TWI264441B - Cold curing aqueous composition - Google Patents

Abstract

There is provided a cold curing aqueous composition which has cold curability as a fluorine-containing coating film component of aqueous coating composition and gives excellent coating film characteristics. The cold curing aqueous composition comprises an aqueous curing agent and a fluorine-containing composite resin (B) obtained by emulsion polymerization of a monomer (b1) having an ethylenic un-saturated group in the presence of a fluorine-containing copolymer (A) having an ethylenic un-saturated group and a water soluble functional group in its molecule.

Description

I

I 1264441 (1) EMBODIMENT OF THE INVENTION [Technical Field] The present invention relates to a fluorine-based coating film component of an aqueous coating composition, which is a room temperature hardenability which provides room temperature hardening property and provides excellent film properties. Aqueous composition. [Prior Art]

Conventionally, a fluorine-containing aqueous dispersion, for example, in the presence of an aqueous dispersion of a sulphuric acid storage fluororesin particle disclosed in Patent Document 1, is subjected to seed polymerization polymerization of an acrylic acid or a methacrylate monomer. technology. The composite resin which is still produced has a low compatibility with the vinylidene chloride-based fluororesin and the (meth)acrylic resin, and it is difficult to introduce a carboxyl group into the vinylidene chloride-based fluororesin as a seed particle in the seed polymerization. Or a disadvantage of a functional group such as a hydroxyl group. Further, Patent Document 2 discloses a fluorine-containing aqueous dispersion obtained by emulsion-polymerizing an ethylenically unsaturated monomer in a reaction system using a fluorine-containing polymer having a carboxyl group bonded to a fluoroalkyl group as a dispersion stabilizer. Add the technology of crosslinker. However, this technique does not add a crosslinking agent having a room temperature curable property as a crosslinking agent, so that problems such as drying hardenability at room temperature are caused. Further, since the ethylene-saturated unsaturated monomer does not use a weather-resistant ethylene monomer, its weather resistance is also insufficient.专利 'Patent Document 3 discloses a fluororesin obtained by copolymerization of a hydrophilic group-containing non-fluorine-based macromonomer having a fluoroalkyl group bonded thereto, and then emulsified to prepare an aqueous dispersion in which an ethylene monomer is further added. Seed polymerization with milk-5 - (2) (2) 1264441 to obtain a composite aqueous fluororesin dispersion. However, since the fluororesin which is a seed crystal is obtained by emulsion polymerization, it is disadvantageous that a water-soluble functional group such as a carboxyl group or a hydroxyl group is not easily introduced into the fluororesin. Further, when the amount of the emulsifier or the like is too large, problems such as the inability to add a crosslinking agent are caused, and the chemical resistance of the coating film, the solvent resistance, and the poor hardness of the coating film and the water resistance are likely to occur. Further, Patent Document 4 discloses a technique for a composition for an aqueous coating obtained by a dispersion of a fluorine-containing resin obtained by emulsion polymerization and a dispersion of an acrylic or methacrylic copolymer obtained by emulsion polymerization. However, the aqueous dispersion of the fluorine-containing resin has poor compatibility with the acrylic or methacrylic aqueous dispersion, and is insufficiently and uniformly mixed, so that the obtained coating film has disadvantages such as poor weather resistance, adhesion, gloss, and the like. . Further, since the curing agent is not added, problems such as chemical resistance, solvent resistance, coating film hardness, and water resistance remain. Further, Patent Document 5 discloses a method in which a (meth) acrylate monomer is polymerized by a seed crystal to form a hydroxy group-containing acrylic resin in the presence of an aqueous dispersion obtained by emulsion polymerization of a fluorocarbon and propylene and ethylene. A fluorine-containing aqueous coating composition obtained from a fluorine-based dispersion and an oxime-based curing agent. However, the fluorine-based resin obtained in this document has low compatibility with the acrylic resin, and the (meth) acrylate monomer is less likely to be dissolved in the fluororesin dispersion during the polymerization of the seed crystal, and as a result, the weather resistance of the coating film is caused. The disadvantages of poor gloss and so on. [Patent Document 1] JP-A-62-3 2] No. 02 (Patent Document 2), JP-A-2013-3-3] 4 2 0 2, -6- (3) (3) 1264441 [Patent Document 3. Japanese Patent Laid-Open No. Hei 7- 2 3 8 2 5 3 [Patent Document 4] Japanese Patent Laid-Open Publication No. Hei 9-5-9 5 No. Disclosure of the Invention The present invention is a technique for solving a room temperature hardenable aqueous composition which is harden at room temperature and which imparts excellent coating film properties, which is proposed to solve the above-mentioned conventional disadvantages. That is, the present invention is an emulsion of an ethylenic unsaturated group-containing monomer (b 1 ) in the presence of a fluorine-containing copolymer (A) having an ethylenically unsaturated group and a water-soluble functional group in the molecule. A room temperature curable aqueous composition composed of an aqueous dispersion of the fluorine-containing composite resin (B) obtained by polymerization and an aqueous hardener. Among them, the acid value of the fluorinated copolymer (A) is preferably from 10 to 250 mg K 〇 H / g. Further, the water-soluble functional group of the fluorinated copolymer (A) is preferably a functional group obtained by neutralizing an anionic functional group with a base. In the fluorinated copolymer (A), the structural unit is at least one perhalo olefin unit selected from the group consisting of tetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene in an amount of 10 to 7 mol%. Copolymers are preferred. Further, the monomer (b 1 ) containing an ethylenically unsaturated group is an acrylic or methacrylic acid group containing at least one monomer having a crosslinkable functional group and an alkyl group having 4 to 1 carbon atoms in a carbon number. A monomer mixture of monomers is preferred. The crosslinkable functional group is preferably at least one selected from the group consisting of a carbonyl group, a hydroxyl group and a carboxyl group, -7 - (4) (4) 1264441. The room temperature curable aqueous composition of the present invention may further contain an emulsion of the non-fluorine-based synthetic resin (C), and further comprise 95 to 5 parts by weight of the solid component containing the fluorine-containing composite resin (b) and a non-fluorine-based synthesis. The solid content of the resin (c) is preferably 5 to 95 parts by weight. Further, the aqueous hardener is a hardener which is at room temperature curable, for example, a ruthenium compound having at least two fluorenyl groups in one molecule, and a ruthenium diene having at least two carbodiimide groups in one molecule. An carbodiimide compound or a hydrophilic polyisocyanate is preferred. In addition, the curing agent is preferably equivalent to 1 to 5 molar equivalents based on 1 equivalent of the total functional group of the fluorine-containing composite resin (B) and the non-fluorine-based synthetic resin (C). The present invention can easily produce a coating film having excellent chemical resistance, solvent resistance, coating film hardness, water resistance and the like at room temperature. The room temperature curable aqueous composition of the present invention is composed of an aqueous dispersion of a specific fluorine-containing composite resin (B) and an aqueous hardener. The fluorine-containing composite resin (B) is a monomer containing an ethylenic unsaturated group in the presence of a fluorine-containing copolymer (A) having an ethylenic unsaturated group and a water-soluble functional group in the molecule ( b 1) Those obtained by emulsion polymerization. The fluorinated copolymer (A) is a fluorinated copolymer having an ethylenic unsaturated group and a water-soluble functional group in the molecule, preferably a fluoroolefin unit c fluoroolefin, for example, tetrafluoroethylene (TFE), One or more of trifluoroethylene (TrFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), fluorinated (5) 1264441 ethylene (VF), and fluorinated vinylidene chloride (vd F), Among them, a perhalogenated olefin monomer containing from 〇 to 7 〇 mol% is preferred. Further, the use of a fluoroolefin as a perfluoroolefin such as TFE or HFP can provide a fluorine-containing polymer having a large fluorine content, and also exhibits an excellent chemical resistance, water solvent resistance, and stain resistance. Coating film for weather resistance and the like. The water-soluble functional group is preferably, for example, a functional group obtained by subjecting an anionic functional group. The anionic functional group such as a carboxyl group, a phosphoric acid group or the like is preferably a carboxyl group from the viewpoint of having excellent water resistance and less corrosion of metal. When the anionic functional group is introduced into the fluorinated copolymer, a side polymerization method in which a monomer having an anionic functional group is copolymerized, and a polymer having a functional group such as a hydroxyl group may be anionic with an acid anhydride. A method of reacting a compound of a functional group (high method) and the like. A monomer which can be used for copolymerization of a carboxyl group of an anionic functional group can be used, for example, formula (I): R3 R5 \ / C-C / \

