JP2023039944A - Coating composition, substrate with adhesive layer, and laminate - Google Patents

Abstract

To provide a coating composition which has excellent coating stability and can form a coating film excellent in transparency, adhesion and weather resistance, a substrate with an adhesive layer, and a laminate.SOLUTION: The coating composition contains: a mixture of polymer particles (A) having a unit (a) derived from a vinyl monomer (a) and an inorganic oxide (B); and/or a composite (C) of the polymer particles (A) and the inorganic oxide (B). The weight average molecular weight of the unit (a) is 10,000-5,000,000. The pH of the coating composition is 7-11.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a coating composition, a substrate with an adhesive layer, and a laminate.

In recent years, there has been a demand for water-based paints in consideration of hygienic conditions at work sites and load on the global environment. An aqueous dispersion obtained by polymerizing a predetermined component can be dried at room temperature or under heat to form a film. It can impart flame retardancy, heat resistance, weather resistance, abrasion resistance, and wear resistance. However, when such paints are used in applications that require transparency, problems such as optical properties such as transparency and cloudiness, discoloration, whitening, and crazes occur due to long-term exposure to the outdoors or ultraviolet rays. can be. In order to suppress deterioration due to ultraviolet rays, it is desirable to include an ultraviolet absorber in the paint, but most ultraviolet absorbers are insoluble in water, making it difficult to apply them to water-based paints.

As a technique for improving the optical properties of a coating film, Patent Document 1 describes a method of incorporating silica into emulsion particles. Moreover, Patent Document 2 describes a method of incorporating an ultraviolet absorbing group into an acrylic copolymer.

JP 2010-100742 A JP-A-2005-97631

The coating composition prepared by the method of Patent Document 1 can form a coating film with excellent transparency, but it is difficult to contain a large amount of ultraviolet absorber in the coating, and it has poor weather resistance. There is room for improvement from this point of view.

The coating composition prepared by the method of Patent Document 2 can form a coating film with excellent weather resistance because it contains an ultraviolet absorber, but it is assumed to be used as a solvent-based coating, and such a technique is difficult to apply as a water-based paint as it is.

The present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide a coating that is excellent in coating stability and can form a coating film that is excellent in transparency, adhesion and weather resistance. An object of the present invention is to provide a composition, a base material with an adhesive layer, and a laminate.

As a result of intensive studies aimed at solving the above problems, the present inventors have found that the problems can be solved by a coating composition having a predetermined structure, and have completed the present invention.

That is, the present invention includes the following aspects.
[1]
A mixture of polymer particles (A) having units (a) derived from a vinyl monomer (a) and an inorganic oxide (B), and/or the polymer particles (A) and an inorganic oxide (B ) A coating composition comprising a complex (C) with
The unit (a) has a weight average molecular weight of 10,000 to 5,000,000,
A coating composition, wherein the coating composition has a pH of 7 to 11.
[2]
The coating composition according to [1], wherein the unit (a) comprises a unit (a-1) derived from an ultraviolet absorbing vinyl monomer (a-1).
[3]
The unit (a) comprises a unit (a-2) derived from a hydroxyl group-containing vinyl monomer (a-2),
The coating composition according to [1] or [2], wherein the content of the unit (a-2) in the unit (a) is 10 to 40% by mass.
[4]
The coating composition according to any one of [1] to [3], further comprising an organic ultraviolet absorber (D).
[5]
The coating composition according to any one of [1] to [4], further comprising a blocked polyisocyanate compound (E).
[6]
The coating composition according to any one of [1] to [5], wherein the unit (a) has a weight average molecular weight of 100,000 to 1,000,000.
[7]
The coating composition according to any one of [1] to [6], wherein the mass ratio of the inorganic oxide (B) to the total solid content of the coating composition is 25% to 60%.
[8]
The coating composition according to any one of [4] to [7], wherein the unit (a-1) and the organic ultraviolet absorber (D) have a mass ratio of 1:0.5 to 1:40. thing.
[9]
The coating composition according to any one of [1] to [8], wherein the inorganic oxide (B) is spherical and/or interconnected silica.
[10]
The coating composition according to any one of [1] to [9], further comprising a chain transfer agent.
[11]
The coating composition according to any one of [1] to [10], wherein the polymer particles (A) comprise emulsion particles having the unit (a).
[12]
a base material;
an adhesive layer disposed on the substrate;
A substrate with an adhesive layer comprising
A substrate with an adhesive layer, wherein the adhesive layer comprises the coating composition according to any one of [1] to [11].
[13]
The substrate with an adhesive layer according to [12];
a hard coat layer disposed on the adhesive layer-attached substrate;
A laminate comprising
The hard coat layer contains a matrix component (H) containing an inorganic oxide (F) and polymer nanoparticles (G),
A laminate in which the Martens hardness HMG of the polymer nanoparticles (G) and the Martens hardness HMH of the matrix component (H) satisfy the relationship HMH/HMG>1.
[14]
The laminate according to [13], wherein the adhesive layer-attached substrate has a haze value H1 higher than the haze value H2 of the laminate.

The coating composition of the present invention is excellent in coating stability and can form a coating excellent in transparency, adhesion and weather resistance.

EMBODIMENT OF THE INVENTION Hereinafter, the form (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. "(Meth)acryl" as used herein means "acryl" and "methacryl" corresponding thereto. In addition, in the present specification, unless otherwise specified, the term "~" means that the numerical values at both ends are included as the upper limit and the lower limit.

The coating composition of the present embodiment is a mixture of polymer particles (A) having units (a) derived from a vinyl monomer (a) and an inorganic oxide (B), and/or the polymer particles A coating composition comprising a composite (C) of (A) and an inorganic oxide (B), wherein the unit (a) has a weight average molecular weight of 10,000 to 5,000,000, and the pH of the coating composition is 7-11. Since the coating composition of the present embodiment is configured as described above, the coating composition is excellent in coating stability, and when a coating film is formed, it is excellent in transparency, adhesion and weather resistance.

[Polymer particles (A)]
The polymer particles (A) in the present embodiment mainly play the role of improving the adhesion to the substrate, and contain the vinyl monomer (a) as a structural unit. That is, the polymer particles (A) have units (a) derived from the vinyl monomer (a). The polymer particles (A) are not particularly limited as long as they are particulate polymers containing the vinyl monomer (a) as a structural unit. It preferably contains particles.

In this embodiment, the unit (a) preferably has a unit (a-1) derived from the UV-absorbing vinyl monomer (a-1). By containing the unit (a-1), even if the UV absorber coexists in the coating composition, the UV absorber can be easily incorporated into the emulsion, improving the coating stability, which will be described later. When the adhesive layer (I) and the laminate (K) are formed, deterioration of adhesion and weather resistance can be prevented.

In the present embodiment, the ultraviolet-absorbing vinyl monomer (a-1) means a vinyl monomer having an ultraviolet-absorbing group, and the ultraviolet-absorbing group is an ultraviolet-absorbing group (wavelength of 400 nm or less). means a functional group having That is, the ultraviolet absorbing vinyl monomer (a-1) includes a (meth)acrylic monomer having an ultraviolet absorbing group in the molecule, and specific examples thereof are not limited to the following: 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-5-acryloxybenzophenone, 2-hydroxy-5-methacryloxybenzophenone, 2-hydroxy-4-( benzophenone compounds such as 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′-methacrylic oxyethyl-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 (manufactured by Nihon Ciba-Geigy Co., Ltd. under the trade name "CGL- 104”) and other benzotriazole compounds.

The content of the unit (a-1) is the unit (a) constituting the polymer particles (A) from the viewpoint of the weather resistance and adhesion of the adhesive layer (I) and the laminate (K) described later. It is preferably contained in an amount of 1 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass of the.
In the present embodiment, when the coating composition contains the composite (C) and the polymer particles (A) separate from it, the polymer particles contained in the composite (C) and the polymer particles separate from it The above content is calculated as the total amount of the polymer particles (A).

The polymer particles (A) in the present embodiment are units (a-2) derived from a hydroxyl group-containing vinyl monomer (a-2) which is a monomer not corresponding to the unit (a-1) and has a hydroxyl group. It is preferred to have Examples of the hydroxyl group-containing vinyl monomer (a-2) include, but are not limited to, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2- Hydroxyalkyl esters of (meth)acrylic acid such as hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide and the like Hydroxyethyl (meth)acrylamide; hydroxyalkyl esters of fumaric acid such as di-2-hydroxyethyl fumarate and mono-2-hydroxyethyl monobutyl fumarate; ) Oxyethylene mono (meth) acrylate; (poly) oxypropylene mono (meth) acrylate having 1 to 100 propylene oxide groups; , trade names of caprolactone addition monomers) and other hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids. These can be used alone or in combination of two or more.

The (poly)oxyethylene mono(meth)acrylate is not particularly limited, but examples include ethylene glycol (meth)acrylate, ethylene glycol methoxy(meth)acrylate, diethylene glycol (meth)acrylate, methoxy(meth)acryl acid diethylene glycol, tetraethylene glycol (meth)acrylate, tetraethylene glycol methoxy(meth)acrylate, and the like.

The content of the unit (a-2) is 10% to 40% by mass, more preferably 20 to 40% by mass, based on the total mass of the vinyl monomer (a) constituting the polymer particles (A). preferably When the content is within the above range, the reaction between the UV-absorbing vinyl monomer and other vinyl monomers tends to proceed favorably, and the hydrophilicity of the polymer particles (A) is ensured. Due to this, there is a tendency to prevent a decrease in transparency when an adhesive layer (I) or a laminate (K), which will be described later, is formed.
In the present embodiment, when the coating composition contains the composite (C) and the polymer particles (A) separate from it, the polymer particles contained in the composite (C) and the polymer particles separate from it The above content is calculated as the total amount of the polymer particles (A).

The polymer particles (A) in the present embodiment may have units derived from other vinyl monomers in addition to the above units (a-1) and (a-2). Examples of other vinyl monomers include, but are not limited to, (meth)acrylic acid esters, (meth)acrylic acid alkyl esters, aromatic vinyl compounds, vinyl cyanide compounds, and carboxyl group-containing vinyl monomers. , epoxy group-containing vinyl monomers, carbonyl group-containing vinyl monomers, and vinyl monomers having secondary and/or tertiary amide groups.

The (meth)acrylic acid ester is not particularly limited, but for example, (meth)acrylic acid alkyl ester having an alkyl portion having 1 to 50 carbon atoms, (poly)oxyethylene having 1 to 100 ethylene oxide groups, di(meth)acrylate and the like.

The (poly)oxyethylene di(meth)acrylate is not particularly limited, but examples include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, diethylene glycol methoxy(meth)acrylate, di(meth) Examples include tetraethylene glycol acrylate.

Examples of the (meth)acrylic acid alkyl ester include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Examples include methylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, and dodecyl (meth)acrylate.

Examples of aromatic vinyl compounds include, but are not limited to, styrene, 4-vinyltoluene, and the like.

Examples of the vinyl cyanide compound include, but are not particularly limited to, acrylonitrile, methacrylonitrile, and the like.

The carboxyl group-containing vinyl monomer is not particularly limited. Half esters of dibasic acids and the like can be mentioned. When a carboxyl group-containing vinyl monomer is used, a carboxyl group can be introduced into the polymer particles (A) in the present embodiment, and the stability as an emulsion is improved by imparting an electrostatic repulsive force between particles. This tends to improve the resistance to external dispersion destruction, such as aggregation during stirring. At this time, from the viewpoint of further improving the electrostatic repulsion, the introduced carboxyl groups are partially or wholly neutralized with ammonia, amines such as triethylamine and dimethylethanolamine, and bases such as NaOH and KOH. can also

Examples of the epoxy group-containing vinyl monomer include, but are not particularly limited to, glycidyl group-containing vinyl monomers. Examples of glycidyl group-containing vinyl monomers include, but are not particularly limited to, glycidyl (meth)acrylate, allyl glycidyl ether, allyl dimethyl glycidyl ether, and the like.

Examples of the carbonyl-containing vinyl monomer include, but are not particularly limited to, diacetone acrylamide.

Vinyl monomers having a secondary and/or tertiary amide group are not particularly limited, but may include, for example, N-alkyl or N-alkylene substituted (meth)acrylamides. Specifically, for example, 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-acryloylmorpholine, N- Methacryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N,N'-methylenebisacrylamide, N,N'-methylenebismethacrylamide, N-vinylacetamide, diacetoneacrylamide, diacetonemethacrylamide, N-methylolacrylamide , N-methylol methacrylamide, and the like.

Further, specific examples of vinyl monomers other than the above are not particularly limited, but include, for example, olefins such as ethylene, propylene, and isobutylene; dienes such as butadiene; vinyl chloride; , Haloolefins such as chlorotrifluoroethylene, vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl benzoate, vinyl pt-butyl benzoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatate , carboxylic acid vinyl esters such as vinyl laurate, carboxylic acid isopropenyl esters such as isopropenyl acetate and isopropenyl propionate, vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether and cyclohexyl vinyl ether, allyl acetate and allyl benzoate allyl esters, allyl ethers such as allyl ethyl ether and allyl phenyl ether, 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2, 2,6,6-pentamethylpiperidine, perfluoromethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluoropropyl (meth) acrylate, vinylpyrrolidone, trimethylolpropane tri (meth) acrylate, (meth) ) Allyl acrylate and the like, and their combined use.

The polymer particles (A) may have a structure derived from 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.

In this embodiment, the polymer particles (A) preferably contain a chain transfer agent. That is, the coating composition of this embodiment preferably contains a chain transfer agent. The chain transfer agent is not particularly limited, and examples thereof include mercaptans such as octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, n-hexadecylmercaptan, n-tetradecylmercaptan, and t-tetradecylmercaptan; dimethylxanthogen; xanthogen disulfides such as disulfide, diethyl xanthogen disulfide and diisopropyl xanthogen disulfide; thiuram disulfides such as tetramethylthiuram disulfide, tetraethyl thiuram disulfide and tetrabutyl thiuram disulfide; halogenated hydrocarbons such as carbon tetrachloride and ethylene bromide; Hydrocarbons such as phenylethane; and acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycolate, terbinolene, α-terpinene, γ-terpinene, dipentene, α-methylstyrene dimer (2,4-diphenyl-4- 50% by weight or more of methyl-1-pentene is preferable), and unsaturated cyclic hydrocarbon compounds such as 9,10-dihydroanthracene, 1,4-dihydronaphthalene, indene, and 1,4-cyclohexadiene; xanthene, Examples include unsaturated heterocyclic compounds such as 2,5-dihydrofuran. These may be used alone or in combination of two or more.
The content of the chain transfer agent in the coating composition of the present embodiment is not particularly limited, but from the viewpoint of coating stability and adhesion of the adhesive layer (I), 0 0.1 mass % to 2 mass % or less, more preferably 0.25 mass % to 1 mass %.
In the present embodiment, when the coating composition contains the composite (C) and the polymer particles (A) separate from it, the polymer particles contained in the composite (C) and the polymer particles separate from it The above content is calculated as the total amount of the polymer particles (A).

