TW200406474A - Waterborne resin dispersion, hydrophilic resin composition and its manufacturing method - Google Patents

Abstract

This invention provides hydrophilic resin compositions which exhibit excellent weatherability and frost resistance and do not form hard binding. The invented waterborne resin dispersion is formed by suspending monomer mixture (A) containing (a) (meth)acrylate, (b) multi-functional crosslinkable monomer and (c) unsaturated monomer with UV stable group to form resin particles with average particle sizes of 1- 100 μ m.

Description

200406474 Rose, Description of the invention: [Technical field to which the invention belongs] & This description relates to an aqueous resin dispersion, an aqueous resin composition, and a method for manufacturing the same. In more detail, it can be used as a coating, a coating agent, an optical component, an electronic material, a medical examination medicine, and the like, as the most effective method of use " As an enamel and a transparent matte coating.先前 [Prior art]: Most matting agent compositions such as light coatings contain inorganic or organic particles in the composition. For aesthetic purposes, the water-based composition Daxi is used for the surface coating of building materials. T 刖, the particles used in the matting agent composition, inorganic particles, especially dioxin-based powders are the main ones, and are used because of their low cost. 'But π' has water resistance because of its water absorption, so it has water resistance. Questions on the subject are 'easy to whiten, and there are also weather resistance'! Health, frost, and eastern problems. On the other hand, there is an aqueous resin combination of a hydrophilic organic solvent in an aqueous dispersion of resin particles obtained by a suspension polymerization method in water by a method of mixing organic resin particles. (1). Xun Liwen However, the aqueous resin composition obtained by this method can form a hard dry knot, but it is easy to separate and sink. Because it forms a hard core, it must cost money to re-disperse, and there is a so-called industrial deficiency. 7 Wack Patent Document 1 Japanese Patent Publication 2000-313720 200406474 [Summary of the Invention] Problem to be Solved by the Invention Therefore, the object of the present invention is to provide a new type of aqueous resin dispersion. It is another object of the present invention to provide an aqueous resin composition excellent in weather resistance and a method for producing the same. Another object of the present invention is to provide an aqueous resin composition having low water absorption and excellent film transparency, high weather resistance and frost resistance, and a method for producing the same. Another objective of this month is to provide a network of particles by adding a tackifier to the suspension polymerization aqueous dispersion to suppress the contact of particles with each other and to suppress the formation of hard bonds, and the obtained aqueous dispersion can be used for several days. A non-settling economical and excellent aqueous resin composition and a method for producing the same. Means for solving the problems The above-mentioned objects are achieved by the following (i) to (7). (1) Aqueous resin dispersion containing (A) which will contain (a) (meth) acrylic acid, (b) a multifunctional crosslinkable monomer, and (0) having an ultraviolet stabilizing group and / or an ultraviolet absorbing group. Resin particles having an average particle size of 100 micrometers produced by suspension polymerization of a monomer component of a saturated monomer (i-th invention). (2) The aqueous resin dispersion according to the above (>), wherein (A) (〇 (fluorenyl) The acrylate is a (fluorenyl) acrylate having a cycloalkyl group and / or a tert-butyl group. (3) An aqueous resin composition containing (A) a compound containing (a) a cycloalkyl group and / or a tert-butyl group. Suspension polymerization of a monomer mixture of (meth) acrylate, (b) polyfunctional crosslinked 200,406,474 monomers and (c) unsaturated monomers having ultraviolet stabilizing groups and / or ultraviolet absorbing groups, and an average particle diameter of 1 to 1 An aqueous resin dispersion of 100 micron resin particles and (B) an aqueous resin dispersion containing resin particles having an average particle size of 0.001 to 1 micron (second invention). (4) Aqueous resin composition By (a) containing (methyl) which will contain (α) a cycloalkyl and / or tert-butyl (methyl Acrylate 50-99% by mass, (b) Polyfunctional crosslinkable monomers 0.1-20% by mass, and ((〇Other monomers 〇-499) Quality:% (wherein (a), (b) And (d) a total amount of 100% by mass) of the monomer mixture in suspension polymerization, and an aqueous resin dispersion containing resin particles having an average particle diameter of 1 to 100 microns and (B) containing an average particle diameter of the core ... Composition of micron-sized resin particles in an aqueous resin dispersion (3rd invention). (5) A method for producing an aqueous resin composition, characterized in that the aqueous resin dispersion contains resin particles having an average particle diameter of 1 to 100 micrometers formed by suspension polymerization. (C) A tackifier is added to the body, and (b) an aqueous resin dispersion containing resin particles having an average particle diameter of 0.01 to 1 micron (4th invention). (6) A method for producing an aqueous resin composition, which is characterized by It consists in containing (A) a (meth) acrylate having a cycloalkyl group and / or a tert-butyl group, (b) a polyfunctional crosslinkable monomer, and (c) containing a UV-stabilizing group and / or ultraviolet absorption. Average particle size of monomer mixtures based on unsaturated monomers (C) A desiccant is added to an aqueous resin dispersion of resin particles of 1 to 100 micrometers, and (B) an aqueous resin dispersion containing resin particles having an average particle diameter of 0 0 micrometers (5th invention). (7) ) A method for producing an aqueous resin composition, comprising 200406474 containing (A) a (meth) acrylic acid ester having a cyclohexyl group and / or a tert-butyl group 5 " mass%, ⑴ polyfunctional crosslinkability A monomer mixture of 0 to 20% by mass and ⑷ other monomers of 0 to 49.9% by mass (wherein "", osmium and osmium total 100% by mass) of a monomer mixture produced by suspension polymerization have an average particle diameter of 1 to 100 microns. (C) A thickening agent is added to the aqueous resin dispersion of resin particles, and an aqueous resin dispersion containing resin particles having an average particle diameter of 0.0M microns is mixed (sixth invention). ADVANTAGE OF THE INVENTION Since the present invention has a structure as described above, the prepared aqueous resin dispersion and aqueous resin composition can form a film excellent in transparency, weather resistance, and frost resistance. In addition, by adding a tackifier to the suspension polymerization aqueous dispersion, a mesh can be formed between the particles, the contact between the particles is suppressed, the formation of hard adhesion is suppressed, and the obtained aqueous dispersion is economical that does not settle after several days. Excellent water-based resin composition. [Embodiment] The (A) (a) (meth) acrylate used as the monomer of the present invention is as follows. (a) Specific examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylate-2 — Ester of (meth) acrylic acid such as ethylhexyl ester and alcohols of C1 to C18 (including aliphatic, cycloaliphatic, and aromatic), ie (meth) methacrylic acid (meth) acrylic acid-2 g, (meth) acrylic acid to 2-hydroxypropyl, monoesters of (meth) acrylic acid and polypropylene glycol, etc. (meth) acrylic acid esters having 200,406,474 hydroxyl groups. Preferred examples include (meth) acrylic acids having a cycloalkyl group and (fluorenyl) acrylic acids having a tert-butyl group, and more preferred are (meth) acrylic acids having a cycloalkyl group. As the cycloalkyl structure in the polymerizable unsaturated monomer having the above-mentioned cycloalkyl group, a 'cyclobutyl structure, a cyclopentyl structure, a cyclohexyl structure, a cycloheptyl structure, a cyclooctyl structure, a cyclononyl structure, a ring Decyl structure, cycloundecyl structure, cyclododecyl structure, cyclotridecyl structure, cyclotetradecyl structure, cyclopentadecyl structure, cyclohexadecyl structure, cycloheptadecane structure A base structure, a ring base structure, etc. are suitable. As the polymerizable unsaturated monomer having the above-mentioned cycloalkyl group, cyclohexyl (meth) acrylic acid, methylcyclohexyl (fluorenyl) acrylate, tert-butylcyclohexyl (meth) acrylate, cyclooctyl ( (Meth) acrylate, cyclododecyl (meth) acrylate, isobornyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: lightweight ester IB-χ), isobornyl acrylate ( Manufactured by Lih Kasei Kogyo Kogyo Co., Ltd., trade name: FA-544A; manufactured by Kyoeisha Chemical Co., Ltd., trade name: light acrylate ΙΒ_χΑ), dicyclopentyl methacrylic acid vinegar (manufactured by Li Kasei Kogyo Co., Ltd., trade name: FA — 513M), dicyclopentyl acrylate (manufactured by Hitachi Chemical Industries, trade name: FA — 513A), 4-methylcyclohexyl fluorenyl acrylate (manufactured by Hitachi Chemical Industries, trade name: CHDMMA), 4-Amidinocyclohexylmethyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, etc. are suitable, and one or two or more of them can be used. Among them, cyclohexyl (fluorenyl) acrylic acid is more preferred, 4-methylcyclohexylmethyl (meth) acrylate, and cyclohexylmethyl (methyl 200406474) acrylate. Examples of the (fluorenyl) acrylic acid having a tert-butyl group include tert-butyl methyl acrylate and tert-butyl acrylate. The amount thereof is not particularly limited in the first, second, fourth, and fifth inventions, but is preferably 5 to 99% by mass, and more preferably 30 to 99% by mass. In the third and sixth inventions, the content is 50 to 99% by mass, preferably 60 to 95%, and more preferably 70 to 90% by mass. Examples of the (A) (b) polyfunctional crosslinking monomer include (meth) acrylic acid and ethylene glycol, propylene glycol, 3-butanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, Polyesters with more than 70 alcohols such as methylpropane, pentaerythritol, and diquaternary tetraol; polyfunctional vinyl compounds such as divinylbenzene; (meth) acrylic and allyl esters such as allyl (meth) acrylate Wait. The amount thereof is not particularly limited in the first, second, and 帛 4, and is preferably Gi to 20 mass%, and more preferably 5 to 15 mass%. Examples of (A) (c) an unsaturated monomer having an ultraviolet-stabilizing group and / or an ultraviolet-absorbing group include 2,4-dihydroxybenzophenone or 2,2,4-trihydroxybenzophenone and ( Glycidyl methacrylic acid reaction 2 2-carboxyl-4 4- [3- (meth) propenyloxy-2 2-hydroxypropoxy] benzophenone, 2, 2'-dihydroxy 1 4- 1 [ 3- (meth) acryloxy-2-hydroxypropoxy] benzophenone monomers such as benzophenone, and 2-a [2, _ mesityl-5, a (methacryloxymethyl) Phenyl] -2H-benzotriazole, 2- [2,1-light-yl-5— (methacryloxyethyl) phenyl] _2H-benzotriazole, 2- [2'-hydroxy_ 5 '-(methacryloxypropyl) phenyl] _2H-benzotriazole, 2- [2'-hydroxyl-5, mono (methacryloxyhexyl) phenyl] 11 200406474

