TW201922972A - Coating film composition capable of forming a coating film excellent in adhesion to a substrate, weather resistance, water resistance, and abrasion resistance - Google Patents

Abstract

The present invention provides a coating film composition, which is excellent in storage stability and capable of forming a coating film excellent in adhesion to a substrate, weather resistance, water resistance, and abrasion resistance. The coating composition of the present invention contains polymer particles and a liquid medium. The polymer particles contain a first polymer having a repeating unit derived from a fluorine-containing vinyl monomer, and a second polymer having a repeating unit derived from an unsaturated carboxylic acid ester and a repeating unit containing a cationic group. The content of the cationic group in the second polymer is preferably 0.5 mmol/100 g or more and 50 mmol/100 g or less. The content of the first polymer in the polymer particles is preferably more than 0% by mass and less than 15% by mass.

Description

Coating composition

The present invention relates to a coating film composition.

The fluorine-containing polymer is excellent in heat resistance, weather resistance, electrical insulation, and the like, and can be used for imparting antifouling properties or chemical resistance to various substrates such as glass, metal, resin, wood, and slate. The composition of the coating agent. However, since the fluorine-containing polymer has poor adhesion to the substrate, there is a problem that sufficient coating film strength or stability cannot be obtained. For example, when the fluorine-containing polymer disclosed in Patent Document 1 or Patent Document 2 is applied to various substrates such as glass or hard aluminum, it is difficult to obtain a coating film having sufficient strength or stability.

In order to improve the strength or stability of the coating film, Patent Document 3 or Patent Document 4 discloses a technique of formulating an organic oxime oligomer in a fluorine-containing polymer. Further, Patent Document 5 discloses an aqueous dispersion of a composite polymer particle of a fluorine-containing polymer and a (meth)acrylic polymer, and a composite polymer particle with an organic ruthenium compound and a (meth)acrylic polymer. Formulation technology for aqueous dispersions. However, when any of the techniques is used, the storage stability of the composition, the adhesion between the obtained coating film and the substrate, and the weather resistance, water resistance, and abrasion resistance of the coating film are insufficient. [Prior Art Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [International Patent Publication No. 98/23680] [Patent Document 5] Japanese Patent Laid-Open Publication No. 2003-286440

[Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and an object of the invention is to provide an excellent storage stability and adhesion to a substrate, weather resistance, water resistance, abrasion resistance, and the like. A composition of a coating film excellent in characteristics.

[Technical means for solving the problem] The invention to solve the above problem is a composition containing polymer particles (hereinafter also referred to as "[A] polymer particles") and a liquid medium (also referred to as "[ B] a liquid medium"), wherein the [A] polymer particles contain a first polymer (hereinafter also referred to as "polymer (Pa)") having a repeating unit derived from a fluorine-containing vinyl monomer, and have A second polymer derived from a repeating unit of an unsaturated carboxylic acid ester and a repeating unit containing a cationic group (hereinafter also referred to as "polymer (Pb)").

The content of the cationic group in the polymer (Pb) is preferably 0.5 mmol/100 g or more and 50 mmol/100 g or less.

The content of the polymer (Pa) in the [A] polymer particles is preferably more than 0% by mass and less than 15% by mass.

[Effects of the Invention] The composition of the present invention is excellent in storage stability over a long period of time, and can form a coating film having excellent properties such as adhesion to a substrate, weather resistance, water resistance, and abrasion resistance. Therefore, the composition can be suitably used as a paint, a paint, or the like.

Hereinafter, preferred embodiments of the present invention will be described in detail. It is to be understood that the invention is not limited to the embodiments described below, and various modifications may be made without departing from the scope of the invention. Further, the term "(meth)acrylic acid-ester" in the present specification is a concept including both "acrylic acid-ester" and "methacrylic acid-ester". The term "(meth)acrylic acid -" is a concept including both "acrylic acid ~" and "methacrylic acid ~".

<Composition> The composition contains [A] polymer particles and [B] a liquid medium. The composition may contain a [C] crosslinking agent as a suitable component, or may contain other optional components within a range that does not impair the effects of the present invention. Hereinafter, each component will be described in detail.

<[A] Polymer Particles> [A] The polymer particles contain a polymer (Pa) having a repeating unit derived from a fluorine-containing vinyl monomer, and having a repeating unit derived from an unsaturated carboxylic acid ester and containing a cationic group a repeating unit of the polymer (Pb). The polymer particles (A) may contain other polymers than the polymer (Pa) and the polymer (Pb), but preferably contain only the polymer (Pa) and the polymer (Pb). [A] The polymer particles are usually latex-like particles dispersed in a [B] liquid medium. The [A] polymer particles may also contain components other than the polymer.

[Polymer (Pa)] The polymer (Pa) has a repeating unit derived from a fluorine-containing vinyl monomer. The polymer (Pa) is a polymer different from the polymer (Pb) described later. The polymer (Pa) may have a repeating unit derived from a monomer other than the fluorine-containing vinyl monomer in addition to the repeating unit.

(Repeating unit derived from fluorine-containing vinyl monomer) The fluorine-containing vinyl monomer is a compound having an ethylenic carbon-carbon double bond and a fluorine atom. Examples of the fluorine-containing vinyl monomer include a fluoroolefin, a fluorochloroolefin, a (meth) acrylate having a fluorine atom, and a perfluoroalkyl vinyl ether. Examples of the fluoroolefins include vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene. Examples of the fluorochloroolefin include chlorotrifluoroethylene and the like, and (meth) acrylate having a fluorine atom. For example, a compound represented by the formula (a) shown below, 3-[4[1-trifluoromethyl-2,2-bis[bis(trifluoromethyl)fluoromethyl)(meth)acrylate may be mentioned. Acetyleneoxy]-2-hydroxypropyl-2(2-[4[1-trifluoromethyl-2,2-bis[bis(trifluoromethyl)fluoromethyl]ethenyloxy]benzoxy]-2-hydroxypropyl (meth As the perfluoroalkyl vinyl ether, for example, trifluoromethyl trifluorovinyl ether or heptafluoropropyl trifluorovinyl ether can be mentioned.

[Chemical 1]

In the formula (a), R ¹ is a hydrogen atom or a methyl group. R ² is a monovalent fluorinated hydrocarbon group having 1 to 18 carbon atoms.

Examples of R ² in the formula (a) include a fluorinated alkyl group having 1 to 12 carbon atoms, a fluorinated aryl group having 6 to 16 carbon atoms, and a fluorinated aralkyl group having 7 to 18 carbon atoms. Among these, a fluorinated alkyl group having 1 to 12 carbon atoms is preferred. Preferred examples of R ² include 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 1,1,1,3,3,3- Hexafluoropropan-2-yl, β-(perfluorooctyl)ethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,4,4,4-hexafluorobutyl, 1H ,1H,5H-octafluoropentyl, 1H,1H,9H-hexadecafluoro-1-indenyl, 1H,1H,11H-icosylfluoroundecyl (1H,1H,11H-icosafluoroundecyl) and perfluoro Xinji.

Among these, as the fluorine-containing vinyl monomer, a fluoroolefin is preferable, and a vinylidene fluoride, a tetrafluoroethylene, and a hexafluoropropylene are more preferable, and a vinylidene fluoride and a hexafluoropropylene are more preferable. Difluoroethylene. When these compounds are used as the fluorine-containing vinyl monomer, the stability of the system is further improved during the emulsion polymerization, and the [A] polymer particles can be formed more efficiently. The fluorine-containing vinyl monomer may be used singly or in combination of two or more.

