JP6841087B2 - How to manufacture paint kits and paint compositions - Google Patents

Description

The present invention relates to a paint kit and a method for producing the paint composition.

The fluorine-containing polymer has excellent heat resistance, weather resistance, electrical insulation, etc., and as a coating agent that imparts stain resistance and chemical resistance to various substrates such as glass, metal, resin, wood, and slate. It is used. However, since the fluorine-containing polymer has poor adhesion to the substrate, there is a problem that sufficient strength and stability of the coating film cannot be obtained. For example, even in the fluorine-containing polymers disclosed in Patent Document 1 and Patent Document 2, when applied on various substrates such as glass and hard aluminum, a coating film having sufficient strength and stability can be obtained. It is hard to say that it can be obtained.

In order to improve the strength and stability of the coating film, Patent Document 3 and Patent Document 4 disclose a technique for blending an organosilicon-based oligomer with a fluorine-containing polymer. Further, in Patent Document 5, an aqueous dispersion of composite polymer particles of a fluorine-containing polymer and a methacrylic polymer and an aqueous dispersion of composite polymer particles of an organosilicon compound and a methacrylic polymer are used. The compounding technology of is disclosed. However, regardless of which technique was used, the stability of the coating composition, the adhesion between the base material and the coating film, and the strength and stability of the coating film were not sufficient.

Japanese Unexamined Patent Publication No. 10-12858 JP-A-2009-227754 Japanese Unexamined Patent Publication No. 08-120211 International Publication No. 98/23680 Japanese Unexamined Patent Publication No. 2003-286440

Therefore, in some aspects of the present invention, by solving the above-mentioned problems, storage stability is excellent, adhesion between the base material and the coating film, and strength of the coating film (for example, weather resistance, water resistance, durability). It provides a coating kit having excellent properties) and stability, and a method for producing the coating composition.

The present invention has been made to solve at least a part of the above-mentioned problems, and can be realized as the following aspects or application examples.

[Application example 1]
One aspect of the paint kit according to the present invention is
A polymer (A) having a repeating unit derived from an unsaturated carboxylic acid,
Cross-linking agent (B1) and
Liquid medium and
With the first composition containing
Cross-linking agent (B2) and
Liquid medium and
With a second composition containing
It is characterized by having.

[Application example 2]
In the paint kit of Application Example 1,
The cross-linking agent (B1) and the cross-linking agent (B2) can be different compounds.

[Application example 3]
In the paint kit of Application Example 1 or Application Example 2.
The polymer (A) can be dispersed as particles in the first composition.

[Application example 4]
In the paint kit of Application Example 3,
The particles can contain a fluorine-containing polymer.

[Application example 5]
One aspect of the method for producing a coating composition according to the present invention is
A polymer (A) having a repeating unit derived from an unsaturated carboxylic acid, a cross-linking agent (B1), a liquid medium, and
To the first composition containing
Cross-linking agent (B2) and
Liquid medium and
With a second composition containing
It is characterized by mixing.

[Application example 6]
In the method for producing a coating composition of Application Example 5,
With respect to 100 parts by mass of polymer (A)
The cross-linking agent (B1) can be mixed in an amount of 0.1 to 30 parts by mass, and the cross-linking agent (B2) can be mixed in an amount of 0.1 to 30 parts by mass.

According to the coating kit according to the present invention, it is possible to form a coating film which is excellent in storage stability for a long period of time, is also excellent in adhesion of a base material, and is excellent in strength and stability. The coating film prepared by using the coating film composition formed by the method for producing the coating film composition according to the present invention has excellent adhesion between the base material and the coating film, and the strength of the coating film, for example, Has excellent weather resistance, water resistance and durability.

Hereinafter, preferred embodiments according to the present invention will be described in detail. It should be noted that the present invention is not limited to the embodiments described below, but should be understood to include various modifications implemented without changing the gist of the present invention. In addition, "-(meth) acrylate" in this specification is a concept which includes both "-acrylate" and "-methacrylate". Further, "(meth) acrylic acid-" is a concept that includes both "acrylic acid-" and "methacrylic acid-".

1. 1. Paint Kit The paint kit according to an embodiment of the present invention (hereinafter, also simply referred to as “kit”) is
A polymer (A) having a repeating unit derived from an unsaturated carboxylic acid,
Cross-linking agent (B1) and
Liquid medium and
With the first composition containing
Cross-linking agent (B2) and
Liquid medium and
With a second composition containing
It is characterized by having. Hereinafter, each kit configuration will be described in detail.

1.1. First Composition The kit according to this embodiment is
A polymer (A) having a repeating unit derived from an unsaturated carboxylic acid, a cross-linking agent (B1), and
Contains a first composition containing a liquid medium.

1.1.1. Polymer (A)
1.1.1.1. Repeating unit derived from unsaturated carboxylic acid Polymer (A) containing a repeating unit derived from unsaturated carboxylic acid contained in the first composition according to the present embodiment (hereinafter, simply "polymer (A)". ) ”) Is preferably in the form of a latex dispersed as particles in a liquid medium. When the polymer (A) contained in the first composition is in the form of latex, the stability of the first composition produced by mixing with a colorant becomes good, and the kit according to the present embodiment. It is preferable because the coating property of the coating composition prepared by using the above is improved.

Since the polymer (A) has a repeating unit derived from an unsaturated carboxylic acid, the dispersion stability as a paint is improved, so that a uniform coating in which colorants and fluorine-containing polymer particles are not locally unevenly distributed. A film can be made. As a result, a coating film having a uniform strength is obtained, which is preferable in that the coating film can be locally peeled off from the substrate and the occurrence of color unevenness due to uneven distribution of the colorant can be effectively suppressed.

The unsaturated carboxylic acid is preferably an ethylenically unsaturated carboxylic acid, and examples thereof include mono or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, which are selected from these. It can be one or more species. Among these, one or more selected from the group consisting of acrylic acid, methacrylic acid and itaconic acid is preferable.

The content ratio of the repeating unit derived from the unsaturated carboxylic acid in the polymer (A) is preferably 0.1% by mass or more, more preferably 0.2% by mass, based on the total mass of the polymer (A). % Or more and 2.5% by mass or less.

1.1.1.2. When the repeating unit polymer (A) derived from the fluorine-containing ethylene-based monomer is in the form of latex dispersed as particles in a liquid medium, the particles may contain the fluorine-containing polymer described below. Suitable. The fluorine-containing polymer preferably has a repeating unit derived from the fluorine-containing ethylene-based monomer.

Examples of the fluorine-containing ethylene-based monomer include an olefin having a fluorine atom and a (meth) acrylate having a fluorine atom. Examples of the olefin having a fluorine atom include vinylidene fluoride, ethylene tetrafluoride, propylene hexafluoride, ethylene trifluorochloride, perfluoroalkyl vinyl ether and the like. Examples of the (meth) acrylate having a fluorine atom include a compound represented by the following general formula (3), (meth) acrylic acid 3 [4 [1-trifluoromethyl-2,2-bis [bis (trifluoromethyl)). ) Fluoromethyl] ethynyloxy] benzooxy] 2-hydroxypropyl and the like.

(In the general formula (3), R ¹ is a hydrogen atom or a methyl group, and R ² is a hydrocarbon group having 1 to 18 carbon atoms containing a fluorine atom.)
^{Examples of R 2} in the general formula (3) include an alkyl fluoride group having 1 to 12 carbon atoms, an aryl fluoride group having 6 to 16 carbon atoms, and an aralkyl fluoride group having 7 to 18 carbon atoms. However, among these, an alkyl fluoride group having 1 to 12 carbon atoms is preferable. ^{Preferred specific examples of R 2 in} the above general formula (3) include, for example, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,1 3,3,3-hexafluoropropan-2-yl group, β- (perfluorooctyl) ethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,4,5,4- Examples thereof include hexafluorobutyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 9H-perfluoro-1-nonyl group, 1H, 1H, 11H-perfluoroundecyl group, perfluorooctyl group and the like. ..

Among these, the fluorine-containing ethylene-based monomer is preferably an olefin having a fluorine atom, and more preferably at least one selected from the group consisting of vinylidene fluoride, ethylene tetrafluoroethylene and propylene hexafluoride. The above-mentioned fluorine-containing ethylene-based monomer may be used alone or in combination of two or more.

When the total of the repeating units constituting the fluorine-containing polymer is 100 mol%, it is preferable that the repeating units derived from the fluorine-containing ethylene-based monomer are contained in a ratio of 5 to 99 mol%, and 10 to 10 mol%. It is more preferably contained in a proportion of 80 mol%, and particularly preferably contained in a proportion of 11 to 75 mol%. When the fluorine-containing polymer does not have a repeating unit derived from silane, it is preferable to contain a repeating unit derived from a fluorine-containing ethylene-based monomer in a proportion of 12 to 75 mol%. On the other hand, when the fluorine-containing polymer has a repeating unit derived from silane, it is preferable to contain the repeating unit derived from the fluorine-containing ethylene-based monomer in a proportion of 11 to 70 mol%. When the content ratio of the repeating unit derived from the fluorine-containing ethylene-based monomer is within the above range, the weather resistance and heat resistance of the coating film can be further improved, and the adhesion to the substrate can be further improved.

