylate and / or sulfonate groups. Examples of anionic monomers from which such polymers may consist are acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulfonic acid. The acidic groups may be wholly or partly present as sodium, potassium, ammonium, mono- or triethanolammonium salt. Preferred monomers are 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.

Anionic polymers which contain 2-acrylamido-2-methylpropanesulfonic acid as the sole or co-monomer can be found to be particularly effective, it being possible for all or some of the sulfonic acid group to be present as sodium, potassium, ammonium, mono- or triethanolammonium salt , More preferably, the homopolymer of 2-acrylamido-2-methyl propane sulfonic acid is obtainable for example under the name Rheothik ^® 11-80 commercially.

Within this embodiment, it may be preferable to use copolymers of at least one anionic monomer and at least one nonionic monomer. With regard to the anionic monomers, reference is made to the substances listed above. Preferred nonionic monomers are acrylamide, methacrylamide, acrylic esters, methacrylic esters, vinylpyrrolidone, vinyl ethers and vinyl esters.

Preferred anionic copolymers are acrylic acid-acrylamide copolymers and in particular polyacrylamide copolymers with sulfonic acid-containing monomers. A particularly preferred anionic copolymer consists of 70 to 55 mol% of acrylamide and 30 to 45 mol% of 2-acrylamido-2-methylpropanesulfonic acid, wherein the suifonic acid group is wholly or partly in the form of sodium, potassium, ammonium, mono- or triethanolammonium Salt is present. This copolymer may also be crosslinked, with crosslinking agents preferably polyolefinically unsaturated compounds such as tetraallyloxyethane, allylsucrose, allylpentaerythritol and methylene-bisaorylamid are used. Such a polymer is contained in the commercial product Sepigel ^® 305 from SEPPIC. The use of this compound, which in addition to the polymer component contains a hydrocarbon mixture (C ₁₃ -C ₁₄ isoparaffin) and a nonionic emulsifier (laureth-7), has proved to be particularly advantageous within the scope of the teaching according to the invention.

Also sold under the name Simulgel ^® 600 as a compound with isohexadecane and polysorbate-80 Natriumacryloyldimethyltaurat copolymers have proved to be particularly effective according to the invention.

Likewise preferred anionic homopolymers are uncrosslinked and crosslinked polyacrylic acids. Allyl ethers of pentaerythritol, sucrose and propylene may be preferred crosslinking agents. Such compounds are for example available under the trademark Carbopol ^® commercially.

Copolymers of maleic anhydride and methyl vinyl ether, especially those with crosslinks, are also color-retaining polymers. A networked with 1, 9-decadiene Maleic acid-methyl vinyl ether copolymer available under the name Stabileze® ^® QM.

Furthermore, amphoteric polymers (G3) can be used as polymers for increasing the activity of the active ingredient complex (A) according to the invention. The term amphoteric polymers includes both those polymers which contain in the molecule both free amino groups and free -COOH or SO ₃ H groups and are capable of forming internal salts, as well as zwitterionic polymers which in the molecule have quaternary ammonium groups and -COO contain ^" - or -SO ₃ ^' groups, and summarized those polymers containing -COOH or SO ₃ H groups and quaternary ammonium groups.

An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin, the methacrylate an Cσpolymeres from tert-butylamino, N- (1,1,3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group Acrylic acid, methacrylic acid and their simple esters.

Preferably used amphoteric polymers are those polymers which are composed essentially

(a) monomers having quaternary ammonium groups of the general formula (G3-I),

R ¹ -CH = CR ² -CO-Z- (C _n H _2n ) -N ⁽⁺⁾ R ³ R ⁴ R ⁵ A ^H (G3-I)

in which R ¹ and R ² independently of one another are hydrogen or a methyl group and R ³ , R ⁴ and R ⁵ independently of one another are alkyl groups having 1 to 4 carbon atoms, Z is an NH group or an oxygen atom, n is an integer from 2 to 5 and A is the anion of an organic or inorganic acid, and

(b) monomeric carboxylic acids of the general formula (G3-II),

R ⁶ -CH = CR ⁷ -COOH (G3-II)

in which R ⁶ and R ^{7 are} independently hydrogen or methyl groups. These compounds can be used both directly and in salt form, which is obtained by neutralization of the polymers, for example with an alkali metal hydroxide, according to the invention. Very particular preference is given to those polymers in which monomers of the type (a) are used in which R ³ , R ⁴ and R ^{5 are} methyl groups, Z is an NH group and A ^{(") is} a halide, methoxysulfate or ethoxy sulfate Is acrylamidopropyltrimethylammonium chloride is a particularly preferred monomer (a) As the monomer (b) for the polymers mentioned, acrylic acid is preferably used.

In another embodiment, the agents according to the invention may contain nonionic polymers (G4).

Suitable nonionic polymers are, for example:

Vinylpyrrolidone / vinyl ester copolymers, as sold, for example, under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each VinylpyrrolidonΛ / inylacetat copolymers are also preferred nonionic polymers.

Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and hydroxypropylcellulose Methylhy- as they are for example sold under the trademark Culminal® ^® and Benecel ^® (AQUALON) and Natrosol ^® grades (Hercules). Starch and its derivatives, in particular starch, such as Structure XL ^® (National Starch), a multifunctional, salt-tolerant starch;

- shellac

Polyvinylpyrrolidones, as sold for example under the name Luviskol ^® (BASF).

Siloxanes. These siloxanes can be both water-soluble and water-insoluble. Both volatile and nonvolatile siloxanes are suitable, nonvolatile siloxanes being understood as meaning those compounds whose boiling point is above 200 ^° C. under normal pressure. Preferred siloxanes are polydi- alkylsiloxanes, such as, for example, polydimethylsiloxane, polyalkylarylsiloxanes, such as, for example, polyphenylmethylsiloxane, ethoxylated polydialkylsiloxanes and polydialkylsiloxanes which contain amine and / or hydroxyl groups.

- Glycosidically substituted silicones. It is also possible according to the invention that the preparations used contain a plurality of, in particular two different polymers of the same charge and / or in each case an ionic and an amphoteric and / or nonionic polymer.

The polymers (G) are contained in the agents according to the invention preferably in amounts of from 0.05 to 10% by weight, based on the total agent. Amounts of 0.1 to 5, in particular from 0.1 to 3 wt .-%, are particularly preferred.

In addition to the substances mentioned, the compositions according to the invention may contain further care substances. With particular preference, these are, for example, vitamins, provitamins or vitamin precursors, so that preferred agents according to the invention are characterized in that they additionally contain at least one substance from the group of vitamins, provitamins and vitamin precursors and their derivatives, with vitamins, pro-vitamins and vitamin precursors preferred are assigned to the groups A, B, C, E, F and H. These have been described in detail above.

Another group of care agents that may be included in the compositions of the invention are the protein hydrolysates and their derivatives (P). Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins). According to the invention, the term protein hydrolyzates also means total hydrolyzates as well as individual amino acids and their derivatives as well as mixtures of different amino acids. Furthermore, according to the invention, polymers made up of amino acids and amino acid derivatives are understood by the term protein hydrolyzates. The latter include, for example, polyalanine, polyasparagine, polyserine, etc. Further examples of compounds which can be used according to the invention are L-alanyl-L-proline, polyglycine, glycyl-L-glutamine or D / L-methionine-S-methylsulfonium chloride. Of course, according to the invention, β-amino acids and their derivatives such as β-alanine, anthranilic acid or hippuric acid can also be used. The molecular weight of the protein hydrolysates which can be used according to the invention is between 75, the molecular weight for glycine, and 200,000, preferably the molecular weight is 75 to 50,000 and very particularly preferably 75 to 20,000 daltons.

According to the invention, protein hydrolysates of both vegetable and animal or marine or synthetic origin can be used. Animal protein hydrolysates are, for example, elastin, collagen, keratin and milk protein protein hydrolysates, which may also be present in the form of salts. Such products are, for example, under the trademarks Dehylan ^® (Cognis), Promois® ^® (Interorgana) Collapuron ^® (Cognis), Nutrilan® ^® (Cognis), Gelita-Sol ^® (German Gelatinefabriken Stoess & Co), Lexein ^® (Inolex) and kerasol tm ^® (Croda) sold.

Preferred according to the invention is the use of protein hydrolysates of plant origin, eg. Soybean, almond, pea, potato and wheat protein hydrolysates. Such products are, for example, under the trademarks Gluadin ^® (Cognis), diamine ^® (Diamalt) ^® (Inolex), Hydrosoy ^® (Croda), hydro Lupine ^® (Croda), hydro Sesame ^® (Croda), Hydro tritium ^® (Croda) and Crotein ^® (Croda) available.

Although the use of the protein hydrolysates is preferred as such, amino acid mixtures otherwise obtained may be used in their place, if appropriate. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products. Such products are sold for example under the names Lamepon® ^® (Cognis), Lexein ^® (Inolex), Crolastin ^® (Croda) or crotein ^® (Croda).

Of course, the teaching of the invention includes all isomeric forms, such as eis - trans - isomers, diastereomers and chiral isomers.

According to the invention it is also possible to use a mixture of several protein hydrolysates (P).

The protein hydrolysates (P) are present in the compositions in concentrations of from 0.01% by weight to 20% by weight, preferably from 0.05% by weight to 15% by weight and most preferably in amounts of 0.05% by weight % up to 5% by weight.

Furthermore, in a preferred embodiment of the invention, an agent according to the invention may also contain UV filters (I). The UV filters to be used according to the invention are not subject to any general restrictions with regard to their structure and their physical properties. On the contrary, all UV filters that can be used in the cosmetics sector are suitable, whose absorption maximum in UVA (315-400 nnn) -, in the UVB (280-315nm) - or in the UVC (<280 nm) range. UV filter with a

Absorption maximum in the UVB range, in particular in the range of about 280 to about

300 nm, are particularly preferred.

