DE102005046918A1 - Ampholytic copolymers prepared from anionic and cationic monomers and a crosslinker optionally in presence of a silicon compound are used as a rheological modifier for hair cosmetics - Google Patents

Abstract

Use is claimed as a rheological modifier for hair cosmetics of an ampholytic copolymer with a molar excess of anionogenic/anionic groups over cationogenic/cation groups or vice-versa, the copolymer being obtained by radical polymerization of specified unsaturated compounds optionally in presence of a silicon compound containing a polyether group and/or a radically polymerizable olefinically unsaturated double bond. Use is claimed as a rheological modifier for hair cosmetics of an ampholytic copolymer with a molar excess of anionogenic/anionic groups over cationogenic/cation groups or vice-versa, the copolymer being obtained (optionally in the presence of a silicon compound containing a polyether group and/or a radically polymerizable olefinically unsaturated double bond) by radical polymerization of (A) a compound with a radically polymerizable alpha ,beta -unsaturated double bond and an anionogenic and/or anionic group; (B) a compound like (a) but having cationgenic/cationic rather than anionogenic/anionic groups; and (C) a radically polymerizable crosslinking compound with >=2 alpha ,beta -unsaturated double bonds. Some of the copolymers are also claimed per se (see also the abstract for ).

Description

The The following invention relates to the use of anionic ampholytic Copolymers as rheology modifiers for hair cosmetic compositions.

At Hair cosmetic compositions often become special requirements in terms of their rheological properties. Often they can only be done with the help of Additives, so-called "thickeners" in the desired application form to be brought. Examples of conventional low molecular weight Thickeners are z. As the alkali and aluminum salts of fatty acids, Fatty alcohols or waxes. The use of the known thickening agents However, depending on the application of the preparation to be thickened, often associated with disadvantages. So either the thickening effect the thickener unsatisfactory, their use undesirable or their incorporation into the preparation to be thickened, for example because of their incompatibility difficult or impossible with the compound to be thickened. difficulties often prepares the delivery of products with a complex Property profile using as small a proportion as possible or preferably few different active substances. For example, there is a need for polymers for hair cosmetic agents that have a setting of rheological properties allow the funds and in addition to good have film-forming properties. moreover are becoming increasingly aesthetic to consumer hair cosmetic products Requirements made. So is currently in such products a preference for clear, opaque formulations in the form of gels observed. Another advantageous property of polymers for hair cosmetic Formulations is the aptitude to transform into a solid form, especially a powder and yet be able to Get used to a thickening composition in a short time to let while reliably the desired To provide rheology properties.

The WO 01/85821 describes polyurethanes and their use for modification rheological properties.

The US 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.

The WO 97/21744 describes crosslinked anionic copolymers and their Use as thickening and dispersing agent in aqueous Systems.

• A) 50 bis 99 Gew.-% monoethylenisch ungesättigten Carbonsäuren und
• B) 1 bis 50 Gew.-% mindestens eines Comonomers, ausgewählt unter a) monoethylenisch ungesättigten Carbonsäureestern mit gesättigten C₈-C₃₀-Alkoholen, b) N-C₈-C₁₈-Alkyl- und N,N-Di-C₈-C₁₈-alkylcarbonsäureamiden, c) Vinylestern aliphatischer C₈-C₃₀-Carbonsäuren, d) C₈-C₁₈-Alkylvinylethern, und Mischungen davon

als Verdicker zur Herstellung von Haarwaschmitteln.EP-A-0 982 021 describes the use of (partially) neutralized copolymers

• A) 50 to 99 wt .-% of monoethylenically unsaturated carboxylic acids and
• B) 1 to 50% by weight of at least one comonomer selected from a) monoethylenically unsaturated carboxylic acid esters with saturated C ₈ -C ₃₀ -alcohols, b) NC ₈ -C ₁₈ -alkyl and N, N-di-C ₈ - C ₁₈ alkylcarboxamides, c) vinyl esters of C ₈ -C ₃₀ aliphatic carboxylic acids, d) C ₈ -C ₁₈ alkyl vinyl ethers, and mixtures thereof

as a thickener for the production of shampoos.

In the US 4,395,524 and the US 4,432,881 are described as thickener effective copolymers based on amide group-containing monomers.

The DE-A-42 13 971 describes copolymers which are at least one olefinic unsaturated Containing acid groups Monomer, at least one olefinically unsaturated quaternary ammonium compound, optionally at least one polyether (meth) acrylate and optionally at least one crosslinker in copolymerized form and their Use as thickener to thicken aqueous Systems, which may be cosmetic preparations.

The EP-A-893 117 and EP-A-913 143 describe crosslinked cationic Copolymers and their use u. a. as a hair-setting gel former in cosmetic compositions.

The EP-A-1 064 924 describes the use of crosslinked cationic Polymers in skin cosmetic and dermatological preparations, u. a. as a thickener.

The US 5,015,708 describes a process for preparing a terpolymer from (i) a vinyl lactam, (ii) an acid group-containing monomer and (iii) a hydrophobic monomer, which may include an ethylenically unsaturated silicone compound, by precipitation polymerization, and the production of powders from these polymers.

• a) 5 bis 50 Gew.-% wenigstens eines α,β-ethylenisch ungesättigten Monomers mit einer tert.-Butylgruppe,
• b) 25 bis 90 Gew.-% wenigstens eines N-Vinylamids und/oder N-Vinyllactams,
• c) 0,5 bis 30 Gew.-% wenigstens einer Verbindung mit einer radikalisch polymerisierbaren, α,β-ethylenisch ungesättigten Doppelbindung und mindestens einer kationogenen und/oder kationischen Gruppe pro Molekül, und
• d) 0 bis 30 Gew.-% wenigstens einer weiteren α,β-ethylenisch ungesättigten Verbindung, wobei es sich um Verbindungen mit mindestens einer anionogenen und/oder anionischen Gruppe pro Molekül handeln kann,

eingebaut enthält.WO 01/62809 describes a cosmetic agent containing at least one water-soluble or water-dispersible polymer

• a) from 5 to 50% by weight of at least one α, β-ethylenically unsaturated monomer having a tert-butyl group,
• b) from 25 to 90% by weight of at least one N-vinylamide and / or N-vinyllactam,
• c) 0.5 to 30 wt .-% of 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, and
• d) 0 to 30% by weight of at least one further α, β-ethylenically unsaturated compound, which may be compounds having at least one anionogenic and / or anionic group per molecule,

incorporated contains.

The EP-A-670 333 describes crosslinked water-soluble polymer dispersions, by polymerization of a monomer mixture containing at least a water-soluble Monomer, at least one crosslinker and optionally hydrophobic and / or amphiphilic monomers in the presence of a polymeric dispersant available are. As water-soluble Monomers can in addition to a variety of other N-vinylpyrrolidone and monomers with cationic / cationizable groups, such as N-vinylimidazole, be used. The polymeric dispersants may be to polyelectrolytes, for example, salts of (meth) acrylic acid as anionic monomer building blocks or quaternized derivatives of N, N-dimethylaminoethyl (meth) acrylate in copolymerized form as cationic building blocks. A mission the polymer dispersions in cosmetics is not described.

The EP-A-929 285 teaches the use of water-soluble copolymers, the vinylcarboxamide units and vinylimidazole units in copolymerized form contained as an ingredient cosmetic agent. Polyelectrolyte complexes of these copolymers with Carboxylic acid group-containing Polymers are not disclosed in this document.

The WO 00/27893 describes aqueous Polymer dispersions based on N-vinylcarboxamides and optionally comonomers, besides a large number further also N-vinylpyrrolidone, N-vinylimidazole and N-vinylimidazole derivatives to be named. The polymerization takes place in the presence at least a polymeric dispersant. An application of these polymer dispersions in cosmetics is only in general and without evidence by one embodiment described.

The EP-A-1038891 describes water-soluble or water-dispersible polymeric salts of at least one polymer and at least one oppositely charged neutralizing agent.

The WO 02/41856 describes the use of polymer dispersions which by polymerizing at least one water-soluble monomer in an aqueous one Saline, which contains at least one polyelectrolyte as dispersant for the cosmetic treatment of keratin materials. Additionally included the dispersions at least one viscosity adjusting agent, for example a polycarboxylic acid or a salt of it. As water-soluble Monomers know cationic, anionic and nonionic monomers are used, preferred are monomer mixtures, at least a cationic monomer and optionally additionally acrylic acid and / or Contain acrylamide.

The WO 2005/004821 describes a cosmetic or pharmaceutical An agent containing at least one polyelectrolyte complex, the at least one water-soluble or water-dispersible copolymer A1) with cationogenic groups, the vinylimidazole and / or a derivative thereof and at least one contains copolymerized copolymerizable monomer in copolymerized form, and at least one acid group-containing Polymer A2).

• a) wenigstens eine α,β-ethylenisch ungesättigte amidgruppenhaltige Verbindung der allgemeinen Formel I
  
  wobei R² für eine Gruppe der Formel CH₂=CR⁴- steht und R¹ und R³ unabhängig voneinander für H, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen, oder R¹ und R³ gemeinsam mit der Amidgruppe, an die sie gebunden sind, für ein Lactam mit 5 bis 8 Ringatomen stehen,
• b) wenigstens eine radikalisch polymerisierbare vernetzende Verbindung mit wenigstens zwei α,β-ethylenisch ungesättigten Doppelbindungen pro Molekül,
• c) wenigstens eine Verbindung mit einer radikalisch polymerisierbaren α,β-ethylenisch ungesättigten Doppelbindung und mindestens einer kationogenen und/oder kationischen Gruppe pro Molekül,

in einem wässrigen Medium in Gegenwart wenigstens eines polymeren anionischen Dispergiermittels D). Beschrieben sind weiterhin kosmetische oder pharmazeutische Mittel, die eine solche Polymerdispersion oder ein durch Trocknen einer solchen Dispersion erhältliches Polymer enthalten.WO 2005/005497 describes an aqueous polymer dispersion Pd) which is obtainable by free-radical polymerization of a monomer mixture M) containing

• a) at least one α, β-ethylenically unsaturated amide group-containing compound of general formula I.
  
  wherein R ^{2 is} a group of the formula CH ₂ = CR ⁴ - and R ¹ and R ^{3 are} independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or R ¹ and R ³ together with the amide group to the they are bound, represent a lactam with 5 to 8 ring atoms,
• b) at least one free-radically polymerisable crosslinking compound having at least two α, β-ethylenically unsaturated double bonds per molecule,
• c) 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,

in an aqueous medium in the presence of at least one polymeric anionic dispersant D). Also described are cosmetic or pharmaceutical compositions containing such a polymer dispersion or a polymer obtainable by drying such a dispersion.

The WO 00/39176 describes a hydrophilic, cationic, ampholytic Copolymer containing 0.05 to 20 mol% of an anionic monomer with at least one carboxy group, 0 to 45 mol% of a cationic Monomers having at least one amino group and optionally one contains copolymerized hydrophobic monomer and / or a crosslinker, wherein the molar ratio from cationic to anionic monomer is about 2: 1 to 16: 1.

• a) wenigstens einer ethylenisch ungesättigten Verbindung mit mindestens einer anionogenen und/oder anionischen Gruppe,
• b) wenigstens einer ethylenisch ungesättigten Verbindung mit mindestens einer kationogenen und/oder kationischen Gruppe,
• c) wenigstens einer ungesättigten amidgruppenhaltigen Verbindung

WO 04/058837 describes an ampholytic copolymer obtained by free-radical copolymerization of

• a) at least one ethylenically unsaturated compound having at least one anionogenic and / or anionic group,
• b) at least one ethylenically unsaturated compound having at least one cationogenic and / or cationic group,
• c) at least one unsaturated amide group-containing compound

such as optionally further comonomers are available. The polymerization may be in the presence of a grafting base, which is u. a. may be a polyalkylene oxide-containing silicone derivative. described are still polyelectrolyte complexes, which contain such an ampholytic copolymer as well as cosmetically or pharmaceutical compositions based on these silicone groups Copolymers and polyelectrolyte complexes.

It There is still a need for thickeners for hair cosmetic compositions with improved properties. So currently for this Applications are still the most common used anionic thickener based on acrylic acid, such as the corresponding carbopols, a number of disadvantages. she are themselves not capable of film formation, so that for the production of fortifying agents always use larger quantities film-forming polymers is required. As anionic thickener based on acrylic acid however incompatible with a variety of polyelectrolytes, come predominantly as formulation partners only nonionic polymers in question. This can be a variety of products with interesting application properties, such as Gels based on cationic polymers, do not produce at all.

• – die erhaltenen Gele sollen möglichst klar sein,
• – sie sollen sich leicht im Haar verteilen lassen und diesem dennoch guten Halt verleihen, was sich besonders gut durch Gele mit thixotropen Eigenschaften erzielen lässt,
• – sie sollen selbst über filmbildende Eigenschaften verfügen und so zur Festigung der Haare beitragen,
• – sie sollen über konditionierende Eigenschaften verfügen und die sensorischen Eigenschaften des Haars verbessern, z. B. ihm Geschmeidigkeit und Glanz verleihen und nach dem Trocken nicht oder nur gering klebrig sein,
• – das mit dem Gel behandelte Haar soll eine gute Nasskämmbarkeit aufweisen (somit lässt sich das frisch behandelte Haar leicht mit dem Kamm in Form bringen, um die gewünschte Frisur zu formen),
• – Befähigung zur Formulierung von Gelen in möglichst allen kosmetisch akzeptablen pH-Bereichen.

In particular, there is a need for polymeric thickeners for hair cosmetic compositions which are useful for formulating gel preparations. These should combine as many of the following properties as possible:

• - the gels obtained should be as clear as possible,
• - They should be easy to distribute in the hair and give it yet good support, which can be achieved particularly well by gels with thixotropic properties,
• - they should have film-forming properties themselves and thus contribute to the strengthening of the hair,
• - they should have conditioning properties and improve the sensory properties of the hair, z. B. give it suppleness and shine and after drying not or only slightly be sticky,
• - the hair treated with the gel should have a good wet combability (thus the freshly treated hair can easily be shaped with the comb to form the desired hairstyle),
• Ability to formulate gels in as far as possible in all cosmetically acceptable pH ranges.

moreover Polymers are to be used as rheology modifiers for cosmetic Compositions for the treatment of hair easily in a solid Form, preferably a powder, can be converted, that are easily incorporated into the formulations to be thickened leaves.

• a1) wenigstens einer Verbindung mit einer radikalisch polymerisierbaren, α,β-ethylenisch ungesättigten Doppelbindung und mindestens einer anionogenen und/oder anionischen Gruppe pro Molekül,
• a2) wenigstens einer Verbindung mit einer radikalisch polymerisierbaren, α,β-ethylenisch ungesättigten Doppelbindung und mindestens einer kationogenen und/oder kationischen Gruppe pro Molekül,
• b) wenigstens einer radikalisch polymerisierbaren vernetzenden Verbindung, die wenigstens zwei α,β-ethylenisch ungesättigte Doppelbindungen pro Molekül enthält,
• c) gegebenenfalls in Gegenwart wenigstens einer eine Polyethergruppe und/oder eine radikalisch polymerisierbare olefinisch ungesättigte Doppelbindung enthaltenden Siliconverbindung,

als Rheologiemodifizierungsmittel für haarkosmetische Zusammensetzungen.According to the invention, this object is achieved by the use of an ampholytic copolymer which has a molar excess of anionogenic / anionic groups with respect to cationogenic / cationic groups and which is obtainable by free-radical copolymerization of

• a1) at least one compound having 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 which contains at least two α, β-ethylenically unsaturated double bonds per molecule,
• c) if appropriate in the presence of at least one silicone compound containing a polyether group and / or a free-radically polymerizable olefinically unsaturated double bond,

as a rheology modifier for hair cosmetic compositions.

In a first embodiment be for the use according to the invention Silicone group-free copolymers used. All are suitable in the German Patent Application 10 2005 034 412.7 described, the a molar excess at anionogenic / anionic groups versus cationogenic / cationic Have groups. The disclosure of this document is related to these copolymers fully referenced.

In a second embodiment be for the use according to the invention Silicone group-containing copolymers used. Suitable for this all described in German Patent Application 10 2005 034 906.4 Copolymers containing a molar excess at anionogenic / anionic groups versus cationogenic / cationic Have groups. The disclosure of this document is related to these copolymers fully referenced.

The Preparation of the invention to be used Copolymers A) can be prepared by conventional polymerization processes, z. B. by solution or bulk polymerization. Copolymers with especially advantageous properties, d. H. with generally higher molecular weights and a better aptitude to form powdered Formulations than obtained by conventional polymerization processes are made by the production by the method of precipitation polymerization receive. A preferred embodiment The invention is therefore the use of copolymers by radical copolymerization by the method of precipitation polymerization are available in at least one organic solvent.

at the precipitation polymerization are the monomers used in the reaction medium (monomer, solvent) soluble, the corresponding polymer but not. The resulting polymer is among the chosen ones Polymerization conditions insoluble and falls from the reaction mixture. In this case, anionogenic / anionic ampholytic copolymers with higher Obtained molecular weights than after other polymerization processes, z. By solution polymerization, particularly advantageous as a rheology modifier (especially Thickener) are suitable.

In the context of the present invention, the term alkyl includes straight-chain and branched alkyl groups. Suitable short-chain alkyl groups are, for. B. straight-chain or branched C ₁ -C ₇ alkyl, preferably C ₁ -C ₆ alkyl and particularly preferably C ₁ -C ₄ alkyl groups. These include in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl , 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 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, octyl, etc.

