JP2005248157A - Normal temperature curable aqueous composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a normal temperature curable aqueous composition having a normal temperature curability as a fluorinated coating component of an aqueous coating composition, and giving an excellent coating property. <P>SOLUTION: The normal temperature curable aqueous composition comprises an aqueous dispersion of the fluorine-containing composite resin (B) obtained by carrying out an emulsion polymerization of an ethylenic unsaturated group-containing monomer (b1) and an aqueous curing agent, in the presence of a fluorine-containing copolymer (A) containing the ethylenic unsaturated group and the aqueous functional group in the molecular. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a room temperature curable aqueous composition having room temperature curability as a fluorine-based film component of an aqueous coating composition and providing excellent film properties.

  Conventionally, as a fluorine-containing aqueous dispersion, for example, Patent Document 1 discloses a technique in which an acrylic or methacrylic acid ester monomer is seed-polymerized and compounded in the presence of an aqueous dispersion of vinylidene-based fluororesin particles. However, the resulting composite resin has low compatibility with vinylidene fluororesins and (meth) acrylic resins, and functional groups such as carboxyl groups and hydroxyl groups have been introduced into vinylidene fluororesins that are seed particles for seed polymerization. There are drawbacks such as difficulty.

  Patent Document 2 discloses that a fluorine-containing polymer having a carboxyl group bonded to fluoroalkyl is used as a dispersion stabilizer, and a crosslinking agent is added to a fluorine-containing aqueous dispersion obtained by emulsion polymerization of an ethylenically unsaturated monomer in this system. Techniques for blending are disclosed. However, this technique does not include a room-temperature curable crosslinking agent as a crosslinking agent, which causes a problem in dry curability at room temperature. Further, no weatherable vinyl monomer is used as the ethylenically unsaturated monomer, which is insufficient in terms of weather resistance.

  Patent Document 3 discloses that an aqueous dispersion is prepared by emulsion polymerization of a fluororesin obtained by copolymerizing a hydrophilic group-containing non-fluorinated macromonomer bonded to fluoroalkyl. Is disclosed in which seed polymerization is performed to obtain a composite aqueous fluororesin dispersion. However, since the fluororesin serving as seed particles is obtained by emulsion polymerization, there is a drawback that water-soluble functional groups such as carboxyl groups and hydroxyl groups are difficult to introduce into the fluororesin. Moreover, since there are many emulsifiers etc. and the crosslinking agent is not mix | blended, there exists a fault that the chemical resistance of a coating film, solvent resistance, coating-film hardness, and water resistance are low.

  Patent Document 4 discloses a technique for an aqueous coating composition comprising a fluororesin aqueous dispersion obtained by emulsion polymerization and an acrylic or methacrylic copolymer dispersion obtained by emulsion polymerization. . However, the compatibility between the fluororesin aqueous dispersion and the acrylic or methacrylic aqueous dispersion is poor, and sufficient uniform mixing cannot be achieved, and the resulting coating film has poor weather resistance, adhesion, gloss, etc. is there. In addition, there is a drawback in that no curing agent is blended and problems remain in chemical resistance, solvent resistance, coating film hardness, water resistance, and the like.

  Patent Document 5 discloses an acrylic resin having a carbonyl group by seed polymerization of a (meth) acrylic acid ester monomer in the presence of an aqueous dispersion obtained by emulsion polymerization of fluoroolefin, propylene and ethylene. A fluorine-containing aqueous coating composition comprising a composite fluorine-containing dispersion and a hydrazine-based curing agent is disclosed. However, the fluororesin obtained in this document has low compatibility with the acrylic resin, and the (meth) acrylic acid ester monomer does not sufficiently dissolve in the fluororesin dispersion during seed polymerization, resulting in a coating film. Have the disadvantage of low weather resistance and gloss.

JP-A-62-32102 Japanese Unexamined Patent Publication No. Sho 63-314202 JP 7-238253 A JP-A-9-59560 JP 2000-129195 A

  An object of the present invention is to provide a room temperature curable aqueous composition that solves the above-mentioned conventional drawbacks, can be cured at room temperature, and provides excellent coating properties.

  That is, in the present invention, an ethylenically unsaturated group-containing monomer (b1) is emulsion-polymerized in the presence of a fluorine-containing copolymer (A) having an ethylenically unsaturated group and a water-soluble functional group in the molecule. The present invention relates to a room temperature curable aqueous composition comprising an aqueous dispersion of the resulting fluorinated composite resin (B) and an aqueous curing agent.

  The fluorine-containing copolymer (A) preferably has an acid value of 10 to 250 mgKOH / g.

  Moreover, it is preferable that the water-soluble functional group which a fluorine-containing copolymer (A) has is a functional group obtained by neutralizing an anionic functional group with an alkali.

  The fluorine-containing copolymer (A) is a copolymer containing 10 to 70 mol% of at least one perhaloolefin unit selected from the group consisting of tetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene as a structural unit. It is preferable that

  Further, as the ethylenically unsaturated group-containing monomer (b1), at least one monomer having a crosslinkable functional group and one acrylic or methacrylic monomer containing an alkyl group having 4 to 10 carbon atoms is used. A monomer mixture containing seeds 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.

  The room temperature curable aqueous composition of the present invention can further contain an emulsion of the non-fluorinated synthetic resin (C), the solid content of the fluorine-containing composite resin (B) is 95 to 5 parts by weight, and the non-fluorinated synthetic resin. It is preferable to contain 5 to 95 parts by weight of the solid content of (C).

  As the aqueous curing agent, a room temperature curing agent is used, and a hydrazide compound having at least two hydrazide groups per molecule, a carbodiimide compound having at least two carbodiimide groups per molecule, or Preferred is a hydrophilic polyisocyanate.

  The curing agent is preferably blended in an amount of 0.1 to 5 molar equivalents relative to 1 equivalent of the total functional groups of the fluorine-containing composite resin (B) and the non-fluorinated synthetic resin (C).

  According to the present invention, a coating film excellent in chemical resistance, solvent resistance, coating film hardness, water resistance and the like can be easily obtained by room temperature drying (curing).

  The room temperature curable aqueous composition of the present invention comprises an aqueous dispersion of a specific fluorine-containing composite resin (B) and an aqueous curing agent.

  This fluorine-containing composite resin (B) is prepared by using an ethylenically unsaturated group-containing monomer (b1) in the presence of a fluorine-containing copolymer (A) having an ethylenically unsaturated group and a water-soluble functional group in the molecule. ) Is obtained by emulsion polymerization.

  The fluorine-containing copolymer (A) is a fluorine-containing copolymer having an ethylenically unsaturated group and a water-soluble functional group in the molecule, and preferably contains a fluoroolefin unit.

  Examples of the fluoroolefin include tetrafluoroethylene (TFE), trifluoroethylene (TrFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), vinyl fluoride (VF), and vinylidene fluoride (VdF). 1 type or 2 types or more are mention | raise | lifted and especially the copolymer containing 10-70 mol% of perhalo olefin units is preferable. Particularly preferred fluoroolefins include perfluoroolefins such as TFE and HFP, which can provide a fluorine-containing polymer having a high fluorine content, such as the advantageous effects of fluororesins, such as chemical resistance, water resistance, and solvent resistance. Gives a coating film excellent in stain resistance and weather resistance.

  The water-soluble functional group is preferably a functional group obtained by neutralizing an anionic functional group with an alkali. Examples of such an anionic functional group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and a carboxyl group is preferable from the viewpoint of good water resistance of the coating film and less corrosion of the metal substrate.

  Examples of a method for introducing an anionic functional group into the fluorinated copolymer (A) include a method of copolymerizing a monomer containing an anionic functional group (copolymerization method) and a functional group such as a hydroxyl group. A method of reacting a polymer with a compound having an anionic functional group such as a dibasic acid anhydride (polymer reaction method) is employed.

  As a monomer for introducing a carboxyl group as an anionic functional group by a copolymerization method, formula (I):

(Wherein R ³ , R ⁴ and R ⁵ are the same or different and all are a hydrogen atom, an alkyl group, a carboxyl group or an ester group; n is from 0 to 20), Examples thereof include unsaturated carboxylic acids such as saturated dicarboxylic acids, monoesters or acid anhydrides thereof. R ³ and R ⁴ are preferably both hydrogen elements, and n is preferably 3 or more and 15 or less. In particular, it is preferable that R ³ , R ⁴ and R ⁵ are all hydrogen elements and n is 6 or more and 10 or less.

  Specific examples of the unsaturated carboxylic acids of the formula (I) include, for example, acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid. , Itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitic acid, 5-hexenoic acid, 5-heptenoic acid, 6 -Heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecylene acid, 11-dodecylene acid, 17-octadecylenic acid, oleic acid and the like. Among them, crotonic acid, itaconic acid, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, 3-allyloxypropionic acid, and 10-undecylenic acid having low homopolymerization properties are difficult to form a homopolymer. Therefore, it is preferable. In particular, 10-undecylenic acid is preferable in that it has good polymerization reactivity and is hardly hydrolyzable.

