Water-based paint composition and method for producing the same, substrate with adhesive layer, laminate, and composition set

Abstract

To provide a coating composition which can form a coating film excellent in transparency and weather resistance and has an excellent pot life, a method for producing the same, a substrate with an adhesive layer, a laminate, and a composition set.SOLUTION: An aqueous coating composition of the present invention contains: a mixture of emulsion particles and an inorganic oxide and / or a composite of the emulsion particles and an inorganic oxide; a blocked polyisocyanate compound; an organic ultraviolet absorber; a light stabilizer; and a water-soluble organic solvent having a boiling point of 80°C or higher and 140°C or lower. The inorganic oxide contains spherical silica and / or silica having a connection structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a water-based paint composition, a method for producing the same, a substrate with an adhesive layer, a laminate, and a composition set. [Background technology]

[0002] Water-based paints are used because the aqueous dispersions obtained by polymerization tend to exhibit barrier properties, stain resistance, chemical resistance, flame retardancy, heat resistance, weather resistance, scratch resistance, and abrasion resistance when dried at room temperature or under heating. However, when such water-based paints are used in applications requiring transparency, prolonged exposure to the outdoors or ultraviolet light can lead to problems such as loss of transparency, cloudiness, discoloration, whitening, and crazing. Furthermore, when the paint is used as a topcoat, abrasion resistance is required for the topcoat. From the standpoint of abrasion resistance, solvent-based paints are sometimes used. Such solvent-based paints can be relatively easily incorporated with organic ultraviolet absorbers while maintaining the properties of the paint and the resulting coating film.

[0003] However, due to concerns about hygiene at the work site and the burden on the global environment, the use of water-based paints is preferred over solvent-based paints. Furthermore, when solvent-based paints are used on resin substrates, depending on the solvent composition and resin type, there is a concern that the paint may corrode the substrate, impairing its transparency and smoothness. For example, polycarbonate, a transparent resin material, is easily corroded by butyl acetate, a typical organic solvent used in solvent-based paints. For this reason, the use of water-based paints is desirable.

[0004] As a technique for improving the optical properties of water-based paints, Patent Document 1 describes a method of compounding cerium oxide, an inorganic ultraviolet absorber, with emulsion particles for the purpose of imparting weather resistance. Furthermore, Patent Document 2 describes a method of adding a hydroxyphenyltriazine compound, which is an organic ultraviolet absorber, to an acrylic polymer dissolved in an organic solvent. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Special Publication No. 2015-527430 [Patent Document 2] WO2011 / 105382 publication [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] However, while the method described in Patent Document 1 can impart weather resistance, it has the problem that the amount of ultraviolet absorber that can be contained in the coating film is small, making it difficult to achieve both high weather resistance and transparency and a long pot life. Furthermore, while the method described in Patent Document 2 can contain a large amount of UV absorber and exhibits excellent weather resistance, it is based on the premise of application to solvent-based paints, and it is difficult to maintain paint stability when applied to water-based paints. In other words, when using water-based paints, if the formulation stability of the water-based paint is insufficient, precipitation and other issues may occur over time, leading to clogging of painting equipment and the appearance of bumps and cloudiness on the paint film surface. In addition, since the paint must be used up within the time that stability is maintained, it must be mixed in small amounts, which has the problem of significantly affecting the productivity of the painting process.

[0007] This invention has been made in view of the problems of the above-mentioned prior art, and its purpose is to provide a water-based paint composition that can form a coating film with excellent transparency and weather resistance and has excellent pot life, a method for producing the same, a substrate with an adhesive layer, a laminate, and a composition set. [Means for solving the problem]

[0008] As a result of diligent research, the inventors of the present invention have found that the above problems can be solved by providing a predetermined water-based paint composition, a method for producing the same, a substrate with an adhesive layer, a laminate, and a composition set, and have completed the present invention. In other words, the present invention encompasses the following embodiments.

[0009] [1] A water-based paint composition comprising a mixture of emulsion particles and an inorganic oxide, and / or a composite of the emulsion particles and the inorganic oxide, a blocked polyisocyanate, an organic ultraviolet absorber, a light stabilizer, and a water-soluble organic solvent having a boiling point of 80°C or higher and 140°C or lower, wherein the inorganic oxide comprises silica in a spherical and / or linked structure.

[0010] [2] The water-based paint composition according to [1], wherein the average particle size of the mixture and / or the composite is 2 to 2000 nm.

[0011] [3] The water-based paint composition according to [1] or [2], further comprising a surfactant.

[0012] [4] The aqueous paint composition according to any one of [1] to [3], wherein the water-soluble organic solvent comprises isopropanol.

[0013] [5] The water-soluble organic solvent content is 40% by mass or less based on 100% by mass of the water-soluble paint composition, according to any one of [1] to [4].

[0014] [6] The water-based paint composition according to any one of [1] to [5], wherein the organic ultraviolet absorber comprises one or more selected from the group consisting of benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, and benzophenone ultraviolet absorbers.

[0015] [7] The water-based paint composition according to any one of [1] to [6], wherein the light stabilizer comprises a hindered amine compound.

[0016] [8] A substrate with an adhesive layer, comprising a substrate and an adhesive layer disposed on the substrate, wherein the adhesive layer contains a cured product of any of the water-based paint compositions described in [1] to [7].

[0017] [9][8] A substrate with an adhesive layer, and a hard coat layer disposed on the adhesive layer of the substrate, wherein the hard coat layer comprises polymer nanoparticles and a matrix component, the matrix component comprises an inorganic oxide, and the Martens hardness of the polymer nanoparticles is HM G And the Martens hardness HM of the matrix component. H HM H / HM G A laminate that satisfies the relationship >1.

[0018]

[10] The laminate according to [9], wherein the haze value H1 of the substrate with the adhesive layer is greater than the haze value H2 of the laminate.

[0019]

[11] A composition set comprising composition A and composition B, wherein composition A comprises a mixture of emulsion particles and an inorganic oxide, and / or a composite of the emulsion particles and the inorganic oxide, a blocked polyisocyanate, and water, and the inorganic oxide comprises spherical and / or linked silica, and composition B comprises an organic ultraviolet absorber, a light stabilizer, and a water-soluble organic solvent having a boiling point of 80°C or higher and 140°C or lower.

[0020]

[12] The composition set according to

[11] , further comprising a surfactant in composition A and / or composition B.

[0021] A method for producing a water-based paint composition, comprising the step of adding composition B described in

[11] or

[12] to composition A while composition A described in

[13] or

[11] or

[12] has been stirred. [Effects of the Invention]

[0022] According to the present invention, it is possible to provide a water-based paint composition that can form a coating film with excellent transparency and weather resistance and has excellent pot life, as well as a method for producing the same, a substrate with an adhesive layer, a laminate, and a composition set. [Modes for carrying out the invention]

[0023] The following describes in detail embodiments for carrying out the present invention (hereinafter simply referred to as "this embodiment"). It should be noted that the present invention is not limited to the following embodiments, and can be implemented in various modifications within the scope of its gist.

[0024] [Water-based paint composition] The water-based paint composition in this embodiment comprises a mixture of emulsion particles and an inorganic oxide, and / or a composite of the emulsion particles and the inorganic oxide, a blocked polyisocyanate, an organic ultraviolet absorber, a light stabilizer, and a water-soluble organic solvent having a boiling point of 80°C or higher and 140°C or lower, wherein the inorganic oxide contains silica in a spherical and / or linked structure.

[0025] [Emulsion particles] The water-based paint composition of this embodiment includes a mixture of emulsion particles and an inorganic oxide, and / or a composite of said emulsion particles and an inorganic oxide. The emulsion particles according to this embodiment serve to impart flexibility and improve adhesion to the substrate. The emulsion particles are not particularly limited, but for example, they are particles composed of one or more types of materials such as polyurethane, polyester, poly(meth)acrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-(meth)acrylate copolymer, rosin derivative, alcohol adduct of styrene-maleic anhydride copolymer, polycarbonyl compounds such as cellulose resins, and silicone compounds. In this embodiment, the emulsion particles are preferably poly(meth)acrylate.

[0026] The method for preparing the emulsion particles in this embodiment is not particularly limited, but it is preferable that the structure is obtained by polymerizing vinyl monomers in the presence of water and an emulsifier. When the emulsion particles obtained in this way are included in the adhesive layer, they tend to maintain better adhesion to the substrate.

[0027] The vinyl monomer is not particularly limited, but examples include (meth)acrylic acid esters, aromatic vinyl compounds, vinyl cyanide compounds, as well as monomers containing functional groups such as carboxyl group-containing vinyl monomers, hydroxyl group-containing vinyl monomers, epoxy group-containing vinyl monomers, carbonyl group-containing vinyl monomers, and vinyl monomers having secondary and / or tertiary amide groups.

[0028] The above-mentioned (meth)acrylic acid esters are not particularly limited, but examples include alkyl (meth)acrylic acid esters with 1 to 50 carbon atoms in the alkyl group, and (poly)oxyethylene di(meth)acrylates with 1 to 100 ethylene oxide groups.

[0029] The alkyl (meth)acrylate esters mentioned above are not particularly limited, but examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, and dodecyl (meth)acrylate.

[0030] The above-mentioned (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, tetraethylene glycol di(meth)acrylate, and the like.

[0031] Aromatic vinyl compounds are not particularly limited, but examples include styrene and 4-vinyltoluene.

[0032] The vinyl cyanide compound is not particularly limited, but examples include acrylonitrile and methacrylonitrile.

[0033] The carboxyl group-containing vinyl monomer is not particularly limited, but examples include (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, or half-esters of dibasic acids such as itaconic acid, maleic acid, and fumaric acid. When a carboxyl group-containing vinyl monomer is used, carboxyl groups can be introduced into the emulsion particles in this embodiment, improving the stability of the emulsion by creating electrostatic repulsion between the particles, and tending to improve resistance to external dispersion disruption, such as aggregation during stirring. In this case, from the viewpoint of further improving the electrostatic repulsion, some or all of the introduced carboxyl groups can be neutralized with ammonia, amines such as triethylamine and dimethylethanolamine, or bases such as NaOH and KOH.

[0034] The hydroxyl group-containing vinyl monomers mentioned above are not particularly limited, but include, for example, hydroxyalkyl esters of (meth)acrylic acid such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; hydroxyalkyl esters of fumaric acid such as di-2-hydroxyethyl fumarate and mono-2-hydroxyethyl monobutyl fumarate; (poly)oxyethylene mono(meth)acrylate with 1 to 100 allyl alcohol or ethylene oxide groups; (poly)oxypropylene mono(meth)acrylate with 1 to 100 propylene oxide groups; and also "Praxel FM, FA monomers" (trade names for caprolactone addition monomers manufactured by Daicel Chemical Corporation) and other hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids.

[0035] The above-mentioned (poly)oxyethylene (meth)acrylate is not particularly limited, but examples include ethylene glycol (meth)acrylate, ethylene glycol methoxy(meth)acrylate, diethylene glycol (meth)acrylate, diethylene glycol methoxy(meth)acrylate, tetraethylene glycol (meth)acrylate, tetraethylene glycol methoxy(meth)acrylate, and tetraethylene glycol methoxy(meth)acrylate.

[0036] (Poly)oxypropylene (meth)acrylate is not particularly limited, but examples include propylene glycol (meth)acrylate, propylene glycol methoxy(meth)acrylate, dipropylene glycol (meth)acrylate, dipropylene glycol methoxy(meth)acrylate, tetrapropylene glycol (meth)acrylate, tetrapropylene glycol methoxy(meth)acrylate, and tetrapropylene glycol methoxy(meth)acrylate.

[0037] The epoxy group-containing vinyl monomers mentioned above are not particularly limited, but examples include glycidyl group-containing vinyl monomers. The glycidyl group-containing vinyl monomers are not particularly limited, but examples include glycidyl (meth)acrylate, allyl glycidyl ether, allyl dimethyl glycidyl ether, etc.

[0038] The above carbonyl group-containing vinyl monomer is not particularly limited, but examples include diacetone acrylamide.

[0039] Furthermore, while not particularly limited, specific examples of vinyl monomers other than those mentioned above include olefins such as ethylene, propylene, and isobutylene; dienes such as butadiene; haloolefins such as vinyl chloride, vinylidene fluoride chloride, tetrafluoroethylene, and chlorotrifluoroethylene; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl benzoate, pt-butylbenzoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatate, and vinyl laurate; isopropenyl carboxylates such as isopropenyl acetate and isopropenyl propionate; ethyl vinyl ether, isobutyl Examples include vinyl ethers such as vinyl ether and cyclohexyl vinyl ether, allyl esters such as allyl acetate and allyl benzoate, allyl ethers such as allyl ethyl ether and allyl phenyl ether, as well as 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, perfluoromethyl (meth)acrylate, perfluoropropyl (meth)acrylate, perfluoropropylmethyl (meth)acrylate, vinylpyrrolidone, trimethylolpropane tri(meth)acrylate, allyl (meth)acrylate, and combinations thereof.

[0040] The vinyl monomer having the secondary and / or tertiary amide groups is not particularly limited, but examples include N-alkyl or N-alkylene-substituted (meth)acrylamides. Specifically, examples include 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, N-isopropylmethacrylamide, N-propylmethacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide Examples include lylamide, 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, diacetone acrylamide, diacetone methacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide.

[0041] The above silicone compounds are not particularly limited, but include, for example, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane, methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, Examples of hydrolysis condensates include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, vinyltrimethoxylane, vinyltriethoxylan, p-styryltrimethoxysilane, p-styryltriethoxysilane, tetramethoxysilane, and tetraethoxysilane.

[0042] The emulsion particles may contain an emulsifier. The emulsifier is not particularly limited and includes, for example, acidic emulsifiers such as alkylbenzenesulfonic acid (e.g., dodecylbenzenesulfonic acid), alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkyl sulfate, polyoxyethylene alkylaryl sulfate, and polyoxyethylene distyrylphenyl ethersulfonic acid; anionic surfactants such as alkali metal (Li, Na, K, etc.) salts of acidic emulsifiers, ammonium salts of acidic emulsifiers, and fatty acid soaps; cationic surfactants of the quaternary ammonium salt, pyridinium salt, or imidazolinium salt type such as alkyltrimethylammonium bromide, alkylpyridinium bromide, and imidazolinium laurate; nonionic surfactants such as polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene oxypropylene poroc copolymer, and polyoxyethylene distyrylphenyl ether, as well as reactive emulsifiers having radically polymerizable double bonds.

[0043] The reactive emulsifier having a radically polymerizable double bond is not particularly limited, but examples include: Eleminor® JS-2 (trade name, manufactured by Sanyo Chemical Industries, Ltd.), Latemul® S-120, S-180A or S-180 (trade name, manufactured by Kao Corporation), Aqualon® HS-10, KH-1025, RN-10, RN-20, RN30, RN50 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekarya Soap® SE1025, SR-1 Examples include 025, NE-20, NE-30, NE-40 (product names, manufactured by Asahi Denka Kogyo Co., Ltd.), ammonium salts of p-styrenesulfonic acid, sodium salts of p-styrenesulfonic acid, potassium salts of p-styrenesulfonic acid, alkyl sulfonic acid (meth)acrylates such as 2-sulfoethyl acrylate, methylpropanesulfonic acid (meth)acrylamide, ammonium salts of allylsulfonic acid, sodium salts of allylsulfonic acid, and potassium salts of allylsulfonic acid.

[0044] The emulsion particles may contain a polymerization initiator. Known polymerization initiators can be used, and are not particularly limited; examples include water-soluble polymerization initiators such as ammonium persulfate, sodium persulfate, and potassium persulfate.

[0045] In the paint composition, it is preferable that the emulsion particles have a functional group (e) having a secondary amide group and / or a tertiary amide group. The functional group (e) having a secondary amide group and / or a tertiary amide group is not particularly limited, but for example, those exemplified as the functional group (e) having a secondary amide group and / or a tertiary amide group in the paint composition (I) described later can be appropriately adopted.

[0046] In the paint composition, it is preferable that the emulsion particles have a functional group having a hydroxyl group. The functional group having a hydroxyl group is not particularly limited, but for example, those exemplified as functional groups having a hydroxyl group in the paint composition (I) described later can be appropriately adopted.

[0047] [Average particle size of emulsion particles] In this embodiment, the average particle diameter of the emulsion particles is determined from the particle size observed by cross-sectional SEM or dynamic light scattering. The average particle diameter of the emulsion particles is not particularly limited, but is preferably 300 nm or less. By adjusting the average particle diameter of the emulsion particles to the above range, it is possible to form an adhesive layer with even better adhesion by improving the contact area with the substrate. Furthermore, from the viewpoint of improving the transparency of the resulting adhesive layer, the average particle diameter is more preferably 200 nm or less, and from the viewpoint of good storage stability of the raw material composition of the adhesive layer, it is preferably 10 nm or more, and more preferably 50 nm or more. The method for measuring the average particle diameter of the emulsion particles can be measured by the method described in the examples below.

[0048] [Inorganic oxides] In this embodiment, the inorganic oxide (the inorganic oxide contained in the mixture with emulsion particles, and the inorganic oxide contained in the composite with emulsion particles, are also referred to as "inorganic oxide (I)") includes spherical and / or linked silica from the viewpoint of improving adhesion through interaction with the hard coat layer. The spherical silica is not particularly limited, and commercially available products can be used. In this embodiment, the inorganic oxide contained in the mixture with emulsion particles and the inorganic oxide contained in the composite with emulsion particles may be the same or different. Furthermore, inorganic oxide (I) may be the same as or different from inorganic oxide (D) described later. As inorganic oxide (I), for example, Snowtex® C and Snowtex® OS manufactured by Nissan Chemical Industries, Ltd. are preferably used. Furthermore, the linked silica is not particularly limited, and commercially available products can be used; for example, Snowtex® PS-SO (water-dispersible colloidal silica) manufactured by Nissan Chemical Industries, Ltd. is preferably used.

[0049] Furthermore, in this embodiment, in addition to the spherical and / or linked silica structure, other inorganic oxides different from the spherical or linked silica structure in this embodiment may be included. The other inorganic oxides are not particularly limited, but examples include oxides of silicon, aluminum, titanium, zirconium, zinc, cerium, tin, indium, gallium, germanium, antimony, molybdenum, niobium, magnesium, bismuth, cobalt, and copper. These may be individual elements or mixtures. From the viewpoint of improving optical properties, it is preferable that the other inorganic oxides include at least one selected from the group consisting of cerium oxide, zinc oxide, aluminum oxide, zirconium oxide, niobium oxide, bismuth oxide, cobalt oxide, copper oxide, tin oxide, and titanium oxide.

[0050] In this embodiment, the primary average particle size of the inorganic oxide is preferably 2 nm or more from the viewpoint of good storage stability of the water-based coating composition. From the viewpoint of good transparency of the laminate as a whole, it is preferably 150 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less. Therefore, the primary average 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 even more preferably 4 nm or more and 50 nm or less. The primary average particle size can be measured by the method described in the examples below.

[0051] While the inorganic oxide is not particularly limited, silica particles, such as dry silica or colloidal silica, are preferred from the viewpoint of interaction with the hydrolyzable silicon compound (b) described later and adhesion to the hard coat layer. Colloidal silica is preferred because it can also be used in the form of an aqueous dispersion.

