MXPA06007618A - Hair styling films and method for producing hair fixing products in film form - Google Patents

Abstract

The invention concerns a method for producing a hair fixing product in film form, during which a viscous, rollable preparation is firstly produced by dissolving or dispersing a polymer in a liquid carrier medium, after which the preparation is shaped into a film by rolling effected by a rolling device, and the liquid carrier medium is evaporated. The invention also concerns hair styling films, which contain at least one hair fixing polymer, advantageously contain additional surfactants or polyols, and which are preferably treated with an adhering, powdery, hydrophobic release agent.

Description

PEL CULAS TO STYLE THE HAIR AND METHOD TO PRODUCE HAIR FIXING PRODUCTS IN THE FORM OF PEL CULA DESCRIPTION OF THE INVENTION The object of the invention is a method for producing hair fixative products in the form of a film as well as hair treatment agents for fixing hair in the form of a solid film, soluble in water, in particular based on of pullulan and optionally additional hair fixative polymers. To provide fixation to human hair or to stabilize a hairstyle made hair treatment agents are used, usually in the form of gels, foams, aerosols or lotions based on liquid solvents. The disadvantage in these solvent-based products is that they are bulky and heavy by virtue of the high content of solvent / propellant, and for this reason they are not well suited to be taken on a trip. The problem is usually solved by packing the products in very small containers. These products have the disadvantage that they only reach for very few applications. In addition, it is not possible to divide them already during manufacturing into fixed, discrete, sufficient portions for an application. Nor is a spatial design possible and provide attractive external forms. In addition, very fluid gels or thixotropic gels that are pressurized under pressure can drain off.

Ref.:173946 hands or hair. By the document JP 01-131109 agents for the treatment of hair in the form of films or plates are known, which are manufactured by casting a solution in molds and evaporating the solvent. This type of films or plates are still not completely satisfactory, in particular as regards the uniformity of the surface, the thickness of the product and the properties of use added thereto, for example, in relation to the speed of dissolution during use . EP 1 317 916 discloses films containing pullulan or modified starch and are made from a disintegration of certain starch derivatives by stretching a film according to the coating method known as "knife-on-roll". and conditioning during the night. It is true that the films described dissolve in a glass with hot water at 37 ° C, however the dissolution behavior on wet hands or damp hair, relevant for applications as hair styling films, is not satisfactory. The method of knife-on-roll coating generally only allows the production of coatings with a thickness of 0.5 mm. The coating thicknesses that can typically be achieved are 1 to 30 mm. Films with a thickness of this magnitude have an unsatisfactory dissolution behavior for applications such as hair styling films. The object -in which the invention is based- was to provide substantially solvent-free films which upon contact with moisture, ie with relatively little water, can be dissolved well by rubbing with the hands, and after being integrated into the hair they develop a hair fixation effect and allow you to make hairstyles. When rubbing, there should not be softened undissolved film particles which, when styling the hairstyle on the head, can lead to undesirable visible or sensitive residues. The films should be stackable and / or so flexible that they can be rolled. They must be resistant against air humidity to such an extent that they do not stick to each other with direct contact and that they can be separated from each other also after prolonged storage. The object of the invention is a method for producing a hair-fixing product in the form of a film, wherein a preparation capable of being laminated by dissolving or dispersing a polymer in a liquid carrier is first produced., and then the form of a film is provided to the preparation by rolling in a rolling device, and simultaneously or the liquid carrier is then evaporated. Also subject of the invention are hair styling films, in particular hair styling films produced in accordance with the invention and the use of these films for fixing hair. The preparation capable of being laminated can have a semi-solid consistency as a mass, or it can also be a viscous liquid with which a suitable support is coated and by lamination with a laminating device the desired film thickness is produced. After drying the finished film is detached from the support. Suitable support materials are, for example, materials capable of being stripped again of silicone, metal, metallized polymers, polytetrafluoroethylene, polyether / polyamide block copolymers, polyurethanes, polyvinyl chloride, nylon, alkylene / styrene copolymers, polyethylene, polyester or others. Suitable lamination devices are, in particular, so-called forward or backward rolling coating applicators with at least two cylinders or rollers that rotate in the same direction or in opposite direction as those skilled in the art of coating and lacquering, wherein a backward rolling method is preferred.

