JP2019081884A - Composition - Google Patents

Abstract

To provide a composition excellent in storage stability and capable of forming a coating film excellent in adhesion to a substrate, weather resistance, water resistance, and wear resistance.SOLUTION: The 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 ethylenic 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 mass% and less than 15 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a composition.

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

  In order to improve the strength and stability of a coating film, Patent Document 3 and Patent Document 4 disclose a technique of blending an organosilicon-based oligomer with a fluorine-containing polymer. In addition, Patent Document 5 discloses an aqueous dispersion of composite polymer particles of a fluorine-containing polymer and a (meth) acrylic polymer, and an aqueous dispersion of composite polymer particles of an organosilicon compound and a (meth) acrylic polymer. Disclosed are compounding techniques with the dispersion. However, regardless of which technology is used, the storage stability of the composition, the adhesion between the resulting coating film and the substrate, and the properties of the coating film such as weather resistance, water resistance and abrasion resistance are sufficient. Absent.

Japanese Patent Application Laid-Open No. 10-120858 JP, 2009-227754, A Unexamined-Japanese-Patent No. 08-120211 gazette WO 98/23680 JP 2003-286440 A

  The present invention has been made based on the above circumstances, and the object of the present invention is to provide a coating which is excellent in storage stability and excellent in properties such as adhesion to a substrate, weather resistance, water resistance and abrasion resistance. It is an object of the present invention to provide a composition capable of forming a film.

  The invention made to solve the above problems contains polymer particles (hereinafter also referred to as “[A] polymer particles”) and a liquid medium (also referred to as “[B] liquid medium”), [A] A polymer particle is a first polymer having a repeating unit derived from a fluorine-containing ethylene-based monomer (hereinafter, also referred to as "polymer (Pa)") and a repeat derived from an unsaturated carboxylic acid ester It is a composition containing a second polymer (hereinafter also referred to as “polymer (Pb)”) having a repeating unit containing a unit and a cationic group.

  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.

  According to the composition of the present invention, it is possible to form a coating film which is excellent in storage stability over a long period of time and which is excellent in 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 coating agent and the like.

  Hereinafter, preferred embodiments according to the present invention will be described in detail. It is to be understood that the present invention is not limited to only the embodiments described below, but also includes various modifications implemented within the scope of the present invention. In addition, "-(meth) acrylate" in this specification is the concept which includes both "-acrylate" and "-methacrylate." "(Meth) acrylic acid ~" is a concept encompassing both "acrylic acid ~" and "methacrylic acid ~".

<Composition>
The composition contains [A] polymer particles and [B] liquid medium. The composition may contain a [C] crosslinking agent as a suitable component, and may contain other optional components as long as the effects of the present invention are not impaired. Each component will be described in detail below.

<[A] polymer particle>
[A] The polymer particle has a polymer (Pa) having a repeating unit derived from a fluorine-containing ethylene-based monomer, and a repeating unit containing a repeating unit derived from an unsaturated carboxylic acid ester and a cationic group It contains a polymer (Pb). [A] The polymer particles may contain other polymers other than the polymer (Pa) and the polymer (Pb), but may be composed only of the polymer (Pa) and the polymer (Pb) preferable. [A] polymer particles are usually latex-like particles dispersed in a [B] liquid medium. [A] The polymer particles may contain components other than the polymer.

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

(Repeating unit derived from fluorine-containing ethylene-based monomer)
The fluorine-containing ethylene-based monomer is a compound having an ethylenic carbon-carbon double bond and a fluorine atom. Examples of the fluorine-containing ethylene-based monomer include fluorinated olefin, fluorinated chlorinated olefin, (meth) acrylate having a fluorine atom, and perfluoroalkyl vinyl ether. As fluorinated olefins, for example, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene and the like, and as fluorinated chlorinated olefins, for example, trifluorinated chlorinated ethylene and the like, and as a (meth) acrylate having a fluorine atom, For example, a compound represented by the formula (a) shown below, (meth) acrylic acid 3- [4 [1-trifluoromethyl-2,2-bis [bis (trifluoromethyl) fluoromethyl] ethynyloxy] benzoxy] -2-hydroxypropyl and the like, and examples of the perfluoroalkylvinylether include trifluoromethyltrifluorovinylether, heptafluoropropyltrifluorovinylether and the like.

In said Formula (a), R ¹ is a hydrogen atom or a methyl group. R ² is a C 1-18 monovalent fluorocarbon group.

Examples of R ² in the formula (a) include C 1-12 fluorinated alkyl groups, C 6-16 fluorinated aryl groups, and C 7-18 fluorinated aralkyl groups. Among these, a C1-C12 fluorinated alkyl group is preferable. Preferred specific examples of R ² include 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,1,3,3,3-hexafluoropropane -2-yl group, β- (perfluorooctyl) ethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,4,4,4-hexafluorobutyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 9H-hexadecafluoro-1-nonyl group, 1H, 1H, 11H-icosafluoroundecyl group and perfluorooctyl group can be mentioned.

  Among these, as the fluorine-containing ethylene-based monomer, fluorinated olefins are preferable, vinylidene fluoride, tetrafluoroethylene and propylene hexafluoride are more preferable, and vinylidene fluoride and propylene hexafluoride are more preferable. Vinylidene fluoride is particularly preferred. When these compounds are used as the fluorine-containing ethylene-based monomer, the stability of the system during emulsion polymerization is further improved, and the polymer particles of [A] can be formed more effectively. The fluorine-containing ethylene-based monomer may be used alone or in combination of two or more.

(Repetitive units derived from other monomers)
As the other monomers, monomers described in WO 2014/112252 can be used, and examples thereof include unsaturated carboxylic acid, α, β-unsaturated nitrile, carbonyl group-containing compound, conjugated diene And aromatic vinyl compounds, vinyl ethers, allyl ethers, polymerizable group-containing alkoxysilanes, unsaturated carboxylic acid esters and the like. The other monomers may be used alone or in combination of two or more.

  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. Among these, acrylic acid, methacrylic acid and itaconic acid are preferred.

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

  Examples of the carbonyl group-containing compound include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, N, N -Dimethylaminopropyl (meth) acrylamide, N- hydroxyethyl (meth) acrylamide, acryloyl morpholine, acrolein etc. are mentioned.

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

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

  Examples of vinyl ethers 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.

