TW201634606A - Composition for coating materials and coated body - Google Patents

Abstract

Provided are: a composition for coating materials, which is capable of forming a coating film that has excellent appearance and excellent hardness, while being suppressed in deterioration of the antifouling properties; and a coated body which is provided with a coating film that is formed from this composition for coating materials. A composition for coating materials according to the present invention is characterized by containing fluorine-containing polymer particles (A), a polyfunctional (meth)acrylate (B) and a liquid medium.

Description

Coating composition and coated body

The present invention relates to a coating composition, a coating material containing the composition, and a coating body comprising the coating composition or the coating film formed of the coating material.

The fluorine-containing polymer is excellent in heat resistance, weather resistance, electrical insulation, and the like, and is used as a coating agent for imparting antifouling properties or chemical resistance to various substrates such as glass, metal, resin, wood, and slate. However, the fluorine-containing polymer has poor adhesion to the substrate, and the formed coating film is too soft. 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 say that a coating film having sufficient hardness can be obtained.

In order to increase the hardness of the coating film, Patent Document 3 or Patent Document 4 discloses a technique of formulating an organic fluorene-based 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 an aqueous solution of a composite polymer particle of an organic cerium compound and a (meth)acrylic polymer. Dispensing technology.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 10-120858

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-227754

[Patent Document 3] Japanese Patent Laid-Open Publication No. 08-120211

[Patent Document 4] International Publication No. 98/23680

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2003-286440

However, when any of the techniques disclosed in the above patent documents is used, the appearance of the coating film and the antifouling property or the coating film hardness which are important characteristics of the coating film are not sufficient.

Therefore, the present invention can solve at least a part of the above-mentioned problems, and can provide a coating composition which can form a coating film which is excellent in appearance and excellent in antifouling property and has excellent hardness, and is provided with the coating material. A coated body of a coating film formed of the composition.

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

[Application Example 1]

The coating composition of the present invention is characterized by containing fluoropolymer particles (A), polyfunctional (meth) acrylate (B), and a liquid medium.

[Application Example 2]

The coating composition according to the first aspect of the invention, wherein the polyfunctional (meth)acrylic acid is contained in an amount of 100 parts by mass based on 100 parts by mass of the total of the fluoropolymer particles (A) and the polyfunctional (meth) acrylate (B). The ester (B) is 20 to 95 parts by mass.

[Application Example 3]

The coating composition of the application example 1 or the application example 2, wherein the total amount of the fluoropolymer particles (A) and the polyfunctional (meth) acrylate (B) is 100 parts by mass, and further contains 1 to 10 parts. Parts by mass of the polymerization initiator (C).

[Application Example 4]

The coating composition according to any one of the first to third aspects, wherein the polyfunctional (meth) acrylate (B) is in the form of an emulsion dispersed in a liquid medium.

[Application 5]

The coating composition according to any one of Application Examples 1 to 4, which further contains a filler.

[Application Example 6]

The coated body of the present invention is characterized in that it has a substrate and a coating film formed by applying a coating composition of any one of Application Examples 1 to 5 on the surface of the substrate and drying it.

According to the coating composition of the present invention, it is possible to provide a coating composition which can form a coating film which is excellent in appearance and antifouling property and has excellent hardness, and a coating film having the above-described characteristics formed of the coating composition. body.

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 spirit and scope of the invention. In addition, in this specification, "~ (meth) acrylate" means the concept of "~ acrylate" and "~ methacrylate". Moreover, "(meth)acrylic acid ~" means the concept of "acrylic acid ~" and "methacrylic acid ~".

Coating composition

The coating composition of the present embodiment contains fluoropolymer particles (A) (hereinafter also referred to as "(A) component") and polyfunctional (meth) acrylate (B) (hereinafter also referred to as "(B) Ingredients") and liquid medium. The following is about this The components contained in the coating composition of the embodiment are described in detail.

1.1. Fluoropolymer particles (A)

The fluoropolymer particles (A) contained in the coating composition of the present embodiment are in the form of a latex in which the particles are dispersed in a liquid medium. When the coating composition is in the form of a latex, the coating property as a coating material is good. The fluoropolymer particles (A) contain a fluorine-containing polymer. Hereinafter, each repeating unit constituting the fluorine-containing polymer will be described.

1.1.1. Repeating units derived from fluorine-containing vinyl monomers

The fluoropolymer used in the present embodiment preferably has a repeating unit derived from a fluorine-containing vinyl monomer. The fluorine-containing vinyl monomer is exemplified by, for example, an olefin having a fluorine atom and a (meth) acrylate having a fluorine atom. The olefin having a fluorine atom is exemplified by, for example, fluorinated ethylene, tetrafluoroethylene, hexafluoropropylene, trifluoroethylene chloride, perfluoroalkyl vinyl ether or the like. The (meth) acrylate having a fluorine atom is exemplified by, for example, a compound represented by the following formula (3), (meth)acrylic acid 3[4[1-trifluoromethyl-2,2-bis[bis(trifluoromethyl) And fluoromethyl]ethynyloxy]benzhydryloxy]2-hydroxypropyl ester.

(In the formula (3), R ⁶ is a hydrogen atom or a methyl group, and R ⁷ is a hydrocarbon group having 1 to 18 carbon atoms of a fluorine-containing atom).

R ⁷ in the above formula (3) is, for example, a fluorinated alkyl group having 1 to 12 carbon atoms, a fluorinated aryl group having 6 to 16 carbon atoms, or a fluorinated aralkyl group having 7 to 18 carbon atoms, but Among them, a fluorinated alkyl group having 1 to 12 carbon atoms is preferred. Preferred specific examples of R ⁷ in the above formula (3) are exemplified by, for example, 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-perfluoro-1-indenyl, 1H, 1H, 11H-perfluoroundecyl, perfluorooctyl and the like.

The fluorine-containing vinyl monomer is preferably an olefin having a fluorine atom, more preferably at least one selected from the group consisting of fluorinated ethylene, tetrafluoroethylene and hexafluoropropylene. The fluorine-containing vinyl monomer may be used singly or in combination of two or more.

When the total of the repeating units of the fluorine-containing polymer constituting the fluoropolymer particles (A) is 100% by mass, the repeating unit derived from the fluorine-containing vinyl monomer may be contained in a ratio of 5 to 99% by mass, or may be contained. The ratio of 10 to 80% by mass is contained. When the content ratio of the repeating unit derived from the fluorine-containing vinyl monomer is in the above range, the film formability or adhesion of the coating film can be further improved.

The fluoropolymer may have only a repeating unit derived from a fluorine-containing vinyl monomer, or may have a repeating unit derived from a repeating unit of a fluorine-containing vinyl monomer derived from another monomer which can be copolymerized as described later.

When the fluorine-containing polymer contains a repeating unit derived from vinylidene fluoride, the content thereof is preferably from 50 to 100 mol%, more preferably from 60 to 98. Moer%. When the fluoropolymer contains a repeating unit derived from tetrafluoroethylene, the content thereof is preferably 50 mol% or less, more preferably 1 to 50 mol%, still more preferably 2 to 30 mol%. When the fluoropolymer contains a repeating unit derived from hexafluoropropylene, the content thereof is preferably from 1 to 50 mol%, more preferably from 2 to 30 mol%.

1.1.2. Other monomers

The fluorine-containing polymer may have a repeating unit derived from a monomer other than a repeating unit derived from a fluorine-containing vinyl monomer. As the other monomer, a monomer described in International Publication No. 2014/112252 or the like can be used. For example, an unsaturated carboxylic acid ester, an unsaturated carboxylic acid, an α,β-unsaturated nitrile, a carbonyl group-containing compound, a conjugated diene, an aromatic vinyl, a vinyl ether, an allyl ether, an alkoxydecane, or the like. When the total of the repeating units of the polymer constituting the fluoropolymer particles (A) is 100% by mass, the monomer may be contained in a ratio of 10 to 90% by mass, or may be in a ratio of 20 to 85% by mass. contain.

The unsaturated carboxylic acid ester is exemplified by, for example, an alkyl ester of an unsaturated carboxylic acid, a cycloalkyl ester of an unsaturated carboxylic acid, a hydroxyalkyl ester of an unsaturated carboxylic acid, or the like.

The unsaturated carboxylic acid is preferably an ethylenically unsaturated carboxylic acid, and examples thereof include a mono or dicarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, oriconic acid, and the like. One or more of these choices. In the above, one or more selected from the group consisting of acrylic acid, methacrylic acid and isaconic acid are preferred.

As the above α,β-unsaturated nitrile, for example, propylene can be exemplified. Nitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethyl acrylonitrile, and vinylidene cyanide may be one or more selected from the above.

As the carbonyl group-containing compound, for example, (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, isopropyl (meth) propylene hydride can be exemplified. Amine, diacetone (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, acryl morpholine, acrolein, etc., may be One or more of these choices.

The conjugated diene can be exemplified by, for example, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro - 1,3-butadiene or the like may be one or more selected from the above.

The aromatic vinyl may, for example, be styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene or p-hydroxystyrene. One or more of the above options.

As the above vinyl ether, for example, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether can be exemplified. Further, one or more selected from the group consisting of 4-hydroxybutyl vinyl ether and 2-aminoethyl vinyl ether.

As the above allyl ether, for example, methyl allyl ether, ethyl allyl ether, propyl allyl ether, butyl allyl ether, hydroxyethyl allyl ether, hydroxypropyl allyl ether, hydroxybutyl group can be exemplified. Allyl ether, allyl glycidyl ether, ethylene glycol monoallyl ether, propylene glycol monoallyl ether, etc., may be selected from the above Choose one or more.

The alkoxydecane is exemplified by at least one monomer selected from the group consisting of monomers represented by the following general formula (4) and the following general formula (5).

R ⁸ _n Si(OR ⁹ ) _4-n ..... (4) (wherein R ⁸ and R ⁹ each independently represent an organic group having 1 to 8 carbon atoms, and n represents an integer of 0 to 3)

R ¹⁰ _m SiO _{(4-m) / 2} (5) (wherein R ¹⁰ represents an organic group having 1 to 8 carbon atoms, and m represents a number of 0 to 3).

In the monomers represented by the above formulas (4) and (5), R ⁸ and R ^{9 are} preferably an alkyl group having 1 to 8 carbon atoms, more preferably a methyl group or an ethyl group. R ^{9 is} exemplified by, for example, an alkyl group having 1 to 8 carbon atoms, an aryl group, an anthracenyl group and the like. The alkyl group is exemplified by methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, n-pentyl and the like. Examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group and the like. The mercapto group is preferably a fluorenyl group having 1 to 6 carbon atoms, and examples thereof include, for example, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, a amyl fluorenyl group, a hexyl fluorenyl group, and the like, and a plurality of R ⁸ are present in the above formula (4). And R ⁹ may be the same or different from each other. These alkoxy decane may be used alone or in combination of two or more.

1.1.3. Modulation of fluoropolymer particles (A)

The fluoropolymer particles (A) are not particularly limited as long as they are obtained as described above. For example, the fluoropolymer particles (A) can be easily produced by a conventional emulsion polymerization step or an appropriate combination. Modulation, such as the method described in /112252.

For example, when the fluoropolymer particles (A) contain a polymer (Aa) having a repeating unit derived from a fluorine-containing vinyl monomer and a polymer (Ab) having a repeating unit derived from an unsaturated carboxylic acid ester, firstly, The polymer (Aa) derived from the repeating unit of the fluorine-containing vinyl monomer is synthesized by a conventional method. Next, a monomer for constituting the polymer (Ab) is added to the polymer (Aa), and the monomer is absorbed in the pinhole structure of the polymer particles containing the polymer (Aa), and then the polymer (Aa) is used. In the needle-eye structure, the absorbed monomer is polymerized into a synthetic polymer (Ab), and the fluoropolymer particles (A) can be easily produced.

The content ratio of the polymer (Aa) in the fluoropolymer particles (A) may be 5 to 99 parts by mass, or 10 to 80% by mass based on 100 parts by mass of the fluoropolymer particles (A). Share. When the fluorine-containing polymer contains the polymer (Aa) in the above range, the balance between film formability and adhesion can be further improved.

The content ratio of the polymer (Ab) in the fluoropolymer particles (A) may be 10 to 90 parts by mass, or 20 to 85 mass, per 100 parts by mass of the fluoropolymer particles (A). Share. When the fluoropolymer particles (A) contain the polymer (Ab) in the above range, the balance between film formability and adhesion can be further improved.

Manufacture of fluoropolymer particles (A), ie polymer (Aa) Polymerization or polymerization of the polymer (Ab) after absorption of the monomer in the obtained polymer (Aa) or both of them may be conventional emulsifiers (surfactants), polymerization initiators, molecular weight regulators, etc. In the presence of it.

1.1.4. Average particle size of fluoropolymer particles (A)

The average particle diameter (Da) of the fluoropolymer particles (A) is preferably in the range of from 30 to 400 nm, more preferably in the range of from 50 to 250 nm. When the average particle diameter (Da) of the fluoropolymer particles (A) is in the above range, a dense coating film can be formed at the time of film formation, so that deterioration of weather resistance can be effectively suppressed.

In addition, the average particle diameter (Da) of the fluoropolymer particles (A) is measured by a particle size distribution measuring apparatus using a light scattering method as a measuring principle, and the cumulative number of particles when the particles are accumulated from small particles is 50. The value of % particle size (D50). Examples of such a particle size distribution measuring device include, for example, COLUTER LS230, LS100, LS13 320 (above, manufactured by Beckman Coulter. Inc.), or FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.). The particle size distribution measuring apparatus is not limited to the primary particles of the polymer particles, and the secondary particles formed by aggregating the primary particles may be used as the evaluation target. Therefore, the particle size distribution measured by the particle size distribution measuring apparatus can be an index of the dispersion state of the polymer particles contained in the coating material.

1.2. Polyfunctional (meth) acrylate (B)

The coating composition of the present embodiment contains a polyfunctional (meth) acrylate (B). Since the coating composition of the present embodiment contains a polyfunctional group The (meth) acrylate (B) can make the obtained coating film dense, improve the hardness, and suppress the deterioration of the antifouling property. Further, when a polyfunctional (meth) acrylate is reacted to form a coating film, a large volume shrinkage is caused. For this reason, the appearance or surface roughness of wrinkles or the like may be deteriorated in the coating film. However, the coating composition of the present embodiment can be used as a coating film having a good surface roughness.

Although the display mechanism of the effect of suppressing the deterioration of the antifouling property of the coating film is not clear, it is considered as follows. That is, it is considered that the fluoropolymer particles (A) are polyfunctional (meth) acrylate (B) because the affinity between the fluoropolymer particles (A) and the polyfunctional (meth) acrylate (B) is good. The film is uniformly dispersed to form a coating film, and the film can maintain a dense film even when exposed to rain or the like. In addition, it is estimated that the fluoropolymer particles (A) are uniformly dispersed in the coating film, so that the fluoropolymer particles (A) are prevented from being deteriorated by sunlight, and as a result, deterioration of the antifouling property can be suppressed.

Further, in general, when a new component is added to a dispersion of polymer particles such as latex, the new component is liable to be triggered and agglomerate. However, since the polyfunctional (meth) acrylate (B) has little influence on the dispersibility of the polymer particles, aggregation can be suppressed. Therefore, when the coating composition of the present invention is mixed with a coloring agent to form a coating material, since there is no component that acts as a trigger, aggregation of the polymer particles or the coloring agent can be suppressed. Therefore, since a more uniform coating film can be produced on the surface of the substrate, it is presumed that the coating system having such a coating film has a good appearance and antifouling property.

Further, it is considered that the fluidity of the coating material can be improved by adding the polyfunctional (meth) acrylate (B) to the coating composition. As a result of improving the fluidity of the coating, it is considered that a coating film having a more uniform thickness can be formed, which can exhibit good Good appearance and antifouling properties.

Specific examples of the polyfunctional (meth) acrylate (B) include, for example, ethylene glycol di(meth)acrylate and 1,3-butylene glycol di(meth)acrylate as the bifunctional compound. 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) Cyanurate di(meth)acrylate or the like; as the trifunctional compound, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(methyl) Acrylate, ginseng (2-hydroxyethyl)isocyanurate tri(meth)acrylate, etc.; as the tetrafunctional compound, for example, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate , dipentaerythritol hexa (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, etc.; and, as a compound having four or more functions, for example, it is possible to use, for example, 4 in the molecule. The above (meth)acryl oxime oligoester (meth) acrylate, oligoether (meth) acrylate having four or more (meth) acryl fluorenyl groups in the molecule, and four molecules in the molecule Poly(meth)acrylic acid of the above (meth)acrylinyl group, oligo epoxy (meth) acrylate, etc., and a compound obtained by adding ethylene oxide or propylene oxide to the hydroxyl group of the compound Ester and the like.

Among these, it is preferred to use dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and di-trimethylolpropane tetra (meth) acrylate. One type of ester selection the above.

Commercial products of the above-mentioned polyfunctional (meth) acrylate can be exemplified by, for example, ARONIX M-208, M-210, M-211B, M-215, M-220, M-225, manufactured by Toago Corporation. M-270, M-240, M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M- 452, M-450, M-408, M-403, M-400, M-402, M-404, M-406, M-405, M-460, M-510, M-520, M-1100, M-1200, M-320, M-233, M-245, M-260, M-1210, M-1310, M-1600, M-221, M-203, TO-924, TO-1270, TO- 1231, TO-595, TO-756, TO-1343, TO-902, TO-904, TO-905, TO-1330, TO-1382, etc.; KAYARAD R-526, NPGDA, manufactured by Nippon Kayaku Co., Ltd. PEG400DA, FM-400, R-167, HX-220, HX-620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA- 330, PET-30, T-1420, RP-1040, DPHA, MAX-3510, DPEA-12, DPHA-2C, DPHA-40H, D-310, D-330, DPCA-20, DPCA-30, DPCA- 60, DPCA-120, DN-0075, DN-2475, TC-120S, SR-295, SR-355, SR-399E, SR-494, SR-9041, SR-368, SR-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9 035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, KS-HDDA, KS- TPGDA, KS-TMPTA, etc.; A-9300, A-TMM-3, A-TMPT, AD-TMP, A-TMMT, A-9550, A-DPH, etc., manufactured by Shin-Nakamura Chemical Co., Ltd.; (Stock) LIGHT ACRYLATE 1, 9-ND-A, PE-4A, DPE-6A, etc.

The polyfunctional (meth) acrylate (B) preferably used in the present invention preferably has a (meth)acrylic acid equivalent of 1,000 g/eq or less, more preferably 50 to 6000 g/eq. By using a polyfunctional (meth) acrylate having a (meth)acrylic equivalent of 1,000 g/eq or less, the scratch resistance and hardness of the formed coating film can be improved. Further, in the present invention, the (meth)acrylic equivalent is a molecular weight of (meth)acryl fluorenyl group per 1 mole, and is (molecular weight of a polyfunctional (meth) acrylate compound) / (polyfunctional (methyl) The value of the acrylate compound per (molecular weight of (meth) acrylonitrile group).

In the present invention, a polyfunctional (meth) acrylate having the same equivalent of (meth)acrylic acid may be used, or a mixture of a plurality of polyfunctional (meth) acrylates having different (meth)acrylic equivalents may be used. In the latter case, the (meth)acrylic acid equivalent of the polyfunctional (meth) acrylate may be evaluated as the average value of the entire mixture.

In the coating composition of the present embodiment, the polyfunctional (meth) acrylate (B) is preferably in the form of an emulsion dispersed in a liquid medium. When the polyfunctional (meth) acrylate (B) is in the form of an emulsion, it is easily dispersed uniformly in the coating composition, so that a homogeneous cured film having good appearance and antifouling properties can be easily obtained.

Further, when the polyfunctional (meth) acrylate (B) is in the form of an emulsion, when a composition for a coating is prepared, a water-soluble solvent is added, and as needed To be heated, the polyfunctional (meth) acrylate (B) can be dissolved in the water-soluble solvent. Such a water-soluble solvent can be exemplified by a guanamine compound such as N-methylpyrrolidone, dimethylformamide, N,N-dimethylacetamide or the like; methanol, ethanol, isopropanol, and n-butyl Alcohol, isobutanol, tert-butanol, etc.; methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, holon, acetophenone, isophorone, etc.; dimethyl Aachen, ring 碸 and other Aachen. For the ruthenium compound or the like, one or more selected from the above may be used. Further, when the fluoropolymer particles (A) are present in the solution, all or a part of the polyfunctional (meth) acrylate (B) can be absorbed in the molecular structure of the fluoropolymer particles (A) in a molecular structure. . Then, when the water-soluble solvent is removed by evaporation or the like, a coating composition containing the fluoropolymer particles (A) in which the polyfunctional (meth) acrylate (B) is incorporated can be obtained. The coating composition thus obtained has a tendency to easily form a coating film having an excellent appearance or hardness.

The ratio of use of the polyfunctional (meth) acrylate (B) used in the present invention is 100 parts by mass in total of the fluoropolymer particles (A) and the polyfunctional (meth) acrylate (B). It is preferably from 20 to 95 parts by mass, more preferably from 30 to 90 parts by mass, and particularly preferably from 35 to 80 parts by mass. By using the ratio of use in the above range, the coating property of the coating composition can be maintained and the hardness of the coating film can be improved.

1.3. Polymerization initiator (C)

The polymerization initiator (C) is a component which generates an active species which starts polymerization of the polyfunctional (meth) acrylate (B) by light irradiation or heating. The polyfunctional (meth) acrylate (B) used in the present invention is preferably heated only by heating. Since the composition for coating is easy to obtain a high-quality coating film without containing the polymerization initiator (C), the polymerization initiator (C) may be optionally contained. The polymerization initiator (C) may be water-soluble or oil-soluble. Specific examples of the polymerization initiator (C) are as follows.

The polymerization initiator (C) which generates an active species by light irradiation can be exemplified by, for example, acetophenone, acetophenone benzyl acetal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1. ,2-diphenylethane-1-one, xanthone, anthrone, benzaldehyde, anthraquinone, anthracene, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone , 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ether, benzyl dimethyl acetal, 1-( 4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethyl thiophene Tons of ketone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinepropan-1-one, 2- Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) Ketone, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentyl oxidation Phosphine, oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)acetone), and the like. Such commercially available products are exemplified by, for example, IRGACURE 127, 184, 369, 379, 651, 500, 819, 907, 784, 2959, OXE01, OXE02, CGI1700, CGI1750, CGI1850, CG24-61 manufactured by BASF Corporation of Japan. DAROCURE 1116, 1173, LUCIRIN TPO, 8893; UBECRYL P36 manufactured by UCB; EZACURE KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75/B manufactured by Fratelli Lamberti Wait.

The polymerization initiator (C) which generates an active species by heating can be exemplified by, for example, hydrogen peroxide, peroxyesters, dialkyl peroxides, peroxyesters, didecyl peroxides, and the like. An organic peroxide such as an oxycarbonate, a peroxyacetal or a ketone peroxide; a persulfate such as ammonium persulfate, sodium persulfate or potassium persulfate; or an azo such as azobisisobutyronitrile; Compounds, etc.

The content ratio of the polymerization initiator (C) in the coating composition of the present embodiment is 100 parts by mass of the total of the fluoropolymer particles (A) and the polyfunctional (meth) acrylate (B). It is preferably 1 to 10 parts by mass, more preferably 2 to 5 parts by mass, and more preferably 2 to 4.5 parts by mass. By using the ratio of use in the above range, the coating property of the coating composition can be maintained and the hardness of the coating film can be improved.

1.4. Surfactant

The coating composition of the present embodiment preferably contains a surfactant (D). The surfactant (D) which may be contained in the coating composition is preferably an anionic surfactant containing an oxygen alkyl chain, more preferably a compound represented by the following formula (1).

XO-(R ¹ O) _n -R ² (1) (In the above formula (1), X is a group having an aromatic ring, R ¹ is an alkylene group having 2 to 4 carbon atoms, and R ² is a hydrogen atom or PO. (OM) ₂ or SO ₃ M (only M is a hydrogen atom, an ammonium ion or a metal ion), and n is an integer from 5 to 150).

The alkylene group of R ¹ may, for example, be 1,2-extended ethyl, 1,2-extended propyl, 1,3-extended propyl, 1,4-tert-butyl, 1,3-tert-butyl or the like. The metal ion of M in R ² is preferably a monovalent cation such as an alkali metal ion such as a sodium ion, a potassium ion or a lithium ion.

The aromatic ring in the above X may, for example, be a substituted or unsubstituted benzene ring, a naphthalene ring or the like, and is preferably a substituted or unsubstituted benzene ring. X is particularly preferably a group represented by the following formula (2).

(In the formula (2), R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group, m is an integer of 1 to 3, and "*" represents a bonding bond).

In the formula (2), the alkyl group of R ³ and R ⁴ is preferably an alkyl group having 1 to 3 carbon atoms, and each of them is independently a methyl group, an ethyl group, a n-propyl group or the like. Particularly preferably, R ³ and R ^{4 are} each independently a methyl group or an ethyl group.

Specific examples of the compound represented by the above formula (1) may be used. It is preferable to use NEWCOL 707-SF, NEWCOL 714-SF, NEWCOL 740-SF, NEWCOL 2607-SF (above, Japanese emulsifier).

The surfactant (D) which can be contained in the coating composition of the present embodiment can be used only by the compound represented by the above formula (1), and can be used in combination with the compound represented by the above formula (1) and another surfactant. As the other surfactant used herein, a conventional emulsifier such as a nonionic emulsifier, an anionic emulsifier, a reactive emulsifier or the like can be preferably exemplified. Examples of such specific examples include alkyl esters of polyglycol or polyalkylene glycol, fatty acid esters, sorbitan fatty acid esters, sorbitan fatty acid esters, alkyl ethers, alkylphenyl ethers, and the like. .

Further, as the anionic emulsifier, for example, a sulfate ester of a higher alcohol, a polyoxyalkylene ether sulfate salt, an alkylbenzenesulfonate, an alkyl diphenyl ether disulfonate, or a fat can be exemplified. Group of sulfonates, aliphatic carboxylates, dehydrophthalates, naphthalene sulfonates. A formaldehyde condensate, a sulfate salt of a nonionic surfactant, and the like. As the reactive emulsifier, for example, a trade name such as LATEMUL S-180A (manufactured by Kao Corporation); ELEMINOL JS-2 (manufactured by Sanyo Chemical Industries Co., Ltd.); AKUARON KH-10 (First Industrial Pharmaceutical Co., Ltd.) )), ADEKA REASOAP SE-10N, SR-1025 (above ADEKA); Antox MS-60 (made by Japan Emulsifier); SURFUMA FP-120 (Toho Chemical Industry Co., Ltd.) Wait.

The content of the surfactant (D) in the coating composition of the present embodiment is preferably 0.01 to 99 parts by mass based on 100 parts by mass of the polyfunctional (meth)acrylate (B).

1.5. Liquid boundary

The coating composition of the present embodiment contains a liquid medium. The liquid medium is preferably an aqueous medium containing water. The aqueous medium may contain a non-aqueous medium other than water. From the viewpoint of improving the coatability, a nonaqueous medium having a standard boiling point of 60 to 350 ° C may be contained. Specific examples of such a non-aqueous medium are, for example, decylamine compounds such as N-methylpyrrolidone, dimethylformamide, N,N-dimethylacetamide, etc.; toluene, xylene, and positive-tenth a hydrocarbon such as dioxane or tetrahydronaphthalene; methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, ethylene glycol, glycerol, propylene glycol, 2-ethyl-1-hexanol , 1-naphthol, lauryl alcohol, etc.; methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, chollon, acetophenone, isophorone, etc.; ethyl acetate, butyl acetate, An ester of benzyl acetate, isoamyl butyrate, methyl lactate, ethyl lactate, butyl lactate, etc.; an amine compound of o-toluidine, m-toluidine, p-toluidine, etc.; γ-butyrolactone, a lactone such as δ-butyrolactone; an amidene such as dimethyl hydrazine or cyclobutyl hydrazine. For the ruthenium compound or the like, one or more selected from the above may be used. When the liquid medium is a non-aqueous medium other than water and water, it is preferably 100% by mass or more of water, and more preferably 98% by mass or more of water. The coating composition of the present embodiment can reduce the adverse effects on the environment by using an aqueous medium as a liquid medium, and the safety of the operator is also high.

The content ratio of the non-aqueous medium contained in the liquid medium is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, per 100 parts by mass of the liquid medium. If the content ratio of the non-aqueous medium is within the above range, Further, the coating property and adhesion of the coating film can be further improved.

1.6. Other additives

The coating composition of the present embodiment may contain an additive other than the above components as needed. Examples of such additives are, for example, tackifiers, crosslinking agents, antifoaming agents, film forming assistants (butyl cellosolve, Texanol, etc.), freeze preventing agents (ethylene glycol, butylene glycol, etc.), pH adjusters ( Ammonia water, ethanolamine, etc.), surface conditioners, fillers, and the like. The amount of the additive to be added may be 60 parts by mass or less based on 100 parts by mass of the component other than the liquid medium of the coating composition of the present embodiment.

The tackifier which can be added to the coating composition of the present embodiment can be exemplified by a cellulose compound such as carboxymethylcellulose, methylcellulose or hydroxypropylcellulose; an ammonium salt or a base of the above cellulose compound. a metal salt; a polycarboxylic acid such as poly(meth)acrylic acid or modified poly(meth)acrylic acid; an alkali metal salt of the above polycarboxylic acid; a polyvinyl alcohol, a modified polyvinyl alcohol, an ethylene-vinyl alcohol copolymer, or the like A polyvinyl alcohol-based (co)polymer; a water-soluble polymer such as an alkali compound of a copolymer of an unsaturated carboxylic acid such as (meth)acrylic acid, maleic acid or fumaric acid and a vinyl ester. Among these, particularly preferred tackifiers are alkali metal salts of carboxymethyl cellulose, alkali metal salts of poly(meth)acrylic acid, and the like.

The coating composition of the present embodiment may contain a crosslinking agent. Examples of the crosslinking agent which can be used are a hydrazine derivative, a carbodiimide compound, an isocyanate compound, an amine compound, an epoxy compound, an oxazoline compound, an acid anhydride, an amine compound, and an aziridine compound.

Defoaming which can be added to the coating composition of this embodiment The agent is exemplified by a oxime-based antifoaming agent, a polymer-based antifoaming agent, and the like.

The coating composition of the present embodiment may contain a surface conditioning agent from the viewpoint of improving the coating property. The surface conditioning agent is exemplified by a siloxane compound, an acrylic copolymer, a methacrylic copolymer, and the like.

The coating composition of the present embodiment may contain a filler in order to improve the antifouling property. As the filler, an inorganic filler having a hydrophilic group is preferred. When the filler is contained in the coating film, since the surface of the coating film is uniformly hydrophilized, it is possible to obtain an effect that diffusion of contaminants adhering to the surface of the coating film is hard to be observed. The inorganic filler is exemplified by, for example, cerium oxide, aluminum oxide, zirconium oxide, titanium oxide, or the like. The content of the filler is preferably 60 parts by mass or less, more preferably 5 to 55 parts by mass, per 100 parts by mass of the component other than the liquid-removing medium of the coating composition of the present embodiment. Further, when the filler is cerium oxide, the average particle diameter of the filler is preferably from 10 to 300 nm, more preferably from 30 to 200 nm.

2. Coating

The term "coating material" as used in the present invention means a fluid applied to the surface of a substrate in order to impart protection, beauty, or sole function. The term "coating film" as used in the present invention means a film formed by applying a coating material to a surface of a substrate and drying it.

Since the above-mentioned coating composition does not have a coloring agent, it can be used as a coating material for transparent coating. In addition, a coloring agent such as an inorganic or organic compound such as an inorganic pigment, an organic pigment, or a filler may be added to the coating composition as described above in order to impart further functions such as coloring to the coating film.

The coating material of this embodiment is characterized by containing the above-mentioned coating composition and coloring agent. According to the coating material of the present embodiment, it is possible to form a coating film which is excellent in appearance, and which is excellent in appearance and excellent in antifouling property, and which is excellent in hardness, which is not only colored, but also has a function of the above-mentioned coating composition. Hereinafter, the components contained in the coating material of the present embodiment will be described in detail. However, the composition for the coating material is omitted as described above.

2.1. Colorants

The coloring agent is not particularly limited, and a suitable material can be selected according to the intended coating film. As a coloring agent can also be added as needed. An inorganic or organic compound such as an inorganic pigment, an organic pigment, a filler, or the like is formulated.

2.2. Other ingredients

The coating material of the present embodiment may contain components other than the above components as needed. Examples of the components include, for example, the non-aqueous medium described in the above "1.5. Liquid medium", the tackifier described in the above "1.6. Other additives", carbon black, molybdenum disulfide, white carbon, calcium carbonate. A filler such as barium sulfate, talc or calcium citrate, or an antifoaming agent described in the above-mentioned "1.6. Other additives", and a surface conditioner as described in the above "1.6. Other additives".

2.3. Method of manufacturing paint

When a coloring agent is used for the coating material of the embodiment, the coating composition, the coloring agent, the liquid medium, and the like can be added as needed. The agent is mixed and manufactured. These mixing can be carried out by stirring by a conventional method. For the mixing and kneading of the coating material, it is necessary to select a mixer which can be stirred to such an extent that the agglomerate of the coloring agent does not remain in the dispersion and sufficient dispersion conditions as needed. As the mixer, for example, a ball mill, a sand mill, a pigment disperser, a masher, an ultrasonic disperser, a homogenizer, a planetary mixer, a HOBART mixer, or the like can be exemplified.

3. Painting body

The coated body of the present embodiment is characterized by comprising a substrate and a coating film formed by applying the above-mentioned coating composition or coating material to the surface of the substrate and drying. The coating film can be formed by applying the above-mentioned coating composition or coating to the surface of a suitable substrate and drying it. The coated body having the coating film is excellent in appearance, has good antifouling properties for a long period of time, and is excellent in surface hardness.

The substrate of the coated body is not particularly limited, and examples thereof include substrates such as cement, tiles, metals, plastics, and glass. A coating film formed by coating the above-mentioned coating composition or coating material on the surface of the substrate can be used as a high durability protective coating material. Further, the coating film can be preferably used as a heat-shielding coating film or an anti-corrosion coating film which is required for durability and stain resistance required for outdoor use in buildings, building materials, automobiles, and the like, and can be preferably used as a pair. Impregnated materials, backing materials, fibers of porous materials such as felt or glass or paper. Protective film for fabric or tatami.

The coating composition or the coating method of the coating material to the substrate is also not particularly limited. Coating can be carried out by doctor blade method, dipping method, reverse roll method, direct roll method, gravure method, extrusion method, dipping method, brush coating method, spray coating, rod Suitable methods such as applicator, knife coater, screen printing, squeezing applicator, applicator, flow applicator, centrifugal applicator, ultrasonic applicator, soft printing, and the like.

4. Examples

Hereinafter, the present invention will be specifically described based on examples, and the present invention is not limited to the examples. The "parts" and "%" in the examples and comparative examples are mass standards unless otherwise specified.

4.1. Example 1 4.1.1. Production of fluoropolymer particles (A)

After the inside of the autoclave having an internal volume of about 6 L of an electromagnetic stirrer was sufficiently replaced with nitrogen, 2.5 L of deoxidized pure water and 25 g of perfluorononanoic acid ammonium as an emulsifier were fed, and the temperature was raised to 60 ° C while stirring at 350 rpm. Next, a mixed gas having a monomer mixture of vinylidene fluoride (VDF) 88 mol%, tetrafluoroethylene (TFE) 6 mol%, and hexafluoropropylene (HFP) 6 mol% is introduced, and the mixture is heated. To 80 ° C. The internal pressure is 2.5 MPa. Subsequently, 25 g of a fluorocarbon 113 solution containing 20% of diisopropyl peroxydicarbonate as a polymerization initiator was pressed in with nitrogen to start polymerization. After the start, a mixed gas of VDF/TFE/HFP=88/6/6 (% by mole) was additionally added so that the internal pressure became 2.5 MPa. After the reaction for 12 hr, the reaction vessel was cooled to complete the reaction, and an aqueous dispersion (latex) in which the fluoropolymer was dispersed in water in the form of particles was obtained. The concentration of the fluoropolymer in the obtained dispersion was 48% by mass, and water was added to prepare a solid content concentration of 40% by mass. As a result of ¹⁹ F-NMR analysis of the obtained fluoropolymer, the molar composition ratio of each monomer was VDF/TFE/HFP = 88/6/6. The obtained fluoropolymer particles had an average particle diameter of 75 nm.

4.1.2. Preparation of an aqueous dispersion of a polyfunctional (meth) acrylate (B)

Into a container made of SUS, 100 parts by mass of dipentaerythritol hexaacrylate (DPHA) was fed, and the temperature was raised to 40 ° C, and then the mixture was stirred at 2000 rpm with a homogenizer, and the emulsifier was put at a time of 1 minute by 4 minutes. 707-SF (trade name, manufactured by Nippon Emulsifier Co., Ltd.) was further added with 93 parts by mass of ion-exchanged water to obtain an aqueous dispersion containing 50% dipentaerythritol hexaacrylate.

4.1.3. Production of coating composition

After the inside of the separable flask having a capacity of 7 L was sufficiently substituted with nitrogen, the aqueous dispersion obtained as a step of "4.1.1. Preparation of fluoropolymer particles (A)" as the fluoropolymer particles (A) was used. 30 parts by mass of the fluoropolymer particles (A), which are sequentially fed into the water dispersion of "4.1.2. Polyfunctional (meth) acrylate (B) as a polyfunctional (meth) acrylate (B) 70 parts by mass of dipentaerythritol hexaacrylate contained in the aqueous dispersion obtained in the step of producing the product, Irgacure 184 (trade name, manufactured by BASF Corporation, Japan) as a polymerization initiator (C), 2.1 parts by mass and Irgacure 907 (trade name, manufactured by BASF Corporation of Japan) 2.1 parts by mass and 100 parts by mass of methyl ethyl ketone, and the mixture was heated to 65 ° C and heated for 2 hours. Subsequently, the mixture was cooled, and methyl ethyl ketone was removed by an evaporator to obtain a coating composition having a total amount of the component (A) and the component (B) of 47% by mass.

4.1.4. Evaluation of coating film <Appearance evaluation>

The coating composition obtained above was applied to a polyethylene terephthalate (product name "COSMOSHINE A4300" having a film thickness of 188 μm, manufactured by Toyobo Co., Ltd., using a bar coater at a film thickness of 5 μm. )on. After drying at 130 ° C for 2 minutes, ultraviolet rays were irradiated with an intensity of 300 mJ/cm ² under an air using a high-pressure mercury lamp to form a cured coating film. The appearance of the thus obtained hardened coating film was visually evaluated. Further, the evaluation criteria are as follows, and the results are shown in Table 1.

. "◎"... smooth, no whitening.

. "○"... The surface is slightly poor, or the film is slightly whitened.

. "X"... The face is quite poor.

<Anti-fouling evaluation>

The coating film obtained by the method similar to the above-mentioned external appearance evaluation was exposed to the south (45 yen) for 45 months on the south side, and the ΔE value was measured by a colorimeter (manufactured by KONICA MINOLTA, CM2002). Further, the evaluation criteria are as follows, and the results are shown in Table 1.

. "◎"...△E is less than 4 and very good.

. "○"... ΔE is 4 or more and less than 5, which is good.

. "△"...△E is 5 or more and less than 6, which is slightly inferior.

. "X"...△E is 6 or more, which is bad.

<Pencil hardness evaluation>

The pencil hardness obtained by the method similar to the above-mentioned external appearance evaluation was evaluated based on JISK5600-5-4. The results are shown together in Table 1.

<Surface smoothness evaluation>

For the coating film obtained by the same method as the above-mentioned appearance evaluation, the surface roughness (Ra value, unit) was measured by AFM (Hitachi Hi-Tech, high-decomposition energy multi-function unit S-image, probe microscope station NanoNaviReal). :nm). The results are shown together in Table 1.

4.2. Examples 2~8, 10~15, 17

In addition to the fluoropolymer particles (A), the polyfunctional (meth) acrylate (B), and the polymerization initiator (C), respectively, the feed amount (parts by mass) and the types described in Table 1, and In Example 1, the composition for coating was also prepared. The composition for the obtained coating material was evaluated in the same manner as in the above Example 1. The results are shown together in Table 1.

4.3. Example 9

After the inside of the separable flask having a capacity of 7 L was sufficiently substituted with nitrogen, the aqueous dispersion obtained as a step of "4.1.1. Preparation of fluoropolymer particles (A)" as the fluoropolymer particles (A) was used. 10 parts by mass of the fluoropolymer particles (A), which are sequentially fed into the water dispersion of "4.1.2. Polyfunctional (meth) acrylate (B) as a polyfunctional (meth) acrylate (B) Dipentaerythritol hexaacrylate 90 contained in the aqueous dispersion obtained by the step of the preparation of the body 2.7 parts by mass of Irgacure 184 (trade name, manufactured by Japan BASF Co., Ltd.) and 2.7 parts by mass of Irgacure 907 (trade name, manufactured by BASF Corporation, Japan) as a polymerization initiator (C), and the temperature was raised to 65 ° C, and then heated. hour. Subsequently, the mixture was cooled to obtain a coating composition having a total amount of the component (A) and the component (B) of 47% by mass. The composition for the obtained coating material was evaluated in the same manner as in the above Example 1. The results are shown together in Table 1.

4.4. Comparative Example 1~2

In addition to the fluoropolymer particles (A), the polyfunctional (meth) acrylate (B), and the polymerization initiator (C), respectively, the feed amount (parts by mass) and the types described in Table 1, and In Example 1, the composition for coating was also prepared. The composition for the obtained coating material was evaluated in the same manner as in the above Example 1. The results are shown together in Table 1.

4.5. Example 16

After the inside of the separable flask having a capacity of 7 L was sufficiently substituted with nitrogen, the aqueous dispersion of the fluoropolymer fine particles obtained by the step of "4.1.1. Preparation of fluoropolymer particles (A)" was 1,600 g ( 640 g of the fluoropolymer, and 150 parts by mass of the fluoropolymer contained in the dispersion, the emulsifier "ADEKA REASOAP SR1025" (trade name, manufactured by ADEKA CORPORATION), 2 parts by mass, methyl Methyl acrylate (MMA) 42.07 parts by mass, 2-ethylhexyl acrylate (EHA) 49.53 parts by mass, butyl acrylate (BA) 0.9 parts by mass, acrylic acid (AA) 2.5 parts by mass and diacetone acrylamide (DAAM) 5 parts by mass and 50 parts by weight of water, liter After warming to 60 ° C, 0.3 parts by mass of ammonium persulfate of a water-soluble polymerization initiator was added, and the mixture was heated to 75 ° C for 3 hours, and further reacted at 85 ° C for 2 hours. Subsequently, after cooling, the reaction was stopped, and the pH was adjusted to 8 with a 10% aqueous ammonia solution to obtain an aqueous dispersion (latex) containing 47% by mass of the fluoropolymer particles (A). The average particle diameter of the fluoropolymer particles was 150 nm.

10 parts by mass of the fluoropolymer particles (A) contained in the aqueous dispersion thus produced were sequentially fed, and as a polyfunctional (meth) acrylate (B) "4.1.2. Polyfunctional (methyl) 90 parts by mass of dipentaerythritol hexaacrylate contained in the aqueous dispersion obtained in the step of producing the aqueous dispersion of acrylate (B), and Irgacure 184 as a polymerization initiator (C) (trade name, BASF Corporation, Japan) 2.7 parts by mass and Irgacure 907 (trade name, manufactured by BASF Corporation, Japan), 2.7 parts by mass, heated to 65 ° C, and heated for 2 hours. Subsequently, the mixture was cooled to obtain a coating composition having a total amount of the component (A) and the component (B) of 47% by mass. The composition for the obtained coating material was evaluated in the same manner as in the above Example 1. The results are shown together in Table 1.

4.6. Comparative Example 3

In addition to the fluoropolymer particles (A), the polyfunctional (meth) acrylate (B), and the polymerization initiator (C), respectively, the feed amount (parts by mass) and the types described in Table 1, In the same manner as in Example 16, the composition for coating was prepared. The composition for the obtained coating material was evaluated in the same manner as in the above Example 1. The results are shown together in Table 1.

4.7. Evaluation results

The composition of the coating composition and the results of each evaluation test are shown in Table 1.

Further, the abbreviations of the respective components in Table 1 mean the following compounds, respectively.

. DPHA: dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD DPHA"

. DPEHA: Ethylene oxide modified dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD DPEA-12"

. PTA: pentaerythritol triacrylate, manufactured by Nippon Kayaku Co., Ltd., product name "KAYARAD PET-30"

. HCPK: 1-hydroxycyclohexyl phenyl ketone, manufactured by BASF, Japan, under the product name "Irgacure 184"

. MMP: 2-[4-(methylthio)benzylidene]-2-(4-morpholinyl)propane, manufactured by BASF, Japan, under the product name "Irgacure 907"

. Cerium oxide particle A: colloidal cerium oxide, manufactured by Fuso Chemical Industry Co., Ltd., product name "PL-3-D", average particle diameter = 60 nm

. Cerium oxide particle B: colloidal cerium oxide, manufactured by Fuso Chemical Industry Co., Ltd., product name "PL-7", average particle diameter = 125 nm

. Cerium oxide particle C: colloidal cerium oxide, manufactured by Fuso Chemical Industry Co., Ltd., product name "PL-10H", average particle diameter = 220 nm

According to Examples 1 to 17, a cured film having good appearance and antifouling property and excellent hardness was obtained. In particular, the coating composition (Examples 1 to 8, 10 to 15, and 17) containing the fluoropolymer particles (A) absorbing polyfunctional (meth) acrylate has a cured film excellent in appearance and hardness. Further, a coating composition for coatings (Examples 5 to 8) to which a filler was added was obtained as a cured film having particularly excellent antifouling properties. From the above results, it can be seen that the composition for coating of the present invention is Show good results. On the other hand, Comparative Examples 1 to 3 which are not the coating composition of the present invention are all or a part of these properties are inferior.

The present invention is not limited to the above embodiments, and various changes can be made. The present invention includes substantially the same configurations as those described in the embodiments (for example, the functions, methods, and results are the same configurations, or the configurations and effects are the same). Further, the present invention includes a configuration in which the non-essential portion of the configuration described in the above embodiment is replaced by another configuration. Furthermore, the present invention also includes a configuration that can achieve the same effects as those described in the above embodiments or achieve the same objectives. Furthermore, the present invention also includes a configuration in which the conventionally described techniques are applied to the configurations described in the above embodiments.

Claims (6)

A coating composition comprising a fluoropolymer particle (A), a polyfunctional (meth) acrylate (B), and a liquid medium. The coating composition according to claim 1, wherein the polyfunctional (meth)acrylic acid is contained in an amount of 100 parts by mass based on 100 parts by mass of the total of the fluoropolymer particles (A) and the polyfunctional (meth) acrylate (B). The ester (B) is 20 to 95 parts by mass. The coating composition according to claim 1 or 2, which further contains 1 to 10 parts by mass based on 100 parts by mass of the total of the fluoropolymer particles (A) and the polyfunctional (meth) acrylate (B). Polymerization initiator (C). The coating composition according to any one of claims 1 to 3, wherein the polyfunctional (meth) acrylate (B) is in the form of an emulsion dispersed in a liquid medium. The coating composition according to any one of claims 1 to 4, which further contains a filler. A coated body comprising a substrate and a coating film formed by applying the coating composition according to any one of claims 1 to 5 and drying the surface of the substrate.