  Another example of a monomer for introducing a carboxyl group as an anionic functional group by a copolymerization method includes a compound represented by the formula (II):

(Wherein R ⁶ and R ⁷ are the same or different and both are saturated or unsaturated linear or cyclic alkyl groups; n is 0 or 1; m is 0 or 1) And monomers.

  Specific examples of the carboxyl group-containing vinyl ether monomer of formula (II) include 3- (2-allyloxyethoxycarbonyl) propionic acid, 3- (2-allyloxybutoxycarbonyl) propionic acid, 3- (2- One or two or more types such as vinyloxyethoxycarbonyl) propionic acid and 3- (2-vinyloxybutoxycarbonyl) propionic acid can be used. Among these, 3- (2-allyloxyethoxycarbonyl) propionic acid and the like are advantageous and preferable in terms of good monomer stability and polymerization reactivity.

  Specific examples of the sulfonic acid group-containing monomer for introducing an anionic functional group include, for example, vinyl sulfonic acid.

  Examples of the polymer reaction method include a method of reacting a hydroxyl group-containing fluoroolefin polymer with a dibasic acid or an anhydride thereof when a carboxyl group is introduced. Examples of the dibasic acid or its anhydride include maleic anhydride, succinic anhydride, methyl succinic anhydride, adipic anhydride, glutamic anhydride, itaconic anhydride, citraconic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 4- Examples include methyl-1,2-cyclohexanedicarboxylic acid, anhydrous cis-4-cyclohexene-1,2-dicarboxylic acid, and anhydrous 1-cyclohexene-1,2-dicarboxylic acid, and among others, anhydrous 1,2-cyclohexanedicarboxylic acid 4-methyl-1,2-cyclohexanedicarboxylic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, and 1-cyclohexene-1,2-dicarboxylic anhydride are preferable. The reaction is carried out using a solvent capable of dissolving the fluorinated copolymer and the dibasic acid anhydride, and when introducing a carboxyl group, a carboxylic acid metal salt, an alkali metal carbonate, an alkali metal alcoholate, a quaternary ammonium salt, a tertiary amine, etc. It is possible to proceed under conditions such as the addition of a catalyst.

  A method for converting these anionic functional groups into water-soluble functional groups will be described later.

  As a method of introducing an ethylenically unsaturated double bond into the fluorine-containing copolymer (A), a method of copolymerizing a monomer having two or more ethylenically unsaturated double bonds (copolymerization method), a functional A monomer having a group (for example, a carboxyl group, a hydroxyl group, an amino group, an epoxy group, a carbonyl group, an isocyanate group, a silanol group, etc.) is copolymerized, and a functional group that can react with these functional groups (for example, a carboxyl group) A hydroxyl group, a silanol group, a hydrazide group, an amino group, and the like) and a compound having an ethylenically unsaturated double bond to introduce an ethylenically unsaturated double bond (polymer reaction method).

  Examples of monomers having two or more ethylenically unsaturated double bonds that can be used in the copolymerization method include diene series such as butadiene, isoprene, chloroprene, fluoroprene, cyanoprene, phenylbutadiene, diphenylbutadiene, and α, ω-diolefin. Monomers; polyfunctional vinyl carboxylates such as divinyl adipate, vinyl acrylate, vinyl methacrylate and vinyl crotonic acid; aromatic vinyl carboxylates such as vinyl cinnamate;

  The polymer reaction method will be described on behalf of, for example, a case where a carboxyl group is a functional group. As a method for introducing a carboxyl group into the copolymer (A), the above-described method for introducing an anionic functional group can be employed.

  The resulting carboxyl group-containing fluoropolymer (a1) is reacted with a functional group capable of reacting with a carboxyl group and a compound (a2) having an ethylenically unsaturated double bond.

  Examples of the functional group capable of reacting with a carboxyl group include an isocyanate group, an epoxy group, an amino group, and a carbodiimide group. Among these, an isocyanate group and an epoxy group are preferable because a reaction with a carboxyl group occurs rapidly. .

  Examples of the compound (a2) include isocyanate group-containing compounds such as 2-isocyanatoethyl methacrylate; epoxy group-containing compounds such as glycidyl methacrylate, glycidyl acrylate and allyl glycidyl ether.

  Of these, 2-isocyanatoethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, and the like are preferable.

  In addition, although an isocyanate group also reacts with a hydroxyl group, reaction with a carboxyl group has priority.

  The reaction between the compound (a2) and the fluoropolymer (a1) can be carried out by mixing both in an organic solvent. As preferable reaction conditions, a reaction temperature of 20 to 150 ° C. and 1 to 15 hours can be employed.

  The organic solvent only needs to dissolve the fluorine-containing polymer and the compound. For example, the organic solvent used for the polymerization of the fluorine-containing polymer (a1) can be used.

  In the compound (a2), the functional group of the compound (a2) is 1 to 0.01 mol, preferably 1 to 0.1, particularly 1 to 0,1 with respect to 1 mol of the carboxyl group in the fluoropolymer (a1). The reaction is carried out in an amount of 9 mol.

  Further, the fluorine-containing copolymer (A) may or may not have a crosslinkable functional group, but in order to improve the coating film strength, water resistance, solvent resistance, adhesion, coating film hardness, etc. It preferably contains a crosslinkable functional group.

  The crosslinkable functional group is selected in accordance with the type of crosslinkable functional group possessed by the curing agent described later or the type of crosslinkable functional group possessed by the non-fluorinated synthetic resin, preferably a carboxyl group, a hydroxyl group and It is at least one selected from the group consisting of carbonyl groups. The combination of the crosslinkable functional group and the curing agent will be described later.

  Specific examples of the carboxyl group-containing monomer as the crosslinkable functional group-containing monomer include the carboxyl group-containing monomer for introducing the anionic functional group. That is, the carboxyl group functions as both an acid value-providing functional group and a crosslinkable functional group, and is preferably converted to a water-soluble functional group in order to make it water-soluble (acid value-giving) as described later.

Specific examples of the hydroxyl group-containing monomer as the crosslinkable functional group-containing monomer include, for example, formula (III):
CH ₂ = CHR ¹ (III)
(Wherein R ¹ is —OR ² or —CH ₂ OR ² (where R ² is an alkyl group having a hydroxyl group)), and hydroxyalkyl vinyl ethers and hydroxyalkyl allyl ethers. R ² is, for example, a group in which 1 to 3, preferably 1 hydroxyl group is bonded to a linear or branched alkyl group having 1 to 8 carbon atoms. Examples of these include 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-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, and the like. Among these, 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether are preferable in view of excellent polymerization reactivity and functional group curability.

  Specific examples of the carbonyl group-containing monomer as the crosslinkable functional group-containing monomer include, for example, formula (IV):

(Wherein R ⁶ , R ⁷ and R ⁸ are the same or different, and all are hydrogen atom, alkyl group, carboxyl group or ester group; n is 0 or 1) ,
Or formula (V):

(Wherein R ⁹ and R ¹⁰ are the same or different and both are saturated or unsaturated chain or cyclic divalent hydrocarbon groups; n is 0 or 1; m is 0 or 1) Carbonyl group-containing vinyl ether monomers or allyl ether monomers.

  Specific examples of the carbonyl group-containing monomer include acrolein, diacetone acrylamide, diacetone methacrylamide, vinyl alkyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, and vinyl butyl ketone.

  Among these, vinyl ether type and allyl ether type are preferable from the viewpoint of good copolymerizability with fluoroolefin.

  If necessary, the fluorinated copolymer (A) may be copolymerized with other copolymerizable monomers.

  Other copolymerizable monomers include carboxylic acid vinyl esters, alkyl vinyl ethers, non-fluorinated olefins, and the like.

  Examples of vinyl carboxylates include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, and benzoic acid. Examples thereof include vinyl and vinyl para-t-butylbenzoate, and can impart properties such as improved compatibility, improved gloss, and increased glass transition temperature.

  Examples of the alkyl vinyl ethers include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and the like, and can impart properties such as improved gloss and improved flexibility.

  Non-fluorinated olefins include, for example, ethylene, propylene, n-butene, isobutene, and the like, and can impart properties such as improved flexibility.

  The molecular weight of the fluorine-containing copolymer (A) is 200,000 or less in terms of number average molecular weight, more preferably 100,000 or less, and particularly preferably 50,000 or less in view of solution polymerization, more preferably 1,000 or more, Those of 4,000 or more, particularly 8,000 or more are preferred from the viewpoint of excellent weather resistance and durability.

