Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/91—Graft copolymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/73—Polysaccharides
  • A61K8/731—Cellulose; Quaternized cellulose derivatives
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/73—Polysaccharides
  • A61K8/737—Galactomannans, e.g. guar; Derivatives thereof
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/02—Preparations for cleaning the hair
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/04—Preparations for permanent waving or straightening the hair
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/10—Preparations for permanently dyeing the hair
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/12—Preparations containing hair conditioners
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
  • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
  • C08L1/08—Cellulose derivatives
  • C08L1/26—Cellulose ethers
  • C08L1/28—Alkyl ethers
  • C08L1/284—Alkyl ethers with hydroxylated hydrocarbon radicals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L89/00—Compositions of proteins; Compositions of derivatives thereof
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/54—Polymers characterized by specific structures/properties
  • A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
  • A61K2800/5426—Polymers characterized by specific structures/properties characterized by the charge cationic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides

Definitions

• the present invention relates to a hair cosmetic additive, a hair cosmetic, and a method for producing a hair cosmetic additive.
• Hair cosmetics such as shampoos, rinses, and hair styling agents for various sets are used for the purpose of imparting a desired texture to the hair.
• Nonionic polymers, anionic polymers, cationic polymers, and the like are used as components of such hair cosmetics.
• Nonionic polymers include polyvinyl pyrrolidone and polyvinyl methyl ether.
• anionic polymers include polymers of vinyl carboxylic acids such as acrylic acid and methacrylic acid. Unlike nonionic polymers, anionic polymers are less susceptible to humidity.
• a polymer for example, polyquaternium-10
• a cationizing agent such as glycidylpropyltrimethylammonium chloride
• cellulose or guar gum is widely used.
• diallyldimethylammonium chloride for example, polyquaternium-6
• acrylamide and diallyldimethylammonium chloride copolymer for example, polyquaternium-7
• Patent Document 1 a method for preparing a graft copolymer of a water-soluble monomer and a polysaccharide
• Patent Document 2 a method of reacting in a solvent that does not dissolve the polysaccharide
• Patent Document 2 a method of polymerizing by irradiation with an electron beam in a state close to the solid phase
• polyvinylpyrrolidone used as a nonionic polymer is susceptible to humidity conditions. Therefore, the film before moisture absorption is hard and easily causes a flaking phenomenon, whereas it becomes very flexible and causes a blocking phenomenon at high temperature and high humidity. As a result, the hairs may stick together and brushing may be difficult.
• polyvinyl methyl ether used as a nonionic polymer the influence of such humidity is further remarkable.
• the anionic polymer film is generally hard. Therefore, although the hair-styling effect is high, there is a problem that it is fragile, and there is a possibility that a flaking phenomenon may occur. Furthermore, the addition of a cationic substance is limited due to its anionic property, and there is a concern about a solidification phenomenon caused by a conditioner agent (cationic) during hair washing.
• a conditioner agent cationic
• the cationic polymer there is room for improvement in that the use of the polymer as a component of hair cosmetics causes the hair to become stiff and firm.
• Patent Document 1 and Patent Document 2 both have the disadvantage of a low reaction rate.
• a monomer having good polymerizability is added continuously or sequentially to make the composition of the copolymer uniform.
• the reaction is difficult.
• the present invention has been made in view of the above circumstances, and has as its main object to provide an additive for hair cosmetics that gives a supple feel to the finish and a hair cosmetic containing the same.
• the present inventors have dissolved a natural polymer and / or a natural polymer derivative having an OH group in water, and then dissolved cationic and nonionic water-soluble solutions in an aqueous medium. It has been found that an additive for hair cosmetics obtained by graft copolymerization of a functional monomer can impart a supple feel to the finish to the hair, and has completed the present invention.
• the present invention is as follows.
• [1] Graft copolymer obtained by graft copolymerization of a cationic water-soluble monomer and a nonionic water-soluble monomer in an aqueous solution containing a natural polymer and / or a natural polymer derivative having an OH group Additive for hair cosmetics containing coalescence.
• the content of the cationic water-soluble monomer in the water-soluble monomer is 5 to 90 mol%
• the additive for hair cosmetics according to the above [1] wherein the content of the nonionic water-soluble monomer in the water-soluble monomer is 10 to 95 mol%.
• the cationic water-soluble monomer is at least diallyldimethylammonium chloride;
• the natural polymer derivative is one or more natural polymer derivatives selected from the group consisting of hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, and hydroxypropyl guar gum.
• Additive for hair cosmetics [6] The additive for hair cosmetics as described in any one of [1] to [5] above, wherein the natural polymer or the natural polymer derivative has a 2% aqueous solution viscosity at 25 ° C. of 20,000 mPa ⁇ s or less.