[0052] [Colloidal silica, which is preferably used as an inorganic oxide] The acidic colloidal silica with water as the dispersion solvent, which is preferably used in this embodiment, is not particularly limited, but can be prepared by the sol-gel method or a commercially available product can be used. When preparing by the sol-gel method, refer to Werner Stober et al; J. Colloid and Interface Sci., 26, 62-69 (1968), Rickey D. Badley et al; Lang muir 6, 792-801 (1990), Journal of the Color Materials Association, 61[9] 488-493 (1988), etc.

[0053] Examples of commercially available products include Snowtex®-O, Snowtex-OS, Snowtex-OXS, Snowtex-O-40, Snowtex-OL, Snowtex-OYL, Snowtex-OUP, Snowtex-PS-SO, Snowtex-PS-MO, Snowtex-AK-XS, Snowtex-AK, Snowtex-AK-L, Snowtex-AK-YL, Snowtex-AK-PS-S (product names, manufactured by Nissan Chemical Industries, Ltd.), Adelite® AT-20Q (product name, manufactured by Asahi Denka Kogyo Co., Ltd.), Crevosol 20H12, and Crevosol 30CAL25 (product names, manufactured by Clariant Japan Co., Ltd.).

[0054] Furthermore, basic colloidal silica includes silica stabilized by the addition of alkali metal ions, ammonium ions, and amines, and is not particularly limited, but for example, Snowtex (registered trademark)-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 (trademark). Examples include Adelite® AT-20 (product name, manufactured by Nissan Chemical Industries, Ltd.), Adelite® AT-30, Adelite AT-20N, Adelite AT-30N, Adelite AT-20A, Adelite AT-30A, Adelite AT-40, Adelite AT-50 (product name, manufactured by Asahi Denka Kogyo Co., Ltd.), Crevozol 30R9, Crevozol 30R50, Crevozol 50R50 (product name, manufactured by Clariant Japan Co., Ltd.), Rudox® HS-40, Rudox HS-30, Rudox LS, Rudox AS-30, Rudox SM-AS, Rudox AM, Rudox HSA, and Rudox SM (product name, manufactured by DuPont).

[0055] Furthermore, while there are no particular limitations on colloidal silica using a water-soluble solvent as the dispersion medium, examples include MA-ST-M (methanol dispersion type with particle size of 20-25 nm), IPA-ST (isopropyl alcohol dispersion type with particle size of 10-15 nm), EG-ST (ethylene glycol dispersion type with particle size of 10-15 nm), EGST-ZL (ethylene glycol dispersion type with particle size of 70-100 nm), NPC-ST (ethylene glycol monopropyl ether dispersion type with particle size of 10-15 nm), and TOL-ST (toluene dispersion type with particle size of 10-15 nm) (product names), all manufactured by Nissan Chemical Industries, Ltd.

[0056] Dry silica particles are not particularly limited, but examples include AEROSIL® manufactured by Nippon Aerosil Co., Ltd. and Rheoroseal® manufactured by Tokuyama Corporation.

[0057] Silica particles may contain inorganic bases (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia) or organic bases (such as tetramethylammonium and triethylamine) as stabilizers.

[0058] [Shape of inorganic oxides] The shape of the inorganic oxide and other inorganic oxides in this embodiment is not particularly limited, but examples include spherical, angular, polyhedral, elliptical, flattened, linear, bead-like, and chain-like shapes. The water-based coating composition of this embodiment may contain one or more of these inorganic oxides or other inorganic oxides having these shapes. In this embodiment, from the viewpoint of hardness and transparency of the laminate, it is preferable that the inorganic oxide has a spherical and / or bead-like or chain-like linked structure. Furthermore, from the viewpoint of adhesion of the laminate, it is even more preferable that the inorganic oxide has a bead-like or chain-like linked structure. Here, bead-like refers to a structure in which spherical primary particles are linked in a bead-like manner, and chain-like refers to a structure in which spherical primary particles are linked in a chain-like manner. In this embodiment, it is particularly preferable that the inorganic oxide is silica having a spherical and / or linked structure.

[0059] [Composite of emulsion particles and inorganic oxides] The inorganic oxide (I) may be pre-compounded with emulsion particles. The complex of emulsion particles and inorganic oxide can be obtained, for example, by polymerizing the vinyl monomer constituting the emulsion particles in the presence of the inorganic oxide. From the viewpoint of interaction with the inorganic oxide, it is preferable that the vinyl monomer contains the vinyl monomer having secondary and / or tertiary amide groups described above. The complex can preferably be formed by hydrogen bonding between the hydroxyl group of the inorganic oxide and the secondary and / or tertiary amide groups.

[0060] In this embodiment, it is preferable that at least one average particle diameter selected from the group consisting of inorganic oxides, emulsion particles, and composites of inorganic oxides and emulsion particles is between 2 nm and 4000 nm from the viewpoint of transparency and adhesion. The above average particle diameter can be measured by the method described in the examples later. Here, the adhesive layer in this embodiment can be obtained by coating a substrate with a water-based paint composition and forming a coating film by heat treatment, ultraviolet irradiation, infrared irradiation, etc. Therefore, if the average particle diameters of inorganic oxides, emulsion particles, and composites of inorganic oxides and emulsion particles in the water-based paint composition are known, they can be used to determine each average particle diameter in the adhesive layer by assuming that they closely match the average particle diameters of inorganic oxides, emulsion particles, and composites of inorganic oxides and emulsion particles in the corresponding adhesive layer.

[0061] In this embodiment, the average particle size of the mixture of emulsion particles and inorganic oxide and / or the composite of emulsion particles and inorganic oxide is more preferably 2 nm or more from the viewpoint of good storage stability of the raw material composition of the adhesive layer, preferably 2000 nm or less from the viewpoint of transparency, more preferably 1000 nm or less, and even more preferably 500 nm or less. The average particle size described above can be measured by the method described in the examples below, and can be adjusted to the range mentioned above by, for example, the mass ratio of emulsion particles to inorganic oxides or the solid content concentration. Furthermore, in this specification, the average particle diameter of a mixture of emulsion particles and an inorganic oxide is defined as the average particle diameter of the mixture being 2 nm or more and 2000 nm or less when both the average particle diameter of the emulsion particles and the primary average particle diameter of the inorganic oxide are 2 nm or more and 2000 nm or less.

[0062] From the viewpoint of adhesion, the mass ratio of emulsion particles to inorganic oxide is preferably 1:0.1 to 1:10, more preferably 1:0.3 to 1:5, and even more preferably 1:0.5 to 1:2. Here, the adhesive layer in this embodiment can be obtained by coating a substrate with a water-based paint composition and forming a coating film by heat treatment, ultraviolet irradiation, infrared irradiation, etc. Therefore, if the mass ratio of emulsion particles to inorganic oxide in the water-based paint composition is known, the mass ratio in the adhesive layer can be determined by assuming that this mass ratio closely matches the mass ratio of emulsion particles to inorganic oxide in the corresponding adhesive layer.

[0063] The total content of the mixture of emulsion particles and inorganic oxides, and the composite of emulsion particles and inorganic oxides, is preferably 0.1% to 20% by mass, more preferably 1% to 15% by mass, and even more preferably 3% to 10% by mass, based on solid content, per 100% by mass of the water-based paint composition.

[0064] [Blocked polyisocyanate] The water-based coating composition of this embodiment contains, from the viewpoint of improving adhesion between the adhesive layer and the substrate, a blocked polyisocyanate obtained by reacting the isocyanate group contained in an isocyanate compound with a blocking agent, as an isocyanate-based crosslinking agent. When blocked polyisocyanates are used as isocyanate-based crosslinking agents together with emulsion particles polymerized from monomers containing hydroxyl group-containing vinyl monomers, the hydroxyl groups of the emulsion particles and the isocyanate groups form urethane bonds during coating film formation. As a result, the resulting coating films tend to have improved adhesion and strength.

[0065] The isocyanate compound used as a raw material for blocked polyisocyanates is a compound having at least one isocyanate group per molecule. The isocyanate compound may also be a compound having two or more isocyanate groups per molecule.

[0066] Such isocyanate compounds are not particularly limited, but include, for example, aliphatic diisocyanates such as 1,4-tetramethylene diisocyanate, ethyl(2,6-diisocyanate)hexanoate, 1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, and 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate; 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, and 2-isocyanate ethyl(2,6-di) Aliphatic triisocyanates such as (isocyanate) hexanoates; alicyclic diisocyanates such as 1,3- or 1,4-bis(isocyanate methylcyclohexane), 1,3- or 1,4-diisocyanate cyclohexane, 3,5,5-trimethyl(3-isocyanate methyl)cyclohexyl isocyanate, and dicyclohexylmethane-4,4'-diisocyanate, 2,5- or 2,6-diisocyanate methylnorbornane; alicyclic triisocyanates such as 2,5- or 2,6-diisocyanate methyl-2-isosinate propylnorbornane Isocyanates; aralkylene diisocyanates such as m-xylylene diisocyanate and α,α,α'α'-tetramethyl-m-xylylene diisocyanate; m- or p-phenylene diisocyanate, torylene-2,4- or 2,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4'-diisocyanate, 4,4'-diisocyanate-3,3'-dimethyldiphenyl, 3-methyl-diphenylmethane-4,4'-diisocyanate, and diphenyl Aromatic diisocyanates such as ether-4,4'-diisocyanate; aromatic triisocyanates such as triphenylmethane triisocyanate and tris(isocyanatephenyl)thiophosphate; and diisocyanates or polyisocyanates having a uretdione structure obtained by cyclodimerizing the isocyanate groups of the above diisocyanates or triisocyanates; polyisocyanates having an isocyanurate structure obtained by cyclotrimerizing the isocyanate groups of the above diisocyanates or triisocyanates;Examples include polyisocyanates having a biuret structure obtained by reacting the above-mentioned diisocyanate or triisocyanate with water; polyisocyanates having an oxadiazinetrione structure obtained by reacting the above-mentioned diisocyanate or triisocyanate with carbon dioxide; polyisocyanates having an allophanate structure obtained by reacting the above-mentioned diisocyanate or triisocyanate with various alcohols; and polyisocyanates obtained by reacting the above-mentioned diisocyanate or triisocyanate with compounds containing active hydrogen, such as polyhydroxy compounds, polycarboxy compounds, and polyamine compounds. Furthermore, the isocyanate compound may contain an alkoxysilane moiety and / or a siloxane moiety within the molecule. Examples of such isocyanate compounds include hydrolysis condensates of 3-isocyanate-propyltriethoxysilane and 3-isocyanate-propyltriethoxysilane. These can be used individually or in combination of two or more.

[0067] The blocking agents used as raw materials for blocked polyisocyanates are not particularly limited, but examples include oxime compounds, alcohol compounds, acid amide compounds, acid imide compounds, phenol compounds, amine compounds, active methylene compounds, imidazole compounds, and pyrazole compounds. These blocking agents can be used individually or in appropriate combinations of two or more.

[0068] Examples of oxime compounds include, but are not limited to, formaldehyde oxime, acetaldehyde oxime, acetooxime, methyl ethyl ketoxime, 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. Examples of acid amide compounds include, but are not limited to, acetanilide, acetic acid amide, ε-caprolactam, δ-valerolactam, and γ-butyrolactam. Examples of acid imide compounds include, but are not limited to, succinimide and maleimide. Examples of phenolic compounds include, but are not limited to, phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrene-phenol, and hydroxybenzoic acid esters. 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.

[0069] The isocyanate compound used as the raw material for block polyisocyanates is more preferably an aliphatic or alicyclic diisocyanate or triisocyanate, aralkylene diisocyanate, or isocyanate derived therefrom, in terms of weather resistance and pot life. Block polyisocyanates are even more preferably those having structures such as burette, isocyanurate, urethane, uretdione, and allophanate within their molecule. Those with a burette structure often exhibit excellent adhesion. Those with an isocyanurate structure often exhibit excellent weather resistance. Those with a urethane structure using an alcohol compound with a long side chain often exhibit excellent elasticity and extensibility. Those with a uretdione or allophanate structure often exhibit low viscosity.

[0070] From the viewpoint of water dispersibility, it is preferable that the blocked polyisocyanate is a water-dispersible blocked polyisocyanate obtained by reacting an isocyanate compound having two or more isocyanate groups in one molecule with a hydroxyl group-containing hydrophilic compound having nonionic and / or ionic hydrophilic groups in an isocyanate group / hydroxyl group equivalent ratio in the range of 1.05 to 1000, and further reacting it with a blocking agent. More preferably, the isocyanate group / hydroxyl group equivalent ratio is in the range of 2 to 200, and even more preferably in the range of 4 to 100. An isocyanate group / hydroxyl group equivalent ratio of 1.05 or higher is preferable because the isocyanate group content in the hydrophilic blocked polyisocyanate is above a predetermined level, resulting in more crosslinking points in the water-based paint composition, which leads to an increase in curing speed or an improvement in the strength of the adhesive layer such as the paint film. An equivalent ratio of 1000 or lower is preferable because it exhibits hydrophilicity. The water-dispersible blocked polyisocyanate is not particularly limited, and commercially available water-dispersible blocked polyisocyanates can be used. For example, WS50-30W (product name) and WM44L-70G (product name) manufactured by Asahi Kasei Corporation are preferably used as they possess the above-described characteristics.

[0071] As the water-dispersible block polyisocyanate, any one can be used without particular limitation as long as it is obtained by introducing a hydrophilic group by a conventionally known method. For example, a reaction product of a compound (m) represented by the general formula R 1 O(R 2 O) n -H (where R 1 represents an alkyl group having 1 to 30 carbon atoms or a group having two or more aromatic rings, and R 2 represents an alkylene group having 1 to 5 carbon atoms. n is an integer of 2 to 250), an isocyanate compound, and a blocking agent; a reaction product of a vinyl polymer having a hydrophilic group and a hydroxyl group, an isocyanate compound, and a blocking agent; a reaction product of an emulsifier obtained by reacting an alkoxypolyalkylene glycol with a dialkanolamine, an isocyanate compound, and a blocking agent, etc. can be mentioned. Among these, the reaction product of the compound (m), an isocyanate compound, and a blocking agent, and the reaction product of a vinyl polymer having a hydrophilic group and a hydroxyl group, an isocyanate compound, and a blocking agent are particularly preferable because of their excellent water dispersibility.

[0072] Examples of compound (m) include alkoxy polyalkylene glycols such as polymethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monopropyl ether, polyethylene glycol monolauryl ether, polyoxyethylene-oxypropylene (random and / or blocked) glycol monomethyl ether, and polyoxyethylene-oxytetramethylene (random and / or blocked) glycol polybutylene glycol monomethyl ether, as well as nonionic surfactants having two or more aromatic rings, such as a (mono-penta) styrene-modified phenyl group, a mono (or di,tri) styrene-methyl-phenyl group, a tribenzylphenyl group, and a β-naphthyl group. These compounds (m) can be used individually or in appropriate combinations of two or more. Among these, polyethylene glycol monomethyl ether and nonionic surfactants having a (mono-penta) styrene-modified phenyl group are preferred in terms of self-emulsifying ability and pot life. These compounds (m) preferably have a molecular weight in the range of 100 to 10000, and more preferably in the range of 300 to 5000.

[0073] Examples of hydrophilic groups in vinyl polymers having hydrophilic and hydroxyl groups include various known anionic groups, cationic groups, and nonionic groups, with nonionic groups being preferred. The nonionic group significantly extends the pot life of the water-based paint composition, and the particle size of the oil droplets of the blocked polyisocyanate becomes smaller, which tends to further improve the water resistance of the formed coating film. Specific examples of vinyl polymers having hydrophilic and hydroxyl groups include, for example, acrylic polymers, fluoroolefin polymers, vinyl ester polymers, aromatic vinyl polymers, and polyolefin polymers. Among these, acrylic polymers are preferred from the viewpoint of weather resistance of the resulting coating film. Polymerization methods for obtaining acrylic polymers suitable as vinyl polymers having hydrophilic and hydroxyl groups are not particularly limited, but examples include suspension polymerization, emulsion polymerization, or solution polymerization. Preferably, the acrylic polymer is obtained by solution polymerization of an ethylenically unsaturated monomer (i) having hydrophilic groups and an ethylenically unsaturated monomer (ii) having hydroxyl groups, and other ethylenically unsaturated monomers (iii) copolymerizable with these may also be used as needed.

[0074] Examples of hydrophilic ethylenically unsaturated monomers (i) include alkoxy polyalkylene glycol (meth)acrylates such as methoxypolyethylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, and butoxypolyethylene glycol (meth)acrylate; polyalkylene glycol di(meth)acrylates such as polyethylene glycol di(meth)acrylate; (meth)acrylamide monomers; and anionic vinyl monomers. In addition, ethylenically unsaturated monomers that have both hydrophilic and hydroxyl groups in their molecules, such as polyalkylene glycol (meth)acrylates, can also be used. These may be used individually or in combination of two or more.

[0075] Other ethylenically unsaturated monomers (iii) copolymerizable with these include, for example, (meth)acrylic acid esters, aromatic vinyl compounds, vinyl cyanides, carbonyl group-containing vinyl monomers, olefins, dienes, haloolefins, vinyl ethers, and allyl esters. These may be used individually or in combination of two or more.

[0076] The vinyl polymer containing hydrophilic groups and hydroxyl groups preferably has a mass-average molecular weight (GPC method on a polystyrene basis) in the range of 2,000 to 100,000, and more preferably in the range of 3,000 to 50,000.

[0077] In a water-based paint composition, the content of block polyisocyanate relative to emulsion particles polymerized from a monomer containing a hydroxyl group-containing vinyl monomer is preferably such that the ratio of moles of hydroxyl groups in the emulsion particles to moles of isocyanate groups in the block polyisocyanate (X = moles of isocyanate groups / moles of hydroxyl groups) is 0.02 or higher. X is more preferably 0.1 or higher from the viewpoint of adhesion between the formed coating film and the substrate, and even more preferably 0.15 or higher from the viewpoint of abrasion resistance of the coating film. Furthermore, from the viewpoint of the stability of the water-based paint composition (resistance to gelation and high viscosity), X is preferably 10 or less, and more preferably 5 or less from the viewpoint of a low water contact angle and high transparency (low haze) of the formed coating film. The ratio (X) may be 0.02 to 10, 0.02 to 5, 0.1 to 10, 0.1 to 5, 0.15 to 10, or 0.15 to 5.

[0078] In one embodiment, the mass ratio of block polyisocyanate to emulsion particles and inorganic oxide (mass of block polyisocyanate / total mass of emulsion particles and inorganic oxide) is preferably 0.001 or higher, more preferably 0.01 or higher, and even more preferably 0.05 or higher from the viewpoint of adhesion. Furthermore, from the viewpoint of transparency, this mass ratio is preferably 1.0 or lower, more preferably 0.7 or lower, and even more preferably 0.5 or lower.

[0079] Commercially available water-dispersible block polyisocyanates can also be used. For example, WS50-30W (product name) and WM44L-70G (product name) manufactured by Asahi Kasei Corporation are preferred as they possess the characteristics described above.

[0080] The aforementioned blocked polyisocyanate may be partially or entirely reacted with a polyol to form a urethane compound.

[0081] [Organic UV absorbers] The water-based coating composition of this embodiment includes an organic ultraviolet absorber from the viewpoint of ensuring optical properties.

