WO2004026270A1

WO2004026270A1 - Hair treatment agents with conditioning properties

Info

Publication number: WO2004026270A1
Application number: PCT/EP2003/009940
Authority: WO
Inventors: Konstanze Mayer; Peter Schmiedel; Michael Heyer
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2002-09-17
Filing date: 2003-09-08
Publication date: 2004-04-01
Also published as: DE10243038A1; AU2003267059A1

Abstract

The invention relates to the use of non-ionic, cross-linked polymers containing (meth)acrylate and having a mean particle diameter of between 50 and 500 nm for improving the physical properties of keratin fibres. The invention also relates to hair treatment agents containing said polymers.

Description

Hair treatment agent with conditioning properties

The present invention relates to the use of nonionic, crosslinked (meth) acrylate-containing polymers with an average particle diameter in the range from 50 to 500 nm to improve the physical properties of keratinic fibers, and to hair treatment compositions which contain these polymers.

Today human hair is treated in a variety of ways with hair cosmetic preparations. These include cleaning the hair with shampoos, care and regeneration with rinses and cures, as well as bleaching, dyeing and shaping the hair with waving agents, tinting agents and styling preparations.

Both the use of shampoos and the decorative design of the hairstyle, for example by dyeing or perming, are interventions which, like environmental influences, influence the natural structure and properties of the hair. Following such treatment or due to environmental influences such as exposure to intense sunlight, for example, the wet and dry combability, the hold, the fullness, the softness and the feel of the hair may be unsatisfactory or the hair may have an increased split ends or may fly "due to electrostatic charge" ".

It has therefore long been customary to subject the hair to a special after-treatment. Here, usually in the form of a rinse or hair treatment, the hair is treated with special active ingredients, for example quaternary ammonium salts or special polymers. Depending on the formulation, this treatment improves the combability, hold and fullness of the hair and reduces the split rate.

Combination preparations have also been developed in order to reduce the complexity of the conventional multi-stage processes, in particular when used directly by the consumer. In addition to the usual components, these preparations also contain active ingredients that were previously reserved for hair after-treatment agents. The consumer thus saves one application step; At the same time, the packaging effort is reduced because one product is used less.

A number of conditioning and conditioning agents are known to the person skilled in the art. However, the active ingredients available for separate post-treatment agents as well as for combination products cannot yet fulfill all of your wishes.

German published patent application DE 19727508 describes the use of hydrogel formers in aqueous compositions with liposomal structures for the treatment of keratin fibers. According to the teaching of this document, agents with a good care effect can be produced which, despite the liposomal structure, have good storage stability.

The international patent application WO 92/07011 describes highly swellable, moderately cross-linked polyvinylpyrrolidone polymers with certain gel volumes and certain viscosities. The polymers are prepared by precipitation polymerization in organic solvents and are used to thicken aqueous and non-aqueous solutions.

European patent application EP-A2 0288012 describes hair cosmetic compositions which contain fine particles of a crosslinked polymer. The polymer is derived from a monofunctional oil-soluble monomer, the polymerization product of which has a glass transition temperature of up to 300 ° K. The polymer is still insoluble in water and ethanol and does not form a film at normal temperature.

There is still a need for new active ingredients that improve the properties of the hair. At the same time, these active ingredients should have as little impact on the hair as possible, and should not undesirably influence its shine, feel and volume. Of particular interest is new active ingredients that give the cosmetics specialist the greatest possible freedom of formulation, ie that can be easily incorporated into hair cosmetic formulations and have as few or even no incompatibilities with the other ingredients of these formulations, in particular anionic components of these formulations.

It has now surprisingly been found that nonionic, crosslinked (meth) acrylate-containing polymers with an average particle diameter in the range from 50 to 500 nm can meet these requirements in an outstanding manner and can bring about a significant improvement in the physical properties of keratinic fibers. In this context, mechanical properties such as wet and dry combability and the tendency of keratinic fibers to electrostatically charge are particularly worth mentioning.

A first object of the invention is therefore the use of a nonionic, cross-linked (meth) acrylate-containing polymer with an average particle diameter in the range from 50 to 500 nm to improve the physical properties of keratin fibers, in particular to improve their mechanical properties such as wet and dry combability and their tendency to electrostatic charging.

According to the invention, keratin fibers are to be understood as meaning furs, wool, feathers, hair and in particular human hair.

The invention further relates to a hair treatment composition which, in addition to conventional cosmetic constituents, furthermore contains a dispersion of a nonionic, crosslinked (meth) acrylate-containing polymer with an average particle diameter in the range from 50 to 500 nm.

In the context of the invention, a crosslinked (meth) acrylate-containing polymer is to be understood as a crosslinked homopolymer or copolymer which is based on two or more monomers, including the crosslinker. At least one of these monomers must be polyfunctional, to create a network. Including the crosslinker, according to the invention at least one of the monomers must furthermore be a derivative of acrylic acid or methacrylic acid, derivative being understood to mean in particular an ester or an amide.

Monomers for the polymers used according to the invention are monounsaturated polymerizable compounds, preferably the esters and amides of acrylic acid and methacrylic acid and vinylpyrrolidone. For the purposes of the invention, esters and amides with alcohols or amines having 1 to 6 carbon atoms are preferred, it being possible for the alcohols or amines to be additionally substituted with 1 to 3 hydroxyl groups. In addition to N-vinylpyrrolidone, particularly suitable monomers are methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, sec-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-dodecyl acrylate, 2-hydroxyl acrylate, 2-hydroxyl acrylate Isopropylacrylamide and the corresponding methacrylic acid derivatives.

Polymers which are particularly preferred for the purposes of the invention are poly-no isopropylacrylamide and N-vinylpyrrolidone / (meth) acrylic ester copolymers.