(Repeating unit derived from another monomer) The monomer or the like described in International Publication No. 2014/112252 can be used as the other monomer, and examples thereof include an unsaturated carboxylic acid, an α,β-unsaturated nitrile, and a carbonyl group-containing one. A compound, a conjugated diene, an aromatic vinyl compound, a vinyl ether, an allyl ether, a polymerizable group-containing alkoxysilane, an unsaturated carboxylic acid ester, or the like. The other monomers may be used singly or in combination of two or more.

The unsaturated carboxylic acid is preferably an ethylenically unsaturated carboxylic acid, and examples thereof include a monocarboxylic acid or a dicarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid. Among these, acrylic acid, methacrylic acid and itaconic acid are preferred.

Examples of the α,β-unsaturated nitrile include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethyl acrylonitrile, and vinylidene cyanide.

Examples of the carbonyl group-containing compound include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and N- Isopropyl (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-hydroxyethyl (meth) propylene Indoleamine, acryloylmorpholine, acrolein, and the like.

Examples of the conjugated diene include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 2-chloro -1,3-butadiene and the like.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene, and p-hydroxystyrene.

Examples of the vinyl ether include ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, and 3-hydroxypropyl vinyl ether. , 4-hydroxybutyl vinyl ether, 2-aminoethyl vinyl ether, and the like.

Examples of the allyl ether include methyl allyl ether, ethyl allyl ether, propyl allyl ether, butyl allyl ether, hydroxyethyl allyl ether, and hydroxypropylene. Propyl ether, hydroxybutyl allyl ether, allyl glycidyl ether, ethylene glycol monoallyl ether, propylene glycol monoallyl ether, and the like.

The alkoxysilane of the polymerizable group may, for example, be a compound represented by the formula (b) shown below. R ³ _n Si(OR ⁴ ) _4-n · (b) (In the formula (b), R ³ is a monovalent organic group having 1 to 8 carbon atoms. Among them, at least one of R ³ .R ⁴ having a polymerizable group as a monovalent organic group having a carbon number .n 1 ~ 8 is an integer of 0 to 3. in the case where a plurality of R ^3, a plurality of R ³ may be the same or different in R ⁴ In the case of multiple, multiple R ⁴ may be the same or different)

The compound represented by the formula (b) forms a repeating unit represented by the formula (c) shown below in the polymer (Pa). R ⁵ _m SiO _{(4-m) / 2} (c) (In the formula (c), R ⁵ is a monovalent organic group having 1 to 8 carbon atoms, wherein at least one of R ⁵ It is a group derived from a group having a polymerizable group. m is a number of 0 to 3. When R ⁵ is plural, a plurality of R ^{5 's} may be the same or different)

In the formula (b) and the formula (c), examples of the polymerizable group in R ³ and R ⁵ include a vinyl group, a 1-propenyl group, and a (meth)acryl fluorenyl group. Among these, a (meth) acrylonitrile group is preferred. Examples of the monovalent organic group having a polymerizable group represented by R ³ include a γ-(meth)acryloxypropyl group. The monovalent organic group of R ³ and R ⁵ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably a methyl group or an ethyl group. The monovalent organic group represented by R ⁴ may, for example, be an alkyl group having 1 to 8 carbon atoms, an aryl group or a fluorenyl group. The alkyl group may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a second butyl group, a tert-butyl group or a n-pentyl group. Examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, and a fluorophenyl group. The mercapto group is preferably a fluorenyl group having 1 to 6 carbon atoms, and examples thereof include an ethyl group, a propyl group, a butyl group, a pentamidine group, and a hexyl group.

Examples of the unsaturated carboxylic acid ester include an alkyl ester of an unsaturated carboxylic acid, a hydroxyalkyl ester of an unsaturated carboxylic acid, and the like. "Alkyl ester" means an ester comprising a linear, branched or cyclic alkyl group.

In the case where the polymer (Pa) has a repeating unit derived from another monomer, the content ratio of the repeating unit is, for example, 0.1% by mass or more and 99.9% by mass based on all the repeating units constituting the polymer (Pa). Hereinafter, it is preferably 10% by mass or less.

The content of the polymer (Pa) in the [A] polymer particles is preferably more than 0% by mass, more preferably 5% by mass or more. The content is preferably less than 15% by mass, and more preferably 10% by mass or less. By setting the content of the polymer (Pa) in the [A] polymer particles to the above range, it is possible to form a coating film having a better balance between film formability and adhesion.

[Polymer (Pb)] The polymer (Pb) has a repeating unit derived from an unsaturated carboxylic acid ester and a repeating unit containing a cationic group. The polymer (Pb) may also have other repeating units than these repeating units.

(Repeating unit derived from unsaturated carboxylic acid ester) Examples of the unsaturated carboxylic acid ester include an alkyl ester of an unsaturated carboxylic acid, a hydroxyalkyl ester of an unsaturated carboxylic acid, and a polyalkylene of an unsaturated carboxylic acid. An alcohol ester, an amino group-containing ester of an unsaturated carboxylic acid, a polymerizable group-containing alkoxy decane, or the like. "Alkyl ester" means an ester containing a linear, branched or cyclic alkyl group. The unsaturated carboxylic acid ester may be used singly or in combination of two or more.

Examples of the alkyl ester of the unsaturated carboxylic acid include methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate. An alkyl ester of (meth)acrylic acid such as cyclohexyl (meth)acrylate.

Examples of the hydroxyalkyl ester of the unsaturated carboxylic acid include a hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate or 3-hydroxypropyl (meth)acrylate.

Examples of the polyalkylene glycol ester of the unsaturated carboxylic acid include (meth)acrylic polyalkylene glycol esters such as polyethylene glycol (meth)acrylate.

Examples of the amino group-containing ester of the unsaturated carboxylic acid include 1,2,2,6,6-pentamethyl-4-piperidyl (meth)acrylate and dimethylamino (meth)acrylate. (Meth)acrylic acid such as ethyl ester contains an amino ester or the like.

Examples of the alkoxysilane having a polymerizable group include a compound exemplified as another monomer of the polymer (Pa). Among these, γ-methacryloxypropyltrimethoxydecane is preferred.

The lower limit of the content ratio of the repeating unit derived from the unsaturated carboxylic acid ester is preferably 30% by mass, and more preferably 60% by mass based on all the repeating units constituting the polymer (Pb). The upper limit of the content ratio is preferably 98% by mass, and more preferably 95% by mass.

(Repeating unit containing a cationic group) Examples of the cationic group include a group of a secondary ammonium salt (a salt of a secondary amine) ((-NH ₂ R ₂ ) ⁺ X ^- ), a tertiary ammonium salt ( a group of a salt of a tertiary amine ((-NHR ₃ ) ⁺ X ^- ), a group of a quaternary ammonium salt ((-NR ₄ ) ⁺ X ^- ), a group of a phosphonium salt ((-SR ₂ ) ⁺ X ^- ), a group of a phosphonium salt ((-PR ₃ ) ⁺ X ^- ), and the like. R is independently a monovalent organic group. X ^{- is} independently a relative anion. Among these, as the cationic group, a group of a secondary, tertiary or quaternary ammonium salt is preferred. The cationic group may be contained alone or in combination.

The lower limit of the content of the cationic group in the polymer (Pb) is preferably 0.5 mmol/100 g, more preferably 1.0 mmol/100 g. As the upper limit of the content, it is preferably 50 mmol/100 g, more preferably 30 mmol/100 g. When the content of the cationic group is in the above range, the film forming property at room temperature and the foaming suppressing property of the liquid are more excellent, and the initial gloss of the coating film, the substrate adhesion, the water resistance, the weather resistance, and the abrasion resistance are further improved. More excellent.