• the mass ratio (A / B) of the total amount (A) of the natural polymer and / or the natural polymer derivative to the total amount (B) of the water-soluble monomer is 5/95 to 80/20.
• the hair cosmetic additive according to any one of the above [1] to [6]. [8] Any one of [1] to [7] above, wherein the total concentration of the natural polymer, the natural polymer derivative and the water-soluble monomer in the graft copolymerization reaction solution is 10 to 50% by mass.
• One hair cosmetic additive. [9] The additive for hair cosmetics as described in any one of [1] to [8] above, wherein the graft copolymer has a weight average molecular weight of 10,000 to 3,000,000.
• the hair cosmetic is shampoo, The hair cosmetic according to [12] above, wherein the content of the cationic water-soluble monomer in the water-soluble monomer is in the range of 5 to 30 mol%.
• a method for producing an additive for hair cosmetics comprising: [16] [15] The method for producing an additive for hair cosmetics as described in [15] above, wherein in the graft copolymerization step, a chain transfer agent is added to the aqueous solution.
• the present embodiment is an illustration of this invention and is not the meaning which limits this invention to the following content.
• the present invention can be implemented with appropriate modifications within the scope of the gist thereof.
• the hair cosmetic additive of the present embodiment grafts a cationic water-soluble monomer and a nonionic monomer in an aqueous solution containing a natural polymer and / or a natural polymer derivative having an OH group. It contains a graft copolymer obtained by copolymerization.
• This graft copolymer is prepared by dissolving a natural polymer having an OH group or a natural polymer derivative, or both in water to form an aqueous solution, and then dissolving the cationic water-soluble monomer and the nonionic water-soluble in the aqueous solution. It is obtained by graft copolymerizing the monomer in a substantially uniform state. In the graft copolymerization reaction, a small amount of a water-soluble organic solvent such as alcohol can be mixed in the aqueous solution as necessary.
• the content of the cationic water-soluble monomer in the water-soluble monomer is not particularly limited, but is preferably in the range of 5 to 90 mol%.
• the content of the nonionic water-soluble monomer in the water-soluble monomer is not particularly limited, but is preferably in the range of 10 to 95 mol%.
• natural polymers and natural polymer derivatives react in an aqueous solution in a substantially uniform state, those having high solubility in water are preferable.
• the natural polymer include starches, guar gum, locust bean gum, xanthan gum, chitosan, carrageenan, julan gum, pullulan, mannan, fenugreek, sericin and the like.
• guar gum, locust bean gum and sericin are preferable from the viewpoint of solubility.
• Examples of natural polymer derivatives include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl guar gum, and hydroxypropyl guar gum.
• hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose and hydroxypropyl guar gum are preferable, and hydroxyethyl cellulose is more preferable.
• a plurality of these natural polymers and natural polymer derivatives can be used in combination.
• the molecular weight of the natural polymer or natural polymer derivative is not particularly limited. However, since graft copolymerization is performed in a substantially uniform aqueous solution state, the 2% aqueous solution viscosity is 20,000 mPa ⁇ s or less at 25 ° C. Is preferred. By setting the viscosity of the 2% aqueous solution to 20,000 mPa ⁇ s or less at 25 ° C., the viscosity of the solution can be prevented from becoming extremely high, and uniform graft copolymerization can be performed.
• the viscosity of the 2% aqueous solution is more preferably in the range of 100 to 10,000 mPa ⁇ s at 25 ° C. in consideration of the viscosity of the reaction solution.
• the 2% aqueous solution viscosity is a viscosity when the water-soluble polymer concentration in deionized water is 2% by mass, and can be measured with a B-type viscometer.
• the mass ratio (A / B) between the total amount (A) of the natural polymer and / or natural polymer derivative and the total amount (B) of the water-soluble monomer is preferably 5/95 to 80/20. More preferably, it is 95 to 50/50.
• the mass ratio (A / B) within the above range, the synergistic action of the natural polymer and the synthetic polymer in the case of the hair cosmetic additive can be exhibited.
• the total amount (A) of the natural polymer and / or natural polymer derivative means the total amount when the natural polymer and the natural polymer derivative are used in combination, and when the natural polymer is used alone. Means the total amount of the natural polymer, and when used alone, means the total amount of the natural polymer derivative.
• the reaction concentration is preferably 10 to 50% by mass, more preferably 10 to 30% by mass, as the total concentration of the natural polymer and / or natural polymer derivative and the water-soluble monomer. preferable.
• tertiary amino group-containing cationic monomers include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl. Examples include (meth) acrylamide and salts thereof.
• Quaternary ammonium base-containing cationic monomers include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminopropyl Examples thereof include dimethylbenzylammonium chloride and (meth) acryloyloxy-2-hydroxypropyltrimethylammonium chloride. Further, allylamine, diallylmethylamine and salts thereof, diallyldimethylammonium chloride and the like can be mentioned. Among them, diallyldimethylammonium chloride is more preferable from the viewpoint of the stability and safety of the polymer. These cationic water-soluble monomers can also be used in combination.