In the event that the polymer used according to the invention consists of several different monomers, the weight ratio of the different monomers to one another is not subject to any particular restrictions.

The present invention required cross-linking of the polymer can be effected by means of a polyfunctional monomer such as N, ^{N-methylenebisacrylamide} or 1-vinyl-3- (E) -ethylidene pyrrolidone. Crosslinking with N, N ^' - methylenebisacrylamide is preferred for the purposes of the invention.

The polymer is about 0.5 to about 20%, but preferably about 2 to about 10% and most preferably about 4 to about 6% cross-linked. A degree of crosslinking of x% is understood to mean that for 100 parts by weight of the total monofunctional monomers on which the polymer is based, x Parts by weight of the crosslinker, ie the polyfunctional monomer or the mixture of polyfunctional monomers.

Nonionic crosslinked (meth) acrylate-containing polymers suitable according to the invention with an average particle diameter in the range from 50 to 500 nm are preferably obtainable by polymerizing the monomers on which the polymer is based with one another in an emulsion polymerization. The crosslinking is expediently effected in that a suitable amount of a polyfunctional monomer or crosslinking agent is added to the monomers or monomer mixture to be polymerized.

The size of the polymer particles depends on the production process used and can be influenced, for example, by the use of emulsifiers and by the choice of the concentration of the reactants during the polymerization. Through simple routine experiments, the person skilled in the art can determine the suitable production conditions for a respectively selected combination of monomers in order to obtain polymer particles of the size suitable according to the invention.

Anionic surfactants such as sodium dodecyl sulfate or alkylaryl polyglycol ether sulfate sodium salt are suitable as emulsifiers for the preparation of the polymers used according to the invention by emulsion polymerization.

The polymers used according to the invention are preferably prepared by emulsion polymerization in water as the dispersant.

Any initiator suitable for such an emulsion polymerization can be used as the polymerization initiator, but water-soluble initiators such as potassium peroxodisulfate are preferably used.

The reaction mixture obtained in the emulsion polymerization can be further purified in a manner known per se. For example, dialysis can remove residual monomers and centrifugation, Filtration, freeze drying or spray drying can reduce the water content to a desired level or the polymers can be obtained in an anhydrous, unswollen state.

The crosslinked (meth) acrylate-containing polymers used according to the invention are nonionic, i. H. they are not anionic, cationic or zwitterionic. This means in particular that they are free of acidic groups, e.g. Carboxylate groups and that they are free of quaternary or basic groups such as e.g. Mono-, di- or trialkylamino groups which would give the cross-linked polymer per se or in acidic solution a cationic character.

The average particle size of the polymers suitable according to the invention is between 50 and 500 nm, the value being based on the average particle diameter in the longitudinal direction, i.e. in the direction of the greatest expansion of the particles. The particle size was determined in the context of the invention by laser diffraction using the Mastersizer-RT device from Malvern.

The polymers suitable according to the invention preferably have a glass transition temperature of more than 30 ° C. and particularly preferably of more than 50 ° C. Here, the person skilled in the art can make the necessary preselection based on the known laws that exist between the glass transition temperatures of the respective homopolymers and the corresponding copolymers.

The type of hair treatment agent is not subject to any fundamental restrictions. It can be, for example, cleaning agents such as shampoos, care agents such as conditioning agents, hair treatments and conditioners, setting agents such as hair fixers, hair sprays and blow dryers, permanent shaping agents such as permanent wave and fixing agents, color-changing agents such as bleaching agents, oxidation dyes and tinting agents based on direct dyes, Trade hair lotions and hair tip fluids. Accordingly, the preparations can be formulated as solutions, emulsions, gels, creams, aerosols or lotions. Furthermore, it can be in the Hair treatment agents according to the invention are both rinse-off and products remaining on the hair (leave-on). The use of the active compounds according to the invention in leave-on products can be a preferred embodiment.

Hair treatment agents preferred according to the invention are hair care agents such as hair rinses, hair treatments, hair pretreatment agents, hair lotions and hairdressing creams and hairdressing pomades.

Hair treatment agents that are particularly preferred in the sense of the invention are hair rinses and hair treatments. Hair rinses are generally formulated in such a way that the active ingredients are rinsed out with water or an at least predominantly water-containing agent after the desired exposure time. The contact time with the hair is usually short. Hair treatments contain the active ingredient combination in a higher concentration than hair rinses and are intended for the treatment of badly damaged hair. The exposure time can be short, for example in the order of the exposure time of hair rinses, but it can also be up to 20 minutes depending on the degree of damage to the hair. The hair treatments according to the invention are generally also rinsed out with water or an at least predominantly water-containing agent after the exposure time has expired, but can also be left on the hair.

The hair treatment compositions according to the invention contain the nonionic, crosslinked (meth) acrylate-containing polymer with an average particle diameter in the range from 50 to 500 nm in amounts of preferably about 0.01 to about 10, in particular about 0.05 to about 5, and particularly preferably about 0 , 1 to about 1 wt .-%, each based on the total weight of the agent.

In a further preferred embodiment, the hair treatment composition according to the invention additionally contains

(a) at least one emulsifier in amounts totaling about 0.1 to about 15% by weight and / or (b) at least one fat and / or a wax in total amounts of about

1 to about 10 wt .-%, each based on the total agent.

Emulsifiers contained in the hair treatment compositions according to the invention can be of natural or synthetic origin. Suitable natural emulsifiers are, for example, phospholipids, in particular lecithin, saponins, bile acids and their derivatives, in particular cholic acid, deoxycholic acid, lithocholic acid and taurocholic acid, tannic acid and abietic acid. Suitable synthetic emulsifiers are, in particular, nonionic synthetic emulsifiers such as, for example, alkoxylated fatty alcohols, and the substances described in the text below as nonionic surfactants.

