DE102005010108A1 - Aqueous preparation, useful in e.g. skin cleaning agent and protecting agent, comprises water soluble/dispersible copolymer (containing polymerized e.g. monomer with protonizable nitrogen) with cationogen groups and carriers - Google Patents

Abstract

Aqueous preparation (I) comprises: (a) at least a water solution or water dispersible copolymer (A) with cationogen groups comprising: (i) at least one monomer with at least one protonizable nitrogen atom; and (ii) at least one additional copolymerizable monomer; and (b) at least one cosmetically acceptable carrier, where the pH of (I) is 4-6.

Description

The The present invention relates to aqueous Preparations containing at least one water-soluble or water-dispersible Copolymer with cationogenic groups containing at least one monomer at least one protonatable nitrogen atom and at least one contains copolymerized copolymerizable monomer in copolymerized form, and at least one cosmetically acceptable carrier, wherein the pH of the aqueous Preparation has a value in the range of pH 4 to pH 6.

The Invention further relates to the use of these aqueous Preparations and process for their preparation.

cosmetic and pharmaceutically acceptable water-soluble polymers found in cosmetics and medicine multiple use. In soaps, creams and lotions for example, they usually serve as a formulating agent, e.g. as a thickener, foam stabilizer or water absorbent or also to lessen the irritating effects of other ingredients or to improve the dermal application of active ingredients.

Your The task in hair cosmetics is to improve the properties of the hair To influence hair. In pharmacy, for example, they serve as a coating agent or binder for solid dosage forms.

For the hair cosmetics For example, film-forming polymers are added as conditioners used to dry and wet comb, feel, shine and to improve appearance as well as antistatic hair To give properties. It is known, water-soluble polymers with cationic functionalities to use in hair conditioners that have a greater affinity to the structural conditionally negatively charged surface of the hair and have an electrostatic charge of the hair prevent. Structure and mode of action of various hair treatment polymers are in Cosmetic & Toiletries 103 (1988) 23. Commercially available cationic conditioner polymers are e.g. cationic hydroxyethylcellulose, cationic polymers based on N-vinylpyrrolidone, e.g. Copolymers of N-vinylpyrrolidone and quaternized N-vinylimidazole or copolymers of acrylamide and diallyldimethylammonium chloride.

to Consolidation of hairstyles, for example, vinyllactam homo- and copolymers and carboxylate group-containing polymers used. Requirements for hair setting resins are for example a strong consolidation in high humidity, Elasticity, Washability from the hair, compatibility in the formulation, as possible Slight stickiness of the formed film and a pleasant grip of the hair treated with it.

difficulties often prepares the delivery of products with a complex Property profile. There is thus a need for cosmetic preparations, which are capable of forming substantially smooth, tack-free films, the hair and the skin good sensory properties, as a pleasant grip, while giving a good Have conditioning effect or strengthening effect.

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 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.

The WO 00/27893 describes aqueous Polymer dispersions based on N-vinylcarboxamides and optionally comonomers, wherein in addition to 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.

The WO 03/92640 relates to cosmetic compositions which comprise at least one water-soluble Copolymer obtained by free radical copolymerization of acrylamide and / or methacrylamide and further water-soluble a, .beta.-ethylenically unsaturated, copolymerizable therewith Compounds, optionally in the presence of a water-soluble polymeric graft base, available are.

It there is still room for improvement in the state of the Technique known preparations for cosmetic and pharmaceutical Applications. This applies in particular to preparations containing Polymers, in addition to good film-forming properties also a Allow adjustment of the rheological properties of the products, so that the e.g. in the form of mousses, foams or gels can.

task It has been the object of the present invention, in particular for mousse and foam applications suitable cosmetic preparation with improved Festi tion properties to find, in addition to the generation elastic hairstyles with strong firming also at high humidity and is further characterized by good washability, preferably low stickiness and good grip of the treated hair distinguished.

These Task is solved through watery Preparations containing at least one water-soluble or water-dispersible Copolymer with cationogenic groups containing at least one monomer at least one protonatable nitrogen atom and at least one contains copolymerized monomer polymerized therewith in addition, and at least one cosmetically acceptable carrier, wherein the pH of the aqueous Preparations has a value in the range of pH 4 to pH 6.

• A) wenigstens ein wasserlösliches oder wasserdispergierbares Copolymer A) mit kationogenen Gruppen, das
• a) wenigstens ein Monomer mit wenigstens einem protonierbaren Stickstoffatom und
• b) wenigstens ein weiteres damit copolymerisierbares Monomer einpolymerisiert enthält, und
• B) wenigstens einen kosmetisch akzeptablen Träger, wobei der pH-Wert der wässrigen Zubereitung einen Wert im Bereich von pH 4 bis pH 6 aufweist.

The invention therefore relates to aqueous preparations containing

• A) at least one water-soluble or water-dispersible copolymer A) having cationogenic groups, the
• a) at least one monomer having at least one protonatable nitrogen atom and
• b) contains in copolymerized form at least one further copolymerizable monomer, and
• B) at least one cosmetically acceptable carrier, wherein the pH of the aqueous preparation has a value in the range of pH 4 to pH 6.

in the Within the scope of this invention, protonatable nitrogen atoms are those Nitrogen atoms by protonation, preferably with the help of acids, can be converted into the cationic charge state.

attitude the pH value

The pH value is a term introduced by Sørensen for the negative decadic logarithm of the concentration of hydrogen ions c (H ⁺ ) in mol / L in aqueous solution.

Of the pH of water (neutral pH range) is 7.0 at 22 ° C. The pH is temperature dependent and increases to higher Temperatures down. The determination of the pH takes place over the Expert known potentiometric measurements with pH electrodes (glass electrodes) or colorimetrically with indicator dyes (pH paper, litmus paper, pH strips). examples for Indicators are in Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, Vol. 17, p 645 to 655 called. For determining the pH value with electrodes can all commercially available pH measuring instruments used become.

The Determination of the pH of the preparations according to the invention is carried out according to a method known to those skilled in the known method at temperatures from 20 to 25 ° C.

According to the invention the pH of the aqueous Prepare a value in the range of pH 4 to pH 6. Prefers This pH is achieved by adding a Bronsted acid set. Preferred Bronsted acids are water-soluble organic and inorganic acids.

When possible organic acids be mono- and polyhydric, optionally substituted aliphatic and aromatic carboxylic acids, mono- and polyvalent, optionally substituted aliphatic and aromatic sulfonic acids or mono- and polyhydric, optionally substituted aliphatic and aromatic phosphonic acids.

preferred organic acids are hydroxycarboxylic acids, i.e. Derivatives of carboxylic acids, in which one or more H atoms replaced by Hyroxylgruppen are.

When examples for hydroxy be glycolic acid, Lactic acid, tartaric acid and citric acid.

Prefers Accordingly, the pH of the preparations is adjusted by addition of a hydroxy acid, being lactic acid is particularly preferred.

When preferred inorganic acids be phosphoric acid, phosphorous acid, Sulfuric acid, sulphurous Acid and hydrochloric acid called.

In a preferred embodiment indicates the pH of the aqueous Preparations have a value of at least 4.5, preferably 5, especially preferably 5.2, in particular 5.4 and a value of at most 6, preferably 5.8, in particular 5.6. According to the invention of pH preferably but also values of 5.1, 5.3, 5.5, 5.7 or 5.9 exhibit.

The Adjustment of the pH of the preparations is carried out according to the invention preferably at a time when the preparation of the component A, ie the polymerization, is completed.

The Preparation of component A is considered completed when the content the preparation of unreacted monomers less than 5, preferably less than 2, more preferably less than 0.1, especially preferably less than 0.05, based on the total mass of component A, is.

According to the invention, the Adjust the pH of the preparations at any time after completed production of component A done.

In addition to inventive setting the pH of the aqueous Preparation after completion of the preparation of component A also the pH values of the monomer solutions before or during the preparation of the component A to values in the range of pH 6 to pH 7 can be adjusted.

It Accordingly, it may also be advantageous to predetermine the pH values of the monomer feeds or while to adjust the polymerization to a value in the range of pH 6 to pH 7 and the pH of the aqueous Preparation after completion of the polymerization according to the invention to a Adjust value of pH 4 to pH 6.

One Another object of the invention is therefore a method for Preparation of the preparation according to the invention, characterized in that the adjustment of the pH value to a Value in the range of 4 to 6 after completed production of Component A) is made.

In a particularly preferred embodiment the pH of the preparation is then adjusted when the preparation already in its application form, for example as gel, foam, Spray, ointment, cream, emulsion, suspension, lotion, milk or paste preparations.

According to the invention that is, the adjustment of the pH preferably on cosmetically acceptable gel, Foam, spray, ointment, cream, emulsion, suspension, lotion, Milk or paste preparations.

In the context of the present invention, the term alkyl includes straight-chain and branched alkyl groups. Short-chain alkyl groups which are suitable according to the invention are, for example, 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, for example, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl ), n-tridecyl (s), n-tetradecyl (s), n-pentadecyl (s), n-hexadecyl (s), n-heptadecyl (s), n-octadecyl (s), n-nonadecyl (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 preparations according to the invention can be formulated under normal conditions advantageously as foam.

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.

Under water-dispersible monomers and polymers are monomers and Polymers understood by applying shear forces, for example by stirring, decompose into dispersible particles.

Hydrophilic Monomers are preferably water-soluble or at least water-dispersible.

to Preparation of Copolymers A) are monomers having at least one protonatable nitrogen atom, in particular N-vinylimidazole and / or its derivatives and amides of α, β-ethylenic unsaturated Mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group, used. In a preferred embodiment of the invention, the copolymer contains A) therefore at least one monomer having at least one protonatable Nitrogen atom selected of N-vinylimidazole and / or a derivative thereof and amides of α, β-ethylenically unsaturated Mono- and dicarboxylic acids with diamines, which at least one primary or secondary amino group have, in non-quaternized form.

Under "quaternized Form "is in this Context of the cationic charge state of the nitrogen atom understood, for example, by alkylation but not by Protonation is generated.

It is possible, too, for the preparation of the copolymers A) further, of uncharged N-vinylimidazole (derivatives) various charged N-vinylimidazole (derivatives) use. Furthermore Is it possible, of N-vinylimidazole (derivatives) various, other cationogenic and / or cationic monomers (i.e., other monomers in non, partial or completely protonated and / or quaternized form).

Prefers contain the copolymers A) no monomers with anionogenic and / or copolymerized anionic groups.

Monomer a)

The in the preparations according to the invention used copolymer A) contains preferably 0.5 to 40% by weight, particularly preferably 1 to 30% by weight, most preferably 3 to 20 wt .-%, and in particular 3 to 15 wt .-%, based on the total weight of the polymerization used monomers, at least one monomer a) copolymerized. In a special embodiment is the proportion of monomers a) at most 25% by weight.

The in the preparations according to the invention used copolymer A) contains at least one monomer having at least one protonatable nitrogen atom in copolymerized form.

einpolymerisiert, worin R⁷ bis R⁹ unabhängig voneinander für Wasserstoff, C₁-C₄-Alkyl oder Phenyl stehen.Preferred monomers having at least one protonatable nitrogen atom are N-vinylimidazole compounds of the general formula (I). The copolymer A) therefore preferably contains as monomer a) at least one N-vinylimidazole compound of the general formula (I)

polymerized in which R ⁷ to R ^{9 are} independently hydrogen, C ₁ -C ₄ alkyl or phenyl.

Me

= Methyl

Ph

= Phenyl

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

me

= Methyl

Ph

= Phenyl

All Particularly preferred monomer a) is 1-vinylimidazole (N-vinylimidazole).

Wobei
R¹⁴ und R¹⁵ unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus Wasserstoff, C₁-C₈ linear- oder verzweigtkettige Alkyl, Methoxy, Ethoxy, 2-Hydroxyethoxy, 2-Methoxyethoxy und 2-Ethoxyethyl. Bevorzugt sind Wasserstoff, Methyl oder Ethyl,
R¹⁷ ist Wasserstoff oder Methyl,
R¹⁸ ist Alkylen oder Hydroxyalkylen mit 1 bis 24 C-Atomen, optional substituiert durch Alkyl, bevorzugt C₂H₄, C₃H₆, C₄H₈, CH₂-CH(OH)-CH₂,
g ist 0 oder 1,
Z ist Stickstoff für g = 1 oder Sauerstoff für g = 0,
R²⁵ bzw. R²⁶ sind jeweils und unabhängig voneinander ausgewählt aus der Gruppe bestehend aus Wasserstoff, C₁-C₄₀ linear- oder verzweigtkettige Alkyl, Formyl, C₁-C₁₀ linear- oder verzweigtkettige Acyl, N,N-Dimethylaminoethyl, 2-Hydroxyethyl, 2-Methoxyethyl, 2-Ethoxyethyl, Hydroxypropyl, Methoxypropyl, Ethoxypropyl oder Benzyl. Bevorzugt sind Wasserstoff, Methyl, Ethyl, n-Propyl und Benzyl.Furthermore, protonatable monomers a) Aminoalkylacrylate- and methacrylates and Aminoalkylacryl- and -methacrylamide of the general formula (II) can be used.

In which
R ¹⁴ and R ^{15 are} independently selected from the group consisting of hydrogen, C ₁ -C ₈ linear or branched chain alkyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl. Preference is given to hydrogen, methyl or ethyl,
R ¹⁷ is hydrogen or methyl,
R ¹⁸ is alkylene or hydroxyalkylene having 1 to 24 C atoms, optionally substituted by alkyl, preferably C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , CH ₂ -CH (OH) -CH ₂ ,
g is 0 or 1,
Z is nitrogen for g = 1 or oxygen for g = 0,
R ²⁵ and R ²⁶ are each and independently selected from the group consisting of hydrogen, C ₁ -C ₄₀ linear or branched chain alkyl, formyl, C ₁ -C ₁₀ linear or branched chain acyl, N, N-dimethylaminoethyl, 2 -Hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, hydroxypropyl, methoxypropyl, ethoxypropyl or benzyl. Preference is given to hydrogen, methyl, ethyl, n-propyl and benzyl.

The amides may be unsubstituted, N-alkyl or N-alkylamino monosubstituted or N, N-dialkyl substituted or N, N-dialkylamino-disubstituted wherein the alkyl or alkylamino groups are C ₁ -C ₄₀ linear, C ₃ -C ₄₀ branched chain, or C ₃ -C ₄₀ carbocyclic units are derived.

preferred protonatable comonomers a) of the formula (II) are N, N-dimethylaminomethyl (meth) acrylate, N, N-diethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, N, N-dimethylaminohexyl (meth) acrylate, N, N-dimethylaminooctyl (meth) acrylate, N, N-Dimethylaminododecyl (meth) acrylate.

