JP2013107975A - Polymer composition, method for producing the same, additive for cosmetic for hair and hair cosmetic comprising the same, and additive for skin cleaning agent and skin cleaning agent comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To achieve a technique of using a light source with a minimum light quantity in the ultraviolet region as a light source with high safety for a working environment when a natural polymer and/or a natural polymer derivative having an OH group is made to be coexist in an aqueous medium and one or more water-soluble monomers having a vinyl group are photopolymerized.SOLUTION: It is found that a polymerization reaction is made to proceed to obtain a polymer composition by irradiating a solution containing a natural polymer and/or a natural polymer derivative having an OH group, one or more water-soluble monomers having a vinyl group, organic coloring matter, and a peroxide as essential components in an aqueous medium with visible light as a method for achieving the technique.

Description

The present invention relates to a solution containing an OH group-containing natural polymer and / or natural polymer derivative, one or more water-soluble monomers having a vinyl group, an organic dye and a peroxide as essential components in an aqueous medium. Polymer composition characterized by being irradiated with visible light and polymerized, and method for producing the same, hair cosmetic additive and hair cosmetic containing the same, skin cleansing additive and skin containing the same It relates to cleaning agents.

  The photopolymerization method is an existing technology for obtaining polymers, and the technology for photopolymerizing and curing photocuring resins is an important method in various industries such as the electric / electronic market, automobile, optics, and medical fields. It has become. A major feature of photopolymerization is that the reaction occurs rapidly by light irradiation in a specific wavelength range. In addition to shortening the reaction time and controlling the reaction, selecting a photopolymerization initiator that can start the reaction with an inexpensive light source has the advantage of reducing the investment in equipment.

The photopolymerization technique is a technique mainly used for the production of a water-insoluble polymer, but there is an example applied to the production of a water-soluble polymer using a water-soluble monomer as a raw material. As a production technique for a water treatment flocculant, a method for producing a high molecular weight acrylic polymer using a movable belt (see Patent Document 1) and a technique for continuous photopolymerization of a water-soluble vinyl monomer are disclosed ( Patent Document 2). In these patent documents, when photopolymerization technology is used for the production of a water-soluble polymer, high concentration polymerization, reduction of residual monomers, high efficiency reaction by continuous production, production of a polymer having a high molecular weight, etc. It is stated that it will be possible.
JP-A-61-155406 JP-A 61-221202

Utilizing the advantages of photopolymerization in the production of water-soluble polymers using the above water-soluble monomers as raw materials, inventions of water-soluble polymers using several photopolymerization techniques have been made so far. (See Patent Documents 3, 4, and 5). The photopolymerization initiators used in these are those in which photolysis proceeds mainly by light irradiation in the ultraviolet region, such as benzoin derivatives and azo compounds, and the reaction starts.
Japanese Patent Laid-Open No. 10-231309 JP 2002-348303 A JP 2003-82596 A

  When using a photopolymerization initiator that initiates a reaction upon irradiation with light in the ultraviolet region, it is necessary to use a light source that emits ultraviolet light. Ultraviolet rays are risk factors such as pigmentation on the skin, wrinkles, cancer, cataracts on the eyeball, etc. Industrial use of light sources that emit ultraviolet rays is undesirable in the working environment, and the use of light sources with as little ultraviolet light as possible is desired. Yes.

From the viewpoint of safety, a method using a riboflavin / fluorescent light active continuous polymerization system is being studied as a photopolymerization method that can also use light energy in the visible region, but the obtained polymer has a low reaction rate and is a satisfactory product. Is not obtained (see Patent Document 6).
JP-A-63-135403

The present inventors have proposed a method for producing a polyacrylamide gel for electrophoresis by photopolymerization using a redox polymerization initiator composed of an oxidizing agent and a reducing agent and a photosensitizer in combination (Patent Document 7). One feature of the present invention is that the added riboflavin and riboflavin derivative function not as a photopolymerization initiator but as a photosensitizer. By using an oxidizing agent and a reducing agent in combination with a photosensitizer, a high-quality polyacrylamide gel for electrophoresis can be produced in a short time.
International Publication No. 2009-025135

  However, the technique described in Patent Document 7 is a technique optimized for the production of a water-insoluble gel such as a polyacrylamide gel for electrophoresis. When this technology is applied to the industrial production of water-soluble polymers using water-soluble monomers as raw materials, or to the production of graft copolymers and / or cross-linked copolymers, redox by the combined use of an oxidizing agent and a reducing agent. The reaction occurs explosively, the polymerization reaction cannot be controlled, and a polymer having the desired molecular weight cannot be obtained. Further, most of the oxidizing agent and reducing agent are consumed at the initial stage of the polymerization reaction, and the residual monomer in the obtained polymer cannot be reduced.

As a trial, the photopolymerization reaction was performed on the technology / hair cosmetic additive developed by the present inventors and the hair cosmetic containing the same (Patent Document 8), and the skin cleanser additive and the skin cleanser containing the same. In order to make use of the advantages of the above, an attempt was made to apply the photopolymerization technique shown in Patent Document 7, but a satisfactory polymer could not be obtained for the reasons described above.
International Publication No. 2010-016543

  An object of the present invention is to provide a safe working environment when photopolymerizing one or more water-soluble monomers having a vinyl group in the presence of a natural polymer and / or a natural polymer derivative having an OH group in an aqueous medium. The aim is to complete a technique using a light source with a low amount of light in the ultraviolet region as a highly reliable light source.

Using the above-described method, a water-soluble monomer having a vinyl group is polymerized by polymerizing a natural polymer and / or a natural polymer derivative having an OH group and a water-soluble monomer having at least one vinyl group in an aqueous medium. Obtaining a polymer composition constructed from a monomer, and proposing a production method thereof, hair cosmetic additive and hair cosmetic containing the same, skin cleansing additive and skin containing the same We propose application to cleaning agents.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that natural polymers and / or natural polymer derivatives having OH groups, water-soluble monomers having one or more vinyl groups, and organic dyes Further, the present inventors have found that a polymer composition can be obtained by irradiating visible light to a solution containing an peroxide as an essential component in an aqueous medium, whereby a polymer composition can be obtained.

  In the present invention, by using a photosensitizer having an absorption band in the visible region, a light source having as little light as possible in the ultraviolet region can be used, and photopolymerization with high safety in the working environment is possible. Furthermore, the polymerization reaction of the polymer composition can be performed in a short time and at a high concentration. Therefore, a polymer composition can be obtained with high production efficiency, and even when the entire reaction solution becomes an elastic body such as a hydrogel during the reaction due to polymerization at a high concentration, the polymerization is completed by continuing to irradiate light. be able to. In the present invention, the main component is either a graft copolymer or a cross-linked copolymer by changing the mass ratio of a natural polymer and / or natural polymer derivative having a OH group and a water-soluble monomer during polymerization. To produce a polymer composition.

  When used as a hair cosmetic additive, the polymer composition containing the graft copolymer shown in Patent Document 8 exhibits an excellent conditioning effect as compared with existing additives such as polyquaternium-7 and 10 . When the polymer composition shown in Patent Document 8 was prepared using the method of the present invention, the polymerization time could be greatly shortened, and the production efficiency could be significantly improved. In addition, when the method of Patent Document 8 is used, the natural polymer and / or natural polymer derivative having an OH group has been used only as the main chain of the graft copolymer. , Natural polymers having an OH group and / or natural polymer derivatives can be used not only as the main chain of the graft copolymer but also as a cross-linking site of the cross-linked copolymer. Coalescence can be obtained.

  As a result, when the polymer composition obtained by the present invention is used as a hair cosmetic additive and a skin cleansing additive, the hair cosmetic additive obtained by the technique shown in Patent Document 8 and the skin Compared with additives for cleaning agents, the effect of improving foam quality and the effect of maintaining a good feel on the surface of the hair or skin is high, and it is possible to maintain a smooth state without squeaky feeling when washing the hair or skin.

Hereinafter, modes for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described. In addition, the following this embodiment is an illustration of this invention and is not the meaning which limits this invention to the following content. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

The water-soluble monomer having a vinyl group is a nonionic monomer, a cationic monomer, an anionic monomer, or a polyfunctional monomer having a plurality of vinyl groups. One type or two or more types may be used. Among these, the cationic monomer is particularly represented by the general formula (1) or the general formula (2).
General formula (1)
[Wherein, R ₁ represents a hydrogen atom or a methyl group, and R ₂ , R ₃ , and R ₄ are the same or different and each represents a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms. Show. Y represents —O—, —NH—, —CH ₂ —, or —O—CH ₂ CH (OH) —, Z represents a linear or branched alkylene group having 1 to 4 carbon atoms, and X ^- represents a conjugate base, a halogen atom or an alkyl sulfate group having 1 to 4 carbon atoms acid]
General formula (2)
[Wherein, R ₅ is the same or different and represents a hydrogen atom or a methyl group, R ₆ and R ₇ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X ⁻ is the same as defined above] Indicates meaning. ]

Examples of nonionic monomers include (meth) acrylamide, dimethylacrylamide, diethylacrylamide, isopropylacrylamide, hydroxyethylacrylamide, vinylpyrrolidone, vinylformamide, vinylacetamide, and the like. A plurality of these nonionic water-soluble monomers can be used in combination, and it is preferable that acrylamide is included because of the ease of the polymerization reaction.

Among the cationic monomers, examples of tertiary amino group-containing cationic monomers include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl. Examples include (meth) acrylamide and salts thereof. 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. It is also possible to use a combination of a plurality of these cationic water-soluble monomers.

Examples of the anionic monomer include (meth) acrylic acid, itaconic acid, 2-acrylamido 2-methylpropane sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, and salts thereof. It is also possible to use a combination of a plurality of these anionic water-soluble monomers.

