EP1735058A2

EP1735058A2 - Hair styling films and method for producing hair fixing products in film form

Info

Publication number: EP1735058A2
Application number: EP05700790A
Authority: EP
Inventors: Sarah Maillefer; Benedikt Zenhäusern; Ute Doepner-Reichenbach; Monika Moenks; Karin Steinbrecht
Original assignee: Wella GmbH
Current assignee: Procter and Gamble Deutschland GmbH
Priority date: 2004-01-21
Filing date: 2005-01-11
Publication date: 2006-12-27
Also published as: WO2005070376A3; CN101184529A; US20080223395A1; JP2007518753A; DE102004002951A1; WO2005070376A2

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

description

Hair styling films and processes for producing hair-fixing products in film form

The invention relates to a process for the production of hair-fixing products in the form of a film, and to hair treatment compositions for setting hair in the form of a solid, water-soluble film, in particular based on pullulan and, if appropriate, additional hair-fixing polymers.

To give human hair strengthening and hold or to stabilize a created hairstyle, hair treatment agents are generally used in the form of gels, foams, sprays or lotions based on liquid solvents. A disadvantage of such solvent-based products is that, owing to the high solvent and / or propellant content, they are voluminous and heavy and are therefore unsuitable for taking along on the go. The problem is usually solved by packaging the products in very small containers. Such products have the disadvantage that they are only sufficient for very few applications. In addition, it is not possible to portion them into solid, discrete pieces that are sufficient for an application during manufacture. Also a spatial one

Designability and the provision of attractive external forms is not possible. Thin gels or thixotropic gels that liquefy under pressure can also run off the hands or hair when used. JP 01-131109 discloses hair treatment agents in the form of sheets or plates, which are produced by pouring a solution into molds and evaporating the solvent. Such sheets or plates are not yet completely satisfactory, in particular with regard to the uniformity of the surface, product thickness and associated application properties, for example based on the dissolution rate during use.

From EP 1 317 916 films are known which contain pullulan or modified starch and are produced from a starch digestion of certain starch derivatives by pulling a film by the so-called knife-over-roll coating method and conditioning overnight. Although the films described are soluble in a glass with water at 37 ° C., the dissolving behavior on wet hands or wet hair, which is relevant for applications as hair styling films, is unsatisfactory. The knife-over-roll coating method usually only allows the production of coatings with a thickness of 0.5 mm. Typical achievable coating thicknesses are 1 to 30 mm. Films of such a thickness have an unsatisfactory dissolving behavior for applications as hair styling films.

The object on which the invention was based was to provide essentially solvent-free films which, when in contact with moisture, ie with relatively little water, can be easily dissolved by rubbing with the hands and, after incorporation into the hair, develop a hair-setting effect and enable hairstyle styling. When rubbing in, no softened, Undissolved film particles remain, which could lead to undesirable, visible or tangible residues when styling the hairstyle on the head. The films should be stackable and / or so flexible that they can be rolled up. They should be resistant to air humidity to such an extent that they do not stick together when they come into direct contact with one another and remain easily detachable even after long storage.

The invention relates to a method for producing a hair-fixing product in the form of a film, a rollable preparation being first produced by dissolving or dispersing a polymer in a liquid carrier medium, and - subsequently the preparation is brought into the form of a film by means of a rolling device by rolling and at the same time or subsequently the liquid carrier medium is evaporated. The invention also relates to hair styling films, in particular hair styling films produced according to the invention, and the use of these films for hair setting.

The rollable preparation can have a semi-solid, dough-like consistency or it can be a viscous liquid with which a suitable carrier is coated and. the desired film thickness is produced by rolling with a rolling device. After drying, the finished film is removed from the carrier. Suitable carrier materials are, for example, silicone, metal, metallized polymers, polytetrafluoroethylene, polyether / polyamide block co polymers, polyurethanes, polyvinyl chloride, nylon, alkylene / styrene copolymers, polyethylene, polyester or other removable materials. Suitable rolling devices are, in particular, the so-called forward roll or reverse roll coater, known per se to the person skilled in the art from coating and coating technology, with at least two co-rotating or counter-rotating rolls or rolls, a reverse roll process being preferred ,

A film in the sense of the invention is a solid, essentially solvent-free product with a planar, flat geometry and a thickness of preferably less than or equal to 1 mm, in particular less than 0.5 mm, e.g. from 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 alone can have film-forming and / or hair-setting properties. However, mixtures of polymers can also be used, the mixture having film-forming and / or hair-setting properties after evaporation of the solvent. The polymer content in the rollable preparation can be from 10 to 80% by weight, from 20 to 70% by weight or from 30 to 60% by weight. After evaporation of the liquid carrier medium, the polymer content in the finished film can be from 50 to 97% by weight, from 60 to 95% by weight or 80 to 95% by weight, a content of greater than or equal to 85% by weight being particularly preferred.

