DE19943417A1 - Composition, useful for the production of hair sprays, comprises water soluble and/or water dispersible silicon modified comb polymers and a physiologically compatible nonionic polymer. - Google Patents

Abstract

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

Description

The present invention relates to combinations based on silicon modified ter sulfonated comb polymers and preparations containing such combinations. In particular, the present invention relates to hair cosmetic active ingredients and zu Preparations for consolidation, shaping, strengthening and structural improvement of the 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 formu lated that they serve not only the care of the individual hair, but also improve the overall appearance of the hairstyle, for example, in that it give the hair more fullness, 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 festivals ger or hair sprays to apply.

There have recently been a number of developments on the hair cosmetic offers that a need for new strengthening agents or new form forms of development. Many of these developments are not based on technical disadvantages or inadequacies of the known means, son the z. B. on environmental considerations, legal requirements or others "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 xier preparations of the prior art, for example, in the Rule components (synthetic or natural polymers) that run the risk with partial or complete replacement of volatile organic components by Water to experience a significant impairment of product properties often has to be compensated by clever wording. Also stand out the fixing preparations of the prior art are often difficult or complex formulation ingredients with insufficient long-term stability, this particularly applies to silicone derivatives that improve 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 len and at the same time a reduced proportion of volatile organic compounds have without the elementary properties of the polymer film on the Haa ren, such as B. Clarity / transparency, surface tactility, gloss, elasticity and out washability are adversely affected 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 combinations of

• a) water-soluble and / or water-dispersible silicone-modified comb polymers, consisting of a polymer main chain and with this polymer main chain poly containing sulfone groups and silicone components linked via ester groups first side arms which are at least partially caused by sodium and lithium counterions were neutralized, with the molar ratio of lithium to sodium between 0.1 and 50, preferably between 0.5 and 25, and
• b) one or more substances selected from the group of physiological compatible nonionic polymers

or hair cosmetic preparations containing an effective amount of com combinations

• a) water-soluble and / or water-dispersible silicone-modified comb polymers, consisting of a polymer main chain and with this polymer main chain poly containing sulfone groups and silicone components linked via ester groups first side arms which are at least partially caused by sodium and lithium counterions were neutralized, with the molar ratio of lithium to sodium between 0.1 and 50, preferably between 0.5 and 25, and
• b) one or more substances selected from the group of physiological compatible nonionic polymers

eliminate or at least mitigate the disadvantages of the prior art.

The combinations according to the invention are notable for good water and alcohol tolerance as well as favorable film properties and high Network assets. 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 term XXX the main body of a polymer backbone, on which via ester functions Molecular groups are connected, which have the designation YYY. The Mon lekülgruppenungen YYY represent both the complete sulfone group and silicon component-containing polyester side arms of the comb polymers according to the invention represent, but 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 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 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 polynorbornyl 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 the reaction of a functional group of the main chain (-COOH in the case of the polycar bonic acids or -OH in the case of polyalcohols) with a corresponding group of Polyester (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 reacted (e.g. anhydrides, esters, halogen compounds gene 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 Mo 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 descendants 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 in such a way that the average molecular weights of the main chain constituents used above are achieved.
D: an aromatic, aliphatic or cycloaliphatic organic unit containing at least two terminal acyl groups with 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 organic unit of the scheme

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 represents} 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 can} also represent an alkyl radical or an aryl radical or an arylalkyl radical.
  The functionality of the components used according to the invention is of course not limited to the use of OH groups, but also includes COOH end groups or mixtures of the two, it also being the case here that at least two COOH groups must be free in the molecule. Reactive derivatives such as anhydrides, esters, epoxides or halides can of course also be used.

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
  
• b) is advantageously between 0.1 and 50 mol%. The average molecular weights were gene preferably between 100 and 100,000 g / mol, the range for mono functional 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.
• c) 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.
• d) Of course, any combination of one or ver several of the connection classes described in a) and b) be applied.