Fats contained in the hair treatment compositions according to the invention are, for example, linear and branched, saturated and unsaturated fatty alcohols or fatty alcohol mixtures based on natural raw materials with 8 to 22 carbon atoms in the alkyl chain, such as, for example, decanol, octanol, octenol, dodecenol, decenol, octadienol, dodecadienol, decadienol, oleyl alcohol, erucic, ricinolyl, stearyl alcohol, isostearyl alcohol, cetyl alcohol, lauryl alcohol, myristyl alcohol, arachidyl alcohol, caprylic alcohol, capric alcohol, linoleyl alcohol, linolenyl alcohol and behenyl alcohol, as well as their Guerbet alcohols and fatty alcohol cuts which are naturally occurring by reducing triglycerides such as beef tallow, palm oil, peanut oil, rapeseed oil, cottonseed , Soybean oil, sunflower oil and linseed oil, or fatty acid esters formed from their transesterification products with corresponding alcohols and thus represent a mixture of different fatty alcohols. Monoesters of fatty acids with alcohols with 6 to 24 carbon atoms and triglycerides of natural origin can also be used as fatty substances.

Paraffin oils and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil, peach seed oil, henna oil from Lawsonia inermis and oil from Cassia auriculata can also be used as fatty substances. Fatty substances in the sense of the invention are furthermore silicone oils, in particular dialkyl and alkylarylsiloxanes, such as, for example, dimethylpolysiloxane and methylphenylpolysiloxane, and their alkoxylated and quaternized analogs. Examples of such silicones are the products sold by Dow Corning under the names DC 190, DC 200, DC 344, DC 345 and DC 1401.

By definition, waxes are esters of long-chain fatty acids with long-chain fatty alcohols. According to the invention, both natural waxes, chemically modified waxes and synthetic waxes can be used. Examples of such waxes are

Vegetable waxes, such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax and montan wax,

Animal waxes such as beeswax, shellac wax, walrus, lanolin and pretzel fat,

• Mineral waxes such as ceresin and ozokerite

Petrochemical waxes such as petrolatum, paraffin waxes and micro waxes,

• Hard waxes such as Montanester waxes, Sasol waxes and hydrogenated jojoba waxes, as well

• Polyalkylene waxes and polyethylene glycol waxes.

Waxes preferred according to the invention are vegetable waxes such as candelilla wax, carnauba wax and Japanese wax and beeswax.

In a further preferred embodiment, the hair treatment composition according to the invention contains an alkoxylated fatty alcohol as component a) (emulsifier) and / or a fatty alcohol as component b) (fatty substance and / or wax).

In a further, particularly preferred embodiment, the hair treatment composition according to the invention additionally contains a conditioning active ingredient, which is preferably selected from the group consisting of cationic Surfactants, cationic polymers, alkylamidoamines and synthetic oils is formed.

Cationic polymers can be preferred as conditioning agents. These are usually polymers that have a quaternary nitrogen atom, for example in

Form of an ammonium group.

Preferred cationic polymers are, for example, quaternized cellulose derivatives, such as are available under the names of Celquat ^® and Polymer JR ^® commercially. The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose derivatives. polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. The products sold under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers. Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as, for example, vinylpyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755.

Vinylpyrrolidone methoimidazolinium chloride copolymers such as those sold under the name Luviquat ^®, quaternized polyvinyl alcohol and under the designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and

Polyquaternium 27 known polymers with quaternary nitrogen atoms in the main polymer chain.

Cationic polymers of the first four groups are particularly preferred. Preferred cationic surfactants are those of the quaternary ammonium compound type, for example ammonium halides, in particular chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauiyldimethylbenzylammonium chloride and tricetylmethylammonium chloride, behenyltrimethylammonium methosulfate, as well as the quaternium ammonium compounds known under the INCI names 83 and 83.

In particular, for environmental reasons these quaternary ammonium compounds can also be so-called esterquats such as N obtainable under the name Armocare® ^® VGH-70 commercially, N-bis (2-palmitoyloxyethyl) dimethyl be used instead.

Another group of conditioning agents that is also of particular interest for ecological reasons are alkylamidoamines such as stearamidopropyldimethylamine, which is commercially available under the name Tegoamid ^® S 18.

Also suitable as conditioning agents are silicone oils, in particular dialkyl and alkylarylsiloxanes, such as dimethylpolysiloxane and methylphenylpolysiloxane, and their alkoxylated and quaternized analogs. Examples of such silicones are the Dow Corning under the names DC 190, DC 200, DC 344, DC 345 and DC 1401 products sold and the commercial products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silyl amodimethicone), Dow Corning ^® 929 emulsion (containing a hydroxylamino-modified silicone, which is also called amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® - Quat 3270 and 3272 (manufacturer: Th Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80). Paraffin oils and vegetable oils such as jojoba oil, sunflower oil, orange oil, almond oil, wheat germ oil and peach seed oil can also be used as conditioning agents.

Likewise suitable hair-conditioning compounds are phospholipids, for example soy lecithin, egg lecithin and cephalins.

In the agents according to the invention, the conditioning agent can contain in amounts of about 0.05 to about 15, preferably about 0.5 to about 10, and particularly preferably about 1 to about 5% by weight, based on the total agent his.

Furthermore, the hair treatment compositions according to the invention can contain at least one physiologically compatible inorganic or organic acid.

Suitable inorganic acids are, for example, phosphoric acid, sulfuric acid and hydrochloric acid.

Of the organic acids, those are preferred which have 1 to 12 carbon atoms. For ecological reasons, too, the edible acids are of particular importance. Organic acids include those that have positive effects on the human organism in the context of normal food intake. Acetic acid, lactic acid, tartaric acid, citric acid, malic acid, ascorbic acid and gluconic acid. Citric acid and tartaric acid can be preferred according to the invention. Polybasic acids, such as tartaric acid, can also be used in the form of their acid salts.