The UV filters used according to the invention can be selected, for example, from substituted benzophenones, p-aminobenzoic acid esters, diphenylacrylic acid esters, cinnamic acid esters, salicylic acid esters, benzimidazoles and o-aminobenzoic acid esters.

Examples of UV filters which can be used according to the invention are 4-aminobenzoic acid, N, N, N-trimethyl-4- (2-oxobrom-3-ylidenemethyl) aniline methylsulfate, 3,3,5-trimethylcyclohexyl salicylate (homosalates ), 2-hydroxy-4-methoxy-benzophenone (benzophenone-3; Uvinul ^® M 40,, 2-phenylbenzimidazole-sulphonic acid and 5-Uvasorb MET ^{®, ®} Neo Heliopan BB, Eusolex ^® 4360) the potassium, sodium - and triethanolamine (Phenylbenzimidazole Sulfonic Acid; Parsol ^® HS; Neo Heliopan Hydro ^®), 3,3 '- (1, 4-phenylenedimethylene) bis (7,7-dimethyl-2-oxo-bicyclo [2.2.1] hept-1-yl-methane-sulfonic acid) and salts thereof, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) propane-1, 3-dione (butyl methoxydibenzoylmethane; Parsol ^® 1789 Eusolex ^® 9020), α- (2-oxoborn-3-ylidene) toluene-4-sulfonic acid and salts thereof, ethoxylated 4-aminobenzoic acid ethyl ester (PEG-25 PABA; Uvinul ^® P 25), 4-methylaminobenzoic acid-2-di- ethylhexyl (octyl dimethyl PABA; Uvasorb ^® DMO, Escalol ^® 507, Eusolex ^® 6007), salicylic acid 2-ethylhexyl ester (octyl salicylate; Escalol ^® 587, Neo Heliopan OS ^®, Uvinul ^® O18), 4-methoxycinnamic acid isopentyl (isoamyl p-methoxycinnamate; Neo Heliopan E 1000 ^®), 4-methoxycinnamic acid 2-ethylhexyl ester (Octyl Methoxycinnamate; Parsol ^® MCX, Escalol ^® 557, Neo Heliopan AV ^®), 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt (Benzophenone-4; Uvinul ^® MS 40; Uvasorb S 5 ^®), 3- (4'-methylbenzylidene) -D, L-camphor (4-Methylbenzyli- dene camphor; Parsol ^® 5000, Eusolex ^® 6300), 3-benzylidene camphor (3-benzylidene camphor), 4-isopropylbenzyl, 2,4,6-trianilino- (p-carbo-2 '-ethylhexyl-1'-oxi) -1, 3,5-triazine, 3-imidazol-4-yl-acrylic acid and its ethyl ester, polymers of N - {(2 and 4) - [2-oxobrom-3-ylidenemethyl ] benzyl} -acrylamids, 2,4-dihydroxybenzophenone (none benzophenone-1; Uvasorb ^® 20 H, Uvinul ^® 400) 1, 1 '-Diphenylacrylonitrilsäure-2-ethylhexyl ester (Octocrylene; Eusolex ^® OCR, Neo Heliopan ^® Type 303, Uvinul ^® N 539 SG), o-aminobenzoic benzoic acid menthyl (menthyl Anthrani late; Neo Heliopan MA ^®), 2,2 ', 4,4'-tetrahydropyran droxybenzophenon (benzophenone-2; Uvinul ^® D-50), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (Benzophenone-6), 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5-sulfonate and 2- natriumsul- cyano-3,3-diphenylacrylate 2'-ethylhexyl acrylate. Preference is given to 4-amino benzoic acid, N, N, N-trimethyl-4- (2-oxoborn-3-ylidenemethyl) aniline methylsulfate, 3,3,5-trimethylcyclohexylsalicylate, 2-hydroxy-4-methoxybenzophenone, 2-phenylbenzimidazole 5-sulfonic acid and its potassium, sodium and triethanolamine salts, 3,3 '- (1, 4-phenylenedimethylene) bis (7,7-dimethyl-2-oxo-bicyclo [2.2.1] hept-1 yl-methanesulfonic acid) and its salts, 1- (4-tert-butylphenyl) -3- (4-methoxyphenyl) -propane-1,3-dione, α- (2-oxoborn-3-ylidene ) -toluene-4-sulfonic acid and its salts, ethoxylated 4-aminobenzoic acid ethyl ester, 2-ethylhexyl 4-dimethylaminobenzoate, 2-ethylhexyl salicylate, 4-methoxycinnamic acid isopentyl ester, 4-methoxycinnamic acid 2-ethylhexyl ester, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, 3- (4'-methylbenzylidene) -D, L-camphor, 3-benzylidene-camphor, 4-isopropylbenzylsalicylate, 2,4,6- Tri-anilino (p-carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine, 3-imidazol-4-yl-acrylic acid and its ethyl ester, polymers of N - {(2 and 4 ) - [2-o xoborn-3-ylidenemethyl] benzyl} acrylamide. Very particularly preferred according to the invention are 2-hydroxy-4-methoxybenzophenone, 2-phenylbenzimidazole-5-sulfonic acid and its potassium, sodium and triethanolamine salts, 1- (4-tert-butylphenyl) -3- (4- methoxyphenyl) -propane-1,3-dione, 4-methoxycinnamic acid 2-ethylhexyl ester and 3- (4'-methylbenzylidene) -D, L-camphor.

