JPH09502456A - Hair hardener - Google Patents

Abstract

  (57) [Summary] Aqueous-based, alcohol-based, or water-alcohol-based hair solidifying agents (A) 0.1 to 20 weight percent of 50 to 100% neutralized shellac, and (B) hydroxypropyl chitosan and hydroxybutyl. It is characterized by containing 0.1 to 20 weight percent of chitosan, hydroxypropyl cellulose and / or hydroxybutyl cellulose. Since the agent of the present invention produces almost no sediment, it does not burden the hair and imparts good gloss to the hair. This drug has a good hair styling property and retains a hair solidifying action even after washing hair. The drug can be nebulized well and is resistant to moisture in the air. Furthermore, the drug has the advantage that the drying time is very short.

Description

DETAILED DESCRIPTION OF THE INVENTION Hair-solidifying agent The present invention relates to an aqueous system, alcohol containing 50 to 100% neutralized shellac in combination with hydroxypropyl chitosan, hydroxybutyl chitosan, hydroxypropyl cellulose and / or hydroxybutyl cellulose. A hair solidifying agent (hair styling agent) based on water-based or water-alcohol system is targeted. Hair can usually be temporarily molded by using a hair-solidifying agent. In this case, the substantial component of the hair-solidifying agent is a film-forming natural or synthetic polymer solution. In this case, examples of synthetic polymers include homopolymers or copolymers of acrylic acid or methacrylic acid, copolymers of acrylic acid and acrylamide, and copolymers of alkyl vinyl ether and maleic acid monoalkyl ester. Such as anionic polymers, amphoteric polymers such as octyl acrylamide, terpolymers of acrylates and butylaminoethyl methacrylate, and homopolymers of vinylpyrrolidone, copolymers of vinylpyrrolidone and vinyl acetate. , And nonionic polymers such as terpolymers of vinylpyrrolidone, vinyl acetate and vinyl propionate. A synthetic polymer having a hair-solidifying action is mainly produced by radical polymerization of a petrochemical product, that is, a non-renewable substance as a raw material. Further, the synthetic polymer contains impurities such as a monomer, a polymerization inhibitor and a polymerization control agent, which are toxicological problems. Natural polymers do not have the disadvantages of the synthetic resins listed above. As a natural resin having a hair-solidifying action, shellac, polysaccharides or polysaccharide derivatives, particularly cellulose derivatives, chitosan or chitosan derivatives are mainly used. A hair styling agent based on shellac, which has a film-forming agent as a hair-solidifying agent, is usually hard to fix because it adheres strongly to the hair. Moreover, such a hair styling agent remains on the hair and is difficult to remove. The hair-solidifying action of the polysaccharide-containing hair styling agent is basically based on the thickening action of the polysaccharide, which is difficult to spray. Furthermore, this hair styling agent produces scales when combing the hair and forms a gray film on the hair. The polymer applied to the hair styling agent must have various properties. For example, it must have good solubility in alcohols or water-alcohol mixtures and must be compatible with commonly used aerosol propellants. Furthermore, the hair styling agent should adhere firmly and flexibly to the hair without impairing the natural feel of the hair and form a transparent, glossy film on the hair. In addition, the polymer must be resistant to moisture in the air, maintain hair-solidifying properties even at high humidity, and be non-greasy to the hair. A common problem in the manufacture of hair styling products is maintaining a tidy hairstyle. That is, the hair-solidifying action of the hair styling agent is lost by washing the hair. A large number of natural or synthetic polymers having various properties are known, but all properties can be satisfied, especially spraying is possible, and the hair has a solidifying action even after hair washing, and the drying time is short, and further It has not yet been possible to provide a hair solidifying agent (hair styling agent) that is resistant to moisture in the air. Therefore, it has been a problem to provide a hair-solidifying agent that eliminates the drawbacks of the conventional hair styling agents. That is, it is necessary that the subject hair styling agent be one that can impart gloss to the hair, has a good hair styling action, and retains a good hair solidifying action even after washing. There is a demand for a hair styling agent that can be sprayed more satisfactorily, is resistant to moisture in the air, can be quickly dried, and does not burden the hair. And, surprisingly, a hair-solidifying agent containing a combination of partially or fully neutralized shellac and hydroxypropyl chitosan, hydroxybutyl chitosan, hydroxypropyl cellulose or hydroxybutyl cellulose, meets the above-mentioned requirements. It has been found that can be satisfied well. That is, the present invention provides (A) 0.1 to 20 weight percent of shellac neutralized to 50 to 100%, and (B) hydroxypropyl chitosan, hydroxybutyl chitosan, hydroxypropyl