At least one of the polymers used is preferably water-soluble. Pullulan is particularly preferred. A suitable Pullulan can have an average molecular weight Mr of 10,000 to 50,000. At least one hair-setting polymer is preferably present, in particular a combination of pullulan and at least one hair-setting polymer. The weight ratio of pullulan to additional hair-setting polymer can be from 1:10 to 10: 1, in particular from 1: 5 to 5: 1 or 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-setting polymer can be selected from anionic, cationic, zwitterionic, nonionic and amphoteric polymers. It can be natural or synthetic polymers. Synthetic polymers are understood to mean those polymers which are of purely synthetic, non-natural origin, in particular those which can be prepared by free-radical polymerization from ethylenically unsaturated monomers or by polycondensation. Natural polymers are understood to mean polymers of natural origin, which can also be modified chemically or physically afterwards. Particularly preferred are those polymers which have sufficient solubility or dispersibility in the carrier medium, in particular in water, alcohol or water / alcohol mixtures, in order to be present in the carrier medium in dissolved or homogeneously dispersed form. According to the invention, hair-fixing polymers are understood to mean those polymers which, when used in 0.01 to 5% aqueous, alcoholic or aqueous-alcoholic solution or dispersion, are able to deposit a polymer film on the hair and to strengthen the hair. Suitable nonionic polymers are homopolymers or copolymers which are composed of at least one of the following monomers: vinyl lactams, in particular vinyl pyrrolidone and vinyl caprolactam, vinyl esters such as vinyl acetate, vinyl alcohols, acrylamides, methacrylamides, alkyl acrylates, dialkyl acrylamides, alkyl methacrylamides, Dialkyl ethacrylamides, dialkylaminoallyl methacrylamides, dialkylaminoalkylacrylamides, alkyl acrylates, alkyl methacrylates, propylene glycol or ethylene glycol, the alkyl groups of these monomers preferably being C_L to C7 alkyl groups, particularly preferably Cl to C3 alkyl groups. Homopolymers of vinylcaprolactan, vinylpyrrolidone or N-vinylformamide are suitable, for example. Other suitable synthetic film-forming, non-ionic, hair-setting polymers are, for example, copolymers of vinyl pyrrolidone and vinyl acetate, terpolymers of vinyl pyrrolidone, vinyl acetate and vinyl propionate, polyacrylamides; Polyvinyl alcohols as well as polyethylene glycol / polypropylene glycol copolymers. Polyvinylpyrrolidone, polyvinylcaprolactam and their copolymers with at least one further nonionic monomer, in particular polyvinylpyrrolidone / vinyl acetate copolymers, are particularly preferred.

Suitable anionic hair-fixing polymers are, for example, synthetic homopolymers or copolymers of monomer units containing acid groups, which are optionally copolymerized with comonomers which contain no acid groups. The acid groups are preferably selected from -COOH, -S0 ₃ H, -OSO ₃ H, -OP0 ₂ H and -OP0 ₃ H ₂ , of which the carboxylic acid groups are preferred. The acid groups can be neutralized, partially or completely neutralized available. They are preferably 50 to 100% in anionic or neutralized form. Organic or inorganic bases suitable for cosmetic purposes can be used as neutralizing agents. Examples of bases are amino alcohols such as, for example, aminomethylpropanol (AMP), triethanolamine, monoethanolamine or tetrahydroxypropylethylenediamine and ammonia, NaOH and others. Suitable monomers are unsaturated, free-radically polymerizable compounds 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 anhydride or their monoesters.

