JP5455186B2 - Hair cosmetic additive and hair cosmetic containing the same - Google Patents

Description

  The present invention relates to a hair cosmetic additive and a hair cosmetic containing the same, and more specifically, after dissolving a natural polymer and / or a natural polymer derivative having an OH group in water, Graft copolymerization of water-soluble monomers and anionic water-soluble monomers as required, and multiple types of water-soluble monomers including nonionic water-soluble monomers that can be copolymerized with them as necessary The present invention relates to an additive for hair cosmetics produced and a hair cosmetic containing the same.

  It is well known to treat hair with a polymer to give it the desired texture. As such a hair cosmetic polymer, nonionic, anionic and cationic polymers are used. Polyvinyl methyl ether, polyvinyl pyrrolidone and the like are used as the nonionic polymer, but polyvinyl pyrrolidone is easily affected by humidity conditions. In other words, the film before moisture absorption is hard and prone to flaking, but when it is hot and humid, it becomes very soft and causes a blocking phenomenon, which may cause hair to stick to each other and make it impossible to brush or brush. is there. In polyvinyl methyl ether, the influence of such humidity is further remarkable.

  Examples of the anionic polymer include copolymers of vinyl carboxylic acids such as acrylic acid and methacrylic acid. This anionic polymer is unlikely to be affected by humidity unlike the nonionic polymer, but in general, the anionic polymer film is hard and has a high hair-styling effect, but on the other hand, it is brittle and may cause flaking. 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.

  As a cationic polymer, a polymer (for example, polyquaternium-10) obtained by reacting a cationizing agent such as glycidylpropyltrimethylammonium chloride with cellulose or guar gum is widely used as an additive for hair cosmetics. However, it was not fully satisfactory in that the hair would become stiff and firm due to continued use. Further, diallyldimethylammonium chloride homopolymer (polyquaternium-6) or acrylamide / diallyldimethylammonium chloride copolymer (polyquaternium-7) is used as an additive for hair cosmetics, for example, polyquaternium-7. When added to shampoo, etc., there was a feeling of sliminess during shampooing and it was not satisfactory.

In addition, regarding a method for preparing a graft copolymer of a water-soluble monomer and a polysaccharide, the reaction is performed in a solvent that does not dissolve the polysaccharide (see Patent Document 1), or polymerization is performed by electron beam irradiation in a state close to a solid phase (Patent Document 2). Reference) methods are disclosed, but all have a drawback that the reaction rate is lowered. In addition, in the copolymerization of two or more kinds of monomers having different copolymerizability ratios, it is a common means to continuously or sequentially add monomers having good polymerizability in order to make the composition of the copolymer uniform. The reaction was difficult in a heterogeneous system.
JP 54-83987 A Special table 2008-509250 gazette

  The object of the present invention is to overcome the respective drawbacks of semi-synthetic hair cosmetic additives typified by polyquaternium-10 and synthetic hair cosmetic additives typified by polyquaternium-6 or 7, and An object of the present invention is to provide an additive for hair cosmetics that gives a supple feel and a hair cosmetic containing the same.

  As a method for solving the above problems, a natural polymer having an OH group and / or a natural polymer derivative is dissolved in water, and then a cationic water-soluble monomer and an anionic water-soluble monomer are essential in an aqueous medium. As a component, if necessary, an additive for hair cosmetics is produced by graft copolymerization of a plurality of types of water-soluble monomers including nonionic water-soluble monomers copolymerizable therewith. The inventors have found that this can be achieved by adding to a hair cosmetic composition, and have reached the present invention.

  The natural polymer and / or natural polymer derivative having an OH group of the present invention contains a cationic water-soluble monomer and an anionic water-soluble monomer as essential components in an aqueous medium, and if necessary, co-polymerizes them. Hair cosmetics containing additives for hair cosmetics obtained by graft copolymerization of multiple types of water-soluble monomers, including non-ionic water-soluble monomers that can be polymerized, are not only excellent in finish, but also versatile Compared with a polymer (polyquaternium-10) obtained by reacting glycidylpropyltrimethylammonium chloride with a product of hydroxyethyl cellulose, the addition amount is small. Further, in the case of acrylamide and diallyldimethylammonium chloride copolymer (polyquaternium-7), when the amount added is increased, a slimy sensation appears during use. On the other hand, the product of the present invention has a feature that there is no unpleasant feeling such as sliminess even when the amount of addition is increased. As a result, when formulating hair cosmetics, a wide range of additions became possible.

  The present invention also includes a natural polymer and / or a natural polymer derivative having an OH group, which contains a cationic water-soluble monomer and an anionic water-soluble monomer as essential components, and can be copolymerized with them if necessary. It is characterized by graft copolymerization of multiple types of water-soluble monomers including ionic water-soluble monomers, but it contains additives for hair cosmetics that are graft-polymerized only with cationic water-soluble monomers. Hair treated with hair cosmetics has a sticky feeling, whereas water-soluble monomers contain cationic water-soluble monomers and anionic water-soluble monomers, and if necessary, non-copolymerizable with them. The hair treated with the product of the present invention in which a plurality of water-soluble monomers including an ionic water-soluble monomer were graft-copolymerized had a smooth feeling and an excellent finish.