Farther are preferably 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, N- [4- (dimethylamino) cyclohexyl] methacrylamide, N- [8- (dimethylamino) octyl] methacrylamide, N- [12- (dimethylamino) dodecyl] methacrylamide, N- [3- (diethylamino) propyl] methacrylamide and N- [3- (diethylamino) propyl] acrylamide.

All particularly preferred are N, N-dimethylaminoethyl methacrylate, N- [3- (dimethylamino) propyl] methacrylamide, N-methylaminoethyl methacrylate, N- [3- (methylamino) propyl] methacrylamide, aminoethyl methacrylate and N- [3-aminopropyl] methacrylamide.

Especially N- [3- (dimethylamino) propyl] methacrylamide is preferred.

wobei R²⁷ Wasserstoff oder C₁ bis C₂₄ Alkyl bedeutet. Besonders bevorzugt sind N,N-Diallylamin und N,N-Diallyl-N-Methylamin, insbesondere N,N-Diallyl-N-Methylamin.Furthermore, the protonatable monomer a) may also be selected from diallylamines of the general formula (III)

where R ^{27 is} hydrogen or C ₁ to C ₂₄ alkyl. Particular preference is given to N, N-diallylamine and N, N-diallyl-N-methylamine, in particular N, N-diallyl-N-methylamine.

Furthermore, the monomer a) may be selected from compounds such as 1,3-divinylimidazolide-2-one or N-disubstituted vinylamines of the general formula (IV): (R ^2a ) ₂ N- (CH ₂ ) _n -CR ¹⁵ = CHR ¹⁴ (IV) in which
R ¹⁴ and R ^{15 are} independently selected from the group consisting of hydrogen, C ₁ -C ₈ linear or branched chain alkyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl. Preference is given to hydrogen, methyl or ethyl,
n is 0, 1 or 2, and
R ^{28 are} selected from the group consisting of hydrogen C ₁ -C ₄₀ linear or branched chain alkyl radicals, formyl, C ₁ -C ₁₀ linear or branched chain acyl, N, N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxy ethyl, 2-ethoxyethyl, hydroxypropyl, methoxypropyl, ethoxypropyl or benzyl, preferably methyl, ethyl, n-propyl and benzyl. In this case, when n = 0, it is not the case that both radicals R ^{28 are} simultaneously hydrogen.

Monomer b)

The in the preparations according to the invention used copolymer A) contains preferably 20 to 99.5% by weight, particularly preferably 20 to 70% by weight, in particular 30 to 70 wt .-%, based on the total weight of monomers used for the polymerization, at least one other, copolymerizable monomer b) copolymerized. In a special embodiment is the proportion of monomers b) at least 50 wt .-%.

Monomer b1)

The copolymer A) additionally contains, in copolymerized form, at least one N-vinyllactam b1). Suitable monomers b1) are unsubstituted N-vinyllactams and N-vinyllactam derivatives which contain, for example, one or more C ₁ -C ₆ -alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert. Butyl, etc. may have. These include, for example, 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., and mixtures thereof.

Prefers are N-vinylpyrrolidone, N-vinylcaprolactam or mixtures thereof used.

In a special embodiment contain the preparations according to the invention as component A) a copolymer which consists only of monomer units of The aforementioned monomers a) and b1).

Prefers these copolymers A) then contain 0.5 to 40 wt .-%, especially preferably 1 to 30 wt .-%, in particular 3 to 20 wt .-% at least of a monomer a) copolymerized. Accordingly, these contain Copolymers A) preferably 60 to 99.5 wt .-%, more preferably 70 to 99 wt .-%, in particular 80 to 97 wt .-% of at least one Monomers b) copolymerized.

In a preferred embodiment contain the preparations according to the invention as component A) a copolymer which in addition to the aforementioned Monomers a) and b1) at least one other, different therefrom Monomer b2) contains polymerized.

Monomer b2)

The Copolymers A) can additionally at least one of the components a) and b1) different, so copolymerizable nonionic water-soluble monomer b2) contain.

Preferably is the proportion of monomers b2) 0 to 50 wt .-%, particularly preferably 5 to 50 wt .-%, in particular 10 to 40 wt .-%, based on the Total weight of the monomers used for the polymerization.

• b2.1) N-Vinylamiden gesättigter C₁-C₈-Monocarbonsäuren,
• b2.2) primären Amiden α,β-ethylenisch ungesättigter Monocarbonsäuren und deren N-Alkyl- und N,N-Dialkylderivaten, die zusätzlich zu dem Carbonyl-Kohlenstoffatom der Amidgruppe höchstens 8 weitere Kohlenstoffatome aufweisen,
• b2.3) Estern α,β-ethylenisch ungesättigter Mono- und Dicarbonsäuren mit Diolen,
• b2.4) Amiden α,β-ethylenisch ungesättigter Mono- und Dicarbonsäuren mit Aminoalkoholen, die eine primäre oder sekundäre Aminogruppe aufweisen,
• b2.5) Polyetheracrylaten

und Mischungen davon.Preferably, component b2) is selected under

• b2.1) N-vinylamides of saturated C ₁ -C ₈ -monocarboxylic acids,
• b2.2) primary amides of α, β-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives which, in addition to the carbonyl carbon atom of the amide group, have at most 8 further carbon atoms,
• b2.3) esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with diols,
• b2.4) amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols which have a primary or secondary amino group,
• b2.5) polyether acrylates

and mixtures thereof.

When Monomers b2.1) 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 and N-vinylbutyramide.

Suitable monomers b2.2) are, for example, acrylamide, methacrylamide, N-Me ethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- (n-butyl) (meth) acrylamide, N- (tert-butyl) (meth) acrylamide, N, N Dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, piperidinyl (meth) acrylamide and morpholinyl (meth) acrylamide, with (meth) acrylic acid amide being preferred and methacrylamide being particularly preferred.

suitable Monomers b2.3) are, for example, 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 Monomers b2.4) are, for example, 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 Monomers b2.5) are polyether acrylates, among which in the context of this General Invention Esters α, β-ethylenic unsaturated Mono- and dicarboxylic acids be understood with polyetherols. Suitable polyetherols are linear or branched, terminal Hydroxyl-containing substances containing ether bonds. In general, they have a molecular weight in the range of about 150 to 20 000 on. Suitable polyetherols are polyalkylene glycols, such as polyethylene glycols, polypropylene glycols, polytetrahydrofurans and alkylene oxide copolymers. Suitable alkylene oxides for the preparation of alkylene oxide copolymers are e.g. Ethylene oxide, propylene oxide, Epichlorohydrin, 1,2- and 2,3-butylene oxide. The alkylene oxide copolymers can the alkylene oxide randomly distributed or copolymerized in the form of blocks contain. Preferred are ethylene oxide / propylene oxide copolymers.

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,
R⁴ für Wasserstoff, C₁-C₃₀-Alkyl oder C₅-C₈-Cycloalkyl steht,
R⁵ für Wasserstoff oder C₁-C₈-Alkyl steht,
Y² für O oder NR⁶ steht, wobei R⁶ für Wasserstoff, C₁-C₃₀-Alkyl oder C₅-C₈-Cycloalkyl steht,Preferred as component b2.5) are polyether acrylates of the general formula V.

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 ^{4 is} hydrogen, C ₁ -C ₃₀ -alkyl or C ₅ -C ₈ -cycloalkyl,
R ^{5 is} hydrogen or C ₁ -C ₈ -alkyl,
Y ^{2 is} O or NR ⁶ , where R ^{6 is} hydrogen, C ₁ -C ₃₀ -alkyl or C ₅ -C ₈ -cycloalkyl,

Prefers k stands for an integer from 1 to 500, especially 3 to 250. Preferred l stands for an integer from 0 to 100.

R ⁵ 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 ⁴ in formula IV is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, octyl, 2-ethylhexyl, decyl, lauryl, palmityl or stearyl ,

Preferably, Y ² in formula IV is O or NH.

Suitable polyether acrylates b2.5) are, for example, the polycondensation products of the abovementioned 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 molecule such as water or a short-chain alcohol R ⁴ -OH. The alkylene oxides can be used individually, alternately in succession or as a mixture. The polyether acrylates c) can be used alone or in mixtures for the preparation of the invention set polymers are used.

Suitable polyether acrylates b2.5) 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.

The aforementioned monomers b2) each used individually or in the form of any mixtures become.

In a preferred embodiment of the invention, the preparations contain, as component A, a terpolymer, the 5 to 15 wt .-% of monomer a), 30 to 70 wt .-% of monomer b1) and 20 to 35 wt .-% of monomer b2) in copolymerized form, with the proviso the sum of the amounts of monomers a) to b2) is 100% by weight.

Monomer b3)

The Copolymers A) can additionally at least one of a), b1) and b2) different water-soluble Monomer b3) in copolymerized form, which is selected under α, β-ethylenic unsaturated water-soluble Compounds with cationic hydrophilic groups.

Preferably is the proportion of monomer b3) 0 to 30 wt .-%, particularly preferably 0 to 20 wt .-%, in particular 0 to 10 wt .-%, based on the total weight the monomers used for the polymerization.

Prefers are the cationic groups of component b3) nitrogen-containing groups such as quaternary ammonium groups.

These charged cationic groups can be generated from the amine nitrogens by quaternization, for example with the alkylating agents mentioned above in component a). Examples of alkylating agents are C ₁ -C ₄ -alkyl halides or sulfates, such as ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. Quaternization can generally be done both before and after the polymerization.

suitable Monomers b3) are those obtainable by quaternization of component a) Links. examples for such charged monomers b3) are quaternized N-vinylimidazoles, in particular 3-methyl-1-vinylimidazolium chloride and methosulfate.

Suitable compounds b3) are furthermore the quaternization products of the esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols. Preferred amino alcohols are C ₂ -C ₁₂ amino alcohols which are C ₁ -C ₈ -dialkylated on the amine nitrogen. Suitable acid components of these esters are, 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 b3) are the quaternization products of N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate and N, N-dimethylaminocyclohexyl (meth) acrylate.

suitable Monomers b3) are furthermore the quaternization products of the amides the aforementioned α, β-ethylenic unsaturated Mono- and dicarboxylic acids with diamines containing at least one primary or secondary amino group exhibit. Preference is given to diamines, one tertiary and one primary or secondary Have amino group.

Suitable as monomers b3) are e.g. the quaternization products of 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 b3) are furthermore the quaternization products of N, N-diallylamines and N, N-diallyl-N-alkylamines. Alkyl is preferably C ₁ -C ₂₄ -alkyl. Preference is given to N, N-diallyl-N, N-dimethylammonium compounds, such as, for example, the chlorides and bromides. These include in particular N, N-diallyl-N, N-dimethylammonium chloride (DADMAC).

suitable Monomers b3) are also the quaternization of various vinyl- and allyl-substituted nitrogen heterocycles, such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine.

The aforementioned monomers b3) each used individually or in the form of any mixtures become.

In a preferred embodiment According to the invention, the preparations contain, as component A, a polymer, the 5 to 15 wt .-% of monomer a), 30 to 70 wt .-% of monomer b1), 20 to 35 wt .-% of monomer b2) and 0 to 10 wt .-% of monomer b3) copolymerized contains with the proviso the sum of the amounts of monomers a) to b3) is 100% by weight.

Monomer c)

The copolymers A) may additionally contain, in copolymerized form, at least one monomer c) different from the monomers a) to b3). The additional monomers c) are preferably selected from esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₁ -C ₃₀ -alkanols, N-alkyl and N, N-dialkylamides of α, β-ethylenically unsaturated monocarboxylic acids, in addition to the carbonyl carbon atom of the amide group having at least 9 other carbon atoms, esters of vinyl alcohol and allyl alcohol with C ₁ -C ₃₀ monocarboxylic acids, vinyl ethers, vinyl aromatics, vinyl halides, vinylidene halides, C ₁ -C ₈ monoolefins, non-aromatic hydrocarbons having at least two conjugated double bonds and mixtures thereof.

Preferably is the proportion of monomers c) 0 to 15 wt .-%, particularly preferably 0.1 to 10 wt .-%, based on the total weight of the polymerization used monomers.

Suitable additional monomers c) are methyl (meth) acrylate, methyl methacrylate, ethyl (meth) acrylate, ethyl methacrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butyl methacrylate, 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 , Preferred monomers c) are the esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₁ -C ₄ -alkanols.

suitable additional Monomers c) are furthermore N- (n-octyl) (meth) acrylamide, N- (1,1,3,3-tetramethylbutyl) (meth) acrylamide, N-ethylhexyl (meth) acrylamide, N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide, N- (n-undecyl) (meth) acrylamide, N-tridecyl (meth) acrylamide, N-myristyl (meth) acrylamide, N-pentadecyl (meth) acrylamide, N-palmityl (meth) acrylamide, N-heptadecyl (meth) acrylamide, N-nonadecyl (meth) acrylamide, N-arrachinyl (meth) acrylamide, N-behenyl (meth) acrylamide, N-lignocerenyl (meth) acrylamide, N-cerotinyl (meth) acrylamide, N-melissinyl (meth) acrylamide, N-palmitoleinyl (meth) acrylamide, N-oleyl (meth) acrylamide, N-linolyl (meth) acrylamide, N-linolenyl (meth) acrylamide, N-stearyl (meth) acrylamide, N-lauryl (meth) acrylamide.

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

suitable additional Monomers c) 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 c) can used individually or in the form of any mixtures.

Crosslinker d)

The Copolymers A) can if desired at least one crosslinker, i. a connection with two or more as two ethylenically unsaturated, contain copolymerized non-conjugated double bonds.

Preferably are crosslinkers in an amount of 0.01 to 3 wt .-%, especially preferably 0.1 to 2 wt .-%, based on the total weight of the Polymerization used monomers used.

suitable Crosslinkers d) 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 trimethylolpropane, 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.

Further suitable crosslinkers d) 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 d) 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 d) 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, e.g. Divinylbenzene, divinyltoluene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene, Trivinylcyclohexane or polybutadienes with molecular weights of 200 to 20,000.

When Crosslinkers d) 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 isophoronediamine. 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 triallylmonoalkylammonium salts, e.g. Triallylmethylammonium chloride or Methyl sulfate, as crosslinker d) suitable.