Comonomers not substituted with acid groups are e.g. Acrylamide, methacrylamide, alkyl and dialkyl acrylamide, alkyl and dialkyl methacrylamide, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, vinyl pyrrolidone, vinyl ester, vinyl alcohol, propylene glycol or ethylene glycol, amine-substituted vinyl monomers such as e.g. Dialkylaminoalkyl acrylate, dialkylaminoalkyl methacrylate, monoalkylaminoalkyl acrylate and monoalkylaminoalkyl methacrylate, the alkyl groups of these monomers preferably being Cl 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 acrylic acid or methacrylic acid esters, acrylamides, methacrylamides and vinylpyrrolidone, homopolymers of crotonic acid and copolymers of crotonic acid with monomers selected from vinyl esters, acrylic acid or methacrylic acid. esters, acrylamides and methacrylamides. A suitable natural polymer is shellac, for example. Preferred anionic polymers are crosslinked or uncrosslinked vinyl acetate / crotonic acid copolymers. Partially esterified copolymers between vinyl methyl ether and maleic anhydride are also preferred. Further preferred anionic polymers are, for example, terpolymers made from acrylic acid, alkyl acrylate and N-alkylacrylamide, in particular acrylic acid / ethyl acrylate / Nt-butylacrylamide, terpolymers or terpolymers made from vinyl acetate, crotonate and vinyl alkanoate, especially vinyl acetate /

Crotonate / vinyl neodecanoate copolymers; Copolymers of acrylic or methacrylic acid and acrylic or methacrylic acid alkyl esters, the alkyl groups preferably containing 1 to 7 carbon atoms and polystyrene sulfonates.

Suitable hair-fixing amphoteric or zwitterionic polymers are polymers which, in addition to acidic or anionic groups, contain basic or cationic groups as further functional groups, in particular primary, secondary, tertiary or quaternary amine groups. Zwitterionic polymers are polymers which are composed of at least one type of monomer which has both quaternary amine groups and acid groups or of polymers which are composed of at least one first type of monomer which has quaternary amine groups and at least one second type of monomer which acid groups having. Amphoteric polymers are composed, for example, of at least one type of monomer which has acid groups and at least one further type of monomer which has basic amine groups. Examples include copolymers formed from alkyl acrylamide (in particular octylacrylamide), alkylamino alkyl methacrylate (in particular t-butylaminoethyl methacrylate) and two or more monomers selected from acrylic acid, methacrylic acid or their C1 to C4 alkyl esters, at least one of the monomers having an acid group, such as are available, for example, under the trade name Amphomer "or Amphomer LV-71 ,

Other suitable polymers are copolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimethylammonium chloride (INCI name: Polyquaternium-47), copolymers of acrylamidopropyltrimethylammonium chloride and acrylates or copolymers of acrylamide, acrylamidopropyltrimethylammonium chloride, 2-amidopropylacrylamino-aminomethyl-aminononate-propyl-acrylamino-aminomethyl-aminononate-propyl-acrylamino-aminomethyl-aminononate-propyl-acrylamino-aminomethyl-aminononate-propyl-acrylamido-aminomethyl-aminononate-propyl-acrylamino-aminomethyl-aminomethyl-aminomethyl-aminomethyl-aminomethyl-aminomethyl-aminomethyl-aminomethyl-aminomethyl-aminomethyl-aminomethyl-aminomethyl-aminomethyl-aminomethyl-aminomethyl- -43). Polymers with monomers bearing betain groups, such as e.g. Copolymers of methacryloylethylbetaine and two or more monomers of acrylic acid or their simple esters, known under the INCI name Methacryloyl Ethyl Betaine / Acrylates Copolymer.

Suitable cationic polymers preferably contain quaternary amine groups. The cationic polymers can be homo- or copolymers, 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, free-radically polymerizable compounds which carry at least one cationic group, in particular ammonium-substituted vinyl monomers such as, for. B. Trialkylmethacryloxyalkyl- ammonium, trialkylacryloxyalkylammoniuiτi, dialkyldiallylammonium and quaternary vinylammonium monomers with cyclic, cationic nitrogen-containing groups such as pyridinium, imidazolium or quaternary pyrrolidones, for example alkylvinylimidazolium, alkylvinylpyridiumnium, or alkyl vinylpyrrolidone. 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, acrylic id, methacrylamide, alkyl- and dialkylacrylamide, alkyl- and dialkylmethacrylamide, alkyl acrylate, alkyl methacrylate, vinyl caprolactone, vinyl caprolactam, vinyl pyrrolidone, vinyl ester, for example vinyl acetate, vinyl alcohol, propylene glycol or ethylene glycol, preferably the alkyl groups of these monomers Are Cl to C7 or Cl to C3 alkyl groups.