• nonionic water-soluble monomers that copolymerize with cationic water-soluble monomers include (meth) acrylamide, dimethylacrylamide, diethylacrylamide, isopropylacrylamide, hydroxyethylacrylamide, vinylpyrrolidone, vinylformamide, vinylacetamide, etc. Is mentioned.
• Acrylamide is more preferable because of the ease of the polymerization reaction. It is also possible to use a combination of a plurality of these nonionic water-soluble monomers. Further, as long as the graft polymer is water-soluble, it is possible to copolymerize hydrophobic monomers such as styrene and alkyl (meth) acrylate.
• the temperature at the time of graft copolymerization needs to be a temperature at which the natural polymer and / or natural polymer derivative dissolves in water, and varies depending on the natural polymer and / or natural polymer derivative used. Do in range.
• Polymerization initiation uses a radical polymerization initiator.
• the initiator is preferably water-soluble, and any of an azo initiator, a redox initiator, a persulfate initiator, and a peroxide initiator can be used.
• water-soluble azo initiators examples include 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dioxide. And hydrogen chloride, 4,4′-azobis (4-cyanovaleric acid), and the like.
• Examples of the redox initiator include a combination of a polymerization initiator such as persulfate such as ammonium persulfate and a reducing agent.
• Examples of the reducing agent include sulfites such as sodium sulfite and sodium bisulfite, trimethylamine, and tetramethylethylenediamine.
• persulfate-based initiator examples include persulfates such as ammonium persulfate and potassium persulfate. Examples of the peroxide-based initiator include peroxides such as hydrogen peroxide.
• persulfate is preferable from the viewpoint of efficient graft copolymerization.
• the polymerization reaction is preferably performed at 50 ° C or higher.
• guar gum, hydroxypropyl guar gum, or the like which has a relatively high aqueous solution viscosity, it may be difficult to advance graft copolymerization efficiently.
• persulfate as an initiator, graft copolymerization can be efficiently performed even when such a substance having a relatively high aqueous solution viscosity is used.
• the presence of a natural polymer and / or a natural polymer derivative dissolved in water causes graft copolymerization of cationic and nonionic water-soluble monomers.
• the polymer may be charged in a lump and purged with nitrogen, followed by addition of a polymerization initiator for polymerization.
• a part or all of the water-soluble monomer may be added in small portions while stirring after adding the polymerization initiator. You may add continuously or sequentially.
• a part of the monomer having good polymerizability may be added continuously or sequentially during the polymerization to make the composition of the copolymer uniform. preferable.
• diallyldimethylammonium chloride and acrylamide it is preferable to add at least part of the acrylamide continuously or sequentially into the aqueous solution. Since the difference between the polymerization rate of diallyldimethylammonium and the polymerization rate of acrylamide is large, if a monomer is charged at a time, polymerization of only acrylamide proceeds, and diallyldimethylammonium tends to remain as a monomer. Therefore, the remaining diallyldimethylammonium tends to be polymerized, and acrylamide graft chains and diallyldimethylammonium chloride graft chains tend to be generated separately. Therefore, the above phenomenon can be effectively prevented by adding acrylamide continuously or sequentially.
• the weight average molecular weight of the graft polymer as measured using gel permeation chromatography (GPC-MALS) by light scattering method is preferably 10,000 to 3,000,000, and more preferably 20,000 to 2,000,000. . By being 3 million or less, the solubility with the various components used when it is set as hair cosmetics can be improved. By setting it to 10,000 or more, a sufficient addition effect can be obtained.
• an amount of a chain transfer agent can be added as needed during the polymerization.
• any compound can be selected from commonly used compounds having chain transfer properties such as isopropyl alcohol, mercaptoethanol, sodium gluconate, sodium formate, and sodium hypophosphite.
• the hair cosmetic additive of the present embodiment can be blended into various hair cosmetics.
• the hair cosmetic containing the hair cosmetic additive of the present embodiment can be suitably used as, for example, a rinse, a conditioner, a treatment, a hair styling agent for setting, a permanent solution, or a hair dye. Moreover, it can use suitably also as a shampoo by adjusting suitably content of the additive for hair cosmetics.
• the additive When the additive is added to the shampoo, if the cation equivalent value is too high, it may form a complex with the anionic surfactant that is the main component of the shampoo composition, thereby preventing insolubilization and clouding. From this point of view, when the hair cosmetic additive of the present embodiment is blended in a shampoo, the content of the cationic water-soluble monomer in the water-soluble monomer is in the range of 5 to 30 mol%. preferable.