  Examples of allyl ethers 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, propylene glycol mono Allyl ether etc. are mentioned.

As a polymeric group containing alkoxysilane, the compound etc. which are represented by Formula (b) shown below are mentioned.
R ³ _n Si (OR ⁴ ) _4-n (b)
(In the above formula (b), R ³ is a monovalent organic group having 1 to 8 carbon atoms. However, at least one of R ³ has a polymerizable group. R ⁴ has 1 carbon atom. And n is an integer of 0 to ^{3. When} R ³ is plural, plural R ^{3 s} may be the same or different, and when R ⁴ is plural, plural R ^{3 s} may be plural. R ⁴ may be the same or different.)

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

In formulas (b) and (c), examples of the polymerizable group in R ³ and R ⁵ include a vinyl group, 1-propenyl group, (meth) acryloyl group and the like. Among these, (meth) acryloyl group is preferable. Examples of the monovalent organic group having a polymerizable group represented by R ³ include γ- (meth) acryloxypropyl group and the like. The monovalent organic group of R ³ and R ^5, preferably an alkyl group having 1 to 8 carbon atoms, more preferably a methyl group and an ethyl group. The monovalent organic group represented by R ^4, for example, an alkyl group having 1 to 8 carbon atoms, an aryl group, an acyl group, and the like. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group and the like. Examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group and the like. The acyl group is preferably an acyl group having a carbon number of 1 to 6, and examples thereof include an acetyl group, a propionyl group, a butyryl group, a valeryl group and a caproyl group.

  Examples of unsaturated carboxylic acid esters include alkyl esters of unsaturated carboxylic acids and hydroxyalkyl esters of unsaturated carboxylic acids. "Alkyl ester" means an ester containing linear, branched and cyclic alkyl groups.

  When 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 based on all repeating units constituting the polymer (Pa) The content is at least 99.9 mass%, preferably at most 10 mass%.

  As content of the polymer (Pa) in [A] polymer particle, more than 0 mass% is preferable, and 5 mass% or more is more preferable. As said content, less than 15 mass% is preferable, and 10 mass% or less is more preferable. [A] By setting the content of the polymer (Pa) in the polymer particles in the above range, a coating film having a better balance between the film forming property and the adhesion can be formed.

[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 have other repeating units other than these repeating units.

(Repeating unit derived from unsaturated carboxylic acid ester)
Examples of unsaturated carboxylic acid esters include alkyl esters of unsaturated carboxylic acids, hydroxyalkyl esters of unsaturated carboxylic acids, polyalkylene glycol esters of unsaturated carboxylic acids, amino group-containing esters of unsaturated carboxylic acids, and polymerizable groups. An alkoxysilane etc. are mentioned. "Alkyl ester" means an ester containing linear, branched and cyclic alkyl groups. The unsaturated carboxylic acid ester may be used alone or in combination of two or more.

  Examples of alkyl esters of unsaturated carboxylic acids include methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, etc. And alkyl esters of (meth) acrylic acid.

  Examples of hydroxyalkyl esters of unsaturated carboxylic acids include hydroxyalkyl esters of (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate.

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

  Examples of amino group-containing esters of unsaturated carboxylic acids include amino (meth) acrylates such as (meth) acrylic acid 1,2,2,6,6-pentamethyl-4-piperidyl, dimethylaminoethyl (meth) acrylate and the like Group containing ester etc. are mentioned.

  As a polymeric group containing alkoxysilane, the compound etc. which were illustrated as another monomer of a polymer (Pa), for example are mentioned. Among these, γ-methacryloxypropyltrimethoxysilane 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 with respect to all the repeating units constituting the polymer (Pb). As an upper limit of the said content rate, 98 mass% is preferable, and 95 mass% is more preferable.

(Repeating unit containing a cationic group)
The cationic groups, for example groups of secondary ammonium salt (secondary amine ^{_{salts) ((-NH 2 R 2)}} + X -), groups of tertiary ammonium salts (salt of a tertiary amine) ((-NHR ₃₎ ⁺ X ^-), groups of quaternary ammonium salt _{^{((-NR 4) + X -}} ), groups of the sulfonium salt _{^{((-SR 2) + X -}} ), groups of phosphonium salt _((-PR ^{3) +} X ^-), and the like. Each R is independently a monovalent organic group. Each of X ^- is independently a counter anion. Among these, as the cationic group, a secondary, tertiary or quaternary ammonium salt group is preferred. The cationic group may contain one kind alone or plural kinds.

  The lower limit of the content of the cationic group in the polymer (Pb) is preferably 0.5 mmol / 100 g, and more preferably 1.0 mmol / 100 g. As a maximum of the content, 50 mmol / 100 is preferable, and 30 mmol / 100 g is more preferable. By making content of a cationic group into the said range, it is excellent by the normal temperature film-forming property and the foaming suppression property of a liquid, and is excellent by the initial stage glossiness of a coating film, base material adhesiveness, water resistance, weather resistance, and abrasion resistance. .

  The content of the cationic group in the polymer (Pb) can be measured, for example, by NMR, ion chromatography, colloid titration or the like. For example, with regard to the quaternary ammonium salt group, after separating the polymer (Pb) from the polymer particles [A] by a method such as solvent extraction, NMR, ion chromatography, and polyvinyl potassium sulfate are used for this polymer (Pb). It can measure by colloid titration etc. which are used as a standard anion.

  As a minimum of the content rate of the repeating unit containing a cationic group, 0.1 mass% is preferred to all the repeating units which constitute polymer (Pb), and 0.5 mass% is more preferred. As an upper limit of the said content rate, 50 mass% is preferable, and 30 mass% is more preferable.

  As a method of introducing a repeating unit containing a cationic group into a polymer (Pb), for example, a method of copolymerizing a monomer containing a cationic group and a polymerizable monomer copolymerizable therewith (first method And a method (second method) in which a compound containing a cationic group is added to the polymer obtained from the polymerizable monomer.

  As a monomer containing a cationic group used in the first method, for example, an unsaturated monomer containing a secondary, tertiary or quaternary ammonium salt group, an unsaturated monomer containing a sulfonium salt group And unsaturated monomers containing a phosphonium salt group.

