JP2024002168A - Coating composition, hard coating film, and substrate with hard coating film - Google Patents

Abstract

To provide a coating composition that is superior in wear resistance, crack resistance and pot life.SOLUTION: A coating composition includes polymer nanoparticles (A), a matrix raw material component (B') including a hydrolyzable silicon compound (b), and a solvent. Considering α as the calculated organic chain length of the hydrolyzable silicon compound (b), given by the equation (1), the resultant weight average αave is 1.3 or more and 2.2 or less, derived from the content of the hydrolyzable silicon compound (b) relative to 100 mass% of the solid content of the coating composition. The Martens hardness HMA' of the polymer nanoparticles (A) and the Martens hardness HMB' of the matrix raw material component (B') satisfy the relationship of HMB'/HMA'>1. Equation (1) is: calculated organic chain length α=organic chain length between Si atoms/number of Si atoms in the molecule. (Within the molecular structure of the compound (b), when divided into a hydrolyzable segment A and the other segment B, the organic chain length between Si atoms is the sum of the organic chain length a of the segment A and the organic chain length b of the segment B).SELECTED DRAWING: None

Description

The present invention relates to a coating composition, a hard coat film, and a substrate with a hard coat film.

Resin materials have excellent moldability and light weight, but are inferior in hardness, barrier properties, stain resistance, chemical resistance, flame retardance, heat resistance, weather resistance, etc. compared to inorganic materials such as metal and glass. There are many. Among them, the hardness of resin materials is significantly lower than that of inorganic glass, and the surface is easily damaged, so they are often used with a hard coat. Hard-coated resin materials are not used in applications that require high abrasion resistance, durability, and weather resistance because it is difficult to maintain performance under humidity or maintain appearance when exposed to ultraviolet light for long periods of time. Not yet.

For the purpose of imparting wear resistance to resin materials, methods using active energy ray-curable resin compositions (for example, see Patent Document 1), methods of adding inorganic oxides to resin materials (for example, Patent Documents 2 and (see Patent Document 3), a method of adding polymer particles to a resin material (for example, see Patent Document 4), and a method of using a compound having a methacryloxy group as a raw material of the resin material.

Japanese Patent Application Publication No. 2014-109712 JP2006-63244A Japanese Patent Application Publication No. 8-238683 Japanese Patent Application Publication No. 2017-114949

The methods of Patent Document 1 and Patent Document 2 are general methods for imparting wear resistance to resin materials, but it is difficult to impart high abrasion resistance.
The method of Patent Document 3 is a general method that uses a flexible silicone polymer and hard inorganic oxide fine particles as a hard coat film, but the silicone polymer corresponding to the matrix component has sufficient hardness. The wear resistance is not sufficient due to the lack of
The method of Patent Document 4 uses polymer particles, silicone polymer, and inorganic oxide fine particles as a hard coat film, and although there is a description of the physical properties of the paint film, there is no description of the physical properties of each component. , wear resistance is not sufficient. Further, depending on the coating method, a desired film thickness may not be obtained and wear resistance may not be exhibited. Further, Patent Document 4 is a water-based paint and contains a hydrolyzable component, which tends to cause problems with pot life.

The present invention has been made in view of the above-mentioned problems with the prior art, and its purpose is to provide a coating composition that can form a coating film with high abrasion resistance and high crack resistance, and has an excellent pot life. The purpose is to provide.

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by providing a coating composition and a coating film that satisfy predetermined components, and have completed the present invention.
That is, the present invention includes the following aspects.
[1]
Polymer nanoparticles (A);
A matrix raw material component (B') containing a hydrolyzable silicon compound (b),
a solvent;
A coating composition comprising:
When the calculated organic chain length of the hydrolyzable silicon compound (b) given by the following calculation formula (1) is α, the amount of the hydrolyzable silicon compound (b) based on 100% by mass of the solid content of the coating composition. The weight average value α _ave obtained based on the content is 1.3 or more and 2.2 or less,
A coating composition, wherein the Martens hardness HM _A ' of the polymer nanoparticles (A) and the Martens hardness HM _B' of the matrix raw material component (B') satisfy the relationship HM _B' /HM _A '>1.
Calculated organic chain length α=organic chain length between Si atoms/number of Si atoms in molecule (1)
(Here, when dividing the molecular structure of the hydrolyzable silicon compound (b) into a hydrolyzable part A and a part B other than the part A, the organic chain length between Si atoms is It is the sum of the organic chain length a and the organic chain length b of part B.The organic chain length a is the value obtained by dividing the number of organooxysilane structures by 2.When the number of Si atoms in the molecular structure is 1 In this case, the organic chain length b is 0. If the number of Si atoms in the molecular structure is 2, the organic chain length b is the shortest distance from one Si atom to another Si atom. is given as the number of atoms constituting the atomic chain.When the number of Si atoms in the molecular structure is 3 or more, the organic chain length b is given as the number of atoms constituting the shortest atomic chain. (Use the average value.)
[2]
the solvent contains water,
The coating composition according to [1], wherein the water content is 40% by mass or more and 90% by mass or less, based on 100% by mass of the coating composition.
[3]
The coating composition according to [1] or [2], wherein the matrix raw material component (B') contains an inorganic oxide (D).
[4]
The coating composition according to [3], wherein the inorganic oxide (D) contains silica particles.
[5]
The coating composition according to any one of [1] to [4], wherein the matrix raw material component (B') contains a catalyst (E).
[6]
The coating composition according to claim 1, wherein the hydrolyzable silicon compound (b) is a compound containing an atomic group represented by the following formula (b-1).
-R ² _n2 SiX ³ _3-n2 (b-1)
In formula (b-1), R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group, R ² may have a substituent, and ³ represents a hydrolyzable group, and n2 represents an integer of 0 to 2.
[7]
A hard coat film comprising the coating composition according to any one of [1] to [6].
[8]
When a Taber abrasion test is conducted in accordance with ASTM D1044 using a worn wheel CS-10F and a load of 500 g, the difference between the haze at 1000 rotations and the haze before the Taber abrasion test is 2 or less. The hard coat coating film according to [7].
[9]
base material and
A hard coat coating film disposed on one side and/or both sides of the base material and containing the coating composition according to any one of [1] to [6];
A base material with a hard coat film.
[10]
The substrate with a hard coat film according to [9], further comprising an adhesive layer disposed between the base material and the hard coat film.
[11]
The base material with a hard coat film according to [9] or [10], which is used for automobile parts.

According to the present invention, it is possible to provide a coating composition and the like that are excellent in wear resistance, crack resistance, and pot life.

FIG. 1 is an explanatory diagram of a method for calculating the calculated organic chain length α when the hydrolyzable silicon compound (b) in this embodiment is methyltrimethoxysilane. FIG. 2 is an explanatory diagram of a method for calculating the calculated organic chain length α when the hydrolyzable silicon compound (b) in this embodiment is 1,2-bis(triethoxysilyl)ethane. FIG. 3 is an explanatory diagram of a method for calculating the calculated organic chain length α when the hydrolyzable silicon compound (b) in this embodiment is tris-(trimethoxysilylpropyl)isocyanurate. FIG. 4 is an explanatory diagram relating to a method for calculating the calculated organic chain length α when the hydrolyzable silicon compound (b) in this embodiment is a reaction product of 3-isocyanatepropyltriethoxysilane and Uvinul 3050.

Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as "this embodiment") will be described in detail. Note that the present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.

[Coating composition]
The coating composition of this embodiment is a coating composition containing polymer nanoparticles (A), a matrix raw material component (B') containing a hydrolyzable silicon compound (b), and a solvent, and includes the following: When the calculated organic chain length of the hydrolyzable silicon compound (b) given by calculation formula (1) is α, the content of the hydrolyzable silicon compound (b) relative to 100% by mass of solid content of the coating composition. The weight average value α _ave obtained based on the amount is 1.3 or more and 2.2 or less, and the Martens hardness HM _A ' of the polymer nanoparticle (A) and the Martens hardness of the matrix raw material component (B') are HM _B' satisfies the relationship HM _B' /HM _A '>1.
Calculated organic chain length α=organic chain length between Si atoms/number of Si atoms in molecule (1)
(Here, when dividing the molecular structure of the hydrolyzable silicon compound (b) into a hydrolyzable part A and a part B other than the part A, the organic chain length between Si atoms is It is the sum of the organic chain length a and the organic chain length b of part B.The organic chain length a is the value obtained by dividing the number of organooxysilane structures by 2.When the number of Si atoms in the molecular structure is 1 In this case, the organic chain length b is 0. If the number of Si atoms in the molecular structure is 2, the organic chain length b is the shortest distance from one Si atom to another Si atom. is given as the number of atoms constituting the atomic chain.When the number of Si atoms in the molecular structure is 3 or more, the organic chain length b is given as the number of atoms constituting the shortest atomic chain. (Use the average value.)
Since the coating composition of this embodiment is configured as described above, it has excellent abrasion resistance, durability, and pot life as a coating material. The coating composition of the present embodiment exhibits high levels of abrasion resistance and paintability, and is therefore useful as a hard coat material for, for example, but not limited to, building materials, automobile parts, electronic devices, and electrical appliances. Especially, it is preferable to use it for automobile parts.

In addition, in this specification, any coating film containing the coating composition of this embodiment is called a coating film (C). That is, the coating film (C) means any coating film obtained by curing the coating composition of this embodiment. Although the solvent derived from the coating composition of this embodiment may remain in the coating film (C), it is preferable that the solvent be removed. That is, the coating film (C) preferably contains the polymer nanoparticles (A) and the matrix component (B) derived from the matrix raw material component (B'). Further, in this specification, a coating film (C) having a Martens hardness HM of 100 N/mm ² or more as measured by the method described below may be particularly referred to as a "hard coat coating film."

[Polymer nanoparticles (A)]
By using the polymer nanoparticles (A) in this embodiment, it is possible to impart shock absorption properties to the coating film (C), and for example, it is possible to reduce the amount of haze change in the Taber abrasion test of a hard coat coating film. The shape of the polymer nanoparticles (A) is not particularly limited as long as the particle size is on the nm order (less than 1 μm).

[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 order of nm (less than 1 μm), and can be determined from the particle size 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 even more preferably 20 nm or more and 100 nm or less, from the viewpoint of optical properties.
The method for measuring the average particle diameter of the polymer nanoparticles (A) is not limited to the following, but for example, an aqueous dispersion of the polymer nanoparticles (A) is prepared as described in the Examples below, and Otsuka Electronics Co., Ltd. Examples include measuring the cumulant particle size of the aqueous dispersion using a dynamic light scattering particle size distribution analyzer (product number: ELSZ-1000) manufactured by Co., Ltd.
The average particle diameter of the polymer nanoparticles (A) can be adjusted within the above range by, for example, the structure and composition ratio of the constituent components of the polymer nanoparticles (A), and/or polymerization conditions.

[Hydrolyzable silicon compound (a)]
It is preferable that the polymer nanoparticle (A) in this embodiment contains 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 condensate.

From the viewpoint of improving wear resistance and weather resistance, the hydrolyzable silicon compound (a) is a compound containing an atomic group represented by the following formula (a-1), its hydrolysis product, and a condensate. It is preferable that there be.
-R ¹ _n1 SiX ¹ _3-n1 (a-1)

In formula (a-1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group, and R ¹ represents a halogen, a hydroxy group, a mercapto group, or an amino group. , a (meth)acryloyl group, or an epoxy group, X ¹ represents a hydrolyzable group, and n1 represents an integer of 0 to 2. The hydrolyzable group is not particularly limited as long as it is a group that produces a hydroxyl group upon hydrolysis, and examples of such groups include halogen, alkoxy group, acyloxy group, amino group, phenoxy group, oxime group, etc. .

Compounds containing the atomic group represented by formula (a-1) include, but are not limited to, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, hexyltrimethoxylane, hexyltriethoxylane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane, methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethoxydiphenylsilane, Ethoxydiphenylsilane, 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(trimethoxysilyl)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)heptane silyl) octane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltri Ethoxysilane, 3-glycidoxypropylmethyldimethoxylane, 3-glycidoxypropylmethyldiethoxylane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Triethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3 -Methacryloxypropylmethyldimethoxysilane, vinyltrimethoxylane, vinyltriethoxylane, p-styryltrimethoxysilane, p-styryltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N -2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, 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-dimethyl-butylidene)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(dimethylamino)dimethylsilane, bis(diethylamino)dimethylsilane, Bis(dimethylamino)methylsilane, bis(diethylamino)methylsilane, 2-[(triethoxysilyl)propyl]dibenzylresorcinol, 2-[(trimethoxysilyl)propyl]dibenzylresorcinol, 2,2,6,6-tetra Methyl-4-[3-(triethoxysilyl)propoxy]piperidine, 2,2,6,6-tetramethyl-4-[3-(trimethoxysilyl)propoxy]piperidine, 2-hydroxy-4-[3- (triethoxysilyl)propoxy]benzophenone, 2-hydroxy-4-[3-(trimethoxysilyl)propoxy]benzophenone, and the like.