  As described above, the functional group-containing fluorine-containing copolymer for water-based paints is generally produced by an emulsion polymerization method and directly prepared in the form of an aqueous dispersion or emulsion (Japanese Patent Laid-Open No. 7-238253). Gazette, JP-A-9-59560, JP-A-2000-129195). However, as described above, the emulsion polymerization method cannot copolymerize many water-soluble functional group-containing monomers and can only have a large molecular weight.

  Therefore, in the present invention, by producing the fluorine-containing copolymer (A) by a solution polymerization method using an organic solvent as a polymerization solvent, a water-soluble functional group-containing monomer can be stably supplied to the polymerization system, A desired water-soluble fluorine-containing copolymer can be produced, and the molecular weight can be adjusted (lower molecular weight).

  A technique for producing such a water-soluble fluorine-containing copolymer by a solution polymerization method is known in the field of electrodeposition coatings (for example, Japanese Patent Application Laid-Open Nos. 62-143915 and 63-152676). , JP-A-1-249866, etc.), these methods can also be used in the present invention.

  More specifically, a fluoroolefin, a monomer containing a functional group (such as a water-soluble functional group or an ethylenically unsaturated double bond), and a monomer copolymerizable therewith are polymerized in an organic solvent. As a result, the fluorine-containing copolymer (A) used in the present invention is produced.

  As polymerization conditions, the polymerization reaction is preferably carried out in an organic solvent in the presence of a polymerization initiator at a polymerization temperature of 10 to 90 ° C. for 1 to 20 hours.

  Examples of organic solvents include esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; hydrocarbons such as hexane, cyclohexane, and octane; benzene, toluene, xylene, naphthalene, and the like Aromatic hydrocarbons; alcohols such as methanol, ethanol, tert-butanol, iso-propanol, ethylene glycol monoalkyl ether; cyclic ethers such as tetrahydrofuran, tetrahydropyran, dioxane; dimethyl sulfoxide, or a mixture thereof Is given. Of these, acetone, ethyl acetate, and isopropanol are advantageous from the viewpoint of solubility of the fluororesin, and acetone and ethyl acetate are most preferable because they are easily distilled off during the preparation of the aqueous emulsion.

  Examples of the polymerization initiator include diacyl peroxides such as octanoyl peroxide, acetyl peroxide and benzoyl peroxide; dialkoxycarbonyl peroxides such as isopropoxycarbonyl peroxide and tert-butoxycarbonyl peroxide; methyl ethyl ketone peroxide Ketone peroxides such as cyclohexanone peroxide; hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide; dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide Alkyl peroxyesters such as tert-butyl peroxyacetate and tert-butyl peroxypivalate Persulfates such as ammonium persulfate and potassium persulfate (and reducing agents such as sodium bisulfite, sodium pyrosulfite, cobalt naphthenate, and dimethylaniline can be used in combination); oxidizing agents (for example, ammonium peroxide, Redox initiators consisting of potassium peroxide, etc.) and a reducing agent (eg, sodium sulfite) and a transition metal salt (eg, iron sulfate); 2,2′-azobisisobutyronitrile, 2,2′-azobis ( 2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylvaleronitrile), 2,2′-azobis (2-cyclopropylpropionitrile), dimethyl 2,2′-azobisisobutyrate, 2, 2′-azobis [2- (hydroxymethyl) propionitrile], 4,4′-azobis (4 Etc. Shianopenten acid) azo compounds such as may be used.

  Further, if necessary, alcohols such as methanol, ethanol and propanol may be used as molecular weight regulators.

  The fluorine-containing copolymer (A) thus obtained can impart a high acid value, that is, an acid value of 10 to 250 mgKOH / g. If the acid value is less than 10 mg KOH / g, the fluoroolefin copolymer will not be water-soluble, and it cannot essentially be dispersed uniformly in water without the aid of a dispersant or emulsifier.

  On the other hand, when the acid value exceeds 250 mgKOH / g, the water resistance, alkali resistance, etc. of the coating film obtained due to excessive hydrophilicity are lowered. The lower limit of the preferred acid value is 40 mgKOH / g, further 50 mgKOH / g, especially 55 mgKOH / g. Further, a preferable upper limit is 150 mgKOH / g, further 130 mgKOH / g, particularly 120 mgKOH / g.

  The obtained fluorinated copolymer (A) is water-soluble by introducing the polymerization reaction solution into water or adding water to the polymerization reaction solution to invert the organic solvent in the polymerization reaction solution to water. The fluorine-containing copolymer is obtained. At this time, in order to increase the water solubility of the fluorinated copolymer, it is preferable to neutralize the anionic functional group before or after phase inversion to water or after phase inversion.

  The neutralizing agent used for neutralization is ammonia; organic amines such as diethylamine, ethylethanolamine, diethanolamine, monoethanolamine, monopropanolamine, isopropanolamine, ethylaminoethylamine, hydroxyethylamine, diethylenetriamine; sodium hydroxide, Examples include alkali metal hydroxides such as potassium hydroxide. Of these, ammonia, triethylamine, and diethanolamine are preferable in terms of convenience in availability and stability of the emulsion, and ammonia and triethylamine are particularly advantageous in terms of easy handling.

  The neutralizing agent is preferably used in the form of an aqueous solution, but may be used in the form of gas or solid content.

  As a result of neutralization, the anionic functional group is in the form of an ammonium salt, an amine salt, or an alkali metal salt.

  Neutralization is carried out by using an anionic functional group corresponding to 1 mg KOH / g or more, preferably 2 mg KOH / g or more, and 250 mg KOH / g or less, preferably 245 mg KOH / g or less of the acid value of the copolymer with a neutralizer. Neutralize.

  In the present invention, the fluorine-containing composite resin (B) obtained by emulsion polymerization of the ethylenically unsaturated group-containing monomer (b1) in the presence of the fluorine-containing copolymer (A) is used.

  As the ethylenically unsaturated group-containing monomer (b1), monomers having various characteristics may be used. For example, in order to impart water solubility and water dispersibility to the fluorine-containing composite resin (B), an ethylenically unsaturated group-containing monomer containing a carboxyl group and / or a sulfonic acid group may be used. In order to impart the property of pigment dispersibility, an ethylenically unsaturated group-containing monomer having a carboxyl group, an amino group, an amide group, or an epoxy group may be used. Moreover, in order to provide the property of crosslinkability, for example, an ethylenically unsaturated group-containing monomer having a hydroxyl group, a carboxyl group, a carbonyl group, or an amino group may be used as the crosslinkable functional group.

  In order to further improve the weather resistance, an ethylenically unsaturated group-containing monomer containing an alkyl group having 4 to 10 carbon atoms is preferred. In particular, a monomer mixture containing at least one monomer each having a crosslinkable functional group and an acrylic or methacrylic monomer containing an alkyl group having 4 to 10 carbon atoms is preferred.

  Specific examples of the ethylenically unsaturated group-containing monomer (b1) include lower alkyl esters of (meth) acrylic acid such as methyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate; C4-C10 alkyl esters of (meth) acrylic acid such as 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate; unsaturated such as acrylic acid, methacrylic acid, maleic acid, crotonic acid Carboxylic acids; acrylamide, methacrylamide, N-methyl acrylamide, N-methylol acrylamide, N-butoxymethyl acrylamide, N-methylol methacrylamide, N-methyl methacrylamide, Amide compounds such as butoxymethyl methacrylamide; hydroxyl group-containing monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate; epoxy groups such as glycidyl acrylate and glycidyl methacrylate Containing monomers; siloxane group-containing monomers such as γ-trimethoxysilane methacrylate and γ-triethoxysilane methacrylate; one or more of aldehyde group-containing monomers such as acrolein .

  Of these, (meth) acrylic monomers are preferred from the standpoint of high polymerizability and the richness of commercially available monomers.

  Emulsion polymerization is referred to as so-called seed polymerization, which is a well-known technique per se and can be carried out, for example, by the method described in JP-A-2002-179871.

  These ethylenically unsaturated group-containing monomers (b1) are 10 parts by weight or more, further 50 parts by weight or more, particularly 100 parts by weight or more with respect to 100 parts by weight of the solid content of the fluorine-containing copolymer (A). 2,000 parts by weight or less, more preferably 1,000 parts by weight or less, and particularly preferably 500 parts by weight or less.

  The room temperature curable aqueous composition of the present invention comprises an aqueous dispersion of the fluorine-containing composite resin (B) thus obtained and an aqueous curing agent, particularly a room temperature curable curing agent.

  What is necessary is just to adjust the solid content density | concentration in the aqueous dispersion of a fluorine-containing composite resin (B) normally in 30-70 weight%.