Also suitable are N-vinyl compounds of urea derivatives, at least divalent amides, cyanurates or urethanes, for example of urea, ethyleneurea, propyleneurea or tartaric acid rediamide, for example N, N'-divinylethyleneurea or N, N'-divinylpropyleneurea.

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

Of course you can too Mixtures of the aforementioned compounds d) can be used. Preferably become water-soluble Crosslinker d) used.

Especially Crosslinkers d) preferably used are, for example, methylenebisacrylamide, Triallylamine and triallylalkylammonium salts, divinylimidazole, pentaerythritol triallyl ether, N, N'-Divinylethylenharnstoff, Reaction products of polyhydric alcohols with acrylic acid or methacrylic acid, methacrylic and acrylic acid esters of polyalkylene oxides or polyhydric alcohols with ethylene oxide and / or propylene oxide and / or epichlorohydrin.

All particularly preferred crosslinkers d) are pentaerythritol triallyl ether, Methylenebisacrylamide, N, N'-divinylethylene, Triallylamine and triallylmonoalkylammonium salts and acrylic esters of glycol, butanediol, trimethylolpropane or glycerol or acrylic acid ester of glycol reacted with ethylene oxide and / or epichlorohydrin, Butanediol, trimethylolpropane or glycerol.

• a) N-Vinylimidazol und/oder ein Derivat davon und
• b1) wenigstens ein N-Vinyllactam
• b2) gegebenfalls wenigstens ein nichtionisches wasserlösliches Monomer ausgewählt aus
• b2.1) N-Vinylamiden gesättigter C₁-C₈-Monocarbonsäuren,
• b2.2) primären Amiden α,β-ethylenisch ungesättigter Monocarbonsäuren und deren N-Alkyl- und N,N-Dialkylderivaten, die zusätzlich zu dem Carbonyl-Kohlenstoffatom der Amidgruppe höchstens 8 weitere Kohlenstoffatome aufweisen,
• b3) gegebenenfalls wenigstens ein Monomer ausgewählt aus den Quaternisierungsprodukten des N-Vinylimidazols und Dimethylaminopropylmethacrylsäureamids.

einpolymerisiert enthält, wobei der pH-Wert der wässrigen Zubereitung einen Wert im Bereich von pH 4 bis pH 6 aufweist.Preference is given to preparations in which the copolymer A)

• a) N-vinylimidazole and / or a derivative thereof and
• b1) at least one N-vinyllactam
• b2) optionally at least one nonionic water-soluble monomer selected from
• b2.1) N-vinylamides of saturated C ₁ -C ₈ -monocarboxylic acids,
• b2.2) primary amides of α, β-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives which, in addition to the carbonyl carbon atom of the amide group, have at most 8 further carbon atoms,
• b3) optionally at least one monomer selected from the quaternization of N-vinylimidazole and Dimethylaminopropylmethacrylsäureamids.

polymerized, wherein the pH of the aqueous preparation has a value in the range of pH 4 to pH 6.

• a) 0.5 bis 40 Gew.-% N-Vinylimidazol und/oder eines Derivats davon,
• b1) 20 bis 99.5 Gew.-% wenigstens eines N-Vinyllactams,
• b2) 0 bis 50 Gew.-% wenigstens eines von den Komponenten a) und b1) verschiedenen, damit copolymerisierbaren nichtionischen wasserlöslichen Monomers, und
• b3) 0 bis 30 Gew.-% wenigstens eines Monomers, das ausgewählt unter α,β-ethylenisch ungesättigten wasserlöslichen Verbindungen mit kationischen hydrophilen Gruppen, mit der Maßgabe, dass die Summe der Mengen der Komponenten a) bis b3) 100 Gew.-% ergibt,

einpolymerisiert enthält, wobei der pH-Wert der wässrigen Zubereitung einen Wert im Bereich von pH 4 bis pH 6 aufweist.Preference is furthermore given to preparations in which the copolymer A)

• a) 0.5 to 40% by weight of N-vinylimidazole and / or a derivative thereof,
• b1) from 20 to 99.5% by weight of at least one N-vinyllactam,
• b2) 0 to 50% by weight of at least one nonionic water-soluble monomer copolymerizable with components a) and b1) thereof, and
• b3) 0 to 30% by weight of at least one monomer selected from α, β-ethylenically unsaturated water-soluble compounds having cationic hydrophilic groups, with the proviso that the sum of the amounts of components a) to b3) is 100% by weight reveals

polymerized, wherein the pH of the aqueous preparation has a value in the range of pH 4 to pH 6.

• a) 1 bis 30 Gew.-% N-Vinylimidazol und/oder eines Derivats davon,
• b1) 20 bis 70 Gew.-% wenigstens eines N-Vinyllactams,
• b2) 5 bis 50 Gew.-% wenigstens eines von den Komponenten a) und b1) verschiedenen, damit copolymerisierbaren nichtionischen wasserlöslichen Monomers, und
• b3) 0 bis 20 Gew.-% wenigstens eines Monomers, das ausgewählt unter α,β-ethylenisch ungesättigten wasserlöslichen Verbindungen mit kationischen hydrophilen Gruppen, mit der Maßgabe, dass die Summe der Mengen der Komponenten a) bis b3) 100 Gew.-% ergibt,

einpolymerisiert enthält, wobei der pH-Wert der wässrigen Zubereitung einen Wert im Bereich von pH 4 bis pH 6 aufweist.Further preferred are preparations wherein the copolymer A)

• a) 1 to 30% by weight of N-vinylimidazole and / or a derivative thereof,
• b1) from 20 to 70% by weight of at least one N-vinyllactam,
• b2) from 5 to 50% by weight of at least one non-ionic, water-soluble monomer copolymerizable with components a) and b1), and
• b3) 0 to 20% by weight of at least one monomer selected from α, β-ethylenically unsaturated water-soluble compounds having cationic hydrophilic groups, with the proviso that the sum of the amounts of components a) to b3) is 100% by weight reveals

polymerized, wherein the pH of the aqueous preparation has a value in the range of pH 4 to pH 6.

• a) 3 bis 20 Gew.-% N-Vinylimidazol und/oder eines Derivats davon,
• b1) 30 bis 70 Gew.-% wenigstens eines N-Vinyllactams,
• b2) 10 bis 40 Gew.-% wenigstens eines von den Komponenten a) und b1) verschiedenen, damit copolymerisierbaren nichtionischen wasserlöslichen Monomers, und
• b3) 0 bis 10 Gew.-% wenigstens eines Monomers, das ausgewählt unter α,β-ethylenisch ungesättigten wasserlöslichen Verbindungen mit kationischen hydrophilen Gruppen, mit der Maßgabe, dass die Summe der Mengen der Komponenten a) bis b3) 100 Gew.-% ergibt,

einpolymerisiert enthält, wobei der pH-Wert der wässrigen Zubereitung einen Wert im Bereich von pH 4 bis pH 6 aufweist.Further preferred are preparations wherein the copolymer A)

• a) 3 to 20% by weight of N-vinylimidazole and / or a derivative thereof,
• b1) 30 to 70% by weight of at least one N-vinyllactam,
• b2) 10 to 40 wt .-% of at least one of the components a) and b1) different, so copolyme risierbaren nonionic water-soluble monomer, and
• b3) 0 to 10% by weight of at least one monomer selected from α, β-ethylenically unsaturated water-soluble compounds having cationic hydrophilic groups, with the proviso that the sum of the amounts of components a) to b3) is 100% by weight reveals

polymerized, wherein the pH of the aqueous preparation has a value in the range of pH 4 to pH 6.

In a preferred embodiment the copolymer A) consists only of repeating units which are of the aforementioned monomers a), b1) and optionally b2) and / or b3).

• a) 3 bis 15 Gew.-% N-Vinylimidazol
• b) 30 bis 70 Gew.-% N-Vinylpyrrolidon
• c) 20 bis 35 Gew.-% Methacrylsäureamid
• d) 0 bis 10 Gew.-% quaterniertes N-Vinylimidazol

mit der Maßgabe, dass die Summe der Mengen der Komponenten a) bis b3) 100 Gew.-% ergibt, einpolymerisiert.In a particularly preferred preparation, copolymer A) contains

• a) 3 to 15 wt .-% N-vinylimidazole
• b) 30 to 70 wt .-% N-vinylpyrrolidone
• c) 20 to 35 wt .-% methacrylamide
• d) 0 to 10 wt .-% quaternized N-vinylimidazole

with the proviso that the sum of the amounts of components a) to b3) gives 100 wt .-%, copolymerized.

The Preparation of the copolymers A) takes place according to customary methods known to the person skilled in the art Method, e.g. by solution, precipitation, Suspension or emulsion polymerization. Preference is given to the preparation through solution or precipitation polymerization.

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 ether the dihydric alcohols, diethylene glycol, triethylene glycol, polyethylene glycols with number average molecular weights up 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.

at the use of water as a solvent component Desalted water is preferably used.

The precipitation For example, in an ester, such as ethyl acetate or butyl acetate as a solvent. The resulting polymer particles precipitate out of the reaction solution and can by usual Methods, such as filtration by means of vacuum, are isolated. at the precipitation polymerization are usually polymers with higher molecular weights than in the solution polymerization receive.

The Polymerization temperatures are preferably in the range from about 30 to 120 ° C, more preferably 40 to 100 ° C. 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 A), the monomers with the aid be polymerized by radical initiators.

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, azobisisobutyronitrile, 2,2 '' - azobis (2-amidinopropane) hydrochloride (V50 from Wako Pure Chemicals Industries, Ltd.), or 2,2'-azobis (2-methylbutyronitrile). Also suitable are initiator mixtures or redox initiator systems, such as ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinate, H ₂ O ₂ / Cu ^I.

to Adjustment of the molecular weight, the polymerization in the presence at least one controller done. As regulators, the usual, known in the art Compounds, such as e.g. Sulfur compounds, e.g. mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid or dodecylmercaptan, as well Tribromochloromethane or other compounds that regulate the Molecular weight of the polymers obtained are used become. A preferred regulator is cysteine.

to Achieving as possible pure polymers with low residual monomer content can be attached to the Polymerization (main polymerization), a post-polymerization step connect. The postpolymerization may be in the presence of one or the other Initiator system as the main polymerization take place. Preferably the postpolymerization takes place at least at the same, optionally at a higher Temperature as the main polymerization. If desired, the reaction mixture following the polymerization or between the first and the second polymerization step of stripping with water vapor or a steam distillation.

According to the invention, the Adjustment of the pH of the aqueous Preparation to a value ranging from pH 4 to pH 6 before or after steam stripping or steam distillation.

Becomes in the preparation of the polymers, an organic solvent used, this can by conventional, known in the art Method, e.g. by distillation at reduced pressure.

The Polymerization is preferably carried out at a pH in the range from 6 to 9, more preferably from 6 to 7.5. The attitude the pH is carried out by adding a suitable acid or by adding a suitable base.

The obtained liquid Polymer compositions can by various drying methods, e.g. Spray drying, Fluidized spray drying, drum drying or freeze drying in Be transferred powder form. Preference is given to spray drying used. The resulting polymer dry powders can be advantageously by dissolving or redispersing in water again in an aqueous solution or dispersion. Powdered copolymers have the advantage of better storability, a simpler of transportation and usually show a lower propensity for microbial attack.

One Another object of the invention is the liquid polymer compositions after completion of the polymerization and before drying and / or transfer into to adjust the powder form to a pH in the range of pH 4 to pH 6.

Cosmetically acceptable carrier B)

• i) Wasser,
• ii) wassermischbaren organischen Lösungsmitteln, vorzugsweise C₂-C₄-Alkanolen, insbesondere Ethanol,
• iii) Ölen, Fetten, Wachsen,
• iv) von iii) verschiedenen Estern von C₆-C₃₀-Monocarbonsäuren mit ein-, zwei- oder dreiwertigen Alkoholen,
• v) gesättigten acyclischen und cyclischen Kohlenwasserstoffen,
• vi) Fettsäuren,
• vii) Fettalkoholen,
• viii) Treibgasen,

und Mischungen davon.The preparations according to the invention have a cosmetically and / or pharmaceutically acceptable carrier B) which is selected from

• i) water,
• ii) water-miscible organic solvents, preferably C ₂ -C ₄ -alkanols, in particular ethanol,
• iii) oils, fats, waxes,
• iv) of iii) various esters of C ₆ -C ₃₀ monocarboxylic acids with mono-, di- or trihydric alcohols,
• v) saturated acyclic and cyclic hydrocarbons,
• vi) fatty acids,
• vii) fatty alcohols,
• viii) propellants,

and mixtures thereof.

The preparations according to the invention have, for example, an oil or fat component B) which is selected from. Low polarity hydrocarbons such as mineral oils; linear saturated hydrocarbons, preferably having more than 8 C atoms, such as tetradecane, hexadecane, octadecane, etc .; cyclic hydrocarbons, such as decahydronaphthalene; branched hydrocarbons; animal and vegetable oils; To grow; Wax esters; Petroleum jelly; Esters, preferably esters of fatty acids, such as the esters of C ₁ -C ₂₄ monoalcohols with C ₁ -C ₂₂ monocarboxylic acids, such as isopropyl isostearate, n-propyl myristate, isopropyl myristate, n-propyl palmitate, iso-propyl palmitate, hexacosanyl palmitate, octacosanyl palmitate , Triacontanyl palmitate, dotriacontanyl palmitate, tetratriacontanyl palmitate, hexancosanyl stearate, octacosanyl stearate, triacontanyl stearate, Dotriacontanyl stearate, tetratriacontanyl stearate; Salicylates such as C ₁ -C ₁₀ salicylates, eg octyl salicylate; Benzoate esters such as C ₁₀ -C ₁₅ alkyl benzoates, benzyl benzoate; other cosmetic esters such as fatty acid triglycerides, propylene glycol monolaurate, polyethylene glycol monolaurate, C ₁₀ -C ₁₅ alkyl lactates, etc., and mixtures thereof.

suitable silicone oils B) are e.g. 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 e.g. commercially called cyclomethicone available.

Preferred oil or Fat components B) 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 B) 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.

suitable hydrophilic carrier B) are selected under water, 1-, 2- or polyhydric alcohols with preferably 1 to 8 carbon atoms, such as ethanol, n-propanol, isopropanol, Propylene glycol, glycerin, sorbitol, etc.

at the preparations according to the invention can it be skin-cosmetic; hair cosmetic, dermatological, hygienic or pharmaceutical preparations. by virtue of their film-forming properties are as described above Preparations in particular for Hair and skin cosmetics.