1.1.1.3. The other monomeric polymer (A) may have a repeating unit derived from a monomer other than the above-mentioned monomer. As the other monomer, the monomer described in International Publication No. 2014/11252 and the like can be used. For example, unsaturated carboxylic acid ester, α, β-unsaturated nitrile, carbonyl group-containing compound, conjugated diene, aromatic vinyl, vinyl ether, allyl ether, alkoxysilane and the like can be mentioned. These monomers can be contained in a proportion of 20 to 99.9 parts by mass when the total of the repeating units of the polymers constituting the fluorine-containing polymer particles is 100 parts by mass.

Examples of the unsaturated carboxylic acid ester include an alkyl ester of an unsaturated carboxylic acid, a cycloalkyl ester of an unsaturated carboxylic acid, and a hydroxyalkyl ester of an unsaturated carboxylic acid.

Examples of the α, β-unsaturated nitrile include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, vinylidene cyanide, and the like, and one or more of them may be selected from these. it can.

Examples of the carbonyl group-containing compound include (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, isopropyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, and hydroxyethyl (meth). ) Acrylamide, acryloylmorpholine, acrolein and the like can be mentioned, and one or more of them can be selected.

Examples of the conjugated diene include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chlor-1,3-butadiene and the like. , It can be one or more selected from these.

Examples of the aromatic vinyl include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene, p-hydroxystyrene and the like, and one or more selected from these. be able to.

Examples of the vinyl ether include ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 2-aminoethyl vinyl ether and the like. It can be one or more selected.

Examples of the allyl ether include methyl allyl ether, ethyl allyl ether, propyl allyl ether, butyl allyl ether, hydroxyethyl allyl ether, hydroxypropyl allyl ether, hydroxybutyl allyl ether, allyl glycidyl ether, ethylene glycol monoallyl ether, and propylene glycol. Monoallyl ether and the like can be mentioned, and one or more kinds selected from these can be mentioned.

Examples of the alkoxysilane include at least one monomer selected from the group consisting of the monomers represented by the following general formula (2) and the following general formula (3).

R ³ _n Si (OR ⁴ ) _4-n ... (2)
(In the formula, R ³ and R ⁴ each independently represent an organic group having 1 to 8 carbon atoms, and n represents an integer of 0 to 3).
R ⁵ _m SiO _{(4-m) / 2} ... (3)
(In the formula, R ⁵ represents an organic group having 1 to 8 carbon atoms, and m represents a number from 0 to 3.)
In the monomers represented by the general formulas (2) and (3), R ³ and R ⁵ are preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group or an ethyl group. .. The R ^4, for example, 1 to 8 carbon atoms, an alkyl group, an aryl group, an acyl group, and the like. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group and the like. Examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group and the like. The acyl group is preferably an acyl group having 1 to 6 carbon atoms, and examples thereof include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a caproyl group. ^{A plurality of R 3} and R ⁴ existing in the above general formula (2) may be the same or different from each other. These arcosixylans may be used alone or in combination of two or more.

1.1.1.4. Preparation of Polymer (A) The polymer (A) can be easily produced by emulsion-polymerizing the above-mentioned monomer and optionally other unsaturated monomers according to a known method. When the polymer (A) is in the form of latex dispersed as particles in a liquid medium, the particles of the polymer (A) are as long as the repeating unit of the polymer (A) has the above-mentioned structure. The synthesis method thereof is not particularly limited, but it can be easily synthesized by, for example, a known emulsion polymerization step or an appropriate combination thereof, and it can be produced by the method described in International Publication No. 2014/11252 or the like. Can be done.

For example, when the particles of the polymer (A) have a polymer 1 having a repeating unit derived from a fluorine-containing ethylene-based monomer and a polymer 2 having a repeating unit derived from an unsaturated carboxylic acid ester. First, a polymer (A) having a repeating unit derived from a fluorine-containing ethylene-based monomer is synthesized by a known method. Next, a monomer for forming the polymer 2 is added to the polymer 1, and the monomer is absorbed into the stitch structure of the polymer particles containing the polymer 1, and then the polymer 2 is subjected to. It is also possible to synthesize the particles of the polymer (A) by polymerizing the absorbed monomers in the stitch structure.

The content ratio of the fluorine-containing polymer in the particles of the polymer (A) can be 5 to 99 parts by mass, or 10 to 80 parts by mass, out of 100 parts by mass of the particles of the polymer (A). it can. By containing the fluorine-containing polymer in the particles of the polymer (A) in the above range, the balance between the film-forming property and the adhesion becomes better.

The content ratio of the polymer (A) in the fluorine-containing polymer particles can be 10 to 90 parts by mass and 20 to 85 parts by mass in 100 parts by mass of the fluorine-containing polymer particles. When the fluorine-containing polymer particles contain the polymer (A) in the above range, the balance between the film-forming property and the adhesion becomes better.

The production of fluorine-containing polymer particles, that is, the polymerization of the polymer (A), the polymerization of the polymer (A) performed after absorbing the monomer in the obtained polymer (A), or both of them are known. It can be carried out in the presence of an emulsifier (surfactant), a polymerization initiator, a molecular weight preparation agent and the like.

1.1.1.5. Physical characteristics of polymer (A) <Transition temperature>
When the particles of the polymer (A) are fluorine-containing polymer particles, the endothermic peak in the temperature range of -50 ° C to + 80 ° C is at least when measured by differential scanning calorimetry (DSC) based on JIS K7121. It is preferable that one is present. The temperature of one of the endothermic peaks of the polymer (A) is more preferably in the range of −30 ° C. to + 70 ° C., and even more preferably in the range of −20 to + 60 ° C. When the temperature of one endothermic peak of the fluorine-containing polymer particles is in the above range, the particles can impart better flexibility and adhesiveness to the coating film, and thus have good adhesion. Is preferable in that it can be further improved.

Further, when the particles of the polymer (A) contain a fluorine-containing polymer, when measured by differential scanning calorimetry (DSC) based on JIS K7121, in addition to the above-mentioned endothermic peak, the temperature is further 80 ° C. to 150. It is preferable to observe one or more endothermic peaks in the temperature range of ° C. When two endothermic peaks are observed in this way, it is understood that the polymer (A) has at least two transition temperatures.

When a paint is applied to a base material such as a building material and dried, it is usually dried in an environment of about room temperature to 80 ° C. In this case, at the drying temperature, the surface layer surface of the polymer (A) needs to be fused and adhered to the adjacent pigment particles or polymer particles. The presence of at least one endothermic peak in the above range indicates that some phase change occurs at this temperature, and as a result, it is considered to promote fusion that improves the coating film strength.

Further, the existence of another endothermic peak in the temperature range of 80 ° C. to 150 ° C. means that the phase does not change under the above-mentioned ordinary drying conditions of the paint, and a phase that finally changes phase at a higher temperature exists in the particles. Means to do. Having such a phase that does not change phase during drying is considered to be preferable because it has the effect of suppressing excessive fluidity of the coating material during drying and improving the uniformity of the coating film.

<Average particle size>
The average particle size (Da) of the particles of the polymer (A) is preferably in the range of 30 to 400 nm, more preferably in the range of 50 to 250 nm. When the average particle size (Da) of the particles of the polymer (A) is within the above range, a dense coating film can be produced when the film is formed, so that deterioration of weather resistance can be effectively suppressed. it can.

The average particle size (Da) of the particles of the polymer (A) is a particle obtained by measuring the particle size distribution using a particle size distribution measuring device based on a light scattering method and accumulating particles from small particles. It is a value of the particle diameter (D50) at which the cumulative frequency of the numbers is 50%. Examples of such a particle size distribution measuring device include Coulter LS230, LS100, LS13 320 (all manufactured by Beckman Coulter. Inc), FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) and the like. These particle size distribution measuring devices can evaluate not only the primary particles of the polymer (A) particles but also the secondary particles formed by agglomeration of the primary particles. Therefore, the particle size distribution measured by these particle size distribution measuring devices can be used as an index of the dispersed state of the particles of the polymer (A) contained in the coating material.

<Tetrahydrofuran (THF) insoluble content>
The THF insoluble content of the polymer (A) is preferably 70% or more, more preferably 80% or more. The THF insoluble content is an index of the solvent resistance of the obtained coating film. Therefore, if the THF insoluble content is within the above range, a coating film is prepared using the coating composition or coating material according to the present embodiment, and then an organic solvent-based coating film is further laminated on the coating film. Even in this case, it is considered to be good because the elution of the polymer (A) into the organic solvent-based coating film can be suppressed. In addition, the THF insoluble content can be one of the indexes of the durability of the obtained coating film. Therefore, if the THF insoluble content is within the above range, it is considered that the durability is improved by forming a coating film on the surface of a tank or the like of a factory that handles organic solvents.

