WO2015059084A1

WO2015059084A1 - Precipitation polymerization in the presence of a tertiary amine and of an anhydride

Info

Publication number: WO2015059084A1
Application number: PCT/EP2014/072423
Authority: WO
Inventors: Son Nguyen-Kim; Wolfgang Jahnel; Rolf Werner; Peter Hössel
Original assignee: Basf Se
Priority date: 2013-10-21
Filing date: 2014-10-20
Publication date: 2015-04-30

Abstract

The present invention relates to a process for producing a copolymer composition A) through free-radical copolymerization of a monomer composition containing a) at least one monomer selected from acrylic acid, salts of acrylic acid, methacrylic acid, salts of methacrylic acid and mixtures thereof, b) at least one crosslinking compound amenable to free-radical polymerization which contains at least two α,β-ethylenically unsaturated double bonds per molecule, c) at least one α,β-ethylenically unsaturated compound containing amide groups, by the method of precipitation polymerization in the presence of an auxiliary composition H) containing H1) at least one compound having at least one tertiary amino group, and H2) at least one anhydride. The present invention further relates to the copolymer composition obtainable by this process and to use of said composition.

Description

Precipitation polymerization in the presence of a tertiary amine and an anhydride

BACKGROUND OF THE INVENTION The present invention relates to a process for producing a copolymer composition by radical copolymerization by the precipitation polymerization method in the presence of an adjuvant composition, to the copolymer composition obtainable by this process and to the use thereof. STATE OF THE ART

Rheology modifiers, which are often processed in solid, powdered form, are used in many technical fields, e.g. As the paints, papermaking, textile industry, hygiene, cosmetic and pharmaceutical agents used. Crosslinked polyacrylic acids are currently among the most widely used rheology modifiers.

US Pat. No. 3,915,921 describes copolymers which contain in copolymerized form an olefinically unsaturated carboxylic acid, a C 10 -C 30 -alkyl (meth) acrylate and optionally a crosslinking monomer having at least two ethylenically unsaturated double bonds. In neutralized form they serve as thickeners for various applications.

US 2,798,053 describes copolymers of acrylic acid and polyethers having at least two allyl groups per molecule.

WO 2007/010034 describes an ampholytic copolymer A) obtainable by free-radical copolymerization of a) at least one compound having a free-radically polymerizable,

b) at least one compound selected from N-vinylimidazole compounds, N- [3- (dimethylamino) propyl] acrylamide,

N- [3- (dimethylamino) propyl] methacrylamide and mixtures thereof, and c) at least one radically polymerizable crosslinking compound containing at least two α, β-ethylenically unsaturated double bonds per molecule. WO 2007/012610 describes a silicone group-containing copolymer A) obtainable by free-radical copolymerization of a) at least one compound having a free-radically polymerizable,

α, β-ethylenically unsaturated double bond and at least one ionogenic and / or ionic group per molecule, b) at least one free-radically polymerizable crosslinking compound which contains at least two α, β-ethylenically unsaturated double bonds per molecule, in the presence of at least one polyether group and / or a free-radically polymerizable olefinically unsaturated double bond-containing silicone compound c), wherein the copolymerization can be carried out by the method of precipitation polymerization.

WO 2007/010035 describes the use of an ampholytic copolymer which has a molar excess of anionogenic / anionic groups over cationogenic / cationic groups or which has a molar excess of cationogenic / cationic groups with respect to anionogenic / anionic groups and which can be obtained is characterized by radical copolymerization of a1) at least one compound with a free-radically polymerizable,

α, β-ethylenically unsaturated double bond and at least one anionogenic and / or anionic group per molecule, a2) at least one compound having a free-radically polymerizable,

α, β-ethylenically unsaturated double bond and at least one cationogenic and / or cationic group per molecule, b) at least one free-radically polymerizable crosslinking compound containing at least two α, β-ethylenically unsaturated double bonds per molecule, c) optionally in the presence of at least a silicone compound containing a polyether group and / or a radically polymerizable olefinically unsaturated double bond, as a rheology modifier for hair cosmetic compositions, wherein the ampholytic copolymer can be prepared by radical copolymerization by the method of precipitation polymerization. WO 2010/026178 relates to a process for the preparation of a crosslinked copolymer with anionogenic / anionic groups by free-radical copolymerization by the method of precipitation polymerization in the presence of glycerol monostearate.

WO 201 1/107460 relates to a process for preparing a crosslinked copolymer having anionogenic / anionic groups by free-radical copolymerization by the precipitation polymerization method in the presence of at least one compound having a block structure and comprising at least one hydrophobic block and at least one hydrophilic block and in the presence of at least one basic compound.

US 4,758,641 describes a process for the preparation of polymers of olefinically unsaturated C3-Cs carboxylic acids in a solvent selected from acetone and lower alkyl acetates and in the presence of a crosslinker.

US 4,692,502 describes a process for the polymerization of olefinically unsaturated carboxylic acids in an organic solvent and in the presence of ionic surfactants. No. 4,526,937 describes a process for the precipitation polymerization of olefinically unsaturated carboxylic acids in the presence of polyoxyethylene-polyoxypropylene block copolymers having terminal OH groups and an HLB value of greater than 10.

No. 4,419,502 describes a process for the precipitation polymerization of olefinically unsaturated carboxylic acids in methylene chloride and in the presence of a polyoxyethylene alkyl ether and / or polyoxyethylene sorbitol ester having an HLB value of greater than 12.

EP 0 584 771 A1 describes a polymer of an olefinically unsaturated carboxylic acid and a steric stabilizer. Suitable steric stabilizers are linear block copolymers and random comb polymers with hydrophilic and hydrophobic units.

US 4,375,533 describes a process for the polymerization of olefinically unsaturated carboxylic acids in a polymerization medium in which the carboxylic acid polymer is insoluble in the presence of a surfactant having an HLB value of less than 10.

No. 4,420,596 describes a process for the polymerization of olefinically unsaturated carboxylic acids in a polymerization medium which contains mineral spirits, in the presence of 1) a sorbitan ester, 2) a nonionic surfactant with an HLB Value of less than 10, which is an ester of glycerol or an alkylene glycol, and 3) a long-chain alcohol.

EP 1 209 198 A1 describes a polymer composition containing A) a crosslinked carboxyl group-containing polymer and B) at least one compound selected from esters of polyhydric alcohols with fatty acids and the alkylene oxide adducts thereof.

WO 2006/044193 describes a crosslinked copolymer based on a vinylamide and an unsaturated carboxylic acid and its use for modifying the rheological properties.

WO 91/00302 describes a process for preparing terpolymers of (i) a vinyllactam, (ii) a polymerizable carboxylic acid and (iii) a hydrophobic monomer in an aliphatic hydrocarbon as a solvent.

No. 5,191,043 describes a precipitation polymerization process in which a solvent mixture containing a saturated C 3 -C 10 -hydrocarbon and a secondary alcohol is used.

WO 99/29735 describes a process for the preparation of vinyl polymers in the presence of an oil as a solvent. Suitable oils are silicone oils, light and heavy mineral oils and water-insoluble esters, specifically isopropyl palmitate and isopropyl myristate.

There is still a need for polymers that are well suited for adjusting the rheological properties of various products, such. B. can be formulated in the form of gels. The copolymer compositions obtained should be distinguished, in particular, by good redispersibility in both an aqueous medium and in an oil-containing medium.

Surprisingly, it has now been found that this object is achieved by a polymerization process, wherein the preparation of a crosslinked copolymer with anionic and / or anionic groups by free radical copolymerization by the method of precipitation polymerization in the presence of a Hilfsstoffzusammenset- tion is at least one compound with contains at least one tertiary amino group and at least one anhydride. Furthermore, it has been found that when carrying out the precipitation polymerization in an aprotic solvent or solvent mixture, a copolymer composition is obtained which is readily redispersible in an aqueous medium and z. B. is advantageous for the preparation of gel formulations. Furthermore, it was found that when the polymerization in a mixture of a cosmetically acceptable oil and an aprotic solvent or solvent mixture and separation of the aprotic solvent or solvent mixture after the polymerization, a copolymer composition is obtained which is well redisper- gierbar in an oil-containing medium and z. B. advantageous for the preparation of oil formulations, especially oil-containing dispersions. The latter can z. B. are used advantageously for the production of milky shower baths.

SUMMARY OF THE INVENTION

A first aspect of the invention is a process for preparing a copolymer composition A) by free-radical copolymerization of a monomer composition comprising a) at least one monomer selected from acrylic acid, salts of acrylic acid, methacrylic acid, salts of methacrylic acid and mixtures thereof, b) at least one free-radically polymerizable crosslinking compound which contains at least two α, β-ethylenically unsaturated double bonds per molecule, c) at least one α, β-ethylenically unsaturated amide group-containing compound, by the method of precipitation polymerization in the presence of an auxiliary composition H), containing

H1) at least one compound having at least one tertiary amino group, and

H2) at least one anhydride. In a specific embodiment, to prepare the copolymer composition A), at least one further adjuvant H3) is additionally used which is selected from silicone group-containing surfactants, preferably polydialkylsiloxane-polyether copolymers, which may additionally have at least one amino group. Another object of the invention is a copolymer composition A) as defined above and below, which is obtainable by this method.

A further subject of the invention is a cosmetic agent comprising A) at least one copolymer composition as defined above and below, B) at least one cosmetically acceptable active ingredient and

C) optionally at least one further cosme- tically acceptable excipient other than A) and B).

Another object of the invention is the use of a copolymer composition A), as defined above and hereinafter, for modifying the rheological properties of an aqueous or oil-containing composition.

Another object of the invention is the use of a copolymer composition A), as defined above and hereinafter, as an emulsifier or stabilizer for an emulsion. A further subject of the invention is the use of a copolymer composition A), as defined above and hereinafter, for improving the redispersibility of a composition containing the copolymer compositions A) in an aqueous medium or in an oil-containing medium. Another object of the invention is the use of a copolymer composition A), as defined above and hereinafter, as an adjuvant in cosmetics, as an adjuvant in the food industry, as an adjuvant in pharmacy, as a surface-active compound, as or in adhesives (n ) as well as in or coating agent (s) for the textile, paper, printing and leather industries.

EMBODIMENTS OF THE INVENTION

More specifically, the invention includes the following preferred embodiments: FIG. A process for preparing a copolymer composition A) by free-radical copolymerization of a monomer composition containing a) at least one monomer selected from acrylic acid, salts of acrylic acid, methacrylic acid, salts of methacrylic acid and mixtures thereof b) at least one free-radically polymerizable crosslinking compound containing at least contains two α, β-ethylenically unsaturated double bonds per molecule, c) at least one α, β-ethylenically unsaturated amide group-containing compound, by the method of precipitation polymerization in the presence of an adjuvant composition H), containing H1) at least one compound having at least one tertiary amino group, and

H2) at least one anhydride.

Method according to embodiment 1, wherein additionally at least one further adjuvant H3) is used which is selected from silicone group-containing surfactants, preferably polydialkylsiloxane-polyether copolymers, which may additionally have at least one amino group.

Method according to embodiment 1 or 2, wherein additionally at least one further adjuvant H4) is used which is selected from nonionic surfactants other than H3), preferably nonionic surfactants having an HLB value of at most 7, in particular nonionic surfactants having an HLB value of at most 5.

Process according to one of the preceding embodiments, in which the monomer composition used to prepare the copolymer composition A) contains at least one amide group-containing monomer c) which is selected from α, β-ethylenically unsaturated amide group-containing compound of the general formula (II)

O

FT N (II)

R ⁶ wherein one of the radicals R ⁴ to R ^{6 is} a group of the formula CH 2 = CR ⁷ - with R ⁷ = H or Ci-C4-alkyl and the remaining radicals R ⁴ to R ^{6 are} independently H, alkyl, cycloalkyl , Heterocycloalkyl, aryl or hetaryl, wherein R ⁴ and R ⁵ together with the amide group to which they are attached, may also be a lactam having 5 to 8 ring atoms, wherein R ⁵ and R ⁶ together with the nitrogen atom to the They are also bonded to a five- to seven-membered heterocycle. A process according to embodiment 4, wherein the compound of the general formula (II) is selected from N-vinylpyrrolidone, N-vinylcaprolactam and mixtures thereof.

Process according to one of the preceding embodiments, in which the monomer composition used to prepare the copolymer composition A) contains at least one amide group-containing monomer c) which has a group of the formulas (IIIa) or (IIIb)

in which

# For the binding site to a group having a radically polymerisierba- reindeer, α, β-ethylenically unsaturated double bond, where in the compounds (IIIa) # not for the binding site to a group of the formula CH ₂ = CR ⁷ - where R ⁷ = H or C 1 -C ₄ -alkyl,

R ^{a is} H or C 1 -C ₄ -alkyl,

R ^{b is} H or C 1 -C ₄ -alkyl, or

R ^a and R ^b together represent (CH 2) i- ₄ .

A process according to embodiment 6, wherein the monomer composition used to prepare the copolymer composition A) comprises at least one monomer c) selected from N- (2-acryloxyethyl) imidazolidin-2-one and N- (2-methacryloxyethyl) imidazolidin-2-one on (2-ureidomethacrylate, UMA).

Method according to one of the preceding embodiments, wherein the monomer composition used to prepare the copolymer composition A) additionally comprises at least one compound d) other than the compounds a) having a free-radically polymerizable, α, β-ethylenically unsaturated double bond and at least one anionogenic and / or anionic one Contains groups per molecule, preferably selected from ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and mixtures thereof.

Method according to one of the preceding embodiments, wherein the monomer composition used to prepare the copolymer composition A) additionally comprises at least one compound e) having a free-radically polymerizable, α, β-ethylenically unsaturated double bond and at least one cationogenic and / or cationic groups per molecule contains.

Process according to embodiment 9, wherein component e) contains or consists of N-vinylimidazole.

Process according to one of the preceding embodiments, in which the monomer composition used to prepare the copolymer composition A) additionally comprises at least one ether group-containing monomer f) selected from compounds of the general formulas IV a) and IV b)

R ⁸ O

I II ₉

H ₂ C = C-CX- (CH ₂ -CH ₂ -O) _k (CH ₂ -CH (CH ₃ ) -O) _| - R

(IV a)

(CH 2 CH ₂ -0) _k (CH2-CH _(CH3) -0) _r

(IV b) in which the sequence of the alkylene oxide units in the compounds (IV a) and (IV b) is arbitrary, k and I independently of one another represent an integer from 0 to 1000, the sum of k and I being at least 5,

R ^{8 is} hydrogen or C 1 -C 4 -alkyl, preferably methyl,

R ^{9 is} hydrogen, C ₁ -C ₃₀ -alkyl, C ₂ -C ₃ o-alkenyl or C ₅ -C ₈ -cycloalkyl,

X is O or a group of the formula NR ¹⁰ , in which R ^{10 is} H, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. Process according to embodiment 1 1, wherein the monomer composition used for the preparation of the copolymer composition A) contains at least one compound f) selected from compounds of the general formula (IV a1)

R ⁸ O

I II ₉

H ₂ C = CC-O- (CH ₂ -CH ₂ -O) _k (CH ₂ -CH (CH ₃ ) -O) _| - R

(IV a1) in which the sequence of the alkylene oxide units is arbitrary, k and I independently of one another represent an integer from 0 to 100,

R ^{8 is} hydrogen or methyl,

R ^{9 is} Ce-Cso-alkyl.

Process according to one of the preceding embodiments, in which the monomer composition used to prepare the copolymer composition A) additionally contains at least one further monomer g) selected from gl) esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C1-C30-alkanols,

g2) esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C2-C30-diols,

g3) amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C 2 -C 30 -aminoalcohols which have a primary or secondary amino group,

g4) urethane (meth) acrylates with alkylene oxide groups,

g5) esters of vinyl alcohol and allyl alcohol with C 1 -C 8 -monocarboxylic acids, g 6) C 1 -C 30 -alkyl vinyl ethers,

g7) vinyl aromatics,

g8) vinyl halides, vinylidene halides. and mixtures thereof. Process according to embodiment 13, wherein the monomer gl) is selected from C 1 -C 3 -alkyl (meth) acrylates, C 8 -C 22 -alkyl (meth) acrylates and mixtures thereof from.

15. The method according to any one of the preceding embodiments, wherein the component H1) in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on monomer a) is used.

16. The method according to any one of the preceding embodiments, wherein the component H2) in an amount of 0.01 to 2 parts by weight, preferably 0.05 to 0.5 parts by weight, based on the total weight of the used for the polymerization Monomers a) and c), and, if present, monomers d), e), f) and g) is used.

17. The method according to any one of the preceding embodiments, wherein the component H3) in an amount of 0.1 to 30 parts by weight, preferably 0.5 to 15 parts by weight, based on the total weight of the monomers used for the polymerization a) , b) and c), and, if present, monomers d), e), f) and g) is used.

18. The method according to any one of the preceding embodiments, wherein the component H4) in an amount of 0.1 to 30 parts by weight, preferably 0.5 to 15

Parts by weight, based on the total weight of the monomers used for the polymerization a), b) and c), and, if present, monomers d), e), f) and g) is used. 19. Method according to one of the preceding embodiments, wherein, for the preparation of the copolymer composition A), based on the total weight of the monomers used for the polymerization,

15 to 89.9% by weight of acrylic acid a)

0 to 15% by weight of methacrylic acid a)

0.1 to 3 wt .-% of at least one crosslinking compound b), and

10 to 84.9 wt .-% of at least one α, β-ethylenically unsaturated amide group-containing compound c) are used.

20. The method according to any one of embodiments 1 to 19, wherein the polymerization is carried out in an aprotic solvent or solvent mixture. 21. Process according to embodiment 20, wherein the polymerization takes place in ethyl acetate or in a mixture of cyclohexane and ethyl acetate. 22. The method according to any one of embodiments 20 or 21, wherein the aprotic solvent or solvent mixture after the polymerization is partially or completely replaced by at least one cosmetically acceptable oil body.

23. The method according to any one of embodiments 1 to 19, wherein the polymerization is carried out in a mixture of a cosmetically acceptable oil body and a different aprotic solvent or solvent mixture.

24. The method according to embodiment 23, wherein the different from the oil body aprotic solvent or solvent mixture is separated after the polymerization. 25. The method according to any one of the preceding embodiments, wherein the water content of the reaction mixture used for the polymerization 0.05 to 3 wt .-%, preferably 0.1 to 2 wt .-% based on the total weight of the reaction mixture. 26. The method according to any one of the preceding embodiments, wherein the adjuvant H2) is added in the course of the polymerization, wherein the addition begins at the beginning, in the course or after completion of the polymerization.

27. The method according to any one of the preceding embodiments, wherein the auxiliary H1) is added in the course of the polymerization, wherein the addition begins only after the beginning of the polymerization.

28. The method according to any one of the preceding embodiments, wherein triethanolamine is used as adjuvant H1).

29. The method according to any one of the preceding embodiments, wherein the adjuvant H2) is selected from acetic anhydride, succinic anhydride, methacrylic anhydride and mixtures thereof. A copolymer composition A) obtainable by a method as defined in any one of Embodiments 1 to 29.

31. Use of a copolymer composition A) according to embodiment 30 in an aqueous or oily composition for modifying the rheological properties of this composition. Use of the copolymer composition A) according to embodiment 30 as an emulsifier or stabilizer for an emulsion. Use of the copolymer composition A) according to embodiment 30 in skin cleansing preparations, skin care and protection agents, nail care products, decorative cosmetics or hair treatment preparations. Use according to embodiment 33 in hair treatment compositions as thickener and / or setting agent. Cosmetic agent containing

A) at least one copolymer composition obtainable by a process as defined in any of embodiments 1 to 29,

B) at least one cosmetically acceptable active ingredient and

C) optionally at least one further cosmetically acceptable excipient other than A) and B). Composition according to embodiment 35 in the form of a gel or dispersion. Composition according to embodiment 35 in the form of a gel which contains no hydrophobic cosmetically acceptable vehicles, in particular no oil. Composition according to embodiment 35 in the form of an emulsion, in particular for the care and protection of the skin. Composition according to embodiment 35 in the form of a shampoo, shower gel, bath gel, skin care agent or hair fix gel. Use of a copolymer composition A) obtainable by a process as defined in any of embodiments 1 to 29 for improving the redispersibility of a composition containing the copolymer compositions A) in an aqueous medium or in an oil-containing medium.