The hydrolyzable silicon compound (a) may include a compound represented by the following formula (a-2), a hydrolysis product thereof, and a condensate.
SiX ² ₄ (a-2)
In formula (a-2), X ² represents a hydrolyzable group. The hydrolyzable group is not particularly limited as long as it is a group that produces a hydroxyl group upon hydrolysis, and examples thereof include halogen, alkoxy group, acyloxy group, amino group, phenoxy group, and oxime group.

Specific examples of the compound represented by formula (a-2) include, 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(methylethylketoxime)silane, tetramethoxysilane, or partially hydrolyzed condensate of tetraethoxysilane (for example, product names "M Silicate 51" and "Silicate 35" manufactured by Tama Chemical Industry Co., Ltd.) , "Silicate 45", "Silicate 40", "FR-3"; product name "MS51", "MS56", "MS57", "MS56S" manufactured by Mitsubishi Chemical; product name "Methyl Silicate 51" manufactured by Colcoat Co., Ltd. ", "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'', ``EMSi48''), etc.

As described above, in this embodiment, the hydrolyzable silicon compound (a) is a compound containing an atomic group represented by the above formula (a-1), a hydrolysis product and a condensate thereof, and a compound containing the atomic group represented by the above formula (a-1), and the above formula ( It is preferable to contain one or more selected from the compounds represented by a-2), their hydrolysis products, and condensates.

[Content of hydrolyzable silicon compound (a) in polymer nanoparticles (A)]
The content of the hydrolyzable silicon compound (a) in this embodiment refers to the proportion based on 100 mass of the nonvolatile components of the hydrolyzable silicon compound (a) contained in the polymer nanoparticles (A). , from the viewpoint that the higher the content, the better the wear resistance, weather resistance, and heat resistance, the higher the content is, the more preferable it is, and the content is preferably 50% by mass or more, and more preferably 60% by mass or more. . The content of the hydrolyzable silicon compound (a) in the polymer nanoparticles (A) is not limited to the following, but is measured by, for example, IR analysis, NMR analysis, elemental analysis, etc. of the polymer nanoparticles (A). be able to.

[Functional group (e)]
In the coating composition of this embodiment, the polymer nanoparticles (A) preferably 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 be easily adsorbed onto the surface of the polymer nanoparticles (A), becoming a protective colloid and becoming stable. As a result, the storage stability of the coating composition tends to improve. 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, so that the coating composition becomes The viscosity increases with respect to the concentration of non-volatile components, and sagging during coating on complex shapes tends to be suppressed, and as a result, the thickness of the coating film (C) tends to become uniform. The fact that the polymer nanoparticles (A) have a functional group (e) means that, for example, IR, GC-MS, pyrolysis GC-MS, LC-MS, GPC, MALDI-MS, TOF-SIMS, TG-DTA, This can be confirmed by composition analysis using NMR, analysis using a combination of these, and the like.

Specific examples of the functional group (e) in this embodiment include, but are not limited to, functional groups consisting of a hydroxyl group, a carboxyl group, an amino group, an amide group, and an ether bond. From the viewpoint of high hydrogen bonding, an amide group is more preferable, and a secondary amide group and/or a tertiary amide group is even more preferable.

Examples of compounds containing the functional group (e) and their reactants include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxy Ethyl 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, N-ethylacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N -Ethyl methacrylamide, N-methyl-N-ethylacrylamide, N-methyl-N-ethyl methacrylamide, N-isopropylacrylamide, Nn-propylacrylamide, N-isopropylmethacrylamide, Nn-propylmethacrylamide, N-Methyl-N-n-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylhexahydroazepine, N-acryloyl Morpholine, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N,N'-methylenebisacrylamide, N,N'-methylenebismethacrylamide, N-vinylacetamide, diacetone acrylamide, diacetone methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, Blenmar PE-90, PE-200, PE-350, PME-100, PME-200, PME-400, AE-350 (product name, manufactured by NOF Corporation), 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 Nyukazai Co., Ltd.), etc. It will be done. In addition, in this specification, (meth)acrylate is simply written as acrylate or methacrylate, and (meth)acrylic acid is simply written as acrylic acid or methacrylic acid.

[Core/shell structure of polymer nanoparticles (A)]
The polymer nanoparticles (A) in this embodiment preferably have a core/shell structure including a core layer and one or more shell layers covering the core layer. The polymer nanoparticles (A) preferably have the above-mentioned functional group (e) from the viewpoint of interaction with the matrix raw material component (B') in the outermost layer of the core/shell structure.

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

Among the polymers that may be included in the above-mentioned polymer nanoparticles (A), a polymer or copolymer of (meth)acrylic acid and (meth)acrylate can be mentioned as a compound particularly excellent in electrostatic repulsion. Specific examples include, but are not limited to, methyl acrylate, (meth)acrylic acid, methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, n-butyl acrylate, 2-hydroxyethyl (meth)acrylate, 2- A polymer or copolymer of hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate Can be mentioned. At this time, in order to further improve the electrostatic repulsion, the (meth)alkrylic acid is partially or completely neutralized with amines such as ammonia, triethylamine, and dimethylethanolamine, or bases such as NaOH and KOH. You can.

Moreover, the polymer nanoparticles (A) may contain an emulsifier. The emulsifier is not particularly limited, and examples include acidic emulsifiers such as alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic 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, fatty acid soaps; quaternary surfactants such as alkyltrimethylammonium bromide, alkylpyridinium bromide, imidazolinium laurate, etc. Cationic surfactants of ammonium salt, pyridinium salt, and imidazolinium salt type; nonionic surfactants such as polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene oxypropylene borolock copolymer, and polyoxyethylene distyrylphenyl ether Examples include reactive emulsifiers having type surfactants and radically polymerizable double bonds.

The reactive emulsifier having a radically polymerizable double bond is not limited to the following, but includes, for example, Eleminol JS-2 (trade name, manufactured by Sanyo Chemical Co., Ltd.), Latemul S-120, and S- 180A or S-180 (product name, manufactured by Kao Corporation), Aqualon HS-10, KH-1025, RN-10, RN-20, RN30, RN50 (product name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adecaria Soap SE1025, SR-1025, NE-20, NE-30, NE-40 (product name, manufactured by Asahi Denka Kogyo Co., Ltd.), ammonium salt of p-styrenesulfonic acid, sodium salt of p-styrenesulfonic acid, p- Potassium salt of styrene sulfonic acid, alkyl sulfonic acid (meth)acrylate such as 2-sulfoethyl acrylate, methylpropanesulfonic acid (meth)acrylamide, ammonium salt of allyl sulfonic acid, sodium salt of allyl sulfonic acid, potassium allyl sulfonic acid Examples include salt.

[Elastic recovery rate η _ITA of polymer nanoparticles (A)]
The elastic recovery rate η _ITA of the polymer nanoparticles (A) in this embodiment is the parameter described as the ratio η _IT of W _elast /W _total in ISO14577-1. It is measured on a coating film of 1, and is expressed as the ratio of the total mechanical work W _total of the depressions to the elastic return deformation work W _elast of the depressions. The higher the elastic recovery rate η _ITA , the more likely the coating film can return to its original state when subjected to impact, and the higher its self-repairing ability against impact. From the viewpoint of effectively demonstrating self-healing ability, the elastic recovery rate η _ITA of the polymer nanoparticles (A) is determined under the measurement conditions (Vickers square pyramid diamond indenter, load increase condition of 2 mN/20 sec, load decrease condition of 2 mN/20 seconds). 20 sec) is preferably 0.30 or more, and from the viewpoint of being able to follow the deformation of the base material and matrix raw material component (B') when forming the coating film (C), η _ITA is 0.90 or less. It is preferable. The elastic recovery rate η _ITA of the polymer nanoparticles (A) is more preferably 0.50 or more, and even more preferably 0.60 or more. The elastic recovery rate of the polymer nanoparticles (A) can be measured by, but not limited to, methods such as centrifugation, ultrafiltration, etc. to separate the polymer nanoparticles (A) and the matrix raw material component (B'). The composition obtained by separating and dispersing the separated polymer nanoparticles (A) in a solvent was coated, and the coating film formed by drying was measured using a microhardness meter Fisherscope (HM2000S manufactured by Fisher Instruments). ), ultra-fine indentation hardness tester (ENT-NEXUS, manufactured by Elionix Co., Ltd.), nanoindenter (iNano, G200, manufactured by Toyo Technica), nanoindentation system (TI980, manufactured by Bruker), etc. be able to. Methods for adjusting the elastic recovery rate η _ITA within the above range include, but are not limited to, adjusting the structure and composition ratio of the constituent components of the polymer nanoparticles (A).

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

[Hydrolyzable silicon compound (b)]
In this embodiment, from the viewpoint of high toughness, the matrix raw material component (B') contains a hydrolyzable silicon compound (b). In this specification, "the matrix raw material component (B') contains a hydrolyzable silicon compound (b)" means that the matrix raw material component (B') is a structural unit derived from the hydrolyzable silicon compound (b). This means that it includes polymers with The hydrolyzable silicon compound (b) is not particularly limited as long as it is a hydrolyzable silicon compound, a hydrolysis product, or a condensate thereof.
The matrix raw material component (B') may contain various components other than the polymer nanoparticles (A) in addition to the above-mentioned polymers. Among them, other polymers that may be included in addition to the above-mentioned polymers include water-soluble resins such as polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, and polyacrylic acid; acrylic resins such as PMMA, PAN, and polyacrylamide; polystyrene, Examples include polymers such as polyurethane, polyamide, polyimide, polyvinylidene chloride, polyester, polycarbonate, polyether, polyethylene, polysulfone, polypropylene, polybutadiene, PTFE, PVDF, and EVA; and copolymers thereof.
The hydrolyzable silicon compound (b) may include a silane compound (Z) having ultraviolet absorbing properties. In the present embodiment, it is preferable to obtain the silane compound (Z) by sufficiently mixing an ultraviolet absorber having reactivity with silanol groups and a silanol group-containing component to cause condensation. When such a silane compound (Z) is used, it tends to be possible to prevent a decrease in performance due to the release of ultraviolet absorbing components during a durability test.

From the viewpoint of further improving wear resistance and weather resistance, the hydrolyzable silicon compound (b) is a compound containing an atomic group represented by the following formula (b-1), a hydrolysis product thereof, and a condensate. , as well as one or more selected from the group consisting of a compound represented by the following formula (b-2), a hydrolysis product thereof, and a condensate.
-R ² _n2 SiX ³ _3-n2 (b-1)
In formula (b-1), R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group, R ² may have a substituent, and ³ represents a hydrolyzable group, and n2 represents an integer of 0 to 2. The hydrolyzable group is not particularly limited as long as it is a group that produces a hydroxyl group upon hydrolysis, and examples of such groups include a halogen atom, an alkoxy group, an acyloxy group, an amino group, a phenoxy group, and an oxime group. It will be done.
SiX ⁴ ₄ (b-2)
In formula (b-2), X ⁴ represents a hydrolyzable group. The hydrolyzable group is not particularly limited as long as it is a group that produces a hydroxyl group upon hydrolysis, and examples of such groups include halogen, alkoxy group, acyloxy group, amino group, phenoxy group, oxime group, etc. .

Specific examples of compounds containing an atomic group represented by general formula (b-1) include, but are not limited to, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and ethyltrimethoxysilane. , ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, hexyltrimethoxylane, hexyltriethoxylane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane , 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(trimethoxysilyl)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(trimethoxysilyl)heptane, ethoxysilyl)octane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane , 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Triethoxysilane, 3-glycidoxypropylmethyldimethoxylane, 3-glycidoxypropylmethyldiethoxylane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl) Ethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, vinyltrimethoxylane, vinyltriethoxylane, p-styryltrimethoxysilane, p-styryltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxy Silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene)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(methylethylketo) silane, phenyltris(methylethylketoxime)silane, bis(methylethylketoxime)silane, methylbis(methylethylketoxime)silane, hexamethyldisilane, 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 N-oxide, 4-{3-[(triethoxy)silyl]propoxy}-1,2,2,6,6-pentamethylpiperidine, 4-(triethoxysilyl propoxy)-2,2,6,6-tetramethylpiperidine N-oxide, 4-{3-[(trimethoxy)silyl]propoxy}-1,2,2,6,6-pentamethylpiperidine, 2-hydroxy- Examples include 4-[3-(trimethoxysilyl)propoxy]benzophenone and 2-hydroxy-4-[3-(trimethoxysilyl)propoxy]benzophenone.

Specific examples of the compound represented by formula (b-2) include, 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(methylethylketoxime)silane, tetramethoxysilane, or partially hydrolyzed condensate of tetraethoxysilane (for example, product names "M Silicate 51" and "Silicate 35" manufactured by Tama Chemical Industry Co., Ltd.) , "Silicate 45", "Silicate 40", "FR-3"; product name "MS51", "MS56", "MS57", "MS56S" manufactured by Mitsubishi Chemical; product name "Methyl Silicate 51" manufactured by Colcoat Co., Ltd. ", "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'', ``EMSi48''), etc.