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 olen with the carboxylic acids or their suitable derivatives (for example alkyl esters, halides and the like) in the presence of an esterification catalyst tors such as alkali metal hydroxides, their carbonates and acetates, alkaline earth metal oxides, hydroxides, carbonates and acetates as well as alkali metal and alkaline earth metal salts of Fatty acids with 6 to 22 carbon atoms. Titan compounds also come such as titanates, metallic tin and organic tin compounds such as mono- and Dialkyltin derivatives are considered 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 Water) is removed by distillation from the condensation product, preferably under ver reduced pressure up to <0.1 mbar.

Educts for the main polymer chain of silicone-modified comb polymers according to the invention can be 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 acid 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 preferably being used.

Also random or block copolymers of the above compound classes with other vinyl monomers such as styrene, acrylamide, α- Methylstyrene, styrene, N-vinylpyrrolidone, N-vinylcaprolactone, 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 Methacrylic acid derivatives (for example free acid or ester), silicon-containing acrylate, Methacrylate or acrylamide derivatives or vinyl acetate can be used to form the poly serve main chain.

As a basis for aromatic, aliphatic or cycloaliphatic organic units containing at least two terminal oxygen atoms with 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 bifunctional 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 tri-, to use tetra- or generally polyfunctional alcohol components, for example se advantageously selected 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 radicals and / or aromatic, aliphatic or cycloaliphatic monocarboxylic acids with C ₁ to C ₂₀₀ alkyl or aryl radicals and / or polyalkoxy compounds of the form -O- [R ⁷ -O] _q - [R ⁸ -O] _r -X, where the residues R ⁷ and R ⁸ alkyl residues, which may be the same or different, represent a carbon number from C ₂ to C ₂₂ and the residue X is both hydrogen and 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 previously 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:

where 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 assume values of 1-5,000 before.

If the silicon-containing components are used for end-capping 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 contents have very favorable application properties against polyester of the general formula I if 1,2-propanediol as diol components and / or diethylene glycol and / or cyclohexanedimethanol, as carboxylic acids iso phthalic acid also with 1,3-cyclohexanedicarboxylic acid or with 2,6-naphthalene  dicarboxylic acid or also with adipic acid and 5-sulfo as residues containing sulfo groups Isophthalic acid sodium salt, the sodium 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. Other polyols from which structural elements of this polymer molecule are derived are pentaerythritol, 1,2-propanediol, dimethylpolysilanol. As containing sulfonate groups Agent, from which structural elements of the polymer molecule are derived, serves in for example 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 is to be assumed. Furthermore, who the certain reactive molecular groups can also be observed for crosslinking two or more polymer chains to form a more or less complex network, as the following molecular scheme also tries to illustrate.

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

The production of silicone modifier comb polymers used according to the invention advantageously follows by adding one or more polyfunctional alcohols with a sulfone acid group-containing substance containing at least two carboxyl groups, for example, 5-sulfoisophthalic acid Na salt, optionally a white teren at least two substance containing carboxyl groups and a polymer with one or more polycarboxylic acids, for example polyacrylic acid or poly methacrylic acid and a mono- or polyfunctional siloxane combined, heated and subjected to the usual preparation steps.

In the cosmetic preparations according to the invention, together with the Comb polymers also one or more physiologically acceptable nonionic poly mere used as film formers to get special product profiles, or Pro product properties such as B. the max. Consolidation level, the curl retention, the Reduction of the formation of residues or the characteristic of the consolidation taking advantage of the individual positive characteristics of the different To influence polymer types and comb polymers as desired.

In hair sprays, the use of synergistic effects can be targeted Disadvantages of high water contents are reduced or reduced to a minimum the.

The film-forming nonionic polymers used according to the invention can partially from the group of the usual in the field of cosmetics, in particular the Raw materials used for hair cosmetics are selected, but also polymers for tech African applications, such as coating and binding agents.

Suitable nonionic polymers are, for example

• - Homopolymers of N-vinylpyrrolidone, which as LUVISKOL® K types from Ge company BASF or PVP-K® types from the company ISP with various medium molar masses as powder or in aqueous or aqueous / alcoholic solution solutions are offered.

The Luviskol K30 is preferred.