A film in the sense of the invention is a solid product, substantially free of solvent with flat, two-dimensional geometry and a thickness preferably less than or equal to 1 mm, in particular less than 0.5 mm, for example 0.05 mm to less than 0.5 mm . The residual solvent content is preferably less than 5% by weight, in particular less than 1% by weight. Polymers Suitable polymers can already have single film-forming and / or hair-setting properties. But it is also possible to use mixtures of polymers, the mixture having film-forming and / or hair-setting properties after evaporation of the solvent. The polymer content in the preparation capable of being laminated can be from 10 to 80% by weight, from 20 to 70% by weight or from 30 to 60% by weight. After evaporating the liquid carrier the polymer content in the finished film can be 50 to 97% by weight, 60 to 95% by weight or 80 to 95% by weight, a content greater than or equal to 85 is particularly preferred. % in weigh. Preferably at least one of the polymers used is soluble in water. Pullulan is particularly preferred. A suitable pullulan can have a mean molecular weight Mr of 10,000 to 5,000,000. Preferably, at least one hair-fixing polymer is present, in particular a combination of pullulan and at least one hair-fixing polymer. The weight ratio of pullulan to the additional hair fixing polymer can be from 1:10 to 10: 1, in particular from 1: 5 to 5: 1 or from 1: 2 to 2: 1. The ratio is preferably less than 2: 1, particularly preferably less than 1: 1, for example, from 1: 2 to less than 1: 1. The hair fixative polymer can be selected from anionic, cationic, hybrid ionic, nonionic and amphoteric polymers. It can be natural polymers or synthetic polymers. Synthetic polymers are understood to be those polymers which are purely synthetic, not natural in origin, in particular those which are produced by radical polymerization from ethylenically unsaturated monomers or by polycondensation. Natural polymers are understood to mean polymers of natural origin that can subsequently also be chemically or physically modified. Particular preference is given to those polymers which have a sufficient solubility or dispersibility in the vehicle, in particular in water, alcohol or water / alcohol mixtures, to exist in the vehicle in dissolved or homogeneously dispersed form. Hair fixing polymers are understood according to the invention to be those polymers which, when used in aqueous, alcoholic or aqueous-alcoholic solution or dispersion at 0.01 to 5%, are capable of depositing a polymeric hair-fixing film on the hair. Suitable nonionic polymers are the homo or copolymers which are composed of at least one of the following monomers: vinyllactams, in particular vinylpyrrolidone and vinylcaprolactam, vinylesters such as, for example, vinyl acetate, vinyl alcohols, acrylamides, methacrylamides, alkyl acrylamides, dialkyl acrylamides, alkyl methacrylamides, dialkyl methacrylamides, dialkylaminoalkyl methacrylamides, dialkylaminoalkylacrylamines, alkyl acrylates, alkyl methacrylates, propylene glycol or ethylene glycol, wherein the alkyl groups of these monomers are preferably Cl to C7 alkyl groups, particularly preferably Cl to C3 alkyl groups. Suitable are, for example, the homopolymers of vinylcaprolactam, vinylpyrrolidone or N-vinylformamide. Other suitable synthetic film-forming nonionic polymers, hair fixatives are, for example, the copolymers of vinylpyrrolidone and vinyl acetate, the terpolymers of vinylpyrrolidone, vinyl acetate and vinyl propionate, polyacrylamides; polyvinyl alcohols as well as polyethylene glycol / polypropylene glycol copolymers. Polyvinylpyrrolidone is particularly preferred, polyvinylcaprolactate and its copolymers with at least one additional non-ionic monomer, in particular polyvinylpyrrolidone / vinyl acetate copolymers. Suitable anionic hair fixative polymers are, for example, homo or synthetic copolymers of monomer units containing acid groups, which optionally are copolymerized with comonomers which do not contain acid groups. The acid groups are preferably selected from -COOH, -S03H, -OS03H, -OP02H and -OP03H2, of which carboxylic acid groups are preferred. Acid groups can exist without neutralizing, partially or completely neutralized. Preferably they are present in up to 50 to 100% in an anionic or neutralized form. As a neutralizing agent it is possible to use organic or inorganic bases suitable for cosmetic purposes. Examples of the bases are aminoalcohols such as, for example, amino ethylpropanol (AMP), triethanolamine, monoethanolamine or tetrahydroxypropyl-ethyldiamine and ammonia, NaOH and others. Suitable monomers are unsaturated compounds capable of radically polymerising which carry at least one acid group, in particular carboxyvinyl monomers. Suitable monomers containing acid groups are, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid or maleic acid anhydride or their monoesters. Comonomers unsubstituted with acidic groups are, for example, acrylamide, methacrylamide, allyl and dialkylacrylamide, alkyl and dialkyl methacrylamide, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, vinyl pyrrolidone, vinylester, vinylalcohol, propylene glycol or ethylene glycol, amine substituted vinyl monomers, such as example, dialkylaminoalkylacrylate, dialkylaminoalkylmethacrylate, monoalkylaminoalkylacrylate and monoalkylaminoalkylmethacrylate, the alkyl groups of these monomers preferably being C1 to C7 alkyl groups, particularly preferably Cl to C3 alkyl