Examples of polyfunctional monomers having a plurality of vinyl groups include methylene bisacrylamide, methylene bismethacrylamide, divinylbenzene, N, N-diallylamine, N, N-diallylamine hydrochloride, N, N, N-tri Allylamine, N, N, N-triallylamine hydrohalide, N-methyl-N, N, N-triammonium halide, N-methyl-N, N, N-triallylammonium halide, N, N, N, N- Examples include tetraallyl ammonium halide, diallyl fumarate, diallyl maleate and the like. It is also possible to use a combination of a plurality of these polyfunctional monomers.

  A natural polymer and / or a natural polymer derivative having an OH group forms a polymer composition with a water-soluble monomer having a vinyl group. It becomes a cross-linked site of coalescence. In the present invention, it is possible to construct a graft copolymer and / or a crosslinked copolymer by adding a natural polymer having an OH group and / or a natural polymer derivative, so that a water-soluble or water-insoluble graft copolymer and / or This leads to a technology capable of producing both cross-linked copolymers. The three-dimensional characteristics of these polymers are very important for exhibiting excellent functions as a cosmetic additive for hair and an additive for skin cleanser.

Examples of natural polymers and / or natural polymer derivatives having an OH group include polysaccharides and polysaccharide derivatives such as cellulose, starches, guar gum, locust bean gum, tamarind gum, xanthan gum, chitosan, carrageenan, duran gum, Examples include pullulan, mannan, fenugreek, and sericin, but guar gum and locust bean gum are preferable from the viewpoint of solubility. Examples of natural polymer derivatives include carboxymethyl cellulose, methyl cellulose, ethyl cellulose, isopropyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, ethyl-hydroxyethyl cellulose, hydroxyethyl guar gum, and hydroxypropyl guar gum. From the viewpoint of solubility, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose and hydroxypropyl guar gum are preferred, and hydroxyethyl cellulose is more preferred. It is also possible to use a combination of these natural polymers or natural polymer derivatives.

Regarding the molecular weight of a natural polymer having an OH group and / or a natural polymer derivative, since the photopolymerization reaction is performed in a state of being uniformly dissolved in an aqueous medium, the viscosity of a 2% aqueous solution is 200,000 mPa · s or less at 25 ° C. It is preferable that A natural polymer and / or a natural polymer derivative having a higher molecular weight than this makes the viscosity of the solution extremely high, making it difficult to handle the solution for production.

The addition amount of the natural polymer having an OH group and / or the natural polymer derivative is desirably 0.001% by mass to 20% by mass with respect to the total amount of the water-soluble monomer having a vinyl group. When the amount exceeds this value, undissolved natural polymer and / or natural polymer derivative remains, and below this value, the function of the natural polymer and / or natural polymer derivative is not fully exhibited. A more preferable addition amount is 0.1% by mass to 10% by mass.

The total concentration of the water-soluble monomer having a vinyl group and the natural polymer and / or natural polymer derivative having an OH group in the solution contained in the aqueous medium is preferably as high as possible from the viewpoint of productivity. The range is from mass% to 90% by mass. When it is low, it is difficult to initiate polymerization, and when it is high, it is difficult to control the heat of polymerization, so the range is particularly preferably from 20% by mass to 60% by mass.

  Examples of organic dyes include riboflavin, folic acid, methylene blue, eosin Y, dibromofluorescein, rhodamine B, pyrogallol, dichlorofluorescein, erythrosine B, fluorescin, uranin, rhodamine 123, fluoresceinamine I, fluoresceinamine II, rose bengal, modern blue 29, Eriochrome cyanine R, naphthochrome green, aurintricarboxylic acid, coumarin 343, proflavine, mercurochrome, methyl red, methyl orange, methyl yellow, bromocresol purple, bromophenol blue, free base porphyrin, free base phthalocyanine, chlorin, Examples include bacteriochlorophyll and derivatives thereof, but organic dyes that dissolve in water within a pH range of 3 to 10 Preferred. Among these, riboflavin or a riboflavin derivative is preferable, and sodium riboflavin-5'-phosphate having high solubility in water or an aqueous medium is most preferable. The addition amount of the organic dye is in the range of 1 ppm to 500 ppm, more preferably in the range of 5 ppm to 100 ppm with respect to the monomer concentration. When the amount of the organic dye added is too small, the polymerization reaction hardly proceeds. When the amount of the organic dye added is too large, all of the light is absorbed near the surface and the polymerization reaction is caused by disproportionation between excited species. May not start.

  In the present embodiment, it is necessary to contain a peroxide together with an organic dye for the purpose of promoting the polymerization reaction. Examples of peroxides include ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, benzoyl peroxide, and ammonium persulfate is desirable from the viewpoint of solubility. The amount of peroxide added is in the range of 10 to 50,000 ppm, more preferably in the range of 500 to 20,000 ppm with respect to the monomer concentration.

  In addition to the above raw materials, additives such as a chain transfer agent may be used as necessary for adjusting the molecular weight. Examples of chain transfer agents can be selected from commonly used compounds having chain transfer properties such as isopropyl alcohol, mercaptoethanol, sodium gluconate, sodium formate, and sodium hypophosphite. .

  As a light source of this embodiment, what mainly emits light of a visible region is preferable. Examples of such light sources include fluorescent lamps, LED fluorescent lamps, metal halide lamps, xenon lamps, high-pressure mercury lamps, and low-pressure mercury lamps. However, they are inexpensive, have a long life, have a low calorific value, and have low energy consumption. A fluorescent lamp is preferred. In the case of fluorescent lamps and LED fluorescent lamps, there are blue, bluish white, green, pink lamps, etc., and therefore, it is possible to select and use a fluorescent lamp suitable for the absorption region of the organic dye to be used. These light sources may be used alone or in combination.

  The illuminance of visible light to be irradiated is preferably 100 to 500,000 lx. If the strength is less than this, the reaction may not proceed sufficiently. If it is too strong, the reaction control becomes difficult and dangerous. A more preferable range is 1,000 to 150,000 lx.

  Although this embodiment is performed in a dissolved state in an aqueous medium, a medium in which a water-soluble organic solvent such as alcohol is mixed as an aqueous medium can be used if necessary for the reaction. Natural polymers having OH groups and / or natural polymer derivatives, peroxides, and organic dyes are previously dissolved in an aqueous medium. The solution and the water-soluble monomer are mixed under light shielding to obtain a reaction solution.

The reaction solution in this embodiment is desirably in the range of pH 2-10. The pH can be adjusted using a suitable pH adjusting solution such as dilute hydrochloric acid, dilute sulfuric acid, sodium hydroxide aqueous solution or the like as necessary.

  In the present embodiment, the polymerization can be performed even in an atmosphere containing oxygen such as air, but if necessary, the reaction solution or the polymerization reaction field is replaced with an inert gas such as nitrogen or argon. Polymerization can also be performed in the state.

  The shape of the polymerization vessel is not particularly limited as long as the reaction solution can be irradiated with visible light. Among them, it is preferable to use a container having a flat bottom and a large surface area because quality control of the obtained product is easy. When a container having a flat bottom and a large surface area is used, the reaction solution can be kept thin and flat, so that visible light irradiation can be performed uniformly.

  The material of the polymerization vessel is not particularly limited as long as it is a top open system when visible light is irradiated from above. When visible light is irradiated from around the container, the material is not particularly limited as long as it is a material that transmits visible light such as glass. Moreover, when installing a light source inside a superposition | polymerization container, the raw material of a superposition | polymerization container is not restrict | limited in particular.

  The temperature at the start of visible light irradiation is preferably in the range of 5 to 60 ° C. If the temperature is lower than this, it takes a long time to start the reaction, and if the temperature is too high, heat may be generated during polymerization and bumping may occur, which is dangerous.

  The visible light irradiation time for photopolymerization is preferably 10 to 120 minutes. If it is less than this, the reaction does not proceed sufficiently, and if it is more than this, a side reaction may occur.

  The hair cosmetic additive of this embodiment can be blended in various hair cosmetics. As examples of hair cosmetics, it can be suitably used for shampoos, rinses, conditioners, treatments, hair styling agents for setting, permanent liquids, hair dyes and the like.

  In the hair cosmetic additive of the present embodiment, the proportion of the cationic water-soluble monomer in the water-soluble monomer having a vinyl group is in the range of 1 to 100 mol%. However, when used in shampoos, if the cation equivalent value is too high, it forms a complex with the anionic surfactant, which is the main component of the shampoo composition, insolubilizes and becomes cloudy, so the range of 1 to 50 mol% is preferred.

When used in rinses, conditioners, and treatments, the main component is a cationic surfactant, so the proportion of the cationic water-soluble monomer in the water-soluble monomer having a vinyl group is required for hair cosmetics. Depending on, it is selected in the range of 5 to 100 mol%, more preferably in the range of 5 to 60 mol%.

In addition, when used in a hair styling agent, a permanent liquid, and a hair coloring agent, since the ionic surfactant is often not included, the proportion of the cationic water-soluble monomer in the water-soluble monomer having a vinyl group is Similarly, it is selected in the range of 5 to 100 mol% depending on the desired effect. There are liquid, cream, emulsion, spray, foam, gel, and the like as a hair styling for setting, but any form can be used.

  When the hair cosmetic additive of the present embodiment is added to the hair cosmetic, it is usually added in an amount of 0.05% to 5% by weight based on the hair cosmetic. The addition amount is not particularly limited within the range shown.

As other components of the hair cosmetic containing the hair cosmetic additive of the present embodiment as an additive component, known additives can be added to the hair cosmetic depending on the use of the hair cosmetic.