-2H-benzotrifluorene, 2_ [m3, -tert-butyl-5, — (methacryloxyethyl) phenyl] -2-benzotrisalyl, 2- [2, _ meridian— 5,: tert-butyl-3 '-(fluorenylpropionyloxyethyl) phenyl] -2H-benzobisalan \ 2— [2'—Cyclo-5' — (methylpropane Oxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2, -hydroxy-5,-(methacryloxyethyl) phenyl] -5_methoxy —2H—benzotriazole, 2— [2, 1-hydroxy ~ 5, — (methacryloxyethyl) phenyl] —5—cyano—2H—benzotriazole, 2— [2, 1 Hydroxy-5, mono (methacryloxyethyl) phenyl] -5-tert-butyl-2H-benzotriazole, 2- [2, monohydroxy_5, mono (methacryloxyethyl) Ethyl) phenyl] -5-tert-butyl_2H-benzotriazole and other benzotriazole-based monomers and other monomers with ultraviolet absorption, 4 (meth) acryloxy-2, 2, 6,6-tetramethylguanidine bite, 4- (fluorenyl) propenylaminoamino-2,2,6,6-tetrafluorenyl. Guaridine, 4- (meth) acrylfluorenyloxy-1,2,2,6,6-pentafluorenylpyridinium, 4- (meth) acrylfluorenylamino-1,2,2, 6,6-pentafluorenylpyridinium, 4-cyano-4pyridinylpropenylfluorenyloxy-2,2,6,6-tetramethylpyridinyl,] _ ((pentyl) propenyl) 4-methyl (4-methyl) propanylamino-2,2,6,6-tetramethylpyridine, 4-crotonyloxy-2,2,6,6-tetramethylpyridine, 4_crotonylamino-2,2,6,6-tetramethylguanidine bite, 1-crotonyl-4, crotonyloxy-2,2,6,6 _tetramethylpyridine, etc. A monomer having a UV-stabilizing function such as a pyrimide polymerizable monomer and the like. The usage amount of such violet, 4 outer-line stabilizing groups and / or ultraviolet absorbing groups is not particularly limited, but is preferably from 0 to 10% by mass, and more preferably from 0.5 to 5% by mass. 'The aqueous resin composition thus prepared Improved financial performance. The total amount of r r 12 200406474 c) is 100% of (a), (b) and mass% of the above monomer mixture. In the first, second, fourth, and fifth inventions of the present application, (d) other monomers are not necessary, but may be added. The amount used is not particularly limited, but is preferably 0 to 94.8% by mass. Any of these (A) (d) other monomers can be used as long as they can be copolymerized with the above monomers. Examples of the main polymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, and (meth)

The purpose of (meth) acrylic acid such as butyl acrylate, (meth) acrylic acid-2 monoethylhexyl ester, and alcohols from C1 to C18 (including aliphatic, cycloaliphatic, and aromatic) is (meth) acrylate ; (Meth) acrylic acid-2 monohydroxyethyl alcohol, (meth) acrylic acid script, (meth) acrylic acid acid 2-via monopropyl alcohol, (meth) acrylic acid and polypropylene glycol (Meth) acrylic esters with hydroxyl groups such as ethyl esters • Ethylene unsaturated monobasic acids such as acrylic acid, methacrylic acid, and crotonic acid; unsaturated polycarboxylic acids such as fumaric acid and itaconic acid; monoethyl maleate