  Hereinafter, the present invention will be described in further detail.

  The hair cosmetic additive of the present invention comprises a cationic water-soluble monomer and an anionic water-soluble monomer in an aqueous medium after dissolving a natural polymer and / or a natural polymer derivative having an OH group in water. It is obtained by graft copolymerizing a plurality of types of water-soluble monomers, including nonionic water-soluble monomers copolymerizable with them, in a substantially uniform state, with the body as an essential component. However, if necessary for the reaction, a small amount of a water-soluble organic solvent such as alcohols may be mixed in the aqueous medium.

  The present invention also provides a water-soluble monomer having a molar ratio of the cationic water-soluble monomer to the anionic water-soluble monomer in a range of 1:20 to 20: 1 in a plurality of types of water-soluble monomers. Although it is characterized by graft copolymerization of the body, the hair treated with the product of the present invention has a smooth feeling and an excellent finish. Outside this range, problems such as stickiness on the treated hair or flaking phenomenon occur.

  Since the natural polymer or natural polymer derivative having an OH group used in the present invention reacts in a substantially uniform state in an aqueous medium, it must have high solubility in water. Typical natural polymers include starches, guar gum, locust bean gum, xanthan gum, chitosan, carrageenan, julan gum, pullulan, mannan, fenugreek, sericin, etc. preferable. Examples of natural polymer derivatives include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl guar gum, hydroxypropyl guar gum, and the like. From the viewpoint of solubility, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and hydroxy Propyl guar gum is preferred, and hydroxyethyl cellulose is more preferred. It is also possible to use a combination of these natural polymers or natural polymer derivatives.

  The molecular weight of the natural polymer or natural polymer derivative having an OH group is preferably 2% aqueous solution viscosity of 20000 mPa · s at 25 ° C. in order to perform graft copolymerization in a substantially uniform aqueous solution state. . A natural polymer or natural polymer derivative having a higher molecular weight than this makes the viscosity of the solution extremely high, making it difficult to perform uniform graft copolymerization. Regarding hydroxyethyl cellulose, which is the most preferred natural polymer derivative, the viscosity of the 2% aqueous solution is preferably in the range of 100 to 10,000 mPa · s at 25 ° C. in consideration of the viscosity of the reaction solution.

  Total amount of natural polymer and / or natural polymer derivative having OH group and cationic water-soluble monomer and anionic water-soluble monomer, if necessary, nonionic water-soluble monomer capable of copolymerization with them The weight ratio with respect to the total amount of the plurality of types of water-soluble monomers including the body is preferably 5:95 to 80:20. It is not demonstrated. More preferably, it is 5: 95-50: 50.

  The graft polymerization in the present invention is usually carried out with stirring in order to cause a uniform reaction. Therefore, if the reaction concentration is too high, stirring becomes difficult, and if the reaction concentration is too low, the final product has a low concentration and the transportation cost increases. Accordingly, the reaction concentration is 10 to 50% by weight as the total concentration of the natural polymer and / or natural polymer derivative having an OH group and a plurality of types of water-soluble monomers, preferably 10 to 30% by weight. is there.

  Examples of tertiary amino group-containing cationic monomers among the cationic water-soluble monomers include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, Examples thereof include diethylaminopropyl (meth) acrylamide and salts thereof. Examples of quaternary ammonium base-containing cationic monomers include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyl. Examples include aminopropyldimethylbenzylammonium chloride and (meth) acryloyloxy 2-hydroxypropyltrimethylammonium chloride. Further, allylamine, diallylmethylamine and salts thereof, diallyldimethylammonium chloride and the like can be mentioned. From the viewpoint of stability and safety of the polymer, diallyldimethylammonium chloride is more preferable. It is also possible to use a combination of a plurality of these cationic water-soluble monomers.

  Examples of anionic water-soluble monomers that copolymerize with cationic water-soluble monomers include (meth) acrylic acid, itaconic acid, 2-acrylamide 2-methylpropanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, styrene Examples thereof include sulfonic acid and salts thereof. Acrylic acid and 2-acrylamido 2-methylpropanesulfonic acid are more preferred because of the ease of the polymerization reaction. It is also possible to use a combination of a plurality of these anionic water-soluble monomers.

  Examples of nonionic water-soluble monomers that copolymerize with cationic and anionic water-soluble monomers as needed include (meth) acrylamide, dimethylacrylamide, diethylacrylamide, isopropylacrylamide, hydroxyethylacrylamide, vinylpyrrolidone , Vinylformamide, vinylacetamide and the like. 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 natural polymer derivative having an OH group dissolve in water, and varies depending on the natural polymer and / or natural polymer derivative to be used. Perform in the range.