  The aqueous curing agent to be blended is a cross-link introduced on the fluorine-containing composite resin (B) or the non-fluorinated synthetic resin (C) side (hereinafter referred to simply as “resin side” in the explanation of the curing agent). Those capable of undergoing a crosslinking reaction with the functional group are employed.

  Examples of the aqueous curing agent include room temperature-curable aqueous curing agents such as carbodiimide compounds, hydrophilic (block type or non-block type) isocyanates, hydrazide compounds, and aziridine.

  Examples of the carbodiimide compound include JP-A 63-264128, US Pat. No. 4,820,863, US Pat. No. 5,108,653, US Pat. No. 5,047,588. US Pat. No. 5,081,173 and the like can be used. As commercial products of carbodiimide compounds for water-based paints, Carbodilite E-01, Carbodilite E-02, Carbodilite V-02, etc. manufactured by Nisshinbo Co., Ltd. are known.

  As the hydrophilic isocyanate, a known blocked isocyanate can be used, but a non-blocked isocyanate compound having excellent room temperature curability is preferable.

  Examples of the non-blocking isocyanate include non-blocking isocyanate compounds modified with polyethylene oxide compounds described in JP-A-11-310700, JP-A-7-330861, JP-A-61-291613 and the like. Is preferred.

  In addition, a non-blocking type isocyanate compound means normal isocyanate compounds other than the block type isocyanate compound obtained by reaction of alcohol or an oxime compound, and an isocyanate compound.

  Specifically, a non-block type aliphatic polyisocyanate compound or a non-block type aromatic polyisocyanate compound modified with a polyethylene oxide compound is exemplified. Among these, non-block type aliphatic isocyanate compounds are preferable from the viewpoint of excellent weather resistance.

  Among the aliphatic polyisocyanate compounds, examples of the chain aliphatic polyisocyanate compound include trimethylene diisocyanate, tetramethylene diisocyanate, 1,6-diisocyanatohexane (= hexamethylene diisocyanate), pentamethylene diisocyanate, and 1,2-propylene. Diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl captroate Diisocyanates such as: lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate Over preparative -4 isocyanatomethyl octane, 1,3,6-triisocyanate hexane, polyisocyanates such as 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanatomethyl octane can be exemplified.

  As the alicyclic polyisocyanate compound among the aliphatic polyisocyanate compounds, for example, 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 1-isocyanato-3,3,5-trimethyl- 5-isocyanatomethyl-cyclohexane (= isophorone diisocyanate), 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or 1,4 -Diisocyanates such as bis (isocyanatomethyl) cyclohexane; 1,3,5-triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 2- (3 Isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo (2.2.1) ) Heptane, 3- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3) -Isocyanatopropyl) -bicyclo (2.2.1) heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo ( .2.1) - heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanate propyl) - bicyclo (2.2.1) polyisocyanates such as heptane may be cited.

  Examples of the aromatic isocyanate compound include tolylene diisocyanate.

  These isocyanate compounds may be used alone or in combination of two or more.

  Examples of the polyethylene oxide compound that is a modifier include polyoxyethylene monooctyl ether, polyoxyethylene monolauryl ether, polyoxyethylene monodecyl ether, polyoxyethylene monocetyl ether, polyoxyethylene monostearyl ether, polyoxyethylene mono Polyoxyethylene C8-24 alkyl ethers such as oleyl ether, preferably polyoxyethylene C10-22 alkyl ethers, especially polyoxyethylene alkyl ethers such as polyoxyethylene C12-18 alkyl ethers; for example polyoxyethylene monooctylphenyl ether , Polyoxyethylene monononyl phenyl ether, polyoxyethylene monodecyl phenyl ether, etc. Polyoxyethylene monoalkylaryl ethers such as 8-12 alkyl-C6-12 aryl ethers; for example, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan Polyoxyethylene sorbitan-mono, di- or tri-C10-24 fatty acid esters such as polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan higher fatty acid esters; for example, polyoxyethylene monolaurate, polyoxyethylene Polyoxyethylene mono higher fatty acid esters such as polyoxyethylene mono C10-24 fatty acid ester such as monostearate Compounds known as nonionic emulsifier can be exemplified. These compounds can be used alone or in combination of two or more. Preferable examples include polyoxyethylene C8-24 alkyl ether and polyoxyethylene C8-12 alkylphenyl ether from the viewpoint of easy water dispersibility.

  The modification can be performed, for example, by a method in which an isocyanate compound is mixed with a modifying agent in a solution and reacted by heating.

  The ratio of the polyisocyanate compound and the modifier is 0.01 to 0.034 equivalent, preferably 0.015 to 0.03 equivalent of an active hydrogen atom of the modifier with respect to 1 equivalent of isocyanate group in the polyisocyanate compound. You can choose from a range of degrees.

  Examples of commercially available polyethylene oxide-modified non-blocked isocyanate compounds include, but are not limited to, Bihijoule 3100, Bihijoule TPLS2150 manufactured by Sumitomo Bayer Urethane Co., Ltd .; and Duranate WB40-100 manufactured by Asahi Kasei Co., Ltd. Is not to be done.

  The non-blocking isocyanate compound is usually used in the form of an aqueous solution or an aqueous dispersion.

  Examples of the hydrazide compound include those described in JP-A-7-268163 and JP-A-9-291186. Specifically, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide. Dicarboxylic acid dihydrazides containing from 2 to 10, in particular from 4 to 6 carbon atoms, such as isophthalic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide; ethylene-1,2-dihydrazine , Aliphatic water-soluble dihydrazine having 2 to 4 carbon atoms such as propylene-1,3-dihydrazine, butylene-1,4-dihydrazine, and the like. Among these, adipic acid dihydrazide, isophthalic acid Dihydrazide, sebacin Dihydrazide is preferable.

For example, the following combinations can be exemplified.
(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, and the like can be given.
Among these, a carbodiimide compound having at least two carbodiimide groups per molecule is preferable from the viewpoint of good room temperature curability.

(2) When the crosslinkable functional group on the resin side is a hydroxyl group:
Examples thereof include hydrophilic isocyanates such as non-blocked isocyanate compounds and blocked isocyanate compounds, and melamine compounds.
Of these, hydrophilic polyisocyanates are particularly preferred in that they have good room temperature curability and good properties as curing agents for water-based paints.

(3) When the crosslinkable functional group on the resin side is a carbonyl group:
Examples thereof include hydrazide compounds and Grignard compounds.
Among these, a hydrazide compound having at least two hydrazide groups per molecule is preferable in that it has good room temperature curability and good properties as a curing agent for water-based paints.

(4) When the crosslinkable functional group on the resin side is an ethylenically unsaturated group:
Examples include active methylene group-containing low molecular weight compounds, active methylene group-containing resins, and the like.
Of these, a 1,3-dicarbonyl compound and a 1,3-dicarbonyl group-containing resin are particularly preferred in that they have good room temperature curability and good properties as a curing agent for water-based paints.

  In any case, the amount of the aqueous curing agent is 0.1 to 5 molar equivalents relative to 1 equivalent of the crosslinkable functional group on the resin side (total functional group of fluorine-containing composite resin (B) or non-fluorinated synthetic resin). It is preferable to mix.

  Furthermore, you may mix | blend a well-known hardening accelerator etc. Examples of the curing accelerator include dibutyltin dilaurate.

  You may mix | blend non-fluorine-type synthetic resin (C) with the aqueous composition of this invention as needed. As a blending form, an aqueous dispersion and an emulsion are preferable. Examples of non-fluorinated synthetic resins include acrylic resins, urethane resins, polyester resins, and epoxy resins. Among these, acrylic resins, urethane resins, and polyester resins are weather resistance, durability, water resistance, hardness, strength. In view of good flexibility, gloss and adhesion, acrylic resin is particularly preferable in terms of further excellent weather resistance, gloss, hardness and water resistance.

  Furthermore, the non-fluorinated synthetic resin (C) may or may not have a crosslinkable functional group. However, in terms of improving weather resistance, water resistance, hardness, stain resistance, etc. It is preferable to introduce. As the crosslinkable functional group, the above-mentioned ones can be adopted including the introduction monomer.

  The blending amount of the fluorine-containing composite resin (B) and the non-fluorinated synthetic resin (C) is (B) 95-5 parts by weight and (C) 5-95 parts by weight, preferably (B) 10- 90 parts by weight and (C) 90 to 10 parts by weight.

  In the present invention, by incorporating an aqueous curing agent, a room temperature curable aqueous composition having excellent weather resistance, water resistance, stain resistance and rain-stain stain resistance can be obtained.

  The room temperature curable aqueous composition of the present invention can be prepared as a solvent type or aqueous coating composition. In that case, as additives for paints that may be blended, in addition to the above-mentioned curing agents, for example, surfactants, pigments, dispersants, thickeners, preservatives, ultraviolet absorbers, antifoaming agents, leveling agents, etc. Is given.