The method for preparing the polymer particles (A) used in the present embodiment is not particularly limited, and various preparation methods such as emulsion polymerization and solution polymerization can be selected. It is preferably prepared by emulsion polymerization of the polymer. That is, the polymer particles (A) are polymer particles (units (a) is preferably an emulsion particle having In other words, the polymer particles (A) are polymer particles derived from the emulsifier and the vinyl monomer (a) (emulsion particles having units (a) derived from the vinyl monomer (a)). is preferred. When the polymer particles (A) thus obtained are contained in the adhesive layer, there is a tendency that the adhesion to the substrate is maintained more excellently. Since the polymer particles (A) obtained as described above are typically accompanied by water, the coating composition used in the present embodiment is preferably a water-based coating composition. Here, "aqueous" means that water is the most abundant component among the components contained in the solvent (M) described later.

A polymerization initiator can be used in the preparation of the polymer particles (A). Examples of the polymerization initiator include, but are not limited to, hydroperoxides such as hydrogen peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, and paramenthane hydroperoxide; oxides, and 2,2′-azobis{2-methyl-N-[2-(1-hydroxybutyl)propionamide]}, 2,2′-azobis[(2-methylpropionamidine) dihydrochloride], 2,2'-azobis[N-(2-carboxyethyl)-2-methyl-propiondiamine]tetrahydrate, 2,2'-azobis(2,4-dimethylvaleronitrile), azobisisobutyronitrile, etc. and inorganic polymerization initiators such as persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate. A so-called redox polymerization initiator, which uses a reducing agent such as sodium bisulfite, ascorbic acid and salts thereof in combination with a polymerization initiator, can also be used.

[Weight average molecular weight of unit (a)]
In this embodiment, the unit (a) has a weight average molecular weight of 10,000 or more and 5,000,000 or less. When the weight-average molecular weight is within the above range, excellent coating stability is achieved even when an ultraviolet absorber is present in the coating composition, and an adhesive layer (I) and a laminate (K), which will be described later, are formed. When coated, it has excellent transparency, adhesion and weather resistance. Further, from the viewpoint of further improving the coating stability and the adhesiveness of the adhesive layer (I) described later, the weight average molecular weight of the unit (a) is more preferably 1,000,000 or less, and the polymer particles (A ) From the viewpoint of stability during synthesis, the weight-average molecular weight of the unit (a) is more preferably 100,000 or more.
In the present embodiment, when the coating composition contains the composite (C) and the polymer particles (A) separate therefrom, the content W1 of the unit (a) in the polymer particles (A) And from the weight average molecular weight Mw1 and the content W2 and weight average molecular weight Mw2 of the unit (a) in the composite (C), the weight average molecular weight Mw of the unit (a) in the coating composition is calculated by the following formula. and
Mw={Mw1×(W1/(W1+W2))+Mw2×(W2/(W1+W2))}/2
The weight-average molecular weight of unit (a) can be measured based on the method described in Examples below. Moreover, the weight average molecular weight of the unit (a) can be adjusted to the range described above by using, for example, the chain transfer agent described above.

[Average particle size of polymer particles (A)]
The average particle size of the polymer particles (A) in the present embodiment is obtained from the size of particles observed by a dynamic light scattering method. Although the average particle size of the polymer particles (A) is not particularly limited, it is preferably 200 nm or less. By adjusting the average particle size of the polymer particles (A) within the above range, there is a tendency that the contact area with the substrate is increased, thereby forming an adhesive layer with even better adhesion. Further, from the viewpoint of improving the transparency of the adhesive layer (I) described later, the average particle size is more preferably 100 nm or less, and from the viewpoint of good storage stability, it is preferably 10 nm or more, and 50 nm or more. is more preferable. The average particle size of the polymer particles (A) can be measured based on the method described in Examples below. The average particle size of the polymer particles (A) can be adjusted within the range described above, for example, by controlling the polymerization conditions.

The content of the polymer particles (A) in the present embodiment is preferably 1% to 40% with respect to 100% by mass of the coating composition, from the viewpoint of obtaining a coating film having excellent transparency, adhesion and weather resistance. , more preferably 2% to 20%, even more preferably 4% to 10%.
Further, when the adhesive layer (I) is formed, the content of the polymer particles (A) with respect to 100% by mass of the adhesive layer is preferably 20% to 60%, more preferably from the same viewpoint as above. 25% to 50%.
In the present embodiment, when the coating composition contains the composite (C) and the polymer particles (A) separate from it, the polymer particles contained in the composite (C) and the polymer particles separate from it The above content is calculated as the total amount of the polymer particles (A).

[Inorganic oxide (B)]
The coating composition of this embodiment contains an inorganic oxide (B) as an essential component. When the coating composition contains the inorganic oxide (B), the interaction between the adhesive layer (I) and the hard coat layer (J) described later improves the transparency and adhesion when the laminate (K) described later is formed. Excellent durability and heat resistance.

Specific examples of the inorganic oxide (B) in the present embodiment include, but are not limited to, silicon, aluminum, titanium, zirconium, zinc, cerium, tin, indium, gallium, germanium, antimony, molybdenum, niobium, magnesium, Oxides of bismuth, cobalt, copper and the like are included. These may be used singly or as a mixture.

From the viewpoint of adhesion to the hard coat layer, the inorganic oxide (B) is preferably silica particles typified by dry silica and colloidal silica. Colloidal silica is also preferred because it can be used in the form of an aqueous dispersion.

[Shape of inorganic oxide (B)]
The shape of the inorganic oxide (B) in the present embodiment is not limited to the following; Mixtures of two or more are included. In the present embodiment, from the viewpoint of the transparency and wear resistance of the laminate (K), the inorganic oxide (B) has a connecting structure such as a spherical shape and/or a beaded or chain shape. preferable. Furthermore, from the viewpoint of adhesion between the adhesive layer (I) and the hard coat layer (J), which will be described later, the inorganic oxide (B) more preferably has a beaded or chained structure. Here, the beaded structure means a structure in which spherical primary particles are connected in a beaded shape, and the chain structure means a structure in which spherical primary particles are connected in a chain shape. In the present embodiment, the inorganic oxide (B) is particularly preferably spherical and/or silica having a linked structure, and most preferably silica having a linked structure.

The average particle size of the inorganic oxide (B) in the present embodiment is preferably 2 nm or more from the viewpoint of good storage stability of the aqueous raw material composition. From the viewpoint of good transparency of the laminate as a whole, the thickness is preferably 150 nm or less, more preferably 100 nm or less. Therefore, the average primary particle size is preferably 2 nm or more and 100 nm or less, more preferably 2 nm or more and 50 nm or less, and still more preferably 4 nm or more and 50 nm or less. The average particle size is not limited to the following, but can be measured, for example, based on the method (dynamic light scattering method) described in Examples below.

[Colloidal silica suitably used as inorganic oxide (B)]
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.

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.

[Composite (C) of polymer particles (A) and inorganic oxide (B)]
In the coating composition of the present embodiment, the polymer particles (A) and the inorganic oxide (B) may be contained as a mixture obtained by mixing both components, or the polymer particles (A) may be It may be contained as a composite (C) obtained by combining with the inorganic oxide (B). The coating composition of the present embodiment preferably contains the composite (C) from the viewpoint of coating stability and the transparency of the adhesive layer (I) and laminate (K) described below. The composite (C) of the polymer particles (A) and the inorganic oxide (B) is obtained by, for example, adding the vinyl monomer constituting the polymer particles (A) in the presence of the inorganic oxide (B). Obtained by polymerization. From the viewpoint of interaction with the inorganic oxide (B), the vinyl monomer is the above-mentioned hydroxyl group-containing vinyl monomer and/or a vinyl monomer having a secondary and/or tertiary amide group. It is preferable to contain the inorganic oxide (B), whereby the complex (C) tends to preferably be formed by hydrogen bonding with the hydroxyl group of the inorganic oxide (B).

In the present embodiment, the mixture of the polymer particles (A) and the inorganic oxide (B) and / or the average particle size of the composite (C) is the adhesive layer (I) described later and the laminate ( From the viewpoint of transparency of K), the thickness is preferably 2 nm or more and 200 nm or less, more preferably 50 nm or more and 150 nm or less. The average particle size is obtained from the size of particles observed by a dynamic light scattering method.

[Mass ratio of inorganic oxide (B) to total solid content of coating composition]
In the present embodiment, from the viewpoint of the transparency, adhesion, and heat resistance of the adhesive layer (I) and laminate (K) described later, the mass ratio of the inorganic oxide (B) to the total solid content of the coating composition is , preferably 25% to 60%, more preferably 35% to 50%. Here, the total solid content of the coating composition represents the total weight of components other than volatile components contained in the coating composition. A solvent (M), which will be described later, mainly corresponds to the volatile component in the paint. In the present embodiment, when the coating composition contains the composite (C) and the inorganic oxide (B) separate from it, the inorganic oxide contained in the composite (C) and the inorganic oxide separate from it The above mass ratio is calculated as the total amount of the inorganic oxide (B) in the body.

[Organic UV absorber (D)]
From the viewpoint of improving weather resistance, the coating composition of the present embodiment preferably contains an organic ultraviolet absorber (D). Specific examples of the organic ultraviolet absorber (D) include, but are not limited to, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane , 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone (trade name “UVINUL3049” manufactured by BASF), 2,2′,4,4′-tetrahydroxy Benzophenone (trade name "UVINUL3050" manufactured by BASF), 4-dodecyloxy-2-hydroxybenzophenone, 5-benzoyl-2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy -benzophenone UV absorbers such as 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-octylphenyl)benzo triazole, 2-(2-hydroxy-3,5-di-tert-octylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α'-dimethylbenzyl)phenyl]benzo triazole), a condensate of methyl-3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate and polyethylene glycol (molecular weight 300) (manufactured by BASF) name “TINUVIN1130”), isooctyl-3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionate (trade name “TINUVIN384” manufactured by BASF), 2- (3-dodecyl-5-methyl-2-hydroxyphenyl) benzotriazole (trade name "TINUVIN571" manufactured by BASF), 2-(2'-hydroxy- 3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-amylphenyl)benzotriazole, 2-(2′- hydroxy-4′-octoxyphenyl)benzotriazole, 2-[2′-hydroxy-3′-(3″,4″,5″,6″-tetrahydrophthalimidomethyl)-5′-methylphenyl]benzotriazole, 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 (trade name, manufactured by BASF) and other benzotriazole-based ultraviolet absorbers; 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]- 4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4 ,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bisbutyloxyphenyl)- 1,3,5-triazine (trade name “TINUVIN460” manufactured by BASF), 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl) -1,3,5-triazine (trade name “TINUVIN479” manufactured by BASF), 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6- Bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis (2,4-Dimethylphenyl)-1,3,5-triazine (product manufactured by BASF name "TINUVIN400"), TINUVIN405, TINUVIN477, TINUVIN1600 (trade name, manufactured by BASF), and other triazine-based UV absorbers; Ester UV absorbers; Anilide UV absorbers such as HOSTAVIN3206 LIQ, HOSTAVINVSUP, HOSTAVIN3212 LIQ (trade name, manufactured by Clariant); salicylate-based UV absorbers such as p-isopropanol phenyl salicylate;
As the organic ultraviolet absorber (D), one type may be used alone, or two or more types may be used in combination. From the viewpoint of weather resistance, the organic UV absorber (D) preferably contains a triazine UV absorber, such as 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6 -bis(4-phenylphenyl)-1,3,5-triazine and/or 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 -bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6- More preferred is a mixture containing bis(2,4-dimethylphenyl)-1,3,5-triazine.

[Mass ratio of unit (a-1) and organic UV absorber (D)]
In the present embodiment, the mass ratio of the UV-absorbing vinyl monomer (a-1) and the organic UV absorber (D) is preferably in the range of 1:0.5 to 1:40. :1 to 1:10, more preferably 1:2 to 1:6. When the mass ratio of the unit (a-1) and the organic ultraviolet absorber (D) is within the above range, the dispersibility of the ultraviolet absorber in the paint is improved, and the adhesive layer (I) described later, And/or it tends to be excellent in transparency, adhesion, and weather resistance when the laminate (K) is formed. In the present embodiment, when the coating composition contains the composite (C) and the polymer particles (A) separate from it, the emulsion particles contained in the composite (C) and the emulsion particles separate from it The above mass ratio is calculated as the total amount of the polymer particles (A).

[Isocyanate compound]
The coating composition in the present embodiment preferably contains an isocyanate compound and/or a urethane compound as a curing agent from the viewpoint of improving the adhesion and heat resistance of the adhesive layer (I) and laminate (K) described later. . An isocyanate compound means a compound having at least one isocyanate group in one molecule. The isocyanate compound may be a compound having two or more isocyanate groups in one molecule. Examples of the isocyanate compound include, but are not limited to, 1,4-tetramethylene diisocyanate, ethyl (2,6-diisocyanato) hexanoate, 1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, Aliphatic diisocyanates such as 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate; 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane , 2-isocyanatoethyl(2,6-diisocyanato)hexanoate; 1,3- or 1,4-bis(isocyanatomethylcyclohexane), 1,3- or 1,4-diisocyanate; Alicyclics such as isocyanatocyclohexane, 3,5,5-trimethyl(3-isocyanatomethyl)cyclohexylisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 2,5- or 2,6-diisocyanatomethylnorbornane Diisocyanate; alicyclic triisocyanates such as 2,5- or 2,6-diisocyanatomethyl-2-isocyanatopropyl norbornane; m-xylylenediisocyanate, α,α,α'α'-tetramethyl - aralkylene diisocyanates such as m-xylylene diisocyanate; m- or p-phenylene diisocyanate, tolylene-2,4- or 2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, Aromatics such as diphenyl-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyl-diphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate aromatic triisocyanates such as triphenylmethane triisocyanate and tris(isocyanatophenyl)thiophosphate; diisocyanates having a uretdione structure obtained by cyclodimerizing the isocyanate groups of the above diisocyanates or triisocyanates; Polyisocyanate; polyisocyanate having an isocyanurate structure obtained by cyclotrimerizing the isocyanate groups of the above diisocyanate or triisocyanate; above diisocyanate or triisocyanate a polyisocyanate having a burette structure obtained by reacting a diisocyanate or triisocyanate with water; a polyisocyanate having an oxadiazinetrione structure obtained by reacting the above diisocyanate or triisocyanate with carbon dioxide; Polyisocyanate having an allophanate structure obtained by reacting with; Polyisocyanate obtained by reacting the above diisocyanate or triisocyanate with a compound containing active hydrogen such as polyhydroxy compound, polycarboxy compound, polyamine compound, etc. . Examples of isocyanate compounds having an alkoxysilane moiety and/or a siloxane moiety in the molecule include 3-isocyanatopropyltriethoxysilane and/or hydrolysis condensates of 3-isocyanatopropyltriethoxysilane and the like. These can be used singly or in combination of two or more.