• the hair cosmetic additive of the present embodiment is used for rinsing, conditioner, or treatment, since the main component is a cationic surfactant, the inclusion of the cationic water-soluble monomer in the water-soluble monomer
• the amount is selected in the range of 5 to 90 mol% depending on the effect required for the hair cosmetic, but more preferably in the range of 5 to 60 mol%.
• the hair cosmetic additive of the present embodiment When used for a hair styling agent, a permanent liquid, or a hair dye for setting, it often does not contain an ionic surfactant, so that it is cationic water-soluble in a water-soluble monomer.
• the proportion of the monomer is selected in the range of 5 to 90 mol% depending on the effect that is similarly required.
• the hair cosmetic additive of the present embodiment is usually added in an amount of 0.05 to 5% by mass in the hair cosmetic, but the amount added is within the range showing the effect required for each hair cosmetic. There is no particular limitation.
• additives such as anionic surfactants, cationic surfactants, betaine surfactants, and nonionic surfactants are added to the hair cosmetics as other components depending on the use of the hair cosmetics. be able to.
• anionic surfactant examples include sodium lauroylmethylalanine, cocoyl glutamic acid triethanolamine, N-lauryl-L-sodium glutamate, N-coconut oil fatty acid-L-glutamic acid triethanolamine, and N-myristylate acyl-L.
• N-N-fatty acid-N-methyltaurine salts such as sodium glutamate, N-mixed fatty acid acyl-L-sodium glutamate, etc., N-fatty acid acyl-L-glutamate, sodium laurate, methyl taurate sodium, coconut oil fatty acid methyl taurine sodium, Salts of N-fatty acid sarcosine condensates such as sodium lauroyl sarcosine, sodium cocoyl sarcosine, acyl sarcosine sodium, acyl glutamate, acyl- ⁇ -alanine sodium, acyl taurate, la N-fatty acid acyl-N-methyl- ⁇ - such as ril sulfate, polyoxyethylene lauryl ether sulfate, sodium N-coconoyl-N-methyl- ⁇ -alanine, N-myristoyl-N-methyl- ⁇ -alanine Examples include alanine salts.
• cationic surfactant examples include lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride and the like.
• betaine surfactants include lauryl dimethylaminoacetic acid betaine, cocoaside propyl betaine, dimethyl lauryl betaine, bis (2-hydroxyethyl) lauryl betaine, coconut oil fatty acid amidopropyl betaine, cocoamphoacetate sodium, cyclohexyl lauryl amine oxide Dimethyl lauryl amine oxide, bis (2-hydroxyethyl) lauryl amine oxide, oleyl betaine, stearyl betaine, myristyl betaine, stearyl dihydroxyethyl betaine and the like.
• nonionic surfactant examples include glyceryl monostearate, sorbitan monopalmitate, polyoxyethylene cetyl ether, polyoxyethylene sorbitan monolaurate, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene Glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil, fatty acid alkanolamide, stearic acid diethanolamide, coconut oil fatty acid diethanolamine And sorbitan sesquioleate, polyoxyethylene stearyl ether, and the like.
• optional components may be blended within a range that does not affect the effect of the present embodiment.
• the optional component include higher fatty acids and derivatives thereof, water-soluble polymers, various ultraviolet absorbers, and the like.
• higher fatty acids and derivatives thereof include hydrocarbons such as liquid paraffin, petrolatum, solid paraffin, squalane, olefin oligomer, ethanol, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl.
• hydrocarbons such as liquid paraffin, petrolatum, solid paraffin, squalane, olefin oligomer, ethanol, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl.