1.1.2. Crosslinker (B1)
The cross-linking agent (B1) contained in the paint kit according to the present embodiment is preferably dissolved in a liquid medium. Since the first composition contains a cross-linking agent (B1), the coating film produced by the coating composition produced by mixing the coating kit of the present invention can be densified by cross-linking. , It is considered that it can be used for long-term outdoor exposure by imparting water resistance.

Examples of the cross-linking agent (B1) include hydrazine derivatives, carbodiimide compounds, isocyanate compounds, amino compounds, epoxy compounds, oxazoline compounds, acid anhydrides, amine compounds, and aziridine compounds.

The hydrazine derivative has at least two hydrazino groups and is blended in an amount of 0.02 to 1 mol, preferably 0.2 to 0.6 mol, per 1 mol of the carbonyl group contained in the acrylic polymer. Will be done. Even if the blending amount of the hydrazine derivative is less than 0.02 mol or more than 1 mol with respect to 1 mol of the carbonyl group contained in the acrylic polymer, the coating film formed from the coating material of the present invention Insufficient heat resistance and solvent resistance.

Hyhydrazine derivatives having at least two hydradino groups include, for example, dihydrazide oxalic acid, dihydrazide malonic acid, dihydrazide adihydrate, dihydrazide adipic acid, dihydrazide adipic acid, dihydrazide isophthalate, dihydrazide sebacic acid, dihydrazide maleate, and dihydrazide maleate. Dicarboxylic acid dihydrazide containing 2 to 10 carbon atoms such as itaconic acid dihydrazide, especially 4 to 6 carbon atoms, as well as ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine and butylene-1,4- Examples thereof include adipic acid dihydrazine having 2 to 4 carbon atoms such as dihydrazine, and among these, adipic acid dihydrazide, isophthalic acid dihydrazide, and sebacic acid dihydrazide are preferable. The hydrazine derivative has an action of reacting the carbonyl group of the polymer (A) with the hydrazino group in the derivative to form a film having a network structure when the water of the coating composition is scattered by drying. A catalyst is not usually used for this cross-linking reaction, but in some cases, a catalyst such as a water-soluble metal salt such as zinc sulfate, manganese sulfate, or cobalt sulfate can be used.

Specific examples of the carbodiimide compound include UCARLNK Crosslinker XL-29SE of Union Carbide, and Carbodilite E-02, E-03A, E-04, E-05, V-02, SV-02, V- of Nisshinbo Chemical Co., Ltd. There are 02-L2, V-04, V-10 and the like, and carbodilites E-05, V-02 and V-10 are preferable.

Specific examples of the isocyanate compound include 2,4-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyldiisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, and the like. n-pentane-1,4-diisocyanate, trimerics thereof, adducts and biurets thereof, polymers having two or more isocyanate groups, lysine triisocyanates, and even blocked. Examples thereof include isocyanates.

Specific examples of the amino compound include melamine resin, urea resin, guanamine resin, amine adduct, polyamide and the like. Commercially available amino compounds include Cymel manufactured by Mitsui Cytec Co., Ltd., Ancamine and Epilink manufactured by Air Products, Versamine and Versamide manufactured by Henkel, Tomide and Fujicure manufactured by Fuji Kasei Kogyo Co., Ltd., and Daiichi General. Examples include Versamide manufactured by Japan Epoxy Resin Co., Ltd., Epicure manufactured by Japan Epoxy Resin Co., Ltd., Sanmide manufactured by Sanwa Chemical Co., Ltd., and Epomate manufactured by Ajinomoto Co., Inc.

Specific examples of epoxy compounds include epoxy resins and epoxy-modified silane coupling agents, and commercially available products include Epicoat and Epilek manufactured by Japan Epoxy Resin Co., Ltd., Cardlight manufactured by Cardlight Co., Ltd., and Momentive Performance. Examples thereof include Coat Jill 1770 and A-187 manufactured by Materials.

Specific examples of the oxazoline compound include Epocross K-1010E, Epocross K-1020E, Epocross K-1030E, Epocross K-1030E, Epocross K-2020E, Epocross K-2030E, and Epocross WS-500 supplied by Nippon Shokubai Co., Ltd. , Epocross WS-700 and the like, and Epocross WS-500 and WS-700 are preferable.

Specific examples of the aziridine compound include Chemitite PZ-33 and DZ-22E supplied by Nippon Shokubai Co., Ltd.

Examples of the method of adding the cross-linking agent include a method of adding the cross-linking agent dissolved or dispersed in water to a coating composition, and a method of dissolving the cross-linking agent in a small amount of a water-soluble organic solvent. Examples thereof include a method of adding to a coating composition, a method of directly adding the above-mentioned cross-linking agent to a coating composition, and the like. The cross-linking agent reacts with the carboxyl group introduced into the polymer (A) to form a cross-linked structure. As a result, it has the effects of improving water resistance such as temperature water resistance, initial water resistance, and stain resistance, and improving the hardness of the coating film.

1.1.3. Liquid medium The first composition according to this embodiment contains a liquid medium. The liquid medium is preferably an aqueous medium containing water. This aqueous medium can contain a non-aqueous medium other than water. From the viewpoint of improving the coatability, a non-aqueous medium having a standard boiling point of 60 to 350 ° C. can be contained. Specific examples of such a non-aqueous medium include amide compounds such as N-methylpyrrolidone, dimethylformamide, N, N-dimethylacetamide; hydrocarbons such as toluene, xylene, n-dodecane and tetralin; methanol and ethanol. , Isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, glycerin, propylene glycol, 2-ethyl-1-hexanol, 1-nonanol, lauryl alcohol and other alcohols; methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone , Holon, acetphenone, isophorone and other ketones; esters such as ethyl acetate, butyl acetate, benzyl acetate, isopentyl butyrate, methyl lactate, ethyl lactate, butyl lactate; amine compounds such as o-toluidine, m-toluidine, p-toluidine; Lactones such as γ-butyrolactone and δ-butyrolactone; sulfoxide-sulfone compounds such as dimethylsulfoxide and sulfolane can be mentioned, and one or more selected from these can be used. When the liquid medium (C) contains water and a non-aqueous medium other than water, 90% by mass or more of the total amount of the liquid medium (C) is preferably water, and 98% by mass or more is water. More preferably. By using an aqueous medium as the liquid medium (C) in the coating composition according to the present embodiment, the degree of adverse effect on the environment is reduced, and the safety to the handling operator is also increased.

The content ratio of the non-aqueous medium contained in the liquid medium is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and substantially not contained in 100 parts by mass of the liquid medium. Is particularly preferable. Here, "substantially free" means that a non-aqueous medium is not intentionally added as a liquid medium, and a non-aqueous medium that is inevitably mixed when producing a coating composition is used. It may be included.

1.1.4. Other Additives The first composition according to the present embodiment may contain additives other than the above-mentioned components, if necessary. Examples of such additives include thickeners, cross-linking agents, defoaming agents, film forming aids, antifreeze agents (ethylene glycol, propylene glycol, etc.), pH adjusters (ammonia water, ethanolamine, etc.), and wetting. Sex improvers (butyl cellosolve, ethyl cellosolve, etc.) and the like can be mentioned. The amount of these additives added may be 40 parts by mass or less with respect to 100 parts by mass in terms of solid content of the coating composition according to the present embodiment.

Examples of the thickener that can be added to the first composition according to the present embodiment include cellulose compounds such as carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose; ammonium salts or alkali metal salts of the above cellulose compounds; poly ( Polycarboxylic acids such as meta) acrylic acid and modified poly (meth) acrylic acid; alkali metal salts of the above polycarboxylic acids; polyvinyl alcohol-based (co) weights such as polyvinyl alcohol, modified polyvinyl alcohol, and ethylene-vinyl alcohol copolymers. Combined; Examples thereof include a water-soluble polymer such as a saponified product of a copolymer of an unsaturated carboxylic acid such as (meth) acrylic acid, maleic acid and fumaric acid and a vinyl ester. Among these, particularly preferable thickeners are alkali metal salts of carboxymethyl cellulose, alkali metal salts of poly (meth) acrylic acid and the like.

Commercially available products of these thickeners include, for example, CMC1120, CMC1150, CMC2200, CMC2280, CMC2450 (above, manufactured by Daicel Corporation), ASE60 (manufactured by Roam and Hearth), SN612, SN615, SN617, SN618, SN621N (above, San Nopco). Maker), ADEKA NOL UH-420 (manufactured by ADEKA) and the like.

Examples of the defoaming agent that can be added to the coating composition according to the present embodiment include a silicone-based defoaming agent and a polymer-based defoaming agent.

1.1.5. PH of the first composition
The pH of the first composition is 6 or more and 9 or less, preferably 7 or more and 8 or less. When the pH of the first composition is in the above range, the aggregation of particles of the polymer (A) having a repeating unit derived from an unsaturated carboxylic acid can be effectively suppressed.

1.2. Second Composition The coating kit according to the present embodiment has a kit configuration containing a second composition containing a cross-linking agent (B2) and a liquid medium.

