JP2023066032A - Coating composition, hard coating film, and substrate with hard coating film - Google Patents

Abstract

To provide a coating composition and the like that have excellent storage stability, abrasion resistance, durability, and coating properties.SOLUTION: A coating composition comprises polymeric nanoparticles (A) and a matrix raw material component (B'), wherein an elastic recovery modulus ηITA of the polymeric nanoparticles (A), measured by an indentation test in accordance with ISO 14577-1, is 0.30 or more and 0.90 or less; Martens hardness HMA of the polymeric nanoparticles (A) and the Martens hardness HMB' of the matrix raw material component (B') satisfy the relationship of HMB'/HMA>1; the matrix raw material component (B') contains a hydrolyzable silicon compound (b); and a silicon content of the hydrolyzable silicon compound (b) is 1.80 mass% or more and 5.00 mass% or less of the total coating composition.SELECTED DRAWING: None

Description

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

Resin materials are excellent in moldability and lightness, but inferior in hardness, barrier properties, stain resistance, chemical resistance, flame resistance, heat resistance, weather resistance, etc. compared to inorganic materials such as metal and glass. There are many. In particular, the hardness of resin materials is significantly lower than that of inorganic glass, and the surface is easily damaged, so it is often used with a hard coat. Hard-coated resin materials are not used for applications that require high wear resistance, durability and weather resistance because it is difficult to maintain performance under low light conditions and to maintain appearance when exposed to ultraviolet light for a long period of time. do not have.

For the purpose of imparting abrasion resistance to the resin material, a method using an active energy ray-curable resin composition (see, for example, Patent Document 1), a method of adding an inorganic oxide to the resin material (see, for example, Patent Document 2 and Patent Document 3) and a method of adding polymer particles to a resin material (see Patent Document 4, for example) have been proposed.

JP 2014-109712 A JP-A-2006-63244 JP-A-8-238683 JP 2017-114949 A

The methods of Patent Literature 1 and Patent Literature 2 are general methods for imparting abrasion resistance to resin materials, but it is difficult to impart high abrasion resistance.
The method of Patent Document 3 is a general method using 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. Wear resistance is not sufficient because it is not
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 coating film, there is no description of the physical properties of each component. , wear resistance is not sufficient. Moreover, depending on the coating method, a desired film thickness may not be obtained, and abrasion resistance may not be exhibited.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a coating composition and the like which are excellent in storage stability, wear resistance, durability and coatability.

As a result of intensive studies, the inventors of the present invention found that the above problems can be solved by adjusting the silicon content of the hydrolyzable silicon compound (b) with respect to the entire coating composition within a predetermined range, and completed the present invention. came to.
That is, the present invention includes the following aspects.
[1]
Polymer nanoparticles (A);
a matrix raw material component (B′);
A coating composition comprising
The elastic recovery rate η _ITA of the polymer nanoparticles (A) measured from an indentation test in accordance with ISO14577-1 is 0.30 or more and 0.90 or less,
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,
The matrix raw material component (B′) contains a hydrolyzable silicon compound (b),
A coating composition, wherein the silicon content of the hydrolyzable silicon compound (b) is 1.80% by mass or more and 5.00% by mass or less based on the entire coating composition.
[2]
The coating composition according to [1], wherein the content of the hydrolyzable silicon compound (b) is 30% by mass or more and 90% by mass or less with respect to 100% by mass of the solid content of the coating composition.
[3]
The coating composition according to [1] or [2], wherein the solid content concentration of the coating composition is 10% or more and 30% or less.
[4]
The coating composition according to any one of [1] to [3], wherein the pH of the coating composition is 2.7 or more and 4.5 or less.
[5]
According to ISO14577-1, the elastic recovery rate η _ITB' of the matrix raw material component (B') measured from an indentation test is 0.60 or more and 0.95 or less [1] to [4] The coating composition according to any one of
[6]
The polymer nanoparticles (A) contain a hydrolyzable silicon compound (a),
The coating composition according to any one of [1] to [5], wherein the content of the hydrolyzable silicon compound (a) in the polymer nanoparticles (A) is 50% by mass or more.
[7]
The hydrolyzable silicon compound (a) is a compound containing an atomic group represented by the following formula (a-1), its hydrolysis product and condensate, and the following formula (a-2): The coating composition according to [6], comprising one or more selected from compounds, hydrolysis products thereof, and condensates thereof.
-R ¹ _n1 SiX ¹ _3-n1 (a-1)
(In the formula (a-1), R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group; R represents a halogen, a hydroxy group, a mercapto group, an amino group, (Meth) acryloyl group, or may have a substituent containing an epoxy group, X represents a hydrolyzable group, n1 represents an integer of 0 to 2.)
SiX ²⁴ ( _a -2)
(In formula (a-2), X ² represents a hydrolyzable group.)
[8]
The coating composition according to any one of [1] to [7], wherein the polymer nanoparticles (A) have a functional group (e) having a secondary amide group and/or a tertiary amide group.
[9]
The matrix raw material component (B′) further includes an inorganic oxide (D), and the inorganic oxide (D) is Si, Ce, Nb, Al, Zn, Ti, Zr, Sb, Mg, Sn, Bi. , Co and Cu, the coating composition according to any one of [1] to [8].
[10]
The coating composition according to [9], wherein the inorganic oxide (D) has an average particle size of 2 nm or more and 150 nm or less.
[11]
A hard coat film comprising the coating composition according to any one of [1] to [10].
[12]
The difference between the haze at 1000 rotations and the haze before the Taber abrasion test is 10 or less when the Taber abrasion test is carried out in accordance with ASTM D1044 under the conditions of an abrasion wheel CS-10F and a load of 500 g. The hard coat film according to [11].
[13]
The hard coat film according to [11] or [12], which has a Martens hardness of 160 N/mm ² or more and 400 N/mm ² or less.
[14]
a substrate;
a hard coat coating film disposed on one side and/or both sides of the substrate and comprising the coating composition according to any one of [1] to [10];
A substrate with a hard coat film.
[15]
The substrate with a hard coat film according to [14], further comprising an adhesive layer disposed between the substrate and the hard coat film.
[16]
The substrate with a hard coat film according to [14] or [15], which is for automobile members.

ADVANTAGE OF THE INVENTION According to this invention, the coating composition etc. which are excellent in storage stability, abrasion resistance, durability, and paintability can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, the form (only henceforth "this embodiment") for implementing this invention is demonstrated in detail. It should be noted that the present invention is not limited to the present embodiment described below, and various modifications can be made within the scope of the gist of the present invention.

<Paint composition>
The coating composition of the present embodiment is a coating composition containing polymer nanoparticles (A) and a matrix raw material component (B'), and is measured from an indentation test in accordance with ISO 14577-1. The elastic recovery rate η _ITA of the polymer nanoparticles (A) is 0.30 or more and 0.90 or less, and the Martens hardness HM _A of the polymer nanoparticles (A) and the matrix raw material component (B′) Martens hardness HM _B′ satisfies the relationship HM _B′ /HM _A >1, the matrix raw material component (B′) contains the hydrolyzable silicon compound (b), and the hydrolyzable silicon compound (b) is The silicon content is 1.80% by mass or more and 5.00% by mass or less based on the entire coating composition.
Since the coating composition of the present embodiment is configured as described above, it is excellent in storage stability, wear resistance, durability and coatability. Since the coating composition of the present embodiment exhibits a high level of wear resistance and paintability, it is not limited to the following, but is useful as a hard coating material for, for example, building materials, automobile members, electronic devices, and electrical products. There is, and especially it is preferable to use it as an object for a motor vehicle member.

In this specification, any coating film containing the coating composition of this embodiment is referred to as coating film (C). That is, the coating film (C) means any coating film obtained by curing the coating composition of this embodiment. Further, in this specification, the coating film (C) having a Martens hardness HM of 100 N/mm ² or more, which is 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 the present embodiment, the coating film (C) can be imparted with impact absorption properties, and the amount of change in haze in the Taber abrasion test of the hard coat coating film can be reduced. The shape of the polymer nanoparticles (A) is not particularly limited as long as the particle size is on the order of nm (less than 1 μm).

[Average particle size of polymer nanoparticles (A)]
The average particle size of the polymer nanoparticles (A) in the present embodiment is not particularly limited as long as it is on the order of nm (less than 1 μm), and can be obtained from the particle size observed by cross-sectional SEM or dynamic light scattering method. . From the viewpoint of optical properties, the average particle size of the polymer nanoparticles (A) is preferably 10 nm or more and 400 nm or less, more preferably 15 nm or more and 200 nm or less, and still more preferably 20 nm or more and 100 nm or less.
The method for measuring the average particle size of the polymer nanoparticles (A) is not limited to the following, but for example, an aqueous dispersion of the polymer nanoparticles (A) is prepared in the manner described in the examples described later, and Otsuka Electronics Examples include measuring the cumulant particle size of the water dispersion with a dynamic light scattering particle size distribution analyzer (product number: ELSZ-1000) manufactured by Co., Ltd.
The average particle size 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 the polymerization conditions.

[Hydrolyzable silicon compound (a)]
The polymer nanoparticles (A) in this embodiment preferably contain a hydrolyzable silicon compound (a). The hydrolyzable silicon compound (a) is not particularly limited as long as it is a hydrolyzable silicon compound, its hydrolysis product, or 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), a hydrolysis product thereof, or a condensate thereof. Preferably.
-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 0-2. The hydrolyzable group is not particularly limited as long as it is a group in which a hydroxyl group is generated by hydrolysis, and examples of such groups include halogen, alkoxy groups, acyloxy groups, amino groups, phenoxy groups, oxime groups, and the like. .

Examples of the compound containing the atomic group represented by formula (a-1) include, but are not limited to, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane, methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethoxydiphenylsilane, di 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(triethoxy 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-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl triethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3 -methacryloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 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 contain a compound represented by the following formula (a-2), its hydrolysis product, and condensate.
SiX ²⁴ ₍ a-2)
In formula (a-2), X ² represents a hydrolyzable group. The hydrolyzable group is not particularly limited as long as it produces a hydroxyl group by hydrolysis, and examples thereof include halogens, alkoxy groups, acyloxy groups, amino groups, phenoxy groups, and oxime groups.