  Specific examples of unsaturated monomers containing a secondary, tertiary or quaternary ammonium salt group are, for example, diallyldimethylammonium stearate, 2-hydroxy-3-allyloxypropyltrimethylammonium chloride, vinylbenzyltrimethylammonium chloride (Meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylammonium chloride, (meth) acryloyloxyethylmethylammonium chloride, 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride, (meth) acryloyloxypropyl Dimethyl benzyl ammonium chloride, (meth) acrylamidopropyl trimethyl ammonium chloride, the formula (1) or (2) shown below It includes the compounds represented by.

  In said Formula (1) and (2), n is an integer of 1-30.

  Examples of the unsaturated monomer containing a sulfonium salt group include vinylbenzyldimethylsulfonium chloride, (meth) acryloyloxyethyldimethylsulfonium chloride and the like. Examples of unsaturated monomers containing a phosphonium salt group include vinylbenzyltrimethylphosphonium chloride, (meth) acryloyloxyethyltrimethylphosphonium chloride and the like. The monomers containing these cationic groups may be used alone or in combination of two or more.

(Other repeat unit)
Examples of the monomer giving other repeating units include carbonyl group-containing compounds such as diacetone acrylamide, N, N-dimethyl acrylamide and acryloyl morpholine, unsaturated carboxylic acids such as (meth) acrylic acid, and α such as acrylonitrile And aromatic vinyl compounds such as .beta.-unsaturated nitrile and styrene.

  When a polymer (Pb) has another repeating unit, 0.1 mass% is preferable as a minimum of the content rate of this repeating unit, and 1 mass% is more preferable. As an upper limit of the said content rate, 30 mass% is preferable, and 15 mass% is more preferable.

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

  As a minimum of content of [A] polymer particles, 75 mass% is preferred to total solid of the composition concerned, and 85 mass% is more preferred. The upper limit of the content is, for example, 100% by mass, preferably 98% by mass. The "total solid content" of the composition refers to the total of components other than the [B] liquid medium of the composition.

<[A] Synthesis Method of Polymer Particles>
[A] The polymer particles can be produced, for example, by emulsion polymerization of a predetermined monomer according to a known method to form polymers (Pa) and (Pb). [A] The method for synthesizing the polymer particles is not particularly limited as long as the repeating units of the polymers (Pa) and (Pb) have the constitution as described above. By combining these as appropriate, they can be easily synthesized, and can be synthesized, for example, by the method described in WO 2014/112252.

  [A] A polymer particle forms, for example, a polymer (Pa) having a repeating unit derived from a fluorine-containing ethylene-based monomer by a known method, and then, a polymer (Pb) is formed on the polymer (Pa) A monomer to form a polymer, and after absorbing the monomer into the mesh structure of particles of the polymer (Pa), a unit amount absorbed in the mesh structure of the polymer (Pa) It can be synthesized by polymerizing the body to form a polymer (Pb), and can be obtained, for example, as an aqueous dispersion containing polymer particles of [A].

  When an aqueous dispersion containing 46% by mass of polymer particles [A] is obtained by the above synthesis method, the upper limit of the content of residual monomer in the aqueous dispersion is preferably 1,200 mass ppm, 1, 000 mass ppm is more preferable, and 800 mass ppm is more preferable. As a lower limit of the content, 1 mass ppm is preferable, and 50 mass ppm is more preferable. [A] By setting the content of residual monomer in the aqueous dispersion containing polymer particles in the above range, outgassing generated when forming a coating film from the composition can be further reduced, and odor The reduction can be achieved. Among the monomers used for the production of the polymer (Pa) or the polymer (Pb) constituting the [A] polymer particles, the "residual monomer" refers to the [A] polymer particles without polymerization reaction. It refers to the one remaining in the contained aqueous dispersion, and its content can be measured using gas chromatography.

[Physical Properties of Polymer Particles]
(Endothermic peak temperature)
[A] The polymer particles preferably have at least one endothermic peak in a temperature range of −50 ° C. or more and + 80 ° C. or less, as measured by differential scanning calorimetry (DSC) according to JIS K7121. [A] One temperature of the endothermic peak of the polymer particles is more preferably in the range of -30 ° C to + 70 ° C, and still more preferably in the range of -20 ° C to + 60 ° C. [A] When the temperature of one endothermic peak of the polymer particles is in the above range, the [A] polymer particles can impart better flexibility and adhesiveness to the coating film Therefore, it is preferable in that the adhesion can be further improved.

  In addition to the above-described endothermic peak, the polymer particle [A] has an endothermic peak in the temperature range of more than 80 ° C. and 150 ° C. or less, as measured by differential scanning calorimetry (DSC) according to JIS K7121. Preferably, more than one are observed.

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

  Furthermore, the existence of another endothermic peak in the temperature range of more than 80 ° C. and 150 ° C. or less means that the phase does not change under the above-mentioned drying conditions of the ordinary paint, and the phase changes only at a higher temperature It is meant to be present in the polymer particles. Having a phase that does not undergo a phase change during such drying is considered to be preferable because it has the effect of suppressing the excessive fluidity of the coating during drying and improving the coating uniformity.

(Average particle size)
[A] The lower limit of the average particle size (Da) of the polymer particles is preferably 30 nm, more preferably 50 nm. As a maximum of the above-mentioned Da, 400 nm is preferred, and 300 nm is more preferred. [A] By setting the Da of the polymer particles in the above-mentioned range, a dense coating film can be formed when forming a film, so that the deterioration of the weather resistance can be effectively suppressed.

  [A] The particle size distribution of the polymer particles is measured using a particle size distribution measuring device based on the light scattering method, and the cumulative frequency of particle numbers when particles are accumulated from small particles is 50%. It is a value of particle diameter (D50). Examples of such a particle size distribution measuring apparatus include "Coulter LS230", "Coulter LS100", "Coulter LS13 320" (hereinafter referred to as Beckman Coulter. Inc.), "FPAR-1000" (Otsuka Electronics Co., Ltd.), etc. . These particle size distribution measuring devices do not evaluate only the primary particles of the polymer particles [A], but can also evaluate secondary particles formed by aggregation of primary particles. Therefore, the particle size distribution measured by these particle size distribution measuring devices can be used as an indicator of the dispersion state of the [A] polymer particles contained in the paint.