Ester, monoethyl itaconic acid, and other ethylenically unsaturated polybasic monocarboxylic acid partially polymerized compounds having a carboxyl group; a polymerizable monomer having a carboxyl group; (fluorenyl) glycidyl acrylate, (meth) acrylic acid 2-methyl Glycidyl ester, allyl glycidyl ether, and other polymerizable monomers having epoxy groups; • Methacryl hydrazine aziridine, (fluorenyl) acrylic acid 2- 2-aziridine. Polymerizable monomers with aziridinyl groups, such as ethyl acetate; • 2-isopropenyl- 2-oxalin, 2-vinyl-. Oxaliline and other polymerizable monomers with an oxazoline group; 13 200406474 · (meth) acrylamide, N ~ -ethyl (meth) acrylamide, N methyl (meth) acrylamide , N, N-Dimethyl (methyl methacrylate) dilute amines and other (meth) propanamine derivatives; · (meth) acrylic acid dimethylaminoethyl ester, dimethylaminoethyl (Methyl) basic polymerizable monomers such as acrylamide, vinylpyridine, vinylimidazole, vinylpyrrolidine, and ketone; • N-hydroxymethyl (meth) acrylamide, N-butoxy Cross-linking (meth) acrylamide such as methylmethyl (meth) acrylamide; • Styrene derivatives such as styrene, vinyl toluene, α-methylstyrene, chloromethylbenzene_ethylene; · Polymer monomers with cyano groups such as (meth) acrylonitrile; • Polymer monomers with acid groups such as (meth) acrylic acid 2-ethyl sulfonate and its salts, vinyl sulfonic acid and its salts Body; • vinyltrimethoxysilane, 7- (meth) acryloxypropyl-methoxysilane, allyltriethoxysilane, trimethoxysilylpropyl Unsaturated monomers with organosilicon groups such as allylamine, vinyl esters such as vinyl acetate, vinyl propionate, etc. • Monofluoroethylene, difluoroethylene, digas ethylene, dichloroethylene, etc. Halogenated monomers • Butadiene, isoprene and other conjugated diene; ethylene, propylene, butene, etc. These polymerizable monomers may be used alone or in combination of two or more kinds. As the polymerization initiator used in the suspension polymerization, an oil-soluble initiator can be used. Examples include lauryl fluorenyl peroxide, benzamyl peroxy 14 200406474 compounds, and tert-butyl peroxyhexanoic acid 2 —Ethyl esters, bu di-tert-butyl—peroxy-2-methylcyclohexane, and other peroxide-based initiators, 2,2, —Azobisisobutene 2 2Azo__2'4 Azo initiators such as dimethylvaleronitrile. The amount of these initiators used is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the monomer mixture. As a hanging ocean? << The dispersion stabilizer used at the time can use fibers such as polyvinyl alcohol, polyethylene base, poly (meth) acrylic acid or its salt, carboxy cellulose, methyl cellulose, methyl warp cellulose, etc. Water-soluble polymers such as pigments and gelatin; inorganic powders such as barium sulfate, osmium sulfate, carbonated carbonate, carbonated carbonate, and phosphoric acid phosphate; anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants All active agents such as agents, high molecular surfactants, and one or more molecules are polymerizable. Reactive surfactants with hydrazone-slavery bonds. These may be one kind or two or more kinds, and the use amount of these dispersion stabilizers is preferably 0.01 to 10 parts by mass, and more preferably 5 to 5 parts by mass relative to 100 parts by mass of the above-mentioned monomer mixture. The aqueous resin dispersion (A), each having resin particles having an average particle diameter of 1 to 100 μm, is obtained by mixing the monomers (0, ⑴, (c) and, if necessary, a monomer mixture (d) or a monomer ( The monomer mixture composed of a), (b) and as required :) is prepared by suspension polymerization in an aqueous solvent in the presence of a dispersion stabilizer or a w-port initiator by a conventional method. The general reaction / dish degree is 50 ~ 100. 〇, preferably 60 ～. The reaction temperature may be constant or changed during the reaction. The polymerization time is not particularly limited, and can be appropriately selected according to the progress of the reaction. The time from the start of polymerization to the end of polymerization is generally 10 hours, preferably 2 to 5 hours. The average particle diameter in the aqueous resin dispersion (A) is micrometers, preferably 5 to 60 micrometers, and more preferably 10 to 50 micrometers. That is, if it is less than 1 m, the matting effect is insufficient, and if it exceeds 100 m, the storage stability of the aqueous resin dispersion obtained by suspension polymerization is significantly reduced. The concentration of the solid portion in the aqueous resin dispersion (A) is 5 to 50% by mass, and preferably 10 to 30% by mass. The use form of the aqueous resin dispersion (A) containing resin particles having an average particle diameter of 1 to 100 micrometers is not particularly limited. The water j dispersion can be used directly, or it can be obtained as a particle powder and mixed, but it is economical in terms of operability. From the standpoint of preference, a method using an aqueous dispersion directly is preferred. The aqueous resin dispersion (B) containing resin particles having an average particle size of # 01 to 1 micron can be obtained by combining any of the above monomers and (a), (b), and CC) as needed or The mixture of two or more kinds of compounds is prepared in an aqueous solvent using an emulsifier and a polymerization initiation method under conventional emulsification polymerization to prepare-usually 60 ~ stages. The reaction temperature can be determined-it can be changed during the reaction. ♦ The time is not particularly limited, but it can be appropriately selected according to the progress of the reaction. It is usually selected from the root to the end, and usually from 1 to 4 hours from the start to the end of the polymerization. The average particle diameter in the above-mentioned aqueous resin dispersion (B) is 0.00 m, preferably 0.04 to 0.05, and further preferably 0.08 to 0.2 micron. The concentration of the solid portion in the aqueous resin dispersion (B / Xin body (B) is 5 to%, preferably 30 to 60% by mass. Perry 16 200406474 The monomer used in the production of the aqueous resin dispersion (B) is It is a polymerizable monomer, and any of them may be used, preferably a) 5 to 99% by mass of an unsaturated monomer having a cycloalkyl group, and (c) an unsaturated precursor having an ultraviolet stabilizing group and / or an ultraviolet absorbing group. 1 ^^^ 10% by mass% 'More preferably a) 30 to 70% by mass of an unsaturated monomer having a cycloalkyl group, (c) an unsaturated monomer having an ultraviolet stabilizing group and / or an ultraviolet absorbing group 0.5 ~ 5 mass%. The calculated Tg of the preferred emulsion is -2 (rc ~ 9 (TC, more preferably 0 ~ 60). Here, Tg (K) is given by:-= W2 WI Wn TS Tgl Tg2 + + 7 ^ n will be composed of The glass transition point temperature of the homopolymer of each monomer of the polymer formed by the n types of monomers is set to TgI (K), and the weight distribution of each monomer is WI. In any of the above-mentioned methods for producing an aqueous resin dispersion The water-based solvent to be used is usually water, and if necessary, hydrophilic solvents such as lower alcohol and _ can be used together. The amount of the aqueous solvent can be an aqueous resin obtained with respect to the total amount of the polymerizable monomer component used. The content of oral dispersion in the dispersion is used within the above-specified range. The emulsifier is not particularly limited, and for example, anionic 2 surfactants, nonionic surfactants, and cationic surfactants can be used. * Two I * All surfactants such as raw surfactants, polymer surfactants, etc. Reactive surfactants with more than one polymerizable carbon-carbon unsaturated in the molecule 17 200406474 and bonds can be used. As anionic list Specific examples of the active agent include alkali metal alkyl sulfates such as sodium dodecyl sulfate and potassium dodecyl sulfate; alkyl ammonium sulfates such as dodecyl sulfate; dodecyl polyethylene glycol Alcohol ether sulphate-sodium, sodium dibasic acid; alkali metal salts of sulfonated alkane esters, ammonium salts of sulfonated alkane esters; etc. alkylates; sodium laurate, triethanolamine oleate, triethanolamine rosin ester, etc. Fatty acid salts; Alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate and metal sulfates of alkali metal phenol hydroxyethylene; high alkyl naphthalene sulfonates; naphthalene sulfonic acid formaldehyde condensates; dialkyl sulfur Substituted succinate; polyoxyethylene alkyl φ sulfate; polyoxyethylene alkyl aryl sulfate, etc. As the nonionic surfactant, specifically, for example, a polyoxyethylene alkylene oxide polyalkylene oxide can be used. Ethers; sorbitol fatty acid vinegar; polyoxyethylene sorbitol fatty acid esters; glycerol monolaurate and other fatty acid monoglycerides; polyoxyethylene propylene oxide copolymers; ethylene oxide and aliphatic amines, amidines Condensation products of amines or acids, etc. Specific examples of molecular surfactants include polyethylene glycol, sodium poly (meth) acrylate, potassium poly (meth) acrylate, poly (methyl) acrylic acid, and polyethylethyl (methyl). Acrylic acid purpose; polyacrylic propyl (fluorenyl) acrylate or two or more copolymers of polymerizable monomers constituting the unit of these polymers, or copolymers with other monomers, etc. Related movements of crown ethers, etc. The catalyst has surface activity, so it can be used as a surfactant. Specific examples of the reactive surfactant include acryl-2-ethylhexyl thio group, thioic acid g, and (formamidine). , Τ 丞 彡 acrylic acid 18 200406474 polyoxyethylene sulfate, polyoxyethylene alkyl propenyl ether ammonium sulfate (meth) acrylic acid polyoxyethylene linoleate, di (polyoxyethylene oxime The base _) structure of methacrylated ammonium sulfate, polyoxyethylene alkylaryl sulfate, and has acryl, isopropenyl, allyl, acrylate, methacrylate, etc. With aggregation And other anionic reactive surfactants; have a structure of polyoxyethylene alkylphenyl ether (meth) acrylate, polyoxyethylene alkyl ether (meth) acrylic acid vinegar, polyoxyethylene alkylene aryl ether, In addition, it has polymerizable nonionic reactive surfactants such as isopropylamyl and aryl. These emulsifiers, i.e., surfactants, may be used singly or in combination of two or more kinds. However, in consideration of the water resistance of a dry coating film of an aqueous resin dispersion, a reactive surfactant is preferred. The use of the emulsifier is not particularly limited. It is preferably 0.3 to 5% by mass, and more preferably 0.5 to 3% by mass with respect to the total amount of the polymerizable monomer component. If the amount of the emulsifier is too much, the water resistance of the coating film is reduced, and if it is too little, the polymerization stability of the resin particles is significantly lowered. The particle size of the resin is greatly affected by the type of emulsifier. Therefore, the amount of the resin must be appropriately selected within the above range according to the emulsifier used. The polymerization initiator is not particularly limited, and specific examples thereof include 2,2, monoazobisisobutyronitrile, 2,2, monoazobis (2-fluorenylpropane), dibasic acid salts, 4, 4. Water-soluble azo compounds such as mono-azobis (4-cyanovaleric acid); persulfates of potassium persulfate; hydrogen peroxide, peracetic acid, stupid peroxide, di-tert-butyl peroxide Such as peroxides. The amount of the polymerization initiator used is not particularly limited, and it is preferably 0.3% by weight, and more preferably ˜2% by weight, based on the total amount of the polymerizable 19 200406474 monomer component. When too much 砀 ° clam of the polymerization initiator is used, the resistance of the coating film is reduced, and when it is too small, the degree of polymerization becomes slow and unreacted monomers are retained. Therefore, it is not preferable. One type of polymerization initiator may be used, or two or more types may be used. In order to speed up the polymerization, metal salts such as sulfite and sodium ferrous sulfate and ferrous sulfate can be used with the above-mentioned polymerization initiators as needed. The method of adding the polymerization initiator is not particularly limited, and may be any method such as adding together, separately, or continuously. In order to accelerate the completion of the polymerization, a part of the polymerization initiator may be specifically added before and after all the monomer components are added dropwise. In addition to the polymerization initiator during the polymerization, a chain transfer agent may be added according to the requirements. For example, a compound having a thiol group such as tertiary undecyl mercaptan and a-fluorenyl styrene dimer may be added. . The neutralizing agent used for neutralizing the acidic group is not particularly limited, and various conventionally known neutralizing agents can be used. Specific examples include metal test compounds such as sodium ammonium oxide and potassium hydroxide; hafnium oxychloride and carbonic acid metal compounds; ammonia; monomethylamine, dimethylamine, trimethylamine, monomethylamine: diamine Water-soluble organic amines such as ethylamine, triethylamine, monopropylamine, dimethyl: propylamine-, ethanolamine, diethanolamine, triethanolamine, and ethylenediethylidenetriamine. Among them, low boiling point amines such as ammonia, dimethylamine, dimethylamine, and dimethylamine are easy to volatilize at normal temperature. Therefore, it is sufficient to prevent Europeanized coatings in coatings containing aqueous resin dispersions. Water resistance is lowered ', so ammonia is preferred, and ammonia is more preferred. The neutralizing agents listed above may be used alone or in combination of two or more. In the 4th and 5th inventions, 'the aqueous resin dispersion (A) containing resin particles having an average particle size of 0 micrometers was added with a quaternary agent (0, and then, the average particle size was mixed with 0.0. ~! ~! A method for producing an aqueous resin composition of an aqueous resin dispersion of micron-sized resin particles. The tackifier (C) is not particularly limited, and an example is given below, for example. (1) Water-soluble polymer as Specific examples of the water-soluble polymer used in the adhesive include, for example, 2-methylcellulose, cellulose ethers (for example, propylmethylcellulose, etc.), polyethylene oxide, polypropylene oxide, and polyethylene. Diols, polypropylene amides, ethylene glycol, etc. (2) Associative thickeners Associative thickeners used as tackifiers are usually connected at the ends of the main chain of the hydrophilic polymer and on the way Hydrophobic side groups such as higher alkyl groups.