As described above, in the present embodiment, the hydrolyzable silicon compound (b) is a compound containing an atomic group represented by the above formula (b-1), a hydrolyzed product and a condensate thereof, and the above formula ( It is preferable to contain one or more selected from the compounds represented by b-2), their hydrolysis products, and condensates.

In this embodiment, the "hydrolyzable silicon compound (a) contained in the polymer nanoparticle (A)" is the same type as the "hydrolyzable silicon compound (b) contained in the matrix raw material component (B')". It may be of a different type or of a different type. Even if they are the same type, the one contained in the polymer nanoparticle (A) is considered to be the hydrolyzable silicon compound (a), and the one contained in the matrix raw material component (B') is considered to be the hydrolyzable silicon compound. It shall be distinguished by referring to it as compound (b).

[Elastic recovery rate η _ITB' of matrix raw material component (B') and elastic recovery rate η _ITB of matrix component (B)]
In the coating composition of this embodiment, the elastic recovery rate η _ITB' of the matrix raw material component (B') is a parameter described as "ratio η _IT of W _elast /W _total " in ISO 14577-1, and This is a measurement of the coating film of the matrix raw material component (B'), and is expressed as the ratio of the total mechanical work W _total of the depressions to the elastic return deformation work W _elast of the depressions. The higher the elastic recovery rate η _ITB' , the more the coating film can return to its original state upon impact, and the higher the self-repair ability against impact. From the viewpoint of effectively demonstrating self-healing ability, the elastic recovery rate η _ITB' of the matrix raw material component (B') is determined under the measurement conditions (Vickers square pyramid diamond indenter, load increase condition 2 mN/20 sec, load decrease condition 2 mN /20sec) is preferably 0.60 or more, more preferably 0.65 or more. Further, from the viewpoint of being able to follow the deformation of the base material and component (A) when forming a coating film, η _ITB' is preferably 0.95 or less. The elastic recovery rate of the matrix raw material component (B') can be measured by, for example, but not limited to, separating the polymer nanoparticles (A) and the matrix raw material component (B') by an operation such as centrifugation, and separating the matrix raw material component (B'). A composition prepared by dissolving the matrix raw material component (B') in a solvent was applied, dried, and the resulting coating film was subjected to microhardness meter Fisherscope (HM2000S manufactured by Fisher Instruments) and ultra-micro indentation. It can be measured using a hardness tester (ENT-NEXUS, manufactured by Elionix Co., Ltd.), a nanoindenter (iNano, G200, manufactured by Toyo Technica), a nanoindentation system (TI980, manufactured by Bruker), etc.
Note that, as described above, a cured product obtained by curing the matrix raw material component (B') by hydrolytic condensation or the like corresponds to the matrix component (B). Therefore, the value of the elastic recovery rate η _ITB' of the matrix raw material component (B') measured by the method described in the Examples described later closely matches the elastic recovery rate η _ITB of the corresponding matrix component (B). As such, the value of the elastic recovery rate η _ITB can be determined. That is, the elastic recovery rate η _ITB of the matrix component (B) in this embodiment is preferably 0.60 or more, more preferably 0.65 or more. Further, from the viewpoint of being able to follow the deformation of the base material and component (A) when forming a coating film, η _ITB is preferably 0.95 or less.
Methods for adjusting the elastic recovery rate η _ITB' and the elastic recovery rate η _ITB within the above ranges include, but are not limited to, the following, for example, adjusting the structure and composition ratio of the constituent components of the matrix raw material component (B'). Examples include:

[Inorganic oxide (D)]
The matrix raw material component (B') in this embodiment preferably contains an inorganic oxide (D). Containing the inorganic oxide (D) not only improves the hardness of the matrix raw material component (B') and improves the wear resistance, but also improves the stain resistance of the coating film due to the hydrophilicity of the hydroxyl groups on the particle surface. There is a tendency to

Specific examples of the inorganic oxide (D) in this embodiment include, but are not limited to, silicon, aluminum, titanium, zirconium, zinc, cerium, tin, indium, gallium, germanium, antimony, molybdenum, niobium, magnesium, At least one inorganic material selected from the group consisting of Si, Ce, Nb, Al, Zn, Ti, Zr, Sb, Mg, Sn, Bi, Co and Cu. It is preferable to contain components. These may be used alone or as a mixture regardless of their shape. The inorganic oxide (D) preferably further contains silica, such as dry silica or colloidal silica, from the viewpoint of interaction with the above-mentioned hydrolyzable silicon compound (b), and from the viewpoint of dispersibility, It is more preferable to further include silica particles, and even more preferable to further include 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 it can be used regardless of whether it is acidic or basic. Colloidal silica that can be included in the inorganic oxide (D) will be described later. In addition, from the viewpoint of weather resistance, inorganic oxides (D) include cerium oxide, niobium oxide, aluminum oxide, zinc oxide, titanium oxide, zirconium oxide, antimony oxide, magnesium oxide, tin oxide, and bismuth oxide, which have ultraviolet absorption ability. , cobalt oxide, and copper oxide, and from the viewpoint of improving weather resistance, at least one selected from the group consisting of niobium oxide, zinc oxide, titanium oxide, and zirconium oxide. It is preferable to include some kind of inorganic component, more preferably cerium oxide. Although not limited to the following, when using commercially available products, for example, 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 “Tynoc” (product name) manufactured by Taki Chemical Co., Ltd., cerium oxide “Needral” (product name), tin oxide “Ceramase” (product name), niobium oxide sol, zirconium oxide sol; manufactured by Nissan Chemical Industries, Ltd. Antimony pentoxide aqueous sol "A-2550" is mentioned.

[Average particle diameter of inorganic oxide (D)]
The average particle diameter of the inorganic oxide (D) in this embodiment is preferably 2 nm or more from the viewpoint of good storage stability of the coating composition, and 150 nm or less from the viewpoint of good transparency. It is preferable that there be. That is, the average particle diameter 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, observation using a transmission micrograph of water-dispersed colloidal silica at a magnification of 50,000 to 100,000 times. However, it is possible to take a photograph so that 100 to 200 inorganic oxide particles are photographed, and to measure from the average value of the major axis and minor axis of the inorganic oxide particles.

[Colloidal silica that can be included in inorganic oxide (D)]
The acidic colloidal silica using water as a dispersion medium, which is preferably used in this embodiment, is not particularly limited, but it can be prepared and used by a sol-gel method, and commercially available products can also be used. When preparing by the sol-gel method, the method described by Werner Stober et al; Colloid and Interface Sci. , 26, 62-69 (1968), Rickey D. Badley et al; Lang muir 6, 792-801 (1990), Color Materials Association Journal, 61 [9] 488-493 (1988), etc. can be referred to. When using commercially available products, for example, 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 name, Nissan Chemical Industries, Ltd. Co., Ltd.), Adelite AT-20Q (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), Crebosol 20H12, Crebosol 30CAL25 (trade name, manufactured by Clariant Japan Co., Ltd.), and the like.

Examples of basic colloidal silica include silica stabilized by the addition of alkali metal ions, ammonium ions, and amines, including, but not limited to, 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, Snowtex-N-40 (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.), Crebosol 30R9, Crebosol 30R50 , Crebosol 50R50 (product name, manufactured by Clariant Japan Co., Ltd.), Ludox HS-40, Ludox HS-30, Ludox LS, Ludox AS-30, Ludox SM-AS, Ludox AM, Ludox HSA, and Ludox SM (product name, DuPont) (manufactured by a company).

In addition, colloidal silica using a water-soluble solvent as a dispersion medium is not particularly limited, but examples include MA-ST-M (methanol dispersion type with a particle size of 20 to 25 nm) manufactured by Nissan Chemical Industries, Ltd., IPA-ST ( Isopropyl alcohol dispersion type with a particle size of 10 to 15 nm), EG-ST (ethylene glycol dispersion type with a particle size of 10 to 15 nm), EGST-ZL (ethylene glycol dispersion type with a particle size of 70 to 100 nm), NPC-ST (ethylene glycol monopropyl ether dispersion type with a particle size of 10 to 15 nm) and TOL-ST (toluene dispersion type with a particle size of 10 to 15 nm).

Examples of the dry silica particles include, but are not particularly limited to, AEROSIL manufactured by Nippon Aerosil Co., Ltd. and Rheolo Seal manufactured by Tokuyama Corporation.

Further, these silica particles may contain an inorganic base (sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, etc.) or an organic base (tetramethylammonium, triethylamine, etc.) as a stabilizer.

[Shape of inorganic oxide (D)]
Further, the shape of the inorganic oxide (D) in this embodiment is not limited to the following, but examples thereof include spherical, angular, polyhedral, elliptical, flat, linear, beaded, pearl-like, etc. From the viewpoint of hardness and transparency of the hard coat film, it is particularly preferable that the hard coat has a spherical shape, a bead shape, or a pearl shape.

[Catalyst (E)]
The coating composition may contain a catalyst (E) as a matrix raw material component (B'). The catalyst (E) is preferably one that promotes the reaction between reactive groups in the coating composition, and when the coating composition contains the catalyst (E), unreactive groups remain in the coating film. Not only does it have higher hardness and wear resistance, but it also tends to have improved weather resistance. The catalyst (E) is not particularly limited, but it is preferably one that can be dissolved or dispersed when obtaining the coating film (C). Examples of such catalyst (E) include, but are not limited to, organic acids, inorganic acids, organic bases, inorganic bases, metal alkoxides, and metal chelates. These catalysts (E) may be used alone or in combination of two or more.
From the viewpoint of suppressing the sol-gel reaction of organooxysilane and further improving the pot life, the pH of the coating composition is preferably 2.1 to 4.5, and preferably 2.7 to 4.5. More preferably, it is 3.3 to 4.5. It is preferable to use a catalyst that can adjust the pH of the coating composition to fall within this range. Specific examples of such preferred catalysts include, but are not limited to, buffer solutions containing a combination of an inorganic acid and an inorganic base or a buffer solution containing a combination of an organic acid and an organic base, and metal chelates specialized for organooxysilane condensation reactions. Examples include catalysts containing.
The content of the catalyst (E) in the coating composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on 100% by mass of the nonvolatile components of the coating composition. %, more preferably 0.3 to 1.5% by mass.

[Other ingredients]
From the viewpoint of further improving the coating properties of the coating composition of this embodiment, the coating composition contains, as the matrix raw material component (B'), a thickener, a leveling agent, a thixotropic agent, in addition to the above-mentioned components, as necessary. antifoaming agent, antifoaming agent, freeze stabilizer, dispersant, wetting agent, rheology control agent, film forming aid, rust preventive agent, plasticizer, lubricant, preservative, antifungal agent, antistatic agent, antistatic agent Components that function as agents and the like and do not fall under the hydrolyzable silicon compound (b), inorganic oxide (D), or catalyst (E) can be blended. From the viewpoint of improving film-forming properties, it is preferable to use a wetting agent or a film-forming aid, and specific examples include, but are not limited to, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and 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, tripropylene glycol-n- Butyl ether, dipropylene glycol methyl ether, tripropylene 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 (product name, manufactured by DIC Corporation), SN Wet 366, SN Wet 980, SN Wet L , SN Wet S, SN Wet 125, SN Wet 126, and SN Wet 970 (trade name, manufactured by San Nopco Co., Ltd.). These compounds may be used alone or in combination of two or more.