Use of a copolymer composition A) obtainable by a process as defined in any of embodiments 1 to 29 as an adjuvant in cosmetics, as an adjuvant in the food industry, as an adjuvant in the pharmaceutical industry. zie, as a surface-active compound, as or in adhesive (s) and as or in coating agent (s) for the textile, paper, printing and leather industries.

DESCRIPTION OF THE INVENTION

In the context of the present invention, among other things, the HLB value (hydrophilic lipophilic balance) is used to characterize the properties of the surfactants used. A definition of the HLB value can be found in W.C. Griffin, J. Soc. Cosmetic Chem., Vol. 5, 249 (1954). For such nonionic as well as ionic surfactants for which the HLB value can not be calculated, an experimental determination by the emulsion comparison method often succeeds. The HLB value of the unknown surfactant is calculated according to the formula:

HLB = - ^(H

N

R = the required HLB value of the oil, which must be known

H = the HLB value of the known surfactant,

S = weight percent of the known surfactant, expressed as a decimal number (e.g.

45% = 0.45),

N = weight percent of the surfactant whose HLB is to be determined, expressed as a decimal.

HLB values and methods for their determination are described in standard works, e.g. B. K. H. Schräder, bases and formulations of cosmetics, Hüthig Verlag, 2nd ed., 1989.

The preparation of the copolymer compositions A) according to the invention is carried out by precipitation polymerization. In the precipitation polymerization, the monomers used are soluble in the reaction medium (monomer, solvent), but the corresponding polymer is not. The resulting polymer becomes insoluble under the chosen polymerization conditions and precipitates out of the reaction mixture. The inventive method itself is characterized by advantageous properties and also leads to copolymer compositions having particularly advantageous properties. The precipitation polymers present in the polymer compositions according to the invention are distinguished by their capability as rheology modifiers (especially as thickeners). When the precipitation polymerization is carried out in an aprotic solvent or solvent mixture (for example in ethyl acetate or a mixture of ethyl acetate and cyclohexane), a copolymer composition A) is obtained which is readily redispersible in aqueous media and which, for. B. advantageous for the preparation of gel formulations. When carrying out the precipitation polymerization in a mixture of a cosmetically acceptable oil and a aprotic solvent or solvent mixture (for example in a mixture of ethyl acetate and soybean oil) and separating only the aprotic solvent or solvent mixture after the polymerization, a copolymer composition A) is obtained which is readily redispersible in oil-containing media and z. B. advantageous for the preparation of oil formulations, especially oil-containing dispersions.

In the context of the present invention, the term alkyl includes straight-chain and branched alkyl groups. These preferably include straight-chain or branched C 1 -C 30 -alkyl groups, particularly preferably C 1 -C 20 -alkyl groups. Suitable short-chain alkyl groups are, for. B. straight-chain or branched Ci-Cz-alkyl, preferably C1-C6-alkyl and particularly preferably Ci-C4-alkyl groups. These include in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl , 1, 1-dimethylpropyl,

2.2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl,

3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl,

2,3-dimethylbutyl, 1, 1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl,

1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1 - Propylbutyl, etc. Suitable longer-chain Cs-Cso-alkyl or Cs-Cso-alkenyl groups are straight-chain and branched alkyl or alkenyl groups. These are preferably predominantly linear alkyl radicals, as also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols, or predominantly linear alkenyl radicals, as also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols, which may be mono-, di- or polyunsaturated. Suitable longer-chain Cs-Cso-alkyl groups are, for. B. n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, Arachinyl, behenyl, lignocerinyl, melissinyl, etc. Suitable longer chain Cs-Cso-alkenyl groups include, for. B. n-octenyl, n-nonenyl, n-decenyl, n-undecenyl, n-dodecenyl, n-tridecenyl, n-tetradecenyl, n-pentadecenyl, n-hexadecenyl, n-heptadecenyl, n-octadecenyl, n-nonadecenyl, n-eicosenyl, n-docosenyl, n-tetracosenyl, hexacosenyl, triacontenyl, etc.

Cycloalkyl is preferably Cs-Cs-cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

Aryl includes unsubstituted and substituted aryl groups and is preferably phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl,

Naphthacenyl and in particular phenyl, tolyl, xylyl or mesityl. Hetaryl: mono-, bi- or trinuclear (monocyclic, bicyclic or tricyclic) aromatic ring system having 5 to 14 ring members, containing in addition to carbon atoms as ring members one, two, three or four heteroatoms selected from O, S and N as ring members.

In the following, compounds which can be derived from acrylic acid and methacrylic acid are sometimes shortened by inserting the syllable "(meth)" into the compound derived from the acrylic acid. The copolymer compositions A) according to the invention can advantageously be formulated as gels under normal conditions (20 ^° C.). "Gel-like consistency" show formulations which have a higher viscosity than a liquid and which are self-supporting, ie retain the shape given to them without a shape-stabilizing coating. However, in contrast to solid formulations, gel formulations can easily be deformed using shear forces. The viscosity of the gel formers is preferably in a range of greater than 600 to about 60,000 mPas, more preferably from 6,000 to 30,000 mPas. Preferably, the gels are hair gels. For the purposes of the present invention, water-soluble monomers and polymers are understood as meaning monomers and polymers which dissolve in water at at least 1 g / l at 20 ° C. Water-dispersible monomers and polymers are understood as meaning monomers and polymers which decompose into dispersible particles with the aid of shearing forces, for example by stirring. Hydrophilic monomers are preferably water-soluble or at least water-dispersible. The copolymers contained in the copolymer compositions A) according to the invention are generally water-soluble.

Monomer a)

The component a) used to prepare the copolymer compositions A) according to the invention is selected from acrylic acid, salts of acrylic acid, methacrylic acid, salts of methacrylic acid and mixtures thereof. The component a) is preferably used in an amount of 10 to 99.89% by weight, based on the total weight of the monomers used for the polymerization (ie monomers a), monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100% by weight). In a preferred embodiment, the component a) in an amount of 15 to 89.9 wt .-%, based on the total weight of the used for the polymerization Monomers (ie, monomers a), b) and c) and, if present d), e) f) and g)) used.

In a first preferred embodiment, component a) consists of acrylic acid or of at least one salt of acrylic acid or of a mixture of acrylic acid and at least one salt of acrylic acid.

In a second preferred embodiment, component a) consists of a mixture of acrylic acid, methacrylic acid and / or at least one salt of (meth) acrylic acid.

Crosslinker b)

For the preparation of the copolymer compositions A), according to the invention at least one crosslinker b), d. H. a compound having two or more than two ethylenically unsaturated, non-conjugated double bonds.

Crosslinkers are preferably used in an amount of 0.01 to 5 wt .-%, particularly preferably 0.05 to 4 wt .-%, based on the total weight of the monomers used for the polymerization (ie monomers a), monomers b), monomers c ) and, if present, monomers d), e), f) and g) add up to 100% by weight).

Suitable crosslinkers b) are, for example, acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols. The OH groups of the underlying alcohols may be completely or partially etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups.

Examples of the underlying alcohols are dihydric alcohols such as

1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol,

2,3-butanediol, 1, 4-butanediol, but-2-en-1, 4-diol, 1, 2-pentanediol, 1, 5-pentanediol,

1, 2-hexanediol, 1, 6-hexanediol, 1, 10-decanediol, 1, 2-dodecanediol, 1, 12-dodecanediol, neopentyl glycol, 3-methylpentane-1, 5-diol, 2,5-dimethyl-1, 3-hexanediol,

2,2,4-trimethyl-1, 3-pentanediol, 1, 2-cyclohexanediol, 1, 4-cyclohexanediol,

1,4-bis (hydroxymethyl) cyclohexane, hydroxypivalic acid neopentyl glycol monoester, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxypropyl) phenyl] propane, diethylglycol, triethylene glycol, Tetraethylene glycol, dipropylene glycol, tripropylene glycol, Tet rapropylenglykol, 3-thiapentane-1, 5-diol, and polyethylene glycols, polypropylene glycols and polytetrahydrofurans having molecular weights of 200 to 10,000. In addition to the homopolymers of ethylene oxide or propylene oxide also block copolymers of ethylene oxide or Propylene oxide or copolymers containing incorporated incorporated ethylene oxide and propylene oxide groups. Examples of additional Basic alcohols having more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1, 2,5-pentanetriol, 1, 2,6-hexanetriol, cyanuric acid, sorbitans, sugars such as sucrose, glucose, mannose. Of course, the polyhydric alcohols can also be used after reaction with ethylene oxide or propylene oxide as the corresponding ethoxylates or propoxylates. The polyhydric alcohols can also initially be converted by reaction with epichlorohydrin into the corresponding glycidyl ethers. Preference is given to ethylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylates. Further suitable crosslinkers b) are the vinyl esters or the esters of monohydric, unsaturated alcohols with ethylenically unsaturated C 3 -C 6 -carboxylic acids, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. Examples of such alcohols are allyl alcohol, 1-buten-3-ol, 5-hexene-1-ol, 1-octen-3-ol,

9-decene-1-ol, dicyclopentenyl alcohol, 10-undecene-1-ol, cinnamyl alcohol, citronellol, crotyl alcohol or cis-9-octadecene-1-ol. However, it is also possible to esterify the monohydric, unsaturated alcohols with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid. Further suitable crosslinkers b) are (meth) acrylic esters, various esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.

Suitable crosslinkers b) are also straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons which have at least two double bonds which may not be conjugated in aliphatic hydrocarbons, eg. B. divinylbenzene, divinyltoluene, 1, 7-octadiene, 1, 9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes having molecular weights of 200 to 20,000.

Further suitable crosslinkers b) are the acrylamides, methacrylamides and N-allylamines of at least difunctional amines. Such amines are for example 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane,

1, 12-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine. Also suitable are the amides of allylamine and unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids, as described above.

Further, triallylamine and Triallylmonoalkylammoniumsalze, z. B. triallylmethylammonium chloride or methyl sulfate, as crosslinking agent b) suitable. Also suitable are N-vinyl compounds of urea derivatives, at least divalent amides, cyanurates or urethanes, for example of urea, ethylene urea, propylene urea or tartaramide, for. N, N'-divinylethyleneurea or N, N'-divinylpropyleneurea.

Further suitable crosslinkers b) are divinyldioxane, tetraallylsilane or tetravinylsilane.

Of course, mixtures of the abovementioned compounds c) can also be used.

Very particularly preferred crosslinkers b) are ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylates, pentaerythritol triallyl ether, methylenebisacrylamide, Ν, Ν'-divinylethyleneurea, triallylamine and triallylmonoalkylammonium salts. Amide group-containing monomer c)

In the context of the present invention, the term "amide group-containing monomer" also includes urea group-containing monomers. Preferably, the component c) in an amount of 0.1 to 90 wt .-%, particularly preferably 1 to 85 wt .-%, in particular 5 to 80 wt .-%, based on the total weight of the monomers used for the polymerization (ie Monomers a), monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100% by weight) are used.

The monomer composition used to prepare the copolymer composition A) preferably contains at least one amide group-containing monomer c) which is selected from α, β-ethylenically unsaturated amide group-containing compounds of the general formula (II)

where one of the radicals R ⁴ to R ^{6 is} a group of the formula CH 2 = CR ⁷ - where R ⁷ = H or

Ci-C4-alkyl and the remaining radicals R ⁴ to R ^{6 are} independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, wherein R ⁴ and R ^5, together with the amide group to which they are attached, may also stand for a lactam having 5 to 8 ring atoms, wherein R ⁵ and R ⁶ together with the nitrogen atom to which they are attached, also for a five - can stand to seven-membered heterocycle.

The monomers c) of the formula (II) are preferably selected from primary amides of .alpha.,. Beta.-ethylenically unsaturated monocarboxylic acids, N-vinylamides of saturated monocarboxylic acids, N-vinyllactams, N-alkyl- and N, N-dialkylamides .alpha., .Beta.-ethylenically unsaturated monocarboxylic acids and mixtures thereof.

Preferred monomers c) are N-vinyl lactams and their derivatives, the z. Example, one or more Ci-C6-alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc., may have. These include z. N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone,

N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N- Vinyl 7-ethyl-2-caprolactam, etc.

Particular preference is given to using N-vinylpyrrolidone and / or N-vinylcaprolactam.

Suitable monomers c) are furthermore acrylamide and methacrylamide.

Suitable monomers c) are furthermore methyl (meth) acrylamide, methylethacrylamide, ethyl (meth) acrylamide, ethylethacrylamide, n-propyl (meth) acrylamide, isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl ( meth) acrylamide, tert-butylethacrylamide, n-pentyl (meth) acrylamide, n-hexyl (meth) acrylamide, n-heptyl (meth) acrylamide, n-octyl (meth) acrylamide, 1,1,3,3-tetramethylbutyl (meth) acrylamide,

Ethylhexyl (meth) acrylamide, n-nonyl (meth) acrylamide, n-decyl (meth) acrylamide, n-undecyl (meth) acrylamide, tridecyl (meth) acrylamide, myristyl (meth) acrylamide,

Pentadecyl (meth) acrylamide, palmityl (meth) acrylamide, heptadecyl (meth) acrylamide, nonadecyl (meth) acrylamide, arrachinyl (meth) acrylamide, behenyl (meth) acrylamide, lignocerenyl (meth) acrylamide, cerotinyl (meth) acrylamide, melissinyl ( meth) acrylamide, palmitoleinyl (meth) acrylamide, oleyl (meth) acrylamide, linolyl (meth) acrylamide,

Linolenyl (meth) acrylamide, stearyl (meth) acrylamide, lauryl (meth) acrylamide,

N-methyl-N- (n-octyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide,

N, N-diethyl (meth) acrylamide, N, N-di (n-octyl) (meth) acrylamide, and mixtures thereof.

Suitable monomers c) are furthermore piperidinyl (meth) acrylamide, morpholinyl (meth) acrylamide and mixtures thereof. Suitable open-chain N-vinylamide compounds as monomers c) are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide,

N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide,

N-vinyl-N-methylpropionamide, N-vinyl-butyramide and mixtures thereof. Preference is given to using N-vinylformamide.

In a further preferred embodiment, the monomer composition used to prepare the copolymeric composition A) contains at least one amide group-containing monomer c) which has a group of the formulas (IIIa) or (IIIb)

a) (IIIb)

in which

# represents the bonding site to a group having a free-radically polymerizable, α, β-ethylenically unsaturated double bond, where in the compounds (IIIa) # does not represent the bonding site to a group of the formula CH 2 = CR ⁷ - where R ⁷ = H or Ci C ₄ alkyl,

R ^{a is} H or C 1 -C ₄ -alkyl, is H or C 1 -C ₄ -alkyl, or

R ^a and R ^b together represent (CH 2) i- ₄ .

The monomers c) of the formulas (IIIa) or (IIIb) are preferably selected from monomers having a group of the formulas (IIIa.1) or (IIIb.1)

l la.1) (lllb.1)

Preferred as monomers c) are the compounds of the formula:

(H, _CH3)

Suitable urea group-containing monomers c) are, for. N-vinyl or N-allyl urea or derivatives of imidazolidin-2-one. These include N-vinyl- and N-allylimidazolidin-2-one, N-vinyloxyethyl-imidazolidin-2-one,

N- (2- (meth) acrylamidoethyl) imidazolidin-2-one,

N- (2- (meth) acryloxyethyl) imidazolidin-2-one (= 2-ureido (meth) acrylate),

N- [2 - ((meth) acryloxyacetamido) ethyl] imidazolidin-2-one, etc.

Preferred urea group-containing monomers c) are

N- (2-Acryloxyethyl) imidazolidin-2-one and N- (2-methacryloxyethyl) imidazolidin-2-one. Particularly preferred is N- (2-methacryloxyethyl) imidazolidin-2-one

(2-ureidomethacrylate, UMA).

Preferably, the amide group-containing monomers c), which have a group of the formulas (IIIa) or (IIIb), in an amount of 0.1 to 20 wt .-%, particularly preferably 0.5 to 10 wt .-%, based on the total weight of the monomers used for the polymerization.

Additional anionogenic / anionic monomer d)

In the process according to the invention for preparing the copolymer composition A), it is possible if desired as component d) to comprise a compound which is different from the compounds of component a) and has a free-radically polymerizable, .alpha.,. Beta.-ethylenically unsaturated double bond and at least one anionogenic and / or anionic group Molecule can be used. If present, component d) is preferably used in an amount of from 0.1 to 40% by weight, particularly preferably from 0.5 to 25% by weight, based on the total weight of the monomers used for the polymerization ( ie monomers a), monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100% by weight).

Preferably, the compounds d) are selected from monoethylenically unsaturated carboxylic acids, phosphonic acids and mixtures thereof. The monomers d) include monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 25, preferably 3 to 6, carbon atoms, which can also be used in the form of their salts or anhydrides. Examples thereof are ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and fumaric acid. The monomers d) furthermore include the half-esters of monoethylenically unsaturated dicarboxylic acids having 4 to 10, preferably 4 to 6, carbon atoms, eg. B. of maleic acid such as monomethyl maleate. The monomers d) also include monoethylenically unsaturated sulfonic acids and phosphonic acids, for example sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, vinyl phosphonic acid and allyl phosphonic acid. The monomers d) also include the salts of the abovementioned acids, in particular the sodium, potassium and ammonium salts and the salts with amines. The monomers d) can be used as such or as mixtures with one another. The stated proportions by weight are all based on the acid reforming.

Preferably, component d) is selected from ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and mixtures thereof.

In a specific embodiment, the monomer composition used to prepare the copolymer composition A) contains no monomer d).

Cationogenic / cationic monomer e)

The monomer composition used to prepare the copolymer composition A) may additionally contain at least one compound e) having a free-radically polymerizable, .alpha.,. Beta.-ethylenically unsaturated double bond and at least one cationogenic and / or cationic group per molecule.

If present, the component e) in an amount of 0.01 to 50 wt .-%, preferably 0.1 to 40 wt .-%, particularly preferably 0.2 to 25 wt .-%, based on the total weight of monomers used for the polymerization (ie monomers a), monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100% by weight).

The copolymers present in the copolymer composition A) preferably have an excess of anionogenic and / or anionic groups. If, therefore, monomers e) are used, then preferably in amounts such that the copolymer in A) faces a molar excess of anionogenic / anionic groups cationogenic / cationic groups of at least 5: 1, preferably at least 10: 1.

The cationogenic and / or cationic groups of component e) are preferably nitrogen-containing groups, such as primary, secondary and tertiary amino groups, and quaternary ammonium groups. Preferably, the nitrogen-containing groups are tertiary amino groups or quaternary ammonium groups. Charged cationic groups can be generated from the amine nitrogens either by protonation or by quaternization with acids or alkylating agents. These include z. As carboxylic acids such as lactic acid, or mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid, or as alkylating C1-C4 alkyl halides or sulfates such as ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. Protonation or quaternization can generally be carried out both before and after the polymerization.

Preferably, component e) is selected from esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols which may be mono- or dialkylated on the amine nitrogen, amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with diamines which contain at least one primary or secondary amino group, Ν, Ν-diallylamine, N, N-diallyl-N-alkylamines and derivatives thereof, vinyl- and allyl-substituted nitrogen heterocycles, vinyl- and allyl-substituted heteroaromatic compounds, and mixtures thereof.

Preferred monomers e) are the esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols. Preferred amino alcohols are

C 2 -C 12 -amino-alcohols which are mono- or dialkylated on the amine nitrogen by C 1 -C 8 -monosubstituted. As the acid component of these esters are z. For example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof. Acrylic acid, methacrylic acid and mixtures thereof are preferably used as the acid component.

Preferred monomers e) are N-methylaminoethyl (meth) acrylate,

N-ethylaminoethyl (meth) acrylate, N- (n-propyl) aminoethyl (meth) acrylate,

N- (tert-butyl) aminoethyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminomethyl (meth) acrylate,

N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate,

N, N-diethylaminopropyl (meth) acrylate and N, N-dimethylaminocyclohexyl (meth) acrylate.

Particular preference is given to N, N-dimethylaminoethyl acrylate,

Ν, Ν-dimethylaminoethyl methacrylate and mixtures thereof. Preferred monomers e) in particular, the quaternization of the aforementioned compounds.

