DE19805432C1 - Hair styling formulation giving flexible hydrophobic polymer film without impairing spraying - Google Patents

Abstract

Hair treatment agent contains fluorinated amine(s) (I) and film-forming polymer(s) (II) with acid groups, which are (partly) neutralised with (I). Preferably (I) is a primary or secondary amine, especially of formula R<1>-NH-R<2> (IA); at least one of R<1> and R<2> = a fluoroalk(en)yl group of the formula (CH2)q(HC=CF)sR<4>; otherwise R<1> = an n-alkyl-group of the formula (CH2)n-CH3 or R<2> = hydrogen (H); R<4> = 1-21 carbon (C) (per)fluoroalkyl; n = 0-20; z = 0-5; s = 0-1; (I) contains >= 2 fluorine (F) atoms. In particular, (I) is of formula CF3-9CF2)x-CH2-NH2 (IB), CF3-(CF2)x-CH2-NH-CH2-(CF2)x-CF3 (IC), RFRF'CC=CH-CH2-NR'R" (ID) or RFRF'CH-CH2-CH2-NR'R" (IE); RF, RF' = F or 1-12 C perfluoroalkyl; R' = 1-20 C (hydroxy)alkyl; R" = H or R'l x = 2-11. PREFERRED POLYMER - (II) is an optionally crosslinked vinyl acetate/crotonic acid, acrylic acid/alkyl acrylate/N-alkylacrylamide or vinyl acetate/crotonate/vinyl alkanoate copolymer; especially a copolymer or alkylacrylamide or alkylaminoalkyl (meth)acrylate with >= 2 monomers selected from (meth)acrylic acid and esters.

Description

The invention relates to a hair treatment composition, which fluorinated amines and polymers with acid contains groups.

Hairstyling products serve primarily to the Hair in shape (for example, gels) the hair State (for example, hair sprays) and the To give hair volume (for example, foaming foams) For styling products, it is a known problem that The grip of the hair after use rough and may seem unnatural. Such a hair feeling is Of the consumer often perceived as disturbing. It is also known that hairstyles with the help of styling agents were created in high humidity quickly lose their shape.

Furthermore, it is known to make the handle of hair conditioning treatment natural by natural that softening substances such. As silicone oils, oils and other substances such. B. triethyl citrate can be incorporated into the recipe. At the same time, these substances also reduce the readiness of polymer films to absorb water vapor, which increases the stability of stability at high humidity. However, the use of these substances has some serious disadvantages:

• - The foaming power of mousses is negative influenced, since the plasticizing substances (esp commonly used silicone oils and other oils) often efficient defoamers are.
• - The spraying image in sprays can already by small Additives to softening substances deteriorate greatly tert.
• - The incorporation into aqueous formulations is due to the often hydrophobic nature of the plasticizers difficult, especially if transparent formulations should be created.
• - The plasticizers bring an additional burden on the hair as they migrate out of the polymer film and attach to the keratinic material can.

It was therefore the task to find a means which does not have the mentioned disadvantages. It has now been found that the addition of fluorinated Amines in hair treatment products containing at least one Contains polymer with acid groups, an improvement of Film flexibility and a hydrophobization causes without any major negative effects other application properties such. B. foaming power  or spray pattern or an additional load of Hair must be accepted.

The invention relates to a hair treatment composition with a content of

• (A) at least one fluorinated amine and
• (B) at least one film-forming polymer having Acid groups, whereby the acid groups of the Completely or partially with the polymer fluorinated amine are neutralized.

Component (A) is preferably in an amount of From 0.01 to 10% by weight, more preferably from 0.05 to 5 weight percent before. Component (B) is located preferably in an amount of 0.01 to 20 Weight percent before. It will be aqueous or aqueous alcoholic solvent systems preferred.

Component (A) is preferably an amine of the general formula NR ¹ R ² R ³ , particularly preferably an amine of the general formula R ¹ -NH-R ² , where R ^{1 is} the radicals (CH ₂ ) _n CH ₃ or (CH ₂ ) _q (HC = CF) _s R ⁴ , R ² and R ³ independently of one another are a hydrogen atom or the radical R ¹ , where at least one of the radicals R ¹ and R ^{2 is} the group (CH ₂ ) _q (HC = CF) _s R ⁴ is, R ^{4 is} a branched or unbranched fluoroalkyl or perfluoroalkyl group having 1 to 21 carbon atoms, n is a number from 0 to 20, q is a number from 0 to 5 and s is a number from 0 to 1 and wherein the Substituents are chosen so that the amine has at least two fluorine atoms. Particularly preferred are primary or secondary amines and those compounds in which the number of fluorine atoms is at least 2.