The additive discovery mechanism of the agent is known to be due to the associativity of the two &lt; mouth forces (e.g., hydrophobic binding forces) of the hydrophobic side groups. Examples of adhesives • Examples of the use of associative step-up agents include polyethylene, associative tackifiers, and acrylic associative tackifiers. $ Vinyl alcohols One solution of the dysprosinic tackifier is to bind hydrophobic side groups at both ends of the polyvinyl alcohol. (3) Acrylic associative tackifiers and acrylic acid associative tackifiers are connected to hydrophobic side groups such as higher alkyl groups in the main chain, terminal or middle of the hydrophilic acrylic polymer. Specific examples of the acrylic-based association 21 200406474 oral pong adhesives include, for example, acrylic monomers and associative monomers having hydrophobic side groups such as high-temperature alkyl groups (for example, hydrophobic groups such as alkyl groups and aromatic groups). (Polyethylene unsaturated monomers (ie, reactive surfactants, etc.) obtained by copolymerizing acrylic side monomers with reactive pendant groups, such as reactive surfactants). Specifically, the tackifier shown in Japanese Patent Application Laid-Open No. 2001-240633 is preferable.

The amount of the drilling aid (C) added was 100 parts by weight, and the aqueous resin dispersion (B) containing the above-mentioned average particle diameter of resin particles (0.0 to 1 micron) was 0.05 parts per ber. It is preferably from 0.005 to 1.5 parts by mass, and more preferably from 0.005 to 0.7. This is because if the amount of the tackifier (C) is less than 0.05 parts by mass, no dryness effect is exhibited. On the other hand, if it exceeds 2 parts by mass, water resistance is reduced. In all the inventions, the amount of the aqueous resin dispersion (A) containing resin particles having an average particle diameter of 1 to 100 micrometers is added in an amount of 100 parts by mass of the aqueous solution containing the resin particles having an average particle diameter of 0.01 to 1 micrometer. The solid portion of the resin dispersion (B) is 1 to 30 parts by mass, and preferably 5 to 25 parts by mass. That is, when the amount of the aqueous resin dispersion (A) is less than i parts by mass, the matting effect is insufficient, and if it exceeds 30 parts by mass, the storage stability is also insufficient.

The aqueous resin composition of the present invention may use only the above-mentioned aqueous resin dispersion directly, or may contain various additives as necessary. As the additives, for example, pigments, film-forming base agents, fillers (fillers), tinting coatings, wetting agents, antistatic agents, pigment dispersants, plasticizers, antioxidants, flow control agents, viscosity modifiers, and the like can be added. Furthermore, other water-soluble resins or water-dispersible resins can be added and mixed. These resins include, for example, methacrylic acid S, acrylic acid, glandular scorch, crushed ketone, second ketone acrylate, urethane acrylate, fluorine, fluorine acrylate, and the like. 22/4 化 __ 述 &quot; ', plus' M' in the special collection of pigments can include titanium oxide, oxide, Erqianlu, Zinc, zinc barium white milk black, yellow boat, ochre orange, iron dan, Main color sensitive ^ Special white pigment 'and carbon

Γ Inorganic pigments; azo compounds such as benzidine, hansa yellow, or copper; organic pigments such as moon blue. These dyes can be used alone or in combination of two or more. In these examples, in order not to reduce the weather resistance of the coating film to be applied, it is preferable to use a pigment having good weather resistance. For example, when producing a self-coloring pigment titanium oxide, it is preferable to use an oxidized rutile structured oxide compared to an anatase heterostructured oxide. When titanium rutile-type titanium oxide is used, it exhibits long-term weather resistance, and it is more preferable to use chlorine-based titanium oxide than sulfuric acid-based oxidation. Examples The present invention will be described in more detail with reference to the following examples. "Parts" and "" are described below and are not particularly limited to mean "parts by mass," and "% by mass,". 1. In a reaction vessel, 0.5 part of polyvinyl alcohol (manufactured by Curaray Co., Ltd., trade name: PVA-CST) and ammonium salt of polyoxyethylene oil ether sulfate (Shenzhen Industrial Pharmaceutical Co., Ltd., trade name: Hayti 0.5 parts of M% aqueous solution of Noro 18E) was dissolved in 154.5 parts of deionized water. Among them, 88 parts of cyclohexylmethacrylate and 4-methacryloxy-2,2,6,6 dimethyltetraoxine (manufactured by Attica Co., Ltd., trade name · Attica Sapporo LA — 87, hereinafter referred to as pyrimidine A) 2 parts, 10 parts of trimethylolpropane trimethacrylate (TMPTMA: manufactured by Nihon Seiki Co., Ltd.), and 1 part of lauryl peroxide Add the mixed monomer mixed solution and stir with a mixer 23 200406474. As a result of visual observation with an optical microscope, a monomer dispersion liquid having a particle size of "10 m" was obtained. This dispersion was added to a 2 liter separation flask, and 254 parts of deionized water was added, and the temperature was raised to 75 C while stirring under a nitrogen atmosphere. After the polymerization started, it was heated up to 8yc, and then cured at 85 ° C for 3 hours' to obtain an aqueous resin dispersion. The average particle diameter of the obtained aqueous resin fraction * liquid dispersion was measured with a Coulter counter (Coulter Counter), and it was about 9 micrometers. Manufacturing Example 2 of Suspension Polymerization Except that the composition of unsaturated monomers was 60 parts of cyclohexyl methacrylate, 10 parts of φ TMPTMA, 2 parts of guaridine (A), and methyl methacrylate (28 parts), and Suspension Polymerization Production Example} The same procedure was performed. The average particle diameter of the obtained aqueous resin dispersion was measured by a Coulter counter to be about 10 microns. Suspension polymerization Production Example 3 except that the unsaturated monomer composition was cyclohexyl methacrylate 4 〇part, 10 parts of TMPTMA, 2 parts of foxidine (A), 2- [2,1-hydroxy-5, ~ r-field ^ methyl propyl oxyethyl) phenyl] -2H-benzotrisigma ( Hereinafter, the same procedure as in suspension polymerization production example 1 was performed except that 1 part of benzylic disial (B)) and 47 parts of fluorenylpropionate vinegar (MMA). The average particle diameter of the obtained aqueous resin dispersion was measured by a Coulter counter and was about 9 m. Production Example 4 of Suspension Polymerization The procedure was the same as that of Production Example 24 200406474 except that the unsaturated monomer composition was 93 parts of cyclohexyl methacrylate, 5 parts of TMPTIMA, and 2 parts of pyrimidine (A). The average particle diameter of the ## aqueous resin dispersion measured by a Coulter counter was about 10 m. Suspension Polymerization Production Example 5 The same procedure as in Suspension Polymerization Production Example 1 was performed except that the unsaturated monomer composition was 83 parts of cyclohexyl methacrylate, 15 parts of TMPTMA, and 2 parts of morphine (A). The average particle diameter of the obtained aqueous resin dispersion was measured by a Coulter counter, and it was about 10 m. Production Example 6 of Suspension Polymerization Except that the unsaturated monomer composition was 70 parts of cyclohexyl methacrylate, 10 parts of MPTMA, and 20 parts of MMA, the same procedures as in the case of suspension polymerization were carried out. ^ The average particle size of the transferred aqueous resin dispersion was measured by a Coulter counter, and it was about Π microns. Suspension Polymerization Production Example 7 The same procedure as in Suspension Polymerization Production Example 1 was performed except that the unsaturated monomer composition q π was difficult again at 0 yu parts MPTθΜΑ1 () parts. Fixed :: The average particle diameter of the aqueous resin dispersion is determined by a Coulter counter. The result is about 9 microns. w 'Yulaihe Manufacturing Example 8 The same procedure as in the suspension polymerization manufacturing example was carried out except that the unsaturated monomer composition was TM. ：: ^^ The average particle size of the dispersion was determined by the Coulter counter, and it was about 12 micro200406474. Suspension polymerization Manufacturing Example 9 Except that the unsaturated monomer composition was cyclohexyl acrylic acid cyclohexyl g (8) N—08 ”) 1 part Except that the average particle diameter of the aqueous resin dispersion liquid which was carried out in the same manner as in the suspension polymerization production example 测定 was measured by a Coulter counter, 10 micrometers. Suspension polymerization production example 10 Except that the unsaturated monomer composition was cyclohexyl acrylate, TMPTMA18 and emulsifier are polyoxyethylene alkyl propenyl benzyl ammonium sulfate acetic acid ammonium salt (Daiichi Pharmaceutical Co., Ltd., product ": Brother y Cheallo BC-10") and suspension polymerization production example i The average particle diameter of the obtained aqueous resin dispersion was about 11 micrometers using a Coulter counter. The production example of suspension polymerization was except that the unsaturated monomer composition was 80 parts of methyl hexanoate, TMPTMA18. The emulsifier is ammonium dimethacrylate sulfate ammonium "" Ethyl ethoxylate phenylene oxide "M (Made by Japan Emulsifier Co., Ltd., Commercial Example 1 Same as Putter ^ Injury, and suspension Polymerization system It was measured by a defrost counter passed by the water-based resin, and it was about u micrometers. 虺 Suspension polymerization using 例 例 Preparation Example 12 Except for unsaturated monomers 纟 &gt; parts, ™ PTMA 15 and emulsifier & ^ methyl propyl Cyclohexanone dilute acid 83