(Tetrahydrofuran (THF) insoluble matter)
As a THF insoluble content of [A] polymer particle, 70 mass% or more is preferable, and 80 mass% or more is more preferable. The THF insoluble matter is an index of the solvent resistance of the resulting coating film. For this reason, after forming a coating film using the said composition or coating material by making THF insoluble content into the said range, even when it laminates | stacks the coating film of an organic solvent type further on it, it is an organic solvent type It is considered to be preferable because the elution of the polymer into the coating can be suppressed. In addition, the THF insoluble matter can also be one of the indicators of the durability of the obtained coating. For this reason, it is thought that durability is improved by forming a coating film on surfaces, such as a tank of a factory which handles an organic solvent, by making THF insoluble content into the said range.

<[B] liquid medium>
The composition contains a [B] liquid medium. [B] As the liquid medium, an aqueous medium containing water is preferable. The aqueous medium may contain a non-aqueous medium other than water. From the viewpoint of improving the coating properties 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 non-aqueous media include, for example, amides such as N-methyl pyrrolidone, dimethylformamide, N, N-dimethylacetamide; hydrocarbons such as toluene, xylene, n-dodecane, tetralin; methanol, ethanol, isopropyl Alcohols such as n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, glycerin, propylene glycol, 2-ethyl-1-hexanol, 1-nonanol, lauryl alcohol, etc .; methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, phorone Ketones such as acetophenone and isophorone; esters such as ethyl acetate, butyl acetate, benzyl acetate, isopentyl butyrate, methyl lactate, ethyl lactate and butyl lactate; o-toluidine, m- Toluidine, p- amines toluidine; .gamma.-butyrolactone, .delta.-lactone of valerolactone; sulfoxides such as dimethyl sulfoxide, and the like sulfone compound of sulfolane. [B] When the liquid medium contains water and a non-aqueous medium other than water, the lower limit of the water content in the [B] liquid medium is preferably 90% by mass, more preferably 95% by mass. By using an aqueous medium as the [B] liquid medium, the composition is less affected to the environment to a lesser extent, and the safety for handling workers is also enhanced.

<[C] Crosslinking Agent>
The composition can contain a [C] crosslinker. When the composition contains a [C] cross-linking agent, the coating film can be densified by crosslinking, and by imparting water resistance, it is considered that it can be used for long-term outdoor exposure. The [C] crosslinking agent is preferably dissolved in the [B] liquid medium.

  [C] As a crosslinking agent, a hydrazine derivative, a carbodiimide compound, an isocyanate compound, an amino compound, an epoxy compound, an oxazoline compound, an acid anhydride, an aziridine compound etc. are mentioned.

  As a hydrazine derivative, the compound etc. which have an at least 2 hydrazino group are mentioned, for example. As a minimum of content of a hydrazine derivative, 0.02 mol is preferred to 1 mol of carbonyl groups contained in [A] polymer particles, and 0.2 mol is more preferred. The upper limit of the content is preferably 1.1 mol, more preferably 1.0 mol. In the coating film formed even if the content of the hydrazine derivative is less than 0.02 mol or more than 1.1 mol with respect to 1 mol of the carbonyl group contained in the polymer particle [A] Water resistance and solvent resistance may be insufficient.

  As a hydrazine derivative having at least two hydrazino groups, for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, maleic acid dihydrazide , A dicarboxylic acid dihydrazide having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, such as fumaric acid dihydrazide and itaconic acid dihydrazide, ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine and butylene-1,4- Aliphatic water-soluble dihydrazine having 2 to 4 carbon atoms such as dihydrazine etc. may be mentioned. Among these, adipic acid dihydrazide, isophthalic acid dihydrazide and sebacic acid dihydrazide are preferable. The hydrazine derivative has the function of forming a film of a network structure by reacting the carbonyl group of the polymer with the hydrazino group in the hydrazine derivative when the water of the composition is scattered by drying. Although a catalyst is not usually used for this crosslinking reaction, water-soluble metal salts such as zinc sulfate, manganese sulfate and cobalt sulfate can be used as a catalyst if necessary.

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

  Specific examples of the isocyanate compound include, for example, 2,4-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine methyl ester diisocyanate, methylcyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate N-Pentane-1,4-diisocyanate, trimers thereof, adducts and biurets thereof, those polymers having two or more isocyanate groups, lysine triisocyanate, blocked isocyanates Etc.

  Specific examples of the amino compound include, for example, melamine resin, urea resin, guanamine resin, amine adduct, polyamide and the like. Commercially available products include Cymel from Mitsui Cytec, Ancamine from Air Products, Epilink from Henkel, Versamine from Henkel, Toroside from Fuji Kasei Kogyo, Fujicure, Versamide from First General, Epicure from Japan Epoxy Resins, Sanmedo manufactured by Sanwa Chemical Co., Ltd., and epomate manufactured by Ajinomoto Co.

  As a specific example of an epoxy compound, an epoxy resin, an epoxy-modified silane coupling agent, etc. are mentioned, for example. Examples of commercially available products include Epikot from Japan Epoxy Resin Co., Ltd., Epilek, Curdlight from Curdlight, Coatsil 1770 from Momentive Performance Materials, and A-187.

  As a commercial item of an oxazoline compound, epocross K-1010E, K-1020E, K-1030E, K-2010E, K-2020E, K-2030E, WS-500, WS-700 etc. of Nippon Shokubai Co., Ltd. are mentioned, for example. Among these, Epocross WS-500 and WS-700 are preferred.

  As a specific example of an aziridine compound, Chemitite PZ-33, DZ-22E etc. of Nippon Shokubai Co., Ltd. are mentioned, for example.

  When the said composition contains a [C] crosslinking agent, 0.1 mass part is preferred to 100 mass parts of [A] polymer particles as a minimum of this content, and 1 mass part is more preferred. As a maximum of the content, 20 parts by mass is preferable, and 10 parts by mass is more preferable.

  As a method of adding a [C] crosslinking agent, for example, a method of adding or dissolving a [C] crosslinking agent in water to a composition, dissolving the [C] crosslinking agent in a small amount of water-soluble organic solvent And the method of adding the [C] crosslinking agent directly to the composition.

<Other optional components>
The said composition can contain other arbitrary components other than a [A]-[C] component as needed. Other optional components include, for example, thickeners, antifoaming agents, film forming aids, antifreeze agents, pH adjusters, wettability improvers, pigments, fillers, weatherability improvers, surface preparation agents, etc. Be These other optional components may be used alone or in combination of two or more.

