DE20023230U1 - Hair treatment agent, useful as styling lotion or mousse, contains terpolymer of vinylpyrrolidone, vinylcaprolactam and basic acrylamide monomer and cationic hair-care substance - Google Patents

Abstract

Hair treatment agent contains (A) terpolymer(s) of vinylpyrrolidone, vinylcaprolactam and a basic acrylamide monomer and (B) hair-care substance(s) with cationic group(s). An independent claim is also included for a hair treatment agent in the form of an aqueous, alcohol or aqueous-alcoholic lotion or non-aerosol spray lotion, combined with suitable mechanical spray, which contains terpolymer(s) (A), other hair-care cationic polymer(s), film-forming, nonionic polymer(s) and cationic surfactant(s).

Description

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1
B es ehr e ibung

Volumizing hair treatment product

The invention relates to a hair treatment agent containing a terpolymer of vinylpyrrolidone, vinylcaprolactam and a basic acrylamide monomer as well as another hair-care cationic substance.

Hair treatment products that give hair more volume and hold are well known. The cosmetic polymers commonly used for this purpose have good setting properties in aqueous or alcoholic solutions, which can shape and set the hair more or less well after application and can also give the hair more volume. However, this effect often does not last long and the desired volume effect is partially lost when the hair is combed through. With fine hair in particular, the hairstyle partially collapses again within a few hours, i.e. the volume effect does not last for a whole day from morning to evening. Many of the setting or volume-giving polymers also often have undesirable side effects, which are noticeable in the treated hair being too rough to the touch, too heavy or insufficiently elastic, or too much visible residue forming on the hair.

From WO 96/19971 terpolymers of vinylpyrrolidone, vinylcaprolactam and 3-(N-dimethylaminopropyl)-methacrylamide are known and their use in hair

setting agents, especially in aerosol and pump sprays. These polymers are particularly suitable for use in water-based spray formulations with a reduced content of volatile organic components (low VOC sprays). The polymers have good setting properties, but give the hair a relatively rough feel and a relatively high level of stress.

The task was therefore to provide a hair treatment product that has the advantages of a typical styling product, is particularly characterized by a long-lasting volume effect, but at the same time also ensures good hair care properties, particularly in terms of elasticity, low stress and low residue. In addition, the components used in the product should be compatible with each other, i.e. the product should be as homogeneous and clear as possible and unintentional precipitation of recipe ingredients should be avoided. 20

It has now been found that the object is achieved by a hair treatment agent containing

(A) at least one terpolymer of vinylpyrrolidone, vinylcaprolactam and a basic acrylamide monomer and

(B) at least one hair care substance having at least one cationic group.

The terpolymer (A) is preferably contained in the agent according to the invention in an amount of 0.01 to 20, particularly preferably 0.1 to 5 percent by weight and the cationic substance (B) in an amount of 0.01 to 10, particularly preferably 0.05 to 5 percent by weight.

Suitable terpolymers (A) are those in which the acrylamide monomer is selected from dialkylaminoalkylmethacrylamide and dialkylaminoalkylacrylamide, where the alkyl groups consist of 1 to 4 carbon atoms. Dimethylaminopropylmethacrylamide is particularly preferred. The preparation of such a polymer is described in WO 96/19971 and is commercially available under the name Aquaflex® SF 4 0 (ISP).

The cationic substance (B) is a substance which has a substantivity to human hair due to cationic or cationizable groups, in particular primary, secondary, tertiary or quaternary amine groups. Suitable cationic substances are selected from cationic surfactants, betainic, amphoteric surfactants, cationic polymers, silicone compounds with cationic or cationizable groups, cationically derivatized proteins or protein hydrolysates and betaine.

Suitable cationic surfactants are surfactants that contain a quaternary ammonium group. These can be cationic or amphoteric, betainic surfactants. Suitable cationic surfactants contain amino groups or quaternized hydrophilic ammonium groups, which carry a positive charge in solution and can be represented by the general formula (I),

N ¹⁺¹ R ¹ R ² R ³ R ⁴ X ^M (I)

where R1 to R4 independently represent aliphatic groups, aromatic groups, alkoxy groups, polyoxyalkylene groups, alkylamido groups, hydroxyalkyl groups,

aryl groups or alkaryl groups having 1 to 22 C atoms and X" represents an anion, for example a halogen, acetate, phosphate, nitrate or alkyl sulfate, preferably a chloride. In addition to the carbon atoms and the hydrogen atoms, the aliphatic groups can also contain cross-links or other groups such as, for example, further amino groups.