Parts, TMPTMA18, and emulsifier are polyoxyalkylene alkyl benzyl thiostilbate ammonium salts (Daiichi Pharmaceutical Co., Ltd., trade name: "Haitino. Get" is the approximate product name: "Yaduz Coase MS-6, is 5Etinol, except for 18E 0.3 parts, 26 200406474 Same as the suspension polymerization manufacturing example 1, r ^, 仃. The average particle size of the aqueous resin dispersion solution of 4 to 4 is used by Could Measured by a counter about 12 microns. Suspension Polymerization Production Example 13 Except that the unsaturated monomer composition was 83 parts of cyclohexyl methacrylate, TMPTMA15, and emulsified densities, 4 & Haiti Except for 0.5 parts of Noro, it is the same as that of suspension polymerization manufacturing example 1. The average particle diameter of the obtained aqueous resin dispersion was measured by a Coulter counter, and the size was about 4 μm, which is about 12 microns. Suspension Polymerization Production Example 14 Except that the unsaturated monomer composition was 83 parts of cyclohexyl methyl acrylate, TMPT Question 5 and emulsifier was 5 parts of pVA- csTi, and 1.5 parts of Hayti Noro 18E. The prefecture injection system was manufactured in the same manner as in Manufacturing Example 1. The average of the obtained aqueous resin dispersion was Private &lt; measured with a Jurde counter using J Curtain, approximately $ microns. Suspension Polymerization Production Example 15 Except that the unsaturated monomer composition was 83 parts of cyclohexyl methyl acrylate, TMPTMA15 and the emulsifier was Lp Except for 0.5 parts, it was carried out in the same manner as in Suspension Polymerization Foot Production Example 1. The average particle size of the obtained aqueous resin dispersion was measured by a Coulter counter and was about 10 μm. Suspension Polymerization Production Example 16 Except for the unsaturated monomer composition It is cyclohexyl methacrylate 83, TMPTMA15, and the starting agent is Lp02. It is the same as that in suspension polymerization manufacturing example 1. t% 仃. The average particle size of the aqueous resin dispersion served is a Coulter counter. It was measured to be about 10 micrometers. Suspension polymerization of 1 to 16 micron or more is shown in Table 1. 27 200406474 Manufacturing Example 16 m 00 in 1 ra (N in dd 〇 Manufacturing Example 15 cn 00 vn 1 &lt; N d U-) dl〇d 〇 2 2 ^ CO 00 1 (N rH Ui rH in rH ◎ bismuth m 00 in 1 (N rH in d 〇cn 00 in 1 CM tH cn d &lt; Manufacturing Example 11 g 00 1 (N rH rH ◎ Manufacturing Example 10 00 1 (S rH ◎ _ ON Bismuth § 00 1 (N xH 〇 Bismuth oo 1 1 tH to o in d 〇m t- Bismuth § o rH 1 1 1 rH in d in o 〇 堋 v〇oo 1 1 tH in d in d 〇cn 00 V〇1 tH 1 rH dv〇d 〇_ two cn 〇 \ 1〇1 (N 1 rH IT) d in d bismuth transport o (N rH rH in d in d 〇 bismuth o (N 1 rH V〇dd 〇Μ ^ oo 00 o 1 (M 1 rH md in d 〇 (polymer) CHMA TMPTMA MMA t-BMA | 呱 （(A) m m ft ㈣ (starter) o (emulsifier) PVA-CST Haitinuolu 18E Haitinuolu N — 08 Yacuialo BC-10 Yalu; Kus MS-60 骅 200406474 Acrylic Oxyoxy-2, 2, 6, ， Product name · Asia Dicasta polymerization stability pyridine (A): 4 ~ methyl 6-tetramethylpyridine (PU LA-87 manufactured by Asahi Kasei Corporation) benzotriazole pyrene: 2 1 [2, hydroxy-5, _ (Methacryloxyethyl) phenylbutan 2H-benzotriwa (Dayuan Chemical Co., Ltd. ^ -93) Production Example of Acrylic Emulsion 1 Equipped with a dropper, stirrer, nitrogen inlet, temperature Add 963.0 parts by mass of pure water to the flask with the reflux cooling officer, slowly blow in nitrogen, and raise the temperature to 75X with stirring. On the other hand, 529.0 parts by mass of methylmethacrylate (MMA), 361.0 parts by mass of 2-ethylhexylpropionate (hereinafter referred to as 2EHA), and 100% of styrene (hereinafter referred to as) 〇80 parts by mass of a 25% aqueous solution of Yakualo BC-10, a polyoxyethylene alkyl phenyl ether (manufactured by Daiichi Kogyo Co., Ltd.) was added to a monomer mixed solution composed of parts by mass and acrylic acid (hereinafter referred to as AA). Non-ionic reactive emulsification (Yakuyalo RN-20) (40 parts by mass of a 25% aqueous solution and 230 parts by mass of pure water, a non-ionic reactive emulsifier manufactured by Daiichi Kogyo Co., Ltd.) Emulsion mixture. 1 Q% by mass of the pre-emulsion mixture was added to the flask, and after maintaining at 75 ° C, 60.0 parts by mass of a 5% ammonium persulfate aqueous solution was added to start polymerization. The reaction system was internally 80. After holding at 0 ° C for 10 minutes, the remaining pre-emulsion mixture was added dropwise uniformly over 180 minutes. After the dropwise addition was completed, the dropping tank was washed with 20 parts by mass of pure water, and the washing solution was added to the flask. During the dropwise addition, the inside of the reaction system was kept at 801, and after the dropwise addition was completed, the mixture was stirred at 80 ° C for 60 minutes while being matured to complete the polymerization. The price was then cooled and the reaction was allowed to proceed. 9.3 g of 25% ammonia water was added to the system at 50 ° C or lower, and after stirring for more than 10 minutes, it was cooled to room temperature and filtered through a 100-mesh wire mesh to obtain a polymerization dispersion. The average particle diameter of the obtained acrylic emulsion was measured by a light-scattering particle size measuring device and was about i50 nm. , Acrylic Emulsion Production Example 2-Into a flask equipped with a dropper, stirrer, nitrogen inlet, thermometer, and reflux cooling tube, add 943.0 parts by mass of pure water, slowly blow in nitrogen, and raise the temperature to 75 ° C while stirring. . On the other hand, 200 parts by mass of CHMA, 102.6 parts by mass of MMA, 137.4 parts by mass of 2EHA, 500,000 parts by mass of n-butylmethyl acrylate (hereinafter referred to as n_BMA), and monomers consisting of AA100 mass were mixed. Add Yakuyalo Be — (a non-ionic reactive emulsifier made by Daiichi Kogyo Co., Ltd.) in a solution of 25% aqueous solution 40 belial, Yakuyalo rN _ 2 (Daiko Pharmaceutical Co., Ltd.) A 20% by mass of a 25% aqueous solution of a non-ionic reactive emulsifier) and 115 of pure water were used to prepare a pre-emulsion mixture 1. 20% by mass of the pre-emulsion mixture 1 was added to the flask and kept at 75. After 〇, 60.0 parts by mass of a 5% ammonium persulfate aqueous solution was added to start polymerization. After the reaction system was kept at 80 ° C for 10 minutes, the remaining pre-emulsion mixture was added dropwise uniformly over 90 minutes. After the dropwise addition was completed, the dropwise addition tank was washed with 20 parts by mass of pure water, and the washing solution was added to the flask. During the dropwise addition, the inside of the reaction system was maintained at 80 ° C. After the dropwise addition was completed, the temperature was maintained at 80 ° C for 30 minutes, and 25% ammonia water was added in 4 · 3 parts by mass. After neutralization, the first-stage polymerization was terminated . Next, the reaction system was maintained at 80 ° C, and at 80 ° C, 900.0 parts by mass of CHMA, 30 200406474 ΜΜ 10.2 · 6 parts, 2EΗΑ 137 · 4, which were manufactured in the same manner as the pre-emulsion 1, were added dropwise uniformly over 90 minutes. Mass parts, n-BMA 5000 mass damage, pyridine (A) 10.0, 25% aqueous solution of Yakuyalo BC-10, 40 parts by weight, 25% aqueous solution of Yakuyalo RN-20 Pre-emulsion mixture 2 consisting of 20 parts by weight and 115 parts by mass of pure water. After the dropwise addition was completed, the strip was added to the strip with pure water · Berry, and the strip was added; I: The strip solution was added to the flask. Ageing was performed at 60 ° C for 60 minutes, and the polymerization in the second stage was completed. After cooling, 50 mass parts of 25% ammonia water was added to the reaction system at 50 ° C or lower, and after stirring for more than 10 minutes, it was cooled to room temperature and filtered through a 100-mesh wire mesh to obtain a polymer dispersion emulsion. The average particle size of the obtained acrylic emulsion was measured by a light scattering particle size measuring device and was about 130 nm. Table 2 shows the above-mentioned acrylic acid emulsion production examples 1-2.