• - Homopolymers of N-vinylcaprolactam, e.g. B. from the company BASF under the trade name LUVISKOL® Plus.
• - Homopolymers of N-vinylformamide.
• - Copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, the as LUVISKOL® VA types from the company BASF or PVPNA ® types from the company ISP in various concentration ratios as powder or be offered in aqueous or aqueous / alcoholic solutions. The LUVISKOL® VA 37E and VA 64W types are preferred here
• - Terpolymers of N-vinylpyrrolidone, vinyl acetate and vinyl propionate, e.g. B. from the BASF company under the trade names LUVISKOL® VAP 343.

The nonionic polymers LUVISKOL® Plus are particularly preferred and LUVISKOL® VA 64W.

The cosmetic preparations according to the invention for setting the hair ent keep the silicone-modified comb polymers preferably in concentrations between 0.5 and 20 percent by weight and the nonionic polymers preferred in Konzentra tions between 0.5 and 20 percent by weight, each based on the overall formulation lation.

A total polymer content of max. 20 percent by weight, bezo gene to the overall formulation, which results from the proportions of the invention Comb polymers and the nonionic polymers.

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 contain the appropriate additives, provided that a corresponding compa tibility is present. These are, for example, other solvents such as lower polyalko hole 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 from at least two components, which in the Re gel from a - usually solid - colloidally divided substance from a long-chain group of molecules stanchions (e.g. gelatin, silica, polysaccharides) as scaffolders and a rivers aqueous dispersants (e.g. water). The colloidally divided substance is often referred to as a thickening or gelling agent. It forms a spatial network in the Dispersant, wherein individual colloidal particles are electrostatic Interaction can be more or less firmly linked. The Tue Spersionsmittel, which surrounds the network, is characterized by electrostatic Affinity for the gelling agent from d. that is, a predominantly polar (in particular: hydrophi les) gelling agent preferably gels a polar dispersing agent (in particular: Water), whereas a predominantly non-polar gelling agent is preferably non-polar Dispersant gelled.

Strong electrostatic interactions, for example in hydrogen bridges kenbindungen between gelling agent and dispersing agent, but also between Di dispersant molecules are realized with each other, can be too strong tion of the dispersant. Hydrogels can be made from almost 100% of what water exist (in addition, for example, about 0.2-1.0% of a gelling agent) and thereby have a firm consistency. The water content is ice-like Structural elements, so that gels therefore have their name origin [from lat. "Gelatum" = "Frozen" about the alchemical expression "gelatina" (16th century) for nhdt. "Gelati ne "] 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 an aluminum silicate, preferably in the case of aqueous-alcoholic or alcoholic gels is a 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 coloring, to make a Fri trade 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 mo lekülteil, for a reduction in the surface tension of the water, the Benet skin, facilitating dirt removal and removal, a slight ab rinse and - as desired - for foam regulation.

The hydrophilic parts of a surfactant molecule are mostly polar functional groups, for example -COO ^- , -OSO ₃ ^2- , -SO ₃ ^- , while the hydrophobic parts generally represent non-polar hydrocarbon radicals. 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 like anionic or cationic surfactants in aqueous solution 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. Non-ionic surfactants bil no ions in an 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 coco yl-hydrolyzed soy protein and sodium / potassium cocoyl-hydrolyzed colla gene,
• 3. Sarcosinates, for example myristoyl sarcosin, TEA-lauroyl sarcosinate, natri umlauroyl 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 alka nolate 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 DEA-oleth-10-phosphate and di laureth-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 sulfosuccinate, disodium lauryl sulfosuccinate and disodium undecylenamido MEA sulfosuccinate
  such as
  Sulfuric acid esters, such as
• 5. alkyl ether sulfate, for example sodium, ammonium, magnesium, MIPA, TIPA laureth sulfate, sodium myreth sulfate and sodium C _12-13 pareth sulfate,
• 6. 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 value, this leads to a positive Charge. Alkyl betaine, alkylamidopropyl betaine and alkylamidopropyl are advantageous hydroxysulfain. The cationic surfactants used according to the invention can also are preferably selected from the group of quaternary ammonium compounds gene, especially benzyltrialkylammonium chlorides or bromides, such as Benzyldimethylstearylammoniumchlorid, further alkyltrialkylammonium salts, for example example, cetyltrimethylammonium chloride or bromide, alkyldimethylhy droxyethylammonium chlorides or bromides, dialkyldimethylammonium chlorides or -bromides, alkylamidethyltrimethylammonium ether sulfates, alkylpyridinium salts, at for example lauryl or cetyl pyrimidinium chloride, imidazoline derivatives and compounds gene with a cationic character such as amine oxides, for example alkyldimethylamine oxi de or alkylaminoethyldimethylamine oxides. Cetyl trimes are particularly advantageous to use thylammonium salts.  