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 partial hydrolysis condensate of tetraethoxysilane (for example, trade names "M Silicate 51" and "Silicate 35" manufactured by Tama Chemical Industry Co., Ltd.) , “Silicate 45”, “Silicate 40”, “FR-3”; trade names “MS51”, “MS56”, “MS57”, “MS56S” manufactured by Mitsubishi Chemical Corporation; trade names “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”) and the like.

As described above, in the present embodiment, the hydrolyzable silicon compound (a) is a compound containing an atomic group represented by the above formula (a-1), its hydrolysis product and condensate, and the above formula ( It preferably contains 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 the present embodiment indicates the solid content weight ratio of the hydrolyzable silicon compound (a) contained in the polymer nanoparticles (A). From the viewpoint of improving wear resistance, weather resistance, and heat resistance, the higher the content, the more preferable, and the content is preferably 50% by mass or more, 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, for example, by IR analysis, NMR analysis, elemental analysis, etc. of the polymer nanoparticles (A). be able to.

[Functional group (e)]
In the coating composition of the present embodiment, the polymer nanoparticles (A) preferably have functional groups (e) that interact with the matrix raw material component (B'). When the polymer nanoparticles (A) have the functional group (e), the matrix raw material component (B') is likely to be adsorbed on the surface of the polymer nanoparticles (A), and tends to become a protective colloid and stabilize. Therefore, as a result, the storage stability of the coating composition tends to be improved. 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′) is strengthened, resulting in Viscosity increases with respect to solid content concentration, and sagging tends to be suppressed when coating a complicated shape, and as a result, the film thickness of the coating film (C) tends to be uniform. The fact that the polymer nanoparticles (A) have functional groups (e) is, for example, IR, GC-MS, pyrolysis GC-MS, LC-MS, GPC, MALDI-MS, TOF-SIMS, TG-DTA, It can be confirmed by composition analysis by NMR, analysis by a combination thereof, and the like.

Specific examples of the functional group (e) in the present embodiment include, but are not limited to, a hydroxyl group, a carboxyl group, an amino group, an amide group, and a functional group consisting of an ether bond. from the viewpoint of high hydrogen bondability, more preferably an amide group, and even more preferably a secondary amide group and/or a tertiary amide group.

Compounds containing a functional group (e) and reactants thereof include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 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 - ethylmethacrylamide, N-methyl-N-ethylacrylamide, N-methyl-N-ethylmethacrylamide, N-isopropylacrylamide, Nn-propylacrylamide, N-isopropylmethacrylamide, Nn-propylmethacrylamide, N-methyl-Nn-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, Blemmer PE-90, PE-200, PE-350, PME-100, PME-200, PME-400, AE-350 (trade 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 Emulsifier Co., Ltd.), etc. be done. In this specification, "(meth)acrylate" simply indicates acrylate or methacrylate, and "(meth)acrylic acid" indicates 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 comprising a core layer and one or more shell layers covering the core layer. The polymer nanoparticles (A) preferably have the functional group (e) described above 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 contained in the polymer nanoparticles (A)]
The polymer nanoparticles (A) according to the present embodiment may contain the following polymers from the viewpoint of improving the stability of the particles by imparting an electrostatic repulsive force 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 poly (Meth)acrylate-silicone, polystyrene-(meth)acrylate, and styrene-maleic anhydride copolymers.

Among the polymers that may be contained in the polymer nanoparticles (A) described above, polymers or copolymers of (meth)acrylic acid and (meth)acrylate are examples of compounds that are 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- Hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate polymer or copolymer mentioned. At this time, (meth)acrylic acid is partially or wholly neutralized with amines such as ammonia, triethylamine and dimethylethanolamine, and bases such as NaOH and KOH, in order to further improve the electrostatic repulsion. may

Moreover, the polymer nanoparticles (A) may contain an emulsifier. The emulsifier is not particularly limited, and examples thereof include acidic emulsifiers such as alkylbenzenesulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkylsulfuric acid, polyoxyethylene alkylarylsulfuric acid, 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; quaternaries such as alkyltrimethylammonium bromide, alkylpyridinium bromide, imidazolinium laurate Ammonium salt, pyridinium salt, imidazolinium salt type cationic surfactant; nonionic such as polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethyleneoxypropylene block copolymer, polyoxyethylene distyrylphenyl ether type surfactants and reactive emulsifiers having radically polymerizable double bonds.

Examples of the reactive emulsifier having a radically polymerizable double bond include, but are not limited to, Eleminol JS-2 (trade name, manufactured by Sanyo Kasei Co., Ltd.), Latemul S-120, S- 180A or S-180 (trade name, manufactured by Kao Corporation), Aqualon HS-10, KH-1025, RN-10, RN-20, RN30, RN50 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria Soap SE1025, SR-1025, NE-20, NE-30, NE-40 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), ammonium salt of p-styrenesulfonic acid, sodium salt of p-styrenesulfonic acid, p- Potassium salt of styrenesulfonic acid, alkylsulfonic acid (meth)acrylate such as 2-sulfoethyl acrylate, methylpropanesulfonic acid (meth)acrylamide, ammonium salt of allylsulfonic acid, sodium salt of allylsulfonic acid, potassium allylsulfonic 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 the present embodiment is the parameter described as the ratio η _IT of W _elast /W _total in ISO14577-1. and is indicated by 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 the coating film can return to its original state when subjected to an impact, and the higher the self-healing ability against impact. From the viewpoint of effectively exhibiting the self-healing ability, the elastic recovery rate η _ITA of the polymer nanoparticles (A) is measured under the measurement conditions (Vickers square pyramid diamond indenter, load increase condition 2 mN / 20 sec, load decrease condition 2 mN / 20 sec) is 0.30 or more, and η _ITA is 0.90 or less from the viewpoint of being able to follow the deformation of the substrate and the matrix raw material component (B′) when forming the coating film (C). The elastic recovery rate _ηITA of the polymer nanoparticles (A) is preferably 0.50 or more, more preferably 0.60 or more. Measurement of the elastic recovery rate of the polymer nanoparticles (A) is not limited to the following. A composition obtained by separating and dispersing the separated polymer nanoparticles (A) in a solvent is applied and dried to form a film. ), ultra-micro 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 the present embodiment, the coating film (C) can be imparted with impact absorption properties, and the 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 the present specification, "the matrix raw material component (B') contains the hydrolyzable silicon compound (b)" means that the matrix raw material component (B') is a structural unit derived from the hydrolyzable silicon compound (b). is meant to include macromolecules having The hydrolyzable silicon compound (b) is not particularly limited as long as it is a hydrolyzable silicon compound, its hydrolysis product or condensate.
The matrix raw material component (B') may contain various components other than the polymer nanoparticles (A), in addition to the polymer described above. Among them, other polymers that can be contained in addition to the above-described polymers include water-soluble resins such as polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, and polyacrylic acid; acrylic resins such as PMMA, PAN, and polyacrylamide; Polymers such as polyurethane, polyamide, polyimide, polyvinylidene chloride, polyester, polycarbonate, polyether, polyethylene, polysulfone, polypropylene, polybutadiene, PTFE, PVDF, EVA; and copolymers thereof.

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 thereof. , and a compound represented by the following formula (b-2), its hydrolysis product, and one or more selected from the group consisting of condensates.
^-R2n2SiX33 _{-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, and R ² represents a halogen, a hydroxy group, a mercapto group, or an amino group. , a (meth)acryloyl group, or an epoxy group, X ³ represents a hydrolyzable group, and n2 represents an integer of 0-2. The hydrolyzable group is not particularly limited as long as it produces a hydroxyl group by hydrolysis, and examples of such groups include halogen atoms, alkoxy groups, acyloxy groups, amino groups, phenoxy groups, and oxime groups. be done.
^SiX44 (b _- 2)
In formula (b-2), X ⁴ represents a hydrolyzable group. The hydrolyzable group is not particularly limited as long as it produces a hydroxyl group by hydrolysis, and examples of such groups include halogen, alkoxy groups, acyloxy groups, amino groups, phenoxy groups, and oxime groups. .

Specific examples of the compound containing the atomic group represented by general formula (b-1) include, but are not limited to, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane. , ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, 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(tri 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-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane 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 xime)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- 4-[3-(trimethoxysilyl)propoxy]benzophenone, 2-hydroxy-4-[3-(trimethoxysilyl)propoxy]benzophenone and the like.

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 partial hydrolysis condensate of tetraethoxysilane (for example, trade names "M Silicate 51" and "Silicate 35" manufactured by Tama Chemical Industry Co., Ltd.) , “Silicate 45”, “Silicate 40”, “FR-3”; trade names “MS51”, “MS56”, “MS57”, “MS56S” manufactured by Mitsubishi Chemical Corporation; trade names “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”) and the like.

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), its hydrolysis product and condensate, and the above formula ( It preferably contains one or more selected from the compounds represented by b-2), their hydrolysis products and condensates.

In the present embodiment, the "hydrolyzable silicon compound (a) contained in the polymer nanoparticles (A)" is the same type as the "hydrolyzable silicon compound (b) contained in the matrix raw material component (B')". It may be of the same type or may be of another type. Even if both are of the same type, the one contained in the polymer nanoparticles (A) is the hydrolyzable silicon compound (a), and the one contained in the matrix raw material component (B′) is the hydrolyzable silicon compound. It shall distinguish by setting it as a 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 the present embodiment, the elastic recovery rate η _{ITB '} of the matrix raw material component (B') is a parameter described as the "W _elast /W _total ratio η _IT " in ISO 14577-1. It is a measurement of the coating film of the matrix raw material component (B′) that has been applied, and is indicated by the ratio of the total mechanical work W _total of the dents to the elastic return deformation work W _elast of the dents. The higher the elastic recovery rate _ηITB' , the more the coating film can return to its original state when receiving an impact, and the higher the self-healing ability against impact. From the viewpoint of effectively exhibiting the self-healing ability, the elastic recovery rate η _{ITB '} of the matrix raw material component (B') is measured under the measurement conditions (Vickers square pyramid diamond indenter, load increase condition 2 mN / 20 sec, load decrease condition 2 mN /20 sec) is preferably 0.60 or more, more preferably 0.65 or more. In addition, η _ITB' is preferably 0.95 or less from the viewpoint of being able to follow the deformation of the base material and component (A) when forming a coating film. The measurement of the elastic recovery rate of the matrix raw material component (B') is not limited to the following, but for example, the polymer nanoparticles (A) and the matrix raw material component (B') are separated by an operation such as centrifugation, and then separated. A composition obtained by dissolving the obtained matrix raw material component (B′) in a solvent is applied and dried to form a film. 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), and the like.
As described above, the matrix component (B) corresponds to a cured product obtained by curing the matrix raw material component (B') by hydrolytic condensation or the like. Therefore, the value of the elastic recovery rate _ηITB' of the matrix raw material component (B') measured by the method described in the examples below closely matches the corresponding elastic recovery rate _ηITB of the matrix component (B). As such, the value of elastic recovery 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. In addition, η _ITB is preferably 0.95 or less from the viewpoint of being able to follow the deformation of the base material and component (A) when forming a coating film.
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, adjusting the structure and composition ratio of the constituent components of the matrix raw material component (B'). and so on.