Cationic polymers with quaternary amine groups are e.g. which in the CTFA Cosmetic Ingredient Dictionary under the

Designations Polyquaternium described polymers 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 e.g. Vinylpyrrolidone / dimethylaminoethyl

Copolymer available under the trade names Gafquat ^® 755 N and Gafquat 734 is distributed, are suitable. Other cationic polymers are, for example, those under the Trade names LUVIQUAT ^® HM 550 copolymer of polyvinylpyrrolidone and imidazolimine methochloride, which is sold under the trade name Merquat ^® Plus 3300 terpolymer of dimethyldiallylammonium chloride, sodium acrylate and

Acrylamide, the terpolymer marketed under the trade name Gaffix ^® VC 713 from vinylpyrrolidone, prostitute thylaminoethyl methacrylate and vinylcaprolactam and the vinylpyrrolidone / methacrylamidopropyltrimethylammonium chloride copolymer sold 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 GOB-NΑAR ³ X ^" G is an anhydroglucose residue, for example starch or cellulose anhydroglucose; B is a divalent connecting group, for example alkyls, oxyalkylene, polyoxyalkylene or hydroxyalkylene; Rl, R2 and R3 are independently alkyl, Aryl, alkylaryl, arylalkyl, alkoxyalkyl or alkoxyaryl each having up to 18 carbon atoms, the total number of carbon atoms in R ¹ , R ² and R ³ preferably being a maximum of 20;

X is a common counter anion X ^" , for example a halogen, acetate, phosphate, nitrate or alkyl sulfate, preferably a 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 marketed by Amerchol under the trade name Polymer LM-200. A suitable cationic guar derivative is sold under the trade name Jaguar ^® R and has the INCI name guar hydroxypropyltrimonium chloride. Particularly preferred cationic substances are chitosan, chitosan salts and chitosan derivatives. Chitosans are completely 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. 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 above 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 preferred chitosan is chitosoniumpyrrolidone is, for example, sold 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, hydroxypropyl or hydroxybutyl chitosan. The chitosans or chitosan derivatives are preferably in neutralized or partially neutralized form. The degree of neutralization for the chitosan or the 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 compatible inorganic or organic acids can be used as neutralizing agents such as, for example, formic acid, malic acid, lactic acid, pyrrolidone carboxylic acid, hydrochloric acid and others, of which pyrrolidonecarboxylic acid and lactic acid are particularly preferred.

transfer medium

Suitable liquid carrier media are e.g. Solvents or dispersants such as water, alcohols, ethers, ketones or hydrocarbons or mixtures of two or more of the substances mentioned, provided that the substances or mixtures of substances are liquid at room temperature (25 ° C). The content of the liquid carrier medium in the rollable preparation can be from 20 to 90% by weight or 30 to 70% by weight. In particular, the lower monohydric or polyhydric alcohols with 1 to 5 carbon atoms commonly used for cosmetic purposes can be used as alcohols. Atoms such as ethanol, isopropanol, ethylene glycol, glycerol and propylene glycols, in particular 1, 2-propylene glycol, may be contained.

Additives For further optimization, the films can contain additives, in particular emulsifiers up to 50% by weight, plasticizers (e.g. glycerol, polyethylene glycols) up to 50% by weight or hair gloss agents, in particular oils such as vegetable oils, hydrocarbon oils or silicone oils up to 30% by weight. The product according to the invention can moreover contain the additional ingredients customary for hair treatment compositions in amounts of typically 0.01 to 15% by weight, humectants, fragrances in an amount of 0.1 to 0.5% by weight; Preservatives in an amount of 0.01 to 1.0% by weight; Buffer substances, such as sodium citrate or sodium phosphate, in an amount of 0.1 to 1.0% by weight; Anfärbe- Substances such as fluorescein sodium salt in an amount of about 0.1 to 1.0% by weight; Hair care substances, such as plant and herbal extracts, protein and silk hydrolyzates, lanolin derivatives, in an amount of 0.1 to 5% 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 30% by weight; Light stabilizers, antioxidants, radical scavengers, anti-dandruff substances in an amount of about 0.01 to 2% by weight; Vitamins, combability enhancers, pigments and / or water-insoluble, particulate solids.