Examples of suitable cationic surfactants are the chlorides or bromides of alkyldimethylbenzylammonium salts, alkyltrimethylammonium salts, for example cetyltrimethylammonium chloride or bromide, tetradecyltrimethylammonium chloride or bromide, alkyldimethylhydroxyethylammonium chlorides or bromides, the dialkyldimethylammonium chlorides or bromides, alkylpyridinium salts, for example lauryl or cetylpyridinium chloride, alkylamidoethyltrimethylammonium ether sulfates and compounds with cationic character such as amine oxides, for example alkylmethylamine oxides or alkylaminoethyldimethylamine oxides. Particularly preferred are cetyltrimethylammonium chloride, which is sold, for example, in the form of a 2-6 percent aqueous solution under the trade name Dehyquart A by Henkel KGaA, Düsseldorf/Germany and under the trade name Genamin ⁵ CTAC by Hoechst AG, Frankfurt/Germany, and in the form of a 50 percent solution in isopropanol under the trade name Arquad® 16-50 by Akzo Chemicals GmbH, Düren/Germany.

Suitable amphoteric surfactants are derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds of the formula (II)

( ^R6 ).

R ⁵ -Y ⁽⁺⁾ -CH ₂ -R ⁷ -Z ⁽ ~' (II)

wherein R5 represents a straight chain or branched chain alkyl, alkenyl or hydroxyalkyl group having 8 to 18 carbon atoms and 0 to about 10 ethylene oxide units and 0 to 1 glycerol unit; Y is an N-, P- or S-containing group; R6 is an alkyl or monohydroxyalkyl group having 1 to 3 carbon atoms; X is 1 if Y is a sulfur atom and X is 2 if Y is a nitrogen atom or a phosphorus atom; R7 is an alkylene or hydroxyalkylene group having 1 to 4 carbon atoms and Z ^M represents a carboxylate, sulfate, phosphonate or phosphate group.

Other amphoteric surfactants such as betaines are also suitable for the hair treatment composition according to the invention. Examples of betaines include C8 to C18 alkyl betaines such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethylalphacarboxyethylbetaine, cetyldimethylcarboxymethylbetaine, oleyldimethylgammacarboxypropylbetaine and lauryl-bis(2-hydroxypropyl)alphacarboxyethylbetaine; C8 to C18 sulfobetaines such as cocodimethylsulfopropylbetaine, stearyldimethylsulfopropylbetaine, lauryldimethylsulfoethylbetaine, laurylbis-(2-hydroxyethyl)sulfopropylbetaine; the carboxyl derivatives of imidazoles, the C8- to C18-alkyldimethylammonium acetates, the C8- to C15-alkyldimethylcarbonylmethylammonium salts and the C8- to C18-fatty acid alkylamidobetaines such as coconut fatty acid amidopropylbetaine, which is sold, for example, in the form of a 30% aqueous solution under the trade name Tego" Betaine L7 by Goldschmidt AG

and N-coconut fatty acid amidoethyl-N-[2-(carboxymethoxy)ethyl]-glycerin (CTFA name: Cocoamphocarboxyglycinate), which is sold, for example, in the form of a 50% aqueous solution under the trade name Miranol" C2M by Miranol Chemical Co. Inc.

The suitable cationic polymers are preferably hair-fixing or hair-conditioning polymers. Suitable polymers of component (B) preferably contain quaternary amine groups. The cationic polymers can be homo- or copolymers, with the quaternary nitrogen groups being contained either in the polymer chain or preferably as a substituent on one or more of the monomers. The monomers containing ammonium groups can be copolymerized with non-cationic monomers. Suitable cationic monomers are unsaturated, radically polymerizable compounds which carry at least one cationic group, in particular ammonium-substituted vinyl monomers such as trialkylmethacryloxyalkylammonium, trialkylacryloxyalkylammonium, dialkyldiallylammonium and quaternary vinylammonium monomers with cyclic groups containing cationic nitrogen such as pyridinium, imidazolium or quaternary pyrrolidones, e.g. alkylvinylimidazolium, alkylvinylpyridinium, or alkylvinylpyrrolidone salts. The alkyl groups of these monomers are preferably lower alkyl groups such as Cl to C7 alkyl groups, particularly preferably Cl to C3 alkyl groups.

The monomers containing ammonium groups can be copolymerized with non-cationic monomers. Suitable comonomers are, for example, acrylamide,

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Methacrylamide, alkyl and dialkyl acrylamide, alkyl and dialkyl methacrylamide, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, vinyl caprolactam, vinyl pyrrolidone, vinyl esters, e.g. vinyl acetate, vinyl alcohol, propylene glycol or ethylene glycol, where the alkyl groups of these monomers are preferably C1 to C7 alkyl groups, particularly preferably C1 to C3 alkyl groups.

Suitable polymers with quaternary amine groups are, for example, the polymers described in the CTFA Cosmetic Ingredient Dictionary under the names Polyquaternium, such as methylvinylimidazolium chloride/vinylpyrrolidone copolymer (Polyquaternium-16) or quaternized vinylpyrrolidone/dimethylaminoethyl methacrylate copolymer (Polyquaternium-11), as well as quaternary silicone polymers or oligomers such as silicone polymers with quaternary end groups (Quaternium-80).