1.2.1. Crosslinker (B2)
The cross-linking agent (B2) contained in the second composition according to the present embodiment is preferably dissolved in a liquid medium. Since the second composition contains a cross-linking agent (B2), the coating film produced by the coating composition produced by mixing the coating kit of the present invention is cross-linked to any of the room temperature and low temperature. Even under the conditions, drying can be completed quickly, and the coating film can be further densified. As a result, it is considered that it can be used for a longer period of outdoor exposure by imparting higher water resistance, acid resistance, and alkali resistance.

Examples of the cross-linking agent (B2) include hydrazine derivatives, carbodiimide compounds, isocyanate compounds, amino compounds, epoxy compounds, oxazoline compounds, acid anhydrides, amine compounds, and aziridine compounds. Specifically, the compound exemplified in the section "1.1.2. Cross-linking agent (B1)" can be used in a timely manner, but the cross-linking agent (B2) is a compound different from the cross-linking agent (B1). Is preferable. By using different cross-linking agents, it is considered that the sites having different reactivity can be effectively cross-linked to make the coating film more dense.

If the cross-linking agent (B1) and the cross-linking agent (B2) are compounds that react if they are mixed in advance, it is not possible to mix them in advance and store the coating composition in one liquid. It is possible. However, such a problem of storage stability can be solved by preparing in advance as a paint manufacturing kit including the first composition and the second composition as in the present invention.

By using these two types of cross-linking agents together, fusion between particles is promoted by forming cross-links in a place where the space near the cross-linking reaction site is narrow and a place where the space near the cross-linking reaction site is wide. Therefore, it is considered that the space in the coating film becomes extremely small and a more dense coating film can be formed.

1.2.2. Liquid medium The second composition according to this embodiment contains a liquid medium. As the liquid medium, the same liquid medium as that used in the first composition can be used, and it is preferable that the liquid medium has the same components as the liquid medium of the first composition. Other Additives The second composition according to the present embodiment may contain additives other than the above-mentioned components, if necessary. As such an additive, the same components as those in the above-mentioned first composition can be used.

1.2.4. pH
The pH of the second composition is preferably such that the pH of the coating composition can be adjusted to about 7 by mixing with the first composition. Specifically, it is 8 or more and 12 or less, preferably 9 or more and 11 or less. When the pH of the second composition is in the above range, the decomposition of the cross-linking agent (B2) can be effectively suppressed and the storage stability can be further improved.

2. 2. Method for Producing Coating Composition The paint composition according to the present embodiment is
A polymer (A) having a repeating unit derived from an unsaturated carboxylic acid, a cross-linking agent (B1), and
Liquid medium and
To the first composition containing
Cross-linking agent (B2) and
Liquid medium and
Can be prepared by mixing a kit containing a second composition containing
The coating composition prepared from the coating kit according to the present invention preferably contains 0.1 to 30 parts by mass of the cross-linking agent (B1) with respect to 100 parts by mass of the polymer (A). It is more preferable to contain 5 to 5 parts by mass. Further, the cross-linking agent (B2) is preferably contained in an amount of 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the polymer (A). By mixing so as to have such a composition, it is possible to produce a coating composition capable of obtaining a coating film having good properties.

When the polymer (A) is dispersed in the dispersion medium in the form of particles, when the contents of the cross-linking agent (B1) and the cross-linking agent (B2) are within the above range, the particles of the polymer (A) are aggregated. Can be effectively suppressed, so that a stable coating composition can be obtained for 1 to 2 hours required for on-site coating.

Further, the content (Ma) [mass%] of the polymer (A) and the content (Mb1) [mass%] of the cross-linking agent (B1) have a relationship of Ma / Mb1 = 0.2 to 2.5. It is preferably possessed, and more preferably 0.8 to 2. When the value of Ma / Mb1 is in the above range, the pH of the first composition can be in the range of 7 or more and 8 or less, so that the aggregation and dissolution of the particles of the polymer (A) can be suppressed. it can.

Further, the content (Ma) [mass%] of the polymer (A) and the content (Mb2) [mass%] of the cross-linking agent (B2) have a relationship of Ma / Mb2 = 0.2 to 2.5. It is preferably possessed, and more preferably 0.8 to 2. When the value of Ma / Mb2 is in the above range, the pH of the second composition can be in the range of 9 or more and 11 or less. Therefore, the pH of the coating composition is adjusted by mixing with the first composition. It can be about 7.

The pH of the coating composition after mixing is in the range of 6 or more and 9 or less, preferably 7 or more and 8 or less. When the pH is in the above range, the polymer (A) is stably dispersed in the coating material without agglutination, so that a coating film having good characteristics can be obtained.

In the method for producing a coating composition according to the present embodiment, the method for mixing the first composition and the second composition is not particularly limited, and the first composition and the second composition can be mixed by a known method in a timely manner. For example, a ball mill, a sand mill, a pigment disperser, a grinder, an ultrasonic disperser, a homogenizer, a planetary mixer, a hovert mixer and the like can be exemplified.

In the method for producing a coating composition according to the present embodiment, in addition to the first composition and the second composition, additives such as colorants may be used together and mixed. These mixing can be carried out by stirring by a known method, and in general, a colorant is dispersed in a liquid medium in the presence of an additive to prepare a colorant dispersion, and the obtained colorant dispersion is used. It can be obtained by mixing with a coating composition.

3. 3. Paint The "paint" in the present invention refers to a fluid that is applied to the surface of a base material in order to protect, beautify, or impart a unique function. The "coating film" in the present invention refers to a film formed by applying a coating film to the surface of a base material and then drying the coating film.

Since the above-mentioned coating composition does not contain a colorant, it can be used as a coating material for clear coating. Further, in order to impart further functions to the coating film by coloring or the like, a colorant such as an inorganic pigment such as an inorganic pigment, an organic pigment or a filler or an organic compound is added to the above-mentioned coating composition as necessary. Can also be used.
The paint according to the present embodiment is characterized by containing the above-mentioned composition for paint and a colorant. According to the paint according to the present embodiment, not only the beauty by coloring but also the function derived from the above-mentioned paint composition, that is, the adhesion to the base material and the strength (for example, weather resistance, water resistance, durability) ) And a coating film having excellent stability can be formed. Hereinafter, the components contained in the coating material according to the present embodiment will be described in detail. However, since the composition for paint is as described above, the description thereof will be omitted.

3.1. Colorant The colorant is not particularly limited, and an appropriate material can be appropriately selected according to the target coating film.

As the colorant, if necessary, an inorganic or organic compound such as an inorganic pigment, an organic pigment, or a filler can be added or blended and used. For example, titanium oxide such as JR-1000 (Taika), CR-97 (Ishihara Sangyo), R-630 (Ishihara Sangyo), iron oxide, yellow iron oxide, zinc oxide, cerium oxide, indium oxide, antimony tin oxide, etc. Aluminum flakes, scaly aluminum, cobalt blue, lithopon, lead sulfide, zinc oxide, etc., phthalocyanine, anthraquinone, quinacridone, azo, perinone, perylene, indigo / thioindigo, dioxazine, methine / azomethine, Isoindolinone-based, diketopyrrolopyrrole-based, carbon black, diamond black, graphite, fullerene, graphene, aniline black, carbon nanotube, carbon nanohorn, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, keiso Soil, limestone, plaster, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, magnesium oxide, alumina, silica, acrylic beads, talc, clay, mica, clay minerals, iron, copper, nickel, gold, silver, zinc , Ferrite, Stainless Steel, Chromium Oxide, Cobalt Oxide, Zinc Oxide, Chromium Green, Cobalt Green, Viridian, Guinet Green, Cobalt Chrome Green, Scheele Green, Green Soil, Manganese Green, Pigment Green, Ultramarine, Navy Blue, Pigment Green, Rock Ultramarine Blue, Cobalt Blue, Cerulean Blue, Copper Borate, Molybdenum Blue, Copper Sulfide, Cobalt Purple, Mars Purple, Manganese Purple, Pigment Violet, Lead Hydroxide, Calcium Lead Acid, Zinc Oxide, Chromium Yellow, Oxide, Cadmium Yellow, Strontium Yellow , Titanium yellow, litharge, pigment yellow, copper oxide, cadmium red, selenium red, chromium vermillion, red iron oxide, zinc white, antimony white, basic lead sulfate, lead silicate, zircon oxide, tungsten white, lead, zinc oxide , Bantison white, lead phthalate, manganese white, lead sulfate, bone black, thermatomic black, vegetable black, potassium titanate whisker, molybdenum disulfide and the like. A system in which a metal chelate is formed on an organic pigment can also be used, and examples thereof include a copper phthalocyanine system. These may be used alone or in combination of two or more.

When the colorant is a pigment particle, the number average particle diameter (Db) thereof is preferably 0.05 to 40 μm. When the number average particle diameter (Db) of the pigment particles is within the above range, by using the pigment particles in combination with the coating composition according to the present embodiment, aggregation is suppressed and the coating material has excellent mechanical stability. Can be done. Therefore, it can be said that a form in which a pigment having such a particle size is used is also one of the suitable forms of the coating material according to the present embodiment.