Depending on the application, matrix raw material components (B') may include pigments, dyes, fillers, anti-aging agents, conductive materials, organic ultraviolet absorbers, light stabilizers, release modifiers, softeners, surfactants, etc. The composition may contain components that function as additives, flame retardants, antioxidants, etc., but do not fall under the hydrolyzable silicon compound (b), inorganic oxide (D), or catalyst (E). In particular, since high weather resistance is required for outdoor use, it is preferable to include an organic ultraviolet absorber and a light stabilizer. Specific examples of organic ultraviolet absorbers and light stabilizers include, but are not limited to, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-methoxybenzophenone-5-sulfone. 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 (trade name "UVINUL3049" manufactured by BASF), 2,2',4,4'- Tetrahydroxybenzophenone (trade name "UVINUL3050" manufactured by BASF), 4-dodecyloxy-2-hydroxybenzophenone, 5-benzoyl-2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, Benzophenone ultraviolet absorbers such as 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-octyl) phenyl)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-benzotriazol-2-yl)-4-hydroxyphenyl]propionate and polyethylene glycol (molecular weight 300) condensate (BASF) Isooctyl-3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionate (trade name "TINUVIN384" manufactured by BASF) , 2-(3-dodecyl-5-methyl-2-hydroxyphenyl)benzotriazole (trade name "TINUVIN571" manufactured by BASF), 2-(2'-hydroxy-3'-tert-butyl-5'-methyl phenyl)-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, 2,2-methylenebis[4-(1, 1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1 -Phenylethyl)phenol (trade name "TINUVIN900" manufactured by BASF), TINUVIN384-2, TINUVIN326, TINUVIN327, TINUVIN109, TINUVIN970, TINUVIN328, TINUVIN171, TINUVIN970, TI NUVIN PS, TINUVIN P, TINUVIN99-2, TINVIN928 (product name, Benzotriazole UV absorbers such as BASF); 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethyl phenyl)-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)-1,3,5-triazine (BASF) 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (BASF) Triazine-based UV absorbers such as "TINUVIN479" (trade name manufactured by BASF), TINUVIN400, TINUVIN405, TINUVIN477, TINUVIN1600 (trade name, manufactured by BASF); HOSTAVIN PR25, HOSTAVIN B-CAP, HOSTAVIN VSU (Product name, manufactured by Clariant ), malonic acid ester UV absorbers such as HOSTAVIN3206 LIQ, HOSTAVIN VSU P, HOSTAVIN3212 LIQ (product name, manufactured by Clariant); anilide UV absorbers such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, Salicylate ultraviolet absorbers such as phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate; ethyl-2-cyano-3,3-diphenylacrylate (trade name "UVINUL3035" manufactured by BASF), (2-ethylhexyl)- 2-Cyano-3,3-diphenylacrylate (trade name "UVINUL3039" manufactured by BASF, 1,3-bis((2'-cyano-3',3'-diphenylacryloyl)oxy)-2,2-bis - Cyanoacrylate UV absorbers such as (((2'-cyano-3',3'-diphenylacryloyl)oxy)methyl)propane (trade name "UVINUL3030" manufactured by BASF); 2-hydroxy-4-acrylate Roxybenzophenone, 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 (trade name "RUVA-93" manufactured by Otsuka Chemical Co., Ltd.), 2-(2'-hydroxy-5'-methacryloxyethyl-3-tert-butylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacrylyloxypropyl-3-tert-butylphenyl)-5-chloro-2H-benzotriazole, 3-methacryloyl-2-hydroxypropyl-3-[3'-(2 ''-benzotriazolyl)-4-hydroxy-5-tert-butyl]phenylpropionate (product name: CGL-104, manufactured by Nippon Ciba Geigy Co., Ltd.), etc., which has a radically polymerizable double bond in the molecule. radically polymerizable ultraviolet absorbers; polymers with ultraviolet absorbing properties 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)propynyl oxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynyloxy]-2,2,6,6-tetramethylpiperidine, bis(1,2,2, A mixture of 6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl-sebacate (trade name "TINUVIN292" manufactured by BASF), bis(1-octoxy Hindered amine light stabilizers such as -2,2,6,6-tetramethyl-4-piperidyl) sebacate, TINUVIN123, TINUVIN144, TINUVIN152, TINUVIN249, TINUVIN292, TINUVIN5100 (trade name, manufactured by 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 Radically polymerizable hindered amine light stabilizers such as -2,2,6,6-tetramethyl-4-piperidyl methacrylate and 4-cyano-1,2,2,6,6-pentamethyl-4-piperidyl methacrylate; Udouble E -133, U-double E-135, U-double S-2000, U-double S-2834, U-double S-2840, U-double S-2818, U-double S-2860 (product name, Nippon Shokubai Co., Ltd.) Coalescence: Examples include ultraviolet absorbers having reactivity with compounds containing silanol groups, isocyanate groups, epoxy groups, semicarbazide groups, and hydrazide groups, and these may be used alone or in combination of two or more. In addition, when a UV absorber that is reactive with a silanol group-containing compound reacts with the silanol group-containing compound and becomes a hydrolyzable silicon compound, it is included in the above-mentioned hydrolyzable silicon compound (b). Let us calculate the weight average value α _ave , which will be described later.

[solvent]
The coating composition of this embodiment contains a solvent. The solvent is not particularly limited, and common solvents can be used. Examples of the solvent include, but are not limited to, 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 monophenyl ether Alcohols such as tetraethylene glycol 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; Acetone and methyl ethyl ketone , methyl isobutyl ketone, cyclohexanone, and other ketones; tetrahydrofuran, dioxane, and other ethers; dimethylacetamide, dimethylformamide, and other amides; chloroform, methylene chloride, carbon tetrachloride, and other halogen compounds; dimethyl sulfoxide, nitrobenzene, etc. These may be used alone or in combination of two or more. Among them, it is particularly preferable to contain water and alcohols from the viewpoint of reducing the environmental load during solvent removal.
In this embodiment, from the viewpoint of coating properties on various substrates and coating film forming properties, the solvent contains water, and the water content is 40% by mass or more based on 100% by mass of the coating composition. It is preferably 90% by mass or less.

[Martens hardness]
The Martens hardness in this embodiment is a hardness based on ISO14577-1, and the indentation depth is 2 mN under measurement conditions (Vickers square pyramid diamond indenter, load increase condition 2 mN/20 sec, load decrease condition 2 mN/20 sec). This is the value calculated from . The Martens hardness in this embodiment can be measured using, for example, a microhardness meter Fischerscope (HM2000S manufactured by Fischer Instruments), an ultra-micro indentation hardness tester (ENT-NEXUS manufactured by Elionix Co., Ltd.), or a nanoindenter (Toyo Technica Co., Ltd.). The Martens hardness can be measured using Nanoindentation System (TI980, manufactured by Bruker), and the shallower the indentation depth, the higher the Martens hardness, and the deeper the indentation depth, the lower the Martens hardness.

[Hardness HM _A of the polymer nanoparticles (A) and hardness HM _B' of the matrix raw material component (B')]
In the coating composition of this embodiment, the Martens hardness HM _A of the polymer nanoparticles (A) and the Martens hardness HM _B' of the matrix raw material component (B') satisfy the relationship of the following formula (1).
HM _B' /HM _A >1 Formula (1)
The coating film (C) is obtained by curing the coating composition of this embodiment, and therefore contains the polymer nanoparticles (A) and the matrix component (B). Since the matrix component (B) corresponds to a cured product obtained by curing the matrix raw material component (B') by hydrolytic condensation or the like, the matrix raw material component (B') is measured by the method described in the Examples below. The value of the Martens hardness HM _{B can be determined by assuming that the value of the Martens hardness HM B' of} ) closely matches the Martens hardness HM _B of the corresponding matrix component (B). Therefore, equation (1) can be rewritten as equation (2).
HM _B /HM _A >1 Formula (2)
Equation (2) indicates that flexible polymer nanoparticles (A) are present in a hard matrix component (B), and this three-dimensional gradient in hardness makes it difficult to form a coating film. (C) can provide abrasion resistance that has not been achieved with conventional coatings. Although the reason for this is not intended to be limited to the following, it is presumed that the flexible nanoparticles absorb impact and the hard matrix component suppresses deformation.
The range of _HMA is preferably 50 N/mm ² or more and 2000 N/mm ² or less, more preferably 100 N/mm ² or more and 800 N/mm ² or less, and even more preferably 100 N/mm ² or more and 350 N/mm ² or less.
The range of HM _B' is preferably 100 N/mm ² or more and 4000 N/mm ² or less, more preferably 150 N/mm ² or more and 4000 N/mm ² or less, and even more preferably 150 N/mm ² or more and 2000 N/mm ² or less.
Each Martens hardness in the coating composition of this embodiment is determined by separating the polymer nanoparticles (A) and the matrix raw material component (B') by, for example, centrifugation, ultrafiltration, etc. However, it can be measured based on the method described in the Examples described later.
The composition of the polymer nanoparticles (A) usually does not change during the curing process. Therefore, the value of the Martens hardness HM _A of the polymer nanoparticles (A) in the coating composition measured by the method described in the Examples below is the value of the Martens hardness HM A of the polymer nanoparticles (A) in the coating film (C). The value of the Martens hardness HM _A of the coating film (C) can be determined as one that closely matches the Martens hardness HM _A of the coating film (C).
The above values of HM _A and HM _B' can be adjusted to have the above-mentioned size relationship depending on the structure and composition ratio of the constituent components of the polymer nanoparticles (A) and matrix raw material component (B'), respectively. However, the method is not particularly limited to this method.

[Other hardness]
The magnitude relationship of the Martens hardness in this embodiment described above can also be estimated by checking the magnitude relationship of the measured values using other hardnesses as indicators. Other hardness is not particularly limited as long as it is an indicator of the material's resistance to deformation when force is applied to it, and it can be measured using an indentation hardness meter such as a microhardness meter or a nanoindentation measuring device. Indices expressed include Vickers hardness and indentation hardness, which are measured by , and logarithmic attenuation rate, which is measured by pendulum-type viscoelasticity, which is typified by a rigid pendulum-type physical property tester. In addition, indicators expressed by adhesion force, phase, friction force, viscoelasticity, adsorption force, hardness, and elastic modulus, which are measured using 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 the hardness of the polymer nanoparticles (A) in these indicators, then the Martens hardness and cohesive force will also be higher than the hardness of the matrix raw material component (B') ( It is estimated that the matrix component (B)) is harder than the polymer nanoparticles (A).

[Weight average value α _ave ]
In the coating composition of the present embodiment, when the calculated organic chain length of the hydrolyzable silicon compound (b) given by the following calculation formula (1) is α, the The weight average value α _ave obtained based on the content of the hydrolyzable silicon compound (b) is 1.3 or more and 2.2 or less.
Calculated organic chain length α=organic chain length between Si atoms/number of Si atoms in molecule (1)
(Here, when dividing the molecular structure of the hydrolyzable silicon compound (b) into a hydrolyzable part A and a part B other than the part A, the organic chain length between Si atoms is It is the sum of the organic chain length a and the organic chain length b of part B.The organic chain length a is the value obtained by dividing the number of organooxysilane structures by 2.When the number of Si atoms in the molecular structure is 1 In this case, the organic chain length b is 0. If the number of Si atoms in the molecular structure is 2, the organic chain length b is the shortest distance from one Si atom to another Si atom. is given as the number of atoms constituting the atomic chain.When the number of Si atoms in the molecular structure is 3 or more, the organic chain length b is given as the number of atoms constituting the shortest atomic chain. (Use the average value.)
The calculated organic chain length α can be calculated from the chemical structure of the hydrolyzable silicon compound (b), and assuming that the hydrolyzable silicon compound (b) is 100% hydrolyzed and condensed, It can be said that this value reflects the chain length of the organic group contained between silicon atoms.
The organooxysilane structure in this embodiment includes alkoxysilane, aryloxysilane, etc., and preferably alkoxysilane.
In the following, methyltrimethoxysilane, 1,2-bis(triethoxysilyl)ethane, and tris-(trimethoxysilylpropyl)isocyanurate, which may fall under the hydrolyzable silicon compound (b), are used as examples (however, hydrolyzable The silicon compound (b) is not limited to these.), and the method for calculating the calculated organic chain length α of these compounds will be explained.

(Calculation example 1 of calculated organic chain length α)
For example, a method for calculating the calculated organic chain length α when the hydrolyzable silicon compound (b) is methyltrimethoxysilane will be explained using FIG. 1.
When all three methoxy groups (portion A in FIG. 1) of methyltrimethoxysilane are hydrolyzed, the number of silanol groups contained in the hydrolyzable silicon compound (b) becomes three. When all three silanol groups are condensed with other hydrolyzable silicon compounds, focusing on the moiety derived from one silanol group, the oxygen present between the Si atom in methyltrimethoxysilane and the Si atom in other molecules There is one atom. Since the number of silanol groups is three, the total number of such oxygen atoms is three. Here, since at least two molecules are involved in the condensation, the value "1.5" obtained by dividing the above "3" by "2" is the organic chain length a.
Next, the portion other than portion A shown in FIG. 1 becomes portion B in methyltrimethoxysilane. Here, since the number of Si atoms in methyltrimethoxysilane is 1, the organic chain length b is 0.
Therefore, when the hydrolyzable silicon compound (b) is methyltrimethoxysilane, the calculated organic chain length α is calculated as 1.5 (=(3/2+0)/1), as shown in Figure 1. .

(Calculation example 2 of calculated organic chain length α)
The method for calculating the organic chain length α when the hydrolyzable silicon compound (b) is 1,2-bis(triethoxysilyl)ethane (having two Si atoms in the molecule) is shown in Figure 2. I will explain.
The ethoxy group (portion A in FIG. 2) that 1,2-bis(triethoxysilyl)ethane has becomes a silanol group by hydrolysis. When these are condensed, as in the case of methyltrimethoxysilane mentioned above, focusing on the moiety derived from one silanol group, the Si atom in 1,2-bis(triethoxysilyl)ethane and the Si atom in other molecules There is one oxygen atom between them. Since the number of silanol groups is six, the total number of such oxygen atoms is six. Here, since at least two molecules are involved in the condensation, the value "3" obtained by dividing the above "6" by "2" becomes the organic chain length a.
Next, the part other than part A shown in FIG. 2 becomes part B in 1,2-bis(triethoxysilyl)ethane. Here, since the number of Si atoms in 1,2-bis(triethoxysilyl)ethane is 2, the organic chain length b is the shortest atomic chain from one Si atom to another Si atom. It is given as the number of atoms. As shown in FIG. 2, the number of atoms in this case is two.
Therefore, when the hydrolyzable silicon compound (b) is 1,2-bis(triethoxysilyl)ethane, the calculated organic chain length α is 2.5 (=(6/2+2) /2) is calculated.