Suitable longer-chain C ₈ -C ₃₀ -alkyl or C ₈ -C ₃₀ -alkenyl groups are straight-chain and branched alkyl or alkenyl groups. These are preferably predominantly linear alkyl radicals, as they also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols, which may optionally be additionally mono-, di- or polyunsaturated. These include z. N-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl , n-tridecyl (s), n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, Arachynyl (s), behenyl (s), lignocerinyl (s), melissinyl (s), etc.

Cycloalkyl is preferably C ₅ -C ₈ -cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

aryl includes unsubstituted and substituted aryl groups and stands preferably for Phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, Phenanthrenyl, naphthacenyl and in particular phenyl, tolyl, xylyl or Mesityl.

in the Following are compounds that differ from acrylic acid and methacrylic acid can derive partially shortened by inserting the syllable "(meth)" in the derived from acrylic acid Called connection.

The used according to the invention Copolymers can be advantageous under normal conditions (20 ° C) formulated as gels. "Gel-like consistency" show formulations, the one higher viscosity as a liquid and which are self-supporting, d. H. the one lent to them Keep shape without shape-stabilizing cladding. In contrast however, gel formulations are easy to form into solid formulations using shear forces deform. The viscosity the gel-like Means are 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.

Under water-soluble Monomers and polymers are monomers in the context of the present invention and polymers understood to be at least 1 g / L at 20 ° C in water to solve. Water-dispersible monomers and polymers are monomers and polymers which are sheared using, for example by stirring, decompose into dispersible particles. Hydrophilic monomers are preferred water soluble or at least water dispersible. The copolymers used in the invention are generally water-soluble.

"Modification rheological properties " within the scope of the present invention. So suitable the ones used in the invention Copolymers generally for thickening the consistency of liquid compounds in a wide range. Depending on the basic consistency of the liquid compound (s) can dependent on from the amount of the copolymer usually flow properties from thin to too hard (not fluent) be achieved. Under "Modification rheological properties " therefore u. a. the increase the viscosity of liquids, the improvement of the Tixotropie properties of gels, the solidification of gels and waxes etc. understood.

The used according to the invention ampholytic copolymers have both anionogenic and / or anionic Groups as well as cationogenic and / or cationic groups. To of their manufacture the oppositely charged / chargeable monomers a1) and a2) together, d. H. in the form of a monomer pair ("monomer salt") can be used. In this monomer composition, the molar ratio of anionogenic and anionic groups of component a1) to cationogenic and cationic groups of component a2) about 1: 1 (i.e., monovalent Monomers become substantially equimolar used). The monomer pairs can thereby before their use be prepared separately for polymerization. However, it is preferred the "in situ" production of the Monomer pairs by common use (eg common feed) in the preparation of the copolymers.

Preferably is the proportion of the monomer pair of the used for the polymerization Compounds at least 1% by weight, preferably at least 2% by weight, in particular at least 3% by weight.

Preferably the copolymers have a significant excess of anionogenic / anionic groups across from cationogenic / cationic groups. In a special design will be for copolymerization monomers with ionic or ionic groups be used in amounts such that the copolymer is a molar excess at anionogenic / anionic groups versus cationogenic / cationic Groups of more than 2: 1, preferably at least 2.5: 1, having.

Monomer a1)

The used according to the invention Copolymers contain as compound a1) at least one compound with a free-radically polymerizable α, β-ethylenically unsaturated Double bond and with at least one anionogenic and / or anionic Group per molecule in copolymerized form. The component a1) is preferably in a Amount of 2 to 70 wt .-%, preferably 3 to 60 wt .-%, based on the total weight of the compounds used for the polymerization (i.e., components a1), a2), b), c) and, if present, d) to g)).

Preferably the compounds a1) are selected under monoethylenically unsaturated Carboxylic acids, sulfonic acids, phosphonic and mixtures thereof.

To the monomers a1) count monoethylenically unsaturated Mono- and dicarboxylic acids with 3 to 25 preferably 3 to 6 C atoms, which are also in the form of their Salts or anhydrides can be used. Examples of these are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic, citraconic, mesaconic, glutaconic, aconitic and fumaric acid. To the monomers a1) count furthermore the half esters of monoethylenically unsaturated dicarboxylic acids with 4 to 10 preferably 4 to 6 C atoms, for. B. of maleic acid such as Maleate. To the monomers a1) count also monoethylenically unsaturated sulfonic acids and phosphonic acids, for example, vinylsulfonic acid, allylsulfonic acid, Sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid and Allylphosphonic. To the monomers a1) count also the salts of the abovementioned acids, in particular the sodium, potassium and ammonium salts and the salts with amines. The monomers a1) can be used as such or used as mixtures with each other. The the weight proportions are all based on the acid form.

Preferably the component a1) is selected under acrylic acid, methacrylic acid, Ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic, Citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid and Mixtures thereof.

Especially the component a1) is preferably selected from acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic, citraconic, mesaconic, glutaconic, aconitic and mixtures thereof.

Especially Preferably, the component a1) is selected from acrylic acid, methacrylic acid and Mixtures thereof. In a specific embodiment, the component comprises a1) methacrylic acid or consists of it.

Monomer a2)

The used according to the invention Copolymers contain at least one compound a2) with at least copolymerized a cationogenic and / or cationic group per molecule. The copolymers preferably contain from 2 to 35% by weight, especially preferably 3 to 30 wt .-%, based on the total weight of the Polymerization used monomers, at least one monomer a2) copolymerized Preferably, the component comprises a2) at least a connection that is selected is α, β-ethylenically unsaturated among esters Mono- and dicarboxylic acids with aminoalcohols which are mono- or dialkylated on the amine nitrogen can, Amides α, β-ethylenic unsaturated Mono- and dicarboxylic acids with diamines containing at least one primary or secondary amino group N, N-diallylamine, N, N-diallyl-N-alkylamines and their Derivatives, vinyl- and allyl-substituted nitrogen heterocycles, vinyl- and allyl-substituted heteroaromatic compounds and Mixtures thereof.

In a preferred embodiment comprises component a2) as vinyl-substituted heteroaromatic Compound at least one N-vinylimidazole compound. In a special embodiment the component a2) is selected under N-vinylimidazole compounds and mixtures containing at least one N-vinylimidazole compound.

The cationogenic and / or cationic groups of component a2) are preferably nitrogen-containing groups, such as primary, secondary and tertiary amino groups, and quaternary ammonia umgruppen. 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, tartaric acid or citric acid, or mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid, or as alkylating agent C ₁ -C ₄ 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 after the polymerization.

worin R⁵ bis R⁷ unabhängig voneinander für Wasserstoff, C₁-C₄-Alkyl oder Phenyl stehen. Bevorzugt stehen R⁵ bis R⁷ für Wasserstoff.Suitable N-vinylimidazole compounds a2) are compounds of the formula

wherein R ⁵ to R ^{7 are} independently hydrogen, C ₁ -C ₄ alkyl or phenyl. Preferably, R ⁵ to R ^{7 are} hydrogen.

einpolymerisiert, worin R⁵ bis R⁷ unabhängig voneinander für Wasserstoff, C₁-C₄-Alkyl oder Phenyl stehen.Furthermore, the copolymer preferably contains as monomer a2) at least one N-vinylimidazole compound of the general formula (II)

polymerized in which R ⁵ to R ⁷ independently of one another are hydrogen, C ₁ -C ₄ -alkyl or phenyl.

• Me = Methyl
• Ph = Phenyl

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

• Me = methyl
• Ph = phenyl

Prefers as monomer a2) is 1-vinylimidazole (N-vinylimidazole) and are mixtures, which contain N-vinylimidazole.

suitable Monomers a2) are also those by protonation or quaternization the aforementioned N-vinylimidazole compounds available Links. examples for such charged monomers a2) are quaternized vinylimidazoles, in particular 3-methyl-1-vinylimidazolium chloride and methosulfate. Suitable acids and alkylating agents are those listed above.

In a special version can the copolymers in place of or in addition to those previously mentioned N-vinylimidazole compounds at least one other monomer a2) copolymerized with at least one cationic and / or cationic groups contain. Preferably the proportion of these monomers a2) in this embodiment 0 to 30 wt .-%, particularly preferably 0.1 to 20 wt .-%, in particular 0.5 to 15 wt .-%, based on the total weight of the polymerization used compounds.

Suitable compounds a2) are the esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols. Preferred aminoalcohols are C ₂ -C ₁₂ -aminoalcohols which are mono- or -dialkylated on the amino nitrogen C ₁ -C ₈ . 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. The acid component used is preferably acrylic acid, methacrylic acid and mixtures thereof.

Preferred monomers a2) are N-tert-butylaminoethyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N- dimethylaminopropyl minopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate and N, N-dimethylaminocyclohexyl (meth) acrylate. Particularly preferred are N-tert-butylaminoethyl (meth) acrylate and N, N-dimethylaminoethyl (meth) acrylate.

suitable Monomers a2) are also the amides of the aforementioned α, β-ethylenic unsaturated mono- and dicarboxylic acids with diamines containing at least one primary or secondary amino group exhibit. Preferred are diamines which have a tertiary and a primary or secondary Have amino group.

Suitable as monomers a2) are z. B. 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.

Suitable monomers a2) are furthermore N, N-diallylamines and N, N-diallyl-N-alkylamines and their acid addition salts and quaternization products. Alkyl is preferably C ₁ -C ₂₄ -alkyl. Preference is given to N, N-diallyl-N-methylamine and N, N-diallyl-N, N-dimethylammonium compounds, such as. As the chlorides and bromides. Particularly preferred is N, N-diallyl-N-methylamine.

suitable Monomers a2) are furthermore vinyl- different from vinylimidazoles. and allyl-substituted nitrogen heterocycles, such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts thereof.

Crosslinker b)

The Copolymers can if desired at least one crosslinker, d. H. a connection with two or more than two ethylenically unsaturated, contain copolymerized non-conjugated double bonds.

Preferably Crosslinkers are in an amount of 0.01 to 5 wt .-%, especially preferably 0.1 to 4 wt .-%, based on the total weight of the Polymerization used monomers used.

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

Examples for 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-ene-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 neopentylglycol monoester, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxypropyl) phenyl] propane, Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, Tripropylene glycol, tetrapropylene glycol, 3-thio-pentane-1,5-diol, and polyethylene glycols, polypropylene glycols and polytetrahydrofurans with molecular weights of 200 to 10,000. Except the Homopolymers of ethylene oxide or propylene oxide can also block copolymers from ethylene oxide or propylene oxide or copolymers containing ethylene oxide and propylene oxide groups incorporated. examples for underlying alcohols with more than two OH groups are trimethylolpnopane, Glycerol, pentaerythritol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, triethoxycyanuric acid, sorbitan, Sugars such as sucrose, glucose, mannose. Of course, the polyhydric alcohols even after reaction with ethylene oxide or propylene oxide are used as the corresponding ethoxylates or propoxylates. The polyhydric alcohols can also first be converted by reaction with epichlorohydrin in the corresponding glycidyl ether. Preferred are 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-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol, dicyclopentenyl alcohol, 10-undecen-1-ol, cinnamyl alcohol , Citronellol, crotyl alcohol or cis-9-octadecen-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 esters of unsaturated carboxylic acids with the above-described polyhydric alcohols, for example, oleic acid, crotonic acid, cinnamic acid or 10-undecenoic.

Suitable as crosslinkers b) are also straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons having at least two double bonds feature, which are not conjugated in aliphatic hydrocarbons allowed to, z. Divinylbenzene, divinyltoluene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes with Molecular weights from 200 to 20,000.

When Crosslinkers b) are also suitable the acrylic acid amides, methacrylic acid amides and N-allylamines of at least dihydric amines. Such amines are, for example, 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine, piperazine, Diethylenetriamine or isophorone diamine. Also suitable are the Amides of allylamine and unsaturated Carboxylic acids, like Acrylic acid, methacrylic acid, itaconic, maleic acid, or at least dibasic carboxylic acids as described above were.

Further are triallylamine and Triallylmonoalkylammoniumsalze, z. B. triallylmethylammonium chloride or Methyl sulfate, as crosslinker c) suitable.

Suitable are also N-vinyl compounds of urea derivatives, at least divalent amides, cyanurates or urethanes, for example of Urea, ethyleneurea, propyleneurea or tartaramide, z. N, N'-divinylethyleneurea or N, N'-divinylpropyleneurea.

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

Of course you can too Mixtures of the aforementioned compounds b) are used.

All particularly preferred crosslinkers b) are ethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylates, pentaerythritol triallyl ether, methylenebisacrylamide, N, N'-Divinylethylenharnstoff, Triallylamine and triallylmonoalkylammonium salts.

Silicone compound c)

In The first embodiment described above are silicone group-free Copolymers used. Therefore are, as already mentioned, all described in German Patent Application 10 2005 034 412.7 Copolymers. In the second embodiment described above The invention uses silicone-group-containing copolymers. As already stated, are suitable for it all described in German patent application 10 2005 034 906.4 Copolymers containing a molar excess at anionogenic / anionic groups versus cationogenic / cationic Have groups.

The used according to the invention Silicone group-containing copolymers are common by polymerization made with at least one silicone compound. The amount used the silicone compound c) is preferably 0.05 to 30 wt .-%, particularly preferably 0.1 to 20 Wt .-%, in particular 0.2 to 10 wt .-%, especially 0.5 to 5 wt .-%, based on the total weight of the polymerization used Links.

suitable Silicone compounds c) are both compounds that are a radical have polymerizable olefinically unsaturated double bond, as well as compounds substituted for such a double bond have a polyether group. Of course it is also suitable Compounds which are both at least one radically polymerizable Have double bond as well as a polyether group.

In a first embodiment, the free-radical copolymerization for the preparation of the silicone-containing copolymers is carried out in the presence of at least one polyether-containing silicone compound c) which does not contain an α, β-ethylenically unsaturated double bond. The copolymerization is then carried out in particular by the method of precipitation polymerization in at least one organic solvent. The polymerization temperature is then preferably at least 70 ° C, particularly preferably at least 80 ° C. In the free-radical copolymerization in the presence of such a component c), copolymers having advantageous properties are obtained. This can be attributed, for example, to an action of component c) as a protective colloid or emulsifier. This can also result, for example, from an at least partial grafting on component c) as a grafting base. However, there are other mechanisms than one Grafting imaginable. The silicone group-containing copolymers used in the invention generally include the products of the radical copolymerization, including z. B. pure graft polymers, mixtures of graft polymers with ungrafted compounds of component c), copolymers of the aforementioned monomers and any mixtures are understood.

Suitable silicone derivatives c) are those known under the INCI-name Dimethicone copolyols or silicone surfactants, such as the (under the trade names Abil ^® from. T. Goldschmidt), Alkasil ^® (Fa. Rhône-Poulenc), Silicone Polyol copolymer ^® (Fa Genesee), Belsil ^® (Fa. Wacker), Silwet ^® (Fa. OSI) or Dow Corning (. 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 6031st

wobei:
die Reste R^a identisch oder unterschiedlich sein können, und ausgewählt sind unter Alkyl, Cycloalkyl, Cycloalkylalkyl, Aryl und Arylalkyl, insbesondere unter C₁-C₈-Alkyl, C₅-C₈-Cycloalkyl, Benzyl und Phenyl,
R^b, R^c und R^d unabhängig voneinander eine der zuvor für R^a angegebenen Bedeutungen haben oder für -(CH₂)_1-6-OH, -(CH₂)_1-6-NHR^e oder einen Rest der Formel (1.1) -(CH₂)_1-6-O-(CH₂CH₂O)_a(CH₂CH(CH₃)O)_b-(C=O)_c-R^f (1.1)stehen, wobei
in der Formel (1.1) die Reihenfolge der Alkylenoxideinheiten beliebig ist,
a und b unabhängig voneinander für eine ganze Zahl von 0 bis 200 stehen, wobei die Summe aus a und b > 0 ist,
c für 0 oder 1 steht,
R^e für Wasserstoff, C₁-C₈-Alkyl oder C₅-C₈-Cycloalkyl steht,
R^f für Wasserstoff, C₁-C₄₀-Alkyl, vorzugsweise Methyl, oder für den Fall, dass c = 0 ist für das Anion einer anorganischen Säure stehen kann,
mit der Maßgabe, dass wenigstens einer der Reste R^b, R^c und R^d für einen Rest der Formel (1.1) steht.Particularly suitable compounds c) are those which contain the following structural elements:

in which:
the radicals R ^{a may be} identical or different and are selected from alkyl, cycloalkyl, cycloalkylalkyl, aryl and arylalkyl, in particular C ₁ -C ₈ -alkyl, C ₅ -C ₈ -cycloalkyl, benzyl and phenyl,
R ^b , R ^c and R ^d independently of one another have one of the meanings given above for R ^a or for - (CH ₂ ) _1-6 -OH, - (CH ₂ ) _1-6 -NHR ^e or a radical of the formula (1.1 ) - (CH ₂ ) _1-6 -O- (CH ₂ CH ₂ O) _a (CH ₂ CH (CH ₃ ) O) _b - (C = O) _c -R ^f (1.1) stand, where
in the formula (1.1) the order of the alkylene oxide units is arbitrary,
a and b independently of one another represent an integer from 0 to 200, the sum of a and b being> 0,
c is 0 or 1,
R ^{e is} hydrogen, C ₁ -C ₈ -alkyl or C ₅ -C ₈ -cycloalkyl,
R ^{f is} hydrogen, C ₁ -C ₄₀ -alkyl, preferably methyl, or in the event that c = 0 is the anion of an inorganic acid,
with the proviso that at least one of R ^b , R ^c and R ^{d is} a radical of formula (1.1).

Preferably x and y are selected the molecular weight of the polysiloxane block is between 300 and 30,000.