groups. Suitable anionic polymers are, in particular, copolymers of acrylic acid or methacrylic acid with monomers selected from esters of acrylic acid or methacrylic acid, acrylamides, methacrylamides and vinylpyrrolidone, crotonic acid homopolymers and copolymers of crotonic acid with monomers which are selected from vinyl esters, esters of acrylic acid or methacrylic acid, acrylamides and methacrylamides. A suitable natural polymer is, for example, shellac. Preferred anionic polymers are crosslinked or non-crosslinked vinyl acetate / crotonic acid copolymers. Likewise, partially esterified copolymers between vinylmethylether and maleic acid anhydride are preferred. Other preferred anionic polymers are, for example, terpolymers of acrylic acid, alkyl acrylate and N-alkyl acrylamide, in particular terpolymers of acrylic acid / ethylacrylate / γ-t-butylacrylamide or terpolymers of vinyl acetate, crotonate and vinylalkanadate, in particular acetate copolymers vinyl / crotonate / vinylneodecanoate; copolymers of acrylic or methacrylic acid and esters of acrylic acid or methacrylic acid, wherein the alkyl groups preferably contain 1 to 7 carbon atoms, as well as polystyrene sulfonates. Suitable hybrid amphoteric or ionic hair fixative polymers are polymers which, in addition to acidic or anionic groups, contain as additional functional groups basic or cationic groups, in particular primary, secondary, tertiary or quaternary amine groups. Hybrid ionic polymers are polymers which are composed of at least one type of monomer comprising both quaternary amine groups and also acid groups, or polymers which are composed of at least one first type of monomer comprising quaternary amine groups and at least a second type of monomer comprising acid groups. The amphoteric polymers are constituted of, for example, at least one type of monomer comprising acid groups and at least one other type of monomer comprising basic amine groups. Examples of this are copolymers formed of alkyl acrylamide (in particular octylacrylamide), alkylaminoalkyl methacrylate (in particular t-butylaminoethylmethacrylate) and two or more monomers selected from acrylic acid, methacrylic acid or their C1 to C4 alkyl esters, wherein at least one of the monomers comprise an acid group, as obtained, for example, under the tradename of Amphomer® or Amphomer® LV-71. Other suitable polymers are copolymers of acrylic acid, methylacrylate and methacrylamidopropyltrimethylammonium chloride (INCI designation: polyquatemium-47), copolymers of acrylamidopropyltrimethylammonium chloride and acrylates or copolymers of acrylamide, acrylamidopropyltrimethylammonium chloride, 2-amidopropylacrylamidosulfonate and dimethylaminopropylamine (designation I? CI: polyquaternium-43). Also suitable are polymers with monomers having betaine groups, such as, for example, metacrilloylethylbetaine copolymers and two or more acrylic acid monomers or their simple esters, known by the designation I? CI methacryloyl ethyl betaine copolymer / acrylates. Suitable cationic polymers 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 substitutes in one or more of the monomers. The monomers containing ammonium groups can not be copolymerized with cationic monomers. Suitable cationic monomers are unsaturated compounds capable of radical polymerization comprising at least one cationic group, in particular ammonium-substituted vinyl monomers such as, for example, trialkyl methacryloxyalkylammonium, trialkylacryloxyalkyl ammonium, dialkyldiallylammonium and quaternary vinylammonium monomers with cyclic groups containing nitrogens cationics such as pyridinium, imidazolium or quaternary pyrrolidones, for example, alkylvinylimidazolium, alkylvinylpyridinium, or alkylvinylpyrrolidone salts. The alkyl groups of these monomers are preferably lower alkyl groups such as, for example, 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, methacrylamide, alkyl and dialkylacrylamide, alkyl and dialkyl methacrylamide, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, vinyl caprolactam, vinyl pyrrolidone, vinylester, for example, vinyl acetate, vinylalcohol, propylene glycol or ethylene glycol, the alkyl groups being of these monomers are preferably Cl to C7 or Cl to C3 alkyl groups.

The cationic polymers with quaternary amine groups are, for example, the polymers which in the CTFA Cosmetic Ingredient Dictionary are described with the designations of polyquaternium as, methyl vinylimidazolium chloride copolymer / vinylpyrrolidone (polyquaternium 16) or quaternized vinylpyrrolidone / copolymer. dimethylaminoethyl ethacrylate (polyquaternium 11) as well as the quaternary silicone polymers and oligomers with, for example, silicone polymers with quaternary terminal groups (quaternium-80). Of the cationic polymers, for example, the copolymer of vinylpyrrolidone / dimethylaminoethylmethacrylate methosulphate, which is marketed under the tradenames Gafquat® 755 N and Gafquat® 734, is suitable. Other cationic polymers are, for example, the copolymer of polyvinylpyrrolidone and imidazole iminmethochloride sold under the tradename LUVIQUAT® HM 550, the terpolymer of dimethyldiallylammonium chloride, sodium acrylate and acrylamide sold under the tradename Merquat® Plus 3300, the terpolymer - vinylpyrrolidone, dimethylaminoethylmethacrylate and vinylcaprolactam which is marketed under the tradename Gaffix® VC 713 and the vinylpyrrolidone / methacrylamidopropyltrimethylammonium chloride copolymer sold under the tradename Gafquat® HS 100.