R4 (CH2) nCOOH (wherein R3, R4 and R5 may be the same or different, which may be a hydroalkyl group, a carboxyl group or an ester group; n is a hydrazine to 20), an unsaturated monounsaturated dicarboxylic acid Two kinds of unsaturated carboxylic acids such as acid, monoester or acid anhydride, etc., which are the most compatible, alkali-resistant, and sulfonic acid base materials. Atom 'carboxylic acid'. Among them, -9 - (6) (6) 1264441 is preferable as R3 and R4 are hydrogen atoms, and η is preferably 3 or more and 5 or less, especially R3, R4 and R5 are The hydrogen atom is more preferably 6 or more and 10 or less. Specific examples of the unsaturated carboxylic acid of the formula (I) include, for example, acrylic acid, methacrylic acid, ethylene acetic acid, crotonic acid, cinnamic acid, and 3-allyl. Oxypropionic acid, 3-(2-allyloxyethoxycarbonyl)propionic acid, itaconic acid, itaconic acid monoester', maleic acid, maleic acid monoester, maleic anhydride, fumaric acid, rich Monoacid of horse acid, vinyl benzoate, vinyl pyromelliate, 5-hexenoic acid, 5-heptenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-decenoic acid, ^癸Oleic acid, 10-undecenoic acid, 1 dodecenoic acid, 17- Octaenoic acid, oleic acid, etc. Among them, crotonic acid, itaconic acid, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, 3-allyloxypropane Acid, 10 - undecylenic acid, etc., are preferred because they are difficult to homopolymerize. In particular, 1 - undecenoic acid has good polymerization reactivity and is difficult to hydrolyze, and is preferred. 〇 The monomer used in the copolymerization of the carboxyl group of the anionic functional group, for example, the formula (Π): CH2 = CH—fCH2-^0 —(rR6OCO R7 COOH (II) (wherein R6 and R7 may be the same or different, and may be a saturated or unsaturated linear or cyclic building group; η is a vinyl ether monomer having a residue of 0 or]), and the like. Specific examples of the vinyl ether monomer, for example, a method selected from the group consisting of -10 - (8) (8) 1644441 reacting with a compound having a bi-storage unsaturated double bond to introduce an ethylenically unsaturated double bond (polymer reaction) Method), a monomer having two or more ethylenic unsaturated double bonds, such as butadiene, isobutylene, chlorobutene, fluorobutene, and amine, which can be used in copolymerization. a diene monomer such as phenylbutadiene, diphenyl butadiene or α,ω-diolene; divinyl adipate, vinyl acrylate, ethylene methacrylate methacrylate, vinyl crotonate, etc. A polyfunctional carboxylic acid vinyl ester; an aromatic carboxylic acid vinyl ester such as vinyl cinnamate; etc. In the polymer reaction method, for example, a carboxyl group is used as a functional group, and a method of introducing a carboxyl group into the copolymer (A) is exemplified, for example. The introduction method of the above anionic functional group or the like can be employed. The obtained carboxyl group-containing fluoropolymer (al) is reacted with a compound (a2) having a functional group reactive with a carboxyl group and an ethylenically unsaturated bond. A functional group reactive with a carboxyl group, for example, an isocyanate group, an epoxy group, an amine group, a carbodiimide group or the like, wherein an isocyanate group and an epoxy group are preferably reacted rapidly with a carboxyl group. The compound (a2), for example, an isocyanate group-containing compound such as 2-isocyanoethyl methacrylate; an epoxy group-containing compound such as glycidyl methacrylate, propylene glycidyl ester or allyl glycidyl ether; . Among them, 2-isocyanoethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, and the like are more preferable. Among them, the isocyanate group can react with a hydroxyl group, but preferentially reacts with a carboxy-12-1246441 oxime group. The reaction of the compound (a2) with the fluoropolymer (a1) can be carried out, for example, in a mixed manner in an organic solvent. The reaction conditions are preferably, for example, a reaction temperature of 20 to 15 (1 to 15 hours at TC). The organic solvent can be used as long as a solvent capable of dissolving the fluoropolymer and the compound is used. For example, a fluoropolymer can be used. (a 1 ) an organic solvent used for the polymerization. The compound (a2 ), relative to the 1 mol of the carboxyl group in the fluoropolymer (a 1 ), the functional group of the compound (a2) is used in an amount of from 1 to 〇. It is preferred to use 1 to 〇·1 mole, more preferably to react with a reaction amount of 1 to 〇·9 moles. Further, the fluorinated copolymer (A) may have a crosslinkable functional group or may have no crosslinking. The functional group may be 'in terms of improving coating film strength, water resistance, solvent resistance, adhesion, film hardness, etc.', and it is preferable to contain a crosslinkable functional group. The crosslinkable functional group' can be described later, for example. The type of the crosslinkable functional group having a curing agent or the type of the crosslinkable functional group having a non-fluorine-based synthetic resin is appropriately selected. Preferably, at least one selected from the group consisting of a carboxyl group, a hydroxyl group and a carbonyl group is used. The combination of a functional group and a hardener will be described later. Specific examples of the monomer-containing carboxyl group-containing monomer include, for example, a carboxyl group-containing monomer used for introducing the above-mentioned negative functional group, that is, 'carboxy group is a function having a functional group capable of imparting an acid value and a crosslinkable functional group', particularly -13- (10) 1264441 is preferred because it can be converted to a water-soluble functional group when it is water-soluble (acidic value is imparted), and is preferably a hydroxyl group-containing monomer having a crosslinkable functional monomer. Specific examples, such as formula (III): CH2 = CHR] (III) [wherein R1 is -OR2 or -CH2OR2 (wherein R2 is an alkyl group having a hydroxyl group)] is a hydroxyalkyl vinyl ether or a hydroxyl group. An alkyl allyl ether or the like. R2, for example, a linear or branched alkyl group having 1 to 8 carbon atoms, and having 1 to 3 linkages, preferably one having a hydroxyl group bonded thereto. , such as 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl Ether, 4-hydroxy-2-methylbutyl vinyl ether, 5-hydroxybenzyl ethyl succinyl ether, 6-ylhexyl ethyl ether, 2-phenylethyl propyl ether, 4-hydroxyl Butylene Propyl ether, glycerol monoallyl ether, etc. Among them, 4 - mercaptobutyl ethyl ether, 2 - ethyl ethyl acetoacetate have excellent polymerization reactivity, hardenability of functional groups, etc. Further, a specific example of a monomer having a crosslinkable functional group such as a carbonyl group-containing monomer, such as (IV): R6 R8