[Blocked polyisocyanate compound (E)]
From the viewpoint of dispersibility in paint, the isocyanate compound is more preferably a blocked polyisocyanate compound (E) obtained by reacting an isocyanate group with a blocking agent.
The blocking agent is not particularly limited, but one that functions as a curing agent can be appropriately selected. , active methylene compounds, imidazole compounds, and pyrazole compounds. Examples of oxime compounds include, but are not limited to, formaldoxime, acetoaldoxime, acetoxime, methylethylketoxime, and cyclohexanone oxime. Examples of alcohol compounds include, but are not limited to, methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, and 2- Butoxyethanol can be mentioned. Examples of acid amide compounds include, but are not limited to, acetanilide, acetic amide, ε-caprolactam, δ-valerolactam, and γ-butyrolactam. Examples of acid imide compounds include, but are not particularly limited to, succinimide and maleic acid imide. Examples of phenolic compounds include, but are not limited to, phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, and hydroxybenzoate. Examples of amine compounds include, but are not limited to, diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, and isopropylethylamine. Examples of active methylene compounds include, but are not limited to, dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone. Examples of imidazole compounds include, but are not limited to, imidazole and 2-methylimidazole. Examples of pyrazole compounds include, but are not limited to, pyrazole, 3-methylpyrazole, and 3,5-dimethylpyrazole.

From the viewpoint of water dispersibility, the blocked polyisocyanate compound (E) includes a polyisocyanate compound having two or more isocyanate groups in one molecule, and a hydroxyl group having a nonionic and/or ionic hydrophilic group. A water-dispersible isocyanate compound obtained by reacting a hydrophilic compound with an equivalent ratio of isocyanate group/hydroxyl group in the range of 1.05 to 1000 is preferably reacted with the blocking agent. The water-dispersible block polyisocyanate compound (E) is not particularly limited, and commercially available products can be employed. It is preferably used as one having the features described above.

[NCO/OH ratio]
The content of the isocyanate compound in the coating composition of the present embodiment with respect to the polymer particles (A) polymerized from the monomer containing the hydroxyl group-containing vinyl monomer (a-2) is in the polymer particles (A) The ratio of the number of moles of hydroxyl groups contained in the isocyanate compound to the number of moles of isocyanate groups contained in the isocyanate compound (NCO/OH ratio) is preferably 0.1 to 1.0, preferably 0.3 to 0.8. is more preferable. When the NCO/OH ratio is within the above range, excellent adhesion and heat resistance are exhibited without impairing transparency when the adhesive layer (I) and laminate (K) described later are formed. can.
In the present embodiment, when the coating composition contains the composite (C) and the polymer particles (A) separate from it, the polymer particles contained in the composite (C) and the polymer particles separate from it The above content is calculated as the total amount of the polymer particles (A).

[Solvent (M)]
The coating composition of the present embodiment preferably contains a solvent (M). From the viewpoint of sanitary conditions at the work site and reduction of the load on the global environment, it is preferable that 50% by mass or more of the solvent (M) is water, more preferably 60% by mass or more, and still more preferably 75% by mass. % or more. Usable solvents other than water are not particularly limited, and common solvents can be used. Examples of solvents include, but are not limited to, 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 Tetraethylene Alcohols such as 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; ketones such as isobutyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; amides such as dimethylacetamide and dimethylformamide; halogen compounds such as chloroform, methylene chloride and carbon tetrachloride; These may be used singly or in combination of two or more. The content of the solvent (M) is preferably 75% by mass or more with respect to 100% by mass of the coating composition from the viewpoint of dispersion stability of the coating composition. 95 mass % or less is preferable.

[Ingredients that may be included in the coating composition]
The coating composition of the present embodiment contains emulsifiers, plasticizers, pigments, dyes, fillers, antioxidants, conductive materials, light stabilizers, release modifiers, softeners, surfactants, and flame retardants, depending on the application. , antioxidants, and catalysts. In particular, from the viewpoint of improving weather resistance, it is preferable to contain a light stabilizer. Specifically, but not limited to, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-tetramethylpiperidyl)sebacate, bis(1, 2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butylmalonate, 1-[2-[3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propynyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynyloxy]-2,2,6, 6-tetramethylpiperidine, a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl-sebacate (BASF manufactured by BASF (trade name “TINUVIN292”), bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, TINUVIN123, TINUVIN144, TINUVIN152, TINUVIN249, TINUVIN292, TINUVIN5100 (trade name, manufactured by BASF ); 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate, 2,2,6,6 -tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-iminopiperidyl methacrylate, 2,2,6,6 ,-tetramethyl-4-iminopiperidyl methacrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-cyano-1,2,2,6,6-pentamethyl-4-piperidyl Radical polymerizable hindered amine light stabilizers such as methacrylates; manufactured by Nippon Shokubai Co., Ltd.).

[Concentration and viscosity of paint composition]
From the viewpoint of paintability, the coating composition of the present embodiment preferably has a solid content concentration of 0.01 to 60% by mass, more preferably 1 to 40% by mass. From the viewpoint of paintability, the viscosity of the coating composition of the present embodiment at 20° C. is preferably 0.1 to 100,000 mPa·s, more preferably 1 to 10,000 mPa·s.

[pH of paint composition]
In this embodiment, the pH of the coating composition is 7-11. When the pH is within the above range, the dispersibility of the polymer particles (A) is improved, resulting in improved paint stability. Further, from the viewpoint of the transparency of the adhesive layer (I), which will be described later, the pH is more preferably in the range of 8 to 11. The pH can be measured based on the method described in Examples below. Also, the pH can be adjusted to the range described above by, for example, adding ammonia.

[Base material with adhesive layer (I)]
The substrate with an adhesive layer (I) of the present embodiment is a substrate with an adhesive layer comprising a substrate and an adhesive layer (I) disposed on the substrate, wherein the adhesive layer (I) contains the coating composition of the present embodiments. The phrase "adhesive layer (I) comprises the coating composition of the present embodiment" is meant to include the fact that the adhesive layer (I) is obtained from the coating composition of the present embodiment. That is, the adhesive layer (I) can be obtained, for example, by coating the coating composition of the present embodiment on a substrate and forming a coating film by heat treatment, ultraviolet irradiation, infrared irradiation, or the like. 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. 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.

The thickness of the adhesive layer (I) is preferably 0.1 μm or more, more preferably 0.3 μm or more, from the viewpoint of adhesion to be described later, and preferably 100.0 μm or less from the viewpoint of transparency. , and more preferably 50.0 μm or less.

Examples of the base material include, but are not particularly limited to, resins, metals, and glass. 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. Moreover, the type of base material is not limited, and examples thereof include sheets, films, fibers, and the like. Among them, resins are preferable from the viewpoint of imparting abrasion resistance and moldability. Examples of the resin used as the base material 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 phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, silicon resin, silicone rubber, SB rubber, natural rubber, thermosetting resin, and elastic elastomers.

[Laminate (K)]
The laminate (K) in the present embodiment is a laminate comprising the adhesive layer-attached base material of the present embodiment and a hard coat layer disposed on the adhesive layer-attached base material, wherein the hard coat layer contains a matrix component (H) containing an inorganic oxide (F) and polymer nanoparticles (G), the Martens hardness HMG of the polymer nanoparticles (G), and the Martens hardness of the matrix component (H) The hardness HMH satisfies the relationship of HMH/HMG>1. Since the laminate (K) in the present embodiment comprises the hard coat layer (J) on the base material with the adhesive layer (I), it has excellent wear resistance, adhesion, durability and optical properties. . Since the laminate (K) of the present embodiment exhibits high levels of wear resistance, adhesion, durability and optical properties, it is not limited to the following, for example, building materials, automobile members, electronic devices and electrical products It is useful as a hard coat for the like, and is particularly preferably used for automobile members.

[Hard coat layer (J)]
The hard coat layer (J) in the present embodiment is arranged on the substrate with the adhesive layer (I) and contains a matrix component (H) containing an inorganic oxide (F) and polymer nanoparticles (G). and contributes to the durability of the laminate (K).

In the present embodiment, from the viewpoint of the wear resistance of the laminate (K), the Martens hardness HMG of the polymer nanoparticles (G) and the Martens hardness HMH of the matrix component (H) are such that HMH/HMG>1. satisfy the relationship Even when it is difficult to confirm the magnitude relationship between the Martens hardness HMG and the Martens hardness HMH, the magnitude of the Martens hardness described above can be determined by comparing the adhesive forces of the polymer nanoparticles (G) and the matrix component (H) described later. Relationships can be inferred. Since the lower the adhesive strength, the higher the elasticity, the lower the adhesive strength, the less the coating film is deformed and the higher the hardness. Specifically, the preferred hard coat layer (J) described above can also be specified as follows. That is, the hard coat layer (J) in the present embodiment contains polymer nanoparticles (G) and a matrix component (H), and is measured in the adhesion force mode of a scanning probe microscope (SPM). The adhesive force F _G of the polymer nanoparticles G and the adhesive force F _H of the matrix component (H) satisfy the relationship of F _G /F _H >1.

In the hard coat layer (J) of this embodiment, the polymer nanoparticles (G) are preferably dispersed in the matrix component (H). "Dispersion" in the present embodiment means that the polymer nanoparticles (G) are dispersed phase, the matrix component (H) is a continuous phase, and the polymer nanoparticles (G) are uniformly or structurally dispersed in the matrix component (H). It is to distribute while forming The dispersion can be confirmed by cross-sectional SEM observation of the hard coat layer. In the hard coat layer of the present embodiment, the polymer nanoparticles (G) are dispersed in the matrix component (H), so the laminate (K) tends to have high wear resistance.

[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).

[Adhesion]
The adhesive force in the present embodiment can be measured with a scanning probe microscope (SPM). Since the lower the adhesive force, the higher the elasticity, the lower the adhesive force, the more difficult the coating film to deform and the higher the hardness. The adhesive force can be measured using, but not limited to, SPM-970 and SPM-9700HT manufactured by Shimadzu Corporation, Dimension ICON manufactured by Bruker AXS, AFM5000II manufactured by Hitachi High-Tech Science, and the like.

[Other hardness]
The magnitude relation of Martens hardness and cohesive strength in the present embodiment described above can also be estimated by confirming the magnitude relation of 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 viscoelasticity typified by a rigid pendulum physical property tester. In addition, indices expressed by 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 component (H) is higher than that of the polymer nanoparticles (G), the Martens hardness and cohesive strength of the matrix component (H) are also higher than that of the polymer. It is presumed to be harder than the nanoparticles (G).

[Martens hardness HMG of polymer nanoparticles (G) and Martens hardness HMH of matrix component (H)]
The Martens hardness HMG of the polymer nanoparticles (G) and the Martens hardness HMH of the matrix component (H) in the present embodiment preferably satisfy the relationship of the following formula (1).
HMH/HMG>1 Formula (1)
Formula (1) expresses that the flexible polymer nanoparticles (G) are present in the hard matrix component (H). Layer (J) tends to impart wear resistance that conventional coatings do not exhibit. 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 HMG is preferably 50 N/mm ² or more, more preferably 100 N/mm ² or more, from the viewpoint of impact absorption, and preferably 2000 N/mm ² or less, and 800 N/mm ² or less from the viewpoint of film formation. More preferably, 350 N/mm ² or less is even more preferable. The range of HMH is preferably 100 N/mm ² or more, more preferably 150 N/mm ² or more, from the viewpoint of impact absorption, and preferably 4000 N/mm ² or less, more preferably 2000 N/mm ² or less from the viewpoint of film formation. .
The hard coat layer (J) can be obtained as a cured product obtained by curing the coating composition (L) described later by hydrolytic condensation or the like. The polymer nanoparticles (G) generally do not change their composition during the curing process. Therefore, the value of the Martens hardness HMG of the polymer nanoparticles (G) in the coating composition (L) measured by the method described in Examples below is The value of the Martens hardness HMG in the hard coat layer (J) can be determined as one that closely matches the Martens hardness HMG of (G). Further, the matrix component (H) corresponds to a cured product obtained by curing a matrix raw material component (H'), which will be described later, by hydrolytic condensation or the like. Therefore, the value of the Martens hardness HMH of the matrix raw material component (H′) measured by the method described in the examples described later agrees well with the Martens hardness HMH of the corresponding matrix component (H). The value of HMH can be determined.
The values of HMG and HMH can be adjusted so as to have the above-described size relationship depending on the structures and composition ratios of the constituent components of the polymer nanoparticles (G) and the matrix raw material component (H′) described later, respectively. It is not particularly limited to this method.

[Adhesive force F _G of polymer nanoparticles (G) and adhesive force F _H of matrix component (H)]
The adhesive force _FG of the polymer nanoparticles (G) and the adhesive force _FH of the matrix component (H) in the present embodiment preferably satisfy the relationship of the following formula (2).
F _G /F _H >1 Formula (2)
Similar to formula (1) above, formula (2) also expresses that the flexible polymer nanoparticles (G) are present in the hard matrix component (H), and thus the hardness is three-dimensionally By having a slope, the hard coat layer (J) tends to be able to impart wear resistance that conventional coating films do not exhibit. 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.
As described above, the adhesive force F _G of the polymer nanoparticles (G) and the adhesive force F _H of the matrix component (H) are correlated with the hardness of each component. Depending on the structure and composition ratio of the constituent components of component (H'), adjustment can be made so as to achieve the above-described size relationship, but the method is not particularly limited to this method.