(Calculation example 3 of calculated organic chain length α)
The method for calculating the organic chain length α when the hydrolyzable silicon compound (b) is tris-(trimethoxysilylpropyl)isocyanurate (having three Si atoms in the molecule) is shown in Figure 3. explain.
The methoxy group (portion A in Figure 3) possessed by tris-(trimethoxysilylpropyl) isocyanurate becomes a silanol group by hydrolysis, and further, by condensation, one oxygen atom is present between each Si atom. . As shown in FIG. 3, the number of methoxy groups that become silanol groups upon hydrolysis is nine, so the total number of such oxygen atoms is nine. Here, since at least two molecules are involved in the condensation, the value "4.5" obtained by dividing the above "9" by "2" becomes the organic chain length a.
Next, the moiety other than moiety A shown in FIG. 3 becomes moiety B in tris-(trimethoxysilylpropyl)isocyanurate. Here, since the number of Si atoms in tris-(trimethoxysilylpropyl)isocyanurate is 3, the organic chain length b constitutes the shortest atomic chain from one Si atom to another Si atom. This is the average value of each value given as the number of atoms. As shown in FIG. 3, the number of atoms constituting the shortest atomic chain is 9 no matter how you count it, so the average value is also 9.
Therefore, when the hydrolyzable silicon compound (b) is tris-(trimethoxysilylpropyl)isocyanurate, the calculated organic chain length α is 4.5 (=(9/2+9)/ 2) is calculated.

As mentioned above, in this embodiment, the calculated organic chain length α and the weight average value α _ave are calculated for the hydrolyzable silicon compound (b), and even compounds containing silicon cannot be hydrolyzed. For other components that do not fall under the hydrolyzable silicon compound (b), such as those that do not have decomposability, the calculated organic chain length α is set to 0, and the weight average value α _ave is calculated.

In the coating composition of the present embodiment, the weight average value α _ave is calculated based on the weight ratio obtained based on the content of the hydrolyzable silicon compound (b) with respect to 100% by mass of the solid content of the coating composition, using the method described above. Multiply by the calculated organic chain length α calculated in , and add up all the obtained values. Note that the "solid content of the coating composition" to be considered when calculating the weight average value α _ave includes polymer nanoparticles (A), hydrolyzable silicon compounds ( b), which targets only the inorganic oxide (D) and the catalyst (E), and is distinguished from the "nonvolatile components" described below. That is, in the present embodiment, "100% by mass solid content of the coating composition" refers to the polymer nanoparticles (A), the hydrolyzable silicon compound (b), the inorganic This means that the total amount of oxide (D) and catalyst (E) is 100% by mass.

A cured resin obtained as a condensate of a hydrolyzable silicon compound with a large calculated organic chain length α generally has a long distance between crosslinking points, and therefore shrinkage during curing tends to be alleviated. A coating film containing such a cured resin tends to have high hardness and recovery rate, and also tends to have improved abrasion resistance. On the other hand, hydrolyzable silicon compounds with a small calculated organic chain length α generally have a small molecular weight and high solubility in solvents, so the hydrolysis and condensation reactions can be easily cured in a short time. This reduces the chance of deterioration of the paint film during durability tests and improves crack resistance. Therefore, from the viewpoint of wear resistance and crack resistance, it is important to adjust the value of the weight average value α _ave .
When the weight average value α _ave is 1.3 or more, the proportion of the hydrolyzable silicon compound (b) with a small number of organic groups and components other than the hydrolyzable silicon compound (b) in the paint decreases, The hardness of the hard coat film increases and the wear resistance improves. In addition, the amount of the hydrolyzable silicon compound (b) having a small number of organic groups is reduced, making it difficult for crosslinking due to sol-gel reaction to proceed in the paint, thereby improving the pot life, which is the storage stability of the paint composition.
When the weight average value α _ave is 2.2 or less, the amount of the hydrolyzable silicon compound (b) having a large number of organic groups is reduced in the paint, and the hydrolysis reaction and condensation reaction are accelerated. Therefore, since the number of unreacted crosslinked sites is reduced during curing, no chemical reaction occurs in the resin during the durability test, and crack resistance is improved.
From the viewpoint of wear resistance, the weight average value α _ave is 1.3 or more, preferably 1.4 or more, and more preferably 1.5 or more.
Further, from the viewpoint of crack resistance, the weight average value α _ave is 2.2 or less, preferably 2.1 or less.

Specifically, the weight average value α _ave can be calculated from each charging amount based on the procedure described in the Examples described below, or the method for specifying the content of the hydrolyzable silicon compound (b) described below. It can also be calculated using the numerical value obtained from . In this embodiment, the "solid content of the coating composition" means the polymer nanoparticles (A), the hydrolyzable silicon compound (b), the inorganic oxide (D), and the catalyst (E), The solid content of 100% by mass means that the total amount of the polymer nanoparticles (A), the hydrolyzable silicon compound (b), the inorganic oxide (D), and the catalyst (E) is 100% by mass.

[Nonvolatile component concentration of coating composition]
The coating composition preferably has a nonvolatile component concentration of 8 to 30% by mass, more preferably 10 to 21% by mass, from the viewpoint of paintability and storage stability. Specifically, the nonvolatile component concentration can be measured based on the procedure described in the Examples described later.

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

[pH of coating composition]
In this embodiment, from the viewpoint of wear resistance and storage stability, the pH is preferably 2.1 to 4.5, more preferably 2.7 to 4.5, and even more preferably 3. It is 3 to 4.5. . pH can be measured based on the method described in the Examples below.

[Content of hydrolyzable silicon compound (b) relative to 100% by mass of nonvolatile component concentration]
In this embodiment, the content of the hydrolyzable silicon compound (b) with respect to 100% by mass of the nonvolatile component concentration of the coating composition is 10% by mass or more and 90% by mass or less from the viewpoint of wear resistance and storage stability. It is preferably 15% by mass or more and 80% by mass or less. The content of the hydrolyzable silicon compound (b) referred to here is also a value calculated from the ratio of the complete hydrolytic condensation weight in the weight excluding volatile components from the amount of each raw material charged at the time of preparing the coating composition. It is specified by The above-mentioned content can be calculated from the amount of each preparation based on the procedure described in the Examples described below, and is not limited to the following, for example, IR analysis, NMR analysis, elemental analysis of the coating film (C), etc. It can also be measured.

<Method for producing coating composition>
Although the method for producing the coating composition of the present embodiment is not particularly limited, for example, the polymer nanoparticles (A) and the matrix raw material component (B') are appropriately selected so as to satisfy the above formula (1), By mixing these and, if necessary, adding a solvent such as water or ethanol to adjust the solid content concentration, or adding a pH adjuster such as triethylamine to adjust the pH, the method of this embodiment can be made. A coating composition can be obtained. In addition, when preparing the matrix raw material component (B'), in order to ensure that the weight average value α _ave is 1.3 or more and 2.2 or less, for example, the calculated organic After calculating the chain length α, the blending ratio of each hydrolyzable silicon compound can be adjusted.

[Coating film (C)]
The coating film (C) (hard coat coating film) of this embodiment contains the coating composition of this embodiment. That is, the coating film (C) is formed by forming (curing) the coating composition of this embodiment. In the coating film (C), the polymer nanoparticles (A) are preferably dispersed in the matrix component (B). In this embodiment, "dispersion" means that the polymer nanoparticles (A) are used as a dispersed phase, the matrix component (B) is used as a continuous phase, and the polymer nanoparticles (A) are uniformly or structured in the matrix component (B). It is to be distributed while forming. The above dispersion can be confirmed by cross-sectional SEM observation of the coating film (C). The coating film (C) of this embodiment tends to have high abrasion resistance because the polymer nanoparticles (A) are dispersed in the matrix component (B).

[Thickness of coating film (C)]
In this embodiment, it is preferable to adjust the film thickness as appropriate from the viewpoint of further developing the abrasion resistance of the coating film (C) and ensuring sufficient followability to deformation of the base material. Specifically, the thickness of the coating film (C) is preferably 1.0 μm or more, more preferably 3.0 μm or more from the viewpoint of wear resistance. Further, the 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 from the viewpoint of weather resistance and substrate conformability. be.

[Martens hardness HM of coating film (C)]
The Martens hardness HM of the coating film (C) is preferably 160 N/mm ² or more from the viewpoint of wear resistance, and a higher value tends to be advantageous in terms of less deformation due to impact and less damage accompanied by destruction. It is in. The Martens hardness HM of the coating film (C) is more preferably 180 N/mm ² or more, still more preferably 200 N/mm ² or more, and from the viewpoint of bending resistance, preferably 400 N/mm ² or less, More preferably, it is 350 N/mm ² or less. Methods for adjusting the Martens hardness HM of the coating film (C) within the above range include, but are not limited to, the following methods, for example, coating the coating composition of this embodiment on a substrate, heat treatment, ultraviolet irradiation, etc. , coating by infrared irradiation, etc. In particular, when the content of the matrix raw material component (B') relative to the total amount of the polymer nanoparticles (A) and the matrix raw material component (B') is increased, the Martens hardness HM of the coating film (C) tends to increase. When the content of the matrix raw material component (B') is reduced, the Martens hardness HM of the coating film (C) tends to decrease.

[Haze change in Taber abrasion test]
The Taber abrasion test in this embodiment is based on the method described in ASTM D1044, and is carried out using a wear wheel CS-10F and a load of 500 g. The smaller the amount of haze change, the more excellent the material will be in wear resistance, and the difference in haze change at 500 rotations from the haze before the test, that is, the difference between the haze at 500 rotations and the haze before the Taber abrasion test, is 10 or less. For example, if it meets the ECE R43 rear quarter glass standard and is 4 or less, it is ANSI/SAE Z. It conforms to the 26.1 standard and can be suitably used as a window material for automobiles. Further, if the amount of haze change at 1000 rotations, that is, the difference between the haze at 1000 rotations and the haze before the Taber abrasion test is 10 or less, it meets the standards for automobile windows and is suitable as an automobile window material. Can be used and if it is 2 or less, it is 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 rotations and the haze before the Taber abrasion test is preferably 2 or less. Methods for adjusting the amount of change in haze within the above range include, but are not limited to, methods such as coating the coating composition of the present embodiment on a substrate and applying heat treatment, ultraviolet irradiation, infrared ray irradiation, etc. An example of this is forming a film.

[Elastic recovery rate η _IT of coating film (C)]
The elastic recovery rate η _IT of the coating film (C) is the ratio of the total mechanical work W _total of the depressions to the elastic return deformation work W _elast of the depressions, and is defined as "the ratio of W _elast /W _total " in ISO14577-1. This is a parameter described as " _ηIT ". The higher the elastic recovery rate η _IT , the more the coating film can return to its original state when deformed, and the higher the self-repair ability against deformation. From the viewpoint of effectively demonstrating self-healing ability, the elastic recovery rate η _IT must be 0.50 or more under measurement conditions (Vickers square pyramid diamond indenter, load increase condition 2 mN/20 sec, load decrease condition 2 mN/20 sec). It is preferable that the value is within this range, and the larger the value within this range, the more preferable it is. More specifically, the elastic recovery rate η _IT is more preferably 0.55 or more, still more preferably 0.60 or more, even more preferably 0.65 or more. The measurement of the elastic recovery rate of the coating film in this embodiment is not limited to the following, but for example, the surface of the coating film (C) is Measured by performing an indentation test using a hardness tester (ENT-NEXUS manufactured by Elionix Co., Ltd.), a nanoindenter (iNano, G200 manufactured by Toyo Technica), a nanoindentation system (TI980 manufactured by Bruker), etc. can do. Methods for adjusting the elastic recovery rate η _IT within the above range include, but are not limited to, methods such as coating the coating composition of this embodiment on a base material, heat treatment, ultraviolet irradiation, infrared ray irradiation, etc. For example, it can be formed into a coating film by

[Method for manufacturing hard coat film]
The method for producing the hard coat film of this embodiment is not particularly limited, but for example, the coating composition of this embodiment is applied to a substrate described below, and formed into a film by heat treatment, ultraviolet irradiation, infrared ray irradiation, etc. This can be obtained by Further, the coating method includes, but is not limited to, a spraying method, a flow coating method, a brush coating method, a dip coating method, a spin coating method, a screen printing method, a casting method, a gravure printing method, a flexo printing method, etc. can be mentioned. When applying to a curved substrate, nozzle flow coating, dip coating, and spraying are particularly preferred. The painted coating composition of the present embodiment can be formed into a film by heat treatment, preferably at room temperature to 250°C, more preferably at 40°C to 150°C, or by irradiation with ultraviolet or infrared rays.

[Substrate with hard coat film]
The base material with a hard coat film according to this embodiment includes a base material and the hard coat film of this embodiment formed on one side and/or both sides of the base material. The hard coat coated base material is present on at least one and/or both sides of the base material.
The base material with a hard coat film of this embodiment is configured as described above, and therefore has high abrasion resistance and high durability. The base material with the hard coat film of this embodiment exhibits a high level of abrasion resistance and stain resistance, so it can be used, for example, in hard coating materials such as building materials, automobile parts, electronic equipment, and electrical appliances, but is not limited to the following. It is useful as a coating, and is particularly preferably used for automobile parts. That is, it is preferable that the hard coat coating film of this embodiment is formed using at least a part of a building material, an automobile member, an electronic device, an electrical appliance, etc. as a base material, and the hard coat coating film of this embodiment is preferably formed using at least a part of an automobile member as a base material. It is more preferable that a hard coat coating film of the form is formed.