[0082] Specific examples of organic UV absorbers are not limited to, but include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-Dihydroxy-4,4'-Dimethoxybenzophenone (BASF brand name "UVINUL® 3049"), 2,2',4,4'-Tetrahydroxybenzophenone (BASF brand name "UVINUL® 3050"), 4-Dodecyloxy-2-Hydroxybenzophenone, 5-Benzoyl-2,4-Dihydroxybenzophenone, 2-Hydroxy-4-Methoxy-2'-Carboxybenzophenone, 2-Hydroxy-4-Stearyloxybenzophenone, and 4,6-Dibenzoyl Benzophenone-based UV absorbers such as resortinol; 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3,5-di-tert-octylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'- Bis(α,α'-dimethylbenzyl)phenyl]benzotriazole), methyl-3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate and polyethylene glycol (molecular weight 300) condensate (BASF trade name "TINUVIN® 1130"), isooctyl-3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionate (BASF trade name "TINUVIN 384"),2-(3-dodecyl-5-methyl-2-hydroxyphenyl)benzotriazole (BASF brand name "TINUVIN571"), 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-[2'-hydroxy-3'-(3",4",5",6"-tetrahydrophthalimidomethyl)-5'-methylphenyl]benzotriazole, 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 (BASF trade name "TINUVIN900"), benzenepropanoic acid, mixture of 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy,C7-9-side chain and linear alkyl ester (BASF trade name "TINUVIN384-2"), TINUVIN326, TINUVIN327, TINUVIN109, TINUVIN970, TINUVIN328, TINUVIN171, TINUVIN970, TINUVIN PS, TINUVIN Benzotriazole-based UV absorbers such as P, TINUVIN99-2, and TINVIN928 (trade names, manufactured by BASF); 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) (Tylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bisbutyloxyphenyl)-1,3,5-triazine (BASF brand name "TINUVIN 460"), 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (BASF brand name "TINUVIN 479"),Triazine-based UV absorbers such as a mixture of 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 (BASF trade name "TINUVIN400"), TINUVIN405, TINUVIN477, and TINUVIN1600 (trade name, BASF); malonic acid ester-based UV absorbers such as HOSTAVIN® PR25, HOSTAVIN B-CAP, and HOSTAVIN VSU (trade name, Clariant); HOSTAVIN3206 LIQ, HOSTAVINVSU P, and HOSTAVIN3212 Anilide-based UV absorbers such as LIQ (trade name, manufactured by Clariant); salicylate-based UV absorbers such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropanolphenyl salicylate; ethyl-2-cyano-3,3-diphenyl acrylate (trade name "UVINUL3035" by BASF), (2-ethylhexyl)-2-cyano-3,3-diphenyl acrylate (trade name "UVINUL3039" by BASF), and 1,3-bis((2'-cyano-3',3'-diphenylacryloyl)oxy)-2,2-bis-(((2'-cyano-3',3'-diphenylacryloyl)oxy)-2,2-bis-(((2'-cyano Cyanoacrylate-based UV absorbers such as no-3',3'-diphenylacryloyl)oxy)methyl)propane (BASF brand name "UVINUL3030"); 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-5-acryloxybenzophenone, 2-hydroxy-5-methacryloxybenzophenone, 2-hydroxy-4-(acryloxy-ethoxy)benzophenone, 2-hydroxy-4-(methacryloxy-ethoxy)benzophenone, 2-hydroxy-4-(methacryloxy-diethoxy)benzophenone, 2-hydroxy-4-(acryloxy-triethoxy)benzophenone,and 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole (product name "RUVA-93" manufactured by Otsuka Chemical Co., Ltd.), 2-(2'-hydroxy-5'-methacryloxyethyl-3-tert-butylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-methacryloxypropyl-3-tert-butylphenyl)-5-chloro-2H-benzotriazole, and 3-methacryloyl-2-hydroxypropyl-3-[3'-(2''-benzotriazoli Examples include radical polymerizable ultraviolet absorbers having a radically polymerizable double bond in the molecule, such as (-4-hydroxy-5-tert-butyl)phenylpropionate (trade name "CGL-104" manufactured by Ciba-Geigy Japan Co., Ltd.); ultraviolet absorbing polymers such as UV-G101, UV-G301, UV-G137, UV-G12, and UV-G13 (trade names manufactured by Nippon Shokubai Co., Ltd.); and ultraviolet absorbers that react with silanol groups, isocyanate groups, epoxy groups, semicarbazide groups, and hydrazide groups. These may be used individually or in combination of two or more. Among these, from the viewpoint of UV absorption capacity, the organic UV absorber preferably contains at least one selected from the group consisting of benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, malonic acid ester UV absorbers, anilide UV absorbers, salicylate UV absorbers, and cyanoacrylate UV absorbers, and more preferably contains at least one selected from the group consisting of benzotriazole UV absorbers, benzophenone UV absorbers, and triazine UV absorbers. It is even more preferable that the organic UV absorber has a hydroxyphenyl group.

[0083] From the viewpoint of optical properties, the content of organic ultraviolet absorbers in the water-based paint composition is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 4 parts by mass or more, per 100 parts by mass of the total of the solid content of the emulsion particles and inorganic oxides, or per 100 parts by mass of the solid content of the composite. Furthermore, from the viewpoint of solubility, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the total of the solid content of the emulsion particles and inorganic oxides, or per 100 parts by mass of the solid content of the composite.

[0084] [Light stabilizer] The water-based coating composition of this embodiment includes a light stabilizer from the viewpoint of ensuring optical properties.

[0085] The light stabilizer is not particularly limited, but it is preferable to include, for example, a hindered amine compound. Specifically, hindered amine compounds include 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, and 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 trade name "TINUVIN® 292"), bis(1-octoxy-2,2,6,6-tetramethyl- 4-Piperidyl)sebacate, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) decandioate, reaction product of 1,1-dimethylethyl hydroperoxide and octane (BASF trade name "TINUVIN123"), TINUVIN144, 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)amino]-6-(2-hydroxy Hindered amine compounds such as ethylamine-1,3,5-triazine (BASF trade name "TINUVIN 152"), TINUVIN 249, a mixture of bis(1,2,2,6,6-pentamethylpiperidine-4-yl) sebacate and methyl(1,2,2,6,6-pentamethylpiperidine-4-yl) sebacate (BASF trade name "TINUVIN 292"), and TINUVIN 5100 (trade name, 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 Examples include radically polymerizable hindered amine compounds such as -piperidyl methacrylate and 4-cyano-1,2,2,6,6-pentamethyl-4-piperidyl methacrylate; and photostable hindered amine polymers such as U-double® E-133, U-double E-135, U-double S-2000, U-double S-2834, U-double S-2840, U-double S-2818, and U-double S-2860 (trade names, manufactured by Nippon Shokubai Co., Ltd.). In this embodiment, the hindered amine compounds also include hindered amine polymers.

[0086] From the viewpoint of optical properties, the content of the light stabilizer in the water-based paint composition is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, and even more preferably 0.5 parts by mass or more, based on 100 parts by mass of the total of the solid content of the emulsion particles and inorganic oxides, or 100 parts by mass of the solid content of the composite. Furthermore, from the viewpoint of paint stability, the content is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, based on 100 parts by mass of the total of the solid content of the emulsion particles and inorganic oxides, or 100 parts by mass of the solid content of the composite.

[0087] [solvent] The water-based paint composition of this embodiment contains, as a solvent, water and a water-soluble organic solvent having a boiling point of 80°C to 140°C. A water-based paint composition refers to a state in which water is the most abundant component of the solvent in the paint composition. In a water-based paint composition, the amount of water is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more, based on 100% by mass of the solvent. Furthermore, the amount of water is preferably 95% or less, more preferably 90% or less, and even more preferably 85% or less, based on 100% by mass of the solvent. By setting the mass percentage of water in the solvent to above the lower limit, it tends to contribute to the stabilization of the mixture of emulsion particles and inorganic oxides, and / or the composite of said emulsion particles and inorganic oxides, as well as the blocked polyisocyanate in the water-based paint composition, while also reducing the environmental burden. Furthermore, by setting the mass percentage of water in the solvent to below the upper limit, it tends to contribute to the stabilization of the organic ultraviolet absorber and light stabilizer in the water-based paint composition.

[0088] The water-based paint composition of this embodiment may contain an organic solvent different from the water-soluble organic solvent with a boiling point of 80°C to 140°C, depending on its purpose and application, as long as it achieves the effects of the present invention. Such an organic solvent is preferably one that does not have functional groups that react with hydroxyl groups and isocyanate groups, and is preferably well compatible with the polyisocyanate composition. Such an organic solvent is not particularly limited, but may be any solvent commonly used as a paint solvent, such as ester compounds, ether compounds, ketone compounds, aromatic compounds, ethylene glycol dialkyl ether compounds, polyethylene glycol dicarboxylate compounds, and hydrocarbon solvents.

[0089] <Water-soluble organic solvents> The coating composition of this embodiment contains, as a solvent, water and a water-soluble organic solvent having a boiling point of 80°C to 140°C. The boiling point of the water-soluble organic solvent being within this range allows for proper stability of the water-based coating composition, which contains a mixture of hydrophilic emulsion particles and inorganic oxides, and / or a composite of said emulsion particles and inorganic oxides, as well as block polyisocyanate and hydrophobic organic ultraviolet absorbers and light stabilizers. Furthermore, when applied to a resin substrate such as polycarbonate, corrosion by the solvent in the water-based coating composition can be prevented.

[0090] The water-soluble organic solvent is not particularly limited as long as it has a boiling point within the above range and dissolves in water at a concentration of 10% or more. Examples of such water-soluble organic solvents include alcohol compounds, glycol ether compounds, ether compounds, ketone compounds, and nitrile compounds, which have a boiling point in the range of 80°C to 140°C and dissolve in water at a concentration of 10% or more.

[0091] Specific examples of alcohol compounds include, but are not limited to, isopropanol, 1-propanol, 2-butanol, 2-methyl-2-propanol, and 2-methyl-1-propanol. Specific examples of glycol ether compounds, though not particularly limited, include 2-methoxy-1-propanol, 1-methoxy-2-propanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl cellosolve, ethyl cellosolve, and dimethyl cellosolve. Specific examples of ether compounds, though not limited to them, include 2-methyltetrahydrofuran and dioxane. Specific examples of ketone compounds, though not limited to them, include methyl propyl ketone and methyl isobutyl ketone. Specific examples of nitrile compounds, though not limited to them, include acetonitrile. These water-soluble organic solvents can be used individually or in appropriate combinations of two or more.

[0092] From the viewpoint of appropriately maintaining the stability of a mixture of hydrophilic emulsion particles and inorganic oxides, and / or a composite of said emulsion particles and inorganic oxides, as well as block polyisocyanates, and hydrophobic organic ultraviolet absorbers and light stabilizers in a water-based paint composition, it is necessary to maintain appropriate polarity in the mixed system of water and water-soluble organic solvents. For this reason, the solubility of the water-soluble organic solvent in water is preferably 15% or more, more preferably 20% or more, and even more preferably 50% or more.

[0093] From the viewpoint of reducing the environmental burden during solvent removal, it is preferable that the water-soluble organic solvent contains an alcohol compound, and it is even more preferable that it contains isopropanol, as this allows for a more favorable maintenance of appropriate polarity in the mixed system of water and the water-soluble organic solvent, and thus better maintains stability.

[0094] In a mixed system of water and a water-soluble organic solvent, the content of the water-soluble organic solvent is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, based on 100% by mass of the water-based paint composition, in order to maintain appropriate polarity more favorably and to further preserve stability. The lower limit is not particularly limited, but for example, it may be 5% by mass or more, or 10% by mass or more.

[0095] [Surfactants] The water-based paint composition of this embodiment may further contain a surfactant to further enhance paint stability. The surfactant is not particularly limited, but specifically, examples include known anionic surfactants, cationic surfactants, amphoteric surfactants, etc. Examples of such surfactants include sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium alkyldiphenyl ether disulfonate, sodium alkanesulfonate, sodium cholate, and sodium deoxycholate. Among these, sodium dodecylbenzenesulfonate is preferred.

[0096] The surfactant content is not particularly limited, but is 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the total of the solid content of the emulsion particles and the inorganic oxide, or per 100 parts by mass of the solid content of the composite.

[0097] [Other additives] The water-based coating composition of this embodiment may contain various additives, depending on the purpose and application, including compounds and polymers not previously mentioned, such as curing accelerators, antioxidants, leveling agents, plasticizers, crosslinking agents, tackifiers, pigments, dyes, fillers, anti-aging agents, conductive materials, release modifiers, softeners, flame retardants, and antioxidants. These additives can be used individually or in appropriate combinations of two or more.

[0098] The curing accelerator catalyst is not particularly limited, but examples include tin compounds, zinc compounds, titanium compounds, cobalt compounds, bismuth compounds, zirconium compounds, and amine compounds. Examples of tin compounds include dibutyltin dilaurate, dibutyltin diacetate, dioctyltin dilaurate, dimethyltin dineodecanoate, and bis(2-ethylhexanoate)tin. Examples of zinc compounds include zinc 2-ethylhexanoate and zinc naphthenate. Examples of titanium compounds include titanium 2-ethylhexanoate and titanium diisopropoxybis(ethylacetonate). Examples of cobalt compounds include cobalt 2-ethylhexanoate and cobalt naphthenate. Examples of bismuth compounds include bismuth 2-ethylhexanoate and bismuth naphthenate. Examples of zirconium compounds include zirconium tetraacetylacetonate, zirconyl 2-ethylhexanoate, and zirconyl naphthenate.

[0099] While not particularly limited, antioxidants include phenolic compounds, amine compounds, phosphorus compounds, and sulfur compounds.

[0100] The pigments are not particularly limited, but examples include titanium dioxide, carbon black, indigo, pearl mica, and aluminum.

[0101] Leveling agents are not particularly limited, but examples include silicone oil.

[0102] The plasticizer is not particularly limited, but examples include phthalate esters, phosphoric acid compounds, and polyester compounds.

[0103] The crosslinking agent is not particularly limited, but examples include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, carbodiimide-based crosslinking agents, oxazoline-based crosslinking agents, aziridine-based crosslinking agents, amine-based crosslinking agents, peroxide-based crosslinking agents, melamine-based crosslinking agents, urea-based crosslinking agents, metal alkoxide-based crosslinking agents, metal chelate-based crosslinking agents, and metal salt-based crosslinking agents.

[0104] From the viewpoint of optical properties, the content of these additives is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, and even more preferably 0.5 parts by mass or more, based on 100 parts by mass of the total solid content of the emulsion particles and inorganic oxides, or 100 parts by mass of the solid content of the composite. Furthermore, from the viewpoint of the stability of the water-based paint composition, it is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 10 parts by mass or less, based on 100 parts by mass of the total solid content of the emulsion particles and inorganic oxides, or 100 parts by mass of the solid content of the composite.

[0105] Furthermore, the water-based paint composition of this embodiment may contain other components, such as compounds, polymers, and additives not previously mentioned. These other components can be used individually or in appropriate combinations of two or more. Such other components are not particularly limited, but examples include thermoplastic resins, thermosetting resins, and rubber / elastomers. Among these, acrylic resins, acrylic urethane resins, urethane resins, and silicone resins are preferred.

[0106] [Properties of water-based paint compositions] From the viewpoint of paintability, the concentration of solids contained in the water-based paint composition is preferably 0.01 to 60% by mass, and more preferably 1 to 40% by mass. Also from the viewpoint of paintability, the viscosity of the water-based paint composition at 20°C is preferably 0.1 to 100,000 mPa·s, and more preferably 1 to 10,000 mPa·s. In this specification, viscosity can be measured with a general E-type viscometer. In one embodiment, viscosity is measured using an E-type viscometer (RE-80U manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 2.5 rpm and 25°C.

[0107] [Composition Set] The composition set of this embodiment comprises composition A and composition B, wherein composition A comprises a mixture of emulsion particles and an inorganic oxide, and / or a composite of the emulsion particles and the inorganic oxide, a blocked polyisocyanate, and water, and the inorganic oxide comprises spherical and / or linked silica, and composition B comprises an organic ultraviolet absorber, a light stabilizer, and a water-soluble organic solvent having a boiling point of 80°C or higher and 140°C or lower. In the composition set, it is preferable that composition A and / or composition B further contain a surfactant in order to further enhance paint stability. Details of each component in the composition set are as described above for each component included in the water-based paint composition.

[0108] The method of preparing composition A is not particularly limited, as long as it includes a mixture and / or complex, a blocked polyisocyanate, and water. Similarly, the method of preparing composition B is not particularly limited, as long as it includes an organic ultraviolet absorber, a light stabilizer, and a water-soluble organic solvent.

[0109] In this embodiment, it is preferable to prepare composition A and composition B in advance, and then mix compositions A and B to prepare a water-based paint composition. While there are no particular limitations on the mixing method, from the viewpoint of the pot life of the water-based paint composition, it is preferable to prepare composition A, which contains a hydrophilic mixture of emulsion particles and inorganic oxides, and / or a composite of said emulsion particles and inorganic oxides, a blocked polyisocyanate, and water, and composition B, which is a hydrophobic organic ultraviolet absorber and a light stabilizer that have been pre-dissolved and mixed in a water-soluble organic solvent, and then mix compositions A and B. More preferably, the mixing method involves adding composition B to composition A and mixing them. That is, by adding composition B, in which the organic ultraviolet absorber and light stabilizer have been pre-dissolved and mixed in a water-soluble organic solvent, to composition A, it is possible to suppress precipitation in the liquid upon addition. Furthermore, by pre-preparing composition A by mixing the mixture of emulsion particles and inorganic oxides, and / or a composite of said emulsion particles and inorganic oxides, and the blocked polyisocyanate in water, it is possible to suppress precipitation due to the water-soluble organic solvent in composition B.

[0110] Furthermore, from the viewpoint of further suppressing the precipitation of hydrophilic substances constituting composition A, it is even more preferable to add composition B dropwise to composition A while stirring composition A and then mix them.

[0111] When using surfactants to improve the stability of water-based paint compositions, the method of adding them is not particularly limited, but it is preferable to add them to composition A and / or composition B beforehand.

[0112] [Method for producing a water-based paint composition] The water-based paint composition of this embodiment is produced, for example, by stirring and mixing a mixture of emulsion particles and an inorganic oxide, and / or a composite of the emulsion particles and the inorganic oxide, a block polyisocyanate, an organic ultraviolet absorber, a light stabilizer, water, and a water-soluble organic solvent having a boiling point of 80°C or higher and 140°C or lower, using manual stirring or stirring equipment such as a mixer and a stirrer.

[0113] Furthermore, as described above, the water-based paint composition may be prepared by first preparing composition A and composition B, and then mixing composition A and composition B. In this manufacturing method, it is preferable to include a step of adding composition B to composition A while composition A is being stirred, as described above.

[0114] [Adhesive layer] The adhesive layer in this embodiment can be obtained, for example, by applying the water-based paint composition of this embodiment to a substrate and forming a coating film through heat treatment, ultraviolet irradiation, and infrared irradiation.