  For the initiation of polymerization, a radical polymerization initiator is used. These initiators are preferably water-soluble and can be polymerized by any of azo, redox and peroxide types. Examples of water-soluble azo initiators include 2,2′-azobis (2-methylpropionamidine) dichloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] And hydrogen chloride, 4,4′-azobis (4-cyanovaleric acid), and the like. Examples of redox systems include a combination of ammonium persulfate and sodium sulfite, sodium hydrogen sulfite, trimethylamine, tetramethylethylenediamine and the like. Examples of persulfates and peroxides include ammonium persulfate, potassium, and hydrogen peroxide. Persulfates are preferred for efficient graft copolymerization. When using a persulfate, the polymerization reaction is preferably performed at 50 ° C or higher.

  The present invention is the presence of a natural polymer and / or a natural polymer derivative having an OH group dissolved in water, and a cationic water-soluble monomer and an anionic water-soluble monomer as essential components, Graft-copolymerize multiple types of water-soluble monomers, including nonionic water-soluble monomers that can be copolymerized with them. After that. Polymerization may be performed by adding a polymerization initiator, but a part or all of a plurality of types of water-soluble monomers may be added continuously or sequentially in small portions under stirring after the addition of the polymerization initiator. Also good. In particular, when the copolymerization ratios of multiple types of monomers to be copolymerized are different, a part of the monomer having good polymerizability is added continuously or sequentially during the polymerization to make the composition of the copolymer uniform. Is preferred. For example, when diallyldimethylammonium chloride, acrylic acid and acrylamide are copolymerized, it is preferable to add a part of acrylic acid and acrylamide continuously during the polymerization. Also, in order to make ionic groups unevenly distributed, a part of acrylamide is continuously added during polymerization, and then all or part of acrylic acid is continuously added. It is also possible to change the addition timing or addition amount of.

  The weight average molecular weight of the graft copolymer measured by GPC-MALS is preferably 10,000 to 3,000,000. When it is 3 million or more, it becomes difficult to dissolve in a hair cosmetic composition containing various components, and when it is 10,000 or less, the effect of addition becomes low. More preferably, it is 20,000-2 million. In order to adjust the molecular weight, a chain transfer agent in an amount necessary for the polymerization can be added. As the chain transfer agent, any compound having commonly used chain transfer properties such as isopropyl alcohol, mercaptoethanol, sodium gluconate, sodium formate, and sodium hypophosphite can be selected.

  The proportion of the cationic water-soluble monomer in the plurality of types of water-soluble monomers is also related to the weight ratio with the natural polymer and / or natural polymer derivative having an OH group, but is 5 to 90 mol%. Range. However, when the hair cosmetic additive of the present invention is used for shampoo, if the cation equivalent value is too high, it forms a complex with the anionic surfactant that is the main component of the shampoo composition and becomes insoluble and cloudy. The range of 5-30 mol% is preferable.

  In addition, when used in rinses, conditioners and treatments, the main component is a cationic surfactant, so the proportion of cationic water-soluble monomers in multiple types of water-soluble monomers is an effect required for hair cosmetics. Accordingly, it is selected in the range of 5 to 90 mol%, but the range of 5 to 60 mol% is more preferable.

  In addition, when used for hair styling, perm liquids, and hair dyes for sets, the ratio of cationic water-soluble monomers in multiple types of water-soluble monomers is often the same because ionic surfactants are often not included. Is selected in the range of 5 to 90 mol% depending on the effect required for the above. There are liquid, cream, emulsion, spray, foam, gel, and the like as a hair styling for setting, but any form can be used.

  The molar ratio of the cationic water-soluble monomer to the anionic water-soluble monomer in the plurality of types of water-soluble monomers is preferably in the range of 1:20 to 20: 1. Outside this range, the characteristics of the amphoteric graft copolymer are not exhibited, as is the case with the graft copolymer of the cationic water-soluble monomer or the anionic water-soluble monomer alone.

  The graft copolymer of the present invention is usually added in an amount of 0.05 to 5% as an additive to the hair cosmetic, but the addition amount is not particularly limited within the range showing the effect required for each hair cosmetic.

