DE19943421A1 - Water soluble and/or water dispersible silicon modified comb polymer, useful for hair treatment agents, consists of a polymer main chain and sulfone and silicon containing polyester side chains. - Google Patents

Abstract

A water soluble and/or water dispersible silicon modified comb polymer (A) comprises a polymer main chain and sulfone and silicon containing polyester side chains, that are at least partially neutralized by sodium and lithium counter ions, whereby the molar ratio of lithium to sodium of 0.1-50, preferably 0.5-25. An Independent claim is included for a hair treatment agent containing the comb polymer (A).

Description

The present invention relates to new silicon-modified sulfonated comb polymers with selected lithium-sodium ratio and preparations, such comb poly containing mere. In particular, the present invention relates to hair cosmetics Active ingredients and preparations for strengthening, shaping, strengthening and structuring improvement of hair.

An appealing looking hairstyle is now generally considered an indispensable part of a neat exterior. Due to current fashion trends apply Again and again hairstyles as chic, which can only be used with many hair types build up certain strengthening agents or for a longer period maintained.

For these reasons, hair care cosmetics have been used for some time, which are intended to be rinsed out of the hair after exposure those, some of which should remain on the hair. The latter can be formulated in this way that they serve not only the care of the individual hair, but also that Improve the overall appearance of the hairstyle, for example by giving it Give hair more volume, fix the hair style over a longer period of time or improve his manageability.

The property of fullness is attributed to a hairstyle, for example, if that Hair does not lie flat on the scalp after treatment and is easy to style.  

The property of volume is attributed to a hairstyle, for example, when the hair is full and bouncy after treatment.

The property of the body is attributed to a hairstyle, for example, if that Hair volume remains large even under external, disturbing influences.

Firming agents, which are usually polymeric compounds deals, can be incorporated into conventional hair cleaners or conditioners the. In many cases, however, it is advantageous to use them in the form of special agents such as hair fixatives or apply hair sprays.

There have been a number of developments in the hair cosmetic field recently, a need for new types of firming agents or new formulations shapes have awakened. Many of these developments are not based on users man-made disadvantages or inadequacies of the known means, but e.g. B. on environmental considerations, legal requirements or other "non- technical "causes.

In particular, a transition from funds based on volatile organi shear compounds (so-called "volatile organic compounds" or in short: VOC's), e.g. As alcohols, aimed at water-based agents.

The state of the art, however, leaves active substances (polymers) and preparations lack which meet the requirements mentioned above. The hairstyle fi Preparations of the prior art generally contain, for example Components (synthetic or natural polymers) that run the risk of partial or complete replacement of volatile organic components Water to experience a significant impairment of product properties often has to be compensated by clever wording. In addition, the Fixing preparations of the prior art often by difficult or formulation components that are difficult to formulate with insufficient long-term stability from, this particularly applies to silicone derivatives that improve the Flexibility and tactility of the polymer film surface can be used.  

It was therefore the task to develop appropriate means that with regard to the application properties, such as spray behavior and Drying time for hair sprays that meet consumer expectations and at the same time a reduced proportion of volatile organic compounds exhibit without the elementary properties of the polymer film on the hair, such as B. Clarity / transparency, surface tactility, gloss, elasticity and washout Ability to be affected negatively and the processability of the formulation components is simple and unproblematic.

It has now been found, and that is the reason for solving the problem, that what ser soluble and / or water dispersible silicone modified comb polymers, best starting from a polymer main chain and with this polymer main chain Polyesters containing sulfone groups and silicone components linked ester groups esterseitenarms, which at least partially by sodium and lithium counterions were neutralized, the molar ratio of lithium to sodium between 0.1 and 50, preferably between 0.5 and 25, the disadvantages of the prior art eliminate or at least mitigate.

The comb polymers according to the invention are distinguished both by good water and Alcohol tolerance as well as favorable film properties and high network fortune. They are also easy to formulate.

The basic structure of the comb polymers according to the invention essentially follows the following scheme:

The interconnected groups mean the name XXX the base body of a polymer backbone, on which Mo lekülgruppungen are connected, which have the designation YYY. The mole cooling groups YYY represent both the complete sulfone group and silicone comm  component-containing polyester side arms of the comb polymers according to the invention, can also represent other molecular groupings.

The main polymer chain of the comb polymers used according to the invention preferably consists of:

• a) polymeric aliphatic, cycloaliphatic or aromatic Polycarbonsäu ren or their derivatives such as polyacrylic acid, polymethacrylic acid and their esters (esters of the two acids with aliphatic, cycloaliphatic or aromatic alcohols with C ₁ to C ₂₂ ), maleic acid, maleic anhydride, fumaric acid and polynorbonic acid. The average molecular weights of the polycarboxylic acid used can be between 200 and 2,000,000 g / mol, the range from 2,000-100,000 g / mol being preferably used.

The polymer main chain can also consist of:

• a) a polymeric aliphatic, cycloaliphatic or aromatic polyalko like polyvinyl alcohol or polynorbonyl alcohol. The middle ones Molecular weights of the polyalcohols used can be between 200 and 2,000,000 g / mol are preferably in the range of 2,000-100,000 g / mol Is used.

In addition, you can

• a) also statistical or block-like copolymers of the two above Ver bond classes with other vinyl monomers such as styrene, Acrylamide, α-methylstyrene, styrene, N-vinylpyrrolidone, N-vinylcaprolactone, acrylic amidopropylene sulfonic acid and its alkali, alkaline earth and ammonium salts, MAPTAC, vinyl sulfonic acid, vinyl phosphonic acid or vinyl acetate are used become. The average molecular weights of the copolymers used can 200 to 2,000,000 g / mol are between 2,000 and 100,000 g / mol is preferably used.

The polyester side chains are connected via an ester group through the Reaction of a functional group of the main chain (-COOH in the case of polycarbonate acids or -OH in the case of polyalcohols) with a corresponding group of the poly esters (OH in the case of polycarboxylic acids and COOH in the case of polyalcohols).  

Of course, reactive derivatives of the components just mentioned can also be used are reacted (for example anhydrides, esters, halogen compounds and the like).