The agents used according to the invention can contain the acids in amounts of about 0.01 to about 10% by weight, based on the total agent. Amounts from about 0.1 to about 5% by weight, in particular from about 0.1 to about 3% by weight, are very particularly preferred. Furthermore, the hair treatment compositions according to the invention can contain at least one protein hydrolyzate or a derivative thereof. Protein hydrolyzates are product mixtures that are obtained by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins).

According to the invention, protein hydrolyzates of both vegetable and animal origin can be used.

Animal protein hydrolyzates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolyzates, which can also be in the form of salts. Such products are, for example, under the trademarks Dehylan ^® (Cognis), Promois ^® (Interorgana), Collapuron ^® (Cognis), Nutrilan ^® (Cognis), Gelita-Sol ^® (Deutsche Gelatine Fabriken Stoess & Co), Lexein ^® (Inolex) and Kerasol ^® (Croda) sold.

According to the invention, the use of protein hydrolysates of plant origin, e.g. B. soy, almond, rice, pea, potato and wheat protein hydrolyzates. Such products are available, for example, under the trademarks Gluadin ^® (Cognis), DiaMin ^® (Diamalt), Lexein ^® (Inolex) and Crotein ^® (Croda).

Although the use of the protein hydrolyzates as such is preferred, amino acid mixtures or individual amino acids, such as arginm ^' , lysine, histidine or pyrroglutamic acid, which have been obtained in some other way, may also be used in their place. It is also possible to use derivatives of the protein hydrolyzates, for example in the form of their fatty acid condensation products. Such products are sold for example under the names Lamepon ^® (Cognis), Gluadin ^® (Cognis), Lexein ^® (Inolex), Crolastin ^® (Croda) or Crotein ^® (Croda).

Cationized protein hydrolyzates can also be used according to the invention, the underlying protein hydrolyzate being derived from animals, for example from collagen, milk or keratin, from the plant, for example from wheat, corn, rice, potatoes, Soy or almonds, from marine life forms, for example from fish collagen or algae, or from biotechnologically obtained protein hydrolyzates. The protein hydrolysates on which the cationic derivatives according to the invention are based can be obtained from the corresponding proteins by chemical, in particular alkaline or acidic hydrolysis, by enzymatic hydrolysis and / or a combination of both types of hydrolysis. The hydrolysis of proteins usually results in a protein hydrolyzate with a molecular weight distribution of approximately 100 daltons up to several thousand daltons. Preferred cationic protein hydrolyzates are those whose underlying protein content has a molecular weight of 100 to 25,000 Daltons, preferably 250 to 5000 Daltons. Cationic protein hydrolyzates also include quaternized amino acids and their mixtures. The quaternization of the protein hydrolyzates or the amino acids is often carried out using quaternary ammonium salts such as, for example, N, N-dimethyl-N- (n-alkyl) -N- (2-hydroxy-3-chloro-n-propyl) ammonium halides. Furthermore, the cationic protein hydrolyzates can also be further derivatized. As typical examples ϋ cationic protein of the invention and derivatives are under the INCI - names in the "International Cosmetic Ingredient Dictionary and Handbook" (seventh edition 1997, The Cosmetic, Toiletry, and Fragrance Association 1101 17 ^th Street, NW, Suite 300 , Washington, DC 20036-4702) and commercially available products: Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimopnium Hydrσxypropyl Hydrolyzed Casein, Cocodimonium Hydroxypropyl Hydrolyzed Collagen, Cocodimonium Hydroxypropyl Hydrolyzed Hair Keratin, Cocodimonium Hydroxypropyl Hydrolyzed Keratin, Cocodimonium Hydroxypropyl Hydroxypropyl Hydrolyzed Silk, Cocodimonium Hydroxypropyl Hydrolyzed Soy Protein, Cocodimonium Hydroxypropyl Hydrolyzed Wheat Protein, Cocodimonium Hydroxypropyl Silk Amino Acids, Hydroxypropyl Arginine Lauryl / Myristyl Ether HCI, Hydroxypropyltrimonium Gelatin, Hydroxypropyltrimonium Hydrolyzed Casei n, hydroxypropyltri onium hydrolyzed collagen, hydroxypropyltrimonium hydrolyzed conchiolin protein, hydroxypropyltrimonium hydrolyzed keratin, hydroxypropyltrimonium hydrolyzed rice bran protein, hydroxypropyltrimonium hydrolyzed silk, hydroxypropyltrimonium hydrolyzed soy protein, hydroxypropyl Hydrolyzed Vegetable Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein, Hydroxypropyltrimonium Hydrolyzed Wheat Protein / Siloxysilicate, Laurdimonium Hydroxypropyl Hydrolyzed Soy Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein, Laurdimonium Hydroxypropyl Hydrolyzed Wheat Protein / Siloxysilicate, Lauryldimonium Hydroxypropyl Hydrolyzedyl Lauryldimonium Hydroxypropyl Hydrolyzedyl Hydroxyl Hydrolyzed Silicon, , Lauryldimonium Hydroxypropyl Hydrolyzed Silk, Lauryldimonium Hydroxypropyl Hydrolyzed Soy Protein, Steardimonium Hydroxypropyl Hydrolyzed Casein, Steardimonium Hydroxypropyl Hydrolyzed Collagen, Steardimonium Hydroxypropyl Hydrolyzed Keratin, Steardimonium Hydroxypropyl Hydrolyzed Rice Protein, Steardimonium Hydroxypropyl Hydrolyzedium Sodium Protein, Steardimonium Hydroxypropyl Hydrolyzed Wheat Protein, Steartrimonium Hydroxyethyl Hydro lyzed collagen, Quaternium-76 hydrolyzed collagen, Quaternium-79 hydrolyzed collagen, Quaternium-79 hydrolyzed keratin, Quaternium-79 hydrolyzed milk. Protein, Quatemiunv7θ Hydrolyzed ilk, Quaternium-79 Hydrolyzed Soy Protein, Quaternium-79 Hydrolyzed Wheat Protein. The plant-based cationic protein hydrolyzates and derivatives are very particularly preferred.