Preference is given to those UV filters whose molar extinction coefficient at the absorption maximum is above 15,000, in particular above 20,000.

Furthermore, it has been found that structurally similar UV filters in many cases, the water-insoluble compound in the teaching of the invention has the higher effect compared to such water-soluble compounds that differ from it by one or more additional ionic groups. For the purposes of the invention, water-insoluble UV filters are those which dissolve in water at not more than 1% by weight, in particular not more than 0.1% by weight, at 20 ^° C. Furthermore, these compounds should be soluble in the usual cosmetic oil components at room temperature to at least 0.1, in particular at least 1 wt .-%). The use of water-insoluble UV filters may therefore be preferred according to the invention.

According to a further embodiment of the invention, preference is given to those UV filters which have a cationic group, in particular a quaternary ammonium group.

These UV filters have the general structure U - Q. The structural part U stands for a UV-absorbing group. This group can in principle be derived from the known UV filters which can be used in the cosmetics sector, in which a group, generally a hydrogen atom, of the UV filter is protected by a cationic group Q, in particular having a quaternary amino function, is replaced. Compounds from which the structural part U can derive are, for example

substituted benzophenones,

p-aminobenzoic acid ester,

- diphenylacrylic acid ester,

- cinnamic acid ester,

Salicylic acid ester,

Benzimidazoles and

o-aminobenzoic acid ester.

Structural parts U, which are derived from cinnamic acid amide or from N, N-dimethylaminobenzoic acid amide, are preferred according to the invention.

The structural parts U can in principle be chosen so that. the absorption maximum of the UV filters can be in the UVA (315-400 nm) as well as in the UVB (280-315 nm) or in the UVC (<280 nm) range. UV filters with an absorption maximum in the UVB range, in particular in the range from about 280 to about 300 nm, are particularly preferred.

Furthermore, the structural part U, also as a function of structural part Q, is preferably selected so that the molar extinction coefficient of the UV filter at the absorption maximum is above 15,000, in particular above 20,000.

The structural part Q preferably contains, as a cationic group, a quaternary ammonium group. This quaternary ammonium group can in principle be connected directly to the structural part U, so that the structural part U represents one of the four substituents of the positively charged nitrogen atom. Preferably, however, one of the four substituents on the positively charged nitrogen atom is a group, especially an alkylene group of 2 to 6 carbon atoms, which functions as a compound between the structural portion U and the positively charged nitrogen atom. Advantageously, the group Q has the general structure - (CH ₂ ) _X -N ⁺ R ¹ R ² R ³ X ^' , where x is an integer from 1 to 4, R ¹ and R ^{2 are} independently C ₁ , ₄ alkyl groups, R ³ is a Ci _-22- alkyl group or a benzyl group and X ^'is a physiologically acceptable anion. In the context of this general structure, x preferably represents the number 3, R ¹ and R ² each represent a methyl group and R ^{3 represents} either a methyl group or a saturated or unsaturated, linear or branched hydrocarbon chain having 8 to 22, in particular 10 to 18, carbon atoms.

Physiologically acceptable anions are, for example, inorganic anions such as halides, in particular chloride, bromide and fluoride, sulfate ions and phosphate ions and organic anions such as lactate, citrate, acetate, tartrate, methosulfate and tosylate.

Two preferred UV filters with cationic groups are the commercially available compounds cinnamic acid-trimethylammonium chloride (lncroquat ^® UV 283) and dodecyl tosylate (Escalol ^® HP 610).

Of course, the teaching of the invention also includes the use of a combination of several UV filters. In the context of this embodiment, the combination of at least one water-insoluble UV filter with at least one UV filter with a cationic group is preferred.

The UV filters (I) are contained in the compositions according to the invention usually in amounts of 0.1-5 wt .-%, based on the total agent. Levels of 0.4-2.5 wt .-% are preferred.

The compositions of the invention may further contain a 2-pyrrolidinone-5-carboxylic acid and its derivatives (J). Preference is given to the sodium, potassium, calcium, magnesium or ammonium salts in which the ammonium ion carries, in addition to hydrogen, one to three C 1 to C ₄ -alkyl groups. The sodium salt is most preferred. The amounts used in the compositions according to the invention are preferably from 0.05 to 10% by weight, based on the total composition, particularly preferably from 0.1 to 5, and in particular from 0.1 to 3,% by weight. Finally, the compositions according to the invention may also contain plant extracts (L).

Usually these extracts are produced by extraction of the whole plant. However, in individual cases it may also be preferred to prepare the extracts exclusively from flowers and / or leaves of the plant.

With regard to the plant extracts which can be used according to the invention, particular reference is made to the extracts listed in the table beginning on page 44 of the 3rd edition of the guideline for the ingredient declaration of cosmetic products, published by the Industrial Association for Personal Care and Detergent e.V. (IKW), Frankfurt.

