JP2010189277A - Additive for hair cosmetic and hair cosmetic containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an additive for hair cosmetics that imparts a pliant finish feeling by alleviating respective drawbacks of a semi-synthesized additive for hair cosmetics represented by polyquaternium-10 and a synthesized additive for hair cosmetics represented by polyquaternium-6 or -7, and a hair cosmetic comprising the same. <P>SOLUTION: The additive for hair cosmetics is manufactured by dissolving a natural polymer and/or a derivative of a natural polymer each bearing an OH group in water and subsequently graft-copolymerizing thereunto in a water medium a plurality of kinds of water-soluble monomers comprising as essential ingredients a cationic water-soluble monomer and a betaine-type water-soluble monomer and, if required, a nonionic water-soluble monomer copolymerizable therewith. The hair cosmetic comprises the additive. <P>COPYRIGHT: (C)2010,JPO&INPIT

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 betaine-type water-soluble monomers as essential components, and if necessary, multiple types of water-soluble monomers including nonionic water-soluble monomers copolymerizable with them 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 a plurality of types of monomers having different copolymerization 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 a betaine-type 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 OH group-containing natural polymer and / or natural polymer derivative of the present invention contains a cationic water-soluble monomer and a betaine-type water-soluble monomer as essential components in an aqueous medium, and can be used together with them as necessary. Hair cosmetics containing an additive for hair cosmetics obtained by graft copolymerization of a plurality of types of water-soluble monomers including polymerizable nonionic water-soluble monomers are not only excellent in finish, Compared with a polymer (polyquaternium-10) obtained by reacting glycidylpropyltrimethylammonium chloride with a general-purpose 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.

  In addition, the present invention comprises a natural polymer and / or a natural polymer derivative having an OH group as essential components of a cationic water-soluble monomer and a betaine-type water-soluble monomer, and a copolymer that 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. While the hair treated with hair cosmetics has a sticky feeling, a cationic water-soluble monomer and a betaine-type water-soluble monomer are included in a plurality of types of water-soluble monomers to be graft copolymerized. The hair treated with the product of the present invention obtained by graft copolymerization with multiple types of water-soluble monomers including nonionic water-soluble monomers that can be copolymerized with them has a smooth feel and an excellent finish. It became a thing.

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

  The additive for hair cosmetics of the present invention comprises dissolving a natural polymer having an OH group and / or a natural polymer derivative in water, and then dissolving a cationic water-soluble monomer and a betaine-type water-soluble monomer in an aqueous medium. 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 betaine-type 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 arise such as stickiness on the treated hair, or no conditioning effect.

  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 polymers and / or natural polymer derivatives having OH groups, cationic water-soluble monomers and betaine-type water-soluble monomers, and if necessary, nonionic water-soluble monomers The weight ratio of the body to the total amount of the plural types of water-soluble monomers is preferably 5:95 to 80:20. Not. 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 betaine-type water-soluble monomers that copolymerize with cationic water-soluble monomers include tertiary amino group-containing cationic monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate. -To, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide and monohaloacetic acid or sodium monohaloacetate reacted. It is also possible to use a combination of a plurality of these betaine-type water-soluble monomers.

  Examples of nonionic water-soluble monomers that are copolymerized with cationic and betaine-type water-soluble monomers as needed are (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 during graft copolymerization requires a temperature at which the natural polymer or natural polymer derivative having an OH group dissolves in water, and varies depending on the natural polymer or natural polymer derivative used, but is usually in the range of 30 to 95 ° C. To do.

  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. 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, a cationic water-soluble monomer and a betaine-type water-soluble monomer as essential components, Graft-copolymerize multiple types of water-soluble monomers, including non-ionic water-soluble monomers that can be copolymerized with them. Then, a polymerization initiator may be added for polymerization, but some or all of the plural types of water-soluble monomers may be added continuously or sequentially little by little with stirring after the polymerization initiator has been added. It may be added. 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, in the case of copolymerizing diallyldimethylammonium chloride, dimethylaminoethyl methacrylate with a betaine monomer obtained by reacting monohaloacetic acid and acrylamide, dimethylaminoethyl methacrylate is reacted with monohaloacetic acid. It is preferred to add part of the mold monomer and acrylamide continuously during the polymerization. In order to make ionic groups unevenly distributed, a part of acrylamide is continuously added during polymerization, and then all or part of betaine monomer is added continuously. It is also possible to change the addition timing or addition amount of each body.

  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 water-soluble monomer is also related to the weight ratio with the natural polymer and / or natural polymer derivative having an OH group, but in the range of 5 to 90 mol%. is there. 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.

  When used in rinses, conditioners and treatments, since the main component is a cationic surfactant, the proportion of the cationic water-soluble monomer in the water-soluble monomer is 5 depending on the effect required for hair cosmetics. It is selected in the range of ˜90 mol%, but more preferably in the range of 5-60 mol%.

  In addition, when used in a hair styling agent, a permanent solution, or a hair dye, it often does not contain an ionic surfactant, so the proportion of the cationic water-soluble monomer in the water-soluble monomer is similarly determined. It is selected in the range of 5 to 90 mol% depending on the effect. There are liquid, cream, emulsion, spray, foam, gel, and the like as a hair styling for setting, but any form can be used.