  As a thickener, for example, cellulose compounds such as carboxymethyl cellulose, methyl cellulose and hydroxypropyl cellulose; ammonium salts or alkali metal salts of the above-mentioned cellulose compounds; polycarboxylic acids such as poly (meth) acrylic acid and modified poly (meth) acrylic acid Alkali metal salts of the above polycarboxylic acids; polyvinyl alcohol (co) polymers such as polyvinyl alcohol, modified polyvinyl alcohol, ethylene-vinyl alcohol copolymer and the like; unsaturations such as (meth) acrylic acid, maleic acid and fumaric acid Examples thereof include water-soluble polymers such as saponified products of copolymers of carboxylic acid and vinyl ester. Particularly preferred thickeners among these are alkali metal salts of carboxymethylcellulose and alkali metal salts of poly (meth) acrylic acid.

  Commercially available thickeners include, for example, CMC1120, CMC1150, CMC2200, CMC2280, CMC2450 (above, Daicel Corporation), ASE60 (Rohm and Haas), SN612, SN615, SN617, SN618, SN621N (above, San Nopco), Adekanol UH-420 (ADEKA) and the like.

  As an antifoamer, a silicone type antifoamer, a mineral oil type antifoamer, a polymer type antifoamer etc. are mentioned, for example.

  As the film forming aid, for example, texanol, butyl carbitol, dipropylene glycol methyl ether acetate, etc., for example, ethylene glycol, propylene glycol, etc., as the antifreeze agent, for example, ammonia water, ethanolamine, for example, as the pH adjuster Examples of the wettability improver include butyl cellosolve and ethyl cellosolve.

  Examples of pigments and fillers include titanium oxide such as JR-1000 (Taika), CR-97, R-630 (above, Ishihara Sangyo Co., Ltd.), iron oxide, yellow iron oxide, zinc oxide, cerium oxide, indium oxide, Antimony tin oxide, aluminum flakes, scale-like aluminum, cobalt blue, lithopone, lead sulfide, zirconium oxide, phthalocyanines, anthraquinones, quinacridones, azos, perinones, perylenes, perylenes, indigo / thioindigos, dioxazines, Each pigment of methine / azo methine type, isoindolinone type and diketopyrrolopyrrole type, carbon black, diamond black, graphite, fullerene, graphene, aniline black, carbon nanotube, carbon nanohorn, white carbon, aluminum hydroxide, iron hydroxide , Silicon nitride, boron nitride, diatomaceous earth, calcium hydroxide, calcium carbonate, calcium carbonate, magnesium carbonate, calcium carbonate, calcium silicate, 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 green, chromium green, cobalt green, viridian, Guiné green, cobalt chromium green, schee green, green earth, Manganese green, pigment green, ultramarine blue, bitumen, pigment green, rock ultramarine blue, cobalt blue, cerulian blue, copper borate, molybdenum blue, copper sulfide, cobalt purple, malus purple, manganese purple, pigment violet, lead oxide, lead acid Calcium, zinc yellow, chrome yellow, yellow soil, kadomi Mutroyellow, strontium yellow, titanium yellow, liserge, pigment yellow, copper oxide, cadmium red, selenium red, chromium vermillion, bengara, zinc white, antimony white, basic lead sulfate, lead silicate, zircon oxide, tungsten white And lead, zinc flower, bunchison white, lead phthalate, manganese white, lead sulfate, bone black, thermophilic black, vegetable black, potassium titanate whisker, molybdenum disulfide and the like. Moreover, the system which formed the metal chelate to the organic pigment can also be used, and the pigment | dye of a copper phthalocyanine type etc. is mentioned.

  Examples of the weatherability improver include silane compounds and hydrolysis / dehydration condensation products thereof, light stabilizers, and ultraviolet light absorbers.

  Examples of silane compounds include methyltriethoxysilane and dimethyldiethoxysilane.

  Examples of the light stabilizer include hindered amine light stabilizers (HALS) and the like. Examples of HALS include low molecular weight HALS such as adecanol UC-605, adecastab LA-52 (above, ADEKA company), tinuvin-123, tinuvin-123 DW (above, BASF company), adecastab LA-63P, adecastab LA-68. High molecular weight type HALS such as (above, ADEKA company), high molecular weight / low molecular weight mixed type HALS such as adequanol UC-606 (ADEKA company), etc. may be mentioned.

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

  Examples of the ultraviolet absorber include adecanol UC-3125, adecanol UC-3140 (above, ADEKA company), tinuvin 384-2 (BASF company) and the like.

  As a surface preparation agent, a siloxane compound, an acryl-type copolymer, a methacryl-type copolymer etc. are mentioned, for example.

  As a method of adding the other optional components as described above, for example, a method in which other optional components dissolved or dispersed in water is added to the composition, and the other optional components are dissolved in a small amount of water-soluble organic solvent The method of adding what was made to the composition, the method of adding other optional components directly to the composition, the method of adding it to the polymerization system when synthesizing the polymer (Pb) which constitutes the polymer particle of [A] Can be mentioned.

[Method of preparing composition]
The composition prepares, for example, a dispersion of a [B] liquid medium containing [A] polymer particles, and, if necessary, a suspension of the [B] liquid medium of a [C] crosslinking agent in this dispersion. It can be prepared by mixing the liquid 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, and still more preferably 30% by mass. As an upper limit of the said solid content concentration, 80 mass% is preferable, 70 mass% is more preferable, and 60 mass% is more preferable.

<Paint, coating agent>
The composition can be suitably used as a paint, a coating agent and the like. "Paint, coating agent" refers to a fluid that is applied to the surface of a substrate to provide a protective, cosmetic or unique function. "Coating film" refers to a film formed by applying a paint, a coating agent or the like to the surface of a substrate and then drying it. The coating film formed from the said composition is excellent in the adhesiveness with a base material, weather resistance, water resistance, abrasion resistance etc. characteristics.

  When the composition does not contain a colorant, it can be used as a paint or a coating agent for clear coating. In addition, in order to impart a further function to the coating film by coloring or the like, the composition may, if necessary, contain a colorant such as an inorganic or organic compound such as an inorganic pigment, an organic pigment and a filler. Therefore, it can also be used as an enamel paint, a coloring coating agent, etc.

<Painted body>
The "painted body" refers to one having a base material and a coating film formed by applying and drying the composition as a paint, a coating agent or the like. Such a coating film can be formed by applying the above-mentioned composition to the surface of an appropriate substrate and drying it.