[0115] The coating method is not particularly limited, but examples include spray coating, flow coating, brush coating, dip coating, spin coating, screen printing, casting, gravure printing, and flexographic printing. After coating, the water-based paint composition is formed into a coating film by heat treatment at preferably 80 to 250°C, more preferably 90 to 150°C, or by infrared irradiation. By performing heat treatment or infrared irradiation, the deblocking of the blocked polyisocyanate contained in the water-based paint composition progresses, and the hydroxyl groups contained in the emulsion particles react with the isocyanate groups to form urethane bonds, which tends to improve coating adhesion and coating strength. Furthermore, this coating can be applied not only to already molded substrates, but also to flat plates before molding, such as pre-coated metals including rust-resistant steel plates.

[0116] From the viewpoint of adhesion, the thickness of the adhesive layer is preferably 0.1 μm or more, more preferably 0.3 μm or more, and from the viewpoint of transparency, it is preferably 100.0 μm or less, more preferably 50.0 μm or less.

[0117] [Substrate with adhesive layer] The adhesive-coated substrate of this embodiment comprises a substrate and an adhesive layer disposed on the substrate, wherein the adhesive layer contains a cured product of the water-based coating composition of this embodiment. The adhesive layer is obtained by coating the substrate with the water-based coating composition and curing it. In this embodiment, the adhesive layer is disposed on one and / or both sides of the substrate.

[0118] [Base material] The substrate in this embodiment is not particularly limited, but examples include resins, metals, and glass. The shape of the substrate is not particularly limited, but examples include plate-like shapes, shapes with irregularities, shapes with curved surfaces, hollow shapes, porous shapes, and combinations thereof. The type of substrate is also not limited, but examples include sheets, films, and fibers. Among these, resins are preferred from the viewpoint of imparting hard coating properties and moldability. The resin is not particularly limited, but examples include thermoplastic resins and thermosetting resins. The thermoplastic resin is not particularly limited, but examples include polyethylene, polypropylene, polystyrene, ABS resin, vinyl chloride resin, methyl methacrylate resin, nylon, fluororesin, polycarbonate, and polyester resin. The thermosetting resin is not particularly limited, but examples include phenolic resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, silicon resin, silicone rubber, SB rubber, natural rubber, and thermosetting elastomer.

[0119] [Laminated structure] The laminate of this embodiment comprises a substrate with an adhesive layer of this embodiment and a hard coat layer disposed on the adhesive layer of the substrate, wherein the hard coat layer comprises polymer nanoparticles and a matrix component, the matrix component comprising an inorganic oxide, and the Martens hardness of the polymer nanoparticles is HM GAnd the Martens hardness HM of the matrix component. H HM H / HM G The relationship >1 is satisfied. In the laminate, it is preferable that the haze value H1 of the substrate with the adhesive layer is greater than the haze value H2 of the laminate. Because the laminate of this embodiment is configured in this way, it has high abrasion resistance, adhesion, and optical properties. Furthermore, by satisfying this relationship, a scattering layer is formed at the interface between the substrate with the adhesive layer and the hard coat layer of the laminate of this embodiment, resulting in the suppression of interference fringe generation and further improvement of optical properties.

[0120] In this embodiment, from the viewpoint of adhesion, the ratio of the haze value H1 of the substrate with the adhesive layer to the haze value H2 of the laminate (H1 / H2) is preferably 2 or more, more preferably 5 or more, even more preferably 10 or more, and particularly preferably 20 or more.

[0121] In this embodiment, from the viewpoint of transparency, the haze value H1 of the substrate with adhesive layer is preferably 60% or less, more preferably 50% or less, and even more preferably 30% or less. From a similar viewpoint, the haze value H2 of the laminate is preferably 5% or less, more preferably 2% or less, and even more preferably 1% or less. Methods for adjusting each haze value to within the above ranges are not particularly limited, but for example, for H1, methods include controlling the particle size of emulsion particles, the particle size and shape of inorganic oxides, the mass ratio of emulsion particles to inorganic oxides, the content of block polyisocyanate, and the content of other additives. For H2, methods include controlling the particle size of polymer nanoparticles (A), the component ratio of polymer nanoparticles (A) to matrix components (B), the content of inorganic oxides (D) in the matrix components (B), and the content of light-shielding agents contained in the hard coat layer. In particular, increasing the amount of inorganic oxides or inorganic oxides (D) tends to increase each haze value, and decreasing them tends to decrease them. Each haze value can be measured by the method described in the examples below. Note that haze value H1 can be measured on the substrate with the adhesive layer, and haze value H2 can be measured on the laminate (substrate with adhesive layer and hard coat layer). Haze values ​​H1 and H2 may also be measured after the substrate with the adhesive layer and the laminate have been formed, respectively.

[0122] Because the laminate of this embodiment is constructed in this manner, it has high abrasion resistance, adhesion, and optical properties. The laminate of this embodiment exhibits high levels of abrasion resistance, adhesion, and optical properties, and is therefore not particularly limited, but is useful as a hard coat for building materials, automotive components, electronic equipment, and electrical products, and is particularly preferred for use in automotive components.

[0123] [Hard coat layer] In this embodiment, the hard coat layer (hereinafter also referred to as "layer (C)") is disposed on the adhesive layer of the substrate with the adhesive layer and contains polymer nanoparticles (A) and a matrix component (B) containing an inorganic oxide. The hard coat layer contributes to the durability of the laminate. In this specification, the Martens hardness HM is 100 N / mm². 2 The layer described above is specifically referred to as the "hard coat layer." In this embodiment, the inorganic oxide contained in the matrix component (B) or the matrix raw material component (B') is also referred to as "inorganic oxide (D)." Inorganic oxide (D) may be the same as or different from the inorganic oxide (I) described above.

[0124] In this embodiment, from the viewpoint of wear resistance, the hard coat layer comprises polymer nanoparticles (A) dispersed in a matrix component (B), and the Martens hardness HM of the polymer nanoparticles (A) G And the Martens hardness HM of the matrix component (B) H HM H / HM G The relationship >1 is satisfied. The Martens hardness HM of the hard coat layer is 100 N / mm². 2 It is preferable that the above conditions are met. Note: Martens hardness HM Gand Martens hardness HM H Even when it is difficult to determine the relative magnitudes of the two components, the relative magnitudes of the Martens hardness can be estimated by comparing the adhesive strengths of the polymer nanoparticles (A) and the matrix component (B). A lower adhesive strength indicates higher elasticity; therefore, a lower adhesive strength means the coating film is less prone to deformation and has higher hardness. Specifically, the preferred layer (C) can also be identified as follows: The preferred layer (C) comprises polymer nanoparticles (A) and a matrix component (B), and the adhesive strength F of the polymer nanoparticles (A) is measured using the adhesive strength mode of a scanning probe microscope (SPM). A And the adhesion force F of the matrix component (B) B F A / F B The relationship >1 is satisfied, and the Martens hardness HM of the hard coat layer is 100 N / mm 2 That's all.

[0125] In layer (C) of this embodiment, it is preferable that the polymer nanoparticles (A) are dispersed in the matrix component (B). In this embodiment, "dispersion" means that the polymer nanoparticles (A) are distributed uniformly or while forming a structure within the matrix component (B), with the polymer nanoparticles (A) acting as the dispersed phase and the matrix component (B) as the continuous phase. The dispersion can be confirmed by cross-sectional SEM observation of the hard coat layer. In the hard coat layer of this embodiment, the dispersion of polymer nanoparticles (A) in the matrix component (B) tends to result in high wear resistance.

[0126] [Martens hardness] In this embodiment, the Martens hardness is a hardness value compliant with ISO 14577-1, and is calculated from the indentation depth at 2 mN under the measurement conditions (Vickers square pyramidal diamond indenter, load increase condition 2 mN / 20 sec, load decrease condition 2 mN / 20 sec). In this embodiment, the Martens hardness can be measured using, for example, a microhardness tester Fischerscope (HM2000S manufactured by Fischer Instruments), an ultra-micro indentation hardness tester (ENT-NEXUS manufactured by Elionix Co., Ltd.), a nanoindenter (iNano, G200 manufactured by Toyo Technica Co., Ltd.), or a nanoindentation system (TI980 manufactured by Bruker). The shallower the indentation depth, the higher the Martens hardness, and the deeper the indentation depth, the lower the Martens hardness.

[0127] [Adhesion] In this embodiment, the adhesion force can be measured with a scanning probe microscope (SPM). Lower adhesion force indicates higher elasticity; therefore, a lower adhesion force results in a less deformable coating and higher hardness. The method for measuring the adhesion force is not particularly limited, but it can be measured using, for example, the Shimadzu SPM-970, SPM-9700HT, Bruker AXS Dimension ICON, and Hitachi High-Tech Science AFM5000II.

[0128] [Other hardness levels] In this embodiment, the relative magnitudes of Martens hardness and adhesive force can also be estimated by confirming the relative magnitudes of measurements using other hardness indicators. These other hardness indicators are not particularly limited, as they indicate the resistance of the material to deformation when force is applied. Examples of such other hardness indicators include Vickers hardness or indentation hardness measured by indentation testers such as microhardness testers and nanoindentation testers, or indicators expressed as logarithmic decay rate measured by pendulum-type viscoelasticity testers such as rigid pendulum-type physical property testers. Other indicators that can be measured by scanning probe microscopes (SPM) and expressed as phase, frictional force, viscoelasticity, adsorption force, hardness, and elastic modulus can also be cited. If it is confirmed that the hardness of the matrix component (B) is higher than that of the polymer nanoparticles (A) in these indicators, then it can be estimated that the matrix component (B) is harder than the polymer nanoparticles (A) in terms of Martens hardness and adhesive force.

[0129] [Martens hardness HM of polymer nanoparticles (A)] G and the Martens hardness HM of the matrix component (B) H ] Martens hardness HM of polymer nanoparticle (A) in this embodiment G And the Martens hardness HM of the matrix component (B) H Preferably, the following relationship (1) is satisfied.

[0130] HM H / HM G >1 formula (1)

[0131] Equation (1) shows that flexible polymer nanoparticles (A) are present within a rigid matrix component (B). This three-dimensional gradient of hardness allows layer (C) to exhibit abrasion resistance not found in conventional coatings. While not limited to this explanation, it is presumed that this is because the flexible nanoparticles absorb impact, while the rigid matrix component suppresses deformation. HM G In terms of impact absorption, the range is 50 N / mm². 2The above is preferable, 100 N / mm 2 The above is more preferable, and from the viewpoint of film formation properties, 2000 N / mm 2 The following is preferable: 800 N / mm 2 The following is more preferable: 350 N / mm 2 The following is even more preferable: HM H From the perspective of shock absorption, the range is 100 N / mm 2 The above is preferable, 150 N / mm 2 The above is more preferable, and from the viewpoint of film formation properties, 4000 N / mm 2 The following is preferable, 2000 N / mm 2 The following are preferable. Layer (C) can be obtained as a cured product by curing the hard coat layer composition described later by hydrolysis condensation or the like. The composition of polymer nanoparticles (A) usually does not change during this curing process. Therefore, the Martens hardness HM of polymer nanoparticles (A) in the hard coat layer composition, as measured by the method described in the examples below, is... G The value of HM represents the Martens hardness of the polymer nanoparticles (A) in layer (C). G As something that closely matches, the Martens hardness HM in layer (C) G The value can be determined. Furthermore, matrix component (B) corresponds to a cured product obtained by hardening the matrix raw material component (B'), described later, by hydrolysis condensation or the like. Therefore, the Martens hardness HM of the matrix raw material component (B') measured by the method described in the examples below is H' The value of is the Martens hardness HM of the corresponding matrix component (B). H A good match is the Martens hardness HM. H The value can be determined. The above HM G and HM H The values ​​of can be adjusted to achieve the aforementioned magnitude relationship based on the structure and composition ratio of the polymer nanoparticles (A) and the matrix raw material components (B') described later, but the method is not limited to this approach.

[0132] [Adhesion force F of polymer nanoparticles (A)]A The adhesion force F of the matrix component (B) B ] Adhesion force F of polymer nanoparticles (A) in this embodiment A And the adhesion force F of the matrix component (B) B Preferably, the following relationship (2) is satisfied.

[0133] F A / F B >1 Formula (2)

[0134] Similar to equation (1) above, equation (2) also indicates that flexible polymer nanoparticles (A) are present within a rigid matrix component (B). This three-dimensional gradient of hardness allows layer (C) to exhibit abrasion resistance not found in conventional coatings. While not intended to be a limiting factor, it is presumed that the flexible nanoparticles absorb impact, while the rigid matrix component suppresses deformation. As described above, the adhesion force F of polymer nanoparticles (A) A and the adhesion force F of the matrix component (B) B This correlates with the hardness of each component, and the relationship between magnitudes can be adjusted to the aforementioned magnitudes by the structure and composition ratio of the polymer nanoparticles (A) and the matrix raw material components (B') described later, but this method is not the only way to achieve this.

[0135] [Martens hardness HM of layer (C)] The Martens hardness HM of layer (C) is 100 N / mm² from the perspective of wear resistance. 2 The above explains why a higher value is advantageous in that it results in less deformation and less damage accompanied by fracture when subjected to impact. The Martens hardness HM of layer (C) is preferably 100 N / mm². 2 The above, and more preferably 150 N / mm 2 The above is true, and more preferably 200 N / mm 2 The above is the most common rating, and from the viewpoint of bending resistance, a rating of 4000 N / mm is preferred. 2 More preferably, 2000 N / mm 2 More preferably, 1500 N / mm 2The following applies. There are no particular limitations on the method for adjusting the Martens hardness HM of layer (C) to within the above range, but for example, a coating composition obtained by dispersing and dissolving a composition of polymer nanoparticles (A) and a matrix raw material component (B') described later, which satisfies a predetermined relationship represented by formula (3) described later, in a solvent, is applied to a substrate and then formed into a coating film by heat treatment, ultraviolet irradiation, infrared irradiation, etc. In particular, increasing the content of matrix component (B) relative to the total amount of polymer nanoparticles (A) and matrix component (B) tends to increase the Martens hardness HM of layer (C), and decreasing the content of matrix component (B) tends to decrease the Martens hardness HM of layer (C).

[0136] [Change in haze in the Taber abrasion test] The Taber wear test in this embodiment is based on the method described in ASTM D1044, and the measurement is performed using a wear wheel CS-10F under a load of 500g. The smaller the haze change, the better the wear resistance of the material. If the haze change after 500 rotations compared to the haze before the test, i.e., the difference between the haze after 500 rotations and the haze before the Taber wear test, is 10 or less, it conforms to the ECE R43 standard for rear quarter glass, and if it is 4 or less, it conforms to the ANSI / SAE Z.26.1 standard and is suitable for use as an automotive window material. Furthermore, if the haze change amount at 1000 revolutions, that is, the difference between the haze at 1000 revolutions and the haze before the Taber abrasion test, is 10 or less, it conforms to the standards for automobile windows and can be suitably used as an automobile window material. If it is 2 or less, it conforms to the standards of ANSI / SAE Z.26.1, ECE R43, and JIS R3211 / R3212 and can be suitably used for all automobile window materials. A haze change amount at 1000 revolutions of 10 or less is preferable, 6 or less is more preferable, and 2 or less is even more preferable. There are no particular limitations on the method for adjusting the haze change amount to the above range, but for example, a paint composition obtained by dispersing and dissolving a composition of polymer nanoparticles (A) and a matrix raw material component (B') described later, which satisfy a predetermined relationship represented by formula (3) described later, in a solvent, is applied to a substrate and a coating film is formed by heat treatment, ultraviolet irradiation, infrared irradiation, etc.

[0137] [Elastic recovery rate of layer (C) η IT ] Elastic recovery rate η of layer (C) IT The total mechanical work W of the depression is total Work done by the elastic return deformation of the depression W elast This is the ratio to ISO14577-1, and is "W elast / W total Ratio η IT This parameter is described as "elastic recovery rate η". IT The higher the elastic recovery rate η, the more likely the coating film is to return to its original state after deformation, indicating a high self-healing capacity against deformation. From the perspective of effectively exhibiting self-healing capacity, the elastic recovery rate η ITThe elastic recovery rate η is preferably 0.50 or higher under the measurement conditions (Vickers square pyramidal diamond indenter, load increase condition 2mN / 20sec, load decrease condition 2mN / 20sec), and within this range, a larger value is preferable. More specifically, the elastic recovery rate η IT It is more preferable that the value is 0.55 or higher, even more preferable that it is 0.60 or higher, and even more preferable that it is 0.65 or higher. The measurement of the elastic recovery rate of the coating film in this embodiment is not particularly limited, but for example, it can be measured by performing an indentation test on the surface of the hard coat layer using a microhardness tester Fischerscope (HM2000S manufactured by Fischer Instruments), an ultra-micro indentation hardness tester (ENT-NEXUS manufactured by Elionix Co., Ltd.), a nanoindenter (iNano, G200 manufactured by Toyo Technica Co., Ltd.), a nanoindentation system (TI980 manufactured by Bruker), etc. Elastic recovery rate η IT Methods for adjusting the above range are not particularly limited, but include, for example, dispersing and dissolving a paint composition in a solvent, which is a mixture of polymer nanoparticles (A) and a matrix raw material component (B') described later that satisfies a predetermined relationship represented by formula (3) described later, onto a substrate, and forming a coating film by heat treatment, ultraviolet irradiation, infrared irradiation, etc.

[0138] [Thickness of layer (C)] In this embodiment, it is preferable to appropriately adjust the film thickness from the viewpoint of further exhibiting the wear resistance of the hard coat layer and ensuring sufficient conformability to the deformation of the substrate. Specifically, the film thickness of layer (C) is preferably 1.0 μm or more, more preferably 3.0 μm or more, from the viewpoint of wear resistance. Furthermore, the film thickness of layer (C) is preferably 100.0 μm or less, more preferably 50.0 μm or less, and even more preferably 20.0 μm or less, from the viewpoint of substrate conformability.

[0139] [convolutional nanoparticles (A)] By using the polymer nanoparticles (A) in this embodiment, shock absorption properties can be imparted to the hard coat layer, and the amount of haze change in the Taber abrasion test of the hard coat layer tends to be reduced. The shape of the polymer nanoparticles (A) is not particularly limited as long as the particle size is on the order of nanometers (less than 1 μm). Note that the Martens hardness of the polymer nanoparticles (A) is HM G This can be controlled within the aforementioned range by the structure and composition ratio of the constituent components of the polymer nanoparticles (A), but is not limited to this method.

[0140] [Average particle size of polymer nanoparticles (A)] The average particle diameter of the polymer nanoparticles (A) in this embodiment is not particularly limited as long as it is on the order of nm (less than 1 μm), and can be determined from the size of the particles observed by cross-sectional SEM or dynamic light scattering method. From the viewpoint of optical properties, the average particle diameter of the polymer nanoparticles (A) is preferably 10 nm or more, more preferably 15 nm or more, and more preferably 20 nm or more. From the viewpoint of transparency, it is preferably 400 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less. The method for measuring the average particle diameter of the polymer nanoparticles (A) is not particularly limited, but for example, it can be done by measuring the cumulant particle diameter using a dynamic light scattering particle size distribution analyzer (model number: ELSZ-1000) manufactured by Otsuka Electronics Co., Ltd. with an aqueous dispersion of polymer nanoparticles (A).