Examples of anionic surfactants include: lauroylmethylalanine sodium, cocoyl glutamate triethanolamine, N-lauryl-L-glutamate sodium, N-coconut oil fatty acid-L-glutamate triethanolamine, N-myristylate acyl-L -N-fatty acid-N-methyl taurine salt such as sodium glutamate, N-fatty acid acyl-L-glutamate such as N-mixed fatty acyl-L-glutamate, methyl laurate sodium, coconut oil fatty acid methyl taurine sodium, Salts of N-fatty acid sarcosine condensates such as sodium lauroyl sarcosine, cocoyl sarcosine sodium, acyl sarcosine sodium, acyl glutamate, acyl-β-alanine sodium, acyl taurate, lauryl Acid salts, polyoxyethylene lauryl ether sulfate, N-coconoyl-N-methyl-β-alanine sodium, N-myristoyl-N-methyl-β-alanine sodium and the like N-fatty acid acyl-N-methyl-β-alanine Examples include salts.

Examples of the cationic surfactant include lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride and the like.

Examples of betaine surfactants include lauryl dimethylaminoacetic acid betaine, cocoaside propyl betaine, dimethyl lauryl betaine, bis (2-hydroxyethyl) lauryl betaine, coconut oil fatty acid amidopropyl betaine, cocoamphoacetate sodium, cyclohexyl lauryl amine oxide Dimethyl lauryl amine oxide, bis (2-hydroxyethyl) lauryl amine oxide, oleyl betaine, stearyl betaine, myristyl betaine, stearyl dihydroxyethyl betaine and the like.

Examples of nonionic surfactants include glyceryl monostearate, sorbitan monopalmitate, polyoxyethylene cetyl ether, polyoxyethylene sorbitan monolaurate, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene Glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil, fatty acid alkanolamide, stearic acid diethanolamide, coconut oil fatty acid diethanolamine And sorbitan sesquioleate, polyoxyethylene stearyl ether, and the like.

  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, alcohols, higher fatty acids and derivatives thereof, water-soluble polymers, and various ultraviolet absorbers.

Examples of hydrocarbons include liquid paraffin, petrolatum, solid paraffin, squalane, olefin oligomers and the like.

Examples of alcohols include ethanol, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, monostearyl glycerin ether, 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyl deca Nord, isostearyl alcohol, octyldodecanol and the like.

Examples of higher fatty acids and derivatives thereof include isopropyl myristate, octyldodecyl myristate, ethyl dodecyl palmitate, stearyl stearate, glycol distearate, polyethylene glycol sorbitol tetraoleate, glyceryl monostearate, diethylpentanediol dineopentanoate, Ester oils such as hydrogenated castor oil polyethylene glycol, lauric acid, myristic acid, palmitic acid, stearic acid, behen (behenyl) acid, oleic acid, 1,2-hydroxystearic acid, undecylenic acid, tallic acid, lanolin fatty acid, Examples include isostearic acid, linoleic acid, linolenic acid, γ-linolenic acid, eicosapentaenoic acid, and the like.

Examples of water-soluble polymers include carrageenan, pectin, agar, quince seed (malmello), algae colloid (sodium extract), starch (rice, corn, potato, wheat), plant polymers such as glycyrrhizic acid, xanthan gum, dextran, Microbial polymers such as pullulan, natural water-soluble polymers such as animal polymers such as collagen and gelatin, methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, sodium carboxymethylcellulose, cation Cellulose polymers such as cellulose acetate, crystalline cellulose, cellulose powder, cationized guar gum, sodium alginate, propylene glycol alginate Semi-synthetic water-soluble polymers such as alginic acid polymers such as ruthenium, vinyl polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer (Carbopol), polyethylene glycol 20,000, 600,000, Examples thereof include polyoxyethylene polymers such as 4,000,000 and synthetic water-soluble polymers such as polyethyleneimine.

Examples of UV absorbers include bentonite, AlMg silicate (beegum), labnite, hectorite, silicic anhydride and other inorganic substances, volatile silicone oil, silicone resin, silicone gum, alkyl-modified silicone, polyethylene glycol-added silicone, amino Silicones such as modified silicones, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, tetrasodium edetate, Sequestering agents such as sodium phosphate, sodium polyphosphate, sodium metaphosphate, gluconic acid, 3- (4'-methylbenzylidene) -d, 1-camphor, 3-benzylidene-d, 1-camphor, urocanic acid, urocanin Acid Este 2-phenyl-5-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-pentane-2 -On, benzoic acid, anthranilic acid, salicylic acid, cinnamic acid, benzophenone and the like.

Examples of other optional components include (poly) ethylene glycol, (poly) propylene glycol, glycerin, 1,3-butylene glycol, maltitol, sorbitol, chondroitin sulfate, hyaluronic acid, atelocollagen, cholesteryl-1,2-hydroxysteare Moisturizers such as rate, sodium lactate, bile salt, 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, refreshing agents such as menthols, stimulating agents such as benzyl nicotinate, vitamins such as vitamins A, B, C, D and E, chlorhexidine gluconate, isopropylmethyl Bactericidal preservatives such as enol and paraoxybenzoate, protein hydrolysates, amino acids, plant extracts, chelating agents such as EDTA-Na, pH adjusters such as succinic acid, sodium succinate, and triethanolamine, foam increase Agent, foaming agent, foam stabilizer, in the case of aerosol products, propellant such as liquefied petroleum gas, dimethyl ether, metal ion scavenger, antifungal agent, disinfectant, emulsion agent, conditioning agent, thickener, antioxidant , Solubilizer, rosin, hydrotrope, hair nourishing agent, herbal medicine, pigment, fragrance and the like.

Also, known cationic, anionic, amphoteric, and nonionic synthetic, semi-synthetic, and natural polymers different from the present embodiment can be used in combination with the present invention.

Examples of the cationic polymer include vinyl imidazolium chloride / vinyl pyrrolidone copolymers such as Rubykat FC370, FC550, FC905, HM552, MonoCP (above, BASF), Cellcut H-100 (viscosity 1000 mPa · s), L-200. (Viscosity: 100 mPa · s) (National Starch Co., Ltd.) Hydroxyethylcellulose / dimethyldiallylammonium chloride, homopolymer of diallyldimethylammonium chloride such as Marquat 100, 550, and copolymer of diallyldimethylammonium chloride and acrylamide, Containing terpolymer (Mercoat 3331), copolymer or terpolymer (Mercoat 2001) containing methacrylamidopropyltrimethylammonium chloride, etc. As described above, vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer such as Nalco), Guffcut 734, 755N, 755 (above, ISP), rubiflex (BASF), copolymers 845, 937, 958 (above, ISP) ) Polyvinyl pyrrolidone / alkylamino acrylate copolymer such as copolymer VC-713 (ISP), etc., polyvinyl pyrrolidone / alkyl amino acrylate / vinyl caprolactam copolymer, vinyl pyrrolidone / methacrylamide propyl such as Guffcut HS-100 (ISP) Trimethylammonium chloride copolymer, N, N-dimethylaminoethyl diethyl methacrylate sulfate, N, N-dimethylacrylamide and dimethacrylic acid whose component names are polyquaternium-52 Polyethylene glycol copolymer, alkylacrylamide / acrylate / alkylaminoalkylacrylamide / polyethylene glycol methacrylate copolymer such as water-soluble polymer compound described in JP-A-2-180911, N-propionylpolyethyleneimine / methylpolysiloxane copolymer, acrylamide / Acrylic acid / alkyl methacrylate ester / methoxypolyethylene glycol copolymer, acrylamide / alkyl acrylate copolymer, and the like.

Examples of the anionic polymer include methyl vinyl ether / maleic anhydride alkyl half ester copolymers such as Gantrez ES-225, ES-425, SP-215 (and above, ISP), Resin 28-1310 (National Starch), Vinyl acetate / crotonic acid copolymer such as Ruby Set CA (BASF), Virni acetate / crotonic acid / neodecanoic acid vinyl copolymer such as Resin 28-2930 (National Starch), Vinyl acetate / croton such as Ruby Set CAP (BASF) Acid / vinyl propionate copolymer, vinyl acetate / maleic acid monobutyl ester / isopolonyl acrylate copolymer such as ADVANTAGEECP (ISP), plus size L53P, L-75CB, L-9540B (reciprocal chemical), Da (Meth) acrylic acid / (meth) acrylic acid alkyl ester copolymer such as Yahold (Mitsubishi Chemical), Ultrahold 8, Ultrahold Strong (above, BASF), Unformer V-42 (National Starch) Such as acrylic acid / acrylic acid alkyl ester / alkyl acrylamide copolymer, polyvinyl pyrrolidone / acrylate / (meth) acrylic acid copolymer 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 amphoteric polymer include N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / methacrylic from Yuka Former SM, 301, 205S, 201, W, etc. (Mitsubishi Chemical Corporation). Examples include acid alkyl ester copolymers, hydroxyform acrylate / butylaminoethyl methacrylate / octylamide acrylate copolymers such as Anformer 28-4910 and LV-71 (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), etc., 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. Polyvinyl pyrrolidone / vinyl acetate copolymer, polyvinyl pyrrolidone / vinyl acetate / vinyl propionate copolymer such as Rubiscol VAP343 (BASF), vinyl acetate / N-vinyl-5-methyl-2- such as Dowtex (Dow Chemical) Examples include oxazoline copolymers.

  The additive for skin cleanser of this embodiment can be mix | blended with various skin cleansing agents. Examples of skin cleansing agents can be suitably used for body shampoos, facial cleansing foams, hand soaps and the like.

  In the skin cleansing additive of the present embodiment, the proportion of the cationic water-soluble monomer in the water-soluble monomer having a vinyl group is in the range of 1 to 100 mol%. The proportion of the cationic water-soluble monomer in the water-soluble monomer having a vinyl group is selected in the range of 5 to 100 mol% depending on the effect required for the skin cleanser, but in the range of 5 to 30 mol%. Is more preferable.