It is furthermore preferred that component (A) is selected from CF ₃ - (CF ₂ ) _x -CH ₂ -NH ₂ , CF ₃ - (CF ₂ ) _x -CH ₂ -NH-CH ₂ - (CF ₂ ) _x - CF ₃ , R _F R _F 'C = CH-CH ₂ -NR'R "and R _F R _F ' CH-CH ₂ -CH ₂ -NR'R", where R _F and R _F 'represent fluorine or is branched or unbranched perfluoroalkyl groups having 1 to 12 carbon atoms, R 'is branched or unbranched alkyl or hydroxyalkyl groups having 1 to 20 carbon atoms, R''is hydrogen or R' and x is a number from 2 to 11.

Examples of suitable fluorinated amines are the primary amines CF ₃ - (CF ₂ ) _x -CH ₂ -NH ₂ where x = 2 to 11 described in US 2,691,043, and the secondary amines CF ₃ - (CF ₂ ) described in US Pat. No. 2,782,184. _x -CH ₂ -NH-CH ₂ - (CF ₂ ) _x -CF ₃ where x = 0 to 10, the unsaturated amines described in US 3,535,381 R _F R _F 'C = CH-CH ₂ -NR'R'' in which R _F and R _F 'are a fluorine atom or a perfluorinated alkyl radical, R' is an alkyl or hydroxyalkyl radical having 1 to 20 carbon atoms and R '' is a hydrogen atom or R 'and the saturated amines described in EP 0 671 382 A1 general formula R _F -CFH-CH ₂ -CH ₂ -NR ₂ , wherein R _{F is} a perfluorinated alkyl radical having 3 to 17 carbon atoms and R is hydrogen, a C 1 to C 4 alkyl or hydroxyalkyl group.

The polymers of component (B) are in the Hair treatment agent according to the invention partially or completely with the amine of component (A) be neutralized. Preferred are such agents, in which in the polymer of component (B) the acidic 0.1 to 50% groups with the amine of component (A) be neutralized and optionally another Neutralization by additional neutralizing agents takes place, which in the hair cosmetics usually be used. As additional neutralization Medium may be organic or inorganic bases be used. Examples of bases are aminomethyl propanol (AMP), ammonia, triethanolamine, monoethanol amine, NaOH and others.

The polymer with acid groups can be a natural or a synthetic homo- or copolymer with acid groups be contained monomer units, which given if with comonomers that are not acid groups contained, copolymerized. Come as acid groups Sulfonic acid, phosphoric acid and carboxylic acid groups in Consider, of which the carboxylic acid groups are preferred are. Suitable acid group-containing monomers are for example, acrylic acid, methacrylic acid, crotonic acid,  Maleic acid or maleic anhydride, aldehydocarbon acids or ketocarboxylic acids.

Not substituted with acid groups are comonomers For example, acrylamide, methacrylamide, alkyl and Dialkylacrylamide, alkyl and dialkylmethacrylamide, Alkyl acrylate, alkyl methacrylate, vinyl caprolactone, Vinyl pyrrolidone, vinyl ester, vinyl alcohol, propylene glycol or ethylene glycol, amine-substituted vinyl monomers such as dialkylaminoalkyl acrylate, Dialkylaminoalkylmethacrylat, monoalkylaminoalkyl acrylate and monoalkylaminoalkyl methacrylate, wherein the Alkyl groups of these monomers preferably C1 to C7 Alkyl groups, more preferably C1 to C3 alkyl groups are.

Suitable polymers with acid groups are in particular uncrosslinked or with polyfunctional agents crosslinked homopolymers of acrylic acid or the Methacrylic acid, copolymers of acrylic acid or Methacrylic acid with monomers selected from acrylic acid or Methacrylic acid esters, acrylamides, methacrylamides and vinylpyrrolidone, homopolymers of crotonic acid as well Copolymers of crotonic acid with monomers selected from Vinyl esters, acrylic acid or methacrylic esters, Acrylamides and methacrylamides. A suitable one natural polymer is shellac, for example.  