The extracts of green tea, oak bark, stinging nettle, witch hazel, hops, henna, chamomile, burdock root, horsetail, hawthorn, linden, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime , Wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root,

Particularly preferred are the extracts of green tea, oak bark, stinging nettle, witch hazel, hops, chamomile, burdock root, horsetail, lime blossom, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage, Rosemary, birch, meadowfoam, quenelle, yarrow, toadstool, meristem, ginseng and ginger root.

Especially suitable for the use according to the invention are the extracts of green tea, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi and melon.

As extraction agent for the preparation of said plant extracts water, alcohols and mixtures thereof can be used. Among the alcohols are lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol and propylene glycol, both as sole extractant and in admixture with water, are preferred. Plant extracts based on water / propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable. The plant extracts can be used according to the invention both in pure and in diluted form. If they are used in diluted form, they usually contain about 2 to 80 wt .-% of active substance and as a solvent used in their extraction agent or extractant mixture.

Furthermore, it may be preferred to use in the compositions according to the invention mixtures of several, especially two, different plant extracts.

In addition, it may prove advantageous if the compositions according to the invention contain penetration aids and / or swelling agents (M). These include, for example, urea and urea derivatives, guanidine and its derivatives, arginine and its derivatives, water glass, imidazole and its derivatives, histidine and its derivatives, benzyl alcohol, glycerol, glycol and glycol ethers, propylene glycol and propylene glycol ethers, for example propylene glycol monoethyl ether, carbonates, bicarbonates, Diols and triols, and in particular 1, 2-diols and 1, 3-diols such as 1, 2-propanediol, 1, 2-pentanediol, 1, 2-hexanediol, 1, 2-dodecanediol, 1, 3-propanediol, 1 , 6-hexanediol, 1,5-pentanediol, 1, 4-butanediol.

Advantageously in the context of the invention, short-chain carboxylic acids (N) may additionally support the active substance complex (A). Short-chain carboxylic acids and their derivatives in the context of the invention are understood to mean carboxylic acids which may be saturated or unsaturated and / or straight-chain or branched or cyclic and / or aromatic and / or heterocyclic and have a molecular weight of less than 750. For the purposes of the invention, preference may be given to saturated or unsaturated straight-chain or branched carboxylic acids having a chain length of from 1 to 16 C atoms in the chain, very particular preference being given to those having a chain length of from 1 to 12 C atoms in the chain.

The short-chain carboxylic acids according to the invention may have one, two, three or more carboxy groups. Preferred within the meaning of the invention are carboxylic acids having a plurality of carboxy groups, in particular di- and tricarboxylic acids. The carboxy groups may be wholly or partly present as esters, acid anhydride, lactone, amide, imidic acid, lactam, lactim, dicarboximide, carbohydrazide, hydrazone, hydroxam, hydroxime, amidine, amido-dim, nitrile, phosphonic or phosphate ester. The carbon Of course, acids can be substituted along the carbon chain or ring skeleton. The substituents of the carboxylic acids according to the invention are, for example, C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, aryl, aralkyl and aralkenyl, hydroxymethyl, C 2 -C 8 -hydroxyalkyl, C 2 -C 8 -hydroxyalkenyl, Aminomethyl, C 2 -C 8 -aminoalkyl, cyano, formyl, oxo, thioxo, hydroxy, mercapto, amino, carboxy or imino groups. Preferred substituents are C 1 -C 8 alkyl, hydroxymethyl, hydroxy, amino and carboxy groups. Particular preference is given to substituents in the D position. Very particularly preferred substituents are hydroxyl, alkoxy and amino groups, where the amino function may optionally be further substituted by alkyl, aryl, aralkyl and / or alkenyl radicals. Furthermore, preferred carboxylic acid derivatives are the phosphonic and phosphate esters.

Examples of carboxylic acids according to the invention include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, oxalic acid, malonic acid, succinic acid. Glutaric, glyceric, glyoxylic, adipic, pimelic, suberic, sebacic, propiolic, crotonic, isocrotonic, elaidic, maleic, fumaric, muconic, citraconic, mesaconic, camphoric, benzoic, o, m, p-phthalic, naphthoic, toluoic, hydratropic acid, atropic acid, cinnamic acid, isonicotinic acid, nicotinic acid, Bicarbaminsäure, 4,4 ^{'-Dicyano-6,6'} -binicotinsäure, 8- Carbamoyloctansäure, 1, 2,4-pentanetricarboxylic acid, 2-pyrrolecarboxylic acid, 1, 2,4,6, 7-naphthalene pentaacetic acid, malonaldehyde acid, 4-hydroxy-phthalamic acid, 1-pyrazolecarboxylic acid, gallic acid or propane tricarboxylic acid, a dicarboxylic acid selected from the group formed by compounds of general formula (NI),

(NI) in the Z is a linear or branched alkyl or alkenyl group having 4 to 12 carbon atoms, n is a number from 4 to 12 and one of the two groups X and Y is a COOH group and the other is hydrogen or a methyl or Ethyl radical, dicarboxylic acids of the general formula (NI), which additionally carry 1 to 3 methyl or ethyl substituents on the cyclohexene ring and dicarboxylic acids formed formally from the dicarboxylic acids according to formula (NI) by addition of a molecule of water to the double bond in the cyclohexene ring.