Suitable cationic polymers derived from natural polymers are cationic derivatives of polysaccharides, for example, cationic cellulose derivatives, starch or guar. Chitosan and chitosan derivatives are also suitable. The cationic polysaccharides have the general formula G-0-B-N +? + R5R6R7 X "G is an anhydroglucose radical, for example, starch or cellulose anhydroglucose, B is a bivalent linking group, for example, alkylene, oxyalkylene, polyoxyalkylene or hydroxyalkylene; R5, R6 and R7 are, independently of each other, alkyl, aryl, alkylaryl, arylalkyl, alkoxyalkyl or alkoxyaryl with respectively up to 18 carbon atoms, the total number of C atoms in R5, R6 and R7 is preferably at most: X "is an anion, for example, a halogen, acetate, phosphate, nitrate or alkyl sulfate, preferably a chloride. A cationic cellulose is marketed by Amerchol under the name of polymer JR and has the designation INCI polyquaternium-10. Another cationic cellulose has the designation INCI polyquaternium-24 and is marketed under the trade name polymer LM-200 by Amerchol. A suitable cationic guar derivative is marketed under the trade name Jaguar® R and has the designation INCI hydroxypropyltrironium guar chloride. Substances with particularly preferred cationic activity are chitosan, chitosan salts and chitosan derivatives. In the case of the chitosans to be used according to the invention, they are totally or partially deacetylated chitins. The molecular weight of the chitosan can be distributed over a broad spectrum, for example, from 20,000 to about 5 million g / mol. Suitable, for example, is a lower molecular chitosan with a molecular weight of 30,000 to 70,000 g / mol. However, the molecular weight is preferably greater than 100,000 g / mol, particularly preferably from 200,000 to 700,000 g / mol. The degree of deacetylation is preferably from 10 to 99%, ideally from 60 to 99%. A suitable chitosan is marketed, for example, by the company. Kyowa Oil &Fat, Japan, under the brand name of Flonac®. It has a molecular weight of 300,000 to 700,000 g / mol and is deacetylated in 70 to 80%. A preferred chitosan salt is chitosonium pyrrolidonecarboxylate, which is marketed, for example, under the name of ytamer® PC. The chitosan it contains has a molecular weight of approximately 200,000 to 300,000 g / mol and is deacetylated in 70 to 85%. Chitosan derivatives include quaternized, alkylated or hydroxyalkylated derivatives, for example, hydroethyl-, hydroxypropyl- or hydroxybutyl-chitosan. Chitosans or chitosan derivatives are preferably present in neutralized or partially neutralized form. The degree of neutralization for the chitosan or the chitosan derivative is preferably at least 50%, ideally between 70 and 100% relative to the number of free base groups. As a neutralizing agent, it is possible in principle to use all tolerable inorganic or organic acids in cosmetics, such as, for example, formic acid, malic acid, lactic acid, pyrrolidonecarboxylic acid, hydrochloric acid and others, of which pyrrolidone is particularly preferred. carboxylic acid and lactic acid. VEHICLE Liquid vehicles, for example, solvents or dispersing agents such as water, alcohols, ether, ketones or hydrocarbons or mixtures of two or more of the named substances when the substances or mixtures of substances are fluid at room temperature are suitable as the liquid vehicle. 25 ° C). The content of the liquid vehicle in the preparation capable of being laminated can be from 20 to 90% by weight or from 30 to 70% by weight. As alcohols, in particular, the mono- or polyvalent lower alcohols usually used for cosmetic purposes with 1 to 5 C atoms, such as, for example, ethanol, isopropanol, ethylene glycol, glycerin and propylene glycols, in particular 1,2-propylene glycol, can be present.