The protein hydrolyzates and their derivatives can be contained in the agents according to the invention in amounts of 0.01 to 10% by weight, based on the total agent. Amounts of 0.1 to 5% by weight, in particular 0.1 to 3% by weight, are very particularly preferred.

The hair treatment compositions according to the invention can furthermore contain at least one surfactant. Both anionic and nonionic, zwitterionic and ampholytic surfactants can be used, the use of at least one anionic surfactant on the one hand and at least one nonionic surfactant on the other hand being preferred.

Surfactants which can be used according to the invention are, for example: anionic surfactants such as in particular soaps from fatty acids, alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and sulfosuccinic acid mono- and dialkyl esters with 8 to 18 carbon atoms in the alkyl group and sulfosuccinic acid mono-alkyl polyoxyethyl ester with 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, non-ionic surfactants such as, in particular, addition products of 2 to 30 mol of ethylene oxide and / or 0 to 5 mol of propylene oxide with linear fatty alcohols with 8 to 22 carbon atoms, with fatty acids with 12 up to 22 carbon atoms and on alkylphenols with 8 to 15 carbon atoms in the alkyl group, C ₁₂ -C ₂₂ fatty acid mono- and diesters of adducts of 1 to 30 mol ethylene oxide with glycerol, C ₈ -C ₂₂ alkyl mono and oligoglycosides and their ethoxylated analogues and addition products of 5 to 60 moles of ethylene oxide with castor oil and hardened castor oil, zwitterionic surfactants, i In particular, the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyl-dimethylmonium glycinate, N-acylaminopropyl-N, N-dimethylammαniu -glycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate , and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl-imidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group as well as the cocoacylaminoethylhydroxyethylcarboxymethylglycinate, ampholytic surfactants such as N-alkylglycine, N-alkylpropionic acid, N-alkyl- aminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, each with about 8 to 18 carbon atoms in the alkyl group,

Depending on the type of agent and the type of surfactant, the surfactants can be present in the agents according to the invention in a total amount of 0 to 25% by weight, based on the agent as a whole; Agents formulated as so-called concentrates can also have higher surfactant contents. The compositions according to the invention preferably contain amounts of a total of 0 to 5% by weight of surfactant, based on the total composition. Preparations according to the invention which are hair coloring or tinting agents can contain at least one oxidation dye precursor of the developer type, if appropriate in combination with oxidation dye precursors of the coupler type, and / or a direct dye and / or a dye which occurs naturally.

In principle, the pH of the agents according to the invention can be between 2-11, the person skilled in the art knowing the preferred pH ranges for the different agents. The pH of the agents according to the invention, provided they are hair care agents, is preferably between 2 and 7, with values from 3 to 5 being particularly preferred.

Furthermore, the hair treatment compositions according to the invention can contain all the additives customary for the respective intended use. In particular, these can be cosmetic additives which have a cleaning, nourishing or other effect on the external appearance of the hair. Such additives which do not have a direct effect on the hair, but otherwise have a positive effect on the scalp or, for example, the hair follicles, can also be present in the agent according to the invention.

Other common components of the hair treatment compositions according to the invention can be:

Anionic, zwitterionic, amphoteric and non-ionic polymers such as, for example, vinyl acetate / crotonic acid copolymers, polydimethylsiloxanes, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic acid and anhydride polyesters, non-crosslinked polymers, non-copolymerized copolymers, copolymers Acrylic amidopropyl trimethylammonium chloride / acrylate copolymers, octylacrylamide / - methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymers, vinylpyrrolidone / dimethylamino-acrylate acrylate and dimethylamino-acrylate acrylate derivatives cellulose ethers.

symmetrical and asymmetrical, linear and branched dialkyl ethers with a total of between 12 to 36 carbon atoms, in particular 12 to 24 carbon atoms, for example di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, di-n-undecyl ether and di-n-dodecyl ether, n-hexyl-n-octyl ether, n-octyl-n-decyl ether, n-decyl -n-undecyl ether, n-undecyl-n-dodecyl ether and n-hexyl-n-undecyl ether as well as di-tert-butyl ether, di-isopentyl ether, di-3-ethyl decyl ether, tert.-butyl-n-octyl ether, iso- Pentyl-n-octyl ether and 2-methyl-pentyl-n-octyl ether, petroleum jelly

Defoamers like silicones,

Thickeners such as gelatin or vegetable gums, for example agar agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean gum, linseed gums, dextrans, cellulose derivatives, e.g. B. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives such as amylose, amylopectin and dextrins, clays and layered silicates such as. B. bentonite or fully synthetic hydrocolloids such. B. polyvinyl alcohol, the Ca, Mg or Zn soaps, structurants such as maleic acid, mono-, di- and oligosaccharides, perfume oils, dimethyl isosorbide and cyclodextrins,

Solubilizers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, dyes for coloring the agent,

Anti-dandruff active ingredients such as piroctone olamine, zinc omadine and climbazole, other substances for adjusting the pH, vitamins and vitamin precursors such as panthenol, its derivatives and biotin, plant and honey extracts, such as in particular extracts from oak bark, nettle, witch hazel, hops, chamomile, Burdock root, horsetail, linden flowers, almond, aloe vera, coconut, mango, apricot, lime, wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, meadow foam, quendel, yarrow, pickled heels, meristem, ginseng and ginger ginger