In a very special embodiment, the component e) consists only of

N, N-dimethylaminoethyl (meth) acrylate or N, N-dimethylaminoethyl (meth) acrylate quaternized with methyl chloride or dimethyl sulfate.

Suitable monomers e) are furthermore the amides of the abovementioned α, β-ethylenically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group. Preferred are diamines having a tertiary and a primary or secondary amino group.

Preferred as monomers e) are z. N- [tert -butylaminoethyl] (meth) acrylamide, N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide , N- [3- (Dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N - [4- (dimethylamino) cyclohexyl] acrylamide and N- [4- (dimethylamino) cyclohexyl] methacrylamide. In a suitable embodiment, component e) comprises as vinyl-substituted heteroaromatic compound at least one N-vinylimidazole compound. In a specific embodiment, component e) is selected from N-vinylimidazole compounds and mixtures containing at least one N-vinylimidazole compound.

Suitable N-vinylimidazole compounds are compounds of the formula

wherein R ¹ to R ^{3 are} independently hydrogen, Ci-C4-alkyl or phenyl. Preferably, R ¹ to R ^{3 are} hydrogen.

Also suitable are N-vinylimidazole compounds of the general formula (I)

(I) wherein R ¹ to R ³ are independently hydrogen, Ci-C4-alkyl or phenyl.

Examples of compounds of the general formula (I) are shown in Table 1 below:

Table 1

Me = methyl

Ph = phenyl

Preferred as monomer e) is 1-vinylimidazole (N-vinylimidazole) and are mixtures containing N-vinylimidazole. Suitable monomers e) are also the compounds obtainable by protonation of the aforementioned N-vinylimidazole compounds. Suitable acids are those listed above. Suitable monomers e) are also vinyl- and allyl-substituted nitrogen heterocycles, other than vinylimidazoles, such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts thereof.

Preferably, the monomer composition used to prepare the copolymer composition A) comprises, as monomer e), N-vinylimidazole or consists of N-vinylimidazole.

Preference is given to using N-vinylimidazole in an amount of from 0.01 to 10% by weight, preferably from 0.1 to 8% by weight, based on the total weight of the monomer composition.

Ether group-containing monomer f)

To prepare the copolymer composition A) according to the invention, it is additionally possible to use at least one monomer f) which is different from the components a) to e) and is copolymerizable therewith.

Suitable monomers f) are selected from compounds of the general formulas IV a) and IV b)

R ⁸ O

I II ₉

H ₂ C = C-CX- (CH ₂ -CH ₂ -O) _k (CH ₂ -CH (CH ₃ ) -O) _| - R

(IV a)

(CH 2 CH ₂ -0) _k (CH2-CH _(CH3) -0) _r

(IV b) wherein the order of the alkylene oxide units in the compounds (IV a) and (IV b) is arbitrary, k and I independently of one another represent an integer from 0 to 1000, the sum of k and I being at least 5,

R ^{8 is} hydrogen or C 1 -C 4 -alkyl, preferably methyl,

R ^{9 is} hydrogen, C ₁ -C 30 -alkyl, C ₂ -C ₃ o-alkenyl or C ₅ -C ₈ -cycloalkyl,

X is O or a group of the formula NR ¹⁰ wherein R ¹⁰ is H, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

In the formulas IV a) and IV b) k is preferably an integer from 1 to 500, in particular 3 to 250. Preferably, I is an integer from 0 to 100.

R ⁸ in the formulas IV a) and IV b) is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl. In particular, R ⁸ in the formulas IV a) and IV b) is hydrogen, methyl or ethyl.

Preferably R ^{9 is} hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 1, 1, 3,3- Tetramethylbutyl, ethylhexyl, n-nonyl, n-decyl, n-undecyl, tridecyl, myristyl, pentadecyl, palmityl, heptadecyl,

Octadecyl, nonadecyl, arrachinyl, behenyl, lignocerenyl, cerotinyl, melissinyl, palmitololyl, oleyl, linolyl, linolenyl, stearyl, lauryl.

Preferably R ^{9 is} cetyl (hexadecyl), stearyl (octadecyl) or cetearyl, ie a mixture of cetyl and stearyl.

Preferably, X in the formula IV a) is O or NH.

Suitable polyether acrylates IV a) are, for. As the polycondensation of the aforementioned α, β-ethylenically unsaturated mono- and / or dicarboxylic acids and their acid chlorides, amides and anhydrides with polyetherols. Suitable polyetherols can easily be prepared by reacting ethylene oxide, 1,2-propylene oxide and / or epichlorohydrin with a starter molecule, such as water or a short-chain alcohol R ⁹ -OH. The alkylene oxides can be used individually, alternately in succession or as a mixture. The polyether acrylates IV a) can be used alone or in mixtures for the preparation of the polymers used according to the invention.

Suitable allyl alcohol alkoxylates IV b) are, for. As the etherification of allyl chloride with corresponding polyetherols. Suitable polyetherols can be easily prepared by reacting ethylene oxide, 1, 2-propylene oxide and / or epichlorohydrin with a Starter alcohol R ⁹ -OH are produced. The alkylene oxides can be used individually, alternately in succession or as a mixture. The allyl alcohol alkoxylates IV b) can be used alone or in mixtures for the preparation of the polymers used according to the invention.

For the preparation of the copolymer composition A) it is preferred to use a monomer f) of the formula (IV a1)

R ⁸ O

I II ₉

H ₂ C = CC-O- (CH ₂ -CH ₂ -O) _k (CH ₂ -CH (CH ₃ ) -O) _| - R

(IV a1)

in which the sequence of the alkylene oxide units is arbitrary, k and I independently of one another represent an integer from 0 to 100, the sum of k and I being at least 5,

R ^{8 is} hydrogen or methyl,

R ^{9 is} Ce-Cso-alkyl.

In the compounds of the formula (IV a1), k is preferably an integer from 5 to 100 and I is 0.

In a specific embodiment, in the compounds of the formula (IV a1) R ^{9 is} cetyl, stearyl or cetearyl.

A mixture of a Ci8-22-alkyl-polyethylene glycol methacrylate with methyl methacrylate is commercially available under the name Plex-6877-Ο. A mixture of a Ci6-i8-alkyl-polyethylene glycol methacrylate with methacrylic acid is commercially available under the name Lutencryl® 250 (C16-18 alkyl-PEG-methacrylate in methacrylic acid (50%)).

If present, the component f) in an amount of 0.01 to 25 wt .-%, preferably 0.1 to 20 wt .-%, particularly preferably 0.2 to 15 wt .-%, based on the total weight of used for the polymerization, used (ie, the monomers a), monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100 wt .-%).

Other monomers g) In a further preferred embodiment, the monomer composition used to prepare the copolymer composition A) may additionally contain, in copolymerized form, at least one further monomer g) other than the monomers a) to f).

The further monomer g) is preferably selected from gl) esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C1-C30-alkanols,

g3) amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C2-C30-

Aminoalcohols having a primary or secondary amino group, g4) urethane (meth) acrylates having alkylene oxide groups,

g7) vinyl aromatics,

g8) vinyl halides, vinylidene halides, and mixtures thereof.

Monomer gl) Suitable esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C1-C30-alkanols are, for example, Methyl (meth) acrylate, methyl methacrylate, ethyl (meth) acrylate, ethyl ethacrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butyl ethacrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 1,1,3,3-tetramethylbutyl (meth) acrylate , Ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate,

n-undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate,

Pentadecyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate,

Nonadecyl (meth) acrylate, arrachinyl (meth) acrylate, behenyl (meth) acrylate,

Lignocerenyl (meth) acrylate, cerotinyl (meth) acrylate, melissinyl (meth) acrylate,

Palmitoleinyl (meth) acrylate, oleyl (meth) acrylate, linolyl (meth) acrylate, linolenyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate and mixtures thereof.

The monomers gl) are advantageously suitable for modifying the properties of the copolymer composition A). Thus, for example, C 1 -C 4 -alkyl (meth) acrylates are characterized by a higher polarity and water solubility than alkyl (meth) acrylates having more than 4 carbon atoms in the alkyl radical. Preferred monomers g1) are the esters of α, β-ethylenically unsaturated monocarboxylic and dicarboxylic acids with C 1 -C 3 -alkanols, in particular methyl methacrylate. Preferred monomers gl) are also the esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C 8 -C 22 -alkanols, in particular stearyl (meth) acrylate, lauryl (meth) acrylate and mixtures thereof.

In a preferred embodiment, the monomer gl) is selected from C 1 -C 3 -alkyl (meth) acrylates, C 8 -C 22 -alkyl (meth) acrylates and mixtures thereof.

If present, the component gl) is used in an amount of from 0.1 to 40% by weight, particularly preferably from 0.5 to 20% by weight, based on the total weight of the monomers used for the polymerization (ie monomers a) , Monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100 wt .-%).

Monomer g2) Suitable additional monomers g2) are furthermore 2-hydroxyethyl acrylate,

2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,

2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate,

3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate,

4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate and 3-hydroxy-2-ethylhexyl methacrylate.

If present, the component g2) in an amount of 0.1 to 1 wt .-%, based on the total weight of the monomers used for the polymerization used (ie monomers a), monomers b), monomers c) and, if present Monomers d), e), f) and g) add up to 100% by weight).

Monomer g3)

Suitable additional monomers g3) are 2-hydroxyethylacrylamide,

2-hydroxyethylmethacrylamide, 2-hydroxyethylethacrylamide, 2-hydroxypropylacrylamide,

2-hydroxypropylmethacrylamide, 3-hydroxypropylacrylamide,

3-hydroxypropylmethacrylamide, 3-hydroxybutylacrylamide,

3-hydroxybutylmethacrylamide, 4-hydroxybutylacrylamide,

4-hydroxybutylmethacrylamide, 6-hydroxyhexylacrylamide,

6-hydroxyhexylmethacrylamide, 3-hydroxy-2-ethylhexylacrylamide and

3-hydroxy-2-ethylhexylmethacrylamid. If present, the component g3) in an amount of 0.1 to 10 wt .-%, based on the total weight of the monomers used for the polymerization, used (ie monomers a), monomers b), monomers c) and, if present Monomers d), e), f) and g) add up to 100% by weight).

Monomer g4)

Suitable urethane (meth) acrylates with alkylene oxide groups g4) are described in DE 19838851 (component e2)), to which reference is made in its entirety. If present, component g4) is used in an amount of from 0.1 to 25% by weight, particularly preferably from 0.5 to 20% by weight, based on the total weight of the monomers used for the polymerization (ie monomers a) , Monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100 wt .-%).

Monomer g5)

Suitable esters of vinyl alcohol with Ci-C3o monocarboxylic acid are, for. Vinyl formate, vinyl acetate, vinyl n-propionate, vinyl isopropanoate, vinyl n-butanoate, vinyl tert-butanoate, vinyl n-pentanoate, vinyl n-hexanoate, vinyl n-heptanoate, vinyl n-octanoate , Vinyl-1, 1, 3, 3-tetramethylbutanoate, vinyl-ethylhexanoate, vinyl-n-nonanoate, vinyl-n-decanoate, vinyl-n-undecanoate, vinyltridecanoate, vinylmyristanoate, vinylpentadecanoate, vinylpalmitanoate, vinylheptadecanoate, vinyloctadecanoate, vinylnonadecanoate, vinylarrachinanoate , Vinylbenhenanoate, vinyllignocerenanoate, vinylcerotinanoate, vinylmelissinanoate, vinylpalmitoleinanoate, vinyloleanoate, vinyllinolanoate, vinyllinolenanoate, vinylstearanoate, vinyl lauroate, and mixtures thereof.

Preferred esters of vinyl alcohol with Ci-C3o monocarboxylic acid are, for. For example, vinyl formate, vinyl acetate and vinyl-n-propionate.

If present, the component g5) in an amount of 0.1 to 10 wt .-%, particularly preferably 0.5 to 20 wt .-%, based on the total weight of the monomers used for the polymerization, used (ie the monomers a ), Monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100% by weight).

Monomer g6) Suitable monomers of g6) are, for. B. n-octyl vinyl ether,

1,1,3,3-tetramethylbutyl vinyl ether, ethylhexyl vinyl ether, n-nonyl vinyl ether, n-decyl vinyl ether, n-undecyl vinyl ether, tridecyl vinyl ether, myristyl vinyl ether,

Pentadecylvinylether, palmitylvinylether, heptadecylvinylether, octadecylvinylether, nonadecylvinylether, arrachinylvinylether, behenylvinylether, lignocerenylvinylether, cerotinylvinylether, melissinylvinylether, palmitoleinylvinylether, oleylvinylether, linolylvinylether, linolenylvinylether, stearylvinylether, laurylvinylether and mixtures thereof.

If present, component g6) is used in an amount of from 0.1 to 10% by weight, based on the total weight of the monomers used for the polymerization (ie monomers a), monomers b), monomers c) and if present, monomers d), e), f) and g) add up to 100 wt .-%).

Monomer g7) Preferred vinylaromatics g7) are styrene, 2-methylstyrene, 4-methylstyrene,

2- (n-butyl) styrene, 4- (n-butyl) styrene, 4- (n-decyl) styrene, and mixtures thereof. Particularly preferred are styrene and 2-methylstyrene, especially styrene.

If present, component g7) is used in an amount of from 0.1 to 10% by weight, based on the total weight of the monomers used for the polymerization (ie monomers a), monomers b), monomers c) and, if present , Monomers d), e), f) and g) add up to 100% by weight).

Monomer g8)

Preferred monomers g8) are vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.

If present, the component g8) in an amount of 0.1 to 10 wt .-%, based on the total weight of the monomers used for the polymerization, used (ie, the monomers a), monomers b), monomers c) and, so far present, monomers d), e), f) and g) add up to 100 wt .-%).

The abovementioned monomers g) can each be used individually or in the form of any desired mixtures.

If present, the component g) (ie, the sum of the monomer g1), g2), g3), g4), g5), g6), g7) and g8) in an amount of 0.1 to 40% by weight. %, based on the total weight of the monomers used for the polymerization (ie monomers a), monomers b), monomers c) and, if present, monomers d), e), f) and g) add up to 100 wt. -%). A suitable amount for additional Monomers g) is in a range of 0.1 to 35 wt .-%, in particular 0.2 to 30 wt .-%, based on the total weight of the monomers used for the polymerization. In a preferred embodiment of the process according to the invention, for the preparation of the copolymer composition A), based on the total weight of the monomers used for the polymerization,

15 to 89.9% by weight of acrylic acid as monomer a),

0 to 15% by weight of methacrylic acid as monomer a),

0.1 to 3 wt .-% of at least one crosslinking compound b), and

10 to 84.9% by weight of at least one α, β-ethylenically unsaturated amide group-containing compound c).

In the abovementioned composition, component c) preferably comprises at least 50% by weight, based on the total weight of component c), of vinylpyrrolidone, 2-ureidomethacrylate and / or vinylcaprolactam. In particular, in the abovementioned composition, component c) comprises at least 50% by weight, based on the total weight of component c), of vinylpyrrolidone.

In particular, for the preparation of the copolymer composition A), based on the total weight of the monomers used for the polymerization,

15 to 89.9% by weight of acrylic acid as monomer a),

0 to 15% by weight of methacrylic acid as monomer a),

0.1 to 3 wt .-% of at least one crosslinking compound b), and

10 to 84.9% by weight of vinylpyrrolidone as monomer c).

In a further preferred embodiment of the process according to the invention, for the preparation of the copolymer composition A), based on the total weight of the monomers used for the polymerization,

15 to 89.9% by weight of acrylic acid as monomer a),

0 to 15% by weight of methacrylic acid as monomer a),

0.1 to 3% by weight of at least one crosslinking compound b), 10 to 84.9% by weight of at least one α, β-ethylenically unsaturated amide group-containing compound c), 0 to 10% by weight, of at least one compound e) with a free-radically polymerizable, α, β-ethylenic unsaturated double bond and at least one cationogenic and / or cationic groups per molecule,

0 to 20 wt .-% of at least one compound f), which is preferably selected from among Cs-C22-alkyl group-terminated polyether (meth) acrylates, with

C 8 -C 22 -alkyl-terminated allyl alcohol alkoxylates, and mixtures thereof,

0 to 40 wt .-%, of at least one compound gl), which is selected from esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C1-C30 alkanols, preferably selected from Ci-C3-alkyl (meth) acrylates, C8 -C22-

Alkyl (meth) acrylates and mixtures thereof,

0 to 25% by weight, of at least one compound g5) selected from C8-C22 carboxylic acid vinyl esters,

0 to 25 wt .-%, at least one compound g6), which is selected from C8-C22-alkyl vinyl ethers used.

In a further preferred embodiment of the process according to the invention, for the preparation of the copolymer composition A), based on the total weight of the monomers used for the polymerization, 15 to 89.9% by weight of acrylic acid are used as monomer a),

0 to 15% by weight of methacrylic acid as monomer a),

0.1 to 3% by weight of at least one crosslinking compound b),

10 to 84.9% by weight of at least one α, β-ethylenically unsaturated amide group-containing compound c),

1 to 10% by weight of N-vinylimidazole as monomer e), 0 to 20% by weight of at least one compound f) selected from C8-C22-alkyl-terminated polyether (meth) acrylates,

0 to 40% by weight, of at least one compound gl), which is selected from esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C1-C30-

Alkanols used. A preferred ester of an α, β-ethylenically unsaturated monocarboxylic acid with a Ci-C3o-alkanol is methyl methacrylate. A mixture of a Ci8-22-Alkylpolyethylen- glycol methacrylate with methyl methacrylate is commercially available under the name Plex- 6877-0. A mixture of a Ci6-i8-alkyl-polyethylene glycol methacrylate with methacrylic acid is commercially available under the name Lutencryl® 250 (50 wt .-% solution in methacrylic acid).

Excipient H1) compound having at least one tertiary amino group

The component H1) is preferably used in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on the monomer component a).

As excipient H1) suitable cyclic amines which have at least one tertiary Aminofunkti- on, z. B. N-alkylimidazoles. A preferred adjuvant H1) is N-methylimidazole.

As adjuvant H1) suitable compounds having at least one tertiary amino group are, for. B. Trialkanolamine, such as triethanolamine, tri-n-propanolamine, tri-n-butanolamine, methyldiethanolamine, ethyldiethanolamine, Ν, Ν-dimethylethanolamine, N, N-dimethylpropanolamine, Ν, Ν-diethylethanolamine, etc. Trialkanol- caused by manufacturing as further component (s) contain the corresponding dialkanolamine and / or monoalkanolamine. Such a mixture is also suitable in the method according to the invention.

Triethanolamine is preferably used as adjuvant H1).

Excipient H2) anhydride

Preferably, the component H2) in an amount of 0.01 to 2 parts by weight, preferably 0.05 to 0.5 parts by weight, based on the total weight of the monomers used for the polymerization a) and c), and, if present, monomers d), e), f) and g) are used. The auxiliary H2) is preferably selected from acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, acrylic anhydride, methacrylic anhydride, phthalic anhydride, etc.

The auxiliary H2) is in particular selected from acetic anhydride, succinic anhydride, methacrylic anhydride and mixtures thereof.

If used as adjuvant H2) is a compound whose hydrolysis products are monomers in the context of the invention, such as. B. (meth) acrylic anhydride, the proportion of the hydrolysis product is attributed to the weight of the corresponding Monomerkompo- nente.

Adjuvant H3) silicon-containing surfactant

If present, the component H3) in an amount of 0.1 to 30 parts by weight, preferably 0.5 to 15 parts by weight, based on the total weight of the monomers used for the polymerization a), b) and c) , and, if present, monomers d), e), f) and g) used.

Suitable silicone-containing surfactants (silicone surfactants) are generally Polydi- alkylsiloxanes, especially polydimethylsiloxanes in which one or more alkyl groups have been replaced by lipophilic, hydrophilic ionic or nonionic radicals. Suitable silicone-containing surfactants H3) are known under the INCI name dimethicone copolyols or silicone surfactants compounds such. B. under the brand names Abil® (Fa. Th. Goldschmidt), Alkasil® (Fa. Rhöne-Poulenc), Silicone Polyol Copolymer® (Fa Genesee), Belsil® (Fa. Wacker), Silwet® ( from OSI) or Dow Corning (from Dow Corning). These include compounds with CAS numbers 64365-23-7; 68937-54-2; 68938-54-5; 68937-55-3. A suitable commercially available compound is Belsil® DMC 6031.