• Alcohols such as alcohol, monostearyl glycerine ether, 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyl decanol, isostearyl alcohol, octyldodecanol, isopropyl myristate, octyldodecyl myristate, ethyl dodecyl palmitate , Stearyl stearate, glycol distearate, polyethylene glycol tetraoleate Sorbitol, glyceryl monostearate, diethylpentanediol dineopentanoate, hydrogenated castor oil polyethylene glycol and other ester oils, lauric acid, myristic acid, palmitic acid, stearic acid, behen (behenyl) acid, oleic acid, 1,2- Higher fatty acids such as hydroxystearic acid, undecylenic acid, toluic acid, lan
• Water-soluble polymers include carrageenan, pectin, agar, quince seed (quince seed), arge colloid (gassilla extract), starch (rice, corn, potato, wheat), plant polymers such as glycyrrhizic acid, xanthan gum, dextran, pullulan
• Natural water-soluble polymers such as microbial polymers such as collagen, gelatin and gelatin, methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, sodium carboxymethylcellulose, cationization
• Cellulose polymers such as cellulose, crystalline cellulose, cellulose powder, cationized gar gum, sodium alginate, propylene glycol alginate
• Semi-synthetic water-soluble polymers such as alginic acid polymers such as tellurium, vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyr
• UV absorbers include bentonite, AlMg silicate (Begum), labnite, hectorite, silicic anhydride, volatile silicone oil, silicone resin, silicone gum, alkyl-modified silicone, polyethylene glycol-added silicone, amino Silicones such as modified silicones, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, tetrasodium edetate, Sequestering agents such as sodium phosphate, sodium polyphosphate, sodium metaphosphate, gluconic acid, 3- (4′-methylbenzylidene) -d, 1-camphor, 3-benzylidene-d, 1-camphor, urocanic acid, urocanin Ethyl acetate Ter, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2- (2'--
• Other optional components include (poly) ethylene glycol, (poly) propylene glycol, glycerin, 1,3-butylene glycol, maltitol, sorbitol, chondroitin sulfate, hyaluronic acid, atelocollagen, cholesteryl-1,2-hydroxystearate Moisturizers such as sodium lactate, bile salts, dl-pyrrolidone carboxylate, short chain soluble collagen, sodium aspartate, antibacterial agents such as hinokitiol, hexachlorophene, benzalkonium chloride, trichlorocarbanilide and pithionol, chloride Vasodilators such as carpronium, refreshing agents such as menthols, stimulating agents such as benzyl nicotinate, vitamins such as vitamins A, B, C, D and E, chlorhexidine gluconate, isopropylmethyl Bactericidal preservatives such as enol and
• cationic polymer examples include, for example, vinyl imidazolium chloride / trade name such as “Rubicut FC370”, “Rubicut FC550”, “Rubicut FC905”, “Rubicut HM552”, “Rubicut MonoCP” (above, manufactured by BASF).
• Hydroxyethylcellulose / dimethyl such as vinylpyrrolidone copolymer, trade name “Celcut H-100 (viscosity 1000 mPa ⁇ s)”, trade name “Celcut L-200 (viscosity 100 mPa ⁇ s)” (National Starch Co., Ltd.)
• Diallylammonium chloride homopolymers of diallyldimethylammonium chloride such as trade names “Mercoat 100” and “Mercoat 550”, and copolymers of diallyldimethylammonium chloride and acrylamide, and tar containing these Remer (for example, trade name “Mercoat 3331”), copolymer or terpolymer (for example, trade name “Mercoat 2001”) containing methacrylamidopropyltrimethylammonium chloride, etc.
• anionic polymer examples include methyl vinyl ether / alkyl maleic anhydride such as trade name “Gantrez ES-225”, trade name “Gantrez ES-425”, trade name “Gantrez SP-215” (above, ISP).
• Half ester copolymer, vinyl acetate / crotonic acid copolymer such as trade name “resin 28-1310” (manufactured by National Starch), trade name “ruby set CA” (manufactured by BASF), trade name “resin 28-2930” (national) ⁇ Vilni acetate / crotonic acid / neodecanoate vinyl copolymer such as Starch), vinyl acetate / crotonic acid / vinyl propionate copolymer such as “Rubiset CAP” (BASF), trade name “ADVANTAGE CP” (ISP) Vinyl acetate / maleic acid, etc.
• trade name “resin 28-1310” manufactured by National Starch
• rubber set CA manufactured by BASF
• trade name “resin 28-2930” national) ⁇ Vilni acetate / crotonic acid / neodecanoate vinyl copolymer such as Starch
• Nobutyl ester / isopolonyl acrylate copolymer trade name “Plus Size L53P”, trade name “Plus Size L-75CB”, trade name “Plus Size L-9540B” (manufactured by Kyoyo Chemical Co., Ltd.), trade name “Diahold” (Meth) acrylic acid / (meth) acrylic acid alkyl ester copolymers such as (Mitsubishi Chemical Corporation), trade names “Ultra Hold 8”, “Ultra Hold Strong” (above, BASF), trade names “Amfor Acrylic acid / alkyl acrylate / alkyl acrylamide copolymer such as Mar V-42 "(National Starch), polyvinylpyrrolidone / acrylate / (meth) acrylic acid such as" Rubiflex VBM35 "(BASF) Ingredient name such as copolymer is "Polyurethane-1" Isophthalic acid is adipic acid, hexylene glycol, neopentyl glycol,
• Examples of the zwitterionic polymer include N-methacryloyloxyethyl having the trade names “Yukaformer SM”, “Yukaformer 301”, “Yukaformer 205S”, “Yukaformer 201”, “Yukaformer W”, etc. -N, N-dimethylammonium- ⁇ -N-methylcarboxybetaine / methacrylic acid alkyl ester copolymer, trade names “Amformer 28-4910”, “Amformer LV-71” (manufactured by National Starch) Such as hydroxypropyl acrylate / butylaminoethyl methacrylate / octylamide copolymer.