Of the cationic polymers that can be contained in the agent according to the invention, for example vinylpyrrolidone/dimethylaminoethyl methacrylate methosulfate copolymer, which is sold under the trade names Gafquat® 755 N and Gafquat® 734 by Gaf Co., USA, and of which Gafquat® 734 is particularly preferred, is suitable. Other cationic polymers are, for example, the copolymer of polyvinylpyrrolidone and imidazolimine methochloride sold by BASF, Germany under the trade name LUVIQUAT® HM 550, the terpolymer of dimethyldiallylammonium chloride, sodium acrylate and acrylamide sold by Calgon/USA under the trade name Merquat Plus 33 00, which is sold by ISP/USA under

the terpolymer of vinylpyrrolidone, dimethylaminoethyl methacrylate and vinylcaprolactam sold under the trade name Gaffix® VC 713 and the vinylpyrrolidone/methacrylamidopropyltrimethylammonium chloride copolymer sold by Gaf under the trade name Gafquat® HS 100.

Suitable cationic polymers derived from natural polymers are cationic derivatives of polysaccharides, for example cationic derivatives of cellulose, starch or guar. Chitosan and chitosan derivatives are also suitable. Cationic polysaccharides have the general formula (III)

GOBN ⁺ R ^a R ^b R ^c X" (III)

G is an anhydroglucose residue, for example starch or cellulose anhydroglucose;
B is a divalent linking group, for example alkylene, oxyalkylene, polyoxyalkylene or hydroxyalkylene;

R ^a , R ^b and R ^c are independently alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl or alkoxyaryl each having up to 18 C atoms, the total number of C atoms in R ^a , R ^b and R ^c preferably being a maximum of 20; X is a common counter anion, has the same meaning as in formula (I) and is preferably chloride. A cationic cellulose is sold under the name Polymer JR by Amerchol and has the INCI name Polyquaternium-10. Another cationic cellulose has the INCI name Polyquaternium-24 and is sold under the trade name Polymer LM-200 by Amerchol. A suitable cationic guar derivative is sold under the trade name

It is sold under the name Jaguar R and has the INCI name Guar Hydroxypropyltrimonium Chloride.

Particularly preferred cation-active substances are chitosan, chitosan salts and chitosan derivatives. The chitosans to be used according to the invention are completely or partially deacetylated chitins. Chitosan is preferably produced from the chitin contained in the shell remains of crustaceans, which is available in large quantities as a cheap and natural raw material. The molecular weight of the chitosan can be distributed over a broad spectrum, for example from 20,000 to approx. 5 million g/mol. A low molecular weight chitosan with a molecular weight of 30,000 to 70,000 g/mol is suitable, for example. However, the molecular weight is preferably over 100,000 g/mol, particularly preferably from 200,000 to 700,000 g/mol. The degree of deacetylation is preferably 10 to 99%, particularly preferably 60 to 99%.

A suitable chitosan is, for example, sold by Kyowa Oil&Fat, Japan, under the trade name "Flonac". It has a molecular weight of 300,000 to 700,000 g/mol and is 70 to 80% deacetylated. A preferred chitosan salt is chitosonium pyrrolidone carboxylate, which is sold, for example, under the name Kytamer PC by Amerchol, USA. The chitosan contained has a molecular weight of approx. 200,000 to 300,000 g/mol and is 70 to 85% deacetylated. Suitable chitosan derivatives are quaternized, alkylated or hydroxyalkylated derivatives, for example hydroxyethyl or hydroxybutyl chitosan.

The chitosans or chitosan derivatives are preferably in neutralized or partially neutralized form. The degree of neutralization for the chitosan or chitosan derivative is preferably at least 50%, particularly preferably between 70 and 100%, based on the number of free base groups. In principle, all cosmetically acceptable inorganic or organic acids can be used as neutralizing agents, such as formic acid, tartaric acid, malic acid, lactic acid, citric acid, pyrrolidonecarboxylic acid, hydrochloric acid, etc., of which pyrrolidonecarboxylic acid is particularly preferred.

Preferred polymers are those which have sufficient alcohol solubility to be present in the agent according to the invention in completely dissolved form. The cationic charge density is preferably 1 to 7 meq/g.

Suitable cation-active silicone compounds preferably have either at least one amino group or at least one ammonium group. Suitable silicone polymers with amino groups are known under the INCI name amodimethicones. These are polydimethylsiloxanes with aminoalkyl groups. The aminoalkyl groups can be lateral or terminal. Suitable aminosilicones are those of the general formula (IV)

R ⁸ R ⁹ R ¹⁰ Si- (OSiR ¹¹ R ¹² ) x- (OSiR ¹³ Q) y-OSiR ¹⁴ R ¹⁵ R ¹⁶ (IV)

R ⁸ , R ⁹ , R ¹⁴ and R ¹⁵ are independently identical or different and are Cl- to ClO-alkyl,

Phenyl, hydroxy, hydrogen, Cl- to ClO-alkoxy or acetoxy, preferably C1-C4-alkyl, particularly preferably methyl;