Additives For further optimization, the films may contain additives, in particular emulsifiers up to 50% by weight, softeners (for example, glycerin, polyethylene glycols) up to 50% by weight or hair brightening active ingredients, in particular oils such as, for example, vegetable oils, hydrocarbon oils or silicone oils up to 30% by weight. The product according to the invention can additionally contain the usual additional components for the hair treatment agents in amounts of typically 0.01 to 15% by weight, moisture preserving agents, aromatic substances in an amount of 0.1 to 0.5% by weight. weight, preservatives in an amount of 0.01 to 1.0% by weight, regulatory substances such as, for example, sodium citrate or sodium phosphate in an amount of 0.1 to 1.0% by weight; coloring substances such as, for example, sodium salt of fluorescein, in an amount of about 0.1 to 1.0% by weight; hair care substances such as, for example, vegetable and herbal extracts, protein and silk hydrolysates, lanolin derivatives in an amount of 0.1 to 5% by weight; physiologically tolerable silicone derivatives, such as, for example, volatile or non-volatile silicone oils or high molecular weight siloxane polymers in an amount of 0.05 to 30% by weight; light protection agents, antioxidants, radical scavengers, antidandruff active agents in an amount of about 0.01 to 2% by weight; vitamins, agents for facilitating combing, pigments and / or solids in the form of water insoluble particles. A particular embodiment of the invention relates to a styling film of the hair having a content of at least 85% by weight, in particular greater than or equal to 85% by weight, to 97% by weight of at least one polymer that fixes the hair. hair and more than 3% by weight, in particular more than 3 to less than 15% by weight of at least one surfactant. Suitable hair fixative polymers are the aforementioned, in particular hair fixative polymers based on polysaccharides and synthetic nonionic hair fixative polymers. A polymer combination of (a) pullulan and (b) at least one polymer selected from polyvinylpyrrolidone and polyvinylpyrrolidone / vinyl acetate copolymer, wherein the weight ratio of (a) to (b) is preferably less than 2: 1 or less than 1: 1, in particular 1:10 or 1: 4 to less than 1: 1. As surfactants it is possible to use nonionic, cationic, anionic or amphoteric surfactants. Anionic surfactants are, for example, fatty alcohol sulfates, alkyl ether sulphates, alkyl benzene sulphonates. Amphoteric surfactants are, for example, betaines such as fatty acid amidoalkylbetaines and sulfobetaines and C8 to C22-betaines alkyl. Preferably the surfactants are selected from nonionic and cationic surfactants. A combination of surfactants consisting of at least one cationic surfactant and at least one nonionic surfactant is particularly preferred. The weight ratio of cationic surfactants to nonionic surfactants can be from 1:10 to 10: 1, from 1: 5 to 5: 1 and in particular from 1: 1.5 to 1.5: 1. Cationic surfactants are surfactants which contain a quaternary ammonium group and can be described by the general formula N, + 1RVR3R4 X (_) where R1 to R4 mean, independently of one another, aliphatic groups, aromatic groups, alkoxy groups, polyoxyalkylene groups, alkylamido groups, hydroxyalkyl groups, aryl groups or alkaryl groups with 1 to 22 C atoms, wherein at least one of the groups R1 to R4 comprises at least 8 C atoms and X represents an anion, for example, a halogen, acetate, phosphate, nitrate or alkyl sulfate, preferably a chloride. The aliphatic groups can also additionally contain the carbon atoms and the hydrogen atoms transverse compounds and other groups such as, for example, other amino groups. Suitable examples for 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, dialkyldimethylammonium chlorides or bromides, alkylpyridinium salts, for example, lauryl or cetylpyridinium chloride, the alkylamidoethyltrimethylammonium sulfoethers as well as cationic compounds such as aminoxides, for example alkylmethylaminoxides or alkylaminoethyldimethyl-aminoxides. Particularly preferred is cetyltrimethylammonium chloride. Nonionic surfactants are listed exemplarily in the "International Cosmetic Ingredient Dictionary and Handbook" (International Dictionary of Cosmetic Ingredients), 7. edition, volume 2 in the "surfactants" section, for example, fatty alcohols oxethylated, oxethylated nonylphenols, mono and diglycerides of fatty acids, ethoxylated and hydrated or non-hydrated castor oil, fatty acid alkanolamides, oxethylated fatty acid esters, sugar fatty acid esters or alkyl glycosides. Preferred surfactants are, for example, ethoxylated fatty alcohols, fatty acids, fatty acid glycerides or alkylphenols, in particular addition products of 2 to 30 mol of ethylene oxide and / or 1 to 5 mol of propylene oxide a C8 to C22 fatty alcohols, to C12 to C22 fatty acids or to alkylphenols with 8 to 15 C atoms in the mono-alkyl group and fatty acid diesters of C12 to C22 of additive products of 1 to 30 mol of oxide from ethylene to glycerin, - addition products of 5 to 60 mol, preferably 20 to 50 mol of ethylene oxide to castor oil or to solidified castor oil (hydrated) - sugar esters of fatty acids, in particular sucrose esters and one or two fatty acids of C8 to C22, INCI: sucrose cocoate, sucrose dilaurate, sucrose distearate, sucrose laurate, sucrose