[Inorganic oxide (D)]
The matrix raw material component (B') in the present embodiment preferably contains an inorganic oxide (D). Including the inorganic oxide (D) not only improves the hardness of the matrix raw material component (B′) and improves the abrasion resistance, but also improves the contamination resistance of the coating film due to the hydrophilicity of the hydroxyl groups on the particle surface. tend to

Specific examples of the inorganic oxide (D) in the present 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 oxide selected from the group consisting of Si, Ce, Nb, Al, Zn, Ti, Zr, Sb, Mg, Sn, Bi, Co and Cu, including oxides such as bismuth, cobalt and copper. Ingredients are preferred. These may be used singly or as a mixture regardless of the shape. The inorganic oxide (D) preferably further contains silica typified by dry silica and colloidal silica from the viewpoint of interaction with the above-mentioned hydrolyzable silicon compound (b), and from the viewpoint of dispersibility, It is preferable to further include colloidal silica as a 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 whether it is acidic or basic. Colloidal silica that can be contained in the inorganic oxide (D) will be described later. In addition, from the viewpoint of weather resistance, the inorganic oxide (D) includes cerium oxide, niobium oxide, aluminum oxide, zinc oxide, titanium oxide, zirconium oxide, antimony oxide, magnesium oxide, tin oxide, and bismuth oxide, all of which have ultraviolet absorption ability. , cobalt oxide and copper oxide, and from the viewpoint of improving weatherability, at least one selected from the group consisting of niobium oxide, zinc oxide, titanium oxide and zirconium oxide. It preferably contains an inorganic component of the species, more preferably cerium oxide. Although not limited to the following, when using commercially available products, for example, CIK Nanotech Co., Ltd. cerium oxide, zinc oxide, aluminum oxide, bismuth oxide, cobalt oxide, copper oxide, tin oxide, ultrafine particle material products of titanium oxide; Titanium oxide "Tynoc" (trade name), cerium oxide "Needral" (trade name), tin oxide "Ceramase" (trade name), niobium oxide sol, zirconium oxide sol manufactured by Taki Chemical Co., Ltd.; manufactured by Nissan Chemical Industries, Ltd. A water sol of antimony pentoxide "A-2550" can be mentioned.

[Average particle size of inorganic oxide (D)]
The average particle size of the inorganic oxide (D) in the present 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. Preferably. That is, the average particle size of the inorganic oxide (D) is preferably 2 nm or more and 150 nm or less, more preferably 2 nm or more and 100 nm or less, and still 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, water-dispersed colloidal silica is observed using a transmission microscope photograph at a magnification of 50,000 to 100,000 times. Then, 100 to 200 inorganic oxide particles are photographed, and the average value of the long and short diameters of the inorganic oxide particles can be used for measurement.

[Colloidal silica that can be contained in the inorganic oxide (D)]
Acidic colloidal silica having water as a dispersion solvent, which is preferably used in the present 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 prepared by a sol-gel method, see Werner Stober et al; Colloid and Interface Sci. , 26, 62-69 (1968), Rickey D. Badley et al; Lang muir 6, 792-801 (1990), Journal of the Society of Color Materials, 61 [9] 488-493 (1988). 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 (trade name, Nissan Chemical Industries Co., Ltd.), Adelite AT-20Q (trade name, Asahi Denka Kogyo Co., Ltd.), Clevosol 20H12, and Clevosol 30CAL25 (trade name, Clariant Japan Co., Ltd.).

Examples of basic colloidal silica include silica stabilized by the addition of alkali metal ions, ammonium ions, and amines, and are not particularly limited. Examples include Snowtex-20, Snowtex-30, Snowtex-XS, Snowtex-50, Snowtex-30L, Snowtex-XL, Snowtex-YL, Snowtex ZL, Snowtex-UP, Snowtex-ST-PS-S, Snowtex ST-PS-M, Snowtex-C , Snowtex-CXS, Snowtex-CM, Snowtex-N, Snowtex-NXS, Snowtex-NS, Snowtex-N-40 (trade 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 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.), Clevosol 30R9, Clevosol 30R50 , Clevozol 50R50 (trade 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 (trade name, DuPont company) and the like.

In addition, the colloidal silica that uses a water-soluble solvent as a dispersion medium is not particularly limited. 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), TOL-ST (toluene dispersion type with a particle size of 10 to 15 nm), and the like.

The dry silica particles are not particularly limited, but examples thereof include AEROSIL manufactured by Nippon Aerosil Co., Ltd., and Rheolosil 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)]
Furthermore, the shape of the inorganic oxide (D) in the present embodiment is not limited to the following, and examples thereof include spherical, angular, polyhedral, elliptical, flattened, linear, beaded, and pearly. From the viewpoint of the hardness and transparency of the hard coat film, it is particularly preferably spherical, beaded, or pearl-shaped.

[Other ingredients]
From the viewpoint of further improving the paintability of the paint composition of the present embodiment, the paint composition contains, as the matrix raw material component (B′), in addition to the components described above, if necessary, a thickener, a leveling agent, a thixotropic agent, antifoaming agent, freeze stabilizer, dispersant, wetting agent, rheology control agent, film forming aid, rust inhibitor, plasticizer, lubricant, antiseptic, antifungal agent, antistatic agent, antistatic agent Agents and the like can be added. From the viewpoint of improving the film-forming property, it is preferable to use a wetting agent or a film-forming aid. Specific examples are not particularly limited, but diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol. mono-2-ethylhexyl ether, 2,2,4-trimethyl-1,3-butanediol isobutyrate, diisopropyl glutarate, propylene glycol-n-butyl ether, dipropylene glycol-n-butyl ether, 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 (trade name, manufactured by DIC Corporation), SN Wet 366, SN Wet 980, SN Wet L , SN Wet S, SN Wet 125, SN Wet 126, SN Wet 970 (trade name, manufactured by San Nopco Co., Ltd.). These compounds may be used singly or in combination of two or more.

In addition, depending on the application, the matrix raw material component (B′) may include solvents, pigments, dyes, fillers, anti-aging agents, conductive materials, organic UV absorbers, light stabilizers, release modifiers, softeners, It may also contain surfactants, flame retardants, antioxidants and catalysts. Especially for outdoor use, high weather resistance is required, so it is preferable to contain an organic UV absorber and a light stabilizer. Specific examples of organic UV absorbers and light stabilizers include, but are not limited to, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-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 UV absorbers such as 2-hydroxy-4-stearyloxybenzophenone, 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), a condensate of methyl-3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate and polyethylene glycol (molecular weight 300) (BASF Corporation (product name “TINUVIN1130” manufactured by BASF), isooctyl-3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionate (product 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, TINUVIN PS, TINUVIN P, TINUVIN99-2, TINVIN928 (product name, BASF Corporation) and other benzotriazole-based UV absorbers; 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 (trade name “TINUVIN460” manufactured by BASF), 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (BASF Triazine UV absorbers such as TINUVIN400, TINUVIN405, TINUVIN477, TINUVIN1600 (trade name, manufactured by BASF); HOSTAVIN PR25, HOSTAVIN B-CAP, HOSTAVIN VSU (trade name, manufactured by Clariant); ), and other malonic ester UV absorbers; HOSTAVIN3206 LIQ, HOSTAVINVSUP, HOSTAVIN3212 LIQ (trade name, manufactured by Clariant), and other anilide UV absorbers; amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, Salicylate-based ultraviolet absorbers such as phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate; 2-cyano-3,3-diphenyl acrylate (manufactured by BASF under the trade name “UVINUL3039”, 1,3-bis((2′-cyano-3′,3′-diphenylacryloyl)oxy)-2,2-bis - ((2'-cyano-3',3'-diphenylacryloyl)oxy)methyl)propane (manufactured by BASF, trade name "UVINUL3030)", and other cyanoacrylate UV absorbers; 2-hydroxy-4-acrylic oxybenzophenone, 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 (trade name "CGL-104" manufactured by Nihon Ciba-Geigy Co., Ltd.) or the like has a radically polymerizable double bond in its molecule. radically polymerizable ultraviolet absorber; UV-G101, UV-G301, UV-G137, UV-G12, UV-G13 (trade name manufactured by Nippon Shokubai Co., Ltd.) and other ultraviolet absorbing polymers; 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 -2,2,6,6-tetramethyl-4-piperidyl) sebacate, TINUVIN123, TINUVIN144, TINUVIN152, TINUVIN249, TINUVIN292, TINUVIN5100 (trade name, manufactured by BASF) and other hindered amine light stabilizers; ,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; -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 (trade name, manufactured by Nippon Shokubai Co., Ltd.). Coalescing: UV absorbers having reactivity with silanol groups, isocyanate groups, epoxy groups, semicarbazide groups, hydrazide groups, etc. may be mentioned, and these may be used alone or in combination of two or more.