R ¹⁰ and R ¹⁶ are independently identical or different and are -(CH ₂ ) _a -NH ₂ with a being 1 to 6, Cl- to ClO-alkyl, phenyl, hydroxy, hydrogen, Clbis ClO-alkoxy or acetoxy, preferably Cl-C4-alkyl, particularly preferably methyl;
R ¹¹ , R ¹² and R ¹³ are independently identical or different and are hydrogen, Cl- to C20-hydrocarbon which may contain O- and N-atoms, preferably Cl- to ClO-alkyl or phenyl, particularly preferably Cl- to C4-alkyl, in particular methyl;

Q is -A-NR ¹⁷ R ¹⁸ , or -AN ⁺ R ¹⁷ R ¹⁸ R ¹⁹ where A is a divalent Cl- to C2 0-alkylene compound group, which can also contain 0 and N atoms and OH groups, and R ¹⁷ , R ¹⁸ and R ¹⁹ are independently identical or different and are hydrogen, Cl- to C22-hydrocarbon, preferably Cl- to C-4-alkyl or phenyl. Preferred radicals for Q are -(CH ₂ ) ₃ -NH ₂ , - (CH ₂ ) 3NHCH ₂ CH ₂ NH ₂ , - (CH ₂ ) ₃ OCH ₂ CHOHCH ₂ NH ₂ and

- (CH ₂ ) 3N(CH ₂ CH ₂ OH) ₂ , -(CH ₂ J ₃ -NH ₃ ⁺ and

- (CH ₂ ) ₃ OCH ₂ CHOHCH ₂ N ⁺ (CH ₃ ) ₂ R ²⁰ , where R ²⁰ is a Cl- to C22-alkyl radical which may also contain OH groups.

X means a number between 1 and 10,000, preferably between 1 and 1,000;

Y means a number between 1 and 500, preferably between 1 and 50.
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The molecular weight of the aminosilicones is preferably between 500 and 100,000. The amine content (meq/g) is preferably in the range from 0.05 to 2.3, particularly preferably from 0.1 to 0.5.

Suitable silicone polymers with two terminal quaternary ammonium groups are known under the INCI name Quaternium-80. These are dimethylsiloxanes with two terminal aminoalkyl groups. Suitable quaternary aminosilicones are those of the general formula (V)

R ²¹ R ²² R ²³ N ⁺ -A-SiR ⁸ R ⁹ -(OSiR ¹¹ R ¹² ) _n -OSiR ⁸ R ⁹ -AN ⁺ R ²¹ R ²² R ²³ 2X~ (V) 10

A has the same meaning as given above for formula (IV) and is preferably

- (CH ₂ ) 3OCH ₂ CHOHCH ₂ N ⁺ (CH ₃ ) ₂ R ²⁰ , where R ²⁰ is a Cl- to C22-alkyl radical which may also have OH groups; R ⁸ , R ⁹ , R ¹¹ and R ¹² have the same meaning as given above for formula (IV) and are preferably methyl; R ²¹ , R ²² , and R ²³ independently of one another are Cl- to C22-alkyl radicals which may contain hydroxyl groups and where preferably at least one of the radicals has at least 10 C atoms and the other radicals have 1 to 4 C atoms;

η is a number from 0 to 200, preferably from 10 to 100.

Such diquaternary polydimethylsiloxanes are sold by GOLDSCHMIDT/Germany under the trade names Abil® Quat 3270, 3272 and 3274.

Other suitable cationic, hair-care compounds are cationically modified protein derivatives or cationically modified protein hydrolysates and are known, for example, under the INCI names Lauryldimonium Hydroxypropyl Hydrolyzed Wheat Protein, Lauryldimonium Hydroxypropyl Hydrolyzed

Casein, Lauryldimonium Hydroxypropyl Hydrolyzed Collagen, Lauryldimonium Hydroxypropyl Hydrolyzed Keratin, Lauryldimonium Hydroxypropyl Hydrolyzed Silk, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein or Hydroxypropyltrimonium Hydrolyzed Wheat, Hydroxypropyltrimonium Hydrolyzed Casein, Hydroxypropyltrimonium Hydrolyzed Collagen, Hydroxypropyltrimonium Hydrolyzed Keratin, Hydroxypropyltrimonium Hydrolyzed Rice Bran Protein, Hydroxypropyltrimonium Hydrolyzed Silk, Hydroxypropyltrimonium Hydrolyzed Soy Protein, Hydroxypropyltrimonium Hydrolyzed Vegetable Protein.

Suitable cationically derivatized protein hydrolysates are substance mixtures that can be obtained, for example, by reacting alkaline, acidic or enzymatically hydrolysed proteins with glycidyltrialkylammonium salts or 3-halo-2-hydroxypropyltrialkylammonium salts. Proteins that serve as starting materials for the protein hydrolysates can be of both plant and animal origin. Common starting materials are, for example, keratin, collagen, elastin, soy protein, rice protein, milk protein, wheat protein, silk protein or almond protein. The hydrolysis produces substance mixtures with molecular weights in the range of approx. 100 to approx. 50,000. Common average molecular weights are in the range of approx. 500 to approx. 1000. The cationically derivatized protein hydrolysates advantageously contain one or two long C8 to C22 alkyl chains and correspondingly two or one short Cl to C4 alkyl chains. Compounds containing a long alkyl chain are preferred.