  The other components of the hair cosmetic containing the graft copolymer of the present invention as an additive component are anionic surfactants known in hair cosmetics (for example, sodium lauroylmethylalanine, depending on the use of the hair cosmetic). Cocoylglutamate triethanolamine, N-lauryl-L-glutamate sodium, N-coconut oil fatty acid-L-glutamate triethanolamine, N-myristylate acyl-L-glutamate sodium, N-mixed fatty acid acyl-L-glutamate sodium, etc. N-fatty acid acyl-L-glutamate, N-fatty acid sodium such as methyl taurine sodium laurate, sodium coconut oil fatty acid methyl taurine sodium, N-fatty acid sarco such as lauroyl sarcosine sodium, cocoyl sarcosine sodium Condensate salt, acyl sarcosine sodium, acyl glutamate, acyl-β-alanine sodium, acyl taurate, lauryl sulfate, polyoxyethylene lauryl ether sulfate, N-coconoyl-N-methyl-β-alanine sodium, N-fatty acid acyl-N-methyl-β-alanine salts such as N-myristoyl-N-methyl-β-alanine sodium), cationic surfactants (eg, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, dichloride chloride) Stearyldimethylammonium, stearyldimethylbenzylammonium chloride, etc.), betaine surfactants (eg, lauryldimethylaminoacetic acid betaine, cocoaside propylbetaine, dimethyllaurylbetaine, bis (2-hydroxyethyl)) Lauryl betaine, palm oil fatty acid amidopropyl betaine, sodium cocoamphoacetate, cyclohexyl lauryl amine oxide, dimethyl lauryl amine oxide, bis (2-hydroxyethyl) lauryl amine oxide, oleyl betaine, stearyl betaine, myristyl betaine, stearyl dihydroxyethyl betaine) , Nonionic surfactants (for example, 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 ether Ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil, fatty acid alkanolamide, stearic acid diethanolamide, coconut oil fatty acid diethanolamide, sorbitan sesquioleate, polyoxyethylene stearyl ether, etc.) It is.

  Further, if necessary, other optional components may be blended within a range that does not affect the effects of the present invention. Examples of optional components 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 alcohol, monostearyl. Alcohols such as glycerin ether, 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, octyldodecanol, isopropyl myristate, octyldodecyl myristate, ethyldodecyl palmitate, stearyl stearate , Glycol distearate, polyethylene glycol sorbite tetraoleate, Ester oils such as glyceryl stearate, diethylpentanediol dineopentanoate, hydrogenated castor oil polyethylene glycol, lauric acid, myristic acid, palmitic acid, stearic acid, behen (behenyl) acid, oleic acid, 1,2-hydroxystearic acid Higher fatty acids such as undecylenic acid, toluic acid, lanolin fatty acid, isostearic acid, linoleic acid, linolenic acid, γ-linolenic acid, eicosapentaenoic acid, and derivatives thereof.

  In addition, plant polymers such as carrageenan, pectin, agar, quince seed (malmello), algae colloid (guckweed extract), starch (rice, corn, potato, wheat), glycyrrhizic acid, and other microorganisms such as xanthan gum, dextran, pullulan, etc. Natural water-soluble polymers such as molecules, animal polymers such as collagen, gelatin, methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, sodium carboxymethylcellulose, cationized cellulose, crystalline cellulose, Cellulose polymers such as cellulose powder, cationized guar gum, sodium alginate, algins such as propylene glycol alginate Semi-synthetic water-soluble polymers such as polymer based polymers, vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer (carbopol), polyethylene glycol 20,000, 4,000,000, 600, Polyoxyethylene polymers such as 000, and synthetic water-soluble polymers such as polyethyleneimine.

  In addition, inorganic substances such as bentonite, silicate AlMg (beegum), labnite, hectorite, silicic anhydride, volatile silicone oil, silicone resin, silicone gum, alkyl-modified silicone, polyethylene glycol-added silicone, amino-modified silicone, etc. 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, tetrasodium edetate, sodium citrate, polyphosphoric acid Metal sequestering agents such as sodium, sodium metaphosphate, gluconic acid, 3- (4'-methylbenzylidene) -d, 1-camphor, 3-benzylidene-d, 1-camphor, urocanic acid, urocanic acid ethyl ester, 2 -Phenyl- -Methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'- Methylphenylbenzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one, benzoic acid series And various ultraviolet absorbers such as anthranilic acid, salicylic acid, cinnamic acid, and benzophenone.

  (Poly) ethylene glycol, (poly) propylene glycol, glycerin, 1,3-butylene glycol, maltitol, sorbitol, chondroitin sulfate, hyaluronic acid, atelocollagen, cholesteryl-1,2-hydroxystearate, sodium lactate, bile acid Moisturizers such as salts, dl-pyrrolidone carboxylate, short chain soluble collagen, sodium aspartate, antibacterial agents such as hinokitiol, hexachlorophene, benzalkonium chloride, trichlorocarbanilide and pithionol, vasodilators such as carpronium chloride , Menthol and other refreshing sensations, benzyl nicotinate and other stimulants, vitamins A, B, C, D, E and other vitamins, chlorhexidine gluconate, isopropylmethylphenol, paraoxy Bactericidal preservatives such as benzoic acid esters, protein hydrolysates, amino acids, plant extracts, chelating agents such as EDTA-Na, succinic acid, sodium succinate, pH adjusters such as triethanolamine, foam boosters, For foam products, foam stabilizers, aerosol products, liquefied petroleum gas, propellants such as dimethyl ether, metal ion scavengers, antifungal agents, fungicides, emulsion agents, conditioning agents, thickeners, antioxidants, Solubilizers, rosins, hydrotropes, hair nourishing agents, herbal medicines, pigments, fragrances, and the like.