cellulose and / or hydroxybutyl cellulose to 0.1. A hair solidifying agent (hair styling agent) based on water, alcohol or a water-alcohol system, which is characterized by containing 1 to 20 weight percent. This hair-solidifying agent preferably contains 0.5 to 10 weight percent of component (A). As the shellac of the component (A), a commercially available shellac, for example, Schellack MHP210 ^R, which is a commercially available product of Pennig (Hamburg, Germany), can be used. For neutralizing shellac, organic or inorganic bases commonly used in cosmetics such as primary, secondary or tertiary amines, amino alcohols, alkali hydroxides or ammonia in the form of an aqueous solution are used. Can be used. The preferred neutralizing agent is 2-amino-2-methylpropanol, triisopropanolamine, sodium hydroxide or ammonia in the form of an aqueous solution. Partial neutralization of shellac is also possible with the hydroxypropyl chitosan and / or hydroxybutyl chitosan used in this drug. The agents according to the invention have a N / O-substitution ratio of 99: 1 to 1:99 of 1. It has a degree of propoxylation or butoxylation of 0 to 5.0 and an intrinsic viscosity (η) of 10 to 150 ml / g (1% solution in 0.2 mol of acetic acid and 0.1 mol of sodium chloride at 20 ° C). It is preferable to include hydroxypropyl chitosan or hydroxybutyl chitosan having Particularly preferred is a degree of propoxylation or butoxylation of 1.5 to 3.0 at an N / O-substitution ratio of 95: 5 to 40:60 and an intrinsic viscosity of 25 to 80 ml / g. It is hydroxypropyl chitosan or hydroxybutyl chitosan having (η). Useful hydroxypropyl chitosans include, for example, those described in European Patent Specification 0 224045, and useful hydroxybutyl chitosans, such as those described in European Patent Specification 0243822. The agent according to the present invention has a degree of propoxylation or butoxylation of 2.0 to 4.0, and a kinematic viscosity of 0.1 to 25 mm ² / sec (using a Ubbelohde viscometer type 501103 (capillary tube 2)). And a hydroxypropyl cellulose or hydroxybutyl cellulose having a 3% solution in 96% ethanol, measured at 20 ° C.]. Particularly preferred is 2.3 to 3. Hydroxypropyl cellulose or hydroxybutyl cellulose having a degree of propoxylation or butoxylation of 8 and a kinematic viscosity of 0.2 to 12 mm ² / sec. Useful hydroxypropylcellulose, e.g. Nippon Soda Co. (Tokyo, Japan) commercial products Nisso ^R HPC or Aqualon Co. (Germany, Dusseldorf) include commercially available products Klucel ^R EF of. The hair-solidifying agent according to the present invention preferably contains the component (B) in an amount of 0.5 to 10% by weight. The agent of the present invention can be provided in the form of an aqueous solution, an alcohol solution or a water-alcohol solution. In this case, examples of the alcohol include lower alcohols having a boiling point of 300 ° C. or lower and having 1 to 5 carbon atoms, which are generally used in cosmetics. Particularly preferred are alcohols having 1 to 3 carbon atoms. The hair-solidifying agent according to the invention can be filled in a compression container together with a propellant and released in the form of an aerosol or foam. Alternatively, it may be provided in the form of a non-aerosol hair spray, a non-aerosol foam or a non-aerosol hair lacquer using a suitable mechanical spraying device. A mechanical spraying device is a device that can spray a liquid without using a liquid propellant. Suitable mechanical atomizers are, for example, elastic vessels equipped with a radiation valve or radiation pumps. In the case of an elastic container, the barber is filled into the container under compression, which causes the elastic container to expand, whereupon the elastic container is contracted so that the barber is continuously released with the opening of the radiant valve. When the agent according to the invention is provided in the form of an aerosol hair spray, an aerosol foam or an aerosol hair lacquer, the agent additionally contains 2 to 80% by weight of propellant and is packed together in a compression container. As a propellant, a volatile fluorinated chlorinated hydrocarbon such as difluorochloromethane, trichloromonofluoromethane or tetrafluorodichloroethane, a lower alkane such as n-butane, i-butane or propane, Alternatively, dimethyl ether, as well as propellants, such as N ₂ , N ₂ O or CO ₂ , which are gaseous under compression, and mixtures thereof are useful. Of the propellants listed above, dimethyl ether alone and mixtures of dimethyl ether and lower alkanes are preferred. However, it is particularly preferred to use dimethyl ether as propellant. The hair-solidifying agent according to the present invention further comprises cosmetic additives commonly used in hair styling agents, such as C ₁₂ to C ₁₈ alkyl ether sulphates, alkyl trimethyl ammonium salts, alkyl pyridinium salts, carboxy derivatives of imidazole, About 0.01 to 3 weight percent of anionic, cationic, amphoteric or nonionic wetting or emulsifying agents such as N-alkyl sulfobetaines or alkylglycols and proglyceryl ethers of saturated or unsaturated aliphatic alcohols, 0.01 