Preferred polymers with acid groups are crosslinked or uncrosslinked vinyl acetate / crotonic acid copolymers, for example in the form of a 60% solution in Isopropanol / water are available. Other suitable anionic polymers are for example terpolymers Acrylic acid, alkyl acrylate and N-alkylacrylamide, in particular acrylic acid / ethyl acrylate / N-t-butylacrylamide Terpolymers or terpolymers of vinyl acetate, crotonate and vinyl alkanoate, especially vinyl acetate / crotonate / vinyl neodecanoate Copolymers.

Further, preferably used polymers with acidic Groups are amphoteric polymers such as Copolymers formed from alkylacrylamide, in particular Octylacrylamide, alkylaminoalkyl methacrylate, in particular t-butylaminoethyl methacrylate and two or more monomers consisting of acrylic acid, Methacrylic acid or its esters.  

In addition, the agent according to the invention can be further Component 0.01 to 50 weight percent, preferably 0.5 to 50 weight percent of at least one syntheti natural or film-forming, nonionic or cationic hair fixative polymer. The hair-setting polymers may be used singly or in be used a mixture. Furthermore you can Polymers with thickening effect can be used.

Under film-forming, hair-setting polymers are intended such polymers are understood which alone in 0.1 to 5% aqueous, alcoholic or aqueous alcoholic solution, are able to to deposit a polymer film on the hair and on this Way to strengthen the hair.

Suitable synthetic, nonionic, film-forming, Hair-setting polymers are, for example, homopolymers of vinylpyrrolidone and homopolymers of N-vinyl formamide. Other suitable synthetic film-forming, Nonionic hair fixing polymers are, for example Copolymers of vinyl pyrrolidone and vinyl acetate,  Terpolymers of vinylpyrrolidone, vinyl acetate and Vinyl propionate, polyacrylamides, polyvinyl alcohols, as well as high molecular weight polyethylene glycol or high molecular copolymers of ethylene glycol with propylene glycol with firming properties.

Suitable natural film-forming polymers with hair Firming effect are, for example, chitosan with a molecular weight of 20,000 to about 5 million, or different saccharide types such as Example polysaccharides or mixtures of oligo-, mono and disaccharides.  

Other suitable natural polymers are Chinese Gum rosin and cellulose derivatives, for example Hydroxypropyl cellulose having a molecular weight of 30,000 to 50,000.

Of the cationic polymers used in the invention may be included, for example Polyvinyl pyrrolidone / dimethylaminoethyl methacrylate Copolymer suitable. Other cationic polymers are for example, the copolymer of polyvinylpyrolidone and Imidazoliminmethochlorid, a terpolymer of dimethyl diallyl ammonium chloride, sodium acrylate and acrylamide, the terpolymer of vinylpyrrolidone, dimethylaminoethyl methacrylate and vinylcaprolactam, quaternized Ammonium salts of hydroxyethyl cellulose and a trimethylammonium-substituted epoxide,  Vinylpyrrolidone / methacrylamidopropyltrimethylammonium chloride copolymer and diquaternary polydimethyl siloxane.

Of the thickeners in the composition of the invention may be included are acrylic acid homopolymers, in particular homopolymers of acrylic acid with a Molecular weight of 2,000,000 to 6,000,000 call. As a further thickener, the inventive composition an acrylic acid homopolymer having a molecular weight of 4 000 000 included. Further thickeners are for example, the polymer of acrylic acid and acrylamide (Sodium salt) with a molecular weight of 2,000,000 to 6,000,000 and sclerotium gum. Especially preferred are the copolymers  of acrylic acid or methacrylic acid.

The agent according to the invention is preferably used in one aqueous or in an aqueous-alcoholic medium assembled. Furthermore, solvents or a mixture of solvents with a boiling point below 400 ° C in an amount of 0.1 to 90 weight percent preferably from 1 to 50 percent by weight be set. Particularly suitable are unbranched or branched hydrocarbons such as pentane, hexane, iso pentane and cyclic hydrocarbons such as cyclopentane and cyclohexane. As alcohols, in particular the commonly used for cosmetic purposes lower alcohols having 1 to 4 carbon atoms such as Example, be included ethanol and isopropanol. Further, particularly preferred water-soluble solutions are glycerol and propylene glycol in an amount to 30 weight percent.