Preferably, the radical R ^{d is} a radical of the formula (1.1).

R ^b and R ^c are preferably C ₁ -C ₈ -alkyl, in particular methyl.

preferred Residues (1.1) are those in which the sum of a + b between 5 and 200 is.

The groups R ^a are preferably selected from the following group: methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, decyl, dodecyl and octadecyl, cycloaliphatic radicals, especially cyclohexyl, aromatic groups, especially phenyl or naphthyl, mixed aromatic-aliphatic radicals such as benzyl or phenylethyl and tolyl, xylyl and radicals of the formula (1.1).

Particularly suitable radicals R ^f are those in which in the case of c = 1 R ^{f is} any alkyl, cycloalkyl or aryl radical which has between 1 and 40 carbon atoms and the other ionic groups such as NH ₂ , COOH, SO ₃ H can wear.

Preferred inorganic radicals R ^f are, in the case where c = 0, phosphate and sulfate.

worin R^d für einen Rest der Formel (1.1) -(CH₂)_1-6-O-(CH₂CH₂O)_a(CH₂CH(CH₃)O)_b-(C=O)_c-R^f (1.1)wie zuvor definiert steht. Speziell handelt es sich um Belsil^® DMC 6031 der Fa. Wacker.Particularly preferred silicone derivatives c) are those having the general structure:

in which R ^{d is} a radical of the formula (1.1) - (CH ₂ ) _1-6 -O- (CH ₂ CH ₂ O) _a (CH ₂ CH (CH ₃ ) O) _b - (C = O) _c -R ^f (1.1) as previously defined. Specifically, it is Belsil® ^® DMC 6031 from. Wacker.

In a further embodiment the silicone compound c) is an α, β-ethylenic unsaturated A compound having at least one polysiloxane group.

worin
D für eine ethylenisch ungesättigte Gruppe steht, die vorzugsweise ausgewählt ist unter Vinylgruppen, Vinyl(C₁-C₄-alkylen)gruppen, Acryloyloxy(C₁-C₄-alkylen)gruppen und Methacryloyloxy(C₁-C₄-alkylen)gruppen,
R^g jeweils unabhängig voneinander für gleiche oder verschiedene Gruppen steht, die ausgewählt sind unter C₁-C₁₀-Alkyl, Phenyl, Benzyl, C₄-C₈-Cycloalkyl sowie Polyalkylen-, Polyoxyalkylen- und Polyalkylenimingruppen, die eine endständige Alkylether-, Ester- oder Amidfunktion aufweisen können,
E die für R^g oder die für D angegebenen Bedeutungen aufweisen kann und
a für eine ganze Zahl von 1 bis 1000, vorzugsweise 2 bis 250, steht.Suitable ethylenically unsaturated monomers c) having a polysiloxane group are, for example, compounds of the general formula V:

wherein
D is an ethylenically unsaturated group which is preferably selected from vinyl groups, vinyl (C ₁ -C ₄ alkylene) groups, acryloyloxy (C ₁ -C ₄ alkylene) groups and methacryloyloxy (C ₁ -C ₄ alkylene) groups .
R ^{g are} each independently of the same or different groups selected from C ₁ -C ₁₀ alkyl, phenyl, benzyl, C ₄ -C ₈ cycloalkyl and also polyalkylene, polyoxyalkylene and polyalkyleneimine groups containing a terminal alkyl ether, May have ester or amide function,
E may have the meanings given for R ^g or those given for D, and
a is an integer from 1 to 1000, preferably 2 to 250.

suitable Compounds of the formula V are z. As described in EP-A-0 408 311, which is incorporated herein by reference in its entirety.

Further suitable silicone compounds c) containing at least one free radical have polymerizable double bond are radically polymerizable, Siloxane-containing urethane (meth) acrylates. Suitable, for example the (meth) acrylate functionalized described in EP-A-0 274 699 Organopolysiloxane-urethane copolymers obtained by reacting a amino-functionalized polysiloxane with urethane (meth) acrylate oligomers available are. The disclosure of this document is hereby incorporated by reference.

• α) wenigstens eine Verbindung, die mindestens ein aktives Wasserstoffatom und mindestens eine radikalisch polymerisierbare, α,β-ethylenisch ungesättigte Doppelbindung pro Molekül enthält,
• β) wenigstens ein Diisocyanat,
• γ) wenigstens eine Verbindung, die zwei aktive Wasserstoffatome pro Molekül enthält,
• δ) wenigstens eine Verbindung, die mindestens ein aktives Wasserstoffatom und mindestens eine Siloxangruppe pro Molekül enthält,

eingebaut enthalten, und die Salze davon.Preference is given to the compounds described in WO 2004/055088. Preference is given to using, as compound c), at least one free-radically polymerizable, siloxane-containing urethane (meth) acrylate, as described in WO 00/12588. These are siloxane-containing urethane (meth) acrylates c), which

• α) at least one compound which contains at least one active hydrogen atom and at least one free-radically polymerizable, α, β-ethylenically unsaturated double bond per molecule,
• β) at least one diisocyanate,
• γ) at least one compound containing two active hydrogen atoms per molecule,
• δ) at least one compound which contains at least one active hydrogen atom and at least one siloxane group per molecule,

incorporated, and the salts thereof.

In the context of the present invention, the term "urethane (meth) acrylates" generally includes compounds which contain at least one olefinically unsaturated free-radically polymerizable double bond exhibit. These include allylic unsaturated compounds. Furthermore, the term "urethane (meth) acrylates" also includes compounds having urea groups in place of or in addition to the urethane groups. Urea groups result in the reaction of an isocyanate group with a primary or secondary amino group.

Component α)

suitable Compounds α) are z. The usual, the vinyl compounds known to the person skilled in the art, which additionally have at least one opposite Having isocyanate groups reactive group, which is preferably selected under hydroxyl groups as well as primary and secondary Amino groups. These include z. As the esters α, β-ethylenic unsaturated Mono- and dicarboxylic acids with at least dihydric alcohols. As α, β-ethylenically unsaturated mono- and / or dicarboxylic acids can z. For example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic, itaconic etc. and mixtures thereof. Suitable alcohols are conventional diols, Triols and polyols, e.g. 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, diethylene glycol, 2,2,4-trimethylpentanediol-1,5, 2,2-dimethylpropanediol-1,3, 1,4-dimethylolcyclohexane, 1,6-dimethylolcyclohexane, glycerol, trimethylolpropane, erythritol, Pentaerythritol, sorbitol, etc. The compounds a) are then z. Hydroxymethyl (meth) acrylate, hydroxyethyl methacrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 3-hydroxy-2-ethylhexyl (meth) acrylate and di (meth) acrylate of 1,1,1-trimethylolpropane or glycerol.

Suitable monomers α) are furthermore the esters and amides of the abovementioned α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₂ -C ₁₂ -aminoalcohols which have a primary or secondary amino group. These include aminoalkyl acrylates and aminoalkyl methacrylates and their N-monoalkyl derivatives, the z. B. carry a NC ₁ -C ₈ -Monoalkylrest, such as aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, N-methylaminomethyl (meth) acrylate, N-ethylaminomethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N - (n-propyl) aminomethyl (meth) acrylate, N-isopropylaminomethyl (meth) acrylate and preferably tert-butylaminoethyl acrylate and tert-butylaminoethyl methacrylate. These also include N- (hydroxy-C ₁ -C ₁₂ -alkyl) (meth) acrylamides, such as N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, etc.

suitable Monomers α) are also the amides of the aforementioned α, β-ethylenically unsaturated Mono- and dicarboxylic acids with di- and polyamines containing at least two primary or two secondary or a primary one and a secondary one Have amino group (s). These include z. B. the corresponding amides of acrylic acid and methacrylic acid, such as Aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide, aminopropyl (meth) acrylamide, Amino-n-butyl (meth) acrylamide, methylaminoethyl (meth) acrylamide, ethylaminoethyl (meth) acrylamide, Methylaminopropyl (meth) acrylamide, ethylaminopropyl (meth) acrylamide, Methylamino-n-butyl (meth) acrylamide, etc.

suitable Monomers a) are also the reaction products of epoxide compounds, having at least one epoxy group, with the aforementioned α, β-ethylenic unsaturated Mono- and / or dicarboxylic acids and their anhydrides. suitable epoxy compounds are for. Glycidyl ether, such as bisphenol A diglycidyl ether, resorcinol diglycidyl ether, 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether Etc.

Component β)

at the component β) it is usual aliphatic, cycloaliphatic and / or aromatic diisocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diphenyl diisocyanate, 2,4- and 2,6-tolylene diisocyanate and their isomer mixtures, o- and m-xylylene diisocyanate, 1,5-naphthylene diisocyanate, 1,4-cyclohexylene diisocyanate, dicyclohexylmethane diisocyanate and mixtures thereof. The component β) is preferably hexamethylene diisocyanate, Isophorone diisocyanate, o- and m-xylylene diisocyanate, dicyclohexylmethane diisocyanate and mixtures thereof. If desired, can up to 3 mol% of said compounds replaced by triisocyanates be.

Component δ)

suitable Compounds of component γ) are z. Diols, diamines, amino alcohols, and mixtures thereof. The molecular weight of these compounds is preferably in one Range from about 56 to 280. If desired can up to 3 mol% of said compounds by triols or triamines be replaced.

suitable Diols γ) are z. As ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, Cyclohexanedimethylol, di-, tri-, tetra-, penta- or hexaethylene glycol and mixtures thereof. Preference is given to neopentyl glycol and / or Cyclohexanedimethylol used.

suitable Amino alcohols γ) are z. B. 2-aminoethanol, 2- (N-methylamino) ethanol, 3-aminopropanol, 4-aminobutanol, 1-ethylaminobutan-2-ol, 2-amino-2-methyl-1-propanol, 4-methyl-4-aminopentan-2-ol Etc.

suitable Diamines γ) are z. Ethylenediamine, propylenediamine, 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane.

preferred Compounds of component γ) are polymers having a number average molecular weight in the Range of about 300 to 5000, preferably about 400 to 4000, in particular 500 to 3000. These include z. As polyester diols, polyetherols, α, ω-diaminopolyether and mixtures from that. Preferably, ether group-containing polymers are used.

at the polyetherols γ) it is preferably polyalkylene glycols, for. For example, polyethylene glycols, Polypropylene glycols, polytetrahydrofurans, etc., block copolymers from ethylene oxide and propylene oxide or block copolymers from ethylene oxide, Propylene oxide and butylene oxide, the alkylene oxide random distributed or in the form of blocks incorporated in copolymerized form.

Suitable α, ω-diaminopolyethers γ) are, for. B. produced by amination of polyalkylene oxides with ammonia.

suitable Polytetrahydrofurans γ) can by cationic polymerization of tetrahydrofuran in the presence of acidic catalysts, such as. For example, sulfuric acid or fluorosulfuric acid produced become. Such production processes are known to the person skilled in the art.

useful Polyester diols γ) preferably have a number average molecular weight in the range of about 400 to 5000, preferably 500 to 3000, in particular 600 to 2000, on.

Suitable polyester diols are all those which are customarily used for the preparation of polyurethanes, in particular those based on aromatic dicarboxylic acids, such as terephthalic acid, isophthalic acid, phthalic acid, Na or K sulfoisophthalic acid, etc., aliphatic dicarboxylic acids, such as adipic acid or succinic acid, etc. and cycloaliphatic dicarboxylic acids, such as 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid. Particularly suitable diols are aliphatic diols, such as ethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, polyethylene glycols, polypropylene glycols, 1,4-dimethylolcyclohexane, and also poly (meth) acrylate diols of the formula HO-C (-R ') (- COOR'') - OH wherein R 'is H or CH ₃ and R "is C ₁ -C ₁₈ alkyl (especially C ₁ -C ₁₂ - or C ₁ -C ₈ alkyl) having a molecular weight of up to about 3000. Such diols are in the usual manner to prepare and commercially available (Tegomer ^® grades MD, BD and OD of Fa. Goldschmidt).

Prefers are polyester diols based on aromatic and aliphatic dicarboxylic acids and aliphatic diols, especially those in which the aromatic dicarboxylic acid 10 to 95 mol%, especially 40 to 90 mol%, and preferably 50 to 85 mole%, of the total dicarboxylic acid portion (Residual aliphatic dicarboxylic acids) accounts.

Particularly preferred polyester diols are the reaction products of phthalic acid / diethylene glycol, isophthalic acid / 1,4-butanediol, isophthalic acid / adipic acid / 1,6-hexanediol, 5-NaSO ₃ -Isophthalic acid / phthalic acid / adipic acid / 1,6-hexanediol, adipic acid / ethylene glycol, Isophthalic acid / adipic acid / neopentyl glycol, isophthalic acid / adipic acid / neopentyl glycol / diethylene glycol / dimethylolcyclohexane and 5-NaSO ₃ -Isophthalic acid / isophthalic acid / adipic acid / neopentyl glycol / diethylene glycol / dimethylolcyclohexane.

The Compounds of component γ) can used individually or as mixtures.

Component δ)

• – Polysiloxanen der allgemeinen Formel VI.1
  
  worin c und d unabhängig voneinander für 2 bis 8 stehen, e für 3 bis 100 steht, R^h und Rⁱ unabhängig voneinander für C₁-C₈-Alkyl, Benzyl oder Phenyl stehen, Z¹ und Z² unabhängig voneinander für OH, NHR^k oder einen Rest der Formel VII -O-(CH₂CH₂O)_v(CH₂CH(CH₃)O)_w-H (VII)stehen, wobei in der Formel VII die Reihenfolge der Alkylenoxideinheiten beliebig ist und v und w unabhängig voneinander für eine ganze Zahl von 0 bis 200 stehen, wobei die Summe aus v und w > 0 ist, R^k für Wasserstoff, C₁-C₈-Alkyl oder C₅-C₈-Cycloalkyl steht;
• – Polysiloxanen der allgemeinen Formel VI.2
  
  worin die Reihenfolge der Siloxaneinheiten beliebig ist, f und g unabhängig voneinander für 0 bis 100 stehen, wobei die Summe aus f und g mindestens 2 ist, h für eine ganze Zahl von 2 bis 8 steht, Z³ für OH, NHR^k oder einen Rest der Formel VII steht, wobei R^k für Wasserstoff, C₁-C₈-Alkyl, C₅-C₈-Cycloalkyl oder einen Rest der Formel -(CH₂)_u-NH₂ steht, wobei u für eine ganze Zahl von 1 bis 10, bevorzugt 2 bis 6, steht,
• – Polysiloxanen mit sich wiederholenden Einheiten der allgemeinen Formel VI.3
  
  worin p für eine ganze Zahl von 0 bis 100 steht, q für eine ganze Zahl von 1 bis 8 steht, R^l und R^m unabhängig voneinander für C₁-C₈-Alkylen stehen, die Reihenfolge der Alkylenoxideinheiten beliebig ist und r und s unabhängig voneinander für eine ganze Zahl von 0 bis 200 stehen, wobei die Summe aus r und s > 0 ist,
• – Polysiloxanen der allgemeinen Formel VI.4
  
  worin Rⁿ für einen C₁-C₈-Alkylenrest steht, R^o und R^p unabhängig voneinander für Wasserstoff, C₁-C₈-Alkyl oder C₅-C₈-Cycloalkyl stehen, die Reihenfolge der Siloxaneinheiten beliebig ist, x, y und z unabhängig voneinander für 0 bis 100 stehen, wobei die Summe aus x, y und z mindestens 3 ist, t für eine ganze Zahl von 2 bis 8 steht, Z⁵ für einen Rest der Formel VIII -(OCH₂CH₂)_i(OCH₂CH(CH₃))_j-R^q (VIII)steht, worin die Reihenfolge der Alkylenoxideinheiten beliebig ist und i und j unabhängig voneinander für eine ganze Zahl von 0 bis 200 stehen, wobei die Summe aus i und j > O ist, R^q für Wasserstoff oder einen C₁-C₈-Alkylrest steht.

und Mischungen davon.Preferably, the component δ) is selected from:

• - Polysiloxanes of the general formula VI.1
  
  in which c and d, independently of one another, are 2 to 8, e is 3 to 100, R ^h and R ^i, independently of one another, are C ₁ -C ₈ -alkyl, benzyl or phenyl, Z ¹ and Z ² are each independently OH, NHR ^k or a radical of formula VII -O- (CH ₂ CH ₂ O) _v (CH ₂ CH (CH ₃ ) O) _w -H (VII) where in the formula VII the sequence of the alkylene oxide units is arbitrary and v and w independently of one another are an integer from 0 to 200, the sum of v and w being> 0, R ^{k is} hydrogen, C ₁ -C ₈ -Alkyl or C ₅ -C ₈ -cycloalkyl;
• - Polysiloxanes of the general formula VI.2
  
  wherein the order of the siloxane units is arbitrary, f and g independently represent 0 to 100, wherein the sum of f and g is at least 2, h is an integer of 2 to 8, Z ^{3 is} OH, NHR ^k or one Rest of the formula VII, wherein R ^{k is} hydrogen, C ₁ -C ₈ alkyl, C ₅ -C ₈ cycloalkyl or a radical of the formula - (CH ₂ ) _u -NH ₂ , wherein u is an integer of 1 to 10, preferably 2 to 6,
• - Polysiloxanes with repeating units of the general formula VI.3
  
  wherein p is an integer from 0 to 100, q is an integer from 1 to 8, R ^l and R ^{m are} independently C ₁ -C ₈ alkylene, the order of the alkylene oxide is arbitrary and r and s independently represent an integer from 0 to 200, the sum of r and s being> 0,
• - Polysiloxanes of the general formula VI.4
  
  in which R ^{n is} a C ₁ -C ₈ -alkylene radical, R ^o and R ^p independently of one another are hydrogen, C ₁ -C ₈ -alkyl or C ₅ -C ₈ -cycloalkyl, the order of the siloxane units is arbitrary, y and z independently of one another represent 0 to 100, the sum of x, y and z being at least 3, t being an integer from 2 to 8, Z ^{5 being} a radical of the formula VIII - (OCH ₂ CH ₂ ) _i (OCH ₂ CH (CH ₃ )) _j -R ^q (VIII) in which the sequence of the alkylene oxide units is arbitrary and i and j independently of one another are an integer from 0 to 200, the sum of i and j being> O, R ^{q is} hydrogen or a C ₁ -C ₈ -alkyl radical ,

and mixtures thereof.