Other active ingredients such as ceramides, allantoin, pyrrolidone carboxylic acids, and bisabolol, light stabilizers,

Consistency enhancers such as sugar esters, polyol esters or polyol alkyl ethers, fatty acid alkanolamides, Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Humectants such as sorbitol, lactic acid salts, glycerol or polysaccharide opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers, pearlescent agents such as ethylene glycol mono- and distearate and PEG-3 distearate, complexing agents such as EDTA, NTA, ß-alanine diacetic acid and phosphonic acid Reducing agents such as thioglycolic acid and its derivatives, thiolactic acid, cysteamine, thio malic acid and α-mercaptoethanesulfonic acid, oxidizing agents such as hydrogen peroxide, potassium bromate and sodium bromate, blowing agents such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ , N ₂ and air and antioxidants.

With regard to further components and quantity ranges for the individual ingredients, reference is made to the manuals known to the person skilled in the art, e.g. K. Schrader, Fundamentals and Recipes for Cosmetics, 2nd edition, Hüthig Buch Verlag, Heidelberg, 1989.

Another object of the present invention is a method for conditioning hair, in which an inventive hair treatment composition, as described in the preceding text, is applied to the hair in an effective amount. The agent can then be rinsed out after a contact time. In a preferred embodiment of the method, however, it is left on the hair until the next hair wash.

It has been found within the scope of the invention that the use of nonionic, crosslinked (meth) acrylate-containing polymers with an average particle diameter in the range from 50 to 500 nm in the hair treatment compositions described in the preceding text has advantages for both the manufacturer and the user of such compositions connected is.

For the formulation of such agents, there are advantages above all in terms of freedom from formulation, since the polymers used according to the invention are excellently compatible with the usual recipe components and in particular there are no incompatibilities, such as, for example, the formation of precipitates, with anionic components. Although the particles are undissolved in the hair treatment compositions according to the invention, ie are in the form of a dispersion, their small size enables problem-free incorporation and the production of transparent formulations.

The advantages in use are, in particular, improved wet and dry combability of the hair and a reduced electrostatic charge, so that the undesired "flying" of the hair is avoided. Furthermore, the hair treated with the agents according to the invention shows increased softness. These effects desired for the user are achieved without the problems known from prior art agents of impairing hair gloss and volume being observed. The use of the copolymers also does not result in an undesirable strain on the hair or a sticky handle.

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

Unless otherwise stated, all quantities are to be understood as% by weight.

Examples

Example 1: Preparation of a polymer starting from N-isopropylacrylamide ("P-N-IPAAm")

470 ml of deionized water (fully demineralized water), 7 g of N-isopropylacrylamide, 0.35 g of N, N-methylenebisacrylamide and 0.094 g of sodium dodecyl sulfate were weighed into a 1 liter four-necked flask and brought to 70 under N2 atmosphere and reflux at 200 rpm ° C warmed. After 30 minutes, 0.28 g of potassium peroxodisulfate in 30 ml of demineralized water was added, and the reaction was ended after a further 4 hours. A milky, cloudy dispersion was obtained, the viscosity of which was 70 MPas (20 ° C., 20 rpm).

The hydrogel particles thus synthesized had a diameter of approx. 200 to 300 nm in the swollen state at room temperature, ie. H. in the state of dispersion. The particle size was determined by laser diffraction using the Malvern Mastersizer-RT. The N-isopropylacrylamide was no longer detectable in the dispersion by means of HPLC (<1ppm).

The polymer dispersion thus prepared was then freeze-dried, the polymer being obtained in a non-swollen form as a white powder in a yield of 95%. It had a glass transition temperature of 152 ° C (measurement using modulated dynamic differential calorimetry, MDSC). For further use the polymer can e.g. redisperse with water to a desired concentration. For example 4, the freeze-dried polymer was redispersed with water to a final concentration of 0.04% by weight, based on the total weight of the aqueous dispersion, corresponding to a concentration of 0.4 g / l of dispersion.

Alternatively, the polymer dispersion obtained in the aforementioned synthesis reaction can be separated from the main amount of the salts and water used in the preparation by centrifugation. In this case the polymer is obtained in a swollen state. Example 2: Preparation of a polymer based on ethyl methacrylate and N-vinylpyrrolidone ("EMA-VP")

480 ml of deionized water, 4.1 g of ethyl methacrylate, 15.9 g of N-vinylpyrrolidone, 5.4 g of alkylarylpolyglycol ether sulfate sodium salt and 1 g of N, N-methylenebisacrylamide were weighed into a 2-liter four-necked flask and under a N ₂ atmosphere and heated to reflux with stirring at 200 rpm to 70 ° C. After 30 minutes, 0.8 g of potassium peroxodisulfate in 30 ml of demineralized water was added, and the reaction was ended after a further 4 hours. A dispersion was obtained, the viscosity of which was 5 MPas (20 ° C., 20 rpm). The aqueous dispersion was then dialyzed to reduce the level of residual monomers, which is desirable for use in cosmetics. After dialysis, the residual content of N-vinylpyrrolidone was 9 ppm and that of ethyl methacrylate was 16 ppm. The hydrogel particles synthesized in this way had an average particle diameter of approximately 100 to 300 nm at room temperature. They showed no glass temperature below 90 ° C (measurement by MDSC).

The reaction product was worked up and an aqueous dispersion with a concentration of 0.4 g polymer / l dispersion was prepared analogously to Example 1.