The content of the cationic group in the polymer (Pb) can be measured, for example, by nuclear magnetic resonance (NMR), ion chromatography (ion chromatography), colloidal titration, or the like. For example, regarding the group of the quaternary ammonium salt, the polymer (Pb) can be separated from the [A] polymer particles by solvent extraction or the like, and NMR, ion chromatography, and polyvinyl potassium sulfate are used as standard anions. The polymer (Pb) was measured by colloidal titration or the like.

The lower limit of the content ratio of the repeating unit containing a cationic group is preferably 0.1% by mass, and more preferably 0.5% by mass based on all the repeating units constituting the polymer (Pb). The upper limit of the content ratio is preferably 50% by mass, and more preferably 30% by mass.

As a method of introducing a repeating unit containing a cationic group into the polymer (Pb), for example, a method of copolymerizing a monomer having a cationic group and a polymerizable monomer copolymerizable therewith (first method) A method (second method) of adding a compound containing a cationic group to a polymer obtained from the polymerizable monomer, or the like.

As the monomer having a cationic group used in the first method, for example, an unsaturated monomer containing a group of a secondary, tertiary or quaternary ammonium salt, and an unsaturated group of a group containing a phosphonium salt may be mentioned. A monomer, an unsaturated monomer containing a sulfonium salt group, or the like.

Specific examples of the unsaturated monomer which is a group containing a secondary, tertiary or quaternary ammonium salt include, for example, diaryldimethyl ammonium stearate, 2-hydroxyl chloride. 2-hydroxy-3-aryloxypropyltrimethyl ammonium chloride, vinylbenzyltrimethylammonium chloride, (meth)acryloyloxyethyltrimethyl chloride Alkyl ammonium, chlorinated (meth) propylene oxiranyl ethyl dimethyl ammonium, chlorinated (meth) propylene methoxyethyl methyl ammonium, chlorinated 2-hydroxy-3-methyl propylene oxy group Propyltrimethylammonium chloride, chlorinated (meth)acryloxypropyldimethylbenzylammonium chloride, (meth)acrylamidoximepropyltrimethylammonium chloride, the formula shown below ( 1) or (2) a compound or the like.

[Chemical 2]

In the above formulae (1) and (2), n is an integer of from 1 to 30.

Examples of the unsaturated monomer having a sulfonium salt-containing group include vinylbenzyldimethyl sulfonium chloride, chlorinated (meth) propylene oxyethyl dimethyl hydrazine, and the like. . Examples of the unsaturated monomer having a sulfonium salt-containing group include vinylbenzyltrimethyl phosphonium chloride, chlorinated (meth) propylene methoxyethyl trimethyl hydrazine, and the like. These cationic group-containing monomers may be used alone or in combination of two or more.

(Other repeating units) Examples of the monomer which provides another repeating unit include a carbonyl group-containing compound such as diacetone acrylamide, N,N-dimethyl decylamine or acryl hydrazinomorph, (meth) An unsaturated carboxylic acid such as acrylic acid, an α,β-unsaturated nitrile such as acrylonitrile, or an aromatic vinyl compound such as styrene.

In the case where the polymer (Pb) has another repeating unit, the lower limit of the content ratio of the repeating unit is preferably 0.1% by mass, and more preferably 1% by mass. The upper limit of the content ratio is preferably 30% by mass, and more preferably 15% by mass.

The content of the polymer (Pb) in the [A] polymer particles is preferably more than 85% by mass, and more preferably 90% by mass or more. The content is preferably less than 100% by mass, more preferably 95% by mass or less.

The lower limit of the content of the [A] polymer particles is preferably 75% by mass, and more preferably 85% by mass based on the total solid content of the composition. The upper limit of the content is, for example, 100% by mass, preferably 98% by mass. The "total solid content" of the composition means the sum of components other than the [B] liquid medium of the composition.

<[A] Method for synthesizing polymer particles> [A] The polymer particles can be produced, for example, by emulsifying a predetermined monomer by a known method to form a polymer (Pa), a polymer (Pb), or the like. [A] Polymer particles As long as the repeating unit of the polymer (Pa) and the polymer (Pb) has the structure as described above, the synthesis method is not particularly limited, and for example, it can be carried out by a known emulsion polymerization step or It can be easily synthesized by appropriate combination, and can be synthesized, for example, by the method described in International Publication No. 2014/112252.

[A] The polymer particles can be synthesized, for example, by forming a polymer (Pa) having a repeating unit derived from a fluorine-containing vinyl monomer by a known method, and then adding it to the polymer (Pa). The monomer forming the polymer (Pb) is absorbed into the network structure of the particles of the polymer (Pa), and then the monomer absorbed in the network structure of the polymer (Pa) is polymerized to form The polymer (Pb) can be obtained, for example, in the form of an aqueous dispersion containing [A] polymer particles.

When the aqueous dispersion containing 46% by mass of [A] polymer particles is obtained by the above-described synthesis method, the upper limit of the content of the residual monomer in the aqueous dispersion is preferably 1,200 ppm by mass, more preferably It is 1,000 ppm by mass, and more preferably 800 ppm by mass. The lower limit of the content ratio is preferably 1 ppm by mass, and more preferably 50 ppm by mass. By setting the content ratio of the residual monomer in the aqueous dispersion containing the [A] polymer particles to the above range, it is possible to further reduce the out gas generated when the coating film is formed from the composition. , thereby reducing odor. The term "residual monomer" means a monomer which is used to produce a polymer (Pa) or a polymer (Pb) constituting the polymer particles of [A], and remains in the [A] polymer particle without polymerization. The monomer in the aqueous dispersion can be measured for its content by gas chromatography.

[[A] Physical Properties of Polymer Particles] (Endothermic Peak Temperature) [A] The polymer particles are preferably measured by Differential Scanning Calorimetry (DSC) according to Japanese Industrial Standards (JIS) K7121. When performing the measurement, at least one endothermic peak exists in a temperature range of -50 ° C or more and +80 ° C or less. More preferably, the temperature of one of the endothermic peaks of the [A] polymer particles is in the range of -30 ° C or more and +70 ° C or less, and more preferably -20 ° C or more and +60 ° C or less. Within the scope. When the temperature of one endothermic peak of the [A] polymer particles is within the above range, the [A] polymer particles can impart more excellent flexibility and adhesion to the coating film, so that the adhesion can be further improved. Sex is better in this respect.

Further, the [A] polymer particles are preferably measured in a temperature range exceeding 80 ° C and 150 ° C in addition to the endothermic peak when measured by differential scanning calorimetry (DSC) according to JIS K7121. To more than one endothermic peak.

When the coating material is applied to a substrate such as a building material and dried, it is usually dried in an environment of room temperature or higher and about 80 ° C or lower. In this case, it is necessary to fuse the surface layer of the polymer particles with the adjacent pigment particles or polymer particles at a temperature at the time of drying. It can be considered that there is at least one endothermic peak in the temperature range, which means that some phase transition occurs at this temperature, and as a result, a fusion which enhances the strength of the coating film is promoted.

Further, there is another endothermic peak in a temperature range exceeding 80 ° C and 150 ° C or less, which means that no phase change occurs under the usual paint drying conditions described above, and a phase which gradually undergoes phase transformation at a high temperature exists. In [A] polymer particles. It is considered that such a phase which does not undergo a phase change upon drying has an effect of suppressing excessive fluidity of the coating material during drying and improving the uniformity of the coating film.