A particular embodiment of the invention relates to a hair styling film with 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 hair-fixing polymer and more than 3% by weight, in particular greater than 3 to less than 15% by weight .% of at least one surfactant. Suitable hair-fixing polymers are the abovementioned, in particular hair-fixing, polymers based on polysaccharide and hair-fixing nonionic, synthetic polymers. A polymer combination of (a) pullulan and (b) at least one polymer selected from polyvinylpyrrolidone and polyvinylpyrrolidone / vinyl acetate copolymer is particularly preferred, the weight ratio of (a) to (b) preferably being less than 2: 1 or less than 1: 1, in particular from 1:10 or 1: 4 to less than 1: 1.

Nonionic, cationic, anionic or amphoteric surfactants can be used as surfactants. Anionic surfactants are, for example, fatty alcohol sulfates, alkyl ether sulfates, alkyl benzene sulfonates. Amphoteric surfactants are, for example, betaines such as Fatty acid amido alkyl betaines and sulfobetaines and C8 to C22 alkyl betaines. The surfactants are preferably selected from nonionic and cationic surfactants. A surfactant combination of at least one cationic and at least one nonionic is particularly preferably used

Surfactant. The weight ratio of cationic to nonionic surfactants can be from L: 10 to 10: 1, from 1: 5 to 5: 1 and in particular from 1: 1.5 to 1.5: 1.

Suitable cationic surfactants are surfactants which contain a quaternary ammonium group and can be represented by the general formula _N ( ₊ ) _R 1 _R 2 _R 3 _R 4 _χ , where _R 1 to _R 4 independently of one another are aliphatic groups, azromatic groups, alkoxy groups, polyoxyalkylene groups, alkylamido groups , Hydroxyalkyl groups, aryl groups or alkaryl groups with 1 to 22 C atoms, where at least one of the groups R 1 to R 4 has at least 8 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 further amino groups.

Examples of suitable cationic surfactants are the chlorides or bromides of alkyldimethylbenzylammonium salts, alkyltrimethylammonium salts, for example cetyltrimethylammonium chloride or bromide, tetradecyltriethylammonium chloride or bromide, alkyldimethylhydroxyethyl amonium chloride or

bromides, the dialkyldimethylammonium chlorides or bromides, Alkylpyridinium salts, for example lauryl or cetylpyridinium chloride, alkylamidoethyltrimethylammonium ether sulfates and compounds with a cationic character such as amine oxides, for example alkylmethylamine oxides or alkylaminoethyldimethylamine oxides. Cetyltrimethylammonium chloride is particularly preferred.

Suitable nonionic surfactants are listed, for example, in the "International Cosmetic Ingredient Dictionary and Handbook", 7th edition, volume 2 in the section "Surfactants", for example, ethoxylated fatty alcohols, ethoxylated nonylphenols, fatty acid mono- and diglycerides, ethoxylated and hydrogenated or non-hydrogenated castor oil, fatty acid alkanolamides , ethoxylated fatty acid esters, fatty acid sugar 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 with C8 to C22 fatty alcohols, with C12 to C22 fatty acids or with alkylphenols with 8 to 15 carbon atoms in the alkyl group, C12 to C22 fatty acid monoesters and diesters of adducts from 1 to 30 mol of ethylene oxide with glycerol adducts from 5 to 60 mol, preferably 20 to 50 mol, of ethylene oxide with castor oil or with hydrogenated (hydrogenated ) Castor oil. Fatty acid sugar esters, in particular esters from sucrose and one or two C8 to C22 fatty acids, INCI: sucrose cocoate, sucrose dilaurate, sucrose distearate, sucrose laurate, sucrose myristate, sucrose oleate, sucrose palmitate, sucrose ricinoleates, sucrose stearate Polyglyceryl fatty acid esters, in particular from one, two or more C8 to C22 fatty acids and polyglycerol with preferably 2 to 20 glyceryl units of alkylglycosides, in particular alkyl oligoclycosides with C6 to C22 alkyl groups.