  As the surfactant, those described above can be used.

  In addition, as a thickener, Primal QR708 (manufactured by Rohm and Haas Co., Ltd.), etc., as an antifoaming agent, Byk023 (Bicchemy Japan Co., Ltd.) and the like, as a dispersant, Byk190 (Bicchemy Japan Co., Ltd.), An example is SN Dispersant 5027 (San Nopco).

  The resulting aqueous paint composition is useful as various paint materials such as weather-resistant paints, electrodeposition paints, coil coat paints, automotive paints, graffiti-preventing paints and heavy anticorrosion paints. As a coating method, a normal coating method used for those paints, for example, roll coating, dipping, brush coating, spraying, roller, or an electrodeposition coating method can be employed.

  The coating film formed from the composition of the present invention can be cured at room temperature. This is due to the fact that a relatively large number of crosslinkable functional groups can be introduced into the fluorine-containing composite resin and that the curing reaction proceeds sufficiently even at room temperature. In addition, you may heat in order to accelerate | stimulate hardening.

  The cured coating film has been sufficiently cured (crosslinked) and improved in coating film strength, solvent resistance and stain resistance compared to the fluororesin aqueous coating obtained by emulsion polymerization. In addition, the appearance is smooth, and coating film defects such as glossiness and dullness are reduced.

  When preparing a solvent-type coating composition, an organic solvent, a pigment, an antifoaming agent, a thickening agent, a dispersing agent, a leveling agent, a curing agent, etc. are blended in the fluorine-containing graft copolymer and dispersed or dissolved. Just do it.

  In addition, the aqueous composition of the present invention can be prepared into a composition such as an adhesive composition and an ink composition by a known method.

  EXAMPLES Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited only to these examples.

Synthesis example 1
To a 6 L stainless steel autoclave, 1.25 kg of acetone, 220 g of Veova-9 (vinyl versatate manufactured by Shell Chemical Co., Ltd.), 47 g of vinyl benzoate and 109 g of hydroxybutyl vinyl ether were added, and the atmosphere was replaced with nitrogen, and 300 g of tetrafluoroethylene was added. The temperature was raised to 5 ° C. Then, 20 g of octanoyl peroxide solution (solid content: 70% by weight) was added with stirring and reacted for 5 hours. The reaction was stopped when the pressure in the reaction vessel dropped to 0.25 MPa · G. The reaction mixture was cooled to room temperature, purged with unreacted monomers, and further purged with nitrogen to obtain 1.8 kg of reaction product (solid content: 31.6% by weight). The obtained copolymer was analyzed by ¹⁹ F-NMR and ¹ H-NMR. The number average molecular weight Mn measured by GPC was 20,000, and the hydroxyl value was 90 mgKOH / g.

Synthesis example 2
Add 900 g of the hydroxyl group-containing polymer obtained in Synthesis Example 1 and 66 g of anhydrous 4-methyl-1,2-cyclohexanedicarboxylic acid (Rikacid MH700 manufactured by Shin Nippon Rika Co., Ltd.) to a 3 L four-necked flask equipped with a stirrer. It was. Further, 4 g of triethylamine was added, and the temperature was gradually raised. After the solution in the flask reached 70 ° C., the temperature was maintained and the reaction was carried out. When the progress of the reaction was traced with an infrared spectrum analyzer, the absorption of acid anhydrides at 1860 cm ^-1 and 1790 cm ^-1 was not observed after 3 hours, and strong absorption of the ester was observed at 1733 cm ^-1. It was. The acid value of this polymer was 90 mgKOH / g.

  15.7 g of 2-isocyanatoethyl methacrylate was added to this polymer, and the reaction was allowed to proceed at 40 ° C. for 3 hours to introduce ethylenically unsaturated groups into the polymer. The obtained copolymer had a hydroxyl value of 70 mgKOH / g.

  Next, 42 g of 28% ammonia water was added to the polymer solution to neutralize the carboxylic acid groups. 0.82 kg of water was gradually added while gradually removing the organic solvent under reduced pressure from the resulting neutralized solution to obtain a uniform aqueous solution (solid content: 30% by weight).

Synthesis example 3
A flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer, and a reflux condenser was charged with 954.6 g of the aqueous solution of the fluorinated copolymer obtained in Synthesis Example 2, and the components of the following composition were added. .
(composition)
67g diacetone acrylamide
Methyl methacrylate 238.2g
120g 2-ethylhexyl acrylate
n-Butyl acrylate 243g

  Then, an aqueous solution in which 0.7 g of ammonium persulfate was dissolved in 6.3 g of water was added, and polymerization was performed at 80 ° C. for 2 hours. Further, 7.7 g of 10 wt% ammonium persulfate aqueous solution was added dropwise, and the temperature was kept at 80 ° C. for 2 hours. After the reaction, the mixture was cooled and then adjusted to pH 8.5 with aqueous ammonia to obtain an aqueous dispersion having a solid content of 52% by weight.

Synthesis example 4
In Synthesis Example 1, the carboxyl group-containing fluorine-containing copolymer was prepared in the same manner as in Synthesis Example 1, except that the amount of Veova-9 was 183.2 g and 22.4 g of vinyl methacrylate was used instead of vinyl benzoate. Obtained. The acid value of this carboxyl group-containing polymer was 90 mgKOH / g.

Synthesis example 5
A flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer, and a reflux condenser was charged with 954.6 g of the aqueous solution of the fluorinated copolymer obtained in Synthesis Example 4, and the components of the following composition were added. .
(composition)
67g diacetone acrylamide
Methyl methacrylate 238.2g
120g 2-ethylhexyl acrylate
n-Butyl acrylate 243g

  Then, an aqueous solution in which 0.7 g of ammonium persulfate was dissolved in 6.3 g of water was added, and polymerization was performed at 80 ° C. for 2 hours. Further, 7.7 g of 10 wt% ammonium persulfate aqueous solution was added dropwise, and the temperature was kept at 80 ° C. for 2 hours. After the reaction, the mixture was cooled, then adjusted to pH 8.5 with aqueous ammonia, and further water was added to obtain an aqueous dispersion having a solid content of 50% by weight.

Example 1 (Preparation of room temperature curable aqueous composition)
A 100-ml polycup was blended with 100 parts by weight of the fluorinated composite resin obtained in Synthesis Example 3 and 15 parts by weight of adipic acid dihydrazide (manufactured by Otsuka Chemical Co., Ltd.) to obtain a curable composition for aqueous paints.

  With respect to 100 parts by weight of the solid content of the curable composition for water-based paints, 50 parts by weight of titanium oxide (Taipaque CR-97, manufactured by Ishihara Sangyo Co., Ltd.) as a filler, and NOPCOSPERS SN5027 (San Nopco) as a dispersant 2 parts by weight of polycarboxylic acid ammonium salt), 1 part by weight of ethylene glycol as an antifreeze agent, 0.5 part by weight of FS Antifoam 013B (manufactured by Dow Corning) as a defoaming agent, CS- as a thickener 10 parts by weight of 12 (manufactured by Chisso Co., Ltd.) was added and thoroughly mixed using a disper stirrer to prepare a paint.

This paint was applied using an applicator, and allowed to stand at room temperature for 5 days to cure the coating film to obtain a test piece. The following characteristics were examined for this test piece. The results are shown in Table 1.
Appearance: The appearance of the coating film is visually observed.

Let C be when there is glossiness or dullness, B when glossiness or slight dullness, and A when there is no glossiness or dullness.
Gloss: Specular gloss of 60 degrees is measured according to JIS K5400.
Hot water resistance: The coating film is immersed in warm water at 50 ° C. for 24 hours, and then the coating film is visually observed.

When there is no abnormality, A is indicated as B, when some cloudiness and glossiness are observed, B is marked when cloudiness and glossiness are observed, and D when the coating film is dissolved.
Solvent resistance test: The surface of the coating film is wiped with a nonwoven fabric impregnated with xylene. The wiping operation is performed until 100 round trips are completed.

After completion of the test, A is defined as no dissolution or gloss reduction in the coating film, B is defined as slight dissolution or gloss reduction in the coating film, and C is defined as significant dissolution or gloss reduction.
Weather resistance test: A 2000-hour accelerated weather resistance test is conducted using a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.).

  The brightness difference (ΔE) is 0 to less than 2 as A, 2 to less than 4 as B, 4 to less than 6 as C, 6 to less than 10 as D, and 10 or more as E. .

Example 2
A paint was prepared in the same manner as in Example 1 except that the polymer produced in Synthesis Example 5 was used as the fluorine-containing composite resin, and a test piece was prepared after applying a coating plate. About the obtained test piece, it carried out similarly to Example 1, and investigated the coating-film characteristic. The results are shown in Table 1.