To a suitable embodiment have the polysiloxanes δ) the general formula VI.1 no alkylene oxide radicals of the general Formula VII on. These polysiloxanes c4) then preferably have a number average molecular weight in the range of about 300 to 5000, preferably 400 to 3000 on.

Suitable polysiloxanes δ) which have no alkylene oxide radicals are, for. B. the Tegomer ^® brands from. Goldschmidt.

According to a further suitable embodiment, the polysiloxanes δ) are silicone poly (alkylene oxide) copolymers of the formula VI.1, where at least one or both radicals Z ¹ and / or Z ^{2 are} a radical of the general formula VII.

Preferably in formula VII the sum of v and w is chosen such that the molecular weight of the polysiloxanes δ) then in a range of is about 300 to 30,000.

Prefers is the total number of alkylene oxide units of polysiloxanes δ), d. H. the sum of v and w in formula VII then in a range of about 3 to 200, preferably 5 to 180.

According to a further suitable embodiment, the polysiloxanes δ) are silicone poly (alkylene oxide) copolymers of the formula VI.2 which have at least one radical Z ^{3 of} the general formula VII.

Preferably then in formula VII the sum of v and w is again chosen so that the molecular weight of the polysiloxanes δ) then in a range of is about 300 to 30,000. The total number of alkylene oxide units is preferably the polysiloxanes δ), d. H. the sum of v and w in formula VII then also in a range of about 3 to 200, preferably 5 to 180.

Suitable silicone poly (alkylene oxide) copolymers δ), which are known under the international non-proprietary name dimethicone, the Tegopren ^® brands from. Goldschmidt, Belsil ^® 6031 from. Wacker and Silvet ^® L Fa. Witco are.

According to a preferred embodiment, the polysiloxanes δ) are silicone-poly (alkylene oxide) copolymers of the formula VI.2 which have at least one radical Z ³ , where Z ^{3 is} NHR ^k and R ^{3 is} hydrogen or a radical of the formula - (CH ₂ ) _u -NH ₂ stands. Preferably, u is an integer of 1 to 10, preferably 2 to 6. These include z. As the MAN and MAR brands of Fa. Hüls and the finish marks of Fa. Wacker, z. Eg Finish WT 1270.

The polysiloxanes δ) preferably comprise at least one compound of the general formula VI.3. Preferably, in the formula VI.3 R ^l and R ^m are each independently a C ₂ -C ₄ alkylene radical. In particular, R ^l and R ^m are independently a C ₂ -C ₃ alkylene radical.

Preferably is the molecular weight of the compound of formula VI.3 in one Range from about 300 to 100,000.

Preferably is in the formula VI.3 p for an integer from 1 to 20, such as. B. 2 to 10.

Prefers is the total number of alkylene oxide units of the compound Formula VI.3, d. H. the sum of r and s, 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 VI.3 are selected from (CH ₃ ) ₃ SiO, H, C ₁ -C ₈ -alkyl and mixtures thereof.

Containing amino groups Compounds with repeating units of the general formula VI.3 preferably have an amine number in a range from about 2 to 50, especially 3 to 20 on.

Suitable alkoxylated siloxane amines of the formula VI.3 are, for. As described in WO-A-97/32917, which is incorporated herein by reference in its entirety. Commercially available compounds are z. As the Silsoft ^® brands from. Witco, z. B. Silsoft® ^® A-843rd

In the formula VI.4, the radical R ⁿ is preferably a C ₂ -C ₄ -alkylene radical.

In the formula VI.4, R ^o and R ^p are each independently of one another hydrogen or C ₁ -C ₄ -alkyl.

Preferably the sum of x, y and z is chosen so that the molecular weight the compound of formula VI.4 in a range of about 300 to 100,000, preferably 500 to 50,000.

Prefers is the total number of alkylene oxide units of the radical of the formula VIII, d. H. the sum of i and j, in a range of about 3 to 200, preferably 5 to 80.

In the formula VIII, the radical R ^q is preferably hydrogen or C ₁ -C ₄ -alkyl.

A suitable compound of the formula VI.4 is z. B. Silsoft® ^® A-858 of the company. Witco.

suitable Polysiloxanes id) are also those described in EP-A-277 816 Polydimethylsiloxanes.

• ε) Verbindungen, die zwei oder mehrere aktive Wasserstoffatome und mindestens eine ionogene und/oder ionische Gruppe pro Molekül enthalten,
• ζ) einwertigen Alkoholen, Aminen mit einer primären oder sekundären Aminogruppe, aliphatischen, cycloaliphatischen oder aromatischen Monoisocyanaten und Mischungen davon,
• η) α,β-ethylenisch ungesättigten Verbindungen, die zusätzlich wenigstens eine Isocyanatgruppe pro Molekül enthalten,

und Mischungen davon.Optionally, the urethane (meth) acrylates according to the invention additionally contain at least one component incorporated below

• ε) compounds which contain two or more active hydrogen atoms and at least one ionogenic and / or ionic group per molecule,
• ζ) monohydric alcohols, amines having a primary or secondary amino group, aliphatic, cycloaliphatic or aromatic monoisocyanates and mixtures thereof,
• η) α, β-ethylenically unsaturated compounds which additionally contain at least one isocyanate group per molecule,

and mixtures thereof.

Monomer d)

wobei
einer der Reste R¹ bis R³ für eine Gruppe der Formel CH₂=CR⁴- mit R⁴ = H oder C₁-C₄-Alkyl steht und die übrigen Reste R¹ bis R³ unabhängig voneinander für H, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen,
wobei R¹ und R² gemeinsam mit der Amidgruppe, an die sie gebunden sind, auch für ein Lactam mit 5 bis 8 Ringatomen stehen können,
wobei R² und R³ gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, auch für einen fünf- bis siebengliedrigen Heterocyclus stehen können,
mit der Maßgabe, dass die Summe der Kohlenstoffatome der Reste R¹, R² und R³ höchstens 8 beträgt.In a preferred embodiment, the copolymers according to the invention contain in addition to the abovementioned monomers a) to c) at least one further amide group-containing monomer d) of the general formula I in copolymerized form

in which
one of the radicals R ¹ to R ^{3 is} a group of the formula CH ₂ = CR ⁴ - with R ⁴ = H or C ₁ -C ₄ -alkyl and the other radicals R ¹ to R ^{3 are} independently H, alkyl, cycloalkyl , Heterocycloalkyl, aryl or hetaryl,
where R ¹ and R ² together with the amide group to which they are attached may also stand for a lactam having 5 to 8 ring atoms,
where R ² and R ³ together with the nitrogen atom to which they are attached may also stand for a five- to seven-membered heterocycle,
with the proviso that the sum of the carbon atoms of the radicals R ¹ , R ² and R ^{3 is} at most 8.

Preferably the compounds of component d) are in addition to the carbonyl carbon atom the amide group at most 7 more carbon atoms.

Prefers the compounds of component d) are selected from primary amides α, β-ethylenic unsaturated Monocarboxylic acids, N-vinylamides more saturated Monocarboxylic acids, N-vinyllactams, N-alkyl and N, N-dialkylamides α, β-ethylenically unsaturated Monocarboxylic acids and mixtures thereof.

Preferred monomers d) are N-vinyl lactams and their derivatives, the z. B. one or more C ₁ -C ₆ alkyl, 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.

Especially N-vinylpyrrolidone and N-vinylcaprolactam are preferably used.

suitable Monomers d) are furthermore acrylamide and methacrylamide.

suitable N-alkyl and N, N-dialkylamides α, β-ethylenic unsaturated Monocarboxylic acids, the additional to the carbonyl carbon atom of the amide group at most 7 further carbon atoms are, for example, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- (n-butyl) (meth) acrylamide, N-tert-butyl (meth) acrylamide, n-pentyl (meth) acrylamide, n-hexyl (meth) acrylamide, n-heptyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, piperidinyl (meth) acrylamide, morpholinyl (meth) acrylamide and mixtures thereof.

When Monomers d) are suitable open-chain N-vinylamide compounds 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.

Suitable monomers d) are also compounds of the formula

Especially preferred are N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide and the compounds of the above formula used.

The used according to the invention Copolymers preferably contain from 5 to 95% by weight, more preferably 10 to 90 wt .-%, based on the total weight of the polymerization used compounds, at least one monomer d) copolymerized.

Monomer e)

The Copolymers of the invention A) can additionally at least one hydrophobic monomer e) in copolymerized form.

Preferably contain silicone group-free copolymers 0.2 to 50 wt .-%, especially preferably 0.5 to 40 wt .-%, in particular 1 to 30 wt .-%, based on the total weight of the compounds used for the polymerization, at least one hydrophobic monomer e) (and / or at least one hydrophobic monomer f) and / or g) copolymerized). Preferably contain silicone group-containing copolymers 0.1 to 30 wt .-%, especially preferably 0.2 to 20 wt .-%, in particular 0.5 to 15 wt .-%, based on the total weight of the compounds used for the polymerization, at least one hydrophobic monomer e) copolymerized.

worin
die Reihenfolge der Alkylenoxideinheiten beliebig ist,
k und l unabhängig voneinander für eine ganze Zahl von 0 bis 1000 stehen, wobei die Summe aus k und l mindestens 5 beträgt,
R⁸ für Wasserstoff oder C₁-C₄-Alkyl, vorzugsweise Methyl, steht,
R⁹ für C₈-C₃₀-Alkyl oder C₈-C₃₀-Alkenyl steht, und
X für O oder eine Gruppe der Formel NR¹⁰ steht, worin R¹⁰ für H, Alkyl, Alkenyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl steht.Suitable compounds e) are selected from compounds of the general formulas IIIa), IIIb), IIIc) and IIId)

wherein
the order of the alkylene oxide units is arbitrary,
k and l independently of one another represent an integer from 0 to 1000, the sum of k and l being at least 5,
R ^{8 is} hydrogen or C ₁ -C ₄ -alkyl, preferably methyl,
R ^{9 is} C ₈ -C ₃₀ alkyl or C ₈ -C ₃₀ alkenyl, and
X is O or a group of the formula NR ¹⁰ , wherein R ^{10 is} H, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

Provided it is used in the invention Copolymers are silicone group-free copolymers are the Compounds e) specially selected among compounds of general formulas IIIa), IIIb) and IIIc).

suitable Monomers of formula IIIa wherein X is O are, for. B. 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.

Suitable monomers of formula IIIa wherein X is NR ¹⁰ are, for. B. 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-di (n-octyl) (meth) acrylamide, and mixtures thereof.

suitable Monomers of the formula IIIb are z. 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, pentadecyl vinyl ether, palmityl vinyl ether, heptadecyl vinyl ether, Octadecyl vinyl ether, nonadecyl vinyl ether, arrachinyl vinyl ether, Behenyl vinyl ether, lignocerenyl vinyl ether, cerotinyl vinyl ether, Melissinyl vinyl ether, palmitoleinyl vinyl ether, oleyl vinyl ether, Linolyl vinyl ether, linolenyl vinyl ether, stearyl vinyl ether, lauryl vinyl ether and mixtures thereof.

In the formulas IIIc) and IIId) k is preferably a whole Number of 1 to 500, in particular 3 to 250. Preferably, l is a whole Number from 0 to 100.

R ⁸ in the formula IIIc) is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, in particular hydrogen, methyl or ethyl.

Preferably, R ⁹ in formulas IIIc) and IIId) is 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, palmitoleinyl, oleyl, linolyl, linolenyl, stearyl, lauryl.

Preferably X in the formula IIIc) stands for O or NH.

Suitable polyether acrylates IIIc) are z. 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 be readily prepared by reacting ethylene oxide, 1,2-propylene oxide and / or epichlorohydrin with a starter alcohol R ⁹ -OH. The alkylene oxides can be used individually, alternately in succession or as a mixture. The polyether acrylates IIIc) can be used alone or in mixtures for the preparation of the polymers used according to the invention.

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

Monomer f)

The copolymers used according to the invention may additionally comprise in copolymerized form at least one monomer f) which is selected from among components e) different esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₁ -C ₇ -alkanols, polyether acrylates other than IIIc), C C ₁ -C ₇ -alkyl vinyl ethers and IIId) different Allylalkoholalkoxilaten.

Preferably is the proportion of monomers f) (and / or g) up to 40 wt .-%, based on the total weight of the compounds used for the polymerization. A suitable amount for additional Monomers f) is in a range of 0.1 to 30 wt .-%, in particular 1 to 25 wt .-%, based on the total weight of the polymerization used compounds.

worin
die Reihenfolge der Alkylenoxideinheiten beliebig ist,
k und l unabhängig voneinander für eine ganze Zahl von 0 bis 1000 stehen, wobei die Summe aus k und l mindestens 5 beträgt,
R⁸ für Wasserstoff oder C₁-C₄-Alkyl, vorzugsweise Methyl, steht,
R^9* für Wasserstoff, C₁-C₈-Alkyl oder C₃-C₈-Alkenyl steht, und
X für O oder eine Gruppe der Formel NR¹⁰ steht, worin R¹⁰ für H, Alkyl, Alkenyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl steht.Preferably, the compound f) is selected from compounds of the general formulas IIIa *), IIIb *), IIIc *) and IIId *)

wherein
the order of the alkylene oxide units is arbitrary,
k and l independently of one another represent an integer from 0 to 1000, the sum of k and l being at least 5,
R ^{8 is} hydrogen or C ₁ -C ₄ -alkyl, preferably methyl,
R ^{9 * is} hydrogen, C ₁ -C ₈ alkyl or C ₃ -C ₈ alkenyl, and
X is O or a group of the formula NR ¹⁰ , wherein R ^{10 is} H, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

Suitable esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₁ -C ₇ -alkanols are, for. For example, methyl (meth) acrylate, methyl methacrylate, ethyl (meth) acrylate, ethyl methacrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butyl methacrylate, n-pentyl (meth) acrylate, n- Hexyl (meth) acrylate, n-heptyl (meth) acrylate, etc. Preferred monomers g) are the esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₁ -C ₃ -alkanols, in particular methyl methacrylate.

In The formulas IIIc *) and IIId *) is preferably k for a whole Number of 1 to 500, in particular 3 to 250. Preferably, l is a whole Number from 0 to 100.

R ⁸ in the formula IIIc) is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, in particular hydrogen, methyl or ethyl.

R ^{9 *} in the formulas IIIc *) and IIId *) is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, in particular for hydrogen, methyl or ethyl.

Preferably X stands in the formula IIIc *) for O or NH.

Suitable polyether acrylates IIIc *) are z. 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 be readily prepared by reacting ethylene oxide, 1,2-propylene oxide and / or epichlorohydrin with water or a starter alcohol R ^{9 *} -OH. The alkylene oxides can be used individually, alternately in succession or as a mixture. The polyether acrylates IIIc) can be used alone or in mixtures for the preparation of the polymers used according to the invention.

Suitable allyl alcohol alkoxilates IIId) are, for. As the etherification of allyl chloride with corresponding polyetherols. Suitable polyetherols can be readily prepared by reacting ethylene oxide, 1,2-propylene oxide and / or epichlorohydrin with water or a starter alcohol R ^{9 *} -OH. The alkylene oxides can be used individually, alternately in succession or as a mixture. The allyl alcohol alkoxilates IIId *) can be used alone or in mixtures for the preparation of the polymers used according to the invention.

Monomer g)

The Copolymers of the invention A) can additionally at least one of the components a) to f) different, so copolymerizable monomer g) in copolymerized form.

Preferably is the proportion of monomers g (and / or f) up to 40 wt .-%, based on the total weight of the compounds used for the polymerization. A suitable amount for additional monomers g) is in a range of 0.1 to 25 wt .-%, in particular 0.5 to 20 wt .-%, based on the total weight of the polymerization used compounds.

The component f) is preferably selected from esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₂ -C ₃₀ -diols, amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₂ -C ₃₀ -aminoalcohols which have a have primary or secondary amino group, esters of vinyl alcohol and allyl alcohol with C ₁ -C ₇ monocarboxylic acids, IIIc) and IIIc *) various polyether acrylates, vinyl aromatics, vinyl halides, vinylidene halides, C ₁ -C ₈ monoolefins, non-aromatic hydrocarbons having at least two conjugated double bonds and mixtures thereof.

suitable additional Monomers g) 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.

suitable additional Monomers g) are furthermore 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-ethylhexylmethacrylamide.

Suitable polyether acrylates g) are also urethane (meth) acrylates with alkylene oxide groups. Such compounds are in the DE 198 38 851 (Component e2)), which is incorporated herein by reference.

suitable additional Monomers g) are also vinyl acetate, vinyl propionate, vinyl butyrate and mixtures thereof.

suitable additional Monomers g) are furthermore ethylene, propylene, isobutylene, butadiene, Styrene, α-methylstyrene, Acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, Vinylidene fluoride and mixtures thereof.

The previously mentioned additional Monomers g) can each used individually or in the form of any mixtures become.