• Nonionic polymers include, for example, trade names “Lubicol K12”, “Rubicol K17”, “Rubicol K30”, “Rubicol K60”, “Rubicol K80”, “Rubicol K90” (above, BASF Corporation). Manufactured), trade names “PVP K15”, “PVP K30”, “PVP K60”, “PVP K90” (and above, manufactured by ISP), etc., trade names “Lubicol VA28”, “Lubicol VA37”, “Lubicole VA55”, “Rubiscole VA64”, “Rubiscole VA73”, “Rubiscole VA37E” (above, manufactured by BASF), trade names “PVP / VA E-735”, “PVP / VA E-635” , “PVP / VA E-535”, “PVP / VA E-335”, “PVP / VA” Polyvinylpyrrolidone / vinyl acetate copolymers such as “S-630” and “PVP / VA W-735” (man
• the method for producing an additive for hair cosmetics of the present embodiment includes a step of dissolving a natural polymer and / or a natural polymer derivative having an OH group in water to form an aqueous solution, and a cationic water-soluble solution in the aqueous solution. Graft copolymerizing the monomer and the nonionic water-soluble monomer.
• the above-described chain transfer agent is preferably added to the aqueous solution.
• the molecular weight of the obtained graft copolymer can be adjusted by adding an amount of a chain transfer agent as required during the graft polymerization.
• the graft copolymerization step it is preferable to add the above-described persulfate as an initiator to the aqueous solution.
• persulfate as an initiator, graft copolymerization can be efficiently performed.
• the polymerization reaction is more preferably performed at 50 ° C. or higher.
• the cationic water-soluble monomer is at least diallyldimethylammonium chloride and the nonionic water-soluble monomer is at least acrylamide
• the graft copolymerization step at least a part of acrylamide is continuously added. It is preferable to add to the aqueous solution manually or sequentially.
• acrylamide having a high polymerization rate continuously or sequentially the composition of diallyldimethylammonium chloride and acrylamide in the graft copolymer can be made uniform.
• the addition amount may be smaller than that of a polymer (polyquaternium-10) obtained by reacting glycidylpropyltrimethylammonium chloride with general-purpose hydroxyethyl cellulose.
• the hair cosmetic additive of the present embodiment has no discomfort such as a slimy feeling even when the amount of addition is increased.
• the amount of addition is not limited when formulating hair cosmetics.
• a cationic polymer and a nonionic water-soluble monomer are graft copolymerized with a natural polymer and / or a natural polymer derivative having an OH group.
• Hair treated with a hair cosmetic containing an additive for hair cosmetics that is graft-polymerized only with a cationic water-soluble monomer has a sticky feeling, whereas nonionic ions are present in the water-soluble monomer to be graft copolymerized.
• the hair treated with the hair cosmetic composition of the present embodiment containing a sex monomer has a smooth feeling and an excellent finish.
• Example 1 In a 500 mL four-necked separable flask equipped with a stirrer, a reflux condenser, a monomer dropping port, and a nitrogen introduction tube, 126.99 g of deionized water, 10.06 g of 50% by mass acrylamide aqueous solution, 65% by mass diallyldimethyl 9.30 g of ammonium chloride aqueous solution and 0.40 g of sodium gluconate were added to obtain a uniform mixed solution. To this mixed solution, 10.00 g of hydroxypropyl cellulose (manufactured by Wako Pure Chemical Industries, Ltd., 2% aqueous solution viscosity at 25 ° C.
• DAWN HELEOS manufactured by WYATT Technology as a GPC-MALS measuring instrument
• TSKgel G6000 PWXL-CP manufactured by Tosoh Corporation as a separation column
• 0.5 M acetic acid + 0.5 M sodium acetate buffer as an eluent
• flow rate When the molecular weight was measured under the conditions of 0.5 mL / min, a temperature of 25 ° C., a sample concentration of 0.1% by mass, and an injection amount of 100 ⁇ L, the weight average molecular weight was 190,000. This was designated as “graft copolymer 1”.
• Example 2 Hydroxypropyl guar gum (trade name “Jaguar HP-08”, manufactured by Sanki Co., Ltd., 2% aqueous solution viscosity at 25 ° C. by B-type viscometer 35000 mPa ⁇ s) is 10% by mass with respect to deionized water. The solution was swollen and dissolved. By adding 1.0% by mass of ammonium persulfate to this hydroxypropyl guar gum and heating to 65 ° C., the viscosity of the 2% aqueous solution was adjusted to 12,500 mPa ⁇ s.
• Example 2 In a reaction vessel similar to that in Example 1, 100 g of a 10% by mass hydroxypropyl guar gum solution having a molecular weight adjusted was placed, and 39.42 g of deionized water, 8.04 g of 50% by mass acrylamide aqueous solution, and 16.5% by weight diallyldimethylammonium chloride aqueous solution 16. 72 g and 0.30 g sodium formate were added to obtain a uniform mixed solution. Nitrogen was introduced from the nitrogen introduction tube, and the internal temperature was adjusted to 65 ° C. using a constant temperature water bath. 30 minutes after the introduction of nitrogen, 1.50 g of a 10% by mass aqueous ammonium persulfate solution was added to initiate polymerization.