The polyesters used according to the invention can advantageously be distinguished by the following generic structural formulas:

etc.

Here p and o can be chosen so that the above-mentioned average moles molecular weights of the main chain components used.

The polyester side chains according to formula I-III advantageously consist of:
G: a siloxane unit containing at least two terminal oxygen atoms, which is advantageously characterized by structural elements as follows:

wherein the silicon atoms can be substituted with the same or different alkyl radicals and / or aryl radicals and / or arylalkyl radicals, which are generally represented here by the radicals R ₉ -R ₁₀ (to say that the number of different radicals is not necessarily limited to up to 2 is). a can advantageously assume values of 1-5,000.
At least some of the abovementioned siloxane units can be replaced in the polymer by aromatic, aliphatic or cycloaliphatic organic units containing at least two terminal oxygen atoms and having a carbon number from C ₂ to C ₂₂ or derivatives of a polyglycol of the form HO- [R ³ -O] _k - [R ⁴ -O] _m -H, corresponding to an organyl unit

OR ³ _k OR ⁴ _m -O-

The R ³ and R ⁴ radicals represent alkylene radicals with a carbon number of C ₂ -C ₂₂ , the two radicals not necessarily having to be different.

The following applies to the coefficients k and m: k + m ≧ 1, k and m also being able to be selected such that the above-mentioned average molecular weights of the main chain components used are available.
D: an aromatic, aliphatic or cycloaliphatic organyl unit containing at least two terminal acyl groups and having a carbon number from C ₂ to C ₂₂ , it also being possible for combinations of several different acid components to be present in the claimed target molecule, for example an organyl unit of the scheme

where R ^{S can represent} aromatic and linear or cyclic, saturated or unsaturated aliphatic bifunctional radicals with carbon numbers from C ₂ to C ₂₂ . Fluorinated or perfluorinated acyl residues are also within the meaning of the invention
or a terminal acyl group and a terminal oxo group contain the aromatic, aliphatic or cycloaliphatic organyl unit with a carbon number from C ₂ to C ₂₂ , whereby combinations of several different acid components can also be contained in the claimed target molecule, for example an organyl unit of the scheme

where R ^{S 'can represent} aromatic and linear or cyclic, saturated or unsaturated aliphatic bifunctional radicals with carbon numbers from C ₂ to C ₂₂ . Fluorinated or perfluorinated acyl residues are also within the meaning of the invention.
T: a compound from the group of the sulfonated aromatic, aliphatic or cycloaliphatic organyl compounds containing at least two terminal acyl groups
R ¹ : lithium and / or sodium along with optionally further counterions, e.g. B., potassium, magnesium, calcium, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, in which the alkyl positions of the amines are independently occupied by C ₁ - to C ₂₂ -alkyl radicals and 0 to 3 hydroxyl groups.
R ² : a molecular residue selected from the groups of

• - Monofunctional linear or branched bridging via ether functions silicon-containing organyl residues,
• aromatic, aliphatic or cycloaliphatic amino functions: (-NH-R ⁵ , -NR ⁵ ₂ where R ^{5 can be} an alkyl or aryl radical with C ₁ to C ₂₂ )
• aromatic, aliphatic or cycloaliphatic monocarboxylic acid groups: (-COOR ⁶ where R ^{6 is} an alkyl or aryl radical with C ₁ to C ₂₀₀ )
• - aromatic, aliphatic or cycloaliphatic organyl residues bridged via ether functions: (-OR ⁵ )
• - Polyalkoxy compounds of the form bridging via ether functions
  -O- [R ⁷ -O] q- [R ⁸ -O] _r -Y
  the radicals R ⁷ and R ⁸ advantageously represent alkylene radicals with a carbon number of C ₂ -C ₂₂ , the two radicals not necessarily having to be different. The radical Y can be either hydrogen or aliphatic in nature with C ₁ -C ₂₂ . The following applies to the coefficients q and r: q + r ≧ 1;
• - Single or multiple ethoxylated sulfonated organyl residues bridging via ether functions or preferably their alkali metal or alkaline earth metal salts, as advantageously characterized, for example, by the generic structural formula
  - (O-CH ₂ -CH ₂ ) _s -SO ₃ R ¹
  with s ≧ 1, and where s can also be chosen so that the afore-mentioned average molecular weights of the main chain components used come to ge.
• - Silicon functions derived from monofunctional silicones according to the generic structural formula
  wherein R ⁹ and R ^{10 have} the properties mentioned, and regardless of which R ^{11 may} also represent an alkyl radical or an aryl radical or an arylalkyl radical.

The functionality of the components used according to the invention is limited of course not on the use of OH groups, but also includes COOH end groupings or mixtures of both, with the fact that here also applies at least two COOH groups must be free in the molecule. Reactive  Derivatives such as anhydrides, esters, epoxides or halides are of course also applicable.

The silicone-containing constituents of the polymer are advantageously present in a proportion of 0.1 to 50 mol%, based on the molar mass of the siloxane unit G and on the total molar mass of the comb polymers according to the invention. The silicon-containing components can be of different chemical nature. The following two types of silicone-containing components are considered to be advantageous embodiments of the present invention:

• a) On the one hand, linear, at least monofunctional, silicon-containing structures can be condensed into the polyester chain.
  The use of monofunctional linear or branched silicone-containing derivatives during the polycondensation leads to the final capping of the polyester chains (corresponds to R ² in formula I).
  The use of silicone components with 2 reactive groups leads to linear polyester structures. The use of silicone components with 3 or more reactive groups can lead to branched or cross-linked structures.
  The silicon content in the groupings
  is advantageously between 0.1 and 50 mol%. The average molecular weights are preferably between 100 and 100,000 g / mol, the range for monofunctional silicone-containing derivatives between 100 and 2,000 g / mol or for at least difunctional silicone-containing derivatives between 100 and 30,000 g / mol being particularly preferred.
• b) On the other hand, at least monofunctional, linear or branched, silicon-containing derivatives can also be incorporated into the polymer main chain.
  With these derivatives too, the silicon content is advantageously between 1 and 50 mol%. The average molecular weights are preferably between 100 and 100,000 g / mol, the range between 100 and 30,000 g / mol being particularly preferred.
  The esters of acrylic or methacrylic acid and silicon-containing monoalcohols are preferably used.
• c) Of course, any combination of one or more can be used rerer of the connection classes described in a) and b) used with each other become.