• a1) wenigstens einer Verbindung mit einer radikalisch polymerisierbaren, α,β-ethylenisch ungesättigten Doppelbindung und mindestens einer anionogenen und/oder anionischen Gruppe pro Molekül,
• a2) wenigstens einer N-Vinylimidazol-Verbindung,
• b) wenigstens einer radikalisch polymerisierbaren vernetzenden Verbindung, die wenigstens zwei α,β-ethylenisch ungesättigte Doppelbindungen pro Molekül ent hält,

wobei wenigstens ein Teil der Verbindungen a1) und a2) in Form eines Monomerenpaares eingesetzt wird, wobei das molare Verhältnis von anionogenen Gruppen der Komponente a1) zu kationogenen Gruppen der Komponente a2) etwa 1:1 beträgt. Speziell handelt es sich dabei um in der deutschen Patentanmeldung 10 2005 034 412.7 beschriebene Copolymere.Preference is given to the use of an ampholytic copolymer obtainable by free-radical copolymerization of

• a1) at least one compound having 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 N-vinylimidazole compound,
• b) at least one free-radically polymerizable crosslinking compound which contains at least two α, β-ethylenically unsaturated double bonds per molecule,

wherein at least part of the compounds a1) and a2) is used in the form of a monomer pair, wherein the molar ratio of anionogenic groups of component a1) to cationogenic groups of component a2) is about 1: 1. Specifically, these are described in the German patent application 10 2005 034 412.7 copolymers.

• – wenigstens 2 Gew.-%, bezogen auf das Gesamtgewicht der zur Polymerisation eingesetzten Monomere, wenigstens eines Monomerenpaars aus N-Vinylimidazol und Acrylsäure und/oder Methacrylsäure,
• – 5 bis 70 Gew.-% Methacrylsäure und/oder Acrylsäure,
• – 0,1 bis 2 Gew.-% wenigstens eines Vernetzers b), vorzugsweise Ethylenglykoldi(meth)acrylat und/oder Pentaerythrittriallylether,
• – 20 bis 95 Gew.-% Vinylpyrrolidon und/oder Vinylcaprolactam,
• – 0 bis 40 Gew.-% wenigstens eines weiteren Monomers, das ausgewählt ist unter Methyl(meth)acrylat, Ethyl(meth)acrylat, n-Butyl(meth)acrylat, C₈-C₂₂-(Meth)acrylaten, mit C₈-C₂₂-Alkylgruppen terminierten Polyether(meth)acrylaten und Mischungen davon.

Particularly preferred is the use of an ampholytic copolymer obtainable by radical copolymerization of

• At least 2% by weight, based on the total weight of the monomers used for the polymerization, of at least one monomer pair of N-vinylimidazole and acrylic acid and / or methacrylic acid,
• From 5 to 70% by weight of methacrylic acid and / or acrylic acid,
• 0.1 to 2% by weight of at least one crosslinker b), preferably ethylene glycol di (meth) acrylate and / or pentaerythritol triallyl ether,
• From 20 to 95% by weight of vinylpyrrolidone and / or vinylcaprolactam,
• 0 to 40% by weight of at least one further monomer selected from methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, C ₈ -C ₂₂ (meth) acrylates, with C C ₈ -C ₂₂ -alkyl-terminated polyether (meth) acrylates and mixtures thereof.

• – wenigstens 2 Gew.-%, bezogen auf das Gesamtgewicht der zur Polymerisation eingesetzten Monomere, wenigstens eines Monomerenpaars aus N-Vinylimidazol und Acrylsäure und/oder Methacrylsäure,
• – 5 bis 70 Gew.-% Methacrylsäure und/oder Acrylsäure,
• – 0,1 bis 2 Gew.-% wenigstens eines Vernetzers b), vorzugsweise Ethylenglykoldi(meth)acrylat und/oder Pentaerythrittriallylether,
• – 20 bis 85 Gew.-% Vinylpyrrolidon und/oder Vinylcaprolactam.

Also particularly preferred is the use of an ampholytic copolymer obtainable by free-radical copolymerization of

• At least 2% by weight, based on the total weight of the monomers used for the polymerization, of at least one monomer pair of N-vinylimidazole and acrylic acid and / or methacrylic acid,
• From 5 to 70% by weight of methacrylic acid and / or acrylic acid,
• 0.1 to 2% by weight of at least one crosslinker b), preferably ethylene glycol di (meth) acrylate and / or pentaerythritol triallyl ether,
• 20 to 85% by weight of vinylpyrrolidone and / or vinylcaprolactam.

• – wenigstens 5 Gew.-%, bezogen auf das Gesamtgewicht der zur Polymerisation eingesetzten Monomere, wenigstens eines Monomerenpaars aus N-Vinylimidazol und Acrylsäure und/oder Methacrylsäure,
• – 5 bis 70 Gew.-% Methacrylsäure und/oder Acrylsäure,
• – 0,1 bis 2 Gew.-% wenigstens eines Vernetzers b), vorzugsweise Ethylenglykoldi(meth)acrylat und/oder Pentaerythrittriallylether,
• – 20 bis 85 Gew.-% Vinylpyrrolidon und/oder Vinylcaprolactam,
• – 5 bis 40 Gew.-% wenigstens eines weiteren Monomers, das ausgewählt ist unter C₁-C₆-(Meth)acrylaten, insbesondere Methyl(meth)acrylat, Ethyl(meth)acrylat, n-Butyl(meth)acrylat und Mischungen davon.

Also particularly preferred is the use of an ampholytic copolymer obtainable by free-radical copolymerization of

• At least 5% by weight, based on the total weight of the monomers used for the polymerization, of at least one monomer pair of N-vinylimidazole and acrylic acid and / or methacrylic acid,
• From 5 to 70% by weight of methacrylic acid and / or acrylic acid,
• 0.1 to 2% by weight of at least one crosslinker b), preferably ethylene glycol di (meth) acrylate and / or pentaerythritol triallyl ether,
• From 20 to 85% by weight of vinylpyrrolidone and / or vinylcaprolactam,
• From 5 to 40% by weight of at least one further monomer selected from C ₁ -C ₆ (meth) acrylates, in particular methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and mixtures from that.

• – wenigstens 5 Gew.-%, bezogen auf das Gesamtgewicht der zur Polymerisation eingesetzten Monomere, wenigstens eines Monomerenpaars aus N-Vinylimidazol und Acrylsäure und/oder Methacrylsäure,
• – 5 bis 70 Gew.-% Methacrylsäure und/oder Acrylsäure,
• – 0,1 bis 2 Gew.-% wenigstens eines Vernetzers b), vorzugsweise Ethylenglykoldi(meth)acrylat und/oder Pentaerythrittriallylether,
• – 20 bis 85 Gew.-% Vinylpyrrolidon und/oder Vinylcaprolactam,
• – 0,5 bis 20 Gew.-%, vorzugsweise 1 bis 10 Gew.-%, wenigstens eines weiteren Monomers, das ausgewählt ist unter C₈-C₃₀-(Meth)acrylaten, mit C₈-C₃₀-Alkylgruppen terminierten Polyether(meth)acrylaten und Mischungen davon, insbesondere unter Stearylmethacrylat, mit C₁₈-C₂₂-Alkylgruppen terminierten Polyethylenglycol(meth)acrylaten und Mischungen davon.

Also particularly preferred is the use of an ampholytic copolymer obtainable by free-radical copolymerization of

• At least 5% by weight, based on the total weight of the monomers used for the polymerization, of at least one monomer pair of N-vinylimidazole and acrylic acid and / or methacrylic acid,
• From 5 to 70% by weight of methacrylic acid and / or acrylic acid,
• 0.1 to 2% by weight of at least one crosslinker b), preferably ethylene glycol di (meth) acrylate and / or pentaerythritol triallyl ether,
• From 20 to 85% by weight of vinylpyrrolidone and / or vinylcaprolactam,
• From 0.5 to 20% by weight, preferably from 1 to 10% by weight, of at least one further monomer selected from C ₈ -C ₃₀ (meth) acrylates, polyethers terminated with C ₈ -C ₃₀ -alkyl groups (meth) acrylates and mixtures thereof, in particular under stearyl methacrylate, with C ₁₈ -C ₂₂ -alkyl-terminated polyethylene glycol (meth) acrylates and mixtures thereof.

In a special version all the above-mentioned silicone group-free, anionic, ampholytic copolymers containing at least 5% by weight of at least one Vinylimidazole contained in copolymerized form, a partial or complete Subjected to quaternization. Suitable quaternizing agents are the following.

• a1) wenigstens einer Verbindung mit einer radikalisch polymerisierbaren, α,β-ethylenisch ungesättigten Doppelbindung und mindestens einer anionogenen und/oder anionischen Gruppe pro Molekül,
• a2) wenigstens einer Verbindung mit einer radikalisch polymerisierbaren, α,β-ethylenisch ungesättigten Doppelbindung und mindestens einer kationogenen und/oder kationischen Gruppe pro Molekül,
• b) wenigstens einer radikalisch polymerisierbaren vernetzenden Verbindung, die wenigstens zwei α,β-ethylenisch ungesättigte Doppelbindungen pro Molekül enthält

in Gegenwart wenigstens einer eine Polyethergruppe und/oder eine radikalisch polymerisierbare olefinisch ungesättigte Doppelbindung enthaltenden Siliconverbindung c). Speziell handelt es sich dabei um in der deutschen Patentanmeldung 10 2005 034 412.7 beschriebenen Copolymere.Also preferred is the use of a silicone group-containing ampholytic copolymer which is obtainable by free-radical copolymerization of

• a1) at least one compound having 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

in the presence of at least one silicone compound containing a polyether group and / or a radically polymerizable olefinically unsaturated double bond c). Specifically, these are described in the German patent application 10 2005 034 412.7 copolymers.

• – wenigstens 2 Gew.-%, bezogen auf das Gesamtgewicht der zur Polymerisation eingesetzten Monomere, wenigstens eines Monomerenpaars aus N-Vinylimidazol a2) und Acrylsäure und/oder Methacrylsäure a1),
• – 5 bis 70 Gew.-% Methacrylsäure und/oder Acrylsäure a1),
• – 0,1 bis 2 Gew.-% wenigstens eines Vernetzers b), vorzugsweise Ethylenglykoldi(meth)acrylat und/oder Pentaerythrittriallylether,
• – 0,05 bis 30 Gew.-%, besonders bevorzugt 0,1 bis 20 Gew.-%, insbesondere 0,1 bis 15 Gew.-%, wenigstens einer Siliconverbindung c),
• – 20 bis 95 Gew.-% Vinylpyrrolidon und/oder Vinylcaprolactam d),
• – 0,1 bis 20 Gew.-% wenigstens einer Verbindung e), die vorzugsweise ausgewählt ist unter C₈-C₂₂-(Meth)acrylaten, C₈-C₂₂-Alkylvinylether, mit C₈-C₂₂-Alkylgruppen terminierten Polyether(meth)acrylaten, mit C₈-C₂₂-Alkylgruppen terminierten Allylalkoholalkoxilaten und Mischungen davon,
• – 5 bis 40 Gew.-% wenigstens eines Monomers f), das vorzugsweise ausgewählt ist unter C₁-C₆-(Meth)acrylaten, insbesondere Methyl(meth)acrylat, Ethyl(meth)acrylat, n-Butyl(meth)acrylat und Mischungen davon.

Particularly preferred is the use of a silicone group-containing ampholytic copolymer, that can be obtained by radical copolymerization of

• At least 2% by weight, based on the total weight of the monomers used for the polymerization, of at least one monomer pair of N-vinylimidazole a2) and acrylic acid and / or methacrylic acid a1),
• From 5 to 70% by weight of methacrylic acid and / or acrylic acid a1),
• 0.1 to 2% by weight of at least one crosslinker b), preferably ethylene glycol di (meth) acrylate and / or pentaerythritol triallyl ether,
• From 0.05 to 30% by weight, particularly preferably from 0.1 to 20% by weight, in particular from 0.1 to 15% by weight, of at least one silicone compound c),
• From 20 to 95% by weight of vinylpyrrolidone and / or vinylcaprolactam d),
• 0.1 to 20% by weight of at least one compound e), which is preferably selected from C ₈ -C ₂₂ (meth) acrylates, C ₈ -C ₂₂ -alkyl vinyl ethers, polyethers terminated with C ₈ -C ₂₂ -alkyl groups (meth) acrylates, C ₈ -C ₂₂ -alkyl-terminated allyl alcohol alkoxylates and mixtures thereof,
• - 5 to 40 wt .-% of at least one monomer f), which is preferably selected from C ₁ -C ₆ - (meth) acrylates, in particular methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and mixtures thereof.

• – wenigstens 5 Gew.-%, bezogen auf das Gesamtgewicht der zur Polymerisation eingesetzten Monomere, wenigstens eines Monomerenpaars aus N-Vinylimidazol a2) und Acrylsäure und/oder Methacrylsäure a1),
• – 5 bis 70 Gew.-% Methacrylsäure und/oder Acrylsäure a1),
• – 0,1 bis 2 Gew.-% wenigstens eines Vernetzers b), vorzugsweise Ethylenglykoldi(meth)acrylat und/oder Pentaerythrittriallylether,
• – 0,05 bis 30 Gew.-%, besonders bevorzugt 0,1 bis 20 Gew.-%, insbesondere 0,1 bis 15 Gew.-%, wenigstens einer Siliconverbindung c),
• – 20 bis 85 Gew.-% Vinylpyrrolidon und/oder Vinylcaprolactam d).

Furthermore, the use of a silicone-group-containing ampholytic copolymer which can be obtained by free-radical copolymerization of

• At least 5% by weight, based on the total weight of the monomers used for the polymerization, of at least one monomer pair of N-vinylimidazole a2) and acrylic acid and / or methacrylic acid a1),
• From 5 to 70% by weight of methacrylic acid and / or acrylic acid a1),
• 0.1 to 2% by weight of at least one crosslinker b), preferably ethylene glycol di (meth) acrylate and / or pentaerythritol triallyl ether,
• From 0.05 to 30% by weight, particularly preferably from 0.1 to 20% by weight, in particular from 0.1 to 15% by weight, of at least one silicone compound c),
• 20 to 85% by weight of vinylpyrrolidone and / or vinylcaprolactam d).

• – wenigstens 5 Gew.-%, bezogen auf das Gesamtgewicht der zur Polymerisation eingesetzten Monomere, wenigstens eines Monomerenpaars aus N-Vinylimidazol a2) und Acrylsäure und/oder Methacrylsäure a1),
• – 5 bis 70 Gew.-% Methacrylsäure und/oder Acrylsäure a1),
• – 0,1 bis 2 Gew.-% wenigstens eines Vernetzers b), vorzugsweise Ethylenglykoldi(meth)acrylat und/oder Pentaerythrittriallylether,
• – 0,05 bis 30 Gew.-%, besonders bevorzugt 0,1 bis 20 Gew.-%, insbesondere 0,1 bis 15 Gew.-%, wenigstens einer Siliconverbindung c),
• – 20 bis 85 Gew.-% Vinylpyrrolidon und/oder Vinylcaprolactam d),
• – 5 bis 40 Gew.-% wenigstens eines weiteren Monomers f), das vorzugsweise ausgewählt ist unter C₁-C₆-(Meth)acrylaten, insbesondere Methyl(meth)acrylat, Ethyl(meth)acrylat, n-Butyl(meth)acrylat und Mischungen davon.

Furthermore, the use of a silicone-group-containing ampholytic copolymer which can be obtained by free-radical copolymerization of

• At least 5% by weight, based on the total weight of the monomers used for the polymerization, of at least one monomer pair of N-vinylimidazole a2) and acrylic acid and / or methacrylic acid a1),
• From 5 to 70% by weight of methacrylic acid and / or acrylic acid a1),
• 0.1 to 2% by weight of at least one crosslinker b), preferably ethylene glycol di (meth) acrylate and / or pentaerythritol triallyl ether,
• From 0.05 to 30% by weight, particularly preferably from 0.1 to 20% by weight, in particular from 0.1 to 15% by weight, of at least one silicone compound c),
• From 20 to 85% by weight of vinylpyrrolidone and / or vinylcaprolactam d),
• From 5 to 40% by weight of at least one further monomer f), which is preferably selected from C ₁ -C ₆ (meth) acrylates, in particular methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and mixtures thereof.

• – wenigstens 5 Gew.-%, bezogen auf das Gesamtgewicht der zur Polymerisation eingesetzten Monomere, wenigstens eines Monomerenpaars aus N-Vinylimidazol a2) und Acrylsäure und/oder Methacrylsäure a1),
• – 5 bis 70 Gew.-% Methacrylsäure und/oder Acrylsäure a1),
• – 0,1 bis 2 Gew.-% wenigstens eines Vernetzers b), vorzugsweise Ethylenglykoldi(meth)acrylat und/oder Pentaerythrittriallylether,
• – 0,05 bis 30 Gew.-%, besonders bevorzugt 0,1 bis 20 Gew.-%, insbesondere 0,1 bis 15 Gew.-%, wenigstens einer Siliconverbindung c),
• – 20 bis 85 Gew.-% Vinylpyrrolidon und/oder Vinylcaprolactam d),
• – 0,5 bis 20 Gew.-%, vorzugsweise 1 bis 10 Gew.-%, wenigstens eines weiteren Monomers, das ausgewählt ist unter C₈-C₂₂-(Meth)acrylaten, C₈-C₂₂-Alkylvinylether, mit C₈-C₂₂-Alkylgruppen terminierten Polyether(meth)acrylaten, mit C₈-C₂₂-Alkylgruppen terminierten Allylalkoholalkoxilaten und Mischungen davon, insbesondere unter Stearylmethacrylat, mit C₁₈-C₂₂-Alkylgruppen terminierten Polyethylenglycol(meth)acrylaten und Mischungen davon.

