JP2005162994A - Fluorine-containing aqueous dispersed composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-containing aqueous dispersed composition, capable of being cured and dried at normal temperature and giving a coated film excellent in solvent resistance, waterproofness weather resistance, coated film hardness, gloss, etc. <P>SOLUTION: This fluorine-containing aqueous-dispersed composition comprises (A) a fluoroolefin copolymer having 10-250 mgKOH/g acid value and (B) non-fluorine-based synthetic emulsion, the fluoroolefin copolymer (A) has at least 1 kind of a structural unit selected from the group consisting of a maleic acid unit, maleic anhydride unit, maleic acid monoester unit, fumaric acid unit and fumaric acid monoester unit, and also at least one of (A) the fluoroolefin copolymers and (B) the non-fluorine-based synthetic resin contains a cross-linking functional group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a fluorine-containing aqueous dispersion composition that can be cured and dried at room temperature, and gives a coating film excellent in solvent resistance, water resistance, weather resistance, coating film hardness, gloss, and the like.

  Conventionally, an aqueous dispersion type curable composition containing a fluororesin has been known to give a coating film having excellent properties such as high weather resistance, water resistance, chemical resistance, and hydrophilicity. It is also known to use maleic acid or fumaric acid as a copolymerization component to give.

  For example, Patent Document 1 discloses a technique relating to an aqueous dispersion of a high acid value fluororesin having a maleic acid monoester unit or a fumaric acid monoester unit. However, since this aqueous dispersion is composed only of a fluororesin, the gloss and adhesion of the coating film are low. Moreover, although use of a hardening | curing agent is also described, there is no description about a room temperature curable hardening system.

  As a fluororesin for water-based paints, as described in Patent Document 2, etc., it is obtained by emulsion polymerization of fluoroolefin and other vinyl monomers such as a hydroxyl group-containing monomer and maleic acid in water using an emulsifier. Aqueous fluororesin dispersions are known. However, the disadvantage that functional groups such as carboxyl groups and hydroxyl groups, which are essential problems when obtaining a fluororesin by emulsion polymerization, is difficult to be introduced into the fluororesin has not been solved. Furthermore, since there are many emulsifiers etc. and a particle diameter is comparatively large, there exist faults, such as film forming property of a coating film being low, water resistance is low, and curability is low.

  Further, all of the prior arts have a drawback that rain-strip contamination derived from fluororesin is likely to occur.

JP-A-8-337620 JP 2002-188052 A

  The present invention uses a fluororesin in which maleic acid or fumaric acid or a derivative thereof is efficiently introduced, and uses the fluororesin in combination with another non-fluorine resin emulsion or a specific curing agent, thereby providing the conventional water-based paint described above. An object of the present invention is to provide a curable composition for water-based paints that can solve the problems of the composition.

  That is, the present invention comprises a fluoroolefin copolymer (A) having an acid value of 10 to 250 mgKOH / g and a non-fluorinated synthetic resin emulsion (B), wherein the fluoroolefin copolymer (A) is a maleic acid unit, Having at least one structural unit selected from the group consisting of maleic anhydride units, maleic acid monoester units, fumaric acid units and fumaric acid monoester units, and the fluoroolefin copolymer (A) and non-fluorine This invention relates to a fluorine-containing aqueous dispersion composition (first invention) in which at least one of the system synthetic resins (B) contains a crosslinkable functional group.

  In such an aqueous dispersion composition, the fluoroolefin copolymer (A) has a carbonyl group as a crosslinkable functional group, and the non-fluorinated synthetic resin (B) has a hydrazide group, or the fluoroolefin copolymer (A). Preferably have an α, β-unsaturated carbonyl group, and the non-fluorinated synthetic resin (B) has an active methylene group.

  Moreover, as a non-fluorine type synthetic resin emulsion (B), an acrylic resin emulsion, a urethane resin emulsion, a polyester resin emulsion, etc. are mention | raise | lifted preferably.

  The aqueous dispersion composition of the first invention may further contain a curing agent (C). As such a curing agent (C), at least one room temperature curing agent (C1) selected from the group consisting of a non-blocking isocyanate compound, a hydrazide compound, a carbodiimide compound and an aziridine is preferable.

  The present invention also comprises a fluoroolefin copolymer (A) having an acid value of 10 to 250 mgKOH / g and a room temperature curing agent (C1), wherein the fluoroolefin copolymer (A) is a maleic acid unit, maleic anhydride. Having at least one structural unit selected from the group consisting of a physical unit, a maleic acid monoester unit, a fumaric acid unit and a fumaric acid monoester unit, and the fluoroolefin copolymer (A) has a crosslinkable functional group. In addition, the present invention relates to a fluorine-containing aqueous dispersion composition (second invention) in which the room temperature curing agent (C1) is at least one selected from the group consisting of a non-blocking isocyanate compound, a hydrazide compound, a carbodiimide compound and an aziridine.

  The present invention further comprises a fluoroolefin copolymer (A2) having an acid value of 10 to 250 mgKOH / g and water, wherein the fluoroolefin copolymer (A2) comprises maleic acid units, maleic anhydride units, maleic acid. Having at least one structural unit selected from the group consisting of a monoester unit, a fumaric acid unit and a fumaric acid monoester unit, and the fluoroolefin copolymer (A2) has a polymerizable unsaturated double bond The fluorine-containing aqueous dispersion composition (third invention).

  In the first and second inventions of the present invention, as the fluoroolefin copolymer (A), a composite fluororesin obtained by seed polymerization of a vinyl monomer to an aqueous dispersion of the fluoroolefin copolymer (A) A composite fluororesin (A3) obtained by seed polymerizing a crosslinkable functional group-containing vinyl monomer to an aqueous dispersion of (A1) or fluoroolefin copolymer (A2) can be used.