Here, the number average particle diameter (Db) of the pigment particles is the cumulative number of particles when the particle size distribution is measured using a particle size distribution measuring device based on a laser diffraction method and the particles are accumulated from small particles. It is a value of the particle diameter (D50) at which the frequency is 50%. Examples of such a laser diffraction type particle size distribution measuring device include the HORIBA LA-300 series and the HORIBA LA-920 series (all manufactured by HORIBA, Ltd.). This particle size distribution measuring device not only evaluates the primary particles of pigment particles, but also evaluates secondary particles formed by agglomeration of primary particles. Therefore, the number average particle diameter (Db) of the pigment particles obtained by this particle size distribution measuring device can be used as an index of the dispersed state of the pigment particles contained in the coating material. The number average particle diameter (Db) of the pigment particles can also be measured by centrifuging the paint to precipitate the pigment particles, removing the supernatant, and measuring the precipitated pigment particles by the above method. can do.

3.2. Other Ingredients The coating material according to the present embodiment may contain components other than the above-mentioned components, if necessary. Examples of such components include non-aqueous media, thickeners, fillers, defoamers, surface conditioners and the like.

3.2.1. Non-aqueous medium The coating material may contain a non-aqueous medium having a standard boiling point of 60 to 350 ° C. from the viewpoint of improving the coatability. Specific examples of such a non-aqueous medium include amide compounds such as N-methylpyrrolidone, dimethylformamide, and N, N-dimethylacetamide; hydrocarbons such as toluene, xylene, n-dodecane, and tetralin; methanol, ethanol, and the like. Alcohols such as isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, glycerin, propylene glycol, 2-ethyl-1-hexanol, 1-nonanol, lauryl alcohol; methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Ketones such as holon, acetophenone, isophorone; esters such as ethyl acetate, butyl acetate, benzyl acetate, isopentyl butyrate, methyl lactate, ethyl lactate, butyl lactate; amine compounds such as o-toluidine, m-toluidine, p-toluidine; γ Lactones such as -butyrolactone and δ-butyrolactone; sulfoxide-sulfone compounds such as dimethyl sulfoxide and sulfolane can be mentioned, and one or more selected from these can be used. Among these, it is preferable to use N-methylpyrrolidone from the viewpoints of stability of polymer particles, workability when applying a paint, and the like.

3.2.2. Thickener The paint may contain a thickener from the viewpoint of improving the coatability. Specific examples of the thickener include various compounds described in "1.4. Other Additives" above.

When the paint contains a thickener, the ratio of the thickener used is preferably 20% by mass or less, more preferably 0.1 to 15% by mass, based on the total solid content of the paint. Particularly preferably, it is 0.5 to 10% by mass.

3.2.3. Filler The filler is not particularly limited, and examples thereof include carbon black, molybdenum disulfide, white carbon, calcium carbonate, barium sulfate, talc, and calcium silicate.

When the paint contains a filler, the ratio of the filler used is preferably 20% by mass or less, more preferably 0.1 to 15% by mass, and particularly preferably 0.1 to 15% by mass, based on the total solid content of the paint. Is 0.5 to 10% by mass.

32.4. Antifoaming agent The above-mentioned coating material may contain an antifoaming agent from the viewpoint of improving the coatability. Specific examples of the defoaming agent include various compounds described in "1.4. Other additives" above.

When the paint contains a defoaming agent, the ratio of the defoaming agent used is preferably 20% by mass or less, more preferably 0.1 to 15% by mass, based on the total solid content of the paint. Particularly preferably, it is 0.5 to 10% by mass.

3.2.5. Surface conditioner The paint may contain a surface conditioner from the viewpoint of improving the coatability. Examples of the surface preparation agent include siloxane compounds, acrylic copolymers, and methacrylic copolymers.

When the coating material contains a surface adjusting agent, the ratio of the surface adjusting agent used is preferably 20% by mass or less, more preferably 0.1 to 15% by mass, based on the total solid content of the coating material. Particularly preferably, it is 0.5 to 10% by mass.

4. Painted body The coated body according to the present embodiment is characterized by comprising a base material and a coating film formed by applying and drying the above-mentioned coating composition or paint on the surface of the base material. .. Such a coating film can be formed by applying the above-mentioned coating composition or coating material on the surface of an appropriate base material and drying the coating film.

The base material of the coated body is not particularly limited, and examples thereof include base materials such as cement, tile, metal, plastic, and glass. The above-mentioned coating composition or coating film formed by applying the coating material to the surface of these base materials can be used as a highly durable protective coating material. In addition, the coating film is suitably used as a heat-shielding coating film or anticorrosion coating film that is required to have durability and stain resistance assuming outdoor use in buildings, building materials, automobiles, etc., as well as felt, glass, paper, etc. It can also be suitably used as an impregnating material for a porous material, a packing material, a protective film for fibers / woven fabrics and tatami mats.

The base material may be surface-treated in advance for the purpose of adjusting the base material, improving the adhesion, sealing the porous base material, smoothing, patterning, and the like. Examples of the surface treatment of the metal-based base material include polishing, degreasing, plating treatment, chromate treatment, flame treatment, coupling treatment and the like, and examples of the surface treatment of the plastic-based base material include blast treatment and the like. Chemical treatment, degreasing, flame treatment, oxidation treatment, steam treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment and the like can be mentioned. Examples of surface treatments for inorganic ceramic base materials include polishing and eye treatment. Examples of the surface treatment for the wood base material include polishing, filling, and insect repellent treatment, and examples of the surface treatment for the paper base material include sealing and sealing. Insect repellent treatment and the like can be mentioned, and as the surface treatment for the deteriorated coating film, for example, keren and the like can be mentioned.

There is no particular limitation on the coating composition or the method of applying the coating material to the base material. For example, doctor blade method, dip method, reverse roll method, direct roll method, gravure method, extrusion method, dipping method, brush coating method, spray coating, bar coater, knife coater, screen printing, spin coater, applicator, etc. An appropriate method such as a flow coater, a centrifugal coater, an ultrasonic coater, flexographic printing, or the like can be used.

The coating composition and the coating amount of the paint are not particularly limited, but the thickness of the coating film formed after removing the liquid medium (a concept including both water and a non-aqueous medium used optionally). However, it is more preferable that the dry film thickness is about 0.05 to 50 μm in one coating and about 0.1 to 100 μm in two coatings.

The coating composition or paint according to the present embodiment can be applied directly on the base material, but depending on the application, an epoxy-based, urethane-based, melamine-based, alkyd-based or other undercoat (primer) may be applied on the base material. ) Layer and intermediate coating layer can be formed in advance and used, or an anticorrosion layer such as zinc rich paint can be provided and used.

The drying method after coating on the substrate (method for removing water and optionally used non-aqueous medium) is also not particularly limited, and for example, drying with warm air, hot air, or low humidity air; vacuum drying; (far). It can be dried by irradiation with infrared rays, electron beams, or the like. The drying rate can be appropriately set so that the liquid medium can be removed as quickly as possible within a speed range in which the coating film does not crack due to stress concentration or the coating film does not peel off from the substrate. ..

5. Examples Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" and "%" in Examples and Comparative Examples are based on mass.

5.1. Synthesis example 1
After sufficiently replacing the inside of an autoclave with an internal volume of about 6 L equipped with an electromagnetic stirrer with nitrogen, 2.5 L of deoxidized pure water and 25 g of ammonium perfluorodecanoate as an emulsifier were charged, and the temperature was 60 ° C. while stirring at 350 rpm. The temperature was raised to. Next, a mixed gas composed of 88% vinylidene fluoride (VDF), 6% tetrafluoroethylene (TFE), and 6% propylene hexafluoride (HFP), which are monomers, was used until the ^{internal pressure reached 20 kg / cm 2.} I prepared it. 25 g of a Freon 113 solution containing 20% of diisopropylperoxydicarbonate as a polymerization initiator was press-fitted using nitrogen gas to initiate polymerization. A mixed gas consisting of 88% VDF, 6% TFE, and 6% HFP was sequentially press-fitted so that the ^{internal pressure was maintained at 20 kg / cm 2} during the polymerization, and the pressure was ^{maintained at 20 kg / cm 2} . Further, since the polymerization rate decreases as the polymerization progresses, after 3 hours, the same amount of the same polymerization initiator solution as before was press-fitted using nitrogen gas, and the reaction was continued for another 3 hours. Then, the reaction solution was cooled and the stirring was stopped at the same time, and the reaction was stopped after releasing the unreacted monomer to obtain an aqueous dispersion containing 40% of the fine particles of the polymer. As a result of analyzing the obtained polymer by ¹⁹ F-NMR, the mass composition ratio of each monomer was VDF / TFE / HFP = 34/4/5.