[Martens hardness HMJ of hard coat layer (J)]
The Martens hardness HMJ of the hard coat layer (J) is 100 N/mm ² or more from the viewpoint of the wear resistance of the laminate (K). Advantageous. The Martens hardness HMJ of the hard coat layer (J) is preferably 100 N/mm ² or more, more preferably 150 N/mm ² or more, and still more preferably 200 N/mm ² or more, from the viewpoint of bending resistance. , preferably 4000 N/mm ² or less, more preferably 2000 N/mm ² or less, still more preferably 1500 N/mm ² or less. Methods for adjusting the Martens hardness HMJ of the hard coat layer (J) within the above range include, but are not limited to, polymer nano A coating composition obtained by dispersing and dissolving a composition obtained by mixing particles (G) and a matrix raw material component (H′) described later in a solvent is coated on a substrate, followed by heat treatment, ultraviolet irradiation, infrared irradiation, or the like. film formation. In particular, when the content of the matrix component (H) with respect to the total amount of the polymer nanoparticles (G) and the matrix component (H) is increased, the Martens hardness HMJ of the hard coat layer (J) tends to increase, and the matrix component ( When the content of H) is reduced, the Martens hardness HMJ of the hard coat layer (J) 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, and the amount of change in haze at 500 rotations relative to the haze before the test, that is, the difference between the haze at 500 rotations and the haze before the Taber abrasion test is 10 or less. For example, if it 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 amount of haze change per 1000 rotations is preferably 10 or less, more preferably 6 or less, and even more preferably 2 or less. Methods for adjusting the amount of change in haze within the above range include, but are not limited to, polymer nanoparticles (G) that satisfy a predetermined relationship represented by formula (3) described later, and polymer nanoparticles (G) described later. A coating composition obtained by dispersing and dissolving a composition in which a matrix raw material component (H') is mixed in a solvent is coated on a base material, and a coating film is formed by heat treatment, ultraviolet irradiation, infrared irradiation, or the like. .

[Volume fraction of polymer nanoparticles (G) in hard coat layer (J)]
In the present embodiment, the volume fraction of the polymer nanoparticles (G) in the hard coat layer (J) is preferably 2% or more, more preferably 3% or more, from the viewpoint of film-forming properties. It is preferably 5% or more, and from the viewpoint of transparency, preferably 80% or less, more preferably 70% or less, and even more preferably 45% or less. The volume fraction of the polymer nanoparticles (G) in the hard coat layer (J) is, for example, the ratio of the polymer nanoparticles (G) in the entire coating film in the cross-sectional SEM image of the hard coat layer (J). Alternatively, it can be calculated from the component ratio of the polymer nanoparticles (G) in the components constituting the hard coat layer (J).

[Constituents of polymer nanoparticles (G)]
[Hydrolyzable silicon compound (g)]
The polymer nanoparticles (G) in this embodiment preferably contain a hydrolyzable silicon compound (g). The hydrolyzable silicon compound (g) 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 (b) is a compound containing an atomic group represented by the following formula (g-1), a hydrolysis product thereof, or a condensate thereof. Preferably.
-R ¹ _n1 SiX ¹ _3-n1 (g-1)

In formula (g-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. , (meth)acryloyl group, or epoxy group-containing substituent, 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 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 formula (g-1) include, but are not limited to, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltri Methoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltri ethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane, methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethoxydiphenyl Silane, diethoxydiphenylsilane, bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, bis(triphenoxysilyl)ethane, 1,1-bis(triethoxysilyl)ethane, 1,2-bis(tri ethoxysilyl)ethane, 1,1-bis(triethoxysilyl)propane, 1,2-bis(triethoxysilyl)propane, 1,3-bis(triethoxysilyl)propane, 1,4-bis(triethoxysilyl) ) butane, 1,5-bis(triethoxysilyl)pentane, 1,1-bis(trimethoxysilyl)ethane, 1,2-bis(trimethoxysilyl)ethane, 1,1-bis(trimethoxysilyl)propane , 1,2-bis(trimethoxysilyl)propane, 1,3-bis(trimethoxysilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1 ,3-bis(triphenoxysilyl)propane, 1,4-bis(trimethoxysilyl)benzene, 1,4-bis(triethoxysilyl)benzene, 1,6-bis(trimethoxysilyl)hexane, 1,6 -bis(triethoxysilyl)hexane, 1,7-bis(trimethoxysilyl)heptane, 1,7-bis(triethoxysilyl)heptane, 1,8-bis(trimethoxysilyl)octane, 1,8-bis (triethoxysilyl) octane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, trifluoropropyl trimethoxysilane, trifluoropropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane , 3-mercaptopropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane , 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3 -methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane Silane, p-styryltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(amino ethyl)-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, methyl triacetoxysilane, 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-tetramethyl- 4-[3-(triethoxysilyl)propoxy]piperidine, 2,2,6,6-tetramethyl-4-[3-(trimethoxysilyl)propoxy]piperidine, 2-hydroxy-4-[3-(tri ethoxysilyl)propoxy]benzophenone, 2-hydroxy-4-[3-(trimethoxysilyl)propoxy]benzophenone and the like.

The hydrolyzable silicon compound (g) can impart high hardness to the hard coat layer, and from the viewpoint of further improving wear resistance, a compound represented by the following formula (g-2), a hydrolysis product thereof, and It preferably contains a condensate.
SiX ² ₄ (g−2)
In formula (a-2), ^X2 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 (g-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 (g) is a compound containing an atomic group represented by the above formula (g-1), its hydrolysis product and condensate, and the above formula ( It preferably contains one or more selected from the compound represented by g-2), its hydrolysis products and condensates.

[Content of hydrolyzable silicon compound (g) in polymer nanoparticles (G)]
The content of the hydrolyzable silicon compound (g) in the present embodiment indicates the solid content weight ratio of the hydrolyzable silicon compound (g) contained in the polymer nanoparticles (G). 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 (g) in the polymer nanoparticles (G) is not limited to the following, but is measured, for example, by IR analysis, NMR analysis, elemental analysis, etc. of the polymer nanoparticles (G). be able to.

[Matrix component (H)]
By using the matrix component (H) in the present embodiment, the hard coat layer (J) can be imparted with impact absorption properties, and the amount of change in haze in the Taber abrasion test of the hard coat layer (J) can be reduced. The hardness HMH of the matrix component (H) can be controlled within the range described above depending on the structure and composition ratio of the constituent components of the matrix raw material component (H'), which will be described later, but is not particularly limited to this method.

[Constituents of matrix component (H)]
[Hydrolyzable silicon compound (h)]
The matrix component (H) in the present embodiment is not particularly limited as long as the polymer nanoparticles (G) can be dispersed. In the present embodiment, from the viewpoint of high toughness, the matrix component (H) preferably contains a hydrolyzable silicon compound (h). In the present specification, "the matrix component (H) contains the hydrolyzable silicon compound (h)" means that the matrix component (H) is a polymer having structural units derived from the hydrolyzable silicon compound (h). is meant to contain The hydrolyzable silicon compound (h) is not particularly limited as long as it is a hydrolyzable silicon compound, its hydrolysis product or condensate.
The matrix component (H) may contain various components other than the polymer nanoparticles (G) other than 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 the wear resistance and weather resistance of the laminate (K), the hydrolyzable silicon compound (h) is a compound containing an atomic group represented by the following formula (h-1), its hydrolysis It preferably contains one or more selected from the group consisting of products, condensates, compounds represented by the following formula (h-2), hydrolysis products thereof, and condensates.
-R ² _n2 SiX ³ _3-n2 (h-1)
In formula (h-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. , (meth)acryloyl group, or epoxy group-containing substituent, 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.
SiX ⁴ ₄ (h-2)
In formula (h-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 (h-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, trifluoropropyltrimeth xysilane, trifluoropropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3 - mercaptopropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2 -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxysilane roxypropyltrimethoxysilane, 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-aminopropyl Trimethoxysilane, 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, methyltriacetoxy silane, methyltris(trichloroacetoxy)silane, trichlorosilane, tribromosilane, methyltrifluorosilane, tris(methylethylketoxime)silane, phenyl Lutris(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, 2-hydroxy-4-[3-(triethoxysilyl) ) propoxy]benzophenone, 2-hydroxy-4-[3-(trimethoxysilyl)propoxy]benzophenone, and the like.

Specific examples of the compound represented by formula (h-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 (h) is a compound containing an atomic group represented by the above formula (h-1), its hydrolysis product and condensate, and the above formula ( It preferably contains one or more selected from the compound represented by h-2), its hydrolysis products and condensates.

In the present embodiment, the "hydrolyzable silicon compound (g) contained in the polymer nanoparticles (G)" is of the same type as the "hydrolyzable silicon compound (h) contained in the matrix component (H)". It may be of a different type. Even if both are of the same type, the one contained in the polymer nanoparticles (G) is the hydrolyzable silicon compound (g), and the one contained in the matrix component (H) is the hydrolyzable silicon compound ( h).

[Inorganic oxide (F)]
The matrix component (H) in this embodiment contains an inorganic oxide (F). By including the inorganic oxide (F), the hardness of the matrix component (H) is improved and the abrasion resistance is improved. In addition, the hydrophilicity of the hydroxyl groups on the surfaces of the inorganic oxide (F) particles tends to improve the contamination resistance of the coating film.

Specific examples of the inorganic oxide (F) in the present embodiment include, but are not limited to, silicon, aluminum, titanium, zirconium, zinc, cerium, tin, indium, gallium, germanium, antimony, molybdenum, niobium, magnesium, Oxides of bismuth, cobalt, copper and the like are included. These may be used singly or as a mixture regardless of the shape. From the viewpoint of interaction with the hydrolyzable silicon compound (h), the inorganic oxide (F) preferably further contains silica particles typified by dry silica and colloidal silica, and from the viewpoint of dispersibility. , preferably further contains colloidal silica in the form of silica particles. When the inorganic oxide (F) contains colloidal silica, it is preferably in the form of an aqueous dispersion, and it can be used whether it is acidic or basic.
In the present embodiment, the inorganic oxide (F) is at least one inorganic oxide selected from the group consisting of Ce, Nb, Al, Zn, Ti, Zr, Sb, Mg, Sn, Bi, Co and Cu. It is preferable to contain a component (hereinafter also simply referred to as “inorganic component”). Including the inorganic component in the inorganic oxide (F) tends to improve weather resistance without impairing wear resistance and durability. 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, and zirconium oxide sol manufactured by Taki Kagaku Co., Ltd. may be mentioned. From the viewpoint of weather resistance improvement performance, the inorganic oxide (F) preferably contains at least one inorganic component selected from the group consisting of Ce, Nb, Zn, Ti and Zr, and more preferably contains Ce. preferable.
The inorganic oxide (F) in the present embodiment is at least one inorganic oxide selected from the group consisting of Ce, Nb, Zn, Ti and Zr from the viewpoint of the balance of wear resistance, durability and weather resistance. (F') is preferably contained, and the content of the inorganic oxide (F') in the hard coat film is not particularly limited. It is preferably at least 2% by mass, more preferably at least 2% by mass. From the viewpoint of transparency, the content is preferably 50% by mass or less, more preferably 30% by mass or less. Here, the above content can be specified as the total amount of Ce, Nb, Zn, Ti and Zr when the hard coat film is taken as 100% by mass.

[Average particle size of inorganic oxide (F)]
The average particle size of the inorganic oxide (F) in the present embodiment is preferably 2 nm or more from the viewpoint of good storage stability of the composition of the hard coat layer (J). From the viewpoint of good transparency of the laminate as a whole, the thickness is preferably 150 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less. Therefore, the average particle diameter is preferably 2 nm or more and 100 nm or less, more preferably 2 nm or more and 50 nm or less. The method for measuring the average particle size (F) of the inorganic oxide is not limited to the following, but for example, the 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 (F)]
The acidic colloidal silica having water as a dispersion solvent, which is suitably used in the present embodiment, is not particularly limited, but it can be prepared and used by a sol-gel method, or a commercially available product can 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 Color Material Association, 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 (F)]
Furthermore, the shape of the inorganic oxide (F) in the present embodiment is not limited to the following, and examples thereof include spherical, angular, polyhedral, elliptical, flattened, linear, beaded, and chain-like. From the viewpoint of hardness and transparency of the hard coat layer, a spherical shape is particularly preferable.

[Functional group (g-3)]
The polymer nanoparticles (G) in the present embodiment can improve the dispersibility of the polymer nanoparticles (G) in the matrix component (B) and improve the abrasion resistance. It preferably has a functional group (g-3) that interacts with H). The fact that the polymer nanoparticles (G) have functional groups (g-3) can be confirmed, for example, by IR, GC-MS, pyrolysis GC-MS, LC-MS, GPC, MALDI-MS, TOF-SIMS, TG- It can be confirmed by composition analysis by DTA and NMR, analysis by a combination thereof, and the like.

Specific examples of the functional group (g-3) 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. It is preferably a functional group having a bond, more preferably an amide group, and even more preferably a secondary amide group and/or a tertiary amide group from the viewpoint of high hydrogen bondability.

Examples of compounds containing a functional group (g-3) and reactants thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2 -hydroxyethyl vinyl ether or 4-hydroxybutyl vinyl ether, 2-hydroxyethyl allyl ether, (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-diethylaminoethyl (meth) acrylates, 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 Acrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylhexahydroazepine, N -acryloylmorpholine, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N,N'-methylenebisacrylamide, N,N'-methylenebismethacrylamide, N-vinylacetamide, diacetoneacrylamide, diacetonemetha Acrylamide, 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 Nyukazai Co., Ltd.) and the like. 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 (G)]
The polymer nanoparticles (G) 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 (G) preferably have a functional group (g-3) from the viewpoint of interaction with the matrix component (H) in the outermost layer of the core/shell structure.

[Other compounds that may be contained in the polymer nanoparticles (G)]
The polymer nanoparticles (G) 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 (G) described above, a compound having particularly excellent electrostatic repulsion is a polymer or copolymer of (meth)acrylic acid and (meth)acrylate. 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 (G) 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.