  When the skin cleansing additive of this embodiment is added to the skin cleanser, it is usually added in an amount of 0.05% to 5% by weight based on the skin cleanser. The addition amount is not particularly limited within the range shown.

  As other components, known additives such as anionic surfactants, cationic surfactants, betaine surfactants, and nonionic surfactants are added to the skin cleanser according to the use of the skin cleanser. be able to.

  Examples of the anionic surfactant include laurate, myristate, palmitate, stearate, behen (behenyl), oleate, 1,2-hydroxystearate, undecylenate, Tall acid salts, lanolin fatty acid salts, isostearic acid salts, linoleic acid salts, linolenic acid salts, γ-linolenic acid salts, higher fatty acid salts such as eicosapentaenoic acid salts and derivatives thereof, sodium lauroylmethylalanine, triethanolamine cocoyl glutamate, N-fatty acid sodium such as N-lauryl-L-glutamate, N-coconut oil fatty acid-L-glutamate triethanolamine, N-myristylate acyl-L-sodium glutamate, N-mixed fatty acyl-L-sodium glutamate L-glutamate, Lau N-fatty acid-N-methyltaurine salt such as methyl taurate sodium, palm oil fatty acid methyl taurine sodium, salt of N-fatty acid sarcosine condensate such as sodium lauroyl sarcosine, sodium cocoyl sarcosine, 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-myristoyl-N-methyl-β-alanine sodium, etc. N-fatty acid acyl-N-methyl-β-alanine salts and the like can be mentioned.

  Examples of the cationic surfactant include lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, and the like.

  Examples of the betaine type surfactant include lauryl dimethylaminoacetic acid betaine, cocoaside propyl betaine, dimethyl lauryl betaine, bis (2-hydroxyethyl) lauryl betaine, coconut oil fatty acid amidopropyl betaine, cocoamphoacetate sodium, cyclohexyl lauryl amine oxide Dimethyl lauryl amine oxide, bis (2-hydroxyethyl) lauryl amine oxide, oleyl betaine, stearyl betaine, myristyl betaine, stearyl dihydroxyethyl betaine and the like.

  Examples of the nonionic surfactant include glyceryl monostearate, sorbitan monopalmitate, polyoxyethylene cetyl ether, polyoxyethylene sorbitan monolaurate, sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene Glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil, fatty acid alkanolamide, stearic acid diethanolamide, coconut oil fatty acid diethanolamine And sorbitan sesquioleate, polyoxyethylene stearyl ether, and the like.

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, alcohols, higher fatty acids and derivatives thereof, water-soluble polymers, and various ultraviolet absorbers.

Examples of hydrocarbons include liquid paraffin, petrolatum, solid paraffin, squalane, olefin oligomers and the like.

Examples of alcohols include ethanol, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, monostearyl glycerin ether, 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyl deca Nord, isostearyl alcohol, octyldodecanol and the like.

Examples of higher fatty acids and derivatives thereof include isopropyl myristate, octyldodecyl myristate, ethyl dodecyl palmitate, stearyl stearate, glycol distearate, polyethylene glycol sorbitol tetraoleate, glyceryl monostearate, diethylpentanediol dineopentanoate, And ester oils such as hydrogenated castor oil polyethylene glycol.

  Water-soluble polymers include carrageenan, pectin, agar, quince seed (quince), arge colloid (gypsum extract), starch (rice, corn, potato, wheat), plant polymers such as glycyrrhizic acid, xanthan gum, dextran, pullulan Natural water-soluble polymers such as microbial polymers such as collagen, gelatin and gelatin, methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropylcellulose, sodium carboxymethylcellulose, cationization Cellulose polymers such as cellulose, crystalline cellulose, cellulose powder, cationized guar gum, sodium alginate, propylene glycol alginate Semi-synthetic water-soluble polymers such as alginic acid polymers such as ruthenium, vinyl-based polymers such as polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer (trade name “Carbopol”), polyethylene glycol 20,000, Examples thereof include polyoxyethylene polymers such as 600,000 and 4,000,000, and polyethyleneimine.

  Various UV absorbers include bentonite, AlMg silicate (Begum), labnite, hectorite, silicic anhydride, volatile silicone oil, silicone resin, silicone gum, alkyl-modified silicone, polyethylene glycol-added silicone, amino Silicones such as modified silicones, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, tetrasodium edetate, Sequestering agents such as sodium phosphate, sodium polyphosphate, sodium metaphosphate, gluconic acid, 3- (4'-methylbenzylidene) -d, 1-camphor, 3-benzylidene-d, 1-camphor, urocanic acid, urocanin Acid S 2-phenyl-5-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-pentane- Examples include 2-one, benzoic acid ultraviolet absorbers, anthranilic acid ultraviolet absorbers, salicylic acid ultraviolet absorbers, cinnamic acid ultraviolet absorbers, and benzophenone ultraviolet absorbers.

  Other optional components include (poly) ethylene glycol, (poly) propylene glycol, glycerin, 1,3-butylene glycol, maltitol, sorbitol, chondroitin sulfate, hyaluronic acid, atelocollagen, cholesteryl-1,2-hydroxystearate Moisturizers such as sodium lactate, bile salts, dl-pyrrolidone carboxylate, short chain soluble collagen, sodium aspartate, antibacterial agents such as hinokitiol, hexachlorophene, benzalkonium chloride, trichlorocarbanilide and pithionol, chloride Vasodilators such as carpronium, refreshing agents such as menthols, stimulating agents such as benzyl nicotinate, vitamins such as vitamins A, B, C, D, E, chlorhexidine gluconate, isopropylmethyl Bactericidal preservatives such as diols and paraoxybenzoic acid esters, protein hydrolysates, amino acids, plant extracts, chelating agents such as EDTA-Na, pH adjusters such as succinic acid, sodium succinate, and triethanolamine, foam increase Agent, foaming agent, foam stabilizer, in the case of aerosol products, propellant such as liquefied petroleum gas, dimethyl ether, metal ion scavenger, antifungal agent, disinfectant, emulsion agent, conditioning agent, thickener, antioxidant , Solubilizer, rosin, hydrotrope, hair nourishing agent, herbal medicine, pigment, fragrance and the like.

  Also, known cationic, anionic, amphoteric or nonionic synthetic, semi-synthetic or natural polymers different from the present embodiment can be used in combination.

  Examples of the cationic polymer include vinyl imidazolium chlorides such as trade names “RUBICUT FC370”, “RUBICUT FC550”, “RUBICUT FC905”, “RUBICUT HM552”, “RUBICUT MonoCP” (above, manufactured by BASF). / Hydroxyethyl cellulose such as vinylpyrrolidone copolymer, trade name “Celcut H-100 (viscosity 1000 mPa · s)”, trade name “Celcut L-200 (viscosity 100 mPa · s)” (National Starch) Dimethyldiallylammonium chloride, homopolymers of diallyldimethylammonium chloride such as trade names “Mercoat 100” and “Mercoat 550”, and copolymers of diallyldimethylammonium chloride and acrylamide, and tarpoly containing these -(For example, trade name "Mercoat 3331"), a copolymer or terpolymer containing methacrylamidopropyltrimethylammonium chloride (for example, trade name "Mercoat 2001"), etc. (above, manufactured by Nalco), trade name "Guffcut 734" , Vinyl pyrrolidone / quaternized dimethylaminoethyl methacrylate copolymers such as “Guff Cut 755N” and “Guff Cut 755” (manufactured by ISP), trade name “Rubiflex” (manufactured by BASF), trade name “Copolymer 845”, Polyvinylpyrrolidone / alkylamino acrylate copolymers such as “Copolymer 937” and “Copolymer 958” (from ISP), and polyvinyl pyrrolidone / alkylamino acrylate / vinyl cap such as “Copolymer VC-713” (from ISP) Lactam copolymer, vinylpyrrolidone / methacrylamidopropyl trimethylammonium chloride copolymer such as trade name “Guffcut HS-100 (ISP)”, N, N-dimethylaminoethyl diethyl methacrylate whose component name is “Polyquaternium-52” A copolymer of sulfate, N, N-dimethylacrylamide and polyethylene glycol dimethacrylate, an alkylacrylamide / acrylate / alkylaminoalkylacrylamide / polyethylene glycol methacrylate copolymer such as a water-soluble polymer described in JP-A-2-180911, N-propionyl polyethyleneimine / methyl polysiloxane copolymer, acrylamide / acrylic acid / methacrylic acid alkyl ester / methoxy polyethylene glycol Copolymers, acrylamide / alkyl acrylate copolymers, and the like.

  Examples of the anionic polymer include methyl vinyl ether / maleic anhydride such as trade name “GANTREZ ES-225”, trade name “GANTREZ ES-425”, trade name “GANTREZ SP-215” (manufactured by ISP). Alkyl half ester copolymer, vinyl acetate / crotonic acid copolymer such as trade name “resin 28-1310” (manufactured by National Starch), trade name “ruby set CA” (manufactured by BASF), trade name “resin 28-2930” ( National Starch Co., Ltd.) and other vinyl acetate / crotonic acid / vinyl neodecanoate copolymers, trade name “Rubiset CAP” (BASF) and other vinyl acetate / crotonate / vinyl propionate copolymers, trade name “ADVANTAGE CP” ( (Made by ISP) Vinyl acetate / maleic acid mono Tyrester / isopolonyl acrylate copolymer, trade name “Plus Size L53P”, trade name “Plus Size L-75CB”, trade name “Plus Size L-9540B” (manufactured by Kyoyo Chemical), trade name “Diahold” (Mitsubishi) (Meth) acrylic acid / (meth) acrylic acid alkyl ester copolymers such as Chemicals), trade names “Ultrahold 8”, “Ultrahold Strong” (above, manufactured by BASF), trade names “Unformer V” -42 "(National Starch Co., Ltd.) and other acrylic acid / acrylic acid alkyl ester / alkyl acrylamide copolymers, and trade name" Rubiflex VBM35 "(BASF Co., Ltd.) and other polyvinylpyrrolidone / acrylate / (meth) acrylic acid copolymers, etc. The component name is “Polyurethane-1” And urethane polymers such as copolymers of isophthalic acid, adipic acid, hexylene glycol, neopentyl glycol, dimethylolpropionic acid and isophorone diisocyanate.