Dicarboxylic acids of the formula (N-I) are known in the literature.

The dicarboxylic acids of the formula (N-I) can be prepared, for example, by reacting polyunsaturated dicarboxylic acids with unsaturated monocarboxylic acids in the form of a Diels-Alder cyclization. Usually one will assume a polyunsaturated fatty acid as the dicarboxylic acid component. Preferred is the linoleic acid obtainable from natural fats and oils. As the monocarboxylic acid component, in particular, acrylic acid, but also e.g. Methacrylic acid and crotonic acid are preferred. Normally, in the case of reactions according to Diels-Alder, mixtures of isomers are formed in which one component is present in excess. These isomer mixtures can be used according to the invention as well as the pure compounds.

In addition to the preferred dicarboxylic acids according to formula (N-I), those dicarboxylic acids which differ from the compounds according to formula (NI) by 1 to 3 methyl or ethyl substituents on the cyclohexyl ring or formally from these compounds by addition of a Molecule water are formed on the double formation of the cyclohexene ring.

The dicarboxylic acid (mixture), which is obtained by reacting linoleic acid with acrylic acid, has proved to be particularly effective according to the invention. It is a mixture of 5- and 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid. Such compounds are commercially available under the designations Westvaco Diacid 1550 Westvaco Diacid ^{® ®} 1595 (manufacturer: Westvaco).

In addition to the short-chain carboxylic acids according to the invention listed above by way of example, their physiologically tolerated salts can also be used used according to the invention. Examples of such salts are the alkali metal salts, alkaline earth metal salts, zinc salts and ammonium salts, which in the context of the present application also includes the mono-, di- and trimethyl-, -ethyl- and -hydroxyethyl ammonium salts. However, in the context of the invention, neutralized acids can very particularly preferably be used with alkaline-reacting amino acids, such as, for example, arginine, lysine, ornithine and histidine. Furthermore, it may be preferred for formulation reasons to select the carboxylic acid from the water-soluble representatives, in particular the water-soluble salts.

Furthermore, it is preferred according to the invention to use hydroxycarboxylic acids and here again in particular the dihydroxy-, trihydroxy- and polyhydroxycarboxylic acids as well as the dihydroxy, trihydroxy and polyhydroxy di-, tri- and polycarboxylic acids together with the active compound (A). It has been found that in addition to the hydroxycarboxylic acids, the hydroxycarboxylic acid esters and the mixtures of hydroxycarboxylic acids and their esters as well as polymeric hydroxycarboxylic acids and their esters can be very particularly preferred. Preferred hydroxycarboxylic acid esters are, for example, full esters of glycolic acid, lactic acid, malic acid, tartaric acid or citric acid. Further basically suitable hydroxycarboxylic acid esters are esters of β-hydroxypropionic acid, tartronic acid, D-gluconic acid, sugar acid, mucic acid or glucuronic acid. Suitable alcohol components of these esters are primary, linear or branched aliphatic alcohols having 8-22 C atoms, ie, for example, fatty alcohols or synthetic fatty alcohols. The esters of C12-C15 fatty alcohols are particularly preferred. Esters of this type are commercially available, eg under the trademark Cosmacol® ^® EniChem, Augusta Industriale. Particularly preferred polyhydroxypolycarboxylic acids are polylactic acid and polyuric acid and their esters.

Further objects of the present invention are the use of corneocyte proteins or polypeptides with a Moimasse of 10 to 40 kDa to improve at least one of the properties

Tensile strength of keratinic fibers, especially human hair;

Stabilizing the moisture balance of keratinic fibers, in particular human hair;

Combability of keratinic fibers, especially human

hair; Delaying the aging process of keratinic fibers, especially human hair;

Restructurability of keratinic fibers, especially human

Hair, during and after the perm process;

Reducing the decrease in elasticity of keratinic fibers, in particular human hair when damaged by atmospheric agents and the use of hair treatment compositions according to the invention for improving at least one of the properties

Tensile strength of keratinic fibers, especially human hair;

Stabilizing the moisture balance of keratinic fibers, in particular human hair;

Combability of keratinic fibers, especially human

hair;

Delaying the aging process of keratinic fibers, especially human hair;

Restructurability of keratinic fibers, especially human

Hair, during and after the perm process;

Reduction in elasticity of keratinic fibers, especially human hair, when damaged by atmospheric agents.

With regard to preferred uses according to the invention, what has been said to be the preferred means according to the invention applies mutatis mutandis.