The average molecular weights of the comb polymers according to the invention can advantageously be between 200 and 2,000,000 g / mol, particularly advantageously between 200 and 100,000 g / mol, the range from 1,000 to 30,000 g / mol preferably being used, very particularly advantageously from 5,000 -15,000 g / mol.

The polyesters according to the invention are advantageously produced by esterification or transesterification of the underlying functional alcohol components and di oils with the carboxylic acids or their suitable derivatives (for example alkyl esters, Halides and the like) in the presence of an esterification catalyst such as Alkali metal hydroxides, their carbonates and acetates, alkaline earth metal oxides, hydroxides, -carbonates and -acetates and alkali metal and alkaline earth metal salts of fatty acids with 6 to 22 carbon atoms. Furthermore, titanium compounds, such as titanates, metallic tin and organic tin compounds, such as mono- and dialkyltin derivatives as esterification catalysts. Preferably the Esterification / transesterification using tin cut or titanium tetraisopropylate carried out as a catalyst.

The esterification / transesterification is preferred at temperatures from 120 ° C to 280 ° C carried out, the resulting low-boiling condensate (alcohols or what ser) is removed by distillation from the condensation product, preferably with min pressure down to <0.1 mbar.

As starting materials for the main polymer chain of silicone-modified comb polymers according to the invention, polymeric aliphatic, cycloaliphatic or aromatic polycarboxylic acids or their derivatives such as, for example, polyacrylic acid, polymethacrylic acid and their esters (esters of the two acids with aliphatic, cycloaliphatic or aromatic alcohols with C ₁ to C ₂₂ ), maleic acid, maleic anhydride, fumaric acid and polynorbornene acid can be used. The average molecular weights of the individual polycarboxylic acids can be between 200 and 2,000,000 g / mol, the range from 2,000-100,000 g / mol being used with preference.

Also random or block copolymers of the above compound classes with other vinyl monomers such as styrene, acrylamide, α-methyl styrene, styrene, N-vinyl pyrrolidone, N-vinyl caprolactone, acrylamidopropylene sulfone acid and its alkali, alkaline earth and ammonium salts, MAPTAC (methacrylamido propyltrimethylammonium chloride), DADMAC, vinylsulfonic acid, vinylphosphonic acid, Crotonic acid, vinyl acetamide, vinyl methylacetamide, vinyl foramide, acrylic acid or meth acrylic acid derivatives (for example free acid or ester), silicon-containing acrylate, meth Acrylate or acrylamide derivatives or vinyl acetate can be used to form the polymers Serve main chain.

As a basis for aromatic, aliphatic or cycloaliphatic organyl units containing at least two terminal oxygen atoms and having a carbon number from C ₂ to C ₂₂ or derivatives of a polyglycol of the form HO- [R ³ -O] _k - [R ⁴ -O] _m -H bi functional alcohol components are used.

At least difunctional aromatic, aliphatic or cycloaliphatic alcohols with a carbon number from C ₂ to C ₂₂ or a poly glycol of the form HO- [R ³ -O] _k - [R ⁴ -O] _m -H are particularly suitable for this. The radicals R ³ and R ⁴ represent alkyl radicals with a carbon number from C ₂ to C ₂₂ , where both radicals can be the same or different. The following applies to the coefficients k and m: k + m ≧ 1, where k and m can furthermore be chosen so that the above-mentioned average molecular weights of the main chain components used are available.

It can be particularly advantageous to use trifunctional alcohol components instead of difunctional alcohol components use tra- or generally polyfunctional alcohol components, for example advantageously chosen from the following group:  

Glycerin

Diglycerin

Triglycerin

Pentaerythritol

Sorbitol

Xylitol

Ascorbic acid

As a basis for aromatic, aliphatic or cycloaliphatic organic units containing at least two terminal acyl groups with a carbon number of C ₂ to C ₂₂ , for example organic units of the scheme

For example, aromatic and linear or cyclic, saturated or unsaturated aliphatic carboxylic acids with a carbon number from C ₂ to C ₂₂ or their anhydrides can be used, for example phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, adipic acid, succinic acid, glutaric acid, pimelic acid, kimelic acid, kimelic acid, kimelic acid, kimelic acid, kimelic acid, kimelic acid, kimelic acid, kimelic acid, kimelic acid, kimelic acid, kimelic acid, kimelic acid, kimic acid, kimic acid, , Azelaic acid, sebacic acid, brassylic acid can be used. Combinations of several different acid components are also possible as a monomer unit in the claimed target molecule.

Suitable sulfone group-containing monomers are sulfonated aromatic, aliphatic or cycloaliphatic dialcohols, diacids or their esters, anhydrides or halogenides, such as, for example, sulfosuccinic acid, 5-sulfoisophthalic acid or their alkali metal or alkaline earth metal salts or mono-, di-, tri- or tetraalkylammonium salts with C. ₁ to C ₂₂ alkyl radicals. Among the alkali salts, lithium and sodium salts are particularly preferred.

Aromatic, aliphatic or cycloaliphatic amines with C ₁ - to C ₂₂ -alkyl or aryl residues and / or aromatic, aliphatic or cycloaliphatic monocarboxylic acids with C ₁ to C ₂₀₀ alkyl or aryl residues and / or polyalkoxy compounds of the form -O- [R ⁷ -O] _q - [R ⁸ -O] _r -X, where the radicals R ⁷ and R ⁸ alkyl radicals, which may be the same or different, represent a carbon number from C ₂ to C ₂₂ and the radical X is both hydrogen and can also be aliphatic in nature with C ₁ -C ₂₂ and the coefficients q and r: q + r ≧ 1 are used.

Also suitable are sulfonated mono- or polyethylene glycols or, preferably, their alkali metal or alkaline earth metal salts: (H- (O-CH ₂ -CH ₂ ) _s -SO ₃ R ¹ with s ≧ 1 where s can also be chosen so that the above-mentioned average molecular weights of the main chain components used.)