  According to the present invention, a fluorine resin in which maleic acid or fumaric acid or a derivative thereof is efficiently introduced is used, and the combined use of such a fluororesin with another non-fluorinated resin emulsion or a specific curing agent allows the solvent resistance. Further, it is possible to provide a curable composition for water-based paints which gives a coating film excellent in water resistance, weather resistance, coating film hardness, gloss and the like.

  The curable composition for water-based paints according to the first aspect of the present invention comprises a non-fluorinated synthetic resin emulsion (B) and a maleic acid unit, a maleic anhydride unit, a maleic acid monoester unit, a fumaric acid unit and fumaric acid. A fluoroolefin copolymer (A) having at least one structural unit selected from the group consisting of monoester units is included.

  First, the specific fluoroolefin copolymer (A) will be described.

  The fluoroolefin unit contained in the fluoroolefin copolymer (A) includes tetrafluoroethylene (TFE), trifluoroethylene (TrFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), vinyl fluoride ( VF), vinylidene fluoride (VdF), and the like. Among these, perhaloolefin units such as TFE, CTFE, and HFP can provide a fluoroolefin copolymer having a high fluorine content. For example, it is preferable from the viewpoint of providing a coating film excellent in chemical resistance, water resistance, solvent resistance, stain resistance, weather resistance and the like.

  The fluoroolefin copolymer (A) contains at least one structural unit selected from the group consisting of maleic acid units, maleic anhydride units, maleic acid monoester units, fumaric acid units, and fumaric acid monoester units.

  The ester moiety of maleic acid monoester or fumaric acid monoester is an alkyl group such as methyl, ethyl, butyl, octyl, lauryl or stearyl; an unsaturated alkyl group such as vinyl group, allyl group, oleyl group or linoleyl group; polyethylene oxide And polyether groups such as one-end alkylated polyethylene oxide groups. Especially, C1-C20 alkyl groups or unsaturated alkyl groups, such as ethyl, butyl, lauryl, stearyl, and oleyl, are preferable, and C1-C20 is more preferable. Further, if necessary, a polyether group such as a polyethylene oxide group or a single-end alkylated polyethylene oxide group is preferred to improve the dispersion stability of the emulsion.

  By introducing these maleic acid or fumaric acid units, adhesion to the substrate is improved.

  The acid value of the fluoroolefin copolymer (A) must be in the range 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.

  Such a high acid value fluoroolefin copolymer cannot be produced by emulsion polymerization. A method for producing the fluoroolefin copolymer (A) used in the present invention will be described later.

  The functional group that gives such a high acid value to the fluoroolefin copolymer is preferably a functional group obtained by neutralizing a water-soluble functional group, particularly an anionic functional group, with an alkali. Examples of such an anionic functional group include a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, and a carboxylic acid 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 a fluoroolefin copolymer include a method of copolymerizing a monomer containing an anionic functional group (copolymerization method) and a polymer containing a functional group such as a hydroxyl group. A method of reacting a compound having an anionic functional group such as dibasic acid anhydride (polymer reaction method) or the like is employed.

  As a monomer for introducing a carboxylic acid 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 hydrogen atoms, alkyl groups, carboxyl groups or ester groups; n is 0 or 1) Unsaturated carboxylic acids such as saturated dicarboxylic acids, monoesters or anhydrides thereof; or 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 vinyl ether monomers.

  Specific examples of unsaturated carboxylic acids of 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, and the like. Among them, crotonic acid, itaconic acid, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, and 3-allyloxypropionic acid having low homopolymerization are low in homopolymerization and are difficult to form a homopolymer. This is preferable.

  Specific examples of the carboxylic acid group-containing vinyl ether monomer of the formula (II) include, for example, 3- (2-allyloxyethoxycarbonyl) propionic acid, 3- (2-allyloxybutoxycarbonyl) propionic acid, 3- (2 One or two or more of -vinyloxyethoxycarbonyl) propionic acid, 3- (2-vinyloxybutoxycarbonyl) propionic acid and the like can be mentioned. 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 carboxylic acid 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.

  Further, the fluoroolefin copolymer used in the present invention may or may not have a crosslinkable functional group, but it improves the coating film strength, water resistance, solvent resistance, adhesion, coating film hardness, etc. Therefore, it is preferable to contain a crosslinkable functional group.

  The crosslinkable functional group is selected according to the type of the crosslinkable functional group possessed by the curing agent described later or the type of the crosslinkable functional group possessed by the non-fluorinated synthetic resin. , At least one selected from the group consisting of a carbonyl group and an ethylenically unsaturated group. The combination of the crosslinkable functional group and the curing agent will be described later.

  Specific examples of the carboxylic acid group-containing monomer as the crosslinkable functional group-containing monomer include the carboxylic acid group-containing monomer for introducing the anionic functional group. That is, the carboxylic acid group functions as both an acid value-providing functional group and a crosslinkable functional group, and it 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, for example, 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.

  Further, a polymerizable unsaturated double bond may be further introduced into the fluoroolefin copolymer (A). By introducing this polymerizable unsaturated double bond, a chemical bond is generated between the vinyl resin and the fluororesin during seed polymerization, and the compatibility between the two is improved. This improves the stability of the emulsion obtained, the durability of the resulting coating film, water resistance, gloss, rain-stain stain resistance, and the like.

  Examples of the polymerizable unsaturated double bond include an acryloyl group, a methacryloyl group, a styryl group, and an unsaturated alkyl group. Of these, unsaturated alkyl groups are preferred. Examples of the unsaturated alkyl group include a vinyl group, an allyl group, an oleyl group, and a linoleyl group. Furthermore, among unsaturated alkyl groups, an oleyl group, a linoleyl group, etc. are still more preferable. When these polymerizable unsaturated double bonds are used, gelation at the time of seed polymerization is easily suppressed, and an emulsion having a relatively small particle diameter can be easily obtained.

  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 butadiene, isoprene, chloroprene, fluoroprene, cyanoprene, phenylbutadiene, diphenylbutadiene, 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.