Examples 3.1-3.23: Preparation of further polymers

The crosslinked polymers 3.1 to 3.23 were prepared in a manner analogous to that in Example 2 (cf. Table 1), 5 additional parts by weight of N, N-methylenebisacrylamide being used for the polymerization reaction per 100 parts by weight of the monomers listed in Table 1. Table 1

Example 4: Investigation of the effectiveness of the polymers according to the invention on hair from an aqueous dispersion

a) Carrying out the measurements

a.1) Wet combability measurements

When determining the combability, the work for combing wet strands of hair was measured. Before the zero measurement, the hair was medium-blonded and then combed in the wet state, the combing forces required thereby being recorded. After the zero measurement, the strands of hair were treated once with the respective formulation (10 minutes, 0.5 g formulation per g hair) and then rinsed for 1 minute with a total of 1 liter of water at 38 ° C. Each measurement was made with 20 strands of hair. It In each case 10 comb values of a strand of hair were determined and compared before application and after application of the formulations in the wet state.

a.2) Dry combability measurements and measurement of the electrostatic charge

The measurements were carried out in a constant climate (25% relative humidity, 30 ° C); the hair strands were conditioned for 24 hours. When determining the combability, the work for combing dry strands of hair was measured. The hair was medium-blonded before the zero measurement and then combed in the dry and conditioned state, the combing forces required being recorded. After the zero measurement, the strands of hair were treated once with the respective formulation (10 minutes, 0.5 g of formulation per g of hair) and then rinsed for 1 minute with a total of 1 liter of water at 38 ° C. and then dried. Each measurement was made with 20 strands of hair. 10 comb values of a strand of hair were determined and compared before and after the application of the formulations in the dry and conditioned state.

The electrostatic charge was examined in parallel with the dry combing work with the approval of the electrostatic charge. The actual measurement was carried out using the charge tapping on a double Faraday cage after performing the 10 combs.

a.3) Sensory assessment

The sensory assessment was determined using an expert panel. The strands of hair used were initially 30 min. pre-cleaned with a 12% Texapon NSO solution (pH 6.5) and 5 min. rinsed with water. The strands were then treated with the respective formulations (0.5 g formulation per g hair, 5 min exposure time, 1 min rinsing time) and at 20% rel. Humidity in the climate box dried overnight. To ensure a defined environment, the tests were carried out in a climate room at 22 ° C and approx. 45% relative humidity with standard daylight lighting. Each subject received new strands of hair. The recipe was assigned to the individual attributes and evaluated against the corresponding reference. The parameters are assessed on the following scale:

The tested attribute lies in the property tested in each case

-1 = significantly worse than standard

- 0.5 = slightly worse than standard

0 = exactly like standard

+ 0.5 = slightly better than standard

+ 1 = significantly better than standard

The determination was made by comparing the hair treated with the respective basic formulation against that with the corresponding hair according to the invention

Recipe treated hair. The panel consisted of 11 experts whose judgments were averaged.

b) application of the polymer dispersion to hair

The application on strands of hair was standardized using a dipping process. Standard European hair was used, which had been pre-cleaned, rinsed and dried. The hair was then immersed in the aqueous polymer dispersions prepared according to Examples 1 and 2 at a concentration of 0.4 g / l. Depending on the application as rinse-off or leave-on products, the strands of hair were then rinsed off if necessary. The samples were then at 25% rel. Humidity and 30 ° C in the air.

c) Determination of wet combability

When determining the combability, the work for combing wet strands of hair is carried out on 20 strands of hair pretreated in accordance with b). The values of 10 combs on hair strands were determined and compared before application of the polymers and after application of the polymers in the wet state. The polymers from Example 1 or Example 2 were in the form of an aqueous dispersion with a concentration of Polymers of 0.4 g / l are used. The test was carried out as a leave-on treatment, ie there was no rinsing before the measurements.

The following values of wet work [mJ] were determined:

Hair untreated 130 mJ

Hair treated with polymer from Example 1: 84.3 mJ (-35%)

Hair untreated: 142.1 mJ

Hair treated with polymer from Example 2: 99.4 mJ (-30%)

In both cases, a significant reduction in wet combing was observed when treating strands of hair with the polymer dispersions according to the invention, which is a sign of a clear conditioning effect.

d) Determination of the antistatic charge

20 strands of hair were pretreated in accordance with b), the strands of hair being rinsed out after application of the polymer dispersion (rinse-off treatment) and then at 25% rel. Humidity and 23 ° C for 12 hours were conditioned. The strands of hair were first combed dry ten times each. The electrostatic charge was then determined using a charge tap on a double Faraday cage.

The following values of the electrostatic charge [V] were determined: Hair untreated: 13.8 V

Hair treated with polymer from Example 1: 1 V (-93%)

Hair untreated: 13.6 V

Hair treated with polymer from Example 2: 6 V (-56%)

In both cases, there was a significant reduction in the electrostatic charge; in the case of the polymer from Example 1, the electrostatic charge was practically completely prevented. e) determination of softness

The softness of the hair was sensed using an expert panel. For this, strands of hair were pretreated in the form of a leave-on treatment. The determination was made against untreated hair with 11 expert panelists on a scale from -1 (significantly rougher) to +1 (significantly softer). The tests were carried out in a constant room climate of 23 ° C and 45% rel. Moisture carried out.

Softness throughout the hair:

Hair treated with polymer from Example 1 against hair untreated: m = 0.5 (some softer); (t-test 90.8%)

Softness in the tips:

Hair treated with polymer from Example 1 against hair untreated: m = 0.5 (some softer); (t-test 9.0%)

There was an increased softness in the entire hair.

f) Determination of hair shine

The hair gloss was determined by means of light reflection. For this purpose, 5 strands of hair were pretreated according to b) in the form of a leave-on treatment and additionally provided with a gloss-reducing film. The gloss intensity of the untreated strands of hair and then the strands of hair treated with the polymers according to the invention were measured and the difference was determined. The measurements were carried out at 25 ° C and 40% rel. Moisture carried out.