Suitable suitable silicone-containing derivatives are, for example, linear siloxane diols, hydroxyalkyl-endmodified siloxanes, differently high ethoxylated or propoxylated silanols or branched derivatives with different functionality. Such are generally characterized by structural elements as follows:

wherein the silicon atoms can be substituted with the same or different alkyl radicals and / or aryl radicals and / or arylkyl radicals, which are generally represented here by the radicals R ₉ -R ₁₀ (to say that the number of different radicals is not necessarily up to 2 is limited). a can advantageously assume values of 1-5,000.

If the silicon-containing components are used for the end-capping of the polyesters, other compounds of the structure prove to be the case

[[(CH ₃ ) ₃ Si-O] ₂ Si [OCH ₃ ]] - O- [R ⁷ -O] _q - [R ⁸ -O] _r -H

as suitable, the radicals R ⁷ and R ⁸ symbolizing alkyl radicals which may be the same or different with a carbon number of C ₂ to C ₂₂ . The following also applies to the coefficients: q + r ≧ 0.

To produce the polyesters according to the invention, those used to form the screen tenkette used alcohols and acids or esters advantageous in the molar Ver ratios of 1: 1 to about 10: 1 (1 or 10 parts di- or polyol) and the alcohol and water and the excess component after con distillation removed. Alcohol and acid components are in the target molecule preferably in an approximate stoichiometric ratio of 1: 1.  

The proportion of acid components containing sulfonic acid residues is 1 to 99 mol%, preferably 10 to 40, particularly preferably 15 to 25 mol%, based on the total amount of carboxylic acids.

The sulfone group-containing properties have very favorable application properties Polyester of the general formula I when 1,2-propanediol as diol components and / or diethylene glycol and / or cyclohexanedimethanol, as carboxylic acids isophthal acid also with 1,3-cyclohexanedicarboxylic acid or with 2,6-naphthalenedicarbon acid or with adipic acid and 5-sulfoisophthal as residues containing sulfo groups acid sodium and / or lithium salt, the sodium and / or lithium salt of Isethionic acid can be used.

Below is a section of a comb polymer molecule according to the invention listed, with a polyacrylic acid chain the backbone of the comb polymer molecule forms. The acid functions are esterified with polyols and / or oligosilanols, which are in turn esterified with an acid function of isophthalic acid molecules. Further Polyols from which structural elements of this polymer molecule are derived Pentaerythritol, 1,2-propanediol, dimethylpolysilanol. As containing sulfonate groups Agent from which structural elements of the polymer molecule are derived is used, for example as the 5-sulfoisophthalic acid dialkyl Na salt.

For reasons of reaction management, which are known to the person skilled in the art, there is no absolute uniformity of the substitution in the target polymer, rather a certain statistical distribution of the substitution can be assumed. Furthermore, certain reactive groupings of molecules can also be observed for the crosslinking of two or more polymer chains to form a more or less complex network, as the following molecular scheme also attempts to illustrate.

The sulfone-containing polyesters to be used according to the invention are colorless to yellow clean, odorless solids. They are readily soluble in water and alcohols. You can NEN advantageously incorporated into cosmetic preparations for setting the hair become.  

The silicone-modified comb polymers according to the invention are advantageously produced adheres by adding one or more polyfunctional alcohols with a sulfonic acid group containing substance containing at least two carboxyl groups, for example 5- Dimethyl sulfoisophthalate sodium salt, optionally at least one more two substance containing carboxyl groups and a polymer with one or more reren polycarboxylic acids, for example polyacrylic acid or polymethacrylic acid and a mono- or multi-functional siloxane combined, heated and the usual processing steps.

In a particular embodiment of the present invention, the inventions inventive water-soluble and / or water-dispersible comb polymers, be consisting of a polyacrylic acid-containing polymer main chain and sulfongrup Pen-containing polyester side arms therefore in cosmetic, especially hair cosms table preparations incorporated.

The cosmetic and dermatological agents according to the invention are used Preparations in the usual way for cosmetics on the hair in sufficient Amount applied.

The cosmetic and dermatological preparations according to the invention can Contain cosmetic auxiliaries, as are usually found in such preparations are used, e.g. B. preservatives, bactericides, perfumes, substances for Prevent foaming, dyes, pigments that have a coloring effect Thickeners, surface-active substances, emulsifiers, emollients moist and / or moisturizing substances, fats, oils, waxes or other substances Liche components of a cosmetic or dermatological formulation such as Alko hole, polyols, polymers, foam stabilizers, electrolytes, organic solvents or silicone derivatives.

In cosmetic preparations for setting the hair, such as. B. hair sprays, hair varnishes, foam fixers, liquid fixers, styling gels, etc., can according to the invention Comb polymers to be used preferably in concentrations of 0.5 to 30 Ge percent by weight are used.  

The compositions according to the invention for setting the hair can be used as Hair sprays or foam aerosols are available and the usual and the state of the Technically appropriate additives contain, provided there is a corresponding compatibility is present. These are, for example, other solvents such as lower polyalcohols and their toxicologically compatible ethers and esters, plasticizers, light and low volatility silicones, high and low volatility branched or unbranched Hydrocarbons, emulsifiers, antioxidants, waxes, stabilizers, pH value Regulators, dyes, consistency agents, antistatic agents, UV absorbers, perfumes, etc.

Should the composition according to the invention as a hair spray or foam aerosol are used, a blowing agent is usually added. Usual blowing agents are lower alkanes, for example propane, butane or isobutane, dimethyl ether, Nitrogen, nitrogen dioxide or carbon dioxide or mixtures of these substances.

When used in mechanical spray or foam devices, for example Spray pumps or manual foam pumps or squeeze systems can do that Blowing agents are generally not required.