Preferred silicone-containing surfactants H3) are polydialkylsiloxane-polyether copolymers, which may additionally have at least one amino group.

Preferred silicone compounds H3) are polysiloxanes of the general formula (E)

(E)

wherein a and b independently of one another stand for 1 to 8, c stands for 2 to 1000,

R ⁿ and R ° independently of one another represent alkyl, cycloalkyl, aryl or arylalkyl, Z ¹ and Z ² independently of one another represent radicals of the formula (F)

- (OCH ₂ CH ₂ ) u (OCH (CH 3) CH ₂ ) v X ¹ -H (F), where in the formula (F) the sequence of the alkylene oxide units is arbitrary, u and v are independently an integer from 0 to 500, where the sum of u and v is> 0,

X ^{1 is} O or N RP, where RP is hydrogen, alkyl, cycloalkyl or aryl.

Preferably, in the formula (E), the sum of u and v is selected so that the molecular weight of the polysiloxanes H1) is in a range of about 300 to 30,000.

Preferably, the total number of alkylene oxide units of the polysiloxanes H3), d. H. the sum of u and v, in a range of about 3 to 200, preferably 5 to 180.

Preferably, in the compounds of the formula (E), the radicals R ⁿ and R ° are independently selected from among methyl, ethyl, cyclohexyl, phenyl and benzyl. More preferably, R ⁿ and R ° are both methyl.

An example of suitable compounds of the formula (E) are the bis (polyethyleneglycol) dimethicones of the general formula (E.1)

(E.1)

wherein c is an integer from 3 to 500, preferably 5 to 250, and u1 and u2 are independently from 2 to 500, especially 3 to 250, especially 5 to 100, stand.

Preferred silicone compounds H3) are furthermore selected from polysiloxanes of the general formula (G)

R R R R

I I I

-Si- -Si-O- -Si- O- -Si- R ^q

(CH ₂ ) _f R ^q

(G)

wherein the sequence of the siloxane units is arbitrary, the radicals R ^{q are} each independently of one another alkyl, cycloalkyl or aryl, d is an integer from 2 to 1000, e is an integer from 2 to 100, f is an integer is from 2 to 8, and is OH, NHR ^r or a radical of the formula (F), as defined above, where R ^{r is} hydrogen, Ci-Cs-alkyl, Cs-Cs-cycloalkyl or a radical of the formula - (CH 2) w -NH 2, where w is an integer from 1 to 10, preferably 2 to 6, and mixtures thereof. An example of suitable compounds of the formula (G) are the ethoxylated and / or propoxylated polydimethylsiloxanes of the general formula (G.1)

(G.1)

O- (CH ₂ CH ₂ O) (CH ₂ CH (CH ₃ ) O) _v - H in which the sequence of the siloxane units is arbitrary, d is an integer from 2 to 1000, preferably 3 to 500, in particular 5 to 100, e is an integer from 2 to 100, preferably from 3 to 50, in particular from 4 to 20, f is an integer from 2 to 8, and u and v independently of one another are an integer from 0 to 500, preferably 0 to 250, wherein the sum of u and v is> 1, preferably> 5, in particular 10.

Suitable compounds of the formula G.1 are obtainable under the name Wacker-Belsil® DMC 6031 and Pluriol® ST 4005 (BASF SE).

Preferred silicone compounds H3) are furthermore polysiloxanes having repeating units of the general formula (I)

wherein d is an integer from 0 to 100, g is an integer from 1 to 8,

R ^s and R ¹ independently of one another are C 1 -C -alkylene, the sequence of the alkylene oxide units is arbitrary and e and f independently of one another are an integer from 0 to 200, the sum of r and s being> 0.

In the formula (J), R ^s and R ¹ are preferably, independently of one another, a C 2 -C 4 -alkylene radical.

In particular, R ^s and R ¹ independently of one another represent a C 2 -C 3 -alkylene radical.

Preferably, the molecular weight of the compound of formula (J) is in a range of about 300 to 100,000.

Preferably, in the formula (J) d is an integer of 1 to 20, such as. 2 to 10. Preferably, the total number of alkylene oxide units of the compound of formula (J), d. H. the sum of e and f, in a range of about 3 to 200, preferably 5 to 180.

Preferably, the end groups of the polysiloxanes having repeating units of the general formula (I) are selected from (CH 3) 3 SiO, H, C 1 -C 8 -alkyl and mixtures thereof. A preferred alkyl end group is methyl.

Amino-containing compounds having repeating units of the general formula (I) preferably have an amine number in a range from about 2 to 50, in particular from 3 to 20.

Suitable alkoxylated Siloxanamine of formula J are, for. As described in WO-A-97/32917, which is incorporated herein by reference in its entirety. Commercially available compounds are z. B. the Silsoft brands of Momentive Performance Materials (formerly Witco), z. Silsoft A-843.

Preferred silicone compounds H3) are also available under the trade name Wetsoft® NE 810 and Wetsoft® NE 820 (Wacker). Preferred silicone compounds H3) are furthermore polysiloxanes having repeating units of the general formula (K)

(K)

wherein R ^{u is} a Ci-Cs-alkylene radical,

R ^v and R ^{w are} independently hydrogen, Ci-Cs-alkyl or Cs-Cs-cycloalkyl, the order of the siloxane units is arbitrary, h, i and k independently represent 0 to 100, wherein the sum of h, i and k is at least 3, I is an integer from 2 to 8,

Z ^{4 is} a radical of the formula (F.1)

- (OCH ₂ CH ₂ ) u (OCH (CH 3) CH ₂ ) v -OR ^x (F.1), where in the formula (F.1) the sequence of the alkylene oxide units is arbitrary, u and v independently of one another Number from 0 to 500, where the sum of u and v is> 0,

R ^{x is} hydrogen or a Ci-Cs-alkyl radical, and mixtures thereof.

In the formula (K), the radical R ^{u is} preferably a C 2 -C 4 -alkylene radical.

Preferably, in the formula (K) R ^v and R ^w independently represent hydrogen or Ci-C ₄ alkyl. Preferably, the sum of h, I and k is chosen such that the molecular weight of the compound of formula (K) is in a range of about 300 to 100,000, preferably 500 to 50,000. The total number of alkylene oxide units of the radical of the formula (F.1), ie the sum of u and v, is preferably in a range from about 3 to 200, preferably 5 to 80.

In the formula (F.1), the radical R ^x is preferably hydrogen or C 1 -C 4 -alkyl. A suitable compound of the formula (K) is z. B. Silsoft A-858 Fa. The Momentive Performance Materials (formerly Witco).

Another preferred silicone compounds H3) is the compound with the INCI name Methoxy PEG / PPG-7/3 Aminopropyl Dimethicone. This is commercially available under the name ABIL® Soft AF 100 from Evonik Industries.

Suitable polysiloxane diamines H3) are Tegomer® A-Si 2122 (Mn = 900 g / mol) and Tegomer® A-Si 2322 (Mn = 2800 g / mol) from Evonik Industries (formerly Th. Goldschmidt).

Excipient H4)

If present, the component H4) in an amount of 0.1 to 15 parts by weight, particularly preferably 0.3 to 10 parts by weight, based on the total weight of the monomers used for the polymerization a), b) and c ), and, if present, monomers d), e), f) and g) are used.

The adjuvant H4) is preferably selected from nonionic surfactants having an HLB value of at most 7, in particular nonionic surfactants having an HLB value of at most 5.

Suitable nonionic surfactants as adjuvant H4) are preferably selected from alkoxylated primary Cs-Cso alcohols,

Esters of Cs-Cso-carboxylic acids with polyhydric alcohols and alkoxilates thereof,

alkoxylated fatty acid alkyl esters,

Amine oxides,

fatty acid alkanolamides,

polyhydroxy fatty acid amides

- Mixtures of the aforementioned surfactants. As H4) suitable alkoxylated primary alcohols preferably have 10 to 22 C-atoms, more preferably 12 to 20 C-atoms. They are preferably from 1 to 50, more preferably 1 to 30, such as. B. 2 to 20 moles alkoxylated alkoxide per mole of alcohol. For alkoxylation z. For example, ethylene oxide, propylene oxide, 1, 2-butylene oxide and mixtures thereof. Preferred is ethylene oxide (EO). They are preferably alcohols having linear or branched alkyl or alkenyl radicals, the latter also being able to have a plurality of nonadjacent double bonds. Preference is given to alcohols in which the alcohol radical is methyl-branched linearly or in the 2-position or are mixtures of alcohols with linear and methyl-branched radicals, as are usually present in oxo alcohol radicals. Particular preference is given to alkoxides, especially ethoxylates with alcohols of native origin, and oxo alcohol alkoxylates and guerbet alcohol alkoxylates. These include, in particular, alkoxilates of alcohols obtainable by reduction of natural fatty acids and alcohol mixtures having 8 to 30, preferably 10 to 22, carbon atoms, eg. Of n-decanol, lauric alcohol, myristic alcohol, cetyl alcohol, stearic alcohol, oleic alcohol, lignoceryl alcohol, ceryl alcohol, etc. The indicated degrees of alkoxylation each represent statistical averages which may be an integer or a fractional number for a particular product. Also suitable are alkoxylated alcohols which have a narrow homolog distribution (narrow rank ethoxylates, NRE). Alkoxylated alcohols containing EO and PO groups together in the molecule can also be used. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, as H2) also mixed alkoxylated primary alcohols can be used, in which EO and PO units are not distributed in blocks, but statistically distributed. Such products are for. B. by simultaneous action of ethylene and propylene oxide on primary alcohols available.

Suitable as adjuvant H4) esters of Cs-Cso-carboxylic acids with polyhydric alcohols are preferably derived from linear or branched, saturated or mono- or polyunsaturated carboxylic acids having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 C atoms in the alkyl or alkenyl radical, such as

Caprylic, pelargonic, undecanoic, lauric, tridecanoic, myristic, pentadecanoic, palmitic, margaric, stearic, isostearic, nonadecanoic, arachidic, behenic, palmitoleic, oleic, linoleic, linolenic, arachidonic and their mixtures. Preference is given to lauric acid, stearic acid, isostearic acid, palmitic acid and oleic acid.

Suitable polyhydric alcohols are preferably selected from straight-chain, branched or carbocyclic, saturated or unsaturated hydrocarbon compounds having at least three carbon atoms and at least three (esterifiable) hydroxyl groups. Unsaturated hydrocarbon compounds may have one or more, preferably 1, 2 or 3 CC double bonds. geminal See such polyols are also usable. The polyol is in particular a straight-chain or branched saturated hydrocarbon having 3 to 30 carbon atoms and 3 to 10 hydroxyl groups. Preferred examples of useful polyols are: glycerol, di-, tri- and polyglycerols, low molecular weight partially or fully hydrolyzed polyvinyl acetate, 1, 2,4-butanetriol, trimethylolmethane, trimethylolethane, trimethylolpropane, trimethylolbutane, 2,2,4- Trimethyl-1, 3-pentanediol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, D-, L- and meso-erythritol, D- and L-arabitol, adonite, xylitol, sorbitol, mannitol, dulcitol, inositols and mixtures thereof. Also suitable as auxiliary H4) are alkoxylates of esters of Cs-C50-carboxylic acids with polyhydric alcohols. The alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide. There may be block copolymers or random copolymers. They usually contain from 1 to 50 mol, preferably from 2 to 30 mol, of at least one alkylene oxide per mole of alcohol. Preferred alkylene oxide is ethylenoxide.

Another class of preferred nonionic surfactants which can be used as adjuvant H4) are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58 / 217598 or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533.

Also suitable as auxiliaries H4) are nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide and also fatty acid alkanolamides. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Further suitable auxiliaries H4) are polyhydroxy fatty acid amides of the formula (2),

O

16, - [Z]

R (2)

¹ 17

R

wherein

R ¹⁶ C (= 0) is an aliphatic acyl radical having 6 to 22 carbon atoms,

R ^{17 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] represents a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.

The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (3)

wherein

R ^{18 is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms,

R ¹⁹ is a linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms or an arylene group having 6 to 8 carbon atoms, and

R ^{20 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, where Ci-C4-alkyl or

Phenyl radicals are preferred, and

[Z] ^{1 represents} a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.

[Z] ¹ is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted, for example, according to WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired polyhydroxy fatty acid amides.

Suitable nonionic surfactants as adjuvant H4) are specific (HLB values and, if appropriate, brand name in brackets):

Sorbitan trioleate (1, 8; Span 85)

Polyoxyethylene sorbitol beeswax derivative (4.0; Atlas G-1727), Propylene glycol fatty acid ester (4.1, Emcol PM-50),

Sorbitan monooleate (4.3; span 80),

Sorbitan monooleate (4,3; Arlacel 80),

Propylene glycol monolaurate (4.5, Atlas G-917),

Propylene glycol monolaurate (4.5, Atlas G-3851),

Propylene glycol fatty acid ester (4.5, Emcol PL-50),

Sorbitan monostearate (4.7, Span 60 or Arlacel 60),

Diethylene glycol monooleate (4.7, Atlas G-2139),

Diethylene glycol fatty acid ester (4.7, Emcol DO-50),

Diethylene glycol monostearate (4.7, Atlas G-2146),

Diethylene glycol fatty acid ester (4.7, Emcol DS-50),

Polyoxyethylene sorbitol beeswax derivative (5.0, Atlas G-1702),

Diethylene glycol fatty acid ester (5.1, Emcol DP-50),

Diethylene glycol fatty acid ester (5.6, Emcol DM-50),

Polyoxyethylene sorbitol beeswax derivative (6.0; Atlas G-1725),

Diethylene glycol monolaurate (6.1, Atlas G-2124),

Diethylene glycol fatty acid ester (6.1, Emcol DL-50),

Diethylene glycol monolaurate (6.5, glaurin),

Sorbitan monopalmitate (6.7, Span 40 or Arlacel 40), and mixtures thereof.

Particularly suitable nonionic surfactants as adjuvant H4) are the Dehymuls® grades from COGNIS Care Chemicals. These include:

Dehymuls HRE 7 (hydrogenated castor oil alkoxylated with 7 moles of ethylene oxide),

Dehymuls LE (PEG-30 dipolyhydroxystearate),

Dehymuls E (mixture of higher molecular weight fatty acid esters, fatty acid salts and oil-binding additives; dicocoyl pentaerythrityl distearyl citrate and sorbitan sesquioleate and beeswax (cera alba) and aluminum stearate),

Dehymuls K (petrolatum and decyl oleate and dicocoyl pentaerythrityl distearyl citrate and sorbitan sesquioleate and microcrystalline wax (cera microcristallina) and mineral oil and beeswax (cera alba) and aluminum stearate),

Dehymuls PGPH (polyglycerol-poly-12-hydroxystearic acid ester),

Dehymule SML (sorbitan monolaurate),

Dehymul's SMO (sorbitan monooleate),

Dehymuls SMS (sorbitan monostearate),

Dehymuls SSO (sorbitan sesquioleate), and mixtures thereof. Further suitable nonionic surfactants as adjuvant H4) are the Hypermer® grades from ICI. These include:

Hypermer LP6 (polymeric fatty acid ester, molecular weight (MW) about 4300), Hypermer LP7,

Hypermer B239 (block copolymer of a polyhydroxy fatty acid and polyethylene oxide, MW about 3500),

Hypermer B246 (block copolymer of a polyhydroxy fatty acid and polyethylene oxide, MW about 7500),

Hypermer B261 (block copolymer of a polyhydroxy fatty acid and polyethylene oxide, MW approx. 9600),

Hypermer 2234,

Hypermer E-464 (copolymer with a long hydrophobic alkylene chain and various anionic / nonionic hydrophiles, MW ca. 2300),

Hypermer IL2296,

Hypermer A-109 (block copolymer of a fatty acid or long-chain alkylene and EO), Hypermer A-409 (block copolymer of a fatty acid or long-chain alkylene and EO).

In a specific embodiment, sorbitan trioleate is used as adjuvant H4). Sorbitan trioleate is commercially available under the trade name Span® 85.

In a further specific embodiment, a mixture of cetearyl glucoside and cetearyl alcohol is used as adjuvant H4). Such a mixture is commercially available under the brand name Emulgade® PL 68/50.

precipitation

According to the invention, the preparation of the copolymer composition A) takes place by the method of precipitation polymerization. For this polymerization, solvents are used in which the starting materials for the polymerization soluble and the resulting polymer are insoluble.

In a first preferred embodiment, the polymerization takes place in an aprotic solvent or solvent mixture.

In a second preferred embodiment, the polymerization is carried out in a mixture of a cosmetically acceptable oil body and a different aprotic solvent or solvent mixture.

Preferably, according to the first embodiment, a substantially anhydrous aprotic solvent or solvent mixture is used. Essentially Anhydrous in the context of the invention means that the aprotic solvents or solvent mixtures are used in a technically available quality and are generally not subjected to removal of residual water. By "essentially anhydrous" is therefore understood water contents of up to 3% by weight, preferably up to 2% by weight, based on the total weight of the aprotic solvent or solvent mixture. Preferably, the water content is in a range of 0.05 to 2 wt .-%. The anhydrides used according to the invention as auxiliary H2) effectively remove water introduced into the reaction mixture with the solvent.

Suitable solvents are, for example, aromatic hydrocarbons such as toluene, xylenes, benzene; aliphatic and cycloaliphatic hydrocarbons, such as n-alkanes or cyclohexane; Esters of acetic acid such as ethyl acetate or butyl acetate; Ether such. B. diethyl ether, dipropyl ether, dibutyl ether, methyl tert-butyl ether or diethylene glycol dimethyl ether; Ketones such as acetone or methyl ethyl ketone, and mixtures of these solvents.

The oil bodies are preferably selected from: vegetable oils, such as palm oil, rapeseed oil, castor oil, coconut oil, cod liver oil, corn oil, soybean oil, linseed oil, olive oil, peanut oil, safflower oil, sesame oil, grapefruit oil, basil oil, apricot oil, ginger oil, geranium oil, orange oil , Rosemary oil, macadamia oil, onion oil, tangerine oil, pine oil, sunflower oil, oxidized vegetable oils,

hydrogenated vegetable oils such as hydrogenated palm oil, hydrogenated rapeseed oil or hydrogenated soybean oil,

Vegetable oil esters, such as rapeseed oil methyl ester,

animal oils such as lard oil, fish oils,

Silicone oils (cyclomethicones, silicon methicone types, etc.),

- aliphatic or naphthenic hydrocarbons, such as. Squalane, squalene or dialkylcyclohexanes,

Paraffin oils, aromatic hydrocarbons and aromatic hydrocarbon mixtures, e.g. Xylene, Solvesso 100, 150 or 200, and the like, Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms,

Esters of linear or branched C6-C22 fatty acids with linear or branched C6-C22 fatty alcohols. These include z. B. myristyl myristate, Myristylpalmi- did Myri styl stea rat, Myristylisostearat, myristyl, Myristylbehenat, Myristyle- rucat, cetyl myristate, cetyl palmitate, cetyl stearate, Cetylisostearat, cetyl oleate, cetyl behenate, Cetylerucat, Stearylmyristat, stearyl palmitate, stearyl stearate, stearic rylisostearat, stearyl oleate, stearyl behenate , Stearyl erucate, isostearyl myristate, Isostearyl palmitate, Isostearylstearat, isostearyl isostearate, Isostearyloleat, Isostea- rylbehenat, Isostearyloleat, oleyl stearate, oleyl palmitate, oleyl stearate, Oleyliso-, oleyl oleate, Oleylbehenat, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl, Behenylisostearat, behenyl oleate, behenyl behenate, Behenyle- rucat, erucyl myristate, erucyl, Erucyl stearate, erucyl isostearate, erucyl oleate,

Erucyl behenate and erucyl erucate. These include, in particular, the esters of linear C6-C22 fatty acids with branched alcohols, in particular esters of 2-ethylhexanol,

Esters of Cs-C50-alkylhydroxycarboxylic acids with linear or branched C6-C22-fatty alcohols, in particular dioctylmalate,

Esters of linear and / or branched fatty acids with polyhydric alcohols (such as, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, dimerdiol (dimeric fatty alcohols) or trimer triol) or guarenteed alcohols,

liquid mono-, di- and triglycerides based on C6-C22-fatty acids and mixtures thereof,

Esters of C6-C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid,

Esters of C 2 -C 12 dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to

6 hydroxyl groups.