Preferably are the preparations of the invention in the form of a gel, foam, spray, a mousse, an ointment, Cream, emulsion, suspension, lotion, milk or paste. If you wish too Liposomes or microspheres be used.

The according to the invention cosmetically or pharmaceutically active preparations may additionally be cosmetically and / or contain dermatologically active agents and adjuvants.

Preferably contain the cosmetic according to the invention Preparations at least one copolymer as defined above A), at least one carrier B) as defined above and at least one different ingredient selected among cosmetically active substances, emulsifiers, surfactants, preservatives, Perfume oils, thickeners, Hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, light stabilizers, Bleaching agents, gelling agents, care products, colorants, tinting agents, Tanning agents, Dyes, pigments, bodying agents, moisturizers, restockers, Collagen, protein hydrolysates, lipids, antioxidants, defoamers, antistatic agents, Emollients and plasticizers.

Common thickener in such formulations are crosslinked polyacrylic acids and their derivatives, polysaccharides and their derivatives, such as xanthan gum, Agar-agar, alginates or tyloses, cellulose derivatives, e.g. carboxymethylcellulose or hydroxycarboxymethylcellulose, fatty alcohols, monoglycerides and fatty acids, Polyvinyl alcohol and polyvinylpyrrolidone. Preference is given to nonionic Thickener used.

Prefers contain the preparations according to the invention additionally at least one nonionic thickener.

Suitable cosmetically and / or dermatologically active agents are, for example, coloring agents, skin and hair pigmenting agents, tinting agents, tanning agents, bleaching agents, keratin-hardening substances, antimicrobial agents, light filter agents, repellent agents, hyperemic substances, keratolytic and keratoplastic substances, antidandruff agents, antiphlogistics, keratinizing substances, antioxidant or radical scavengers active ingredients, skin moisturizing or moisturizing substances, moisturizing agents, antierythimatös or antiallergically active ingredients and mixtures thereof.

Artificially skin-tanning Active ingredients that are suitable to the skin without natural or artificial Browning irradiation with UV rays are e.g. dihydroxyacetone, Alloxan and walnut shell extract. Suitable keratin-hardening substances are usually active substances, as they are also used in antiperspirants can be used, such as 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 deodorizing substance which causes the formation or the intensity of body odor reduced. These include e.g. 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 e.g. ricinoleate, Triclosan, undecylenic acid alkylolamides, triethyl citrate, Chlorhexidine etc. Suitable light filtering agents are substances that are ultraviolet rays in the UV-B and / or Absorb UV-A region. Suitable UV filters are e.g. 2,4,6-triaryl-1,3,5-triazines in which the aryl groups may each bear at least one substituent, the preferably selected is hydroxy, alkoxy, especially methoxy, alkoxycarbonyl, especially Methoxycarbonyl and ethoxycarbonyl and mixtures thereof. Suitable are furthermore 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 e.g. 2-ethyl-1,3-hexanediol, N, N-diethyl-m-toluamide, etc. Suitable hyperemic acting substances, which stimulate the blood circulation of the skin are e.g. essential oils, like 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 e.g. salicylic acid, Calcium thioglycolate, thioglycolic acid and their salts, sulfur, etc. Suitable anti-dandruff agents are e.g. Sulfur, sulfur polyethylene glycol sorbitan monooleate, Sulfuricinol polyethoxylate, zinc pyrithione, aluminum pyrithione, etc. Suitable antiphlogistics, which counteract skin irritation, are e.g. Allantoin, bisabolol, dragosantol, chamomile extract, panthenol, Etc.

The cosmetic according to the invention Preparations can as a cosmetic and / or pharmaceutical active substance (as well as optionally as adjuvant) at least one more cosmetically or pharmaceutically contain acceptable polymer. These include, in general, cationic, amphoteric and neutral polymers.

The aqueous according to the invention Preparations can furthermore of copolymer A) different water-soluble polymers contain.

Suitable polymers are, for example, cationic polymers having the INCI name Polyquaternium, eg copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat ^® FC, Luviquat ^® HM, Luviquat ^® MS, Luviquat ^® Care, Luviquat ^® Ultra 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 (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, For example, guar polymers, such as the Jaguar ^® brands Fa. Rhodia.

Other suitable polymers are also neutral polymers, such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinylpropionate and / or stearyl (meth) acrylate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their Salts, cellulose derivatives, polyaspartic acid salts and derivatives. These included a Luviflex® ^® Swing (partially hydrolyzed copolymer of polyvinyl acetate and polyethylene glycol, Messrs. BASF) or Kollicoat ^® IR.

suitable Polymers are also those described in WO 03/092640, in particular as Examples 1 to 50 (Table 1, page 40 et seq.) and Examples 51 to 65 (Table 2, page 43) described (meth) Acrylsäureamidcopolymere, to the full extent at this point Reference is made.

Suitable polymers are also nonionic, water-soluble or water-dispersible polymers or oligomers, such as polyvinylcaprolactam, for example, Luviskol ^® Plus (BASF), or polyvinyl pyrrolidone and their copolymers, in particular with Vinylestern such as vinyl acetate, for example, Luviskol ^® VA 37 (BASF); Polyamides, for example based on itaconic acid and aliphatic diamines, as described, for example, in DE-A-43 33 238.

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 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 methacroylethylbetaine / methacrylate copolymers, which are 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 example, polyether siloxanes, such as Tegopren ^® (Fa. Goldschmidt) or Belsil ^® (Fa. Wacker).

Also suitable are also biopolymers, i. Polymers made from naturally renewable Raw materials are obtained and built from natural monomer building blocks are, e.g. Cellulose derivatives, chitin, chitosan, DNA, hyaluronic acid and RNA derivatives.

Further preparations according to the invention contain at least one other water-soluble polymer, in particular Chitosans (poly (D-glucosamine)) of various molecular weights and / or chitosan derivatives.

anionic polymers

Further for the preparations according to the invention suitable polymers are carboxylic acid group-containing Copolymers. These are polyelectrolytes with a larger number anionic dissociable groups in the main chain and / or a Side chain. You are capable with the copolymers A) to form polyelectrolyte complexes (symplexes).

In a preferred embodiment have the in the inventive compositions used polyelectrolyte complexes an excess of anionogenic / anionic Groups on.

The Polyelectrolyte complexes include in addition to at least one of the above mentioned copolymers A) also at least one acid group-containing polymer.

The Polyelectrolyte complexes preferably contain copolymers) A) and Containing acid groups Polymers in a weight ratio of about 50: 1 to 1:20, more preferably from 20: 1 to 1: 5.

suitable Carboxylic acid group-containing Polymers are e.g. by radical polymerization α, β-ethylenic unsaturated Monomers available. In this case, monomers m1) are used which at least one free radical polymerizable, α, β-ethylenic unsaturated Double bond and at least one anionogenic and / or anionic Group per molecule contain.

suitable Containing carboxylic acid groups Polymers are also carboxylic acid group-containing Polyurethanes.

Preferably the monomers are selected under monoethylenically unsaturated Carboxylic acids, sulfonic acids, phosphonic acids and Mixtures thereof.

The monomers m1) include monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 25, preferably 3 to 6, carbon atoms, which can also be used in the form of their salts or anhydrides. Examples thereof are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and fumaric acid. The monomers also include the half-esters of monoethylenically unsaturated dicarboxylic acids having 4 to 10, preferably 4 to 6, carbon atoms, for example of maleic acid, such as monomethyl maleate. The monomers also include 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 acid. The monomers also include the salts of the abovementioned acids, in particular the sodium, potassium and ammonium salts and the salts with the abovementioned amines. The monomers can be used as such or as mixtures with one another. The stated proportions by weight are all based on the acid form.

Preferably the monomer m1) 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 and Mixtures thereof, particularly preferably acrylic acid, methacrylic acid and Mixtures thereof.

The aforementioned monomers m1) each used individually or in the form of any mixtures become.

in principle are suitable as comonomers for the preparation of the carboxylic acid group-containing Polymers the compounds previously mentioned as components of the copolymer A) a) to d) with the proviso, the mole fraction of anionogenic and anionic groups containing the Carboxylic acid group-containing Contains copolymerized polymer, is larger as the mole fraction of cationogenic and cationic groups.

In a preferred embodiment contain the carboxylic acid group-containing Polymers copolymerized at least one monomer which is selected among the aforementioned crosslinkers d). On suitable and preferred Crosslinker d) is referred to.

worin
R¹ für Wasserstoff oder C₁-C₈-Alkyl steht,
Y¹ für O, NH oder NR³ steht, und
R² und R³ unabhängig voneinander für C₁-C₃₀-Alkyl oder C₅-C₈-Cycloalkyl stehen, wobei die Alkylgruppen durch bis zu vier nicht benachbarte Heteroatome oder Heteroatom-haltige Gruppen, die ausgewählt sind unter O, S und NH unterbrochen sein können.Furthermore, the polymers containing carboxylic acid groups preferably contain in copolymerized form at least one monomer m2) which is selected from compounds of the general formula (VI)

wherein
R ^{1 is} hydrogen or C ₁ -C ₈ -alkyl,
Y ^{1 is} O, NH or NR ³ , and
R ² and R ^{3 are} independently C ₁ -C ₃₀ alkyl or C ₅ -C ₈ cycloalkyl, wherein the alkyl groups are substituted by up to four nonadjacent heteroatoms or heteroatom-containing groups selected from O, S and NH can be interrupted.

In the formula VI, R ¹ is preferably hydrogen or C ₁ -C ₄ -alkyl, in particular hydrogen, methyl or ethyl.

R ² in the formula VI is preferably C ₁ -C ₈ -alkyl, preferably methyl, ethyl, n-butyl, isobutyl, tert-butyl or a group of the formula -CH ₂ -CH ₂ -NH-C (CH _{3 3} .

If R ^{3 is} alkyl, then preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, n-butyl, isobutyl and tert-butyl.

suitable Monomers m2) are methyl (meth) acrylate, methyl ethacrylate, ethyl (meth) acrylate, Ethyl ethacrylate, tert-butyl (meth) acrylate, tert-butyl ethacrylate, 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 m2) are furthermore acrylic acid amide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- (n-butyl) (meth) acrylamide, N- (tert .-Bu tyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, piperidinyl (meth) acrylamide and morpholinyl (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (1,1,3,3-tetramethylbutyl) (meth) acrylamide, N-ethylhexyl (meth) acrylamide, N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide, N- (n-undecyl) (meth) acrylamide, N-tridecyl (meth) acrylamide, N-myristyl (meth) acrylamide, N-pentadecyl (meth) acrylamide, N-palmityl (meth) acrylamide, N-heptadecyl (meth) acrylamide, N-nonadecyl (meth) acrylamide, N-arrachinyl (meth) acrylamide, N-behenyl (meth) acrylamide, N-lignocerenyl (meth) acrylamide, N-cerotinyl (meth) acrylamide, N-melissinyl (meth) acrylamide, N-palmitoleinyl (meth) acrylamide, N-oleyl (meth) acrylamide, N-linolyl (meth) acrylamide, N-linolenyl (meth) acrylamide, N-stearyl (meth) acrylamide and N-lauryl (meth) acrylamide.

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,
R⁴ für Wasserstoff, C₁-C₃₀-Alkyl oder C₅-C₈-Cycloalkyl steht,
R⁵ für Wasserstoff oder C₁-C₈-Alkyl steht,
Y² für O oder NR⁶ steht, wobei R⁶ für Wasserstoff, C₁-C₃₀-Alkyl oder C₅-C₈-Cycloalkyl steht.Furthermore, the polymers containing carboxylic acid groups preferably contain, in copolymerized form, at least one monomer m3) which is selected from compounds of the general formula VII

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 ^{4 is} hydrogen, C ₁ -C ₃₀ -alkyl or C ₅ -C ₈ -cycloalkyl,
R ^{5 is} hydrogen or C ₁ -C ₈ -alkyl,
Y ^{2 is} O or NR ⁶ , wherein R ^{6 is} hydrogen, C ₁ -C ₃₀ alkyl or C ₅ -C ₈ cycloalkyl.

Prefers is in formula VII k for an integer from 1 to 500, especially 3 to 250. Preferred l stands for an integer from 0 to 100.

R ⁵ 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.

In the formula VII, R ⁴ is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, octyl, 2-ethylhexyl, decyl, lauryl, palmityl or stearyl ,

Preferably, Y ² in formula VII is O or NH.

Suitable polyether acrylates VII) are, for example, the polycondensation products of the abovementioned 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 molecule such as water or a short-chain alcohol R ⁴ -OH. The alkylene oxides can be used individually, alternately in succession or as a mixture. The polyether acrylates VII) can be used alone or in mixtures for the preparation of the polymers used according to the invention. Suitable polyether acrylates II) 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.

Examples of anionic polymers which are preferred as carboxylic acid-containing polymers are, for example, homo- and copolymers of acrylic acid and methacrylic acid and salts thereof. These include crosslinked polymers of acrylic acid, such as those available under the INCI name Carbomer. Such crosslinked homopolymers of acrylic acid are available commercially for example under the name Carbopol ^® by the company Noveon. Also hydrophobically modified crosslinked polyacrylate polymers such as Carbopol ^® Ultrez 21 are preferably from Noveon.

Polyelectrolyte complexes based on homo- and copolymers of acrylic acid and methacrylic acid are particularly suitable for formulation as gels, for example for feasting gels, as well as for the formulation of foams.

Further examples of suitable anionic polymers are copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible Po lyester, 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, for example, acrylate / beheneth-25-methacrylate copolymers, which are available under the name Aculyn ^® from Rohm and Haas. Particularly suitable polymers are also copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (for example, Luvimer ^® 100P, Luvimer ^® Pro55), copolymers of ethyl acrylate and methacrylic acid (eg Luviumer ^® MAE), copolymers of N-tert-butylacrylamide, ethyl acrylate, acrylic acid ( Ultrahold ^® 8, Ultrahold ^® Strong), copolymers of vinyl acetate, crotonic acid and optionally further Vinylester (eg Luviset ^® brands), maleic anhydride copolymers, optionally reacted with alcohol, anionic polysiloxanes, for example carboxy, t-butyl acrylate, methacrylic acid (for example, 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, as are, for example, under the names Resyn ^® (National Starch) and Gafset ^® (GAF), and vinyl pyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF) , Other suitable polymers are the commercially available under the name Luviflex VBM-35 ^® (BASF) vinylpyrrolidone / acrylate terpolymer and polyamides or sodium sulfonate sodium sulfonate polyester.