  Moreover, it is preferable that the molar ratio of the cationic water-soluble monomer to the betaine-type water-soluble monomer in the plurality of types of water-soluble monomers is in the range of 1:20 to 20: 1. Outside this range, the characteristics of the graft copolymer of the present invention are not manifested, as is the case with a graft copolymer of a cationic water-soluble monomer or a betaine-type 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 (eg 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 (gypsum extract), starch (rice, corn, potato, wheat), glycyrrhizic acid, and other microbial systems such as xanthan gum, dextran, and pullulan 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.

  Also, 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 vinyl imidazolium chloride / vinyl pyrrolidone copolymers such as Rubycut FC370, FC550, FC905, HM552, MonoCP (above, BASF), Cellcut 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, polyvinyl pyrrolidone / alkylamino acrylate copolymer such as ISP), polyvinyl pyrrolidone / alkyl amino acrylate / vinyl caprolactam copolymer such as copolymer VC-713 (ISP), and vinyl pyrrolidone such as Guffcut HS-100 (ISP). / Methramidopropyltrimethylammonium 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 / alkyl methacrylate ester / methoxy polyethylene glycol copolymer, acrylamide / alkyl acrylate 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 / alkyl acrylate / 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, 134.31 g of deionized water, 5.22 g of 50% acrylamide aqueous solution, 65% diallyldimethylammonium chloride aqueous solution 21.72 g, 1.64 g of a betaine monomer aqueous solution obtained by reacting 70% dimethylaminoethyl methacrylate with monohaloacetic acid (Osaka Organic) and 0.35 g of 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 the introduction of nitrogen, 1.60 g of 10% ammonium persulfate aqueous solution was added to initiate polymerization. On the other hand, a betaine monomer aqueous solution (produced by Osaka Organic Chemical Co., Ltd.) obtained by reacting monohaloacetic acid with 19.64 g of 50% acrylamide aqueous solution, 1.64 g of 25% sodium formate aqueous solution and 70% dimethylaminoethyl methacrylate. 31 g was added 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 350,000. This is designated as graft copolymer 1.

  In a reaction vessel similar to that in Example 1, 138.45 g of deionized water, 6.08 g of 50% aqueous acrylamide, 3.17 g of 80% aqueous methacryloyloxyethyltrimethylammonium chloride, 70% dimethylaminoethyl methacrylate. 1.63 g of a betaine monomer aqueous solution (produced by Osaka Organic Chemicals) reacted with monohaloacetic acid and 0.35 g of 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, 1.40 g of 25% aqueous sodium formate was reacted with 22.88 g of 50% aqueous acrylamide, 11.92 g of 80% aqueous methacryloyloxyethyltrimethylammonium chloride and 70% dimethylaminoethyl methacrylate with monohaloacetic acid. 6.15 g of a betaine monomer aqueous solution (produced by Osaka Organic Chemicals) was added 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, 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 1.9 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 inlet tube in the same reaction vessel as in Example 1 was charged with 134.01 g of deionized water and a 50% acrylamide aqueous solution 6. .64 g, 65% diallyldimethylammonium chloride aqueous solution 15.78 g, 70% dimethylaminoethylmethacrylate reacted with monohaloacetic acid 1.78 g, manufactured by Osaka Organic Chemicals, sodium formate 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 the introduction of nitrogen, 1.60 g of 10% ammonium persulfate aqueous solution was added to initiate polymerization. On the other hand, a betaine monomer aqueous solution (produced by Osaka Organic Chemical Co., Ltd.) obtained by reacting 1.40 g of 25% sodium formate aqueous solution with 24.97 g of 50% acrylamide aqueous solution and 70% dimethylaminoethyl methacrylate with monohaloacetic acid. 71 g was added 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 850,000. This is designated as graft copolymer 3.

  In the same reaction vessel as in Example 1, in the same reaction vessel as in Example 1, 124.98 g of deionized water, 5.47 g of 50% acrylamide aqueous solution, 4.98 g of 80% methacryloyloxyethyltrimethylammonium chloride aqueous solution, 70 A uniform mixed solution was prepared by adding 5.14 g of a betaine monomer aqueous solution (manufactured by Osaka Organic Chemicals) obtained by reacting% dimethylaminoethyl methacrylate with monohaloacetic acid and 0.35 g of sodium formate. 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, 1.40 g of 25% sodium formate aqueous solution was reacted with 20.56 g of 50% acrylamide aqueous solution, 18.75 g of 80% methacryloyloxyethyltrimethylammonium chloride aqueous solution, and 70% dimethylaminoethyl methacrylate was reacted with monohaloacetic acid. 19.34 g of an aqueous betaine monomer solution (manufactured by Osaka Organic Chemicals) was added 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, 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 1,500,000. 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 during shampooing, smoothness during shampooing, following the fingers during shampooing, sliminess during shampooing, speed of rinsing, and squeaking 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 polymer-free product, the feeling of use of the graft polymers 1 to 4, and the feeling of use of the commercial cationic polymer that is 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 subjected to sensory evaluation 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 (19)