C. Amphoteric surfactants

Amphoteric surfactants to be used advantageously

• 1. Acyl- / dialkylethylenediamine, for example sodium acylamphoacetate, disodium acylamphodipropionate, disodium alkyl amphodiacetate, sodium acylamphohydro xypropyl 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, glycerol, Sor bitan or other alcohols arise,
• 5. ethers, for example ethoxylated / propoxylated alcohols, ethoxylated / propoxy lated esters, ethoxylated quarter propoxylated glycerol esters, ethoxylated / propoxylated Cholesterols, ethoxylated / propoxylated triglyceride esters, ethoxylated propoxy gelled 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 anioni is within the meaning of the present invention , amphoteric and / or non-ionic surfactants compared to the use preferred of cationic surfactants.

The cosmetic and dermatological contain active ingredients and auxiliary substances, such as them usually for this type of hair care and treatment  be used. Preservatives, surface-active agents, serve as auxiliary substances Substances, substances for preventing foaming, thickeners, emul gators, fats, oils, waxes, organic solvents, bactericides, perfumes, colors substances or pigments, the task of which is the hair or the cosmetic or dermatological preparation to dye itself, electrolytes, substances against that Greasing the hair.

In the context of the present invention, electrolytes include water-soluble alkali metal, Ammonium, 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 distinguish 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 active substance, or mixtures of such substances in an aqueous medium and aids, as are usually used for this. The surface active Substance or the mixtures of these substances can be in a concentration between 1% 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 the Cosmetics usual additives, for example perfume, thickeners, dyes, Des odorants, antimicrobials, lipid replenishing agents, complexing and se  questing 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-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 redimethyl ester Na salt, isophthalic acid, the corresponding siloxane diol (M _n about 4000 g / mol-Aldrich) and polyacrylic acid. It is then evacuated twice and rendered inert with N ₂ . The mixture is then heated to 170 ° C. within 30 minutes with stirring. 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 condensed for a further 30 minutes. The pressure is then reduced to the best vacuum in 30 minutes and condensed at 220 ° C. for 1 hour. Then it is 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 KPG stirrer, internal thermometer, gas inlet tube and distillation bridge, briefly stirred and then sodium carbonate and 5-sulfoisophthalic acid redimethyl ester Na salt, 5-sulfoisophthalic acid, Li salt , Isophthalic acid, polyacrylic acid and the corresponding silicone (viscosity 1800-2200 Centistokes - Aldrich) entered. It is then evacuated twice and rendered inert with N ₂ . The mixture is then heated to 170 ° C. within 30 minutes with stirring. 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 condensed for a further 30 minutes. The pressure is then reduced to the best vacuum (<1 mbar) in 30 minutes 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-sulfoisophthalic acid Na salt, 5-sulfoisophthalic acid Li salt and titanium traisopropylate are placed in a 2-liter four-necked flask with KPG stirrer, internal thermometer, gas inlet tube and distillation bridge, briefly stirred and stirred then sodium carbonate, isophthalic acid, polyacrylic acid and the corresponding silicone (viscosity 1800-2200 Centi stokes - Aldrich) entered. It is then evacuated twice and rendered inert with N ₂ . The mixture is then heated to 170 ° C. within 30 minutes with stirring. 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 condensed for a further 30 minutes. The pressure is then reduced to the best vacuum in 30 minutes. 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-sulfoisophthalic acid dimethyl ester are added , 5-sulfoisophthalic acid Li salt, isophthalic acid the corresponding silicone (Silvet 867 - WITCO (propoxylated trisiloxane - monofunctional with respect to the reactive group, in this case OH)) and polyacrylic acid. It is then evacuated twice and rendered inert with N ₂ . The mixture is then heated to 170 ° C. within 30 minutes with stirring. 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 condensed for a further 30 minutes. The pressure is then reduced to the best vacuum in 30 minutes and condensed at 220 ° C. for 1 hour. It is then aerated with N ₂ and the melt is discharged.