C = C / \ (IV) R7 (CH2) nCONHC (CH3) 2CH2COCH3 (wherein R6, R7 and R8 are the same or different and are a hydrogen atom, alkyl-14-(11) 1264441 'carboxy or ester group ; η is ο or ]) does not contain a pseudo-ethyl group. Or as in formula (V): CH2= CH—(r CH2*^r 〇R9OCO R10CONHC (CH3) 2CH2COCH3 (wherein R9 and R1() are the same or different and are saturated or not chained or cyclic a specific example of a divalent hydrocarbon group; η is 0 or 1; m is 0 or 1) a carbonyl-containing vinyl ether type monomer or an allyl ether type ruthenium containing carbonyl monomer, for example, acrolein, diacetone C, and bis A vinyl alkyl ketone such as acetone methacrylamide, vinyl methyl ketone, vinyl or vinyl butyl ketone, etc. Among them, a copolymerization property of a vinyl ether type and an allyl ether type and a fluoroolefin Preferably, the fluorinated copolymer (A) may be copolymerized with other copolymerizable copolymers if necessary. Other copolymerizable monomers, such as carboxylic acid vinyl ester vinyl ethers, non-fluorine systems Olefins, etc. Vinyl carboxylates such as vinyl acetate, vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, vinyl versatate, vinyl laurate, Stearic acid, vinyl cyclohexylcarboxylate, vinyl benzoate, p-butyl butyl acetate, etc. It can improve compatibility and gloss Elevated glass (V) saturated monomer such as ketamine ethyl ketone has good monomer, phenolic ester, hexanoic acid benzoic acid glass transfer -15 - (12) (12) 1264441 temperature and other characteristics The base B (tetra) acid, such as methyl ethyl (tetra) acid, ethyl ethanoic acid, butyl ethyl phthalate, etc., can improve the properties of gloss, flexibility, etc. Non-fluorine olefins, such as ethylene 'propylene , butene, isobutyl, etc., which have the property of extracting properties. The molecular weight of the copolymer (A) is a number average molecular weight of 2 〇〇 5 〇〇〇 or less '1 0 0, 0 0 0 or less, particularly a copolymer of 5 Å or less, which is preferable from the viewpoint of easy polymerization, and 1 or more, and 4,500 or more 'especially 8, The above copolymer is preferably characterized by excellent weather resistance, durability, etc. As described above, the method for producing a functional group-containing fluorinated copolymer for aqueous coatings is to employ an emulsifying method. The preparation is generally prepared in the form of an aqueous dispersion or an emulsion (JP-A-7-2 3 8 2 S3, Kaiping 9 - 5 9 5 6 0, JP-A 2 Ο Ο 0 - 1 2 9 1 5 9). However, the emulsion polymerization method does not allow a large amount of monomers containing water-soluble functional groups to be copolymerized, so as before In general, only a polymer having a relatively large molecular weight can be formed. More specifically, a monomer having a fluoroolefin and a functional group (water-soluble functional group, ethylenic unsaturated double bond, etc.), and if necessary The monomer copolymerized with it is polymerized in an organic solvent to produce the fluorinated copolymer (A) used in the present invention. The polymerization condition, preferably in an organic solvent, in the presence of a polymerization initiator, the polymerization temperature is The polymerization is carried out at 1 to 20 ° C for 1 to 20 hours. Organic solvents such as methyl acetate, ethyl acetate, propyl acetate, esters such as -16-(13) (13) 1264441 butyl acetate, ketones such as acetone 'methyl ethyl ketone, cyclohexanone; a hydrocarbon such as cyclohexane or octane; an aromatic hydrocarbon such as benzene, toluene, xylene or naphthalene; an alcohol such as methanol, ethanol, tert-butanol, iso> butanol or ethylene glycol monoalkyl ether; a cyclic ether such as tetrahydrofuran 'tetrahydropyran or dioxane; dimethyl hydrazine or the like, or a mixture thereof. Among the above solvents, acetone, ethyl acetate, isopropyl alcohol or the like is preferred from the viewpoint of solubility of the fluororesin, and acetone and ethyl acetate are easily distilled off when preparing an aqueous emulsion. optimal. As the polymerization initiator, for example, dioxins such as octyl peroxide, acetonitrile peroxide, and benzoquinone peroxide; dialkyloxycarbonyl groups such as isopropoxycarbonyl peroxide and tert-butoxycarbonyl peroxide can be used. Peroxides; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc. Oxide; dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide; tert-butyl peroxyacetate, tert-butyl peroxytrimethyl Alkyl peroxyalkyl esters such as acetate; persulfate such as ammonium persulfate or potassium persulfate (which can be reduced with sodium hydrogen sulfite, sodium metabisulfite, chromium naphthenate, dimethyl benzyl ammonium, etc.) a redox initiator such as an oxidizing agent (such as ammonium peroxide, potassium peroxide, etc.) and a reducing agent (such as sodium sulfite) and a transition metal salt (such as iron sulfate); azobisisobutyronitrile, azo Bis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylvaleronitrile), 2,2'-azobis(2- Propylpropionitrile, 2 2 dimethyl azobisisobutyrate, 2: 2 '-azobis[2-(hydroxyindenyl)propanenitrile], 4,4 Μ禺N 2 (4 1 ampere) Pentenoic acid), etc., even 17 - (14) (14) 1264441 Nitrogen compounds. Further, if necessary, an alcohol such as methanol, ethanol or propanol of a molecular weight modifier may be used. The fluorinated copolymer (A) obtained as described above has a high acid value of 5 to impart an acid value of 10 to 25 mg of KOH/g. When the acid value is less than 1 OmgKOH/g, the fluorocarbon copolymer does not form water solubility, and it cannot be uniformly dispersed in water without being assisted by a dispersing agent or an emulsifier. Further, when the acid value exceeds 250 mg KOH/g, the hydrophilicity of the coating film is too large, and the water resistance and alkali resistance of the obtained coating film are lowered. The lower limit of the acid value is preferably 40 mgKOH/g, more preferably 50 mgKOH/g, most preferably 55 mgKOH/g. Further, the upper limit is preferably 1 50 mgKOH/g, more preferably -130 mg K〇H/g, most preferably 120 mg K〇H/g. ^ The obtained fluorinated copolymer (A) can be converted into an aqueous phase by introducing a polymerization reaction liquid into water or adding water to the polymerization reaction liquid to form a water-soluble phase. Fluorine copolymer. In this case, in order to increase the water solubility of the fluorinated copolymer, it is preferred to carry out the neutralization treatment before the phase transition of the anionic functional group to water, or at the time of phase inversion, or after the phase inversion. Neutralizing agent used for neutralization, for example, ammonia; diethylamine, ethylethanolamine, diethanolamine, monoethanolamine, monopropanolamine, isopropanolamine, ethylamine ethylamine, hydroxyethylamine There are group amines such as diethylenetriamine; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Among them, ammonia, triethylamine, diethanolamine, etc. are preferred, and suspension stability is preferred, especially ammonia and triethylamine are easy to be -18 - (15) (15) 1264441 rationality And for the better. The neutralizing agent may be used in the form of an aqueous solution or in the form of a gas or a solid. As a result of the neutralization, the anionic functional group can be formed into an ammonium salt, an amine salt or an alkali metal salt. The neutralization is carried out by using an anionic functional group of 1 mgKOH/g or more, preferably 2 mgKOH/g or more or 250 mgKOH/g or less, preferably 245 mgKOH/g or less, in the acid value of the copolymer. Neutralization of the neutralizing agent is preferred. The present invention is a fluorine-containing composite resin (B) obtained by emulsion polymerization of a monomer (b 1 ) containing an ethylenically unsaturated group in the presence of the above-mentioned fluorine-containing copolymer (A). As the monomer (b1) containing an ethylenic unsaturated group, monomers having various characteristics can be used. For example, a monomer containing an ethylenically unsaturated group capable of imparting a water-soluble or water-dispersible carboxyl group and/or a sulfonic acid group in the fluorine-containing composite resin (B) can be used. Further, for example, a monomer having an ethylenically unsaturated group such as a carboxyl group, an amine group, a guanamine group or an epoxy group which imparts properties such as adhesion and pigment dispersibility may be further contained. Further, a crosslinkable functional group which imparts properties such as crosslinkability is, for example, a monomer having an ethylenically unsaturated group such as a hydroxyl group, a carboxyl group, a carbonyl group or an amine group. Further, it is preferred to use a flame-retardant group containing an alkyl group having a carbon number of 4 to 10 inclusive. In particular, a monomer mixture obtained by containing at least one monomer having a crosslinkable functional group and an acrylic acid or methacrylic monomer having an alkyl group having 4 to 10 carbon atoms is preferred. -19- (16) (16) 1264441 Specific examples of the monomer (b 1 ) containing an ethylenically unsaturated group, for example, one or more selected from the group consisting of methyl acrylate and n-butyl chloroformate , methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, etc. (lower alkyl esters of (meth)acrylic acid; 2-ethylhexyl acrylate methyl acrylate acid, 2-ethylhexyl acrylate An alkyl ester having 4 to 10 carbon atoms of (meth)acrylic acid such as cyclohexyl acrylate or cyclohexyl methacrylate; unsatisfied acid, methacrylic acid, maleic acid, crotonic acid, etc. Carboxylic acid; acrylamide, methacrylamide, N-methylolmethacrylamide, N-methylolmethylmethacrylamide, N-butoxymethylpropenamide, etc. Amine compounds; hydroxyl group-containing monomers such as hydroxyethyl acrylate and hydroxypropyl methacrylate; epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; 7-trimethoxy chopper A siloxane-containing monomer such as acrolein or an aldehyde-containing monomer such as acrolein or the like. Among them, in view of the high degree of polymerizability and the richness of commercially available monomer types, it is preferred to use a (meth)acrylic monomer. The emulsion polymerization, which is called seed polymerization, is itself a conventionally known technique. For example, it can be carried out by the method described in JP-A-2002-197987. The monomer (b 1 ) containing the ethylenic unsaturated group is used in an amount of 1 part by weight or more, more preferably 50 parts by weight, based on 1 part by weight of the solid content of the fluorinated copolymer (A). The above is particularly preferably used in an amount of 00 parts by weight or more and 2,000 parts by weight or less, more preferably 1 part by weight or less, and most preferably 500 parts by weight or less. -20- (17) (17) 1264441 The room temperature curable aqueous composition of the present invention can be obtained from the aqueous dispersion of the fluorine-containing composite resin (B) obtained above and an aqueous hardener, particularly a hardener of room temperature curability. . The solid content concentration in the aqueous dispersion of the fluorine-containing composite resin (B) is generally adjusted to a range of from 30 to 70% by weight. The aqueous hardener to be added may be introduced into the fluorine-containing composite resin (B) or a non-fluorine-based synthetic resin (C) to be described later (hereinafter, the contents of the curing agent are simply referred to as "resin side". The cross-linking functional group of the) produces a cross-linking reaction. The aqueous hardener is, for example, a carbodiimide compound, a hydrophilic (block type or non-block type) isocyanate, a hydrazine compound, an oxycyclopropane or the like, and a room temperature hardenable aqueous hardener. As the carbodiimide compound, for example, JP-A-63- 2 6 4 1 2 8 , US Pat. No. 4,8 2 0 5 8 3 3, and US Pat. No. 5,1 0 8,6 can be used. U.S. Patent No. 5, No. 5, the specification of U.S. Patent No. 5,088, and the specification of U.S. Patent No. 5,0,817. Among the carbodiimide compounds for aqueous coatings, commercially available products such as Kelba E-01, Kalba E-02, Kalba V-02, and the like are commercially available. As the hydrophilic isocyanate, for example, a known block isocyanate can be used, but a non-block type isocyanate compound having excellent room temperature hardenability is preferred. For the non-block type isocyanate, for example, JP-A No. 1 1 - 3 1 0 7 〇 、 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The non-block isocyanate-21 - (18) 1264441 compound obtained by modifying the compound described is preferred. Further, the non-block type isocyanate compound means a general isocyanate compound other than the block type isocyanate obtained by reacting an alcohol or an ester with an isocyanate compound. Specifically, for example, a non-inserted aliphatic isocyanate compound or a block-type aromatic polyisocyanate obtained by modifying polyethylene oxide is used. Among them, a non-block type aliphatic isocyanate compound is preferred from the viewpoint of excellent weather resistance and the like. Among the aliphatic polyisocyanate compounds, a chain aliphatic polyisoester ester compound, for example, a trimethyl methyl diisocyanate, a tetra-methyl diester, a U6-diisocyanatohexane (=hexamethylene diisocyanate Methyl diisocyanate, 1,2-propyl diisocyanate, 152-yl diisocyanate, 2:3-butylene diisocyanate, 1,3 -butyl butyl cyanate, 254; 4- or trimethyl Diisocyanates such as methyl hexamethyl isocyanate 2; 6-diisocyanate methyl decyl ester; lysine cyanate, 1,4,8-triisocyanate octane,]565 11-triisocyanate , polyisocyanate such as diisocyanate isocyanate methyl octane,] triester hexane, 2 5 5 ; 7-trimethyl-1 : 8 -diisocyanate-5-isocyanatooctane. Among the isocyanate compounds, the alicyclic polyisocyanate is, for example, U3-cyclopentane diisocyanate, 1,4-cyclohexanediisoester, 1:3-cyclohexane diisocyanate, h isocyanate group-3: 3 : 5-yl-5-isocyanate methyl-cyclohexane (=isophorone diisocyanate, 4:4 ^methyl bis(cyclohexyl isocyanate), A · 2,4 -cyclization of segmental esterification using isocyanate cyanide), dibutyl--, isocyanate methyl ester, trimethyl cyanate) hexane-22 - (19 (19) 1264441 Diisocyanate, methyl-2:6-cyclohexane diisocyanate, diisocyanate such as 1:3- or 14-bis(isocyanatemethyl)cyclohexane; 1: 3 J-triisocyanate ring Hexane,],3; 5-trimethylisocyanate cyclohexane, 2-(3-isocyanatepropyl)-2,5-di(isocyanatemethyl)-2,6-di(isocyanatemethyl)-di Ring (2.2. 1) heptane, 3-(3-isocyanatepropyl)-2 5 5 -di(isocyanatemethyl)-2,6-di(isocyanate methylbicyclo(^2.2 .1) heptane, 5-(2-isocyanateethyl)-2-isocyanatemethyl-3 - '(3-isocyanatepropyl)-bicyclo(2 · 2 . 1 ) heptane, 6 - (2-isocyanate ethyl)-2 -isocyanate methyl-3-(3-isocyanatepropyl)-bicyclo(2.2.1)heptane, 5-(2-isocyanateethyl)-2-isocyanate methyl-2-(3-isocyanatepropyl) -bicyclo(2.2.1) heptane, 6-(2-isocyano-esterethyl)-2, isocyanate Polyisocyanates such as keto-2-(3-isocyanatepropyl)-di-cyclo(2.2.1)heptane. Aromatic polyisocyanate compounds such as toluene isocyanate, etc. Alkane, such as known poly(ethylene oxide) monooctyl ether, polyethylene oxide monolauryl ether, polyethylene oxide monodecyl ether, polyethylene oxide monoclavyl ether, polyepoxy a polyethylene oxide C8 to C24 alkyl ether such as ethane monostearyl ether or polyethylene oxide monooleyl ether, preferably polyethylene oxide CIO to C22 alkyl ether, more preferably poly ring Polyethylene oxide alkyl ethers such as oxyethylene C 1 2 to C 18 alkyl ethers. Further, for example, polyethylene oxide monooctyl phenyl ether, polyethylene oxide monodecyl phenyl ether, polyethylene oxide monodecyl phenyl ether, polyethylene oxide C. 8 to C12 alkyl group -C6 to C] polyalkylene oxide monoalkyl aryl ethers such as 2 alkyl ethers; for example, polyethylene oxide sucrose monolaurate, polyethylene oxide mountain sucrose mono- 23- (20) (20)1264441 Stearate, polyethylene oxide mountain selenol monooleate, polyethylene oxide mountain isosorbide distearate, polyethylene oxide mountain Polyethylene oxide sorbitol higher fatty acid esters such as sugar alcohol tristearate such as polyethylene oxide sorbitol-mono, di- or tri-C] 0 to C 2 4 fatty acid ester. Further, for example, polyethylene oxide monolaurate, polyethylene oxide monostearate, etc., polyethylene oxide j; complete C 10 0 to C 2 4 fatty acid ester, etc. An anionic emulsifier such as vinegar. The above compounds may be used singly or in combination of two or more kinds. Preferably, for example, from the viewpoint of having excellent water dispersibility, etc., it is preferred to use an alkyl ether of C8 to C24, a C8 to C12 basic acid of polyepoxidation, and the like. The modification method can be carried out, for example, by mixing an isocyanate compound with a modifier in a solution and reacting it by heating. The ratio of the polyisocyanate compound to the modifier may be from 1 equivalent of the isocyanate group in the polyisocyanate compound, and the active gas atom of the modifier is from 0.01 to 0 034 equivalents, preferably from 0.015 to 〇. Make the appropriate choice. A commercial product of a non-block type isocyanate compound in which polyethylene oxide is modified, such as Bailey 3 1 住 by the U.S. Bayer Company, Bilber Tp L 2 ] 5 〇, etc. and Asahi Kasei Corporation Dura WB40- ] 00, etc., but not limited to this. The non-block type isocyanate compound is usually used in the form of an aqueous solution or an aqueous dispersion. _ 肼 compound, for example, a compound described in Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei No. Hei No. 2-6 8 No. 63, No. 9 - 2 9 1 ], and a specific example, such as oxalic acid di-24 - (21) (21) 1264441 Bismuth, diammonium malonate, diterpene succinate, diammonium glutarate, diterpene adipate, diammonium isophthalate, diterpene sebacate, maleic acid An anthracene, a fumaric acid diterpene, a itaconic acid diterpene or the like containing 2 to 〇, preferably a dicarboxylic acid diterpene having 4 to 6 carbon atoms; ethylene-1:2-di An aliphatic, water-soluble diterpene having 2 to 4 carbon atoms, such as hydrazine, propylene-1; 3-dioxene, butylene dioxime, etc., wherein diammonium adipate and isophthalic acid are further Diterpenoids, azelaic acid diterpenes, etc. are preferred. For example, the combination below. (1) When the crosslinkable functional group on the resin side is a carboxyl group: for example, an epoxy compound, a carbodiimide compound, a melamine compound or the like. Among them, in particular, a carbodiimide compound having at least two or more carbodiimide groups in the molecule is more preferable because of its good room temperature hardenability. (2) When the crosslinkable functional group on the resin side is a hydroxyl group: for example, a hydrophilic isocyanate such as a non-block isocyanate compound or a block isocyanate compound, or a melamine compound. Among them, in particular, the hydrophilic polyisocyanate has good room temperature hardenability and is preferable as a curing agent for a good aqueous coating. -25 - (22) (22) 1264441 (3) When the crosslinkable functional group on the resin side is a carbonyl group: for example, an anthracene compound, a Grignard compound or the like. In particular, it is more preferable that the ruthenium compound having at least two or more sulfhydryl groups in the molecule has good room temperature hardenability and exhibits properties as a curing agent for a good aqueous coating. (4) When the crosslinkable functional group on the resin side is an ethylenically unsaturated group: ‘For example, a low molecular weight compound containing an active methyl group, a resin containing an active methyl group, and the like. Among them, in particular, the 1,3 -dicarbonyl compound and the 1,3-dicarbonyl-containing resin have good room temperature hardenability and are more excellent in characteristics as a hardening agent for a good aqueous coating. In any case, the amount of the aqueous hardener added is 0.1 to 5 equivalent to 1 equivalent of the crosslinkable functional group (the total functional group of the fluorine-containing composite resin (B) or the non-fluorine-based synthetic resin) on the resin side. Moore equivalent is ·