Furthermore, the use of a silicone-group-containing ampholytic copolymer which can be obtained by free-radical copolymerization of

• At least 5% by weight, based on the total weight of the monomers used for the polymerization, of at least one monomer pair of N-vinylimidazole a2) and acrylic acid and / or methacrylic acid a1),
• From 5 to 70% by weight of methacrylic acid and / or acrylic acid a1),
• 0.1 to 2% by weight of at least one crosslinker b), preferably ethylene glycol di (meth) acrylate and / or pentaerythritol triallyl ether,
• From 0.05 to 30% by weight, particularly preferably from 0.1 to 20% by weight, in particular from 0.1 to 15% by weight, of at least one silicone compound c),
• From 20 to 85% by weight of vinylpyrrolidone and / or vinylcaprolactam d),
• From 0.5 to 20% by weight, preferably from 1 to 10% by weight, of at least one further monomer selected from C ₈ -C ₂₂ (meth) acrylates, C ₈ -C ₂₂ -alkyl vinyl ethers, with C C ₈ -C ₂₂ -alkyl-terminated polyether (meth) acrylates, with C ₈ -C ₂₂ alkyl-terminated allyl alcohol alkoxylates and mixtures thereof, in particular under stearyl methacrylate, with C ₁₈ -C ₂₂ -alkyl-terminated polyethyleneglycol (meth) acrylates and mixtures thereof.

In a specific embodiment, all of the abovementioned anionic silicone group-containing copolymers A) which contain at least 5% by weight of at least one vinylimidazole compound in copolymerized form are subjected to partial or complete quaternization. Suitable quaternizing agents are those in the Following mentioned.

In a special version the radical copolymerization of the aforementioned components takes place a1), a2), b) and, if present, d) to g) in the presence of at least a polyether-containing compound which is not copolymerizable Having double bond. These are special copolymers with advantageous properties receive. This can be, for example, an effect of the polyether component as a protective colloid or emulsifier. This can for example also from an at least partial grafting on the polyether component as a grafting result. However, there are other mechanisms than a grafting conceivable. The copolymers used in the invention include in general, the process products of radical copolymerization under which z. B. pure graft polymers, mixtures of graft polymers with ungrafted compounds of the polyether component and any Mixtures are understood.

Preferably is the amount of polyether component (if any) used 0.1 to 50 wt .-%, particularly preferably 1 to 25 wt .-%, based on the total weight of the components used for the polymerization.

suitable Polyether-containing compounds are, for example, water-soluble or water-dispersible nonionic polymers, the alkylene oxide repeating units exhibit. Preferably the proportion of alkylene oxide repeating units is at least 30% by weight, based on the total weight of the compound. Suitable polyether-containing Compounds are, for example, polyalkylene glycols, as is customary also be used as nonionic surfactants. Suitable polyalkylene glycols generally have a number average molecular weight in the range from about 150 to 100,000, preferably from 300 to 50,000, more preferably 500 to 40,000 on. Suitable polyalkylene glycols are, for example Polyethylene glycols, polypropylene glycols, polytetrahydrofurans and Alkylene oxide. Suitable alkylene oxides for the preparation of Alkylene oxide copolymers are, for. For example, ethylene oxide, propylene oxide, epichlorohydrin, 1,2- and 2,3-butylene oxide. The alkylene oxide copolymers may be the Alkylene oxide randomly distributed or polymerized in the form of blocks contain. Advantageously, homopolymers of the Ethylene oxide or copolymers containing ethylene oxide. Preferably is the proportion of repeating units derived from ethylene oxide 40 to 99 wt .-%. Suitable examples are copolymers of Ethylene oxide and propylene oxide, copolymers of ethylene oxide and Butylene oxide and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide.

The Preparation of the invention used Copolymers are made according to customary, known in the art, for. B. by solution, precipitation, suspension or emulsion. Also suitable is the W / W polymerization in water with a suitable Displacer, z. A salt such as NaCl.

preferred solvent for solution polymerization are watery Solvent, such as water and mixtures of water with water-miscible solvents, for example, alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol and cyclohexanol and glycols such as ethylene glycol, propylene glycol and butylene glycol and the methyl or ethyl ethers of dihydric alcohols, diethylene glycol, Triethylene glycol, polyethylene glycols of number average molecular weights to about 3000, glycerol and dioxane. Particularly preferred is the Polymerization in water or a water / alcohol mixture, for example in a water / ethanol mixture. The polymerization temperatures are in solution polymerization preferably in a range of about 30 to 120 ° C, especially preferably 40 to 100 ° C.

The Production of the copolymers is particularly preferably carried out by precipitation polymerization.

The precipitation is preferably carried out in a largely anhydrous, aprotic solvent or solvent mixture, preferably in ethyl acetate and / or n-butyl acetate. Under a largely anhydrous, aprotic solvent or solvent mixture becomes a solvent or solvent mixture with a water content of at most 5% by weight understood.

The precipitation polymerization preferably takes place at a temperature in the range from 70 to 140.degree. C., preferably from 75 to 100.degree. C., in particular from 80 to 95.degree. The resulting polymer particles precipitate out of the reaction solution and can be isolated by conventional techniques such as vacuum filtration. For precipitation polymerization, it is possible to use surface-active, polymeric compounds, preferably based on polysiloxanes. In the precipitation polymerization are usually polymers with higher molecular weight obtained as in the solution polymerization.

The Polymerization usually takes place under atmospheric Pressure, but it can also be under reduced or elevated pressure expire. A suitable pressure range is between 1 and 5 bar.

to Preparation of the polymers can the monomers are polymerized by means of radical-forming initiators become.

As initiators for the radical polymerization, the peroxo and / or azo compounds customary for this purpose can be used, for example alkali or ammonium peroxydisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl permalate, cumene hydroperoxide, diisopropyl peroxydicarbamate, bis (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide, azo-bis-isobutyronitrile, azo-bis (2-midinopropane) dihydrochloride or 2-2'-azobis (2-methyl-butyronitrile). Also suitable are initiator mixtures or redox initiator systems, such as. As ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinate, H ₂ O ₂ / Cu ^l .

to Achieving as possible pure polymers can the polymers z. B. a washing step with a suitable solvent, z. B. are also subjected to the solvent used for the polymerization.

The copolymers can be converted into a solid form, in particular a powder, by various drying methods. Polymers obtained by precipitation polymerization are preferably isolated by filtration before drying. Preference is given to using vacuum drying methods, such as vacuum fluidized bed drying. The solid copolymer compositions thus obtained can be advantageously redissolved or redispersed in aqueous media. Suitable aqueous media are water and mixtures of water with at least one water-miscible solvent. Preference is given to water and water / alcohol mixtures, wherein the alcohol is preferably selected from C ₁ -C ₄ -alkanols, such as ethanol, isopropanol, n-butanol and tert-butanol. Solid copolymers have the advantage of better shelf life, easier transportability and usually show a lower propensity for microbial attack.

The anionogenic groups (acid groups) of the copolymers can be partially or completely neutralized with a base. As a base for the neutralization of the polymers alkali metal bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate 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. B. 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. trialkanolamines, such as triethanolamine, Alkyldialkanolamine, such as methyl or ethyldiethanolamine and Dialkylalkanolamine, such as dimethylethanolamine and 2-amino-2-methyl-1-propanol. NaOH, KOH, 2-amino-2-methyl-1-propanol, 2-amino-2-ethylpropane-1,3-diol, diethylaminopropylamine and triisopropanolamine have proved suitable for use in hair treatment compositions for neutralizing the acid group-containing polymers. The neutralization of the acid groups can also be carried out with the aid of mixtures of several bases, for. B. mixtures of sodium hydroxide solution and triisopropanolamine. Neutralization can be partial or complete depending on the application. A partial neutralization is preferably understood to mean a neutralization of up to 95%, preferably up to 50%, especially of up to 25% of the acid groups contained in the polymer. A partial neutralization is furthermore preferably understood as meaning a neutralization of at least 1%, preferably at least 5%, of the acid groups contained in the polymer.

Charged cationic groups can be prepared from the cationogenic nitrogen-containing groups present either by protonation, e.g. As with mono- or polybasic carboxylic acids such as lactic acid or tartaric acid, or with mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid, or by quaternization, for. B. with alkylating agents, such as C ₁ -C ₄ -alkyl halides or sulfates produce. Examples of such alkylating agents are ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate. and diethyl sulfate.

Should the invention used Copolymers both quaternized and neutralized, so Preferably, the quaternization and then the Neutralization.

The copolymers described above are advantageously suitable for modifying the rheolo properties of hair cosmetics. In particular, these are aqueous compositions. Advantageously, the compositions of the copolymers are generally clear. Thus, the hair cosmetic formulations can be stained without being affected by the intrinsic color of the compositions. Furthermore, the compositions may be formulated in the form of opaque to clear gels.

The used according to the invention anionic ampholytic copolymers are especially useful as rheology modifiers with more than the pH controllable properties. They are special as pH-switchable thickener for a pH range greater or equal to 6.

The used according to the invention anionic ampholytic copolymers are also particularly suitable as Rheology modifier for saline compositions. On the other hand can be with the copolymers of the invention also thicken salt-free compositions.

advantageously, act the invention used anionic ampholytic copolymers also as film-forming and / or conditioning rheology modifiers. They are suitable thus special for Hair fixatives as "firming Thickener "and in Hair care products as "conditioning Thickeners ".

The Copolymers are suitable both for producing homogeneous-phase aqueous Compositions as well as for the formulation of heterogeneous phase Compositions in addition at least one water-insoluble (hydrophobic) liquid or solid compound. "Homogeneous phase compositions" are independent of the number of its constituents only a single phase. "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, e.g. B. O / W and W / O formulations containing at least one of the following in more detail described oil or fatty components and water as immiscible phases. In principle, the Copolymers used in both the water phase and in the oil phase become. Generally, heterogeneous liquid / liquid compositions contain the copolymers essentially in the water phase.

• A) wenigstens ein ampholytisches Copolymer, wie zuvor definiert,
• B) gegebenenfalls wenigstens ein von A) verschiedenes Haarpolymer,
• C) wenigstens einen kosmetisch akzeptablen Träger, und
• D) gegebenenfalls wenigstens einen von A) und B) verschiedenen kosmetisch akzeptablen Wirk- und/oder Hilfsstoff.

Another object of the invention is a hair cosmetic agent containing

• A) at least one ampholytic copolymer as defined above
• B) optionally at least one hair polymer other than A),
• C) at least one cosmetically acceptable carrier, and
• D) optionally at least one of A) and B) different cosmetically acceptable active ingredient and / or excipient.

The used according to the invention ampholytic copolymers A) are advantageously not distinguished only by good thickening properties, but also by film-forming Properties off. You can thus in the hair cosmetics as hair-setting component be used so that the use of additional Festigerpolymere B) only required in a reduced amount or even completely unnecessary can. The ampholytic copolymers A) are advantageously characterized also by conditioning properties and can the improve the sensory properties of the hair, e.g. it suppleness and give shine. Hair treated with the copolymers A) not sticky or very slightly sticky.

The used according to the invention ampholytic copolymers A) are characterized by their good application properties in the pH range from 6 to 10, preferably 6.5 to 8.

The Cosmetic agents contain the polymer component A) preferably in a proportion of about 0.1 to 10 wt .-%, more preferably 0.2 to 6 wt .-%, in particular 0.3 to 3 wt .-%, based on the total weight of the agent.

suitable Hair polymers B) are generally film-forming polymers that are cosmetically are compatible and for the formulation of hair cosmetic compositions application Find. Preferably, it is water-soluble or water-dispersible Polymers. Particularly preferred are water-soluble hair polymers. This includes completely generally different from the copolymers A) anionic, cationic, amphoteric and nonionic polymers.

Examples of anionic polymers are homopolymers and copolymers of acrylic acid and methacrylic acid or their salts, copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, polyaspartic acid and its salts and derivatives, 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 (z. B. Luvimer 100P ^®), copolymers of ethyl acrylate and methacrylic acid (eg. B. Luviumer MAE ^®), copolymers of N-tert-butylacrylamide, ethyl acrylate, acrylic acid (Ultrahold ^® 8, strong), copolymers of vinyl acetate, crotonic acid and optionally further Vinylester (z. B. Luviset ^® types), maleic anhydride copolymers, optionally reacted with alcohol, anionic polysiloxanes, eg. B. carboxy, t-butyl acrylate, methacrylic acid (z. B. Luviskol ^® VBM), copolymers of acrylic acid and methacrylic acid with hydrophobic monomers, such as. 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. Examples of anionic polymers are also vinyl acetate / crotonic acid copolymers, such as (National Starch) and Gafset ^® (GAF) are commercially available and, for example, under the names Resyn ^® vinylpyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF) , Further suitable polymers are the VBM-35 under the name Luviflex ^® (BASF) available vinylpyrrolidone / acrylate terpolymer and sodium sulfonate-containing polyamides or sodium sulfonate-containing poly ester. Also suitable are vinyl pyrrolidone / ethyl methacrylate / methacrylic acid copolymers such as those sold by the company. Stepan under the names Stepanhold-Extra and -R1 and Carboset ^® brands from. BF Goodrich.

Suitable cationic polymers are, for. As cationic polymers called Polyquaternium INCI, z. For example, 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 11), 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 polymers are also polyethyleneimines and their salts and polyvinylamines and their salts. Suitable cationic (quaternized) polymers are also Merquat ^® (polymer based on dimethyldiallylammonium chloride), Gafquat ^® (quaternary polymers are formed by reacting polyvinylpyrrolidone with quaternary ammonium compounds), Polymer JR (hydroxyethylcellulose with cationic groups) and cationic polymers based on plants, z. As guar polymers, such as the Jaguar ^® brands Fa. Rhodia.

Especially suitable polymers are nonionic polymers, such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone and nonionic cellulose derivatives. This includes, for example Luviflex® ^® Swing (partially hydrolyzed copolymer of polyvinyl acetate and polyethylene glycol, Messrs. BASF).

Suitable polymers are also nonionic, water-soluble or water-dispersible polymers or oligomers, such as polyvinyl caprolactam, z. B. Luviskol ^® Plus (BASF), or polyvinylpyrrolidone and their copolymers, in particular with vinyl esters, such as vinyl acetate, z. B. Luviskol ^® VA 37 (BASF); 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 described for example in the German patent applications DE 39 29 973 . DE 21 50 557 . DE 28 17 369 and DE 37 08 451 are disclosed. Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts are preferred zwitterionic polymers. Further suitable zwitterionic polymers are Methacroylethylbe tain / methacrylate copolymers, which are commercially available under the name Amersette ^® (AMERCHOL), and copolymers of hydroxyethyl methacrylate, methyl methacrylate, N, N-dimethylaminoethyl methacrylate and acrylic acid (Jordapon ^® ).

Suitable polymers are also nonionic, siloxane-containing, water-soluble or -dispersible polymers, for. As polyether siloxanes, such as Tegopren ^® (Goldschmidt) or Belsil ^® (Wacker).

The Cosmetic agents contain the hair polymers B) preferably in a proportion of about 0.001 to 30 wt .-%, particularly preferably 0.01 to 15 wt .-%, in particular 0.1 to 7 wt .-%, based on the total weight of the agent.

Preferably the compositions have a carrier component C) which is selected under water, hydrophilic components, hydrophobic components and Mixtures thereof.

Suitable hydrophilic carrier C) are z. As water, monohydric, dihydric or polyhydric alcohols having preferably 1 to 8 carbon atoms, such as ethanol, n-propanol, isopropanol, propylene glycol, glycerol, sorbitol, etc. Preferred hydrophilic carriers are water and mixtures of water and at least one C. ₂ -C ₆ alkanol, such as ethanol, n-propanol and isopropanol.

• i) Ölen, Fetten, Wachsen,
• ii) von iii) verschiedenen Estern von C₆-C₃₀-Monocarbonsäuren mit ein-, zwei- oder dreiwertigen Alkoholen,
• iii) gesättigten acyclischen und cyclischen Kohlenwasserstoffen,
• iv) Fettsäuren,
• v) Fettalkoholen,
• vi) Treibgasen,

und Mischungen davon.Suitable hydrophobic carriers C) are preferably selected from

• i) oils, fats, waxes,
• ii) of iii) various esters of C ₆ -C ₃₀ monocarboxylic acids with mono-, di- or trihydric alcohols,
• iii) saturated acyclic and cyclic hydrocarbons,
• iv) fatty acids,
• v) fatty alcohols,
• vi) propellants,

and mixtures thereof.

suitable silicone oils C) are z. B. linear polydimethylsiloxanes, poly (methylphenylsiloxanes), cyclic siloxanes and mixtures thereof. The number average molecular weight the polydimethylsiloxanes and poly (methylphenylsiloxanes) are preferably in a range of about 1000 to 150000 g / mol. Preferred cyclic Siloxanes have 4- to 8-membered rings. Suitable cyclic Siloxanes are z. B. under the name cyclomethicone commercially available.

Preferred oil or Fat components C) are selected under paraffin and paraffin oils; Petroleum jelly; natural Fats and oils, like castor oil, Soybean oil, Peanut oil, Olive oil, Sunflower oil, Sesame oil, Avocado oil, cocoa butter, Almond oil, Peach kernel oil, castor oil, Cod liver oil, lard, spermaceti, sperm oil, sperm oil, wheat germ oil, macadamia nut oil, evening primrose oil, jojoba oil; Fatty alcohols, such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, Oleyl alcohol, cetyl alcohol; Fatty acids, such as myristic acid, stearic acid, palmitic acid, oleic acid, linoleic acid, and linolenic acid of which various saturated, unsaturated and substituted fatty acids; Grow, such as beeswax, carnauba wax, candililla wax, spermaceti and mixtures of the aforementioned oil or fat components.

suitable cosmetically and pharmaceutically acceptable oil or fat components C) are in Karl-Heinz Schrader, basics and formulations of cosmetics, 2nd edition, publisher Hüthig, Heidelberg, pp. 319-355 described, which is hereby incorporated by reference.

preferred carrier C) are still blowing agents. Suitable blowing agents C) are the for hair sprays or aerosol foams usually used. Preference is given to mixtures of propane / butane, pentane, dimethyl ether, 1,1-difluoroethane (HFC-152a), carbon dioxide, nitrogen or compressed air.