  Examples of the zwitterionic polymer include N-methacryloyloxy having the trade names “Yukaformer SM”, “Yukaformer 301”, “Yukaformer 205S”, “Yukaformer 201”, “Yukaformer W”, and the like (manufactured by Mitsubishi Chemical Corporation). Ethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / methacrylic acid alkyl ester copolymer, trade names “Amformer 28-4910”, “Amformer LV-71” (National Starch, Inc.) ) And other hydroxypropyl acrylate / butylaminoethyl methacrylate / octylamide acrylate copolymers.

  Nonionic polymers include, for example, trade names “Lubicol K12”, “Rubicol K17”, “Rubicol K30”, “Rubicol K60”, “Rubicol K80”, “Rubicol K90” (above, BASF). ), Trade names “PVP K15”, “PVP K30”, “PVP K60”, “PVP K90” (and above, manufactured by ISP), etc., trade names “Lubicol VA28”, “Lubicol VA37” , “Luviscor VA55”, “Luviscor VA64”, “Lubicol VA73”, “Lubicol VA37E” (manufactured by BASF), trade names “PVP / VA E-735”, “PVP / VA E-635” ”,“ PVP / VA E-535 ”,“ PVP / VA E-335 ”,“ PVP / VA S-63 ” ”,“ PVP / VA W-735 ”(manufactured by ISP Co., Ltd.), etc., and polyvinyl pyrrolidone / vinyl acetate / vinyl propionate copolymers such as“ Lubicol VAP343 ”(BASF Corp.) And vinyl acetate / N-vinyl-5-methyl-2-oxazoline copolymer such as trade name “Dowtex” (manufactured by Dow Chemical Co., Ltd.).

(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.

50 mass% acrylamide aqueous solution 506.14 g, 65 mass% diallyldimethylammonium chloride aqueous solution 379.90 g, 5 mass% hydroxyethyl cellulose (manufactured by Sumitomo Seika Co., Ltd., 2 mass% aqueous solution viscosity at 25 ° C. by B-type viscometer is 450 mPa · s) ) 50.00 g of aqueous solution and 38.97 g of pure water were mixed and adjusted to pH 5.0 with dilute sulfuric acid. To the mixed solution was added 12.50 g of 0.2% by weight aqueous sodium riboflavin-5′-phosphate ester solution under light shielding and 12.50 g of 10% by weight aqueous ammonium persulfate solution, and while replacing the dissolved oxygen with nitrogen gas, The temperature was adjusted to 25 ° C. The whole amount of the aqueous solution was supplied to a stainless steel container (408 mm × 290 mm) coated with polyvinylidene chloride resin, and the upper part was covered with one polyvinylidene chloride film (Asahi Kasei Home Products Co., Ltd.). Above this, a 20 W fluorescent lamp (Toshiba FL20SS-EDC / 18PDL) was installed, and the illuminance was adjusted to 20,000 lx. The temperature of the aqueous solution immediately increased after the start of visible light irradiation, and reached the peak temperature after 5 minutes. The polymer obtained by irradiation with visible light for 60 minutes was a transparent and elastic water-containing gel. The obtained hydrogel was cut into small pieces with scissors and then dissolved with pure water to a concentration of 1% by mass, and the viscosity at 25 ° C. (B-type viscometer, rotor rotation speed 30 rpm) was measured. -Shown s. This is designated as Polymer 1.

509.82 g of 50 mass% acrylamide aqueous solution, 223.22 g of 65 mass% diallyldimethylammonium chloride aqueous solution, 1.5 mass% guar gum (RG500 manufactured by MRC Polysaccharide Co., Ltd., 2 mass% aqueous solution viscosity at 25 ° C. by B-type viscometer Was mixed with 66.67 g of an aqueous solution and 182.30 g of pure water, and the pH was adjusted to 4.0 using dilute sulfuric acid. To the mixed solution was added 0.200% by weight sodium riboflavin-5′-phosphate ester aqueous solution 6.00 g and 12.00 g of 10% by weight aqueous hydrogen peroxide solution under light shielding, while replacing dissolved oxygen with nitrogen gas, The liquid temperature was adjusted to 25 ° C. The whole amount of the aqueous solution was supplied to a stainless steel container (408 mm × 290 mm) coated with polyvinylidene chloride resin, and the upper part was covered with one polyvinylidene chloride film (Asahi Kasei Home Products Co., Ltd.). Above this, a 20 W fluorescent lamp (Toshiba FL20SS-EDC / 18PDL) was installed, and the illuminance was adjusted to 20,000 lx. The temperature of the aqueous solution immediately increased after the start of visible light irradiation, and reached the peak temperature after 18 minutes. The polymer obtained by irradiation with visible light for 70 minutes was in the form of a transparent and elastic hydrous gel. The obtained hydrogel was cut into small pieces with scissors, dissolved in pure water to a concentration of 1% by mass, and the viscosity at 25 ° C. (B-type viscometer, rotor rotation speed 30 rpm) was measured. -Shown s. This is designated as Polymer 2.

397.17 g of a 50% by weight acrylamide aqueous solution, 463.72 g of a 65% by weight diallyldimethylammonium chloride aqueous solution, 1.5% by weight hydroxypropyl guar gum (Jaguar HP-08, manufactured by Sanki Co., Ltd., 2 at 25 ° C. using a B-type viscometer 100.00 g of an aqueous solution having a mass% aqueous solution viscosity of 35,000 mPa · s) and 2.86 g of pure water were mixed, and the pH was adjusted to 4.5 using dilute sulfuric acid. To the mixed solution was added 6.25 g of 0.2% by mass riboflavin-5′-phosphate sodium phosphate aqueous solution and 30.00 g of 10% by mass ammonium persulfate aqueous solution under light shielding, while replacing the dissolved oxygen with nitrogen gas. The temperature was adjusted to 25 ° C. The whole amount of the aqueous solution was supplied to a stainless steel container (408 mm × 290 mm) coated with polyvinylidene chloride resin, and the upper part was covered with one polyvinylidene chloride film (Asahi Kasei Home Products Co., Ltd.). Above this, a 20 W fluorescent lamp (Toshiba FL20SS-EDC / 18PDL) was installed, and the illuminance was adjusted to 20,000 lx. The temperature of the aqueous solution immediately increased after the start of visible light irradiation, and reached the peak temperature after 10 minutes. The polymer obtained by irradiation with visible light for 50 minutes was a transparent and elastic hydrous gel. The obtained hydrogel was cut into small pieces with scissors, dissolved in pure water to a concentration of 1% by mass, and the viscosity at 25 ° C. (B-type viscometer, rotor rotation speed 30 rpm) was measured. -Shown s. This is designated as Polymer 3.

50% by mass acrylamide aqueous solution 478.86 g, 65% by mass diallyldimethylammonium chloride aqueous solution 93.18 g, 1.5% by mass locust bean gum (manufactured by Wako Pure Chemical Industries, Ltd., 2% by mass aqueous solution viscosity at 25 ° C. by B-type viscometer (1,350 mPa · s) 60.00 g of an aqueous solution and 334.21 g of pure water were mixed and adjusted to pH 5.0 with dilute sulfuric acid. To the mixed solution, 3.75 g of 0.2% by weight sodium riboflavin-5′-phosphate ester aqueous solution and 30.00 g of 10% by weight ammonium persulfate aqueous solution were added under light shielding, and the dissolved oxygen was replaced with nitrogen gas. The temperature was adjusted to 25 ° C. The whole amount of the aqueous solution was supplied to a stainless steel container (408 mm × 290 mm) coated with polyvinylidene chloride resin, and the upper part was covered with one polyvinylidene chloride film (Asahi Kasei Home Products Co., Ltd.). Above this, a 20 W LED lamp (Toshiba LDL20T · N / 13/12) was installed, and the illuminance was adjusted to 20,000 lx. The temperature of the aqueous solution immediately increased after the start of visible light irradiation, and reached the peak temperature after 5 minutes. The polymer obtained by irradiation with visible light for 25 minutes was in the form of a transparent and elastic hydrous gel. The obtained water-containing gel was cut into small pieces with scissors, dissolved in pure water to a concentration of 1% by mass, and the viscosity at 25 ° C. (B-type viscometer, rotor rotation speed 30 rpm) was measured. -Shown s. This is designated as Polymer 4.

50 mass% acrylamide aqueous solution 506.14 g, 80 mass% methacryloyloxyethyltrimethylammonium chloride aqueous solution 396.21 g, 5 mass% hydroxyethyl cellulose (manufactured by Sumitomo Seika Co., Ltd., 2 mass% aqueous solution viscosity at 25 ° C. by B type viscometer is 450 mPa S) 50.00 g of an aqueous solution and 22.65 g of pure water were mixed and adjusted to pH 5.5 using dilute sulfuric acid. Under a light shielding condition, 12.50 g of a 0.2% by weight rose bengal aqueous solution and 12.50 g of a 10% by weight aqueous ammonium persulfate solution were added to the mixed solution, and the liquid temperature was adjusted to 25 ° C. while replacing the dissolved oxygen with nitrogen gas. . The whole amount of the aqueous solution was supplied to a stainless steel container (408 mm × 290 mm) coated with polyvinylidene chloride resin, and the upper part was covered with one polyvinylidene chloride film (Asahi Kasei Home Products Co., Ltd.). Above this, a 20 W fluorescent lamp (Toshiba FL20SS-EDC / 18PDL) was installed, and the illuminance was adjusted to 20,000 lx. The temperature of the aqueous solution immediately increased after the start of visible light irradiation, and reached the peak temperature after 40 minutes. The polymer obtained by irradiation with visible light for 80 minutes was a transparent and elastic hydrous gel. The obtained hydrogel was cut into small pieces with scissors and then dissolved with pure water to a concentration of 1% by mass, and the viscosity at 25 ° C. (B-type viscometer, rotor rotation speed 30 rpm) was measured. -Shown s. This is designated as Polymer 5.