[Other components that may be included in the hard coat layer (J)]
The hard coat layer (J) in the present embodiment contains solvents, emulsifiers, plasticizers, pigments, dyes, fillers, antioxidants, conductive materials, ultraviolet absorbers, light Stabilizers, release modifiers, softeners, surfactants, flame retardants, antioxidants, catalysts may also be included. In particular, since high weather resistance is required for outdoor use, it is preferable to contain an ultraviolet absorber and a light stabilizer.
Specific examples of UV absorbers and light stabilizers include, but are not limited to, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2 -hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-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, 2-hydroxy- Benzophenone UV absorbers such as 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-octylphenyl)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) (manufactured by BASF, trade name "TINUVIN1130"), isooctyl-3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionate (manufactured by BASF under the trade name "TINUVIN384"), 2-( 3-dodecyl-5-methyl-2-hydroxyphenyl)benzotriazole (trade name "TINUVIN571" manufactured by BASF), 2-(2'-hydroxy- 3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole, 2-(2′-hydroxy-3′,5′-di-tert-amylphenyl)benzotriazole, 2-(2′- hydroxy-4′-octoxyphenyl)benzotriazole, 2-[2′-hydroxy-3′-(3″,4″,5″,6″-tetrahydrophthalimidomethyl)-5′-methylphenyl]benzotriazole, 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 (trade name, manufactured by BASF) and other benzotriazole-based ultraviolet absorbers; 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]- 4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4 ,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bisbutyloxyphenyl)- 1,3,5-triazine (trade name “TINUVIN460” manufactured by BASF), 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl) - Triazine-based UV absorbers such as 1,3,5-triazine (trade name "TINUVIN479" manufactured by BASF), TINUVIN400, TINUVIN405, TINUVIN477, TINUVIN1600 (trade name, manufactured by BASF); HOSTAVIN PR25, HOSTAVIN B-CAP , HOSTAVIN VSU (trade name, manufactured by Clariant), and the like; HOSTAVIN3206 LIQ, HOSTAVINVSU P , HOSTAVIN3212 LIQ (trade name, manufactured by Clariant), etc.; salicylate UV absorbers such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, etc. Absorbent; Ethyl-2-cyano-3,3-diphenyl acrylate (trade name “UVINUL3035” manufactured by BASF), (2-ethylhexyl)-2-cyano-3,3-diphenyl acrylate (trade name manufactured by BASF) "UVINUL3039", 1,3-bis((2'-cyano-3',3'-diphenylacryloyl)oxy)-2,2-bis-(((2'-cyano-3',3'-diphenylacryloyl ) Oxy) methyl) propane (trade name “UVINUL3030” manufactured by BASF), and other cyanoacrylate UV absorbers; 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy- 5-acryloxybenzophenone, 2-hydroxy-5-methacryloxybenzophenone, 2-hydroxy-4-(acryloxy-ethoxy)benzophenone, 2-hydroxy-4-(methacryloxy-ethoxy)benzophenone, 2-hydroxy-4-(methacryloxy -diethoxy)benzophenone, 2-hydroxy-4-(acryloxy-triethoxy)benzophenone, 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd., trade name "RUVA -93”), 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- Radically polymerizable UV absorbers having a radically polymerizable double bond in the molecule such as butyl]phenylpropionate (trade name “CGL-104” manufactured by Nihon Ciba-Geigy Co., Ltd.); UV-G101, UV-G301, UV - Ultraviolet absorption such as G137, UV-G12, UV-G13 (product name manufactured by Nippon Shokubai Co., Ltd.) Absorbent 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)propynyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynyloxy]-2,2,6,6-tetramethyl Piperidine, a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl-sebacate (manufactured by BASF, trade name "TINUVIN292"), bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, hindered amines such as TINUVIN123, TINUVIN144, TINUVIN152, TINUVIN249, TINUVIN292, TINUVIN5100 (trade name, manufactured by BASF) System light stabilizer; 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate, 2,2,6,6-tetramethyl- 4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-iminopiperidyl methacrylate, 2,2,6,6,-tetramethyl - Radicals such as 4-iminopiperidyl methacrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-cyano-1,2,2,6,6-pentamethyl-4-piperidyl methacrylate Polymerizable hindered amine light stabilizers; U-double E-133, U-double E-135, U-double S-2000, U-double S-2834, U-double S-2840, U-double S-2818, U-double S-2860 (trade name, Nippon Shokubai Co., Ltd. ); UV absorbers reactive with silanol groups, isocyanate groups, epoxy groups, semicarbazide groups, hydrazide groups; cerium oxide, zinc oxide, aluminum oxide, zirconium oxide, niobium oxide , bismuth oxide, cobalt oxide, copper oxide, tin oxide, oxide Inorganic UV absorbers such as titanium may be mentioned, and these may be used singly or in combination of two or more.

[Manufacturing method of hard coat layer (J)]
The method for producing the hard coat layer in the present embodiment is not particularly limited, but for example, it can be obtained by applying a coating composition (L) described later and forming a coating film by heat treatment, ultraviolet irradiation, infrared irradiation, or the like. 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. are mentioned. The coated coating composition (L) can be formed into a coating film by heat treatment, preferably at room temperature to 250° C., more preferably at 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 layer]
From the viewpoint of weather resistance, the hard coat layer (J) in the present embodiment may have its surface treated with silica to form a silica layer. The method for forming the silica layer is not particularly limited, but specific examples include silica processing by PECVD in which silicone or silazane is vapor-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.

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

[Paint composition (L)]
In this embodiment, the hard coat layer (J) is preferably obtained by using, for example, the following coating composition (L). The coating composition (L) is a coating composition containing an inorganic oxide (F), a polymer nanoparticle (G), and a matrix raw material component (H'), and conforms to ISO 14577-1, indentation The elastic recovery rate η _ITG of the polymer nanoparticles (G) measured from a test is 0.30 or more and 0.90 or less, and the Martens hardness HMG of the polymer nanoparticles (G) and the matrix raw material The Martens hardness HMH' of the component (H') preferably satisfies the relationship HMH'/HMG>1.
Regarding each component contained in the coating composition (L), details of points not mentioned below are as described above for each component contained in the hard coat layer (J).

[Hardness HMG of polymer nanoparticles (G) and hardness HMH' of matrix raw material component (H')]
In the coating composition (L), the Martens hardness HMG of the polymer nanoparticles (G) and the Martens hardness HMH' of the matrix raw material component (H') preferably satisfy the relationship of the following formula (3).
HMH'_'/HMG>1 Formula (3)
As described above, since the above relationship is satisfied in the coating composition (L), in the hard coat layer (J) obtained by using the coating composition (L), the polymer nanoparticles (G) have a Martens hardness HMG Then, the Martens hardness HMH' of the matrix raw material component (H') also satisfies the above formula (3). Each Martens hardness in the coating composition (L) is determined by, for example, separating the polymer nanoparticles (G) and the matrix raw material component (H′) by an operation such as centrifugation or ultrafiltration, and On the other hand, it can be measured based on the method described in Examples described later.
The values of HMG and HMH can be adjusted so as to satisfy the above-described magnitude relationship depending on the structures and composition ratios of the constituent components of the polymer nanoparticles (G) and the matrix raw material component (H'), respectively. The method is not limited.

[Elastic recovery rate η _ITG of polymer nanoparticles (G)]
The elastic recovery rate η _ITG of the polymer nanoparticles (G) in the present embodiment is the parameter described as the W _elast /W _total ratio η _IT in ISO14577-1. and is indicated by the ratio of the total mechanical work of the indentation W _total to the elastic return deformation work of the indentation W _elast . The higher the elastic recovery rate η _ITG , 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 _ITG of the polymer nanoparticles (G) 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 0.30 or more, and η _ITG is preferably 0.90 or less from the viewpoint of being able to follow the deformation of the base material and the matrix raw material component (H′) when forming a coating film. The elastic recovery rate _ηITG of the polymer nanoparticles (A) is more preferably 0.50 or more, and even more preferably 0.60 or more. Measurement of the elastic recovery rate of the polymer nanoparticles (G) is not limited to the following. A composition obtained by separating and dispersing the separated polymer nanoparticles (G) 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 _ηITG within the above range include, but are not limited to, adjusting the structure and composition ratio of the constituent components of the polymer nanoparticles (G).
The hard coat layer (J) can be obtained as a cured product obtained by curing the coating composition (L) by hydrolytic condensation or the like. The polymer nanoparticles (G) generally do not change their composition during the curing process. Therefore, the value of the elastic recovery rate η _ITG of the polymer nanoparticles (G) in the coating composition (L) measured by the method described in the examples below is the value of the polymer in the hard coat layer (J). As a good match to the elastic recovery rate η _ITG of the nanoparticles (G), the value of the elastic recovery rate η _ITG in the hard coat layer (J) can be determined.

[Elastic Recovery Rate η _{ITH of Matrix Raw Material Component (H′)} and Elastic Recovery Rate η _ITH of Matrix Component (H)]
In the coating composition (L), the elastic recovery rate η _{ITH '} of the matrix raw material component (H') is a parameter described in ISO 14577-1 as the "W _elast /W _total ratio η _IT ". It is a measurement of the coating film of the matrix raw material component (H'), 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 _ηITH' , 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 _{ITH '} of the matrix raw material component (H') 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 _ITH' is preferably 0.95 or less from the viewpoint of being able to follow the deformation of the base material and component (G) when forming a coating film. The measurement of the elastic recovery rate of the matrix raw material component (G') is not limited to the following, but for example, the polymer nanoparticles (G) and the matrix raw material component (H') are separated by an operation such as centrifugation, and then separated. A composition obtained by dissolving the obtained matrix raw material component (H′) 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 (H) corresponds to a cured product obtained by curing the matrix raw material component (H') by hydrolytic condensation or the like. Therefore, the value of the elastic recovery rate _ηITH' of the matrix raw material component (H') measured by the method described in the examples described later agrees well with the elastic recovery rate _ηITH of the corresponding matrix component (H). As such, the value of the elastic recovery η _ITH can be determined. That is, the elastic recovery rate η _ITH of the matrix component (H) in this embodiment is preferably 0.60 or more, more preferably 0.65 or more. In addition, η _ITH is preferably 0.95 or less from the viewpoint of being able to follow the deformation of the base material and component (G) when forming a coating film.
Methods for adjusting the elastic recovery rate _ηITH' and the elastic recovery rate _ηITH 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 (H'). and so on.

[Solvent (N)]
The coating composition (L) in the present embodiment preferably contains a solvent (N). 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.

[Properties of coating composition (L)]
The coating composition (L) preferably has a solid content concentration of 0.01 to 60% by mass, more preferably 1 to 40% by mass, from the viewpoint of coating properties. From the viewpoint of paintability, the viscosity of the coating composition (L) at 20° C. is preferably 0.1 to 100000 mPa·s, preferably 1 to 10000 mPa·s.

[Haze value H1 of substrate with adhesive layer (I) and haze value H2 of laminate (K)]
In the present embodiment, the haze value H1 of the substrate with the adhesive layer (I) is preferably higher than the haze value H2 of the laminate. By satisfying such a relationship, in the laminate (K) of the present embodiment, a scattering layer is formed at the interface between the substrate with the adhesive layer (I) and the hard coat layer (J), resulting in interference fringes. The production tends to be suppressed, and the optical properties tend to improve.

In the present embodiment, from the viewpoint of transparency, the haze value H1 of the substrate with the adhesive layer (I) is preferably 60% or less, more preferably 40% or less, and still more preferably 20% or less. . From the same viewpoint, the haze value H2 of the laminate (K) is preferably 5% or less, more preferably 2% or less, and still more preferably 1% or less. The method for adjusting each haze value within the above range is not limited to the following, but for example, H1 is the particle size of the polymer particles (A), the particle size and shape of the inorganic oxide (B), the polymer Examples include controlling the weight ratio of the particles (A) and the inorganic oxide (B), the content of the organic ultraviolet absorber (D), the content of the blocked polyisocyanate compound (E) and other additives. can control the particle size of the polymer nanoparticles (G), the component ratio of the polymer nanoparticles (G) and the matrix component (H), and the content of the inorganic oxide (F) in the matrix component (H). mentioned. In particular, each haze value tends to increase when the amount of the inorganic oxide (B) or the inorganic oxide (F) is increased, and tends to decrease when the amount is decreased.
Each haze value can be measured by the method described in Examples below. The haze value H1 is measured for the substrate with the adhesive layer, and the haze value H2 is measured for the laminate (K) (the substrate with the adhesive layer (I) and the hard coat layer (J)). can be measured. The haze values H1 and H2 may be measured after forming the base material with the adhesive layer (I) and the laminate (K), respectively.

[Surface roughness Ra1 of substrate with adhesive layer (I) and surface roughness Ra2 of laminate (K)]
In the laminate of the present embodiment, the surface roughness Ra1 of the substrate with the adhesive layer (I) is preferably larger than the surface roughness Ra2 of the laminate (K) of the laminate. By satisfying such a relationship, in the laminate (K) of the present embodiment, a scattering layer is formed at the interface between the substrate with the adhesive layer (I) and the hard coat layer (J), resulting in interference fringes. The production tends to be suppressed, and the optical properties tend to improve.

In the present embodiment, from the viewpoint of transparency, the surface roughness Ra1 of the substrate with the adhesive layer (I) is preferably 500 nm or less, more preferably 300 nm or less, still more preferably 200 nm or less, and most preferably 200 nm or less. It is preferably 150 nm or less. In the present embodiment, from the viewpoint of adhesion, the surface roughness Ra1 of the substrate with the adhesive layer (I) is preferably 10 nm or more, more preferably 20 nm or more, and still more preferably 40 nm or more. .
From the viewpoint of transparency, the surface roughness Ra2 of the laminate (K) is preferably less than 100 nm, more preferably 50 nm or less, still more preferably 30 nm or less, and even more preferably 20 nm or less. be.
The method for adjusting the surface roughnesses Ra1 and Ra2 within the above range is not limited to the following, but for example, Ra1 is the particle size of the polymer particles (A), the particle size and shape of the inorganic oxide (B) , the weight ratio of the polymer particles (A) and the inorganic oxide (B), the content of the organic ultraviolet absorber (D), the content of the blocked polyisocyanate compound (E) and other additives are controlled. Ra2 controls the particle size of the polymer nanoparticles (G), the component ratio of the polymer nanoparticles (G) and the matrix component (H), and the content of the inorganic oxide (F) in the matrix component (H). to do. In particular, when the amount of inorganic oxide (B) or inorganic oxide (F) is increased, each surface roughness Ra tends to increase, and when the amount is decreased, it tends to decrease.
Each surface roughness Ra1 and Ra2 can be measured by the method described in Examples below. The surface roughness Ra1 can be measured for the substrate with the adhesive layer (I), and the surface roughness Ra2 can be measured for the laminate (K). The surface roughnesses Ra1 and Ra2 may be measured after forming the base material with the adhesive layer (I) and the laminate (K), respectively. Alternatively, the surface roughness Ra may be calculated by measuring the shape of the interface between the adhesive layer (I) and the hard coat layer (J) from the cross-sectional SEM image of the laminate (K).