The following examples are intended to illustrate the subject matter of the invention without limiting it. Examples:

Care shampoo

Lauryl myristyl ether sulfate sodium salt (about 68% to 73% active ingredient content ';

INCI name: Sodium Myreth Sulfate) (Cognis)

Cocoamidopropyl betaine (Cognis)

Alkypolyglucoside (Cognis); INCI: COCO GLUCOSIDE

Fatty alcohol (C12-C14) + 2 EO (Cognis)

# Intermediate filament protein from wool, MW = 3 to 4 KDa (Croda) ## mixture of intermediate filament protein from wool, MW = 40 to 60 KDa and

Wool intermediate filament protein, MW = 3 to 4 KDa (Croda)

Hair Conditioner

Fatty Alcohol Methyltriethanolammoniummethylsulfatdialkylester mixture (INCI name: Distearoylethyl Hydroxyethylmonium Methosulfate, Cetearyl Alcohol) (COGNIS) Myristyl Laurate

Cetyl trimethyl ammonium chloride

N, N, N-trimethyl-2 [(methyl-1-oxo-2-propenyl) oxy] ethanaminium chloride homopolymer (50% active ingredient; INCI name: Polyquaternium-37 (and) propylene glycol dicaprilate dicaprate (and) PPG) 1 Trideceth-6) (ALLIED COLLOIDS)

# Wool intermediate filament protein, MW = 3 to 4 KDa (Croda) ## Mixture of wool intermediate filament protein, MW = 40 to 60 KDa and wool intermediate filament protein, MW = 3 to 4 KDa (Croda)

Hair cure leave-on

cationic silicone emulsion (Dow Corning)

INCI: Carbomer (Noveon)

INCI: Hydrolyzed Creatine (Adinop) Cationic Protein Derivative (Cognis)

# Intermediate filament protein from wool, MW = 3 to 4 KDa (Croda) ## mixture of intermediate filament protein from wool, MW = 40 to 60 KDa and

Wool intermediate filament protein, MW = 3 to 4 KDa (Croda)

Claims

claims:

1. hair treatment composition containing 0.05 to 5 wt .-% of at least one Komeozyt- protein or polypeptide or a structurally related protein having a molecular weight of 10 to 4O kDa.

2. Hair treatment composition according to claim 1, characterized in that the corneocyte protein or polypeptide or a structurally related protein has a molecular weight of 12.5 to 37.5 kDa, preferably from 15 to 35 kDa and in particular from 20 to 30 kDa.

3. hair treatment composition according to any one of claims 1 or 2, characterized in that the corneocyte protein or polypeptide or a structurally related protein comprises 200 to 500 amino acids, preferably 250 to 450 amino acids, more preferably 275 to 400 amino acids and in particular 300 to 350 amino acids ,

4. Hair treatment composition according to one of claims 1 to 3, characterized in that the / the Korneozyt- protein (s) or - polypeptide (s) or a structurally related protein, is selected from the group Involucrin, Loricrin, Cornifin, trichohyalin, Scielline, profilaggrin and keratoline.

5. hair treatment agent according to any one of claims 1 to 4, characterized in that the / the Korneozyt- protein (s) or - polypeptide (s) have the amino acid sequence glycine-serine, wherein preferred proteins are characterized in that in the amino acid sequence glycine -Serin bound amino acids make up at least 5%, preferably at least 10% and in particular at least 15% of all amino acids contained in the protein or polypeptide.

6. hair treatment composition according to any one of claims 1 to 5, characterized in that the / the Korneozyt- protein (s) or - polypeptide (s) have the amino acid sequence glycine-serine-cysteine, wherein preferred proteins are characterized in that in the Amino acid sequence glycine-serine-cysteine bound amino acids at least 5%, preferably at least 10% and in particular at least 15% of all amino acids contained in the protein or polypeptide turn off.

7. hair treatment composition according to any one of claims 1 to 6, characterized in that it - based on its weight - 0.5 to 70 wt .-%, preferably 1 to 60 wt .-% and in particular 5 to 25 wt .-% of anionic (s) and / or nonionic (s) and / or cationic (s) and / or amphoteric surfactant (s).

8. Hair treatment composition according to one of claims 1 to 7, characterized in that it contains vitamins, pro-vitamins and vitamin precursors, which are assigned to the groups A, B, C, E, F and H, preferred compositions of said compounds in amounts of from 0.1 to 5 wt .-%, preferably from 0.25 to 4 wt .-% and in particular from 0.5 to 2.5 wt .-%, each based on the total agent included.

9. hair treatment composition according to one of claims 1 to 8, characterized in that it additionally silicone (s), preferably in amounts of 0.1 to 10 wt .-%, preferably from 0.25 to 7 wt .-% and in particular of 0.5 to 5 wt .-%, each based on the total agent contains.

10. hair treatment composition according to one of claims 1 to 9, characterized in that it comprises at least one silicone of the formula I.

(CHaJsSKO-SKCHs) x-O-SKCHaJa (I), in which x is a number from 0 to 100, preferably from 0 to 50, more preferably from 0 to 20 and in particular 0 to 10.