The oil body is preferably selected from vegetable oils such as palm oil, rapeseed oil, castor oil, coconut oil, cod liver oil, corn oil, soybean oil, linseed oil, olive oil, peanut oil, safflower oil, sesame seed oil, grapefruitol, basil oil, apricot oil, ginger oil, geranium oil, orange oil, rosemary oil, macadamia oil, Onion oil, tangerine oil, pine oil and sunflower oil.

A particularly preferred oil body is soybean oil. Another particularly preferred oil body is the ester of linear or branched C6-C22 fatty acids with ethylene glycol and / or propylene glycol. In a preferred embodiment, the oil body is Waglinol® 2/7680 (INCI: propylene glycol dicaprylate / caprate).

The polymerization according to the first embodiment is preferably carried out in ethyl acetate or in a mixture of cyclohexane and ethyl acetate. When the polymerization is carried out in a mixture of cyclohexane and ethyl acetate, the ratio of cyclohexane to ethyl acetate is preferably in a range of 45:55 to 55:45.

The polymerization according to the second embodiment preferably takes place in a mixture of soybean oil and ethyl acetate. The ratio of soybean oil to ethyl acetate is preferably in a range of 1: 3 to 3: 1, more preferably 1: 2 to 2: 1. Furthermore, the polymerization according to the second embodiment is preferably carried out in a mixture of esters of linear or branched C 6 -C 22 fatty acids with ethylene glycol and / or propylene glycol and ethyl acetate. The ratio of ester of linear or branched fatty acids with ethylene glycol and / or propylene glycol to ethyl acetate is preferably in the range of 1: 5 to 5: 1. In a specific embodiment, the polymerization takes place in a mixture of Waglinol® 2/7680 (INCI: propylene glycol dicaprylate / caprate) and ethyl acetate. The ratio of Waglinol® 2/7680 (INCI: propylene glycol dicaprylate / caprate) to ethyl acetate is preferably in the range of 1: 5 to 5: 1.

The precipitation polymerization is usually carried out at temperatures of 40 to 100 ^° C, preferably 50 to 95 ^° C, in particular 60 to 90 ^° C. The precipitation polymerization is usually carried out at pressures of 1 to 15 bar, in particular 1 to 6 bar. If the polymerization is not carried out under elevated pressure, the solvent or solvent mixture determined by the corresponding boiling temperatures, the maximum reaction temperature. To prepare the polymers, the monomers can be polymerized by means of free-radical initiators.

As initiators for the free-radical polymerization, the customary peroxo and / or azo compounds can be used, for example alkali metal or ammonium peroxidisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide,

Di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate,

tert-butyl peroxy-2-ethylhexanoate, tert-butylpermaleinate, cumene hydroperoxide,

Diisopropyl peroxydicarbamate, bis (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, tert-butyl peroctoate, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide, 2,2 ' Azo-bis-isobutyronitrile, azo-bis (2-amidinopropane) dihydrochloride, azobis (2,4-dimethylvaleronitrile) or

2,2'-azo-bis- (2-methyl-butyronitrile).

Also suitable are initiator mixtures or redox initiator systems, such as. B.

Ascorbic acid / iron (II) sulfate / sodium peroxodisulfate,

tert-butyl hydroperoxide / sodium disulfite,

tert-butyl hydroperoxide / sodium hydroxymethanesulfinate,

In a specific embodiment, at least two free-radical initiators are used for the preparation of the copolymers according to the invention, which are essentially independent of each other. allow for slow initiation in at least two phases. In this case, copolymers can be achieved with particularly low residual monomer contents. For copolymerization, at least two initiators whose decomposition temperatures differ from one another by at least 10 ° C. are preferably used. In the context of the invention, the decomposition temperature is defined as the temperature at which 50% of the molecules decompose into free radicals within 2.5 hours. Preferably, the copolymerization in this procedure is carried out until completion of the precipitation of the copolymer at a temperature greater than or equal to the lower decomposition temperature and less of the higher decomposition temperature, and after the precipitation further reaction takes place at a temperature greater than or equal to the higher decomposition temperature.

The process according to the invention preferably comprises a first polymerization phase at a first polymerization temperature and a second polymerization phase at a second polymerization temperature above the first polymerization temperature, at least two initiators being used for the polymerization, of which

Half-times at the first polymerization temperature differ so that at least one of these initiators during the first polymerization phase decomposes into free radicals and at least one of these initiators during the first polymerization phase substantially does not decompose into radicals and during the second polymerization phase decomposes into free radicals. Preferably, in this procedure, the second polymerization phase essentially begins after precipitation of the copolymer. "Substantially" after precipitation of the copolymer is understood to mean that the copolymer is preferably at least 80% by weight, preferably at least 90% by weight, in particular at least 95% by weight, based on the total weight of the copolymer , in precipitated form.

The half-life of an initiator can be determined by conventional methods known to those skilled in the art, such as. In the publication "Initiators for high polymers", Akzo Nobel, No. 10737. Preferably, the half-life of the first polymerization initiator at the first polymerization temperature and the second polymerization initiator at the second polymerization temperature is in a range of about 1 minute to 3 hours, more preferably 5 minutes to 2.5 hours. If desired, shorter half-lives z. From 1 second to 1 minute or longer half lives than 3 hours, as long as it is ensured that the initiator (s) decomposing at the higher temperature essentially decomposes into free radicals during the second polymerization phase.

Preferably, the initiator system used contains at least two initiators whose decomposition temperatures differ by at least 15 ° C from each other. The initiator which decomposes at the lower temperature preferably has a decomposition temperature of 50 to 100 ° C on. The decomposing at the higher temperature initiator preferably has a decomposition temperature of 80 to 150 ° C.

The precipitation polymerization is preferably carried out in such a way that a part of the solvent or solvent mixture is initially introduced, heated and the polymerization is carried out by addition of initiator, monomer (s), crosslinker, auxiliaries (in each case possibly dissolved in the same or a different solvent or solvent mixture). If the polymerization takes place in a mixture of a cosmetically acceptable oil body and a different aprotic solvent or solvent mixture, the aprotic solvent or solvent mixture other than the oil body is preferably separated off after the polymerization. The auxiliary H2) (anhydride) is preferably added in the course of the polymerization, the addition beginning with the beginning of the polymerization.

The adjuvant H1) (compound having at least one tertiary amino group) is preferably added in the course of the polymerization, with the addition beginning at the beginning, in the course of or only after the end of the polymerization.

Insofar as at least one silicone-containing surfactant is used as auxiliary H3) to prepare the copolymer composition A), component H3) is preferably added after the start of the polymerization.

Insofar as at least one nonionic surfactant is used as auxiliary H4) for the preparation of the copolymer composition A), the component H4) is preferably initially charged at least in part before the beginning of the polymerization. H4) are particularly preferably initially charged before the beginning of the polymerization.

If at least one adjuvant H3) is used, the addition is preferably carried out after at least 90% of the monomers have reacted.

In a first embodiment, the precipitated polymer is isolated from the reaction mixture following polymerization. For isolation, any general method that can be used to isolate the polymers in conventional precipitation polymerization is suitable. Such methods are for. As filtration, centrifugation, evaporation of the solvent or combinations of these methods. In particular, polymers, the polymerization being carried out in an aprotic solvent or solvent mixture, are isolated from the reaction mixture after the polymerization. The copolymer composition may be subjected to purification if desired. This serves z. B. for the separation of unpolymerized components and / or at least a portion of the excipients. In a preferred embodiment, the copolymer composition A) is isolated after the precipitation polymerization and subjected to washing with a liquid washing medium. Suitable washing media are in principle the same solvents as are suitable for the polymerization. For easier drying of the polymers, it is recommended, however, low-boiling solvents such. B acetone, to use.

To remove impurities, the copolymer composition A) may be subjected to a treatment with a washing medium one or more times in succession. For this purpose, the copolymer composition is brought into intimate contact with the washing medium in a suitable device and the washing medium is subsequently separated from the copolymer composition. Suitable devices are for. B. stirred tank. The treatment with the washing medium can be carried out in the container used for the polymerization. The separation of copolymer and washing medium takes place z. B. by filtration or centrifugation. For acceleration, the filtration can be carried out under pressure increased on the polymer side or reduced on the outlet side.

In a second embodiment, the reaction mixture is subjected to a partial or complete solvent exchange with the precipitated polymer following the polymerization. In particular, polymers in which the polymerization takes place in an aprotic solvent or solvent mixture are subjected to a partial or complete solvent exchange after the polymerization. In this case, the aprotic solvent or solvent mixture is preferably partially or completely replaced by at least one cosmetically acceptable oil body. Preferably, the solvent exchange is carried out by distillation. Preferably, a portion of the aprotic solvent or solvent mixture is first removed by distillation. The proportion of the solvent or solvent mixture initially removed by distillation is preferably from 5 to 95% by weight, more preferably from 10 to 90% by weight, in particular from 20 to 80% by weight, based on the total amount of the aprotic solvent or solvent mixture. Subsequently, during the further distillative removal of the aprotic solvent or solvent mixture, at least one oil body is added. The choice of the aprotic solvent or solvent mixture and the oil body is then carried out in accordance with a sufficient difference in the boiling points. In a specific embodiment, ethyl acetate is used as the aprotic solvent and at least one vegetable oil is used as the oil body. In an even more specific embodiment, ethyl acetate is used as the aprotic solvent and soybean oil is used as the oil body. In a More special version is used as the aprotic solvent ethyl acetate and oil body Waglinol.

In a third embodiment, a mixture of a cosmetically acceptable oil body and a different aprotic solvent or solvent mixture is used to prepare the copolymer composition A). Then the aprotic solvent or solvent mixture is partially or completely removed following the polymerization. Preferably, the removal of the aprotic solvent or solvent mixture is carried out by distillation. The choice of the aprotic solvent or solvent mixture and the oil body is then carried out in accordance with a sufficient difference in the boiling points. In a specific embodiment, ethyl acetate is used as the aprotic solvent and at least one vegetable oil is used as the oil body. In an even more specific embodiment, ethyl acetate is used as the aprotic solvent and soybean oil is used as the oil body. In another specific embodiment, ethyl acetate is used as aprotic solvent and waglinol as oil body.

Copolymer Composition A further subject matter of the invention is the copolymer composition A) obtainable by the process described above.

In the context of the present invention, the term "copolymer composition A)" also encompasses the products obtained therefrom by at least one workup and / or purification step. Suitable work-up and purification steps are, for example, washing, drying and shaping.

The copolymer composition A) is preferably in the form of a powder or an oil dispersion.

The copolymer composition A) according to the invention may contain at least one further component in addition to the polymer particles obtained in the precipitation polymerization. This includes at least one of the adjuvants H1) and / or H2). The adjuvants H1) and / or H2) can, if desired, be partly or completely removed from the copolymer composition A), for example. By at least one washing step, as previously described.

If at least one adjuvant H3) is used to prepare the copolymer composition A) according to the invention, then A) may obtain the adjuvant (s) H3) as further component. A specific embodiment is therefore a copolymer composition A) which contains at least one component H3). A) then contains preferably at least one component H3) in an amount of 0.01 to 15 wt .-%, particularly preferably 0, 1 to 10 wt .-%, based on the total weight of the copolymer composition A). The adjuvant H3) may have an advantageous effect on the performance properties of the copolymer composition A), z. Example by increasing the dissolution rate or reduced dust formation.

The adjuvants H 1), H 2) and / or H 3) may also have an advantageous effect on one or more other performance properties of the copolymer composition A), eg. By promoting low-crystallinity products or control of particle size, molecular weight, morphology, etc.

The adjuvants H 1), H 2) and / or H 3) can also have an advantageous effect on one or more other performance properties of formulations of the copolymer composition A). So z. B. the presence of at least one of these adjuvants advantageously affect the clarity of formulated with A) gels.

The copolymer compositions A) according to the invention and the copolymers contained therein are distinguished by their pH-dependent solubility.

The anionic groups (acid groups) of the copolymers contained in the copolymer compositions A) can be partially or completely neutralized with a base. As the base for the neutralization of the polymers, alkali metal bases such as caustic soda, potassium hydroxide, soda, sodium bicarbonate, potassium carbonate or potassium hydrogencarbonate and alkaline earth metal bases such as calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate and amines can be used. Suitable amines are, for. For example, C 1 -C 6 -alkylamines, preferably n-propylamine and n-butylamine, dialkylamines, preferably diethylpropylamine and dipropylmethylamine, trialkylamines, preferably triethylamine and triisopropylamine. Preference is given to amino alcohols, for. B. Tri- alkanolamines, such as triethanolamine, Alkyldialkanolamine, such as methyl or ethyldiethanolamine and dialkylalkanolamines, such as dimethylethanolamine and 2-amino-2-methyl-1 - propanol. The neutralization of the acid groups can also be carried out with the aid of mixtures of several bases. The copolymers contained in the copolymer composition A) are advantageously suitable for modifying the rheological properties of aqueous compositions. It may be z. B. be an aqueous active or Effektstoffzusammensetzung. In general, they may be, for example, cosmetic compositions, pharmaceutical compositions, hygiene products, paints, compositions for the paper industry and the textile industry. In a preferred embodiment, the compositions contain at least one water-soluble or at least water-dispersible active or effect substance. Of course, the copolymers contained in the copolymer composition A) are also suitable for modifying the rheological properties of compositions containing at least one water-insoluble (hydrophobic) active or effect substance.

"Modification of rheological properties" is widely understood in the context of the present invention. The copolymers contained in the copolymer composition A) are generally suitable for thickening the consistency of aqueous compositions in a wide range. Depending on the basic consistency of the liquid compositions, depending on the amount of copolymer used, as a rule, flow properties can be achieved from low viscosity to solid (in the sense of "no longer flowing"). Under "modification rheological properties" is therefore u. a. Increasing the viscosity of liquids, improving the thixotropic properties of gels, the solidification of gels and waxes, etc. understood. The compositions according to the invention are preferably suitable for the formulation of aqueous cosmetic and pharmaceutical products. Preferably, the copolymer composition A) are generally clear. Advantageously, it is thus possible to stain formulations, in particular cosmetic formulations, without being adversely affected by the intrinsic color of the compositions. Furthermore, the compositions can be formulated in the form of clear gels.

Overall, the copolymer compositions A) prepared in the presence of the adjuvant system of the invention are distinguished by advantageous rheological properties. Further control of the rheology-modifying properties can take place via the type and amount of the monomers used to prepare the copolymer compositions A). This applies especially to the type and amount of crosslinker used c). This also applies specifically to the use of surface-active monomers in the production of A), such as. B. the polyether acrylates IV c) or Allylalkoholalkoxilate IV d). A 0.2% strength by weight aqueous solution of a copolymer composition A) generally has a viscosity in the range from 5000 to 15000 mPa.s (values determined by means of Brookfield viscometer at 23 ° C. and 100 s ^-1 ).

A 0.5% strength by weight aqueous solution of a copolymer composition A) generally has a viscosity in the range from 20,000 to 60,000 mPa.s (values determined by means of Brookfield viscometer at 23 ° C. and 100 s ^-1 ). The copolymer compositions A) are suitable both for preparing homogeneous-phase aqueous compositions and for formulating heterogeneous phase compositions which additionally comprise at least one water-insoluble (hydrophobic) liquid or solid compound. "Homogeneous phase compositions" have only a single phase regardless of the number of their constituents. "Heterogeneous phase compositions" are disperse systems of two or more immiscible components. These include solid / liquid, liquid / liquid and solid / liquid / liquid compositions, such as dispersions and emulsions, eg. As O / W and W / O formulations containing at least one of the oil or fat components described in more detail below and water as immiscible phases. In principle, the copolymer compositions A) can be used both in the water phase and in the oil phase. In general, heterogeneous liquid / liquid compositions contain the copolymer compositions A) substantially in the water phase.

The copolymer compositions A) according to the invention are generally suitable for the preparation of active or effect compositions comprising A) at least one copolymer composition as defined above,

B) at least one active or effect substance and

C) optionally at least one further excipient other than A) and B). Active ingredients for cosmetics (eg hair or skin cosmetics), pharmaceuticals, hygiene products, textile treatment agents, etc., ie substances which generally have an effect in low concentrations, eg. As a cosmetic effect on the skin and / or hair, a pharmacological action in an organism, a cleaning and / or disinfecting effect, a modification of a textile material, for. As wrinkle-free equipment, as well as effect substances that give sentient beings or inanimate substrates a specific property, for example, color pigments for make-up or emulsion paints, are often formulated and applied in the form of aqueous active or Ffektstoffzusammensetzungen. The active and effect compositions according to the invention contain the copolymer compositions A), preferably in an amount of from 0.01 to 50% by weight, particularly preferably from 0.05 to 30% by weight, in particular from 0.1 to 20% by weight on the total weight of the agent. Advantageously, the copolymer compositions according to the invention exhibit good application-technical properties, even in small quantities, eg. B. a good thickening effect. In a special embodiment, the active ingredient and effect composition according to the invention contain Polymer component A) in an amount of 0.1 to 5 wt .-%, based on the total weight of the composition.

Components B) and C) are selected according to the desired area of use of the composition. In addition to typical use components (eg certain pharmaceutical agents) they are z. B. selected from carriers, excipients, emulsifiers, surfactants, preservatives, fragrances, of component A) different thickeners, polymers, gelling agents, dyes, pigments, light stabilizers, bodying agents, antioxidants, defoamers, antistatic agents, resins, solvents, solubilizers, neutralizing agents , Stabilizers, sterilants, blowing agents, drying agents, opacifiers, etc.

Preferably, the compositions comprise a carrier component C) selected from water, hydrophilic carriers other than water, and mixtures thereof.

Suitable hydrophilic carrier C) are z. B. mono-, di- or polyhydric alcohols having preferably 1 to 8 carbon atoms, such as ethanol, n-propanol, isopropanol, propylene glycol, glycerol, sorbitol, etc.

The compositions of the invention may be used as active ingredient, for. B. as a cosmetic and / or pharmaceutical active ingredient B) (as well as optionally as excipient C)), at least one polymer which differs from the inventive copolymer compositions A). These include, in general, anionic, cationic, amphoteric and neutral polymers.

Examples of anionic polymers are copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes, eg. B. Luviset PUR® Fa. BASF, and polyureas. Particularly suitable polymers are copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (for example Luvimer® 100P), copolymers of ethyl acrylate and methacrylic acid (for example Luvimer® MAE), copolymers of N-tert-butylacrylamide, ethyl acrylate , Acrylic acid (Ultrahold® 8, strong), copolymers of vinyl acetate, crotonic acid and optionally further vinyl esters (eg Luviset® brands), maleic anhydride copolymers, optionally reacted with alcohol, anionic polysiloxanes, eg. Carboxy-functional, t-butyl acrylate, methacrylic acid (eg Luviskol® VBM), copolymers of acrylic acid and methacrylic acid with hydrophobic monomers, such as e.g. B.

C 4 -C 30 -alkyl esters of (meth) acrylic acid, C 4 -C 30 -alkyl vinyl esters, C 4 -C 30 -alkyl vinyl ethers and hyaluronic acid. An example of an anionic polymer is furthermore the methyl methacrylate / methacrylic acid / acrylic acid / urethane acrylate copolymer available under the name Luviset® Shape (INCI name: Polyacrylate-22). Examples of anionic Polymers are also vinyl acetate / crotonic acid copolymers, such as those sold under the names Resyn® (National Starch) and Gafset® (GAF) and vinylpyrrolidone / vinyl acrylate copolymers, available for example under the trademark Luviflex® (BASF). Further suitable polymers are the vinylpyrrolidone / acrylate terpolymer available under the name Luviflex® VBM-35 (BASF) and sodium sulfonate-containing polyamides or sodium sulfonate-containing polyesters. Also suitable are vinylpyrrolidone / ethyl methacrylate / methacrylic acid copolymers such as those sold by Stepan under the names Stepanhold-Extra and -R1 and the Carboset® grades from BF Goodrich.