Further, a known hardening accelerator or the like can be added. A hardening accelerator such as dibutyltin laurate or the like. The aqueous composition of the present invention may be further added with a non-fluorine-based synthetic resin (C) as necessary. The addition form is preferably in the form of an aqueous dispersion or suspension. Non-fluorine-based synthetic resin, such as acrylic resin, urethane resin, polyester resin, epoxy resin, etc., among which acrylic resin, urethane resin, epoxy resin, etc., can improve weather resistance and durability It is preferred because of its properties such as water resistance, hardness, and stain resistance. In particular, -26 - (23) (23) 1264441 is more preferable because acrylic resin has more excellent weather resistance, gloss, hardness, water resistance and the like. Further, the non-fluorine-based synthetic resin (C) may or may not have a crosslinkable functional group, but introduces a crosslinkable functional group when considering properties such as improvement in weather resistance, water resistance, hardness, and stain resistance. It is better. The crosslinkable functional group contains a monomer for introduction in addition to the above substances. The combination of the fluorine-containing composite resin (B) and the non-fluorine-based synthetic resin (C) is, in terms of solid content, (B) 95 to 5 parts by weight and (C) 5 to 95 parts by weight, more preferably (B) 10 to 90 parts by weight and (C) 90 to 1 part by weight. In the present invention, by adding an aqueous curing agent, a room temperature curable aqueous composition having excellent properties such as excellent weather resistance, water resistance, stain resistance, and rain pollution resistance can be obtained. The room temperature curable aqueous composition of the present invention can be prepared into a solvent type hydrazine or an aqueous coating composition. In this case, an additive for coating which can be added, in addition to the above-mentioned curing agent, such as a surfactant, a pigment, a dispersing agent, a tackifier, a preservative, an ultraviolet absorber, an antifoaming agent, a smoothing agent and the like. As the surfactant, for example, the aforementioned compounds can be used. Further, as the tackifier, for example, Prasm QR7 0 8 (manufactured by Rohm and Haas Co., Ltd.) or the like can be used, and for example, Byk 0 2 3 (manufactured by Daiwa Co., Ltd.) can be used. For the dispersing agent, for example, B y k ] 90 (manufactured by Dainippon Japan Co., Ltd.), SN Diss 5 0 2 7 (manufactured by Yamano Co., Ltd.), or the like can be used. The obtained composition for water-based paint can be used as a weather-resistant paint, an electric paint, a corona paint, an automobile material, a paint for preventing writing, and a coating material such as anti-corrosion coating. As the coating method, for example, a coating method generally using the coating such as roll coating, dip coating, bristle coating, spray coating, roll coating, or the like, or electrocoat coating may be employed. The coating film formed by the composition of the present invention can be cured at normal temperature. In this case, since a large amount of a crosslinkable functional group is introduced into the fluorine-containing composite resin, the reaction can be sufficiently carried out even at room temperature. Further, it is also possible to heat treatment in order to promote hardening. When the coating film obtained by hardening is sufficiently hardened, it has better film strength, solvent resistance, and stain resistance when compared with the fluororesin aqueous coating material obtained by emulsion polymerization, and the appearance liquid is smoother and can also be reduced in color. Defects such as plaque 'black spots and other coatings. Further, when preparing a solvent-based coating composition, an organic solvent, a pigment, an antifoaming agent, a tackifier, a dispersing agent, a smoothing agent, a curing agent, or the like may be added to the fluorine-containing graft copolymer to disperse or dissolve the composition. can. Further, the aqueous composition of the present invention can be modified into a composition such as an adhesive composition or an ink composition by a known method. The invention will be more specifically described by the following examples, but the invention is not limited by the following examples. [Examples] Synthesis Example] A 6 liter stainless steel autoclave was charged with acetone].25 kg, Berba-9 (ethyl salicylate manufactured by Shell Chemical Co., Ltd.) 2200 g, ethyl benzoate After 4 7 g of hydroxybutyl vinyl ether] 0 9 g, it was replaced with nitrogen, -28 - (25) (25) 1264441 and then 300 g of tetrafluoroethylene was added thereto, and the temperature was raised to 61.5 t. Subsequently, 2 Og of a perylene octoate solution (solid content: 70% by weight) was added under stirring to carry out a reaction for 5 hours, and the reaction was stopped when the pressure in the reaction vessel was lowered to 22.5 MPa-G. The reaction mixture was cooled to room temperature, and the unreacted monomer was washed with nitrogen, and then the reaction product was 1.8 kg (solid content: 31.6 wt%). The obtained copolymer was analyzed by 19F-NMR and 1H-NMR to find that tetrafluoroethylene/Berba-9/ethyl benzoate/hydroxybutyl vinyl ether=46/27/7/20 (mole%) The GPC measurement results showed that the number average molecular weight Μη was 20,000, and the hydroxyl group value was 90 mgKOH/g. Synthesis Example 2 In a 3 liter four-necked flask equipped with a stirrer, 900 g of the warp-containing polymer obtained in Synthesis Example 1 was added. Anhydrous 4-methyl-1,2-cyclohexanyl di-residual acid (Nippon Chemical and Chemical Co., Ltd. MH700) 66g. After further adding 4 g of triethylamine, the temperature was gradually raised. After the solution in the flask reached 70 ° C, the reaction was carried out at this temperature. The reaction state was followed by using an infrared analyzer to observe the results. After 3 hours, no acid anhydride was observed at I 860 cnT1 and 1 790 (: 0 ^ absorption, while at 1 7 3 3 cm · 1 a strong ester absorption peak appeared. The acid value of the polymer is 90 mgKOH/g. In this polymer, 15.7 g of 2-isocyanatoethyl methacrylate is added, and the reaction is carried out at 40 ° C for 3 hours to make the ethylenic unsaturated. The base is introduced into the polymer. The hydroxyl value of the obtained copolymer is 7〇mgKOH/g. Then, 48g of 28% amine water is added to the polymer solution to neutralize the carboxylic acid group with -29-(26) 1264441. The obtained neutralizing solution slowly removes the organic solvent IJ under reduced pressure and slowly adds 82.82 kg of water to obtain a uniform aqueous solution (solid content of 30% by weight). Synthesis Example 3 is provided with a dropping funnel, a stirrer, and inertness. Gas introduction tube, temperature