[0141] [Volume fraction of polymer nanoparticles (A) in layer (C)] In this embodiment, the volume fraction of polymer nanoparticles (A) in layer (C) is preferably 2% or more, more preferably 3% or more, and even more preferably 5% or more, from the viewpoint of film formation, and preferably 80% or less, more preferably 70% or less, and even more preferably 45% or less, from the viewpoint of transparency. The volume fraction of polymer nanoparticles (A) in layer (C) can be calculated, for example, from the proportion of polymer nanoparticles (A) in the entire coating film in a cross-sectional SEM image of layer (C), or from the component ratio of polymer nanoparticles (A) in the components constituting layer (C).

[0142] [Components of polymer nanoparticles (A)] [Hydrolyzable silicon compounds (a)] In this embodiment, the polymer nanoparticles (A) preferably contain a hydrolyzable silicon compound (a). The hydrolyzable silicon compound (a) is not particularly limited as long as it is a hydrolyzable silicon compound, its hydrolysis product, or a condensate.

[0143] From the viewpoint of improving wear resistance and weather resistance, the hydrolyzable silicon compound (a) is preferably a compound containing the atomic group represented by the following formula (a-1), its hydrolysis product, and condensate.

[0144] -R 1 n1 SiX 1 3-n1 (a-1)

[0145] In formula (a-1), R 1 R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group. 1 X may have substituents containing halogen, hydroxyl, mercapto, amino, (meth)acryloyl, or epoxy groups. 1 n1 represents a hydrolyzable group, and n1 represents an integer from 0 to 2. The hydrolyzable group is not particularly limited as long as it is a group that generates a hydroxyl group upon hydrolysis. Examples of such groups include halogens, alkoxy groups, acyloxy groups, amino groups, phenoxy groups, and oxime groups.

[0146] Specific examples of compounds containing the atomic group represented by formula (a-1) are not particularly limited, but include, for example, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, hexyltrimethoxylane, hexyltriethoxylane, octyltrimethoxysilane, octyltriethoxysilane, decyltri Ethoxysilane, 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 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) Xysilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1,3-bis(triphenoxysilyl)propane, 1,4-bis(trimethoxysilyl)benzene, 1,4-bis(triethoxysilyl)benzene, 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,7-bis(trimethoxysilyl)heptane, 1,7-bis(triethoxysilyl)heptane, 1,8-bis(trimethoxysilyl)octane, 1,8-Bis(triethoxysilyl)octane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-Methacryloxypropyltriethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, Vinyltrimethoxylane, Vinyltriethoxylan, p-Styryltrimethoxysilane, p-Styryltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxy Sisilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, 3-trimethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, 3-triethoxysilyl-N-(1,3-Dimethyl-butylidene)propylamine, triacetoxysilane, tris(trichloroacetoxy)silane, tris(trifluoroacetoxy)silane, tris-(trimethoxysilylpropyl)isocyanurate, tris-(triethoxysilylpropyl)isocyanurate, methyltriacetoxysilane, methyltris(trichloroacetoxy)silane, trichlorosilane, tribromosilane, methyltrifluorosilane, tris(methylethylketoxime)silane, phenyltris(methylethylketoxime)silane, bis(methylethylketoxime)silane, methylbis(methylethylketoxime)silane, hexamethyldisilane, hexamethylcyclotrisilazane, bis Examples include bis(dimethylamino)dimethylsilane, bis(diethylamino)dimethylsilane, bis(dimethylamino)methylsilane, bis(diethylamino)methylsilane, 2-[(triethoxysilyl)propyl]dibenzylresorcinol, 2-[(trimethoxysilyl)propyl]dibenzylresorcinol, 2,2,6,6-tetramethyl-4-[3-(triethoxysilyl)propoxy]piperidine, 2,2,6,6-tetramethyl-4-[3-(trimethoxysilyl)propoxy]piperidine, 2-hydroxy-4-[3-(triethoxysilyl)propoxy]benzophenone, and 2-hydroxy-4-[3-(trimethoxysilyl)propoxy]benzophenone.

[0147] From the viewpoint of imparting high hardness to the hard coat layer and further improving wear resistance, the hydrolyzable silicon compound (a) preferably includes the compound represented by the following formula (a-2), its hydrolysis product, and condensate.

[0148] SiX 2 4(a-2)

[0149] In formula (a-2), X 2 The symbol represents a hydrolyzable group. A hydrolyzable group is not particularly limited as long as it is a group that generates a hydroxyl group through hydrolysis, and examples include halogens, alkoxy groups, acyloxy groups, amino groups, phenoxy groups, and oxime groups.

[0150] Specific examples of compounds represented by formula (a-2) are not limited to tetramethoxysilane, tetraethoxysilane, tetra(n-propoxy)silane, tetra(i-propoxy)silane, tetra(n-butoxy)silane, tetra(i-butoxy)silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraacetoxysilane, tetra(trichloroacetoxy)silane, tetra(trifluoroacetoxy)silane, tetrachlorosilane, tetrabromosilane, tetrafluorosilane, tetra(methylethylketoxyme)silane, tetramethoxysilane, or tetraethoxysilane. Examples include partial hydrolysis condensates of methyl silicate (for example, "M Silicate 51", "Silicate 35", "Silicate 45", "Silicate 40", and "FR-3" manufactured by Tama Chemical Industry Co., Ltd.; "MS51", "MS56", "MS57", and "MS56S" manufactured by Mitsubishi Chemical Corporation; and "Methyl Silicate 51", "Methyl Silicate 53A", "Ethyl Silicate 40", "Ethyl Silicate 48", "EMS-485", "N-103X", "PX", "PS-169", "PS-162R", "PC-291", "PC-301", "PC-302R", "PC-309", and "EMSi48" manufactured by Colcoat Co., Ltd.).

[0151] As described above, in this embodiment, it is preferable that the hydrolyzable silicon compound (a) includes one or more selected from compounds containing the atomic group represented by formula (a-1), their hydrolysis products and condensates, and compounds represented by formula (a-2), their hydrolysis products and condensates.

[0152] [Content of hydrolyzable silicon compound (a) in polymer nanoparticles (A)] In this embodiment, the content of hydrolyzable silicon compound (a) refers to the solid mass percentage of hydrolyzable silicon compound (a) contained in polymer nanoparticles (A). A higher content is preferable from the viewpoint of improving abrasion resistance, weather resistance, and heat resistance, and the content is preferably 50% by mass or more, and more preferably 60% by mass or more. The content of hydrolyzable silicon compound (a) in polymer nanoparticles (A) is not particularly limited, but can be measured, for example, by IR analysis, NMR analysis, elemental analysis, etc. of polymer nanoparticles (A).

[0153] [Matrix component (B)] By using matrix component (B) in this embodiment, shock absorption properties can be imparted to the hard coat layer, and the amount of haze change in the Taber abrasion test of the hard coat layer can be reduced. Hardness HM of matrix component (B) H This can be controlled within the aforementioned range by the structure and composition ratio of the matrix raw material components (B') described later, but is not limited to this method.

[0154] [Components of matrix component (B)] [Hydrolyzable silicon compounds (b)] The matrix component (B) in this embodiment is not particularly limited as long as it is a component that can disperse polymer nanoparticles (A). In this embodiment, from the viewpoint of high toughness, it is preferable that the matrix component (B) contains a hydrolyzable silicon compound (b). In this specification, "the matrix component (B) contains a hydrolyzable silicon compound (b)" means that the matrix component (B) contains a polymer having constituent units derived from the hydrolyzable silicon compound (b). The hydrolyzable silicon compound (b) is not particularly limited as long as it is a hydrolyzable silicon compound, its hydrolysis product, and condensate.

[0155] As the matrix component (B), various components excluding the polymer nanoparticles (A) may be included. Examples of such components include polymers. Examples of polymers include water-soluble resins such as polyvinyl alcohol, polyethylene glycol, polyvinyl pyrrolidone, and polyacrylic acid; acrylic resins such as PMMA, PAN, and polyacrylamide; polymers such as polystyrene, polyurethane, polyamide, polyimide, polyvinylidene chloride, polyester, polycarbonate, polyether, polyethylene, polysulfone, polypropylene, polybutadiene, PTFE, PVDF, and EVA; and copolymers thereof.

[0156] From the viewpoint of further improving the abrasion resistance and weather resistance, the hydrolyzable silicon compound (b) preferably contains at least one selected from the group consisting of a compound containing an atomic group represented by the following formula (b-1), its hydrolysis product, and condensate, and a compound represented by the following formula (b-2), its hydrolysis product, and condensate.

[0157] -R 2 n2 SiX 3 3-n2 (b-1)

[0158] In formula (b-1), R 2 represents a hydrogen atom, an alkyl group, alkenyl group, alkynyl group, or aryl group having 1 to 10 carbon atoms, R 2 may have a substituent containing a halogen, hydroxy group, mercapto group, amino group, (meth)acryloyl group, or epoxy group, X 3 represents a hydrolyzable group, and n2 represents an integer of 0 to 2. The hydrolyzable group is not particularly limited as long as it generates a hydroxy group by hydrolysis, and examples of such a group include a halogen atom, alkoxy group, acyloxy group, amino group, phenoxy group, and oxime group.

[0159] SiX 4 4(b-2)

[0160] In formula (b-2), X4 represents a hydrolyzable group. The hydrolyzable group is not particularly limited as long as it is a group that generates a hydroxyl group by hydrolysis, and examples of such groups include halogen, an alkoxy group, an acyloxy group, an amino group, a phenoxy group, an oxime group, and the like.

[0161] Specific examples of compounds containing the atomic group represented by general formula (b-1) are not particularly limited, but include trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, hexyltrimethoxylane, hexyltriethoxylane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxy Sisilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxysilane, diethoxysilane, methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethoxydiphenylsilane, diethoxydiphenylsilane, bis(trimethoxysilyl)methane, bis(triethoxysilyl)methane, bis(triphenoxysilyl)ethane, 1,1-bis(triethoxysilyl) Ethane, 1,2-bis(triethoxysilyl)ethane, 1,1-bis(triethoxysilyl)propane, 1,2-bis(triethoxysilyl)propane, 1,3-bis(triethoxysilyl)propane, 1,4-bis(triethoxysilyl)butane, 1,5-bis(triethoxysilyl)pentane, 1,1-bis(trimethoxysilyl)ethane, 1,2-bis(trimethoxysilyl)ethane, 1,1-bis(trimethoxysilyl)propane, 1,2-bis(trimethoxysilyl)propane, 1,3-bis(trimethoxy Sisilyl)propane, 1,4-bis(trimethoxysilyl)butane, 1,5-bis(trimethoxysilyl)pentane, 1,3-bis(triphenoxysilyl)propane, 1,4-bis(trimethoxysilyl)benzene, 1,4-bis(triethoxysilyl)benzene, 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,7-bis(trimethoxysilyl)heptane, 1,7-bis(triethoxysilyl)heptane, 1,8-bis(trimethoxysilyl)octane, 1,8-Bis(triethoxysilyl)octane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-Methacryloxypropyltriethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, Vinyltrimethoxylane, Vinyltriethoxylan, p-Styryltrimethoxysilane, p-Styryltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxy Sisilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, 3-trimethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, 3-triethoxysilyl-N-(1,3-Dimethyl-butylidene)propylamine, triacetoxysilane, tris(trichloroacetoxy)silane, tris(trifluoroacetoxy)silane, tris-(trimethoxysilylpropyl)isocyanurate, tris-(triethoxysilylpropyl)isocyanurate, methyltriacetoxysilane, methyltris(trichloroacetoxy)silane, trichlorosilane, tribromosilane, methyltrifluorosilane, tris(methylethylketoxime)silane, phenyltris(methylethylketoxime)silane, bis(methylethylketoxime)silane, methylbis(methylethylketoxime)silane, hexamethyldisilane, hexamethylcyclotrisilazane, bis Examples include bis(dimethylamino)dimethylsilane, bis(diethylamino)dimethylsilane, bis(dimethylamino)methylsilane, bis(diethylamino)methylsilane, 2-[(triethoxysilyl)propyl]dibenzylresorcinol, 2-[(trimethoxysilyl)propyl]dibenzylresorcinol, 2,2,6,6-tetramethyl-4-[3-(triethoxysilyl)propoxy]piperidine, 2,2,6,6-tetramethyl-4-[3-(trimethoxysilyl)propoxy]piperidine, 2-hydroxy-4-[3-(triethoxysilyl)propoxy]benzophenone, and 2-hydroxy-4-[3-(trimethoxysilyl)propoxy]benzophenone.

[0162] Specific examples of compounds represented by formula (b-2) are not limited to tetramethoxysilane, tetraethoxysilane, tetra(n-propoxy)silane, tetra(i-propoxy)silane, tetra(n-butoxy)silane, tetra(i-butoxy)silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraacetoxysilane, tetra(trichloroacetoxy)silane, tetra(trifluoroacetoxy)silane, tetrachlorosilane, tetrabromosilane, tetrafluorosilane, tetra(methylethylketoxyme)silane, tetramethoxysilane, or tetraethoxysilane. Examples include partial hydrolysis condensates of methyl silicate (for example, "M Silicate 51", "Silicate 35", "Silicate 45", "Silicate 40", and "FR-3" manufactured by Tama Chemical Industry Co., Ltd.; "MS51", "MS56", "MS57", and "MS56S" manufactured by Mitsubishi Chemical Corporation; and "Methyl Silicate 51", "Methyl Silicate 53A", "Ethyl Silicate 40", "Ethyl Silicate 48", "EMS-485", "N-103X", "PX", "PS-169", "PS-162R", "PC-291", "PC-301", "PC-302R", "PC-309", and "EMSi48" manufactured by Colcoat Co., Ltd.).

[0163] As described above, in this embodiment, it is preferable that the hydrolyzable silicon compound (b) includes one or more selected from compounds containing the atomic group represented by formula (b-1), their hydrolysis products and condensates, and compounds represented by formula (b-2), their hydrolysis products and condensates.

[0164] In this embodiment, the "hydrolyzable silicon compound (a) contained in the polymer nanoparticle (A)" may be the same type as the "hydrolyzable silicon compound (b) contained in the matrix component (B)," or it may be a different type. Even if the two are the same type, they are distinguished by designating the one contained in the polymer nanoparticle (A) as hydrolyzable silicon compound (a) and the one contained in the matrix component (B) as hydrolyzable silicon compound (b).

[0165] [Inorganic oxides (D)] In this embodiment, the matrix component (B) includes an inorganic oxide (D). The inclusion of the inorganic oxide (D) improves the hardness of the matrix component (B) and enhances its abrasion resistance. Furthermore, the hydrophilicity of the hydroxyl groups on the particle surface of the inorganic oxide (D) tends to improve the stain resistance of the coating film.

[0166] Specific examples of the inorganic oxide (D) in this embodiment are not particularly limited, but include oxides of silicon, aluminum, titanium, zirconium, zinc, cerium, tin, indium, gallium, germanium, antimony, molybdenum, niobium, magnesium, bismuth, cobalt, and copper. These can be used individually or as a mixture, regardless of their form. From the viewpoint of interaction with the hydrolyzable silicon compound (b), the inorganic oxide (D) preferably further contains silica particles, such as dry silica or colloidal silica, and from the viewpoint of dispersibility, it is preferable that it further contains colloidal silica in the form of silica particles. When the inorganic oxide (D) contains colloidal silica, it is preferably in the form of an aqueous dispersion and can be used in either acidic or basic conditions.

[0167] Furthermore, in this embodiment, it is preferable that the inorganic oxide (D) contains at least one inorganic component selected from the group consisting of Ce, Nb, Al, Zn, Ti, Zr, Sb, Mg, Sn, Bi, Co, and Cu (hereinafter also simply referred to as "inorganic component"). When the inorganic oxide (D) contains such inorganic component, weather resistance tends to be improved without impairing wear resistance and durability. Although not particularly limited, when using commercially available products, examples include ultrafine particle material products of cerium oxide, zinc oxide, aluminum oxide, bismuth oxide, cobalt oxide, copper oxide, tin oxide, and titanium oxide manufactured by CIK Nanotech Co., Ltd.; and titanium oxide "Tynock" (registered trademark), cerium oxide "Needral" (registered trademark), tin oxide "Ceramase" (registered trademark), niobium oxide sol, and zirconium oxide sol manufactured by Taki Chemical Co., Ltd. From the viewpoint of improved weather resistance, it is preferable that the inorganic oxide (D) contains at least one inorganic component selected from the group consisting of Ce, Nb, Zn, Ti, and Zr, and it is more preferable that it contains Ce.

[0168] In this embodiment, the inorganic oxide (D) preferably contains at least one inorganic oxide (D') selected from the group consisting of Ce, Nb, Zn, Ti, and Zr, from the viewpoint of balancing abrasion resistance, durability, and weather resistance. The content of inorganic oxide (D') in the hard coat coating is not particularly limited, but from the viewpoint of balancing abrasion resistance, durability, and weather resistance, it is preferably 1% by mass or more, and more preferably 2% by mass or more. Furthermore, from the viewpoint of transparency, the above content is preferably 50% by mass or less, and 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 coating is considered as 100% by mass.

[0169] [Average particle size of inorganic oxides (D)] In this embodiment, the average particle size of the inorganic oxide (D) is preferably 2 nm or more from the viewpoint of improving the storage stability of the hard coat layer composition. From the viewpoint of improving the transparency of the laminate as a whole, it is preferably 150 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less. For this reason, the average particle size is preferably 2 nm or more and 100 nm or less, and more preferably 2 nm or more and 50 nm or less. The method for measuring the average particle size (D) of the inorganic oxide is not particularly limited, but for example, it can be measured by observing water-dispersible colloidal silica using a transmission microscope at a magnification of 50,000 to 100,000 times, taking a photograph so that 100 to 200 inorganic oxide particles are visible, and measuring from the average value of the major and minor axes of the inorganic oxide particles.

[0170] [Colloidal silica that can be included in inorganic oxides (D)] The acidic colloidal silica with water as the dispersion solvent, which is preferably used in this embodiment, is not particularly limited, but can be prepared by the sol-gel method or a commercially available product can be used. When preparing by the sol-gel method, refer to Werner Stober et al; J. Colloid and Interface Sci., 26, 62-69 (1968), Rickey D. Badley et al; Lang muir 6, 792-801 (1990), Journal of the Color Materials Association, 61[9] 488-493 (1988), etc. Examples of commercially available products include Snowtex®-O, Snowtex-OS, Snowtex-OXS (water-dispersible colloidal silica), Snowtex-O-40, Snowtex-OL, Snowtex-OYL, Snowtex-OUP, Snowtex-PS-SO, Snowtex-PS-MO, Snowtex-AK-XS, Snowtex-AK, Snowtex-AK-L, Snowtex-AK-YL, Snowtex-AK-PS-S (product names, manufactured by Nissan Chemical Industries, Ltd.), Adelite® AT-20Q (product name, manufactured by Asahi Denka Kogyo Co., Ltd.), Crevosol 20H12, and Crevosol 30CAL25 (product names, manufactured by Clariant Japan Co., Ltd.).

[0171] Furthermore, basic colloidal silica includes silica stabilized by the addition of alkali metal ions, ammonium ions, and amines, and is not particularly limited, but for example, Snowtex (registered trademark)-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 (trademark). Examples include Adelite® AT-20 (product name, manufactured by Nissan Chemical Industries, Ltd.), Adelite® AT-30, Adelite AT-20N, Adelite AT-30N, Adelite AT-20A, Adelite AT-30A, Adelite AT-40, Adelite AT-50 (product name, manufactured by Asahi Denka Kogyo Co., Ltd.), Crevozol 30R9, Crevozol 30R50, Crevozol 50R50 (product name, manufactured by Clariant Japan Co., Ltd.), Rudox® HS-40, Rudox HS-30, Rudox LS, Rudox AS-30, Rudox SM-AS, Rudox AM, Rudox HSA, and Rudox SM (product name, manufactured by DuPont).