(Average particle diameter) The lower limit of the average particle diameter (Da) of the [A] polymer particles is preferably 30 nm, more preferably 50 nm. As the upper limit of the Da, it is preferably 400 nm, more preferably 300 nm. By setting Da of the [A] polymer particles to the above range, a dense coating film can be formed at the time of film formation, and thus deterioration of weather resistance can be effectively suppressed.

[A] The Da of the polymer particles is a particle diameter distribution in which the particle size distribution is measured using a particle size distribution measuring apparatus using a light scattering method as a measurement principle, and the number of cumulative numbers of particles when the particles are accumulated from small particles is 50% ( The value of D50). Examples of such a particle size distribution measuring device include "Coulter LS230", "Coulter LS100", and "Coulter LS13 320" (above Beckman Coul) Beckman Coulter. Inc., "FPAR-1000" (Otsuka Electronics Co., Ltd.), and the like. In the particle size distribution measuring apparatus, not only the primary particles of the [A] polymer particles but also the secondary particles which can be formed by aggregating the primary particles are also evaluated. Therefore, the particle size distribution measured by the particle size distribution measuring apparatus can be used as an index of the dispersion state of the [A] polymer particles contained in the coating material.

(Tetrahydrofuran (THF) insoluble component) The THF insoluble component of the [A] polymer particles is preferably 70% by mass or more, and more preferably 80% by mass or more. The THF insoluble component is an indicator of the solvent resistance of the obtained coating film. Therefore, when the THF-insoluble component is in the above range, it is possible to suppress polymerization even when an organic solvent-based coating film is further laminated thereon after the coating film is formed using the composition or the coating material. It is more preferable that the object is eluted to the organic solvent-based coating film. Further, the THF insoluble component can also be an indicator of the durability of the obtained coating film. Therefore, it is considered that the coating film is formed on the surface of a tank such as a factory for treating an organic solvent by setting the THF-insoluble component to the above range, whereby durability is improved.

<[B] Liquid medium> The composition contains [B] a liquid medium. As the liquid medium [B], an aqueous medium containing water is preferred. The aqueous medium can contain a non-aqueous medium other than water. From the viewpoint of improving the coatability of the composition, a non-aqueous medium having a standard boiling point of 60 ° C or more and 350 ° C or less can be contained. Specific examples of such a non-aqueous medium include, for example, N-methylpyrrolidone, dimethylformamide, and decylamine such as N,N-dimethylacetamide; toluene, xylene, and n-dodecane. Hydrocarbon such as tetrahydronaphthalene; methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, ethylene glycol, glycerin, propylene glycol, 2-ethyl-1-hexanol, 1-nonanol An alcohol such as lauryl alcohol; a ketone such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, phorbolone, acetophenone or isophorone; ethyl acetate, butyl acetate, benzyl acetate, An ester of isoamyl butyrate, methyl lactate, ethyl lactate, butyl lactate; an amine such as o-toluidine, m-toluidine or p-toluidine; a lactone such as γ-butyrolactone or δ-valerolactone; An anthraquinone such as methyl hydrazine or an anthracene compound such as cyclobutyl hydrazine. When the liquid medium contains a non-aqueous medium other than water and water, the lower limit of the content of water in the liquid medium [B] is preferably 90% by mass, and more preferably 95% by mass. The composition is used as the [B] liquid medium by using an aqueous medium, and the degree of adverse effect on the environment is lowered, and the safety of the treatment operator is also improved.

<[C] Crosslinking Agent> The composition can contain a [C] crosslinking agent. It is considered that the composition contains a [C] crosslinking agent, and the coating film can be densified by crosslinking, and water resistance can be imparted, whereby it can be used under long-term outdoor exposure. As the [C] crosslinking agent, it is preferably dissolved in the [B] liquid medium.

Examples of the [C] crosslinking agent include an anthracene derivative, a carbodiimide compound, an isocyanate compound, an amine compound, an epoxy compound, an oxazoline compound, an acid anhydride, and an aziridine compound.

The anthracene derivative may, for example, be a compound having at least two anthracene groups. The lower limit of the content of the anthracene derivative is preferably 0.02 mol, more preferably 0.2 mol, based on 1 mol of the carbonyl group contained in the [A] polymer particles. With respect to the upper limit of the content, it is preferably 1.1 moles, more preferably 1.0 moles. The content of the anthracene derivative is less than 0.02 mol or more than 1.1 mol, relative to the carbonyl group 1 mol contained in the [A] polymer particles, and sometimes the water resistance or solvent resistance of the formed coating film is changed. Not enough.

Examples of the anthracene derivative having at least two mercapto groups include dioxane oxalate, diammonium malonate, diterpene succinate, diammonium glutarate, diammonium adipate, and m-benzene. The carbon number of diterpene diformate, diterpene azelaic acid, dinonyl dodecanoate, diterpene maleate, diterpene fumarate, and itaconic acid diterpene are 2 to 12, Preferably, the carbon has a carbon number of 2 to 4, such as 4 to 6 dicarboxylic acid diterpene, ethylene-1,2-difluorene, propylene-1,3-dioxin, butene-1,4-dioxene. The water-soluble diterpene of the family. Among these, diterpene adipate, dioxonium isophthalate and diterpene sebacate are preferred. The anthracene derivative has a function of reacting a carbonyl group of the polymer with a thiol group in the anthracene derivative to form a membrane of a network structure when the water of the composition scatters due to drying. In the crosslinking reaction, a catalyst is usually not used, and a water-soluble metal salt such as zinc sulfate, manganese sulfate or cobalt sulfate can be used as a catalyst, if necessary.

As a commercial item of the carbodiimide compound, for example, Union Carbide's UCARLNK Crosslinker XL-29SE, Nisshinbo Chemical's Capodi Carbodilite E-02, Carbodilite E-03A, Carbodilite E-04, Carbodilite E-05, Carbodilite V- 02, Carbodilite SV-02, Carbodilite V-02-L2, Carbodilite V-04, Carbodilite V-10, etc. Among these, Carbodilite E-05, Carbodilite V-02 and Carbodilite V-10 are preferred.

Specific examples of the isocyanate compound include 2,4-toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylene diisocyanate, isophorone diisocyanate, and methyl amide. Isocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, n-pentane-1,4-diisocyanate, terpolymers of these, adducts or condensations of these A diurea or a compound having two or more isocyanate groups among these polymers, a triisocyanate tribasic acid ester, a blocked isocyanate or the like.

Specific examples of the amine compound include a melamine resin, a urea resin, a guanamine resin, an amine adduct, and a polyamine. As a commercial item, Cymel of Mitsui Cytec, Ancamine, Epilink of Air Products, Henkel (Henkel) ) The company's Versamine, Versamid, Fuji Chemical Industry's Tohmide, Fujicure, and Daiichi General's Versamid , Epicure of Nippon Epoxy Resin, Sanmide of Sanwa Chemical, Epomate of Ajinomoto Wait.

Specific examples of the epoxy compound include an epoxy resin and an epoxy-modified decane coupling agent. As a commercial item, Epipe, Epire, Neckon Epoxy Resin, Cardlite, and Cardolite are used. Motoive Performance Materials' Coatosil 1770, Coatosil A-187, etc.

As a commercial item of the oxazoline compound, for example, Epocros K-1010E, Epocros K-1020E, and Epocros K- of Japan Catalyst Co., Ltd. 1030E, Epocros K-2010E, Epocros K-2020E, Epocros K-2030E, Epocros WS-500, Aibocas (Epocros) WS-700 and so on. Among these, Epocros WS-500 and Epocros WS-700 are preferred.