In a preferred embodiment, the agent according to the invention additionally contains at least one non-ionic surfactant. The non-ionic surfactant is preferably present in an amount of 0.01 to 15, particularly preferably 0.05 to 5 percent by weight.

Preference is given to ethoxylated surfactants, the number of ethylene oxide units being between 1 and 1000, preferably between 1 and 300, particularly preferably between 1 and 15. Preference is given to fatty alcohol ethoxylates, fatty amine ethoxylates, fatty acid alkanolamide ethoxylates and fatty acid ester ethoxylates, each with 1 to 15 ethylene oxide units. Examples of suitable fatty alcohol ethoxylates are ethoxylated lauryl, tetradecyl, cetyl, oleyl or stearyl alcohol, which can be used alone or in a mixture, and fatty alcohols of ethoxylated lanolin or ethoxylated lanolin. The ethoxylated fatty alcohols sold under the type name Dehydol by Henkel or under the type name Brij® by ICI Surfactants are also suitable for the hair treatment agent according to the invention.

Among the fatty acid ester ethoxylates, diglyceride ethoxylates are particularly noteworthy, such as castor oil ethoxylated with 25 ethylene oxide units with the INCI name PEG-25 Hydrogenated Castor Oil, sold by ICI Surfactants under the trade name Arlatone G, castor oil ethoxylated with 35 ethylene oxide units with the INCI name PEG-35 Castor Oil, sold by BASF under the trade name Cremophor® El, castor oil ethoxylated with 40 ethylene oxide units with the INCI name PEG-35 Castor Oil, sold by BASF under the trade name Cremophor® RH 410,

hydrogenated castor oil with the INCI name PEG-4O Hydrogenated Castor Oil, and the one from the company Witco

Surfactants are raw materials sold under the name Rewoderm LI.
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Furthermore, the ethoxylated fatty acid sugar esters known as non-ionic surfactants, in particular the ethoxylated sorbitan fatty acid ester, but also non-ethoxylated surfactants, such as the fatty acid sugar esters sold by ICI Surfactants under the trade name Tween® and Arlacel, as well as the alkyl polyglycosides sold by Henkel under the trade name Plantaren® or Plantacare® or by

sold by Seppic under the trade name Oramix, can be used for the cosmetic preparation according to the invention.

In general, it can be said that non-ionic surfactants are suitable for the hair treatment agent according to the invention if they have an HLB value of at most 20, preferably from 5 to 18. A mixture of two surfactants is particularly preferred, with one surfactant having an average HLB value of approx. 8 to 11 and the other surfactant having a higher HLB value of approx. 14 to 17. A mixture of tetraethoxylauryl ether (HLB 9.5) and polysorbate-40 (HLB 15.6) is suitable, for example.

In a further preferred embodiment, the agent according to the invention additionally contains 0.01 to 15 percent by weight, preferably 0.5 to 10 percent by weight of at least one synthetic or natural nonionic film-forming polymer. Preference is given to

in particular those polymers which have sufficient solubility in alcohol or water/alcohol mixtures to be present in the agent according to the invention in completely dissolved form. 5

According to the invention, film-forming polymers are understood to mean polymers which, when used in 0.01 to 5% aqueous, alcoholic or aqueous-alcoholic solution, are capable of depositing a polymer film on the hair.

Suitable synthetic, non-ionic film-forming, hair-fixing polymers are homo- or copolymers which are composed of at least one of the following monomers: vinylpyrrolidone, vinylcaprolactam, vinyl esters such as vinyl acetate, vinyl alcohol, acrylamide, methacrylamide, alkyl and dialkylacrylamide, alkyl and dialkylmethacrylamide, alkyl acrylate, alkyl methacrylate, propylene glycol or ethylene glycol, where the alkyl groups of these monomers are preferably C1 to C7 alkyl groups, particularly preferably C1 to C3 alkyl groups.

Homopolymers of vinyl caprolactam, vinyl pyrrolidone or N-vinylformamide are suitable. Other suitable synthetic film-forming, non-ionic, hair-fixing polymers are, for example, copolymers of vinyl pyrrolidone and vinyl acetate, terpolymers of vinyl pyrrolidone, vinyl acetate and vinyl propionate, polyacrylamides, which are sold, for example, under the trade names Akypomine® P 191 by CHEM-Y, Emmerich, or Sepigel® 305 by Seppic; polyvinyl alcohols, which are sold, for example, under the trade names Elvanol® by Du Pont or Vinol® 523/540 by Air Products, as well as

Polyethylene glycol/polypropylene glycol copolymers, which are sold, for example, under the trade name Ucon by Union Carbide. Polyvinylpyrrolidone and polyvinylpyrrolidone/vinyl acetate copolymers are particularly preferred.