In addition, the agents according to the invention as component D) at least one further, different from A) and B) contain cosmetic active or excipient.

The Components D) are according to the desired application of the Composition selected. In addition to typical use components, they are preferred selected among cosmetically active substances, excipients, emulsifiers, Surfactants, preservatives, fragrances (eg perfume oils), from Component A) different thickeners, different from component A) Polymers (eg hair polymers, hair conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers), gelling agents, dyes, Pigments, sunscreens, bodying agents, antioxidants, Bleaching agents, care products, tinting agents, Tanning agents, Dyes, pigments, bodying agents, moisturizers, fats, Collagen, protein hydrolysates, lipids, emollients, plasticizers, Defoamers, antistatic agents, Resins, solvents, Solubilizers, Neutralizing agents, stabilizers, sterilants, propellants, Drying agents, opacifiers, Etc.

The copolymers A) can be used together with conventional thickeners D). Suitable conventional thickeners are crosslinked polyacrylic acids and their derivatives, polysaccharides and their derivatives, such as xanthan gum, agar-agar, alginates or tyloses, cellulose derivatives, eg. As carboxymethylcellulose or hydroxycarboxymethylcellulose, fatty alcohols, monoglycerides and fatty acids, polyvinyl alcohol and polyvinylpyrrolidone. Preferred thickeners are compounds which give the formulation a pseudoplastic flow behavior, ie high viscosity at rest and low viscosity in the agitated state. Particularly preferred are Xanthan Gum ^® (Kelzan ^® from. Kelco), Rhodopol ^® 23 (Rhone Poulenc), Veegum ^® (from RT Vanderbilt) or Attaclay ^® (Engelhardt).

Preferably are the agents of the invention in the form of a gel, foam, spray, ointment, cream, emulsion, Suspension, lotion, milk or paste in front. If you wish too Liposomes or microspheres be used.

by virtue of their thickening and film-forming properties are suitable previously described copolymers A), in particular as additives for formulation in the form of gels.

preferred cosmetically active agents are z. Bleaching agents, keratin-hardening substances, antimicrobial agents, light filtering agents, repellent agents, hyperemic substances, keratolytic and keratoplastic active substances, anti-dandruff agents, antiphlogistics, keratinizing acting substances, antioxidant or radical scavengers active ingredients, deodorizing Active substances, sebostatic agents, plant extracts, antierythimatös or antiallergic active agents and mixtures thereof.

suitable Keratin-hardening Substances are usually active substances, as they are also used in antiperspirants be used, such. Potassium aluminum sulfate, aluminum hydroxychloride, Aluminum lactate, etc. Antimicrobial agents are used to destroy microorganisms or to inhibit their growth and thus serve both as a preservative as well as a deodorant substance which causes the formation or the intensity of body odor reduced. These include z. Usual, Preservatives known to the person skilled in the art, such as p-hydroxybenzoic acid esters, Imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc. Such deodorizing substances are z. B. 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 the aforementioned. Also suitable are p-aminobenzoic acid esters, cinnamic, Benzophenones, camphor derivatives and UV-blocking pigments, such as titanium dioxide, talc and zinc oxide. Suitable repellent agents are Compounds that are capable of certain animals, in particular Insects, to discourage or expel people. This includes z. B. 2-ethyl-1,3-hexanediol, N, N-diethyl-m-toluamide, etc. Suitable hyperemic acting substances, which stimulate the blood circulation of the skin are z. As essential oils, such as Mountain pine, lavender, rosemary, juniper berry, horse chestnut extract, Birch leaf extract, Hayflower extract, ethyl acetate, camphor, menthol, peppermint oil, rosemary extract, Eucalyptus oil, etc. Suitable keratolytic and keratoplastic substances are z. Salicylic acid, Calcium thioglycolate, thioglycolic acid and their salts, sulfur, etc. Suitable anti-dandruff agents are z. Sulfur, sulfur polyethylene glycol sorbitan monooleate, Sulfuricinol polyethoxylate, zinc pyrithione, aluminum pyrithione, etc. Suitable antiphlogistics, which counteract skin irritation, are z. B. allantoin, bisabolol, dragosantol, chamomile extract, panthenol, Etc.

Preferably are the hair treatment compositions according to the invention in the form of a mousse, hair mousse, hair gel, hair wax, Shampoos, hair sprays, hair mousse, top fluids, leveling agents for perms or "hot oil treatments", especially in Shape of a hair gel, hair wax or shampoo before. Depending on the application can the hair cosmetic preparations as (aerosol) spray, (aerosol) foam, gel, gel spray, Cream, lotion or wax are applied. Hairsprays include both aerosol sprays and pump sprays without propellant. Hair mousses include both aerosol foams and also pump foams without propellant. Hairsprays and hair foams preferably comprise predominantly or exclusively water-soluble or water-dispersible components. Are those in the hairsprays according to the invention and hair foams water-dispersible compounds used, they can be in the form of aqueous Microdispersions with particle diameters of usually 1 to 350 nm, preferably 1 to 250 nm, are used. The solids content of these preparations usually lie here in a range of about 0.5 to 20 wt%. These microdispersions need usually no emulsifiers or surfactants for their stabilization.

• – 0,05 bis 5 Gew.-% wenigstens eines Copolymers A),
• – 0 bis 7 Gew.-%, z.B. 0,01 bis 5 Gew.-% wenigstens eines Haarfestigerpolymers B),
• – 83 bis 99,95 Gew.-% wenigstens eines Trägers, ausgewählt unter Wasser und Wasser/Alkohol-Gemischen, die bis zu 20 Gew.-% Alkohol, bezogen auf das Gewicht des Wasser/Alkohol-Gemischs enthalten, sowie Treibmitteln,
• – 0 bis 5 Gew.-%, vorzugsweise 0,01 bis 3 Gew.-% wenigstens eines weiteren Bestandteils.

The hair cosmetic formulations of the invention comprise in a preferred embodiment

• From 0.05 to 5% by weight of at least one copolymer A),
• From 0 to 7% by weight, for example from 0.01 to 5% by weight, of at least one hair-setting polymer B),
• From 83 to 99.95% by weight of at least one carrier selected from water and water / alcohol mixtures containing up to 20% by weight of alcohol, based on the weight of the water / alcohol mixture, and propellants,
• - 0 to 5 wt .-%, preferably 0.01 to 3 wt .-% of at least one further ingredient.

Under Alcohol are all alcohols commonly used in cosmetics, z. For example, ethanol, isopropanol, n-propanol.

Under other constituents are the additives customary in cosmetics, for example defoamers, surfactants Compounds, d. H. Surfactants, emulsifiers, foaming agents and solubilizers. The used surface-active Connections can anionic, cationic, amphoteric or neutral. Other common ingredients can also be z. Preservatives, perfume oils, opacifiers, active ingredients, UV filters, Nursing substances such as panthenol, collagen, vitamins, protein hydrolysates, Alpha and beta hydroxycarboxylic acids, Stabilizers, pH regulators, dyes, viscosity regulators, Gel formers, salts, humectants, moisturizers, complexing agents and more usual Additives.

Farther counting for this purpose all known in cosmetics styling and conditioner polymers, used in combination with the polymers of the invention can be if very special properties should be set.

When conventional Hair cosmetic polymers are, for example, the aforementioned cationic, anionic, neutral, nonionic and amphoteric Polymers to which reference is hereby made.

to Setting certain properties, the preparations may also be Contain conditioning substances based on silicone compounds. Suitable silicone compounds are, for example, polyalkylsiloxanes, Polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes, silicone resins or dimethicone copolyols (CTFA) and amino functional silicone compounds like amodimethicones (CTFA).

When Emulsifiers can all in hair foams usually used emulsifiers are used. Suitable emulsifiers can nonionic, cationic or anionic or amphoteric.

Examples for nonionic Emulsifiers (INCI nomenclature) are Laurethe, z. Laureth-4; Cetethe, z. Cetheth-1, polyethylene glycol cetyl ether; Cetearethe, z. Cetheareth-25, Polyglycol fatty acid glycerides, hydroxylated Lecithin, lactyl ester of fatty acids, Alkylpolyglycosides.

Examples for cationic Emulsifiers are cetyldimethyl-2-hydroxyethylammonium dihydrogen phosphate, Cetyltrimonium chloride, cetyltrimmonium bromide, cocotrimonium methylsulfate, Quaternium-1 to x (INCI).

anionic Emulsifiers can for example, selected are selected from the group of alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, Alkylarylsulfonates, alkylsuccinates, alkylsulfosuccinates, N-alkoylsarcosinates, acyltaurates, Acyl isothionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, Alpha olefin sulfonates, in particular the alkali and alkaline earth metal salts, z. As sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can be used between 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule exhibit.

• a) 0,1 bis 5 Gew.-% wenigstens eines Copolymers A),
• b) 0 bis 5 Gew.-% wenigstens eines von A) verschiedenen kosmetisch akzeptablen wasserlöslichen oder wasserdispergierbaren Haarfestigerpolymers B),
• c) 80 bis 99,85 Gew.-% Wasser und/oder Alkohol,
• d) 0 bis 1 Gew.-% eines von A) verschiedenen Gelbildners,
• e) 0 bis 20 Gew.-% weitere Bestandteile.

A preparation suitable for styling gels according to the invention can be composed, for example, as follows:

• a) from 0.1 to 5% by weight of at least one copolymer A),
• b) 0 to 5% by weight of at least one cosmetically acceptable water-soluble or water-dispersible hair setting polymer B) other than A),
• c) from 80 to 99.85% by weight of water and / or alcohol,
• d) 0 to 1% by weight of a gelling agent other than A),
• e) 0 to 20 wt .-% further ingredients.

As additional gelling agents, it is possible to use all gel formers customary in cosmetics. These include slightly crosslinked polyacrylic acid, for example carbomer (INCI), cellulose derivatives, eg. Hydroxypropyl cellulose, hydroxyethyl cellulose, cationic modified celluloses, polysaccharides, e.g. Xanthan gum, caprylic / capric triglyceride, sodium acrylate copolymers, polyquaternium-32 (and) paraffin liquidum (INCI), sodium acrylate copolymers (and) paraffin liquidum (and) PPG-1 trideceth-6, acrylamidopropyltrimonium chloride / acrylamide copolymers, Steareth-10 Allyl Ether Acrylate Copolymers, Polyquaternium-37 (and) Paraffinum Liquidum (and) PPG-1 Trideceth-6, Polyquaternium 37 (and) Propylene Glycol Dicaprate Dicaprylate (and) PPG-1 Trideceth-6, Polyquaternium-7, Polyquaternium-44. Suitable additional gelling agents suitable cross-linked homopolymers of acrylic acid are available commercially for example under the name Carbopol ^® by the company BF Goodrich. Also hydrophobically modified crosslinked polyacrylate polymers, such as Carbopol ^® Ultrez 21 from Noveon are preferred. Further examples of anionic polymers suitable as gelling agents are copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes and polyureas. Particularly suitable Polymers are copolymers of (meth) acrylic acid and polyether acrylates, wherein the polyether chain is terminated with a C ₈ -C ₃₀ -alkyl radical. These include z. B. Acrylate / beheneth-25-methacrylate copolymers, which are available under the name Aculyn ^® from Rohm and Haas.

The Copolymers of the invention A) can used in hair cosmetic preparations as conditioning agents become.

To a further preferred embodiment the agents according to the invention are a shampoo formulation.

Such Formulations contain at least one copolymer and usually anionic surfactants as base surfactants and amphoteric and / or nonionic Surfactants as cosurfactants. Other suitable active ingredients and / or auxiliaries are generally selected among lipids, perfume oils, dyes, organic acids, Preservatives and antioxidants as well as thickeners / gelling agents, Skin conditioners and moisturizers.

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

In the shampoo preparations can all in body cleansers usually used anionic, neutral, amphoteric or cationic surfactants be used.

suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, Alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoylsarcosinates, acyltaurates, acylisothionates, alkylphosphates, Alkyl ether phosphates, alkyl ether carboxylates, alpha olefin sulfonates, in particular the alkali and alkaline earth metal salts, e.g. Sodium, Potassium, magnesium, calcium, as well as ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can between 1 to 10 ethylene oxide or propylene oxide units, preferred 1 to 3 ethylene oxide units in the molecule.

To counting z. Sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, Ammonium lauryl ether sulfate, sodium lauryl sarcosinate, sodium oleyl succinate, Ammonium laurylsulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate.

suitable amphoteric surfactants are for. B. alkylbetaines, alkylamidopropyl betaines, Alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or propionates, alkyl amphodiacetates or dipropionates.

For example can Cocodimethyl sulphopropyl betaine, lauryl betaine, cocamidopropyl betaine or sodium cocamphopropionate.

When Nonionic surfactants are suitable, 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 up to 60 moles per one mole of alcohol. Furthermore, alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, ethoxylated fatty acid amides, alkylpolyglycosides or sorbitan ether esters.

In addition, the Shampoos usual contain cationic surfactants, such as. B. quaternary ammonium compounds, for example Cetyltrimethylammonium chloride.

Farther can the shampoo formulations thickener, such. Saline, PEG-55, propylene glycol oleate, PEG-120 methyl glucose dioleate and others, as well as preservatives, contain further active ingredients and auxiliaries and water.

In the shampoo formulations, customary conditioning agents can be used in combination with the copolymers A) to achieve certain effects. These include, for example, the aforementioned cationic polymers having the INCI name Polyquaternium, 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, egg white hydrolysates are 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 such as amodimethicones (CTFA). Furthermore, cationic guar derivatives such as guar hydroxypropyltrimonium chloride (INCI) can be used.

The used according to the invention Copolymers are preferably suitable for shampoos that have no or only small amounts of inorganic salts, especially alkali and Alkaline earth chlorides such as NaCl. They are thus advantageous for the production of mild shampoos and baby shampoos.

One Another object of the invention is a method for cosmetic Treatment of hair, in which one has a hair cosmetic agent, such as previously defined, and, where appropriate, with the aid of Hands, of combs, to brush etc. and / or of water and optionally with subsequent action of warm air applied to the hair to be treated. In a special design This procedure is the hair after the application and optionally a washing-out time (e.g. in the form of a shampoo). In a second embodiment, the funds remain after application on the hair as long as the one connected to them hair cosmetic effect persists or desired is and will only be removed by washing.

The The invention will be apparent from the following non-limiting Examples closer explained.

General manufacturing instructions A:

Example 23: VP / MAS / VI / MMA / C _16-18 -PEG-MA / EGDMA copolymer

In a stirring device with reflux condenser, internal thermometer and four feeders were at 85 to 88 ° C inlet 1 and feed 2 added in two hours. After that, the reaction mixture became at about 88 ° C 2 h further stirred. Subsequently Feed 3 was added in 30 minutes and postpolymerized at 90 ° C for 3 hours. That as white Powder precipitated product was added with methyl chloride (feed 4) quaternized at a temperature between 70 and 100 ° C. After cooling to about 40 ° C the product was partially neutralized with triethanolamine (feed 5) in 1 h at 40 ° C. The powder was over sucked a suction filter, washed at least twice with acetone and at 40 ° C dried in vacuo.

To prepare the polymers 26-40 were laid Belsil® ^® DMC 6031, Messrs. Wacker, in the template before.

In analogously, the polymers indicated in Table I 2, 5, 7, 9, 13 to 17, 20, 24, 25, 26, 31, 32, 34, 35, 36, 38, 39 and 40 produced.

The Polymers 3, 4, 6, 8, 10, 11, 12, 27 to 30 and 33 were analogous manufactured to manufacturing specification A, except that Partial neutralization with triethanolamine was omitted.

The Polymers 1, 18, 19, 21, 22 and 37 were analogous to the preparation instructions A made, besides being the quaternization with methyl chloride accounted for.

II. Application Engineering Examples

Application examples 1 - 40:

Hair gels with a nonionic hair fixative:

production:

phase 1 was weighed and stirred homogenized at a temperature in the range of 20 to 50 ° C. After about 3 Hours resulted in a milky dispersion. Triethanolamine was added while stirring. After about 2 hours, an (almost) homogeneous, highly viscous gel was formed educated. Then stirred Phase 2 slowly into Phase 1. The gel was at room temperature stirred for another hour. This resulted in a stable, clear gel.

In the same way, a standard gel (Comparative Gel VG) with Carbopol 940 and Luviskol K90, using Phase 1 instead of 2.0 Wt .-% of the polymer from Example No. 1 and 1.5 wt .-% Luviskol K90 0.5% by weight of Carbopol 940 and 3% by weight of Luviskol K90.

hair gels Application Examples 5, 16, 30 and 35, respectively, which describe the polymer from Examples Nos. 5, 16, 30 and 35 each in one Amount of 2.0 wt .-% and Luviskol K90 each in an amount of 1.5 wt .-%, were based on their performance properties (Clarity, stickiness, wet combability and consolidation). As a comparison served the previously described bene Comparative gel VG. The polymer content of both the gels according to the invention, as well as the comparison gel was thus 3.5%.