[Use of laminate]
The laminate (K) of this embodiment has excellent wear resistance and durability. Therefore, the use of the laminate (K) is 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, Interior components such as instrument panels and center consoles, lamp components such as headlamps and rear lamps, vehicle-mounted camera lens components, lighting covers, decorative films, and various glass replacement components.
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 laminate (K) in the present embodiment can be applied to various fields such as machine parts, agricultural materials, fishery materials, transport containers, packaging containers, playground equipment and miscellaneous goods.

EXAMPLES The present embodiment will be described in detail below with reference to examples and comparative examples, but the present embodiment is not limited to these examples.

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

(1) Weight Average Molecular Weight of Unit (a) Contained in Polymer Particles (A) and Composite (C) From the chromatogram measured by gel permeation chromatography of the unit (a) extracted by diluting to % by mass and passing through a membrane filter with a diameter of 0.45 μm, the polymer particles ( A weight average molecular weight of the unit (a) contained in A) was calculated. For the gel permeation chromatograph, "HLC-8420GPC" (manufactured by Tosoh Corporation) was used. As columns, "TSKgel guardcolumn SuperAW-H", two "TSKgel SuperAWM-H", and "TSKgel SuperH-RC" (both manufactured by Tosoh Corporation, trade names) were used for a total of four columns, and a mobile phase; Dimethylformamide, measurement temperature: 40°C, flow rate: 0.6 mL/min, detector: RI.
Also, the weight average molecular weight of the unit (a) contained in the composite (C) obtained by the method described later was calculated in the same manner as described above.
In addition, when both the polymer particles (A) and the composite (C) are contained in the coating composition, the content W1 and the weight average molecular weight Mw1 of the unit (a) in the polymer particles (A) and the composite From the content W2 and the weight average molecular weight Mw2 of the unit (a) in (C) (here, the content W1 and W2 were obtained from the feed ratio.), Considering the mass ratio, the following formula is used for the coating composition The weight average molecular weight Mw of the unit (a) in the product was calculated.
Mw={Mw1×(W1/(W1+W2))+Mw2×(W2/(W1+W2))}/2

(2) Average particle of polymer particles (A), inorganic oxide (B), mixture of polymer particles (A) and inorganic oxide (B), composite (C), and polymer particles (F) Otsuka The cumulant particle size is measured with a dynamic light scattering particle size distribution analyzer (product number: ELSZ-1000) manufactured by Denshi Co., Ltd., and the polymer particles (A), the inorganic oxide (B), the polymer particles (A) and the inorganic The average particle size of the mixture with the oxide (B), the composite (C), or the polymer particles (F) was used.

(3) Paint stability evaluation of the paint composition The paint composition was left to stand for 1 h at room temperature in a container for preparing the paint composition immediately after preparation, and from the state of the paint after standing, the paint stability was evaluated visually as follows.
S: no generation of aggregates;
A: A small amount of aggregates is generated (a state where aggregates are attached to the wall surface of the container),
B: A large amount of aggregates are generated (a state in which precipitates of aggregates are observed on the bottom of the container)

(4) pH of the coating composition
The pH of the coating composition was measured using a pH meter (HM-25R type) manufactured by DKK Toa Co., Ltd.

(5) Base material with adhesive layer (I), evaluation of transparency of laminate (K) Base material with adhesive layer (I), transparency of laminate (K) is manufactured by Nippon Denshoku Industries Co., Ltd. The haze value measured by the method specified in JIS K7136 was evaluated using a meter (product number: NDH5000SP). The haze value H1 was measured by the above method for the base material with the adhesive layer. The haze value H2 was measured by the above method for the laminate (adhesive layer-attached substrate (I) and hard coat layer (J)).

(6) Measurement of Martens hardness HMG and elastic recovery rate η _ITG of polymer nanoparticles (G) was applied to a glass substrate (material: white plate glass, thickness: 2 mm) so that the film thickness was 3 μm, and dried at 130 ° C. for 2 hours. The surface on which the film is to be formed was targeted for the measurement. 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 HMG of the polymer nanoparticles (G) was measured based on the indentation test method conforming to ISO 14577-1. In addition, using the coating film obtained as described above, an indentation test using a Fischer scope (product number: HM2000S) manufactured by Fisher Instruments (test conditions; indenter: Vickers square pyramid diamond indenter, load increase condition: 2 mN / 20 sec, load reduction condition: 2 mN / 20 sec), and based on the indentation test method in accordance with ISO 14577-1, the elastic return deformation work W _elast of the dent with respect to the total mechanical work W _total of the dent , that is, the value of W _elast /W _total was measured as the elastic recovery rate η _ITG of the polymer nanoparticles (G).

(7) Measurement of Martens hardness HMH' and elastic recovery rate η _ITH' of component (H') / 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 glass, Thickness: 2 mm) and dried at 130° C. for 2 hours to measure 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 HMH' and η _ITH' (=W _elast /W _total ) were measured based on the indentation test method conforming to ISO14577-1. As will be described later, the component (H) corresponds to the hydrolytic condensate of the corresponding component (H'), so the Martens hardness HM _B' and the elastic recovery of the component (H') measured as described above The values of the modulus η _ITH′ were determined as being in good agreement with the Martens hardness HMH and elastic recovery η _ITH of _the matrix component (H), respectively.

(8) Evaluation of abrasion resistance of the laminate (K) Evaluation of the abrasion resistance of the laminate (K) uses a Taber type abrasion tester (No. 101) manufactured by Yasuda Seiki Co., Ltd. and conforms to the ASTM D1044 standard. I did. 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 500 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 (ΔHaze) from the haze before the test was taken to evaluate the abrasion resistance as follows.
For 500 rotations S: ΔHaze is 4 or less,
A: ΔHaze is more than 4 and 10 or less,
B: ΔHaze is over 10

(9) Adhesion Evaluation of Adhesive Layer (I) and Hard Coat Layer (J) <Cross-cut Test>
By the crosscut method specified in JIS K5600-5-6, a cutter blade is used to cut 25 squares at 1mm intervals on the hard coat layer side of the laminate, and tape (Nichiban Co., Ltd. crosscut test / crosscut test compliant tape). was attached to a square, and the adhesion was evaluated as follows from the number of squares where the coating film remained when peeled off. Further, the adhesive layer (I) side of the base material with the adhesive layer (I) was subjected to the same operation as described above, and the adhesiveness of the adhesive layer (I) was evaluated as follows.
S: 25 squares A: 20-24 squares,
B: 10 to 19 squares C: less than 10 squares

(10) Evaluation of weather resistance The weather resistance of the laminate (K) was evaluated by subjecting the hard coat layer side of the laminate to ultraviolet irradiation using a xenon arc (manufactured by Suga Test Instruments Co., Ltd., product name SX-75). 1, and Δb before and after irradiation at 2000 MJ/m ² was evaluated as follows.
S: Δb<1
A: Δb = 1 to 4
B: Δb>4

(11) Evaluation of heat resistance Evaluation of the heat resistance of the laminate (K) was carried out by visual evaluation of changes in appearance after the laminate was allowed to stand in a dryer at 120°C for 24 hours, as follows.
S: No cracks A: Partial cracks B: Overall cracks C: Cracks during deposition

(12) Evaluation of chemical resistance Evaluation of the chemical resistance of the laminate (K) was performed by conducting an immersion test for five kinds of chemicals according to ECE UN R43. Based on the number of chemicals that changed the appearance of the laminate (K), evaluation was made as follows.
S: 0 types A: 1 to 2 types B: 3 to 5 types

(13) Mass ratio (content) of each component
The content of the unit (a-2) in the unit (a) was obtained from the charged amount ratio based on the charged amount of 2-hydroxyethyl methacrylate.
The mass ratio between the unit (a-1) and the organic ultraviolet absorber (D) was obtained from the charged amount ratio between the monomer (a) and the D component.

(14) NCO/OH molar ratio The NCO/OH molar ratio was calculated from the amount of 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylamide used and the amount of blocked polyisocyanate compound (E) used. Here, the number of moles of NCO was calculated from the charged amount and effective NCO %.

(15) Ratio of inorganic oxide (B) in solid content of coating composition The mass ratio of component B to the mass removed (the mass of the solid content of the coating composition) was calculated from the charge ratio.

[Preparation of polymer particle (A-1) aqueous dispersion]
An aqueous dispersion of polymer particles (A-1) used in Examples described later was synthesized as follows.
<Polymer particle (A-1) aqueous dispersion>
In a reactor equipped with a reflux condenser, a dropping tank, a thermometer and a stirring device, 500 g of ion-exchanged water, 22 g of a 10% dodecylbenzenesulfonic acid aqueous solution, 28 g of a 2% ammonium persulfate aqueous solution, and an ultraviolet-absorbing vinyl monomer "RUVA- 93” (trade name, manufactured by Otsuka Chemical Co., Ltd.) was dissolved in a mixture of 62.1 g of butyl acrylate, 46.0 g of 2-hydroxyethyl methacrylate, 1.2 g of acrylic acid and 0.58 g of 1-dodecanethiol. Polymerization was carried out by a general emulsion polymerization method in an environment of 80° C. using the resulting monomer mixture. After the polymerization, the polymer particles (A-1) were filtered through a wire mesh of 100 mesh and adjusted to a solid concentration of 15% by mass with purified water to obtain an aqueous dispersion of polymer particles (A-1). The particle diameter of the obtained polymer particles (A-1) was 39 nm, and the weight average molecular weight of the unit (a) was 600,000.

[Preparation of composite (C) of polymer particles (A) and inorganic oxide (B)]
A composite (C) aqueous dispersion used in the examples described later was synthesized as follows.
<Composite (C-1) aqueous dispersion>
A reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirrer contains 150 g of ion-exchanged water and water-dispersed colloidal silica "Snowtex PS-SO" (trade name, Nissan Chemical Industries, Ltd.) as an inorganic oxide (B). 15 mass% solid content, average particle size 80 nm by dynamic light scattering method) 1150 g, 33 g of 10% dodecylbenzenesulfonic acid aqueous solution, 42 g of 2% ammonium persulfate aqueous solution, and UV-absorbing vinyl monomer "RUVA-93" (trade name, manufactured by Otsuka Chemical Co., Ltd.) was dissolved in a mixture of 162.2 g of butyl acrylate, 1.7 g of acrylic acid and 0.86 g of 1-dodecanethiol. Polymerization was carried out by a general emulsion polymerization method under the environment. After polymerization, the pH was adjusted to 8 with a 25% aqueous ammonia solution, filtered through a 100-mesh wire mesh, and the solid concentration was adjusted to 15% with purified water to obtain an aqueous dispersion of the composite (C-1). The composite (C-1) thus obtained had an average particle diameter of 40 nm, and the weight average molecular weight of the unit (a) was 1,600,000.

<Composite (C-2) aqueous dispersion>
A reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirrer contains 150 g of ion-exchanged water and water-dispersed colloidal silica "Snowtex PS-SO" (trade name, Nissan Chemical Industries, Ltd.) as an inorganic oxide (B). solid content 15% by mass) 1150 g, 33 g of 10% dodecylbenzenesulfonic acid aqueous solution, 42 g of 2% ammonium persulfate aqueous solution, and UV-absorbing vinyl monomer “RUVA-93” (trade name, manufactured by Otsuka Chemical Co., Ltd.) 8 .6 g was dissolved in a mixture of 144.9 g of butyl acrylate, 17.3 g of 2-hydroxyethyl methacrylate, 1.7 g of acrylic acid and 1.73 g of 1-dodecanethiol. Polymerization was carried out by a general emulsion polymerization method described below. After polymerization, the pH was adjusted to 9 with a 25% aqueous ammonia solution, filtered through a 100-mesh wire mesh, and the solid concentration was adjusted to 15% with purified water to obtain an aqueous dispersion of the composite (C-2). The composite (C-2) thus obtained had an average particle size of 48 nm, and the weight average molecular weight of the unit (a) was 200,000.

<Composite (C-3) aqueous dispersion>
A reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirrer contains 150 g of ion-exchanged water and water-dispersed colloidal silica "Snowtex PS-SO" (trade name, Nissan Chemical Industries, Ltd.) as an inorganic oxide (B). solid content 15 mass%) 1150 g, 33 g of 10% dodecylbenzenesulfonic acid aqueous solution, 42 g of 2% ammonium persulfate aqueous solution, and UV-absorbing vinyl monomer “RUVA-93” (trade name, manufactured by Otsuka Chemical Co., Ltd.) 8 .6 g was dissolved in a mixture of 127.7 g of butyl acrylate, 34.5 g of 2-hydroxyethyl methacrylate, 1.7 g of acrylic acid and 0.43 g of 1-dodecanethiol. Polymerization was carried out by a general emulsion polymerization method described below. After polymerization, the pH was adjusted to 9 with a 25% aqueous ammonia solution, filtered through a 100-mesh wire mesh, and the solid concentration was adjusted to 15% with purified water to obtain an aqueous dispersion of the composite (C-3). The composite (C-3) thus obtained had an average particle size of 56 nm and a weight average molecular weight of the unit (a) of 900,000.

<Composite (C-4) aqueous dispersion>
A reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirrer contains 150 g of ion-exchanged water and water-dispersed colloidal silica "Snowtex PS-SO" (trade name, Nissan Chemical Industries, Ltd.) as an inorganic oxide (B). solid content 15 mass%) 1150 g, 33 g of 10% dodecylbenzenesulfonic acid aqueous solution, 42 g of 2% ammonium persulfate aqueous solution, and UV-absorbing vinyl monomer “RUVA-93” (trade name, manufactured by Otsuka Chemical Co., Ltd.) 8 .6 g was dissolved in a mixture of 127.7 g of butyl acrylate, 34.5 g of 2-hydroxyethyl methacrylate, 1.7 g of acrylic acid and 0.17 g of 1-dodecanethiol. Polymerization was carried out by a general emulsion polymerization method described below. After polymerization, the pH was adjusted to 10 with a 25% aqueous ammonia solution, filtered through a 100-mesh wire mesh, and the solid concentration was adjusted to 15% with purified water to obtain an aqueous dispersion of the composite (C-4). The resulting composite (C-4) had an average particle size of 54 nm, and the unit (a) had a weight average molecular weight of 4,400,000.