After sufficiently replacing the inside of the separable flask with a capacity of 7 L with nitrogen, 107.5 parts by mass (43 parts by mass of the polymer) and 9 parts by mass of water of the aqueous dispersion containing the fine particles of the polymer obtained in the above step. Was prepared. In a separate container, 2 parts by mass of the emulsifier "Adecaria Soap SR1025" (trade name, manufactured by ADEKA Co., Ltd.) and 25 parts by mass of methyl methacrylate (MMA) with respect to 43 parts by mass of the polymer contained in this aqueous dispersion. , 2-ethylhexyl acrylate (EHA) 36 parts by mass, cyclohexyl methacrylate (CHMA) 20 parts by mass, hydroxyethyl methacrylate (HEMA) 5 parts by mass, 3- (trimethoxysilyl) propyl methacrylate 0.5 parts by mass, PE-200 (trade name, Nichiyu Co., Ltd.) 5 parts by mass, diacetone acrylamide (DAAM) 5 parts by mass, N, N-dimethylacrylamide (DMAA) 3 parts by mass, 2-ethylhexylthioglycolate 0.3 parts by mass And 0.5 parts by mass of acrylic acid (AA) and 80 parts by mass of water were mixed and sufficiently stirred to prepare a monomeric emulsion. Then, the temperature of the separable flask was started to be raised in a water bath, and when the internal temperature of the separable flask reached 50 ° C., 0.3 parts by mass of ammonium persulfate was added as a polymerization initiator. When the internal temperature of the separable flask reaches 75 ° C., the addition of the monomeric emulsion prepared above is started, and 2 of the monomeric emulsion is added while maintaining the internal temperature of the separable flask at 75 ° C. It was added slowly over time. Then, the internal temperature of the separable flask was raised to 85 ° C., and this temperature was maintained for 1 hour to carry out the polymerization reaction. Then, the separable flask was cooled to stop the reaction, and ammonium water was added to prepare the pH at 7.6 to obtain an aqueous dispersion containing 46% by mass of the particles of the polymer S1.

<Average particle size>
For the aqueous dispersion, measure the particle size distribution using a particle size distribution measuring device (manufactured by Otsuka Electronics Co., Ltd., model "FPAR-1000") based on the dynamic light scattering method, and calculate the average particle size from the particle size distribution. As a result, the average particle size of the particles of the polymer S1 was 120 nm.

<Measurement of THF insoluble matter and DSC>
About 10 g of the obtained aqueous dispersion was weighed into a Teflon (registered trademark) petri dish having a diameter of 8 cm, and dried at 120 ° C. for 1 hour to form a film. 1 g of the obtained membrane (polymer) was immersed in 400 mL of tetrahydrofuran (THF) and shaken at 50 ° C. for 3 hours. Next, the THF phase was filtered through a wire mesh of 300 mesh to separate the insoluble matter, and then the weight (Y (g)) of the residue obtained by evaporating and removing the dissolved THF was measured. When the THF insoluble content was determined by 6), the THF insoluble content of the polymer (A) was 80%.

THF insoluble content (%) = ((1-Y) / 1) x 100 ... (6)
Further, when the obtained polymer S1 was measured by a differential scanning calorimeter (DSC), endothermic peaks were observed at 9 ° C. and 90 ° C., respectively.

5.2. Synthesis Examples 2 to 20
An aqueous dispersion containing particles of the polymers S2 to S20 was prepared in the same manner as in Synthesis Example 1 above, except that the composition of the monomer and the amount of the molecular weight-preparing agent were changed to the amounts shown in Table 1. Further, water was removed or added under reduced pressure according to the solid content concentration of the prepared aqueous dispersion to obtain an aqueous dispersion containing 46% by mass of the particles of the polymers S2 to S20.

The average particle size, THF insoluble matter, and endothermic peak temperature of each were evaluated in the same manner as in Synthesis Example 1. The results are shown in Table 1.

The abbreviations for each component in Table 1 mean the following compounds.
-VDF: Vinylidene Fluoride-TFE: Ethylene Tetrafluoroethylene-HFP: Propylene Hexoxide-MMA: Methyl Methacrylate-EHA: 2-ethylhexyl Acrylic Acid-CHMA: Cyclohexyl Methacrylate-HEMA: 2-Hydroxyethyl Methacrylate- MAPS: γ-methacryloxypropyltrimethoxysilane ・ BA: butylacrylic acid ・ PEGMA: polyethylene glycol methacrylate (manufactured by Nichiyu Co., Ltd., trade name “PE-200”, average number of moles of oxyethylene added: 4.5)
PMPMA: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (manufactured by ADEKA Corporation, trade name "LA-82")
-AA: Acrylic acid-MAA: Methacrylic acid-DAAM: Diacetone acrylamide-DMAA: N, N-dimethylacrylamide 5.3. Synthesis Examples 21 to 31
An aqueous dispersion containing particles of the polymers S22 to S31 was prepared in the same manner as in Synthesis Example 1 above, except that the composition of the monomer and the amount of the molecular weight modifier were changed to the amounts shown in Table 8. Further, water was removed or added under reduced pressure according to the solid content concentration of the prepared aqueous dispersion to obtain an aqueous dispersion containing 46% by mass of the particles of the polymers S22 to S31. The average particle size, THF insoluble matter, and endothermic peak temperature of each were evaluated in the same manner as in Synthesis Example 1. The results are shown in Table 8.

5.4. Synthesis example 32
After sufficiently replacing the inside of an autoclave with an internal volume of about 6 L equipped with an electromagnetic stirrer with nitrogen, 2.5 L of deoxidized pure water and 25 g of ammonium perfluorodecanoate as an emulsifier were charged, and the temperature was 60 ° C. while stirring at 350 rpm. The temperature was raised to. Next, a mixed gas composed of 88% vinylidene fluoride (VDF), 6% tetrafluoroethylene (TFE), and 6% propylene hexafluoride (HFP), which are monomers, was charged until the internal pressure reached 20 kg / cm2. That's right. 25 g of a Freon 113 solution containing 20% of diisopropylperoxydicarbonate as a polymerization initiator was press-fitted using nitrogen gas to initiate polymerization. A mixed gas consisting of 88% VDF, 6% TFE, and 6% HFP was sequentially press-fitted so that the internal pressure was maintained at 20 kg / cm2 during the polymerization, and the pressure was maintained at 20 kg / cm2. Further, since the polymerization rate decreases as the polymerization progresses, after 3 hours, the same amount of the same polymerization initiator solution as before was press-fitted using nitrogen gas, and the reaction was continued for another 3 hours. Then, the reaction solution was cooled and the stirring was stopped at the same time, and the reaction was stopped after releasing the unreacted monomer to obtain an aqueous dispersion containing 40% of the fine particles of the polymer. As a result of analyzing the obtained polymer by 19F-NMR, the mass composition ratio of each monomer was VDF / TFE / HFP = 34/4/5.

After sufficiently replacing the inside of the separable flask with a capacity of 7 L with nitrogen, 107.5 parts by mass (43 parts by mass of the polymer) and 9 parts by mass of water of the aqueous dispersion containing the fine particles of the polymer obtained in the above step. Was prepared. In a separate container, 1 part by mass of the emulsifier "ADEKA CORPORATION" (trade name, manufactured by ADEKA Corporation) and 24 parts by weight of methyl methacrylate (MMA) with respect to 43 parts by mass of the polymer contained in this aqueous dispersion. , 2-ethylhexyl acrylate (EHA) 34 parts by mass, cyclohexyl methacrylate (CHMA) 20 parts by mass, 3- (trimethoxysilyl) propyl methacrylate (MAPS) 0.5 parts by mass, PE-200 (trade name, Japan) Oil Co., Ltd.) (PEGMA) 2 parts by mass, methacrylate 1,2,2,6,6-pentamethyl-4-piperidyl (trade name LA-82; manufactured by ADEKA Corporation) (PMPMA) 1 part by mass and acrylic acid (PMPMA) AA) 0.5 parts by mass, polyoxyethylene dodecyl ether sodium sulfate 1 part by mass, 2-ethylhexylthioglycolate 0.3 parts by mass, "ADEKA CORPORATION ER40" (trade name, manufactured by ADEKA Corporation) 0.5 mass Parts, 1 part by mass of 2-amino-2-methyl-1-propanol and 65 parts by mass of water were mixed and sufficiently stirred to prepare a monomeric emulsion 1. In a separate container, 5 parts by mass of hydroxyethyl methacrylate (HEMA), 3 parts by mass of PE-200 (trade name, Nichiyu Co., Ltd.) (PEGMA), 3 parts by mass of N, N-dimethylacrylamide (DMAA), die. 5 parts by mass of acetone acrylamide (DAAM), 2 parts by mass of sodium styrene sulfonate and 1 part by mass of emulsifier "Adecaria Soap SR10" (trade name, manufactured by ADEKA Co., Ltd.), acrylic resin W. P. 0.1 part of 20 (manufactured by VANORA) and 20 parts by mass of water were mixed and sufficiently stirred to prepare a monomeric emulsion 2.