[0172] Furthermore, while there are no particular limitations on colloidal silica using a water-soluble solvent as the dispersion medium, examples include MA-ST-M (methanol dispersion type with particle size of 20-25 nm), IPA-ST (isopropyl alcohol dispersion type with particle size of 10-15 nm), EG-ST (ethylene glycol dispersion type with particle size of 10-15 nm), EGST-ZL (ethylene glycol dispersion type with particle size of 70-100 nm), NPC-ST (ethylene glycol monopropyl ether dispersion type with particle size of 10-15 nm), and TOL-ST (toluene dispersion type with particle size of 10-15 nm) (all are trade names) manufactured by Nissan Chemical Industries, Ltd.

[0173] Dry silica particles are not particularly limited, but examples include AEROSIL® manufactured by Nippon Aerosil Co., Ltd. and Rheoroseal® manufactured by Tokuyama Corporation.

[0174] Furthermore, these silica particles may contain inorganic bases (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia) or organic bases (such as tetramethylammonium and triethylamine) as stabilizers.

[0175] [Shape of inorganic oxides (D)] Furthermore, the shape of the inorganic oxide (D) in this embodiment is not particularly limited, but examples include spherical, angular, polyhedral, elliptical, flattened, linear, bead-like, and chain-like shapes. From the viewpoint of hardness and transparency of the hard coat layer, a spherical shape is particularly preferred.

[0176] [Functional group (e)] In this embodiment, the polymer nanoparticles (A) preferably have a functional group (e) that interacts with the matrix component (B), from the viewpoint of improving the dispersibility of the polymer nanoparticles (A) in the matrix component (B) and improving wear resistance. The presence of a functional group (e) in the polymer nanoparticles (A) can be confirmed, for example, by compositional analysis using IR, GC-MS, pyrolysis GC-MS, LC-MS, GPC, MALDI-MS, TOF-SIMS, TG-DTA, NMR, and combinations thereof.

[0177] Specific examples of functional group (e) in this embodiment are not particularly limited, but include hydroxyl groups, carboxyl groups, amino groups, amide groups, and functional groups consisting of ether bonds. From the viewpoint of interaction, it is preferable that the functional group has hydrogen bonds, and from the viewpoint of high hydrogen bonding ability, it is more preferable that it is an amide group, and even more preferable that it is a secondary amide group and / or a tertiary amide group.

[0178] Compounds containing functional group (e) and their reaction products include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl vinyl ether or 4-hydroxybutyl vinyl ether, 2-hydroxyethyl allyl ether, (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-diethylaminoethyl (meth)acrylate, 2-di-n-propylaminoethyl (meth)acrylate, 3-dimethylaminopropyl (meth)acrylate, 4-dimethylaminobutyl (meth)acrylate, N-[2-(meth)acryloyloxy]ethylmorpholine, vinylpyridine, N-vinylcarbazole, N-vinylquinoline, N-methylacrylamide, N-methylmethacrylamide Lylamide, N-ethylacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N-ethylmethacrylamide, N-methyl-N-ethylacrylamide, N-methyl-N-ethylmethacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, N-propylmethacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylhexahydroazepine, N-acryloylmorpholine, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N,N'-methylenebisacrylamide, N,Examples include N'-methylenebismethacrylamide, N-vinylacetamide, diacetone acrylamide, diacetone methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, Bremmer PE-90, PE-200, PE-350, PME-100, PME-200, PME-400, AE-350 (trade name, manufactured by Nippon Oil & Fats Co., Ltd.), MA-30, MA-50, MA-100, MA-150, RA-1120, RA-2614, RMA-564, RMA-568, RMA-1114, MPG130-MA (trade name, manufactured by Nippon Emulsifier Co., Ltd.). In this specification, (meth)acrylate is a simplified notation for acrylate or methacrylate, and (meth)acrylic acid is a simplified notation for acrylic acid or methacrylic acid.

[0179] [Core / shell structure of polymer nanoparticles (A)] In this embodiment, the polymer nanoparticle (A) preferably has a core / shell structure comprising a core layer and one or more shell layers covering the core layer. From the viewpoint of interaction with the matrix component (B) in the outermost layer of the core / shell structure, the polymer nanoparticle (A) preferably has a functional group (e).

[0180] [Other compounds that may be included in polymer nanoparticles (A)] The polymer nanoparticles (A) according to this embodiment may include the following polymers in order to improve particle stability by providing electrostatic repulsion between particles. Examples include polyurethane-based, polyester-based, poly(meth)acrylate-based, poly(meth)acrylic acid-based, polyvinyl acetate-based, polybutadiene-based, polyvinyl chloride-based, chlorinated polypropylene-based, polyethylene-based, and polystyrene-based polymers, or poly(meth)acrylate-silicone-based, polystyrene-(meth)acrylate-based, and styrene-maleic anhydride-based copolymers.

[0181] Among the polymers that may be included in the polymer nanoparticles (A) described above, polymers or copolymers of (meth)acrylic acid and (meth)acrylate are particularly excellent in terms of electrostatic repulsion. Specific examples, though not particularly limited, include polymers or copolymers of methyl acrylate, (meth)acrylic acid, methyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, n-butyl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. In this case, to further improve the electrostatic repulsion force, part or all of the (meth)acrylic acid may be neutralized with amines such as ammonia, triethylamine, or dimethylethanolamine, or bases such as NaOH or KOH.

[0182] Furthermore, polymer nanoparticles (A) may contain an emulsifier. The emulsifier is not particularly limited and includes, for example, acidic emulsifiers such as alkylbenzenesulfonic acid (e.g., dodecylbenzenesulfonic acid), alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkyl sulfate, polyoxyethylene alkylaryl sulfate, and polyoxyethylene distyrylphenyl ethersulfonic acid; anionic surfactants such as alkali metal (Li, Na, K, etc.) salts of acidic emulsifiers, ammonium salts of acidic emulsifiers, and fatty acid soaps; cationic surfactants of the quaternary ammonium salt, pyridinium salt, and imidazolinium salt type such as alkyltrimethylammonium bromide, alkylpyridinium bromide, and imidazolinium laurate; nonionic surfactants such as polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene oxypropylene poroc copolymer, and polyoxyethylene distyrylphenyl ether, as well as reactive emulsifiers having radically polymerizable double bonds.

[0183] The reactive emulsifier having a radically polymerizable double bond is not particularly limited, but examples include: Eleminor® JS-2 (trade name, manufactured by Sanyo Chemical Industries, Ltd.), Latemul® S-120, S-180A or S-180 (trade name, manufactured by Kao Corporation), Aqualon® HS-10, KH-1025, RN-10, RN-20, RN30, RN50 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adekarya Soap® SE1025, SR-1 Examples include 025, NE-20, NE-30, NE-40 (product names, manufactured by Asahi Denka Kogyo Co., Ltd.), ammonium salts of p-styrenesulfonic acid, sodium salts of p-styrenesulfonic acid, potassium salts of p-styrenesulfonic acid, alkyl sulfonic acid (meth)acrylates such as 2-sulfoethyl acrylate, methylpropanesulfonic acid (meth)acrylamide, ammonium salts of allylsulfonic acid, sodium salts of allylsulfonic acid, and potassium salts of allylsulfonic acid.

[0184] The polymer nanoparticles (A) may contain a polymerization initiator. Known polymerization initiators can be used, and are not particularly limited; examples include water-soluble polymerization initiators such as ammonium persulfate, sodium persulfate, and potassium persulfate.

[0185] [Other ingredients that may be included in layer (C)] The layer (C) of this embodiment may contain, depending on the application, a matrix component (B) including a solvent, emulsifier, plasticizer, pigment, dye, filler, antioxidant, conductive material, ultraviolet absorber, light stabilizer, release modifier, softener, surfactant, flame retardant, antioxidant, and catalyst. In particular, for outdoor applications where high weather resistance is required, it is preferable to include an ultraviolet absorber and a light stabilizer.

[0186] Specific examples of UV absorbers and light stabilizers are not limited to, but include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (BASF trade name "UVINUL(registered trademark) 3049"), 2,2',4,4'-tetrahydroxybenzophenone (BASF trade name "UVINUL3050"), and 4-dodecyl Benzophenone-based UV absorbers such as oxy-2-hydroxybenzophenone, 5-benzoyl-2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-stearyloxybenzophenone, and 4,6-dibenzoylresortinol; 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5-di-tert-octylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,Condensate of α'-dimethylbenzyl)phenyl]benzotriazole), methyl-3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate and polyethylene glycol (molecular weight 300) (BASF trade name "TINUVIN® 1130"), isooctyl-3-[3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propionate (BASF trade name "TINUVIN 384"), 2-(3-dodecyl-5-methyl-2-hydroxyphenyl)benzotriazole (BASF trade name "TINUVIN 571"), 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-benzotriazole-2-yl)phenol], 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (BASF brand name "TINUVIN900"), TINUVIN384-2, TINUVIN326, TINUVIN327, TINUVIN109, TINUVIN970, TINUVIN328, TINUVIN171, TINUVIN970, TINUVIN Benzotriazole-based UV absorbers such as PS, TINUVIN P, TINUVIN99-2, and TINVIN928 (trade names, manufactured by BASF); 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,Triazine-based UV absorbers such as 4-bisbutyloxyphenyl)-1,3,5-triazine (BASF brand name "TINUVIN 460"), 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (BASF brand name "TINUVIN 479"), TINUVIN 400, TINUVIN 405, TINUVIN 477, and TINUVIN 1600 (brand name, BASF); malonic acid ester-based UV absorbers such as HOSTAVIN® PR25, HOSTAVIN B-CAP, and HOSTAVIN VSU (brand name, Clariant); HOSTAVIN 3206 LIQ, HOSTAVIN VSU P, and HOSTAVIN 3212 Anilide-based UV absorbers such as LIQ (trade name, manufactured by Clariant); salicylate-based UV absorbers such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropanolphenyl salicylate; ethyl-2-cyano-3,3-diphenyl acrylate (trade name "UVINUL3035" manufactured by BASF), (2-ethylhexyl)-2-cyano-3,3-diphenyl acrylate (trade name "UVINUL3039" manufactured by BASF), and 1,3-bis((2'-cyano-3',3'-diphenylacryloyl)oxy)-2,2-bis-(((2'-cyano-3',Cyanoacrylate-based UV absorbers such as 3'-diphenylacryloyl(oxy)methyl(propane) (BASF brand name "UVINUL3030"); 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) Roxydiethoxy)benzophenone, 2-hydroxy-4-(acryloxytriethoxy)benzophenone, 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole (product name "RUVA-93" manufactured by Otsuka Chemical Co., Ltd.), 2-(2'-hydroxy-5'-methacryloxyethyl-3-tert-butylphenyl)-2H-benzotriazole, and 2-(2'-hydroxy-5'-methacryloxypropyl-3-tert-butylphenyl)-5-chloro-2H-benzotriazole, 3-methacrylo Radical polymerizable ultraviolet absorbers having a radically polymerizable double bond in the molecule, such as yl-2-hydroxypropyl-3-[3'-(2''-benzotriazolyl)-4-hydroxy-5-tert-butyl]phenylpropionate (trade name "CGL-104" manufactured by Ciba-Geigy Japan Co., Ltd.); ultraviolet absorbing polymers such as UV-G101, UV-G301, UV-G137, UV-G12, and UV-G13 (trade names manufactured by Nippon Shokubai Co., Ltd.); bis(2,2,6,6-tetramethyl-4-piperidyl) succinate, bis(2,2,6,6- Tetramethylpiperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-butylmalonate, 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propynyloxy]-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,Hindered amine-based light-emitting agents such as a mixture of 6-pentamethyl-4-piperidyl sebacate (BASF trade name "TINUVIN292"), bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, TINUVIN123, TINUVIN144, TINUVIN152, TINUVIN249, TINUVIN292, and TINUVIN5100 (trade name, BASF). Stabilizers; 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-iminopipe Examples include radical polymerizable hindered amine-based light stabilizers such as lysyl methacrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, and 4-cyano-1,2,2,6,6-pentamethyl-4-piperidyl methacrylate; photostable polymers such as U-double® E-133, U-double E-135, U-double S-2000, U-double S-2834, U-double S-2840, U-double S-2818, and U-double S-2860 (trade names, manufactured by Nippon Shokubai Co., Ltd.); UV absorbers reactive with silanol groups, isocyanate groups, epoxy groups, semicarbazide groups, and hydrazide groups; and inorganic UV absorbers such as cerium oxide, zinc oxide, aluminum oxide, zirconium oxide, niobium oxide, bismuth oxide, cobalt oxide, copper oxide, tin oxide, and titanium oxide. These may be used individually or in combination of two or more.

[0187] [Transparency of the hard coat layer] In this embodiment, the transparency of the hard coat layer can be evaluated from the viewpoint of appearance change by the total light transmittance maintenance rate obtained by the following formula. In this embodiment, the total light transmittance maintenance rate of the hard coat layer is preferably 90% or more, more preferably 95% or more from the viewpoint of ensuring daylighting, and particularly preferably 98% or more from the viewpoint of ensuring visibility through the material. The total light transmittance maintenance rate of the hard coat layer can be adjusted to the above range by, for example, employing the above-mentioned preferred embodiments as polymer nanoparticles (A) and matrix components (B).

[0188] Total light transmittance retention rate of the hard coat layer (%) = (Total light transmittance of the laminate (%) / Total light transmittance of the substrate (%)) × 100

[0189] <Hard coat layer composition> In this embodiment, layer (C) is preferably obtained by using, for example, a hard coat layer composition. The hard coat layer composition is a composition comprising polymer nanoparticles (A) and matrix raw material components (B'). The elastic recovery rate η of the polymer nanoparticles (A) is measured in accordance with ISO 14577-1 based on the indentation test method. ITA However, the Martens hardness HM of polymer nanoparticles (A) is between 0.30 and 0.90. G And the Martens hardness HM of the matrix raw material component (B') H' HM H' / HM G It is preferable that the relationship >1 is satisfied and the matrix raw material component (B') contains an inorganic oxide (D). In the hard coat layer composition, the inorganic oxide (D) preferably contains at least one inorganic component selected from the group consisting of Ce, Nb, Al, Zn, Ti, Zr, Sb, Mg, Sn, Bi, Co, and Cu.

[0190] Regarding each component of the hard coat layer composition, details not mentioned below are as described above for each component of layer (C).

[0191] [Hardness of polymer nanoparticles (A) HM G and the hardness HM of the matrix raw material component (B') H' ] In a hard coat layer composition, the Martens hardness HM of polymer nanoparticles (A) G And the Martens hardness HM of the matrix raw material component (B') H' Preferably, the following relationship (3) is satisfied.

[0192] HM H' / HM G >1 Formula (3)

[0193] As described above, in the hard coat layer composition, the above relationship is satisfied, and in the layer (C) obtained by using the hard coat layer composition, the Martens hardness HM of the polymer nanoparticles (A) G And the Martens hardness HM of the matrix raw material component (B') H' The above equation (3) relationship will also be satisfied. The Martens hardness of each component in the hard coat layer composition can be measured by separating the polymer nanoparticles (A) and the matrix raw material components (B') by operations such as centrifugation and ultrafiltration, and measuring each separated component based on the method described in the examples below. The measurement method may be described above. The above HM G and HM H' The values ​​of can be adjusted to achieve the aforementioned magnitude relationship based on the structure and composition ratio of the polymer nanoparticles (A) and the matrix raw material components (B'), respectively, but the method is not limited to this approach.

[0194] [Elastic recovery rate η of polymer nanoparticles (A)] ITA ] Elastic recovery rate η of polymer nanoparticle (A) in this embodiment ITA This is W in ISO14577-1 elast / W total Ratio η IT The parameters listed were measured using a coating of deposited polymer nanoparticles (A), and the total mechanical work W of the depression was measured. total Work done by the elastic return deformation of the depression Welast It is expressed as a ratio to the elastic recovery rate η. ITA The higher the elastic recovery rate η of polymer nanoparticles (A), the better the coating can return to its original state after being subjected to impact, indicating a high self-healing capacity against impact. From the perspective of effectively exhibiting self-healing capacity, the elastic recovery rate η of polymer nanoparticles (A) ITA It is preferable that the value is 0.30 or higher under the measurement conditions (Vickers square pyramidal diamond indenter, load increase condition 2mN / 20sec, load decrease condition 2mN / 20sec), and from the viewpoint of being able to follow the deformation of the substrate and matrix raw material components (B') when forming the coating film, η ITA It is preferable that it is 0.90 or less. Elastic recovery rate η of polymer nanoparticle (A) ITA It is more preferable that the elastic recovery rate is 0.50 or higher, and even more preferable that it is 0.60 or higher. The measurement of the elastic recovery rate of polymer nanoparticles (A) is not particularly limited, but for example, polymer nanoparticles (A) and matrix raw material components (B') can be separated by operations such as centrifugation and ultrafiltration, the separated polymer nanoparticles (A) can be dispersed in a solvent to obtain a composition, the composition can be applied, and the coating film can be dried to measure the elastic recovery rate using a microhardness tester Fischerscope (HM2000S manufactured by Fischer Instruments), an ultra-micro indentation hardness tester (ENT-NEXUS manufactured by Elionix Co., Ltd.), a nanoindenter (iNano, G200 manufactured by Toyo Technica Co., Ltd.), a nanoindentation system (TI980 manufactured by Bruker), etc. Elastic recovery rate η ITA Methods for adjusting the above range are not particularly limited, but include, for example, adjusting the structure and composition ratio of the constituent components of polymer nanoparticles (A). Layer (C) can be obtained as a cured product by curing the hard coat layer composition by hydrolysis condensation or the like. The composition of polymer nanoparticles (A) usually does not change during this curing process. Therefore, the elastic recovery rate η of polymer nanoparticles (A) in the hard coat layer composition ITA The value of η represents the elastic recovery rate of polymer nanoparticles (A) in layer (C). ITA As something that closely matches this, the elastic recovery rate η in layer (C) ITA The value can be determined.

[0195] [Solvent (H)] The hard coat layer composition in this embodiment preferably contains a solvent (H). The usable solvent (H) is not particularly limited, and general solvents can be used. The solvent is not particularly limited, but for example, water; ethylene glycol, butyl cellosolve, isopropanol, n-butanol, 2-butanol, ethanol, methanol, denatured ethanol, 2-methoxy-1-propanol, 1-methoxy-2-propanol, diacetone alcohol glycerin, monoalkyl monoglyceryl ether, propylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, and diethylene glycol monophenyl ether Examples of solvents include 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; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran and dioxane; amides such as dimethylacetamide and dimethylformamide; halogen compounds such as chloroform, methylene chloride, and carbon tetrachloride; dimethyl sulfoxide and nitrobenzene; and these may be used individually or in combination of two or more. Among these, it is more preferable to include water and alcohols from the viewpoint of reducing the environmental burden during solvent removal.