Suitable cationic polymers are, for. As cationic polymers called Polyquaternium INCI, z. B. Copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviset Clear®, Luviquat® Supreme®, Luviquat® Care), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat® PQ 1 1), copolymers of N-

Vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® Hold); cationic cellulose derivatives (polyquaternium-4 and -10), acrylamidocopolymers (polyquaternium-7) and chitosan. Suitable cationic (quaternized) polymers are also Merquat® (polymer based on dimethyldiallylammonium chloride), Gafquat® (quaternary polymers formed by reaction of polyvinylpyrrolidone with quaternary ammonium compounds), polymer JR (hydroxyethylcellulose with cationic groups) and cationic polymers on vegetable Base, z. As guar polymers, such as the Jaguar® brands of Fa. Rhodia. Very particularly suitable polymers are neutral polymers, such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their salts, cellulose derivatives, Polyaspartic acid salts and derivatives. These include, for example, Luviflex® Swing (partially saponified copolymer of polyvinyl acetate and polyethylene glycol, BASF).

Suitable polymers are also nonionic, water-soluble or water-dispersible polymers or oligomers, such as polyvinyl caprolactam, z. B. Luviskol® Plus (BASF SE), or polyvinylpyrrolidone and copolymers thereof, in particular with vinyl esters, such as vinyl acetate, z. Luviskol® VA 37, VA 55, VA 64, VA 73 (BASF SE); Polyamides, z. B. based on itaconic acid and aliphatic diamines, as z. B. in DE-A-43 33 238 are described.

Suitable polymers are also amphoteric or zwitterionic polymers, such as those available under the names Amphomer® (National Starch) octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate 2-hydroxypropyl methacrylate copolymers and zwitterionic polymers, as disclosed for example in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451. Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts are preferred zwitterionic polymers. Further suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are commercially available under the name Amersette® (AMERCHOL), and copolymers of hydroxyethyl methacrylate, methyl methacrylate, Ν, Ν-dimethylaminoethyl methacrylate and acrylic acid (Jordapon®). Suitable polymers are also nonionic, siloxane-containing, water-soluble or

dispersible polymers, e.g. As polyether siloxanes, such as Tegopren® (Goldschmidt) or Belsil® (Wacker).

In a specific embodiment, the compositions according to the invention comprise at least one polymer which differs from the polymers contained in the copolymer compositions A) and which acts as a thickener.

Suitable polymeric thickeners are, for example, optionally modified polymeric natural substances (carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and the like) as well as synthetic polymeric thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides). These include the polyacrylic and polymethacrylic compounds, some of which have already been mentioned above, for example the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkylene polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name: carbomer). Such polyacrylic acids are u. a. from the company BF Goodrich under the trade name Carbopol ® available, z. Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 (molecular weight about 125,000) or Carbopol 934 (molecular weight about 3,000,000). Furthermore, these include acrylic acid copolymers which are obtainable, for example, from Rohm & Haas under the trade names Aculyn® and Acusol®, eg. The anionic non-associative polymers Aculyn 22, Aculyne 28, Aculyn 33 (crosslinked), Acusol 810, Acusol 823 and Acusol 830 (CAS 25852-37-3). Also particularly suitable are associative thickeners, for. B. based on modified polyurethanes (HEUR) or hydrophobically modified acrylic or methacrylic acid copolymers (HASE thickener, high alkali swellable emulsion).

The amount of additional thickener used is preferably in a range of 0.001 to 10 wt .-%, preferably 0.1 to 5%, based on the total weight of the composition. Examples of effect substances which can be formulated as aqueous active substance composition according to the invention are dyes: z. For example, the dyes described in DE-A 102 45 209 and the color Index referred to as a disperse dyes and as solvent dyes compounds, which are also referred to as disperse dyes. A compilation of suitable disperse dyes can be found, for example, in Ullmanns Enzyklopadie der technischen Chemie, 4th Edition, Vol. 10, pp. 155-165 (see also Vol. 7, pp. 585ff - anthraquinone dyes; Vol. 8, pp. 244ff - azo dyes; Vol. 9, p. 313ff - quinophthalone dyes). This reference and the compounds mentioned therein are hereby incorporated by reference. Disperse dyes and solvent dyes which are suitable according to the invention comprise a wide variety of different chromophore classes of dyes, for example anthraquinone dyes, monoazo and disazo dyes, quinophthalones, methine and azamethine dyes, naphthalimide dyes, naphthoquinone dyes and nitro dyes. Examples of disperse dyes which are suitable according to the invention are the disperse dyes of the following Color Index list: CI Disperse Yellow 1 - 228, CI Disperse Orange 1 - 148, CI Disperse Red 1 - 349, CI Disperse Violet 1 - 97, CI Disperse Blue 1 - 349, CI Disperse Green 1 - 9, CI Disperse Brown 1 - 21, CI Disperse Black 1 - 36. Examples of solvent dyes suitable according to the invention are the compounds of the following Color Index list: CI Solvent Yellow 2 - 191, CI Solvent Orange 1 - 1 13, CI Solvent Red 1 - 248, CI Solvent Violet 2 - 61, CI Solvent Blue 2 - 143, CI Solvent Green 1 - 35, CI Solvent Brown 1 - 63, CI Solvent Black 3 - 50. Dyes which are suitable according to the invention are also derivatives of naphthalene, of anthracene, of perylene, of terrylene, of quaterrylene, as well as diketopyrrolopyrrole dyes, perinone dyes, coumarin dyes, isoindoline and isoindolinone dyes, porphyrin dyes, phthalocyanine and naphthalocyanine dyes.

In addition to the abovementioned constituents, the active ingredient and effect compositions according to the invention may also contain conventional surface-active substances and other additives. Surfactants include surfactants, dispersing aids and wetting agents. The other additives include, in particular, thickeners, defoamers, preservatives, antifreeze agents, stabilizers, etc. In principle, anionic, cationic, nonionic and amphoteric surfactants are usable, wherein polymer surfactants and surfactants with heteroatoms are included in the hydrophobic group.

The anionic surfactants include, for example, carboxylates, especially alkali, alkaline earth and ammonium salts of fatty acids, eg. B. potassium stearate, which are commonly referred to as soaps; glutamates; Sarcosinates, e.g. Eg sodium lauroylsarcosinate; taurates; Methylcelluloses; Alkyl phosphates, especially mono- and diphosphoric acid alkyl esters; Sulfates, in particular alkyl sulfates and alkyl ether sulfates; Sulphonates, other alkyl and alkylarylsulphonates, in particular alkali, alkaline earth and ammonium salts of arylsulfonic acids and alkyl-substituted arylsulfonic acids, alkylbenzenesulfonic acids, such as lignin and phenolsulfonic acid, naphthalene and dibutylnaphthalenesulfonic acids, or dodecylbenzenesulfonates, alkylnaphthalenesulfonates, alkylmethylsulfonates, condensation products of sulfonated Naphthalene and derivatives thereof with formaldehyde, condensation products of naphthalenesulfonic acids, phenol and / or phenolsulfonic acids with formaldehyde or with formaldehyde and urea, mono- or Dialkylbernsteinsäureestersulfonate; as well as protein hydrolysates and lignin sulphite waste liquors. The aforementioned sulfonic acids are advantageously used in the form of their neutral or optionally basic salts.

The cationic surfactants include, for example, quaternized ammonium compounds, in particular alkyltrimethylammonium and dialkyldimethylammonium compounds.

Halides and alkylsulfates and pyridine and imidazoline derivatives, in particular alkylpyridinium halides.

Nonionic surfactants include, for example:

Fatty alcohol polyoxyethylene esters, for example lauryl alcohol polyoxyethylene ether acetate,

Alkyl polyoxyethylene and polyoxypropylene ethers, e.g. From iso-tridecyl alcohol and fatty alcohol polyoxyethylene ether,

Alkylaryl alcohol polyoxyethylene ethers, e.g. Octylphenol polyoxyethylene ethers, alkoxylated animal and / or vegetable fats and / or oils, for example, corn oil ethoxylates, castor oil ethoxylates, tallow fatty ethoxylates,

Glycerol esters, such as glycerol monostearate,

Fatty alcohol alkoxylates and oxo alcohol alkoxylates, in particular of the type

RO- (Ri80) r (Ri90) _s R2o with Rie and R19 independently = C2H4, C3H6,

C ₄ H ₈ and R 20 = H, or Ci-Ci ₂ alkyl, R = C ₃ -C ₃ o-alkyl or C ₆ -C ₃ o-alkenyl, r and s are independently 0 to 50, wherein not both are 0, such as iso-tridecyl alcohol and oleyl alcohol polyoxyethylene ether,

Alkylphenol alkoxylates, such as, for example, ethoxylated isooctyl, octyl or nonylphenol, tributylphenol polyoxyethylene ethers,

Fatty amine alkoxylates, fatty acid amide and fatty acid diethanolamide alkoxylates, in particular their ethoxylates,

Sugar surfactants, sorbitol esters, such as, for example, sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, alkyl polyglycosides, N-alkylgluconamides,

alkyl methyl, Alkyldimethylphosphine oxides, such as, for example, tetradecyldimethylphosphine oxide.

The amphoteric surfactants include, for example, sulfobetaines, carboxybetaines and alkyldimethylamine oxides, e.g. B. tetradecyldimethylamine oxide.

Other surfactants which are to be mentioned as examples here are perfluorosurfactants, silicone surfactants, phospholipids, such as lecithin or chemically modified lecithins, amino acid surfactants, eg. B. N-lauroylglutamate. Unless specified, the alkyl chains of the surfactants listed above are linear or branched radicals of usually 8 to 20 carbon atoms.

The active or effect compositions according to the invention may contain water-soluble salts as component B) and / or C), eg. B. NaCl.

The active or effect compositions according to the invention may contain organic solvents, oils and / or fats for some applications. Preferred are such solvents, oils and / or fats that are environmentally friendly or biocompatible. These include z. B .:

Paraffin oils, aromatic hydrocarbons and aromatic hydrocarbon mixtures, e.g. Xylenes, Solvesso 100, 150 or 200, and the like, phenols and alkylphenols, e.g. Phenol, hydroquinone, nonylphenol, etc., ketones with more than 4 C atoms such as cyclohexanone, isophorone, acetophenone, acetonaphthone,

Alcohols with more than 4 C atoms, such as acetylated lanolin alcohol, cetyl alcohol, 1-decanol, 1-heptanol, 1-hexanol, isooctadecanol, isopropyl alcohol, oleyl alcohol, benzyl alcohol,

- Carboxylic acid esters, eg. For example, dialkyl adipate, such as

Adipic acid bis (2-ethylhexyl) ester, dialkyl phthalate, as

Phthalic acid bis (2-ethylhexyl) esters, alkyl acetates (also branched alkyl groups), such as ethyl acetate and ethyl acetoacetate, stearates such as butyl stearate, glycerol monostearate, citrates such as acetyltributyl citrate, furthermore cetyl octanoate, methyl oleate, methyl p-hydroxybenzoate, methyl tetradecanoate , Propyl p-hydroxybenzoate, methyl benzoate, lactic acid esters, such as isopropyl lactate, butyl lactate and 2-ethylhexyl lactate,

Vegetable oils, such as palm oil, rapeseed oil, castor oil and derivatives thereof, such. B. oxidized, coconut oil, cod liver oil, corn oil, soybean oil, linseed oil, olive oil, peanut oil, safflower oil, sesame seed oil, grapefruit oil, basil oil, apricot oil, Ginger oil, geranium oil, orange oil, rosemary oil, macadamia oil, onion oil, tangerine oil, pine oil, sunflower oil,

hydrogenated vegetable oils such as hydrogenated palm oil, hydrogenated rapeseed oil, hydrogenated soybean oil,

- animal oils such as lard oil, fish oils,

Dialkylamides medium to long chain fatty acids, eg. B. Hallcomide, as well

Vegetable oil esters such as rapeseed oil methyl ester.

The copolymer compositions A) can be used together with conventional compressors. These include the aforementioned polymers acting as thickeners. These also include polysaccharides and organic layer minerals such as Xanthan Gum ^® (Kelzan ^® from. Kelco), Rhodopol ^® 23 (Rhone Poulenc) or VEE gum ^® (from RT Vanderbilt) or Attaclay ^® (Engelhardt). Suitable thickening agents are also organic natural thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein) and inorganic thickeners (polysilicic acids, clay derivatives such as montmorillonite , Zeolites, silicic acids). Further thickeners are the polysaccharides and heteropolysaccharides, in particular the polysaccharide gums, for example gum arabic, agar, alginates, carrageenes and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, eg. B. propoxylated guar, and their mixtures. Other polysaccharide thickeners are, for example, starches of various origins and starch derivatives, eg. As hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropyl-methyl or hydroxyethyl methyl cellulose or cellulose acetate. As thickeners, it is also possible to use phyllosilicates. These include, for example, available under the trade name Laponite ® magnesium or sodium magnesium phyllosilicates from Solvay Alkali and the magnesium silicates from Süd-Chemie.

The amount of additional thickener used is preferably in a range of 0.001 to 10 wt .-%, preferably 0.1 to 5%, based on the total weight of the composition. As for the invention dispersions suitable antifoam agents are, for example, silicone emulsions (such as, for example, silicone ^® SRE, from Wacker, or Rhodorsil ^® from Rhodia), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof. Bactericides may be added to stabilize the compositions of the invention against attack by microorganisms. Suitable bactericides are play as Proxel ^® from. ICI or Acetide ^® RS from. Thor Chemie and Kathon ^® MK from Rohm & Haas.

Suitable antifreeze are organic polyols, eg. As ethylene glycol, propylene glycol or glycerol. These are usually given in quantities of not more than

10 wt .-%, based on the total weight of the active ingredient composition used in order not to exceed the desired content of volatile compounds. In one embodiment of the invention, the proportion thereof of various volatile organic compounds is preferably not more than 1 wt .-%, in particular not more than 1000 ppm.

Optionally, the active compound compositions of the invention may contain 1 to 5 wt .-% buffer, based on the total amount of the formulation prepared, for pH regulation, wherein the amount and type of buffer used depends on the chemical properties of the active ingredient or the active ingredients. Examples of buffers are alkali salts of weak inorganic or organic acids such. For example, phosphoric acid, boric acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid. In a particularly preferred embodiment, the copolymer compositions according to the invention are used as component in a cosmetic agent. As described above, they can serve to modify the rheological properties of a cosmetic agent based on an aqueous medium. Another object of the invention is a cosmetic agent containing

A) at least one copolymer composition obtainable by a method as defined above, B) at least one cosmetically acceptable active ingredient and

C) optionally at least one further cosmetically acceptable excipient other than A) and B). Component C) preferably comprises at least one cosmetically or pharmaceutically acceptable carrier.

Preferably, the carrier component C) is selected from i) water, ii) water-miscible organic solvents, preferably C 2 -C 4 alkanols, in particular ethanol,

iii) oils, fats, waxes,

iv) of (iii) various esters of C6-C3o-monocarboxylic acids with monohydric, dihydric or trihydric alcohols,

v) saturated acyclic and cyclic hydrocarbons,

vi) fatty acids,

vii) fatty alcohols,

viii) propellants, and mixtures thereof.

Suitable components C) are the aforementioned organic solvents, oils and fats.

Especially suitable cosmetically acceptable oil or fat components C) are described in Karl-Heinz Schräder, bases and formulations of cosmetics, 2nd edition, Verlag Hüthig, Heidelberg, pp. 319-355, to which reference is made here. The cosmetic agents according to the invention may be skin-cosmetic, hair-cosmetic, dermatological, hygienic or pharmaceutical agents. Because of their thickening properties, the above-described copolymer compositions A) are particularly suitable as additives for hair and skin cosmetics. They are especially suitable for the formulation of gels.

The agents according to the invention are preferably in the form of a gel, foam, spray, ointment, cream, emulsion, suspension, lotion, milk or paste. If desired, liposomes or microspheres can also be used. The copolymer compositions are also particularly suitable as emulsifier or stabilizer for emulsions.

The cosmetically active agents according to the invention may additionally contain cosmetically and / or dermatologically active active substances and effect substances as well as auxiliaries. In principle, the previously mentioned active ingredients B) and auxiliaries C) are suitable.

The cosmetic compositions according to the invention preferably comprise at least one copolymer composition A) as defined above, at least one carrier C as defined above and at least one different constituent thereof, which is preferably selected from cosmetically active ingredients, emulsifiers, Surfactants, preservatives, perfume oils, additional thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, light stabilizers, bleaches, gelling agents, conditioners, tinting agents, tanning agents, dyes, pigments, consistency regulators, humectants, restoats, collagen, Protein hydrolysates, lipids, antioxidants, defoamers, antistatic agents, emollients and plasticizers.

Conventional thickeners suitable for use in cosmetic compositions in addition to the copolymer compositions A) are those mentioned above.

Suitable cosmetically and / or dermatologically active agents are, for. As skin and hair pigmenting agents, tanning agents, bleaching agents, keratin-hardening substances, antimicrobial agents, light filter agents, repellents, hyperemic substances, keratolytic and keratoplastic substances, Antischuppenwirkstof- fe, anti-inflammatory drugs, keratinizing substances, antioxidant or as Radical scavengers active ingredients, skin moisturizing or moisturizing substances, moisturizing agents, deodorizing agents, sebostatic agents, plant extracts, antierythym matically or antiallergically active agents and mixtures thereof. Artificial skin tanning agents that are suitable for tanning the skin without natural or artificial irradiation with UV rays, z. Dihydroxyacetone, alloxan and walnut shell extract. Suitable keratin-hardening substances are generally active ingredients, as used in antiperspirants, such as. For example, potassium aluminum sulfate, aluminum hydroxychloride, aluminum lactate, etc. Antimicrobial agents are used to destroy or inhibit their growth microorganisms and thus serve both as a preservative and as a deodorizing substance, which reduces the formation or intensity of body odor. These include z. As usual preservatives known in the art, such as p-hydroxybenzoic acid, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc. Such deodorizing substances are, for. Zinc ricinoleate, triclosan, undecylenic acid alkylolamides, triethyl citrate, chlorhexidine, etc. Suitable light filtering agents are substances that absorb UV rays in the UV-B and / or UV-A range. Suitable UV filters are those mentioned above. Also suitable are p-aminobenzoic acid esters, cinnamic acid esters, benzophenones, camphor derivatives and UV-radiation-stopping pigments, such as titanium dioxide, talc and zinc oxide. Suitable repellents are compounds capable of preventing or repelling certain animals, particularly insects, from humans. This includes z. B. 2-ethyl-1, 3-hexanediol, N, N-diethyl-m-toluamide, etc. Suitable hyperemic substances which stimulate the circulation of the skin are, for. B. essential oils, such as mountain pine, lavender, rosemary, juniper berry, horse chestnut extract, birch leaf extract, hay flower extract, ethyl acetate, camphor, men thol, peppermint oil, rosemary extract, eucalyptus oil, etc. Suitable keratolytic and keratoplastic substances are for. For example, salicylic acid, calcium thioglycolate, thioglycolic acid and its salts, sulfur, etc. Suitable antidandruff agents are, for. As sulfur, Schwefelpolyethylenglykolsorbitanmonooleat, Schwefelricinolpolyethoxylat, Zinkpyrithion, Aluminiumpyrithion, etc. Suitable antiphlogistics, which counteract skin irritation, z. Allantoin, bisabolol, dragosantol, chamomile extract, panthenol, etc.

The cosmetic agents according to the invention may contain as cosmetic active ingredient (as well as optionally as adjuvant) at least one cosmetically or pharmaceutically acceptable polymer which differs from the copolymer compositions A) according to the invention. These include, in general, anionic, cationic, amphoteric and neutral polymers. The aforementioned polymers are fully incorporated herein by reference.

According to a preferred embodiment, the agents according to the invention are a skin cleanser.

Preferred skin cleansing agents are soaps of liquid to gelatinous consistency, such as transparent soaps, luxury soaps, de-soaps, cream soaps, baby soaps, skin soaps, abrasive soaps and syndets, pasty soaps, greases and washing pastes, liquid detergents, shower and bath preparations such as washing lotions, shower baths and gels , Bubble baths, oil baths and scrub preparations, shaving foams, lotions and creams.

According to a further preferred embodiment, the agents according to the invention are cosmetic agents for the care and protection of the skin, nail care preparations or preparations for decorative cosmetics. Suitable skin cosmetic agents are, for. For example, face lotions, face masks, deodorizers, and other cosmetic lotions. Means for use in decorative cosmetics include, for example, masking pens, theatrical paints, mascara and eye shadows, lipsticks, kohl pencils, eyeliners, rouges, powders, and eyebrow pencils. In addition, the copolymer compositions A) can be used in nasal strips for pore cleansing, in anti-acne agents, repellents, shaving agents, depilatories, personal care products, foot care products and in baby care.