455.52 g of 50 mass% acrylamide aqueous solution, 378.53 g of 75 mass% acryloylaminopropyltrimethylammonium chloride aqueous solution, 5 mass% hydroxyethyl cellulose (manufactured by Sumitomo Seika Co., Ltd., 2 mass% aqueous solution viscosity at 25 ° C. by B-type viscometer is 450 mPa S) 45.00 g of an aqueous solution and 98.45 g of pure water were mixed and adjusted to pH 5.0 using dilute sulfuric acid. To the mixed solution was added 11.25 g of 0.2% by weight aqueous sodium riboflavin-5′-phosphate ester solution under shading, and 11.25 g of 10% by weight aqueous ammonium persulfate aqueous solution. The temperature was adjusted to 25 ° C. The whole amount of the aqueous solution was supplied to a stainless steel container (408 mm × 290 mm) coated with polyvinylidene chloride resin, and the upper part was covered with one polyvinylidene chloride film (Asahi Kasei Home Products Co., Ltd.). Above this, a 20 W fluorescent lamp (Toshiba FL20SS-EDC / 18PDL) was installed, and the illuminance was adjusted to 20,000 lx. The temperature of the aqueous solution immediately increased after the start of visible light irradiation, and reached the peak temperature after 5 minutes. The polymer obtained by irradiation with visible light for 40 minutes was a transparent and elastic water-containing gel. The obtained hydrogel was cut into small pieces with scissors, dissolved in pure water to a concentration of 1% by mass, and the viscosity at 25 ° C. (B-type viscometer, rotor rotation speed 30 rpm) was measured. -Shown s. This is designated as Polymer 6.

253.07 g of 50% by weight acrylamide aqueous solution, 189.95 g of 65% by weight diallyldimethylammonium chloride aqueous solution (manufactured by Sumitomo Seika Co., Ltd., 2% by weight aqueous solution viscosity at 25 ° C. by B-type viscometer is 450 mPa · s) ) 25.00 g of aqueous solution and 19.48 g of pure water were mixed and adjusted to pH 6.0 using dilute sulfuric acid. To the mixed solution was added 6.25 g of 0.2% by mass aqueous sodium riboflavin-5′-phosphate ester solution under light shielding and 6.25 g of 10% by mass aqueous ammonium persulfate solution, and while replacing the dissolved oxygen with nitrogen gas, The temperature was adjusted to 25 ° C. The entire amount of the aqueous solution was supplied to a hard glass petri dish (φ120 mm × 60 mm), and the upper part was covered with one hard glass plate (150 mm × 150 mm). Above this, a 20 W fluorescent lamp (Toshiba FL20SS-EDC / 18PDL) was installed, and the illuminance was adjusted to 20,000 lx. The temperature of the aqueous solution immediately increased after the start of visible light irradiation, and reached the peak temperature after 5 minutes. The polymer obtained by irradiation with visible light for 60 minutes was a transparent and elastic water-containing gel. The obtained hydrogel was cut into small pieces with scissors and then dissolved with pure water to a concentration of 1% by weight. As a result, some insoluble components remained. When the viscosity (B-type viscometer, rotor rotation speed 30 rpm) at 25 ° C. of 1% by mass was measured, it was 10.0 mPa · s. This is designated as Polymer 7.

50 mass% acrylamide aqueous solution 506.14 g, 65 mass% diallyldimethylammonium chloride aqueous solution 379.90 g, 10 mass% hydroxyethyl cellulose (manufactured by Sumitomo Seika Co., Ltd., 2 mass% aqueous solution viscosity at 25 ° C. by B-type viscometer is 450 mPa · s) ) 100.00 g of aqueous solution and 1.47 g of pure water were mixed and adjusted to pH 5.5 with dilute sulfuric acid. To this mixed solution, 6.25 g of 0.4 mass% riboflavin-5′-phosphate sodium aqueous solution and 6.25 g of 20 mass% ammonium persulfate aqueous solution were added under light shielding, while replacing the dissolved oxygen with nitrogen gas, The temperature was adjusted to 25 ° C. The whole amount of the aqueous solution was supplied to a stainless steel container (408 mm × 290 mm) coated with polyvinylidene chloride resin, and the upper part was covered with one polyvinylidene chloride film (Asahi Kasei Home Products Co., Ltd.). Above this, a 20 W fluorescent lamp (Toshiba FL20SS-EDC / 18PDL) was installed, and the illuminance was adjusted to 20,000 lx. The temperature of the aqueous solution immediately increased after the start of visible light irradiation, and reached the peak temperature after 5 minutes. The polymer obtained by irradiation with visible light for 60 minutes was a transparent and elastic water-containing gel. The obtained hydrogel was cut into small pieces with scissors and then dissolved with pure water to a concentration of 1% by weight. As a result, some insoluble components remained. When the viscosity (B-type viscometer, rotor rotation speed 30 rpm) at 25 ° C. of 1% by mass was measured, it was 1.0 mPa · s. This is designated as Polymer 8.

470.75 g of 80% by weight acryloyloxyethyltrimethylammonium chloride aqueous solution, 5.50 g of 5% by weight hydroxyethyl cellulose (manufactured by Sumitomo Seika, 2% by weight aqueous solution viscosity at 25 ° C. with a B-type viscometer is 450 mPa · s), pure 12.50 g of water was mixed and adjusted to pH 5.0 using dilute sulfuric acid. To the mixed solution was added 9.38 g of 0.2% by weight aqueous sodium riboflavin-5′-phosphate ester solution under light shielding and 1.88 g of 10% by weight aqueous potassium persulfate solution, and the dissolved oxygen was replaced with nitrogen gas. The liquid temperature was adjusted to 25 ° C. The whole amount of the aqueous solution was supplied to a stainless steel container (408 mm × 290 mm) coated with polyvinylidene chloride resin, and the upper part was covered with one polyvinylidene chloride film (Asahi Kasei Home Products Co., Ltd.). Above this, a 20 W fluorescent lamp (Toshiba FL20SS-EDC / 18PDL) was installed, and the illuminance was adjusted to 20,000 lx. The temperature of the aqueous solution immediately increased after the start of visible light irradiation, and reached the peak temperature after 15 minutes. The polymer obtained by irradiation with visible light for 60 minutes was a transparent and elastic water-containing gel. The obtained hydrogel was cut into small pieces with scissors and then dissolved with pure water to a concentration of 1% by mass, and the viscosity at 25 ° C. (B-type viscometer, rotor rotation speed 30 rpm) was measured to be 45.5 mPa. -Shown s. This is designated as Polymer 9.

50% by weight acrylamide aqueous solution 397.20 g, 80% by weight acrylic acid aqueous solution 251.75 g, 10% by weight sericin (manufactured by Cashiro Sangyo Co., Ltd., 2% by weight aqueous solution viscosity at 25 ° C. by B-type viscometer is 16 mPa · s) 00 g and 77.95 g of pure water were mixed, and the pH was adjusted to 8.5 using 233.10 g of a 48% by mass aqueous sodium hydroxide solution. To the mixed solution was added 10.00 g of 0.2% by mass aqueous sodium riboflavin-5′-phosphate ester solution under light shielding and 10.00 g of 10% by mass aqueous ammonium persulfate solution, and the solution was replaced with nitrogen gas while replacing dissolved oxygen. The temperature was adjusted to 25 ° C. The whole amount of the aqueous solution was supplied to a stainless steel container (408 mm × 290 mm) coated with polyvinylidene chloride resin, and the upper part was covered with one polyvinylidene chloride film (Asahi Kasei Home Products Co., Ltd.). Above this, a 20 W fluorescent lamp (Toshiba FL20SS-EDC / 18PDL) was installed, and the illuminance was adjusted to 20,000 lx. The temperature of the aqueous solution immediately increased after the start of visible light irradiation, and reached the peak temperature after 10 minutes. The polymer obtained by irradiation with visible light for 60 minutes was a transparent and elastic water-containing gel. The obtained hydrogel was cut into small pieces with scissors and then dissolved with pure water to a concentration of 1% by mass, and the viscosity at 25 ° C. (B-type viscometer, rotor rotation speed 30 rpm) was measured to be 65.0 mPa -Shown s. This is designated as Polymer 10.