Furthermore, for example, the group of suitable anionic polymers comprises Balance CR ^® (National Starch; Acrylate Copolymer), balance 0/55 ^® (National Starch; Acrylate Copolymer), Balance ^® 47 (National Starch; octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer) Aquaflex ^® FX 64 (ISP; isobutylene / ethylmaleimide / hydroxyethylmaleimide copolymer) Aquaflex ^® SF-40 (ISP / National Starch; VP / vinyl caprolactam / DMAPA acrylates copolymer), Alliance ^® LT-120 (ISP / Rohm &Haas; acrylate / C1-2 succinate / hydroxyacrylate copolymer), Aquarez ^® HS (Eastman, polyester-1), and ^® Diaformer Z-400 (Clariant; methacryloylethylbetaine / methacrylate copolymer), ^® Diaformer Z-711 (Clariant; methacryloylethyl N-oxide / methacrylate copolymer), ^® Diaformer Z-712 (Clariant; methacryloylethyl N-oxide / methacrylate copolymer), Omnirez ^® 2000 (ISP; monoethyl ester of poly (methyl vinyl ether / maleic acid in ethanol), Amphomer ^® HC (National Starch; acrylate / Octylacrylamid- copolymer), Amphomer ^® 28-4910 (National Starch; octyl-acrylamide / acrylate / butylaminoethyl methacrylate copolymer), Advantage ^® HC 37 (ISP; Terpolymer of vinylcaprolactam / vinylpyrrolidone / dimethylaminoethyl methacrylate), Advantage ^® LC55 and LC80 or LC A and LC E, Advantage ^® Plus (ISP; VA / Butyl Maleate / Isobornyl Acrylate Copolymer), Aculyne ^® 258 (Rohm &Haas; acrylate / Hydroxyesteracrylat copolymer ), Luviset ^® PUR (BASF, polyurethane-1), Luviflex ^® Silk (BASF), Eastman ^® AQ 48 (Eastman), Styleze ^® CC-10 (ISP, VP / DMAPA Acrylates copolymer), Styleze ^® 2000 (ISP; VP / Acrylates / lauryl Methacrylate copolymer), DynamX ^® (National Starch; Polyuretha ne-14 AMP-Acrylates copolymer), Resyn XP ^® (National Starch; Acrylates / octylacrylamide copolymer), Fixomer ^® A-30 (Ondeo Nalco, polymethacrylic acid (and) acrylamidomethylpropane sulfonic acid), Fixate G-100 ^® (Noveon; AMP-Acrylates / allyl Methacrylate copolymer).

Suitable carboxylic acid group-containing polymers are also those in the US 3,405,084 described terpolymers of vinyl pyrrolidone, C ₁ -C ₁₀ alkyl, cycloalkyl and aryl (meth) acrylates and acrylic acid. Suitable polymers containing carboxylic acid groups are furthermore the terpolymers of vinylpyrrolidone, tert-butyl (meth) acrylate and (meth) acrylic acid described in EP-A-0 257 444 and EP-A-0 480 280. Suitable polymers containing carboxylic acid groups are furthermore the copolymers described in DE-A-42 23 066, which contain at least one (meth) acrylic ester, (meth) acrylic acid and also N-vinylpyrrolidone and / or N-vinylcaprolactam in copolymerized form. The disclosure of these documents is hereby incorporated by reference.

The Preparation of the aforementioned carboxylic acid group-containing polymers takes place by known methods, for example the solution, precipitation, Suspension or emulsion polymerization as before for the copolymers A).

suitable Carboxylic acid group-containing Polymers are also carboxylic acid group-containing Polyurethanes.

The EP-A-636361 discloses suitable block copolymers with polysiloxane blocks and Polyurethane / polyurea, the carboxylic acid and / or sulfonic acid groups exhibit. Suitable silicone-containing polyurethanes are also in the WO 97/25021 and EP-A-751 162.

suitable Polyurethanes are also described in DE-A-42 25 045, whereupon is hereby fully incorporated by reference.

The acid groups of the carboxylic acid group-containing polymers may be partially or completely neutralized. Then at least a part of the acid groups is present in deprotonated form, the counteri are preferably selected from alkali metal ions, such as Na ⁺ , K ⁺ , ammonium ions and their organic derivatives, etc.

The preparations according to the invention can also be used in the field of pharmacy.

The Formulation basis of pharmaceutical preparations according to the invention contains preferably pharmaceutically acceptable excipients. pharmaceutical acceptable in the field of pharmacy, food technology and adjacent areas of known adjuvants, in particular those in pertinent conditions pharmacopoeia (e.g., DAB Ph. Eur. BP NF), as well as other excipients whose Properties of a physiological application do not oppose.

suitable Excipients can be: lubricants, wetting agents, emulsifying and suspending agents, preservatives Agents, anti-oxidants, anti-irritants, chelating agents, emulsion stabilizers, Film formers, gelling agents, odor masking agents, resins, hydrocolloids, Solvents Solubilizers, Neutralizing agents, permeation enhancers, pigments, quaternary ammonium compounds, refatting and superfatting agents, Ointment, cream or oil bases, Silicone derivatives, stabilizers, sterilants, blowing agents, drying agents, Opacifiers, Thickeners, waxes, softeners, white oils. A related embodiment based on expert Knowledge, as for example in Fiedler, N. P. Encyclopedia of excipients for pharmacy, Cosmetics and adjacent areas, 4th ed., Aulendorf: ECV Editio Kantor Verlag, 1996, shown are.

to Production of dermatological according to the invention Means can the active ingredients mixed with a suitable excipient (excipient) or diluted become. Excipients can solid, semi-solid or liquid Be materials that act as a vehicle, carrier or medium for the drug can serve. If desired, the admixing of further auxiliaries takes place in the person skilled in the art known way. Furthermore, the preparations are suitable as auxiliaries in pharmacy, preferably in coating agent (s) or binder (s) for fixed Dosage forms. You can also in creams and as a tablet coating agent and tablet binders.

To a preferred embodiment If the preparations according to the invention are a skin cleanser.

preferred Skin cleansers are soaps of liquid to gel consistency, like transparent soaps, luxury soaps, de-icing soaps, cream soaps, baby soaps, Skin protection soaps, abrasive soaps and syndets, pasteurized soaps, soft soaps and washing pastes, liquid Washing, shower and bath preparations, like washing lotions, shower baths and gels, bubble baths, oil baths and Scrub preparations, shaving foams, lotions and creams.

To a further preferred embodiment If the preparations according to the invention are cosmetic Means for the care and protection of the skin, nail care preparations or Preparations for the decorative cosmetics.

suitable Skin-cosmetic agents are e.g. Face waters, facial masks, deodorants and other cosmetic lotions. Means for use in the decorative Cosmetics include, for example, concealers, theatrical paints, mascara and eyeshadows, lipsticks, kohl pencils, eyeliners, rouges, powders and eyebrow pencils.

at the skin care agents according to the invention These are in particular W / O or O / W skin creams, day and night creams, Eye creams, face creams, anti-wrinkle creams, moisturizing creams, Bleaching creams, vitamin creams, skin lotions, body lotions and moisturizing lotions.

skin cosmetic and dermatological agents based on the preparations described above show advantageous effects. The preparations can under for moisturizing and conditioning the skin and improving it the skin feeling contribute. The preparations can also act as thickeners in the formulations. By adding the polymers of the invention In certain formulations, a significant improvement in the skin compatibility be achieved.

Skin cosmetic according to the invention and dermatological preparations preferably contain at least Copolymer A) in a proportion of about 0.001 to 30 wt .-%, preferably 0.01 to 20 wt .-%, most preferably 0.1 to 12 wt .-%, based on the total weight of the preparation.

Especially Light stabilizers based on the copolymers A) have the property the residence time of the UV-absorbing ingredients in comparison to common To increase aids such as polyvinylpyrrolidone.

ever according to application the preparations according to the invention in a form suitable for skin care, e.g. as a cream, foam, Gel, pen, mousse, milk, spray (pump spray or propellant Spray) or lotion.

The Skin-cosmetic according to the invention Preparations can in addition to the copolymers A) and suitable carriers, other active ingredients customary in skin cosmetics and adjuvants as described above. These are preferably Emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, Light stabilizers, bleaching agents, colorants, tinting agents, Tanning agents, Collagen, protein hydrolysates, Stabilizers, pH regulators, dyes, Salts, thickeners, gelling agents, bodying agents, silicones, humectants, refatting and more usual ones Additives.

Preferred oil and fat components of the skin-cosmetic and dermatological agents are the aforementioned mineral and synthetic oils, such as paraffins, silicone oils and aliphatic hydrocarbons having more than 8 carbon atoms, animal and vegetable oils, such as sunflower oil, coconut oil, avocado oil, olive oil, lanolin, or waxes, fatty acids, fatty acid esters, such as triglycerides of C ₆ -C ₃₀ fatty acids, wax esters, such as jojoba oil, fatty alcohols, vaseline, hydrogenated lanolin and acetylated lanolin, and mixtures thereof.

The preparations according to the invention can also conventional Contain polymers if special properties are set should.

to Adjustment of certain properties, e.g. Improvement of the feeling of touch, the Spreading behavior, water resistance and / or binding of active substances and excipients, such as pigments, may be the skin and cosmetic dermatological preparations additionally also conditioning Contain substances based on silicone compounds. suitable Silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, Polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.

The Production of cosmetic or dermatological preparations takes place according to usual, known to those skilled in the process.

Prefers Are the cosmetic and dermatological preparations in the form emulsions especially as water-in-oil (W / O) or oil-in-water (O / W) emulsions. It but it is also possible to choose other types of formulations, for example, hydrodispersions, gels, oils, oleogels, multiple emulsions, for example in the form of W / O / W or O / W / O emulsions, anhydrous Ointments or ointment bases, etc.

The Emulsions are prepared by known methods. The Emulsions contain, in addition to at least one copolymer A) in the Usually usual Ingredients, such as fatty alcohols, fatty acid esters and in particular fatty acid triglycerides, fatty acids, Lanolin and derivatives thereof, natural or synthetic oils or Waxes and emulsifiers in the presence of water. The selection of Emulsion type specific additives and the preparation of suitable emulsions is described, for example in Schrader, basics and recipes of cosmetics, Hüthig book Verlag, Heidelberg, 2nd edition, 1989, third part, which hereby expressly Reference is made.

A suitable emulsion, e.g. For a skin cream, etc., contains generally an aqueous one Phase, by means of a suitable emulsifier in an oil or Fat phase is emulsified. To provide the aqueous Phase may be a preparation of the invention be used.

preferred Fat components which are contained in the fatty phase of the emulsions could be, are: hydrocarbon oils, like paraffin oil, purCellin, Perhydrosqualene and solutions microcrystalline waxes in these oils; animal or vegetable oils, such as Sweet almond oil, avocado oil, calophilum oil, lanolin and derivatives thereof, castor oil, Sesame oil, Olive oil, jojoba oil, Sheathing oil, hoplostethus oil; mineral oils whose Start of distillation under atmospheric pressure at about 250 ° C and their Distillation endpoint at 410 ° C is such as vaseline oil; Saturated esters or unsaturated fatty acids, such as alkyl myristates, e.g. i-propyl, butyl or cetyl myristate, hexadecyl stearate, Ethyl or i-propyl palmitate, Octane or Decansäuretriglyceride and cetylricinoleate.

The Fat phase can also be found in other oils soluble Silicone oils, such as dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and fatty alcohols.

Next the copolymers A) can waxes may also be used, e.g. Carnauba Wax, Candililla Wax, Beeswax, microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates, myristates, linoleates and stearates.

Farther may be an emulsion according to the invention as O / W emulsion. Such an emulsion usually contains an oil phase, Emulsifiers containing the oil phase stabilize in the water phase, and an aqueous phase, usually thickened present. As emulsifiers are preferably O / W emulsifiers, such as polyglycerol esters, sorbitan esters or partially esterified glycerides, into consideration.

To a further preferred embodiment If the preparations according to the invention are a shower gel, a shampoo formulation or a bathing preparation.

Such formulations according to the invention contain at least one copolymer A) 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, and thickeners / gelling agents, skin conditioners and humectants.

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 washing, shower and bath 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 Alkylethercarbo xylate can between 1 to 10 ethylene oxide or propylene oxide units, preferred 1 to 3 ethylene oxide units in the molecule.

To counting e.g. 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 e.g. Alkyl betaines, 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 Washing, shower and bath preparations usual cationic Surfactants, e.g. quaternary ammonium compounds, for example Cetyltrimethylammonium chloride.

Farther can the shower gel / shampoo formulations include thickeners, such as e.g. Saline, PEG-55, propylene glycol oleate, PEG-120 methyl glucose dioleate and others, as well as preservatives, other active ingredients and excipients and water included.

To a further preferred embodiment If the preparations according to the invention are a hair treatment agent.

Hair treatment agents according to the invention preferably contain at least one copolymer A) in an amount in the range of about 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the total weight of the agent.

Preferably are the hair treatment compositions according to the invention in the form of a mousse, hair mousse, hair gel, shampoo, Hair sprays, hair mousse, top fluids, perms, hair coloring and bleach or "hot oil treatments". Depending on the application can the hair cosmetic preparations as (aerosol) spray, (aerosol) foam, Gel, gel spray, cream, lotion or wax can be applied. hairsprays include both aerosol sprays and pump sprays without propellant gas. hair foams include both aerosol foams as well as pump foams without propellant. Hair sprays 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.

• A) 0,05 bis 20 Gew.-% wenigstens eines Copolymeren A)
• B) 20 bis 99,95 Gew.-% Wasser und/oder Alkohol,
• C) 0 bis 50 Gew.-% wenigstens eines Treibgases,
• D) 0 bis 5 Gew.-% wenigstens eines Emulgators,
• E) 0 bis 3 Gew.-% wenigstens eines Verdickers, sowie
• F) bis zu 25 Gew.-% weitere Bestandteile

wobei der pH-Wert der Formulierung wird einen Wert im Bereich von pH 4 bis pH 6 aufweist.The hair cosmetic formulations of the invention comprise in a preferred embodiment

• A) 0.05 to 20% by weight of at least one copolymer A)
• B) from 20 to 99.95% by weight of water and / or alcohol,
• C) 0 to 50% by weight of at least one propellant gas,
• D) 0 to 5% by weight of at least one emulsifier,
• E) 0 to 3 wt .-% of at least one thickener, and
• F) up to 25 wt .-% further ingredients

wherein the pH of the formulation will have a value in the range of pH 4 to pH 6.