Suitable natural film-forming polymers are, for example, cellulose derivatives, e.g. hydroxypropyl cellulose with a molecular weight of 30,000 to 50,000 g/mol, which is sold, for example, under the trade name Nisso Sl by Lehmann & Voss, Hamburg.

The agent according to the invention is preferably formulated in an aqueous, alcoholic or aqueous-alcoholic medium with preferably at least 10 percent by weight of water. Alcohols which can be present are in particular the lower alcohols with 1 to 4 carbon atoms which are usually used for cosmetic purposes, such as ethanol and isopropanol. The agent according to the invention can be present in a pH range of 2.0 to 9.5. The pH range between 2.5 and

Organic solvents or a mixture of solvents with a boiling point below 400 ^° C can be included as additional cosolvents in an amount of 0.1 to 15 percent by weight, preferably 1 to 10 percent by weight. Unbranched or branched hydrocarbons such as pentane, hexane, isopentane and cyclic hydrocarbons such as cyclopentane and cyclohexane are particularly suitable as additional cosolvents. Other, particularly preferred water-soluble solvents are glycerin, ethylene glycol and propylene glycol in an amount of up to 30 percent by weight.

The agent according to the invention can furthermore contain the additional ingredients customary for hair treatment agents, for example wetting agents or emulsifiers from the classes of anionic or amphoteric surface-active surfactants, such as fatty alcohol sulfates, alkylbenzenesulfonates, alkyltrimethylammonium salts, alkylbetaines, in an amount of 0.1 to 15 percent by weight; humectants; perfume oils in an amount of 0.1 to 0.5 percent by weight; opacifiers, such as ethylene glycol distearate, in an amount of about 0.2 to 5.0 percent by weight; pearlescent agents, such as a mixture of fatty acid monoalkylolamide and ethylene glycol distearate, in an amount of about 1.0 to 10 percent by weight; bactericidal and fungicidal active ingredients such as 2,4,4-trichloro-2-hydroxydiphenyl ether or methylchloroisothiazoline ion, in an amount of 0.01 to 1.0 percent by weight; thickeners such as coconut fatty acid diethanolamide, in an amount of about 0.2 to 3.0 percent by weight, buffer substances such as sodium citrate or sodium phosphate, in an amount of 0.1 to 1.0 percent by weight; colorants such as fluorescein sodium salt, in an amount of about 0.1 to 1.0 percent by weight; care substances such as plant and herbal extracts, protein and silk hydrolysates, lanolin derivatives, in an amount of 0.1 to 5 percent by weight; physiologically compatible silicone derivatives such as volatile or non-volatile silicone oils or high molecular weight siloxane polymers in an amount of 0.05 to 20 percent by weight; Sunscreens, antioxidants, radical scavengers, anti-dandruff agents, in an amount of about 0.01 to 2% by weight; direct hair dyes, hair dyes which

oxidatively developed, oxidizing agents, reducing agents, fatty alcohols, shine enhancers, vitamins, softeners, combability improvers, moisturizing agents and defoamers.
5

The agent according to the invention can be used in various application forms, such as, for example, as a lotion, as a non-aerosol spray lotion, which is used by means of a mechanical device for spraying, as an aerosol foam or as a non-aerosol foam, which is present in combination with a suitable mechanical device for foaming the composition. Use in the form of a lotion thickened with a conventional thickener is also possible.

If the agent according to the invention is in the form of a firming hair lotion, it is in the form of a non-viscous solution, dispersion or emulsion containing at least 10 percent by weight, preferably 20 to 95 percent by weight, of a cosmetically acceptable alcohol. Alcohols that can be used are in particular the lower alcohols with 1 to 4 carbon atoms that are usually used for cosmetic purposes, such as ethanol and isopropanol. The lotion according to the invention is packaged in a portion bottle and can be applied directly to the hair from this. To achieve a volume effect directly from the hairline, the packaging can be equipped with a nozzle, by means of which it can be applied directly to the hairline.

A particularly preferred application form is a non-aerosol spray lotion. Here, the inventive

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The cosmetic agent according to the invention is sprayed using a suitable mechanically operated spray device. Mechanical spray devices are those devices which enable the spraying of a liquid without the use of a propellant. A suitable mechanical spray device can be, for example, a spray pump or an elastic container provided with a spray valve into which the cosmetic agent according to the invention is filled under pressure, the elastic container expanding and from which the agent is continuously released as a result of the contraction of the elastic container when the spray valve is opened.

If the agent according to the invention is in the form of a setting hair mousse, it contains at least one foaming substance known for this purpose. The agent is foamed with or without the aid of propellant gases or chemical blowing agents and worked into the hair as a foam and left in the hair without rinsing. A hair mousse according to the invention has as an additional component a chemical blowing agent and/or a mechanical device for foaming the composition.

Mechanical foaming devices are those devices that enable the foaming of a liquid with or without the use of a propellant. A commercially available pump foamer or an aerosol foam head can be used as a suitable mechanical foaming device.