  The fluoroolefin copolymer (A) may be copolymerized with other copolymerizable monomers as necessary.

  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 fluoroolefin copolymer is 200,000 or less in terms of number average molecular weight, more preferably 100,000 or less, particularly preferably 50,000 or less in view of solution polymerizability, 1,000 or more, further 4,000. As described above, those having 8,000 or more are particularly preferable in terms of excellent weather resistance and durability.

  Specific preferred fluoroolefin copolymers (A) are exemplified below, but the present invention is not limited to these copolymers.

  Tetrafluoroethylene / ethyl vinyl ether / maleic acid copolymer, tetrafluoroethylene / vinyl acetate / maleic acid copolymer, tetrafluoroethylene / vinyl versatic acid / maleic acid copolymer, tetrafluoroethylene / vinyl pivalate / maleic Acid copolymer, hexafluoropropylene / ethyl vinyl ether / maleic acid copolymer, hexafluoropropylene / vinyl acetate / maleic acid copolymer, hexafluoropropylene / vinyl versatic acid / maleic acid copolymer, hexafluoropropylene / Vinyl pivalate / maleic acid copolymer, tetrafluoroethylene / ethyl vinyl ether / monoethyl maleate copolymer, tetrafluoroethylene / vinyl acetate / monoethyl maleate copolymer, tetrafluoro Ethylene / vinyl versatate / monoethyl maleate copolymer, tetrafluoroethylene / vinyl pivalate / monoethyl maleate copolymer, hexafluoropropylene / ethyl vinyl ether / monoethyl maleate copolymer, hexafluoropropylene / vinyl acetate / Monoethyl maleate copolymer, hexafluoropropylene / vinyl versatate / monoethyl maleate copolymer, hexafluoropropylene / vinyl pivalate / monoethyl maleate copolymer, tetrafluoroethylene / ethyl vinyl ether / monooleyl maleate copolymer Polymer, tetrafluoroethylene / vinyl acetate / monooleyl maleate copolymer, tetrafluoroethylene / vinyl versatate / monooleyl maleate copolymer, Lafluoroethylene / vinyl pivalate / monooleyl copolymer, hexafluoropropylene / ethyl vinyl ether / monooleyl maleate copolymer, hexafluoropropylene / vinyl acetate / monooleyl maleate copolymer, hexafluoropropylene / versatic acid Vinyl / maleic acid monooleyl copolymer, hexafluoropropylene / vinyl pivalate / monooleic acid maleate copolymer, tetrafluoroethylene / ethyl vinyl ether / fumaric acid copolymer, tetrafluoroethylene / vinyl acetate / fumaric acid copolymer, Tetrafluoroethylene / vinyl versatate / fumaric acid copolymer, tetrafluoroethylene / vinyl pivalate / fumaric acid copolymer, hexafluoropropylene / ethyl vinyl ether Ru / fumaric acid copolymer, hexafluoropropylene / vinyl acetate / fumaric acid copolymer, hexafluoropropylene / vinyl versatic acid / fumaric acid copolymer, hexafluoropropylene / vinyl pivalate / fumaric acid copolymer, Tetrafluoroethylene / ethyl vinyl ether / monoethyl fumarate copolymer, tetrafluoroethylene / vinyl acetate / monoethyl fumarate copolymer, tetrafluoroethylene / vinyl versatic acid / monoethyl fumarate copolymer, tetrafluoroethylene / pivalic acid Vinyl / monoethyl fumarate copolymer, hexafluoropropylene / ethyl vinyl ether / monoethyl fumarate copolymer, hexafluoropropylene / vinyl acetate / monoethyl fumarate copolymer, hexafluoropropylene / versa Vinyl acrylate / monoethyl fumarate copolymer, hexafluoropropylene / vinyl pivalate / monoethyl fumarate copolymer, tetrafluoroethylene / ethyl vinyl ether / monooleyl fumarate copolymer, tetrafluoroethylene / vinyl acetate / monooleyl fumarate Copolymer, tetrafluoroethylene / vinyl versatate / monooleyl fumarate copolymer, tetrafluoroethylene / vinyl pivalate / monooleyl fumarate copolymer, hexafluoropropylene / ethyl vinyl ether / monooleyl fumarate copolymer, hexa Fluoropropylene / vinyl acetate / monooleyl fumarate copolymer, hexafluoropropylene / vinyl versatate / monooleyl fumarate copolymer, hexafluoropropylene / piva Nsan vinyl / fumaric acid monooleyl copolymer.

  As described above, the functional group-containing fluoroolefin copolymer for an aqueous coating is generally produced by an emulsion polymerization method and directly prepared in the form of an aqueous dispersion or emulsion. However, as described above, the emulsion polymerization method cannot copolymerize many functional group-containing monomers for introducing an acid value, and can only have a large molecular weight.

  Therefore, in the present invention, the functional group-containing fluoroolefin copolymer is produced by a solution polymerization method using an organic solvent as a polymerization solvent, whereby the functional group-containing monomer for introducing an acid value is stably converted into a polymerization system. The desired high acid value fluoroolefin copolymer can be produced, and the molecular weight can be adjusted (lower molecular weight).

  Techniques for producing such a high acid value fluoroolefin copolymer by a solution polymerization method are known in the field of electrodeposition coatings (for example, Japanese Patent Application Laid-Open Nos. 62-143915 and 63-152777). These methods can be used also in the present invention.

  More specifically, by polymerizing a fluoroolefin and a functional group (functional group for introducing acid value, crosslinkable functional group) -containing monomer and, if necessary, a monomer copolymerizable therewith in an organic solvent. The high acid value fluoroolefin copolymer 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 Can be 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 Alkylperoxyesters such as tert-butyl peroxyacetate and tert-butylperoxypivalate; ammonium persulfate, Persulfates such as potassium sulfate (and reducing agents such as sodium bisulfite, sodium pyrosulfite, cobalt naphthenate, and dimethylaniline if necessary); oxidizing agents (eg ammonium peroxide, potassium peroxide, etc.) Redox initiators consisting of a reducing agent (such as sodium sulfite) and a transition metal salt (such as iron sulfate); 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvalero) Nitrile), 2,2′-azobis (2-methylvaleronitrile), 2,2′-azobis (2-cyclopropylpropionitrile), dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis [2 -(Hydroxymethyl) propionitrile], 4,4′-azobis (4-cyanopentenoic acid) Zo compounds can be used.