[catalyst]
As described above, the coating composition of the present embodiment may contain a catalyst as the matrix raw material component (B'). When the coating composition contains a catalyst that promotes the reaction between reactive groups, unreactive groups are less likely to remain in the coating film, resulting in increased hardness and improved abrasion resistance as well as improved weather resistance. point is preferable. The catalyst is not particularly limited, but preferably dissolves or disperses when a hard coat film is obtained. Examples of such catalysts include, but are not limited to, organic acids, inorganic acids, organic bases, inorganic bases, metal alkoxides, metal chelates, etc. These catalysts may be used singly or in combination of two or more. I don't mind.

[solvent]
As described above, the coating composition of the present embodiment may contain a solvent as the matrix raw material component (B'). Solvents that can be used are not particularly limited, and common solvents can be used. Examples of solvents 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; , methyl isobutyl ketone, ketones such as cyclohexanone; ethers such as tetrahydrofuran and dioxane; amides such as dimethylacetamide and dimethylformamide; halogen compounds such as chloroform, methylene chloride and carbon tetrachloride; These may be used singly 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 burden when removing the solvent.

[Martens hardness]
Martens hardness in the present embodiment is a hardness in accordance with ISO14577-1, and the indentation depth at 2 mN under the measurement conditions (Vickers square pyramid diamond indenter, load increase condition 2 mN/20 sec, load decrease condition 2 mN/20 sec) is a value calculated from Martens hardness in the present embodiment, for example, micro hardness tester Fisher scope (HM2000S manufactured by Fisher Instruments), ultra-micro indentation hardness tester (ENT-NEXUS manufactured by Elionix Co., Ltd.), nanoindenter (Toyo Technica (iNano, G200, manufactured by Bruker) and a nanoindentation system (TI980, manufactured by Bruker).

[Hardness HM _A of polymer nanoparticles (A) and hardness HM _B′ of matrix raw material component (B′)]
In the coating composition of the present 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 the present 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 in good agreement with _{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)
Formula (2) expresses that the flexible polymer nanoparticles (A) are present in the hard matrix component (B). (C) can impart wear resistance that has not been exhibited in conventional coating films. Although not intended to be limited to the following, the reason for this is presumed to be that the soft nanoparticles absorb impact and the hard matrix component suppresses deformation.
The range of HM _A 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 still 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 still more preferably 150 N/mm ² or more and 2000 N/mm ^{2 or} less.
Each Martens hardness in the coating composition of the present embodiment is determined, for example, by separating the polymer nanoparticles (A) and the matrix raw material component (B′) by an operation such as centrifugation or ultrafiltration, and In contrast, it can be measured based on the method described in Examples described later.
The polymer nanoparticles (A) generally do not change their composition 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 Examples below is The value of the Martens hardness HM _A in the coating (C) can be determined as being in good agreement with the Martens hardness HM _A of .
The above values of HM _A and HM _B' can be adjusted so as to satisfy the above-described magnitude relationship depending on the structure and composition ratio of the constituent components of the polymer nanoparticles (A) and the matrix raw material component (B'). , 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 confirming the magnitude relationship of the measured values using other hardness as an index. Other hardness is not particularly limited as long as it is an index that indicates the difficulty of deformation of the material when force is applied to the material. Vickers hardness, indentation hardness, and logarithmic decrement measured by pendulum-type viscoelasticity typified by a rigid-body pendulum-type physical property tester. In addition, indices represented by adhesive force, phase, frictional force, viscoelasticity, adsorptive force, hardness and elastic modulus measured by a scanning probe microscope (SPM) can also be used. In these indices, if it is confirmed that the hardness of the matrix raw material component (B') is higher than the hardness of the polymer nanoparticles (A), then the Martens hardness and cohesive strength of the matrix raw material component (B') ( It is assumed that the matrix component (B)) is harder than the polymer nanoparticles (A).

[Silicon content of hydrolyzable silicon compound (b) in coating composition]
In the present embodiment, from the viewpoint of wear resistance and paintability, the silicon content of the hydrolyzable silicon compound (b) is 1.80% by mass or more and 5.00% by mass or less of the entire coating composition. .90% by mass or more and 4.00% by mass or less.
If the silicon content of the hydrolyzable silicon compound (b) is less than 1.80% by mass, the strength of the hard coat film will be low and the abrasion resistance will be low. If the silicon content of the hydrolyzable silicon compound (b) is more than 5.00% by mass, cross-linking due to a sol-gel reaction is likely to proceed, resulting in reduced storage stability of the coating composition.
The silicon content of the hydrolyzable silicon compound (b) with respect to the entire coating composition is calculated from the following formulas (3) and (4). Here, the hydrolyzable silicon compound (b) contains n kinds of hydrolyzable compounds, each represented by bX (X=1 to n).
The silicon content of the hydrolyzable silicon compound (bX) is calculated assuming that the silicon atomic weight is 28.0855.
[Silicon content of hydrolyzable silicon compound (bX)] =
[Silicon atomic weight]×[Number of silicon atoms in bX]/[Molecular weight of bX] Formula (3)

The silicon content of the hydrolyzable silicon compound (b) with respect to the entire coating composition can be specifically calculated from each charging amount based on the procedure described in the examples described later, and is not limited to the following. However, for example, the paint composition is ultrafiltered, the dried filtrate containing the obtained hydrolyzable silicon compound (b) is heat-treated to convert it to silicon dioxide, and the weight is calculated. You can also Conversion to silicon dioxide and gravimetric determination can be performed, for example, by a thermogravimetric apparatus.

[Solid content concentration of coating composition]
The coating composition preferably has a solid content concentration of 10 to 30% by mass, more preferably 12 to 21% by mass, from the viewpoint of coating properties and storage stability. In the present embodiment, the "solid content of the coating composition" refers to the non-volatile means the sexual component. Specifically, the solid content concentration can be measured based on the procedures described in Examples described later.

[Viscosity of coating composition]
In the present embodiment, 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, from the viewpoint of coating properties.

[pH of paint composition]
In this embodiment, the pH is preferably 2.7 to 4.5, more preferably 3.3 to 4.5 or less, from the viewpoint of abrasion resistance and storage stability. The pH can be measured based on the method described in Examples below.

[Content of hydrolyzable silicon compound (b) with respect to solid concentration of 100% by mass]
In the present embodiment, the content of the hydrolyzable silicon compound (b) with respect to the solid content concentration of 100% by mass of the coating composition is preferably 30% by mass or more and 90% by mass or less from the viewpoint of abrasion resistance and storage stability. , more preferably 50% by mass or more and 80% by mass or less. The content of the hydrolyzable silicon compound (b) here is also a value calculated from the ratio of the weight converted to complete hydrolysis condensation to the weight excluding volatile components from the amount of each raw material charged at the time of preparation of the coating composition. identified. The above content can be calculated from each charging amount based on the procedure described in the examples described later, and is not limited to the following, for example, IR analysis, NMR analysis, elemental analysis, etc. of the coating film (C) can also be measured by

<Method for producing paint composition>
The method for producing the coating composition of the present embodiment is not particularly limited. By mixing these and, if necessary, adding a solvent such as ethanol to adjust the solid content concentration, or adding a pH adjuster such as triethylamine to adjust the pH, the coating composition of the present embodiment can get things. At that time, the amount of each component is such that the silicon content of the hydrolyzable silicon compound (b) calculated from the above formulas (3) and (4) is 1.80% by mass or more and 5.00% by mass or less. to adjust.

<Coating film (C)>
The coating film (C) of the present embodiment contains the coating composition of the present embodiment. That is, the coating film (C) is formed (cured) from the coating composition of the present embodiment. In the coating film (C), the polymer nanoparticles (A) are preferably dispersed in the matrix component (B). "Dispersion" in the present embodiment means that the polymer nanoparticles (A) are dispersed phase, the matrix component (B) is a continuous phase, and the polymer nanoparticles (A) are uniformly or structurally dispersed in the matrix component (B). It is to distribute while forming The dispersion can be confirmed by cross-sectional SEM observation of the coating film (C). In the coating film (C) of the present embodiment, the polymer nanoparticles (A) are dispersed in the matrix component (B) and thus tend to have high abrasion resistance.

[Film thickness of coating film (C)]
In the present embodiment, it is preferable to appropriately adjust the film thickness from the viewpoint of further expressing the abrasion resistance of the coating film (C) and from the viewpoint of sufficiently ensuring the ability to follow the deformation of the substrate. Specifically, the film thickness of the coating film (C) is preferably 1.0 μm or more, more preferably 3.0 μm or more, from the viewpoint of abrasion resistance. Furthermore, the film thickness of the coating film (C) is preferably 100.0 μm or less, more preferably 50.0 μm or less, and still 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. 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. The method for adjusting the Martens hardness HM of the coating film (C) within the above range is not limited to the following, but for example, the coating composition of the present embodiment is applied onto a substrate, followed by heat treatment and ultraviolet irradiation. , infrared irradiation and the like to form a coating film. In particular, increasing the content of the matrix raw material component (B') with respect to the total amount of the polymer nanoparticles (A) and the matrix raw material component (B') tends to increase the Martens hardness HM of the coating film (C). 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 amount in Taber abrasion test]
The Taber abrasion test in this embodiment conforms to the measurement method described in ASTM D1044, and is measured under the conditions of a wear wheel CS-10F and a load of 500 g. The smaller the amount of change in haze, the more excellent the material is in abrasion resistance. For example, if it conforms to the ECE R43 standard for reactor glass, and if it is 4 or less, it conforms to ANSI/SAE Z. 26.1 standard, and can be suitably used as a window material for automobiles. Further, if the amount of haze change at 1000 rpm, that is, the difference between the haze at 1000 rpm and the haze before the Taber abrasion test is 10 or less, it conforms to automotive window standards and is suitable as an automotive window material. ANSI/SAE Z.V. 26.1, ECE R43, and JIS R3211/R3212 standards, and can be suitably used for all automotive window materials. The difference between the haze at 1000 rotations and the haze before the Taber abrasion test is preferably 10 or less, more preferably 6 or less, and even more preferably 2 or less. The method for adjusting the haze change amount within the above range is not limited to the following, but for example, the coating composition of the present embodiment is applied onto a substrate, followed by heat treatment, ultraviolet irradiation, infrared irradiation, or the like. film formation.