200.00 g of 50 mass% acrylamide aqueous solution, 5 mass% hydroxyethylcellulose (manufactured by Sumitomo Seika, 2 mass% aqueous solution viscosity at 25 ° C. by B-type viscometer is 450 mPa · s), 200.00 g of aqueous solution, and 595.00 g of pure water. Mix and adjust to pH 5.5 using dilute sulfuric acid. To the mixed solution, 2.50 g of 0.2% by mass aqueous sodium riboflavin-5′-phosphate ester solution and 2.50 g of 10% by mass ammonium persulfate aqueous solution were added under light shielding, and the dissolved oxygen was replaced with nitrogen gas. The temperature was adjusted to 25 ° C. The whole amount of the aqueous solution was supplied to a stainless steel container (408 mm × 290 mm) coated with polyvinylidene chloride resin, and the upper part was covered with one polyvinylidene chloride film (Asahi Kasei Home Products Co., Ltd.). Above this, a 20 W fluorescent lamp (Toshiba FL20SS-EDC / 18PDL) was installed, and the illuminance was adjusted to 20,000 lx. The temperature of the aqueous solution immediately increased after the start of visible light irradiation, and reached the peak temperature after 20 minutes. The polymer obtained by irradiation with visible light for 60 minutes was a transparent and elastic water-containing gel. The obtained hydrogel was cut into small pieces with scissors and then dissolved with pure water to a concentration of 1% by weight. As a result, some insoluble components remained. When the viscosity (B-type viscometer, rotor rotation speed 30 rpm) at 25 ° C. of 1% by mass was measured, it was 2.0 mPa · s. This is designated as Polymer 11.

(Comparative Example 1)
50 mass% acrylamide aqueous solution 506.14 g, 65 mass% diallyldimethylammonium chloride aqueous solution 379.90 g, 5 mass% hydroxyethyl cellulose (manufactured by Sumitomo Seika Co., Ltd., 2 mass% aqueous solution viscosity at 25 ° C. by B-type viscometer is 450 mPa · s) ) Mix 50.00 g of aqueous solution and 51.47 g of pure water, add 12.50 g of 0.2 mass% riboflavin-5′-phosphate sodium salt aqueous solution to the mixture under light shielding, and dissolve dissolved oxygen with nitrogen gas. While replacing, the liquid temperature was adjusted to 25 ° C. The whole amount of the aqueous solution was supplied to a stainless steel container (408 mm × 290 mm) coated with polyvinylidene chloride resin, and the upper part was covered with one polyvinylidene chloride film (Asahi Kasei Home Products Co., Ltd.). Above this, a 20 W fluorescent lamp (Toshiba FL20SS-EDC / 18PDL) was installed, and the illuminance was adjusted to 20,000 lx. No heat was generated due to the heat of polymerization after the start of visible light irradiation.

(Comparative Example 2)
50 mass% acrylamide aqueous solution 506.14 g, 65 mass% diallyldimethylammonium chloride aqueous solution 379.90 g, 5 mass% hydroxyethyl cellulose (manufactured by Sumitomo Seika Co., Ltd., 2 mass% aqueous solution viscosity at 25 ° C. by B-type viscometer is 450 mPa · s) ) 50.00 g of aqueous solution and 51.47 g of pure water were mixed, and 12.50 g of 10 mass% ammonium persulfate aqueous solution was added to the mixture under light shielding, and the liquid temperature was 25 ° C. while replacing the dissolved oxygen with nitrogen gas. Adjusted. The whole amount of the aqueous solution was supplied to a stainless steel container (408 mm × 290 mm) coated with polyvinylidene chloride resin, and the upper part was covered with one polyvinylidene chloride film (Asahi Kasei Home Products Co., Ltd.). Above this, a 20 W fluorescent lamp (Toshiba FL20SS-EDC / 18PDL) was installed, and the illuminance was adjusted to 20,000 lx. No heat was generated due to the heat of polymerization after the start of visible light irradiation.

(Comparative Example 3)
50 mass% acrylamide aqueous solution 506.14 g, 65 mass% diallyldimethylammonium chloride aqueous solution 379.90 g, 5 mass% hydroxyethyl cellulose (manufactured by Sumitomo Seika Co., Ltd., 2 mass% aqueous solution viscosity at 25 ° C. by B-type viscometer is 450 mPa · s) ) 50.00 g of an aqueous solution and 22.30 g of pure water were mixed, and 3 wt% 2,2′-azobis [N- (2-hydroxyethyl) -2-methylpropanamide] aqueous solution was added to the mixture under light shielding. 67 g was added, and the liquid temperature was adjusted to 25 ° C. while replacing dissolved oxygen with nitrogen gas. The whole amount of the aqueous solution was supplied to a stainless steel container (408 mm × 290 mm) coated with polyvinylidene chloride resin, and the upper part was covered with one polyvinylidene chloride film (Asahi Kasei Home Products Co., Ltd.). Above this, a 20 W fluorescent lamp (Toshiba FL20SS-EDC / 18PDL) was installed, and the illuminance was adjusted to 20,000 lx. No heat was generated due to the heat of polymerization after the start of visible light irradiation.

(Comparative Example 4)
50 mass% acrylamide aqueous solution 506.14 g, 65 mass% diallyldimethylammonium chloride aqueous solution 379.90 g, 5 mass% hydroxyethyl cellulose (manufactured by Sumitomo Seika Co., Ltd., 2 mass% aqueous solution viscosity at 25 ° C. by B-type viscometer is 450 mPa · s) ) 50.00 g of an aqueous solution and 9.80 g of pure water were mixed, and the mixed solution was shielded from light by 0.2% by weight of a 0.2% by weight riboflavin-5′-phosphate sodium aqueous solution and 3% by weight 2,2′-azobis. 41.67 g of an [N- (2-hydroxyethyl) -2-methylpropanamide] aqueous solution was added, and the liquid temperature was adjusted to 25 ° C. while replacing the dissolved oxygen with nitrogen gas. The whole amount of the aqueous solution was supplied to a stainless steel container (408 mm × 290 mm) coated with polyvinylidene chloride resin, and the upper part was covered with one polyvinylidene chloride film (Asahi Kasei Home Products Co., Ltd.). Above this, a 20 W fluorescent lamp (Toshiba FL20SS-EDC / 18PDL) was installed, and the illuminance was adjusted to 20,000 lx. No heat was generated due to the heat of polymerization after the start of visible light irradiation.

  Table 1 shows Examples 1 to 11, Table 2 Comparative Examples 1 and 2, Table 3 Comparative Examples 3 and 4, monomer composition, monomer concentration, organic dye addition amount, peroxide addition amount, light source Type, time to reach temperature rise peak due to heat generation, 1% by mass viscosity measurement value at 25 ° C (B-type viscometer, rotor rotation speed 30 rpm), and whether the photopolymerization reaction of each example condition progressed The result of whether or not was described. Under each reaction condition, sudden heat generation occurred within 120 minutes after the start of visible light irradiation, and the reaction proceeded (○) when it became a solid state such as a high-viscosity solution or hydrous gel, and visible light irradiation started. Even after 120 minutes passed, no exotherm occurred, and it was judged that the reaction did not proceed (x) when the liquid state having the same viscosity as before the reaction started was maintained.

(Table 1)
Monomer composition: mol%
AAm: acrylamide DADMAC: diallyldimethylammonium chloride MMCQ: methacryloyloxyethyltrimethylammonium chloride DMAPAAQ: acryloylaminopropyltrimethylammonium chloride AMCQ: acryloyloxyethyltrimethylammonium chloride AA: acrylic acid HEC: hydroxyethylcellulose GUR: guar gum HPG: hydroxypropyl guar gum LBG : Locust bean gum Rf: Riboflavin-5′-phosphate sodium salt Rb: Rose Bengal APS: Ammonium persulfate KPS: Potassium persulfate H ₂ O ₂ : Hydrogen peroxide

(Table 2)
Monomer composition: mol%

(Table 3)
Monomer composition: mol%
VA086: 2,2′-azobis [N- (2-hydroxyethyl) -2-methylpropanamide]

  As is apparent from the results of Table 1, in the process of polymerizing a natural polymer having an OH group and / or a natural polymer derivative and one or more water-soluble monomers having a vinyl group, an organic dye and a peroxide are polymerized. Coexisting, the reaction proceeded sufficiently by irradiation with visible light, and the intended polymer was obtained. However, as shown in Table 2, when the organic dye alone (Comparative Example 1) or peroxide alone (Comparative Example 2) was added, the temperature did not increase after visible light irradiation and the reaction did not proceed. Table 3 shows the results using VA086, which is a general photopolymerization initiator used under ultraviolet irradiation. VA086 alone (Comparative Example 3), VA086 and riboflavin-5'-sodium phosphate sodium were added at the same time (Comparative Example 4), but no increase in temperature was observed with visible light irradiation under any conditions. The reaction did not proceed. From these results, when polymerizing a natural polymer having an OH group and / or a natural polymer derivative and a water-soluble monomer having one or more vinyl groups by irradiation with visible light, an organic dye and a peroxide It has been found that satisfactory polymer can be obtained by simultaneous addition.

Polymers 1-8, commercially available cationic polymer HC-100 (polyquaternium-10) manufactured by Toho Chemical Co., Ltd. and MERQUAT550 (polyquaternium-7) manufactured by Nalco were dissolved in the composition shown in Table 4 to prepare a shampoo solution. However, insoluble components were present in the dissolved solutions of polymers 7 and 8, and the insoluble components remained in the prepared shampoo solution, so they were excluded from this shampoo test. 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 5 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 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 The sensory evaluation was performed on the feeling and feeling of the comb after washing, and the usability of a 0.6 mass% shampoo solution of polyquaternium-10 was evaluated as a standard value 3 and evaluated according to the criteria shown in Table 5. The results are shown in Table 6, and the feeling of use of a commercial cationic polymer as a control product is shown in Table 7.

(Table 4) Shampoo solution composition

(Table 5)

(Table 6)

(Table 7)

As is clear from the comparison of the results in Table 6 and Table 7, in Polyquaternium-10, the conditioning effect is reduced when the addition amount is 0.4% by mass or less, whereas the polymers 1 to 6 of the present invention are It was found that a high conditioning effect can be obtained with an addition amount of about 0.1% by mass. Moreover, in the case of polyquaternium-7, the spinnability was caused by the addition of 0.2% by mass or more, which hindered foaming. It was found that polymers 1 to 6 of the present invention did not cause unpleasant spinnability despite high addition, and produced fine creamy bubbles in a short time from the start of foaming. In particular, the polymers 1 and 3 having a high cationic monomer content are remarkably excellent in the effect of improving the foam quality, and the polymers 2 and 4 having a low cationic monomer content are refreshed relatively quickly. It was found to be a characteristic to show the touch. By comparing the results of the polymers 5 and 6 with the polymers 1 to 4, it was also found that the feeling of use can be changed by changing the type of the cationic monomer.