Into a flask of a reflux meter and a reflux condenser, 954.6 g of an aqueous solution of the fluorine-containing copolymer obtained in Synthesis Example 2 was added, and a component having the following composition was added. (composition) diacetone acrylamide 67g methyl methacrylate 23 8.2g 2-ethylhexyl acrylate 1 20g n-butyl acrylate 243g was then added to 6.3g of water to dissolve 0.7g of ammonium persulfate to obtain a water-soluble solution, The polymerization was carried out for 2 hours at 8 (TC), followed by dropping 7·7 g of 1% by weight of ammonium persulfate, and then cooling the reaction solution after maintaining the reaction at 80 ° C for 2 hours. Further, aqueous ammonia was added to adjust the pH to 8.5 to obtain an aqueous dispersion having a solid content of 52% by weight. Synthesis Example 4 In Synthesis Example 1, except that the amount of the Berbata 9 was changed to 1 8 3.2 g, benzoic acid was used. The vinyl ester was replaced by ethyl methacrylate 22·4g, and the other -30-(27) (27) 1264441 was obtained by the same method as in Synthesis Example 1. The carboxyl group-containing fluorinated copolymer was used. The valence of the fluorocopolymer aqueous solution obtained in Synthesis Example 4 was 9 5 4 · 6 g, and the flask containing the dropping funnel, the stirrer, the inert gas introduction tube, the thermometer and the reflux cooler was added, and A component having the following composition is added. (Composition) Diacetone propylene Indoleamine 6 7 g methyl methacrylate 238.2 g 2-ethylhexyl acrylate I20 g n-butyl acrylate 243 g Subsequently, an aqueous solution obtained by dissolving 〇. 7 g of ammonium persulfate in 6.3 g of water was added and carried out at 80 ° C. 2 hours of polymerization, followed by dropwise addition of 7.7 g of 10% by weight ammonium persulfate water, and after maintaining the reaction at 8 CTC for 2 hours, the reaction solution was cooled, and then aqueous ammonia was added to adjust the pH to 8.5. Further, water was added to obtain an aqueous dispersion having a solid content of 50% by weight. Example 1 (Preparation method of room temperature curable aqueous composition) Fluorine obtained in Synthesis Example 3 was added to a bottle of 100 m 1 1 part by weight of the composite resin and diammonium adipate (manufactured by Otsuka Chemical Co., Ltd.); [5 -31 - (28) (28) 1264441 parts by weight to obtain a curable resin for aqueous coatings. To 100 parts by weight of the solid content of the curable resin for water-based paint, 50 parts by weight of titanium oxide (Dai Peike CR-97, manufactured by Ishihara Sangyo Co., Ltd.) and SN Diss 5 0 2 7 (dispersant) were added. 2 parts by weight of ammonium polycarboxylate prepared by Shanneng Co., Ltd. 0.5 parts by weight of FS Anji Peak 0 1 3 B (manufactured by Dow Corning Co., Ltd.) and 10 parts by weight of a tackifier CS - 1 2 (manufactured by Alizarin Co., Ltd.), and thoroughly mixed with a dispersing mixer to prepare The coating was applied by a coater, and then allowed to stand at room temperature for 5 days to cure the coating film, and then used as a test piece. The following characteristics were investigated for the test piece, and the results are shown in Table 1. . Appearance: The appearance of the coating film was visually observed.

When there is a stain or excessive black spots, it is B when there is a stain or a little black spot. If there is no stain or excessive dark spots, B is A gloss: according to the ΤΙ S K5 40 0 benchmark, the specular gloss is measured at 60 degrees 〇 Temperature resistance: The film was immersed in 5 (TC water for 24 hours, and the coating film was visually observed.

When no abnormality was found, A was found to be slightly cloudy, B was found to be significantly cloudy when staining, and C was found when the stain was dissolved. D Solvent resistance test: Wiping the coating with a non-woven fabric impregnated with xylene-32- (29 ) 1264441 Surface. The wiping process ends after repeating 1 重复 往返 round trips. At the end of the test, when the film is not dissolved or the gloss is lowered, the film A is only slightly dissolved or the gloss is lowered. When the film is significantly dissolved or the gloss is lowered, the weather resistance test is C. The weather tester is used. The tester company can perform a rapid weathering test of 2000 hours.

When the luminance difference (Δ E ) is 0 or more and less than 2, the case where A 2 or more is less than 4 is B 6 or more and less than 10 0. The case where C 1 0 or more is D. Example 2 Except fluorine-containing composite The polymer obtained in Synthesis Example 5 was used as a resin, and the coating was prepared in the same manner as in Example 1 except that a test piece was prepared on the coated plate. The obtained test piece was examined for the coating film characteristics in the same manner as in Example 1. The results are shown in Table 1. -33- (30) (30)1264441