myristate, sucrose oleate, sucrose palmitate, sucrose ricinoleate, sucrose stearate - esters of ac polyglyceride fatty acids, in particular one, two or more fatty acids of C8 to C22 and polyglycerol with preferably 2 to 20 glyceryl units - alkyl glycosides, in particular alkyl oligoglycosides with C6 to C22 alkyl groups. In a particular embodiment, gas bubbles of a suitable gas, preferably air, are enclosed in the films. Films that have gas bubbles enclosed are characterized by particularly good dissolution properties and a particularly good ease of rubbing and incorporation into the hair. The introduction of the gas bubbles can be carried out according to a known method of production of synthetic material containing bubbles, for example, according to one of the following methods: (1) Use of an inflation agent or propulsion (blowing agent = inflation agent as it is known in English), (2) foaming by mechanical agitation of the vehicle mass still liquid or viscous, (3) by a chemical reaction that produces gas, (4) use of a easily volatile solvent and evaporation at elevated temperatures, (5) injection of a liquefied gas into the still viscous vehicle mass. Inflation agents are chemical substances that, when heated, disintegrate and release a gas, for example, nitrogen, carbon dioxide, carbon monoxide, ammonia or hydrogen. The inorganic inflation agents are, for example, carbonates, bicarbonates, boron hydrides, silicon oxyhydrides, etc. Organic inflation agents such as those used in the manufacture of porous or bubble-containing synthetic materials are particularly preferred. In a preferred embodiment, the hair styling film contains at least 50% by weight of hair fixing polymers, being that it contains pullulan in combination with at least one other hair-fixing polymer and the weight ratio of pullulan with respect to the additional hair-fixing polymer is less than 1: 1, that is, the amount of pullulan used is less than that of the additional hair fixative polymer. The pullulan content is preferably 15 to 45% by weight, and the content of the additional hair-fixing polymer is preferably 30 to 70% by weight. Combinations of pullulan with synthetic styling polymers can lead to films that by virtue of a certain fragility and friability are still not completely satisfactory. This can be improved by a polyol content. For this reason, in another preferred embodiment, the hair styling film additionally contains at least one polyol. A polyol is an organic compound comprising two or more alcoholic hydroxy groups. Suitable polyols are, for example, polyvalent alcohols with preferably up to 5 C atoms, in particular glycols and glycerin, as well as sugar alcohols and liquid polyethylene glycols at 25 ° C. The glycols are, for example, ethylene glycol, propylene glycol or butylene glycol. The sugar alcohols are, for example, sorbitol, mannitol, malitol and lactitol. The liquid polyethylene glycols are, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, etc., preferably those with a degree of polymerization of up to about 12 and a molecular weight of up to about 600. A combination of 50 to 97% by weight of hair fixative polymer and 1 to 50% by weight, in particular more than 5% by weight, for example, 5 to 20 or 10 to 15% by weight of polyol relative to the dry, anhydrous film, being particularly preferred the glycerin. The polyol content in particular improves the transparency and elasticity of the film, ie the films do not break so easily. At higher ambient temperatures and / or higher air humidity there is a risk that the styling films adhere to each other in the package and it is no longer possible to separate them well and remove them from the packaging. This can be improved by the use of suitable separation agents. A further preferred embodiment therefore relates to films for styling the hair which are treated with a separation agent in powder form. The preferably hydrophobic separation agent adheres externally to the film and prevents a cohesion of the films, in particular when storing them or using them with high air humidity. Suitable separating agents are, for example, talc, starch or modified starch. The modification of the starch can be carried out in one of the generally known forms, including physical, chemical or enzymatic modifications. Physical modifications are, for example, thermal treatments or treatments with cutting forces. Chemical modifications are, for example, crosslinking, acetylation, esterification, hydroxyethylation, hydroxypropylation, phosphorylation, succinates and substituted succinates. Modified starches are preferred with the designations INCI octenyl succinate and starch and modified corn starch (aluminum starch octenylsuccinate and corn starch modified as known in English). The separation agent is applied on finished dried films. Typical amounts of use are from about 0.01 to 0.1 g, preferably 0.02 to 0.05 g per film of a size of 4 x 4 cm and a thickness of up to 0.5 mm. The films treated with the separation agent are characterized by a better non-stickiness and can still be removed well from the packaging even after several weeks without cohesion. At the same time, used to stylize the hair as it is established, the separation agents unexpectedly leave no visible residue on the hair. Use The films can be packed very compact and space-saving, for example as a roll or