The skin care compositions according to the invention are in particular W / O or O / W skin creams, day and night creams, eye creams, face creams, anti-aging creams. creams, moisturizing creams, bleaching creams, vitamin creams, skin lotions, body lotions and moisturizing lotions.

Skin cosmetic and dermatological compositions based on the above-described copolymer composition A) have advantageous effects. Among other things, the copolymer composition can contribute to moisturizing and conditioning the skin and to improving the feel on the skin. By adding the copolymer composition according to the invention, in certain formulations a considerable improvement in the skin compatibility can be achieved.

Skin cosmetic and dermatological compositions preferably contain at least one copolymer composition A) in a proportion of about 0.001 to 30% by weight, preferably 0.01 to 20% by weight, very particularly preferably 0.1 to 12% by weight, based on the total weight of the agent.

Depending on the field of application, the compositions of the invention in a form suitable for skin care, such. B. as a cream, foam, gel, pen, mousse, milk, spray (pump spray or propellant spray) or lotion can be applied. In addition to the copolymer compositions A) and suitable carriers, the skin cosmetic preparations may contain other active ingredients and adjuvants customary in skin cosmetics, as described above. These preferably include emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, light stabilizers, bleaching agents, tanning agents, collagen, protein hydrolysates, stabilizers, pH regulators, dyes , Salts, thickeners, gelling agents, bodying agents, silicones, humectants, moisturizers and other common additives.

Preferred oil and fat components of the skin cosmetic and dermatological agents are the aforementioned mineral and synthetic oils, such as. As paraffins, silicone oils and aliphatic hydrocarbons having more than 8 carbon atoms, animal and vegetable oils, such as. As sunflower oil, coconut oil, avocado oil, olive oil, lanolin, or waxes, fatty acids, fatty acid esters, such as. B. triglycerides of

C6-C3o fatty acids, wax esters, such as. As jojoba oil, fatty alcohols, Vaseline, hydrogenated lanolin and acetylated lanolin and mixtures thereof.

It is also possible to mix the copolymer compositions A) according to the invention with conventional polymers as described above if special properties are to be set. To set certain properties such. B. Improvement of the feeling of touch, the spreading behavior, the water resistance and / or the binding of active ingredients and excipients, such as pigments, the skin cosmetic and dermatological preparations may additionally contain conditioning substances based on silicone compounds. Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.

The preparation of the cosmetic or dermatological preparations is carried out by customary methods known to the person skilled in the art.

The cosmetic and dermatological agents are preferably in the form of emulsions, in particular as water-in-oil (W / O) or oil-in-water (O / W) emulsions. However, it is also possible to choose other types of formulations, for example hydrodispersions, gels, oils, oleogels, multiple emulsions, for example in the form of W / O / W or O / W / O emulsions, anhydrous ointments or ointment bases, etc.

Emulsions are prepared by known methods. In addition to at least one copolymer composition A), the emulsions generally contain conventional constituents, such as fatty alcohols, fatty acid esters and, in particular, fatty acid triglycerides, fatty acids, lanolin and derivatives thereof, natural or synthetic oils or

Waxes and emulsifiers in the presence of water. The selection of the emulsion type-specific additives and the preparation of suitable emulsions is described for example in Schräder, bases and formulations of cosmetics, Hüthig Buch Verlag, Heidelberg, 2nd edition, 1989, third part, which is hereby incorporated by reference.

A suitable emulsion, for. As for a skin cream, etc., generally contains an aqueous phase which is emulsified by means of a suitable emulsifier in an oil or fat phase. To provide the aqueous phase, a copolymer composition A) can be used.

Preferred fat components which may be included in the fat phase of the emulsions are: hydrocarbon oils such as paraffin oil, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in these oils; animal or vegetable oils, such as sweet almond oil, avocado oil, calophilum oil, lanolin and derivatives thereof, castor oil, seed oil, olive oil, jojoba oil, karite oil, hoplostethus oil; Mineral oils whose beginning of distillation under atmospheric pressure at about 250 ^° C and the distillation end point at 410 ^° C, such. Vaseline oil; Esters of saturated or unsaturated fatty acids, such as alkyl myristates, e.g. For example, i-propyl, butyl or cetyl myristate, hexadecyl stearate, ethyl or i-propyl palmitate, octanoic or Decansäuretriglyceride and Cetylricinoleat. The fat phase may also contain other oil-soluble silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and fatty alcohols. In addition to the copolymer compositions A) waxes can be used, such as. Carnauba wax, candililla wax, beeswax, microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates, myristates, linoleates and

Stearates. Furthermore, an emulsion of the invention may be present as O / W emulsion. Such an emulsion usually contains an oil phase, emulsifiers that stabilize the oil phase in the water phase, and an aqueous phase that is usually thickened. Suitable emulsifiers are preferably O / W emulsifiers, such as polyglycerol esters, sorbitan esters or partially esterified glycerides into consideration.

According to a further preferred embodiment, the agents according to the invention are a shower gel, a shampoo formulation or a bathing preparation. Such formulations contain at least one copolymer composition A) and usually anionic surfactants as base surfactants and amphoteric and / or nonionic surfactants as cosurfactants. Other suitable active ingredients and / or adjuvants are generally selected from lipids, perfume oils, dyes, organic acids, preservatives and antioxidants, as well as thickeners / gelling agents, skin conditioners and humectants.

These formulations preferably contain from 2 to 50% by weight, preferably from 5 to 40% by weight, particularly preferably from 8 to 30% by weight of surfactants, based on the total weight of the formulation.

In the washing, shower and bath preparations all anionic, neutral, amphoteric or cationic surfactants commonly used in personal care products can be used. Suitable surfactants are the aforementioned.

Furthermore, the shower gel / shampoo formulations additional thickeners, such. As sodium chloride, PEG-55, propylene glycol oleate, PEG-120-Methylglucose dioleate and others, as well as preservatives, other active ingredients and excipients and water contained. According to a further preferred embodiment, the agents according to the invention are a hair treatment agent.

Hair treatment agents according to the invention preferably contain at least one copolymer composition A) in an amount in the range of about 0.01 to

10 wt .-%, preferably 0.1 to 8 wt .-%, based on the total weight of the composition.

Preferably, the hair treatment compositions according to the invention are in the form of a hair mousse, hair gel, shampoos, shower gels. Depending on the field of application, the hair cosmetic preparations can be sprayed as (aerosol) spray, (aerosol) foam,

Mousse, gel, gel spray, cream, lotion or wax can be applied. Hairsprays include both aerosol sprays and pump sprays without propellant gas. Hair foams include both aerosol foams and pump foams without propellant gas. Hair sprays and hair foams preferably comprise predominantly or exclusively water-soluble or water-dispersible components. If the compounds used in the hair sprays and hair foams according to the invention are water-dispersible, they can be used in the form of aqueous microdispersions with particle diameters of usually 1 to 350 nm, preferably 1 to 250 nm. The solids contents of these preparations are usually in a range of about 0.5 to 20 wt .-%.

In a preferred embodiment, the hair treatment agent is in the form of a gel. In a further preferred embodiment, the hair treatment agent is in the form of an emulsion. Preference is given here to the use in surfactant-containing formulations.

In a preferred embodiment, the hair cosmetic formulations according to the invention comprise a) from 0.05 to 5% by weight, preferably from 0.1 to 3% by weight, of at least one copolymer composition A), b) from 20 to 99.95% by weight of water or water / alcohol mixture, c) 0 to 70% by weight of at least one surfactant,

0 to 5 wt .-% of at least one of a) different emulsifier or stabilizer, e) 0 to 3 wt .-% of at least one of a) different thickener, and f) 0 to 20 wt .-%, preferably 0 to 10 wt .-%, of at least one of a) to e) and g) different water-soluble or water-dispersible hair polymer, g) 0 to 45 wt .-%, preferably 0.05 to 25 wt .-%, further ingredients, wherein the components a) to g) add up to 100 wt .-%.

By alcohol, all alcohols customary in cosmetics are to be understood, for. For example, ethanol, isopropanol, n-propanol. The proportion of alcohols b) in the hair cosmetic formulations of the invention is preferably 0 to 20 wt .-%.

Other constituents are understood to include the additives customary in cosmetics, for example antifoams, surface-active compounds, d. H. Surfactants, emulsifiers, foaming agents and solubilizers. The surface-active compounds used can be anionic, cationic, amphoteric or neutral. Other common ingredients may also be z. As preservatives, perfume oils, opacifiers, active ingredients, UV filters, care agents such as panthenol, collagen, vitamins, protein hydrolysa- te, alpha- and beta-hydroxycarboxylic acids, stabilizers, pH regulators, dyes, viscosity regulators, gel formers, salts , Humectants, moisturizers, complexing agents and other common additives.

Hair polymers are all styling and conditioner polymers known in cosmetics, which can be used in combination with the copolymer composition A) used according to the invention, if very special properties are to be set.

Suitable conventional hair cosmetic polymers are, for example, the abovementioned cationic, anionic, neutral, nonionic and amphoteric polymers, to which reference is made here.

To adjust certain properties, the preparations may additionally contain conditioning substances based on silicone compounds. Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyaryl siloxanes, polyethersiloxanes, silicone resins or dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicones (CTFA).

The copolymer compositions according to the invention are particularly suitable as thickeners in hairstyling preparations, in particular hair foams and hair gels. As emulsifiers, all emulsifiers commonly used in hair foams can be used. Suitable emulsifiers may be nonionic, cationic or anionic or amphoteric. A preparation suitable for styling gels according to the invention can be composed, for example, as follows:

0.1 to 5% by weight of at least one copolymer composition A),

0 to 5 wt .-% of at least one of A) different cosmetically acceptable water-soluble or water-dispersible hair polymer,

80 to 99.90% by weight of water or water / alcohol mixture,

0 to 1% by weight of a gelling agent other than A),

0 to 20 wt .-% further ingredients.

The proportion of alcohols c) in the styling gel formulations according to the invention is preferably 0 to 20 wt .-%.

As additional gelling agents, it is possible to use all gel formers customary in cosmetics. For this purpose, reference is made to the aforementioned conventional thickener.

The copolymer compositions A) according to the invention are also suitable for shampoo formulations. Preferred shampoo formulations comprise: a) 0.05-10% by weight of the copolymer composition A) obtainable by the process according to the invention,

b) 25-94.95% by weight of water,

c) 5 - - 50 wt .-% surfactants,

d) 0-5% by weight of a conditioning agent,

e) 0 - - 10 wt .-% further cosmetic ingredients.

In the shampoo formulations all anionic, neutral, amphoteric or cationic surfactants commonly used in shampoos can be used.

Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosines, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, especially the alkali and alkaline earth metal salts, e.g. As sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule. Suitable z. Sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauroyl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecyl benzene sulfonate, triethanolamine dodecyl benzene sulfonate. Suitable amphoteric surfactants are, for. Alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or

Propionates, alkyl amphodiacetates or dipropionates.

For example, cocodimethylsulfopropyl betaine, lauryl betaine, cocamidopropyl betaine or sodium cocamphopropionate can be used.

Suitable nonionic surfactants are, for example, the reaction products of aliphatic alcohols or alkylphenols having 6 to 20 C atoms in the alkyl chain, which may be linear or branched, with ethylene oxide and / or propylene oxide. The amount of alkylene oxide is about 6 to 60 moles per mole of alcohol. Also suitable are alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, alkylpolyglycosides or sorbitan ether esters.

In addition, the shampoo formulations may contain conventional cationic surfactants, such as. For example, quaternary ammonium compounds, for example Cetyltrimethylammoni- umchlorid.

Conventional conditioning agents in combination with the copolymer compositions A) can be used in the shampoo formulations to achieve certain effects. These include, for example, the abovementioned cationic polymers with the name Polyquaternium according to INCI, in particular copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviquat® Care), copolymers of N-vinylpyrrolidone / Dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat® PQ 11), copolymers of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® Hold); cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7). Furthermore, protein hydrolysates can be used, as well as conditioning substances based on silicone compounds, for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins. Other suitable silicone compounds are dimethicone copolyols (CTFA) and amino-functional silicone compounds. fertilize like Amodimethicone (CTFA). Furthermore, cationic guar derivatives such as guar hydroxypropyltrimonium chloride (INCI) can be used.

The copolymer compositions A) according to the invention are particularly suitable for oil-containing formulations.

The copolymer compositions A) to be used according to the invention are also suitable for use in modifying the rheological properties in pharmaceutical preparations of any kind.

Preferred agents which comprise the copolymer composition A) obtainable by the process according to the invention are:

shampoos,

· Hairstyling gels,

Hydroalcoholic gels,

Moisturizing gels,

bath gels,

Hand, body and face lotions,

· Creams,

Sunscreen lotions.

Another object of the invention is the use of a copolymer composition A), as defined above, as an adjuvant in pharmacy.

Contain typical pharmaceutical compositions

A) a copolymer composition as defined above

B) at least one pharmaceutically acceptable active substance and

C) optionally at least one further pharmaceutically acceptable excipient other than A) and B).

Pharmaceutically acceptable excipients C) are the excipients known to be useful in the pharmaceutical, food technology and related fields, in particular those listed in relevant pharmacopoeias (eg DAB, Ph. Eur., BP, NF) and other excipients whose properties are physiological application.

Suitable auxiliaries C) may be: lubricants, wetting agents, emulsifying and suspending agents, preserving agents, antioxidants, anti-irritants, chelating agents, emulsion stabilizers, film formers, gelling agents, odor masking agents, resins, Hydrocolloids, solvents, solubilizers, neutralizing agents, permeation accelerators, pigments, quaternary ammonium compounds, lipid and superfatting agents, ointment, cream or oil bases, silicone derivatives, stabilizers, sterilants, blowing agents, drying agents, opacifiers, additional thickeners, waxes, plasticizers , White oils. A related embodiment is based on expert knowledge, as shown for example in Fiedler, HP Lexicon of excipients for pharmacy, cosmetics and related fields, 4th ed., Aulendorf: ECV Editio-Kantor-Verlag, 1996. For the preparation of pharmaceutical agents of the invention, the active ingredients may be mixed or diluted with a suitable excipient. Excipients may be solid, semi-solid or liquid materials which may serve as a vehicle, carrier or medium for the active ingredient. If desired, the admixing of further auxiliaries takes place in the manner known to the person skilled in the art. In particular, these are aqueous solutions or solubilisates for oral or parenteral administration. Furthermore, the copolymer composition to be used according to the invention are also suitable for use in oral dosage forms such as tablets, capsules, powders, solutions. Here they can provide the poorly soluble drug with increased bioavailability. In the case of parenteral administration, emulsions, for example fat emulsions, can be used in addition to solubilisates.

Pharmaceutical formulations of the abovementioned type can be obtained by processing the pharmaceutical compositions A) to be used according to the invention by conventional methods and using known and new active compounds.

The content of copolymer A) in the pharmaceutical compositions, depending on the active ingredient, is in the range from 0.01 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight .-%, based on the total weight of the agent.

In principle, all pharmaceutical active ingredients and prodrugs are suitable for the production of the pharmaceutical agents according to the invention. These include benzodiazepines, antihypertensives, vitamins, cytostatic drugs - especially taxol, anesthetics, neuroleptics, antidepressants, antibiotics, antifungals, fungicides, chemotherapeutics, urologics, antiplatelet agents, sulfonamides, spasmolytics, hormones, immunoglobulins, sera, thyroid drugs, psychotropic drugs, Parkinson's and other antihyperkinetics, Ophthalmics, neuropathy preparations, calcium metabolism regulators, muscle relaxants, anesthetics, lipid-lowering drugs, liver therapeutics, coronary agents, cardiac drugs, immunotherapeutics, regulatory peptides and their inhibitors, hypnotics, sedatives, gynecologics, gout, fibrinolytics, enzyme preparations and transport proteins. teines, enzyme inhibitors, emetics, circulation-promoting agents, diuretics, diagnostics, corticoids, cholinergics, biliary tract therapies, antiasthmatics, broncholytics, beta-receptor blockers, calcium antagonists, ACE inhibitors, arteriosclerotic agents, antiphlogistics, anticoagulants, antihypotonics, antihypoglycemics, antihypertensives, antifibrinolytics, antiepileptics, antiemetics , Antidotes, antidiabetics, antiarrhythmics, antianemics, antiallergic drugs, anthelmintics, analgesics, analeptics, aldosterone antagonists, weight loss agents. Examples of suitable active pharmaceutical ingredients are in particular the active substances mentioned in paragraphs 0105 to 0131 of US 2003/0157170.

In addition to the application in cosmetics and in the pharmaceutical industry, the copolymer compositions A) to be used according to the invention are also suitable in the foodstuffs sector for modifying the rheological properties. The invention therefore also relates to food-grade preparations which contain at least one of the copolymer compositions A) to be used according to the invention. Food preparations are in the context of the present invention, dietary supplements such. As food-containing preparations and dietary foods to understand. In addition, the abovementioned copolymer compositions A) are also suitable for modifying the rheological properties of feed additives for animal nutrition.

In addition, the copolymer compositions A) are suitable for preparing aqueous preparations of dietary supplements such as water-insoluble vitamins and provitamins such as vitamin A, vitamin A acetate, vitamin D, vitamin E, tocopherol derivatives such as tocopherol acetate and vitamin K.

Another object of the invention is the use of a copolymer composition A), as defined above, as auxiliaries in pharmacy, preferably as or in coating agent (s) for solid dosage forms, for modifying rheological properties, as a surface-active compound, as or in adhesive (s) and as or in coating agent (s) for the textile, paper, printing and leather industries.

The invention will be further illustrated by the following non-limiting examples.

Examples: Abbreviations:

AS acrylic acid

MAS methacrylic acid

VI vinylimidazole VP vinyl pyrrolidone

LUMA C 16-C 18 -alkyl (EO) 25-methacrylate

Lutencryl® 250 LUMA: MAS (weight ratio 1: 1)

MMA methylmethacrylate

UMA ureidomethacrylate

PETAE pentaerythritol triallyl ether

Wetsoft® NE 810 polyether aminofunctional silicone fluid, available from

brave

Emulgade PL 68/50 Mixture of alkyl (Ci6-i8) -polyglucoside and

Cetyl / stearyl alcohol (1: 1), available from BASF SE

Span® 85 sorbitan trioleate

Wako® V65 azobis (2,4-dimethylvaleronitrile), available from

Wako Chemicals

Waglinol® 2/7680 Propylene Glycol Dicaprylate / Caprate

General Procedure A

(Example 2 in Table I)

Initial ethyl acetate 512 g

Feed 1 ethyl acetate 106 g

Acrylic acid 222 g

Lutencryl® 250 24 g

Pentaerythritol triallyl ether 1, 65 g

Acetic anhydride 0.9 g

Feed 2 ethyl acetate 98 g

Vinyl pyrrolidone 51 g

Vinylimidazole 3 g

Feed 3 ethyl acetate 247 g

Wako® V65 0.06 g

tert.-butyl peroctoate 0.55 g feed 4 ethyl acetate 423 g

Wetsoft® NE 810 0.9 g

Triethanolamine 2.76 g

Execution of the reaction: In a pressure apparatus with reflux condenser, internal thermometer and four separate feed devices, the original was heated to about 70 ° C. under IS pass-through and stirring at 200 rpm. Thereafter, the feed of feed 1, feed 2 and feed 3 was started at this temperature. Feed 1 and feed 2 were metered in over 5 h and feed 3 in 7.5 h, the first turbidity being observed within about 15 to 25 minutes , 2 hours after completion of the addition of feed 1, feed 4 was metered in over 3 hours. After the addition of Feed 3 was complete, the reaction mixture was heated to 75 ° C and polymerized with stirring at 75 ° C over a period of 12 hours.

The product obtained, after cooling to room temperature, was filtered off and washed twice with ethyl acetate. Thereafter, the moist product was dried in an oven at about 70 ° C for 20 h.