Example 1 2 Fluorinated Acrylic Composite Dispersion Synthesis Example No. Synthesis Example 3 Synthesis Example 5 Adding amount (solid component parts by weight) 1 00 1 00 Hardener (parts by weight) Dioxane adipic 15 15 Coating physical appearance AA Glossy 80 82 Water-resistant AA Solvent-resistant AA Weather-resistant AA Synthesis Example 6 In a 6-liter stainless steel autoclave, 1.25 kg of acetone and ethyl trimethylacetate (manufactured by Nippon Vinegar Co., Ltd.) 244.4 g, 10 -10 were added. After 192.0 g of monocarboic acid, it was replaced with nitrogen, and then 300 g of tetrafluoroethylene was added thereto, and the temperature was raised to 61.5 °C. Subsequently, 11.6 g of a bismuth peroxide solution (solid content of 7 〇% by weight) was added under stirring to carry out a reaction for 8 hours, and the reaction was stopped when the pressure in the reaction vessel was lowered to 0.25 MPa-G. The reaction mixture was cooled to room temperature, and the unreacted monomer was washed with nitrogen and then reacted with nitrogen to obtain 2.0 kg (solid content: 35.3 wt%) of the product -34 - (31) 1264441. The obtained copolymer' was analyzed by 19F-NMR and 1H-NMR, and it was found that tetrafluoroethylene/triethylacetate/10-undecenoic acid = 45/35/20 (% by mole) 'G PC As a result of the measurement, it was found that the number average molecular weight Μη was 8,000' acid value of 90 mgKOH/g. Synthesis Example 7 After adding 821.5 g of the polymer obtained in Synthesis Example 6 and 8.70 g of glycidyl methacrylate and benzyltriethylammonium 〇.87 g to a 3 liter four-necked flask equipped with a stirrer and a reflux condenser. The mixture was inverted at 120 ° C for 5 hours to introduce an ethylenic unsaturated group into the polymer. Subsequently, 47 g of triethylamine was added to the polymer solution to neutralize the carboxylic acid group. The obtained neutralized solution was gradually removed from the organic solvent under reduced pressure and slowly added to 700 g of water to obtain a uniform aqueous solution (solid content % by weight). Synthesis Example 8 Into a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a meter and a reflux condenser, 400 g of the copolymer-containing aqueous solution obtained in Synthesis Example 7 was added, and a component having the following composition was added. (Contents of composition) Diacetone acrylamide 67g Methyl methacrylate 1 1 7 · 4 g A bottle is a propensity agent 30 Peg fluoride -35 - 1264441 (32) Cyclohexyl methacrylate 1 1 7.5g Η-butyl acrylate 243 g 2 -ethylhexyl methacrylate 120 g acrylic acid 3.3 g New Cole 7 〇 7 SF l〇g Subsequently, an aqueous solution obtained by dissolving 〇. 7 g of ammonium persulfate in 6.3 g of water was added thereto, and The polymerization was carried out at 80 ° C for 2 hours, then a 7.7 g of 10% by weight ammonium persulfate water was added dropwise, and after maintaining the reaction at 80 ° C for 2 hours, the reaction solution was cooled, and then ammonia water was added. The pH was adjusted to 8.5 to obtain an aqueous dispersion having a solid content of 50% by weight. Synthesis Example 9 In a 6-liter stainless steel autoclave, acetone 15-30 kg, Berber-9 315.9 g, and 10-non-carboic acid 225.9 g were added, and then replaced with nitrogen, and then 300 g of tetrafluoroethylene was added thereto, and the temperature was raised to 61.5 °. C. Subsequently, 1 2 g of a perylene octoate solution (solid content of 70% by weight) was added under stirring to carry out a reaction for 8 hours, and the reaction was stopped when the pressure in the reaction vessel was lowered to 〇25 MPa-G. The reaction mixture was cooled to room temperature. The unreacted monomer was washed and replaced with nitrogen to obtain a reaction product of 2 · 1 k g (solid content of 3 9 · 0% by weight). The obtained copolymer was analyzed by 19f_nmr and 1H-NMR to find that tetrafluoroethylene/belba=9/1 〇-Ί carbenoic acid = 4 6/3 0.9/2 3.1 (% by mole), by GPC As a result of the measurement, it was found that the number average molecular weight Μη was 9,0〇〇, and the acid value was 90 mgKOH/g. -36- (33) (33) 1264441 Synthesis Example 1 Into a 3 liter four-necked flask equipped with a stirrer and a reflux condenser, the polymer obtained in Synthesis Example 9 was added to 7.4 g of 3.6 g and glycidyl methacrylate 8.70. After g and 0.87 g of benzyltriethylammonium, the mixture was reacted at 120 ° C for 5 hours to introduce an ethylenically unsaturated group into the polymer. Subsequently, 47 g of triethylamine was added to the polymer solution to neutralize the carboxylic acid group. The obtained neutralized liquid was gradually removed from the organic solvent under reduced pressure, and 700 g of water was gradually added thereto to obtain a uniform aqueous solution (solid content: 30% by weight). Synthesis Example 1 1 Into a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer and a reflux condenser, 400 g of a fluorine-containing copolymer aqueous solution obtained in Synthesis Example 1 was added, and a component having the following composition was added. (Composition) Diacetone acrylamide 67g Methyl methacrylate 1 17.4g Cyclohexyl methacrylate 114.2g n-butyl acrylate 243 g 2-ethylhexyl methacrylate 120g 2-hydroxyethyl methacrylate 3.3 g of acrylic acid 3. 3 g New Cole 707SF l〇g -37- (34) (34) 1264441 Subsequently, an aqueous solution obtained by dissolving 〇.7 g of ammonium persulfate in 6.3 g of water was added and carried out at 80 ° C 2 After an hour of polymerization, 7.7 g of 10% by weight ammonium persulfate water was added dropwise, and after maintaining the reaction at 8 ° C for 2 hours, the reaction solution was cooled, and then aqueous ammonia was added to adjust the pH to 8.5. An aqueous dispersion having a solid content of 50% by weight was obtained. Synthesis Example 1 2 In a 6-liter stainless steel autoclave, 3.7 kg of acetone, 373.7 g of ethyl trimethylacetate (manufactured by Nippon Vinegar Co., Ltd.), and 69.8 g of acrylic acid were added, and then replaced with nitrogen, and then 300 g of tetrafluoroethylene was added. Warm up to 61.5 °C. Then, 9.8 g of a perylene octoate solution (solid content: 70% by weight) was added under stirring, and the reaction was carried out for 8 hours, and the pressure was lowered in the reaction vessel.