Under Alcohol are all alcohols commonly used in cosmetics, e.g. Ethanol, isopropanol, n-propanol.

Under other constituents are the additives customary in cosmetics, for example propellants, 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 further, e.g. Preservatives, perfume oils, opacifiers, active ingredients, UV filters, Nursing substances such as panthenol, collagen, vitamins, protein hydrolysates, Alpha and beta hydroxycarboxylic acids, protein hydrolysates, Stabilizers, pH regulators, dyes, viscosity regulators, Gelling agents, dyes, salts, humectants, moisturizers, Complexing agents and other common 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, polyanilalkylsiloxanes, polyethersiloxanes, silicone resins or dimethicone copolyols (CTFA) and amino functional silicone compounds like amodimethicones (CTFA).

The polymers according to the invention are particularly suitable as setting agents in hairstyling preparations, in particular hair sprays (aerosol sprays and pump sprays without propellant gas) and hair mousses (Aerosol foams and pump foams without propellant).

• A) 0,1 bis 3 Gew.-% wenigstens eines Copolymeren A),
• B) 0,1 bis 3 Gew.-% wenigstens eines weiteren Polymers,
• C) 20 bis 99,9 Gew.-% Wasser und/oder Alkohol,
• D) 0 bis 70 Gew.-% wenigstens eines Treibmittel,
• E) 0 bis 20 Gew.-% weitere Bestandteile.

wobei der pH-Wert der Zubereitung einen Wert im Bereich von pH 4 bis pH 6 aufweist.In a preferred embodiment, spray formulations contain

• A) 0.1 to 3% by weight of at least one copolymer A),
• B) 0.1 to 3% by weight of at least one further polymer,
• C) 20 to 99.9% by weight of water and / or alcohol,
• D) 0 to 70% by weight of at least one blowing agent,
• E) 0 to 20 wt .-% further ingredients.

wherein the pH of the preparation has a value in the range of pH 4 to pH 6.

propellant are the for Hairsprays or aerosol foams commonly used Propellant. Preference is given to mixtures of propane / butane, pentane, dimethyl ether, 1,1-difluoroethane (HFC-152a), carbon dioxide, nitrogen or compressed air.

• A) 0,1 bis 10 Gew.-% wenigstens eines Copolymeren A),
• B) 55 bis 99,8 Gew.-% Wasser und/oder Alkohol,
• C) 5 bis 20 Gew.-% eines Treibmittel,
• D) 0,1 bis 5 Gew.-% eines Emulgators,
• E) 0 bis 10 Gew.-% weitere Bestandteile,

wobei der pH-Wert der Zubereitung einen Wert im Bereich von pH 4 bis pH 6 aufweist.A preferred formulation for aerosol hair foams according to the invention

• A) 0.1 to 10% by weight of at least one copolymer A),
• B) 55 to 99.8% by weight of water and / or alcohol,
• C) 5 to 20% by weight of a blowing agent,
• D) 0.1 to 5% by weight of an emulsifier,
• E) 0 to 10% by weight of further constituents,

wherein the pH of the preparation has a value in the range of pH 4 to pH 6.

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, e.g. Laureth-4; Cetethe, e.g. Cetheth-1, polyethylene glycol cetyl ether; Ceteareth, e.g. Cetheareth-25, Polyglycolfettsäureglyceride, hydroxylated lecithin, lactyl esters 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 isethionates, alkyl phosphates, 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, preferably 1 to 3 ethylene oxide units in the molecule exhibit.

• A) 0,1 bis 10 Gew.-% wenigstens eines Copolymeren A),
• B) 80 bis 99,85 Gew.-% Wasser und/oder Alkohol,
• C) 0 bis 3 Gew.-%, bevorzugt 0,05 bis 2 Gew.-%, eines Gelbildners,
• D) 0 bis 20 Gew.-% weitere Bestandteile,

wobei der pH-Wert der Zubereitung einen Wert im Bereich von pH 4 bis pH 6 aufweist.A preparation suitable for styling gels according to the invention can be composed, for example, as follows:

• A) 0.1 to 10% by weight of at least one copolymer A),
• B) 80 to 99.85% by weight of water and / or alcohol,
• C) 0 to 3 wt .-%, preferably 0.05 to 2 wt .-%, of a gelling agent,
• D) 0 to 20% by weight of further constituents,

wherein the pH of the preparation has a value in the range of pH 4 to pH 6.

Of the Use of gelling agents may be beneficial to special rheological or to adjust other application properties of the gels. As a gelling agent can all usual in cosmetics gel formers be used.

For this counting for example, cellulose derivatives, e.g. Hydroxypropyl cellulose, hydroxyethyl cellulose, cationic modified celluloses, polysaccharides, e.g. Xanthan gum, caprylic / capric triglyceride, Sodium acrylate copolymers, Polyquaternium-32 (and) Paraffinum Liquidum (INCI), Sodium Acrylate Copolymers (and) Paraffinum Liquidum (and) PPG-1 trideceth-6, acrylamidopropyltrimonium chloride / acrylamide copolymers, steareth-10 Allyl ether acrylate copolymers, Polyquaternium-37 (and) paraffin Liquidum (and) PPG-1 trideceth-6, polyquaternium 37 (and) propylene glycol dicaprate dicaprylate (and) PPG-1 trideceth-6, polyquaternium-7, polyquaternium-44.

The preparations according to the invention can used in cosmetic preparations as conditioning agents become.

• A) 0,05 bis 10 Gew.-% wenigstens eines Copolymeren A),
• B) 25 bis 94,95 Gew.-% Wasser,
• C) 5 bis 50 Gew.-% Tenside,
• D) 0 bis 5 Gew.-% eines weiteren Konditioniermittels,
• E) 0 bis 10 Gew.-% weitere kosmetische Bestandteile,

wobei der pH-Wert der Zubereitung einen Wert im Bereich von pH 4 bis pH 6 aufweist.The preparations according to the invention can preferably be used in shampoo formulations as setting and / or conditioning agents. Contain preferred shampoo formulations

• A) from 0.05 to 10% by weight of at least one copolymer A),
• B) from 25 to 94.95% by weight of water,
• C) 5 to 50% by weight of surfactants,
• D) 0 to 5% by weight of a further conditioning agent,
• E) 0 to 10% by weight of other cosmetic ingredients,

wherein the pH of the preparation has a value in the range of pH 4 to pH 6.

In the shampoo formulations all in shampoos usually used anionic, neutral, amphoteric or cationic Surfactants are used.

suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, Alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isethionates, alkyl phosphates, 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.

Suitable For example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, Ammonium lauryl ether sulfate, sodium lauroyl sarcosinate, sodium oleyl succinate, Ammonium laurylsulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate.

suitable amphoteric surfactants are, for example, 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, alkyl polyglycosides or sorbitan ether esters suitable.

In addition, the Shampoo formulations usual cationic surfactants, e.g. quaternary ammonium compounds, for example Cetyltrimethylammonium chloride.

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, Luviquat ^® Ultra Care), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized (11 ^© Luviquat PQ) with diethyl sulfate, a copolymer of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat Hold ^®); cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7). Furthermore, protein hydrolysates can be used, as well as conditioning substances based on silicone compounds, for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins. Other suitable silicone compounds are dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicones (CTFA). Furthermore, cationic guar derivatives such as guar hydroxypropyltrimonium chloride (INCI) can be used.

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

The Monomers are given as weight%.

1. Preparation of copolymers (radical polymerization in solution)

• Example S1: Copolymer of N-vinylpyrrolidone (VP) / N-vinylimidazole (VI) / methacrylamide (MAM) (55/10/35) Template: Monomer mixture 121.5 g fully desalted (= VE) water 17.5 g Methacrylamide solution (15% by weight in water) 0.75 g N-vinylimidazole 4.12 g N-vinylpyrrolidone 0.03 g Wako ^® V 50 [2,2'-azobis (2-amidinopropane) dihydrochloride] Feed 1: Monomer mixture of: 78.5 g N-vinylpyrrolidone 14.2 g N-vinylimidazole 332 g Methacrylamide solution (15% by weight in water) Feed 2: Initiator solution from: 0.6 g Wako ^® V 50 20.97 g VE water Feed 3: Initiator solution from: 0.45 g Wako ^® V 50 10.5 g VE water

In a 1 liter pilot agitator with dosage, reflux condenser, internal thermometer and 3 separate feeders, the receiver was placed under nitrogen atmosphere and with stirring Heated to 70 ° C. at Reaching the temperature of 70 ° C Infeed 1 in three and feed 2 in four hours were added. Subsequently was postpolymerized for two hours.

At 70 ° C feed 3 was added in 10 minutes and postpolymerized for another four hours. It was then steam distilled for 30 minutes and cooled to 40 ° C. Example S2: Copolymer of N-vinylpyrrolidone (VP) / N-vinylimidazole (VI) / methacrylamide (MAM) / N-vinylimidazole methosulphate (QVI) (60/5/30/5) Template: Monomer mixture 164 g VE water 14.4 g Methacrylamide solution (15% by weight in water) 0.36 g N-vinylimidazole 4.32 g N-vinylpyrrolidone 0.8 g N-vinylimidazole-methosulphate solution (45% strength by weight in water) 0.04 g Wako ^® V 50 [2,2'-azobis (2-amidinopropane) dihydrochloride] Feed 1: Monomer mixture of: 86.0 g N-vinylpyrrolidone 7.1 g N-vinylimidazole 285.0 g Methacrylamide solution (15% by weight in water) 16.0 g N-vinylimidazole-methosulphate solution (45% strength by weight in water) Feed 2: Initiator solution from: 0.85 g Wako ^® V 50 20.97 g VE water Feed 3: Initiator solution from: 0.45 g Wako ^® V 50 10.49 g VE water

In a 1 liter pilot agitator with dosage, reflux condenser, internal thermometer and 3 separate feeders, the receiver was placed under nitrogen atmosphere and with stirring Heated to 65 ° C. at Reaching the temperature of 65 ° C Infeed 1 in three and feed 2 in four hours were added. Subsequently was postpolymerized for two hours.

At 65 ° C feed 3 was added in 10 minutes and postpolymerized for another four hours. It was then steam distilled for 30 minutes and cooled to 40 ° C. Example S3: Copolymer of N-vinylpyrrolidone (VP) / N-vinylimidazole (VI) / methacrylamide (MAM) / N-vinylimidazole methosulphate (QVI) (55/5/35/5) Template: Monomer mixture 121.5 g VE water 17.5 g Methacrylamide solution (15% by weight in water) 0.37 g N-vinylimidazole 4.1 g N-vinylpyrrolidone 0.82 g N-vinylimidazole-methosulphate solution (45% strength by weight in water) 0.04 g Wako ^® V 50 [2,2'-azobis (2-amidinopropane) dihydrochloride] Feed 1: Monomer mixture of: 78 g N-vinylpyrrolidone 7.1 g N-vinylimidazole 332.5 g Methacrylamide solution (15% by weight in water) 15.9 g N-vinylimidazole-methosulphate solution (45% strength by weight in water) Feed 2: Initiator solution from: 0.70 g Wako ^® V 50 20.97 g VE water Feed 3: Initiator solution from: 0.45 g Wako ^® V 50 10.49 g VE water

In a 1 l pilot agitator with dosage, reflux condenser, internal thermometer and 3 separate feeders, the receiver was placed under nitrogen atmosphere and with stirring Heated to 70 ° C. Intake 1 was made by adding lactic acid adjusted to a pH of 5.5. When the temperature is reached of 70 ° C were Infeed 1 in three and feed 2 in four hours. Subsequently was postpolymerized for two hours.

At 70 ° C feed 3 was added in 10 minutes and postpolymerized for another four hours. It was then steam distilled for 30 minutes and cooled to 40 ° C. Example S4: Copolymer of N-vinylpyrrolidone (VP) / N-vinylimidazole (VI) / methacrylamide (MAM) / N-vinylimidazole methosulphate (QVI) (55/5/35/5) Template: Monomer mixture 121.5 g VE water 17.5 g Methacrylamide solution (15% by weight in water) 0.37 g N-vinylimidazole 4.04 g N-vinylpyrrolidone 0.82 g N-vinylimidazole-methosulphate solution (45% strength by weight in water) 0.04 g Wako ^® V 50 [2,2'-azobis (2-amidinopropane) dihydrochloride] Feed 1: Monomer mixture of: 78 g N-vinylpyrrolidone 7.1 g N-vinylimidazole 332.5 g Methacrylamide solution (15% by weight in water) 15.9 g N-vinylimidazole-methosulphate solution (45% strength by weight in water) Feed 2: Initiator solution from: 0.70 g Wako ^® V 50 20.97 g VE water Feed 3: Initiator solution from: 0.45 g Wako ^® V 50 10.49 g VE water

In a 1 l pilot agitator with dosage, reflux condenser, internal thermometer and 3 separate feeders, the receiver was placed under nitrogen atmosphere and with stirring Heated to 70 ° C. at Reaching the temperature of 70 ° C Infeed 1 in three and feed 2 in four hours were added. Subsequently was postpolymerized for two hours.

At 70 ° C feed 3 was added in 10 minutes and postpolymerized for another four hours. It was then steam distilled for 30 minutes and cooled to 40 ° C. Example S5: Copolymer of N-vinylpyrrolidone (VP) / N-vinylimidazole (VI) / methacrylamide (MAM) (55/10/35) Template: Monomer mixture 121.5 g VE water 17.5 g Methacrylamide solution (15% by weight in water) 0.75 g N-vinylimidazole 4.10 g N-vinylpyrrolidone 0.03 g Wako ^® V 50 [2,2'-azobis (2-amidinopropane) dihydrochloride] Feed 1: Monomer mixture of: 78.0 g N-vinylpyrrolidone 14.0 g N-vinylimidazole 332.5 g Methacrylamide solution (15% by weight in water) Feed 2: Initiator solution from: 0.55 g Wako ^® V 50 20.97 g VE water Feed 3: Initiator solution from: 0.45 g Wako ^® V 50 10.49 g VE water

In a 1 l pilot stirrer with dosing, reflux condenser, internal thermometer and 3 separate feeds The apparatus was heated under nitrogen atmosphere and stirring at 70 ° C. Feed 1 was adjusted to a pH of 5.5 by addition of lactic acid. Upon reaching the temperature of 70 ° C feed 1 were added in three and feed 2 in four hours. The mixture was then postpolymerized for two hours.