[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 dents to the elastic return deformation work W _elast of the dents, and is defined in ISO 14577-1 as the ratio of W _elast /W _total η _IT ”. 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-repairing ability against deformation. From the viewpoint of effectively exhibiting the self-healing ability, the elastic recovery rate η _IT is 0.50 or more under the 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 there is a certain value, and within this range, the larger the value, the better. More specifically, the elastic recovery rate η _IT is more preferably 0.55 or more, still more preferably 0.60 or more, and even more preferably 0.65 or more. The measurement of the elastic recovery rate of the coating film in the present embodiment is not limited to the following, but for example, the surface of the coating film (C) is measured using a micro hardness tester Fischerscope (HM2000S manufactured by Fisher Instruments Co.) with an ultra-micro indentation. Hardness tester (ENT-NEXUS manufactured by Elionix Co., Ltd.), nanoindenter (iNano, G200 manufactured by Toyo Technica Co., Ltd.), nanoindentation system (TI980 manufactured by Bruker), etc. Measured by performing an indentation test. can do. Methods for adjusting the elastic recovery rate η _IT within the above range include, but are not limited to, the coating composition of the present embodiment, applied onto a substrate, heat treatment, ultraviolet irradiation, infrared irradiation, and the like. It is mentioned that it is made into a coating film by.

<Method for producing hard coat film>
The method for producing the hard coat coating film of the present embodiment is not particularly limited, but for example, the coating composition of the present embodiment is applied to a substrate described later, and the film is formed by heat treatment, ultraviolet irradiation, infrared irradiation, or the like. can be obtained by Further, the coating method is not limited to the following, but includes, for example, 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, and the like. is mentioned. Nozzle flow coating, dip coating, and spraying are particularly preferred for application to curved substrates. The coated coating composition of the present embodiment can be formed into a coating film by heat treatment at preferably room temperature to 250° C., more preferably 40° C. to 150° C., UV irradiation, or infrared irradiation.

<Base material with hard coat film>
The substrate with a hard coat film according to this embodiment includes a substrate and the hard coat film of this embodiment formed on one side and/or both sides of the substrate. A substrate with a hard coat film has it on at least one side and/or both sides of the substrate.
Since the substrate with a hard coat film of the present embodiment is configured as described above, it has high abrasion resistance and high durability. Since the substrate with a hard coat film of the present embodiment exhibits a high level of wear resistance and stain resistance, it is not limited to the following, for example, hard coating materials such as building materials, automobile members, electronic devices and electrical products It is useful as a coat, and is particularly preferably used for automotive parts. That is, it is preferable that the hard coat coating film of the present embodiment is formed using at least a portion of a building material, an automobile member, an electronic device, an electrical product, or the like as a base material, and the present embodiment uses at least a portion of an automobile member as a base material. It is more preferable that a hard coat coating film having a shape is formed.

[Base material]
The base material in the present embodiment is not particularly limited, but resins, pottery, metals, glass and the like can be mentioned. Examples of the shape of the substrate include, but are not limited to, a plate shape, a shape including unevenness, a shape including curved surfaces, a hollow shape, a porous shape, and combinations thereof. Also, any type of base material can be used, and examples thereof include sheets, films, and fibers. The substrate preferably contains a transparent resin and/or glass from the viewpoint of transparency, and preferably a transparent resin from the viewpoint of moldability. That is, a substrate with a hard coat film having a substrate containing a transparent resin and a hard coat film containing the coating composition of the present embodiment has better abrasion resistance, moldability, and weather resistance. There is a tendency. Examples of the transparent resin used as the substrate include, but are not limited to, thermoplastic resins and thermosetting resins. Examples of the thermoplastic resin 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, and polyester resin. . The thermosetting resin used as the base material is not limited to the following, but for example, phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, silicone resin, silicone rubber, SB rubber, natural rubber, A thermosetting elastomer etc. are mentioned.

[transparency]
The transparency of the substrate with a hard coat film of the present embodiment can be evaluated by total light transmittance from the viewpoint of change in appearance. In the present embodiment, the total light transmittance of the substrate with a hard coat film 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. Especially preferred.

[Adhesion layer]
The substrate with a hard coat film according to this embodiment may further have an adhesive layer between the substrate and the hard coat film. As the adhesive layer, a generally used adhesive layer can be used, and is not particularly limited. Urethane-based resins, urethane-based resins, silicone-based resins, and the like are preferred. Moreover, the adhesive layer may contain any appropriate additive as necessary. Examples of additives include, but are not limited to, cross-linking agents, tackifiers, plasticizers, pigments, dyes, fillers, anti-aging agents, conductive materials, ultraviolet absorbers, inorganic oxides, light stabilizers, and release agents. Modifiers, softeners, surfactants, flame retardants, antioxidants, and the like. Examples of cross-linking agents include, but are not limited to, isocyanate-based cross-linking agents, epoxy-based cross-linking agents, carbodiimide-based cross-linking agents, oxazoline-based cross-linking agents, aziridine-based cross-linking agents, amine-based cross-linking agents, peroxide-based cross-linking agents, and melamine-based cross-linking agents. Cross-linking agents, urea-based cross-linking agents, metal alkoxide-based cross-linking agents, metal chelate-based cross-linking agents, metal salt-based cross-linking agents and the like can be mentioned.

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

<Method for producing base material with hard coat film>
The method for producing the substrate with a hard coat film of the present embodiment is not particularly limited. can be obtained by Furthermore, the coating method is not limited to the following, but includes, for example, 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, and the like. is mentioned. Nozzle flow coating, dip coating, and spraying are particularly preferred when applying to curved substrates. The coated coating composition of the present embodiment can be formed into a coating film by heat treatment at preferably room temperature to 250° C., more preferably 40° C. to 150° C., UV irradiation, or infrared irradiation. Furthermore, this coating can be applied not only to already molded substrates, but also to pre-coated flat plates before molding, such as pre-coated metal containing 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 the present embodiment may be processed 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/cured, and silica processing technology in which the surface is modified into silica by irradiating 155 nm ultraviolet rays. In particular, surface processing by PECVD is preferable because a layer that is difficult to permeate oxygen and water vapor can be produced without degrading the surface. Silicones or silazanes that can be used for PECVD include, but are not limited to, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, vinylmethoxysilane, vinyl Methoxysilane, dimethyldimethoxysilane, TEOS, tetramethyldisiloxane, tetramethyltetravinylcyclotetrasiloxane, hexamethyldisilazane, etc., may be mentioned, and these may be used singly or in combination of two or more.

<Uses of the hard coat film and the substrate with the hard coat film>
The hard coat film and the substrate with the hard coat film of the present embodiment have excellent abrasion resistance and durability. Therefore, applications of the hard coat film and the base material with the hard coat film are not particularly limited, but examples thereof include building materials, vehicle members, electronic devices, and electric products.
Examples of building material applications include, but are not limited to, window glass for construction machinery, window glass for buildings, houses, greenhouses, etc., roofs for garages and arcades, lights such as lighting and traffic lights, wallpaper surface materials, and signboards. , sanitary products such as bathtubs and washbasins, exterior wall materials for kitchen building materials, flooring materials, cork materials, tiles, cushion floors, and interior floor materials such as linoleum.
Examples of vehicle members include, but are not limited to, parts used in automobiles, aircraft, and trains. Specific examples include front, rear, front door, rear door, rear quarter, sunroof glass, front and rear bumpers, spoilers, door mirrors, front grills, emblem covers, exterior parts such as the body, center panels, door panels, Examples include interior members such as instrument panels and center consoles, lamp members such as headlamps and rear lamps, lens members for vehicle-mounted cameras, lighting covers, decorative films, and various glass replacement members.
Electronic devices and electrical products are not limited to the following, but for example, mobile phones, personal digital assistants, personal computers, portable game machines, OA equipment, solar cells, flat panel displays, touch panels, optical discs such as DVDs and Blu-ray discs, polarized light Optical parts such as plates, optical filters, lenses, prisms, and optical fibers, and optical films such as antireflection films, oriented films, polarizing films, and retardation films are preferred.
In addition to the above, the hard coat coating film and the substrate with the hard coat coating film of the present embodiment can be applied to various fields such as machine parts, agricultural materials, fishing materials, transport containers, packaging containers, playground equipment and miscellaneous goods. It is possible.

Hereinafter, the present embodiment will be described with specific examples and comparative examples, but the present embodiment is not limited to these.

(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 size of polymer nanoparticles (A) Using the polymer nanoparticles (A) aqueous dispersion obtained by the method described later, a dynamic light scattering particle size distribution analyzer (product number : ELSZ-1000) was used as the average particle size of the polymer nanoparticles (A).

(3) Primary average particle size of inorganic oxide (D) Observe at 50,000 to 100,000 times magnification using a transmission microscope photograph, so that 100 to 200 inorganic oxide particles appear. A photograph was taken, and the average value of the major axis and minor axis of the inorganic oxide particles was measured, and the value was defined as the primary average particle size of the inorganic oxide (D).

(4) Silicon content of hydrolyzable silicon compound (b) in coating composition was calculated using the following formulas (3) and (4). The silicon content of the hydrolyzable silicon compound (bX) was calculated assuming that the silicon atomic weight was 28.0855.
[Silicon content of hydrolyzable silicon compound (bX)] =
[Silicon atomic weight]×[Number of silicon atoms in bX]/[Molecular weight of bX] Formula (3)

(5) Solid content concentration of coating composition and content of hydrolyzable silicon compound (b) with respect to solid content concentration of 100% by mass It was calculated from the ratio to the mass of the non-volatile component obtained by drying.
Next, the content of the hydrolyzable silicon compound (b) with respect to a solid content concentration of 100% by mass is calculated by combining the mass of the non-volatile component and the content of the hydrolyzable silicon compound (b) as described above. calculated from the ratio of In such calculations, the content of the hydrolyzable silicon compound (b) was the weight in terms of complete hydrolysis and condensation. Here, the weight converted to complete hydrolysis and condensation is the weight when the hydrolyzable groups of the hydrolyzable silicon compound used in the preparation are 100% hydrolyzed to form SiOH groups, which are then completely condensed to form siloxane. bottom.