Synthesis Example 6
To a 6 L stainless steel autoclave, 1.25 kg of acetone, 244.4 g of vinyl pivalate (manufactured by Nihon Acetate / Poval Co., Ltd.), 192.0 g of 10-undecenoic acid, nitrogen substitution, and 300 g of tetrafluoroethylene were added, 61 The temperature was raised to 5 ° C. Next, 11.6 g of octanoyl peroxide solution (solid content: 70% by weight) was added with stirring and reacted for 8 hours. The reaction was stopped when the internal pressure of the reaction vessel dropped to 0.25 MPa · G. The reaction mixture was cooled to room temperature, purged with unreacted monomers, and further purged with nitrogen to obtain 2.0 kg of reaction product (solid content: 35.3% by weight). The obtained copolymer was analyzed by ¹⁹ F-NMR and ¹ H-NMR, and found to be tetrafluoroethylene / vinyl pivalate / 10-undecenoic acid = 45/35/20 (molar ratio). The measured number average molecular weight Mn was 8,000, and the acid value was 90 mgKOH / g.

Synthesis example 7
8.82 g of glycidyl methacrylate and 0.87 g of benzyltriethylammonium were added to 821.5 g of the polymer obtained in Synthesis Example 6 placed in a 3 L four-necked flask equipped with a stirrer and a reflux condenser, and reacted at 120 ° C. for 5 hours. To introduce an ethylenically unsaturated group into the polymer.

  Next, 47.0 g of triethylamine was added to the polymer solution to neutralize the carboxylic acid group. 700 g of water was gradually added while gradually removing the organic solvent under reduced pressure from the resulting neutralized solution to obtain a uniform aqueous solution (solid content 30 wt%).

Synthesis example 8
400 g of the aqueous solution of the fluorinated copolymer obtained in Synthesis Example 7 was placed in a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer, and a reflux condenser, and the components of the following composition were added thereto. .
(composition)
67g diacetone acrylamide
Methyl methacrylate 117.4g
Cyclohexyl methacrylate 117.5g
n-Butyl acrylate 243g
120g 2-ethylhexyl methacrylate
Acrylic acid 3.3g
New Coal 707SF (Nippon Emulsifier Co., Ltd.) 10g

  Then, an aqueous solution in which 0.7 g of ammonium persulfate was dissolved in 6.3 g of water was added, and polymerization was performed at 80 ° C. for 2 hours. Further, 7.7 g of 10 wt% ammonium persulfate aqueous solution was added dropwise, and the temperature was kept at 80 ° C. for 2 hours. After the reaction, the mixture was cooled, then adjusted to pH 8.5 with aqueous ammonia, and further water was added to obtain an aqueous dispersion having a solid content of 50% by weight.

Synthesis Example 9
A 6 L stainless steel autoclave was added with 1.25 kg of acetone, 315.9 g of Veover 9, 225.9 g of 10-undecenoic acid, purged with nitrogen, added 300 g of tetrafluoroethylene, and heated to 61.5 ° C. Then, 12 g of octanoyl peroxide solution (solid content: 70% by weight) was added with stirring and reacted for 8 hours. The reaction was stopped when the pressure in the reaction vessel dropped to 0.25 MPa · G. The reaction mixture was cooled to room temperature, purged with unreacted monomers, and then purged with nitrogen to obtain 2.1 kg of reaction product (solid content: 39.0% by weight). The obtained copolymer was analyzed by ¹⁹ F-NMR and ¹ H-NMR, and found to be tetrafluoroethylene / veova-9 / 10-undecenoic acid = 46 / 30.9 / 23.1 (mole% ratio). The number average molecular weight Mn measured by GPC was 9,000, and the acid value was 90 mgKOH / g.

Synthesis Example 10
8.74 g of glycidyl methacrylate and 0.87 g of benzyltriethylammonium were added to 743.6 g of the polymer obtained in Synthesis Example 9 placed in a 3 L four-necked flask equipped with a stirrer and a reflux condenser, and reacted at 120 ° C. for 5 hours. To introduce an ethylenically unsaturated group into the polymer.

  Next, 47.0 g of triethylamine was added to the polymer solution to neutralize the carboxylic acid group. 700 g of water was gradually added while gradually removing the organic solvent under reduced pressure from the resulting neutralized solution to obtain a uniform aqueous solution (solid content 30 wt%).

Synthesis Example 11
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 aqueous solution of the fluorine-containing copolymer obtained in Synthesis Example 10 was added, and the components having the following composition were added.
(composition)
67g diacetone acrylamide
Methyl methacrylate 117.4g
114.2 g of cyclohexyl methacrylate
n-Butyl acrylate 243g
120g 2-ethylhexyl methacrylate
2-hydroxyethyl methacrylate 3.3 g
Acrylic acid 3.3g
New Call 707SF 10g

  Then, an aqueous solution in which 0.7 g of ammonium persulfate was dissolved in 6.3 g of water was added, and polymerization was performed at 80 ° C. for 2 hours. Further, 7.7 g of 10 wt% ammonium persulfate aqueous solution was added dropwise, and the temperature was kept at 80 ° C. for 2 hours. After the reaction, the mixture was cooled, then adjusted to pH 8.5 with aqueous ammonia, and further water was added to obtain an aqueous dispersion having a solid content of 50% by weight.

Synthesis Example 12
To a 6 L stainless steel autoclave, 1.25 kg of acetone, 373.7 g of vinyl pivalate (manufactured by Nihon Acetate / Poval), 69.8 g of acrylic acid, nitrogen substitution, 300 g of tetrafluoroethylene were added, and 61.5 The temperature was raised to ° C. Next, 9.8 g of octanoyl peroxide solution (solid content: 70% by weight) was added with stirring and reacted for 8 hours. The reaction was stopped when the internal pressure of the reaction vessel dropped to 0.25 MPa · G. The reaction mixture was cooled to room temperature, purged with unreacted monomers, and further purged with nitrogen to obtain 2.0 kg of reaction product (solid content: 32.6% by weight). The obtained copolymer was analyzed by ¹⁹ F-NMR and ¹ H-NMR, and found to be tetrafluoroethylene / vinyl pivalate / acrylic acid = 45/35/20 (molar ratio), and measured by GPC. The number average molecular weight Mn was 6,000, and the acid value was 90 mgKOH / g.

Synthesis Example 13
To 889.6 g of the polymer obtained in Synthesis Example 12 placed in a 3 L four-necked flask equipped with a stirrer and a reflux condenser, 8.70 g of glycidyl methacrylate and 0.87 g of benzyltriethylammonium were added and reacted at 120 ° C. for 5 hours. To introduce an ethylenically unsaturated group into the polymer.

  Next, 47.0 g of triethylamine was added to the polymer solution to neutralize the carboxylic acid group. 700 g of water was gradually added while gradually removing the organic solvent under reduced pressure from the resulting neutralized solution to obtain a uniform aqueous solution (solid content 30 wt%).

Synthesis Example 14
A flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer, and a reflux condenser was charged with 247.5 g of the aqueous solution of the fluorinated copolymer obtained in Synthesis Example 13, and components of the following composition were added. .
(composition)
67g diacetone acrylamide
Methyl methacrylate 117.4g
Cyclohexyl methacrylate 117.5g
n-Butyl acrylate 243g
120g 2-ethylhexyl methacrylate
Acrylic acid 3.3g
New Call 707SF 10g

  Then, an aqueous solution in which 0.7 g of ammonium persulfate was dissolved in 6.3 g of water was added, and polymerization was performed at 80 ° C. for 2 hours. Further, 7.7 g of 10 wt% ammonium persulfate aqueous solution was added dropwise, and the temperature was kept at 80 ° C. for 2 hours. After the reaction, the mixture was cooled, then adjusted to pH 8.5 with aqueous ammonia, and further water was added to obtain an aqueous dispersion having a solid content of 50% by weight.

Synthesis Example 15
A flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer, and a reflux condenser was charged with 954.6 g of the aqueous solution of the fluorinated copolymer obtained in Synthesis Example 10, and the components of the following composition were added. .
(composition)
67g diacetone acrylamide
Methyl methacrylate 231.6g
n-Butyl acrylate 243g
120g 2-ethylhexyl methacrylate
2-hydroxyethyl methacrylate 3.3 g
Acrylic acid 3.3g
New Call 707SF 10g

  Then, an aqueous solution in which 0.7 g of ammonium persulfate was dissolved in 6.3 g of water was added, and polymerization was performed at 80 ° C. for 2 hours. Further, 7.7 g of 10 wt% ammonium persulfate aqueous solution was added dropwise, and the temperature was kept at 80 ° C. for 2 hours. After the reaction, the mixture was cooled, then adjusted to pH 8.5 with aqueous ammonia, and further water was added to obtain an aqueous dispersion having a solid content of 50% by weight.