31 200406474 Table 2 Manufacturing Examples 1 to 2 of Manufacturing Acrylic Emulsion 1 Manufacturing Example 2 (monomer composition) First stage Second stage St 100.0 MMA 529.0 102.6 102.6 2EHA 361.0 137.4 137.4 CHAM 200.0 200.0 η — ΒΜΑ 50.0 ΑΑ 10.0 10.0 Biting (A) 10.0 1000.0 500.0 500.0 (starter) APS 3.0 3.0 (emulsifier) Yakuyalo BC -1025 20.0 10.0 10.0 Yakuyalo RN —2025 10.0 5.0 5.0 Non-volatile matter (%) 43.0 43.0

Example 1 To 29.0 parts of the aqueous resin dispersion prepared in suspension polymerization manufacturing example 1, 0.3 parts of 25% ammonia water and a thickener WR-600 (non-volatile content: 32 ZUU4U04 / 4 viscosity of 1260 mPa.s. was added thereto. Acrylic Emulsion 2 Cellulose I! Acrylic Emulsion ⑽. 0 parts, Butyl Cellulose / CS — 12 (2, 2, 4-Isobutyl Acetate: Made by Chisso Corporation) : Soil 1 1-3-Yeast 1 (SN Di Fu Ma 777: Yi Er ;: 5.1 parts of the mixed liquid, vice Ming coating composition. Refer to W G. 2 parts and dilution water, to get ρΗ8.5. "", Non-volatile content 37.0%, viscosity 650 mPa.s, Example 2 was the same as Example i except that instead of suspension polymerization, ^ 650 mPa.s, pH 8.5 using suspension polymerization ^ 4 Non-volatile content 36.9%, dryness Example 3 was the same as Example 1 except that it replaced suspension polymerization system 1. Nursing: 1: 670 mPa.s, pH 8.6 of suspension polymerization manufacturing example 3 was used. Japanese standard is non-volatile content 37.1%, dryness Example 4 The same as Example 1 except that the suspension polymerization was used to produce Example 4 and the non-volatile content was 37.1%. _ 700mPa.s, ρΗ8.4. Example 5 was the same as Example 1 except that instead of suspension polymerization, 36.8% non-volatile content and viscosity were used. Phase 1 Example 5 uses suspension polymerization to produce Example 5 &quot; 680mPa.s, ρΗ8 · 5 〇 Example 6 33 200406474 The same as κ Example 1 except that Suspension Polymerization Manufacturing Example 6 was used instead of Suspension Polymerization Manufacturing Example 1. The index is a non-volatile content of 670 mPa.s, ρΗ8.5 ° Example 7 Except Instead of suspension polymerization manufacturing example 1, suspension polymerization manufacturing example 7 was used, and the same image as in Example 1 was' non-volatile 37.3%, viscosity 720 mPa.s, ρΗ8.3. Example 8 except for the manufacturing example of acrylic emulsion. 1 Except for manufacturing example 2 using acrylic emulsion, it is the same as that of the conventional example. The indicators are 371% non-volatile content, viscosity 650 mPa.s, ρΗ8.5. Example 9 except that instead of suspension polymerization, manufacturing example 1, manufacturing using suspension polymerization Example 2, except that the acrylic acid emulsion manufacturing example 2 was used instead of the propionic acid emulsion manufacturing example. "Example 1 is the same. The indicators are 37.0% non-volatile content, viscosity 650 mPa.s, pH 8.6. Example 10, except replacing Xuanyang. Polymerization Production Example 1 Production using suspension polymerization 3, = Production Example 1 of Acrylic Acid Emulsion Using Acrylic Emulsion Production Example 2, "Example 1 is the same. The indicators are 36.7% non-volatile content, viscosity 71.0 mPa.s, pH 8.70. Example 11, except Instead of suspension polymerization manufacturing example 1, suspension polymerization manufacturing example 4 was used, and acrylic emulsion manufacturing example 1 was used instead of acrylic emulsion manufacturing example 2. 34 200406474 The same as Example 1. Indicating the day ‘is 37.3% non-volatile content, 700 mPa.s viscosity, ρΗ8.5. Example 12 except that suspension polymerization manufacturing example 5 is used instead of suspension polymerization manufacturing example 1, and acrylic emulsion manufacturing example 2 is used instead of propylene H manufacturing method. "Example 1 is the same. The index is 36.8% non-volatile content , Viscosity 650 mPa.s, ρΗ 8. · 6. Example 13 The same as Example 1 except that suspension polymerization manufacturing example 6 was used instead of suspension polymerization manufacturing example 1, &lt; This means that it is known as non-volatile content of 36.9%, viscosity of 680 mPa.s, and ρΗ8.4. Example 14. Except for Suspension / Prepolymerization Production Example 1, Suspension Polymerization Production Example 7 was used, and Acrylic Emulsion Production Example was replaced. 1 The same as Example 1 except that the acrylic emulsion was used to produce Example 2. Refers to: I; no volatile content of 37.0%, non-volatile content of 700 mPa.s, pH 8.6, Example 15 except that instead of suspension polymerization