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

  The high acid value fluoroolefin copolymer (A) thus obtained can be given a high acid value as described above, that is, an acid value of 10 to 250 mgKOH / g.

  The obtained high acid value fluoroolefin copolymer 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 fluoroolefin copolymer is obtained. At this time, in order to increase the water solubility of the fluoroolefin 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.

  Examples of the non-fluorinated synthetic resin emulsion (B) that is a main component of the curable composition for water-based paints of the present invention include acrylic resin emulsion, urethane resin emulsion, polyester resin emulsion, alkyd resin emulsion, phenol resin emulsion, and epoxy resin. Among these, acrylic resin emulsions, urethane resin emulsions, and polyester resin emulsions are preferable in terms of good weather resistance, chemical resistance, and solvent resistance. In particular, acrylic resin emulsions are further fluorinated resins and curing agents. It is preferable in that it has good compatibility with water and is excellent in water resistance, solvent resistance, and substrate adhesion.

  In addition, the non-fluorinated synthetic resin may or may not have a crosslinkable functional group, but a crosslinkable functional group is introduced because of its excellent weather resistance, water resistance, solvent resistance, substrate adhesion, etc. It is preferable to do. As the crosslinkable functional group, those described for the fluoroolefin copolymer can be used including the introduction monomer.

  For example, when the fluoroolefin copolymer (A) has a carbonyl group as a crosslinkable functional group and the non-fluorinated synthetic resin (B) has a hydrazide group, room temperature curability and storage stability as a one-component crosslinkable type It is advantageous in terms of sex.

  The fluoroolefin copolymer (A) has an α, β-unsaturated carbonyl group (for example, a group derived from acrylate or methacrylate), and the non-fluorinated synthetic resin (B) has an active methylene group (for example, 2- (Groups derived from (acetoacetoxy) ethyl methacrylate) is advantageous in terms of room temperature curability and storage stability as a one-component crosslinking type.

  In the present invention, when the high acid value fluoroolefin copolymer has two or more crosslinkable functional groups and has a function as a crosslinking agent, a curing agent may not be used separately. In order to reliably realize the crosslinking reaction and to give the coating film strength, water resistance, weather resistance, solvent resistance and the like to the coating film, it is desirable to add a curing agent.

  The curing agent to be blended is a crosslinkable functional group introduced on the high acid value fluoroolefin copolymer and / or non-fluorinated synthetic resin side (hereinafter simply referred to as “resin side” in the explanation of the curing agent). Those capable of undergoing a crosslinking reaction are employed.

  Examples of the curing agent include room temperature curable aqueous curing agents such as carbodiimide compounds, non-blocked isocyanates, hydrazide compounds, and aziridines.

  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 commercially available carbodiimide compounds for water-based paints, Carbodilite E-01, Carbodilite E-02, Carbodilite V-02, etc. manufactured by Nisshinbo Co., Ltd. are known.

  Examples of the non-blocking isocyanate compound include a non-blocking isocyanate compound modified with a polyethylene oxide compound 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.

Examples of combinations with the crosslinkable functional group on the resin side include the following combinations.
(1) When the crosslinkable functional group on the resin side is a carboxyl group:
Examples thereof include carbodiimide compounds, non-blocked isocyanate compounds, hydrazide compounds, and the like.
Among these, a carbodiimide compound having at least two carbodiimide groups per molecule is preferable from the viewpoint of good reactivity with a carboxyl group.

(2) When the crosslinkable functional group on the resin side is a hydroxyl group:
For example, non-block type isocyanate compounds, hydrazide compounds, carbodiimide compounds, aziridines and the like can be mentioned.
Of these, non-blocked isocyanate compounds are particularly preferred in terms of good reactivity with hydroxyl groups.

(3) When the crosslinkable functional group on the resin side is a carbonyl group:
Examples thereof include hydrazide compounds and carbodiimide compounds.
Of these, hydrazide compounds having at least two or more hydrazide groups per molecule are preferred in terms of good reactivity with carbonyl groups.

  In any case, the curing agent is preferably blended in an amount of 0.1 to 5 molar equivalents per 1 equivalent of functional groups on the resin side (total functional groups of the fluoroolefin copolymer and non-fluorine synthetic resin).

  In the present invention, the fluoroolefin copolymer (A) can be blended into the non-fluorinated synthetic resin emulsion in the form of an emulsion or an aqueous dispersion (liquid), or in the form of a solid or an aqueous solution.

  When blended in the form of an emulsion or an aqueous dispersion, the weight ratio of the solid content of the non-fluorinated synthetic resin (B) / fluoroolefin copolymer (A) is preferably 99/1 to 1/99. The lower limit is 98/2, more preferably 97/3, in particular 95/5, and the upper limit is 2/98, further 3/97, in particular 5/95.

  When the fluoroolefin copolymer (A) is added in a solid or aqueous solution, the weight ratio of the solid content of the non-fluorinated synthetic resin (B) / fluoroolefin copolymer (A) is 99/1 to 49 /. 51 is preferred. The lower limit is 98/2, further 97/3, in particular 95/5, and the upper limit is 52/48, further 55/45, in particular 60/40.

  The fluorine-containing aqueous dispersion composition of the first invention of the present invention was prepared by adding the high acid value fluoroolefin copolymer to the non-fluorinated synthetic resin emulsion in the form of a solid or an aqueous solution and stirring appropriately. it can. What is necessary is just to adjust solid content concentration in the range of 30 to 70 weight% normally. You may mix | blend a well-known hardening accelerator etc. with a curable composition further. Examples of the curing accelerator include dibutyltin dilaurate.