as plates stacked on top of each other. Movies can be rubbed with wet or damp hands. Next, the total or partially dissolved film can be applied to the dry or wet hair, and a styling configuration can be effected as with the use of a conventional styling gel. The films can also be applied directly on wet or damp hair and be incorporated by hand into the hair. The following examples should explain the object of the invention in greater detail. EXAMPLES Example 1 Preparation capable of being laminated 45 g of polyvinyl pyrrolidone (Luviskol® K90) 5 g of Rewoteric® AM CAS (cocamidopropyl hydroxysultaine, 50% in water) 0.25 g of perfume to 100 g of ethanol Example 2: styling film 42.5 g of polyvinyl pyrrolidone (Luviskol® K90) 42.0 pullulan 7.5 g cetyltrimethylammonium chloride 7.5 g PEG-40, hydrated castor oil 0.5 g perfume Example 3 styling films From compositions A, B and C, masses capable of being laminated with water as a solvent are produced. By rolling the masses, films are produced, and the films are then dried. The films are rated according to the following criteria: (a) solubility behavior when rubbing with hands with very little water: ++; good: +; Sufficient: 0; bad: - (b) foaming behavior when incorporated into the hair without foaming: +; with foaming: - (c) good tackiness: +; bad stickiness: - (d) flocculation behavior when incorporated in the hair: no flocculation, no formation of visible residues: +; with flocculation, visible residues: - (e) fixation behavior: good hair fixation: +; weak hair fixation: 0; without hair fixation: - Example 4 Styling films containing glycerin Example 5 Preparations for producing styling films with and without glycerin The hair styling films produced from preparation A are very elastic and can work very well, that is, dissolve in the hand with some water and incorporate into the hair. In contrast, the films produced from preparation B are more fragile and friable and can not work as well. Example 6 styling films treated with separating agent (1) Aluminum starch octenylsuccinate, hydrophobic starch (2) Aluminum starch octenylsuccinate, hydrophobic starch (3) Modified corn starch; hydrophobic starch; Ca salt of the ester formed by the reaction of 3- (dodecenyl) dihydro-2,5-furandione and corn starch Films with a size of 4 x 4 mm are produced and treated in each case with 0.03 g of treatment agent later. All films are not sticky and can be separated well from each other. In contrast, the corresponding films without subsequent treatment are stuck together after some storage time and it is no longer possible to separate them easily from each other.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (27)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. Method for the production of a hair-fixing product in the form of a film, characterized in that a preparation capable of being laminated is produced first by dissolving or dispersing a polymer in a liquid vehicle, and then the preparation is brought into the form of a film by rolling with a rolling device, and - the liquid vehicle evaporates simultaneously or later.
2. 2. Method according to claim 1, characterized in that the polymer is a film-forming polymer and / or hair fixative. Method according to one of the preceding claims, characterized in that the liquid carrier is selected from water, alcohols, ethers, ketones and hydrocarbons, or from mixtures of the mentioned substances, provided that the substances or mixtures of substances are liquid to the ambient temperature of 25 ° C. Method according to one of the preceding claims, characterized in that in the preparation capable of being laminated the content of the polymer is from 10 to 80% by weight and the content of the liquid vehicle from 20 to 90% by weight. Method according to one of the preceding claims, characterized in that after evaporating the liquid vehicle the proportion of the polymer in the film is 50 to 97% by weight. Method according to one of the preceding claims, characterized in that the preparation contains at least one water-soluble polymer. Method according to one of the preceding claims, characterized in that the preparation contains pullulan. 8. Method according to claim 7, characterized in that the pullulan has an average molecular weight of 10,000 to 5,000,000. Method according to one of claims 7 to 8, characterized in that at least one hair-fixing polymer is additionally contained. Method according to claim 9, characterized in that the weight ratio of pullulan to the additional hair fixing polymer is from 1:10 to 10: 1. Method according to claim 10, characterized in that the additional hair-fixing polymer is selected from polymers consisting of at least one monomer selected from vinyllactams, vinylesters, vinyl alcohols, acrylamides, methacrylamides, alkyl acrylates, dialkylacrylamides, alkyl methacrylamides, dialkyl methacrylamides, dialkylamino alkyl methacrylamides, dialkylaminoalkylacrylamides, alkyl acrylates, alkyl methacrylates, propylene glycol or ethylene glycol; - of polymers consisting of at least one monomer selected from acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic acid anhydride, monoesters of maleic acid; - of polymers consisting of at least one monomer selected from trialkyl methacryloxyalkyl ammonium, trialkylacryloxyalkyl ammonium, dialkyldiallylammonium, alkyl vinylimidazolium, alkylvinylpyridinium