The aqueous preparations according to the invention optionally advantageously contain Alcohols, diols or polyols of low C number, and their ethers, preferably etha nol, isopropanol, propylene glycol, glycerin, ethylene glycol, ethylene glycol monoethyl or monobutyl ether, propylene glycol monomethyl, monoethyl or monobutyl ether, Diethylene glycol monomethyl or monoethyl ether and analog products, also Al low carbon number, e.g. As ethanol, isopropanol, 1,2-propanediol, glycerin and in particular one or more thickeners, which or which advantageous can be selected from the group silicon dioxide, aluminum silicates, Polysac charide or its derivatives, e.g. B. hyaluronic acid, xanthan gum, hydroxypropylme ethyl cellulose, particularly advantageously from the group of polyacrylates, preferably a Polyacrylate from the group of the so-called carbopoles, for example carbopoles Types 980, 981, 1382, 2984, 5984, each individually or in combination.

In the technical sense, gels are understood to mean: Relatively stable, light deformable disperse systems consisting of at least two components, which as a rule from a - mostly solid - colloidally divided substance from long-chain molecular groups  gene (e.g. gelatin, silica, polysaccharides) as a scaffold and a liquid Dispersing agents (e.g. water) exist. The colloidally divided substance is often called Thickeners or gelling agents called. It forms a spatial network in the Di Spersionsmittel, whereby individual colloidal particles on electrostatic Interaction can be more or less firmly linked. The Tue Spersionsmittel, which surrounds the network, is characterized by electrostatic Af fineness to the gelling agent, d. that is, a predominantly polar (in particular: hydrophilic) Gelling agent preferably gels a polar dispersing agent (in particular: water), whereas a predominantly non-polar gelling agent preferably non-polar di dispersant gelled.

Strong electrostatic interactions, for example in hydrogen bridges kenbundungen between gelling agent and dispersing agent, but also between Disper Sion agent molecules are realized with each other, can lead to strong crosslinking also lead the dispersant. Hydrogels can be almost 100% water exist (in addition, for example, about 0.2-1.0% of a gelling agent) and thereby have a firm consistency. The water content lies in an ice-like structure elements, so that the gel originates from the name [from lat. "gelatum" = "Ge frorenes "about the alchemical expression" gelatina "(16th century) for nhdt." gelatin "] do justice.

Gels according to the invention usually contain low C number alcohols, e.g. B. Ethanol, isopropanol, 1,2-propanediol, glycerin and water in the presence of a ver thickening agent, which in the case of oily-alcoholic gels, preferably silicon dioxide or a Aluminum silicate, preferably in the case of aqueous-alcoholic or alcoholic gels Is polyacrylate.

In the case of cosmetic and dermatological preparations according to the invention for example, it can also be a shampoo, preparation to blow-dry or insert hair, preparations for dyeing, hairstyling or treatment lotion.

Preparations according to the invention can optionally be advantageously by Mark the content of surfactants. Surfactants are amphiphilic substances that are organic, un  can dissolve polar substances in water. They care, due to their specific The molecular structure with at least one hydrophilic and one hydrophobic mole cooling part, for a reduction in the surface tension of the water, the wetting the skin, facilitating dirt removal and removal, an easy rinse and - as desired - for foam regulation.

The hydrophilic portions of a surfactant molecule are usually polar functional groups, for example -COO ^- , -OSO ₃ ^2- , -SO ₃ ^- , while the hydrophobic portions generally represent non-polar hydrocarbon residues. Surfactants are generally classified according to the type and charge of the hydrophilic part of the molecule. There are four groups:

• - anionic surfactants,
• - cationic surfactants,
• - amphoteric surfactants and
• - nonionic surfactants.

Anionic surfactants generally have carboxylate, sulfate or sulfonate groups as functional groups. In aqueous solution they form negatively charged organic ions in acidic or neutral medium. Cationic surfactants are almost exclusively characterized by the presence of a quaternary ammonium group. In aqueous solution, they form positively charged organic ions in an acidic or neutral environment. Amphoteric surfactants contain both anionic and cationic groups and accordingly behave in aqueous solution like anionic or cationic surfactants depending on the pH. They have a positive charge in a strongly acidic environment and a negative charge in an alkaline environment. In the neutral pH range, however, they are zwitterionic, as the following example should illustrate:

RNH ₂ ⁺ CH ₂ CH ₂ COOH X ^- (at pH = 2) X ^- = any anion, e.g. B. Cl ^-
RNH ₂ ⁺ CH ₂ CH ₂ COO ^- (at pH = 7)
RNHCH ₂ CH ₂ COO ^- B ⁺ (at pH = 12) B ⁺ = any cation, e.g. B. Na ⁺

Polyether chains are typical of non-ionic surfactants. Form non-ionic surfactants no ions in aqueous medium.  

A. Anionic surfactants

Anionic surfactants to be used advantageously
Acylamino acids (and their salts), such as

• 1. Acylglutamates, for example sodium acylglutamate, di-TEA-palmitoylaspartate and Sodium caprylic / capric glutamate,
• 2. Acyl peptides, for example palmitoyl-hydrolyzed milk protein, sodium cocoyl hydrolyzed soy protein and sodium / potassium cocoyl hydrolyzed collagen,
• 3. Sarcosinates, for example myristoyl sarcosin, TEA-lauroyl sarcosinate, sodium lauroyl sarcosinate and sodium cocoyl sarcosinate,
• 4. taurates, for example sodium lauroyl taurate and sodium methyl cocoyl taurate,
• 5. Acyl lactylates, lauroyl lactylate, caproyl lactylate
• 6. Alaninate

Carboxylic acids and derivatives, such as

• 1. Carboxylic acids, for example lauric acid, aluminum stearate, magnesium alkano lat and zinc undecylenate,
• 2. Ester carboxylic acids, for example calcium stearoyl lactylate, Laureth-6 citrate and Sodium PEG-4 lauramide carboxylate,
• 3. ether carboxylic acids, for example sodium laureth-13 carboxylate and sodium PEG-6 cocamide carboxylate,

Phosphoric acid esters and salts, such as, for example, DEA-oleth-10-phosphate and dilau-reth-4-phosphate,
Sulfonic acids and salts such as

• 1. acyl isethionates, e.g. B. sodium / ammonium cocoyl isethionate,
• 2. alkylarylsulfonates,
• 3. alkyl sulfonates, for example sodium coconut monoglyceride sulfate, sodium C _12-14 olefin sulfonate, sodium lauryl sulfoacetate and magnesium PEG-3 cocamide sulfate,
• 4. Sulfosuccinates, for example dioctyl sodium sulfosuccinate, disodium laureth sulfo succinate, disodium lauryl sulfosuccinate and disodium undecylenamido MEA-Sul fosuccinate

such as
Sulfuric acid esters, such as

• 1. alkyl ether sulfate, for example sodium, ammonium, magnesium, MIPA, TIPA laureth sulfate, sodium myreth sulfate and sodium C _12-13 pareth sulfate,
• 2. Alkyl sulfates, for example sodium, ammonium and TEA lauryl sulfate.