  Next, the second invention of the present invention will be described.

  The second invention comprises a fluoroolefin copolymer (A) having an acid value of 10 to 250 mgKOH / g and a room temperature curing agent (C1), wherein the fluoroolefin copolymer (A) is a maleic acid unit, maleic acid. It has at least one structural unit selected from the group consisting of an anhydride unit, a maleic acid monoester unit, a fumaric acid unit and a fumaric acid monoester unit, and the fluoroolefin copolymer (A) is a crosslinkable functional group And the room temperature curing agent (C1) is at least one selected from the group consisting of a non-blocking isocyanate compound, a hydrazide compound, a carbodiimide compound and an aziridine.

  That is, the feature of the second invention is that a non-fluorinated synthetic resin emulsion is not blended as a film forming component, and consists of the fluoroolefin copolymer (A) used in the first invention and a specific room temperature curing agent. It is a fluorine-containing aqueous dispersion composition. The room temperature curing agent used is also the non-blocking isocyanate compound, hydrazide compound, carbodiimide compound and aziridine described in the first invention.

  According to the second invention, since the fluorine content of the coating film is high, the weather resistance, durability and chemical resistance of the coating film obtained are remarkably good.

  Next, the third invention of the present invention will be described.

  The third invention comprises a fluoroolefin copolymer (A2) having an acid value of 10 to 250 mgKOH / g and water, wherein the fluoroolefin copolymer (A2) comprises a maleic acid unit, a maleic anhydride unit, a maleic acid. And at least one structural unit selected from the group consisting of an acid monoester unit, a fumaric acid unit and a fumaric acid monoester unit, and the fluoroolefin copolymer (A2) has a polymerizable unsaturated double bond. A fluorine-containing aqueous dispersion composition.

  That is, a feature of the third invention resides in that a fluoroolefin copolymer (A2) containing a polymerizable unsaturated double bond as an essential component is used as a high acid value fluoroolefin copolymer.

  According to the third invention, a chemical bond is formed between the vinyl polymer seed-polymerized and the fluoroolefin copolymer at the time of seed polymerization of the coating film, and the compatibility of both is improved. This improves the stability of the emulsion obtained, the durability of the resulting coating film, water resistance, gloss, rain-stain stain resistance, and the like.

  Examples of the polymerizable unsaturated double bond include those described above. Among them, an unsaturated alkyl group such as a vinyl group, an allyl group, an oleyl group, or a linoleyl group is preferable, and among the unsaturated alkyl groups, an oleyl group is preferable. Further, a linoleyl group and the like are more preferable. When these polymerizable unsaturated double bonds are used, an effect of easily obtaining an emulsion having a relatively small particle diameter, in which gelation at the time of seed polymerization is easily suppressed, is achieved.

  As a method for introducing a polymerizable unsaturated double bond into the fluoroolefin copolymer (A2), the above copolymerization method or polymer reaction method can be employed.

  Further, the fluoroolefin copolymer (A2) is seed-polymerized with a crosslinkable functional group-containing vinyl monomer to obtain a composite fluororesin (A3), which is used in the first or second invention of the present invention. Can be used as the fluoroolefin copolymer (A). Examples of the crosslinkable functional group-containing vinyl monomer that undergoes seed polymerization include the crosslinkable functional group-containing monomers described in the first invention.

  The 1st-3rd aqueous dispersion composition of this invention can mix | blend a normal additive, and can prepare it in an aqueous coating material. Examples of paint additives that may be incorporated into the aqueous dispersion composition of the present invention include surfactants, pigments, dispersants, thickeners, preservatives, ultraviolet absorbers, antifoaming agents, leveling agents and the like. It is done.

  As the surfactant, for example, an anionic emulsifier, a nonionic emulsifier, or a combination thereof can be used. In some cases, an amphoteric emulsifier or a cationic surfactant can also be used.

  As the anionic surfactant, for example, a sodium salt of a higher alcohol sulfate, a sodium alkylbenzene sulfonate, a sodium salt of a dialkyl succinate sulfonic acid or a sodium salt of an alkyl diphenyl ether sulfonic acid can be used. Among these, preferred examples include sodium alkylbenzene sulfonate, sodium lauryl sulfate, polyoxyethylene alkyl (or alkylphenyl) ether sulfonate, and the like. As the nonionic emulsifier, for example, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether can be used. Preferred specific examples are polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, and the like. As the amphoteric emulsifier, lauryl betaine and the like are suitable. As the cationic surfactant, for example, alkyl pyridinium chloride, alkyl ammonium chloride and the like can be used. In addition, an emulsifier that is copolymerizable with the monomer, such as sodium styrenesulfonate, sodium alkylarylsulfonate, and the like can also be used.

  Moreover, as a thickener, Primal QR708 (made by Rohm and Haas), etc., as an antifoaming agent, Byk023 (Bic Chemie Japan Co., Ltd.), etc., as a dispersing agent, Byk190 (Bic Chemie Japan Co., Ltd.), Dispersant SN5027 (San Nopco) can be exemplified.

  The aqueous dispersion composition of the present invention is useful as various paint materials such as weather-resistant paints, electrodeposition paints, coil coat paints, automobile 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.

  When a relatively large number of crosslinkable functional groups are introduced into the fluoroolefin copolymer (A) and a room temperature curing agent is used as the curing agent, the coating film formed from the composition of the present invention can be cured 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.

  Next, the present invention will be specifically described with reference to production examples and examples, but the present invention is not limited to these production examples and examples.