At 70 ° C feed 3 was added in 10 minutes and postpolymerized for another four hours. The mixture was then steam-distilled for 30 minutes and cooled to 40 ° C. Example S6: Copolymer of N-vinylpyrrolidone (VP) / N-vinylimidazole (VI) / methacrylamide (MAM) (55/10/35) Template: Monomer mixture 121 g VE water 17.65 g Methacrylamide solution (15% by weight in water) 0.7 g N-vinylimidazole 3.77 g N-vinylpyrrolidone 0.03 g Wako ^® V 50 [2,2'-azobis (2-amidinopropane) dihydrochloride] 0.3 g lactic acid Feed 1: Monomer mixture of: 79.0 g N-vinylpyrrolidone 14.0 g N-vinylimidazole Feed 2: Monomer mixture of: 332.0 g Methacrylamide solution (15% by weight in water) 4.8 g lactic acid Feed 3: Initiator solution from: 0.6 g Wako ^® V 50 20.97 g VE water Inlet 4: Initiator solution 0.45 g Wako ^® V 50 10.5 g VE water

In a 1 l pilot stirrer with dosing, reflux condenser, internal thermometer and 4 separate feed devices, the original was heated to 70 ° C. under nitrogen atmosphere and with stirring. Upon reaching the temperature of 70 ° C feed 1 were added in three and feeds 2 and 3 in four hours. The mixture was then postpolymerized for two hours. At 70 ° C feed 3 was added in 10 minutes and postpolymerized for another four hours. It was then steam distilled for 30 minutes and cooled to 40 ° C. Example S7: Copolymer of N-vinylpyrrolidone (VP) / N-vinylimidazole (VI) / methacrylamide (MAM) / N-vinylimidazole methosulphate (QVI) (55/5/35/5) Template: Monomer mixture 121.5 g VE water 17.5 g Methacrylamide solution (15% by weight in water) 0.37 g N-vinylimidazole 4.10 g N-vinylpyrrolidone 0.83 g N-vinylimidazole-methosulphate solution (45% strength by weight in water) 0.04 g Wako ^® V 50 [2,2'-azobis (2-amidinopropane) dihydrochloride] Feed 2: Monomer mixture of: 79.0 g N-vinylpyrrolidone 16.0 N-vinylimidazole-methosulphate solution (45% strength by weight in water) 7.1 g N-vinylimidazole Feed 1: Monomer mixture of: 332.0 g Methacrylamide solution (15% by weight in water) Feed 3: Initiator solution from: 0.70 g Wako ^® V 50 20.97 g VE water Inlet 4: Initiator solution 0.45 g Wako ^® V 50 10.49 g VE water

In a 1 l pilot stirrer with dosing, reflux condenser, internal thermometer and 4 separate feed devices, the original was heated to 65 ° C. under nitrogen atmosphere and with stirring. Feed 2 was adjusted to a pH of 6.0 by addition of lactic acid. When the temperature reached 65 ° C., feeds 1 and 3 were metered in for four hours and feed 2 for three hours. The mixture was then postpolymerized for two hours. At 65 ° C feed 4 was added in 10 minutes and postpolymerized for another four hours. The mixture was then steam-distilled for 30 minutes and cooled to 40 ° C, the pH was adjusted by the addition of lactic acid to a value of pH 5.5. Example S8: Copolymer of N-vinylpyrrolidone (VP) / N-vinylimidazole (VI) / methacrylamide (MAM) / N-vinylimidazole methosulphate (QVI) (55/8/29/8) Template: Monomer mixture 166.0 g VE water 15.7 g Methacrylamide solution (15% by weight in water) 0.65 g N-vinylimidazole 4.45 g N-vinylpyrrolidone 1.45 g N-vinylimidazole-methosulphate solution (45% strength by weight in water) 0.04 g Wako ^® V 50 [2,2'-azobis (2-amidinopropane) dihydrochloride] Feed 1: Monomer mixture of: 274.0 g Methacrylamide solution (15% by weight in water) 78 g N-vinylpyrrolidone 25.2 g N-vinylimidazole-methosulphate solution (45% strength by weight in water) 11.3 g N-vinylimidazole Feed 2: Initiator solution from: 0.70 g Wako ^® V 50 20.97 g VE water Feed 3: Initiator solution 0.45 g Wako ^® V 50 10.49 g VE water

In a 1 l pilot stirrer with dosing, reflux condenser, internal thermometer and 3 separate feed devices, the original was heated to 70 ° C. under nitrogen atmosphere and with stirring. Feed 1 was adjusted to a pH of 6.0 by addition of lactic acid. When the temperature reached 70 ° C., feed 1 was metered in over three hours and feed 2 for four hours. The mixture was then postpolymerized for two hours. At 70 ° C feed 3 was added in 10 minutes and postpolymerized for another four hours. It was then steam distilled for 30 minutes and cooled to 40 ° C. The pH was adjusted to pH 5.5 by addition of lactic acid. Example S9: Copolymer of N-vinylpyrrolidone (VP) / N-vinylimidazole (VI) / methacrylamide (MAM) / N-vinylimidazole-methochloride (QVI) (55/10/29/6) Template: Monomer mixture 166.0 g VE water 15.7 g Methacrylamide solution (15% by weight in water) 0.80 g N-vinylimidazole 4.45 g N-vinylpyrrolidone 1.10 g N-vinylimidazole-methochloride solution (45% strength by weight in water) 0.04 g Wako ^® V 50 [2,2'-azobis (2-amidinopropane) dihydrochloride] Feed 1: Monomer mixture of: 274.0 g Methacrylamide solution (15% by weight in water) 78.0 g N-vinylpyrrolidone 19.0 g N-vinylimidazole-methochloride solution (45% strength by weight in water) 14.2 g N-vinylimidazole Feed 2: Initiator solution from: 0.70g Wako ^® V 50 20.97 g VE water Feed 3: Initiator solution 0.45 g Wako ^® V 50 10.49 g VE water

In a 1 l pilot stirrer with dosing, reflux condenser, internal thermometer and 3 separate feed devices, the original was heated to 70 ° C. under nitrogen atmosphere and with stirring. Feed 1 was adjusted to a pH of 6.0 by addition of lactic acid. When the temperature reached 70 ° C., feed 1 was metered in over three hours and feed 2 for four hours. The mixture was then postpolymerized for two hours. At 70 ° C feed 3 was added in 10 minutes and postpolymerized for another four hours. It was then steam distilled for 30 minutes and cooled to 40 ° C. Example S10: Copolymer of N-vinylpyrrolidone (VP) / N-vinylimidazole (VI) / methacrylamide (MAM) / N-vinylimidazole methosulphate (QVI) (55/10/29/6) Template: Monomer mixture 324.0 g VE water 31.8 g Methacrylamide solution (15% by weight in water) 1.6 g N-vinylimidazole 9.0 g N-vinylpyrrolidone 2.2 g N-vinylimidazole-methosulphate solution (45% strength by weight in water) 0.08 g Wako ^® V 50 [2,2'-azobis (2-amidinopropane) dihydrochloride] Feed 1: Monomer mixture of: 548.0 g Methacrylamide solution (15% by weight in water) 156 g N-vinylpyrrolidone 37.8 g N-vinylimidazole-methosulphate solution (45% strength by weight in water) 28.5 g N-vinylimidazole Feed 2: Initiator solution from: 1.4 g Wako ^® V 50 41.9 g VE water Feed 3: Solution 1.28 g tert-butyl hydroperoxide 70% 20 g VE water Inlet 4: Solution 0.76 g sodium metabisulfite 11 g VE water

In a 2 l pilot stirrer with dosing, reflux condenser, internal thermometer and 3 separate feed devices, the original was heated to 70 ° C. under nitrogen atmosphere and with stirring. Feed 1 was adjusted to a pH of 6.5 by addition of phosphoric acid. When the temperature reached 70 ° C., feed 1 was metered in over three hours and feed 2 for four hours. The mixture was then postpolymerized for two hours. The temperature was raised to 75 ° C. At 75 ° C feed 3 batch was added. After 10 minutes, feed 4 was added in 2 portions within 5 minutes and postpolymerized for 3 hours. It was then steam distilled for 30 minutes and cooled to 40 ° C. Example S11: Copolymer of N-vinylpyrrolidone (VP) / dimethylaminopropylmetacrylamide (DMAPMAM) / methacrylamide (MAM) Template: Monomer mixture 121.5 g VE water 17.5 g Methacrylamide solution (15% by weight in water) 0.75 g dimethylaminopropylmethacrylamide 4.12 g N-vinylpyrrolidone 0.03 g Wako ^® V 50 [2,2'-azobis (2-amidinopropane) dihydrochloride] Feed 1: Monomer mixture of: 82.5 g N-vinylpyrrolidone 15 g dimethylaminopropylmethacrylamide 350 g Methacrylamide solution (15% by weight in water) Feed 2: Initiator solution from: 0.6 g Wako ^® V 50 20.97 g water Feed 3: Initiator solution from: 0.45 g Wako ^® V 50 10.5 g water

In a 1 l pilot agitator with dosage, reflux condenser, internal thermometer and 3 separate feeders, the receiver was placed under nitrogen atmosphere and with stirring Heated to 70 ° C. at Reaching the temperature of 70 ° C feed 1 was metered in three and feed 2 in four hours. Subsequently was postpolymerized for two hours.

at 70 ° C was Feed 3 metered in 10 minutes and postpolymerized for another four hours. Subsequently was for Steam distilled for 30 minutes and cooled to 40 ° C.

applications

The copolymers synthesized according to Synthesis Examples S1 to S11 were prepared according to the following composition as foam formulations (Examples SF1 to SF16). SF1-SF16: foam formulations: 2,00 g Luviquat Mono ^® LS 0.20 g perfume oil 2,00 g WS * polymer 0.10 g Euxyl ^® K 100 qs Phenonip ^® ad 100 g Water that. 10.00 g Propane / butane 3.5 bar

production: The components were weighed and slowly homogenized at room temperature with stirring. Thereafter, the preparation was filled into a suitable container and added the propellant gas.

* WS: active ingredient polymer stands for the mass polymer in g in 100g of the total formulation

SF2, SF4, SF7, SF9, SF14: The pH of foam formulations based on the polymers as specified in Table 2 was with lactic acid adjusted to the pH indicated in Table 2.

SF11 and SF12 are foam formulations in which the pH of the aqueous Preparation after completion of the polymerization but before the formulation was set as a foam.

SF16, SF18: the pH of the foam formulation based on the polymer as reported in Ta Table 2 was adjusted to the pH indicated in Table 2 with phosphoric acid.

SF1, SF3, SF5, SF6, SF8, SF10, SF13 and SF15 are foam formulations, where the pH of the aqueous Preparation not adjusted after complete polymerization was (Comparative Examples).

determination of the K value

The K values are calculated according to Fikentscher, Cellulose Chemistry, Vol. 13, p. 58 to 64 (1932) at 25 ° C in watery / ethanolic or ethanolic solution measured and provide a measure of the molecular weight dar. The aqueous / ethanolic or ethanolic solution contains the polymers 1 g of polymer in 100 ml of solution. In the case, that the polymers are in the form of aqueous dispersions, become dependent of the polymer content of the dispersion corresponding amounts of the dispersion filled with ethanol to 100 ml, so that the concentration of 1 g of polymer in 100 ml of solution arise. The K value is measured in a micro Ubbelohde capillary Type M Ic from Schott.

calculation of K value with mixing correction for water in ethanol The below listed Factors in the equation of the mixture correction are exclusive to this type of capillary at a measuring temperature of 25 ° C.

Calculation K-value:

• 

Relative viscosity:

• η rel  = (t lsg  - HC lsg ) / (T LM  - HC LM )

Calculation of the mixture correction:

mixtures of water in ethanol show nonproportional changes the viscosity of the solvent mixture in terms of the proportion of water.

On Reason for the nature of the sample (aqueous dispersion of a polymer) gets into the ethanolic sample solution introduced water through the sample weight. This amount of water is by the mixing correction in the running time of the solvent calculated so that the relative viscosity according to the admixture is corrected by water.

Runtime solvent mixture:

• t LM  = t O  + t M

Time Correction:

• t M  = -7.486100e-5 · c w 4  + 3,785,884 E-3 · c w 3  - 8.063441E-2 · c w 2  + 1,999,207 · c w  + 2,959,258E-2

Solvent content of water:

• c w = c / FG / 100 * (1 - FG / 100)

  c

  Concentration of Measuring solution [g / 100ml]

  c _w

  Concentration of water in the measuring solution [g / 100ml]

  FG

  Solids content of Sample [g / 100g]

  HC _LM

  Hagenbach correction of the solvent [-S]

  HC _Lsg

  Hagenbach correction the measuring solution [-s]

  t _LM

  Lead time of the solvent mixed-corrected [s]

  _tsol

  Lead time of the Measurement solution, measured [s]

  t ₀

  Lead time of the Solvent, measured [s]

  t _M

  Time Correction for the Solvent mixture, calculated [s]

  z

  η _rel in the Fikentscher equation (K value calculation)

CurI Retention:

The wet strand of hair is expressed between filter paper, dipped three times in the polymer solution (formulation without propellant gas), stripped in between with the fingers and again pressed between filter paper. Then the hair is wrapped around a Teflon stick and fastened with filter paper and rubber ring. Subsequently, the hair strands are dried for about 90 min at 70 to 80 ° C in a warming cabinet. After cooling to room temperature, the curls are stripped off while preserving the shape and hung on a specially prepared frame and measured the curl length (L ₀ ) on the scale in cm.

For the determination of a CurI retention value, 5 hair curls should be used. The Curls are hanging in a climatic chamber at 20 ° C and 75% and 90% rel. Humidity set. After 5 hours, the Length (Lt) read.

L

= Länge der Haare (15,5 cm)

L₀

= Länge der Haarlocke nach dem Trocknen

L_t

= Länge der Haarlocke nach Klimabehandlung

The CurI retention is calculated as follows:

L

= Length of hair (15.5 cm)

L ₀

= Length of hair lock after drying

L _t

= Length of hair lock after climate treatment

When CurI Retention is the average of the 5 individual measurements after 5 h at 20 ° C and 75% and 90% rel. Humidity indicated.

Bending strength:

The dry, weighed strands are dipped three times in demineralised water, stripped, between filter paper pulled the trigger and weighed. Subsequently become the strands three times in the to be tested polymer solution (Formulation without propellant gas) dipped, when pulling out with the Stripped fingers and also pressed between filter paper and weighed. After that, the strand becomes shaped by hand so that the Cross section as possible becomes round. The strand becomes free-hanging to dry with a clamp in a climatic chamber (21 ° C and 65% RH) overnight suspended.