The reaction was stopped at 0.25 MPa-G. The reaction mixture was cooled to room temperature, and the unreacted monomer was washed and replaced with nitrogen to obtain 2.0 kg of a reaction product (solid content: 32.6% by weight). The obtained copolymer was analyzed by 19F-NMR and 1Η-N MR to find tetrafluoroethylene/trimethylacetate/acrylic acid=4 5/3 5/2 0 (% by mole), as determined by GPC. As a result, it was found that the number average molecular weight Μη was 6,000, and the acid value was 90 mgKOH/g. Synthesis Example 13 In a 3 liter four-necked flask equipped with a stirrer and a reflux condenser, 'the polymer obtained in Synthesis Example 12 was added, 8 8 9.6 g of glycidyl methacrylate 8.70 g and benzyltriethylammonium 0.8 7 g. Thereafter, the reaction was carried out at 120 ° C for 5 hours to introduce an ethylenically unsaturated group into the polymer. -38-(35)1264441 Subsequently, 4 7 g of triethylamine was added to the polymer solution to neutralize the carboxylic acid group. The resulting neutralized liquid was gradually removed under reduced pressure, and 7 g of water was gradually added thereto to obtain a uniform aqueous solution (solid weight %). Synthesis Example 1 4 Into a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube meter and a reflux condenser, 247.5 g of an aqueous copolymer solution obtained in Synthesis Example 13 was added, and a solvent having the following composition was added thereto. Divided into 30, warm fluorine content (composition content) diacetone acrylamide 67g methyl methacrylate 1 17.4g cyclohexyl methacrylate 1 17.5g n-butyl acrylate 243 g 2-ethylhexyl methacrylate 120g Acrylic acid 3.3g New Cole 707SF l〇g Subsequently, a solution obtained by dissolving 0.7 g of ammonium persulfate in 6.3 g of water was added, and polymerization was carried out at 80 ° C for 2 hours, followed by 7.7 g of 10% by weight. Ammonium sulfate water, after maintaining the reaction at 80 ° C for an hour, the reaction solution is cooled, and then added with ammonia water to dissolve the PH 値 water into the line 2 to adjust -39- (36) 1264441 to 8.5, the solid content is 5 〇% by weight of water 3 Synthesis Example 1 5 To a flask equipped with a dropping funnel, a stirrer, a tolerometer and a reflux condenser, 9 5 4.6 g of a synthetic copolymer aqueous solution was added, and the following dispersion was added. Gas-introducing tube, composition of fluorine-containing composition obtained by warming (1 composition (dimensions) diacetone acrylamide 67g methyl methacrylate 23 1. 6g n-butyl acrylate 243 g 2-ethylhexyl methacrylate 120g 2-hydroxyethyl methacrylate 3.3g Acrylic acid 3.3g New Kohl 707 SF l〇g Then added to 6 · 3 g of water to dissolve 0 · 7 g of liquid, and at 80 ° C for 2 hours Polymerization of 7.7 g of 10% by weight of ammonium persulfate water, and after the reaction for a few hours, the reaction solution was cooled, and then added to the 8.5 to obtain a water-soluble solution of the aqueous ammonium sulfate having a solid content of 50% by weight. Then drip into the temple at 80 ° C for 2, the water will adjust the pH 、, the bulk. Synthesis Example 1 6 -40- (37) (37) 1264441 Adding 1.25 kg of acetone, ethyl trimethylacetate (manufactured by Nippon Vinegar Co., Ltd.) 212.9 g, hydroxybutyl vinyl ether in a 6-liter stainless steel high-pressure seal 28.5g, 10-Ί^-carboic acid 192.Og, replaced with nitrogen, then added tetrafluoroethylene 300 g, and the temperature was raised to 6 1. 5 °C. Subsequently, 12 g of a perylene octoate solution (solid content % by weight) was added thereto under stirring for 8 hours, and the reaction was stopped when the pressure in the reaction vessel was lowered to 0.25 MPa-G. The reaction mixture was cooled to room temperature, and the unreacted monomer was washed and replaced with nitrogen to obtain a reaction product of 1.8 kg (solid content of 3 5 · 2 wt%). The obtained copolymer was analyzed by 19F-NMR and 1H-NMR to find tetrafluoroethylene/trimethylacetate/hydroxybutyl vinyl ether/10-i-carboic acid=45/3 3.7. /4.0/1 7.3 (% molar ratio), as a result of GPC measurement, the number average molecular weight Μη was 7,000, the hydroxyl value was 20 mgKOH/g, and the acid value was 90 mgKOH/g. Synthesis Example 1 7 In a 3 liter four-necked flask equipped with a stirrer and a reflux condenser, % 22.8 g of the polymer obtained in Synthesis Example 16 and 14.5 g of 2-isocyanatoethyl methacrylate were added. The reaction was carried out at ° C for 1 hour to introduce an ethylenically unsaturated group into the polymer. Subsequently, 47 g of triethylamine was added to the polymer solution to neutralize the carboxylic acid group. The obtained neutralized liquid was gradually removed from the organic solvent under reduced pressure, and water of 7 〇 〇 g was gradually added to prepare a uniform aqueous solution (solid content: 3 重量% by weight). -41 - (38) (38)1264441 Synthesis Example] 8 A fluorinated copolymer obtained in Synthesis Example 7 was placed in a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, and a temperature δ ten and a back k cooler. After an aqueous solution of 4,000 g and a component of the composition of Synthesis Example 8 was added, the same operation was carried out to obtain an aqueous dispersion having a solid content of 5% by weight. Synthesis Example 1 In a 6-liter stainless steel autoclave, 1.25 kg of acetone, 269.9 g of Berba-9, 322 g of hydroxybutyl vinyl ether, and 221.0 g of decyl-carbenoic acid were added, and then replaced with nitrogen. Add 3 〇〇g of tetrafluoroethylene and raise the temperature to 6 1 . 5 C. Subsequently, 1 2 g of a perylene octoate solution (solid content of 7 〇% by weight) was added under stirring to carry out a reaction for 8 hours, and the reaction was stopped when the pressure in the reaction vessel was lowered to 0.25 MPa-G. The reaction mixture was cooled to room temperature. The unreacted monomer was washed with nitrogen and then replaced with nitrogen to obtain 2.1 kg of a reaction product (solid content: 38. 4% by weight). The obtained copolymer was analyzed by 19F-NMR and]H-NMR to find that tetrafluoroethylene/Berba-9/hydroxybutyl vinyl ether/10-undecenoic acid = 4 6/2 6.4/5.0 /22.6 (% molar ratio), as a result of GPC measurement, the number average molecular weight Μη was 10: 〇〇〇, the hydroxyl value was 20 mgKOH/g, and the acid value was 90 nigKOH/g. Synthesis Example 20 In a 3 liter four-necked flask equipped with a stirrer and a reflux condenser, -42 - (39) (39) 1264441 was added to the polymer obtained in Synthesis Example 7 5 5.2 g and 2-isocyanatoethyl After the methacrylate was 1 4 · 5 g, the reaction was carried out for 1 hour at 6 Torr to introduce the ethylgeric unsaturated group into the polymer. Subsequently, 4 7 g of triethylamine was added to the polymer solution to neutralize the acid group. The obtained neutralized liquid was gradually removed from the organic solvent under reduced pressure, and 700 g of water was gradually added thereto to obtain a uniform aqueous solution (solid content: 30% by weight). Synthesis Example 2 1 Into a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer, and a reflux condenser, 400 g of the fluorinated copolymer aqueous solution obtained in Synthesis Example 20 was added, and the components of the composition of the synthesis example n were added. 'After performing the same operation, an aqueous dispersion having a solid content of 50% by weight was obtained. Synthesis Example 22 In a 6-liter stainless steel autoclave, 1.25 kg of acetone, 9 347 g of Berba, 23.5 g of 2-hydroxyethyl methacrylate, and 5.4 g of acrylic acid were added, and then replaced with nitrogen, and then tetrafluoroethylene was added. 〇〇g, the temperature is raised to 61.5C. Subsequently, 9.8 g of a peroxyoctanoic acid solution (solid content of 70% by weight) was added under stirring for 8 hours, and the reaction was stopped when the pressure in the reaction vessel was lowered to 0.25 MPa-G. The reaction mixture was cooled to room temperature, and the unreacted monomer was washed and then replaced with nitrogen to obtain a reaction product of 2 · 〇 k g (solid content 3 1 · 1% by weight). The obtained copolymer was analyzed by using -43-(40)(40)1264441 19F-NMR and W-NMR to find that tetrafluoroethylene/elbabar-9/2-hydroxyethyl methacrylate/acrylic acid = 30/ 4 4·0/4·8/2 1·2 (% molar ratio), as a result of GPC measurement, the number average molecular weight Μη was 6,000, the hydroxyl value was 20 mgKOH/g, and the acid value was 90 mgKOH/g. Synthesis Example 2 3 Into a 3 liter four-necked flask equipped with a stirrer and a reflux condenser, 93 2.5 g of the polymer obtained in Synthesis Example 22 and 14.5 g of 2,1 isocyanatoethyl methacrylate were added at 60 °. The reaction was carried out for 1 hour at C to introduce an ethylenically unsaturated group into the polymer. Subsequently, 47 g of triethylamine was added to the polymer solution to neutralize the carboxylic acid group. The obtained neutralized liquid was gradually removed from the organic solvent under reduced pressure, and water of 7 〇 〇 g was gradually added to prepare a uniform aqueous solution (solid content of 30% by weight). Synthesis Example 2 4 To a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer and a reflux condenser, an aqueous solution of the fluorinated copolymer obtained in Synthesis Example 2 2 4 · 5 · 5 g was added, and Synthesis Example 8 was added. After the components of the composition were subjected to the same operation, an aqueous dispersion having a solid content of 5 〇% by weight was obtained. Synthesis Example 2 5 Into a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer and a reflux condenser, 'A fluorine-44-(41) (41) 1644441 copolymer aqueous solution obtained by adding the synthesis example 2 was added. 4 · 6 g ' and add the component with the following composition 0 (composition content) diacetone acrylamide 67g methyl methacrylate 231.6g n-butyl acrylate 243g 2-ethylhexyl methacrylate 120g methacrylic acid 2-hydroxyethyl ester 3.3g Acrylic acid 3.3g Neocol 7 0 7 SF l〇g Subsequently, an aqueous solution obtained by dissolving 0.7 g of ammonium persulfate in 6.3 g of water was added, and polymerization was carried out at 80 ° C for 2 hours. Then, 7.7 g of 10% by weight ammonium persulfate water was added dropwise, and after maintaining the reaction at 80 ° C for 2 hours, the reaction liquid was cooled, and then the aqueous solution was adjusted to pH 8.5 by adding ammonia water to obtain a solid content. 50% by weight of an aqueous dispersion. Synthesis Example 2 6 To a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer and a reflux condenser, an aqueous solution of the fluorinated copolymer obtained in Synthesis Example 2 was added to 5 5 4 · 6 g, and the following was added. Composition of the composition -45-1264441 (42) (Content of composition) Styrene 234.9g n-butyl acrylate 243 g 2-ethylhexyl methacrylate I20g Acrylic acid 3.3g New Cole 707SF 1 〇g Subsequently added to 6 · The water-soluble % solution obtained by dissolving 〇· 7 g of persulfate in 3 g of water was polymerized at 80 ° C for 2 hours. Then 7.7 g of 10% by weight ammonium persulfate water was added dropwise, and then kept. After reacting at 80 ° C for 2 hours, the reaction solution was cooled, and then aqueous ammonia was added to adjust the pH to 8.5 to obtain an aqueous dispersion having a solid content of 50% by weight. Examples 3 to 10 and Comparative Examples 1 to 2 The fluorine-containing composite resin was prepared by the same method as in Example 1 except that the polymer obtained in each of the synthesis examples shown in Table 2 was used, and then A test piece was prepared by coating. The obtained test piece was examined for the film properties in the same manner as in Example 1. The results are shown in Table 2. -46 - 1264441 (42) (Composition) Styrene 2 3 4.9 g η-butyl acrylate 24 3 g 2 -ethylhexyl methacrylate vinegar 12 0g propane acid 3. 3 g New Cole 7 0 7 SF lOg was then added to 6.3 g of water to dissolve 0.7 g of liquid, and polymerized at 80 ° C for 2 hours to reverse 7.7 g of 10% by weight of ammonium persulfate, and then reacted for a few hours. The reaction solution was cooled, and ammonia was further added to 8.5 to obtain an aqueous component having a solid content of 50% by weight. Examples 3 to 10 and Comparative Examples 1 to 2 The fluorine-containing composite resin was used in the same manner as the polymer shown in Table 2. The test pieces were prepared on the coated panels by the same procedure as in Example 1. The resulting test piece bin method was used to investigate the film properties. The results are shown in Table 2. The water obtained by ammonium sulfate is dissolved, and then dripped into the temple at 80 °C for 2, and the water is adjusted to pH •. The method prepared by each synthesis example was used to make a coating, the same as in Example 1 - 46 _ (43) 1264441 2