Then, the temperature was started while stirring the separable flask in a water bath, and when the internal temperature of the separable flask reached 50 ° C., 0.3 parts by mass of ammonium persulfate was added as a polymerization initiator. When the internal temperature of the separable flask reaches 75 ° C., the addition of the monomeric emulsion 1 prepared above is started, and the monomeric emulsion 1 is maintained while maintaining the internal temperature of the separable flask at 75 ° C. Was added slowly over 1.5 hours. After the addition of the emulsion 1 is completed, the addition of the monomeric emulsion 2 prepared above is started, and the monomeric emulsion 2 is slowly added over 1 hour while maintaining the internal temperature of the separable flask at 75 ° C. Added. Then, the internal temperature of the separable flask was raised to 85 ° C., and this temperature was maintained for 1 hour to further carry out the polymerization reaction. Then, the separable flask was cooled to 25 ° C. to stop the reaction, and ammonium water was added to prepare the pH at 7.6 to obtain an aqueous dispersion containing 46% by mass of the particles of the polymer S32. ..

5.5. Synthesis Examples 33-42
An aqueous dispersion containing particles of the polymers S33 to S42 was prepared in the same manner as in Synthesis Example 32, except that the composition of the monomer and the amount of the molecular weight modifier were changed to the amounts shown in Table 9. Further, water was removed or added under reduced pressure according to the solid content concentration of the prepared aqueous dispersion to obtain an aqueous dispersion containing 46% by mass of the particles of the polymers S33 to S42. The average particle size, THF insoluble matter, and endothermic peak temperature of each were evaluated in the same manner as in Synthesis Example 1. The results are shown in Table 9.

5.6. Example 1
5.6.1. Preparation of First Composition 311.5 parts by mass (143.3 parts by mass of polymer (A)) of the aqueous dispersion containing the particles of the polymer (A) obtained above was added as a cross-linking agent (B1). 5.2 parts by mass (2.08 parts by mass) of an aqueous dispersion containing 40% of carbodiimide compound V-02 (manufactured by Nisshinbo Co., Ltd., trade name "Carbodilite V-02") was charged, and at 300 rpm. The first composition was prepared by stirring.

<Freezing temperature evaluation>
In general, the storage environment of a coating composition cannot be strictly controlled in temperature from the viewpoint of cost, and therefore, it is often exposed to an environment close to 0 ° C. due to a change in air temperature. Therefore, in the following evaluation of the freezing temperature, freezing at 0 ° C. is unacceptable, and the freezing temperature is required to be −0.2 ° C. or lower. Therefore, when the freezing temperature is −0.2 ° C. or lower, it is good, and when it is −0.5 ° C. or lower, the stability of the coating composition is high, and it can be judged that it is even better.

The first composition prepared above was filled with 1000 parts by mass in a polybin, then stored in a freezer at −10 ° C., and the temperature at which freezing started (freezing temperature) was measured. As a result, the freezing temperature of the first composition prepared above was −0.5 ° C.

5.6.2. Preparation of Second Composition An aqueous dispersion containing 40% of carbodiimide compound V-10 (manufactured by Nisshinbo Holdings, Inc., trade name "Carbodilite V-10") as a cross-linking agent (B2) was prepared as the second composition. ..

5.6.3. Preparation of composition for paint The first composition and the second composition prepared above were filled and sealed in separate polybins, and stored in a storage set at 23 ° C. for one month. Then, the first composition after storage is 316. .. 7 parts by mass (containing 143.3 parts by mass of the polymer (A) and 2.08 parts by mass of the cross-linking agent (B1)) and 3.57 parts by mass of the second composition after storage (cross-linking agent (B2)) Was mixed with 1.43 parts by mass) and stirred at 300 rpm to prepare a coating composition.

5.6.4. Evaluation of coating film <Initial gloss of coating film>
The coating composition obtained above is applied to a hard aluminum base material which has been previously coated with a water-based epoxy undercoat material and fired at 150 ° C. using an applicator having a gap value of 200 μm, and at room temperature (23 ° C.). A coating film was formed by leaving it for one week. The 60 ° glossiness of the coating film thus obtained was measured using a "precision gloss meter GM-26 Pro" manufactured by Murakami Color Technology Research Institute. When glossiness is required for the coating film, it is more preferable that the initial gloss is large, but it can be judged that it is good if it is 65 or more. The initial gloss values are also shown in Table 2.

<Evaluation of room temperature curability>
On a hard aluminum base material obtained by the same method as for initial gloss measurement, the coating composition obtained above was applied under normal temperature and humidity (23 ° C., 55% RH) conditions using an applicator with a gap value of 200 μm. And dry to the touch (when the pad of the finger lightly touches the paint film, the paint does not adhere to the finger) and semi-curing dry (the painted surface is gently rubbed with the fingertips, and no rubbing marks are left on the painted surface). ) Was evaluated. The evaluation criteria are as follows, and the results are also shown in Table 2.
・ If the time required for touch drying and semi-curing drying is within 1 hour, it is judged that the room temperature curability is very good, and "◎" is displayed.
-If the time required for touch drying and semi-curing drying exceeds 1 hour and is within 3 hours, it is judged that the room temperature curability is good and "○" is displayed.
-If the time required for touch drying and semi-curing drying exceeds 3 hours and is less than 5 hours, it is judged that the room temperature curability is slightly good and "△".
・ If the time required for touch drying and semi-curing drying is 5 hours or more, it is judged that the room temperature curability is poor and "x" is displayed.
<Evaluation of low temperature curability>
On a hard aluminum base material obtained by the same method as for initial gloss measurement, the coating composition obtained above was applied under low temperature and humidity (5 ° C., 30% RH) conditions using an applicator with a gap value of 200 μm. And evaluated the degree of touch drying and semi-curing drying. The evaluation criteria are as follows, and the results are also shown in Table 2.
-If the time to dry to the touch is within 2 hours and the time to semi-curing drying is within 3 hours, it is judged that the low temperature curability is very good and "◎".
-If the time to dry to the touch exceeds 2 hours and is within 5 hours, and the time to semi-curing dry is more than 3 hours and is within 8 hours, it is judged that the low-temperature curability is good and "○".
-If the time to dry to the touch exceeds 5 hours and is less than 8 hours, and the time to dry to semi-curing is more than 8 hours and less than 12 hours, it is judged that the low temperature curability is slightly good and "△"
-If the time to dry to the touch is 8 hours or more and the time to semi-curing dry is 12 hours or more, it is judged that the low temperature curability is poor and "x" is displayed.
<Water resistance evaluation>
The coating composition obtained above was applied to a slate substrate to which an aqueous epoxy undercoat material had been applied in advance and left at room temperature (23 ° C.) for 1 week using an applicator having a gap value of 200 μm, and the composition was applied at room temperature for 1 week. A coating film was formed by leaving it to stand. The slate plate with the coating film thus obtained was immersed in ion-exchanged water at 23 ° C. for 168 hours, left at room temperature for 2 hours, and then the swelling, cracking, and peeling of the coating film were visually observed. , The water resistance of the coating film was evaluated. The evaluation criteria are as follows, and the results are also shown in Table 2.
-If no swelling, cracking, or peeling of the coating film is observed, it is judged that the water resistance is very good and "◎".
-If swelling, cracking, or peeling of the coating film is observed but is very slight, it is judged that the water resistance is good and "○" is displayed.
-If the coating film is required to swell, crack, or peel off significantly, it is judged that the water resistance is poor and "x" is displayed.
Further, the 60 ° gloss of the coating film after the above-mentioned visual observation was measured by the same method as the initial gloss, and the gloss retention rate (gloss after test / gloss before test;%) was calculated. The evaluation criteria are as follows, and the results are also shown in Table 2.
-When the gloss retention rate is 80% or more, the gloss retention rate is very good.
-When the gloss retention rate is 60% or more and less than 80%, the gloss retention rate is good.
-When the gloss retention rate is less than 60%, the gloss retention rate is poor.

<Acid resistance evaluation>
The coating composition obtained above was applied to a glass substrate to which a water-based epoxy undercoat material had been applied in advance and left at room temperature (23 ° C.) for 1 week using an applicator having a gap value of 200 μm, and then at room temperature (23 ° C.). A coating film was formed by leaving it underneath for 1 week. The slate plate with the coating film thus obtained was immersed in a 0.5% sulfuric acid aqueous solution at 23 ° C. for 168 hours, left at room temperature for 2 hours, and then the swelling, cracking, and peeling of the coating film were visually observed. The water resistance of the coating film was evaluated. The evaluation criteria are as follows, and the results are also shown in Table 2.
-If no swelling, cracking, or peeling of the coating film is observed, it is judged that the water resistance is very good and "◎".
-If swelling, cracking, or peeling of the coating film is observed but is very slight, it is judged that the water resistance is good and "○" is displayed.
-If the coating film is required to swell, crack, or peel off significantly, it is judged that the water resistance is poor and "x" is displayed.
Further, the 60 ° gloss of the coating film after the above-mentioned visual observation was measured by the same method as the initial gloss, and the gloss retention rate (gloss after test / gloss before test;%) was calculated. The evaluation criteria are as follows, and the results are also shown in Table 2.
-When the gloss retention rate is 80% or more, the gloss retention rate is very good.
-When the gloss retention rate is 60% or more and less than 80%, the gloss retention rate is good.
-When the gloss retention rate is less than 60%, the gloss retention rate is poor.