[0196] The following describes the components, size, and composition ratio of polymer nanoparticles (A) contained in the hard coat layer composition. Details regarding points not mentioned below are as previously described for polymer nanoparticles (A) contained in layer (C). Furthermore, the matrix raw material component (B') contained in the hard coat layer composition is hardened by hydrolysis condensation or the like during the process of obtaining layer (C). In other words, the matrix raw material component (B') contained in the hard coat layer composition becomes the corresponding matrix component (B) in the resulting layer (C). The constituent components, size, composition ratio, etc. of the matrix raw material component (B') will be explained below, but details of points not mentioned below are as described above for the matrix component (B) contained in layer (C).

[0197] In a hard coat layer composition, it is preferable that the polymer nanoparticles (A) contain a hydrolyzable silicon compound (a), and the matrix raw material component (B') contains a hydrolyzable silicon compound (b). Furthermore, it is preferable that the hydrolyzable silicon compound (a) in the hard coat layer composition includes one or more selected from compounds containing the atomic group represented by formula (a-1), their hydrolysis products and condensates, and compounds represented by formula (a-2), their hydrolysis products and condensates. Similarly, it is preferable that the hydrolyzable silicon compound (b) in the hard coat layer composition includes one or more selected from compounds containing the atomic group represented by formula (b-1), their hydrolysis products and condensates, and compounds represented by formula (b-2), their hydrolysis products and condensates.

[0198] Details of the hydrolyzable silicon compounds (a) and (b) in the hard coat layer composition are as described above for the polymer nanoparticles (A) and matrix component (B) contained in layer (C).

[0199] [Content of hydrolyzable silicon compound (a) in polymer nanoparticles (A)] In a hard coat layer composition, the content of hydrolyzable silicon compound (a) refers to the solid mass percentage of hydrolyzable silicon compound (a) contained in polymer nanoparticles (A). A higher content is preferable from the viewpoint of improving abrasion resistance, weather resistance, and heat resistance. The content is preferably 50% by mass or more, and more preferably 60% by mass or more. The content of hydrolyzable silicon compound (a) in polymer nanoparticles (A) is not particularly limited, but can be measured, for example, by IR analysis, NMR analysis, elemental analysis, etc. of the polymer nanoparticles (A).

[0200] [Functional group (e)] In a hard coat layer composition, it is preferable that polymer nanoparticles (A) have a functional group (e) that interacts with the matrix raw material component (B'). When polymer nanoparticles (A) have a functional group (e), the matrix raw material component (B') tends to adsorb more easily onto the surface of polymer nanoparticles (A), forming a protective colloid and stabilizing it. As a result, the storage stability of the hard coat layer composition tends to improve. Furthermore, when polymer nanoparticles (A) have a functional group (e), the interaction between polymer nanoparticles (A) and the matrix raw material component (B') becomes stronger, increasing the viscosity of the hard coat layer composition with respect to the solid content concentration, which tends to suppress sagging when coating complex shapes, and as a result, the film thickness of the layer (C) tends to become more uniform. The presence of a functional group (e) in polymer nanoparticles (A) can be confirmed, for example, by compositional analysis using IR, GC-MS, pyrolysis GC-MS, LC-MS, GPC, MALDI-MS, TOF-SIMS, TG-DTA, NMR, and combinations thereof.

[0201] Specific examples of functional group (e) in this embodiment are not particularly limited, but include hydroxyl groups, carboxyl groups, amino groups, amide groups, and functional groups consisting of ether bonds. From the viewpoint of interaction, it is preferable that the functional group has hydrogen bonds, and from the viewpoint of high hydrogen bonding ability, it is more preferable that it is an amide group, and even more preferable that it is a secondary amide group and / or a tertiary amide group.

[0202] Compounds containing functional group (e) and their reaction products include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl vinyl ether or 4-hydroxybutyl vinyl ether, 2-hydroxyethyl allyl ether, (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, 2-diethylaminoethyl (meth)acrylate, 2-di-n-propylaminoethyl (meth)acrylate, 3-dimethylaminopropyl (meth)acrylate, 4-dimethylaminobutyl (meth)acrylate, N-[2-(meth)acryloyloxy]ethylmorpholine, vinylpyridine, N-vinylcarbazole, N-vinylquinoline, N-methylacrylamide, N-methylmethacrylamide Lylamide, N-ethylacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N-ethylmethacrylamide, N-methyl-N-ethylacrylamide, N-methyl-N-ethylmethacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, N-propylmethacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylhexahydroazepine, N-acryloylmorpholine, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N,N'-methylenebisacrylamide, N,Examples include N'-methylenebismethacrylamide, N-vinylacetamide, diacetone acrylamide, diacetone methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, Bremmer PE-90, PE-200, PE-350, PME-100, PME-200, PME-400, AE-350 (trade name, manufactured by Nippon Oil & Fats Co., Ltd.), MA-30, MA-50, MA-100, MA-150, RA-1120, RA-2614, RMA-564, RMA-568, RMA-1114, MPG130-MA (trade name, manufactured by Nippon Emulsifier Co., Ltd.). In this specification, (meth)acrylate is a simplified notation for acrylate or methacrylate, and (meth)acrylic acid is a simplified notation for acrylic acid or methacrylic acid.

[0203] [Elastic recovery rate η of matrix raw material component (B')] ITB' and the elastic recovery rate η of the matrix component (B) ITB ] In a hard coat layer composition, the elastic recovery rate η of the matrix raw material component (B') ITB' This is "W" in ISO14577-1. elast / W total Ratio η IT The parameter described as "measures the coating film of the deposited matrix raw material component (B'), and the total mechanical work W of the depression" is measured. total Work done by the elastic return deformation of the depression W elast It is expressed as a ratio to the elastic recovery rate η. ITB' The higher the value, the more likely the coating film is to return to its original state after being subjected to impact, indicating a high self-healing capacity against impact. From the perspective of effectively exhibiting self-healing capacity, the elastic recovery rate η of the matrix raw material component (B') is important. ITB' The value is preferably 0.60 or higher, and more preferably 0.65 or higher, under the measurement conditions (Vickers square pyramidal diamond indenter, load increase condition 2mN / 20sec, load decrease condition 2mN / 20sec). Furthermore, from the viewpoint of being able to follow the deformation of the substrate and polymer nanoparticles (A) when forming the coating film, η ITB'It is preferable that the value is 0.95 or less. The measurement of the elastic recovery rate of the matrix raw material component (B') is not particularly limited, but for example, polymer nanoparticles (A) and matrix raw material component (B') can be separated by an operation such as centrifugation, the separated matrix raw material component (B') can be dissolved in a solvent to form a composition, which can then be applied to a coating film that has been dried and measured using a microhardness tester Fischerscope (HM2000S manufactured by Fischer Instruments), an ultra-micro indentation hardness tester (ENT-NEXUS manufactured by Elionix Co., Ltd.), a nanoindenter (iNano, G200 manufactured by Toyo Technica Co., Ltd.), a nanoindentation system (TI980 manufactured by Bruker), etc.

[0204] As mentioned above, the hardened product obtained by hydrolysis condensation of the matrix raw material component (B') corresponds to matrix component (B). Therefore, the elastic recovery rate η of the matrix raw material component (B') ITB' The value of is the elastic recovery rate η of the corresponding matrix component (B). ITB As something that closely matches, the elastic recovery rate η ITB The value of can be determined. That is, the elastic recovery rate η of the matrix component (B) in this embodiment. ITB Preferably, η is 0.60 or higher, and more preferably 0.65 or higher. Also, from the viewpoint of being able to follow the deformation of the substrate and polymer nanoparticles when forming the coating film, ITB It is preferable that the value is 0.95 or less.

[0205] Elastic recovery rate η ITB' and elastic recovery rate η ITB Methods for adjusting the above range are not particularly limited, but include, for example, adjusting the structure and composition ratio of the components of the matrix raw material component (B').

[0206] In the hard coat layer composition, the hydrolyzable silicon compound (a) contained in the polymer nanoparticles (A) may be the same type as or a different type from the hydrolyzable silicon compound (b) contained in the matrix raw material component (B'). Even when both are of the same type, the one contained in the polymer nanoparticles (A) shall be defined as the hydrolyzable silicon compound (a), and the one contained in the matrix raw material component (B') shall be defined as the hydrolyzable silicon compound (b) for distinction purposes.

[0207] [Inorganic oxide (D)] In the hard coat layer composition, the matrix raw material component (B') contains an inorganic oxide (D). By containing the inorganic oxide (D), not only the hardness of the matrix raw material component (B') is improved and the abrasion resistance is enhanced, but also due to the hydrophilicity of the hydroxyl groups on the particle surface, the stain resistance of the coating film tends to be improved.

[0208] The inorganic oxide (D) in the hard coat layer composition may be a single substance or a mixture regardless of its shape. From the perspective of the interaction with the hydrolyzable silicon compound (b), it is preferable to further contain silica particles. From the perspective of dispersibility, it is more preferable to further contain colloidal silica as the form of the silica particles. When the inorganic oxide (D) contains colloidal silica, it is preferably in the form of an aqueous dispersion and can be used regardless of whether it is acidic or basic.

[0209] From the perspective of good storage stability of the hard coat layer composition, the average particle diameter of the inorganic oxide (D) in the hard coat layer composition is preferably 2 nm or more. From the perspective of good transparency of the entire laminate, it is preferably 150 nm or less, more preferably 100 nm or less, and still more preferably 50 nm or less. Therefore, the average particle diameter is preferably 2 nm or more and 100 nm or less, and more preferably 2 nm or more and 50 nm or less. The measurement method of the average particle diameter of the inorganic oxide (D) in the hard coat layer composition is the same as described above for the inorganic oxide (D) contained in the layer (C).

[0210] As for the remaining features of the inorganic oxide (D) in the hard coat layer composition, they are the same as those described above for the inorganic oxide (D) contained in the layer (C).

[0211] [Volume fraction of the polymer nanoparticles (A) with respect to the total of the polymer nanoparticles (A) and the matrix raw material component (B’)] In the hard coat layer composition, the volume fraction of the polymer nanoparticles (A) with respect to the total of the polymer nanoparticles (A) and the matrix raw material component (B’) is preferably 2% or more, more preferably 3% or more, still more preferably 5% or more from the viewpoint of film-forming property, and preferably 80% or less, more preferably 70% or less, still more preferably 45% or less from the viewpoint of transparency. The volume fraction of the polymer nanoparticles (A) in the hard coat layer composition can be calculated, for example, from the ratio of the polymer nanoparticles (A) in the entire coating film in the cross-sectional SEM image after forming the layer (C), or from the component ratio of the polymer nanoparticles (A) in the components constituting the hard coat layer composition.

[0212] [Core / shell structure of the polymer nanoparticles (A)] In the hard coat layer composition, the polymer nanoparticles (A) preferably have a core / shell structure including a core layer and one or more shell layers covering the core layer. The polymer nanoparticles (A) preferably have the functional group (e) described above also from the viewpoint of the interaction with the matrix raw material component (B’) in the outermost layer of the core / shell structure. That the polymer nanoparticles (A) have a core / shell structure can be confirmed, for example, by a transmission electron microscope image of the coating film cross-section or the like.

[0213] [Other components that may be contained in the hard coat layer composition] From the viewpoint of further improving the paintability of the hard coat layer composition, the hard coat layer composition may, in addition to the above-mentioned components, optionally contain wetting agents, film-forming aids, ultraviolet absorbers, light stabilizers, thickeners, leveling agents, thixotropizing agents, defoaming agents, freeze stabilizers, dispersants, wetting agents, rheology control agents, rust inhibitors, plasticizers, preservatives, fungicides, antistatic agents, and antistatic agents as matrix raw material components (B').

[0214] From the viewpoint of improving film formation, it is preferable to use wetting agents and film formation aids. The wetting agents and film formation aids are not particularly limited, but for example, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol mono-2-ethylhexyl ether, 2,2,4-trimethyl-1,3-butanediol isobutyrate, diisopropyl glutarate, propylene glycol-n-butyl ether, dipropylene glycol-n-butyl ether, tripropylene glycol-n-butyl ether, dipropylene glycol methyl Examples include methyl ether, tripropylene glycol methyl ether, Megafac® F-443, F-444, F-445, F-470, F-471, F-472SF, F-474, F-475, F-477, F-479, F-480SF, F-482, F-483, F-489, F-172D, and F-178K (all trade names, manufactured by DIC Corporation), SN Wet 366, SN Wet 980, SN Wet L, SN Wet S, SN Wet 125, SN Wet 126, and SN Wet 970 (all trade names, manufactured by Sunopco Corporation). These compounds may be used individually or in combination of two or more.

[0215] [UV absorber] From the viewpoint of further improving the weather resistance of the hard coat layer, the hard coat layer composition may contain an ultraviolet absorber and / or a light stabilizer. While there are no particular limitations on such ultraviolet absorbers and light stabilizers, the exemplified ultraviolet absorbers and light stabilizers can be appropriately adopted as other components that may be included in layer (C), for example.

[0216] [catalyst] The hard coat layer composition may contain a catalyst as a matrix raw material component (B'). When the hard coat layer composition contains a catalyst that promotes the reaction between reactive groups, it is preferable because unreactive groups are less likely to remain in the coating film, resulting in higher hardness, improved abrasion resistance, and improved weather resistance. The catalyst is not particularly limited, but it is preferable that it dissolves or disperses when obtaining the hard coat layer coating film. Examples of such catalysts, though not particularly limited, include organic acids, inorganic acids, organic bases, inorganic bases, metal alkoxides, and metal chelates. These catalysts may be used individually or in combination of two or more.

[0217] [Properties of the hard coat layer composition] From the viewpoint of paintability, the hard coat layer composition has a preferred solid content concentration of 0.01 to 60% by mass, more preferably 1 to 40% by mass. Also from the viewpoint of paintability, the viscosity of the hard coat layer composition at 20°C is preferably 0.1 to 100,000 mPa·s, more preferably 1 to 10,000 mPa·s.

[0218] <Method for manufacturing the hard coat layer> The method for producing the hard coat layer in this embodiment is not particularly limited, but for example, it can be obtained by dispersing and dissolving polymer nanoparticles (A), matrix raw material components (B'), inorganic oxides (D), and other components as appropriate in a solvent to create a hard coat layer composition, coating the substrate with this composition, and then forming a coating film by heat treatment, ultraviolet irradiation, infrared irradiation, etc. Furthermore, the coating method is not particularly limited, but examples include spray coating, flow coating, brush coating, dip coating, spin coating, screen printing, casting, gravure printing, and flexographic printing. After coating, the hard coat layer composition is preferably formed into a coating film by heat treatment at room temperature to 250°C, more preferably 40°C to 150°C, or by ultraviolet or infrared irradiation. Furthermore, this coating can be applied not only to already molded substrates, but also to pre-coated flat plates before molding, such as pre-coated metals including rust-resistant steel plates.

[0219] [Surface treatment of the hard coat layer] In this embodiment, the hard coat layer may be formed by silica processing the surface for weather resistance. While not particularly limited, methods for forming the silica layer include, for example, silica processing by PECVD (plasma-enhanced chemical vapor deposition) to vapor-deposit / cur a silicone or silazane, and silica processing techniques that modify the surface to silica by 155 nm ultraviolet irradiation. Surface processing by PECVD is particularly preferred because it allows for the creation of a layer that is impermeable to oxygen and water vapor without degrading the surface. While not particularly limited, examples of silicones or silazanes that can be used in PECVD include octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, vinylmethrixylane, vinylmethoxysilane, dimethyldimethoxysilane, TEOS (tetraethoxysilane), tetramethyldisiloxane, tetramethyltetravinylcyclotetrasiloxane, and hexamethyldisilazane. One or more of these may be used in combination.

[0220] In this embodiment, a functional layer may be further provided on at least one surface of the hard coat layer. The functional layer is not particularly limited, but examples include an anti-reflective layer, an anti-fouling layer, a polarizing layer, and an impact-absorbing layer.

[0221] <Applications of laminates> The laminate of this embodiment has excellent abrasion resistance and durability. Therefore, applications for the hard coat coating and the substrate with the hard coat coating include, for example, building materials, vehicle components, electronic equipment, and electrical products.

[0222] While not particularly limited, examples of building material applications include windows for construction machinery, windows for buildings, houses, and greenhouses, roofs for garages and arcades, lighting fixtures such as lights and traffic signals, wallpaper, signs, sanitary products such as bathtubs and washbasins, exterior wall materials for kitchens, flooring materials, cork, tiles, cushion flooring, and interior flooring materials such as linoleum.

[0223] Vehicle components are not particularly limited, but examples include parts used in automobiles, aircraft, and trains. Specific examples include various types of glass such as front, rear, front doors, rear doors, rear quarter windows, and sunroofs; exterior components such as front and rear bumpers, spoilers, door mirrors, front grilles, emblem covers, and bodywork; interior components such as center panels, door panels, instrument panels, and center consoles; components for lamps such as headlamps and taillights; lens components for on-board cameras; lighting covers; decorative films; and various glass substitute components.

[0224] Although not particularly limited as electronic devices and electrical products, for example, mobile phones, portable information terminals, personal computers, portable game machines, OA equipment, solar cells, flat panel displays, touch panels, optical discs such as DVDs and Blu-ray discs, optical components such as polarizing plates, optical filters, lenses, prisms, and optical fibers, and optical films such as antireflection films, alignment films, polarizing films, and retardation films are preferably mentioned. In addition to the above, the laminate of the present embodiment can be applied to various fields such as mechanical parts, agricultural materials, fishery materials, transport containers, packaging containers, toys, and miscellaneous goods.

Examples

[0225] Hereinafter, the present embodiment will be described with specific examples and comparative examples, but the present embodiment is not limited thereto.

[0226] Various physical properties in the examples and comparative examples described later were measured by the following methods.

[0227] (1) Measurement of thickness The thickness of each layer was measured using a reflection spectroscopic film thickness meter (product number: FE-3000) manufactured by Otsuka Electronics Co., Ltd.

[0228] (2) Average particle diameter of emulsion particles, composite of emulsion particles and inorganic oxide, average particle diameter of polymer nanoparticles (A), and primary average particle diameter of inorganic oxide Using the aqueous dispersions of various particles and composites obtained by the method described later, the cumulative particle diameter was measured by a dynamic light scattering particle size distribution measuring device (manufactured by Otsuka Electronics Co., Ltd., product number: ELSZ-1000), and the average particle diameter of various particles and composites was used. The primary average particle diameter of the inorganic oxide was observed by magnifying a transmission microscope photograph 50,000 to 100,000 times, photographed so that 100 to 200 inorganic oxides appeared as particles, and the average value of the major axis and minor axis of the inorganic oxide particles was measured, and that value was used as the primary average particle diameter of the inorganic oxide.

[0229] (3) Measurement of haze Haze was measured using a turbidimeter (model number: NDH5000SP) manufactured by Nippon Denshoku Industries Co., Ltd., according to the method specified in JIS K7136. Haze value H1 was measured using the above method for substrates with adhesive layers. Haze value H2 was measured using the above method for laminates (substrates with adhesive layers and hard coat layers).

[0230] (4) Measurement of Martens hardness HM of the hard coat layer Microhardness was measured using an indentation test (test conditions: indenter: Vickers square pyramidal diamond indenter, load increase condition: 2 mN / 20 sec, load decrease condition: 2 mN / 20 sec) with a Fischerscope (model number: HM2000S) manufactured by Fischer Instruments, and the Martens hardness HM of the hard coat layer was measured based on the indentation test method compliant with ISO 14577-1.