Of course, the agents of the invention Also other common cosmetic additives, such as for example, non-solidifying nonionic polymers, such as polyethylene glycols or copolymers Ethylene glycol and propylene glycol, non-solidifying anionic polymers and unnatural natural Polymers and their combination in an amount of  preferably 0.01-50% by weight; Perfume oils in an amount of preferably 0.01-5% by weight; Opacifiers such as ethylene glycol distearate, in an amount of preferably 0.01-5 weight percent; Wetting agents or emulsifiers from the classes the anionic, cationic, amphoteric or not ionic surfactants without washing Effect like fatty alcohol sulfates, ethoxylated fat alcohols, fatty acid alkanolamides or the Esters of hydrogenated castor oil fatty acids in an amount preferably 0.1-30% by weight; further Humectants, dyes, light stabilizers, Antioxidants, shine and preservatives in an amount of preferably 0.01-10% by weight contain.

Other additives include suitable silicone polymers for Example can be used: polydimethylsiloxane (INCI: Dimethicone), α-hydro-ω-hydroxypolyoxydimethylsilylene (INCI: dimethiconol), cyclic dimethylpolysiloxane (INCI: cyclomethicone), trimethyl (octadecyloxy) silane (INCI: stearoxytrimethylsilane), dimethylsiloxane-glycol Copolymer (INCI: dimethicone copolyol), dimethylsiloxane aminoalkylsiloxane copolymer having hydroxy end groups (INCI: Amodimethicone), Monomethylpolysiloxane with Lauryl side chains and polyoxyethylene and / or poly oxypropylene end chains, (INCI: Laurylmethicon Copolyol), Dimethylsiloxane-Glycol Copolymer Acetate (INCI:  Dimethicone copolyol acetate) dimethy siloxane-aminoalkyl siloxane copolymer with trimethylsilyl end groups (INCI: Trimethyl). Preferred silicone polymers are: Dimethicone, Cyclomethicone, and Dimethiconole.

The terms given above in parentheses comply with the INCI nomenclature (International Cosmetic Ingredients) as they are used for labeling cosmetic active ingredients and excipients are determined.

Also mixtures of silicone polymers are suitable as for example a mixture of dimethicone and Dimethiconol.  

The agent according to the invention can be used in various ways Application forms find application, such as in aerosol preparations as a foam or as a spray, the other than non-aerosol, which by means of a pump or as "pump and spray" is used. The Use in standard O / W and W / O emulsions is the same possible as in application forms as gel, wax or Microemulsion. The agent according to the invention can also as a hair care product such as dyeing or grooming for example as a color stabilizer and hair conditioner be formulated.

If the agent according to the invention is in the form of an aerosol hair spray or aerosol hair lacquer, it additionally contains 15 to 85% by weight, preferably 25 to 75% by weight, of a propellant and is filled in a pressure vessel. Suitable blowing agents are, for example, lower alkanes, such as n-butane, i-butane and propane, or mixtures thereof with dimethyl ether and further at the pressures in question gaseous propellant, such as N ₂ , N ₂ O and CO ₂ and Mixtures of the aforementioned blowing agents suitable.

The inventive means for strengthening the hair can also take the form of one with the help of a suitable one sprayed mechanically operated spray device Non-aerosol hair sprays or a non-aerosol hair lacquer  available. Among mechanical spraying devices are to understand such devices that the Spraying a liquid without using a Allow propellant. As suitable mechanical Sprayer, for example, a spray pump or an elastic provided with a spray valve Container in which the cosmetic according to the invention Medium is filled under pressure, with the elastic container expands and out of the means as a result of the contraction of the elastic container Opening the spray valve is discharged continuously be used.

Furthermore, with the polymer combination according to the invention nation the production of concentrates possible, which a reduced water or solvent content respectively. The concentrates are after transport and optionally storage by adding the required Amount of water or solvent in an application capable hair treatment agent.

Under hair treatment should be the treatment of the human head hair especially for the purpose of Making a hairstyle or hair care be understood.

The inventive agent causes an improved Flexibility of the films and increased resistance  the films to water, without the application important sizes such as foaming power or spray pattern too affect or strain the hair.