In a particular embodiment, gas bubbles of a suitable gas, preferably air, are enclosed in the foils. Films with enclosed gas bubbles are characterized by particularly good dissolving properties. and a particularly good rubability and incorporability into the hair. The introduction of gas bubbles can be carried out by a method known per se for the production of bubble-containing plastics, e.g. according to one of the following processes: (1) use of a blowing agent (blowing agent) (2) foaming by mechanical stirring of the still liquid or viscous carrier mass (3) by a gas-generating chemical reaction (4) use of a volatile solvent and evaporation at elevated temperatures (5) injection of a liquefied gas into the still viscous carrier mass

Blowing agents are chemical substances that decompose on heating and release a gas, e.g. Nitrogen, carbon dioxide, carbon monoxide, ammonia or other hydrogen.

Inorganic blowing agents are, for example, carbonates, hydrogen carbonates, borohydrides, silicon oxyhydrides etc. Organic blowing agents such as those used by Joei in the production of porous or blister-containing plastics are particularly preferred. In a preferred embodiment, the hair styling film contains at least 50% by weight of hair-setting polymer, pullulan being present in combination with at least one further hair-setting polymer and the weight ratio of pullulan to the further hair-setting polymer being less than 1: 1, ie the amount used Pullulan is less than that of the other hair-fixing polymer. The pullulan content is preferably 15 to 45% by weight and the content of additional hair-fixing polymer is preferably 30 to 70% by weight.

Combinations of pullulan with synthetic! Styling polymers can lead to films that are not yet completely satisfactory due to their certain brittleness and fragility. This can be improved by containing polyols. In a further preferred embodiment, the hair styling film therefore additionally contains at least one polyol. A polyol is an organic compound that has two or more alcoholic hydroxyl groups. Suitable polyols are, for example, polyhydric alcohols with preferably up to 5 carbon atoms, in particular glycols and glycerol, and also sugar alcohols and polyethylene glycols which are liquid at 25 ° C. Glycols are, for example, ethylene glycol, propylene glycol or butylene glycol. Sugar alcohols are, for example, sorbitol, manitol, malitol or lactitol. 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-fixing polymer and 1 Ibis 50% by weight is preferred, in particular more than 5% by weight, for example 5 to 20 or 10 to 15 % By weight of polyol, based on the dried, anhydrous film, glycerol being particularly preferred. The polyol content in particular improves the clarity and the elasticity of the film, ie the films do not break through so easily.

At higher ambient temperatures and / or higher air humidity there is a risk that hair styling foils stick to one another in the packaging and can no longer be separated well and removed from the packaging. This can be improved by using suitable release agents. A further preferred embodiment therefore relates to hair styling films which have been treated with a powdery release agent. The preferably hydrophobic release agent adheres externally to the film and prevents the films from sticking, particularly when stored or used in high air humidity. Suitable release agents are, for example, talc, starch or modified starch. The starch can be modified in one of the generally known ways, including physical, chemical or enzymatic modifications. Physical modifications are, for example, thermal treatments or treatments with shear forces. Chemical modifications include crosslinking, acetylation, esterification, hydroxyethylation, hydroxypropylation, phosphorylation, succinates and substituted succinates. Modified starches with the INCI names Aluminum Starch Octenylsuccinate and Corn Starch modified are preferred. The release agent is applied to the finished, dried films. Typical amounts used are about 0.01 to 0.1 g, preferably 0.02 to 0.05 g per film with a size of 4 x cm and a thickness of up to 0.5 mm.

The films treated with the release agent are characterized by improved non-tack and can still be removed from the packaging well after several weeks without sticking to one another. At the same time, the release agents unexpectedly leave no visible residues on the hair after a proper hair styling application.

application

The foils can be packed very compactly and in a space-saving manner, for example as a roll or as stacked plates. The foils can be rubbed with wet or damp hands. The completely or partially dissolved film can then be applied to the dry or damp hair and a hairstyle can be designed as if using a conventional styling gel. The films can also be applied directly to wet or damp hair and worked into the hair by hand.