(6) Measurement of Martens hardness HM of hard coat coating Indentation test using Fisher Scope (product number: HM2000S) manufactured by Fisher Instruments (test conditions; indenter: Vickers square pyramid diamond indenter, load increase condition: 2 mN / 20 sec, load decreasing condition: 2 mN/20 sec) to measure the microhardness, and measure the Martens hardness HM of the hard coat film based on the indentation test method in accordance with ISO 14577-1.

(7) Measurement of elastic recovery rate η _IT of hard coat coating Indentation test using Fisher Scope (product number: HM2000S) manufactured by Fisher Instruments (test conditions; indenter: Vickers square pyramid diamond indenter, load increasing conditions: 2 mN / 20 sec, load reduction condition: 2 mN / 20 sec) to measure the microhardness of the hard coat coating film, and based on the indentation test method compliant with ISO 14577-1, the elasticity of the dents relative to the total mechanical work load W _total of the dents The ratio of the return deformation work W _elast , that is, the value of W _elast /W _total was measured as the elastic recovery rate η _IT of the hard coat coating film.

(8) Evaluation of abrasion resistance of hard coat coating The abrasion resistance of the hard coat coating is evaluated using a Taber abrasion tester (No. 101) manufactured by Yasuda Seiki Co., Ltd., in accordance with ASTM D1044 standards. gone. That is, a Taber abrasion test was performed under the conditions of an abrasion 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) was measured by the method specified in JIS R3212, and the difference between the haze at 1000 rotations and the haze before the test was evaluated as follows.
A: haze difference is 2 or less,
B: Haze difference is more than 2 and 4 or less,
B': Haze difference is more than 4 and 10 or less,
C: Haze difference is more than 10 and 30 or less D: Haze difference is more than 30

(9) Evaluation of Film Formability Film formability was evaluated as follows by visually confirming whether cracks occurred in the coating film after forming the hard coat coating film.
A: Appearance is good B: Cracks occur in part C: Cracks occur all over the coating film

(10) Evaluation of storage stability Storage stability was evaluated by the time until the paint gelled as described below.
A: More than 24 hours B: More than 8 hours and 24 hours or less C: 5 hours or more and 8 hours or less D: Less than 5 hours

(11) Evaluation of transparency The transparency of the substrate with a hard coat film is measured by measuring the total light transmittance using a turbidity meter (product number: NDH5000SP) manufactured by Nippon Denshoku Industries Co., Ltd., and evaluated as follows. bottom.
A: 90% or more,
B: 80% or more and less than 90%,
C: less than 80%

(12) Measurement of initial adhesion of hard coat coating film It was evaluated whether or not the hard coat film was retained on the base material with the adhesive layer when it was attached to the film side and peeled off.

(13) Measurement of Martens hardness HM _A and elastic recovery rate η _ITA of _polymer nanoparticles (A) Coated on a glass substrate (material: white plate glass, thickness: 2 mm) using a bar coater so that the film thickness is 5 μm, and dried at 130 ° C. for 1.5 hours to obtain a coating film. and measured in the same manner as in (4) above. The measurement is an indentation test using a Fisher Scope (product number: HM2000S) manufactured by Fisher Instruments (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 conforming to ISO 14577-1. In addition, the elastic recovery rate η _ITA (=W _elast /W _total ) was measured in the same manner as in (5) above.

(14) Content of hydrolyzable silicon compound (a) in polymer nanoparticles (A) The content of hydrolyzable silicon compound (a) in polymer nanoparticles (A) is Particles (A) It was calculated from the ratio of the weight converted to complete hydrolysis and condensation to the total weight of water, dodecylbenzenesulfonic acid and ammonium persulfate removed from the total amount charged when preparing the aqueous dispersion of particles (A). Here, the weight converted to complete hydrolysis and condensation is the weight when the hydrolyzable groups of the hydrolyzable silicon compound used in the preparation are 100% hydrolyzed to form SiOH groups, which are then completely condensed to form siloxane. bottom.

(15) Measurement of Martens hardness HM _{B '} and elastic recovery rate η _ITB' of component ( _B ') / ethanol / acetic acid (composition ratio 77% by mass / 20% by mass / 3% by mass), and the resulting solution is coated with a glass substrate (material: white plate) so that the film thickness is 5 μm using a bar coater Glass, thickness: 2 mm), dried at 130° C. for 1.5 hours, and measured using the obtained coating film. The measurement is an indentation test using a Fisher Scope (product number: HM2000S) manufactured by Fisher Instruments (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′ and η _ITB′ (=W _elast /W _total ) were measured based on the indentation test method conforming to ISO 14577-1. Since the component (B) corresponds to the hydrolysis condensation product of the corresponding component (B'), the Martens hardness HM _B' and the elastic recovery rate η _ITB' of the component (B') measured as described above The values of Martens _hardness HM _B and elastic recovery η _ITB were determined as well corresponding to the Martens hardness HM _B and elastic recovery η ITB of the matrix component (B), respectively.

[Preparation of adhesive layer composition liquid]
<Adhesive layer (Z-1) composition liquid>
E2050S aqueous dispersion (manufactured by Asahi Kasei Corporation, solid content concentration 46%, minimum film formation temperature 55 ° C.) 15 g, water-dispersed colloidal silica “Snowtex C” (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass , Primary average particle diameter 15 nm, minimum film formation temperature over 150 ° C.) 14 g, Tinuvin 400 as a light shielding agent (trade name, manufactured by BASF Japan Ltd.) 2.1 g, Tinuvin 123 as a light stabilizer (trade name, manufactured by BASF Japan Ltd.) 0.1 g, 33 g of water, and 35 g of ethanol were mixed at room temperature to obtain an adhesive layer (Z-1) composition liquid. The solid content concentration of the adhesive layer (Z-1) composition liquid was 12% by mass, and the solid content ratio of each component was E2050S/Snowtex C/Tinuvin400/Tinuvin123=100/40/30/2.

<Composite Particle (FG-1) Aqueous Dispersion>
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-dispersed colloidal silica "Snowtex PSSO" (trade name, manufactured by Nissan Chemical Industries, Ltd.) as an inorganic oxide (G) were Solid content 15% by mass) 778 g, 10% dodecylbenzenesulfonic acid aqueous solution 22 g, 2% ammonium persulfate aqueous solution 25 g, butyl acrylate 45 g, 2-hydroxyethyl methacrylate 45 g, diethylacrylamide 23 g, acrylic acid 1 g, reactive emulsifier (product Using 3 g of "Adekari Soap SR-1025", manufactured by ADEKA Co., Ltd., 25% solid content aqueous solution), polymerization was carried out in an environment of 80° C. by a general emulsion polymerization method. After the polymerization, the pH was adjusted to 9 with a 25% aqueous ammonia solution and filtered through a 100-mesh wire mesh to obtain an aqueous dispersion of composite particles (FG-1). The mass ratio of the adhesive emulsion particles (F) and the inorganic oxide (G) in the obtained composite particles (FG-1) (adhesive emulsion particles (F)/inorganic oxide (G)) was 1/1. The average particle size was 80 nm, and the solid content was 12% by mass.

<Adhesive layer (Z-2) composition liquid>
218.8 g of the composite particles (FG-1) described above, polyisocyanate A (WT30-100, manufactured by Asahi Kasei Co., Ltd.) as a curing agent, Tinuvin 400 (trade name, manufactured by BASF Japan Ltd.) as a light shielding agent, 2.1 g, 0.1 g of Tinuvin 123 (trade name, manufactured by BASF Japan Ltd.) as a light stabilizer, 50 g of water, and 60 g of ethanol were mixed at room temperature to obtain an adhesive layer (Z-2) composition liquid. The solid content concentration of the adhesive layer (Z-2) composition liquid was 10% by mass, and the solid content ratio of each component was FG-1/Tinuvin400/Tinuvin123/polyisocyanate A=200/16/3/40.

[Production of substrate with adhesive layer]
<Base material P1 with adhesive layer>
An adhesive layer was formed on the surface of one side of a polycarbonate substrate (manufactured by Takiron Co., Ltd., product number 1600, thickness: 2 mm) in the following manner. That is, the adhesive layer (Z-1) composition liquid was applied onto a polycarbonate substrate using a bar coater. Then, the coating liquid was dried at 130° C. for 1 hour to form an adhesive layer having a film thickness of 5.0 μm on the polycarbonate substrate. Thus, a substrate P1 with an adhesive layer was obtained.

<Base material P2 with adhesive layer>
A substrate P2 with an adhesive layer was obtained in the same manner as the substrate P1 with an adhesive layer, except that the adhesive layer (Z-2) composition liquid was used instead of the adhesive layer (Z-1) composition liquid.

[Preparation of polymer nanoparticles (A) aqueous dispersion]
Polymer nanoparticles (A) aqueous dispersion used in the examples described later were synthesized as follows.

<Polymer nanoparticles (A-1) aqueous dispersion>
A reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirrer was charged with 750 g of ion-exchanged water, 45 g of a 10% dodecylbenzenesulfonic acid aqueous solution, and methyltrimethoxysilane (trade name “KBM13”, manufactured by Shin-Etsu Chemical Co., Ltd.). 105 g, 23 g of phenyltrimethoxysilane (trade name “KBM103”, manufactured by Shin-Etsu Chemical Co., Ltd.), and 27 g of tetraethoxysilane (trade name “KBE04”, manufactured by Shin-Etsu Chemical Co., Ltd.) were used in an environment of 50 ° C. Polymerization was carried out by a general emulsion polymerization method. After polymerization, after the temperature was set to 80° C., 43 g of a 2% aqueous ammonium persulfate solution, 11 g of butyl acrylate, 12 g of diethylacrylamide, 1 g of acrylic acid, 3-methacryloxypropyltrimethoxysilane (trade name “KBM503”, Shin-Etsu Chemical Co., Ltd. Co., Ltd.) was used to perform polymerization by a general emulsion polymerization method, followed by filtration through a 100-mesh wire mesh to obtain an aqueous dispersion of polymer nanoparticles (A-1). The obtained polymer nanoparticles (A-1) had a core-shell structure, an average particle diameter of 60 nm, and a solid content of 11.8% by mass.