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

Examples

The following fluorinated amines were used:

AM131: R _F -CF = CH-CH ₂ -NH-CH ₃ , R _F = C 5 -C 12 perfluoroalkyl, prepared according to US 3,535,381.
AM156: R _F -CFH-CH ₂ -CH ₂ -NH-CH ₂ , R _F = C 5 -C 12 perfluoroalkyl, according to EP 0 671 382 A1.
H ₂ N-CH ₂ - (CF ₂ ) ₆ CF ₃ : Preparation described in US 2,691,043
HN- [CH ₂ - (CF ₂ ) ₂ CF ₃ ] ₂ : Preparation described in USP 2,782,184.

example 1 aerosol spray

In the recipe of a hair spray with extra strong Consolidation was acrylate / acrylamide copolymer (Ultrahold 8, BASF / Germany; 12.2 wt .-%) with AM131 and with Aminomethylpropanol (AMP) according to Table 1 neutrali Siert. Except the neutralization conditions according to Table 1, the formulations 1A to 1E are identical.  

Table 1

Indication of neutralizing agents used in the neutralization in Example 1A to 1E; Percentage data relative to the amount of base required for complete neutralization of Ultrahold® 8.

Table 2 Composition of Formulations 1A to 1E

Ethanol (99.8% pure) (87.6-x)% Ultrahold 8 12.0% Neutralizing agent acc. Tab. 1 % Baysilon Oel PD 5 defoamer 0.4%

Filling ratio: active ingredient solution: 50 g
P / B 1.5 bar: 50 g.

With increasing content of AM131 resulted in one Increasing the flexibility of the polymer film and a  decreasing water solubility of the polymer film. The Increasing the flexibility of the polymer film can be determined by the polymer film between Thumb and forefinger of both hands is held and by torsional or pulling forces is tried, a Achieve breaking the movie.

There was also a reduced water vapor absorption the polymer film festge at high humidity provides. For this purpose, the substance to be tested in Weighed the analytical glass exactly to approx. 10 g. Thereafter, the samples are at 100 ° C for 6 hours dried in a convection oven and at 31% relative air moisture conditioned for 7 days. Well be Weighed the samples 7 days at 75.5% relative Humidity stored and weighed again. From the Weight difference is the water absorption in percent calculated. It is a measure of the hydrophilicity of the Film. There are each triple regulations performed. The results are in Table 3 shown.  

Table 3

Measurement of water vapor absorption

The influence of the neutralizing agent on that for the Application important spray picture was made by multiple Measurement of the droplet size distribution determined. The Results of measurements of droplet size distribution Lungs are shown in Table 4. in this connection d (v, 0.1) denotes the size of the droplets in Micrometer, below the 10 percent of all droplets lie, d (v, 0.5) denotes the size of the droplets in Micrometer, below the 50 percent of all droplets lie. The change of the quantities d (v, 0.1) and d (v, 0.5) are very low for all patterns 1A to 1E and for d (v, 0.9) low. Fluctuations of 10 to 15% around the Mean value of the measurements are in a range that typically due to manufacturing variations Valves and spray heads is caused. The  Sprühbild is thus by the plasticization with the fluorinated amine is not adversely affected.

Table 4

Measurement of droplet size distributions

Example 2 mousse

In a mousse with amphomer as a solidifier component and polyethylene glycol (4) lauryl ether (Dehydol® LS 4, Henkel) as a foamer component the amphomer (t-octylacrylamide / acrylic acid / t-butylamino ethyl methacrylate copolymer) as follows neutral (Table 2-1). The total recipe is in table 2-2:  

Table 2-1

Indication of neutralization agent used for neutralization in percent relative to the total neutralization

Table 2-2

Solution for 2A to 2C

Filling ratio: 92% by weight of active substance solution
8% by weight of propane / butane 5.0 bar.

With increasing content of AM156 was an increase flexibility and decreasing water solubility of the polymer film, without that in the application  important foaming behavior was adversely affected or an additional burden on the hair took place.

Example 3 mousse

In a mousse with amphomer as a solidifier component and Oramix® NS 10 (Decyl Glucoside; Seppic) as a foaming component became the amphomer neutralized as follows (Table 3-1). The Total formulation is shown in Table 3-2:

Table 3-1

Indication of neutralization agent used for neutralization in percent relative to the total neutralization

Table 3-2

Active ingredient solution for 3A to 3C

Filling ratio: 92% by weight of active substance solution
8% by weight of propane / butane 5.0 bar.