[Base material]
The base material in this embodiment is not particularly limited, but includes resin, ceramics, metal, glass, and the like. The shape of the base material is not limited to the following, but includes, for example, a plate shape, a shape including unevenness, a shape including a curved surface, a hollow shape, a porous shape, a combination thereof, and the like. Moreover, the type of base material does not matter, and examples thereof include sheets, films, fibers, and the like. From the viewpoint of transparency, the base material preferably contains a transparent resin and/or glass, and from the viewpoint of moldability, a transparent resin is preferred. That is, a base material with a hard coat film, which has a base material containing a transparent resin and a hard coat film containing the coating composition of this embodiment, has better scratch resistance, moldability, and weather resistance. There is a tendency. Examples of the transparent resin used as the base material include, but are not limited to, thermoplastic resins and thermosetting resins. Thermoplastic resins used as the base material include, but are not limited to, polyethylene, polypropylene, polystyrene, ABS resin, vinyl chloride resin, methyl methacrylate resin, nylon, fluororesin, polycarbonate, polyester resin, etc. . Thermosetting resins used as base materials include, but are not limited to, phenolic resins, urea resins, melamine resins, unsaturated polyester resins, epoxy resins, silicone resins, silicone rubber, SB rubber, natural rubber, Examples include thermosetting elastomers.

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

[Adhesive layer]
The base material with a hard coat film according to this embodiment may further have an adhesive layer between the base material and the hard coat film. As the adhesive layer, commonly used adhesive layers can be used, and there is no particular limitation, examples include thermoplastic resins, thermosetting resins, rubber/elastomers, etc. Among them, acrylic resins, acrylic resins, etc. Preferred are urethane resins, urethane resins, silicone resins, and the like. Further, the adhesive layer may contain any appropriate additives, if necessary. Examples of additives include, but are not limited to, crosslinking agents, tackifiers, plasticizers, pigments, dyes, fillers, anti-aging agents, conductive materials, ultraviolet absorbers, inorganic oxides, light stabilizers, and release agents. Examples include modifiers, softeners, surfactants, flame retardants, antioxidants, and the like. Examples of the crosslinking agent include, but are not limited to, an isocyanate crosslinking agent, an epoxy crosslinking agent, a carbodiimide crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, an amine crosslinking agent, a peroxide crosslinking agent, and a melamine crosslinking agent. Examples include cross-linking agents, urea-based cross-linking agents, metal alkoxide-based cross-linking agents, metal chelate-based cross-linking agents, and metal salt-based cross-linking agents.

In this embodiment, a functional layer may further be provided on at least one surface of the hard coat coating. Examples of the functional layer include, but are not limited to, an antireflection layer, an antifouling layer, a polarizing layer, a shock absorbing layer, and the like.

[Method for manufacturing base material with hard coat film]
The method for producing the base material with the hard coat film of the present embodiment is not particularly limited, but for example, the coating composition of the present embodiment is applied to the base material, and the coating film is formed by heat treatment, ultraviolet irradiation, infrared ray irradiation, etc. It can be obtained by converting Further, the coating method includes, but is not limited to, a spraying method, a flow coating method, a brush coating method, a dip coating method, a spin coating method, a screen printing method, a casting method, a gravure printing method, a flexographic printing method, etc. can be mentioned. When applying to a curved substrate, nozzle flow coating, dip coating, and spraying are particularly preferred. The painted coating composition of the present embodiment can be formed into a film by heat treatment, preferably at room temperature to 250°C, more preferably at 40°C to 150°C, or by irradiation with ultraviolet or infrared rays. Furthermore, this coating can be applied not only to base materials that have already been molded, but also to flat plates before molding, such as pre-coated metals including rust-proof steel plates.

[Surface treatment of hard coat film]
From the viewpoint of weather resistance, the surface of the hard coat coating film of this embodiment may be treated with silica to form a silica layer. The method for forming the silica layer is not particularly limited, but specific examples include silica processing by PECVD in which silicone or silazane is deposited and cured, and silica processing technology in which the surface is modified to silica by irradiation with 155 nm ultraviolet rays. In particular, surface processing by PECVD is preferable because a layer that is difficult to pass through oxygen and water vapor can be created without deteriorating the surface. Silicones or silazane that can be used in PECVD include, but are not limited to, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, vinylmethryxylan, vinyl Examples include methoxysilane, dimethyldimethoxylane, TEOS, tetramethyldisiloxane, tetramethyltetravinylcyclotetrasiloxane, and hexamethyldisilazane, and these may be used alone or in combination of two or more.

[Applications of hard coat coatings and substrates with hard coat coatings]
The hard coat coating film and the base material with the hard coat coating film of this embodiment have excellent abrasion resistance and durability. Therefore, the uses of the hard coat coating film and the base material with the hard coat coating film are not particularly limited, but include, for example, building materials, vehicle parts, electronic equipment, electrical products, and the like.
Applications for building materials include, but are not limited to, the following: window glass for construction machinery, window glass for buildings, houses, greenhouses, etc., roofs for garages and arcades, lighting equipment such as lights and traffic lights, wallpaper surface materials, and signboards. , sanitary products such as bathtubs and washstands, exterior wall materials for kitchen buildings, flooring materials, cork materials, tiles, cushion floors, and interior flooring materials such as linoleum.
Vehicle members include, but are not limited to, parts used in automobiles, aircraft, and trains, for example. Specific examples include front, rear, front door, rear door, rear quarter, sunroof glass, front bumper, rear bumper, spoiler, door mirror, front grill, emblem cover, exterior parts such as body, center panel, door panel, Examples include interior parts such as instrument panels and center consoles, lamp parts such as headlamps and rear lamps, lens parts for vehicle cameras, lighting covers, decorative films, and various glass substitute parts.
Examples of 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, and polarized light. Preferred examples include optical components such as plates, optical filters, lenses, prisms, and optical fibers, and optical films such as antireflection films, oriented films, polarizing films, and retardation films.
In addition to the above, the hard coat coating film and the base material with the hard coat coating film of this embodiment can be applied to various fields such as machine parts, agricultural materials, fishing materials, transportation containers, packaging containers, play equipment, and miscellaneous goods. It is possible.

Hereinafter, the present embodiment will be described in detail with reference to Examples and Comparative Examples, but the present embodiment is not limited to these examples.

Various physical properties in Examples and Comparative Examples described below were measured by the following methods.

(1) Measurement of Thickness The thickness of each layer was measured using a reflection spectroscopic film thickness meter (product number: FE-3000) manufactured by Otsuka Electronics Co., Ltd.

(2) Average particle diameter of polymer nanoparticles (A) A dynamic light scattering particle size distribution analyzer manufactured by Otsuka Electronics Co., Ltd. (product no. :ELSZ-1000) was used to measure the cumulant particle diameter, which was taken as the average particle diameter of the polymer nanoparticles (A).

(3) Primary average particle size of inorganic oxide (D) Observe using a transmission microscope at a magnification of 50,000 to 100,000 times so that 100 to 200 inorganic oxide particles can be seen. The inorganic oxide particles were photographed, the average value of the major axis and the minor axis of the inorganic oxide particles was measured, and the value was taken as the primary average particle diameter of the inorganic oxide (D).

(4) Calculated organic chain length α
The calculated organic chain lengths α of methyltrimethoxysilane, 1,2-bis(triethoxysilyl)ethane, and tris-(trimethoxysilylpropyl)isocyanurate were calculated as shown in FIGS. 1 to 3, respectively.
Since dimethyldimethoxysilane and tetraethoxysilane each have one Si atom in the molecule, the calculated organic chain length α was calculated in the same manner as in FIG.
Since the number of Si atoms in the molecule of 1,2-bis(trimethoxysilyl)hexane is 2, the calculated organic chain length α was calculated in the same manner as in FIG. Regarding the silane compound (Z1) corresponding to the reaction product of 3-isocyanatepropyltriethoxysilane and Uvinul3050, as shown in Figure 4, the number of Si atoms in the molecule is 2, and the calculated organic chain length α is 12 ( = (6/2+21)/2).

(5) Weight average value α _ave
The weight average value α _ave obtained based on the content of the hydrolyzable silicon compound (b) with respect to 100% by mass of the solid content of the coating composition was calculated.
In all Examples and Comparative Examples, all of the nonvolatile components contained in the coating composition were polymer nanoparticles (A), hydrolyzable silicon compound (b), inorganic oxide (D), and catalyst (E). The weight ratio of the hydrolyzable silicon compound (b) was calculated based on the mass of the nonvolatile component obtained by drying the coating composition.
The value of the content of the hydrolyzable silicon compound (b) used in the calculation was the weight in terms of complete hydrolytic condensation. Here, the complete hydrolytic condensation equivalent weight is the weight when the hydrolyzable groups of the hydrolyzable silicon compound used for preparation are 100% hydrolyzed to become SiOH groups and further completely condensed to become siloxane. did.

(6) Measurement of Haze Haze is determined by JIS K7136 for laminates (base material with adhesive layer and hard coat layer) using a turbidimeter manufactured by Nippon Denshoku Industries Co., Ltd. (product number: NDH5000SP). It was measured by the method.

(8) Measurement of Martens hardness HM _A of polymer nanoparticles (A) Martens hardness HM _A of polymer nanoparticles (A) is measured by coating an aqueous dispersion of polymer nanoparticles (A) with a bar coater. It was coated on a glass substrate (material: white plate glass, thickness: 2 mm) so that the thickness was 3 μm, and was dried at 130° C. for 2 hours, and the resulting coating film was measured. The measurement was an indentation test using a Fisherscope manufactured by Fisher Instruments (product number: HM2000S) (test conditions; indenter: Vickers square pyramid diamond indenter, load increase condition: 2 mN/20 sec, load decrease condition: 2 mN/20 sec) ), and the Martens hardness HM _A of the polymer nanoparticles (A) was measured based on the indentation test method according to ISO14577-1.

(9) Measurement of Martens hardness HM _B' of matrix raw material component (B') Martens hardness HM _B' of component (B') is determined by water/ethanol/acetic acid The resulting solution was coated on a glass substrate (material: white glass, thickness: 2 mm) using a bar coater so that the film thickness was 3 μm. ) and dried at 130° C. for 2 hours, and the resulting coating film was used for measurement. The measurement was an indentation test using a Fisherscope manufactured by Fisher Instruments (product number: HM2000S) (test conditions; indenter: Vickers square pyramid diamond indenter, load increase condition: 2 mN/20 sec, load decrease condition: 2 mN/20 sec) ), and HM _B' was measured based on the indentation test method according to ISO14577-1. As described later, the matrix component (B) corresponds to a hydrolyzed condensate of the corresponding component (B'). From this, it is assumed that the value of the Martens hardness HM _B' of the component (B') measured as described above closely matches the Martens hardness HM _{B '} of the matrix component (B). The value was taken as the value of Martens hardness HM _B.

(10) Evaluation of the abrasion resistance of the hard coat layer in the laminate The abrasion resistance of the hard coat layer in the laminate was evaluated using a Taber type ablation tester (No. 101) manufactured by Yasuda Seiki Co., Ltd. according to the ASTM D1044 standard. This was done in accordance with the. That is, a Taber wear test was carried out using a wear wheel CS-10F and a load of 500 g, and the haze before the test and the haze at 1000 rotations were measured using a turbidity meter manufactured by Nippon Denshoku Industries Co., Ltd. (product number: NDH5000SP). ), the wear resistance of the hard coat layer in the laminate was evaluated as follows by measuring the haze according to the method specified in JIS R3212 and taking the difference from the haze before the test.
(Evaluation criteria)
○: Haze difference before and after the test is 2 or less.
×: Haze difference before and after the test exceeds 2.

(11) Evaluation of crack resistance of the hard coat layer in the laminate The crack resistance of the hard coat layer in the laminate was evaluated using a HAST chamber manufactured by ESPEC Co., Ltd. and left standing in an environment of 120° C. and 100 RH% for 1 hour. Thereafter, it was left standing in a dryer at 120° C. for 1 hour. Thereafter, the appearance was visually confirmed, and the crack resistance of the hard coat layer in the laminate was evaluated as follows.
(Evaluation criteria)
◎: No cracks at all 〇: Two or three cracks originating from bumps can be visually confirmed 〇': Linear cracks can be seen on some of the edges △: Linear cracks on the entire edge Can be seen, but can withstand use. ×: Cracks are visible on the entire surface, and cannot withstand use.

(12) Evaluation of pot life The coating composition obtained by the method described below was allowed to stand at room temperature for 24 hours. The water-based paint composition 24 hours after preparation was visually evaluated for the presence or absence of sedimentation, and the residue after filtering through a 400-mesh stainless wire mesh was visually evaluated as follows.
(Evaluation criteria)
○: No sedimentation was observed visually, and a slight residue was observed when the coating solution was filtered through a 400-mesh stainless wire mesh.
Δ: Slight sedimentation was visually confirmed, and residue was observed when the coating solution was filtered through a 400-mesh stainless steel wire mesh, but it could withstand use.
×: Clear sedimentation was observed visually, and the sample could not be used.