<Polymer nanoparticles (A-2) aqueous dispersion>
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 10% dodecylbenzenesulfonic acid aqueous solution, 105 g of methyltrimethoxysilane, 23 g of phenyltrimethoxysilane and 27 g of tetraethoxysilane were used. Then, polymerization was carried out by a general emulsion polymerization method in an environment of 50°C. After the polymerization, after the temperature was raised to 80° C., 43 g of a 2% aqueous solution of ammonium persulfate, 11 g of butyl acrylate, 12 g of diethylacrylamide, 1 g of acrylic acid, 1 g of 3-methacryloxypropyltrimethoxysilane, RUVA-93 (trade name, Otsuka (manufactured by Kagaku Co., Ltd.), polymerization was performed by a general emulsion polymerization method, and filtration was performed through a 100-mesh wire mesh to obtain an aqueous dispersion of polymer nanoparticles (A-2). The resulting polymer nanoparticles (A-2) had a core-shell structure, an average particle size of 55 nm, and a solid content of 6.3% by mass.

<Polymer nanoparticles (A-3) aqueous dispersion>
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 10% dodecylbenzenesulfonic acid aqueous solution, 105 g of methyltrimethoxysilane, 23 g of phenyltrimethoxysilane and 27 g of tetraethoxysilane were used. Then, polymerization was carried out by a general emulsion polymerization method in an environment of 50°C. After the polymerization, the temperature was adjusted to 80° C., and then 43 g of a 2% aqueous ammonium persulfate solution, 24 g of butyl acrylate, 1 g of acrylic acid, and 1 g of 3-methacryloxypropyltrimethoxysilane were used to polymerize by a general emulsion polymerization method. and filtered through a 100-mesh wire mesh to obtain an aqueous dispersion of polymer nanoparticles (A-3). The resulting polymer nanoparticles (A-3) had a core-shell structure, an average particle size of 57 nm, and a solid content of 6.3% by mass.

<Polymer nanoparticles (A-4) aqueous dispersion>
In a reactor equipped with a reflux condenser, dropping tank, thermometer and stirrer, 1500 g of ion-exchanged water, 45 g of 10% dodecylbenzenesulfonic acid aqueous solution, 44 g of dimethyldimethoxysilane, and 27 g of phenyltrimethoxysilane were added to the temperature of 50°C. Polymerization was carried out by a general emulsion polymerization method under the environment. After polymerization, the temperature was raised to 80° C., and then 43 g of a 2% aqueous ammonium persulfate solution, 35 g of butyl acrylate, 70 g of diethylacrylamide, 3 g of acrylic acid, 3 g of 3-methacryloxypropyltrimethoxysilane, 89 g of tetraethoxysilane, and phenyltrimethoxy. Using 38 g of silane, polymerization was carried out by a general emulsion polymerization method and filtered through a 100-mesh wire mesh to obtain an aqueous dispersion of polymer nanoparticles (A-4). The obtained polymer nanoparticles (A-4) had a core-shell structure, an average particle diameter of 70 nm, and a solid content of 14% by mass.

[Preparation of matrix raw material component (B′) coating composition liquid]
A matrix raw material component (B′) coating composition liquid used in the examples described later was prepared as follows.

<Matrix raw material component (B'-1) coating composition liquid>
As the hydrolyzable silicon compound (b), tris-(trimethoxysilylpropyl) isocyanurate (trade name “KBM9659”, manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 615.86, described as “KBM9659” in the table (same below) ) 90.44 g, 1,2-bis(triethoxysilyl) ethane (trade name “Dynasylan® BTSE”, manufactured by Evonik, molecular weight 354.59, described as “BTSE” in the table (hereinafter the same)) 26.82 g, inorganic Water-dispersed colloidal silica “Snowtex OXS” (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 10% by mass, average particle size 5 nm, described as “STOXS” in the table (hereinafter the same)) 100 as the oxide (D) 00 g were mixed at room temperature to obtain a coating composition liquid of matrix raw material component (B'-1).

<Matrix raw material component (B'-2) coating composition liquid>
90.44 g of tris-(trimethoxysilylpropyl)isocyanurate and 13.41 g of 1,2-bis(triethoxysilyl)ethane as hydrolyzable silicon compound (b); water-dispersed colloidal silica as inorganic oxide (D) "Snowtex OXS" 130.00 g, water-dispersed cerium oxide sol "Needral B-10" (trade name, manufactured by Taki Chemical Co., Ltd., average particle diameter 8 nm, solid content 10% by mass, described as "B-10" in the table (the same shall apply hereinafter)) were mixed at room temperature to obtain a coating composition liquid of the matrix raw material component (B'-1).

<Matrix raw material component (B'-3) coating composition liquid>
As the hydrolyzable silicon compound (b), methyltrimethoxysilane (trade name “KBM13”, manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 136.22, described as “KBM13” in the table (hereinafter the same)) 10.14 g, 1 , 2-bis(triethoxysilyl)ethane 13.41 g, tris-(trimethoxysilylpropyl) isocyanurate 82.91 g, and water-dispersed colloidal silica "Snowtex OXS" 150.00 g as inorganic oxide (D) under room temperature conditions. By mixing below, a coating composition liquid of matrix raw material component (B'-3) was obtained.

<Matrix raw material component (B'-4) coating composition liquid>
As the hydrolyzable silicon compound (b), dimethyldimethoxysilane (trade name “KBM22”, manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 120.22, described as “KBM22” in the table (same below)) 8.11 g, Tris- 90.44 g of (trimethoxysilylpropyl) isocyanurate and 150.00 g of water-dispersed colloidal silica "Snowtex OXS" as inorganic oxide (D) were mixed at room temperature, and coated with matrix raw material component (B'-4). A composition liquid was obtained.

<Matrix raw material component (B'-5) coating composition liquid>
As the hydrolyzable silicon compound (b), 1,2-bis(triethoxysilyl)ethane 13.41 g, tris-(trimethoxysilylpropyl) isocyanurate 75.37 g, 3-glycidoxypropyltrimethoxysilane (product Name "KBM403", manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 236.34, described as "KBM403" in the table (hereinafter the same)) 21.20 g, water-dispersed colloidal silica "Snowtex OXS" 150 as inorganic oxide (D) 00 g were mixed at room temperature to obtain a coating composition liquid of matrix raw material component (B'-5).

<Matrix raw material component (B'-6) coating composition liquid>
111.56 g of methyltrimethoxysilane as a hydrolyzable silicon compound (b) and 250.00 g of water-dispersible colloidal silica "Snowtex OXS" as an inorganic oxide (D) were mixed at room temperature to form a matrix raw material component (B A coating composition liquid of '-6) was obtained.

<Matrix raw material component (B'-7) coating composition liquid>
90.44 g of tris-(trimethoxysilylpropyl)isocyanurate and 13.41 g of 1,2-bis(triethoxysilyl)ethane as hydrolyzable silicon compound (b); water-dispersed colloidal silica as inorganic oxide (D) "Snowtex C" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass, average particle size 12 nm, described as "STC" in the table (hereinafter the same)) 50.00 g was mixed under room temperature conditions, A coating composition liquid of matrix raw material component (B'-7) was obtained.

<Matrix raw material component (B'-8) coating composition liquid>
As a hydrolyzable silicon compound (b), 105.52 g of tris-(trimethoxysilylpropyl) isocyanurate and 13.41 g of 1,2-bis(triethoxysilyl) ethane were mixed at room temperature to form a matrix raw material component. A coating composition liquid (B'-8) was obtained.

<Matrix raw material component (B'-9) coating composition liquid>
52.76 g of tris-(trimethoxysilylpropyl)isocyanurate, 53.63 g of 1,2-bis(triethoxysilyl)ethane, 20.28 g of methyltrimethoxysilane, and inorganic oxides as hydrolyzable silicon compounds (b) As (D), 150.00 g of water-dispersed colloidal silica "Snowtex OXS" was mixed at room temperature to obtain a coating composition liquid of matrix raw material component (B'-9).

<Matrix raw material component (B'-10) coating composition liquid>
27.13 g of tris-(trimethoxysilylpropyl)isocyanurate and 44.62 g of methyltrimethoxysilane as the hydrolyzable silicon compound (b); 400 g of water-dispersible colloidal silica "Snowtex OXS" as the inorganic oxide (D) 00 g were mixed at room temperature to obtain a coating composition liquid of matrix raw material component (B'-10).

<Matrix raw material component (B'-11) coating composition liquid>
45.22 g of tris-(trimethoxysilylpropyl) isocyanurate and 40.57 g of methyltrimethoxysilane as the hydrolyzable silicon compound (b); 300 g of water-dispersed colloidal silica "Snowtex OXS" as the inorganic oxide (D) 00 g were mixed at room temperature to obtain a coating composition liquid of matrix raw material component (B'-11).

<Matrix raw material component (B'-12) coating composition liquid>
75.37 g of tris-(trimethoxysilylpropyl) isocyanurate and 202.84 g of methyltrimethoxysilane as the hydrolyzable silicon compound (b); 50 g of water-dispersed colloidal silica "Snowtex OXS" as the inorganic oxide (D); 00 g were mixed at room temperature to obtain a coating composition liquid of matrix raw material component (B'-12).

<Matrix raw material component (B'-13) coating composition liquid>
81.00 g of tris-(trimethoxysilylpropyl) isocyanurate and 48.00 g of tetraethoxysilane (molecular weight: 208.33) as the hydrolyzable silicon compound (b); water-dispersed colloidal silica as the inorganic oxide (D); Snowtex OXS” (333.00 g) was mixed at room temperature to obtain a coating composition liquid of matrix raw material component (B′-11).

<Matrix raw material component (B'-14) coating composition liquid>
63.00 g of tetraethoxysilane and 66.00 g of methyltrimethoxysilane as the hydrolyzable silicon compound (b) and 500.00 g of water-dispersed colloidal silica "Snowtex OXS" as the inorganic oxide (D) were mixed under room temperature conditions. to obtain a coating composition liquid of the matrix raw material component (B'-12).