B. Cationic surfactants

Cationic surfactants which may be used advantageously are

• 1. alkylamines,
• 2. alkylimidazoles,
• 3. Ethoxylated amines and
• 4. Quaternary surfactants
• 5. Esterquats

Quaternary surfactants contain at least one N atom with 4 alkyl or aryl groups pen is covalently connected. Regardless of the pH, this leads to a positive Charge. Alkyl betaine, alkyl amidopropyl betaine and alkyl amidopropyl hy are advantageous droxysulfain. The cationic surfactants used according to the invention can also are preferably selected from the group of quaternary ammonium compounds, especially benzyltrialkylammonium chlorides or bromides, such as Ben zyldimethylstearylammonium chloride, further alkyltrialkylammonium salts, for example Cetyltrimethylammonium chloride or bromide, alkyldimethylhydroxyethylammo nium chlorides or bromides, dialkyldimethylammonium chlorides or bromides, alkyl amidethyltrimethylammonium ether sulfates, alkylpyridinium salts, for example lauryl or cetylpyrimidinium chloride, imidazoline derivatives and compounds with cationic Character such as amine oxides, for example alkyldimethylamine oxides or alkylamino ethyldimethylamine oxides. Cetyltrimethylammonium salts are particularly advantageous use.

C. Amphoteric surfactants

Amphoteric surfactants to be used advantageously

• 1. Acyl- / dialkylethylenediamine, for example sodium acylamphoacetate, disodium acylamphodipropionate, disodium alkyl amphodiacetate, sodium acylamphohydroxy propyl sulfonate, disodium acyl amphodiacetate and sodium acyl amphopropionate,
• 2. N-alkylamino acids, for example aminopropylalkylglutamide, alkylaminopropi onic acid, sodium alkylimidodipropionate and lauroamphocarboxyglycinate.

D. Non-ionic surfactants

Non-ionic surfactants to be used advantageously

• 1. alcohols,
• 2. alkanolamides, such as cocamides MEA / DEA / MIPA,
• 3. amine oxides, such as cocoamidopropylamine oxide,
• 4. esters by esterification of carboxylic acids with ethylene oxide, glycerin, Sorbi tan or other alcohols
• 5. ethers, for example ethoxylated / propoxylated alcohols, ethoxylated / propoxylated te esters, ethoxylated / propoxylated glycerol esters, ethoxylated / propoxylated Cho lesterine, ethoxylated quarter propoxylated triglyceride esters, ethoxylated propoxylated Lanolin, ethoxylated / propoxylated polysiloxanes, propoxylated POE ethers and Alkyl polyglycosides such as lauryl glucoside, decyl glycoside and cocoglycoside.
• 6. sucrose esters, ether
• 7. Polyglycerol esters, diglycerol esters, monoglycerol esters
• 8. Methyl glucose esters, esters of hydroxy acids.

It is also advantageous to use a combination of anionic and / or amphoteric surfactants with one or more non-ionic surfactants.

As a rule, the use of anionic, amphoteric and / or non-ionic surfactants compared to the use of cationic surfactants preferred.

The cosmetic and dermatological preparations contain active ingredients and Excipients, such as those commonly used for this type of hair care and preparation Hair treatment can be used. Preservatives serve as auxiliary substances, surface-active substances, substances to prevent foaming, Thickeners, emulsifiers, fats, oils, waxes, organic solvents, bacteria ricides, perfumes, dyes or pigments, whose job is to remove the hair or the cosmetic or dermatological preparation to dye itself, electrolytes, sub punch against greasy hair.  

Water-soluble alkali metal, am monium, alkaline earth (including magnesium) and zinc salts anorga African anions and any mixtures of such salts to understand, where it must be ensured that these salts are pharmaceutical or cosmetic Mark harmlessness.

The anions according to the invention are preferably selected from the group of Chlorides, the sulfates and hydrogen sulfates, the phosphates, hydrogen phosphates and the linear and cyclic oligophosphates as well as the carbonates and hydrogen car bonate.

Cosmetic preparations, which are a shampoo, contain preferably at least one anionic, non-ionic or amphoteric surface tive substance, or mixtures of such substances in an aqueous medium and Tools, as they are usually used for this. The surface active sub punch or the mixtures of these substances in a concentration between 1% by weight and 50% by weight are present in the shampoo.

A cosmetic preparation in the form of a lotion that is not rinsed off, in particular special a lotion for inlaying the hair, a lotion that is used to blow-dry the hair is used, a hairdressing and treatment lotion, generally represents an aq Rige, alcoholic or aqueous-alcoholic solution and contains the Invention moderate comb polymers.

The compositions according to the invention optionally contain those in Kos Metics usual additives, for example perfume, thickeners, dyes, Des odorants, antimicrobials, lipid-replenishing agents, complexing and seque treatment agents, pearlescent agents, plant extracts, vitamins, active ingredients and the like.

The following examples are intended to illustrate the present invention without it restrict. All quantities, parts and percentages are, if not otherwise stated, on the weight and the total amount or on the total weight of the preparations.  