  After dissolving a natural polymer and / or a natural polymer derivative having an OH group in water, a cationic water-soluble monomer and a betaine-type water-soluble monomer are essential components in an aqueous medium. An additive for hair cosmetics, which is obtained by graft copolymerization of a plurality of types of water-soluble monomers including a nonionic water-soluble monomer that can be copolymerized with a cosmetic.   The molar ratio of the cationic water-soluble monomer to the betaine-type water-soluble monomer in the plurality of types of water-soluble monomers is in the range of 1:20 to 20: 1. The additive for hair cosmetics according to 1.   The weight ratio of the total amount of the natural polymer and / or natural polymer derivative having the OH group to the total amount of the plurality of water-soluble monomers is 5:95 to 80:20. The additive for hair cosmetics according to 1.   The additive for hair cosmetics according to claim 1, wherein the viscosity of a 2% aqueous solution of the natural polymer or natural polymer derivative having an OH group is 20000 mPa · s or less at 25 ° C.   The additive for hair cosmetics according to claim 1, wherein the graft copolymerization initiator is a persulfate, and the polymerization reaction is carried out at 50 ° C or higher.   The additive for hair cosmetics according to claim 9, wherein the betaine-type monomer and a part of acrylamide are graft-copolymerized with stirring while being continuously or sequentially added.   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.   2. The main component of the plurality of types of water-soluble monomers is diallyldimethylammonium chloride, betaine monomer obtained by reacting dimethylaminoethyl methacrylate with monohaloacetic acid, and acrylamide. Additives for hair cosmetics as described in 1.   The natural polymer having OH group is a natural polymer selected from guar gum, locust bean gum and sericin, and the natural polymer derivative having OH group is hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose and hydroxypropyl. The additive for hair cosmetics according to claim 1, wherein the additive is a natural polymer derivative selected from guar gum.   The natural polymer derivative having the OH group without using a natural polymer is hydroxyethyl cellulose having a 2% aqueous solution viscosity of 100 to 10000 mPa · s at 25 ° C., and the main component of the plurality of types of water-soluble monomers. Is a betaine monomer and acrylamide obtained by reacting diallyldimethylammonium chloride, dimethylaminoethyl methacrylate with monohaloacetic acid, and adding part of the betaine monomer and acrylamide continuously or sequentially. The additive for hair cosmetics according to claim 1, wherein persulfate is used as an initiator under stirring and is graft copolymerized at 50 ° C or higher.   After dissolving a natural polymer and / or a natural polymer derivative having an OH group in water, a cationic water-soluble monomer and a betaine-type water-soluble monomer are essential components in an aqueous medium. A hair cosmetic comprising an additive for hair cosmetics obtained by graft-copolymerizing a plurality of types of water-soluble monomers including a nonionic water-soluble monomer copolymerizable with a cosmetic.   The weight ratio of the total amount of the natural polymer and / or natural polymer derivative having the OH group to the total amount of the plurality of water-soluble monomers is 5:95 to 80:20. 11. Hair cosmetics according to 11.   The hair cosmetic according to claim 11, wherein the viscosity of a 2% aqueous solution of the natural polymer or natural polymer derivative having an OH group is 20000 mPa · s or less at 25 ° C.   The hair cosmetic according to claim 11, wherein the weight-average molecular weight of the graft-copolymerized additive for hair cosmetic is 10,000 to 3,000,000.   The hair cosmetic composition according to claim 11, wherein the hair cosmetic composition is a shampoo, and the cationic water-soluble monomer in the plurality of types of water-soluble monomers is in the range of 5 to 30 mol%. Fee.   Hair cosmetics are rinse, conditioner, treatment, hair styling for set, perm solution, hair dye, and the cationic water-soluble monomer in the plurality of types of water-soluble monomers is in the range of 5 to 90 mol%. The hair cosmetic composition according to claim 11, wherein   12. The main component of the plurality of types of water-soluble monomers is diallyldimethylammonium chloride, betaine monomer obtained by reacting dimethylaminoethyl methacrylate with monohaloacetic acid, and acrylamide. Hair cosmetics described in 1.   The natural polymer having OH group is a natural polymer selected from guar gum, locust bean gum and sericin, and the natural polymer derivative having OH group is hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose and hydroxypropyl. The hair cosmetic composition according to claim 11, which is a natural polymer derivative selected from guar gum.   The natural polymer derivative having an OH group without using a natural polymer is hydroxyethyl cellulose having a 2% aqueous solution viscosity of 100 to 10000 mPa · s at 25 ° C., and the main component of the plural types of water-soluble monomers. Is a betaine monomer and acrylamide obtained by reacting diallyldimethylammonium chloride, dimethylaminoethyl methacrylate with monohaloacetic acid, and adding part of the betaine monomer and acrylamide continuously or sequentially. The hair cosmetic composition according to claim 11, which is graft-copolymerized at 50 ° C or higher using a persulfate as an initiator under stirring.