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

Examples

Example 1 Rollable preparation 45 g of polyvinylpyrrolidone (Luviskol ^® K90) 5 g Rewoteric ^® AM CAS (cocamidopropyl hydroxysultaine, 50% in water) 0.25 g perfume ad 100 g ethanol

Example 2 Styling Foil 42.5 g Polyvinylpyrrolidone (Luviskol ^® K90) 42.0 g Pullulan 7.5 g Cetyltrimethylammonium Chloride 7.5 g PEG-40 Hydrogenated Castor Oil 0.5 g Perfume

Example 3 Styling foils

Rollable doughs are prepared from compositions A, B and C using water as the solvent. By rolling the dough, foils are made and the foils are then dried. The films were assessed on the basis of the following criteria: (a) very good solubility behavior when rubbed with hands with a little water: ++; good: +; sufficient: 0; bad: - (b) foaming behavior when worked into the hair no foaming: +; Foaming: - (c) stickiness behavior good stickiness: +; bad stickiness: - (d) flocculation behavior when worked into the hair: no flocculation, no formation of visible residues: + flocculation, visible residues: - (e) setting behavior: good hair fixation: +, - weak hair fixation: 0; no hair fixation: -

Example 4 Styling Films Containing Glycerin

Example 5 Preparations for the production of styling films with and without glycerin

Hair styling films made from preparation A are very elastic and can be processed easily, ie they can be dissolved with a little water in the hand and worked into the hair. Films made from preparation B, on the other hand, are brittle and brittle and are less easy to process.

Example 6 Styling Films Treated With Release Agent

Aluminum Starch Octenylsuccinate; hydrophobic starch ⁽²⁾ Aluminum Starch Octenylsuccinate; hydrophobic starch ^<3) Corn Starch Modified; 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 each treated with 0.03 g of aftertreatment agent. All foils are not sticky and can be separated easily. The corresponding films without post-treatment, on the other hand, stick to one another after storage for some time and can no longer be easily separated from one another.

Claims

claims

1. A process for the production of a hair-fixing product in the form of a film, wherein - a rollable preparation is first produced by dissolving or dispersing a polymer in a liquid carrier medium and - then the preparation is brought into the form of a film by rolling using a rolling device and - simultaneously or then the liquid carrier medium is evaporated.

2nd A method according to claim 1, characterized in that the polymer is a film-forming and / or hair-fixing polymer.

3. The method according to any one of the preceding claims, characterized in that the liquid carrier medium is selected from water, alcohols, ethers, ketones and hydrocarbons or from mixtures of the substances mentioned, provided that the substances or mixtures of substances are liquid at room temperature (25 ° C).

4. The method according to any one of the preceding claims, characterized in that the content of the polymer in the rollable preparation is from 10 to 80% by weight and the content of the liquid carrier medium is from 20 to 90% by weight.

5. The method according to any one of the preceding claims, characterized in that in the film after evaporation of the liquid carrier medium, the proportion of the polymer is from 50 to 97% by weight. ^'6. A method according to any one of the preceding claims, characterized in that the preparation contains at least one water soluble polymer. 7. The method according to any one of the preceding claims, characterized in that the preparation contains pullulan.

8. The method according to claim 7, characterized in that the pullulan has an average molecular weight of 10,000 to 5,000,000.

9. The method according to any one of claims 7 to 8, characterized in that it additionally contains at least one hair-setting polymer.

10. The method according to claim 9, characterized in that the weight ratio of pullulan to additional hair-fixing polymer is from 1:10 to 10: 1.