  In addition, known cationic, anionic, amphoteric and nonionic synthetic, semi-synthetic and natural polymers different from the product of the present invention can be used in combination with the product of the present invention. Examples of the cationic polymer include, for example, vinyl imidazolium chloride / vinyl pyrrolidone copolymers such as Rubykat FC370, FC550, FC905, HM552, MonoCP (above, BASF), Celcut H-100 (viscosity 1000 mPa · s), L- 200 (viscosity 100 mPa · s) (above, National Starch Co., Ltd.) hydroxyethyl cellulose / dimethyldiallylammonium chloride, marcoat 100, 550 etc. homopolymer of diallyldimethylammonium chloride and copolymer of diallyldimethylammonium chloride and acrylamide, etc. A terpolymer (Mercoat 3331), a copolymer or a terpolymer (Mercoat propyltrimethylammonium chloride) 2001) and the like (Narco), Guffcut 734, 755N, 755 (and above, ISP) and other vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymers, Rubiflex (BASF), copolymers 845, 937 and 958 ( As described above, polyvinylpyrrolidone / alkylaminoacrylate copolymer such as ISP), polyvinylpyrrolidone / alkylaminoacrylate / vinylcaprolactam copolymer such as copolymer VC-713 (ISP), and vinylpyrrolidone such as Guffcut HS-100 (ISP). / Methacrylamidopropyl trimethylammonium chloride copolymer, N, N-dimethylaminoethyl diethyl methacrylate, N, N-dimethylacrylamide, whose component designation is polyquaternium-52 Copolymers of polyethylene glycol dimethacrylate, alkylacrylamide / acrylate / alkylaminoalkylacrylamide / polyethylene glycol methacrylate copolymers such as water-soluble polymer compounds described in JP-A-2-180911, N-propionyl polyethyleneimine / methyl polysiloxane copolymer Acrylamide / acrylic acid / methacrylic acid alkyl ester / methoxypolyethylene glycol copolymer, acrylamide / acrylic acid alkyl ester copolymer, and the like. Examples of the anionic polymer include methyl vinyl ether / alkyl maleic anhydride alkyl half ester copolymers such as Gantrez ES-225, ES-425, SP-215 (and above, ISP), Resin 28-1310 (National Starch), Rubyset. Vinyl acetate / crotonic acid copolymer such as CA (BASF), vinyl acetate / crotonic acid copolymer such as resin 28-2930 (National Starch), vinyl acetate / crotonic acid such as rubyset CAP (BASF) / Vinyl propionate copolymer, vinyl acetate / maleic acid monobutyl ester / isopolonyl acrylate copolymer such as ADVANTAGECP (ISP), plus size L53P, L-75CB, L-9540B (Kyoto Chemical Co., Ltd.), (Meth) acrylic acid / (meth) acrylic acid alkyl ester copolymers such as Earhold (Mitsubishi Chemical), Ultrahold 8, Ultrahold Strong (above BASF), Unformer V-42 (National Starch) ) And other acrylic acid / acrylic acid alkyl ester / alkyl acrylamide copolymers, polyvinylpyrrolidone / acrylate / (meth) acrylic acid copolymers such as Rubiflex VBM35 (BASF), etc. And urethane polymers such as copolymers of hexylene glycol, neopentyl glycol, dimethylolpropionic acid and isophorone diisocyanate. Examples of the zwitterionic polymer include N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / methacrylic acid such as Yucaformer SM, 301, 205S, 201, W (Mitsubishi Chemical Corporation). Examples include alkyl ester copolymers, hydroxypropyl acrylate / butylaminoethyl methacrylate / octylamide acrylate copolymers such as Anformer 28-4910, LV-71 (above National Starch). Nonionic polymers include, for example, polyvinylpyrrolidone such as Rubiscol K12, 17, 30, 60, 80, 90 (above, BASF), PVP K15, 30, 60, 90 (above, ISP), Lubiscol VA28, 37, 55, 64, 73, VA37E (above, BASF), PVP / VA E-735, E-635, E-535, E-335, S-630, W-735 (above, ISP), etc. Polyvinylpyrrolidone / vinyl acetate copolymer, polyvinylpyrrolidone / vinyl acetate / vinyl propionate copolymer such as Rubiscol VAP343 (BASF), vinyl acetate / N-vinyl-5-methyl-2-oxazoline such as Dowtex (Dow Chemical) A copolymer etc. are mentioned.

(Example)
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to a following example, unless the summary is exceeded.