In an analogous manner, the precipitation polymers of Examples 1 and 3 to 1 1 in Table I were prepared. The precipitated polymers obtained by Process A are listed in Table I. Homogenizing the precipitation polymers in water:

2 g of powder of the precipitation polymer from Example 1 - 1 1 was slowly sprinkled into 98 g of water. After complete. Wetting of the powder (up to 10 min), the polymer sponge was homogenized by stirring in finely divided particles. The time for the two steps of wetting and homogenizing is given in Table II.

Homogenizing the precipitation polymers in oil:

1 g of powder of the precipitation polymer from Example 1 - 1 1 was homogenized with stirring in 19 g of Waglinol® 2/7680. The time is given in Table II.

TABLE I Inventive precipitation polymers

all monomer data in wt .-%, based on 100 wt .-% of the monomer composition

H1 ¹ > triethanolamine, [relative to AS + MAS]

H2 ²⁾ acetic anhydride, based on the total weight of the monomer composition of AS, VP, MAS, LUMA and, if used, VI,

MMA, UMA

H3 ³ > Wetsoft® NE810, based on 100% by weight of the monomer composition

H4 ⁴⁾ Emulgade® PL 68/50, based on 100% by weight of the monomer composition

Table II:

General procedure B

(Polymerization in acetic acid ethyl ester, then conversion into soybean oil) (Example 12 in Table III)

Initial ethyl acetate 512 g feed 1 ethyl acetate 106 g

Acrylic acid 222 g Lutencryl® 250 24 g pentaerythritol triallyl ether 1, 65 g acetic anhydride 0.9 g

Feed 2 ethyl acetate 98 g

Vinyl pyrrolidone 51 g

Vinylimidazole 3 g Feed 3 Acetic acid ethyl ester 247 g

Wako®65 0.06 g tert-butyl peroctoate 0.55 g

Feed 4 ethyl acetate 423 g

Wetsoft® NE 810 0.9 g triethanolamine 2.76 g Feed 5 soy oil 750 g

Reaction: In a pressure apparatus with reflux condenser, internal thermometer and five separate feed devices, the original was heated to about 70 ° C. under IS flow and stirring at 200 rpm. Thereafter, the feed of feed 1, feed 2 and feed 3 was started at this temperature. Feed 1 and feed 2 were metered in over 5 h and feed 3 in 7.5 h, during which the first turbidity was obtained within about 15 to 25 minutes - looked after. 2 hours after the beginning of the addition of feed 1 feed 4 was added in 3 h. After the addition of Feed 3 was complete, the reaction mixture was heated to 75 ° C and polymerized with stirring at 75 ° C over a period of 10 hours. Thereafter, about 50% of ethyl acetate at a bath temperature of

Distilled off 100 ° C under atmospheric pressure. Then, feed 5 was added at a bath temperature of 100 ° C., and the remaining ethyl acetate was distilled off in vacuo (about 10-20 mbar). A fine about 30% oil dispersion was obtained. In an analogous manner, the precipitation polymer of Example 15 were prepared in Table III.

General procedure C

(Polymerization in ethyl acetate / Waglinol, then distillative removal of ethyl acetate)

(Example 14 in Table III)

Initial ethyl acetate 375 g

Waglinol® 2/7680 375 g

Emulgade® PL 68/50 25 g

Feed 1 Waglinol® 2/7680 72 g

Acrylic acid 185 g

Lutencryl® 250 20 g

Pentaerythritol triallyl ether 1, 28 g

Acetic anhydride 0.25 g

Feed 2 Waglinol® 2/7680 70 g

Vinyl pyrrolidone 42.5 g Vinylimidazole 2.5 9

Feed 3 Waglinol® 2/7680 85 g

Wako® V65 0.05g

tert-butyl peroctoate 0.45 g

Triethanolamine 2.30 g

Reaction: In a pressure apparatus with reflux condenser, internal thermometer and four separate

Feeders, the template was heated to about 70 ° C under IS -passing and stirring at 250 rpm. Thereafter, the feed of feed 1, feed 2 and feed 3 was started at this temperature. Feed 1 and feed 2 were metered in over 3 hours and feed 3 in 5 hours, during which the first turbidity was observed within about 15 to 25 minutes , 2 h after the addition of feed 3 had ended, the reaction mixture was heated to 75 ° C. and polymerized with stirring at 75 ° C. over a period of 3 hours. Thereafter, the reaction mixture was heated to 80 ° C and polymerized for a further 10 h with stirring. Thereafter, the ethyl acetate was distilled off at an external temperature of 100 ° C in vacuo. An approximately 30% oil dispersion was obtained.

In an analogous manner, the precipitation polymers of Examples 13, 16 and 17 in Table III were prepared.

The precipitation polymers obtained by the method B or C are listed in Table III. Table IV lists homogenizing data.

Homogenization of the obtained precipitation polymers in oil:

5 g of the 30% oil dispersion from Example 12-17 was added to 20 g of soybean oil with stirring. This gave a thoroughly homogenized dispersion. The time is given in Table IV: TABLE III Inventive precipitation polymers

all monomer data in wt .-%, based on 100 wt .-% of the monomer composition

H1 ¹ > triethanolamine, [relative to AS + MAS]

H2 ²⁾ acetic anhydride, based on the total weight of the monomer composition of AS, VP, VI, MAS, and LUMA

H3 ³ > Wetsoft® NE 810, based on the total weight of the monomer composition

H4 ⁴⁾ Emulgade® PL 68/50, based on the total weight of the monomer composition

H4 ⁵⁾ Span® 85, based on the total weight of the monomer composition

Comparative Example V1:

Example 12 was repeated except that the ethyl acetate was replaced with soybean oil. There was no stable dispersion. After about 4 h at room temperature, phase separation occurred.

Comparative Example V2:

Example 12 was repeated except that the ethyl acetate was replaced with Waglinol. There was no stable dispersion. After about 4 h at room temperature, phase separation occurred.

Comparative Example C3:

Example 13 was repeated, but the ethyl acetate was replaced with soybean oil. There was no stable dispersion. After about 4 h at room temperature, phase separation occurred.

Comparative Example V4:

Example 13 was repeated except that the ethyl acetate was replaced with Waglinol. There was no stable dispersion. After about 4 h at room temperature, phase separation occurred.

Table IV

Application examples

Exemplary cosmetic preparations which contain the copolymer composition A) or a copolymer obtainable therefrom are shown below.

A: Hair cosmetic preparation: 1) hair gels

Thickening phase (phase 1):

Copolymer from example 1 (powder) g

Water 143 g

Euxyl ^® K100 qs

Adjust to pH 6.5 - 7.2 with triethanolamine (99%)

Fixing phase (phase 2):

Luviskol® K90 (PVP) 6 g

Cremophor ^® WO Perfume [4: 1 w / w] 0.3 g

Dissolve water with water to 50 g

Phases 1 and 2 were homogenized separately with stirring; This gave a cla res, thick gel (thickener phase) and a Festigerphase. Thereafter, the setting phase was slowly stirred into the thickening phase to give a nearly clear, firm gel.

Analogous hair gels are prepared with the copolymers of Examples 2, 3 and 4.

2) Surfactant-containing formulation

2.1. Standard oily shampoos wt%

Copolymer from Example 15 (30% in soybean oil)

Soybean oil 9.0

Texapon ^® NSO 28% ig 50.0

Comperlan® ^® KD 1 0

Water 10.0

Perfume oil q.s.

B) water 28.0

Sodium chloride 1, 0

Preservatives q.s.

production:

Weigh out and with stirring separate phases A and B and mix, slowly stir phase B into phase A. The formulation was then 10%. NaOH solution adjusted to pH 5 to 6.5. Analogous oily shampoos were made with the copolymers of Examples 16 and 17.

2.2. Standard shampoos% by weight

A) Texapon ^® NSO 28% ig 50.0

Comperlan® ^® KD 1 0

Water 10.0

Perfume oil q.s.

B) Copolymer from example 8 (powder) 0.5

Water 37.5

Sodium chloride 1, 0

NaOH solution (10%) adjusted to pH 5 to 6.5 Preservative q.s.

production:

Weigh out and, while stirring, homogenize phases A and B separately. Slowly stir phase B into phase A.

In an analogous manner, a shampoo was prepared with the copolymer of Example 9.

B. Skin Cosmetic Preparations 3) Standard O / W Cream

Oil phase: wt% CTFA

Cremophor ^® A6 3.3 Ceteareth-6 (and) stearyl alcohol Cremophor ^® A25 3.3 Ceteareth-25

Copolymer from Example 12 1, 0

(30% in soybean oil)

Glycerol monostearate s.e. 2.5 glyceryl stearates

Paraffin Oil 7.5 Paraffin Oil

Cetyl alcohol 2.5 cetyl alcohol

Luvitol ^® EHO 3.2 Cetearyl octanoate

Vitamin E acetate 1, 0 tocopheryl acetate

Nip-nip 0.1 methyl and propyl 4-hydroxybenzoates

(7: 3) Water phase:% by weight

Water 74.0 Water

1, 2-propylene glycol 1, 5 propylene glycol

Germall II 0.1 imidazolidinyl urea

Production:

Weigh out and, while stirring, homogenize the oil phase and the water phase separately at a temperature of approx. 80 ° C. The oil phase was then adjusted to pH 6.5 to 7.2 with triethanolamine. Slowly stir the water phase in oil phase; Slowly cool to room temperature while stirring.

Analogous O / W creams were prepared with the copolymers of Examples 13, 14 and 15.

4) Standard Day Lotion

Oil phase:% CTFA name

Cremophor ^® A6 Ceteareth-6 (and) stearyl alcohol

Cremophor ^® A25 Ceteareth-25

Copolymer from Example 12

(30% in soybean oil)

Glycerol monostearate s.e. 5.0 glyceryl stearate

Uvinul ^® MS 40 Benzophenone-4 0.5

Paraffin oil 3.5 paraffin oil

Cetyl alcohol 0.5 cetyl alcohol

Luvitol ^® EHO 10.0 cetearyl octanoates

D-panthenol 50 P 3.0 panthenol and propylene glycol

Vitamin E Acetates 1, 0 Tocopheryl Acetates

Tegiloxan 100 ^® 0.3 Dimethicone

Nip-Nip 0.1 methyl and propyl 4-hydroxybenzoates (7: 3) water phase:

Water 71, 0 Water

1, 2-propylene glycol 1, 5 propylene glycol

Germall II 0.1 imidazolidinyl urea production:

Analogous lotions were made with the copolymers of Examples 13, 14 and 15.

Claims

claims

1 . A process for preparing a copolymer composition A) by free-radical copolymerization of a monomer composition containing a) at least one monomer selected from acrylic acid, salts of acrylic acid, methacrylic acid, salts of methacrylic acid and mixtures thereof b) at least one free-radically polymerizable crosslinking compound containing at least contains two α, β-ethylenically unsaturated double bonds per molecule, c) at least one α, β-ethylenically unsaturated amide group-containing compound, by the method of precipitation polymerization in the presence of an auxiliary composition H) containing

H1) at least one compound having at least one tertiary amino group, and

H2) at least one anhydride.

2. The method of claim 1, wherein additionally at least one further adjuvant H3) is used, which is selected from silicone group-containing surfactants, preferably polydialkylsiloxane polyether copolymers, which may additionally have at least one amino group.

3. The method according to claim 1 or 2, wherein additionally at least one further adjuvant H4) is used, which is selected from H3) different nonionic surfactants, preferably nonionic surfactants having an HLB value of at most 7, in particular nonionic surfactants with a HLB Not more than 5. 4. A process according to any one of the preceding claims, wherein the monomer composition used to prepare the copolymer composition A) contains at least one amide group-containing monomer c) selected from α, β-ethylenically unsaturated amide group-containing compound of the general formula (II)

where one of the radicals R ⁴ to R ^{6 is} a group of the formula CH 2 = CR ⁷ - where R ⁷ = H or C 1 -C 4 -alkyl and the remaining radicals R ⁴ to R ⁶ independently of one another are H, alkyl, cycloalkyl, heterocycloalkyl , Aryl or hetaryl, wherein R ⁴ and R ⁵ together with the amide group to which they are attached may also be a lactam having 5 to 8 ring atoms, R ⁵ and R ⁶ together with the nitrogen atom to which they are bonded may also stand for a five- to seven-membered heterocycle.

A process according to claim 4, wherein the compound of the general formula (II) is selected from N-vinylpyrrolidone, N-vinylcaprolactam and mixtures thereof.

Process according to one of the preceding claims, in which the monomer composition used for the preparation of the copolymer composition A) contains at least one amide group-containing monomer c) which has a group of the formulas (IIIa) or (IIIb)

la) (IIIb)

in which # represents the binding site to a group having a free-radically polymerizable, α, β-ethylenically unsaturated double bond, where in the compounds (IIIa) # does not represent the bond to a group of the formula CH ₂ = CR ⁷ - R ⁷ = H or C 1 -C ₄ -alkyl, R ^{a is} H or C 1 -C ₄ -alkyl,

R ^{b is} H or C 1 -C ₄ -alkyl, or R ^a and R ^b together are (CH 2) i- ₄ .

7. Process according to claim 6, wherein the monomer composition used to prepare the copolymer composition A) comprises at least one monomer c) selected from N- (2-acryloxyethyl) imidazolidin-2-one and N- (2-methacryloxyethyl) imidazolidin-2-one.

8. The method according to any one of the preceding claims, wherein the monomer composition used to prepare the copolymer composition A) additionally at least one of the compounds a) different compound d) having a free-radically polymerizable, α, β-ethylenically unsaturated double bond and at least one anionogenic and / or contains anionic groups per molecule, preferably selected from ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraaconic acid, mesaconic acid, glutaconic acid, aconitic acid and mixtures thereof.

9. The method according to any one of the preceding claims, wherein the monomer composition used to prepare the copolymer composition A) additionally contains at least one compound e) having a free-radically polymerizable, α, β-ethylenically unsaturated double bond and at least one cationogenic and / or cationic groups per molecule.

10. The method of claim 9, wherein component e) contains or consists of N-vinylimidazole. 1 1. The method according to any one of the preceding claims, wherein the monomer composition used for the preparation of the copolymer composition A) additionally contains at least one ether group-containing monomer f), which is selected from compounds of the general formulas IV a) and IV b)

R ⁸ O

III ₉

H ₂ C = C-CX- (CH ₂ -CH ₂ -O) _k (CH ₂ -CH (CH ₃ ) -O) _| - R

(IV a)

H ₂ C = C H-CH ₂ -O- (CH ₂ -CH ₂ -O) _k (CH ₂ -CH (CH ₃ ) -O) _| -R ⁹

R ^{8 is} hydrogen or C 1 -C 4 -alkyl, preferably methyl,

X is O or a group of the formula NR ¹⁰ , in which R ^{10 is} H, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

Process according to Claim 1 1, in which the monomer composition used to prepare the copolymer composition A) comprises at least one compound f) selected from compounds of the general formula (IV a1)

R ⁸ O

I II ₉

H ₂ C = CC-O- (CH ₂ -CH ₂ -O) _k (CH ₂ -CH (CH ₃ ) -O) _| - R

R ^{8 is} hydrogen or methyl,

R ^{9 is} Ce-Cso-alkyl.

Process according to one of the preceding claims, in which the monomer composition used to prepare the copolymer composition A) additionally contains at least one further monomer g) selected from gl) esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C1-C30-alkanols,

g2) esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C2-C30-diols, g3) amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C 2 -C 30 -aminoalcohols which have a primary or secondary amino group,

g4) urethane (meth) acrylates with alkylene oxide groups,

g5) esters of vinyl alcohol with C 1 -C 8 -monocarboxylic acids or esters of alkyl alcohol with C 1 -C 30 -monocarboxylic acids,

g6) C 1 -C 30 -alkyl vinyl ethers,

g7) vinyl aromatics,

g8) vinyl halides or vinylidene halides and mixtures thereof.

The method of claim 13, wherein the monomer gl) is selected from C 1 -C 3 alkyl (meth) acrylates, C 8 -C 22 alkyl (meth) acrylates and mixtures thereof.

Method according to one of the preceding claims, wherein the component H1) in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on monomer a) is used.

Method according to one of the preceding claims, wherein the component H2) in an amount of 0.01 to 2 parts by weight, preferably 0.05 to 0.5 parts by weight, based on the total weight of the monomers used for the polymerization a) and c), and, if present, monomers d), e), f) and g) is used.

17. The method according to any one of the preceding claims, wherein the component H3) in an amount of 0.1 to 30 parts by weight, preferably 0.5 to 15 parts by weight, based on the total weight of the monomers used for the polymerization a) , b) and c), and, if present, monomers d), e), f) and g) is used.

18. The method according to any one of the preceding claims, wherein the component H4) in an amount of 0.1 to 30 parts by weight, preferably 0.5 to 15 parts by weight, based on the total weight of the monomers used for the polymerization a) , b) and c), and, if present, monomers d), e), f) and g) is used.

19. The method according to any one of the preceding claims, wherein for the preparation of the copolymer composition A), based on the total weight of the monomers used for the polymerization,

15 to 89.9% by weight of acrylic acid a)

0 to 15% by weight of methacrylic acid a)

0.1 to 3 wt .-% of at least one crosslinking compound b), and 10 to 84.9 wt .-% of at least one α, β-ethylenically unsaturated amide group-containing compound c) are used.

20. The method according to any one of claims 1 to 19, wherein the polymerization is carried out in an aprotic solvent or solvent mixture.

21. A process according to claim 20, wherein the polymerization is carried out in ethyl acetate or in a mixture of cyclohexane and ethyl acetate.

22. The method according to any one of claims 20 or 21, wherein the aprotic solvent or solvent mixture is replaced after the polymerization partially or completely against at least one cosmetically acceptable oil body.

23. The method according to any one of claims 1 to 19, wherein the polymerization is carried out in a mixture of a cosmetically acceptable oil body and a different aprotic solvent or solvent mixture thereof.

24. The method of claim 23, wherein the different from the oil body aprotic solvent or solvent mixture is separated after the polymerization. 25. The method according to any one of the preceding claims, wherein the water content of the reaction mixture used for the polymerization 0.05 to 3 wt .-%, preferably 0.1 to 2 wt .-%, based on the total weight of the reaction mixture. 26. The method according to any one of the preceding claims, wherein the adjuvant H2) is added in the course of the polymerization or after completion of the polymerization, wherein the addition begins at the beginning, in the course or after completion of the polymerization. 27. The method according to any one of the preceding claims, wherein the adjuvant H1) is added in the course of the polymerization, wherein the addition begins only after the beginning of the polymerization.

28. The method according to any one of the preceding claims, wherein triethanolamine is used as adjuvant H1).

29. The method according to any one of the preceding claims, wherein the adjuvant H2) is selected from acetic anhydride, succinic anhydride, methacrylic anhydride and mixtures thereof. A copolymer composition A) obtainable by a process as defined in any one of claims 1 to 29.

31. Use of a copolymer composition A) according to claim 30 in an aqueous or oily composition for modifying the rheological properties of said composition.

32. Use of the copolymer composition A) according to claim 30 as an emulator or stabilizer for an emulsion. 33. Use of the copolymer composition A) according to claim 30 in skin cleansing preparations, skin care and protection agents, nail care products, decorative cosmetics or hair treatment preparations.

34. Use according to claim 33 in hair treatment compositions as thickener

and / or fixer.

35. Cosmetic agent containing

A) at least one copolymer composition obtainable by a process as defined in any one of claims 1 to 29,

B) at least one cosmetically acceptable active ingredient and

C) optionally at least one further cosmetically acceptable excipient other than A) and B).

36. Composition according to claim 35 in the form of a gel or dispersion.

37. Composition according to claim 35 in the form of a gel which does not contain any hydrophobic, cosmetically acceptable carriers, in particular no oil.

38. Composition according to claim 35 in the form of an emulsion, in particular for the care and protection of the skin. 39. Composition according to claim 35 in the form of a shampoo, shower gel, bath gel, skin care product or hair fix gel. Use of a copolymer composition A) obtainable by a process as defined in any one of claims 1 to 29 for improving the re-dispersibility of a composition containing the copolymer compositions A) in an aqueous medium or in an oil-containing medium.

Use of a copolymer composition A) obtainable by a process as defined in any one of claims 1 to 29 as an adjuvant in cosmetics, as an adjuvant in the food industry, as an adjuvant in pharmacy, as a surface-active compound, as or in adhesive (s) and as or in coating agent (s) for the textile, paper, printing and leather industries.