11. The method according to claim 10, characterized in that the additional hair-fixing polymer is selected - from polymers which are composed of at least one monomer selected from vinyl lactams, vinyl esters, vinyl alcohols, acrylamides, methacrylamides, alkyl acrylamides, dialkylacrylamides, alkyl methacrylate amides, dialkylmethacrylamides, dialkylaminoalkylmethacrylamides, dialkylaminoalkyl acrylamides, alkyl acrylates, alkyl methacrylates, propylene glycol or ethylene glycol; - from polymers which are composed of at least one monomer selected from acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, monoesters of maleic acid; from polymers which are composed of at least one monomer selected from trialkylmethacryloxyalkylammonium, trialkylacryloxyalkylammonium, dialkyldiallylammonium, alkylvinylimidazolium, alkylvinylpyridinium or alylvinylpyrrolidone; from polymers which are composed of at least one type of monomer which has acid groups and at least one further type of monomer which has basic amine groups; from polymers which are composed of at least one type of monomer which has both quaternary amine groups and acid groups or of polymers which are composed of at least one first type of monomer which has quaternary amine groups and at least one second type of monomer which has acid groups. A method according to claim 11, characterized in that the additional polymer is selected from polyvinyl pyrrolidone, polyvinyl caproactam, polyacrylic ide, vinyl pyrrolidone / vinyl acetate copolymer, crosslinked or uncrosslinked vinyl acetate / crotonic acid copolymers, terpolymers from vinylpyrrolidone, vinyl acetate and vinyl alkanoate, ter- polymers of vinyl acetate, crotonate and vinyl alkanoate, partially esterified copolymers between vinyl methyl ether and maleic anhydride, copolymers of acrylic and / or methacrylic acid with alkyl acrylates, alkyl methacrylates, N-alkyl acrylamides, N-alkyl methacrylamides and / or polystyrene sulfonates, copolymers of alkyl acrylamide, Alkylaminoalkyl methacrylate and two or more monomers selected from acrylic acid, methacrylic acid or their C1 to C4 alkyl esters, at least one of the monomers having an acid group; , Copolymers of acrylic acid, methyl acrylate and methacrylic amidopropyltrimethylammonium chloride, copolymers of acrylamidopropyltrimethylammonium chloride and acrylates, copolymers of acrylamide, acrylamidopropyltrimethylammonium chloride, 2-amidopropylacrylamidesulfonate and dirnetl ylaminopropylamine, copolymers or ethyleneamidyl acrylate and copolymers of methacryloyl methyl acrylate and two or more of them chloride / vinylpyrrolidone copolymer, polyvinylpyrrolidone / dialkylaminoalkyl methacrylate copolymers, quaternized vinylpyrrolidone / dialkylaminoalkyl methacrylate copolymer, homopolymers of dimethyldiallylammonium chloride and copolymers of dimethyldiallylammonium chloride and at least one other monomer, quaternarized acrylamate or hydroxymethylated acrylate, methacrylate-derived aminopolymer, from methylethyl or acrylate, Vinyl pyrrolidone / methacrylamidoalkyl trimethyl ammonium chloride copolymers.

13. The method according to any one of the preceding claims, characterized in that the film additionally contains at least one substance selected from emulsifiers, plasticizers, hair gloss agents, preservatives, fragrances, pigments, product stains and water-insoluble, particulate solids.

14. The method according to any one of the preceding claims, characterized in that the film has a thickness of less than 0.5 mm after being rolled out.

15. The method according to any one of the preceding claims, characterized in that gas bubbles are introduced into the film.

16. Hair styling film, produced by a method according to any one of claims 1 to 15.

17. Hair styling film containing at least 85% by weight of at least one hair-fixing polymer and more than 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 polysaccharide and nonionic, synthetic polymers.

19. Hair styling film according to claim 18, characterized in that the hair-fixing polymers are a combination of (a) pullulan and (b) at least one polymer, selected from polyvinylpyrrolidone and polyvinylpyrrolidone / vinyl acetate copolymer is contained, the weight ratio of (a) to (b) being less than 1: 1.

20. Hair styling film according to one of claims 17 to 19, characterized in that the surfactants are a mixture of at least one cationic and at least one nonionic surfactant, the weight ratio of cationic to nonionic surfactants being 1:10 to 10: 1.

21. Hair styling film containing at least 50% by weight of hair-fixing polymers, pullulan being present in combination with at least one further hair-fixing polymer and the weight ratio of pullulan to the further hair-fixing polymer being less than 1: 1.

22. Hair styling film according to claim 21, characterized in that the content of pullulan is 15 to 45% by weight and the content of additional hair-setting polymer is 30 to 70% by weight, provided that the weight ratio of pullulan: additional hair-setting polymer is smaller Is 1: 1.

23. Hair styling film according to one of claims 17 to 22, characterized in that the film thickness is less than 0.5 mm.

24. Hair styling film according to one of claims 17 to 23, characterized in that it contains enclosed gas 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, glycerins, sugar alcohols and polyethylene glycols which are liquid 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 powdery release agent adhering to the film.