• Example 3 To the same reaction vessel as in Example 1, 129.99 g of deionized water, 10.06 g of 50% by mass acrylamide aqueous solution, 9.30 g of 65% by mass diallyldimethylammonium chloride aqueous solution, and 0.40 g sodium gluconate were added and mixed uniformly. It was set as the solution. While stirring, 10.00 g of hydroxyethyl cellulose (manufactured by Sumitomo Seika Co., Ltd., 2% aqueous solution viscosity at 25 ° C.
• Example 4 To the same reaction vessel as in Example 1, 164.37 g of deionized water, 10.05 g of 50% by mass acrylamide aqueous solution, 20.90 g of 65% by mass diallyldimethylammonium chloride aqueous solution, and 0.075 g sodium formate were added to obtain a uniform mixed solution. It was. While stirring, 12.50 g of hydroxyethyl cellulose (manufactured by Wako Pure Chemical Industries, Ltd., 2% aqueous solution viscosity at 25 ° C.
• Example 5 To the same reaction vessel as in Example 1, 126.19 g of deionized water, 10.06 g of 50 mass% acrylamide aqueous solution, 9.30 g of 65 mass% diallyldimethylammonium chloride aqueous solution, and 0.80 g sodium gluconate were added and mixed uniformly. It was set as the solution. While stirring, 10.00 g of locust bean gum (manufactured by Wako Pure Chemical Industries, 2% aqueous solution viscosity at 25 ° C. by B-type viscometer 1350 mPa ⁇ s) is added, nitrogen is introduced from a nitrogen inlet tube, and the internal temperature is increased by a constant temperature water bath. Was adjusted to 75 ° C. 30 minutes after the introduction of nitrogen, 1.50 g of a 10% by mass aqueous ammonium persulfate solution was added to initiate polymerization.
• locust bean gum manufactured by Wako Pure Chemical Industries, 2% aqueous solution viscosity
• Example 2 In a reaction vessel similar to that in Example 1, 150 g of a 10% by weight guar gum solution having a molecular weight adjusted was placed, 44.22 g of deionized water, 12.05 g of 50% by weight acrylamide aqueous solution, 25.07 g of 65% by weight diallyldimethylammonium chloride aqueous solution, 0.90 g of sodium formate was added to obtain a uniform mixed solution. Nitrogen was introduced from the nitrogen introduction tube, and the internal temperature was adjusted to 65 ° C. using a constant temperature water bath. 30 minutes after the introduction of nitrogen, 2.25 g of a 10% by mass aqueous ammonium persulfate solution was added to initiate polymerization.
• Example 7 To the same reaction vessel as in Example 1, 129.22 g of deionized water, 8.04 g of 50% by weight aqueous acrylamide solution, 16.72 g of 65% by weight diallyldimethylammonium chloride aqueous solution, and 0.40 g of sodium gluconate were added and mixed uniformly. It was set as the solution. While stirring, 10.00 g of sericin (manufactured by Kashiro Sangyo Co., Ltd., 2% aqueous solution viscosity at 25 ° C. with a B-type viscometer of 16 mPa ⁇ s) was added, nitrogen was introduced from a nitrogen introduction tube, and the internal temperature was 65 ° C. with a constant temperature water bath. Adjusted. 30 minutes after the introduction of nitrogen, 1.50 g of a 10% by mass aqueous ammonium persulfate solution was added to initiate polymerization.
• sericin manufactured by Kashiro Sangyo Co., Ltd.,
• Example 8> To a reaction vessel similar to Example 1, 137.96 g of deionized water, 7.77 g of 50% by weight acrylamide aqueous solution, 3.54 g of 80% by weight methacryloyloxyethyltrimethylammonium chloride aqueous solution, and 0.35 g of sodium formate were added, and uniform. A mixed solution was obtained. While stirring, 8.00 g of hydroxyethyl cellulose (manufactured by Wako Pure Chemical Industries, 2% aqueous solution viscosity at 25 ° C.
• Example 9 To a reaction vessel similar to that in Example 1, 205.54 g of deionized water, 11.68 g of 50% by mass acrylamide aqueous solution, 5.65 g of 75% by mass acryloylaminopropyltrimethylammonium chloride aqueous solution, and 0.53 g of sodium formate were added. A mixed solution was obtained. While stirring, add 12.00 g of hydroxyethyl cellulose (manufactured by Wako Pure Chemical Industries, Ltd., 2% aqueous solution viscosity at 25 ° C. with a B-type viscometer is 152 mPa ⁇ s), introduce nitrogen from the nitrogen introduction tube, and adjust the internal temperature with a constant temperature water bath.