The exams be in a climate room at 21 ° C and 65% rel. Humidity by means of a tension / compression tester (Typ Easytest 86 802, Fa.Frank) performed. The strand of hair is symmetrical on two cylindrical rollers (diameter 4 mm, distance 90 mm) of the sample holder. In the middle is now from the top with a rounded stamp the strand is bent 40 mm (breaking the polymer film). The one for it required force is measured with a load cell (50 N or 10 N) and stated in Newton. Each polymer solution will be at 5 different strands of hair checked.

When Result, the mean value from the 5 individual measurements is used.

The Determination of the K value, the pH, the CurI retention and the flexural strength was for those listed in Table 2 Formulations performed.

Table 2

• * Comparative experiments

PF1 to PF11) Pump spray

Furthermore can preservatives, soluble ethoxylated silicone, Perfume oil and more cosmetic usual Ingredients are added.

production: All components are weighed in slowly at room temperature with stirring homogenized and the pH with lactic acid or phosphoric acid set a value of pH 5 to pH 6.

GF1 to GF11) gel solidifier 1

Furthermore can preservatives, soluble ethoxylated silicone, Perfume oil and more cosmetically usual Ingredients are added.

production: All components are weighed in slowly at room temperature with stirring homogenized and the pH with lactic acid or phosphoric acid on set a value of pH 5 to pH 6.

GF12 to GF22) gel strengthener 2

Furthermore can preservatives, soluble ethoxylated silicone, Perfume oil and more cosmetic usual Ingredients are added.

production: All components are weighed and submerged at room temperature stir slowly homogenized.

HS1 to HS11) Aqueous hand pump sprays

Furthermore can preservatives, soluble ethoxylated silicone, Perfume oil and more cosmetic usual Ingredients are added.

production: All components are weighed and submerged at room temperature stir slowly homogenized.

SF19 to SF29) Mousse 1

Furthermore can preservatives, soluble ethoxylated silicone, Perfume oil and more cosmetic usual Ingredients are added.

production: The components are weighed and slowly homogenized at room temperature with stirring. Thereafter, the preparation is bottled and the propellant gas is added.

SF30 to SF40) Mousse 2

Furthermore can preservatives, soluble ethoxylated silicone, Perfume oil and more cosmetic usual Ingredients are added.

production: The components are weighed and slowly homogenized at room temperature with stirring. Thereafter, the preparation is bottled and the propellant gas is added.

SF41 to SF51) Mousse 3

Furthermore can preservatives, soluble ethoxylated silicone, Perfume oil and more cosmetic usual Ingredients are added.

production: The components are weighed and slowly homogenized at room temperature with stirring. Thereafter, the preparation is bottled and the propellant gas is added.

CS1 to CS11) Conditioner Shampoo 1

Furthermore can preservatives, soluble ethoxylated silicone, Perfume oil and more cosmetic usual Ingredients are added.

weigh out and stirring Solve phases A and B separately. Phase A with lactic acid (20 wt .-% in water) to a pH of 5 to 6 and adjust with water to 100% by weight fill up. Phase B is slowly stirred into Phase A.

CS12 to CS22) Conditioner Shampoo 2

weigh out and stirring Solve phases A and B separately. Phase A with lactic acid (20 wt .-% in water) to a pH of 5 to 6 and adjust with water to 100 wt .-% fill. Phase B is slowly stirred into Phase A.

CS23 to CS33) Conditioner Shampoo 3

Furthermore can preservatives, soluble ethoxylated silicone, Perfume oil and more cosmetic usual Ingredients are added.

production: The components are weighed in slowly at room temperature with stirring homogenized, the pH with lactic acid or phosphoric acid set a value of pH 5 to pH 6 and with water to 100 % By weight filled up.

CM1 to CM11) Conditioner Mousse 1

Furthermore can preservatives, soluble ethoxylated silicone, Perfume oil and more cosmetic usual Ingredients are added.

production: The components are weighed in slowly at room temperature with stirring homogenized, the pH with lactic acid or phosphoric acid set a value of pH 5 to pH 6 and with water to 100 % By weight filled up. Thereafter, the preparation is bottled and the propellant gas is added.

CM12 to CM22) Conditioner Mousse 2

In addition, preservatives, soluble ethoxylated silicone, par fümöl and other cosmetic usual ingredients are added.

production: The components are weighed in slowly at room temperature with stirring homogenized, the pH with lactic acid or phosphoric acid set a value of pH 5 to pH 6 and with water to 100 % By weight filled up. Thereafter, the preparation is bottled and the propellant gas is added.

SM1 to SM11) Styling Mousse 1

production: The components for phases A and B are weighed in slowly at room temperature with stirring homogenized, the pH of phase B with lactic acid or phosphoric acid adjusted to a value of pH 5 to pH 6 and phase B with water made up to 100% by weight. Then A and B are mixed, the preparation bottled and the propellant (phase C) added.

SM12 to SM22) Styling Mousse 2

production: The components for phases A and B are weighed in slowly at room temperature with stirring homogenized, the pH of phase B with lactic acid or phosphoric acid adjusted to a value of pH 5 to pH 6 and phase B with water made up to 100% by weight. Then A and B are mixed, the preparation bottled and the propellant (phase C) added.

SM23 to SM33) Styling Mousse 3

production: The components for phases A and B are weighed in slowly at room temperature with stirring homogenized, the pH of phase B with lactic acid or phosphoric acid adjusted to a value of pH 5 to pH 6 and phase B with water made up to 100% by weight. Then A and B are mixed, phase C added, the preparation bottled and the propellant gas (phase D) added.

SM34 to SM44) Styling Mousse 4

production: The components for phases A and B are weighed in slowly at room temperature with stirring homogenized, the pH of phase B with lactic acid or phosphoric acid adjusted to a value of pH 5 to pH 6 and phase B with water made up to 100% by weight. Then A and B are mixed, phase C added, the preparation bottled and the propellant gas (phase D) added.

SM45 to SM55) Styling Mousse 5

production: Weigh in and stir Solve phases A and B separately and mix. Phase B with lactic acid or phosphoric acid to a pH of pH 5 to pH 6, phase A or B if necessary add other substances such as preservatives or perfume oil. bottling and propellant (phase C).

SM56 to SM66) Styling Mousse 6

production: Weigh in and stir Solve phases A and B separately and mix. Phase B with lactic acid or phosphoric acid to a pH of pH 5 to pH 6, phase A or B if necessary add other substances such as preservatives or perfume oil. bottling and propellant (phase C).

SM67 to SM77) Styling Mousse 7

production: Weigh in and stir Solve phases A and B separately and mix. Phase B with lactic acid or phosphoric acid to a pH of pH 5 to pH 6, phase A or B if necessary add other substances such as preservatives or perfume oil. bottling and propellant (phase C).

SM78 to SM88) Styling Mousse 8

production: Weigh in and stir Solve phases A and B separately and mix. Phase B with lactic acid or phosphoric acid to a pH of pH 5 to pH 6, phase A or B if necessary add other substances such as preservatives or perfume oil. bottling and propellant (phase C).

SM89 to SM99) Styling Mousse 9

production: Weigh in components and dissolve with stirring and mix. With lactic acid or phosphoric acid on Set a pH of pH 5 to pH 6, if necessary Add further substances such as preservatives or perfume oil. bottling and add propellant gas.

use in the skin cosmetics:

C1 to C11) Standard O / W Cream

production: Weigh in and stir the oil phases and water phase separately homogenize at a temperature of about 80 ° C, aqueous Phase with lactic acid or phosphoric acid to a pH value of pH 5 to pH 6. Water phase slowly Stir in oil phase. Under stir cool slowly to RT.

T1 to T11 daily lotion

production: Weigh in and stir the oil phases and water phase separately homogenize at a temperature of about 80 ° C. Water phase with lactic acid or phosphoric acid to a pH of pH 5 to pH 6 and slowly in oil phase Stir. While stirring cool slowly to RT.

Claims (25)

aqueous Containing preparation A) at least one water-soluble or water-dispersible copolymer A) with cationogenic groups, the a) at least one monomer having at least one protonatable Nitrogen atom and b) at least one further copolymerizable with it Contains monomer in copolymerized form, and B) at least one cosmetically acceptable carrier, in which the pH of the aqueous Preparation has a value in the range of pH 4 to pH 6. aqueous Preparation according to claim 1, wherein the copolymer A) a) at least a monomer having at least one protonatable nitrogen atom selected from N-vinylimidazole, Derivatives thereof and Amides of α, β-ethylenically unsaturated Mono- and dicarboxylic acids with diamines containing at least one primary or secondary amino group have and b) at least one further copolymerizable with it Contains monomer copolymerized. aqueous Preparation according to the claims 1 or 2, wherein the copolymer A) a) N-vinylimidazole and / or a derivative thereof and b) at least one further copolymerizable with it Contains monomer copolymerized. A preparation according to claim 3, wherein the copolymer A) a) N-vinylimidazole and / or a derivative thereof and b1) at least one N-vinyl lactam contains polymerized. A preparation according to claims 1 to 4, wherein the copolymer A) additionally comprises at least one nonionic water-soluble monomer b2) which is different from a) and b1) and is copolymerizable with b2.1) N-vinylamides of saturated C ₁ -C ₈ -monocarboxylic acids, b2 .2) primary amides of α, β-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives which have at most 8 further carbon atoms in addition to the carbonyl carbon atom of the amide group, b2.3) esters α, β-ethylenic unsaturated mono- and dicarboxylic acids with diols, b2.4) amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols which have a primary or secondary amino group, b2.5) in copolymerized form polyether acrylates and mixtures thereof. A preparation according to claims 1 to 5, wherein the copolymer A) additionally at least one monomer b3) which is selected from α, β-ethylenic unsaturated water-soluble In-polymerized compounds with cationic hydrophilic groups contains. A preparation according to claim 6, wherein the monomer b3) selected is among the quaternization products of monomer a). A preparation according to claims 1 to 7, wherein the copolymer A) contains 0.5 to 40% by weight of N-vinylimidazole and / or a derivative thereof, b1) 20 to 99.5% by weight of at least one N-vinyllactam, b2) 0 to 50% by weight of at least one monomer b2) which is selected from b2.1) N-vinylamides of saturated C ₁ -C ₈ monocarboxylic acids, b2.2) primary amides of α, β-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives which, in addition to the carbonyl carbon atom of the amide group, have at most 8 further carbon atoms, b2.3) esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with diols, b2.4) amides α, β- ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols having a primary or secondary amino group, b2.5) polyether acrylates and mixtures thereof and b3) 0 to 30% by weight of at least one monomer selected from α, β-ethylenically unsaturated water-soluble Compounds with cationic hydrophilic groups, in copolymerized form, with the proviso that the sum of the amounts of components a) to b3) gives 100 wt .-%. A preparation according to claim 8, wherein the copolymer A) a) 1 to 30% by weight of the monomer a), b1) 20 to 70 Wt .-% of the monomer b1), b2) from 5 to 50% by weight of the monomer b2) and b3) 0 to 30% by weight of the monomer b3) in copolymerized form contains with the proviso the sum of the amounts of components a) to b3) is 100% by weight results. A preparation according to claim 9, wherein the copolymer A) a) 3 to 20% by weight of the monomer a), b1) 30 to 70 Wt .-% of the monomer b1), b2) from 10 to 40% by weight of the monomer b2), and b3) 0 to 10% by weight of the monomer b3) in copolymerized form contains with the proviso the sum of the amounts of components a) to b3) is 100% by weight results. A preparation according to any one of claims 8 to 10, wherein the copolymer A) a) N-vinylimidazole, b1) N-vinylpyrrolidone, b2) optionally at least one monomer b2) b3) if applicable at least one monomer b3) selected from quaternization products N-vinylimidazole and dimethylaminopropylmethacrylamide, in copolymerized form contains. Preparation according to one of claims 1 to 11, wherein the copolymer A) a) 3 to 15 wt .-% N-vinylimidazole b1) From 30 to 70% by weight of N-vinylpyrrolidone b2) from 20 to 35% by weight of methacrylamide b3) 0 to 10 wt .-% quaternized N-vinylimidazole in copolymerized form contains with the proviso the sum of the amounts of components a) to b3) is 100% by weight results. A preparation as claimed in any of claims 1 to 12, wherein component B) is selected from water, water-miscible organic solvents, preferably C ₂ -C ₄ -alkanols, in particular ethanol, oils, fats, waxes, iv of iii) Esters of C ₆ -C ₃₀ monocarboxylic acids with mono-, di- or trihydric alcohols, saturated acyclic and cyclic hydrocarbons, vi fatty acids, vii fatty alcohols, viii propellant gases and mixtures thereof. A preparation according to any one of claims 1 to 13, containing at least one of the components A) and B) various additives which are selected from cosmetically active ingredients, emulsifiers, surfactants, preservatives, perfume oils, thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, light stabilizers, bleaching agents, gelling agents, conditioners, Colorants, tints, tanning agents, dyes, pigments, bodying agents, moisturizers, restoats, collagen, protein hydrolysates, lipids, antioxidants, defoamers, antistatic agents, emollients and plasticizers. Preparation according to one of claims 1 to 14, containing at least one further water-soluble polymer. A preparation according to claim 15, wherein the water-soluble polymer Chitosan and / or a chitosan derivative is. Preparation according to one of claims 1 to 16 in the form of a gel, foam, spray, a mousse, ointment, cream, Emulsion, suspension, lotion, milk or paste. Preparation according to one of claims 1 to 17, which additionally at least contains a nonionic thickener. A preparation according to any one of claims 1 to 18, wherein the pH Value has a value in the range of pH 5 to pH 6. A preparation according to any one of claims 1 to 19, wherein the pH by adding hydroxycarboxylic acid is set. A preparation according to any one of claims 1 to 19, wherein the pH by adding inorganic acid is set. Process for the preparation of an aqueous Preparation according to the claims 1 to 21, characterized in that the adjustment of the pH value after completion of the preparation of component A) is made. Use of a preparation according to one of claims 1 to 21 in skin cleansing preparations, preparations for the care and protection of Skin, nail care products, preparations for decorative cosmetics and Hair treatment agents. Use according to claim 23 in hair treatment compositions as a fixative and / or as a conditioner. Use according to claims 23 or 24, wherein the Preparations in the form of a hair gel, shampoos, mousse, hair lotions, Hair sprays or hair foam is present.