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

In the case where the composition contains the [C] crosslinking agent, the lower limit of the content of the [A] polymer particles is preferably 0.1 part by mass, more preferably 1 part by mass, based on 100 parts by mass of the [A] polymer particles. The upper limit of the content is preferably 20 parts by mass, more preferably 10 parts by mass.

As a method of adding a [C] crosslinking agent, for example, a method in which a solution or a dispersion obtained by dissolving or dispersing a [C] crosslinking agent in water is added to a composition, and [C] is crosslinked. A method in which a solution obtained by dissolving a small amount of a water-soluble organic solvent is added to a composition, a method of directly adding a [C] crosslinking agent to a composition, and the like.

<Other optional components> The composition may contain any components other than the components [A] to [C] as needed. Examples of other optional components include a thickener, an antifoaming agent, a film forming aid, an antifreeze, a pH adjuster, a wettability improver, a pigment, a filler, a weatherability enhancer, and a surface preparation agent. These other optional components may be used alone or in combination of two or more.

Examples of the thickener include a cellulose compound such as carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose; an ammonium salt or an alkali metal salt of the cellulose compound; poly(meth)acrylic acid, a polycarboxylic acid such as modified poly(meth)acrylic acid; an alkali metal salt of the polycarboxylic acid; a polyvinyl alcohol-based (co)polymer such as polyvinyl alcohol, modified polyvinyl alcohol or ethylene-vinyl alcohol copolymer; A water-soluble polymer such as a saponified product of a copolymer of an unsaturated carboxylic acid such as (meth)acrylic acid, maleic acid or fumaric acid and a vinyl ester. Among these, a particularly preferred thickener is an alkali metal salt of carboxymethylcellulose and an alkali metal salt of poly(meth)acrylic acid.

Examples of the commercially available product as a thickener include CMC1120, CMC1150, CMC2200, CMC2280, CMC2450 (above, Daicel), ASE60 (Rohm & Haas), SN612, SN615, SN617, SN618, SN621N (above is San-nopco), Adekanol UH-420 (ADEKA), etc.

Examples of the antifoaming agent include a fluorene-based antifoaming agent, a mineral oil-based antifoaming agent, and a polymer-based antifoaming agent.

Examples of the film-forming auxiliary agent include 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (Texanol), butyl carbitol, and dipropylene glycol methyl ether acetate. Examples of the antifreeze agent include ethylene glycol and propylene glycol. Examples of the pH adjuster include ammonia water and ethanolamine. Examples of the wettability improver include butyl cellosolve and ethyl cellosolve.

Examples of the pigment and the filler include titanium oxide, iron oxide, iron oxide yellow, zinc oxide, and oxidation, such as JR-1000 (Tayca), CR-97, and R-630 (the above is Ishihara Shoji Co., Ltd.). Antimony, indium oxide, antimony-tin oxide, aluminum flakes, scaly aluminum, cobalt blue, zinc antimony white, lead sulfide, zirconia, phthalocyanine, lanthanide, quinacridone , azo, perinone, perylene, indigo/thioindigo, dioxazine, methine/methylimine, isoindolinone, Each pigment of the ketopyrrolopyrrole system, carbon black, diamond black, graphite, fullerene, graphene, nigrosine, carbon nanotubes, carbon nanohorns, white carbon, aluminum hydroxide, Iron hydroxide, tantalum carbide, tantalum nitride, boron nitride, diatomaceous earth, hydrated lime, gypsum, barium carbonate, calcium carbonate, magnesium carbonate, calcium citrate, barium sulfate, bentonite, magnesium oxide, aluminum oxide, cerium oxide , acrylic beads, talc, clay, mica, clay Matter, iron, copper, nickel, gold, silver, zinc, ferrite, stainless steel, chromium oxide, cobalt oxide, zinc green, chrome green, cobalt green, viridian, Guignet Green, cobalt chrome green, scheele's green, smectite, manganese green, pigment green, ultramarine blue, iron blue, rock group blue, cobalt blue, sky blue, copper borate, molybdenum blue, copper sulfide, cobalt violet, Mars Purple (Mars Violet), Manganese Violet, Pigment Violet, Lead Dioxide, Calcium Lead, Zinc Yellow, Chrome Yellow, Loess, Cadmium Yellow, Yellow, Titanium, Lithalge, Pigment Yellow, Cuprous Oxide , cadmium red, selenium red, chrome vermilion, iron dan, zinc white, bismuth white, basic lead sulfate, lead citrate, zirconia, tungsten white, lead, zinc, Bantison white, neighbor Lead phthalate, manganese white, lead sulfate, bone black, thermal black, phytoblack, potassium titanate whisker, molybdenum disulfide, etc. Further, a system in which a metal chelate is formed in the organic pigment can be used, and examples thereof include a copper indigo dye.

Examples of the weather resistance improving agent include a decane compound, a hydrolysis-dehydration condensation product thereof, a light stabilizer, and an ultraviolet absorber.

Examples of the decane compound include methyl triethoxy decane, dimethyl diethoxy decane, and the like.

Examples of the light stabilizer include Hindered Amine Light Stabilizers (HALS). Examples of the HALS include: Adekanol UC-605, Adekastab LA-52 (above, ADEKA), and Tinuvin-123. Low-molecular-weight HALS such as Tinuvin-123DW (above BASF); Adekastab LA-63P, Adekastab LA-68 (above High-molecular-weight type HALS such as ADEKA, and high molecular weight/low molecular weight hybrid HALS such as Adekanol UC-606 (ADEKA).

When the composition contains HALS as the other optional component, the lower limit of the content of the solid content of the HALS with respect to the total solid content of the composition is preferably 0.5% by mass, and more preferably 0.7% by mass. The upper limit of the content is, for example, 20% by mass. Since the composition contains HALS in the range of the content, weather resistance, particularly gloss retention, is further improved. The "solid component" of HALS means the sum of components other than the solvent (including water) in HALS. As the HALS, a high molecular weight/low molecular weight mixed HALS is preferred, and Adekanol UC-606 is more preferred.

Examples of the ultraviolet absorber include, for example, Adekanol UC-3125, Adekanol UC-3140 (above, ADEKA), and Tinuvin 384-. 2 (BASF) and so on.

Examples of the surface preparation agent include a decane compound, an acrylic copolymer, and a methacrylic copolymer.

As a method of adding the other optional component as described above, for example, a method in which a solution or a dispersion obtained by dissolving or dispersing other optional components in water is added to the composition, and other optional components are dissolved in a small amount of water. A method in which a solution obtained in an organic solvent is added to a composition, a method in which other optional components are directly added to a composition, and a method of adding a polymer (Pb) constituting the polymer particles of [A] to a polymerization system Method etc.

[Method for Preparing Composition] The composition can be prepared, for example, by preparing a dispersion of [B] liquid medium containing [A] polymer particles, in which, if necessary, mixing [C] A suspension of the [B] liquid medium of the crosslinking agent and/or other optional components. The lower limit of the solid content concentration of the composition is preferably 1% by mass, more preferably 10% by mass, still more preferably 30% by mass. The upper limit of the solid content concentration is preferably 80% by mass, more preferably 70% by mass, still more preferably 60% by mass.

<Coating Material, Coating Agent> The composition can be suitably used as a coating material, a coating agent, or the like. The term "paint, paint" refers to a fluid applied to the surface of a substrate in order to impart protection, aesthetics, or self-standing function. The "coating film" refers to a film formed by applying a coating material, a coating agent, or the like to a surface of a substrate and then drying it. The coating film formed from the composition is excellent in properties such as adhesion to a substrate, weather resistance, water resistance, and abrasion resistance.