  Although it does not specifically limit as a base material of a coating body, For example, base materials, such as a cement, a tile, a slate, a metal, a plastics, glass, are mentioned. A coating film formed by applying the composition to the surface of these substrates can be used as a highly durable protective coating material. Further, the coating film is suitably used as a thermal barrier coating film or an anticorrosion coating film requiring durability and contamination resistance assuming outdoor use such as construction, building materials, automobiles, etc., felt, glass, paper, etc. It can also be suitably used as a processing material impregnated with the porous material of the above, a packing material, a protective film of fibers / textiles and tatami mats.

  It does not specifically limit about the coating method to the base material of the said composition. As the coating method, for example, doctor blade method, dip method, reverse roll method, direct roll method, gravure method, extrusion method, immersion method, brush coating method, spray coating, roller coating, bar coater, knife coater, screen printing, Suitable methods, such as a spin coater, an applicator, a flow coater, a centrifugal coater, an ultrasonic coater, and flexographic printing, may be mentioned.

  The application amount of the composition is also not particularly limited, but the thickness of the coating formed after removal of the liquid medium (which is a concept including both water and an optionally used non-aqueous medium) is The film thickness is preferably about 0.05 to 50 μm in single coating and about 0.1 to 100 μm in double coating.

  The composition can also be applied directly onto the substrate, but depending on the application, an epoxy, urethane, melamine, alkyd or other primer (primer) layer or intermediate layer may be formed in advance on the substrate. In addition to coating on this layer, an anticorrosion layer such as zinc rich paint can be provided and coated on this layer.

  There is no particular limitation on the drying method (water and optionally used non-aqueous medium removal method) after coating on a substrate, for example, in addition to natural drying, drying with warm air, hot air, low humidity air; vacuum Drying: Drying by irradiation of (far) infrared radiation, electron beam or the like can be used. The drying speed is appropriately set so that the [B] liquid medium can be removed as fast as possible within a speed range in which the coating film does not crack or peel off the substrate due to stress concentration. be able to.

  The lower limit of the arithmetic mean roughness (Ra) of the surface of the coating film in the coated body is preferably 0.5 nm, more preferably 0.7 nm, and still more preferably 0.9 nm. As an upper limit of said Ra, 100 nm is preferable, 70 nm is more preferable, and 60 nm is more preferable. When the Ra of the surface of the coating is in the above range, the blocking resistance and the staining resistance of the coated body can be further improved. Ra of the surface of a coating film is the value calculated | required by the measuring method based on JISB0601: 2013.

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

<[A] Synthesis of Polymer Particles>
Synthesis Example 1
After thoroughly replacing the inside of the autoclave with an internal volume of about 6 liters equipped with a magnetic stirrer with nitrogen, 2.5 liters of deoxygenated pure water and 25 grams of ammonium perfluorodecanoate as an emulsifier are charged, and 60 with stirring at 350 rpm It heated up to ° C. Next, a mixed gas consisting of 88% by mass of vinylidene fluoride (VDF) as a monomer, 6% by mass of tetrafluoroethylene (TFE) and 6% by mass of propylene hexafluoride (HFP) was used as an internal pressure of 20 kg / cm ^2. Was charged until it reached. 25 g of a fluorocarbon 113 solution containing 20% by mass of diisopropyl peroxydicarbonate as a polymerization initiator was injected using nitrogen gas to initiate polymerization. During the polymerization, a mixed gas consisting of 88% by mass of VDF, 6% by mass of TFE, and 6% by mass of HFP was successively introduced so as to maintain the internal pressure at 20 kg / cm ² . In addition, since the polymerization rate decreases as the polymerization proceeds, after 3 hours, a polymerization initiator solution having the same composition and the same composition as the polymerization initiator solution is injected using nitrogen gas, and the reaction is continued for another 3 hours did. Then, stirring was stopped simultaneously with cooling the reaction liquid and reaction was stopped after releasing unreacted monomer, to obtain an aqueous dispersion containing 40% by mass of particles of the polymer (Pa). About the obtained polymer, as a result of analyzing by < ¹⁹ > F-NMR, mass composition ratio of each monomer was VDF / TFE / HFP = 14/1/2.

  The inside of the separable flask is sufficiently purged with nitrogen, and then 42.5 parts by mass of the aqueous dispersion containing particles of the polymer (Pa) obtained above (17 parts by mass of polymer), sodium polyoxyethylene dodecyl ether sulfate 1 part by mass and 9 parts by mass of water were charged. In a separate container, 2 parts by mass of "Adecaria soap SR 1025" (ADEKA Corporation) as an emulsifier and 26.3 parts by mass of methyl methacrylate (MMA) with respect to 17 parts by mass of the polymer contained in the aqueous dispersion 40 parts by mass of 2-ethylhexyl acrylate (EHA), 20 parts by mass of cyclohexyl methacrylate (CHMA), 5 parts by mass of hydroxyethyl methacrylate (HEMA), polyethylene glycol methacrylate (PEGMA) (manufactured by NOF Corporation "PE-200" 1 part by weight, 1 part by weight of 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (PPMMA) ("LA-82" from ADEKA), 5 parts by weight of diacetone acrylamide (DAAM), And 0.5 parts by mass of an ammonium ion-containing compound (A) represented by the formula (A) shown in AA) were mixed 1.2 parts by mass of 80 parts by weight of water to prepare a well stirred monomer emulsion. Then, the temperature rise of the separable flask was started with 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.

  When the internal temperature of the separable flask reaches 75 ° C., addition of the prepared monomer emulsion is started, and the monomer emulsion is maintained for 2 hours while maintaining the internal temperature of the separable flask at 75 ° C. Was added slowly. Thereafter, the internal temperature of the separable flask is raised to 85 ° C., and the temperature is maintained for 1 hour to carry out a polymerization reaction to form a polymer (Pb), and a polymer (Pa) and a polymer (Pb) Polymer particles (S1) were synthesized.

Thereafter, the separable flask was cooled, aqueous ammonia and water were added to adjust the pH to 7.6, and an aqueous dispersion containing 46% by mass of polymer particles (S1) was obtained. In addition, when content of the ammonium ion group in a polymer (Pb) was quantified by < ¹ > H-NMR, it was 0.8 mmol / 100g.