  In a four-necked 500 ml separable flask equipped with a stirrer, reflux condenser, monomer dropping port, and nitrogen inlet tube, deionized water 132.98 g, 50% acrylamide aqueous solution 5.83 g, 65% diallyldimethylammonium chloride aqueous solution 24.26 g, 60% acrylic acid aqueous solution 0.82 g and sodium formate 0.35 g were added to obtain a uniform mixed solution. While stirring, 8.00 g of hydroxyethyl cellulose was added, nitrogen was introduced from a nitrogen introduction tube, and the internal temperature was adjusted to 65 ° C. with a constant temperature water bath. One hour after the introduction of nitrogen, 1.60 g of 10% ammonium persulfate aqueous solution was added to initiate polymerization. On the other hand, 21.94 g of 50% aqueous acrylamide solution and 3.09 g of 60% aqueous acrylic acid solution were added to 1.40 g of 25% aqueous sodium formate solution to prepare a mixed solution. Polymerization was carried out while dripping this mixed solution into the system over 5 hours immediately after the start of the reaction. After 5 hours, 1.60 g of a 10% ammonium persulfate aqueous solution was added again, and polymerization was continued for 17 hours to complete the reaction. When the molecular weight was measured by GPC-MALS, the weight average molecular weight was 400,000. This is designated as graft copolymer 1.

  In a reaction vessel similar to Example 1, 133.78 g of deionized water, 7.33 g of 50% aqueous acrylamide, 3.82 g of 80% aqueous methacryloyloxyethyltrimethylammonium chloride, 1.77 g of 60% aqueous acrylic acid, sodium formate 0.35 g was added to obtain a uniform mixed solution. While stirring, 8.00 g of hydroxyethyl cellulose was added, nitrogen was introduced from a nitrogen introduction tube, and the internal temperature was adjusted to 65 ° C. with a constant temperature water bath. One hour after introduction of nitrogen, 0.80 g of 2% aqueous ammonium persulfate solution was added to initiate polymerization. On the other hand, 50% acrylamide aqueous solution 27.57 g, 80% methacryloyloxyethyltrimethylammonium chloride aqueous solution 14.37 g, 60% acrylic acid aqueous solution 6.65 g were added to 25% sodium formate aqueous solution 1.40 g to prepare a mixed solution. did. Polymerization was carried out while dripping this mixed solution into the system over 5 hours immediately after the start of the reaction. After 5 hours, 0.80 g of a 2% aqueous ammonium persulfate solution was added again, and the polymerization was continued for 17 hours to complete the reaction. When the molecular weight was measured by GPC-MALS, the weight average molecular weight was 1.8 million. This is designated as graft copolymer 2.

A 4-neck 500 ml separable flask equipped with a stirrer, a reflux condenser, a monomer dropping port, and a nitrogen introduction tube in the same reaction vessel as in Example 1 was charged with 132.00 g of deionized water and a 50% acrylamide aqueous solution 7 .49 g, 65% diallyldimethylammonium chloride aqueous solution 17.81 g, 60% acrylic acid aqueous solution 0.90 g and sodium formate 0.35 g were added to obtain a uniform mixed solution. While stirring, 8.00 g of hydroxyethyl cellulose was added, nitrogen was introduced from a nitrogen introduction tube, and the internal temperature was adjusted to 65 ° C. with a constant temperature water bath. One hour after the introduction of nitrogen, 1.60 g of 10% ammonium persulfate aqueous solution was added to initiate polymerization. On the other hand, 28.19 g of 50% acrylamide aqueous solution and 3.40 g of 60% acrylic acid aqueous solution were added to 1.40 g of 25% sodium formate aqueous solution to prepare a mixed solution. Polymerization was carried out while dripping this mixed solution into the system over 5 hours immediately after the start of the reaction. After 5 hours, 1.60 g of a 10% ammonium persulfate aqueous solution was added again, and polymerization was continued for 17 hours to complete the reaction. When the molecular weight was measured by GPC-MALS, the weight average molecular weight was 9
0,000. This is designated as graft copolymer 3.

  In the same reaction vessel as in Example 1, 136.25 g of deionized water, 5.47 g of 50% acrylamide aqueous solution, 4.98 g of 80% methacryloyloxyethyltrimethylammonium chloride aqueous solution, 60 in the same reaction vessel as in Example 1. A 2.3% aqueous acrylic acid solution and 0.35 g sodium formate were added to obtain a uniform mixed solution. While stirring, 8.00 g of hydroxyethyl cellulose was added, nitrogen was introduced from a nitrogen introduction tube, and the internal temperature was adjusted to 65 ° C. with a constant temperature water bath. One hour after introduction of nitrogen, 0.80 g of 2% aqueous ammonium persulfate solution was added to initiate polymerization. On the other hand, 50% acrylamide aqueous solution 20.56 g, 80% methacryloyloxyethyltrimethylammonium chloride aqueous solution 18.75 g, 60% acrylic acid aqueous solution 8.67 g were added to 25% sodium formate aqueous solution 1.40 g to prepare a mixed solution. did. Polymerization was carried out while dripping this mixed solution into the system over 5 hours immediately after the start of the reaction. After 5 hours, 0.80 g of a 2% aqueous ammonium persulfate solution was added again, and the polymerization was continued for 17 hours to complete the reaction. When the molecular weight was measured by GPC-MALS, the weight average molecular weight was 1.6 million. This is designated as graft polymer 4.