When the composition does not contain a coloring agent, it can be used as a coating material or a coating agent for transparent coating. In addition, the composition can impart a further function to the coating film for coloring or the like, and if necessary, a coloring agent such as an inorganic pigment or an inorganic pigment such as an inorganic pigment or a filler, and the like can be contained, thereby serving as an enamel coating. , coloring agents, etc.

<Coating body> The term "coating body" means an object including a substrate and a coating film formed by coating the coating material, the coating agent, and the like, and drying the coating film. The coating film can be formed by coating the above-described composition on a suitable substrate surface and drying it.

The base material of the coating body is not particularly limited, and examples thereof include a base material such as cement, ceramic tile, slate, metal, plastic, or glass. A coating film formed by coating the composition on the surface of these substrates can also be used as a high durability protective coating material. Further, the coating film can be suitably used as a felt (felt) in addition to an insulating coating film or an anti-corrosive coating film which is required for outdoor use, such as construction, building materials, automobiles, and the like, which is required for durability and contamination resistance. ) or impregnated materials of porous materials such as glass and paper, packaging materials, protective films for fibers, fabrics or mats.

The coating method of the composition onto the substrate is not particularly limited. Examples of the coating method include a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, and an extrusion method. , dipping method, brush coating method, spray coating, roll coating, bar coater, blade coater, screen printing, spin coater, applicator, flow coater, centrifugal coater, ultrasonic A suitable method such as a coater or flexographic printing.

The coating amount of the composition is not particularly limited, and the thickness of the coating film formed by removing the liquid medium (concept of water and any non-aqueous medium used arbitrarily) is preferably a dry film thickness. In the case of coating once, the thickness is about 0.05 μm to 50 μm, and when it is applied twice, the thickness is about 0.1 μm to 100 μm.

Although the composition can be directly applied to a substrate, it is also possible to form a primer (primer) such as an epoxy-based, urethane-based, melamine-based, or alkyd-based resin on the substrate in accordance with the use. A layer or an intermediate coating layer is applied to this layer, and in addition, an anti-corrosion layer of a zinc-rich paint or the like can be provided and coated on the layer.

The drying method (the method of removing water and any non-aqueous medium to be used) which is applied to the substrate is not particularly limited. For example, in addition to natural drying, drying by warm air, hot air or low humidity can be used; Drying; drying by irradiation of (far) infrared rays, electron beams, or the like. The drying speed can be appropriately set in such a manner that the liquid medium [B] can be removed as quickly as possible within a speed range in which cracks occur in the coating film due to stress concentration or peeling of the coating film from the substrate.

The lower limit of the arithmetic mean roughness (Ra) of the surface of the coating film in the coating body is preferably 0.5 nm, more preferably 0.7 nm, and still more preferably 0.9 nm. The upper limit of the Ra is preferably 100 nm, more preferably 70 nm, and still more preferably 60 nm. When the Ra of the surface of the coating film is in the above range, the blocking resistance and the stain resistance of the coated body can be further improved. Ra on the surface of the coating film is a value obtained by a measurement method according to JIS B0601:2013. [Examples]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited by these examples.

<[A] Synthesis of Polymer Particles> [Synthesis Example 1] After the inside of the autoclave having an internal volume of about 6 L including an electromagnetic stirrer was sufficiently replaced with nitrogen, 2.5 L of deoxidized pure water and emulsifier were added. 25 g of perfluorononanoic acid was heated to 60 ° C while stirring at 350 rpm. Next, a mixed gas containing 88% by mass of vinylidene fluoride (VDF), 6% by mass of tetrafluoroethylene (TFE), and 6% by mass of hexafluoropropylene (HFP) as a monomer was added until the internal pressure reached 20 kg/cm ^{2 .} until. The polymerization was started by injecting 25 g of a trichlorotrifluoroethane (Flon-113) solution containing 20% by mass of diisopropyl peroxydicarbonate as a polymerization initiator. In the polymerization, a mixed gas containing 88% by mass of VDF, 65% by mass of TFE, and 65% by mass of HFP was sequentially introduced so as to maintain the internal pressure at 20 kg/cm ² . Further, as the polymerization progressed, the polymerization rate was lowered. Therefore, after 3 hours, the same composition as the polymerization initiator solution and the same polymerization initiator solution were introduced by using nitrogen gas, and the reaction was further continued for 3 hours. Then, the reaction liquid was cooled while stirring was stopped, and the unreacted monomer was released, and the reaction was stopped, whereby an aqueous dispersion containing 40% by mass of the polymer (Pa) particles was obtained. The obtained polymer was analyzed by ¹⁹ F-NMR, and as a result, the mass composition ratio of each monomer was VDF/TFE/HFP = 14/1/2.

After sufficiently replacing the inside of the separable flask with nitrogen, 42.5 parts by mass of the obtained aqueous dispersion containing the polymer (Pa) (17 parts by mass of the polymer), polyoxyethylene lauryl ether sulfate 1 part by mass of sodium and 9 parts by mass of water. In another container, "Adeka Reasoap SR1025" (ADEKA) was mixed as an emulsifier with respect to 17 parts by mass of the polymer contained in the aqueous dispersion. Parts by mass, methyl methacrylate (MMA) 26.3 parts by mass, 2-ethylhexyl acrylate (EHA) 40 parts by mass, cyclohexyl methacrylate (CHMA) 20 parts by mass, hydroxyethyl methacrylate (HEMA) 5 parts by mass, polyethylene glycol methacrylate (PEGMA) ("PE-200" of Nippon Oil Co., Ltd.) 1 part by mass, 1,2,2,6,6-pentamethyl-4-methacrylate 1 part by mass of piperidine ester (PMPMA) ("LA-82" of ADEKA), 5 parts by mass of diacetone acrylamide (DAAM), and ammonium represented by the formula (A) shown below After 0.5 parts by mass of the ionic compound (A), 1.2 parts by mass of acrylic acid (AA), and 80 parts by mass of water, the monomer emulsion was prepared by sufficiently stirring. Then, the separable flask was started to be heated by a water bath, and 0.3 parts by mass of ammonium persulfate as a polymerization initiator was added at the time when the internal temperature of the separable flask reached 50 °C.

[Chemical 3]

When the internal temperature of the separable flask reached 75 ° C, the preparation of the prepared monomer emulsion was started, and the monomer emulsion was slowly added for 2 hours while maintaining the internal temperature of the separable flask at 75 ° C. . Then, the internal temperature of the separable flask was raised to 85 ° C, and the temperature was maintained for 1 hour to carry out a polymerization reaction to form a polymer (Pb), and a polymer particle containing the polymer (Pa) and the polymer (Pb) was synthesized. (S1).

Then, the separable flask was cooled, aqueous ammonia and water were added, and the pH was adjusted to 7.6 to obtain an aqueous dispersion containing 46% by mass of the polymer particles (S1). Further, the content of the ammonium ion group in the polymer (Pb) was quantified by ¹ H-NMR and found to be 0.8 mmol/100 g.

(Average particle size) The particle size distribution is measured using a particle size distribution measuring apparatus ("FPAR-1000" of Otsuka Electronics Co., Ltd.) using a dynamic light scattering method as a measurement principle, and the particle size distribution is obtained from the particle size distribution. As a result of the average particle diameter, the average particle diameter of the particles of the polymer particles (S1) was 160 nm.