With increasing content of AM131 was an increase flexibility and decreasing water solubility of the polymer film, without that in the application important foaming behavior was adversely affected or an additional burden on the hair took place.

Example 4 mousse

In a mousse with amphomer as a solidifier component and Amphoram® F (polyfluorohexyl betaine; Company Ceca Ato) as a foaming component was the  Amphomer neutralized as follows (Table 4-1). The total formulation is shown in Table 4-2:

Table 4-1

Indication of neutralization agent used for neutralization in percent relative to the total neutralization

Table 4-2

Drug solution for 4A to 4C

Filling ratio: 92% by weight of active substance solution
8% by weight of propane / butane 5.0 bar.

With increasing content of AM156 was an increase flexibility and decreasing water solubility of the polymer film, without that in the application important foaming behavior was adversely affected or an additional burden on the hair took place.

Example 5 mousse

In a mousse with vinyl acetate / crotonic acid Copolymer (Luviset® CA-66, BASF) as a solidifying component and Amphoram® F (polyfluorohexyl betaine; Ceca Ato) as a foaming component was the Luviset® CA-66 neutralized as follows (Table 5-1). The Total formulation is shown in Table 5-2:

Table 5-1

Indication of neutralization agent used for neutralization in percent relative to the total neutralization

Table 5-2

Drug solution for 5A to 5C

Filling ratio: 92% by weight of active substance solution
8% by weight of propane / butane 5.0 bar.

With increasing content of AM131 was an increase flexibility and decreasing water solubility of the polymer film, without that in the application important foaming behavior was adversely affected or an additional burden on the hair took place.

Example 6 mousse

In a mousse with Luviset® CA-66 (vinyl acetate / crotonic acid copolymer) as Fixing component Oramix® NS 10 (decyl glucoside) as foaming component The Luviset® CA-66 was neutralized as follows  (Table 6-1). The total formulation is in Table 6-2 shown:

Table 6-1

Indication of neutralization agent used for neutralization in percent relative to the total neutralization

Table 6-2

Drug solution for 6A to 6C

Filling ratio: 92% by weight of active substance solution
8% by weight of propane / butane 5.0 bar.

With increasing content of AM156 was an increase flexibility and decreasing water solubility of the polymer film, without that in the application important foaming behavior is negatively influenced or an additional burden on the hair took place.

Example 7 mousse

In a mousse with vinyl acetate / crotonic acid Copolymer, (60% solution in isopropanol / water, ARISTOFLEX® A from Hoechst / Germany) as Fixer component and Oramix® NS 10 (decyl-glucoside) as Foam component became the Aristoflex® A neutralized as follows (Table 7-1). The Total formulation is shown in Table 7-2:

Table 7-1

Indication of neutralization agent used for neutralization in percent relative to the total neutralization

Table 7-2

Drug solution for 7A to 7C

Filling ratio: 92% by weight of active substance solution
8% by weight of propane / butane 5.0 bar.

With increasing content of AM131 was an increase flexibility and decreasing water solubility of the polymer film, without that in the application important foaming behavior was adversely affected or an additional burden on the hair took place.  

Example 8 mousse

In a mousse with Aristoflex® A (vinyl acetate / crotonic acid Copolymer) as a setting component and Fluowet® SB (anionic fluorosurfactant; Clariant) as a foaming component was the Aristoflex® A is neutralized as follows (Table 8- 1). The total formulation is shown in Table 8-2:

Table 8-1

Indication of neutralization agent used for neutralization in percent relative to the total neutralization

Table 8-2

Drug solution for 8A to 8C

Filling ratio: 92% by weight of active substance solution
8% by weight of propane / butane 5.0 bar.

With increasing content of AM156 was an increase flexibility and decreasing water solubility of the polymer film, without that in the application important foaming behavior was adversely affected or an additional burden on the hair took place.