Each graft polymer of Examples 1 to 4 and a commercially available cationic polymer were dissolved in the composition shown in Table 1 to prepare a shampoo solution. Table 2 shows the added concentration and the appearance of the shampoo solution at the time of dissolution. About each sample, the usability | use_condition as a hair shampoo was sensory-evaluated by the following method, and the reference | standard shown by Table 3 evaluated.
(1) Adjusted purified water of component A was heated to 60 ° C., an anionic surfactant, a betaine surfactant, and monoethanolamide were added and stirred. The heating was stopped, 1,3-butanediol, phenoxyethanol, EDTA · 2Na · 2H ₂ O was added and stirred, and then cooled to room temperature.
(2) Preparation of Component B Each graft polymer and commercially available cationic polymer were dissolved in purified water at room temperature.
(3) The adjustment component A of the shampoo solution was heated to 60 ° C., the component B was added and sufficiently stirred, and then cooled to room temperature.
(4) Evaluation method For each shampoo solution, a panel test was conducted by five panelists. Foaming at the time of washing the hair, smoothness at the time of washing the hair, following the fingers at the time of washing, the feeling of slimness at the time of washing, the speed of rinsing, and the squeak after washing Sensory evaluation was performed on the feeling and feeling of the comb after washing, and the usability of 1.0% shampoo solution of polyquaternium-10 was evaluated as a standard value 3, and evaluated according to the criteria shown in Table 3. The results are shown in Table 4, and the feeling of use of a commercial cationic polymer as a control product is shown in Table 5.

(Table 1)
Shampoo composition

(Table 2)

(Table 3)

(Table 4)

(Table 5)

  As is clear from the comparison of the results in Tables 4 and 5, Polyquaternium-10 requires about 1.0% addition to obtain a high conditioning effect, whereas the graft polymers 1 to 4 of the present invention are required. It was found that the same effect can be obtained with an addition amount of about 0.1%. In addition, in the case of polyquaternium-7, the addition of 0.2% or more makes the shampoo solution slightly turbid and is accompanied by a strong slime feeling during use, while the graft polymers 1 to 4 of the present invention are also related to high addition. It became clear that there was no sliminess. Furthermore, it was confirmed that the graft polymers 1 to 4 are characterized by a fast rinsing speed and a strong refreshing feeling after use, and a smooth feeling after use and a strong moist feeling after washing. .

Graft polymers 1 to 4 and a commercially available cationic polymer were dissolved in the composition shown in Table 6 to prepare a conditioner solution. About each sample, the usability | use_condition as a hair conditioner was sensory-evaluated by the following method, and the evaluation shown by Table 7 was evaluated.
(1) Preparation of Component A A cationic surfactant, stearyl alcohol, and glutamic acid were stirred and melted at 75 ° C. Next, ion-exchanged water warmed to 75 ° C. was added to further dissolve.
(2) Preparation of Component B Each graft polymer and commercially available cationic polymer were dissolved in purified water at room temperature.
(3) Adjustment component A of the conditioner liquid was heated to 75 ° C., component B was added and sufficiently stirred, and then cooled to room temperature.
(4) Evaluation method For each conditioner liquid, a practical test was conducted by five panelists. Before using the conditioner, a shampoo having no composition added with a composition shown in Table 1 was prepared and used to wash the hair. After washing, the softness when applying each conditioner used, the smoothness when applying, the smoothness when rinsing hair, the goodness of fingers after towel drying, the goodness of fingers after drying, the goodness of fingers after drying The sensory evaluation was performed on the smoothness of the hair and the moisture feeling of the hair the day after drying, and the evaluation was made according to the criteria shown in Table 7. In the evaluation, a standard value 3 was used as the conditioner's comfort adjusted without addition of a cationic polymer. Table 8 shows the feeling of use of the polymer additive-free products, the graft polymers of Examples 4 and 8, and Comparative Example 1, and the feeling of use of the commercially available cationic polymer as a control product.

(Table 6)

(Table 7)

(Table 8)

  From the result comparison of Table 8, it was found that the graft polymers 1 to 4 exhibited a high conditioning effect when added to the conditioner. This effect was higher than that of the existing product Polyquaternium-6. In addition, it was confirmed that the product of the present invention has a high effect of maintaining a good hair condition immediately after drying and the next day after drying, and also has an effect of softening the feel of the hair after drying.