Synthesis Example 16
To a 6 L stainless steel autoclave, add 1.25 kg of acetone, 212.9 g of vinyl pivalate (manufactured by Nihon Acetate / Poval), 28.5 g of hydroxybutyl vinyl ether, and 192.0 g of 10-undecenoic acid. 300 g of fluoroethylene was added and the temperature was raised to 61.5 ° C. Then, 12 g of octanoyl peroxide solution (solid content: 70% by weight) was added with stirring and reacted for 8 hours. The reaction was stopped when the pressure in the reaction vessel dropped to 0.25 MPa · G. The reaction mixture was cooled to room temperature, purged with unreacted monomers, and then purged with nitrogen to obtain 1.8 kg of reaction product (solid content: 35.2% by weight). When the obtained copolymer was analyzed by ¹⁹ F-NMR and ¹ H-NMR, tetrafluoroethylene / vinyl pivalate / hydroxybutyl vinyl ether / 10-undecenoic acid = 45 / 33.7 / 4.0 / 17. The number average molecular weight Mn measured by GPC was 7,000, the hydroxyl value was 20 mgKOH / g, and the acid value was 90 mgKOH / g.

Synthesis Example 17
18.2 g of 2-isocyanatoethyl methacrylate was added to 823.9 g of the polymer obtained in Synthesis Example 16 placed in a 3 L four-necked flask equipped with a stirrer and a reflux condenser, and the reaction was allowed to proceed at 60 ° C. for 1 hour. Ethylenically unsaturated groups were introduced into the polymer.

  Next, 47.0 g of triethylamine was added to the polymer solution to neutralize the carboxylic acid group. 700 g of water was gradually added while gradually removing the organic solvent under reduced pressure from the resulting neutralized solution to obtain a uniform aqueous solution (solid content 30 wt%).

Synthesis Example 18
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 aqueous solution of the fluorinated copolymer obtained in Synthesis Example 17 was placed. In addition, the same operation was performed to obtain an aqueous dispersion having a solid content of 50% by weight.

Synthesis Example 19
To a 6 L stainless steel autoclave, add 1.25 kg of acetone, 269.9 g of veova-9, 32.2 g of hydroxybutyl vinyl ether, 221.0 g of 10-undecenoic acid, purge with nitrogen, add 300 g of tetrafluoroethylene, 61. The temperature was raised to 5 ° C. Then, 12 g of octanoyl peroxide solution (solid content: 70% by weight) was added with stirring and reacted for 8 hours. The reaction was stopped when the pressure in the reaction vessel dropped to 0.25 MPa · G. The reaction mixture was cooled to room temperature, purged with unreacted monomers, and then purged with nitrogen to obtain 2.1 kg of reaction product (solid content: 38.4% by weight). The obtained copolymer was analyzed by ¹⁹ F-NMR and ¹ H-NMR. As a result, tetrafluoroethylene / veova-9 / hydroxybutyl vinyl ether / 10-undecenoic acid = 46 / 26.4 / 5.0 / 22. The number average molecular weight Mn measured by GPC was 10,000, the hydroxyl value was 20 mgKOH / g, and the acid value was 90 mgKOH / g.

Synthesis Example 20
14.5 g of 2-isocyanatoethyl methacrylate was added to 755.2 g of the polymer obtained in Synthesis Example 19 placed in a 3 L four-necked flask equipped with a stirrer and a reflux condenser, and the reaction was allowed to proceed at 60 ° C. for 1 hour. Ethylenically unsaturated groups were introduced into the polymer.

  Next, 47.0 g of triethylamine was added to the polymer solution to neutralize the carboxylic acid group. 700 g of water was gradually added while gradually removing the organic solvent under reduced pressure from the resulting neutralized solution to obtain a uniform aqueous solution (solid content 30 wt%).

Synthesis Example 21
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 aqueous solution of the fluorinated copolymer obtained in Synthesis Example 20 was placed. In addition, the same operation was performed to obtain an aqueous dispersion having a solid content of 50% by weight.

Synthesis Example 22
A 6L stainless steel autoclave was added with 1.25 kg of acetone, 347 g of Veova-9, 23.5 g of 2-hydroxyethyl methacrylate, 65.4 g of acrylic acid, purged with nitrogen, and 300 g of tetrafluoroethylene was added. The temperature was raised to. Next, 9.8 g of octanoyl peroxide solution (solid content: 70% by weight) was added with stirring and reacted for 8 hours. The reaction was stopped when the internal pressure of the reaction vessel dropped to 0.25 MPa · G. The reaction mixture was cooled to room temperature, purged with unreacted monomers, and then purged with nitrogen to obtain 2.0 kg of reaction product (solid content: 31.1% by weight). When the obtained copolymer was analyzed by ¹⁹ F-NMR and ¹ H-NMR, tetrafluoroethylene / veova-9 / 2-hydroxyethyl methacrylate / acrylic acid = 30 / 44.0 / 4.8 / 21. The number average molecular weight Mn measured by GPC was 6,000, the hydroxyl value was 20 mgKOH / g, and the acid value was 90 mgKOH / g.

Synthesis Example 23
14.5 g of 2-isocyanatoethyl methacrylate was added to 932.5 g of the polymer obtained in Synthesis Example 22 placed in a 3 L four-necked flask equipped with a stirrer and a reflux condenser, and the reaction was allowed to proceed at 60 ° C. for 1 hour. Ethylenically unsaturated groups were introduced into the polymer.

  Next, 47.0 g of triethylamine was added to the polymer solution to neutralize the carboxylic acid group. 700 g of water was gradually added while gradually removing the organic solvent under reduced pressure from the resulting neutralized solution to obtain a uniform aqueous solution (solid content 30 wt%).

Synthesis Example 24
A flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer, and a reflux condenser was charged with 247.5 g of the aqueous solution of the fluorinated copolymer obtained in Synthesis Example 23. The components were added and the same operation was performed to obtain an aqueous dispersion having a solid content of 50% by weight.

Synthesis Example 25
Into a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer, and a reflux condenser, 954.6 g of the aqueous solution of the fluorinated copolymer obtained in Synthesis Example 20 was placed. added.
(composition)
67g diacetone acrylamide
Methyl methacrylate 231.6g
n-Butyl acrylate 243g
120g 2-ethylhexyl methacrylate
2-hydroxyethyl methacrylate 3.3 g
Acrylic acid 3.3g
New Call 707SF 10g

  Then, an aqueous solution in which 0.7 g of ammonium persulfate was dissolved in 6.3 g of water was added, and polymerization was performed at 80 ° C. for 2 hours. Further, 7.7 g of 10 wt% ammonium persulfate aqueous solution was added dropwise, and the temperature was kept at 80 ° C. for 2 hours. After the reaction, the mixture was cooled, then adjusted to pH 8.5 with aqueous ammonia, and further water was added to obtain an aqueous dispersion having a solid content of 50% by weight.

Synthesis Example 26
Into a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer, and a reflux condenser, 954.6 g of the aqueous solution of the fluorinated copolymer obtained in Synthesis Example 20 was placed. added.
(composition)
234.9 g of styrene
n-Butyl acrylate 243g
120g 2-ethylhexyl methacrylate
Acrylic acid 3.3g
New Call 707SF 10g

  Then, an aqueous solution in which 0.7 g of ammonium persulfate was dissolved in 6.3 g of water was added, and polymerization was performed at 80 ° C. for 2 hours. Further, 7.7 g of 10 wt% ammonium persulfate aqueous solution was added dropwise, and the temperature was kept at 80 ° C. for 2 hours. After the reaction, the mixture was cooled, then adjusted to pH 8.5 with aqueous ammonia, and further water was added to obtain an aqueous dispersion having a solid content of 50% by weight.

Examples 3-10 and Comparative Examples 1-2
A coating material was prepared in the same manner as in Example 1 except that the polymer produced in each synthesis example shown in Table 2 was used as the fluorine-containing composite resin, and a test piece was prepared after applying a coating plate. About the obtained test piece, it carried out similarly to Example 1, and investigated the coating-film characteristic. The results are shown in Table 2.

Synthesis Example 27
To a 6 L stainless steel autoclave, add 1.25 kg of acetone, 306.7 g of veova-9, 5.2 g of hydroxybutyl vinyl ether, 237.5 g of 10-undecenoic acid, purge with nitrogen, add 300 g of tetrafluoroethylene, and add 61.5 The temperature was raised to ° C. Then, 11.8 g of octanoyl peroxide solution (solid content: 70% by weight) was added with stirring and reacted for 8 hours. The reaction was stopped when the pressure in the reaction vessel dropped to 0.35 MPa · G. The reaction mixture was cooled to room temperature, purged with unreacted monomers, and further purged with nitrogen to obtain 2.0 kg of reaction product (solid content: 39.2% by weight). The obtained copolymer was analyzed by ¹⁹ F-MNR and ¹ H-MNR. As a result, tetrafluoroethylene / veova-9 / hydroxybutyl vinyl ether / 10-undecenoic acid = 46/30 / 0.8 / 23. The number average molecular weight Mn measured by GPC was 8,000, the hydroxyl value was 3 mgKOH / g, and the acid value was 90 mgKOH / g.