[Example 1]
The polymer nanoparticles (A- 1) A mixture was obtained by mixing the aqueous dispersion and the matrix raw material component (B'-1) prepared above. Using an aqueous solution with an ethanol concentration of 20% by mass as a solvent, the mixture was added so that the solid content concentration was 20% by mass, and then the pH was adjusted to 3.5 using triethylamine as a pH adjuster. 500.00 g of composition are obtained. Next, after applying the coating composition to the substrate P2 with an adhesive layer by a dip coating method, it is dried at 130 ° C. for 1.5 hours, and has a hard coat coating film with a thickness of 3.0 μm. got the wood.
Table 1 shows the results of various evaluations of the base material with the hard coat film and the hard coat film.
The matrix component in the coating film derived from the matrix raw material component (B'-1) in the coating composition is referred to as component (B-1). The matrix component in the coating film derived from 2) or the like is referred to as (B-2) or the like. That is, it can be said that the matrix components (B-1) to (B-14) are hydrolyzed condensates of the matrix raw material components (B'-1) to (B'-14), respectively.

Martens hardness HM _A and elastic recovery rate η _ITA of the polymer nanoparticles (A-1) used in the above examples, Martens hardness HM _B' and elastic recovery rate η _ITB' of the matrix raw material component (B'-1), Also, the Martens hardness HM _B and the elastic recovery rate η _ITB of the matrix component (B-1) were measured according to the above-described measuring methods. The evaluation results are shown in Tables 5-7.

In the following examples, pH was adjusted using triethylamine or dodecylbenzenesulfonic acid as necessary, and the coating composition was applied by a dip coating method. Tables 1 to 4 show the pH of the coating composition and the film thickness of the hard coat film of the obtained substrate with the hard coat film.

[Example 2]
A substrate with a hard coat film was obtained in the same manner as in Example 1, except that the solvent was added so that the solid content concentration was 12% by mass. Evaluation results of each physical property were obtained by the same evaluation method as in Example 1.

[Example 3]
A substrate with a hard coat film was prepared in the same manner as in Example 1 except that (B'-2) was used as the matrix raw material component (B') and a solvent was added so that the solid content concentration was 15% by mass. Obtained. Evaluation results of each physical property were obtained by the same evaluation method as in Example 1.

[Example 4]
Polymer nanoparticles (A) and matrix component (B) have a solid content mass ratio of (A-1):(B-3)=100:800, and a solvent is added so that the solid content concentration is 25% by mass. A substrate with a hard coat film was obtained in the same manner as in Example 1, except that Evaluation results of each physical property were obtained by the same evaluation method as in Example 1.

[Example 5]
A substrate with a hard coat film was obtained in the same manner as in Example 3, except that (B'-4) was used as the matrix raw material component (B'). Evaluation results of each physical property were obtained by the same evaluation method as in Example 1.

[Example 6]
A substrate with a hard coat film was obtained in the same manner as in Example 3, except that (B'-5) was used as the matrix raw material component (B') and the adhesive layer-attached substrate P1 was used as the substrate. Evaluation results of each physical property were obtained by the same evaluation method as in Example 1.

[Example 7]
A substrate with a hard coat film was obtained in the same manner as in Example 3, except that (B'-6) was used as the matrix raw material component (B'). Evaluation results of each physical property were obtained by the same evaluation method as in Example 1.

[Example 8]
A hard coat film was prepared in the same manner as in Example 3, except that the polymer nanoparticles (A) and the matrix component (B) had a solid content mass ratio of (A-2):(B-3) = 100:400. A base material was obtained. Evaluation results of each physical property were obtained by the same evaluation method as in Example 1.

[Example 9]
A substrate with a hard coat film was obtained in the same manner as in Example 6, except that (B'-7) was used as the matrix raw material component (B'). Evaluation results of each physical property were obtained by the same evaluation method as in Example 1.

[Example 10]
A hard coat film was prepared in the same manner as in Example 6 except that the polymer nanoparticles (A) and the matrix component (B) had a solid content mass ratio of (A-1):(B-8) = 100:300. A base material was obtained. Evaluation results of each physical property were obtained by the same evaluation method as in Example 1.

[Example 11]
A hard coat film was prepared in the same manner as in Example 6 except that the polymer nanoparticles (A) and the matrix component (B) had a solid content mass ratio of (A-3):(B-3) = 100:400. A base material was obtained. Evaluation results of each physical property were obtained by the same evaluation method as in Example 1.

[Example 12]
A substrate with a hard coat film was obtained in the same manner as in Example 8, except that (A-4) was used as the polymer nanoparticles (A). Evaluation results of each physical property were obtained by the same evaluation method as in Example 1.

[Example 13]
A substrate with a hard coat film was obtained in the same manner as in Example 1, except that the pH was adjusted to 2.6. Evaluation results of each physical property were obtained by the same evaluation method as in Example 1.

[Example 14]
A substrate with a hard coat film was obtained in the same manner as in Example 3, except that (B'-9) was used as the matrix raw material component (B'). Evaluation results of each physical property were obtained by the same evaluation method as in Example 1.

[Example 15]
A substrate with a hard coat film was obtained in the same manner as in Example 6 except that (B'-10) was used as the matrix raw material component (B'). Evaluation results of each physical property were obtained by the same evaluation method as in Example 1.

[Comparative Example 1]
A hard coat film was prepared in the same manner as in Example 3, except that the polymer nanoparticles (A) and the matrix component (B) had a solid content mass ratio of (A-1):(B-11) = 100:100. A base material was obtained. Evaluation results of each physical property were obtained by the same evaluation method as in Example 1.

[Comparative Example 2]
The polymer nanoparticles (A- 1) A mixture was obtained by mixing the aqueous dispersion and the matrix raw material component (B'-12) prepared above. Using an aqueous solution with an ethanol concentration of 20% by mass as a solvent, the mixture was added so that the solid content concentration was 18% by mass, and the coating composition of Comparative Example 2 was blended. One hour after blending, the coating composition gelled. , could not be painted.

[Comparative Example 3]
Example except that the polymer nanoparticles (A) and the matrix component (B) had a solid content mass ratio of (A-1):(B-13) = 100:300 and the solid content concentration was 8% by mass. A substrate with a hard coat film was obtained in the same manner as in 6. Evaluation results of each physical property were obtained by the same evaluation method as in Example 1.

[Comparative Example 4]
Example except that the polymer nanoparticles (A) and the matrix component (B) had a solid content mass ratio of (A-1):(B-14) = 90:100 and the solid content concentration was 13% by mass. A substrate with a hard coat film was obtained in the same manner as in 1. Evaluation results of each physical property were obtained by the same evaluation method as in Example 1.

Various evaluation results of Examples 1-16 and Comparative Examples 1-4 are shown in Tables 1-4.

The substrate with a hard coat film, the hard coat film, and the coating composition provided by the present invention are useful as hard coats for building materials, automobile members, electronic devices, and electric products.

Claims (16)

Polymer nanoparticles (A);
a matrix raw material component (B′);
A coating composition comprising
The elastic recovery rate η _ITA of the polymer nanoparticles (A) measured from an indentation test in accordance with ISO14577-1 is 0.30 or more and 0.90 or less,
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,
The matrix raw material component (B′) contains a hydrolyzable silicon compound (b),
A coating composition, wherein the hydrolyzable silicon compound (b) has a silicon content of 1.80% by mass or more and 5.00% by mass or less of the entire coating composition. 2. The coating composition according to claim 1, wherein the content of said hydrolyzable silicon compound (b) is 30% by mass or more and 90% by mass or less with respect to 100% by mass of the solid content of said coating composition. The coating composition according to claim 1 or 2, wherein the coating composition has a solid content concentration of 10% or more and 30% or less. The coating composition according to any one of claims 1 to 3, wherein the coating composition has a pH of 2.7 or more and 4.5 or less. Any one of claims 1 to 4, wherein the matrix raw material component (B') has an elastic recovery rate η _ITB' of 0.60 or more and 0.95 or less as measured by an indentation test in accordance with ISO14577-1. 1. The coating composition according to claim 1. The polymer nanoparticles (A) contain a hydrolyzable silicon compound (a),
The coating composition according to any one of claims 1 to 5, wherein the content of the hydrolyzable silicon compound (a) in the polymer nanoparticles (A) is 50% by mass or more. The hydrolyzable silicon compound (a) is a compound containing an atomic group represented by the following formula (a-1), its hydrolysis product and condensate, and the following formula (a-2): 7. The coating composition according to claim 6, comprising one or more selected from compounds, their hydrolysis products and condensates.
-R ¹ _n1 SiX ¹ _3-n1 (a-1)
(In the formula (a-1), R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group; R represents a halogen, a hydroxy group, a mercapto group, an amino group, (Meth) acryloyl group, or may have a substituent containing an epoxy group, X represents a hydrolyzable group, n1 represents an integer of 0 to 2.)
SiX ²⁴ ( _a -2)
(In formula (a-2), X ² represents a hydrolyzable group.) The coating composition according to any one of claims 1 to 7, wherein the polymer nanoparticles (A) have functional groups (e) having secondary amide groups and/or tertiary amide groups. The matrix raw material component (B′) further includes an inorganic oxide (D), and the inorganic oxide (D) is Si, Ce, Nb, Al, Zn, Ti, Zr, Sb, Mg, Sn, Bi. , Co and Cu, the coating composition according to any one of claims 1 to 8. The coating composition according to claim 9, wherein the inorganic oxide (D) has an average particle size of 2 nm or more and 150 nm or less. A hard coat coating comprising the coating composition according to any one of claims 1 to 10. The difference between the haze at 1000 rotations and the haze before the Taber abrasion test is 10 or less when the Taber abrasion test is carried out in accordance with ASTM D1044 under the conditions of an abrasion wheel CS-10F and a load of 500 g. The hard coat coating film according to claim 11. The hard coat film according to claim 11 or 12, which has a Martens hardness of 160 N/mm ² or more and 400 N/mm ² or less. a substrate;
a hard coat coating film disposed on one side and/or both sides of the substrate and comprising the coating composition according to any one of claims 1 to 10;
A substrate with a hard coat film. 15. The substrate with a hard coat coating according to claim 14, further comprising an adhesive layer disposed between said substrate and said hard coat coating. 16. The substrate with a hard coat film according to claim 14 or 15, which is used for automobile members.