(A) Manufacturing examples example 1 Reaction management

1,2-propanediol, diethylene glycol and titanium tetraisopropoxide are placed in a 2-l four-necked flask with a KPG stirrer, internal thermometer, gas inlet tube and distillation bridge, briefly stirred and then sodium carbonate and 5-sulfoisophthalic acid, dimethyl ester Na salt, isophthalic acid, the corresponding siloxane acid Diol (M _n about 4000 g / mol-Aldrich) and polyacrylic acid entered. It is then evacuated twice and rendered inert with N ₂ . With stirring, it is now within 30 min. heated to 170 ° C. The transesterification or distillation begins at approx. 173 ° C. The internal temperature is raised to 210 ° C. in the course of 2 hours. The internal temperature is then increased to approximately 220 ° C. and a further 30 minutes. condensed. Subsequently, in 30 min. the pressure is reduced to the best vacuum and condensed at 220 ° C for 1 hour. It is then aerated with N ₂ and the melt is discharged.

Example 2 Reaction management

1,2-propanediol, diethylene glycol and titanium tetraisopropoxide are placed in a 2-liter four-necked flask with a KPG stirrer, internal thermometer, gas inlet tube and distillation bridge, briefly stirred and then sodium carbonate and 5-sulfoisophthalic acid, dimethyl ester Na salt, isophthalic acid, polyacrylic acid and the corresponding silicone (Viscosity 1800-2200 Centistokes - Aldrich) entered. It is then evauated twice and rendered inert with N ₂ . With stirring, it is now within 30 min. heated to 170 ° C. The transesterification or distillation begins at approx. 173 ° C. The internal temperature is raised to 210 ° C. in the course of 2 hours. The internal temperature is then increased to approximately 220 ° C. and a further 30 minutes. condensed. Subsequently, in 30 min. the pressure is reduced to the best vacuum (<1 mbar) and condensed at 220 ° C for 1 hour. It is then aerated with N ₂ and the melt is discharged.

Example 3 Reaction management

1,2-propanediol, diethylene glycol, sodium isethionate, 5-sulphoisophthalic acid Na salt and titanium tetraisopropylate are placed in a 2-liter four-necked flask with KPG stirrer, internal thermometer, gas inlet tube and distillation bridge, briefly stirred and then sodium carbonate, isophthalic acid and polyacrylic acid the corresponding silicone (viscosity 1800-2200 Centistokes - Aldrich) entered. It is then evacuated twice and rendered inert with N ₂ . With stirring, it is now within 30 min. heated to 170 ° C. The transesterification or distillation begins at approx. 173 ° C. Over the course of 2 hours, the inside temperature is increased to 210 ° C. The internal temperature is then increased to approximately 220 ° C. and a further 30 minutes. condensed. Subsequently, in 30 min. the pressure is reduced to the best vacuum. It is then aerated with N ₂ and the melt is discharged.

Example 4 Reaction management

1,2-propanediol, diethylene glycol, sodium isethionate, 1,4-cyclohexanedicarboxylic acid and titanium tetraisopropylate are placed in a 2-liter four-necked flask with KPG stirrer, internal thermometer, gas inlet tube and distillation bridge, briefly stirred and then sodium carbonate and 5-sulfoisophthalate dimethyl acid Salt, isophthalic acid, the corresponding silicone (Silvet 867 - WITCO (propoxylated trisiloxane - mono functional with respect to the reactive group, in this case OH)) and polyacrylic acid. It is then evacuated twice and rendered inert with N ₂ . With stirring, it is now within 30 min. heated to 170 ° C. The transesterification or distillation begins at approx. 173 ° C. The internal temperature is raised to 210 ° C. in the course of 2 hours. The internal temperature is then increased to approximately 220 ° C. and a further 30 minutes. condensed. Subsequently, in 30 min. the pressure is reduced to the best vacuum and condensed at 220 ° C for 1 hour. It is then aerated with N ₂ and the melt is discharged.

Example 5 Reaction management

In a 2-liter four-necked flask with a KPG stirrer, internal thermometer, gas inlet tube and distillation bridge, 1,2-propanediol, diethylene glycol, sodium isethionate and tantetraisopropylate are initially introduced, stirred briefly and then sodium carbonate and 5-sulfoisophthalic acid Li salt, isophthalic acid, 1.4 -Cyclohexanedicarboxylic acid and the corresponding silicone (dimer of dimethyldihydroxysilanol, corresponds to an OH-end functionalized polydimethylsiloxane) and polyacrylic acid. It is then evacuated twice and rendered inert with N ₂ . With stirring, it is now within 30 min. heated to 170 ° C. The transesterification or distillation begins at approx. 173 ° C. The internal temperature is raised to 210 ° C. in the course of 2 hours. The internal temperature is then increased to approximately 220 ° C. and a further 30 minutes. condensed. Subsequently, in 30 min. the pressure is reduced to the best vacuum (<1 mbar) and condensed at 220 ° C for 1 hour. It is then aerated with N ₂ and the melt is discharged.

Example 6 Reaction management

1,4-cyclohexanedimethanol, 1,4-cyclohexanedicarboxylic acid, 1,2-propanediol, diethylene glycol, sodium isethionate and titanium tetraisopropylate are placed in a 2-liter four-necked flask with KPG stirrer, internal thermometer, gas inlet tube and distillation bridge, briefly stirred and then sodium carbonate, 5- Sulfoisophthalic acid Li salt ("LI-SIM"), 5-sulfoisophthalic acid dimetylester Na salt ("NA-SIM"), isophthalic acid, pentaerythritol, the corresponding silicone (dimer of dimethyldihydroxysilanol, corresponds to a double-ended OH-functionalized polydimethylsiloxane ) and polyacrylic acid entered. It is then evacuated twice and rendered inert with N ₂ . With stirring, it is now within 30 min. heated to 170 ° C. The transesterification or distillation begins at approx. 173 ° C. The internal temperature is raised to 210 ° C. in the course of 2 hours. The internal temperature is then increased to approximately 220 ° C. and a further 30 minutes. condensed. Subsequently, in 30 min. the pressure is reduced to the best vacuum (<1 mbar) and condensed at 220 ° C for 1 hour. It is then aerated with N ₂ and the melt is discharged.