(13) Weather resistance evaluation The weather resistance of the laminate was evaluated by UV irradiation using a xenon arc (manufactured by Suga Test Instruments Co., Ltd., product name SX-75) in accordance with the conditions of the ANSI/SAE Z26.1 standard, at 2000 MJ/m ² The Δb values of the laminate before and after irradiation were evaluated as follows. If the evaluation result is S or A, there is no practical problem.
S:Δb<1
A: Δb = 1 to 4
B: Δb > 4

<Preparation of base material with adhesive layer (F-1)>
[Preparation of composite particle water dispersion]
Composite particle water dispersion 1 was synthesized as follows as a raw material for a base material with an adhesive layer (F-1) used for producing a laminate described later.
In a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirring device, 960 g of ion-exchanged water and water-dispersible colloidal silica "Snowtex (registered trademark) PS-SO" (trade name, Nissan Chemical Industries, Ltd.) as an inorganic oxide were added. Co., Ltd., solid content 15% by mass, primary average particle size: 15nm) 778g, 10% dodecylbenzenesulfonic acid aqueous solution 22g, 2% ammonium persulfate aqueous solution 25g, butyl acrylate 45g, 2-hydroxyethyl methacrylate 45g, N, 23 g of N-diethylacrylamide, 1 g of acrylic acid, and 3 g of a reactive emulsifier (trade name ``Adekariasoap (registered trademark) SR-1025'', manufactured by ADEKA Co., Ltd., 25% solids content aqueous solution) were added. Thereafter, polymerization was carried out using a general emulsion polymerization method in an environment of 80°C. After polymerization, the pH was adjusted to 9 with a 25% ammonia aqueous solution and filtered through a 100 mesh wire mesh to obtain a composite particle aqueous dispersion 1. The mass ratio of emulsion particles to inorganic oxide (emulsion particles/inorganic oxide) contained in composite particle water dispersion 1 is 1/1, and the average particle diameter of the composite of emulsion particles and inorganic oxide is was 80 nm, and the solid content of the composite was 12% by mass.

[Preparation of water-based paint composition]
56.0 g of composite particle water dispersion 1 as a composite of emulsion particles and inorganic oxide, 5.0 g of water-dispersible block polyisocyanate (WS50-30W (trade name) manufactured by Asahi Kasei Corporation) as a curing agent, interface Liquid A was obtained by mixing 1.0 g of a 10% aqueous sodium dodecylbenzenesulfonate solution as an activator and 19.1 g of water at room temperature.
Next, 0.54 g of Tinuvin (registered trademark) 400 (trade name, manufactured by BASF Japan Ltd.) was used as an organic ultraviolet absorber, and 0.54 g of Tinuvin (registered trademark) 123 (trade name, manufactured by BASF Japan Ltd.) was used as a light stabilizer. .10 g and 18.3 g of isopropanol as a water-soluble organic solvent were mixed at room temperature to obtain Solution B.
A water-based coating composition was obtained by adding liquid B dropwise to the stirring liquid A over 5 minutes at room temperature and mixing. The solid content concentration of the water-based coating composition was 9% by mass. Further, the solid content ratio (parts by mass) of each component in the water-based coating composition was composite particles/block polyisocyanate/Tinuvin400/Tinuvin123=100/26.8/8/1.5. The composition (parts by mass) of the solvent contained in the water-based coating composition is water/isopropanol = 80/20, and the number of moles of hydroxyl groups contained in the emulsion particles and the number of moles of isocyanate groups contained in the block polyisocyanate are the same. The ratio to the number (X=number of moles of isocyanate groups/number of moles of hydroxyl groups) was 0.6.
[Preparation of base material with adhesive layer]
Next, the above water-based coating composition was applied onto the polycarbonate base material 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 base material. In this way, a base material with an adhesive layer (F-1) was obtained.

<Preparation of polymer nanoparticles (A)>
Polymer nanoparticles (A) used in the production of the hard coat layer described below were prepared as follows.
In a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirring device, 1500 g of ion-exchanged water, 45 g of a 10% aqueous solution of dodecylbenzenesulfonic acid, 105 g of methyltrimethoxysilane, 23 g of phenyltrimethoxysilane, and 27 g of tetraethoxysilane were added. added. Thereafter, polymerization was carried out using a general emulsion polymerization method in an environment of 50°C. After the polymerization, the temperature was set to 80°C, and then using 43 g of a 2% aqueous ammonium persulfate solution, 11 g of butyl acrylate, 12 g of N,N-diethylacrylamide, 1 g of acrylic acid, and 1 g of 3-methacryloxypropyltrimethoxysilane, Polymerization was carried out using a general emulsion polymerization method. After polymerization, the mixture was filtered through a 100-mesh wire mesh to obtain an aqueous dispersion of polymer nanoparticles (A). The obtained polymer nanoparticles (A) had a core-shell structure, had an average particle diameter of 60 nm, and had a solid content of 5.9% by mass. Further, the Martens hardness HM _A of the polymer nanoparticles (A) measured according to the above-mentioned measuring method was 150 N/mm ² .

<Preparation of matrix raw material component (B')>
A matrix raw material component (B') used in the production of the hard coat layer described below was prepared as follows.

[Preparation of matrix raw material component (B'-1)]
As the hydrolyzable silicon compound (b), 45 g of methyltrimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name) , manufactured by Shin-Etsu Chemical Co., Ltd.) 15 g, water-dispersible colloidal silica "Snowtex (registered trademark) OXS" (trade name, manufactured by Nissan Chemical Co., Ltd., solid content 10% by mass, primary average) as the inorganic oxide (D) Particle size: 5 nm) were mixed at room temperature to obtain a matrix raw material component (B'-1).

[Preparation of matrix raw material component (B'-2)]
As the hydrolyzable silicon compound (b), 46 g of methyltrimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name) , manufactured by Shin-Etsu Chemical Co., Ltd.) 15 g, water-dispersible colloidal silica "Snowtex (registered trademark) OXS" (trade name, manufactured by Nissan Chemical Co., Ltd., solid content 10% by mass, primary average) as the inorganic oxide (D) Particle size: 5 nm) were mixed at room temperature to obtain a matrix raw material component (B'-2).

[Preparation of matrix raw material component (B'-3)]
As the hydrolyzable silicon compound (b), 30 g of methyltrimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name) , manufactured by Shin-Etsu Chemical Co., Ltd.) 11 g, 1,2-bis(triethoxysilyl)ethane (indicated as "BTSE" in the table) 7 g, 1,2-bis(trimethoxysilyl)hexane "KBM-3066" (Product name, manufactured by Shin-Etsu Chemical Co., Ltd.) 13 g, water-dispersible colloidal silica "Snowtex (registered trademark) OXS" as inorganic oxide (D) (Product name, manufactured by Nissan Chemical Co., Ltd., solid content 10% by mass) , primary average particle diameter: 5 nm) were mixed at room temperature to obtain a matrix raw material component (B'-3).

[Preparation of matrix raw material component (B'-4)]
As the hydrolyzable silicon compound (b), 30 g of methyltrimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name) , manufactured by Shin-Etsu Chemical Co., Ltd.) 11 g, 1,2-bis(triethoxysilyl)ethane 7 g, 1,2-bis(trimethoxysilyl)hexane "KBM-3066" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 13 g, 75 g of water-dispersible colloidal silica "Snowtex (registered trademark) OXS" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 10% by mass, primary average particle diameter: 5 nm) as an inorganic oxide (D) at room temperature The mixture was mixed under the following conditions to obtain a matrix raw material component (B'-4).

[Preparation of matrix raw material component (B'-5)]
As the hydrolyzable silicon compound (b), 57 g of methyltrimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name) , manufactured by Shin-Etsu Chemical Co., Ltd.) 19 g, water-dispersible colloidal silica "Snowtex (registered trademark) OXS" as the inorganic oxide (D) (trade name, manufactured by Nissan Chemical Co., Ltd., solid content 10% by mass, primary average Particle size: 5 nm) were mixed at room temperature to obtain a matrix raw material component (B'-5).

[Preparation of matrix raw material component (B'-6)]
As the hydrolyzable silicon compound (b), 58 g of methyltrimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name) , manufactured by Shin-Etsu Chemical Co., Ltd.) 19 g, water-dispersible colloidal silica "Snowtex (registered trademark) OXS" (trade name, manufactured by Nissan Chemical Co., Ltd., solid content 10% by mass, primary average) as the inorganic oxide (D) Particle size: 5 nm) were mixed at room temperature to obtain a matrix raw material component (B'-6).

[Preparation of matrix raw material component (B'-7)]
As the hydrolyzable silicon compound (b), 30 g of methyltrimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name) , manufactured by Shin-Etsu Chemical Co., Ltd.) 11 g, 1,2-bis(triethoxysilyl)ethane 7 g, 1,2-bis(trimethoxysilyl)hexane "KBM-3066" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 13 g, 59 g of water-dispersible colloidal silica "Snowtex (registered trademark) OXS" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 10% by mass, primary average particle diameter: 5 nm) as an inorganic oxide (D) and water 15 g of dispersed cerium oxide sol "Needral B-10" (trade name, manufactured by Taki Kagaku Co., Ltd., primary average particle diameter 8 nm, solid content 10% by mass) was mixed at room temperature to obtain matrix raw material component (B'-7). I got it.

[Preparation of silane compound (Z1)]
A silane compound (Z1) used in the preparation of a matrix raw material component (B'-8) to be described later was synthesized as follows. In a 100 mL flask equipped with a stirrer, condenser, and thermometer, 20 g of 3-isocyanatepropyltriethoxysilane "KBE-9007N" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and a hydroxyl group-containing benzophenone compound "Uvinul 3050" (trade name, BASF Japan Co., Ltd., solid content: 100% by mass) was charged and stirred at 120° C. for 3 hours, and the obtained solid was designated as a silane compound (Z1). The structure of the silane compound (Z1) is shown in FIG.

[Preparation of matrix raw material component (B'-8)]
As the hydrolyzable silicon compound (b), 42 g of methyltrimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name) , manufactured by Shin-Etsu Chemical Co., Ltd.) 15 g, 2 g of a silane compound (Z1), and water-dispersible colloidal silica "Snowtex (registered trademark) OXS" (trade name, manufactured by Nissan Chemical Co., Ltd.) as an inorganic oxide (D). Solid content: 10% by mass, primary average particle diameter: 5 nm) 74g were mixed at room temperature to obtain a matrix raw material component (B'-8).

[Preparation of matrix raw material component (B'-9)]
As the hydrolyzable silicon compound (b), 45 g of tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), 7 g of 1,2-bis(triethoxysilyl)ethane , 75 g of water-dispersible colloidal silica "Snowtex (registered trademark) OXS" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 10% by mass, primary average particle diameter: 5 nm) as an inorganic oxide (D) was heated at room temperature. The mixture was mixed under the following conditions to obtain a matrix raw material component (B'-9).

[Preparation of matrix raw material component (B'-10)]
As the hydrolyzable silicon compound (b), 35 g of methyltrimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and tetraethoxysilane "KBE-04" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) were used. ) 35 g, 175 g of water-dispersible colloidal silica "Snowtex (registered trademark) OXS" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 10% by mass, primary average particle diameter: 5 nm) as the inorganic oxide (D). were mixed under room temperature conditions to obtain a matrix raw material component (B'-10).

[Preparation of matrix raw material component (B'-11)]
As the hydrolyzable silicon compound (b), 81 g of methyltrimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and dimethyldimethoxysilane "KBM-22" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) were used. ) 4 g, 25 g of water-dispersible colloidal silica "Snowtex (registered trademark) OXS" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 10% by mass, primary average particle diameter: 5 nm) as the inorganic oxide (D). were mixed under room temperature conditions to obtain a matrix raw material component (B'-11).

[Preparation of matrix raw material component (B'-12)]
As the hydrolyzable silicon compound (b), 15 g of methyltrimethoxysilane "KBM-13" (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), tris-(trimethoxysilylpropyl) isocyanurate "KBM-9659" (trade name) , manufactured by Shin-Etsu Chemical Co., Ltd.) 30 g, 1,2-bis(triethoxysilyl)ethane 7 g, 1,2-bis(triethoxysilyl)ethane 7 g, tetraethoxysilane "KBE-04" (trade name, Shin-Etsu Chemical Co., Ltd.) (manufactured by Kogyo Co., Ltd.) 9 g, water-dispersible colloidal silica "Snowtex (registered trademark) OXS" as inorganic oxide (D) (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 10% by mass, primary average particle diameter: 5nm) at room temperature to obtain a matrix raw material component (B'-12).

Note that the matrix component in the hard coat layer derived from the matrix raw material component (B'-1) in the hard coat layer composition is referred to as component (B-1). It can be said that matrix components (B-1) to (B-12) in the hard coat layer are hydrolyzed condensates of matrix raw material components (B'-1) to (B'-12).