Ik Example 1 was the same as Example i except that Suspension Polymerization Production Example 9 was used. ? Said non-volatile content 37.0%, viscosity 700 mPa.s, ρΗ8.5. Example 16 was the same as Example 1 except that the suspension polymerization production example was replaced. The index is 1. Non-volatile content 37.0% of Production Example 10 was used. Viscosity 35 200406474 690 mPa.s, ρΗ8.6. 〇 Example 17 Except using suspension polymerization Production Example 11 instead of suspension polymerization Production Example 1, and Example 1 same. The index was 37.3% non-volatile matter, viscosity 690 mPa.s, and ρΗ8.5. Example 18 was the same as Example 1 except that Suspension Polymerization Production Example 12 was used instead of Suspension Polymerization Production Example 1. The index was 36.7% of non-volatile content, viscosity of 670 mPa.s, and ρΗ8 · 7 °. Example 19 was the same as Example 1 except that suspension polymerization manufacturing example 13 was used instead of suspension polymerization manufacturing example 1. The index was 37.0% non-volatile matter, viscosity 690 mPa.s, and ρΗ8.5. Example 20 was the same as Example 1 except that suspension polymerization manufacturing example 14 was used instead of suspension polymerization manufacturing example 1. The index was 37.1% nonvolatile matter, viscosity 700 mPa.s, and ρΗ8.4. Example 21 was the same as Example 1 except that Suspension Polymerization Production Example 15 was used instead of Suspension Polymerization Production Example 1. The index was 37.0% non-volatile matter, viscosity 700 mPa.s, and ρΗ8.5. Example 22 was the same as Example 1 except that suspension polymerization manufacturing example 16 was used instead of suspension polymerization manufacturing example 1. The index is 37.3% non-volatile matter, viscosity 200406474 670mpa s, ρΗ8.6. Example 23 Except for Example 1 instead of Suspension Polymerization Manufacturing Example 1, use Suspension Polymerization Manufacturing Example 9 instead of acrylic emulsion manufacturing example Only β 1 J 丄 Example 2 using acrylic silicone emulsion manufacturing example, and the same example! same. It means' is a non-volatile content of 36.7%, a viscosity of 700 mPa.s, and ρΗ8.5. Example 24

In addition to replacing the manufacturing example of the ocean polymerization! The same procedure as in Example 1 was carried out except that the suspension polymerization production example 10 was used and the acrylic acid emulsion production was used instead of the acrylic acid emulsion production. The index is 37 .; [%, non-volatile content 690mpa s, ρΗ8.4. Example 25 The same as Example 丄 except that Suspension Polymerization Production Example 丄 1 was used instead of Suspension Polymerization Production Example 1 and Acrylic Silicone Emulsion Production Example 1 was used instead of Acrylic Emulsion Production Example 1 '. The index is 36.8% non-volatile, sticky

67〇mPa.s, ρΗ8.7. Example 26 The same as Example 1 except that Suspension Polymerization Production Example 12 was used instead of Suspension Polymerization Production Example 1 'instead of Acrylic Emulsion Production Example 1 and Acrylic Silicone Emulsion was used. The index is 36.9% non-volatile matter, viscosity 670mpa s, ρΗ8.7. Example 27 The same procedure as in Example 1 was carried out except that the suspension polymerization production example I3 was used instead of the suspension polymerization production example I3 'instead of the acrylic emulsion production example 1 using farinoic silicone emulsion emulsion 20042004474 2'. The indicators are non-volatile content μ%, dryness of 680 mPa.s, ρΗ8.5. Example 28 In addition to using Suspension Polymerization Manufacturing Example i instead of Suspension Polymerization Manufacturing Example 14, and instead of acrylic emulsion manufacturing Example! The same procedure as in Example 1 was carried out except for the use of the acrylic acid emulsion emulsion. The indicators are 37.2% non-volatile content, 700 mPa.s viscosity, and ρ 8.50. Example 29. Except for the suspension polymerization manufacturing example, the suspension polymerization manufacturing example 15 is used, _ instead of the acrylic emulsion manufacturing example χ is using acrylic acid. Except for Silicone Emulsion Production Example 2, it was the same as Example 1. The index is 36.3% non-volatile matter, 700 mPa.s viscosity, ρΗ8.6. Example 30 The same as Example i except that Suspension Polymerization Production Example 16 was used instead of Suspension Polymerization Production Example i and Acrylic Emulsion Production Example 1 was used instead of Acrylic Silicone Emulsion Production Example 2. The indicators are 37.3% non-volatile matter, 710 mPa.s viscosity, ρΗ8.6. Comparative Example 1 was the same as Example 1 except that Suspension Polymerization Production Example 8 was used instead of Suspension Polymerization Production Example 1. The indicators are 37.0% non-volatile matter, viscosity 650 mPa.s, and ρΗ8.5. Comparative Example 2 The same as Example 丄 except that Suspension Polymerization Manufacturing Example 8 was used in place of Suspension Polymerization Manufacturing Example 8 'instead of Acrylic Emulsion Manufacturing Example 1 manufactured using acrylic silicone emulsion 38 200406474 2'. The index is non-volatile content μ %% 680mPa.s, ρΗ8.5. ^ Comparative Example 3 To 4 · 4 parts of silicon dioxide ρ 526 (made by Mizusawa Chemical Co., Ltd.) was added 1000 parts of the acrylic emulsion prepared in the acrylic emulsion manufacturing example 1 and tackifier wr —600 (non-volatile content · 5 · 〇%) 2 · 9 parts, defoaming agent (sn. Fermat-777: made by Senopugo) 0.2 parts, dispersant (SN Di Isparteto "π: made by Senopugo) 1 0 parts and diluted water to obtain a clear coating composition. The index is 37.3% non-volatile content, viscosity 920 mPa.s, pH 8 · 2. Comparative Example 4 Except using Acrylic Emulsion Production Example 2 instead of Suspension Polymerization Production Example 1, and Comparative Example 3 is the same. The indicators are 37.2% non-volatile content, 900 mPa.s viscosity, and ρΗ8.1. The physical properties of Examples 1 to 30 and Comparative Examples 1 to 4 are shown in Tables 3 and 4.

39 200406474 Example ο m (N 〇〇〇 ◎ Xi α wear (M 〇〇〇 ◎ key 00 {_ rH ra 〇〇in 〇 ◎ Example 7 t &gt; rH 〇〇VO 〇〇 Example 6 VO τ-Η 〇〇in 〇〇rH 〇〇ί〇〇〇 series in inch M inch τ-Η 〇〇Ό 〇〇m IK cn rH 〇〇〇〇〇〇〇 辑 次 N M (N rH 〇〇ν〇〇〇m TH 〇 〇 \ 〇〇〇 &lt; / ^ \ Sao mw ^ § bismuth a / ^ \ invite 〇mil wa Μ M_ _m IE 鳏 鳏 Ϊ 6 Example 20 〇t &gt; &lt; 〇 舾 cq rH 〇〇inch ◎ 〇H rH 〇〇cn ◎ 〇 匡 yH τ-Η 〇〇 inch ◎ 〇m m U ο 〇〇 inch ◎ 〇m bond sn 〇 \ rH 〇〇〇〇 Marina. U ο (N 〇〇m 〇 ◎ m boring 2 1¾ v〇 (Ν 〇〇in 〇 ◎ series 2 IK VT &gt; &lt; Ν 〇〇in 〇 ◎ IK (N 〇〇Ό〇〇 ◎ &lt; donkey mm #i / ^ Ν 〇 Bi Can Mi 1 shed M Μ age Gong strip &amp; ll_m bacteria 200406474 IK VO (N 〇〇〇 ◎ 鹣 uo (N 〇〇inch ◎ ◎ N (N 〇〇VO 〇 ◎ Xi 5 CO CM 〇〇inch ◎ ◎ 1 «C4 (N 〇〇CO ◎ ◎ IK yH 04 〇〇m ◎ ◎ U U (M 〇〇inch ◎ ◎ m U ON CN 〇〇1〇〇 ◎ {_ v〇t-H 〇〇 卜 &lt; 〇 匡 集 3 Μ vn rH 〇〇 寸 〇〇 &lt; // ^ \ 骑 群 m _ (m # ir ^ \ invite ο bismuth 嫠rm1 Feet% &lt; □ ff Gongff Assistant Sword II m IE paste ts fi Comparative Example 4 using silicon dioxide 04 〇X (white turbid) XX Comparative Example 3 using silicon dioxide 〇X (white turbid) cn XX CM CM00 cs 〇 〇00 〇〇AJ J-Λ rH 镒 00 τΗ 〇〇On 〇 &lt;] ^ LJ JA &lt; mm »m # 1 / ^ N 〇milmil P a 鶬&lt; ίπ 18V Μ m barn %% bonus II m IE paste δ 200406474 Example 31 In 100 parts of the aqueous dispersion prepared in suspension polymerization manufacturing example 1, 100% 25% ammonia water and a tackifier were added RW — 600 (non-volatile content · 5.0%) 10 parts (viscosity 1260 mPa.s), and the time until settling at room temperature was observed. After the household descends, stir the sediment with a stir bar to confirm the presence of hard adhesion (re-gassing). Comparative Example 5 To 100 parts of the aqueous dispersion prepared in suspension polymerization manufacturing example 1 was added butylcellulose as a film-forming aid / CS_ 12 == 17 丄 / 17 / 吧 合 液 5 · ι part (15 mPa.s dryness), and the time until settling at room temperature was observed. After sedimentation, the sediment was stirred with a stirring rod to confirm the presence or absence of hard adhesion. lOmPa.s) It is indeed possible to observe the hardness of 100 parts of the water dispersion of Production Example 1 (time for viscosity to settle. After settling, the sediment is stirred with a stirring rod to make it sticky. Test method <non-volatile content> The obtained water dispersion was dried at 105 ° C for 1 hour. The weight percentage was expressed in terms of weight percent relative to the coating composition before drying <pH>. The drying residue was taken as the weight ratio. The nonvolatile matter was dried with hot air. F ~ 23 "manufactured by Digfield Co., Ltd.) was measured with a pH meter (value at ° C) at 25 ° C. <Viscosity> BM type dumometer (manufactured by Tokyo Keiki Co., Ltd. at 30rpm, 42 200406474 at 25 ° C.) The rotor to be used is selected according to the viscosity. <Average particle diameter> The average particle diameter of the suspended polymer is measured using a Coulter counter (Beckman Coultel: Inc., model; multiple sizing machine π). • Analysis of average particle size of acrylic emulsion. Light scattering particle control measurement device (model: NICOMP380, manufactured by Particale Sizing Systems, USA). <Appearance matting property> The obtained coating composition was black-colored acrylic. The acid plate (made by Taiyou Machinery Co., Ltd.) was coated with a 4 mil dispenser. After finishing at room temperature for 5 minutes, it was measured with a gloss meter (60. Gloss) and dried in a hot air dryer at 1000 ° C (1) Minute finish (light).