or alkylvinylpyrrolidone; - of polymers consisting of at least one type of monomer comprising acid groups and at least one additional monomer type comprising basic amine groups; - of polymers consisting of at least one type of monomer comprising both quaternary amine groups and also acid groups, or of polymers which consist of at least one first type of monomer comprising quaternary amine groups and at least one second type of monomer containing acid groups. Method according to claim 11, characterized in that the additional polymer is selected from polyvinylpyrrolidone, polyvinylcaprolactam, polyacrylamide, vinylpyrrolidone / vinyl acetate copolymer, crosslinked or non-crosslinked copolymers of vinyl acetate / crotonic acid, terpolymers of vinylpyrrolidone, acetate of vinyl and vinyl alkanoate, vinyl acetate terpolymer, crotonate and vinyl alkanoate, partially esterified copolymers between vinyl methyl ether and maleic anhydride, copolymers of acrylic acid and / or methacrylic acid with alkyl acrylates, alkyl methacrylates, N-alkylaryl amides, N-alkyl ethacrylamides and / or polystyrene sulfonates, alkyl acrylamide copolymers, alkylaminoalkylmethacrylate and two or more monomers selected from acrylic acid, methacrylic acid or their alkyl esters with Cl to C4, wherein at least one of the monomers comprises an acid group; copolymers of acrylic acid, methacrylate and methacrylamidopropyltrimethylammonium chloride, copolymers of acrylamidopropyltrimethylammonium chloride and acrylates, copolymers of acrylamide, acrylamidopropyltrimethylammonium chloride, 2-amodiopropylacrylamide sulfonate and dimethylaminopropylamino, copolymers of methacryloylethylbetaine and two or more monomers of acrylic acid or their simple esters, copolymer of methylvinylimidazolium chloride / vinylpyrrolidone, polyvinylpyrrolidone / dialkylaminoalkylmethacrylate copolymers, quaternized vinylpyrrolidone / dialkylamino-alkylmethacrylate copolymers, dimethyldiallylammonium chloride homopolymers, dimethyldiallylammonium chloride copolymers and at least one additional monomer, quaternized hydroxyethylcellulose derivatives or quaternized guar derivatives, terpolymers of vinylpyrrolidone, vinylcaprolactam and a basic monomer of acrylamide or methacrylamide and copolymers of vinylpyrrolidone / methacrylamide chloride alkyltr imethylammonium Method according to one of the preceding claims, characterized in that the film additionally contains at least one substance that is selected from emulsifiers, softeners, hair brightening active ingredients, preservatives, aromatic substances, pigments, coloring substances of the product and solids in the form of water-insoluble particles 14. Method according to one of the preceding claims, characterized in that after rolling the film has a thickness of less than 0.5 mm. 15. Method according to one of the preceding claims, characterized in that gas bubbles are introduced into the film. 16. Hair styling film, characterized in that it is produced according to a method according to one of claims 1 to 15. 17. Hair styling film characterized in that it contains at least 85% by weight of at least one hair fixative polymer and more of 3% by weight of at least one surfactant. 18. Hair styling film according to claim 17, characterized in that the hair-fixing polymer is selected from polymers based on polysaccharides and synthetic non-ionic polymers. 19. Hair styling film according to claim 18, characterized in that as hair-fixing polymer it contains a combination of pullulan and at least one polymer selected from polyvinylpyrrolidone and polyvinylpyrrolidone / vinyl acetate copolymer, the weight ratio being of pullulan to the polymer is less than 1: 1. The hair styling film according to one of claims 17 to 19, characterized in that, as surfactants, it contains a mixture of at least one cationic surfactant and at least one nonionic surfactant, the weight proportion of surfactants being Cationic to non-ionic surfactants is from 1:10 to 10: 1. 21. Hair styling film, characterized in that it contains at least 50% by weight of hair fixing polymers, being that it contains pullulan in combination with at least one additional hair fixative polymer and the weight ratio of pullulan to the additional hair fixative polymer is less than 1: 1. 22. Hair styling film according to claim 21, characterized in that the pullulan content is from 15 to 45% by weight and the content of the additional hair fixing polymer is from 30 to 70% by weight, with the proviso that the weight ratio of pullulan to additional hair fixative polymer is less than 1: 1. 23. Hair styling film according to one of claims 17 to 22, characterized in that the thickness of the film is less than 0.5 mm. 24. Hair styling film according to one of claims 17 to 23, characterized in that it contains enclosed bubbles. 25. Hair styling film according to one of claims 17 to 24, characterized in that it additionally contains at least one polyol. 26. Hair styling film according to claim 25, characterized in that the polyols are contained in an amount of 1 to 50% by weight and are selected from glycols, glycerines, sugar alcohols and liquid polyethylene glycols at 25 ° C. 27. Hair styling film containing at least 50% by weight of hair fixing polymers, characterized in that the film is treated with a separating agent in the form of powder that adheres to the film.