to 0.7 weight percent of a preservative such as salicylic acid or mandelic acid, an anti-dandruff agent such as zinc-pyridine-thione, a cosmetic dye such as fluorescein-sodium salt, a fatty acid ester. Approximately 0.01 to 3 weight percent of a hair protectant such as a steal, an aliphatic alcohol, a fatty acid glyceride, a lanolin derivative or pantothenic acid, a hydrophobizing agent such as silicone oil such as polydimethylsiloxane, polymethylphenylsiloxane or cyclomethicone. Agents, for example softeners such as phthalates or alkyl citrates, combing improvers such as cetyltrimethylammonium chloride, cationic polymers such as cationic chitosan derivatives or cellulose derivatives 0.01 to 0. .2% by weight, and may further contain complexing agents, foam stabilizers, buffer substances, sunscreens or perfume oils in amounts of about 0.01 to 0.8% by weight. The chemical | medical agent of this invention can be used for dyeing or toning by adding a dye as needed. Such a preparation is commercially available, especially as a dyeing hair styling agent or a toning hair styling agent, and is known. These are auxiliary, known dyes which are commonly used in hair styling agents and which can be dyed directly on the hair, such as 1,4-diamino-2-nitrobenzene, piclamic acid, 1-hydroxy-2-amino. Aromatic nitro dyes such as -4-nitrobenzene or 1,4-bis-[(2-hydroxyethyl) amino] -2-nitro-5-chlorobenzene, such as Acid Brown 4 (C.I. 14805). Such an azo dye, for example, an anthraquinone dye such as Disperse Violet 4 (C.I. 61105) or a triphenylmethane dye such as Basic Violet 1 (C.I. 42535) is contained. These dyes are acidic, nonionic or basic depending on the kind of the substituent. The working concentration of these dyes is usually about 0.01 to 2.0 weight percent. Since the agent of the present invention produces almost no sediment, it does not burden the hair and imparts good gloss to the hair. This drug has a good hair styling property and retains a hair solidifying action even after washing hair. The drug is also well nebulizable and resistant to moisture in the air. Furthermore, the drug has the advantage that the drying time is very short. The subject of the invention will now be described in more detail on the basis of examples. Examples Example 1: Non-aerosol hair spray (normal hair styling) shellac 2.0 g Hydroxypropyl chitosan (European patent specification 1.5 g prepared on the basis of 0224045. Degree of propoxylation N: 1.84, O: 0.39. , 0.2% acetic acid and 1% solution in 0.1 mol sodium chloride, η = 50.4 ml / g at 20 ° C.) 1N aqueous solution of sodium hydroxide 2.8 g Perfume 0.2 g Ethanol 89. 9 g water 3.6 g 100.0 g Example 2: non-aerosol hair spray (normal hair styling) shellac 1.9 g hydroxybutyl chitosan (prepared according to European patent specification 1.7 g 0243822; degree of butoxylation N: 1.98, O: 0.56, 1% solution in 0.2 mol of acetic acid and 0.1 mol of sodium chloride, η = 7 at 20 ° C. .3ml / g) 1 defined aqueous 2.6g perfume 0.2g ethanol 89.0g water 4.6 g 100.0 g Example of sodium hydroxide 3: Non-aerosol Heyasupure (thin for hair) shellac 2.3g Hydroxypropyl cellulose (Example: Aqualon 1.0 g Klucel EF ^R ) 1N aqueous solution of sodium hydroxide 3.2 g Perfume 0.2 g Ethanol 90.0 g Water 3.3 g 100.0 g Example 4: Non-aerosol hair spray (strong hair styling) Shellac 3.5 g Hydroxypropyl chitosan (prepared according to European patent specification 3.0 g 0224045. Degree of propoxylation N: 1.84, O: 0.39, 0.2 mol of acetic acid and 0.1 of sodium chloride. 1% solution in mole, η = 50.4 ml / g at 20 ° C) 1 of sodium hydroxide Constant aqueous 4.9g perfume 0.2g ethanol 86.0g water 2.4 g 100.0 g Example 5: Aerosol Heyasupure (usually hairdressing, VOC80%) shellac 1.50g Hydroxypropyl Chitosan (European patent specification 1.50g 0224045 Propoxylation degree N: 1.84, O: 0.39, 1% solution in 0.2 mol of acetic acid and 0.1 mol of sodium chloride, η = 50.4 ml at 20 ° C. / g) 1 defined aqueous solution of sodium hydroxide 2.00g perfume 0.15g ethanol 22.40g water 22.45g dimethyl ether 50.00 g 100.0 g example 6: birch extract containing hair fixative shellac 1.20g hydroxypropyl chitosan (European Manufactured based on patent specification 1.10 g 0224045. Degree of propoxylation N: 1.84, O: 0.39, 1% solution in 0.2 mol of acetic acid and 0.1 mol of sodium chloride, η = 50.4 ml / g at 20 ° C) Hydroxylation cationic Se 0.10g cellulose derivatives birch extract based on 1 N aqueous solution 1.70g perfume 0.15g U.S. patent 3,472,840 of sodium: ethanol 15 (eg Germany, Holzminden, Doragoko 0.30g Co. Extrapon ^R Birke in) .00g water 80.45G 100.00 g example 7 mousse strong hair fixative shellac 1.5g hydroxypropyl cellulose (e.g. Aqualon Company 2.5g Klucel EF ^R) 1 defined aqueous 2.1g perfume 0 sodium hydroxide. 1 g 1.0 g cetylstearyl oxyethylated with 20 mol of ethylene oxide Cole ethanol 8.0 g Water 84.8 g 100.0 g Example 8: Toning hairdressing shellac 1.00 g Hydroxypropyl cellulose (eg: 1.50 g Klucel EF ^{R from} Aqualon) 1.40 g of 1N aqueous solution of sodium hydroxide Fragrance 0.15 g Acid Brown 4 (CI. 14805) 0.05 g Oxyethylated with 35 mol of ethylene oxide 0.15 g Castor oil ethanol 8.00 g Water 87.75 g 100.00 g