(Average particle size)
The particle size distribution of the aqueous dispersion was measured using a particle size distribution measuring apparatus ("FPAR-1000" manufactured by Otsuka Electronics Co., Ltd.) based on the dynamic light scattering method, and the average particle size was determined from the particle size distribution. The average particle diameter of the particles of the polymer particles (S1) was 160 nm.

(THF insoluble matter and DSC measurement)
About 10 g of the obtained aqueous dispersion was weighed into a petri dish made of Teflon (registered trademark) 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 is filtered through a 300-mesh wire mesh to separate insolubles, and then the THF solvent is removed by evaporation from the THF phase. The measured values of the mass (Y (g)) of the residue are shown below. The THF insoluble matter (%) was determined by equation (6).
THF insoluble matter (%) = ((1-Y) / 1) × 100 (6)
The THF insoluble matter of the polymer particles (S1) was 86% by mass.
Moreover, when the polymer particles (S1) were measured by a differential scanning calorimeter (DSC), endothermic peaks were observed at 11 ° C. and 91 ° C., respectively.

(Zeta potential)
The obtained aqueous dispersion was diluted to have a solid content concentration of 0.01% by mass, and the zeta potential was measured using "ELS-6000" manufactured by Otsuka Electronics Co., Ltd. The measured values of zeta potential are shown in Table 1 and Table 2.
The larger the absolute value of the zeta potential, the higher the stability of the polymer particles [A]. The zeta potential is "S" (very good) when the absolute value is 50mV or more, and "A" (good) when the absolute value is 30mV or more and less than 50mV, and the absolute value is 10mV or more and less than 30mV If the absolute value is less than 10 mV, it can be evaluated as "C" (poor).
The zeta potential of the polymer particles (S1) was −41 mV.

Synthesis Examples 2 to 29
The polymer particles (S2) to (S29) are contained at 46% by mass in the same manner as in Synthesis Example 1 except that the types and amounts of monomers and molecular weight modifiers used are as shown in Tables 1 and 2. Aqueous dispersions were obtained. In the synthesis of the polymer (Pb), when using 0.5 parts by mass of the compound (A) (molecular weight 657) which is a monomer containing a cationic group in 100 parts by mass of all the monomers, The content of the cationic group in Pb) is estimated to be 0.76 mmol / 100 g. "-" In Table 1 and Table 2 shows that the applicable compound was not used.

Synthesis Example 30
After thoroughly replacing the interior of the separable flask with nitrogen, 0.5 parts by mass of "ADEKAREASOAP SR1025" as an emulsifier, 1 part by mass of MMA, 1 part by mass of CHMA, 0.5 part by mass of AA and 30 parts by mass of water are mixed and mixed After stirring, the mixture was sufficiently stirred to prepare a monomer emulsion. Thereafter, the temperature rise is started by a water bath, and when the internal temperature of the separable flask reaches 50 ° C., 0.3 parts by mass of ammonium persulfate as a polymerization initiator is added, and the temperature is raised to 75 ° C. An aqueous dispersion 21.3 parts by mass (8.5 parts by mass of polymer) containing particles of the polymer (Pa) obtained in Example 1 was charged.
In a separate container, 21.3 parts by mass (8.5 parts by mass of the polymer) of the aqueous dispersion containing particles of the polymer (Pa) obtained in the above Synthesis Example 1 and 1 part by mass of sodium polyoxyethylene dodecyl ether sulfate Parts and 9 parts by mass of water were charged. 0.5 parts by mass of "Adekaria soap SR 1025" as an emulsifier, 20.3 parts by mass of MMA, 39 parts by mass of EHA, 1 part by mass of CHMA, 5 parts by mass of HEMA with respect to 8.5 parts by mass of the polymer contained in this aqueous dispersion , 1 part by mass of PEGMA, 1 part by mass of PMPMA, 5 parts by mass of DAAM, 0.5 parts by mass of compound (A), 0.7 parts by mass of AA and 50 parts by mass of water were sufficiently stirred to prepare a monomer emulsion .
The addition of the monomer emulsion prepared above was started 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. Thereafter, the internal temperature of the separable flask is raised to 85 ° C., and the temperature is maintained for 1 hour to carry out a polymerization reaction to form a polymer (Pb), and a polymer (Pa) and a polymer (Pb) Polymer particles (S30) were synthesized.

The abbreviation of each monomer in Table 1 and Table 2 shows the following compounds, respectively.
VDF: vinylidene fluoride TFE: ethylene tetrafluoride HFP: propylene hexafluoride MMA: methyl methacrylate EHA: 2-ethylhexyl acrylate LA: lauryl acrylate CHMA: cyclohexyl methacrylate HEMA: 2-hydroxyethyl methacrylate MAPS: γ -Methacryloxypropyl trimethoxysilane BA: butyl acrylate PEGMA: polyethylene glycol methacrylate ("PE-200" from NOF Corporation, average oxyethylene addition mole number: 4.5)
PMPMA: methacrylic acid 1,2,2,6,6-pentamethyl-4-piperidyl ("LA-82" from Adeka)
DAAM: diacetone acrylamide DMAA: N, N-dimethyl acrylamide AA: acrylic acid

  Moreover, the compound (B) in Table 1 and Table 2 shows the compound represented by Formula (B) shown below.

  The average particle size, THF insoluble matter, endothermic peak temperature and zeta potential of each [A] polymer particle were evaluated. The evaluation results are shown in Table 1 and Table 2.

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

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

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

(Other optional ingredients)
(Filler) Sulfonic acid modified colloidal silica ("PL-3D" from Sakai Chemical Industry Co., Ltd.)
(Weatherability improver) Hindered amine light stabilizer (ADEKA's "ADECANOL UC-606")
(Deposition aid) Texanol

Example 1
[A] 108.7 parts by mass of an aqueous dispersion containing polymer particles (S1) as polymer particles (containing 50 parts by mass of polymer particles (S1)), (C) as a crosslinking agent -3) An aqueous suspension consisting of 1.1 parts by mass of (adipic acid dihydrazide) and 1.65 parts by mass of water was added and stirred at 300 rpm. Furthermore, 5 parts by mass of texanol as a film forming aid was added, and the mixture was stirred again at 300 rpm to prepare a composition (T1).

[Examples 2 to 27 and Comparative Examples 1 to 7]
Composition (T2) to (A) in the same manner as in Example 1 except that the types and amounts of [A] polymer particles, [C] crosslinking agent and other optional components are changed as shown in Tables 3 and 4. (T27) and (CT1) to (CT7) were prepared. "-" In Table 3 and Table 4 shows that the applicable component was not used.

<Evaluation>
The following items were evaluated by the method shown below about the obtained composition. The evaluation results are shown in Table 3 and Table 4.

[Normal temperature film forming property of coating film]
The composition obtained above is applied using an applicator having a gap value of 200 μm onto a hard aluminum substrate which has been coated with an aqueous epoxy primer and fired at 120 ° C. in advance, and then one week at ordinary temperature (25 ° C.) The coating film was formed by leaving it to stand. The appearance of the formed coating was visually observed. The normal temperature film forming property of the coating film is “A” (good) when no crack or swelling is observed in the coating film appearance, and “B” when crack or swelling is observed in the coating film appearance (at an end or the like) When the film was half or more powdery and was not formed as a film, it was evaluated as "C" (poor).

Initial gloss
The 60 ° gloss of the obtained coating film was measured using BYK Gardner "Microtrigloss-S". When the coating film is required to have gloss, the initial gloss is preferably as large as possible. The initial gloss was evaluated as “A” (good) in the case of 70 or more, “B” (slightly poor) in the case of 50 or more and less than 70, and “C” (bad) in the case of less than 50.

[Base material adhesion]
The obtained coating film was cross-cut (25 squares of 5 × 5) into a 2 mm square with a cutter, and an adhesion test using Cellotape (registered trademark) manufactured by Nichiban Co., Ltd. was performed and evaluated based on the following criteria. The adhesion of the substrate is “A” (good) when there is no peeling of the coating, and “B” (somewhat poor) when the peeling of the coating is less than half, and the peeling of the coating is more than half Was rated as "C" (defect).

[water resistant]
The obtained composition was applied onto a glass substrate using an applicator with a gap value of 200 μm, and a coating film was formed by standing for 1 week at normal temperature (25 ° C.). The coated glass plate thus obtained was immersed in warm water at 50 ° C. for 24 hours, and the whitening and swelling of the coated film immediately after removal were visually observed to evaluate the water resistance of the coated film.
Regarding the whitening of the coating film, no whitening of the coating film is observed, or clear whiteness, and when the whitening of the coating film disappears after 5 hours at normal temperature after taking out, "A" (very good), Although opaque whitening is observed in the film, when whitening of the coating disappears after 5 hours at normal temperature after taking out, opaque whitening is recognized as “B” (good), and 5 after taking-out is normal temperature When whitening did not disappear after the lapse of time, it was evaluated as "C" (defect).
With regard to the swelling of the coating, the swelling of the coating is observed as “A” (very good) when the swelling of the coating is not observed, and as “B” (good) when the swelling of the coating is very slight. When it was recognized significantly, it was evaluated as "C" (defect).

[Weatherability]
A film obtained by the same method as the normal temperature film formability evaluation of a coating film was subjected to an accelerated weathering test for 1,000 hours by a metal weather (Dypra Wintess Co., Ltd.), and 60 ° of the coating film before and after the test. The gloss was measured, and the gloss retention (gloss after test × 100 / gloss before test) (%) was calculated. The test conditions are as follows: Irradiate light of 295-780 nm with KF-1 filter using metal halide lamp light source, irradiated (75 mW / cm ² under 63 ° C. 50% RH) 4 hours and dark (30 ° C. 98% RH) 4 hr Cycle conditions. The weather resistance is “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%. If it is less than%, it can be evaluated as "C" (defect).
In addition, the occurrence of cracks on the film surface after the test was visually observed. Regarding cracks, when a large number of cracks are observed in the coating, “A” (good) if no cracks are observed in the coating, and “B” (good) if very small cracks are observed in the coating. Was judged as "C" (defect).

[Abrasion resistance]
The paint film obtained by the same method as for water resistance evaluation was set to a friction fastness tester ("RT-300" manufactured by Daiei Scientific Seiki Seisakusho Co., Ltd.). Fix Bencot (Asahi Kasei Co., Ltd.) on a friction element (500 g of its own weight), reciprocate 10 times on the coated film, and change the haze before and after the test with a haze meter ("NDH-5000" by Nippon Denshoku Kogyo Co. It was measured. The abrasion resistance is “S” (very good) when the haze change is less than 0.3, and “A” (good) when the haze change is 0.3 or more and less than 0.6. When the change was 0.6 or more and less than 1.0, it was judged as "B" (slightly good), and when the haze change was 1.0 or more, it was judged as "C" (defect).

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

[Bubbling of liquid]
5 g of the composition prepared above was filled in a 20 mL screw tube bottle, shaken by hand up and down 20 times by hand, and bubbles on the liquid surface after standing for 5 minutes were visually observed. With regard to the bubbling of the solution, if the foam is extinguished “A” (good), if the foam is almost extinguished, “B” (somewhat good), and if many bubbles remain “C” (poor) It was evaluated.

(Arithmetic mean roughness of the surface of the coating)
The arithmetic mean roughness (Ra) of the surface of the coating film obtained by the same method as for the normal temperature film formability evaluation of the coating film is measured according to JIS B0601: 2013, using an atomic force microscope (“Dimension” by Bruker AXS) It measured using "FastScan".
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.

  According to Examples 1 to 27, it has become clear that the composition has good storage stability and good water resistance, weather resistance and abrasion resistance of the coating. On the other hand, in the compositions of Comparative Examples 1 to 7, some of these properties were poor.

  The present invention is not limited to these embodiments, and various modifications are possible. The present invention encompasses configurations substantially the same as the configurations described in the embodiments (for example, configurations having the same function, method and result, or configurations having the same purpose and effect). The present invention also encompasses configurations in which nonessential parts of the configurations described in these embodiments are replaced with other configurations. Furthermore, the present invention also encompasses configurations having the same operational effects as the configurations described in these embodiments or configurations capable of achieving the same object. Furthermore, the present invention also encompasses configurations obtained by adding known techniques to the configurations described in these embodiments.

According to the composition of the present invention, it is possible to form a coating film which is excellent in storage stability over a long period of time and which is excellent in 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 coating agent and the like.

Claims (3)

Polymer particles,
Containing a liquid medium and
The polymer particles are
A first polymer having a repeating unit derived from a fluorine-containing ethylene-based 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 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 composition according to claim 1 or 2, wherein the content of the first polymer in the polymer particles is more than 0% by mass and less than 15% by mass.