In a particularly preferred embodiment, the agent according to the invention is in the form of an aqueous,

alcoholic or aqueous-alcoholic non-aerosol spray lotion in combination with a suitable mechanical spraying device or in the form of an aqueous, alcoholic or aqueous-alcoholic lotion containing

(A) 0.01 to 20, preferably 0.1 to 5, percent by weight of at least one terpolymer of vinylpyrrolidone, vinylcaprolactam and a basic acrylamide monomer,

(B) 0.01 to 10, preferably 0.05 to 5, percent by weight of at least one further hair-care cationic polymer

(C) 0.01 to 15, preferably 0.5 to 10, percent by weight of at least one film-forming, nonionic polymer and

(D) 0.01 to 10, preferably 0.05 to 5, percent by weight of at least one cationic surfactant,

wherein the proportions of components (A) to (D) are preferably adjusted so that a clear solution results.

The cosmetic product according to the invention is used by applying it to damp, towel-dried hair in an amount sufficient to achieve the volume effect. The hairstyle can then be styled in the usual way or the hair can be styled and finally blow-dried. However, it is also possible to apply the product directly to dry hair to refresh the volume effect.

The following examples are intended to illustrate the subject matter of the invention in more detail.

22 Examples

Example 1: Aerosol mousse

IA IB Polyquaternium-11 - 1.8g Vinylcaprolactam/PVP/DMAPA
Copolymer 1.8g Cetyltrimethylammonium chloride 0.1g 0.1g Laureth-4 0.18g 0.18g Perfume 0.2g 0.2g Ethanol 8.9g 8.9g Water Ad 100 g Ad 100 g

The active ingredient mixture was filled into an aerosol can with a foam valve in a ratio of 95:5 with propane/butane 5.0 as propellant.

In half-side tests, one half of the hair of a test person was treated with the aerosol foam IA according to the invention and the other half of the hair was treated with the foam IB, which was not according to the invention. The treated hair was assessed sensorially by trained hairdressers. The following assessments were obtained:

Comparison IA vs IB:

The handle is better in both wet and dry hair for Pattern IA. The lay-up is better for Pattern IA and less dusting of the polymer from dry hair is observed for Pattern IA.

Example 2: Pump spray lotion

2A 2 B PVP/VA copolymer - 2.5g Vinylcaprolactam/PVP/DMAPA
Copolymer 1.5g Cetyltrimethylammonium chloride 0.2g 0.2g PEG-4 0 Hydrogenated Castor Oil 0.2g 0.2g Perfume 0.25g 0.25g Ethanol 27g 27g Water Ad 100 g Ad 100 g

In half-side tests, one half of the hair of a test person was treated with the spray lotion 2A according to the invention and the other half of the hair was treated with the spray lotion IB not according to the invention. The treated hair was sensorially assessed by trained hairdressers. The following assessments were obtained:

Comparison 2A vs 2B:

Despite the reduced amount of polymer, a stronger strengthening was observed for sample 2A. Sample 2A showed an improved spray pattern.

Example 3: Pump mousse

3A 3B 3C Polyvinylpyrrolidone (K80) - - 1.4g Vinylcaprolactam/PVP/
DMAPA copolymer 1.4g 0.9g Cocamidopropyl
Hydroxysultaine 0.6g 0.6g 0.6g Cetrimonium chloride 0.25g 0.25g 0.25g Betaine 0.1g o,i g 0.1g citric acid o,i g o,i g o,i g Perfume 0.15g 0.15g 0.15g Ethanol 2.5g 2.5g 2.5g Water Ad 100 g Ad 100 g Ad 100 g

In half-side tests, one half of the hair of a test person was treated with the pump foam 3A according to the invention or the pump foam 3B according to the invention and the other half of the hair was treated with the pump foam 3C not according to the invention. The treated hair was assessed sensorially by trained hairdressers. The following assessments were obtained:

Comparison 3A vs 3C:

With a comparable amount of polymer, more hold was achieved for sample 3A. For sample 3A, the elasticity of the treated hair was greater with less stress and a more natural feel.

Comparison 3B vs 3C:
Despite the reduced amount of polymer, the same hold was achieved for sample 3B. Less visible residue was observed on dry hair for sample 3B.

Example 4: Aerosol mousse

Vinyl caprolactam/PVP/DMAPA copolymer 1.20g Polyquaternium-11 0.80g Betaine 0.15g PEG 2 5 PABA 0.50g Cetrimonium chloride 0.07g Perfume 0.15g Ethanol 8.9g Water Ad 100 g

The active ingredient mixture was filled into an aerosol can with a foam valve in a ratio of 95:5 with propane/butane 5.0 as propellant.

Example 5: Pump spray lotion

Vinyl caprolactam/PVP/DMAPA copolymer 100 g Polyquaternium-16 0.20g Chitosan 0.40g PVP/VA copolymer 2.50g Formic acid 0.12g Cetrimonium phosphate 0.15g Laureth-4 0.10g Perfume 0.10g Ethanol 33g Water Ad 100 g

The hair treated with the spray lotion shows a volume effect that lasts all day, with good hold and is easy to style and blow-dry.