Production Example 1
A 6L stainless steel autoclave was charged with 0.875 kg of acetone and 0.375 kg of ethanol, 104 g of ethyl vinyl ether (EVE), 86.7 g of vinyl acetate (VAc) and 49.7 g of maleic acid monoethyl ester (MME). 300 g of fluoroethylene (TFE) was added and the temperature was raised to 61.5 ° C. Next, 20.0 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 0.30 MPa · G. The reaction mixture was cooled to room temperature, purged with unreacted monomers, and further purged with nitrogen to obtain 1.66 kg of reaction product (solid content 24.6% by weight). This solution was concentrated to give a 50% solids solution. The obtained copolymer was analyzed by ¹⁹ F-MNR and ¹ H-MNR, and was TFE / EVE / VAc / MME = 35/30/21/14 (mole% ratio), which was measured by GPC. The average molecular weight Mn was 10,800, and the acid value was 58.3 mgKOH / g.

  While stirring, 2.89 g of triethylamine was added to 50.0 g of an acetone / ethanol solution (solid content: 50% by weight) of the copolymer, and then 30.0 g of water was slowly added and stirred. Subsequently, acetone / ethanol was distilled off under reduced pressure while heating to 50 ° C. to obtain an aqueous fluoroolefin copolymer dispersion (solid content: 48.1% by weight).

Production Examples 2-5
Using the monomers shown in Table 1, a fluoroolefin copolymer was produced in the same manner as in Production Example 1, and then neutralized with the amount of triethylamine shown in Table 1 to obtain an aqueous dispersion of the fluoroolefin copolymer. Obtained.

Abbreviations of monomers in Table 1 are as follows.
TFE: tetrafluoroethylene HFP: hexafluoropropylene EVE: ethyl vinyl ether VAc: vinyl acetate VPi: vinyl propionate VV-10: vinyl versatate DAAM manufactured by Shell Chemical Co., Ltd .: diacetone acrylamide MME: maleic acid monoethyl ester FME: fumarate Acid monoethyl ester

Production Example 6
Fluoroolefin copolymer of TFE / EVE / VPi / maleic anhydride (MAN) = 35/16/35/14 (mole ratio) using the monomers shown in Table 2 in the same manner as in Production Example 1. A coalescence was synthesized.

  While stirring, 1.44 g of 2-hydroxyethyl methacrylate (HEMA) and 1.02 g of ethanol (EtOH) were added to 50.0 g of an acetone solution (solid content: 50% by weight) of this fluoroolefin copolymer. 70 g was added slowly. The mixture was heated and stirred at 55 ° C. for 4 hours and then returned to room temperature, and 35.0 g of water was slowly added and stirred. Subsequently, acetone was distilled off under reduced pressure while heating to 50 ° C. to obtain an aqueous fluoroolefin copolymer dispersion (solid content: 46.1% by weight).

Production Examples 7 to 10
Using the monomers shown in Table 2, a fluoroolefin copolymer was produced in the same manner as in Production Example 6, then modified with the compounds shown in Table 2, and further with triethylamine in the amount shown in Table 2. This was combined to obtain a fluoroolefin copolymer aqueous dispersion.

Production Example 11
Using the monomers shown in Table 2, a fluoroolefin copolymer of TFE / EVE / VPi / maleic anhydride = 35/16/35/14 (mole% ratio) was synthesized in the same manner as in Production Example 1. did.

To 50.0 g of this fluoroolefin copolymer acetone solution (solid content 50% by weight), 1.91 g of oleyl alcohol (C ₁₈ H ₃₆ O, manufactured by Shin Nippon Rika Co., Ltd.) (OLA) was added while stirring. Further, 0.72 g of triethylamine was slowly added. The mixture was heated and stirred at 55 ° C. for 4 hours and then returned to room temperature. Then, 7.19 g of 28% ammonium hydroxide water and 29.0 g of water were slowly added and stirred. Subsequently, acetone was distilled off under reduced pressure while heating to 50 ° C. to obtain an aqueous fluoroolefin copolymer dispersion (solid content: 45.5% by weight) containing a polymerizable unsaturated double bond.

Abbreviations of monomers in Table 2 are as follows.
TFE: tetrafluoroethylene EVE: ethyl vinyl ether VAc: vinyl acetate VPi: vinyl propionate VV-10: vinyl versatate MAN manufactured by Shell Chemical Company: maleic anhydride HEMA: 2-hydroxyethyl methacrylate DAOH: diacetone alcohol EtOH: Ethanol OLA: oleyl alcohol

Example 1
To 50.0 g of the aqueous dispersion (a-1) produced in Production Example 1, 0.5 g of a thickener (Primal QR708), 0.25 g of an antifoaming agent (Byk023), 2.0 g of a film-forming aid ( Texanol: manufactured by Eastman Chemical Co., Ltd.), 20.0 g of carbodiimide compound Carbodilite E-01 (manufactured by Nisshinbo Co., Ltd.) as a curing agent of 0.64 g was added and stirred well. An aqueous dispersion composition using the polymer alone was obtained. This composition was filtered through a mesh, and coated with an applicator on an aluminum plate that had been previously coated with a solvent-soluble crosslinkable fluorine paint (white) and subjected to sanding to prepare a coated plate. The coated plate was allowed to stand at room temperature for 10 days to be cured to obtain a test piece. The following characteristics were examined. The results are shown in Table 3.

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.

Pencil hardness: Measured according to JIS K5400.

Solvent resistance test: The surface of the coating film is wiped with a nonwoven fabric impregnated with methyl ethyl ketone (MEK). The wiping operation is performed until 10 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.

Water resistance: The coating film is immersed in warm water at 60 ° 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.

Rain resistant stain resistance: The coating film is exposed outdoors at an angle of 45 degrees with respect to a horizontal plane, and the difference in brightness from the initial one month later and the difference in brightness after six months are measured.
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. .

Examples 2-7
An aqueous dispersion composition was prepared in the same manner as in Example 1 using the formulation shown in Table 3, and coated to prepare test pieces, and the physical properties of the coating film were examined. The results are shown in Table 3.