<Composite (C-5) aqueous dispersion>
A reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirrer contains 150 g of ion-exchanged water and water-dispersed colloidal silica "Snowtex PS-SO" (trade name, Nissan Chemical Industries, Ltd.) as an inorganic oxide (B). solid content 15 mass%) 1150 g, 22 g of 10% dodecylbenzenesulfonic acid aqueous solution, 28 g of 2% ammonium persulfate aqueous solution, and UV-absorbing vinyl monomer “RUVA-93” (trade name, manufactured by Otsuka Chemical Co., Ltd.) 5 .8 g was dissolved in a mixture of 62.1 g of butyl acrylate, 46.0 g of 2-hydroxyethyl methacrylate, 1.2 g of acrylic acid and 0.58 g of 1-dodecanethiol. Polymerization was carried out by a general emulsion polymerization method described below. After polymerization, the pH was adjusted to 9 with a 25% aqueous ammonia solution, filtered through a 100-mesh wire mesh, and the solid concentration was adjusted to 15% with purified water to obtain an aqueous dispersion of the composite (C-5). The composite (C-5) thus obtained had an average particle size of 68 nm and a weight average molecular weight of the unit (a) of 600,000.

<Composite (C-6) aqueous dispersion>
A reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirrer contains 150 g of ion-exchanged water and water-dispersed colloidal silica "Snowtex PS-SO" (trade name, Nissan Chemical Industries, Ltd.) as an inorganic oxide (B). solid content 15 mass%) 1150 g, 22 g of 10% dodecylbenzenesulfonic acid aqueous solution, 28 g of 2% ammonium persulfate aqueous solution, and UV-absorbing vinyl monomer “RUVA-93” (trade name, manufactured by Otsuka Chemical Co., Ltd.) 5 .8 g was dissolved in a mixture of 50.6 g of butyl acrylate, 57.5 g of 2-hydroxyethyl methacrylate, 1.2 g of acrylic acid and 0.58 g of 1-dodecanethiol. Polymerization was carried out by a general emulsion polymerization method described below. After polymerization, the pH was adjusted to 7.5 with a 25% aqueous ammonia solution, filtered through a 100-mesh wire mesh, and the solid concentration was adjusted to 15% with purified water to obtain an aqueous dispersion of the composite (C-6). . The resulting composite (C-6) had an average particle size of 79 nm and a weight average molecular weight of unit (a) of 400,000.

<Composite (C-7) aqueous dispersion>
A reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirrer contains 150 g of ion-exchanged water and water-dispersed colloidal silica "Snowtex PS-SO" (trade name, Nissan Chemical Industries, Ltd.) as an inorganic oxide (B). 1150 g of 10% dodecylbenzenesulfonic acid aqueous solution, 28 g of 2% ammonium persulfate aqueous solution, 67.9 g of butyl acrylate, 46.0 g of 2-hydroxyethyl methacrylate and 1.2 g of acrylic acid. Using the mixed monomer solution, polymerization was carried out in an environment of 80° C. by a general emulsion polymerization method. After polymerization, the pH was adjusted to 9.0 with a 25% aqueous ammonia solution, filtered through a 100-mesh wire mesh, and the solid concentration was adjusted to 15% with purified water to obtain an aqueous dispersion of the composite (C-7). . The resulting composite (C-7) had an average particle size of 65 nm, and the unit (a) had a weight average molecular weight of 7,200,000.

[Preparation of polymer nanoparticles (G) aqueous dispersion]
An aqueous dispersion of polymer nanoparticles (G) used in Examples described later was synthesized as follows.
<Polymer Nanoparticles (G-1) 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 raised to 80° C., and then 43 g of a 2% aqueous solution of ammonium persulfate, 11 g of butyl acrylate, 12 g of diethylacrylamide, 1 g of acrylic acid, and 1 g of 3-methacryloxypropyltrimethoxysilane were used for general emulsion polymerization. Polymerization was carried out by the method of No. 2, filtration was performed with a 100-mesh wire mesh, and the solid content concentration was adjusted to 5% with purified water to obtain an aqueous dispersion of polymer nanoparticles (G-1). The resulting polymer nanoparticles (G-1) had a core-shell structure and an average particle size of 60 nm. Further, the polymer particles (G-1) had a Martens hardness HMG of 150 N/mm ³ and an elastic recovery rate η _ITG of 0.70, which were measured according to the above-described measurement method.

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

<Matrix raw material component (H'-1) coating composition liquid>
35 g of 1,2-bis(triethoxysilyl)ethane and 81 g of tris-(trimethoxysilylpropyl) isocyanurate as the hydrolyzable silicon compound (h), and water-dispersed colloidal silica "Snowtex OXS" as the inorganic oxide (F). ” (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 10% by mass, average particle size 5 nm by TEM observation method) 333 g were mixed at room temperature, and the coating composition liquid of the matrix raw material component (H′-1) was mixed. Obtained. The matrix raw material component (H'-1) had a Martens hardness HMH' of 420 N/mm ³ and an elastic recovery rate η _ITH' of 0.71, which were measured according to the above-described measurement method.

[Preparation of hard coat layer composition liquid]
<Hard coat layer (J-1) composition liquid>
The polymer nanoparticles (G- 1) A mixture was obtained by mixing the aqueous dispersion and the matrix raw material component (H'-1) prepared above. An aqueous solution having an ethanol concentration of 20% by mass was used as a solvent, and the mixture was added so that the solid content concentration was 10% by mass to obtain a hard coat composition liquid (J-1). The hard coat layer (J-1) had a Martens hardness HMJ' of 380 N/mm ³ and an elastic recovery rate η _ITJ of 0.70, which were measured according to the above-described measurement method.

[Example 1]
15 g of polymer particles (A-1), 19 g of water-dispersed colloidal silica "Snowtex PS-SO" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 15% by mass) as inorganic oxide (B), organic Tinuvin400 (trade name, manufactured by BASF Japan Ltd., solid content concentration 85%) 0.52 g as an ultraviolet absorber, Tinuvin123 (trade name, manufactured by BASF Japan Ltd.) 0.07 g as a light stabilizer, WM44-L70G as a curing agent (trade name, manufactured by Asahi Kasei Corporation, solid content concentration 70% by mass, effective NCO 5.3% by mass) 2.15 g, water 12.86 g, ethanol 10 g were mixed at room temperature, and pH was 10.0 with 25% ammonia aqueous solution. to obtain a coating composition of Example 1. The solid content concentration of the coating composition was 12% by mass.
Then, the coating composition of Example 1 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, the substrate with an adhesive layer of Example 1 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with the adhesive layer of Example 1 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a thickness of 3.0 μm. A laminate having layers was obtained.
Table 1 shows the results of various evaluations of the coating composition of Example 1, the substrate with an adhesive layer, and the laminate.

[Example 2]
30 g of the composite (C-1) aqueous dispersion, 0.51 g of Tinuvin400 (trade name, manufactured by BASF Japan Co., Ltd., solid content concentration 85%) as an organic ultraviolet absorber, and Tinuvin123 (trade name, BASF) as a light stabilizer Japan Co., Ltd.), 3.90 g of water, and 6.91 g of ethanol were mixed at room temperature to obtain a coating composition of Example 2. The coating composition had a solid content concentration of 12% by mass and a pH of 7.5.
Then, the coating composition of Example 2 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a substrate with an adhesive layer of Example 2 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with the adhesive layer of Example 2 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a thickness of 3.0 μm. A laminate having layers was obtained.
Table 1 shows the results of various evaluations of the coating composition of Example 2, the substrate with an adhesive layer, and the laminate.

[Example 3]
30 g of the composite (C-2) aqueous dispersion, 0.51 g of Tinuvin 400 (trade name, manufactured by BASF Japan Ltd., solid content concentration 85%) as an organic ultraviolet absorber, and Tinuvin 123 (trade name, BASF) as a light stabilizer Japan Co., Ltd.) 0.07 g, WM44-L70G as a curing agent (trade name, Asahi Kasei Corporation, solid content concentration 70% by mass, effective NCO 5.3% by mass) 0.53 g, water 6.06 g, ethanol 7. 45 g were mixed under room temperature conditions to obtain the coating composition of Example 3. The coating composition had a solid content concentration of 12% by mass and a pH of 8.5.
Next, the coating composition of Example 3 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a substrate with an adhesive layer of Example 3 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with the adhesive layer of Example 3 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a thickness of 3.0 μm. A laminate having layers was obtained.
Table 1 shows the results of various evaluations of the coating composition of Example 3, the substrate with an adhesive layer, and the laminate.

[Example 4]
30 g of the composite (C-3) aqueous dispersion, 0.52 g of Tinuvin 400 (trade name, manufactured by BASF Japan Ltd., solid content concentration 85%) as an organic ultraviolet absorber, and Tinuvin 123 (trade name, BASF) as a light stabilizer Japan Co., Ltd.) 0.07 g, WM44-L70G as a curing agent (trade name, Asahi Kasei Corporation, solid content concentration 70% by mass, effective NCO 5.3% by mass) 1.07 g, water 8.29 g, ethanol 8. 01 g were mixed at room temperature to obtain a coating composition of Example 4. The coating composition had a solid content concentration of 12% by mass and a pH of 8.3.
Next, the coating composition of Example 4 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a substrate with an adhesive layer of Example 4 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with the adhesive layer of Example 4 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a thickness of 3.0 μm. A laminate having layers was obtained.
Table 1 shows the results of various evaluations of the coating composition of Example 4, the substrate with an adhesive layer, and the laminate.

[Example 5]
30 g of the composite (C-4) aqueous dispersion, 0.52 g of Tinuvin 400 (trade name, manufactured by BASF Japan Co., Ltd., solid content concentration 85%) as an organic ultraviolet absorber, and Tinuvin 123 (trade name, BASF) as a light stabilizer Japan Co., Ltd.) 0.07 g, WM44-L70G as a curing agent (trade name, Asahi Kasei Corporation, solid content concentration 70% by mass, effective NCO 5.3% by mass) 1.07 g, water 8.30 g, ethanol 8. 01 g were mixed at room temperature to obtain a coating composition of Example 5. The coating composition had a solid content concentration of 12% by mass and a pH of 9.4.
Then, the coating composition of Example 5 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a substrate with an adhesive layer of Example 5 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with the adhesive layer of Example 5 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a thickness of 3.0 μm. A laminate having layers was obtained.
Table 1 shows the results of various evaluations of the coating composition of Example 5, the substrate with an adhesive layer, and the laminate.

[Example 6]
30 g of the composite (C-5) aqueous dispersion, 0.41 g of Tinuvin400 (trade name, manufactured by BASF Japan Co., Ltd., solid content concentration 85%) as an organic ultraviolet absorber, and Tinuvin123 (trade name, BASF) as a light stabilizer Japan Co., Ltd.) 0.06 g, WM44-L70G as a curing agent (trade name, Asahi Kasei Corporation, solid content concentration 70% by mass, effective NCO 5.3% by mass) 1.71 g, water 10.30 g, ethanol 8. 60 g were mixed under room temperature conditions to obtain the coating composition of Example 6. The coating composition had a solid content concentration of 12% by mass and a pH of 8.1.
Next, the coating composition of Example 6 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a substrate with an adhesive layer of Example 6 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with an adhesive layer of Example 6 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a thickness of 3.0 μm. A laminate having layers was obtained.
Table 1 shows the results of various evaluations of the coating composition of Example 6, the substrate with an adhesive layer, and the laminate.

[Example 7]
30 g of the composite (C-5) aqueous dispersion, Tinuvin400 (trade name, manufactured by BASF Japan Ltd., solid content concentration 85%) and Tinuvin479 (trade name, manufactured by BASF Japan Ltd., solid content concentration 100) as ultraviolet absorbers %) mixture (“U1” in Table 1, solid content ratio 85/15, solid content concentration 87.0%) 0.40 g, Tinuvin 123 as a light stabilizer (trade name, manufactured by BASF Japan Ltd.) 0.06 g, As a curing agent, 1.71 g of WM44-L70G (trade name, manufactured by Asahi Kasei Corporation, solid content concentration of 70% by mass, effective NCO of 5.3% by mass), 10.24 g of water, and 8.59 g of ethanol were mixed at room temperature, A coating composition of Example 7 was obtained. The coating composition had a solid content concentration of 12% by mass and a pH of 8.3.
Next, the coating composition of Example 7 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a substrate with an adhesive layer of Example 7 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with the adhesive layer of Example 7 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a thickness of 3.0 μm. A laminate having layers was obtained.
Table 1 shows the results of various evaluations of the coating composition of Example 7, the substrate with an adhesive layer, and the laminate.

[Example 8]
30 g of the composite (C-6) aqueous dispersion, Tinuvin400 (trade name, manufactured by BASF Japan Co., Ltd., solid concentration 85%) as an organic ultraviolet absorber 0.41 g, Tinuvin123 (trade name, BASF) as a light stabilizer Japan Co., Ltd.) 0.06 g, WM44-L70G as a curing agent (trade name, Asahi Kasei Corporation, solid content concentration 70% by mass, effective NCO 5.3% by mass) 2.13 g, water 12.05 g, ethanol 9. 04 g were mixed at room temperature to obtain a coating composition of Example 8. The coating composition had a solid content concentration of 12% by mass and a pH of 7.1.
Then, the coating composition of Example 8 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a substrate with an adhesive layer of Example 8 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with the adhesive layer of Example 8 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a film thickness of 3.0 μm. A laminate having layers was obtained.
Table 1 shows the results of various evaluations of the coating composition of Example 8, the substrate with an adhesive layer, and the laminate.

[Example 9]
30 g of the composite (C-5) aqueous dispersion, Tinuvin400 (trade name, manufactured by BASF Japan Co., Ltd., solid content concentration 85%) as an organic ultraviolet absorber 0.10 g, Tinuvin123 (trade name, BASF) as a light stabilizer Japan Co., Ltd.) 0.01 g, WM44-L70G as a curing agent (trade name, Asahi Kasei Corporation, solid content concentration 70% by mass, effective NCO 5.3% by mass) 3.41 g, water 15.50 g, ethanol 10. 16 g were mixed under room temperature conditions to obtain the coating composition of Example 9. The coating composition had a solid content concentration of 12% by mass and a pH of 8.2.
Then, the coating composition of Example 9 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a substrate with an adhesive layer of Example 9 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with the adhesive layer of Example 9 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a thickness of 3.0 μm. A laminate having layers was obtained.
Table 2 shows the results of various evaluations of the coating composition of Example 9, the substrate with an adhesive layer, and the laminate.