The results of calculating the calculated organic chain length α of the hydrolyzable silicon compound (b) used in the preparation of the matrix raw material component are shown in Table 1 below. Among these, the results of calculating the calculated organic chain length α for methyltrimethoxysilane, 1,2-bis(triethoxysilyl)ethane, tris-(trimethoxysilylpropyl)isocyanurate, and silane compound (Z1) are respectively , shown in Figures 1-4.

[Example 1]
Polymer nanoparticles (A) prepared above such that the solid content mass ratio of polymer nanoparticles (A) and matrix component (B-1) is (A):(B-1) = 20:80. A mixture was obtained by mixing the aqueous dispersion and the matrix raw material component (B'-1) prepared above. Furthermore, 10 g of a solution obtained by mixing 1M normal acetic acid and 1M normal acetic acid Na at a volume ratio of 1:1 was prepared as a catalyst (E), and this was added to the mixture. Next, using an aqueous solution with an ethanol concentration of 20% by mass as a solvent, a mixture (a mixture containing polymer nanoparticles, matrix raw material components, and catalyst) was added so that the solid content concentration was 10% by mass, and the coating composition (1 ) was obtained. Next, the hard coat layer composition was applied to the adhesive layer of the base material with adhesive layer (F-1) using a bar coater, and then dried at 130°C for 2 hours to form a hard coat layer with a thickness of 4.0 μm. , a laminate was obtained. Various evaluations were performed on the coating composition and laminate of Example 1. The results are shown in Table 2.

[Example 2]
Polymer nanoparticles (A) prepared above such that the solid content mass ratio of polymer nanoparticles (A) and matrix component (B-2) is (A):(B-2) = 20:80. A mixture was obtained by mixing the aqueous dispersion and the matrix raw material component (B'-2) prepared above. Next, using an aqueous solution with an ethanol concentration of 20% by mass as a solvent, a mixture was added so that the solid content concentration was 10% by mass to obtain a coating composition (2). A laminate was obtained in the same manner as in Example 1, except that coating composition (2) was used instead of coating composition (1). Various evaluations were performed on the coating composition and laminate of Example 2. The results are shown in Table 2.

[Example 3]
Polymer nanoparticles (A) prepared above such that the solid content mass ratio of polymer nanoparticles (A) and matrix component (B-3) is (A):(B-3) = 20:80. A mixture was obtained by mixing the aqueous dispersion and the matrix raw material component (B'-3) prepared above. Furthermore, 40 g of a 1% by mass aqueous dodecylbenzenesulfonic acid solution (DBS) was prepared as the catalyst (E), and this was added to the mixture. Next, using an aqueous solution with an ethanol concentration of 20% by mass as a solvent, a mixture (mixture containing polymer nanoparticles, matrix raw material components, and catalyst) was added so that the solid content concentration was 10% by mass, and a coating composition (3 ) was obtained. A laminate was obtained in the same manner as in Example 1, except that coating composition (3) was used instead of coating composition (1). Various evaluations were performed on the coating composition and laminate of Example 3. The results are shown in Table 2.

[Example 4]
Polymer nanoparticles (A) prepared above such that the solid content mass ratio of polymer nanoparticles (A) and matrix component (B-4) is (A):(B-4) = 20:80. A mixture was obtained by mixing the aqueous dispersion and the matrix raw material component (B'-4) prepared above. Furthermore, 25 g of an aluminum catalyst DX-9740 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., solid content: 100% by mass) diluted with ethanol to 1% by mass was prepared as a catalyst (E), and this was added to the mixture. Next, using an aqueous solution with an ethanol concentration of 20% by mass as a solvent, a mixture (mixture containing polymer nanoparticles, matrix raw material components, and catalyst) was added so that the solid content concentration was 10% by mass, and the coating composition (4 ) was obtained. A laminate was obtained in the same manner as in Example 1, except that coating composition (4) was used instead of coating composition (1). Various evaluations were performed on the coating composition and laminate of Example 4. The results are shown in Table 2.

[Example 5]
Polymer nanoparticles (A) prepared above such that the solid content mass ratio of polymer nanoparticles (A) and matrix component (B-5) is (A):(B-5) = 10:90. A mixture was obtained by mixing the aqueous dispersion and the matrix raw material component (B'-5) prepared above. Furthermore, 10 g of a solution obtained by mixing 1M normal acetic acid and 1M normal acetic acid Na at a volume ratio of 1:1 was prepared as a catalyst (E), and this was added to the mixture. Next, using an aqueous solution with an ethanol concentration of 20% by mass as a solvent, a mixture (mixture containing polymer nanoparticles, matrix raw material components, and catalyst) was added so that the solid content concentration was 10% by mass, and the coating composition (5% ) was obtained. A laminate was obtained in the same manner as in Example 1, except that coating composition (5) was used instead of coating composition (1). Various evaluations were performed on the coating composition and laminate of Example 5. The results are shown in Table 2.

[Example 6]
Polymer nanoparticles (A) prepared above such that the solid content mass ratio of polymer nanoparticles (A) and matrix component (B-6) is (A):(B-6) = 10:90. A mixture was obtained by mixing the aqueous dispersion and the matrix raw material component (B'-6) prepared above. Furthermore, 25 g of an aluminum catalyst DX-9740 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., solid content: 100% by mass) diluted with ethanol to 1% by mass was prepared as a catalyst (E), and this was added to the mixture. Next, using an aqueous solution with an ethanol concentration of 20% by mass as a solvent, a mixture (a mixture containing polymer nanoparticles, matrix raw material components, and catalyst) was added so that the solid content concentration was 10% by mass, and a coating composition (6% ) was obtained. A laminate was obtained in the same manner as in Example 1, except that coating composition (6) was used instead of coating composition (1). Various evaluations were performed on the coating composition and laminate of Example 6. The results are shown in Table 2.

[Example 7]
Polymer nanoparticles (A) prepared above such that the solid content mass ratio of polymer nanoparticles (A) and matrix component (B-7) is (A): (B-7) = 20:80. A mixture was obtained by mixing the aqueous dispersion and the matrix raw material component (B'-7) prepared above. Furthermore, 10 g of a solution obtained by mixing 1M normal acetic acid and 1M normal acetic acid Na at a volume ratio of 1:1 was prepared as a catalyst (E), and this was added to the mixture. Next, using an aqueous solution with an ethanol concentration of 20% by mass as a solvent, a mixture (a mixture containing polymer nanoparticles, matrix raw material components, and catalyst) was added so that the solid content concentration was 10% by mass, and a coating composition (7% ) was obtained. A laminate was obtained in the same manner as in Example 1, except that coating composition (7) was used instead of coating composition (1). Various evaluations were performed on the coating composition and laminate of Example 7. The results are shown in Table 2.

[Example 8]
Polymer nanoparticles (A) prepared above such that the solid content mass ratio of polymer nanoparticles (A) and matrix component (B-8) is (A): (B-8) = 20:80. A mixture was obtained by mixing the aqueous dispersion and the matrix raw material component (B'-8) prepared above. Furthermore, 10 g of a solution obtained by mixing 1M normal acetic acid and 1M normal acetic acid Na at a volume ratio of 1:1 was prepared as a catalyst (E), and this was added to the mixture. Next, using an aqueous solution with an ethanol concentration of 20% by mass as a solvent, a mixture (mixture containing polymer nanoparticles, matrix raw material components, and catalyst) was added so that the solid content concentration was 10% by mass, and the coating composition (8% ) was obtained. A laminate was obtained in the same manner as in Example 1, except that coating composition (8) was used instead of coating composition (1). Various evaluations were performed on the coating composition and laminate of Example 8. The results are shown in Table 2.

[Comparative example 1]
Polymer nanoparticles (A) prepared above such that the solid content mass ratio of polymer nanoparticles (A) and matrix component (B-9) is (A): (B-9) = 20:80. A mixture was obtained by mixing the aqueous dispersion and the matrix raw material component (B'-9) prepared above. Next, using an aqueous solution with an ethanol concentration of 20% by mass as a solvent, a mixture was added so that the solid content concentration was 10% by mass to obtain a coating composition (9). A laminate was obtained in the same manner as in Example 1, except that coating composition (9) was used instead of coating composition (1). Various evaluations were performed on the coating composition and laminate of Comparative Example 1. The results are shown in Table 3.

[Comparative example 2]
Polymer nanoparticles (A) prepared above so that the solid content mass ratio of polymer nanoparticles (A) and matrix component (B-10) is (A): (B-10) = 10:90. A mixture was obtained by mixing the aqueous dispersion and the matrix raw material component (B'-10) prepared above. Next, using an aqueous solution with an ethanol concentration of 20% by mass as a solvent, a mixture was added so that the solid content concentration was 10% by mass to obtain a coating composition (10). A laminate was obtained in the same manner as in Example 1, except that coating composition (10) was used instead of coating composition (1). Various evaluations were performed on the coating composition and laminate of Comparative Example 2. The results are shown in Table 3.

[Comparative example 3]
Polymer nanoparticles (A) prepared above so that the solid content mass ratio of polymer nanoparticles (A) and matrix component (B-11) is (A): (B-11) = 20:80. A mixture was obtained by mixing the aqueous dispersion and the matrix raw material component (B'-11) prepared above. Next, using an aqueous solution with an ethanol concentration of 20% by mass as a solvent, a mixture was added so that the solid content concentration was 10% by mass to obtain a coating composition (11). A laminate was obtained in the same manner as in Example 1, except that coating composition (11) was used instead of coating composition (1). Various evaluations were performed on the coating composition and laminate of Comparative Example 3. The results are shown in Table 3.

[Comparative example 4]
Polymer nanoparticles (A) prepared above such that the solid content mass ratio of polymer nanoparticles (A) and matrix component (B-12) is (A): (B-12) = 20:80. A mixture was obtained by mixing the aqueous dispersion and the matrix raw material component (B'-12) prepared above. Next, using an aqueous solution with an ethanol concentration of 20% by mass as a solvent, a mixture was added so that the solid content concentration was 10% by mass to obtain a coating composition (12). A laminate was obtained in the same manner as in Example 1, except that coating composition (12) was used instead of coating composition (1). Various evaluations were performed on the coating composition and laminate of Comparative Example 4. The results are shown in Table 3.

The coating composition, hard coat film, and substrate with hard coat film provided by the present invention are useful as hard coats for building materials, automobile parts, electronic devices, electrical products, etc., for example.

Claims (11)

Polymer nanoparticles (A);
A matrix raw material component (B') containing a hydrolyzable silicon compound (b),
a solvent;
A coating composition comprising:
When the calculated organic chain length of the hydrolyzable silicon compound (b) given by the following calculation formula (1) is α, the amount of the hydrolyzable silicon compound (b) based on 100% by mass of the solid content of the coating composition. The weight average value α _ave obtained based on the content is 1.3 or more and 2.2 or less,
A coating composition, wherein the Martens hardness HM _A ' of the polymer nanoparticles (A) and the Martens hardness HM _B' of the matrix raw material component (B') satisfy the relationship HM _B' /HM _A '>1.
Calculated organic chain length α=organic chain length between Si atoms/number of Si atoms in molecule (1)
(Here, when dividing the molecular structure of the hydrolyzable silicon compound (b) into a hydrolyzable part A and a part B other than the part A, the organic chain length between Si atoms is It is the sum of the organic chain length a and the organic chain length b of part B.The organic chain length a is the value obtained by dividing the number of organooxysilane structures by 2.When the number of Si atoms in the molecular structure is 1 In this case, the organic chain length b is 0. If the number of Si atoms in the molecular structure is 2, the organic chain length b is the shortest distance from one Si atom to another Si atom. is given as the number of atoms constituting the atomic chain.When the number of Si atoms in the molecular structure is 3 or more, the organic chain length b is given as the number of atoms constituting the shortest atomic chain. (Use the average value.) the solvent contains water,
The coating composition according to claim 1, wherein the water content is 40% by mass or more and 90% by mass or less, based on 100% by mass of the coating composition. The coating composition according to claim 1, wherein the matrix raw material component (B') contains an inorganic oxide (D). The coating composition according to claim 3, wherein the inorganic oxide (D) contains silica particles. The coating composition according to claim 1, wherein the matrix raw material component (B') contains a catalyst (E). The coating composition according to claim 1, wherein the hydrolyzable silicon compound (b) is a compound containing an atomic group represented by the following formula (b-1).
-R ² _n2 SiX ³ _3-n2 (b-1)
In formula (b-1), R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group, R ² may have a substituent, and ³ represents a hydrolyzable group, and n2 represents an integer of 0 to 2. A hard coat coating film comprising the coating composition according to any one of claims 1 to 6. When a Taber abrasion test is conducted in accordance with ASTM D1044 using a worn wheel CS-10F and a load of 500 g, the difference between the haze at 1000 rotations and the haze before the Taber abrasion test is 2 or less. The hard coat coating film according to claim 7. base material and
A hard coat coating film disposed on one side and/or both sides of the base material and comprising the coating composition according to any one of claims 1 to 6;
A base material with a hard coat film. The substrate with a hard coat coating according to claim 9, further comprising an adhesive layer disposed between the substrate and the hard coat coating. The base material with a hard coat film according to claim 9, which is used for automobile parts.