Example 9 mousse

7.50 g Aristoflex® A (vinyl acetate / crotonic acid copolymer) (40% in isopropanol) 0.23 g AMP 95% 0.11 g H ₂ N-CH ₂ - (CF ₂ ) ₆ CF ₃ 1.00 g Polyvinylpoyrrolidon 0.70 g Vinylpyrrolydon-vinyl acetate copolymer 1.00 g Oramix® NS 10 (decyl glucoside) 30.00 g ethanol 59.46 g water 100.00 g

Filling ratio: 92% by weight of active ingredient solution;
8% by weight of propane / butane 5.0 bar.

Example 10 mousse

7.50 g Aristoflex® A (vinyl acetate / crotonic acid copolymer) (40% in isopropanol) 0.23 g AMP 95% 0.11 g HN- [CH ₂ - (CF ₂ ) ₂ CF ₃ ] ₂ 1.00 g polyvinylpyrrolidone 0.70 g Vinylpyrrolidone-vinyl acetate copolymer 1.00 g Oramix® NS 10 (decyl glucoside) 30.00 g ethanol 59.46 g water AL = R <100.00 g

Filling ratio: 92% by weight of active ingredient solution;
8% by weight of propane / butane 5.0 bar

Example 11 mousse

3.00 g Amphomer.RTM 0.57 g AMP 95% 0.26 g HN- [CH ₂ - (CF ₂ ) ₂ CF ₃ ] ₂ 1.00 g polyvinylpyrrolidone 0.70 g Vinylpyrrolidone-vinyl acetate copolymer 1.00 g Oramix® NS 10 (decyl glucoside) 30.00 g ethanol 63.47 g water AL = R <100.00 g

Filling ratio: 92% by weight of active ingredient solution;
8% by weight of propane / butane 5.0 bar

Example 12 mousse

3.00 g Aristoflex® A (vinyl acetate / crotonic acid copolymer) (40% in isopropanol) 0.57 g AMP 95% 0.27 g H ₂ N-CH ₂ - (CF ₂ ) ₆ CF ₃ 1.00 g polyvinylpyrrolidone 0.70 g Vinylpyrrolidone-vinyl acetate copolymer 1.00 g Oramix® NS 10 (decyl glucoside) 30.00 g ethanol 63.46 g water AL = R <100.00 g

Filling ratio: 92% by weight of active ingredient solution;
8% by weight of propane / butane 5.0 bar.

Example 13 liquid setting

5.00 g Vinyl acetate / crotonic acid copolymer, 60% solution in isopropanol / water (ARISTOFLEX® from Hoechst / Germany) 0.21 g AMP 0.33 g AM131 50.00 g ethanol 0.50 g perfume oil 43.75 g water AL = R <100.00 g

Example 14 Gel-shaped solidifier

3.00 g Luviset® CA-66 (vinyl acetate / crotonic acid copolymer) 1.34 g AMP 2.14 g AM156 30.00 g ethanol 66.52 g Carbopol® 980; 1% in water, neutralized to pH 7 with AMP AL = R <100.00 g

Example 15 Gel-shaped solidifier

3.00 g Luviset® CA-66 (vinyl acetate / crotonic acid copolymer) 1.34 g AMP 2.14 g AM131 30.00 g ethanol 2,00 g Vinylpyrrolidone-vinyl acetate copolymer 64.52 g Carbopol® 980 (homopolymers of acrylic acid); 1% in water, neutralized to pH 7 with AMP AL = R <100.00 g

Example 16 Gel-shaped solidifier

3.00 g Luviset® CA-66 (vinyl acetate / crotonic acid copolymer) 1.21 g AMP 0.60 g H ₂ N-CH ₂ - (CF ₂ ) ₆ CF ₃ 30.00 g ethanol 2,00 g Vinylpyrrolidone-vinyl acetate copolymer 63.19 g Carbopol® 980 (homopolymers of acrylic acid); 1% in water, neutralized to pH 7 with AMP AL = R <100.00 g

Example 17 Gel-shaped solidifier

3.00 g Luviset® CA-66 (vinyl acetate / crotonic acid copolymer) 1.21 g AMP 0.57 g HN- [CH ₂ - (CF ₂ ) ₂ CF ₃ ] ₂ 30.00 g ethanol 2,00 g Vinylpyrrolidone-vinyl acetate copolymer 63.22 g Carbopol® 980 (homopolymers of acrylic acid); 1% in water, neutralized to pH 7 with AMP AL = R <100.00 g