GL25 or less ... 〇, GL26 or more. X <Transparency> The transparency of the coated plate manufactured by the same method as the above-mentioned appearance matting property was measured with a color difference meter. L value is 10 or less, 〇, B value is u or more, χ <absorptivity> A release paper is affixed to a glass plate, and an i-sheet with a thickness of about 300 micrometers (thickness) is manufactured thereon. The finished coating composition is flowed into the template to make a mold. After finishing for 5 minutes, it was dried in a hot-air dryer for 100 minutes for 10 minutes to prepare a test film. After the test film was left at room temperature for 24 hours, it was cut into 4 cm x 4 cm and the weight (w0) was measured. Then, it was immersed in normal temperature water and immersed. After one week, it was taken out and wiped off the surface 200406474. The film was immediately reset (W1). The test film was then placed at 150. Dry in a hot air drier for "solid hours, and measure its weight (w2). Calculate the water absorption of the coating film by the following formula. Water absorption (%) = ((Wl-W2) / W2) χι〇〇 〈temperature resistance Water test> The varnished plate manufactured by the same method as the above-mentioned matt appearance was left at room temperature for 25 hours, and then immersed in 6 "c warm water to be impregnated. After that, the varnished plate was dried at room temperature Day i. The appearance of the dried coated plate is compared with the untested plate (initial plate). <Weather resistance (M — W 〇 Μ)> A solvent-based sealing material is coated on the asbestos plate, and dried to 20 micrometers. 2. After drying at room temperature for 1 day, use a 4mil liquid dispenser to apply the primer coating prepared below. After finishing for 5 minutes, dry in a hot air dryer at ⑽.C for 10 minutes. Leave at room temperature After i days, the obtained coating composition was coated with a 4 mil liquid dispenser, and after finishing for 5 minutes, it was dried in a hot-air dryer for 10 minutes to produce a coated board. The coated board that passed i days after manufacture was used to super promote weather resistance Test (Super accelerated weathering test: M — WOM condition) Put the above-mentioned coating 饬 揣 Meng Na on a test machine of Daipura Mitaru Uhuiza, made by Uytis, a company of Daipura, G.M.A., and t 、 A a′I. Plate, for 6 hours of irradiation (temperature 63 ° C-humidity 50%), shower 10 seconds, Xiaxia ~ &amp; road for 2 hours (temperature 30 ° C-humidity 95% or more), shower 10 seconds as The test is repeated for 700 hours for one to 100%. The appearance of the coating film in 700 hours is not abnormal in 1000 hours. ◎ 44 &quot;, hanging ........, the color of the coating film changes △, the coating film Cracks on the surface ... x (combination of primer coating) ◎ Acrylic emulsion (Pakurisin WX-35: Japan Catalyst Co., Ltd.) ◎ White paste (adjustment paste described below): 135 parts by weight, • Dispersant (Di Mauro EP: manufactured by Kao Corporation): 60% weight::, 50 (Di Isgoto N-14: Part by Industrial Pharmaceutical Co., Ltd. by weight, • Wetting agent (Huima Lugu 909: manufactured by Kao Corporation): 10 parts by weight, • ethylene glycol: 60 parts by weight, • deionized water: 210 parts by weight, • titanium oxide (CR-95: Ishihara Industry Co.): 1_ parts by weight, Foaming agent (Nuopugo 8034L: made by Senovopu): weight • glass beads: 500 parts by weight, mix the above materials with 3000 rpm stirrer. Add all the ingredients and stir for 60 minutes to adjust. ◎ Film formation Auxiliary agent (butylcellulose) 15 parts by weight ◎ (CS 12 · made by Chisso Co., Ltd.) 15 parts by weight ◎ black paste (Nunironto 88: Yokohama Chemical Co., Ltd.): 10 parts by weight Parts ◎ Defoaming agent (Nuopu 8034L: made by Xenopu Co.): 15 parts by weight 45

Claims (1)

200406474 Scope of patent application: 1. An aqueous resin dispersion containing (A) will contain (a) (meth) propanoate, (b) a multifunctional crosslinkable monomer, and (c) have UV stability Resin particles having an average particle diameter of 1 to 100 micrometers, which are generated by suspension polymerization of monomer components of unsaturated monomers based on ultraviolet and / or ultraviolet absorbing groups. 2. The aqueous resin dispersion according to item 1 of the scope of patent application, wherein (A) (a) (meth) acrylate is (meth) acrylic acid ester having cycloalkyl and / or tert-butyl . 3. An aqueous resin composition comprising (A) a (meth) acrylate containing (a) a cycloalkyl group and / or a tert-butyl group, (b) a polyfunctional crosslinkable monomer, and (c) (B) Aqueous resin dispersion containing resin particles having an average particle diameter of 1 to 100 micrometers and suspension polymerization of a monomer mixture of an unsaturated monomer having an ultraviolet-stabilizing group and / or an ultraviolet-absorbing group, and an average particle diameter of 0.01 Consisting of an aqueous resin dispersion of ~ 1 micron resin particles. 4. An aqueous resin composition comprising (A) 50 to 99% by mass of a (meth) acrylate having a cycloalkyl group and / or a tert-butyl group, and (b) a polyfunctional crosslinkable monomer ( ^ ~ Such as mass% and (d) other monomers ^ 0 ~ 49.9% by mass of monomer mixture produced by suspension polymerization of an aqueous resin dispersion of resin particles having an average particle diameter of 100 microns, in which (a), (b), and (d) ) A total of 100% by mass, and (B) A composition containing an aqueous resin dispersion having an average particle size of micron. 46 200406474 5. A method for producing an aqueous resin composition, characterized in that it contains an average particle size 1 generated by suspension polymerization. Add (c) a tackifier and mix (B) an aqueous resin dispersion containing resin particles with an average particle size of 0.01 to 1 micron to an aqueous resin dispersion of ~ 100 micron resin particles. 6. An aqueous A method for producing a resin composition, comprising (A) (a) a (meth) acrylic acid ester having a cycloalkyl group and / or a tert-butyl group, and (b) a polyfunctional crosslinkable monomer. And (e) contains an ultraviolet stabilizing group and / or an ultraviolet absorbing group (C) Bulking agent is added to an aqueous resin dispersion of resin particles having an average particle diameter of 1 to 100 micrometers, which is obtained by suspension polymerization of a monomer mixture of unsaturated monomers, and mixed with an average particle diameter of 0. 01 to 1 Aqueous resin dispersion of micron resin particles. 7. A method for producing an aqueous resin composition, characterized by containing (A) (a) (meth) acrylic acid having a cycloalkyl group and / or a tert-butyl group. 50 to 99% by mass of vinegar, (b) polyfunctional crosslinkable monomers of 0 to 20% by mass, and (d) other monomers of 0 to 49.9% by mass of the monomer mixture, the average particle size resulting from suspension polymerization is 1 to 1 Add (C) a tackifier 'to an aqueous resin dispersion of resin particles of OO micrometers and mix (B) an aqueous resin dispersion containing resin particles having an average particle size of 0.001 to 1 micrometer, where (a), (B) and (d) total 100% by mass. (2) 200406474 The step of separating the above-mentioned compound from a fluoroalcohol. -13- 200406474 (1) Designated representative map: (1) The designated representative map in this case is: (). (2) A brief description of the element representative symbols of this representative figure: Object J. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: