Paint composition, hard coat coating, and substrate with hard coat coating.

Abstract

To provide a coating composition or the like that excels in wear resistance, weather resistance, initial appearance, and pot life.SOLUTION: A coating composition includes polymer nanoparticles (A) and a matrix base component (B'). The matrix base component (B') includes an organic ultraviolet absorber (Z) with an alkoxysilane site. Martens hardness HMA of the polymer nanoparticles (A) and Martens hardness HMB' of the matrix base component (B') satisfy the relationship of HMB' / HMA>1.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a paint composition, a hard coat coating, and a substrate with a hard coat coating. [Background technology]

[0002] While resin materials offer excellent moldability and lightweight properties, they are often inferior to inorganic materials such as metals and glass in terms of hardness, barrier properties, stain resistance, chemical resistance, flame retardancy, heat resistance, and weather resistance. In particular, the hardness of resin materials is significantly lower than that of inorganic glass, and their surfaces are easily scratched. Therefore, they are often used with a hard coat. However, hard coat coatings have difficulty resisting staining from soot and dust, maintaining performance under high temperature and humidity conditions, and preserving their appearance after prolonged exposure to ultraviolet light. As a result, hard-coated resin materials are not used in applications requiring high abrasion resistance, durability, and weather resistance.

[0003] To impart abrasion resistance to resin materials, there are methods using active energy ray curable resin compositions (see, for example, Patent Document 1), methods adding inorganic oxides to resin materials (see, for example, Patent Documents 2, 3, and 4), and methods adding polymer particles to resin materials (see, for example, Patent Document 5). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2014-109712 [Patent Document 2] Japanese Patent Publication No. 2006-63244 [Patent Document 3] Japanese Patent Application Publication No. 8-238683 [Patent Document 4] International Publication No. 2019-117088 [Patent Document 5] Japanese Patent Publication No. 2017-114949 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The methods described in Patent Documents 1 and 2 are general methods for imparting wear resistance to resin materials, but it is difficult to impart high wear resistance. The method described in Patent Document 3 is a general method that uses a flexible silicone polymer and hard inorganic oxide fine particles as a hard coat coating, but the silicone polymer, which is the matrix component, does not have sufficient hardness, resulting in insufficient wear resistance. The method described in Patent Document 4 uses a flexible silicone polymer and hard inorganic oxide fine particles as a hard coat coating, in addition to an ultraviolet absorber. Although it describes the physical properties of the coating, its abrasion resistance is not sufficient. The method described in Patent Document 5 uses polymer particles, silicone polymer, and inorganic oxide fine particles as a hard coat coating. While it describes the physical properties of the coating film, it does not describe the physical properties of each component, and therefore the abrasion resistance is insufficient. Furthermore, depending on the coating method, the desired film thickness may not be obtained, and abrasion resistance may not be achieved.

[0006] This invention has been made in view of the problems of the above-mentioned prior art, and its purpose is to provide a coating composition that can form a coating film with high abrasion resistance, weather resistance, and good initial appearance, and has excellent pot life. [Means for solving the problem]

[0007] As a result of diligent research, the inventors of the present invention have found that the above problems can be solved by providing a paint composition and coating film that satisfy predetermined components, and have completed the present invention. In other words, the present invention encompasses the following embodiments.

[0008] [1] Polymer nanoparticles (A) and Matrix raw material component (B'), A paint composition containing, The matrix raw material component (B') includes an organic ultraviolet absorber (Z) having an alkoxysilane moiety. Martens hardness HM of the polymer nanoparticle (A) A And the Martens hardness HM of the matrix raw material component (B') B' HM B' / HM A A paint composition characterized by satisfying the relationship >1.

[0009] [2] The paint composition according to [1], wherein the paint composition contains a solvent, and the main component of the solvent is water.

[0010] [3] The coating composition according to [1] or [2], wherein the organic ultraviolet absorber (Z) comprises at least one selected from the group consisting of benzophenone-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, malonic acid ester-based ultraviolet absorbers, and oxalic acid anilide-based ultraviolet absorbers.

[0011] [4] The paint composition according to any one of [1] to [3], characterized in that the amount of the organic ultraviolet absorber (Z) is 0.5% by mass or more and 13% by mass or less, based on the solid content of the paint composition.

[0012] [5] The paint composition according to any one of [1] to [4], wherein the matrix raw material component (B') further comprises an inorganic oxide (D).

[0013] [6] The paint composition according to [5], wherein the inorganic oxide (D) is silica particles.

[0014] [7] A hard coat coating comprising the paint composition described in any of [1] to [6].

[0015] [8] The hard coat coating described in [7], wherein, in accordance with ASTM D1044, when a Taber abrasion test is performed using a CS-10F abrasion wheel and a load of 500g, the difference between the haze at 1000 rotations and the haze before the Taber abrasion test is 10 or less.

[0016] [9] Substrate and A hard coat coating film according to [7] or [8] is disposed on one and / or both sides of the substrate, A substrate with a hard coat coating, comprising the above features.

[0017]

[10] The hard coat coated substrate according to [9], further comprising an adhesive layer disposed between the substrate and the hard coat coating.

[0018]

[11] A hard-coated substrate according to [9] or

[10] , for use in automotive components. [Effects of the Invention]

[0019] According to the present invention, it is possible to provide a paint composition with excellent abrasion resistance, weather resistance, initial appearance, and pot life. [Modes for carrying out the invention]

[0020] The following describes in detail embodiments for carrying out the present invention (hereinafter simply referred to as "this embodiment"). It should be noted that the present invention is not limited to the following embodiments, and can be implemented in various modifications within the scope of its gist.

[0021] [Paint composition] The paint composition of this embodiment is a paint composition comprising polymer nanoparticles (A) and a matrix raw material component (B'), wherein the matrix raw material component (B') comprises an organic ultraviolet absorber (Z) having an alkoxysilane moiety, and the Martens hardness of the polymer nanoparticles (A) is HM A and the Martens hardness HM of the matrix raw material component (B') B' HMB' / HM A It is characterized by satisfying the relationship of >1.

[0022] Since the paint composition of this embodiment is configured as described above, it is excellent in abrasion resistance, weather resistance, and pot life as a paint. The paint composition of this embodiment exhibits high-level abrasion resistance and paintability, and is useful, for example, as a hard coat material for building materials, automotive parts, electronic devices, electrical products, etc., although not limited to the following. In particular, it is preferably used for automotive parts.

[0023] In this specification, any coating film containing the paint composition of this embodiment is referred to as coating film (C). That is, coating film (C) means any coating film obtained by curing the paint composition of this embodiment. Also, in this specification, the martens hardness HM measured by the method described later is 100 N / mm 2 A coating film (C) that is more than the above may be particularly referred to as a "hard coat coating film".

[0024] [Polymer Nanoparticles (A)] By using the polymer nanoparticles (A) in this embodiment, impact absorbency can be imparted to the coating film (C), and the amount of haze change in the Taber abrasion test of the hard coat coating film can be reduced. The shape of the polymer nanoparticles (A) is not particularly limited as long as its particle size is on the nm order (less than 1 μm).

[0025] [Average Particle Diameter of Polymer Nanoparticles (A)] The average particle diameter of the polymer nanoparticles (A) in this embodiment is not particularly limited as long as it is on the nm order (less than 1 μm), and is determined from the size of the particles observed by cross-sectional SEM or dynamic light scattering method. The average particle diameter of the polymer nanoparticles (A) is preferably 10 nm or more and 400 nm or less, more preferably 15 nm or more and 200 nm or less, and still more preferably 20 nm or more and 100 nm or less from the viewpoint of optical properties. The method for measuring the average particle size of polymer nanoparticles (A) is not limited to the following, but examples include preparing an aqueous dispersion of polymer nanoparticles (A) in accordance with the procedure described in the examples below, and measuring the cumulant particle size of the aqueous dispersion using a dynamic light scattering particle size distribution analyzer (model number: ELSZ-1000) manufactured by Otsuka Electronics Co., Ltd. The average particle size of polymer nanoparticles (A) can be adjusted to the above-mentioned range by, for example, the structure and composition ratio of the constituent components of polymer nanoparticles (A), and / or polymerization conditions. [Hydrolyzable silicon compounds (a)] In this embodiment, the polymer nanoparticles (A) preferably contain a hydrolyzable silicon compound (a). The hydrolyzable silicon compound (a) is not particularly limited as long as it is a hydrolyzable silicon compound, its hydrolysis product, or a condensate.

[0026] From the viewpoint of improving wear resistance and weather resistance, the hydrolyzable silicon compound (a) is preferably a compound containing the atomic group represented by the following formula (a-1), its hydrolysis product, and condensate. -R 1 n1 SiX 1 3-n1 (a-1)

[0027] In formula (a-1), R 1 R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group. 1 X may have substituents containing halogen, hydroxyl, mercapto, amino, (meth)acryloyl, or epoxy groups. 1 n1 represents a hydrolyzable group, and n1 represents an integer from 0 to 2. The hydrolyzable group is not particularly limited as long as it is a group that generates a hydroxyl group upon hydrolysis. Examples of such groups include halogens, alkoxy groups, acyloxy groups, amino groups, phenoxy groups, and oxime groups.

[0028] Compounds containing the atomic group represented by formula (a-1) are not limited to the following, but include, for example, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, hexyltrimethoxylane, hexyltriethoxylane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxy Sisilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane, methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, bis(triphenoxysilyl)ethane, 1,1-bis(triethoxysilyl) Ethane, 1,2-bis(triethoxysilyl)ethane, 1,1-bis(triethoxysilyl)propane, 1,2-bis(triethoxysilyl)propane, 1,3-bis(triethoxysilyl)propane, 1,4-bis(triethoxysilyl)butane, 1,5-bis(triethoxysilyl)pentane, 1,1-bis(trimethoxysilyl)ethane, 1,2-bis(trimethoxysilyl)ethane, 1,1-bis(trimethoxysilyl)propane, 1,2-bis(trimethoxysilyl)propane, 1,3-bis(trimethoxy Sisilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1,3-bis(triphenoxysilyl)propane, 1,4-bis(trimethoxysilyl)benzene, 1,4-bis(triethoxysilyl)benzene, 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,7-bis(trimethoxysilyl)heptane, 1,7-bis(triethoxysilyl)heptane, 1,8-bis(trimethoxysilyl)octane, 1,8-Bis(triethoxysilyl)octane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-Methacryloxypropyltriethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, Vinyltrimethoxylane, Vinyltriethoxylan, p-Styryltrimethoxysilane, p-Styryltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxy Sisilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, 3-trimethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, 3-triethoxysilyl-N-(1,3-Dimethyl-butylidene)propylamine, triacetoxysilane, tris(trichloroacetoxy)silane, tris(trifluoroacetoxy)silane, tris-(trimethoxysilylpropyl)isocyanurate, tris-(triethoxysilylpropyl)isocyanurate, methyltriacetoxysilane, methyltris(trichloroacetoxy)silane, trichlorosilane, tribromosilane, methyltrifluorosilane, tris(methylethylketoxime)silane, phenyltris(methylethylketoxime)silane, bis(methylethylketoxime)silane, methylbis(methylethylketoxime)silane, hexamethyldisilane, hexamethylcyclotrisilazane, bis Examples include bis(dimethylamino)dimethylsilane, bis(diethylamino)dimethylsilane, bis(dimethylamino)methylsilane, bis(diethylamino)methylsilane, 2-[(triethoxysilyl)propyl]dibenzylresorcinol, 2-[(trimethoxysilyl)propyl]dibenzylresorcinol, 2,2,6,6-tetramethyl-4-[3-(triethoxysilyl)propoxy]piperidine, 2,2,6,6-tetramethyl-4-[3-(trimethoxysilyl)propoxy]piperidine, 2-hydroxy-4-[3-(triethoxysilyl)propoxy]benzophenone, and 2-hydroxy-4-[3-(trimethoxysilyl)propoxy]benzophenone.

[0029] The hydrolyzable silicon compound (a) may include the compound represented by the following formula (a-2), its hydrolysis product, and condensate. SiX 2 4(a-2) In formula (a-2), X 2 The symbol represents a hydrolyzable group. A hydrolyzable group is not particularly limited as long as it is a group that generates a hydroxyl group through hydrolysis, and examples include halogens, alkoxy groups, acyloxy groups, amino groups, phenoxy groups, and oxime groups.

[0030] Specific examples of compounds represented by formula (a-2) are, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetra(n-propoxy)silane, tetra(i-propoxy)silane, tetra(n-butoxy)silane, tetra(i-butoxy)silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraacetoxysilane, tetra(trichloroacetoxy)silane, tetra(trifluoroacetoxy)silane, tetrachlorosilane, tetrabromosilane, tetrafluorosilane, tetra(methylethylketoxyme)silane, tetramethoxysilane, or tetraethoxysilane. Examples include partial hydrolysis condensates of ore (for example, "M-Silicate 51", "Silicate 35", "Silicate 45", "Silicate 40", and "FR-3" manufactured by Tama Chemical Industry Co., Ltd.; "MS51", "MS56", "MS57", and "MS56S" manufactured by Mitsubishi Chemical Corporation; and "Methyl Silicate 51", "Methyl Silicate 53A", "Ethyl Silicate 40", "Ethyl Silicate 48", "EMS-485", "N-103X", "PX", "PS-169", "PS-162R", "PC-291", "PC-301", "PC-302R", "PC-309", and "EMSi48" manufactured by Colcoat Co., Ltd.).

[0031] As described above, in this embodiment, it is preferable that the hydrolyzable silicon compound (a) includes one or more selected from compounds containing the atomic group represented by formula (a-1), their hydrolysis products and condensates, and compounds represented by formula (a-2), their hydrolysis products and condensates.

[0032] [Content of hydrolyzable silicon compound (a) in polymer nanoparticles (A)] In this embodiment, the content of hydrolyzable silicon compound (a) refers to the solid weight percentage of hydrolyzable silicon compound (a) contained in polymer nanoparticles (A). A higher content is preferable from the viewpoint of improving abrasion resistance, weather resistance, and heat resistance, and the content is preferably 50% by mass or more, and more preferably 60% by mass or more. There is no particular upper limit to the content of hydrolyzable silicon compound (a), but it may be 95% by mass, 90% by mass, or 85% by mass. The content of hydrolyzable silicon compound (a) in polymer nanoparticles (A) is not limited to the following, but can be measured by, for example, IR analysis, NMR analysis, elemental analysis, etc. of polymer nanoparticles (A).

[0033] [Functional group (e)] In the coating composition of this embodiment, it is preferable that the polymer nanoparticles (A) have a functional group (e) that interacts with the matrix raw material component (B'). When the polymer nanoparticles (A) have a functional group (e), the matrix raw material component (B') tends to adsorb more easily to the surface of the polymer nanoparticles (A), forming a protective colloid and stabilizing it, which in turn tends to improve the storage stability of the coating composition. Furthermore, when the polymer nanoparticles (A) have a functional group (e), the interaction between the polymer nanoparticles (A) and the matrix raw material component (B') becomes stronger, increasing the viscosity of the coating composition with respect to the solid content concentration, which tends to suppress sagging when coating complex shapes, and as a result, the film thickness of the coating film (C) tends to become more uniform. The presence of a functional group (e) in the polymer nanoparticles (A) can be confirmed, for example, by compositional analysis using IR, GC-MS, pyrolysis GC-MS, LC-MS, GPC, MALDI-MS, TOF-SIMS, TG-DTA, NMR, and combinations thereof.

[0034] Specific examples of functional group (e) in this embodiment include, but are not limited to, hydroxyl groups, carboxyl groups, amino groups, amide groups, and functional groups consisting of ether bonds. From the viewpoint of interaction, it is preferable that the functional group has hydrogen bonds, and from the viewpoint of high hydrogen bonding ability, it is more preferable that it is an amide group, and even more preferable that it is a secondary amide group and / or a tertiary amide group.

[0035] Compounds containing functional group (e) and their reaction products include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl vinyl ether or 4-hydroxybutyl vinyl ether, 2-hydroxyethyl allyl ether, (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-diethylaminoethyl (meth)acrylate, 2-di-n-propylaminoethyl (meth)acrylate, 3-dimethylaminopropyl (meth)acrylate, 4-dimethylaminobutyl (meth)acrylate, N-[2-(meth)acryloyloxy]ethylmorpholine, vinylpyridine, N-vinylcarbazole, N-vinylquinoline, N-methylacrylamide, N-methylmethacrylamide Lylamide, N-ethylacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N-ethylmethacrylamide, N-methyl-N-ethylacrylamide, N-methyl-N-ethylmethacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, N-propylmethacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylhexahydroazepine, N-acryloylmorpholine, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N,N'-methylenebisacrylamide, N,Examples include N'-methylenebismethacrylamide, N-vinylacetamide, diacetone acrylamide, diacetone methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, Bremmer PE-90, PE-200, PE-350, PME-100, PME-200, PME-400, AE-350 (trade name, manufactured by Nippon Oil & Fats Co., Ltd.), MA-30, MA-50, MA-100, MA-150, RA-1120, RA-2614, RMA-564, RMA-568, RMA-1114, MPG130-MA (trade name, manufactured by Nippon Emulsifier Co., Ltd.). In this specification, (meth)acrylate is a simplified notation for acrylate or methacrylate, and (meth)acrylic acid is a simplified notation for acrylic acid or methacrylic acid.

[0036] [Core / shell structure of polymer nanoparticles (A)] In this embodiment, the polymer nanoparticle (A) preferably has a core / shell structure comprising a core layer and one or more shell layers covering the core layer. From the viewpoint of interaction with the matrix raw material component (B') in the outermost layer of the core / shell structure, the polymer nanoparticle (A) preferably has the aforementioned functional group (e).

[0037] [Other compounds that may be included in polymer nanoparticles (A)] The polymer nanoparticles (A) according to this embodiment may include the following polymers, from the viewpoint of improving particle stability by providing electrostatic repulsion between particles. Examples include polyurethane-based, polyester-based, poly(meth)acrylate-based, poly(meth)acrylic acid-based, polyvinyl acetate-based, polybutadiene-based, polyvinyl chloride-based, chlorinated polypropylene-based, polyethylene-based, and polystyrene-based polymers, or poly(meth)acrylate-silicone-based, polystyrene-(meth)acrylate-based, and styrene-maleic anhydride-based copolymers.

[0038] Among the polymers that may be included in the polymer nanoparticles (A) described above, polymers or copolymers of (meth)acrylic acid and (meth)acrylate are particularly excellent in terms of electrostatic repulsion. Specific examples, though not limited to those listed below, include polymers or copolymers of methyl acrylate, (meth)acrylic acid, methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, n-butyl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. In this case, to further improve the electrostatic repulsion force, part or all of the (meth)acrylic acid may be neutralized with amines such as ammonia, triethylamine, or dimethylethanolamine, or bases such as NaOH or KOH.

[0039] Furthermore, polymer nanoparticles (A) may contain an emulsifier. The emulsifier is not particularly limited and includes, for example, acidic emulsifiers such as alkylbenzene sulfonic acid, alkyl sulfonic acid, alkyl sulfosuccinic acid, polyoxyethylene alkyl sulfate, polyoxyethylene alkylaryl sulfate, and polyoxyethylene distyrylphenyl ether sulfonic acid; anionic surfactants such as alkali metal (Li, Na, K, etc.) salts of acidic emulsifiers, ammonium salts of acidic emulsifiers, and fatty acid soaps; cationic surfactants of the quaternary ammonium salt, pyridinium salt, or imidazolinium salt type such as alkyltrimethylammonium bromide, alkylpyridinium bromide, and imidazolinium laurate; nonionic surfactants such as polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene oxypropylene poroc copolymer, and polyoxyethylene distyrylphenyl ether, as well as reactive emulsifiers having radically polymerizable double bonds.

[0040] Examples of the reactive emulsifier having a radically polymerizable double bond include, but are not limited to, Eleminol JS-2 (trade name, manufactured by Sanyo Chemical Industries, Ltd.), Latemul S-120, S-180A or S-180 (trade name, manufactured by Kao Corporation), Aqualon HS-10, KH-1025, RN-10, RN-20, RN30, RN50 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekarya Soap SE1025, SR-1025, NE-20, NE-30, NE-40 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), alkyl sulfonic acid (meth)acrylates such as ammonium salt of p-styrenesulfonic acid, sodium salt of p-styrenesulfonic acid, potassium salt of p-styrenesulfonic acid, and methylpropanesulfonic acid (meth)acrylamide, ammonium salt of allylsulfonic acid, sodium salt of allylsulfonic acid, and potassium salt of allylsulfonic acid.

[0041] [Elastic recovery rate η of polymer nanoparticles (A)] ITA ] Elastic recovery rate η of polymer nanoparticle (A) in this embodiment ITA This is W in ISO14577-1 elast / W total Ratio η IT The parameters listed were measured using a coating of deposited polymer nanoparticles (A), and the total mechanical work W of the depression was measured. total Work done by the elastic return deformation of the depression W elast It is expressed as a ratio to the elastic recovery rate η. ITA The higher the elastic recovery rate η of polymer nanoparticles (A), the better the coating can return to its original state after being subjected to impact, indicating a high self-healing capacity against impact. From the perspective of effectively exhibiting self-healing capacity, the elastic recovery rate η of polymer nanoparticles (A) ITA The value is 0.30 or higher under the measurement conditions (Vickers square pyramidal diamond indenter, load increase condition 2mN / 20sec, load decrease condition 2mN / 20sec), and from the viewpoint of being able to follow the deformation of the substrate and matrix raw material components (B') when forming the coating film (C), η ITA It is 0.90 or less. Elastic recovery rate η of polymer nanoparticle (A) ITAThe elastic recovery rate η is preferably 0.50 or higher, and more preferably 0.60 or higher. The elastic recovery rate of polymer nanoparticles (A) can be measured, but is not limited to the following: for example, polymer nanoparticles (A) and matrix raw material components (B') can be separated by operations such as centrifugation and ultrafiltration, the separated polymer nanoparticles (A) can be dispersed in a solvent to obtain a composition, the composition can be applied, dried to form a film, and the resulting film can be measured using a microhardness tester Fischerscope (HM2000S, Fischer Instruments), an ultra-micro indentation hardness tester (ENT-NEXUS, Elionix Co., Ltd.), a nanoindenter (iNano, G200, Toyo Technica Co., Ltd.), a nanoindentation system (TI980, Bruker, etc.). ITA Methods for adjusting the above range include, but are not limited to, adjusting the structure and composition ratio of the constituent components of polymer nanoparticles (A).

[0042] The amount of polymer nanoparticles (A) is preferably 3% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 55% by mass or less, and even more preferably 10% by mass or more and 50% by mass or less, based on the solid content of the paint composition.

[0043] [Matrix raw material component (B')] By using the matrix raw material component (B') in this embodiment, shock absorption properties can be imparted to the coating film (C), and the amount of haze change in the Taber abrasion test of the coating film (C) can be reduced.

[0044] [Hydrolyzable silicon compounds (b)] In this embodiment, from the viewpoint of high toughness, the matrix raw material component (B') includes a hydrolyzable silicon compound (b). In this specification, "the matrix raw material component (B') includes a hydrolyzable silicon compound (b)" means that the matrix raw material component (B') includes a polymer having constituent units derived from the hydrolyzable silicon compound (b). The hydrolyzable silicon compound (b) is not particularly limited as long as it is a hydrolyzable silicon compound, its hydrolysis product, and condensate.

[0045] The matrix raw material component (B') may include various components other than the polymer nanoparticles (A), in addition to the polymers mentioned above. Other polymers that may be included in addition to the polymers mentioned above include water-soluble resins such as polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, and polyacrylic acid; acrylic resins such as PMMA, PAN, and polyacrylamide; polymers such as polystyrene, polyurethane, polyamide, polyimide, polyvinylidene chloride, polyester, polycarbonate, polyether, polyethylene, polysulfone, polypropylene, polybutadiene, PTFE, PVDF, and EVA; and copolymers thereof.

[0046] From the viewpoint of further improving abrasion resistance and weather resistance, the hydrolyzable silicon compound (b) preferably contains one or more compounds selected from the group consisting of compounds containing the atomic group represented by the following formula (b-1), their hydrolysis products, and condensates, and compounds represented by the following formula (b-2), their hydrolysis products, and condensates. -R 2 n2 SiX 3 3-n2 (b-1) In formula (b-1), R 2 R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group. 2 X may have substituents containing halogen, hydroxyl, mercapto, amino, (meth)acryloyl, or epoxy groups. 3 n² represents a hydrolyzable group, and n² represents an integer from 0 to 2. The hydrolyzable group is not particularly limited as long as it is a group that generates a hydroxyl group upon hydrolysis. Examples of such groups include halogen atoms, alkoxy groups, acyloxy groups, amino groups, phenoxy groups, and oxime groups. SiX 4 4(b-2) In formula (b-2), X 4The symbol represents a hydrolyzable group. A hydrolyzable group is not particularly limited as long as it is a group that generates a hydroxyl group through hydrolysis. Examples of such groups include halogens, alkoxy groups, acyloxy groups, amino groups, phenoxy groups, and oxime groups.

[0047] Specific examples of compounds containing the atomic group represented by general formula (b-1) are, but are not limited to, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, hexyltrimethoxylane, hexyltriethoxylan, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxy Sisilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane, methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, bis(triphenoxysilyl)ethane, 1,1-bis(triethoxysilyl) Ethane, 1,2-bis(triethoxysilyl)ethane, 1,1-bis(triethoxysilyl)propane, 1,2-bis(triethoxysilyl)propane, 1,3-bis(triethoxysilyl)propane, 1,4-bis(triethoxysilyl)butane, 1,5-bis(triethoxysilyl)pentane, 1,1-bis(trimethoxysilyl)ethane, 1,2-bis(trimethoxysilyl)ethane, 1,1-bis(trimethoxysilyl)propane, 1,2-bis(trimethoxysilyl)propane, 1,3-bis(trimethoxy Sisilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1,3-bis(triphenoxysilyl)propane, 1,4-bis(trimethoxysilyl)benzene, 1,4-bis(triethoxysilyl)benzene, 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,7-bis(trimethoxysilyl)heptane, 1,7-bis(triethoxysilyl)heptane, 1,8-bis(trimethoxysilyl)octane, 1,8-Bis(triethoxysilyl)octane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-Methacryloxypropyltriethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, Vinyltrimethoxylane, Vinyltriethoxylan, p-Styryltrimethoxysilane, p-Styryltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxy Sisilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, 3-trimethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, 3-triethoxysilyl-N-(1,3-Dimethyl-butylidene)propylamine, triacetoxysilane, tris(trichloroacetoxy)silane, tris(trifluoroacetoxy)silane, tris-(trimethoxysilylpropyl)isocyanurate, tris-(triethoxysilylpropyl)isocyanurate, methyltriacetoxysilane, methyltris(trichloroacetoxy)silane, trichlorosilane, tribromosilane, methyltrifluorosilane, tris(methylethylketoxime)silane, phenyltris(methylethylketoxime)silane, bis(methylethylketoxime)silane, methylbis(methylethylketoxime)silane, hexameth Ludisilane, hexamethylcyclotrisilazane, bis(dimethylamino)dimethylsilane, bis(diethylamino)dimethylsilane, bis(dimethylamino)methylsilane, bis(diethylamino)methylsilane, 2-[(triethoxysilyl)propyl]dibenzylresorcinol, 2-[(trimethoxysilyl)propyl]dibenzylresorcinol, 2,2,6,6-tetramethyl-4-[3-(triethoxysilyl)propoxy]piperidine, 2,2,6,6-tetramethyl-4-[3-(trimethoxysilyl)propoxy]piperidine, 4-(triethoxysilylpropoxy)-2,2,6,6-tetramethylpiperidine Examples include N-oxide, 4-{3-[(triethoxy)silyl]propoxy}-1,2,2,6,6-pentamethylpiperidine, 4-(triethoxysilylpropoxy)-2,2,6,6-tetramethylpiperidine, 4-{3-[(trimethoxy)silyl]propoxy}-1,2,2,6,6-pentamethylpiperidine, 2-hydroxy-4-[3-(triethoxysilyl)propoxy]benzophenone, and 2-hydroxy-4-[3-(trimethoxysilyl)propoxy]benzophenone.

[0048] Specific examples of compounds represented by formula (b-2) are, but are not limited to, tetramethoxysilane, tetraethoxysilane, tetra(n-propoxy)silane, tetra(i-propoxy)silane, tetra(n-butoxy)silane, tetra(i-butoxy)silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraacetoxysilane, tetra(trichloroacetoxy)silane, tetra(trifluoroacetoxy)silane, tetrachlorosilane, tetrabromosilane, tetrafluorosilane, tetra(methylethylketoxyme)silane, tetramethoxysilane, or tetraethoxysilane. Examples include partial hydrolysis condensates of ore (for example, "M-Silicate 51", "Silicate 35", "Silicate 45", "Silicate 40", and "FR-3" manufactured by Tama Chemical Industry Co., Ltd.; "MS51", "MS56", "MS57", and "MS56S" manufactured by Mitsubishi Chemical Corporation; and "Methyl Silicate 51", "Methyl Silicate 53A", "Ethyl Silicate 40", "Ethyl Silicate 48", "EMS-485", "N-103X", "PX", "PS-169", "PS-162R", "PC-291", "PC-301", "PC-302R", "PC-309", and "EMSi48" manufactured by Colcoat Co., Ltd.).

[0049] As described above, in this embodiment, it is preferable that the hydrolyzable silicon compound (b) includes one or more selected from compounds containing the atomic group represented by formula (b-1), their hydrolysis products and condensates, and compounds represented by formula (b-2), their hydrolysis products and condensates.

[0050] [Organic UV absorber containing an alkoxysilane moiety (Z)] In this embodiment, from the viewpoint of high weather resistance and pot life, the matrix raw material component (B') includes an organic ultraviolet absorber (Z) having an alkoxysilane moiety. By using an ultraviolet absorber having an alkoxysilane moiety, higher weather resistance can be obtained compared to ultraviolet absorbers without an alkoxysilane moiety, through co-condensation with other types of matrix raw material component (B'). As for the organic ultraviolet absorber (Z) having an alkoxysilane moiety, it is preferable to have two or more silicon atoms in the molecule from the viewpoint of enhancing co-condensation properties.

[0051] [Types of organic UV absorbers (Z) containing alkoxysilane moieties] In this embodiment, the organic ultraviolet absorber (Z) having an alkoxysilane moiety preferably contains one or more of the following from the viewpoint of high weather resistance: benzophenone-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, malonic acid ester-based ultraviolet absorbers, oxalic acid anilide-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. Furthermore, from the viewpoint of pot life, it is more preferable that the ultraviolet absorber contains one or more of the following: benzophenone-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, malonic acid ester-based ultraviolet absorbers, and oxalic acid anilide-based ultraviolet absorbers. Among organic UV absorbers (Z) having an alkoxysilane moiety, examples of organic UV absorbers from which the alkoxysilane moiety has been removed include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (BASF trade name "UVINUL3049"), and 2,2',4,4'-tetrahydroxybenzophenone. Benzophenone-based UV absorbers such as benzophenone (BASF brand name "UVINUL3050"), 4-dodecyloxy-2-hydroxybenzophenone, 5-benzoyl-2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-stearyloxybenzophenone, 4,6-dibenzoylresortinol, and ethyl-2-cyano-3,3-diphenylacrylate (BASF brand name "UVINUL3035"), (2-ethylhexyl)-2-cyano-3,3-diphenylacrylate (BASF brand name "UVINUL3039"), 1,3-bis((2'-cyano-3',3'-diphenylacryloyl)oxy)-2,2-bis-(((2'-cyano-3',Cyanoacrylate-based UV absorbers such as 3'-diphenylacryloyl(oxy)methyl(propane) (BASF brand name "UVINUL3030"); malonic acid ester-based UV absorbers such as HOSTAVIN PR25, HOSTAVIN B-CAP, HOSTAVIN VSU (brand name, manufactured by Clariant); HOSTAVIN3206 LIQ, HOSTAVINVSU P, HOSTAVIN3212 Anilide-based UV absorbers such as LIQ (trade name, manufactured by Clariant), 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-octylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α'-dimethylbenzyl)phenyl]benzotriazole), methyl-3-[3-tert-butyl-5-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate, and polyethylene glycol (molecular weight 300) (BASF trade name "TIN UVIN1130"), isooctyl-3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionate (BASF brand name "TINUVIN384"), 2-(3-dodecyl-5-methyl-2-hydroxyphenyl)benzotriazole (BASF brand name "TINUVIN571"), 2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-[2'-hydroxy-3'-(3",4",5",6"-tetrahydrophthalimidomethyl)-5'-methylphenyl]benzotriazole, 2,2-methylenebis[4-(1,1,3,3-Tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol, 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (BASF brand name "TINUVIN900"), TINUVIN384-2, TINUVIN326, TINUVIN327, TINUVIN109, TINUVIN970, TINUVIN328, TINUVIN171, TINUVIN970, TINUVIN PS, TINUVIN Benzotriazole-based UV absorbers such as P, TINUVIN99-2, TINVIN928 (trade names, manufactured by BASF), 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyl) Examples of triazine-based UV absorbers include oxyphenyl)-6-(2,4-bisbutyloxyphenyl)-1,3,5-triazine (BASF trade name "TINUVIN460"), 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (BASF trade name "TINUVIN479"), TINUVIN400, TINUVIN405, TINUVIN477, and TINUVIN1600 (trade names, manufactured by BASF). Examples of the structure of the alkoxysilane moiety in the organic UV absorber (Z) having an alkoxysilane moiety include, for example, a silane structure in which a 1-6, preferably 1-3, alkoxy group is monosubstituted, disubstituted, or trisubstituted.

[0052] [Weight fraction of organic UV absorbers (Z) containing alkoxysilane moieties in the solid content] In this embodiment, from the viewpoint of high abrasion resistance, high weather resistance, and pot life, the organic ultraviolet absorber (Z) having an alkoxysilane moiety is preferably 0.5% by mass or more and 13% by mass or less in weight fraction of the solid content of the paint composition. When it is 0.5% by mass or more, sufficient ultraviolet absorption intensity is obtained and weather resistance is improved. When it is 13% by mass or less, both sufficient abrasion resistance and the formation of a coating film with a good appearance can be achieved. From the viewpoint of weather resistance, the lower limit of the weight fraction of the organic ultraviolet absorber (Z) having an alkoxysilane moiety in the solid content is preferably in the range of 0.5% by mass or more, more preferably in the range of 3% by mass or more, and even more preferably in the range of 6% by mass or more. Furthermore, from the viewpoint of abrasion resistance and appearance, the upper limit of the weight fraction of this ultraviolet absorber (Z) in the solid content is preferably in the range of 13% by mass or less, and more preferably in the range of 10% by mass or less.

[0053] In this embodiment, the "hydrolyzable silicon compound (a) contained in the polymer nanoparticle (A)" may be the same type as the "hydrolyzable silicon compound (b) contained in the matrix raw material component (B')", or it may be a different type. Even if the two are the same type, they are distinguished by designating the one contained in the polymer nanoparticle (A) as hydrolyzable silicon compound (a) and the one contained in the matrix raw material component (B') as hydrolyzable silicon compound (b).

[0054] [Elastic recovery rate η of matrix raw material component (B')] ITB' and the elastic recovery rate η of the matrix component (B) ITB ] In the coating composition of this embodiment, the elastic recovery rate η of the matrix raw material component (B') ITB' This is "W" in ISO14577-1. elast / W total Ratio η IT The parameter described as "measures the coating film of the deposited matrix raw material component (B'), and the total mechanical work W of the depression" is measured. total Work done by the elastic return deformation of the depression W elast It is expressed as a ratio to the elastic recovery rate η. ITB'The higher the value, the more likely the coating film is to return to its original state after being subjected to impact, indicating a high self-healing capacity against impact. From the perspective of effectively exhibiting self-healing capacity, the elastic recovery rate η of the matrix raw material component (B') is important. ITB' The value is preferably 0.60 or higher, and more preferably 0.65 or higher, under the measurement conditions (Vickers square pyramidal diamond indenter, load increase condition 2mN / 20sec, load decrease condition 2mN / 20sec). Furthermore, from the viewpoint of being able to follow the deformation of the substrate and component (A) when forming the coating film, η ITB' It is preferable that the value is 0.95 or less. The measurement of the elastic recovery rate of the matrix raw material component (B') is not limited to the following, but for example, polymer nanoparticles (A) and matrix raw material component (B') can be separated by an operation such as centrifugation, the separated matrix raw material component (B') can be dissolved in a solvent to form a composition, which can then be applied to a surface, dried, and the resulting coating can be measured using a microhardness tester Fischerscope (Fischer Instruments HM2000S), an ultra-micro indentation hardness tester (Erionix Co., Ltd. ENT-NEXUS), a nanoindenter (Toyo Technica Co., Ltd. iNano, G200), a nanoindentation system (Bruker TI980), etc. As described later, the cured product obtained by hardening the matrix raw material component (B') by hydrolysis condensation, etc., corresponds to matrix component (B). Therefore, the elastic recovery rate η of the matrix raw material component (B') measured by the method described in the examples below ITB' The value of is the elastic recovery rate η of the corresponding matrix component (B). ITB As something that closely matches, the elastic recovery rate η ITB The value of can be determined. That is, the elastic recovery rate η of the matrix component (B) in this embodiment. ITB Preferably, it is 0.60 or higher, and more preferably 0.65 or higher. Also, from the viewpoint of being able to follow the deformation of the substrate and component (A) when forming the coating film, η ITB It is preferable that the value is 0.95 or less. Elastic recovery rate η ITB' and elastic recovery rate η ITBMethods for adjusting the above range include, but are not limited to, adjusting the structure and composition ratio of the components of the matrix raw material component (B').

[0055] [Inorganic oxides (D)] In this embodiment, the matrix raw material component (B') preferably contains an inorganic oxide (D). Including an inorganic oxide (D) not only improves the hardness of the matrix raw material component (B') and enhances its abrasion resistance, but also tends to improve the stain resistance of the coating film due to the hydrophilicity of the hydroxyl groups on the particle surface.

[0056] Specific examples of the inorganic oxide (D) in this embodiment include, but are not limited to, oxides of silicon, aluminum, titanium, zirconium, zinc, cerium, tin, indium, gallium, germanium, antimony, molybdenum, niobium, magnesium, bismuth, cobalt, copper, and others. Preferably, it contains at least one inorganic component selected from the group consisting of Si, Ce, Nb, Al, Zn, Ti, Zr, Sb, Mg, Sn, Bi, Co, and Cu. These can be used individually or as a mixture, regardless of their form. From the viewpoint of interaction with the hydrolyzable silicon compound (b) described above, it is preferable for the inorganic oxide (D) to further contain silica, such as dry silica or colloidal silica, and from the viewpoint of dispersibility, it is preferable to further contain colloidal silica in the form of silica particles. When the inorganic oxide (D) contains colloidal silica, it is preferably in the form of an aqueous dispersion and can be used in either an acidic or basic solution. Colloidal silica that can be included in the inorganic oxide (D) will be described later. Furthermore, from the viewpoint of weather resistance, the inorganic oxide (D) preferably contains at least one selected from the group consisting of cerium oxide, niobium oxide, aluminum oxide, zinc oxide, titanium oxide, zirconium oxide, antimony oxide, magnesium oxide, tin oxide, bismuth oxide, cobalt oxide, and copper oxide, which have ultraviolet light absorption ability. From the viewpoint of improving weather resistance performance, it preferably contains at least one inorganic component selected from the group consisting of niobium oxide, zinc oxide, titanium oxide, and zirconium oxide, and more preferably cerium oxide. When using commercially available products, although not limited to the following, examples include ultrafine particle material products of cerium oxide, zinc oxide, aluminum oxide, bismuth oxide, cobalt oxide, copper oxide, tin oxide, and titanium oxide manufactured by CIK Nanotech Co., Ltd.; titanium oxide "Tynock" (trade name), cerium oxide "Needral" (trade name), tin oxide "Ceramase" (trade name), niobium oxide sol, and zirconium oxide sol manufactured by Taki Chemical Co., Ltd.; and antimony pentoxide aqueous sol "A-2550" manufactured by Nissan Chemical Industries, Ltd.

[0057] [Average particle size of inorganic oxides (D)] In this embodiment, the average particle size of the inorganic oxide (D) is preferably 2 nm or more from the viewpoint of good storage stability of the paint composition, and preferably 150 nm or less from the viewpoint of good transparency. That is, the average particle size of the inorganic oxide (D) is preferably 2 nm or more and 150 nm or less, more preferably 2 nm or more and 100 nm or less, and even more preferably 2 nm or more and 50 nm or less. The method for measuring the average particle size of the inorganic oxide (D) is not limited to the following, but for example, it can be measured by observing water-dispersed colloidal silica using a transmission microscope at a magnification of 50,000 to 100,000 times, taking a photograph so that 100 to 200 inorganic oxide particles are visible, and measuring from the average value of the major and minor axes of the inorganic oxide particles.

[0058] [Colloidal silica that can be included in inorganic oxides (D)] The acidic colloidal silica with water as the dispersion solvent, which is preferably used in this embodiment, is not particularly limited, but can be prepared by the sol-gel method or a commercially available product can be used. When preparing by the sol-gel method, refer to Werner Stober et al; J. Colloid and Interface Sci., 26, 62-69 (1968), Rickey D. Badley et al; Lang muir 6, 792-801 (1990), Journal of the Color Materials Association, 61[9] 488-493 (1988), etc. Examples of commercially available products include Snowtex-O, Snowtex-OS, Snowtex-OXS, Snowtex-O-40, Snowtex-OL, Snowtex-OYL, Snowtex-OUP, Snowtex-PS-SO, Snowtex-PS-MO, Snowtex-AK-XS, Snowtex-AK, Snowtex-AK-L, Snowtex-AK-YL, Snowtex-AK-PS-S (product names, manufactured by Nissan Chemical Industries, Ltd.), Adelite AT-20Q (product name, manufactured by Asahi Denka Kogyo Co., Ltd.), Crevosol 20H12, and Crevosol 30CAL25 (product names, manufactured by Clariant Japan Co., Ltd.).

[0059] Furthermore, basic colloidal silica includes silica stabilized by the addition of alkali metal ions, ammonium ions, and amines, and is not particularly limited, but examples include Snowtex-20, Snowtex-30, Snowtex-XS, Snowtex-50, Snowtex-30L, Snowtex-XL, Snowtex-YL, Snowtex-ZL, Snowtex-UP, Snowtex-ST-PS-S, Snowtex-ST-PS-M, Snowtex-C, Snowtex-CXS, Snowtex-CM, Snowtex-N, Snowtex-NXS, Snowtex-NS, and Snowtex-N-4. Examples include 0 (product name, manufactured by Nissan Chemical Industries, Ltd.), Adelite AT-20, Adelite AT-30, Adelite AT-20N, Adelite AT-30N, Adelite AT-20A, Adelite AT-30A, Adelite AT-40, Adelite AT-50 (product name, manufactured by Asahi Denka Kogyo Co., Ltd.), Crevozol 30R9, Crevozol 30R50, Crevozol 50R50 (product name, manufactured by Clariant Japan Co., Ltd.), Rudox HS-40, Rudox HS-30, Rudox LS, Rudox AS-30, Rudox SM-AS, Rudox AM, Rudox HSA, and Rudox SM (product name, manufactured by DuPont).

[0060] Furthermore, while there are no particular limitations on colloidal silica using a water-soluble solvent as the dispersion medium, examples include MA-ST-M (methanol dispersion type with particle size of 20-25 nm), IPA-ST (isopropyl alcohol dispersion type with particle size of 10-15 nm), EG-ST (ethylene glycol dispersion type with particle size of 10-15 nm), EGST-ZL (ethylene glycol dispersion type with particle size of 70-100 nm), NPC-ST (ethylene glycol monopropyl ether dispersion type with particle size of 10-15 nm), and TOL-ST (toluene dispersion type with particle size of 10-15 nm), all manufactured by Nissan Chemical Industries, Ltd.

[0061] Dry silica particles are not particularly limited, but examples include AEROSIL manufactured by Nippon Aerosil Co., Ltd. and Rheoroseal manufactured by Tokuyama Corporation.

[0062] Furthermore, these silica particles may contain inorganic bases (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia) or organic bases (such as tetramethylammonium and triethylamine) as stabilizers.

[0063] [Shape of inorganic oxides (D)] Furthermore, the shape of the inorganic oxide (D) in this embodiment is not limited to the following, but examples include spherical, angular, polyhedral, elliptical, flattened, linear, bead-like, and pearl-like shapes. From the viewpoint of hardness and transparency of the hard coat film, spherical, bead-like, or pearl-like shapes are particularly preferred.

[0064] The amount of inorganic oxide (D) is preferably 1% by mass or more and 50% by mass or less, more preferably 2% by mass or more and 40% by mass or less, and even more preferably 3% by mass or more and 30% by mass or less, based on the solid content of the paint composition.

[0065] [Other ingredients] From the viewpoint of further improving the paintability of the paint composition of this embodiment, the paint composition may, in addition to the above-mentioned components, optionally contain thickeners, leveling agents, thixotropizing agents, defoaming agents, freeze stabilizers, dispersants, wetting agents, rheology control agents, film-forming aids, rust inhibitors, plasticizers, lubricants, preservatives, fungicides, antistatic agents, and antistatic agents as matrix raw material components (B'). From the viewpoint of improving film-forming properties, it is preferable to use wetting agents and film-forming aids, and specifically, although not particularly limited, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol mono-2-ethylhexyl ether, 2,2,4-trimethyl-1,3-butanediol isobutyrate, diisopropyl glutarate, propylene glycol-n-butyl ether, dipropylene glycol-n-butyl ether, and tripropylene glycol-n-butyl Examples include ethers, dipropylene glycol methyl ether, tripylene glycol methyl ether, Megafac F-443, F-444, F-445, F-470, F-471, F-472SF, F-474, F-475, F-477, F-479, F-480SF, F-482, F-483, F-489, F-172D, F-178K (trade names, manufactured by DIC Corporation), SN Wet 366, SN Wet 980, SN Wet L, SN Wet S, SN Wet 125, SN Wet 126, SN Wet 970 (trade names, manufactured by Sunopco Corporation). These compounds may be used individually or in combination of two or more.

[0066] Furthermore, depending on the application, the matrix raw material component (B') may include solvents, pigments, dyes, fillers, antioxidants, conductive materials, organic ultraviolet absorbers, light stabilizers, release modifiers, softeners, surfactants, flame retardants, and antioxidants. In particular, for outdoor applications where high weather resistance is required, it is preferable to include organic ultraviolet absorbers and light stabilizers. If the ultraviolet absorber containing alkoxysilane, which is an essential component in this invention, is omitted, it is preferable to add it in an amount that does not impair the appearance or other physical properties. Specific examples of organic UV absorbers and light stabilizers include, but are not limited to, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2, Benzophenone-based UV absorbers such as 2'-dihydroxy-4,4'-dimethoxybenzophenone (BASF brand name "UVINUL3049"), 2,2',4,4'-tetrahydroxybenzophenone (BASF brand name "UVINUL3050"), 4-dodecyloxy-2-hydroxybenzophenone, 5-benzoyl-2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-stearyloxybenzophenone, and 4,6-dibenzoylresortinol;2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-octylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α'-dimethylbenzyl)phenyl] Condensate of benzotriazole, methyl-3-[3-tert-butyl-5-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate and polyethylene glycol (molecular weight 300) (BASF brand name "TINUVIN 1130"), isooctyl-3-[3-(2H-benzotriazole-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionate (BASF brand name "TINUVIN 384"), 2-(3-dodecyl-5-methyl-2-hydroxyphenyl) Nyl)benzotriazole (BASF brand name "TINUVIN571"), 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-[2'-hydroxy-3'-(3",4",5",6"-tetrahydrophthalimidomethyl)-5'-methylphenyl]benzotriazole, Benzotriazole-based UV absorbers such as 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol], 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (BASF trade name "TINUVIN900"), TINUVIN384-2, TINUVIN326, TINUVIN327, TINUVIN109, TINUVIN970, TINUVIN328, TINUVIN171, TINUVIN970, TINUVINPS, TINUVINP, TINUVIN99-2, and TINVIN928 (trade names, manufactured by BASF);2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bisbutyloxyphenyl) Triazine-based UV absorbers such as -1,3,5-triazine (BASF brand name "TINUVIN 460"), 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (BASF brand name "TINUVIN 479"), TINUVIN 400, TINUVIN 405, TINUVIN 477, TINUVIN 1600 (product names, BASF); malonic acid ester-based UV absorbers such as HOSTAVIN PR25, HOSTAVIN B-CAP, HOSTAVIN VSU (product names, Clariant); HOSTAVIN 3206 LIQ, HOSTAVIN VSU P, HOSTAVIN 3212 Anilide-based UV absorbers such as LIQ (trade name, manufactured by Clariant); salicylate-based UV absorbers such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanolphenyl salicylate; ethyl-2-cyano-3,3-diphenyl acrylate (trade name "UVINUL3035" manufactured by BASF). Cyanoacrylate-based UV absorbers such as (2-ethylhexyl)-2-cyano-3,3-diphenylacrylate (BASF brand name "UVINUL3039") and 1,3-bis((2'-cyano-3',3'-diphenylacryloyl)oxy)-2,2-bis-(((2'-cyano-3',3'-diphenylacryloyl)oxy)methyl)propane (BASF brand name "UVINUL3030");2-Hydroxy-4-acryloxybenzophenone, 2-Hydroxy-4-methacryloxybenzophenone, 2-Hydroxy-5-acryloxybenzophenone, 2-Hydroxy-5-methacryloxybenzophenone, 2-Hydroxy-4-(acryloxy-ethoxy)benzophenone, 2-Hydroxy-4-(methacryloxy-ethoxy)benzophenone, 2-Hydroxy-4-(methacryloxy-diethoxy)benzophenone, 2-Hydroxy-4-(acryloxy-triethoxy)benzophenone, 2-(2'-Hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole (product name "RUVA-93" manufactured by Otsuka Chemical Co., Ltd.), 2-(2'-Hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole Radical polymerizable ultraviolet absorbers having radically polymerizable double bonds in their molecules, such as tacryloxyethyl-3-tert-butylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacrylyloxypropyl-3-tert-butylphenyl)-5-chloro-2H-benzotriazole, and 3-methacryloyl-2-hydroxypropyl-3-[3'-(2''-benzotriazolyl)-4-hydroxy-5-tert-butyl]phenylpropionate (trade name "CGL-104" manufactured by Ciba-Geigy Japan Co., Ltd.); ultraviolet absorbing polymers such as UV-G101, UV-G301, UV-G137, UV-G12, and UV-G13 (trade names manufactured by Nippon Shokubai Co., Ltd.);Bis(2,2,6,6-tetramethyl-4-piperidyl) succinate, bis(2,2,6,6-tetramethylpiperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butylmalonate, 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynyloxy]-2,2,6,6-tetramethyl Hindered amine light stabilizers such as lupiperidine, a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl-sebacate (BASF brand name "TINUVIN292"), bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, TINUVIN123, TINUVIN144, TINUVIN152, TINUVIN249, TINUVIN292, and TINUVIN5100 (brand names, BASF). ;1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-iminopiperidyl methacrylate, 2,2,6,6-tetramethyl-4-iminopiperidyl methacrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-cyano-1,2, Examples include radically polymerizable hindered amine-based light stabilizers such as 2,6,6-pentamethyl-4-piperidyl methacrylate; photostable polymers such as U-double E-133, U-double E-135, U-double S-2000, U-double S-2834, U-double S-2840, U-double S-2818, and U-double S-2860 (trade names, manufactured by Nippon Shokubai Co., Ltd.); and UV absorbers that react with isocyanate groups, epoxy groups, semicarbazide groups, and hydrazide groups. These may be used individually or in combination of two or more.

[0067] [catalyst] The paint composition may contain a catalyst. A paint composition containing a catalyst that promotes the reaction between reactive groups is preferable because it reduces the likelihood of unreactive groups remaining in the coating film, resulting in higher hardness, improved abrasion resistance, and enhanced weather resistance. The catalyst is not particularly limited, but it is preferable that it dissolves or disperses when obtaining the hard coat layer. Examples of such catalysts, though not particularly limited, include organic acids, inorganic acids, organic bases, inorganic bases, metal alkoxides, and metal chelates. These catalysts may be used individually or in combination of two or more. From the viewpoint of pot life, a catalyst that can be adjusted to a pH of 2.7 to 4.5, and more preferably 3.3 to 4.5 or lower, is preferable as a method to suppress the sol-gel reaction of alkoxysilanes. Specifically, catalysts that combine inorganic acids and inorganic bases to form a buffer solution, or catalysts containing metal chelates specialized for the condensation reaction of alkoxysilanes, are preferred. The amount of additive is preferably in the range of 0.1 to 10% relative to the solid content of the paint, more preferably in the range of 0.2 to 5%, and even more preferably in the range of 0.3 to 1.5%.

[0068] [solvent] As described above, the coating composition of this embodiment may contain a solvent. The usable solvent is not particularly limited, and general solvents can be used. The solvent is not limited to the following, but for example, water; ethylene glycol, butyl cellosolve, isopropanol, n-butanol, 2-butanol, ethanol, methanol, denatured ethanol, 2-methoxy-1-propanol, 1-methoxy-2-propanol, diacetone alcohol glycerin, monoalkyl monoglyceryl ether, propylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, diethylene glycol mono Examples of solvents include alcohols such as phenyl ether, tetraethylene glycol, and monophenyl ether; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, cyclohexane, and heptane; esters such as ethyl acetate and n-butyl acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran and dioxane; amides such as dimethylacetamide and dimethylformamide; halogen compounds such as chloroform, methylene chloride, and carbon tetrachloride; dimethyl sulfoxide and nitrobenzene; and these may be used individually or in combination of two or more. Among these, it is particularly preferable to include water and alcohols from the viewpoint of reducing the environmental burden during solvent removal. It is preferable that the main component of the solvent be water. When the main component of the solvent is water, it means that 50% or more by mass of the solvent is water.

[0069] [Martens hardness] In this embodiment, the Martens hardness is a hardness value compliant with ISO 14577-1, and is calculated from the indentation depth at 2 mN under the measurement conditions (Vickers square pyramidal diamond indenter, load increase condition 2 mN / 20 sec, load decrease condition 2 mN / 20 sec). In this embodiment, the Martens hardness can be measured using, for example, a microhardness tester Fischerscope (HM2000S manufactured by Fischer Instruments), an ultra-micro indentation hardness tester (ENT-NEXUS manufactured by Elionix Co., Ltd.), a nanoindenter (iNano, G200 manufactured by Toyo Technica Co., Ltd.), or a nanoindentation system (TI980 manufactured by Bruker). The shallower the indentation depth, the higher the Martens hardness, and the deeper the indentation depth, the lower the Martens hardness.

[0070] [Hardness of polymer nanoparticles (A) HM A and the hardness HM of the matrix raw material component (B') B' ] In the coating composition of this embodiment, the Martens hardness HM of the polymer nanoparticle (A) A And the Martens hardness HM of the matrix raw material component (B') B' This satisfies the relationship shown in equation (1) below. HM B' / HM A >1 formula (1)

[0071] Equation (1) is 20 > HM B' / HM A It is preferable that the relationship >1 is satisfied, and 15>HM B' / HM A It is more preferable that the relationship >1.2 is satisfied, and 10 > HM B' / HM A It is even more preferable that the relationship >1.5 is satisfied.

[0072] The coating film (C) is formed by curing the paint composition of this embodiment, and therefore the coating film (C) contains polymer nanoparticles (A) and a matrix component (B). Since the matrix component (B) corresponds to a cured product obtained by curing the matrix raw material component (B') by hydrolysis condensation or the like, the Martens hardness HM of the matrix raw material component (B') is measured by the method described in the examples below. B' The value of the corresponding matrix component (B) is the Martens hardness HM B A good match is the Martens hardness HM. B The value of can be determined. Therefore, equation (1) can be rewritten as equation (2). HM B / HM A >1 Formula (2)

[0073] Equation (2) shows that flexible polymer nanoparticles (A) are present within a rigid matrix component (B). This three-dimensional gradient of hardness allows the coating film (C) to exhibit abrasion resistance not found in conventional coating films. While not limited to the above, this is presumed to be because the flexible nanoparticles absorb impact, and the rigid matrix component suppresses deformation.

[0074] HM A The range is 50 N / mm 2 More than 2000N / mm 2 The following is preferable: 100 N / mm 2 More than 800N / mm 2 The following is more preferable: 100 N / mm 2 More than 350N / mm 2 The following is even more preferable. HM B' The range is 100 N / mm 2 More than 4000N / mm 2 The following is preferable: 150 N / mm 2 More than 4000N / mm 2 The following is more preferable: 150 N / mm 2 More than 2000N / mm 2 The following is even more preferable.

[0075] In the paint composition of the present embodiment, each martensitic hardness can be measured based on the method described in the examples below for each of the separated polymer nanoparticles (A) and matrix raw material component (B') by operations such as centrifugation and ultrafiltration to separate them.

[0076] It is normal for the composition of the polymer nanoparticles (A) not to change during such a curing process. Therefore, the martensitic hardness HM of the polymer nanoparticles (A) in the paint composition measured by the method described in the examples below A is considered to closely match the martensitic hardness HM of the polymer nanoparticles (A) in the paint film (C), and the value of the martensitic hardness HM A in the paint film (C) can be determined. A The values of the above HM

[0077] and HM A and HM B' can be adjusted to have the above-described magnitude relationship according to the structure and composition ratio of the constituent components of the polymer nanoparticles (A) and the matrix raw material component (B'), respectively, but are not particularly limited to this method.

[0078] [Other hardness] The relative magnitudes of Martens hardness in the above-described embodiment can also be estimated by confirming the relative magnitudes of measured values ​​using other hardness indicators. Other hardness indicators are not particularly limited as long as they indicate the resistance of a material to deformation when force is applied to it. Examples include Vickers hardness and indentation hardness measured with indentation hardness testers such as microhardness testers and nanoindentation measuring instruments, and logarithmic decay rate measured with pendulum-type viscoelasticity testers such as rigid pendulum-type physical property testers. In addition, indicators expressed as adhesion force, phase, friction force, viscoelasticity, adsorption force, hardness, and elastic modulus, measured with a scanning probe microscope (SPM), can also be mentioned. If it is confirmed that the hardness of the matrix raw material component (B') is higher than that of the polymer nanoparticles (A) in these indicators, then it can be estimated that the matrix raw material component (B') (matrix component (B)) is harder than the polymer nanoparticles (A) in terms of Martens hardness and adhesion force.

[0079] [Solid content concentration of paint composition] The paint composition has a preferred solid content concentration of 10 to 30% by mass, more preferably 12 to 21% by mass, from the viewpoint of paintability and storage stability. In this embodiment, "solid content of the paint composition" refers to the non-volatile components in the paint composition, including polymer nanoparticles (A), hydrolyzable silicon compounds (b), organic ultraviolet absorbers having alkoxysilane moieties (Z), and inorganic oxides (D). The solid content concentration can be measured specifically based on the procedure described in the examples below.

[0080] [Viscosity of paint composition] In this embodiment, from the viewpoint of paintability, the viscosity of the paint composition at 20°C is preferably 0.1 to 100,000 mPa·s, and preferably 1 to 10,000 mPa·s.

[0081] [pH of paint composition] In this embodiment, from the viewpoint of wear resistance and storage stability, the pH is preferably 2.7 to 4.5, and more preferably 3.3 to 4.5 or lower.

[0082] [Content of hydrolyzable silicon compound (b) per 100% by mass of solid content] In this embodiment, the content of hydrolyzable silicon compound (b) relative to 100% by mass of the solid content of the paint composition is preferably 10% by mass or more and 90% by mass or less, and more preferably 15% by mass or more and 80% by mass or less, from the viewpoint of abrasion resistance and storage stability. The content of hydrolyzable silicon compound (b) referred to here is also determined by a value calculated from the ratio of the weight equivalent to complete hydrolysis condensation in the weight excluding volatile components from the amount of each raw material charged during the preparation of the paint composition. The above content can be calculated from the amount of each ingredient charged based on the procedure described in the examples below, or it can be measured by, for example, IR analysis, NMR analysis, elemental analysis, etc. of the coating film (C), although this is not limited to the following.

[0083] <Method for manufacturing paint composition> The method for producing the coating composition of this embodiment is not particularly limited, but for example, the coating composition of this embodiment can be obtained by appropriately selecting polymer nanoparticles (A) and matrix raw material components (B') so as to satisfy the above formula (1), mixing them, and, if necessary, adding a solvent such as ethanol to adjust the solid content concentration or a pH adjuster such as triethylamine to adjust the pH.

[0084] [Coating film (C)] The coating film (C) of this embodiment contains the paint composition of this embodiment. That is, the coating film (C) is formed (cured) from the paint composition of this embodiment. In the coating film (C), it is preferable that the polymer nanoparticles (A) are dispersed in the matrix component (B). In this embodiment, "dispersion" means that the polymer nanoparticles (A) are in a dispersed phase and the matrix component (B) is in a continuous phase, and the polymer nanoparticles (A) are distributed uniformly or while forming a structure within the matrix component (B). The above dispersion can be confirmed by cross-sectional SEM observation of the coating film (C). In the coating film (C) of this embodiment, the polymer nanoparticles (A) are dispersed in the matrix component (B), which tends to result in high abrasion resistance.

[0085] [Film thickness of coating film (C)] In the present embodiment, from the viewpoint of further expressing the abrasion resistance of the coating film (C) and ensuring sufficient followability to the deformation of the base material, it is preferable to appropriately adjust the film thickness. Specifically, from the viewpoint of abrasion resistance, the film thickness of the coating film (C) is preferably 1.0 μm or more, more preferably 3.0 μm or more. Further, from the viewpoints of weather resistance and substrate followability, the film thickness of the coating film (C) is preferably 100.0 μm or less, more preferably 50.0 μm or less, and even more preferably 20.0 μm or less.

[0086] [Martens hardness HM of coating film (C)] The Martens hardness HM of the coating film (C) is preferably 160 N / mm 2 or more. The higher it is, the less deformation occurs against impact, and it tends to be advantageous in that there is less damage accompanied by fracture. The Martens hardness HM of the coating film (C) is more preferably 180 N / mm 2 or more, and even more preferably 200 N / mm 2 or more. From the viewpoint of flexural resistance, it is preferably 400 N / mm 2 or less, and more preferably 350 N / mm 2 or less. As a method for adjusting the Martens hardness HM of the coating film (C) within the above range, it is not limited to the following, but for example, the coating composition of the present embodiment is applied onto a base material and formed into a coating film by heat treatment, ultraviolet irradiation, infrared irradiation, etc. In particular, when increasing the content of the matrix raw material component (B') with respect to the total amount of the polymer nanoparticles (A) and the matrix raw material component (B'), the Martens hardness HM of the coating film (C) tends to increase, and when decreasing the content of the matrix raw material component (B'), the Martens hardness HM of the coating film (C) tends to decrease.

[0087] [Amount of haze change in Taber abrasion test] The Taber wear test in this embodiment is based on the method described in ASTM D1044, and the measurement is performed using a wear wheel CS-10F under a load of 500g. The smaller the haze change, the better the wear resistance of the material. If the haze change after 500 rotations compared to the haze before the test, i.e., the difference between the haze after 500 rotations and the haze before the Taber wear test, is 10 or less, it conforms to the ECE R43 standard for rear quarter glass, and if it is 4 or less, it conforms to the ANSI / SAE Z.26.1 standard and is suitable for use as an automotive window material. Furthermore, if the haze change amount at 1000 revolutions, that is, the difference between the haze at 1000 revolutions and the haze before the Taber abrasion test, is 10 or less, it conforms to the standards for automobile windows and can be suitably used as an automobile window material. If it is 2 or less, it conforms to the standards of ANSI / SAE Z.26.1, ECE R43, and JIS R3211 / R3212 and can be suitably used for all automobile window materials. The difference between the haze at 1000 revolutions and the haze before the Taber abrasion test is preferably 10 or less, more preferably 6 or less, and even more preferably 2 or less. Methods for adjusting the haze change amount to within the above range are not limited to the following, but include, for example, applying the paint composition of this embodiment onto a substrate and forming a coating film by heat treatment, ultraviolet irradiation, infrared irradiation, etc.

[0088] [Elastic recovery rate η of coating film (C)] IT ] Elastic recovery rate η of coating film (C) IT The total mechanical work W of the depression is total Work done by the elastic return deformation of the depression W elast This is the ratio to ISO14577-1, and is "W elast / W total Ratio η IT This parameter is described as "elastic recovery rate η". IT The higher the elastic recovery rate η, the more likely the coating film is to return to its original state after deformation, indicating a high self-healing capacity against deformation. From the perspective of effectively exhibiting self-healing capacity, the elastic recovery rate η ITThe elastic recovery rate η is preferably 0.50 or higher under the measurement conditions (Vickers square pyramidal diamond indenter, load increase condition 2mN / 20sec, load decrease condition 2mN / 20sec), and within this range, a larger value is preferable. More specifically, the elastic recovery rate η IT It is more preferable that the value is 0.55 or higher, even more preferably 0.60 or higher, and even more preferably 0.65 or higher. The measurement of the elastic recovery rate of the coating film in this embodiment is not limited to the following, but for example, it can be measured by performing an indentation test on the surface of the coating film (C) using a microhardness tester Fischerscope (HM2000S manufactured by Fischer Instruments), an ultra-micro indentation hardness tester (ENT-NEXUS manufactured by Elionix Co., Ltd.), a nanoindenter (iNano, G200 manufactured by Toyo Technica Co., Ltd.), a nanoindentation system (TI980 manufactured by Bruker), etc. Elastic recovery rate η IT Methods for adjusting the values ​​to the above range include, but are not limited to, applying the paint composition of this embodiment onto a substrate and forming a coating film by heat treatment, ultraviolet irradiation, infrared irradiation, etc.

[0089] [Substrate with hard coat coating] The hard coat coated substrate according to this embodiment includes a substrate and the hard coat coating of this embodiment formed on one and / or both sides of the substrate. As described above, the hard-coated substrate of this embodiment has high abrasion resistance and high durability. The hard-coated substrate of this embodiment exhibits high levels of abrasion resistance and stain resistance, and is therefore useful as a hard coat for building materials, automotive components, electronic equipment, electrical products, etc., although it is not limited to the following, and is particularly preferable for use in automotive components. That is, it is preferable that the hard-coated substrate of this embodiment is formed on at least a portion of building materials, automotive components, electronic equipment, electrical products, etc. as the substrate, and it is more preferable that the hard-coated substrate of this embodiment is formed on at least a portion of automotive components as the substrate.

[0090] [Base material] The substrate in this embodiment is not particularly limited, but examples include resins, ceramics, metals, and glass. The shape of the substrate is not limited to the following, but examples include plate-like shapes, shapes with irregularities, shapes with curved surfaces, hollow shapes, porous shapes, and combinations thereof. Furthermore, the type of substrate is not limited, but examples include sheets, films, and fibers. From the viewpoint of transparency, the substrate preferably contains a transparent resin and / or glass, and from the viewpoint of moldability, a transparent resin is preferred. That is, a substrate with a hard coat coating having a substrate containing a transparent resin and a hard coat coating film containing the coating composition of this embodiment tends to have better abrasion resistance, moldability, and weather resistance. The transparent resin used as the substrate is not limited to the following, but examples include thermoplastic resins and thermosetting resins. The thermoplastic resin used as the substrate is not limited to the following, but examples include polyethylene, polypropylene, polystyrene, ABS resin, vinyl chloride resin, methyl methacrylate resin, nylon, fluororesin, polycarbonate, and polyester resin. Furthermore, while not limited to the following, thermosetting resins used as base materials include phenolic resins, urea resins, melamine resins, unsaturated polyester resins, epoxy resins, silicon resins, silicone rubber, SB rubber, natural rubber, and thermosetting elastomers.

[0091] [Transparency] The transparency of the hard-coated substrate in this embodiment can be evaluated by the total light transmittance from the viewpoint of appearance change. In this embodiment, the total light transmittance of the hard-coated substrate is preferably 80% or more, more preferably 85% or more from the viewpoint of ensuring daylighting, and particularly preferably 90% or more from the viewpoint of ensuring visibility through the material.

[0092] [Adhesive layer] The substrate with a hard coat coating according to this embodiment may further have an adhesive layer between the substrate and the hard coat coating. The adhesive layer can be a commonly used adhesive layer, and is not particularly limited; examples include thermoplastic resins, thermosetting resins, rubber / elastomers, and among these, acrylic resins, acrylic urethane resins, urethane resins, and silicone resins are preferred. Furthermore, the adhesive layer may contain any suitable additives as needed. Examples of additives, but not limited to, include crosslinking agents, tackifiers, plasticizers, pigments, dyes, fillers, antioxidants, conductive materials, ultraviolet absorbers, inorganic oxides, light stabilizers, release modifiers, softeners, surfactants, flame retardants, and antioxidants. Crosslinking agents are not limited to the following, but examples include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, carbodiimide-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, amine-based crosslinking agents, peroxide-based crosslinking agents, melamine-based crosslinking agents, urea-based crosslinking agents, metal alkoxide-based crosslinking agents, metal chelate-based crosslinking agents, and metal salt-based crosslinking agents.

[0093] In this embodiment, a functional layer may be further provided on at least one surface of the hard coat coating. Examples of functional layers include, but are not limited to, an anti-reflective layer, an anti-fouling layer, a polarizing layer, and an impact-absorbing layer.

[0094] [Method for manufacturing a substrate with a hard coat coating] The method for manufacturing the hard coat coated substrate of this embodiment is not particularly limited, but for example, it can be obtained by applying the coating composition of this embodiment to the substrate and forming a coating film by heat treatment, ultraviolet irradiation, infrared irradiation, etc. Furthermore, the coating method is not limited to the following, but examples include spray application, flow coating, brush application, dip coating, spin coating, screen printing, casting, gravure printing, flexographic printing, etc. When applying to a curved substrate, the nozzle flow coating method, dip coating method, and spray application method are particularly preferred. The coated coating composition of this embodiment can be formed into a coating film by heat treatment at room temperature to 250°C, more preferably 40°C to 150°C, or by ultraviolet or infrared irradiation, etc. Furthermore, this coating can be applied not only to already molded substrates, but also to pre-coated flat plates before molding, such as pre-coated metals including rust-resistant steel plates.

[0095] [Surface treatment of hard coat coating] The hard coat coating of this embodiment may have a silica layer formed on its surface by silica processing, from the viewpoint of weather resistance. The method for forming the silica layer is not particularly limited, but specific examples include silica processing by PECVD, which involves vapor deposition / curing of silicone or silazane, and silica processing technology, which modifies the surface to silica by 155 nm ultraviolet irradiation. Surface processing by PECVD is particularly preferred because it can produce a layer that is impermeable to oxygen and water vapor without degrading the surface. Silicones or silazanes that can be used in PECVD are not limited to the following, but specifically include octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, vinylmethrixylane, vinylmethoxysilane, dimethyldimethoxylane, TEOS, tetramethyldisiloxane, tetramethyltetravinylcyclotetrasiloxane, hexamethyldisilazane, and others, and one or more of these may be used in combination.

[0096] [Applications of hard coat coatings and hard coat coated substrates] The hard coat coating and hard coat coated substrate of this embodiment have excellent abrasion resistance and durability. Therefore, the applications of the hard coat coating and hard coat coated substrate are not particularly limited, but examples include building materials, vehicle components, electronic equipment, and electrical products.

[0097] While not limited to the following, examples of building material applications include windows for construction machinery, windows for buildings, houses, greenhouses, roofs for garages and arcades, lighting fixtures such as lights and traffic signals, wallpaper, signs, sanitary products such as bathtubs and washbasins, exterior wall materials for kitchens, flooring materials, cork, tiles, cushion flooring, and interior flooring materials such as linoleum.

[0098] Vehicle components include, but are not limited to, parts used in automobiles, aircraft, and trains. Specific examples include various types of glass such as front, rear, front doors, rear doors, rear quarter windows, and sunroofs; exterior components such as front and rear bumpers, spoilers, door mirrors, front grilles, emblem covers, and bodywork; interior components such as center panels, door panels, instrument panels, and center consoles; components for lamps such as headlamps and taillights; lens components for on-board cameras; lighting covers; decorative films; and various glass substitute components.

[0099] Examples of preferred electronic devices and electrical products include, but are not limited to, mobile phones, personal digital assistants, personal computers, portable game consoles, office automation equipment, solar cells, flat panel displays, touch panels, optical discs such as DVDs and Blu-ray discs, optical components such as polarizing plates and optical filters, lenses, prisms, and optical fibers, and optical films such as anti-reflective films, alignment films, polarizing films, and phase difference films.

[0100] In addition to the above, the hard coat coating and the substrate with the hard coat coating of this embodiment can be applied to a variety of fields, including machine parts, agricultural materials, fishing materials, transport containers, packaging containers, toys, and general merchandise. [Examples]

[0101] The following describes this embodiment with reference to specific examples and comparative examples, but this embodiment is not limited to these.

[0102] The various physical properties in the examples and comparative examples described later were measured by the following methods.

[0103] (1) Measurement of thickness The thickness of each layer was measured using a reflection spectrometer (model number: FE-3000) manufactured by Otsuka Electronics Co., Ltd.

[0104] (2) Average particle size of polymer nanoparticles (A) The cumulant particle size was measured using a dynamic light scattering particle size distribution analyzer (model number: ELSZ-1000) manufactured by Otsuka Electronics Co., Ltd., with the aqueous dispersion of polymer nanoparticles (A) obtained by the method described later, and this was determined as the average particle size of polymer nanoparticles (A).

[0105] (3) Primary average particle size of inorganic oxides (D) Using a transmission microscope, the samples were observed at a magnification of 50,000 to 100,000 times, with images taken to capture 100 to 200 inorganic oxide particles. The average values ​​of the major and minor axes of these inorganic oxide particles were measured, and these values ​​were defined as the primary mean particle diameter of inorganic oxide (D).

[0106] (4) Solid content concentration of the paint composition and weight ratio of hydrolyzable silicon compound (b) to 100% by mass of solid content concentration The solid content concentration of the paint composition was calculated from the ratio of the total mass of the paint composition to the mass of the non-volatile components obtained by drying the composition. Next, the weight ratio of hydrolyzable silicon compound (b) to 100% solid content by mass was calculated from the ratio of the mass of the non-volatile component to the content of hydrolyzable silicon compound (b), which was calculated as described above. In this calculation, the content of hydrolyzable silicon compound (b) was expressed as the weight equivalent to complete hydrolysis and condensation. Here, the weight equivalent to complete hydrolysis and condensation was defined as the weight when the hydrolyzable groups of the hydrolyzable silicon compound used in the preparation undergo 100% hydrolysis to become OSiO groups, and then completely condense to form a siloxane.

[0107] (5) Measurement of haze Haze was measured using a turbidimeter (model number: NDH5000SP) manufactured by Nippon Denshoku Industries Co., Ltd., according to the method specified in JIS K7136.

[0108] (6) Measurement of Martens hardness HM of the hard coat layer Microhardness was measured using an indentation test (test conditions: indenter: Vickers square pyramidal diamond indenter, load increase condition: 2 mN / 20 sec, load decrease condition: 2 mN / 20 sec) with a Fischerscope (model number: HM2000S) manufactured by Fischer Instruments, and the Martens hardness HM of the hard coat layer was measured based on the indentation test method compliant with ISO 14577-1.

[0109] (7) Martens hardness HM of polymer nanoparticles (A) A Measurement Martens hardness HM of polymer nanoparticles (A) AThe measurement was performed using a coating film obtained by coating a glass substrate (material: white glass plate, thickness: 2 mm) with a film thickness of 3 μm using a bar coater and drying it at 130°C for 2 hours. The microhardness was measured by an indentation test (test conditions: indenter: Vickers square pyramidal diamond indenter, load increase condition: 2 mN / 20 sec, load decrease condition: 2 mN / 20 sec) using a Fischerscope (model: HM2000S) manufactured by Fischer Instruments, and the Martens hardness HM of the polymer nanoparticle (A) was measured based on the indentation test method compliant with ISO 14577-1. A We measured it.

[0110] (8) Martens hardness HM of matrix raw material component (B') B' Measurement Martens hardness HM of component (B') B' The measurement was performed by dissolving or dispersing component (B') at a solid content concentration of 8% by mass in water / ethanol / acetic acid (composition ratio 77% by mass / 20% by mass / 3% by mass). The resulting solution was applied to a glass substrate (material: white glass plate, thickness: 2 mm) using a bar coater to a film thickness of 3 μm, and dried at 130°C for 2 hours. The measurement was then performed using the resulting coating film. The measurement involved measuring the microhardness using an indentation test (test conditions; indenter: Vickers square pyramidal diamond indenter, load increase condition: 2 mN / 20 sec, load decrease condition: 2 mN / 20 sec) with a Fischerscope (model number: HM2000S) manufactured by Fischer Instruments, and was performed based on the indentation test method in accordance with ISO 14577-1. B' The following was measured. As mentioned above, matrix component (B) corresponds to the hydrolysis condensate of the corresponding component (B'). From this, the Martens hardness HM of component (B') measured as described above was B' The value is the Martens hardness HM of the matrix component (B). B A good match is the Martens hardness HM. B' The value of Martens hardness HM B This was used as the value.

[0111] (9) Evaluation of the abrasion resistance of the hard coat layer in the laminate (indicated as "ΔH" in the table) The abrasion resistance of the hard coat layer in the laminate was evaluated using a Taber ablation tester (No. 101) manufactured by Yasuda Seiki Co., Ltd., in accordance with the ASTM D1044 standard. Specifically, a Taber abrasion test was conducted using a CS-10F abrasion wheel and a load of 500g. The haze before the test and the haze after 1000 rotations were measured using a turbidimeter (model number: NDH5000SP) manufactured by Nippon Denshoku Industries Co., Ltd., according to the method specified in JIS R3212. The abrasion resistance of the hard coat layer in the laminate was evaluated as follows by taking the difference between the haze before the test and the haze after 1000 rotations. (Evaluation Criteria) ○: The haze difference before and after the test is 10 or less. ×: The haze difference before and after the exam exceeds 10.

[0112] (10) Weather resistance evaluation of the hard coat layer in the laminate (indicated as "Δb after weather resistance evaluation" in the table) Weather resistance evaluation of the laminate was performed by UV irradiation using a super xenon weathermeter (Suga Test Instruments Co., Ltd., product name SX-75) according to the conditions of the ANSI / SAE Z26.1 standard, at 2000 MJ / m 2 The following evaluation was performed using Δb before and after irradiation. (Evaluation Criteria) ○:Δb≦2 ×:Δb>2

[0113] (11) Initial appearance evaluation of coating film in laminates (referred to as "initial haze" in the table) The haze of the laminated coating films prepared by the methods described in the Examples and Comparative Examples was measured, and the haze value H was evaluated as follows. ○:H<1 △: 1 ≤ H < 3 ×: 3≦H

[0114] (12) Evaluation of pot life (as indicated by "pot life" in the table) The paint compositions obtained by the method described later were left to stand for 24 hours at room temperature. Subsequently, the presence or absence of sedimentation in the water-based paint compositions was visually evaluated, and the residue after filtration through a 400-mesh stainless steel mesh was visually evaluated as follows. (Evaluation Criteria) ○: No sedimentation was observed visually, and a small amount of residue was visible when the coating solution was filtered through a 400-mesh stainless steel mesh. △: Slight sedimentation was observed visually, and residue was seen when the coating solution was filtered through a 400-mesh stainless steel mesh, but it is still usable. ×: Clear subsidence was observed visually, making it unsuitable for use.

[0115] <Preparation of a composite of emulsion particles and inorganic oxides> [Preparation of Composite Particle Aqueous Dispersion] In a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirrer, 960 g of deionized water, 778 g of water-dispersible colloidal silica "Snowtex® PS-SO" (trade name, manufactured by Nissan Chemical Industries, Ltd., solids content 15% by mass, primary average particle size: 15 nm) as an inorganic oxide, 22 g of 10% dodecylbenzenesulfonic acid aqueous solution, 25 g of 2% ammonium persulfate aqueous solution, 45 g of butyl acrylate, 45 g of 2-hydroxyethyl methacrylate, 23 g of N,N-diethylacrylamide, 1 g of acrylic acid, and 3 g of reactive emulsifier (trade name "Adekaria Soap® SR-1025", manufactured by ADEKA Corporation, solids content 25% aqueous solution) were added. Polymerization was then carried out at 80°C using a general emulsion polymerization method. After polymerization, the pH was adjusted to 9 with a 25% ammonia aqueous solution, filtered through a 100-mesh wire mesh to obtain a composite particle aqueous dispersion. The mass ratio of emulsion particles to inorganic oxide (emulsion particles / inorganic oxide) in the obtained composite particle aqueous dispersion was 1 / 1, the average particle size of the composite of emulsion particles and inorganic oxide was 80 nm, and the solid content of the composite was 12% by mass.

[0116] <Preparation of the adhesive-coated substrate (F)> Solution A was obtained by mixing 56.0 g of a composite particle aqueous dispersion as a composite of emulsion particles and inorganic oxides, 5.0 g of water-dispersible block polyisocyanate (WS50-30W (product name) manufactured by Asahi Kasei Corporation) as a curing agent, 1.0 g of a 10% aqueous solution of sodium dodecylbenzenesulfonate as a surfactant, and 19.1 g of water under room temperature conditions. Next, solution B was obtained by mixing 0.54 g of Tinuvin® 400 (trade name, manufactured by BASF Japan Ltd.) as an organic ultraviolet absorber, 0.10 g of Tinuvin® 123 (trade name, manufactured by BASF Japan Ltd.) as a light stabilizer, and 18.3 g of isopropanol as a water-soluble organic solvent under room temperature conditions. A water-based paint composition was obtained by stirring liquid A and then adding liquid B dropwise over 5 minutes at room temperature and mixing. The solid content concentration of the water-based paint composition was 9% by mass. The solid content ratio (parts by mass) of each component in the water-based paint composition was composite particles / block polyisocyanate / Tinuvin400 / Tinuvin123 = 100 / 26.8 / 8 / 1.5. The solvent composition (parts by mass) in the paint composition was water / isopropanol = 80 / 20, and the ratio of the number of moles of hydroxyl groups in the emulsion particles to the number of moles of isocyanate groups in the block polyisocyanate (X = number of moles of isocyanate groups / number of moles of hydroxyl groups) was 0.6. Next, the aforementioned water-based coating composition was applied onto a polycarbonate substrate using a bar coater and dried at 130°C for 2 hours to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, an adhesive-coated substrate (F-1) was obtained.

[0117] <Preparation of aqueous dispersion of polymer nanoparticles (A)> The aqueous dispersion of polymer nanoparticles (A-1) used in the hard coat layer described later was synthesized as follows. In a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirrer, 1500 g of deionized water, 45 g of 10% dodecylbenzenesulfonic acid aqueous solution, 105 g of methyltrimethoxysilane, 23 g of phenyltrimethoxysilane, and 27 g of tetraethoxysilane were added. Polymerization was then carried out at 50°C using a general emulsion polymerization method. After polymerization, the temperature was raised to 80°C, and further polymerization was carried out using a general emulsion polymerization method with 43 g of 2% ammonium persulfate aqueous solution, 11 g of butyl acrylate, 12 g of N,N-diethylacrylamide, 1 g of acrylic acid, and 1 g of 3-methacryloxypropyltrimethoxysilane. After polymerization, the mixture was filtered through a 100-mesh wire mesh to obtain an aqueous dispersion of polymer nanoparticles. The obtained polymer nanoparticles (A-1) had a core-shell structure, an average particle size of 60 nm, and a solid content of 5.9% by mass. The Martens hardness HM of the polymer nanoparticles (A-1) was also measured according to the measurement method described above. A It is 150 N / mm 2 That was the case.

[0118] <Synthesis of an organic ultraviolet absorber (Z) containing an alkoxysilane group> The component (Z) used in the examples and comparative examples described later was synthesized as follows. [Synthesis of an organic UV absorber containing an alkoxysilane group (Z-1)] 20 g of 3-isocyanatetopropyltriethoxysilane "KBE-9007N" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and 10 g of hydroxyl group-containing benzophenone compound "Uvinul3050" (trade name, BASF Japan, 100% solids by mass) were charged into a 100 mL flask equipped with a stirrer, condenser, and thermometer. The mixture was stirred at 120°C for 3 hours, and the resulting solid was designated as an alkoxysilane group-containing organic ultraviolet absorber (Z-1).

[0119] [Synthesis of an alkoxysilane group-containing organic ultraviolet absorber (Z-2)] Except for using 30 g of 3-isocyanate-propyltriethoxysilane "KBE-9007N" (product name, manufactured by Shin-Etsu Chemical Co., Ltd.), the same method as in (Z-1) was used to produce the alkoxysilane group-containing organic ultraviolet absorber (Z-2).

[0120] [Synthesis of an organic UV absorber containing an alkoxysilane group (Z-3)] Except for using 10 g of 3-isocyanate-propyltriethoxysilane "KBE-9007N" (product name, manufactured by Shin-Etsu Chemical Co., Ltd.), the same method as in (Z-1) was used to produce the alkoxysilane group-containing organic ultraviolet absorber (Z-3).

[0121] <Adjustment of matrix raw material component (B')> The component (B') used in the examples and comparative examples described below was prepared.

[0122] [Preparation of matrix raw material component (B'-1)] 4 g of an alkoxysilane group-containing organic ultraviolet absorber (Z-1), 24 g of trimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as hydrolyzable silicon compounds (b), 11 g of tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 7 g of 1,2-bis(triethoxysilyl)ethane, 13 g of 1,2-bis(trimethoxysilyl)hexane "KBM-3066" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), and 75 g of water-dispersible colloidal silica "Snowtex® OXS" (trade name, manufactured by Nissan Chemical Industries, Ltd., solids content 10% by mass, primary average particle size: 5 nm) as an inorganic oxide (D) were mixed under room temperature conditions to obtain matrix raw material component (B'-1).

[0123] [Preparation of matrix raw material component (B'-2)] 9 g of an alkoxysilane group-containing organic ultraviolet absorber (Z-1), 18 g of trimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as hydrolyzable silicon compounds (b), 11 g of tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 7 g of 1,2-bis(triethoxysilyl)ethane, 13 g of 1,2-bis(trimethoxysilyl)hexane "KBM-3066" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), and 75 g of water-dispersible colloidal silica "Snowtex® OXS" (trade name, manufactured by Nissan Chemical Industries, Ltd., solids content 10% by mass, primary average particle size: 5 nm) as an inorganic oxide (D) were mixed under room temperature conditions to obtain matrix raw material component (B'-2).

[0124] [Preparation of matrix raw material component (B'-3)] 2 g of an alkoxysilane group-containing organic ultraviolet absorber (Z-1), 27 g of trimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as hydrolyzable silicon compounds (b), 11 g of tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 7 g of 1,2-bis(triethoxysilyl)ethane, 13 g of 1,2-bis(trimethoxysilyl)hexane "KBM-3066" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), and 75 g of water-dispersible colloidal silica "Snowtex® OXS" (trade name, manufactured by Nissan Chemical Industries, Ltd., solids content 10% by mass, primary average particle size: 5 nm) as an inorganic oxide (D) were mixed under room temperature conditions to obtain matrix raw material component (B'-3).

[0125] [Preparation of matrix raw material component (B'-4)] 4 g of an alkoxysilane group-containing organic ultraviolet absorber (Z-2), 24 g of trimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as hydrolyzable silicon compounds (b), 11 g of tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 7 g of 1,2-bis(triethoxysilyl)ethane, 13 g of 1,2-bis(trimethoxysilyl)hexane "KBM-3066" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), and 75 g of water-dispersible colloidal silica "Snowtex® OXS" (trade name, manufactured by Nissan Chemical Industries, Ltd., solids content 10% by mass, primary average particle size: 5 nm) as an inorganic oxide (D) were mixed under room temperature conditions to obtain matrix raw material component (B'-4).

[0126] [Preparation of matrix raw material component (B'-5)] 5 g of an alkoxysilane group-containing organic ultraviolet absorber (Z-3), 24 g of trimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as hydrolyzable silicon compounds (b), 11 g of tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 7 g of 1,2-bis(triethoxysilyl)ethane, 13 g of 1,2-bis(trimethoxysilyl)hexane "KBM-3066" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), and 75 g of water-dispersible colloidal silica "Snowtex® OXS" (trade name, manufactured by Nissan Chemical Industries, Ltd., solids content 10% by mass, primary average particle size: 5 nm) as an inorganic oxide (D) were mixed under room temperature conditions to obtain matrix raw material component (B'-5).

[0127] [Preparation of matrix raw material component (B'-6)] 4 g of an alkoxysilane group-containing organic ultraviolet absorber (Z-1), 40 g of trimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as hydrolyzable silicon compounds (b), 11 g of tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 7 g of 1,2-bis(triethoxysilyl)ethane, and 75 g of water-dispersible colloidal silica "Snowtex® OXS" (trade name, manufactured by Nissan Chemical Industries, Ltd., solids content 10% by mass, primary average particle size: 5 nm) as an inorganic oxide (D) were mixed under room temperature conditions to obtain matrix raw material component (B'-6).

[0128] [Preparation of matrix raw material component (B'-7)] 4 g of an alkoxysilane group-containing organic ultraviolet absorber (Z-1), 40 g of trimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and 15 g of tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as hydrolyzable silicon compounds (b), and 75 g of water-dispersible colloidal silica "Snowtex® OXS" (trade name, manufactured by Nissan Chemical Industries, Ltd., solids content 10% by mass, primary average particle size: 5 nm) as an inorganic oxide (D) were mixed under room temperature conditions to obtain matrix raw material component (B'-7).

[0129] [Preparation of matrix raw material component (B'-8)] As hydrolyzable silicon compound (b), 46 g of trimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 11 g of tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), and 7 g of 1,2-bis(triethoxysilyl)ethane were mixed under room temperature conditions to obtain matrix raw material component (B'-8). As inorganic oxide (D), 75 g of water-dispersible colloidal silica "Snowtex® OXS" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 10% by mass, primary average particle size: 5 nm) was mixed to obtain matrix raw material component (B'-8).

[0130] [Preparation of matrix raw material component (B'-9)] 11 g of an alkoxysilane group-containing organic ultraviolet absorber (Z-1), 30 g of trimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a hydrolyzable silicon compound (b), 11 g of tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 7 g of 1,2-bis(triethoxysilyl)ethane, and 75 g of water-dispersible colloidal silica "Snowtex® OXS" (trade name, manufactured by Nissan Chemical Industries, Ltd., solids content 10% by mass, primary average particle size: 5 nm) as an inorganic oxide (D) were mixed under room temperature conditions to obtain matrix raw material component (B'-9).

[0131] [Preparation of matrix raw material component (B'-10)] As hydrolyzable silicon compound (b), 43g of trimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 11g of tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), and 7g of 1,2-bis(triethoxysilyl)ethane were mixed under room temperature conditions to obtain matrix raw material component (B'-10). As inorganic oxide (D), 75g of water-dispersible colloidal silica "Snowtex® OXS" (trade name, manufactured by Nissan Chemical Industries, Ltd., solids content 10% by mass, primary average particle size: 5nm) and 15g of water-dispersible cerium oxide sol "Needral B-10" (trade name, manufactured by Taki Chemical Co., Ltd., primary average particle size 8nm, solids content 10% by mass) were mixed to obtain matrix raw material component (B'-10).

[0132] [Preparation of matrix raw material component (B'-11)] As hydrolyzable silicon compounds (b), 43g of trimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 11g of tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), and 7g of 1,2-bis(triethoxysilyl)ethane were mixed under room temperature conditions to obtain matrix raw material component (B'-11). As inorganic oxide (D), 75g of water-dispersible colloidal silica "Snowtex® OXS" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 10% by mass, primary average particle size: 5nm) was mixed. As other components, 2g of 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (trade name "TINUVIN479", manufactured by BASF Ltd.) was mixed to obtain matrix raw material component (B'-11).

[0133] Furthermore, the matrix components in the hard coat layer derived from the matrix raw material components (B'-1) to (B'-11) in the hard coat layer composition are referred to as components (B-1) to (B'-11). The matrix components (B-1) to (B'-11) in the hard coat layer can be said to be hydrolysis condensates of the matrix raw material components (B'-1) to (B'-11).

[0134] [Example 1] A mixture was obtained by mixing the polymer nanoparticle (A) aqueous dispersion prepared above with the matrix raw material component (B'-1) prepared above, such that the solid content mass ratio of polymer nanoparticles (A-1) and matrix component (B-1) was (A):(B) = 20:80. Furthermore, 10 g of a solution obtained by mixing 1 M N acetic acid and 1 M N sodium acetate in a volume ratio of 1:1 was added to the mixture. Next, an aqueous solution of 20% by mass ethanol was used as a solvent, and the mixture was added so that the solid content concentration became 10% by mass to obtain coating composition (1). Then, coating composition (1) was applied to the adhesive layer of the substrate with adhesive layer (F) using a bar coater, and dried at 130°C for 2 hours to obtain a laminate having a hard coat layer with a film thickness of 4.0 μm. Various evaluations were performed on the coating composition and laminate of Example 1. The results are shown in Table 1.

[0135] [Examples 2-7] A laminate was obtained in the same manner as in Example 1, such that the polymer nanoparticles (A-1) and matrix components (B-2) to (B-7) were in a solid content mass ratio of (A):(B) = 20:80. Various evaluations were performed on the coating compositions and laminates of Examples 2 to 7. The results are shown in Table 1.

[0136] [Comparative Examples 1-3] A laminate was obtained in the same manner as in Example 1, such that the polymer nanoparticles (A-1) and matrix components (B-8) to (B-10) were in a solid content mass ratio of (A):(B) = 20:80. Various evaluations were performed on the paint compositions and laminates of Comparative Examples 1 to 3. The results are shown in Table 1.

[0137] [Comparative Example 4] A mixture was obtained by mixing the aqueous dispersion of polymer nanoparticles (A) prepared above with the matrix raw material component (B'-11) prepared above, such that the solid content mass ratio of polymer nanoparticles (A-1) and matrix component (B'-11) was (A):(B) = 20:80. Next, an aqueous solution of ethanol with a concentration of 20% by mass was used as the solvent, and the mixture was added to obtain a paint composition (11) with a solid content concentration of 10% by mass. When a laminate was obtained in the same manner as in Example 1, a whitened paint film was obtained. When the initial haze was measured, it exceeded 3, so paint film evaluation could not be performed. Furthermore, when the pot life of the obtained paint composition (11) was checked, a clear precipitate was observed after 24 hours. The results are shown in Table 1.

[0138] [Table 1] [Industrial applicability]

[0139] The paint composition, hard coat film, and hard coat film-coated substrate provided by the present invention are useful, for example, as hard coats for building materials, as well as automotive components, electronic equipment, and electrical products.

Claims

1. Polymer nanoparticles (A) and Matrix raw material component (B'), A paint composition containing, The matrix raw material component (B') comprises an organic ultraviolet absorber (Z) having a silane structure trisubstituted with alkoxy groups having 1 to 6 carbon atoms, and a hydrolyzable silicon compound (b). The amount of the organic ultraviolet absorber (Z) is 0.5% by mass or more and 13% by mass or less, based on the solid content of the paint composition. The Martens hardness HM of the polymer nanoparticles (A) A The Martens hardness HM of the matrix raw material component (B') B' HM B' / HM A A paint composition characterized by satisfying the relationship >1.

2. The paint composition according to claim 1, wherein the paint composition contains a solvent, and the main component of the solvent is water.

3. The paint composition according to claim 1 or 2, wherein the organic ultraviolet absorber (Z) comprises at least one selected from the group consisting of benzophenone-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, malonic acid ester-based ultraviolet absorbers, and oxalic acid anilide-based ultraviolet absorbers.

4. The paint composition according to any one of claims 1 to 3, wherein the matrix raw material component (B') further comprises an inorganic oxide (D).

5. The paint composition according to claim 4, wherein the inorganic oxide (D) is silica particles.

6. A hard coat film comprising the paint composition according to any one of claims 1 to 5.

7. The hard coat coating according to claim 6, wherein when a Taber abrasion test is performed in accordance with ASTM D1044, using a CS-10F abrasion wheel and a load of 500g, the difference between the haze at 1000 rotations and the haze before the Taber abrasion test is 10 or less.

8. Substrate and A hard coat coating film according to claim 6 or 7 is disposed on one and / or both sides of the substrate, A substrate with a hard coat coating, comprising the above features.

9. The hard coat coated substrate according to claim 8, further comprising an adhesive layer disposed between the substrate and the hard coat coating.

10. A substrate with a hard coat coating according to claim 8 or 9, for use in automotive components.

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