Polymers 1, 3, 6 and commercially available cationic polymer MERQUAT100 (polyquaternium-6) manufactured by Nalco were dissolved in the composition shown in Table 8 to prepare a conditioner solution. The balance in Table 8 means the residual amount obtained by subtracting the described amounts of component A and component B from the total component of 100% by mass. About each sample, the usability as a hair conditioner was sensory-evaluated by the following method and evaluated according to the criteria shown in Table 9.
(1) Preparation of Component A A cationic surfactant, stearyl alcohol, and glutamic acid were stirred and melted at 75 ° C. Subsequently, purified water warmed to 75 ° C. was added to further dissolve.
(2) Preparation of Component B Each 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 4 was prepared and used to wash the hair. After washing, the softness when applying each conditioner used, smoothness when applying, smoothness when rinsing hair, good fingering after towel drying, good fingering right after drying, right 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 performed according to the criteria shown in Table 9. In the evaluation, a standard value 3 was used as the conditioner's comfort adjusted without addition of a cationic polymer. Table 10 shows the feeling of use of the polymer-free product, the polymers of Examples 1, 3, and 6, and the feeling of use of the commercial cationic polymer as a control product.

(Table 8)

(Table 9)

(Table 10)

From comparison of the results in Table 10, it was found that the polymers 1, 3, and 6 exhibited a high conditioning effect when added to the conditioner. This effect was higher than that of the existing product Polyquaternium-6. It was also 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 has an effect of softening the feel of the hair after drying.

Polymers 1, 3, and 6 and commercially available cationic polymer MERQUAT100 (Polyquaternium-6) manufactured by Nalco, MERQUAT550 (Polyquaternium-7) manufactured by Nalco, and HC-100 (Polyquaternium-10) manufactured by Toho Chemical Co., respectively, by 0.5% by mass Dissolved in concentration. 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 bundle of hair having a length of 35 cm was immersed in a dissolved 0.5 mass% 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 11 shows the blank values, the L0, L1, and L2 values of each of the polymers of Examples 1, 3, and 6 and the commercial cationic polymer that is a control and the feel after use.

(Table 11)

As is clear from the results in Table 11, in the polymers 1, 3, and 6, 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.

A polymer shampoo solution was prepared by dissolving Polymers 1 to 6 or a commercially available cationic polymer as Component B and dissolving it with Component A so as to have the composition shown in Table 12. For each sample, the feeling of use as a body shampoo was subjected to a sensory evaluation by the following method, and the feeling of use when the conditioner's comfort adjusted with no addition of a cationic polymer was set to the standard value 3 was based on the criteria shown in Table 13. evaluated.
(1) Preparation of component A Purified water was heated to 70 ° C., and lauric acid and myristic acid were added and stirred until dissolved. Normal potassium hydroxide was dissolved using a part of purified water, and the solution was added as an aqueous potassium hydroxide solution. Then, sodium laureth 3-sulfate and a betaine surfactant were added and stirred. Thereafter, stirring after addition of EDTA · 2Na · 2H ₂ O, cooled to room temperature.
(2) Preparation of Component B Each polymer and commercially available cationic polymer were dissolved in purified water at room temperature.
(3) Preparation of body shampoo solution Component A was heated to 70 ° C. and component B was added to obtain the composition shown in Table 12. Then, after fully stirring, it cooled to room temperature.
(4) Evaluation method For each body shampoo solution, a panel test was conducted by five panelists, and the sensory evaluation of foaming during washing, fineness of foam during washing, speed of rinsing, feel after rinsing, and feeling after towel drying did. The feeling of use of the body shampoo solution to which no cationic polymer was added was evaluated as “standard value: 3”, and the results are shown in Table 14. The feeling of use of the control commercial cationic polymer was also evaluated at the same time, and the results are shown in Table 14.

(Table 12)

(Table 13)

(Table 14)

As is apparent from Table 14, the polymers 1 to 6 were found to improve the foaming of the body shampoo. The generated foam is finer and creamy than Polyquaternium-7 and 10, and the amount of foam is large. It was confirmed that rinsing was quick and the feeling after rinsing was good. It was found that the feeling after towel drying was very good, and the skin was moist and smooth despite the fact that no moisturizer was used. When a body shampoo to which polyquaternium 7 or 10 was added was used, an unpleasant squeak was felt after towel drying, whereas the feel when using a body shampoo with addition of polymers 1 to 6 was very good. In particular, the polymers 1 and 3 having a high cationic monomer content are remarkably excellent in the effect of improving the foam quality, and the polymers 2 and 4 having a low cationic monomer content are refreshed relatively quickly. It was found that the touch was characteristic. By comparing the results of the polymers 5 and 6 with the polymers 1 to 4, it was also found that the feeling of use can be changed by changing the type of the cationic monomer.

By utilizing the present invention, it is possible to perform photopolymerization using a light source having as little light as possible in the ultraviolet region and a photosensitizer having an absorption band in the visible region, which is highly safe in the work environment. Furthermore, since the polymerization reaction of the polymer composition can be carried out in a short time and at a high concentration, and the polymer composition can be obtained with high production efficiency, it is considered that adaptation to the industry is extremely effective. In addition, the hair cosmetic additive obtained by the present invention and the hair cosmetic containing the same exhibit a high conditioning effect when added to the shampoo and conditioner, and are excellent in performance when added to the styling agent. It can be used for various hair cosmetics. Furthermore, the skin cleansing additive and the skin cleansing agent containing the same obtained by the present invention can finish the skin with a moist and smooth feel, and can be used in a wide range of applications including body shampoos, facial cleansing foams, hand soaps, etc. Can be used.

Claims (14)

Visible light irradiation to a solution containing an OH group-containing natural polymer and / or natural polymer derivative, a water-soluble monomer having one or more vinyl groups, an organic dye, and a peroxide in an aqueous medium. A polymer composition characterized by being polymerized. The total concentration of the water-soluble monomer and the natural polymer and / or natural polymer derivative having an OH group in the solution contained in the aqueous medium is 5% by mass to 90% by mass. The polymer composition according to claim 1. The polymer composition according to claim 1 or 2, wherein the organic dye is soluble in an aqueous medium in a pH range of 3 to 10. The polymer composition according to claim 1, wherein the light source for visible light irradiation is at least one selected from a fluorescent lamp, an LED fluorescent lamp, a metal halide lamp, a xenon lamp, and a mercury lamp. 4. The polymer according to claim 1, wherein at least one of the water-soluble monomers is a cationic monomer represented by the general formula (1) or the general formula (2). Composition.
General formula (1)
[Wherein, R ₁ represents a hydrogen atom or a methyl group, and R ₂ , R ₃ , and R ₄ are the same or different and each represents a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms. Show. Y represents —O—, —NH—, —CH ₂ —, or —O—CH ₂ CH (OH) —, Z represents a linear or branched alkylene group having 1 to 4 carbon atoms, and X ^- represents a conjugate base, a halogen atom or an alkyl sulfate group having 1 to 4 carbon atoms acid]
General formula (2)
[Wherein, R ₅ is the same or different and represents a hydrogen atom or a methyl group, R ₆ and R ₇ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X ⁻ is the same as defined above] Indicates meaning. ] Visible light irradiation to a solution containing an OH group-containing natural polymer and / or natural polymer derivative, a water-soluble monomer having one or more vinyl groups, an organic dye, and a peroxide in an aqueous medium. And polymerizing the polymer composition. Visible light irradiation to a solution containing an OH group-containing natural polymer and / or natural polymer derivative, a water-soluble monomer having one or more vinyl groups, an organic dye, and a peroxide in an aqueous medium. A hair cosmetic additive characterized by being polymerized. Visible light irradiation to a solution containing an OH group-containing natural polymer and / or natural polymer derivative, a water-soluble monomer having one or more vinyl groups, an organic dye, and a peroxide in an aqueous medium. A cosmetic for hair containing a hair-polymerized additive for hair. The hair cosmetics are rinses, conditioners, treatments, hair styling agents for setting, perm liquids, and hair dyes. Among the water-soluble monomers, the cationic water-soluble monomer is in the range of 5 to 100 mol%. The hair cosmetic composition according to claim 8, wherein the hair cosmetic composition is provided.   The hair cosmetic composition according to claim 8, wherein the hair cosmetic composition is a shampoo, and the cationic water-soluble monomer in the water-soluble monomer is in the range of 1 to 50 mol%. Visible light irradiation to a solution containing an OH group-containing natural polymer and / or natural polymer derivative, a water-soluble monomer having one or more vinyl groups, an organic dye, and a peroxide in an aqueous medium. An additive for skin cleanser characterized by being polymerized. Visible light irradiation to a solution containing an OH group-containing natural polymer and / or natural polymer derivative, a water-soluble monomer having one or more vinyl groups, an organic dye, and a peroxide in an aqueous medium. A skin cleanser containing an additive for skin cleanser which has been polymerized.   The skin cleanser is a body shampoo, a face-wash foam, a hand soap, or the like, and among the water-soluble monomers, the cationic water-soluble monomer is in the range of 5 to 100 mol%. 12. A skin cleanser as described in 12. The skin cleanser is a body shampoo, a face-wash foam, a hand soap, or the like, and a cationic water-soluble monomer in the water-soluble monomer is in a range of 5 to 50 mol%. 12. A skin cleanser as described in 12.