[Example 10]
30 g of the composite (C-5) aqueous dispersion, Tinuvin400 (trade name, manufactured by BASF Japan Co., Ltd., solid concentration 85%) as an organic ultraviolet absorber 0.21 g, Tinuvin123 (trade name, BASF) as a light stabilizer Japan Co., Ltd.) 0.03 g, WM44-L70G as a curing agent (trade name, Asahi Kasei Corporation, solid content concentration 70% by mass, effective NCO 5.3% by mass) 3.41 g, water 16.10 g, ethanol 10. 23 g were mixed under room temperature conditions to obtain the coating composition of Example 10. The coating composition had a solid content concentration of 12% by mass and a pH of 8.3.
Next, the coating composition of Example 10 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a substrate with an adhesive layer of Example 10 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with the adhesive layer of Example 10 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a thickness of 3.0 μm. A laminate having layers was obtained.
Table 2 shows the results of various evaluations of the coating composition of Example 10, the substrate with an adhesive layer, and the laminate.

[Example 11]
30 g of the composite (C-5) aqueous dispersion, 0.62 g of Tinuvin 400 (trade name, manufactured by BASF Japan Co., Ltd., solid content concentration 85%) as an organic ultraviolet absorber, and Tinuvin 123 (trade name, BASF) as a light stabilizer Japan Co., Ltd.) 0.09 g, WM44-L70G as a curing agent (trade name, Asahi Kasei Corporation, solid content concentration 70% by mass, effective NCO 5.3% by mass) 1.28 g, water 9.75 g, ethanol 8. 29 g were mixed under room temperature conditions to obtain the coating composition of Example 11. The coating composition had a solid content concentration of 12% by mass and a pH of 8.6.
Next, the coating composition of Example 11 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a substrate with an adhesive layer of Example 11 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with an adhesive layer of Example 11 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a thickness of 3.0 μm. A laminate having layers was obtained. Table 2 shows the results of various evaluations of the coating composition of Example 11, the substrate with an adhesive layer, and the laminate.

[Example 12]
30 g of the composite (C-5) aqueous dispersion, 1.03 g of Tinuvin 400 (trade name, manufactured by BASF Japan Ltd., solid content concentration 85%) as an organic ultraviolet absorber, and Tinuvin 123 (trade name, BASF) as a light stabilizer Japan Co., Ltd.) 0.15 g, WM44-L70G as a curing agent (trade name, Asahi Kasei Corporation, solid content concentration 70% by mass, effective NCO 5.3% by mass) 1.28 g, water 12.15 g, ethanol 8. 54 g were mixed under room temperature conditions to obtain the coating composition of Example 12. The coating composition had a solid content concentration of 12% by mass and a pH of 8.4.
Next, the coating composition of Example 12 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a substrate with an adhesive layer of Example 12 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with the adhesive layer of Example 12 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a film thickness of 3.0 μm. A laminate having layers was obtained. Table 2 shows the results of various evaluations of the coating composition of Example 12, the substrate with an adhesive layer, and the laminate.

[Example 13]
16 g of polymer particles (A-1), 30 g of composite (C-5) aqueous dispersion, Tinuvin 400 as an organic UV absorber (trade name, manufactured by BASF Japan Ltd., solid content concentration 85%) 0.96 g , Tinuvin 123 as a light stabilizer (trade name, manufactured by BASF Japan Co., Ltd.) 0.14 g, WM44-L70G as a curing agent (trade name, manufactured by Asahi Kasei Corporation, solid content concentration 70% by weight, effective NCO 5.3% by weight) 3 .98 g, 23.31 g of water, and 14.79 g of ethanol were mixed under room temperature conditions to obtain a coating composition of Example 13. The coating composition had a solid content concentration of 12% by mass and a pH of 7.2.
Next, the coating composition of Example 13 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a substrate with an adhesive layer of Example 13 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with an adhesive layer of Example 13 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a thickness of 3.0 μm. A laminate having layers was obtained. Table 2 shows the results of various evaluations of the coating composition of Example 13, the substrate with an adhesive layer, and the laminate.

[Example 14]
6 g of polymer particles (A-1), 30 g of composite (C-5) aqueous dispersion, Tinuvin 400 as an organic UV absorber (trade name, manufactured by BASF Japan Ltd., solid content concentration 85%) 0.62 g , Tinuvin 123 as a light stabilizer (trade name, manufactured by BASF Japan Co., Ltd.) 0.09 g, WM44-L70G as a curing agent (trade name, manufactured by Asahi Kasei Corporation, solid content concentration 70% by mass, effective NCO 5.3% by mass) 2 0.56 g, 15.18 g of water and 10.92 g of ethanol were mixed under room temperature conditions to obtain the coating composition of Example 14. The coating composition had a solid content concentration of 12% by mass and a pH of 8.0.
Then, the coating composition of Example 14 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a substrate with an adhesive layer of Example 14 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with the adhesive layer of Example 14 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a thickness of 3.0 μm. A laminate having layers was obtained. Table 2 shows the results of various evaluations of the coating composition of Example 14, the substrate with an adhesive layer, and the laminate.

[Example 15]
Composite (C-5) 30 g of aqueous dispersion, 5 g of water-dispersed colloidal silica “Snowtex PS-SO” (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 15% by mass) as inorganic oxide (B), Tinuvin400 (trade name, manufactured by BASF Japan Ltd., solid content concentration 85%) 0.41 g as an organic UV absorber, Tinuvin123 (trade name, manufactured by BASF Japan Ltd.) 0.06 g as a light stabilizer, WM44 as a curing agent -L70G (trade name, manufactured by Asahi Kasei Corporation, solid content concentration 70% by mass, effective NCO 5.3% by mass) 1.71 g, water 10.45 g, ethanol 9.70 g were mixed under room temperature conditions. A coating composition was obtained. The coating composition had a solid content concentration of 12% by mass and a pH of 8.4.
Then, the coating composition of Example 15 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a substrate with an adhesive layer of Example 15 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with an adhesive layer of Example 15 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a film thickness of 3.0 μm. A laminate having layers was obtained. Table 2 shows the results of various evaluations of the coating composition of Example 15, the substrate with an adhesive layer, and the laminate.

[Example 16]
Composite (C-5) 30 g of aqueous dispersion, 16 g of water-dispersed colloidal silica “Snowtex PS-SO” (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 15% by mass) as inorganic oxide (B), Tinuvin400 (trade name, manufactured by BASF Japan Ltd., solid content concentration 85%) 0.41 g as an organic UV absorber, Tinuvin123 (trade name, manufactured by BASF Japan Ltd.) 0.06 g as a light stabilizer, WM44 as a curing agent -L70G (trade name, manufactured by Asahi Kasei Corporation, solid content concentration 70% by mass, effective NCO 5.3% by mass) 1.71 g, water 10.78 g, ethanol 12.12 g are mixed under room temperature conditions. A coating composition was obtained. The coating composition had a solid content concentration of 12% by mass and a pH of 7.6.
Then, the coating composition of Example 16 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a substrate with an adhesive layer of Example 16 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with the adhesive layer of Example 16 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a film thickness of 3.0 μm. A laminate having layers was obtained. Table 2 shows the results of various evaluations of the coating composition of Example 16, the substrate with an adhesive layer, and the laminate.

[Comparative Example 1]
Water-dispersed colloidal silica “Snowtex PS-SO” (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 15% by mass) as inorganic oxide (B) 30 g, Tinuvin 400 as organic UV absorber (trade name, BASF Japan Co., Ltd., solid content concentration 85%) 0.62 g, Tinuvin 123 (trade name, manufactured by BASF Japan Co., Ltd.) 0.09 g as a light stabilizer, WM44-L70G as a curing agent (trade name, manufactured by Asahi Kasei Corporation, solid content Concentration 70% by mass, effective NCO 5.3% by mass) 1.28 g, water 9.75 g, and ethanol 8.29 g are mixed at room temperature, and the pH is adjusted to 9.0 with a 25% aqueous ammonia solution. A composition was obtained. The solid content concentration of the coating composition was 12% by mass.
Next, the coating composition of Comparative Example 1 was applied onto a polycarbonate substrate using a bar coater and dried at 130°C for 1 hour to form an adhesive layer having a thickness of 5.0 µm. It was not possible to form a viable film. Table 3 shows the results of various evaluations of the coating composition of Comparative Example 1.

[Comparative Example 2]
30 g of polymer particles (A-1), 1.54 g of Tinuvin 400 (trade name, manufactured by BASF Japan Ltd., solid content concentration 85%) as an organic ultraviolet absorber, Tinuvin 123 (trade name, BASF Japan Co., Ltd.) as a light stabilizer Company) 0.22 g, WM44-L70G (trade name, manufactured by Asahi Kasei Corporation, solid content concentration 70% by mass, effective NCO 5.3% by mass) as a curing agent 3.20 g, water 23.02 g, ethanol 10.82 g. The mixture was mixed at room temperature and adjusted to pH 9.0 with a 25% aqueous ammonia solution to obtain a coating composition of Comparative Example 2. The solid content concentration of the coating composition was 12% by mass.
Then, the coating composition of Comparative Example 2 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a base material with an adhesive layer of Comparative Example 2 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with the adhesive layer of Comparative Example 2 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a thickness of 3.0 μm. A laminate having layers was obtained. Table 3 shows the results of various evaluations of the coating composition of Comparative Example 2, the substrate with an adhesive layer, and the laminate.

[Comparative Example 3]
15 g of polymer particles (A-1), 19 g of water-dispersed colloidal silica "Snowtex PS-SO" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 15% by mass) as inorganic oxide (B), organic Tinuvin400 (trade name, manufactured by BASF Japan Co., Ltd., solid content concentration 85%) 0.77 g as an ultraviolet absorber, Tinuvin123 (trade name, manufactured by BASF Japan Ltd.) 0.11 g as a light stabilizer, WM44-L70G as a curing agent (trade name, manufactured by Asahi Kasei Corporation, solid content concentration 70% by mass, effective NCO 5.3% by mass) 1.60 g, water 12.08 g, and ethanol 9.59 g were mixed at room temperature, and pH was 6 with a 25% ammonia aqueous solution. 0 to obtain a coating composition of Comparative Example 3. The solid content concentration of the coating composition was 12% by mass.
Then, the coating composition of Comparative Example 3 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a base material with an adhesive layer of Comparative Example 3 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with the adhesive layer of Comparative Example 3 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a film thickness of 3.0 μm. A laminate having layers was obtained. Table 3 shows the results of various evaluations of the coating composition of Comparative Example 3, the substrate with an adhesive layer, and the laminate.

[Comparative Example 4]
30 g of the composite (C-7), Tinuvin 400 (trade name, manufactured by BASF Japan Ltd., solid content concentration 85%) as an organic ultraviolet absorber 0.62 g, Tinuvin 123 (trade name, BASF Japan Ltd.) as a light stabilizer ) 0.09 g, WM44-L70G (trade name, manufactured by Asahi Kasei Corporation, solid content concentration 70% by mass, effective NCO 5.3% by mass) as a curing agent 1.29 g, water 9.79 g, ethanol 8.30 g at room temperature After mixing under these conditions, a coating composition of Comparative Example 4 was obtained. The coating composition had a solid content concentration of 12% by mass and a pH of 8.4.
Then, the coating composition of Comparative Example 4 was applied onto a polycarbonate substrate using a bar coater and dried at 130° C. for 1 hour to form an adhesive layer having a thickness of 5.0 μm on the polycarbonate substrate. . Thus, a base material with an adhesive layer of Comparative Example 4 was obtained.
Furthermore, after applying the hard coat layer composition liquid (J-1) to the substrate with the adhesive layer of Comparative Example 4 using a bar coater, it was dried at 130 ° C. for 1.5 hours to obtain a hard coat with a film thickness of 3.0 μm. A laminate having layers was obtained. Table 3 shows the results of various evaluations of the coating composition of Comparative Example 4, the substrate with an adhesive layer, and the laminate.

Various evaluation results of Examples 1-16 and Comparative Examples 1-4 are shown in Tables 1-3.

[Evaluation results]
From Tables 1 to 3, it was found that the coating composition of this embodiment can form a coating excellent in transparency, adhesion and weather resistance. In addition, as described above, the laminates of Examples 1 to 16 exhibit high levels of transparency and abrasion resistance as well as high levels of weather resistance, and therefore can be preferably applied as window materials for automobiles. evaluated as a thing.

The coating composition, adhesive layer-attached substrate, and laminate provided by the present invention are useful as hard coats for building materials, automobile members, electronic devices, and electrical products.

Claims (14)

A mixture of polymer particles (A) having units (a) derived from a vinyl monomer (a) and an inorganic oxide (B), and/or the polymer particles (A) and an inorganic oxide (B ) A coating composition comprising a complex (C) with
The unit (a) has a weight average molecular weight of 10,000 to 5,000,000,
A coating composition, wherein the coating composition has a pH of 7 to 11. The coating composition according to claim 1, wherein the unit (a) comprises a unit (a-1) derived from an ultraviolet absorbing vinyl monomer (a-1). The unit (a) comprises a unit (a-2) derived from a hydroxyl group-containing vinyl monomer (a-2),
The coating composition according to claim 1, wherein the content of said unit (a-2) in said unit (a) is 10 to 40% by mass. The coating composition according to claim 1, further comprising an organic ultraviolet absorber (D). The coating composition according to Claim 1, further comprising a blocked polyisocyanate compound (E). The coating composition according to claim 1, wherein the unit (a) has a weight average molecular weight of 100,000 to 1,000,000. The coating composition according to claim 1, wherein the mass ratio of said inorganic oxide (B) to the total solid content of said coating composition is 25% to 60%. 5. The coating composition according to claim 4, wherein the unit (a-1) and the organic ultraviolet absorber (D) have a mass ratio of 1:0.5 to 1:40. The coating composition according to claim 1, wherein the inorganic oxide (B) is spherical and/or interconnected silica. The coating composition of Claim 1, further comprising a chain transfer agent. The coating composition according to claim 1, wherein said polymer particles (A) comprise emulsion particles having said units (a). a base material;
an adhesive layer disposed on the substrate;
A base material with an adhesive layer comprising
A substrate with an adhesive layer, wherein the adhesive layer comprises the coating composition according to any one of claims 1 to 11. A substrate with an adhesive layer according to claim 12;
a hard coat layer disposed on the adhesive layer-attached substrate;
A laminate comprising
The hard coat layer contains a matrix component (H) containing an inorganic oxide (F) and polymer nanoparticles (G),
A laminate in which the Martens hardness HMG of the polymer nanoparticles (G) and the Martens hardness HMH of the matrix component (H) satisfy the relationship HMH/HMG>1. The laminate according to claim 13, wherein the haze value H1 of the adhesive layer-attached substrate is higher than the haze value H2 of the laminate.