────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Franzke, Michael             Germany, Day 64380 Roche             Dorf, Alter Darmstadt               Wake 41 (72) Inventor Wendel, Harald             Germany, Day-64372 Orbe             Le Ramstadt, Grabengasse             Three

Claims (1)

[Claims] 1. (A) 0.1 to 20 weight percent of 50 to 100% neutralized shellac, and (B) 0.1 to 20 weight percent of hydroxypropyl chitosan, hydroxybutyl chitosan, hydroxypropyl cellulose and / or hydroxybutyl cellulose. A water-based, alcohol-based, or water-alcohol-based hair solidifying agent characterized by containing. 2. The hair solidifying agent according to claim 1, which contains 0.5 to 10 weight percent of the component (A). 3. Hydroxypropyl chitosan has a N / O-substitution ratio of 99: 1 to 1:99, a degree of propoxylation of 1.0 to 5.0, and an intrinsic viscosity (η) of 10 to 150 ml / g. The hair solidifying agent according to claim 1 or 2, characterized in that: 4. Hydroxybutyl chitosan having a N / O-substitution ratio of 99: 1 to 1:99, a butoxylation degree of 1.0 to 5.0, and an intrinsic viscosity (η) of 10 to 150 ml / g. The hair solidifying agent according to any one of claims 1 to 3, characterized in that. 5. Hydroxypropyl chitosan has a N / O-substitution ratio of 95: 5 to 40:60, a degree of propoxylation of 1.5 to 3.0, and an intrinsic viscosity (η) of 25 to 80 ml / g. The hair solidifying agent according to any one of claims 1 to 4, which is characterized in that: 6. Hydroxybutyl chitosan having an N / O-substitution ratio of 95: 5 to 40:60, a butoxylation degree of 1.5 to 3.0 and an intrinsic viscosity (η) of 25 to 80 ml / g. The hair solidifying agent according to any one of claims 1 to 5, characterized in that: 7. The hair solidifying agent according to any one of claims 1 to 6, wherein the component (B) is contained in an amount of 0.5 to 10% by weight. 8. Hydroxypropyl cellulose has a degree of propoxylation of 2 to 4 and an O.V. The hair solidifying agent according to claim 1, which has a kinematic viscosity of 1 to 25 mm ² / sec. 9. 9. The hair solidifying agent according to claim 1, wherein the hydroxybutyl cellulose has a degree of butoxylation of 2 to 4 and a kinematic viscosity of 0.1 to 25 mm ² / sec. Ten. 10. The hair solidifying agent according to claim 1, wherein the hydroxypropyl cellulose has a degree of propoxylation of 2.3 to 3.8 and a kinematic viscosity of 0.2 to 12 mm ² / sec. 11. 11. Hair setting according to any one of claims 1 to 10, characterized in that the hydroxybutyl cellulose has a butoxylation degree of 2.3 to 3.8 and a kinematic viscosity of 0.2 to 12 mm ² / s. Agent. 12． 12. Neutralizing agent for shellac is selected from primary, secondary or tertiary amines, amino alcohols, alkali hydroxides or ammonia, according to any one of claims 1 to 11. The hair solidifying agent described. 13. The hair solidifying agent according to claim 1, wherein the neutralizing agent for shellac is ammonia, 2-amino-2-methylpropanol, triisopropanolamine or sodium hydroxide.