The test was based on the following rating scale:

Application examples 41-80:

Hair gels with a nonionic hair fixative:

production:

phase 1 was weighed and stirred homogenized at a temperature in the range of 20 to 50 ° C. After about 3 Hours resulted in a milky dispersion. Triethanolamine was added while stirring. After about 2 hours, an (almost) homogeneous, highly viscous gel was formed educated. Then stirred Phase 2 slowly into Phase 1. The gel was at room temperature stirred for another hour. This resulted in a stable, clear gel.

Hair gels of the application examples 45, 56, 70 and 75, respectively, the polymer from Examples Nos. 5, 16, 30 and 35 in an amount of 1.8 wt .-% and Luviskol K90 in an amount of 1.0 wt .-% were examined for their performance properties. As comparative gel was the previously described. The polymer content of the gels according to the invention was thus only 2.8%, that of the comparison gel 3.5%. The test was based on the above rating scale:

As The table can be seen are, with the gels of the invention achieved even with reduced polymer content better formulations as with the comparison gel.

Application examples 81-120:

Hair gels with poly (vinyl pyrrolidone / vinyl acetate)

production:

phase 1 was weighed and stirred homogenized at a temperature in the range of 20 to 50 ° C. After about 3 Hours resulted in a milky dispersion. Triethanolamine was added while stirring. After about 2 hours, an (almost) homogeneous, highly viscous gel was formed educated. Then stirred Phase 2 slowly into Phase 1. The gel was at room temperature stirred for another hour. This resulted in a stable, almost clear to clear gel.

Application examples 121-160:

Hair gels with a cationic hair polymer

production:

phase 1 was weighed and stirred homogenized at a temperature in the range of 20 to 50 ° C. After about 3 Hours resulted in a milky dispersion. Triethanolamine was added while stirring. After about 2 hours, an (almost) homogeneous, highly viscous gel was formed educated. Then stirred Phase 2 slowly into Phase 1.

The Gel was stirred at room temperature for a further 1 hour. This resulted in a stable, almost clear to clear gel.

Application examples 161 to 200:

Flexible hair setting gels

production:

phase 1 was weighed and stirred homogenized at a temperature in the range of 20 to 50 ° C. After about 3 Hours resulted in a milky dispersion. Triethanolamine was added while stirring. After about 2 hours, an (almost) homogeneous, highly viscous gel was formed educated. Then stirred Phase 2 slowly into Phase 1. The gel was at room temperature stirred for another hour. This resulted in a stable, almost clear to clear gel.

Application examples 201 to 240:

mousse

manufacturing

phase 1: Stir polymer in water. The polymer was stirred neutralized with triethanolamine and dissolved. Phase 2 in Phase 1 slow Stir. bottling and add propellant gas.

Application examples 241 to 280:

mousse

manufacturing

phase 1: Stir polymer in water. The polymer was stirred neutralized with triethanolamine and dissolved. Phase 2 in Phase 1 slow Stir. bottling and add propellant gas.

Application examples 281-320:

Shampoo (without salt additive)

production:

weigh out and stirring Solve phases 1 and 2 separately and mix. Slowly stir phase 2 into phase 1.

Claims (32)

Use of an ampholytic copolymer, the a molar excess at anionogenic / anionic groups versus cationogenic / cationic Has groups and that available is by radical copolymerization of a1) at least a compound having a radically polymerizable, α, β-ethylenic unsaturated Double bond and at least one anionogenic and / or anionic Group per molecule, a2) at least one compound with a free-radically polymerizable, α, β-ethylenic unsaturated Double bond and at least one cationogenic and / or cationic Group per molecule, b) at least one free-radically polymerizable crosslinking compound, the at least two α, β-ethylenic unsaturated Double bonds per molecule contains c) optionally in the presence of at least one polyether group and / or a radically polymerizable olefinically unsaturated double bond containing silicone compound, as a rheology modifier for hair cosmetic Compositions. Use according to claim 1, wherein the ampholytic Copolymer available by radical copolymerization by the method of precipitation polymerization. Use according to one of claims 1 or 2, wherein at least a part of the compounds a1) and a2) in the form of a monomer pair is used, wherein the molar ratio of anionogenic groups of Component a1) to cationogenic groups of component a2) about 1: 1 is. Use according to claim 3, wherein the proportion of the Monomer pair of the compounds used for the polymerization at least 1% by weight, preferably at least 2% by weight, in particular at least 3% by weight. Use according to one of claims 3 or 4, wherein the im Deficit used component a1) or a2) completely as Component of the monomer pair is used. Use according to any one of the preceding claims wherein the ampholytic copolymer has a molar excess of anionogenic / anionic groups over cationogenic / cationic groups of more than 2: 1, preferably at least 2.5: 1. Use according to one of the preceding claims, wherein the component a1) selected is under acrylic acid, methacrylic acid and mixtures, the acrylic acid and / or methacrylic acid contain. Use according to claim 7, wherein the component a1) methacrylic acid includes or consists of. Use according to one of the preceding claims, wherein the component a2) selected is among N-vinylimidazole compounds and mixtures which are at least contain an N-vinylimidazole compound. Use according to one of the preceding claims, wherein the component a1) acrylic acid and / or methacrylic acid comprises or consists thereof and the component a2) at least one N-vinylimidazole compound comprises or consists of. Use according to one of the preceding claims, of an ampholytic copolymer whose cationogenic groups were quaternized after the copolymerization with CHCl ₃ or dimethyl sulfate. Use according to one of the preceding claims, one ampholytic copolymer whose anionogenic groups after the copolymerization with a base, preferably a trialkanolamine, especially triethanolamine, were partially neutralized. Use according to one of the preceding claims, wherein the ampholytic copolymer additionally contains in copolymerized form at least one further monomer d) which is selected from α, β-ethylenically unsaturated amide group-containing compound of general formula I.

where one of the radicals R ¹ to R ^{3 is} a group of the formula CH ₂ = CR ⁴ - where R ⁴ = H or C ₁ -C ₄ -alkyl and the other radicals R ¹ to R ³ independently of one another are H, alkyl, Cycloalkyl, heterocycloalkyl, aryl or hetaryl, where R ¹ and R ² together with the amide group to which they are attached, may also be a lactam having 5 to 8 ring atoms, wherein R ² and R ³ together with the nitrogen atom, to that they are bonded, may also stand for a five- to seven-membered heterocycle, with the proviso that the sum of the carbon atoms of the radicals R ¹ , R ² and R ^{3 is} at most 8. Use according to one of the preceding claims, in which the ampholytic copolymer additionally comprises, in copolymerized form, at least one further monomer e) selected from compounds of the general formulas IIIa), IIIb), IIIc) and IIId)

in which the sequence of the alkylene oxide units is arbitrary, k and l independently of one another are an integer from 0 to 1000, the sum of k and 1 being at least 5, R ^{8 being} hydrogen or C ₁ -C ₄ -alkyl, preferably methyl, R ^{9 is} C ₈ -C ₃₀ -alkyl or C ₈ -C ₃₀ -alkenyl, and X is O or a group of formula NR ¹⁰ , wherein R ^{10 is} H, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl stands. Use according to one of the preceding claims, in which the ampholytic copolymer additionally comprises, in copolymerized form, at least one compound f) selected from compounds of the general formulas IIIa *), IIIb *), IIIc *) and IIId *)

wherein the sequence of the alkylene oxide units is arbitrary, k and l independently of one another are an integer from 0 to 1000, the sum of k and l being at least 5, R ^{8 being} hydrogen or C ₁ -C ₄ -alkyl, preferably methyl , R ^{9 * is} hydrogen, C ₁ -C ₈ alkyl or C ₃ -C ₈ alkenyl, and X is O or a group of formula NR ¹⁰ , wherein R ^{10 is} H, alkyl, alkenyl, cycloalkyl, heterocycloalkyl , Aryl or hetaryl. Use according to any one of the preceding claims, wherein the ampholytic copolymer additionally contains at least one copolymer according to one of the preceding claims which additionally comprises in copolymerized form at least one compound g) selected from esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₂ - C ₃₀ -diols, amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₂ -C ₃₀ -aminoalcohols having a primary or secondary amino group, esters of vinyl alcohol and allyl alcohol with C ₁ -C ₇ -monocarboxylic acids, of IIIc) and IIIc *) different therefrom polyether acrylates, vinyl aromatics, vinyl halides, vinylidene halides, C ₁ -C ₈ monoolefins, nonaromatic hydrocarbons having at least two conjugated double bonds and mixtures thereof. Use of an ampholytic copolymer according to one of the claims 1 to 16, available is by radical copolymerization of a1) at least a compound having a radically polymerizable, α, β-ethylenically unsaturated Double bond and at least one anionogenic and / or anionic Group per molecule, a2) at least one N-vinylimidazole compound, b) at least a radically polymerizable crosslinking compound which at least two α, β-ethylenic unsaturated Double bonds per molecule contains in which at least part of the compounds a1) and a2) in the form of a monomer pair is used, the molar ratio of anionogenic groups of component a1) to cationogenic groups of component a2) 1: 1. Use according to claim 17, wherein the ampholytic copolymer is obtainable by free-radical copolymerization of at least 2% by weight, based on the total weight of the monomers used for the polymerization, of at least one monomer pair of N-vinylimidazole and acrylic acid and / or methacrylic acid 70 wt .-% of methacrylic acid and / or acrylic acid, - 0.1 to 2 wt .-% of at least one crosslinker b), preferably ethylene glycol di (meth) acrylate and / or pentaerythritol triallyl ether, - 20 to 95 wt .-% vinylpyrrolidone and / or vinylcaprolactam, - 0 to 40 wt .-% of at least one further monomer selected from methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, C ₈ -C ₂₂ - (meth) acrylates, with C ₈ -C ₂₂ alkyl-terminated polyether (meth) acrylates and mixtures thereof. Use according to claim 17, wherein the ampholytic Copolymer available is by radical copolymerization of - at least 2 wt .-%, based on the total weight of the polymerization used Monomers, at least one monomer pair of N-vinylimidazole and acrylic acid and / or methacrylic acid, - 5 to 70% by weight of methacrylic acid and / or acrylic acid, - 0.1 to 2% by weight of at least one crosslinker b), preferably ethylene glycol di (meth) acrylate and / or pentaerythritol triallyl ether, 20 to 85% by weight of vinylpyrrolidone and / or vinylcaprolactam. Use according to claim 17, wherein the ampholytic copolymer is obtainable by free-radical copolymerization of at least 5% by weight, based on the total weight of the monomers used for the polymerization, of at least one monomer pair of N-vinylimidazole and acrylic acid and / or methacrylic acid 70 wt .-% methacrylic acid and / or acrylic acid, - 0.1 to 2 wt .-% of at least one crosslinker b), preferably ethylene glycol di (meth) acrylate and / or pentaerythritol triallyl ether, - 20 to 85 wt .-% vinylpyrrolidone and / or Vinylcaprolactam, - 5 to 40 wt .-% of at least one other monomer selected from C ₁ -C ₆ - (meth) acrylates, in particular methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and mixtures thereof. Use according to claim 17, wherein the ampholytic copolymer is obtainable by free-radical copolymerization of at least 5% by weight, based on the total weight of the monomers used for the polymerization, of at least one monomer pair of N-vinylimidazole and acrylic acid and / or methacrylic acid 70 wt .-% methacrylic acid and / or acrylic acid, - 0.1 to 2 wt .-% of at least one crosslinker b), preferably ethylene glycol di (meth) acrylate and / or pentaerythritol triallyl ether, - 20 to 85 wt .-% vinylpyrrolidone and / or Vinylcaprolactam, - 0.5 to 20 wt .-%, preferably 1 to 10 wt .-%, of at least one other monomer selected from C ₈ -C ₃₀ - (meth) acrylates having C ₈ -C ₃₀ alkyl groups terminated polyether (meth) acrylates and mixtures thereof, in particular under stearyl methacrylate, with C ₁₈ -C ₂₂ -alkyl-terminated polyethyleneglycol (meth) acrylates and mixtures thereof. Use of a silicone group-containing ampholytic Copolymer according to one of the claims 1 to 16, available is by radical copolymerization of a1) at least a compound having a radically polymerizable, α, β-ethylenic unsaturated Double bond and at least one anionogenic and / or anionic Group per molecule, a2) at least one compound with a free-radically polymerizable, α, β-ethylenic unsaturated Double bond and at least one cationogenic and / or cationic Group per molecule, b) at least one free-radically polymerizable crosslinking compound, the at least two α, β-ethylenic unsaturated Double bonds per molecule contains in Present at least one a polyether group and / or a free radical polymerizable olefinically unsaturated double bond-containing Silicone compound c). Use according to claim 22, wherein the silicone group-containing ampholytic copolymer is obtainable by free-radical copolymerization of at least 2% by weight, based on the total weight of the monomers used for the polymerization, of at least one monomer pair of N-vinylimidazole a2) and acrylic acid and / or Methacrylic acid a1), 5 to 70% by weight of methacrylic acid and / or acrylic acid a1), 0.1 to 2% by weight of at least one crosslinker b), preferably ethylene glycol di (meth) acrylate and / or pentaerythritol triallyl ether, 0, From 05 to 30% by weight, particularly preferably from 0.1 to 20% by weight, in particular from 0.1 to 15% by weight, of at least one silicone compound c), from 20 to 95% by weight of vinylpyrrolidone and / or vinylcaprolactam d), - 0.1 to 20 wt .-% of at least one compound e), which is preferably selected from C ₈ -C ₂₂ - (meth) acrylates, C ₈ -C ₂₂ -alkyl vinyl ether, with C ₈ -C ₂₂ - Alkyl-terminated polyether (meth) acrylates, with C ₈ -C ₂₂ alkyl-terminated All yl alcohol alkoxylates and mixtures thereof, - 5 to 40 wt .-% of at least one monomer f), which is preferably selected from C ₁ -C ₆ - (meth) acrylates, in particular methyl (meth) acrylate, ethyl (meth) acrylate, n- Butyl (meth) acrylate and mixtures thereof. Use according to claim 22, wherein the silicone group-containing ampholytic copolymer is available by radical copolymerization of - At least 5 wt .-%, based on the total weight of the monomers used for the polymerization, at least one monomer pair of N-vinylimidazole a2) and acrylic acid and / or methacrylic acid a1), - 5 to 70% by weight of methacrylic acid and / or acrylic acid a1), - 0.1 to 2% by weight of at least one crosslinker b), preferably ethylene glycol di (meth) acrylate and / or pentaerythritol triallyl ether, 0.05 to 30% by weight, especially preferably 0.1 to 20 wt .-%, in particular 0.1 to 15 wt .-%, at least one Silicone compound c), - 20 to 85% by weight of vinylpyrrolidone and / or vinylcaprolactam d). Use according to claim 22, wherein the silicone group-containing ampholytic copolymer is obtainable by radical copolymerization of - at least 5 wt .-%, based on the total weight of the monomers used for the polymerization, at least one monomer pair of N-vinylimidazole a2) and acrylic acid and / or Methacrylic acid a1), 5 to 70% by weight of methacrylic acid and / or acrylic acid a1), 0.1 to 2% by weight of at least one crosslinker b), preferably ethylene glycol di (meth) acrylate and / or pentaerythritol triallyl ether, From 05 to 30% by weight, particularly preferably from 0.1 to 20% by weight, in particular from 0.1 to 15% by weight, of at least one silicone compound c), From 20 to 85% by weight of vinylpyrrolidone and / or vinylcaprolactam d), 5 to 40% by weight of at least one further monomer f), which is preferably selected from C ₁ -C ₆ (meth) acrylates, in particular methyl ( meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and mixtures thereof. Use according to claim 22, wherein the silicone group-containing ampholytic copolymer is obtainable by radical copolymerization of - at least 5 wt .-%, based on the total weight of the monomers used for the polymerization, at least one monomer pair of N-vinylimidazole a2) and acrylic acid and / or Methacrylic acid a1), 5 to 70% by weight of methacrylic acid and / or acrylic acid a1), 0.1 to 2% by weight of at least one crosslinker b), preferably ethylene glycol di (meth) acrylate and / or pentaerythritol triallyl ether, 0, From 05 to 30% by weight, particularly preferably from 0.1 to 20% by weight, in particular from 0.1 to 15% by weight, of at least one silicone compound c), from 20 to 85% by weight of vinylpyrrolidone and / or vinylcaprolactam d), - 0.5 to 20 wt .-%, preferably 1 to 10 wt .-%, of at least one monomer e), which is selected from C ₈ -C ₂₂ - (meth) acrylates, C ₈ -C ₂₂ - Alkyl vinyl ethers, with C ₈ -C ₂₂ alkyl-terminated polyether (meth) acrylates, with C ₈ -C ₂₂ alkyl groups terminated allyl alcohol alkoxylates and mixtures thereof. Use according to one of the preceding claims Improvement of strengthening effect and / or improvement of wet combing the hair cosmetic composition. Use according to any one of the preceding claims in compositions with a pH in the range of 6 to 10, preferably 6.5 till 8. Hair cosmetic containing A) at least an ampholytic copolymer as in any of claims 1 to 26 defines B) optionally at least one different from A) Hair polymer C) at least one cosmetically acceptable carrier, and D) optionally at least one of A) and B) cosmetically acceptable active ingredient and / or excipient. Means according to claim 29 in the form of a mousse stabilizer, Hair mousses, hair gels, hair waxes, shampoos, hair sprays, hair mousse, Top fluids, perming or hot-oil treatments, especially in the form of a hair gel, hair wax or shampoo. Procedure for the cosmetic treatment of hair, in which one provides an agent as defined in any of claims 29 or 30 and applied to the hair to be treated. A method according to claim 31, wherein the hair after the application and optionally a time of action a washout subjects.