Comparative Example 1
A water-based fluororesin varnish similar to Example 5 of JP-A-8-337620 was produced, and no coating agent was added. The others were coated in the same manner as in Example 1, and the coating film properties were examined. The results are shown in Table 3.

Production Example 12
To a 300 ml four-necked flask was added 24.2 parts by weight of ion-exchanged water, 0.24 parts by weight of a sulfate ester type anionic surfactant (Newcol-707SF manufactured by Nippon Emulsifier Co., Ltd., solid content 30%), The mixture was heated and stirred at 80 ° C. To this, 6.70 parts by weight of 2- (acetoacetoxy) ethyl methacrylate, 0.32 parts by weight of acrylic acid, 11.8 parts by weight of styrene, 12.0 parts by weight of methyl methacrylate, 36.3 parts by weight of n-butyl acrylate Part, Newcol-707SF 6.45 parts by weight, ammonium persulfate 0.13 parts by weight pre-emulsion was added dropwise over 3 hours. After completion of the dropwise addition, a mixture of 0.05 parts by weight of ammonium persulfate and 0.10 parts by weight of ion-exchanged water was added dropwise over 1 hour, and the mixture was further heated and stirred at 80 ° C. for 1 hour to obtain an aqueous acrylic resin emulsion (solid content 50 .5 wt%). This aqueous acrylic resin emulsion is designated as b-1.

Production Example 13
An aqueous acrylic resin emulsion (b-2) was produced in the same manner as in Production Example 12 except that the monomers having the compositions shown in Table 4 were used.

Abbreviations of monomers in Table 4 are as follows.
AAMA: 2- (acetoacetoxy) ethyl methacrylate AA: Acrylic acid St: Styrene MMA: Methyl methacrylate BA: n-butyl acrylate EHA: 2-ethylhexyl acrylate

Example 8
35.0 g of the fluorinated aqueous dispersion (a-6) produced in Production Example 6 and 15.0 g of the aqueous acrylic resin emulsion (b-1) produced in Production Example 12 were added and stirred well, and an aqueous tetraethylammonium hydroxide solution was added. The pH was adjusted to 8.5. To this, 0.5 g of a thickener (Primal QR708), 0.25 g of an antifoaming agent (Byk023) and 2.0 g of a film-forming auxiliary (texanol) were added and stirred well to obtain an aqueous fluororesin dispersion composition. . This composition was filtered through a mesh, and coated with an applicator on an aluminum plate that had been previously coated with a solvent-soluble crosslinkable fluorine paint (white) and subjected to sanding to prepare a coated plate. The coated plate was allowed to stand at room temperature for 10 days to be cured to obtain a test piece, and the same coating film properties as in Example 1 were examined. The results are shown in Table 5.

Examples 9-11
According to the formulation shown in Table 5, an aqueous dispersion composition was prepared in the same manner as in Example 8, and coated to prepare a test piece. The coating film properties similar to those in Example 1 were examined. The results are shown in Table 5.

Production Example 14
71.2 g of 1,6-hexanediol, 102 g of adipic acid, and 22.7 g of 2,2-dimethylolpropionic acid were mixed, the temperature was raised to 180 ° C., and the reaction was carried out over 24 hours to obtain an acid with a hydroxyl value of 60 mgKOH / g. A polyester having a value of 60 mg KOH / g was obtained. This polyester is dissolved in 300 g of acetone, to which 30.0 g of 2,2-dimethylolpropionic acid and 27.0 g of cyclohexanedimethanol are mixed, and 236 g of 4,4-dicyclohexylmethane diisocyanate is added while stirring at 70 ° C. The temperature was raised to 80 ° C. The reaction was allowed to proceed for 6 hours, followed by cooling to obtain a polyurethane solution. To this polyurethane solution, a mixed solution of 21.0 g of 80% hydrazine aqueous solution, 40.0 g of triethylamine and 1500 g of water was gradually added while stirring at high speed. The obtained solution was heated to 60 ° C., the solvent was distilled off under reduced pressure, and the concentration was adjusted with water to obtain an aqueous polyurethane emulsion having a solid content of 23.7% by weight. This aqueous polyurethane emulsion is designated as b-3.

Example 12
20.0 g of the fluorine-containing aqueous dispersion (a-8) produced in Production Example 8 and 63.0 g of the aqueous polyurethane emulsion (b-3) produced in Production Example 14 were added and stirred well. A thickener (Primal QR708) and 0.25 g of antifoaming agent (Byk023) were added and stirred well to obtain an aqueous fluororesin composition. This composition was filtered through a mesh, and coated with an applicator on an aluminum plate that had been previously coated with a solvent-soluble crosslinkable fluorine paint (white) and subjected to sanding to prepare a coated plate. The coated plate was allowed to stand at room temperature for 10 days to be cured to obtain a test piece, and the same coating film properties as in Example 1 were examined. The results are shown in Table 6.

Example 13
Using the fluorine-containing aqueous dispersion (a-9) produced in Production Example 9, an aqueous dispersion composition was prepared in the same manner as in Example 12 with the formulation shown in Table 6, and coated to prepare a test piece. The same coating film properties as in Example 1 were examined. The results are shown in Table 6.

Example 14
50 g of the fluorinated aqueous dispersion (a-1) was placed in 300 ml, the temperature was raised to 80 ° C. while stirring, 0.24 g of glycidyl methacrylate was added, and the mixture was stirred for 1 hour. Next, 5.68 g of methyl methacrylate, 3.00 g of cyclohexyl methacrylate, 13.0 g of n-butyl acrylate, 2.0 g of diacetone acrylamide, 0.12 g of 1,6-hexanediol diacrylate, acrylic acid are added to this solution. A mixture of 0.20 g, 20.0 g of water and 0.40 g of a sulfate ester type anionic surfactant (Newcol-707SF manufactured by Nippon Emulsifier Co., Ltd., solid content: 30% by weight) was added dropwise over 1 hour. Immediately after the start of dropping, 0.60 g of an aqueous solution of 10% ammonium persulfate was added. After completion of the dropwise addition, the temperature was raised to 90 ° C., and the mixture was further stirred and heated for 2 hours for seed polymerization to obtain a composite aqueous fluororesin dispersion.