The following changes in gloss intensity resulted [%]

Hair treated with gloss-reducing film and polymer from Example 1 minus hair treated only with gloss-reducing film: - 1.0% (t test. 92.7%) Hair treated with gloss-reducing film and polymer from Example 2 minus hair treated only with gloss-reducing film: -1.2% (t-test 93.9%)

In both cases there was a statistically indistinguishable value of the gloss intensity. The polymers according to the invention accordingly showed no negative effect on the hair gloss.

g) Determination of hair volume

The volume was determined analytically by casting shadows on the strands of hair. For this purpose, the strands of hair were pretreated in the form of a leave-on treatment. The area of 10 of the untreated and then of the treated strands of hair was determined and compared in each case.

The following values of the volume [mm ² ] resulted:

Hair untreated: 3464 mm ²

Hair treated with polymer from Example 1: 3203 mm ² (t test. 81, 66%)

Hair untreated: 3266 mm ²

Hair treated with polymer from Example 2: 3398 mm ² (t test 89.38%)

In both cases there was a statistically indistinguishable value of the volume. The polymers according to the invention accordingly showed no negative effect on the hair volume.

Example 5: Investigation of the effectiveness of the polymers according to the invention on hair from a rinsing formulation

a) Carrying out the measurements

The measurements were carried out as described in Example 4, a). b) Conditioners used

Formulation 5.0 (comparison): 4.00% StenoM618 ¹⁾ 0.60% Eumulgin B2 ²⁾ 3.00% Dehyquart A-CA ³⁾ 0.20% Euxyl KIOO nB ⁾ Citric acid nB. NaCI ad 100 water pH: 4.0 - 4.5

¹⁾ Cetearyl alcohol

²⁾ Cetylstearyl alcohol with 20 EO

³⁾ Trimethylhexadecylammonium chloride, approx. 25% active substance (COGNIS) ⁴⁾ nB = as required

Formulation 5.1a (according to the invention):

Like formulation 5.0, but additionally containing the polymer from example 1 in a concentration of 0.4 g / l, based on the entire formulation

Formulation 5.2a (according to the invention):

Like formulation 5.0, but additionally containing the polymer from example 2 in a concentration of 0.4 g / l, based on the entire formulation

Formulation 5.1 b (according to the invention):

Like formulation 5.0, but additionally containing the polymer from example 1 in a concentration of 4.0 g / l, based on the entire formulation

Formulation 5.2b (according to the invention):

Like formulation 5.0, but additionally containing the polymer from example 2 in a concentration of 4.0 g / l, based on the entire formulation c) Determination of wet combability

Result: the polymers according to the invention lead to a significant reduction in the wet combing work, the polymer from example 1 exhibiting a better action than the polymer from example 2.

d) Determination of dry combability

Result: in the rinse, the polymer from Example 2 leads to a significant reduction in the combing forces compared to the pure rinsing formulation, i.e. to a conditioning effect.

e) Determination of the electrostatic charge

Result: in the conditioner, the polymers according to the invention bring about a significant reduction in the electrostatic charge on the hair, the Polymer from Example 1 shows a significantly stronger effect than the polymer from Example 2.

f) Sensory assessment

Result: the formulation 5.1a shows a significantly increased softness compared to the comparison formulation 5.0.

Claims

claims

1. Use of a nonionic, crosslinked (meth) acrylate-containing polymer with an average particle diameter in the range from 50 to 500 nm to improve the physical properties of keratin fibers.

2. Hair treatment composition containing conventional cosmetic ingredients, characterized in that the composition further contains a dispersion of a nonionic, crosslinked (meth) acrylate-containing polymer with an average particle diameter in the range from 50 to 500 nm.

3. Hair treatment composition according to claim 2, characterized in that the polymer is based on at least one monomer from the group formed by N-vinylpyrrolidone, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, sec-butyl acrylate, n- Hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-dodecyl acrylate, 2-hydroxyethyl acrylate, N-isopropyl acrylamide and the corresponding methacrylic acid derivatives.

4. Hair treatment composition according to claim 2 or 3, characterized in that the polymer contains poly-N-isopropylacrylamide or an N-vinylpyrrolidone / (meth) acrylic ester copolymer.

5. Hair treatment composition according to one of claims 2 to 4, characterized in that the polymer is cross-linked with N, N'-methylenebisacrylamide.

6. Hair treatment composition according to one of claims 2 to 5, characterized in that the polymer is cross-linked to 0.5 to 20%.

7. Hair treatment composition according to one of claims 2 to 6, characterized in that the polymer has a glass transition temperature of more than 30 ° C.

8. Hair treatment composition according to one of claims 2 to 7, characterized in that the polymer in an amount of 0.01 to 10 wt .-%, preferably from 0.05 to 5 wt .-%, and particularly preferably from 0.1 is up to 1 wt .-%, based on the total weight of the agent.

9. Hair treatment composition according to one of claims 2 to 8, characterized in that it a) 0.1 to 15 wt .-% of at least one emulsifier and / or b) 1, 0 to 10 wt .-% of at least one fat and / or contains a wax.

10. Hair treatment composition according to claim 9, characterized in that it contains as component a) an alkoxylated fatty alcohol and / or as component b) a fatty alcohol.

11. Hair treatment composition according to one of claims 2 to 10, characterized in that it contains at least one conditioning active ingredient which is selected from the group formed by cationic surfactants, cationic polymers, alkylamidoamines and synthetic oils.

12. A method for conditioning hair, characterized in that an agent according to one of claims 2 to 11 is applied to the hair in an effective amount.

13. The method according to claim 12, characterized in that the agent is left there after application to the hair until the next hair wash.