Synthesis Example 28
To a 3 L four-necked flask equipped with a stirrer and a reflux condenser, 1.35 g of 2-isocyanatoethyl methacrylate was added to 382.6 g of the polymer obtained in Synthesis Example 27, and the reaction was allowed to proceed at 60 ° C. for 1 hour. Unsaturated groups were introduced into the polymer.

  Next, 14.5 g of 28% aqueous ammonia was added to the polymer solution to neutralize the carboxylic acid groups. From the resulting neutralized solution, 750 g of water was gradually added while gradually removing the organic solvent under reduced pressure to obtain a uniform aqueous solution (solid content of 16.7% by weight).

Synthesis Example 29
Into a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer, and a reflux condenser, 900 g of the aqueous dispersion of the fluorinated copolymer obtained in Synthesis Example 28 was placed. added.
(composition)
Methyl methacrylate 150.0g
Cyclohexyl acrylate 180.0g
2-ethylhexyl acrylate 270.0g

  Next, an aqueous solution in which 0.6 g of ammonium persulfate was dissolved in 5.4 g of water was added, and polymerization was carried out at 80 ° C. for 2 hours. 6.0 g of 10% by weight ammonium persulfate aqueous solution was added dropwise, and the mixture was kept at 80 ° C. for 2 hours. After the reaction, the mixture was cooled, then adjusted to pH 8.5 with aqueous ammonia, and further water was added to obtain an aqueous dispersion having a solid content of 50% by weight.

Synthesis Example 30
To a 6L stainless steel autoclave, add 1.2kg of butyl acetate, 420.4g of Veova-9, 152g of hydroxybutyl vinyl ether, 241.6g of 10-undecenoic acid, purge with nitrogen, add 600g of tetrafluoroethylene, up to 61.5 ° C The temperature rose. Next, 19 g of an octanoyl peroxide solution (solid content: 70% by weight) was added with stirring and reacted for 8 hours. The reaction was stopped when the internal pressure of the reaction vessel dropped to 0.4 MPa · G. The reaction mixture was cooled to room temperature, purged with unreacted monomers, and further purged with nitrogen to obtain 2.4 kg (solid content 50.3% by weight) of a reaction product. The obtained copolymer was analyzed by ¹⁹ F-MNR and ¹ H-MNR, and found to be tetrafluoroethylene / veova-9 / hydroxybutyl vinyl ether / 10-undecenoic acid = 45 / 25.6 / 14.7 / 14. The number average molecular weight Mn measured by GPC was 14,400, the hydroxyl value was 60 mgKOH / g, and the acid value was 60 mgKOH / g.

Synthesis Example 31
To a 3L four-necked flask equipped with a stirrer and a reflux condenser, 3.15 g of 2-isocyanatoethyl methacrylate was added to 695.8 g of the polymer obtained in Synthesis Example 30, and the reaction was allowed to proceed at 60 ° C. for 1 hour. Unsaturated groups were introduced into the polymer.

  Next, 24.1 g of triethylamine was added to the polymer solution to neutralize the carboxylic acid group. 700 g of water was gradually added while gradually removing the organic solvent under reduced pressure from the resulting neutralized solution to obtain a uniform aqueous solution (solid content: 33.3% by weight).

Synthesis Example 32
Into a flask equipped with a dropping funnel, a stirrer, an inert gas introduction tube, a thermometer, and a reflux condenser, the aqueous dispersion of the fluorinated copolymer obtained in Synthesis Example 31 was placed, and the following composition was added. Ingredients added.
(composition)
Methyl methacrylate 70.0g
Cyclohexyl methacrylate 175.0g
2-ethylhexyl methacrylate 105.0 g

  Then, an aqueous solution in which 0.35 g of ammonium persulfate was dissolved in 3.15 g of water was added and polymerization was carried out at 80 ° C. for 2 hours. Further, 3.5 g of 10 wt% ammonium persulfate aqueous solution was added dropwise, and the temperature was kept at 80 ° C. for 2 hours. After the reaction, the mixture was cooled, then adjusted to pH 8.5 with aqueous ammonia, and further water was added to obtain an aqueous dispersion having a solid content of 50% by weight.

Example 11 (Preparation of room temperature curable aqueous composition)
A 100-ml polycup was blended with 100 parts by weight of the fluorinated composite resin obtained in Synthesis Example 29 and 5.0 parts by weight of PERMUTEX XR-2500 (Aziridine curing agent manufactured by Stahl) to obtain a curable composition for aqueous paints. .

  With respect to 100 parts by weight of the solid content of the curable composition for water-based paints, 50 parts by weight of an acid value titanium (Taipaque CR-97, manufactured by Ishihara Sangyo Co., Ltd.) is used as a filler, and Nop Cosperth 5027 (San Nopco Co., Ltd.) is used as a dispersant. ) Polycarboxylic acid ammonium salt) 2 parts by weight, 1 part by weight of ethylene glycol as an antifreeze agent, FS Antifoam 013B (manufactured by Dow Corning) 0.5 part by weight as an antifoaming agent, Adecanol as a thickener Add 5 parts by weight of UH-420 (Asahi Denka Kogyo Co., Ltd.) and 7.5 parts by weight of CS-12 (Chisso Co., Ltd.) as a film-forming aid and mix thoroughly using a disper stirrer. Was prepared.

  Test pieces were prepared in the same manner as in Example 1, and then the coating film characteristics were examined in the same manner as in Example 1. The results are shown in Table 3.

Example 12
A coating material was prepared in the same manner as in Example 11 except that 20 parts by weight of Carbodilite V-02 (carbodiimide type curing agent manufactured by Nisshinbo Co., Ltd.) was used as a curing agent, and a test piece was prepared after applying a coating plate. About the obtained test piece, it carried out similarly to Example 11, and investigated the coating-film characteristic. The results are shown in Table 3.

Example 13
In Example 11, the fluorine-containing composite resin of Synthesis Example 32 was used as the fluorine-containing composite resin, and Bihijoule 3100 (polyethylene oxide-modified non-blocked isocyanate-based curing agent manufactured by Sumitomo Bayer Urethane Co., Ltd.) was used as the curing agent. A coating material was prepared in the same manner except that 5 parts by weight was used, and a test piece was further prepared to examine the coating properties. The results are shown in Table 3.

Claims (11)

Fluorine-containing composite obtained by emulsion polymerization of ethylenically unsaturated group-containing monomer (b1) in the presence of a fluorine-containing copolymer (A) having an ethylenically unsaturated group and a water-soluble functional group in the molecule Room temperature-curable aqueous composition comprising an aqueous dispersion of a fluorinated resin (B) and an aqueous curing agent. The room temperature-curable aqueous composition according to claim 1, wherein the acid value of the fluorine-containing copolymer (A) is 10 to 250 mgKOH / g. The room temperature-curable aqueous composition according to claim 1 or 2, wherein the water-soluble functional group is a functional group obtained by neutralizing an anionic functional group with an alkali. The fluorine-containing copolymer (A) contains 10 to 70 mol% of at least one perhaloolefin unit selected from the group consisting of tetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene as a structural unit. The room temperature curable aqueous composition according to any one of 1 to 3. The ethylenically unsaturated group-containing monomer (b1) contains at least one monomer each having a crosslinkable functional group and an acrylic or methacrylic monomer containing an alkyl group having 4 to 10 carbon atoms. The room temperature-curable aqueous composition according to any one of claims 1 to 4. 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. Furthermore, the normal temperature curable aqueous composition in any one of Claims 1-6 containing the emulsion of a non-fluorine-type synthetic resin (C). The room temperature-curable aqueous composition according to claim 7, comprising 95 to 5 parts by weight of the solid content of the fluorine-containing composite resin (B) and 5 to 95 parts by weight of the solid content of the non-fluorinated synthetic resin (C). The room temperature curable aqueous composition according to claim 1, wherein the aqueous curing agent is a room temperature curable curing agent. The water-based curing agent is a hydrazide compound having at least 2 or more hydrazide groups per molecule, a carbodiimide compound having at least 2 or more carbodiimide groups per molecule, or a hydrophilic polyisocyanate. A room temperature-curable aqueous composition as described in 1. The said hardening | curing agent mix | blends 0.1-5 molar equivalent with respect to 1 equivalent of total functional groups of a fluorine-containing composite resin (B) and a non-fluorine-type synthetic resin (C). The room temperature curable aqueous composition as described.