(B) Recipe examples

Hair sprays

Examples 1-6

mousse

Examples 7-8

Styling gels

Examples 13-16

Styling shampoos

Example 17-18

Claims (6)

1. water-soluble and / or water-dispersible silicone-modified comb polymers, consisting of a polymer main chain and with this polymer main chain via esters groups linked polyester pages containing sulfone groups and silicone components poor, which is at least partially neutralized by sodium and lithium counterions with the molar ratio of lithium to sodium between 0.1 and 50, preferably between 0.5 and 25. 2. Comb polymers according to claim 1, characterized in that their main polymer chain is selected from the group of polymeric aliphatic, cycloaliphatic or aromatic polycarboxylic acids or their derivatives such as polyacrylic acid, polymethacrylic acid and their esters (esters of the two acids with aliphatic, cycloaliphatic or aromatic alcohols with C ₁ to C ₂₂ ), maleic acid, maleic anhydride, fumaric acid and polynorbonic acid. 3. Comb polymers according to claim 1, characterized in that they are selected from the group of polyesters of the following generic structural formulas
etc.
where p and m are chosen such that average molecular weights of the main chain components used are between 200 and 2,000,000 g / mol, the range from 2,000-100,000 g / mol being preferably used,
the polyester side chains according to formula I-III advantageously consist of:
G: a siloxane unit containing at least two terminal oxygen atoms, which is advantageously characterized by structural elements as follows:
wherein the silicon atoms can be substituted with the same or different alkyl radicals and / or aryl radicals and / or arylakyl radicals, which are generally represented here by the radicals R ₉ -R ₁₀ (to say that the number of different radicals is not necessarily limited to up to 2 is). a can advantageously assume values of 1-5,000,
and the aromatic, aliphatic or cycloaliphatic organyl units containing at least two terminal oxygen atoms and having a carbon number from C ₂ to C ₂₂ or derivatives of a polyglycol of the form HO- [R ³ - O] _k - [R ⁴ -O] _m -H, corresponding to an organyl unit
OR ³ _k OR ⁴ _m -O-
the radicals R ³ and R ^{4 represent} alkylene radicals with a carbon number of C ₂ -C ₂₂ , the two radicals not necessarily having to be different,
where for the coefficients k and m applies: k + m ≧ 1 where k and m can also be chosen so that the above-mentioned average molecular weights of the main chain components used come into play.
D: an aromatic, aliphatic or cycloaliphatic organyl unit containing at least two terminal acyl groups and having a carbon number from C ₂ to C ₂₂ , it also being possible for combinations of several different acid components to be present in the claimed target molecule, for example an organyl unit of the scheme
where R ^{S can represent} aromatic and linear or cyclic, saturated or unsaturated aliphatic bifunctional radicals with carbon numbers from C ₂ to C ₂₂ . Fluorinated or perfluorinated acyl residues are also within the meaning of the invention
or a terminal acyl group and a terminal oxo group containing aromatic, aliphatic or cycloaliphatic organic unit with a carbon number from C ₂ to C ₂₂ , whereby combinations of several different acid components can also be present in the claimed target molecule, for example an organic unit of the scheme
where R ^{S 'can represent} aromatic and linear or cyclic, saturated or unsaturated aliphatic bifunctional radicals with carbon numbers from C ₂ to C ₂₂ . Fluorinated or perfluorinated acyl residues are also within the meaning of the invention.
T: a compound from the group of the sulfonated aromatic, aliphatic or cycloaliphatic organyl compounds containing at least two terminal acyl groups
R ¹ : lithium and / or sodium along with optionally further counterions, e.g. B., potassium, magnesium, calcium, ammonium, monoalkylammonium, dialkylammonium, trialkylammonium or tetraalkylammonium, in which the alkyl positions of the amines are independently occupied by C ₁ - to C ₂₂ -alkyl radicals and 0 to 3 hydroxyl groups.
R ² : a molecular residue selected from the groups of

• monofunctional linear or branched silicone-containing organyl residues bridging via ether functions,
• aromatic, aliphatic or cycloaliphatic amino functions: (-NH-R ⁵ , -NR ⁵ ₂ where R ^{5 can be} an alkyl or aryl radical with C ₁ to C ₂₂ )
• aromatic, aliphatic or cycloaliphatic monocarboxylic acid groups: (-COOR ⁶ where R ^{6 is} an alkyl or aryl radical with C ₁ to C ₂₀₀ )
• - aromatic, aliphatic or cycloaliphatic organyl residues bridged via ether functions: (-OR ⁵ )
• - Polyalkoxy compounds of the form bridging via ether functions
  - (O- [R ⁷ -O] _q - [R ⁸ -O] _r -Y
  The radicals R ⁷ and R ⁸ advantageously represent alkylene radicals with a carbon number of C ₂ -C ₂₂ , the two radicals not necessarily having to be different. The radical Y can be either hydrogen or aliphatic in nature with C ₁ -C ₂₂ . The following applies to the coefficients q and r: q + r ≧ 1.
• - Single or multiple ethoxylated sulfonated organyl residues bridging via ether functions or preferably their alkali metal or alkaline earth metal salts, as advantageously characterized, for example, by the generic structural formula
  - (O-CH ₂ -CH ₂ ) _s -SO _s R ¹
  with s ≧ 1, and where s can also be chosen so that the afore-mentioned average molecular weights of the main chain components used come to an end.
• - Silicon functions derived from monofunctional silicones according to the generic structural formula
  wherein R ₉ and R _{10 have} the properties mentioned, and regardless of which R ^{11 may} also represent an alkyl radical or an aryl radical or an aryalkyl radical.

4. Comb polymers according to claim 1, characterized in that the silicon portion in the groupings
is between 0.1 and 50 mol%, the average molecular weights preferably being between 100 and 100,000 g / mo I, the range for monofunctional silicone-containing derivatives between 100 and 2,000 g / mol or for at least difunctional silicone-containing derivatives between 100 and 30,000 g / mol is particularly preferred. 5. Comb polymers according to claim 1, characterized in that their average moles Specular weights are advantageously between 200 and 2,000,000 g / mol, in particular some are between 200 and 100,000 g / mol, the range from 1,000-30,000 g / mol is preferably used, very particularly advantageous of 5,000-15,000 g / mol.   6. Hair treatment agents with an effective content of one or more Comb polymers according to one of claims 1-5.