• hydroxyethyl cellulose manufactured by Wako Pure Chemical Industries, Ltd., 2% aqueous solution viscosity at 25 ° C. with a B-type viscometer is 152 mPa ⁇ s
• Example 10 To the same reaction vessel as in Example 1, 204.32 g of deionized water, 5.78 g of 50% by mass acrylamide aqueous solution, 48.07 g of 65% by mass diallyldimethylammonium chloride aqueous solution, and 0.30 g sodium formate were added, and a uniform mixed solution was added. It was. While stirring, 15.00 g of hydroxyethyl cellulose (manufactured by Wako Pure Chemical Industries, Ltd., 2% aqueous solution viscosity at 25 ° C.
• ⁇ Comparative Example 1> In a reaction vessel similar to that in Example 1, 140.85 g of deionized water and 46.15 g of 65 mass% diallyldimethylammonium chloride aqueous solution were added to obtain a uniform mixed solution. While stirring, 10.00 g of hydroxyethyl cellulose (manufactured by Wako Pure Chemical Industries, 2% aqueous solution viscosity at 25 ° C. by a B-type viscometer is 152 mPa ⁇ s) is added, nitrogen is introduced from a nitrogen introduction tube, and the internal temperature is adjusted by a constant temperature water bath. Adjusted to 65 ° C.
• Example 11 Each graft polymer or commercially available cationic polymer of Examples 1 to 10 and Comparative Example 1 was made Component B and dissolved with Component A so as to have the composition shown in Table 1 to prepare a shampoo solution.
• Tables 2 and 3 show the concentration of the added component B and the appearance of the shampoo solution at the time of dissolution.
• the graft polymers of Example 10 and Comparative Example 1 formed an ion complex with the anionic surfactant and did not dissolve in Component A of the shampoo solution. Therefore, the shampoo test was not performed.
• use_condition as a hair shampoo was sensory-evaluated by the following method, and the reference
• Example 12 Each of the graft polymers of Examples 4 and 10 and Comparative Example 1 and a commercially available cationic polymer were dissolved in the composition shown in Table 7 to prepare a conditioner solution. About each sample, the usability as a hair conditioner was sensory-evaluated by the following method and evaluated according to the criteria shown in Table 8. (1) Preparation of Component A A cationic surfactant, stearyl alcohol and glutamic acid were stirred and melted at 75 ° C. Next, ion exchange water warmed to 75 ° C. was added and further dissolved. (2) Preparation of Component B Each graft polymer and commercially available cationic polymer were dissolved in purified water at room temperature.
• Example 13 Each of the graft polymers of Examples 4 and 10 and Comparative Example 1 and a commercially available cationic polymer were dissolved at a concentration of 0.5% by mass. This solution was used as a hair styling agent for sets having curl retention, and the feeling of use was subjected to sensory evaluation by the following method. Evaluation method A bundle of hair having a length of 35 cm was immersed in a dissolved 0.5% by mass polymer aqueous solution for 15 seconds. After taking out, the water was lightly cut, the whole hair was wound around a hair curler having a diameter of 2 cm, and dried with a high-temperature dryer for 15 minutes.
• the hair With the hair wound around a hair curler, the hair was allowed to stand for 30 minutes in a temperature-controlled room at a temperature of 26 ° C. and a humidity of 60% by mass. Thereafter, the hair was removed from the hair curler, and the length from the root of the hair bundle to the tip of the hair was measured. The length at this time was L0. The hair after measurement was hung and allowed to stand for another 30 minutes. The length of the whole subsequent hair was measured and this value was set to L1. A comb was passed 5 times through the hair after measurement, and the value measured again was recorded as L2. The hair feel after use was also evaluated at the same time. The curl retention strength was evaluated by comparing the L0, L1, and L2 values.
• Table 10 shows the blank values, the values of L0, L1, and L2 of the graft polymers of Examples 4 and 10 and Comparative Example 1 and the commercial cationic polymer that is a control and the feeling after use.
• the hair cosmetic composition of the present embodiment has excellent curling ability and holding ability, and the produced curl is durable against combing.
• the graft polymer 11 (Comparative Example 1) that did not use a nonionic monomer had almost no curling ability.
• the feel after use the hair becomes dry and lumpy with the blank, the polymer-derived stickiness remains in the polyquaternium-6 and polyquaternium-7, and the hair becomes solid and solid in the polyquaternium-10. It became a terrible feel.
• the hair cosmetic composition of this embodiment has a soft feel after use, and can impart moisture and a smooth feeling to the hair.
• the hair cosmetic additive of the present invention and the hair cosmetic containing the same can give a supple feel to the finish, including shampoos, rinses, various conditioners, hair styling agents for setting, perm liquids, hair dyes, etc. It can be used for a wide range of applications.

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