(Measurement of THF-insoluble matter and DSC) About 10 g of the obtained aqueous dispersion was weighed into a Teflon (registered trademark) dish having a diameter of 8 cm, and dried at 120 ° C for 1 hour to form a film. 1 g of the obtained film (polymer) was immersed in 400 mL of tetrahydrofuran (THF), and shaken at 50 ° C for 3 hours. Then, the THF phase was filtered through a 300-mesh metal mesh to separate the insoluble components, and then the THF solvent was evaporated from the THF phase, and the measured value of the mass (Y (g)) of the obtained residue was expressed by the following formula (6). The THF insoluble matter (%) was determined. THF-insoluble matter (%) = ((1 - Y) / 1) × 100 (6) The THF-insoluble content of the polymer particles (S1) was 86% by mass. Further, the polymer particles (S1) were measured by a differential scanning calorimeter (DSC), and as a result, an endothermic peak was observed at 11 ° C and 91 ° C, respectively.

(Empirical potential) The obtained aqueous dispersion was diluted so that the solid content concentration was 0.01% by mass, and the kinematic potential was measured using "ELS-6000" of Otsuka Electronics Co., Ltd. The measured values of the kinematic potential are shown together in Tables 1 and 2. The larger the absolute value of the kinematic potential, the higher the stability of the [A] polymer particles. The dynamic potential can be evaluated as "S" (very good) when the absolute value is 50 mV or more, and "A" (good) when the absolute value is 30 mV or more and less than 50 mV. When the value is 10 mV or more and less than 30 mV, it is evaluated as "B" (slightly defective), and when the absolute value is less than 10 mV, it is evaluated as "C" (poor). The dynamic potential of the polymer particles (S1) was -41 mV.

[Synthesis Example 2 to Synthesis Example 29] The composition and the amount of the monomer and the molecular weight modifier to be used were as shown in Tables 1 and 2, respectively. An aqueous dispersion of % by mass of polymer particles (S2) to polymer particles (S29). In the synthesis of the polymer (Pb), when 0.5 parts by mass of the compound (A) (molecular weight 657) as a monomer having a cationic group is used in 100 parts by mass of all the monomers, the polymer (Pb) is presumed. The content of the cationic group in the mixture was 0.76 mmol/100 g. "-" in Tables 1 and 2 indicates that the corresponding compound was not used.

[Synthesis Example 30] After sufficiently replacing the inside of the separable flask with nitrogen, 0.5 parts by mass of "Adeka Reasoap SR1025" as an emulsifier, 1 part by mass of MMA, and 1 part by mass of CHMA were added. 0.5 parts by mass of AA and 30 parts by mass of water were mixed and thoroughly stirred to prepare a monomer emulsion. Then, the temperature was raised by a water bath, and when the internal temperature of the separable flask reached 50 ° C, 0.3 parts by mass of ammonium persulfate as a polymerization initiator was added, and the temperature was raised to 75 ° C, and the polymerization containing the synthesis example 1 was added. 21.3 parts by mass of the aqueous dispersion of the particles of the material (Pa) (8.5 parts by mass of the polymer). In another container, 21.3 parts by mass (8.5 parts by mass of the polymer) of the polymer-containing (Pa)-containing particles obtained in Synthesis Example 1 and polyoxyethylene lauryl ether sulfate 1 mass were added. 9 parts by weight and water. 0.5 parts by mass of "Adeka Reasoap SR1025" as an emulsifier, 0.23 parts by mass of MMA, 39 parts by mass of EHA, and CHMA 1 were mixed with 8.5 parts by mass of the polymer contained in the aqueous dispersion. Parts by mass, HEMA 5 parts by mass, PEGMA 1 part by mass, 1 part by mass of PMPMA, 5 parts by mass of DAAM, 0.5 parts by mass of the compound (A), 0.7 parts by mass of AA, and 50 parts by mass of water, and sufficiently stirred to prepare a monomer emulsion liquid. The prepared monomer emulsion was started to be added to the separable flask, and the monomer emulsion was slowly added over 2 hours while maintaining the internal temperature of the separable flask at 75 °C. Then, the internal temperature of the separable flask was raised to 85 ° C, and the temperature was maintained for 1 hour to carry out a polymerization reaction to form a polymer (Pb), and a polymer particle containing the polymer (Pa) and the polymer (Pb) was synthesized. (S30).

The abbreviations of the respective monomers in Tables 1 and 2 represent the following compounds, respectively. VDF: vinylidene fluoride TFE: tetrafluoroethylene HFP: hexafluoropropylene MMA: methyl methacrylate EHA: 2-ethylhexyl acrylate LA: lauryl acrylate CHMA: cyclohexyl methacrylate HEMA: methacrylic acid 2-hydroxyethyl ester MAPS: γ-methacryloxypropyltrimethoxydecane BA: butyl acrylate PEGMA: polyethylene glycol methacrylate ("PE-200" of Nippon Oil Co., Ltd., average oxygen extension Ethyl addition molar number: 4.5) PMPMA: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate ("LA-82" by ADEKA) DAAM : Diacetone acrylamide DMAA: N,N-dimethyl methacrylate AA: Acrylic acid

Further, the compound (B) in Tables 1 and 2 represents a compound represented by the formula (B) shown below.

[Chemical 4]

The average particle diameter, the THF-insoluble component, the endothermic peak temperature, and the kinematic potential were evaluated for each [A] polymer particle. The evaluation results are shown together in Tables 1 and 2.

[Table 1]

[Table 2]

(Content of Residual Monomer) The content of the residual monomer in the aqueous dispersion containing 46% by mass of the polymer particles (S5) was 690 ppm by mass (MMA: 150 ppm by mass, EHA: 140 mass) Ppm, CHMA: 400 mass ppm). Further, the content of the residual monomer in the aqueous dispersion containing 46% by mass of the polymer particles (S28) was 1,100 ppm by mass (MMA: 520 ppm by mass, EHA: 250 ppm by mass, and CHMA: 330 ppm by mass).

<Preparation of Composition> The components other than the synthesized [A] polymer particles used to prepare the composition are shown below.

([C] Crosslinker) C-1: "Carbodilite V-02" by Nisshinbo Chemical Co., Ltd. C-2: "Carbodilite E-05" by Nisshinbo Chemical Co., Ltd. C- 3: Diterpene adipate

(Other optional ingredients) (filler) sulfonic acid modified colloidal cerium oxide ("Pl-3D" of Fuso Chemical Industry Co., Ltd.) (weathering enhancer) hindered amine light stabilizer (ADEKA) "Adekanol UC-606") (filming aid) 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (Texanol)

[Example 1] 108.7 parts by mass (containing 50 parts by mass of polymer particles (S1)) containing an aqueous dispersion of polymer particles (S1) as the polymer particles of [A], added as [C] 1.1 parts by mass of the (C-3) (dioxalate adipate) and 1.65 parts by mass of water were suspended in an aqueous suspension at 300 rpm. Further, 5 parts by mass of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate as a coalescence aid was added, and the mixture was again stirred at 300 rpm to prepare a composition (T1).

[Examples 2 to 27 and Comparative Examples 1 to 7] Except that the types and amounts of [A] polymer particles, [C] crosslinking agent, and other optional components were changed as shown in Tables 3 and 4 A composition (T2) to a composition (T27) and a composition (CT1) to a composition (CT7) were prepared in the same manner as in the above Example 1. "-" in Tables 3 and 4 indicates that the corresponding ingredients are not used.

<Evaluation> The following items were evaluated by the methods shown below for the obtained composition. The evaluation results are shown together in Tables 3 and 4.