The graft polymers 1 to 4 and the commercially available cationic polymer were each dissolved at a concentration of 0.5%. This solution was used as a hair styling agent for sets having curl retention, and the feeling of use was sensory evaluated by the following method.
(1) Evaluation method A 35 cm long bundle of hair was immersed in a dissolved 0.5% polymer solution for 15 seconds. After removal, the water was lightly cut, the entire hair was wound around a hair curler having a diameter of 2 cm, and dried with a high-temperature dryer for 15 minutes. While the hair was wound around the curler, it was allowed to stand for 30 minutes in a temperature-controlled room at a temperature of 26 ° C. and a humidity of 60%. 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. At that time, L0, L1, and L2 values of the hair bundle immersed in only water were measured to obtain a blank. Table 9 shows the blank values, the graft polymers 1 to 4, and the values of L0, L1 and L2 of commercially available cationic polymers as controls and the feeling after use.

(Table 9)

  As is clear from the results in Table 9, in the graft polymers 1 to 4, all the values of L0, L1, and L2 were small. From these results, it was found that the product of the present invention has an excellent curling force and holding force, and the generated curl is durable against combing. As for the feeling after use, in the case of a blank, the hair dries and does not have a feeling of clumping, and in Polyquaternium-6 and 7, the stickiness derived from the polymer remains in the hair, and in Polyquaternium-10, the hair becomes bundled and stiff. Although the feel was bulky, the product of the present invention had a feature that the feel after use was soft, and the hair was moist and smooth.

Claims (11)

As natural polymer derivative having an OH group, hydroxyethyl cellulose, hydroxypropyl cellulose, and natural polymers derivative selected from hydroxypropyl methylcellulose and hydroxypropyl guar gum, diallyl dimethyl ammonium chloride as a cationic water-soluble monomers, anionic acrylic acid as sex-soluble monomer, it to the aqueous medium of a plurality of kinds of water-soluble monomers including acrylamide as these copolymerizable nonionic water-soluble monomers, acrylic acid and acrylamide water A hair cosmetic additive obtained by graft copolymerization at 50 ° C. or higher using a persulfate as an initiator under stirring while continuously or sequentially adding a solution containing a part of a functional monomer . The molar ratio of the cationic water-soluble monomer to the anionic water-soluble monomer in the plurality of types of water-soluble monomers in the aqueous medium is in the range of 1:20 to 20: 1. The additive for hair cosmetics according to claim 1. The weight ratio of the total amount of natural polymer derivatives having OH groups in the aqueous medium to the total amount of the plurality of types of water-soluble monomers is 5:95 to 80:20. The additive for hair cosmetics as described. Hair cosmetic additive according to claim 1, characterized in that not more than 20000 mPa · s 2% aqueous solution viscosity of natural polymer derivatives at 25 ° C. with the OH group. The molecular weight is adjusted by adding a chain transfer agent as necessary in the graft copolymerization, and the weight average molecular weight of the produced graft copolymer is 10,000 to 3,000,000. Hair cosmetic additive. As natural polymer derivative having an OH group, hydroxyethyl cellulose, hydroxypropyl cellulose, and natural polymers derivative selected from hydroxypropyl methylcellulose and hydroxypropyl guar gum, diallyl dimethyl ammonium chloride as a cationic water-soluble monomers, anionic acrylic acid as sex-soluble monomer, it to the aqueous medium of a plurality of kinds of water-soluble monomers including acrylamide as these copolymerizable nonionic water-soluble monomers, acrylic acid and acrylamide water A hair cosmetic additive that is graft-copolymerized at 50 ° C. or higher using a persulfate as an initiator under stirring while continuously or sequentially adding a solution containing a part of a functional monomer Hair cosmetics. The weight ratio of the total amount of the total amount and the plurality of types of the water-soluble monomer of natural polymer derivatives having the OH groups in the aqueous medium is 5: 95 to 80: claim 6, characterized in that a 20 Hair cosmetics described in 1. The hair cosmetic composition according to claim 6, 2% aqueous solution viscosity of natural polymer derivatives having the OH group is equal to or less than 20000 mPa · s at 25 ° C.. The hair cosmetic composition according to claim 6 , wherein the graft copolymer additive has a weight average molecular weight of 10,000 to 3,000,000. A hair cosmetic composition is a shampoo, in claim 6, wherein the cationic water-soluble monomer of a plurality of kinds of water-soluble monomers in in the aqueous medium is in the range of 5 to 30 mol% The hair cosmetic composition described. The hair cosmetic is rinse, conditioner, treatment, hair conditioner for setting, perm solution, hair dye, and the cationic water-soluble monomer in the plurality of types of water-soluble monomers in the aqueous medium is 5 to 90. The hair cosmetic composition according to claim 6 , wherein the cosmetic composition is in the range of mol%.