Example 6: Pump mousse

Vinyl caprolactam/PVP/DMAPA copolymer 1.1g Polyquaternium-11 0.4g Cocamidopropyl Hydroxysultaine 0.6g citric acid 0.1g Betaine o,i g Perfume &ogr;,&igr; g Ethanol 8.9g Water Ad 100 g

Claims (16)

1. Hair treatment products containing A) at least 0.01% by weight of at least one terpolymer of vinylpyrrolidone, vinylcaprolactam and a basic acrylamide monomer and B) at least 0.01% by weight of at least one hair care substance having at least one cationic group. 2. Agent according to claim 1, characterized in that the basic acrylamide monomer is selected from dialkylaminoalkylmethacrylamide and dialkylaminoalkylacrylamide, wherein the alkyl groups consist of 1 to 4 carbon atoms. 3. Agent according to claim 1 or 2, characterized in that the hair-care cationic substance is selected from cationic surfactants, polymers with cationic or cationizable groups, silicone compounds with cationic or cationizable groups, cationically derivatized proteins or protein hydrolysates and betaine. 4. Agent according to claim 3, characterized in that the cationic surfactant is selected from compounds of the general formula (I)

N ⁽⁺⁾ R ¹ R ² R ³ R ⁴ X ^(-) (I)

where R1 to R4 independently of one another represent aliphatic groups, aromatic groups, alkoxy groups, polyoxyalkylene groups, alkylamido groups, hydroxyalkyl groups, aryl groups or alkaryl groups having 1 to 22 C atoms and X ^- represents an anion. 5. Agent according to claim 3, characterized in that the polymer with cationic or cationizable groups is selected from methylvinylimidazolium chloride/vinylpyrrolidone copolymers, quaternized vinylpyrrolidone/dimethylaminoethyl methacrylate copolymers, cationically derivatized polysaccharides, chitosan, chitosan salts and chitosan derivatives. 6. Agent according to one of the preceding claims, characterized in that it additionally contains at least one non-ionic film-forming polymer. 7. Agent according to claim 6, characterized in that the nonionic polymer is selected from polyvinylpyrrolidone and polyvinylpyrrolidone/vinyl acetate copolymers. 8. Agent according to one of the preceding claims, characterized in that it is in the form of a lotion, a non-aerosol spray lotion in combination with a mechanical device for spraying, in the form of an aerosol foam in combination with a propellant or in the form of a non-aerosol foam in combination with a mechanical device for foaming. 9. Agent according to one of the preceding claims, characterized in that it is in the form of an aqueous-alcoholic, volumizing hair lotion. 10. Agent according to one of the preceding claims, characterized in that it is in the form of an aqueous-alcoholic non-aerosol spray lotion in combination with a mechanical device for spraying. 11. Hair treatment agent according to one of the preceding claims, characterized in that it - in the form of an aqueous-alcoholic non-aerosol spray lotion - in combination with a suitable mechanical device for spraying and has a content of - at least 0.01% by weight of at least one terpolymer of vinylpyrrolidone, vinylcaprolactam and a dialkylaminoalkylmethacrylamide and - at least 0.01% by weight of at least one cationic surfactant. 12. Hair treatment agent according to claim 1 in the form of an aqueous, alcoholic or aqueous-alcoholic non-aerosol spray lotion in combination with a suitable mechanical device for spraying or in the form of an aqueous, alcoholic or aqueous-alcoholic lotion containing A) at least 0.01% by weight of at least one terpolymer of vinylpyrrolidone, vinylcaprolactam and a basic acrylamide monomer, B) at least 0.01% by weight of at least one other hair-care cationic polymer, C) at least 0.01% by weight of at least one film-forming, non-ionic polymer and D) at least 0.01% by weight of at least one cationic surfactant. 13. Agent according to claim 12, characterized in that the basic acrylamide monomer is selected from dialkylaminoalkylmethacrylamide and dialkylaminoalkylacrylamide, wherein the alkyl groups consist of 1 to 4 carbon atoms. 14. Agent according to one of claims 12 or 13, characterized in that the cationic polymer is selected from methylvinylimidazolium chloride/vinylpyrrolidone copolymers, quaternized vinylpyrrolidone/dimethylaminoethyl methacrylate copolymers, cationically derivatized polysaccharides, chitosan, chitosan salts and chitosan derivatives. 15. Agent according to one of claims 12 to 14, characterized in that the nonionic polymer is selected from polyvinylpyrrolidone and polyvinylpyrrolidone/vinyl acetate copolymers. 16. Agent according to one of claims 12 to 15, characterized in that the cationic surfactant is selected from compounds of formula (I)

N ⁽⁺⁾ R ¹ R ² R ³ R ⁴ X ^(-) (I)

where R1 to R4 independently of one another represent aliphatic groups, aromatic groups, alkoxy groups, polyoxyalkylene groups, alkylamido groups, hydroxyalkyl groups, aryl groups or alkaryl groups having 1 to 22 C atoms and X ^- represents an anion.