  To 50.0 g of the obtained composite aqueous fluororesin dispersion, 0.5 g thickener (Primal QR708), 0.25 g antifoaming agent (Byk023), 2.0 g film-forming aid (texanol), 0.51 g of a curing agent (adipic acid dihydrazide) was added and stirred well to obtain a composite fluororesin aqueous coating composition. This coating composition was filtered through a mesh, and coated with an applicator on an aluminum plate that had been previously coated with a solvent-soluble cross-linking fluorine coating (white) and sanded to prepare a coated plate. The coated plate was allowed to stand at room temperature for 10 days to be cured to obtain a test piece, and the same coating film properties as in Example 1 were examined. The results are shown in Table 7.

Examples 15-17
A composite water-based fluororesin dispersion was produced by seed polymerization in the same manner as in Example 14 using the monomers shown in Table 7, and an aqueous coating composition was prepared in the same manner as in Example 14, coated and tested. A piece was prepared, and the same physical properties as those in Example 1 were examined. The results are shown in Table 7.

Examples 18-21
A composite aqueous fluororesin dispersion was produced by seed polymerization in the same manner as in Example 14 using the monomers shown in Table 7 except that glycidyl methacrylate was not added in Example 14, and as in Example 14. A water-based coating composition was prepared and coated to prepare a test piece, and the coating film properties similar to those of Example 1 were examined. The results are shown in Table 7.

Abbreviations in Table 7 are as follows.
MMA: methyl methacrylate CHMA: cyclohexyl methacrylate BA: n-butyl acrylate EHA: 2-ethylhexyl acrylate DAAM: diacetone acrylamide HDA: 1,6-hexanediol diacrylate AA: acrylic acid 707SF: sulfate ester type anionic surface activity Agent. Newcol-707SF manufactured by Nippon Emulsifier Co., Ltd.
APS: ammonium persulfate

Example 22
When the composite aqueous fluororesin dispersion obtained in Example 14 was stored at 50 ° C. for 2 months and a coating film was produced in the same manner as in Example 14, no abnormality was observed in the appearance.

Comparative Example 2
According to Example 2 of JP-A-63-314202, an aqueous fluororesin dispersion in which an acrylic resin was combined was obtained. When this was stored at 50 ° C. for 2 months to prepare a coating film, the appearance of the coating film was clouded.

Claims (12)

It comprises a fluoroolefin copolymer (A) having an acid value of 10 to 250 mgKOH / g and a non-fluorinated synthetic resin emulsion (B). The fluoroolefin copolymer (A) is a maleic acid unit or a maleic anhydride unit. , At least one structural unit selected from the group consisting of a maleic acid monoester unit, a fumaric acid unit and a fumaric acid monoester unit, and the fluoroolefin copolymer (A) and non-fluorinated synthetic resin (B ) Is a fluorine-containing aqueous dispersion composition containing at least one of crosslinkable functional groups. The aqueous dispersion composition according to claim 1, wherein the fluoroolefin copolymer (A) has a polymerizable unsaturated double bond. The aqueous dispersion composition according to claim 1 or 2, wherein the fluoroolefin copolymer (A) has a carbonyl group as a crosslinkable functional group, and the non-fluorinated synthetic resin (B) has a hydrazide group. The aqueous dispersion composition according to claim 1 or 2, wherein the fluoroolefin copolymer (A) has an α, β-unsaturated carbonyl group and the non-fluorinated synthetic resin (B) has an active methylene group. The aqueous dispersion composition according to any one of claims 1 to 4, wherein the non-fluorinated synthetic resin emulsion (B) is an acrylic resin emulsion, a urethane resin emulsion, or a polyester resin emulsion. The aqueous dispersion composition according to any one of claims 1 to 5, further comprising a curing agent (C). The aqueous dispersion composition according to claim 6, wherein the curing agent (C) is at least one room temperature curing agent (C1) selected from the group consisting of a non-blocked isocyanate compound, a hydrazide compound, a carbodiimide compound and an aziridine. It consists of a fluoroolefin copolymer (A) having an acid value of 10 to 250 mgKOH / g and a normal temperature curing agent (C1). The fluoroolefin copolymer (A) is a maleic acid unit, a maleic anhydride unit, a maleic acid Having at least one structural unit selected from the group consisting of a monoester unit, a fumaric acid unit and a fumaric acid monoester unit, and the fluoroolefin copolymer (A) contains a crosslinkable functional group, A fluorine-containing aqueous dispersion composition, wherein the room temperature curing agent (C1) is at least one selected from the group consisting of a non-blocked isocyanate compound, a hydrazide compound, a carbodiimide compound, and an aziridine. The aqueous dispersion composition according to claim 8, wherein the fluoroolefin copolymer (A) has a polymerizable unsaturated double bond. The fluoroolefin copolymer (A) is a composite fluororesin (A1) obtained by seed polymerization of a vinyl monomer in an aqueous dispersion of the fluoroolefin copolymer (A). An aqueous dispersion composition according to claim 1. A fluoroolefin copolymer (A2) having an acid value of 10 to 250 mgKOH / g and water, the fluoroolefin copolymer (A2) comprising maleic acid units, maleic anhydride units, maleic acid monoester units, fumarate Fluorine-containing aqueous solution having at least one structural unit selected from the group consisting of an acid unit and a fumaric acid monoester unit, and wherein the fluoroolefin copolymer (A2) has a polymerizable unsaturated double bond Dispersion composition. The fluoroolefin copolymer (A) is a composite fluororesin (A3) obtained by seed polymerizing a crosslinkable functional group-containing vinyl monomer to an aqueous dispersion of the fluoroolefin copolymer (A2). The aqueous dispersion composition according to any one of 1 to 9.