Example 18 Non-aerosol hair spray

1.00 g Amphomer.RTM 0.20 g AMP 95% 0.06 g AM131 3.00 g Vinylpyrrolidone-vinyl acetate copolymer 95.74 g ethanol AL = R <100.00 g

Example 19 Non-aerosol hair spray

1.00 g Amphomer.RTM 0.20 g AMP 95% 0.08 g HN- [CH ₂ - (CF ₂ ) ₂ CF ₃ ] ₂ 3.00 g Vinylpyrrolidone-vinyl acetate copolymer 95.21 g ethanol AL = R <100.00 g

Example 20 Non-aerosol hair spray

1.00 g Amphomer.RTM 0.20 g AMP 95% 0.06 g AM156 3.00 g Vinylpyrrolidone-vinyl acetate copolymer 50.00 g water 45.74 g ethanol AL = R <100.00 g

Example 21 Aerosol hairspray

0.12 g AM131 0.40 g AMP 95% 2,00 g Amphomer.RTM 3.00 g Vinylpyrrolidone-vinyl acetate copolymer 49.78 g ethanol 44.70 g Propane / butane AL = R <100.00 g

Claims (12)

1. hair treatment products containing

• (A) at least one fluorinated amine and
• (B) at least one film-forming polymer having acid groups, wherein the acid groups of the polymer are completely or partially neutralized with the fluorinated amine.

2. Composition according to claim 1, characterized in that from 0.01 to 10% by weight of component (A) contains. 3. Composition according to one of the preceding claims, characterized in that component (A) a is primary or a secondary amine. 4. Composition according to one of the preceding claims, characterized in that component (A) has the general formula R ¹ -NH-R ² , wherein R ^{1 is} the radicals (CH ₂ ) -CH ₃ or (CH ₂ ) _q (HC = CF) _s R ⁴ , R ^{2 is} a hydrogen atom or the radical R ¹ , wherein at least one of R ¹ and R ^{2 is} the group (CH ₂ ) _q (HC = CF) _s R ⁴ , R ^{4 is} a branched or unbranched fluoroalkyl or perfluoroalkyl group having 1 to 21 carbon atoms, n is a number from 0 to 20, q is a number from 0 to 5 and s is a number from 0 to 1 and wherein the substituents are selected such that the amine is at least has two fluorine atoms. 5. Composition according to one of the preceding claims, characterized in that component (A) is selected from CF ₃ - (CF ₂ ) _x -CH ₂ -NH ₂ , CF ₃ - (CF ₂ ) _x -CH ₂ -NH-CH ₂ - (CF ₂ ) _x -CF ₃ -R _F R _F 'C = CH-CH ₂ -NR'R "and R _F R _F ' CH-CH ₂ -CH ₂ -NR'R", where R _F and R _F 'are fluorine or branched or unbranched perfluoroalkyl groups having 1 to 12 carbon atoms, R' is branched or unbranched alkyl or hydroxyalkyl groups having 1 to 20 carbon atoms, R '' is hydrogen or R 'and x is one Number from 2 to 11 means. 6. Composition according to one of the preceding claims, characterized in that it is 0.01 to 20 Weight percent of component (B) contains. 7. Composition according to one of the preceding claims, characterized in that 0.1 to 50 percent of Acid groups of the polymer with at least one fluorinated amine are neutralized. 8. Composition according to one of the preceding claims, characterized in that component (B) is selected from networked or non-networked Vinyl acetate / crotonic acid copolymers, acrylic acid /  Alkyl acrylate / N-alkylacrylamide copolymers and Vinyl acetate / crotonate / vinyl alkanoate copolymers. 9. Composition according to one of the preceding claims, characterized in that component (B) a amphoteric polymer. 10. Composition according to one of the preceding claims, characterized in that component (B) is selected from copolymers formed from Alkylacrylamide, Alkylaminoalkylacrylat or methacrylate and at least two monomers selected from acrylic acid, methacrylic acid or their esters, wherein at least one of the monomers contains at least one acid group. 11. Composition according to one of the preceding claims, characterized in that it is in an aqueous or in an aqueous-alcoholic solvent system is present. 12. Composition according to one of the preceding claims, characterized in that it additionally a natural or synthetic, cationic or non-ionic, film-forming, hair-setting Contains polymer.