[Normal Temperature Film Forming Property of Coating Film] The obtained film was coated on a hard aluminum substrate which was previously coated with a water-based epoxy undercoat material and calcined at 120 ° C using an applicator having a gap value of 200 μm. The composition was allowed to stand at normal temperature (25 ° C) for 1 week to form a coating film. The appearance of the formed coating film was visually observed. The film-forming property at room temperature of the coating film was evaluated as "A" (good) when no crack or bulge was observed in the appearance of the coating film, and cracks or bulging were observed in the appearance of the coating film (at the end portion, etc.). The evaluation was "B" (slightly defective), and it was evaluated as "C" (poor) when half or more of the coating film was powdery and was not formed into a film.

[Initial Gloss] The 60° gloss of the obtained coating film was measured using a "Micro-Tri-Gloss-S" of BYK-GARDNER. In the case where glossiness is required for the coating film, the larger the initial gloss value, the better. The initial gloss was evaluated as "A" (good) in the case of 70 or more, "B" (slightly defective) in the case of 50 or more and less than 70, and "C" in the case of less than 50 ( bad).

[Substrate Adhesion] The obtained coating film was cross-cut in a 2 mm square using a cutter (25 squares of 5 × 5), and a glass tape (Sellotape) manufactured by Nichiban was used. The adhesion test of (registered trademark) was evaluated according to the following criteria. The adhesion of the substrate was evaluated as "A" (good) when there was no peeling of the coating film, and "B" (slightly defective) when the peeling of the coating film was less than half, and peeling off of the coating film It is evaluated as "C" (bad) for more than half of the cases.

[Water resistance] The obtained composition was applied onto a glass substrate using an applicator having a gap value of 200 μm, and left at room temperature (25 ° C) for one week to form a coating film. The glass plate with a coating film obtained in this manner was immersed in warm water of 50 ° C for 24 hours, and the whitening and bulging state of the coating film immediately after taking out was visually observed, and the water resistance of the coating film was evaluated. Regarding the whitening of the coating film, it was evaluated as "A" (very good) in the case where whitening of the coating film was not observed, or whitening was passed through and the whitening of the coating film disappeared after leaving for 5 hours at normal temperature. The opaque whitening was observed, but after the removal, the whitening of the coating film disappeared at room temperature for 5 hours, and it was evaluated as "B" (good), opaque whitening was observed in the coating film, and it was passed at room temperature after removal. In the case where whitening did not disappear after an hour, it was evaluated as "C" (poor). Regarding the bulging of the coating film, it was evaluated as "A" (very good) in the case where the coating film was not bulged, and it was evaluated as "B" (good) in the case where the coating film bulging was slightly permitted, and visible coating was observed. When the film was greatly bulged, it was evaluated as "C" (poor).

[Weather resistance] The coating film obtained by the same method as the film-forming property evaluation of the film at room temperature was subjected to a metal weatherer (Daipla-Wintes) for 1,000 hr. The weather resistance test was accelerated, and the 60° gloss of the coating film before and after the test was measured, and the gloss retention ratio (gloss after test × 100 / gloss before the test) (%) was calculated. For the test conditions, light of 295 nm to 780 nm was irradiated with a KF-1 filter using a metal halide lamp source, and irradiation (63 ° C, 50% RH and 75 mW/cm ² ) 4 hr and dark (30 ° C) , 98% RH) 4 hr cycle conditions. The weather resistance can be evaluated as "A" (very good) when the gloss retention is 80% or more, and "B" (good) when the gloss retention is 60% or more and less than 80%. When the gloss retention rate was less than 60%, it was evaluated as "C" (poor). Further, visual observation of crack occurrence on the film surface after the test was performed. When the crack is not observed in the coating film, it is judged as "A" (good), and when the crack is slightly permitted in the coating film, it is judged as "B" (good), and a large number of cracks are observed in the coating film. In the case, it is judged as "C" (bad).

[Abrasion resistance] The coating film obtained by the same method as the water resistance evaluation was placed in a friction fastness tester ("RT-300" of Daiei Scientific Seiki Co., Ltd.). A dust-free paper (Bemcot) (Asahi Kasei Co., Ltd.) was fixed on a rubbing head (self-weight of 500 g), and the film was reciprocated 10 times on a film, and the fog before and after the test was measured by a haze meter ("NDH-5000" by Nippon Denshoku Industries Co., Ltd.). Degree change (difference in value). Regarding the abrasion resistance, when the haze change is less than 0.3, it is judged as "S" (very good), and when the haze change is 0.3 or more and less than 0.6, it is judged as "A" (good), in haze When the change is 0.6 or more and less than 1.0, it is judged as "B" (slightly good), and when the haze change is 1.0 or more, it is judged as "C" (bad).

[Storage Stability of Liquid] The prepared composition was filled in a resin bottle of 1,000 g, and stored in a room set at 25 ° C for 6 months, and the change in viscosity of the composition after storage was measured. The storage stability of the liquid was evaluated as "A" (good) when the viscosity change was less than 10%, and "B" (bad) when the viscosity change was 10% or more.

[Foaming property of liquid] 5 g of the prepared composition was filled in a 20 mL screw-bottomed vial, and shaken up and down 20 times by hand, and the bubble of the liquid surface after being left for 5 minutes was visually observed. Regarding the foaming property of the liquid, if the bubble disappeared, it was evaluated as "A" (good), and if the bubble basically disappeared, it was evaluated as "B" (slightly good), and if the bubble was largely left, it was evaluated as "C" (bad).

(Arithmetic average roughness of the surface of the coating film) According to JIS B0601:2013, the atomic force microscope (Bruker AXS) "Dimension Fast Scan" was used to measure the film forming property at room temperature of the coating film. The arithmetic mean roughness (Ra) of the surface of the coating film obtained by the same method. The Ra of the surface of the coating film obtained from the composition (T5) was 2.3 nm. The Ra of the surface of the coating film obtained from the composition (T25) was 20.0 nm. The Ra of the surface of the coating film obtained from the composition (CT4) was 1.1 nm.

[table 3]

[Table 4]

According to Example 1 to Example 27, the storage stability of the composition and the water resistance, weather resistance and abrasion resistance of the coating film were good. On the other hand, some of these characteristics of the compositions of Comparative Examples 1 to 7 were defective.

The present invention is not limited to the embodiment described above, and various modifications can be made. The present invention includes substantially the same structures as those described in the embodiments (for example, structures having the same functions, methods, and results, or structures having the same objects and effects). Moreover, the present invention encompasses a structure in which non-essential portions of the structures described in the embodiments are replaced with other structures. Furthermore, the present invention also includes a configuration that exhibits the same operational effects as those described in the embodiments, or a configuration that can achieve the same object. Furthermore, the present invention also includes a structure obtained by adding a known technique to the structures described in the embodiments. [Industrial availability]

According to the composition of the present invention, it is excellent in storage stability over a long period of time, and it is possible to form a coating film having excellent properties such as adhesion to a substrate, weather resistance, water resistance, and abrasion resistance. Therefore, the composition can be suitably used as a paint, a paint, or the like.

no

no

Claims (3)

A coating film composition comprising: polymer particles and a liquid medium, the polymer particles comprising: a first polymer having a repeating unit derived from a fluorine-containing vinyl monomer; and a second polymer having A repeating unit derived from an unsaturated carboxylic acid ester and a repeating unit containing a cationic group. The coating film composition according to claim 1, wherein the content of the cationic group in the second polymer is 0.5 mmol/100 g or more and 50 mmol/100 g or less. The coating film composition according to the above aspect, wherein the content of the first polymer in the polymer particles is more than 0% by mass and less than 15% by mass.