<Alkali resistance evaluation>
The coating composition obtained above was applied to a slate substrate to which an aqueous epoxy undercoat material had been applied in advance and left at room temperature (23 ° C.) for 1 week using an applicator having a gap value of 200 μm, and the composition was applied at room temperature for 1 week. A coating film was formed by leaving it to stand. The slate plate with the coating film thus obtained was immersed in a saturated calcium hydroxide aqueous solution at 23 ° C. for 168 hours, left at room temperature for 2 hours, and then the swelling, cracking, and peeling of the coating film were visually observed. The water resistance of the coating film was evaluated by observing. The evaluation criteria are as follows, and the results are also shown in Table 2.
-If no swelling, cracking, or peeling of the coating film is observed, it is judged that the water resistance is very good and "◎".
-If swelling, cracking, or peeling of the coating film is observed but is very slight, it is judged that the water resistance is good and "○" is displayed.
-If the coating film is required to swell, crack, or peel off significantly, it is judged that the water resistance is poor and "x" is displayed.
Further, the 60 ° gloss of the coating film after the above-mentioned visual observation was measured by the same method as the initial gloss, and the gloss retention rate (gloss after test / gloss before test;%) was calculated. The evaluation criteria are as follows, and the results are also shown in Table 2.
-When the gloss retention rate is 80% or more, the gloss retention rate is very good.
-When the gloss retention rate is 60% or more and less than 80%, the gloss retention rate is good.
-When the gloss retention rate is less than 60%, the gloss retention rate is poor.

<Weather resistance evaluation>
An accelerated weather resistance test of 500 hours was performed on the coating film obtained by the same method as for the initial gloss measurement using a metal weather (manufactured by Daipla Wintes), and the 60 ° gloss of the coating film was measured to measure the gloss retention (after the test). Gloss / gloss before test;%) was calculated. The test conditions are as follows: Irradiation of light of 295 to 780 nm with a KF-1 filter using a metal halide lamp light source, irradiation (75 mW / cm ² under 63 ° C. 50% RH) 4 hr and dark (30 ° C. 98% RH) 4 hr. It was set as a cycle condition. The evaluation criteria are as follows, and the results are also shown in Table 2.
-When the gloss retention rate is 80% or more, the weather resistance is very good.
-When the gloss retention rate is 60% or more and less than 80%, the weather resistance is good.
-When the gloss retention rate is less than 60%, the weather resistance is poor.

<Adhesion evaluation>
The coating composition obtained above was applied onto glass using an applicator having a gap value of 200 μm, and left at room temperature (23 ° C.) for 1 week to form a coating film. The coating film thus obtained was cross-cut (5 × 5 25 squares) into a 1 mm square with a cutter, and an adhesion test using Nichiban cellophane tape (registered trademark) was performed and evaluated according to the following criteria. The evaluation criteria are as follows, and the results are shown in Table 2.
・ If there is no peeling of the coating film, it is judged that the adhesion is very good and "◎"
・ If the peeling of the coating film is less than half, it is judged that the adhesion is good and "○" is displayed.
・ If the peeling of the coating film is more than half, it is judged that the adhesion is poor and "x" is displayed.
<Tensile elongation evaluation>
Tensile elongation was evaluated as one of the indexes of how much the coating film can follow the bending of the coated substrate and the expansion and contraction due to the temperature change without breaking the coating film. It can be judged that the larger the tensile elongation is, the more the substrate followability is improved. Such tensile elongation characteristics were evaluated by the following method.

The coating film formed by applying the coating composition obtained above on a glass plate so as to have a film thickness of 0.2 to 0.4 mm and leaving it at room temperature (23 ° C.) for 1 week was formed as No. 7. A test piece was prepared by punching with a dumbbell. The tensile elongation of this test piece was measured using an autograph (manufactured by Shimadzu Corporation, AG-X type) at a tensile speed of 50 mm / min according to JIS A6909. The evaluation criteria are as follows, and the results are shown in Table 2.
・ If the tensile elongation is 300% or more, it is judged that the tensile elongation is very good and "◎"
-If the tensile elongation is 200% or more and less than 300%, it is judged that the tensile elongation is good and "○" is displayed.
・ If the tensile elongation is less than 200%, it is judged that the tensile elongation is poor and "x" is displayed.
5.7. Examples 2-46, Comparative Examples 1-15
The first composition was prepared and evaluated in the same manner as in Example 1 except that the polymer (A), the cross-linking agent (B1) and the additive were changed to the types and amounts shown in Tables 2 to 4. Further, a second composition was prepared in the same manner as in Example 1 except that the cross-linking agent (B2) was changed to the types shown in Tables 2 to 4, and the coating material provided with the first composition and the second composition was prepared. A kit for use was prepared.

The prepared paint kit was stored in the same manner as in Example 1. Then, the first composition and the second composition after storage are mixed so as to have the types and amounts of the polymer (A), the cross-linking agent (B1) and the cross-linking agent (B2) shown in Tables 2 to 4. A coating composition was prepared by mixing in the same manner as in Example 1 and used for evaluation. The evaluation results are also shown in Tables 2-4.

The abbreviations for each component in Tables 2 to 4 mean the following compounds, respectively.
・ Colloidal silica: Made by ADEKA Corporation, product name "AT-50"
-Carbodiimide compound: Nisshinbo Co., Ltd., trade name "Carbodilite V-02"
-Carbodiimide compound: Nisshinbo Co., Ltd., trade name "Carbodilite E-02"
-Carbodiimide compound: Nisshinbo Co., Ltd., trade name "Carbodilite E-05"
-Oxazoline compound: Nippon Shokubai Co., Ltd., trade name "Epocross WS-700"
-Carbodiimide compound: Nisshinbo Co., Ltd., trade name "Carbodilite V-10"
-Isocyanate compound: Asahi Kasei Chemicals Co., Ltd., trade name "Duranate WT30-100"
5.8. Comparative Examples 16 to 61
The polymer (A), the cross-linking agent (B1) and the cross-linking agent (B2) are added in order to a predetermined amount of water and mixed in advance so as to obtain the types and amounts shown in Tables 5 to 7 to prepare a coating composition. , Stored at 23 ° C. for 1 day. Then, the coating film was evaluated in the same manner as in Example 1. The results are shown in Tables 5-7.

5.9. Examples 71-92
The first composition was prepared and evaluated in the same manner as in Example 1 except that the polymer (A), the cross-linking agent (B1) and the additive were changed to the types and amounts shown in Table 10. Further, except that the cross-linking agent (B2) was changed to the type shown in Table 10, a second composition was prepared in the same manner as in Example 1, and a coating kit provided with the first composition and the second composition. Was produced. The prepared paint kit was stored in the same manner as in Example 1. Then, the first composition and the second composition after storage were subjected to Examples so as to have the types and amounts of the polymer (A), the cross-linking agent (B1) and the cross-linking agent (B2) shown in Table 10. A coating composition was prepared by mixing in the same manner as in No. 1, and was used for evaluation. The evaluation results are also shown in Table 10.

5.10. Comparative Examples 71-93
The polymer (A), the cross-linking agent (B1) and the cross-linking agent (B2) were added in this order to a predetermined amount of water and mixed in advance so as to obtain the types and amounts shown in Table 11 to prepare a coating composition. Stored at ° C for 1 day. Then, the coating film was evaluated in the same manner as in Example 1. The results are shown in Table 11.

5.11. Results According to Examples 1 to 46, it was clarified that the coating composition of the present invention shows good results. On the other hand, comparative examples 1 to 15 which are not the coating compositions of the present invention, and comparison of coating compositions in which the first composition and the second composition were prepared and then stored at 23 ° C. per day. In Examples 16 to 61, the characteristics were poor.

The present invention is not limited to the above embodiment, and various modifications are possible. The present invention includes a configuration substantially the same as the configuration described in the embodiment (for example, a configuration having the same function, method and result, or a configuration having the same purpose and effect). The present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration. Further, the present invention also includes a configuration that exhibits the same effects as the configuration described in the above embodiment or a configuration that can achieve the same object. Further, the present invention also includes a configuration in which a known technique is added to the configuration described in the above embodiment.

Claims (3)

Particles of the polymer (A) having a repeating unit derived from an unsaturated carboxylic acid and a repeating unit derived from a fluorine-containing ethylene-based monomer , and
Hydrazine derivative (B1) and
Liquid medium and
With the first composition containing
Carbodiimide compound (B2) and
Liquid medium and
With a second composition containing
A kit for paints. And particles of a polymer having a repeating unit (A) derived from repeating units and fluorine-containing ethylenic monomer derived from an unsaturated carboxylic acid, a hydrazine derivative (B1), a first composition containing a liquid medium To things,
Carbodiimide compound and (B2), a method of a mixture of a second composition comprising a liquid medium to produce a coating composition. With respect to 100 parts by mass of the particles of the polymer (A)
Hydrazine derivative (B1) in an amount of 0.1 to 30 parts by mass ,
Carbodiimide compound (B2) in an amount of 0.1 to 30 parts by mass ,
The method for producing a coating composition according to claim 2 , wherein the composition is mixed so as to be.