11. Hair treatment composition according to one of claims 1 to 10, characterized in that it is an amino-functional silicone of the formula (II)

R ^t aG ₃ . _a -Si (OSiG ₂ ) _n - (OSiG _b R ¹ _{2- b} ) _m -O-SiG _3-a -R ^I _a (II),

contains, in which means:

G is H, phenyl, -OH, -O-CH ₃ , -CH ₃ , -O-CH ₂ CH ₃ , -CH ₂ CH ₃ , -O-CH ₂ CH ₂ CH ₃₁ -CH ₂ CH ₂ CH _3, -O-CH _{(CH3) 2l} -CH (CH _{S) 2,} -0-CH ₂ CH ₂ CH ₂ CH _3, -CH ₂ CH ₂ CH ₂ CH ₃ , -O-CH ₂ CH (CH ₃ ) ₂ , -CH ₂ CH (CH ₃ ) ₂ , -O-CH (CH ₃ ) CH ₂ CH ₃ , -CH (CH ₃ ) CH ₂ CH ₃ , -GC (CHS) ₃ , -C (CH ₃ ) ₃ ;

a is a number between 0 and 3, in particular 0;

b is a number between 0 and 1, in particular 1,

m and n are numbers whose sum (m + n) is between 1 and 2000, preferably between 50 and 150, where n is preferably values from 0 to 1999 and in particular from 49 to 149 and m preferably values from 1 to 2000, in particular from 1 to 10,

R 'is a monovalent radical selected from O -QN (R ") - CH ₂ -CH ₂ -N (R") ₂ o -QN (R ¹¹ J ₂ O -QN ⁺ (R ¹¹ J ₃ A ^" o - QN ⁺ H (R ") ₂ A- o -QN ⁺ H ₂ (R") A- o -QN (R ¹¹ J-CH ₂ -CH ₂ -N ⁺ R ¹¹ H ₂ A ^" where each Q is a chemical bond, -CH ₂ -, -CH ₂ -CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -C (CH ₃ J ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ C ( CH ₃ ) ₂ -, -CH (CH ₃ ) CH ₂ CH ₂ -, R "represents identical or different radicals from the group -H, -phenyl, -benzyl, -CH ₂ -CH (CH ₃ ) Ph, the Ci.ao-alkyl radicals, preferably -CH ₃ , -CH ₂ CH ₃ , - CH ₂ CH ₂ CH ₃ , -CH (CH ₃ J ₂ , -CH ₂ CH ₂ CH ₂ H ₃ , -CH ₂ CH (CH ₃ J ₂ , -CH (CH ₃ ) CH ₂ CH ₃ , -C (CH ₃ ) ₃ , and A represents an anion, which is preferably selected from chloride, bromide, iodide or methosulfate.

12. hair treatment composition according to any one of claims 1 to 11, characterized in that it comprises at least one silicone of the formula III

10-Si (CHaUr (IH)

in which x is a number from 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and in particular 0, 1, 2, 3, 4, 5 or 6 stands.

13. hair treatment composition according to any one of claims 1 to 12, characterized in that it comprises at least one silicone of the formula IV

R _{3 is} -Si- [O-SiR ₂ ] _x - (CH ₂ ) _n - [O-SiR ₂ ] _y -O-SiR ₃ (IV), contains, in the R for identical or different radicals from the group -H, -phenyl, -benzyl, -CH ₂ -CH (CH ₃ ) Ph, the C ₁ . _{20 -alkyl>} preferably -CH _3, -CH ₂ CH _3, -CH ₂ CH ₂ CH _3, -CH (CH 3) -CH ₂ CH 2 CH _{2 2ι} H3, -CH 2 CH (CH ₃₎ 2, -CH (CH3) CH ₂ Cπ ₃ , C (CH ₃ ) ₃ , x and y is a number from 0 to 200, preferably from 0 to 10, more preferably from 0 to 7 and in particular 0, 1, 2, 3, 4, 5 or 6, and n is a number from 0 to 10, preferably from 1 to 8 and especially for 2, 3, 4, 5, 6.

14. hair treatment composition according to any one of claims 1 to 13, characterized in that it additionally contains a water-soluble silicone.

15. Use of corneocyte proteins or polypeptides with a molecular weight of 10 to 40 kDa to improve at least one of the properties

Tensile strength of keratinic fibers, especially human hair;

Stabilizing the moisture balance of keratinic fibers, in particular human hair; ,

Combability of keratinic fibers, especially human

hair;

Delaying the aging process of keratinic fibers, especially human hair;

Restructurability of keratinic fibers, especially human

Hair, during and after the perm process;

Reduction in elasticity of keratinic fibers, especially human hair, when damaged by atmospheric agents.

16. Use of hair treatment composition according to one of claims 1 to 14 for the improvement of at least one of the properties

Tensile strength of keratinic fibers, especially human hair;

Stabilizing the moisture balance of keratinic fibers, in particular human hair;

Combability of keratinic fibers, especially human

hair; Delaying the aging process of keratinic fibers, especially human hair;

Restructurability of keratinic fibers, especially human

Hair, during and after the perm process;

Reduction in elasticity of keratinic fibers, especially human hair, when damaged by atmospheric agents.