D-1·1~—*—Example 3 4 5 6 7 8 9 10 1 2 Fluorinated acrylic acid composite dispersion Synthesis Example No. Synthesis Example S Synthesis Example π Synthesis Example M Synthesis Example] 5 Synthesis Example 8 Synthesis Example 2 Synthesis Example 24 Synthesis Example 25 々TiS Example] 4 昧 昧 still add amount (solid component parts by weight) 〇0 100 100 100 100 100 100 ]00 mouth / recognition l/'JJ, ]〇〇a RK 171] ^-0 1 ΠΠ Hardener (parts by weight) J uu Adipic acid dihydrate 15 15 15 15 15 15 ]5 ]5 0 涂 Coating properties u Appearance AAAAAAAAAA Gloss 80 8] 82 8] 81 82 82 8] 86 95 Heat-resistant water AAAAAAAA cc Solvent-resistant AAAAAAAA cc Weather resistance AAAAAAAAAD Synthesis Example 2 7 In a 6-liter stainless steel high-pressure cap, add 1.25 kg of acetone, belba-9 3 〇 6.7 g, butyl butyl ethene ether 5.2 After g, l〇-undecic acid 2 3 7 · 5 g, replaced with nitrogen, then added 300 g of tetrafluoroethylene, and the temperature was raised to 6 ] · 5 °C. Subsequently, a solution of 丨1.8 g of octoate octoate (solid content of 70% by weight) was added under stirring for 8 hours, and the reaction was stopped when the pressure in the reaction vessel was lowered to 0.35 MPa-G. The reaction mixture was cooled to room temperature, and the unreacted monomer was washed with nitrogen and then replaced with nitrogen to obtain a reaction -47 > (44) (44) 1264441 product 2.0 k g (solid component 3 9.2% by weight). The obtained copolymer was analyzed by 19 F · NMR and 1 Η - NMR to find that tetrafluoroethylene/Berba-9/hydroxybutyl vinyl ether/10-undecenoic acid = 46/30/0.8/ 23.2 (% molar ratio), the GP C measurement results show that the number average molecular weight Μη is 8,000, the hydroxyl value is 3 mgKOH/g, and the acid value is 90 mgKOH/g. Synthesis Example 28 8 liters with a blender and a reflux cooler In a four-necked flask, 382.6 g of the polymer obtained in Synthesis Example 27 and 1.35 g of 2-isocyanatoethyl methacrylate were added, and then reacted at 6 (TC for 1 hour to introduce an ethylenic unsaturated group into the polymerization. Then, 14.5 g of 28% aqueous ammonia was added to the polymer solution to neutralize the carboxylic acid group, and the obtained neutralized liquid was gradually removed under reduced pressure to gradually remove the organic solvent and slowly added 75 Og of water. A uniform aqueous solution (solid content: 6.7 wt%) was obtained. Synthesis Example 2 9 To a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer and a reflux condenser, a fluorine-containing copolymer obtained in Synthesis Example 28 was added. The aqueous dispersion was 900 g, and the ingredients having the following composition contents were added. (Composition) -48- (45) 1264441 Methyl methacrylate 150.Og Propylene cyclohexyl ester 1 80.0g 2-Ethylhexyl acrylate 2 7 0.0g Dissolved in 2 uric acid to the interior of the chamber ^ ( Μη Subsequently added to the solution obtained by dissolving 0. 6 g of ammonium persulfate in 5 · 4 g of water, and polymerization was carried out at 80 ° C for 2 hours, followed by dropping 6. 10% by weight of 〇g After the ammonium sulfate water was further reacted at 80 ° C for an hour, the reaction liquid was cooled. Then, the pH was adjusted to 8.5 by adding ammonia water to obtain an aqueous dispersion having a solid content of 50% by weight. In a 6-liter stainless steel autoclave, add 1.2 kg of acetone, 420.4 g of beriba-9, 152 g of hydroxybutyl vinyl ether, and 1.6 g of 10-11 carbon, then replace with nitrogen, then add tetrafluoroethylene. 600g, heating at 6 1 · 5 ° C. Then add 19 g of octyl peroxide solution (solid content 7 〇 wt%) with stirring, and let it react for 8 hours, when the pressure of the reaction vessel drops to 〇.4MPa-G The reaction was stopped. The reaction mixture was cooled to a temperature. The unreacted monomer was washed and replaced with nitrogen to obtain a reaction yield of 2.4 kg ( The solid content was 50·3 wt%. The obtained copolymer was subjected to 19F-NMR and 1H-NMR analysis to find that tetrafluoroethylene/Berba/Pentylbutyl Ethyl acetal /10 -11 ^ carbon maid Acid = 45/25.6/14.7/14.: molar %)) The number average molecular weight was 14,400, the hydroxyl value was 60 mgKOH/g, and the acid value was 60 mgKOH/g -49-(46)1264441 by GPC measurement. Cyanate was added without copolymerization and 33.3 synthesizing amount of copolymerization component (group methylmethylmethyl solution 3.5 g Example 31 in a 3 liter four-necked flask equipped with a stirrer and a reflux condenser, the polymer obtained in Synthesis Example 30 After 695.8 g of 2-isoethylethyl methacrylate 3 · 15 g, the reaction was carried out at 60 ° C for 1 hour to introduce an ethylene saturated group into the polymer. Subsequently, 2 4 · 1 g of triethylamine was added to the polymer solution, and the carboxylic acid group was neutralized. The obtained neutralized solution was gradually removed from the organic solvent under reduced pressure, and 7 g of water was added thereto to prepare a uniform aqueous solution (% by weight of solid content). Example 32 Into a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, and a temperature and reflux cooler, the aqueous fluorine-containing dispersion 1 obtained in Synthesis Example 31 was added, 〇50 g, and the following composition was added. It

Contents) Methyl acrylate 70 Propylene cyclohexyl ester 175 Propionic acid 2-ethylhexyl ester 105 • 〇g • 〇g • 〇g Subsequently added to 3 · 15 g water dissolved ο . 3 5 g persulfuric acid Ammonium-derived water, and polymerized at 8 (TC for 2 hours, then 10% by weight of ammonium persulfate water, and then kept at 80 ° C for 2 -50-(47) (47) After the reaction of 1264441 hours, the reaction solution was cooled, and then aqueous ammonia was added to adjust the pH to 8.5 to obtain an aqueous dispersion having a solid content of 50% by weight. Example 1] (Preparation method of room temperature curable aqueous composition) The 100 parts by weight of the fluorine-containing composite resin obtained in Synthesis Example 29 and 5 · 0 parts by weight of PER MUTEX XR-2500 (azacyclopropane manufactured by Stahl Co., Ltd.) were added to a 100-pound special bottle to obtain a curable property for an aqueous coating. 50 parts by weight of a titanium oxide (Dai Peike CR-97, manufactured by Ishihara Sangyo Co., Ltd.) and a dispersant are added to the solid content of the solid content of the curable resin for the aqueous coating material. 2 parts by weight of SN Diss 502 7 (ammonium salt of polycarboxylate manufactured by Shanneng Co., Ltd.) and ethylene glycol 1 of freezing inhibitor重量 - 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份 份After 7.5 parts by weight of CS-12 (manufactured by Daicel Corporation), the mixture was thoroughly mixed using a dispersing mixer to prepare a coating. # A test piece was produced in the same manner as in Example 1, and then the film properties were examined in the same manner as in Example 1. Example 1 The sclerosing agent was prepared by the same method as in Example II except that 20 parts by weight of Kalba V > 〇 2 (carbonized bismuth imide hydrating agent manufactured by Nippon Spinning Co., Ltd.) was used. The test piece was examined for the film properties in the same manner as in the Example. The results are shown in Table 3. -51 - (48) 1264441 Example 1 3 In Example 1], the synthesis example 3 was used except for the fluorine-containing composite resin. The fluorine-containing composite resin, and the hardener is used in the same manner as the Babel 3 1 0 0 (polyethylene oxide-modified non-block isocyanate-based hardener manufactured by Bayer), and the others are the same. Method for making paint, then making test pieces and investigating the film Characteristics. The results are shown in Table 3. Table 3

Example 11 12 13 Fluorinated acrylic acid composite dispersion Synthesis Example No. Synthesis Example 2 Synthesis Example 2 Synthesis Example 3 2 Adding amount (parts by weight) 1 00 100 1 00 Hardener (parts by weight) PERMUTEX XR- 25 0 0 5 Kalba V-02 20 _ Bill 3 1 0 〇 5 One --- ^ ^ Coating physical appearance AAA gloss 82 8 1 78 Water resistance AAA Solvent resistance AAA Nile JI__ _-____—- AAA -52-

Claims (1)

(1) 1264441 X. Patent application scope Patent application No. 93 1 3 6909 Patent application Chinese patent scope amendments Republic of China 丨 9 5V year f month? ;^ :month p $ 1 . A room temperature curable aqueous composition characterized by containing an ethylenically unsaturated group in the presence of a fluorine-containing copolymer (A) having an ethylenic unsaturated group and a water-soluble functional group in the molecule An aqueous dispersion of the fluorine-containing composite resin (B) obtained by emulsion polymerization of the monomer (b 1 ) and an aqueous hardener containing room temperature curable, which is relative to 1 equivalent of the fluorine-containing composite resin (B) The functional group is added to 0.1 to 5 molar equivalents. 2. The room temperature curable aqueous composition according to claim 1, wherein the fluorinated copolymer (A) has an acid value of 10 to 250 mgKOH/g. 3. The room temperature curable aqueous composition of claim 1 wherein 'the water-soluble functional group is a functional group obtained by neutralizing an anionic functional group with a base. The room temperature hardening aqueous composition of any one of the above-mentioned fluorocopolymers (A), wherein the structural unit of the fluorinated copolymer (A) is 10 to 70 mol% of tetrafluoroethylene, At least one perhalo olefin unit selected from the group consisting of hexafluoropropylene and chlorotrifluoroethylene. The room temperature curable aqueous composition according to any one of claims 1 to 3, wherein the monomer containing the ethylenic unsaturated group ((2) 1264441 bl ) contains at least one of the species A monomer having a crosslinkable functional group and an acrylic or methacrylic monomer having an alkyl group having 4 to 10 carbon atoms. 6. The room temperature curable aqueous composition according to claim 5, wherein the crosslinkable functional group is at least one selected from the group consisting of a carbonyl group, a hydroxyl group and a carboxyl group. The room temperature curable aqueous composition according to any one of claims 1 to 3, wherein the cerium contains an emulsion of a non-fluorine-based synthetic resin (C). 8. The room temperature curable aqueous composition of claim 7 which is a solid component containing 95 to 5 parts by weight of the solid component containing the cut-off composite resin (B) and a non-fluorine-based synthetic resin (C) 5 to 95 parts by weight. The ambient curable aqueous composition according to any one of the above claims, wherein the aqueous hardening agent is an anthraquinone compound having at least two or more mercapto groups in one molecule, and one molecule At least 2 More than one carbonized monomethylene imide carbodiimide compound or hydrophilic polyisocyanate. The ambient temperature curable aqueous composition of the seventh aspect of the invention, wherein the curing agent is equivalent to the total functional group I equivalent of the fluorine-containing composite resin (B) and the non-fluorine synthetic resin (C). Add 〇1 to 5 molar equivalents. -2-