Example 5 Reaction management

1,2-propanediol, diethylene glycol, sodium isethionate and titanium tantetraisopropylate are placed in a 2-l four-necked flask with KPG stirrer, internal thermometer, gas inlet tube and distillation bridge, briefly stirred and then sodium carbonate, 5-sulfoisophthalic acid methyl ester Na salt and 5-sulfoisophthalic acid 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 . The mixture is then heated to 170 ° C. within 30 minutes with stirring. 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 condensed for a further 30 minutes. The pressure is then reduced to the best vacuum (<1 mbar) in 30 minutes 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 initially introduced into 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 dimethyl ester Na salt ("NA-SIM"), isophthalic acid, pentaerythritol, the corresponding silicone (dimer of dimethyldihydroxysilanol, corresponds to an OH on both sides end-functionalized polydimethylsiloxane) and polyacrylic acid entered. It is then evacuated twice and rendered inert with N ₂ . The mixture is then heated to 170 ° C. within 30 minutes with stirring. 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 condensed for a further 30 minutes. The pressure is then reduced to the best vacuum (<1 mbar) in 30 minutes 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 1-15

Foam setting agent: Examples 16-17

Styling gels: Examples 18-21

Claims (8)

1. Combinations of

• a) water-soluble and / or water-dispersible silicone-modified comb polymers consisting of a polymer main chain and sulfone group and silicone component-containing polyester side arms linked to this polymer main chain via ester groups, which were at least partially neutralized by sodium and lithium counterions, the molar ratio of lithium to sodium being between 0.1 1 and 50, preferably between 0.5 and 25, and
• b) one or more substances selected from the group of physiologically compatible nonionic polymers.

2. Hair cosmetic preparations containing an effective amount of combinations

• a) water-soluble and / or water-dispersible silicone-modified comb polymers, consisting of a polymer main chain and polyester side arms containing sulfone groups and silicone components linked to this polymer main chain via ester groups, which were at least partially neutralized by sodium and lithium counterions, the molar ratio of lithium to sodium being between 0.1 1 and 50, preferably between 0.5 and 25, and
• b) one or more substances selected from the group of physiologically compatible nonionic polymers

3. Combinations according to claim 1 or preparations according to claim 2, characterized in that the polymeric main chain of the comb polymers is selected from the group of polymeric aliphatic, cycloaliphatic or aromatic polycarboxylic acids or their derivatives such as polyacrylic acid, polymeth acrylic 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 polynorbornenic acid. 4. Combinations according to claim 1 or preparations according to claim 2, characterized in that the comb polymers 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 preferably being 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, 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 descendants 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 selected so that the above-mentioned average molecular weights of the main chain components used come about.
D: an aromatic, aliphatic or cycloaliphatic organic unit containing at least two terminal acyl groups with 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 organic unit of the scheme
T: a compound from the group of the sulfonated aromatic, aliphatic or cyclo aliphatic 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 AI 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 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 about.
• - 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.

5. Combinations according to claim 1 or preparations according to claim 2, 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 / 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 is particularly preferred. 6. Combinations according to claim 1 or preparations according to claim 2, characterized characterized in that their average molecular weights advantageously between 200 and 2,000,000 g / mol are particularly advantageously between 200 and 100,000 g / mol the range of 1,000-30,000 g / mol is preferably used, entirely particularly advantageous from 5,000-15,000 g / mol. 7. Combinations according to claim 1 or preparations according to claim 2, characterized in that the or the nonionic polymers are selected from the group of

• - Homopolymers of N-vinyl pyrrolidone
• Homopolymers of N-vinylcaprolactam,
• - Homopolymers of N-vinylformamide
• Copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate,
• - Terpolymers of N-vinylpyrrolidone, vinyl acetate and vinyl propionate.