[0231] (5) Martens hardness HM of polymer nanoparticles (A) G Measurement Martens hardness HM of polymer nanoparticles (A) G The measurement was performed using a coating film obtained by coating a glass substrate (material: white glass plate, thickness: 2 mm) with a film thickness of 3 μm using a bar coater and drying it at 130°C for 2 hours. The microhardness was measured by an indentation test (test conditions: indenter: Vickers square pyramidal diamond indenter, load increase condition: 2 mN / 20 sec, load decrease condition: 2 mN / 20 sec) using a Fischerscope (model: HM2000S) manufactured by Fischer Instruments, and the Martens hardness HM of the polymer nanoparticle (A) was measured based on the indentation test method compliant with ISO 14577-1. G We measured it.

[0232] (6) Martens hardness HM of matrix raw material component (B') H' Measurement Martens hardness HM of component (B') H'The measurement was performed by dissolving or dispersing component (B') at a solid content concentration of 8% by mass in water / ethanol / acetic acid (composition ratio 77% by mass / 20% by mass / 3% by mass). The resulting solution was applied to a glass substrate (material: white glass plate, thickness: 2 mm) using a bar coater to a film thickness of 3 μm, and dried at 130°C for 2 hours. The measurement was then performed using the resulting coating film. The measurement involved measuring the microhardness using an indentation test (test conditions; indenter: Vickers square pyramidal diamond indenter, load increase condition: 2 mN / 20 sec, load decrease condition: 2 mN / 20 sec) with a Fischerscope (model number: HM2000S) manufactured by Fischer Instruments, and was performed based on the indentation test method in accordance with ISO 14577-1. H' The following was measured. As will be described later, the matrix component (B) corresponds to the hydrolysis condensate of the corresponding component (B'). From this, the Martens hardness HM of component (B') measured as described above was H' The value is the Martens hardness HM of the matrix component (B). H A good match is the Martens hardness HM. H' The value of Martens hardness HM H This was used as the value.

[0233] (7) Evaluation of the abrasion resistance of the hard coat layer in the laminate The abrasion resistance of the hard coat layer in the laminate was evaluated using a Taber ablation tester (No. 101) manufactured by Yasuda Seiki Co., Ltd., in accordance with the ASTM D1044 standard. Specifically, a Taber abrasion test was conducted using a CS-10F abrasion wheel and a load of 500g. The haze before the test and the haze after 1000 rotations were measured using a turbidimeter (model number: NDH5000SP) manufactured by Nippon Denshoku Industries Co., Ltd., according to the method specified in JIS R3212. The abrasion resistance of the hard coat layer in the laminate was evaluated as follows by taking the difference between the haze before the test and the haze after 1000 rotations. (Evaluation Criteria) ○: The haze difference before and after the test is 2 or less. ×: The haze difference before and after the exam exceeds 2.

[0234] (8) Evaluation of weather resistance The weather resistance of the laminate was tested by ultraviolet irradiation using a xenon weather meter (Suga Test Instruments Co., Ltd., product name SX-75) according to the conditions of the ANSI / SAE Z26.1 standard, at 2000 MJ / m². 2 The Δb before and after irradiation was evaluated as follows, and a score of △ or higher was considered a pass. (Evaluation Criteria) ○:Δb≦2 △:2<Δb≦4 ×:Δb>4

[0235] (9) Corrosion resistance of water-based paint compositions on polycarbonate The water-based paint composition obtained by the method described later was applied to a polycarbonate substrate using a bar coater and left to stand for 1 hour at room temperature. After that, the substrate surface was washed with water and the surface was visually observed and evaluated as follows. (Evaluation Criteria) ○: No whitening, blistering, or erosion is observed on the surface. ×: Whitening, blistering, erosion, etc. are visible on the surface.

[0236] (10) Pot Life The water-based paint composition obtained by the method described later was allowed to stand for 6 hours at room temperature. After that, the presence or absence of sedimentation in the water-based paint composition was evaluated visually, and the residue after filtration through a 400-mesh stainless steel mesh was evaluated visually as follows. (Evaluation Criteria) ◎: No sedimentation was observed visually, and no residue was found when the paint composition was filtered through a 400-mesh stainless steel mesh. ○: No sedimentation was observed visually, and a small amount of residue was visible when the coating solution was filtered through a 400-mesh stainless steel mesh. △: Slight sedimentation was observed visually, and residue was seen when the coating solution was filtered through a 400-mesh stainless steel mesh, but it is still usable. ×: Clear subsidence was observed visually, making it unsuitable for use.

[0237] [Preparation of Emulsion Particle Aqueous Dispersion] The emulsion particle aqueous dispersion used in the examples described later was synthesized as follows. In a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirrer, 960 g of deionized water, 22 g of 10% dodecylbenzenesulfonic acid aqueous solution, 25 g of 2% ammonium persulfate aqueous solution, 45 g of butyl acrylate, 45 g of 2-hydroxyethyl methacrylate, 23 g of diethylacrylamide, 1 g of acrylic acid, and 3 g of reactive emulsifier (product name "Adekaria Soap (registered trademark) SR-1025," manufactured by ADEKA Corporation, 25% solids aqueous solution) were added. Polymerization was then carried out at 80°C using a general emulsion polymerization method. After polymerization, the mixture was filtered through a 100-mesh wire mesh, and the concentration was adjusted with purified water to obtain an aqueous dispersion of emulsion particles. The solids content of the obtained emulsion particles was 10% by mass. The average particle size of the emulsion particles was 50 nm.

[0238] [Preparation of composites of emulsion particles and inorganic oxides] <Preparation of Composite Particle Aqueous Dispersion> In a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirrer, 960 g of deionized water, 778 g of water-dispersible colloidal silica "Snowtex® PS-SO" (trade name, manufactured by Nissan Chemical Industries, Ltd., solids content 15% by mass, primary average particle size: 15 nm) as an inorganic oxide, 22 g of 10% dodecylbenzenesulfonic acid aqueous solution, 25 g of 2% ammonium persulfate aqueous solution, 45 g of butyl acrylate, 45 g of 2-hydroxyethyl methacrylate, 23 g of N,N-diethylacrylamide, 1 g of acrylic acid, and 3 g of reactive emulsifier (trade name "Adekaria Soap® SR-1025", manufactured by ADEKA Corporation, solids content 25% aqueous solution) were added. Polymerization was then carried out at 80°C using a general emulsion polymerization method. After polymerization, the pH was adjusted to 9 with a 25% ammonia aqueous solution, filtered through a 100-mesh wire mesh to obtain a composite particle aqueous dispersion. The mass ratio of emulsion particles to inorganic oxide (emulsion particles / inorganic oxide) in the obtained composite particle aqueous dispersion was 1 / 1, the average particle size of the composite of emulsion particles and inorganic oxide was 80 nm, and the solid content of the composite was 12% by mass.

[0239] [Preparation of aqueous dispersion of polymer nanoparticles (A)] The aqueous dispersion of polymer nanoparticles (A) used in the examples described later was synthesized as follows. In a reactor equipped with a reflux condenser, a dropping tank, a thermometer, and a stirrer, 1500 g of deionized water, 45 g of 10% dodecylbenzenesulfonic acid aqueous solution, 105 g of methyltrimethoxysilane, 23 g of phenyltrimethoxysilane, and 27 g of tetraethoxysilane were added. Polymerization was then carried out at 50°C using a general emulsion polymerization method. After polymerization, the temperature was raised to 80°C, and further polymerization was carried out using a general emulsion polymerization method with 43 g of 2% ammonium persulfate aqueous solution, 11 g of butyl acrylate, 12 g of N,N-diethylacrylamide, 1 g of acrylic acid, and 1 g of 3-methacryloxypropyltrimethoxysilane. After polymerization, the mixture was filtered through a 100-mesh wire mesh to obtain an aqueous dispersion of polymer nanoparticles. The obtained polymer nanoparticles (A) had a core-shell structure, an average particle size of 60 nm, and a solid content of 5.9% by mass. The Martens hardness HM of polymer nanoparticles (A) was also measured according to the measurement method described above. G It is 150 N / mm 2 That was the case.

[0240] [Preparation of matrix raw material component (B')] The matrix raw material component (B') used in the examples described later was prepared as follows. As a hydrolyzable silicon compound (b), 35 g of 1,2-bis(triethoxysilyl)ethane and 81 g of tris-(trimethoxysilylpropyl) isocyanurate were mixed under room temperature conditions to obtain matrix raw material component (B'). Furthermore, the matrix component in the hard coat layer derived from matrix raw material component (B') in the hard coat layer composition is referred to as component (B). Matrix component (B) in the hard coat layer can be said to be a hydrolysis condensate of matrix raw material component (B'). In addition, the Martens hardness HM of matrix raw material component (B') measured according to the measurement method described above is... H' It is 420 N / mm 2 The Martens hardness HM of the polymer nanoparticle (A) described above was HM G Based on the measurement results, in the examples and comparative examples, HM H' / HM G It was confirmed that >1. Also, from this result, HM H / HM G I confirmed that it is >1.

[0241] [Preparation of hard coat layer composition] A mixture was obtained by mixing the aqueous dispersion of polymer nanoparticles (A) prepared above with the matrix raw material component (B') prepared above, such that the solid content mass ratio of polymer nanoparticles (A) to matrix component (B) was (A):(B) = 100:200. An aqueous solution of ethanol with a concentration of 20% by mass was used as the solvent, and the mixture was added to obtain a hard coat layer composition with a solid content concentration of 10% by mass. The Martens hardness HM of the hard coat layer measured according to the above method was 380 N / mm². 2 That was the case.

[0242] [Preparation of water-based paint compositions, substrates with adhesive layers, and laminates] [Example 1] Solution A was obtained by mixing 56.0 g of a composite particle aqueous dispersion as a composite of emulsion particles and inorganic oxides, 5.0 g of water-dispersible block polyisocyanate (WS50-30W (product name) manufactured by Asahi Kasei Corporation) as a curing agent, 1.0 g of a 10% aqueous solution of sodium dodecylbenzenesulfonate as a surfactant, and 19.1 g of water under room temperature conditions. Next, solution B was obtained by mixing 0.54 g of Tinuvin® 400 (trade name, manufactured by BASF Japan Ltd.) as an organic ultraviolet absorber, 0.10 g of Tinuvin® 123 (trade name, manufactured by BASF Japan Ltd.) as a light stabilizer, and 18.3 g of isopropanol as a water-soluble organic solvent under room temperature conditions. A water-based paint composition was obtained by stirring liquid A and then adding liquid B dropwise over 5 minutes at room temperature and mixing. The solid content concentration of the water-based paint composition was 9% by mass. The solid content ratio (parts by mass) of each component in the water-based paint composition was composite particles / block polyisocyanate / Tinuvin400 / Tinuvin123 = 100 / 26.8 / 8 / 1.5. The solvent composition (parts by mass) in the paint composition was water / isopropanol = 80 / 20, and the ratio of the number of moles of hydroxyl groups in the emulsion particles to the number of moles of isocyanate groups in the block polyisocyanate (X = number of moles of isocyanate groups / number of moles of hydroxyl groups) was 0.6. Next, the aqueous coating composition of Example 1 was applied onto a polycarbonate substrate using a bar coater and dried at 130°C for 2 hours to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 1 was obtained. Furthermore, the hard coat layer composition was applied to the adhesive layer of the substrate with adhesive layer in Example 1 using a bar coater, and then dried at 130°C for 2 hours to obtain a laminate having a hard coat layer with a thickness of 3.0 μm. Various evaluations were performed on the coating composition, substrate with adhesive layer, and laminate of Example 1. The results are shown in Table 1.

[0243] [Example 2] Solution A was obtained by mixing 34.0 g of an emulsion particle aqueous dispersion, 22.7 g of water-dispersible colloidal silica "Snowtex (registered trademark) PS-SO" (product name, manufactured by Nissan Chemical Industries, Ltd., solids content 15% by mass, primary average particle size: 15 nm) as an inorganic oxide, 5.0 g of water-dispersible block polyisocyanate (manufactured by Asahi Kasei Corporation, WS50-30W (product name)) as a curing agent, 0.62 g of a 10% sodium dodecylbenzenesulfonate aqueous solution as a surfactant, and 8.7 g of water under room temperature conditions. Next, solution B was obtained by mixing 0.54 g of Tinuvin® 400 (trade name, manufactured by BASF Japan Ltd.) as an organic ultraviolet absorber, 0.10 g of Tinuvin® 123 (trade name, manufactured by BASF Japan Ltd.) as a light stabilizer, and 18.3 g of isopropanol as a water-soluble organic solvent under room temperature conditions. A water-based paint composition was obtained by stirring liquid A and then adding liquid B dropwise over 5 minutes at room temperature and mixing. The solid content concentration of the water-based paint composition was 9% by mass. The solid content ratio (parts by mass) of each component in the water-based paint composition was emulsion particles / Snowtex PS-SO / block polyisocyanate / Tinuvin 400 / Tinuvin 123 = 100 / 100 / 26.8 / 16 / 3.0. The solvent composition (parts by mass) in the paint composition was water / isopropanol = 80 / 20, and the ratio (X) of the number of moles of hydroxyl groups in the emulsion particles to the number of moles of isocyanate groups in the block polyisocyanate was 0.6. Using the aqueous coating composition of Example 2, a substrate with an adhesive layer and a laminate were obtained in the same manner as in Example 1. Various evaluations were performed on the coating composition, substrate with adhesive layer, and laminate of Example 2. The results are shown in Table 1.

[0244] [Example 3] Except for not using a surfactant in the aqueous coating composition, an aqueous coating composition, a substrate with an adhesive layer, and a laminate were obtained in the same manner as in Example 1. The solid content concentration of the aqueous coating composition was 9% by mass. The solid content ratio (parts by mass) of each component in the aqueous coating composition was composite particles / block polyisocyanate / Tinuvin400 / Tinuvin123 = 100 / 26.8 / 8 / 1.5. The solvent composition (parts by mass) contained in the coating composition was water / isopropanol = 80 / 20, and the ratio (X) of the number of moles of hydroxyl groups contained in the emulsion particles to the number of moles of isocyanate groups contained in the block polyisocyanate was 0.6. Various evaluations were performed on the coating composition, substrate with adhesive layer, and laminate of Example 3. The results are shown in Table 1.

[0245] [Example 4] In the same manner as in Example 1, liquid A and liquid B of the water-based paint composition were obtained. Then, while liquid B was stirred, liquid A was added dropwise over 5 minutes at room temperature and mixed to obtain the water-based paint composition. The solid content concentration of the water-based paint composition was 9% by mass. The solid content ratio (parts by mass) of each component in the water-based paint composition was composite particles / block polyisocyanate / Tinuvin400 / Tinuvin123 = 100 / 26.8 / 8 / 1.5. The solvent composition (parts by mass) contained in the paint composition was water / isopropanol = 80 / 20, and the ratio (X) of the number of moles of hydroxyl groups contained in the emulsion particles to the number of moles of isocyanate groups contained in the block polyisocyanate was 0.6. Using the aqueous coating composition of Example 4, a substrate with an adhesive layer and a laminate were obtained in the same manner as in Example 1. Various evaluations were performed on the coating composition, substrate with adhesive layer, and laminate of Example 4. The results are shown in Table 1.

[0246] [Example 5] A water-based coating composition, a substrate with an adhesive layer, and a laminate were obtained in the same manner as in Example 1, except that Tinuvin® 384-2 (trade name, manufactured by BASF Japan Ltd.) was used instead of Tinuvin® 400 (trade name) as the organic ultraviolet absorber. The solid content concentration of the water-based coating composition was 9% by mass. The solid content ratio (parts by mass) of each component in the water-based coating composition was composite particles / block polyisocyanate / Tinuvin 384-2 / Tinuvin 123 = 100 / 26.8 / 8 / 1.5. The solvent composition (parts by mass) contained in the coating composition was water / isopropanol = 80 / 20, and the ratio (X) of the number of moles of hydroxyl groups contained in the emulsion particles to the number of moles of isocyanate groups contained in the block polyisocyanate was 0.6. Various evaluations were performed on the coating composition, substrate with adhesive layer, and laminate of Example 5. The results are shown in Table 1.

[0247] [Example 6] A water-based paint composition, a substrate with an adhesive layer, and a laminate were obtained in the same manner as in Example 1, except that Uvinul® 3050 (trade name, manufactured by BASF) was used instead of Tinuvin® 400 (trade name) as the organic ultraviolet absorber. The solid content concentration of the water-based paint composition was 9% by mass. The solid content ratio (parts by mass) of each component in the water-based paint composition was composite particles / block polyisocyanate / Uvinul 3050 / Tinuvin 123 = 100 / 26.8 / 8 / 1.5. The solvent composition (parts by mass) contained in the paint composition was water / isopropanol = 80 / 20, and the ratio (X) of the number of moles of hydroxyl groups contained in the emulsion particles to the number of moles of isocyanate groups contained in the block polyisocyanate was 0.6. Various evaluations were performed on the coating composition, substrate with adhesive layer, and laminate of Example 6. The results are shown in Table 1.

[0248] [Example 7] A water-based paint composition, a substrate with an adhesive layer, and a laminate were obtained in the same manner as in Example 1, except that the solid content ratio (parts by mass) of each component in the water-based paint composition was set to composite particles / block polyisocyanate / Tinuvin400 / Tinuvin123 = 100 / 26.8 / 4 / 1.5. The solid content concentration of the water-based paint composition was 9% by mass. The solvent composition (parts by mass) in the paint composition was water / isopropanol = 80 / 20, and the ratio (X) of the number of moles of hydroxyl groups in the emulsion particles to the number of moles of isocyanate groups in the block polyisocyanate was 0.6. Various evaluations were performed on the coating composition, substrate with adhesive layer, and laminate of Example 7. The results are shown in Table 1.

[0249] [Example 8] A water-based coating composition, a substrate with an adhesive layer, and a laminate were obtained in the same manner as in Example 1, except that Tinuvin® 152 (trade name, manufactured by BASF Japan Ltd.) was used as a light stabilizer instead of Tinuvin® 123 (trade name). The solid content concentration of the water-based coating composition was 9% by mass. The solid content ratio (parts by mass) of each component in the water-based coating composition was composite particles / block polyisocyanate / Tinuvin 400 / Tinuvin 152 = 100 / 26.8 / 8 / 1.5. The solvent composition (parts by mass) in the coating composition was water / isopropanol = 80 / 20, and the ratio (X) of the number of moles of hydroxyl groups in the emulsion particles to the number of moles of isocyanate groups in the block polyisocyanate was 0.6. Various evaluations were performed on the coating composition, substrate with adhesive layer, and laminate of Example 8. The results are shown in Table 1.

[0250] [Example 9] A water-based coating composition, a substrate with an adhesive layer, and a laminate were obtained in the same manner as in Example 1, except that Tinuvin® 292 (trade name, manufactured by BASF Japan Ltd.) was used instead of Tinuvin® 123 (trade name) as a light stabilizer. The solid content concentration of the water-based coating composition was 9% by mass. The solid content ratio (parts by mass) of each component in the water-based coating composition was composite particles / block polyisocyanate / Tinuvin 400 / Tinuvin 292 = 100 / 26.8 / 8 / 1.5. The solvent composition (parts by mass) contained in the coating composition was water / isopropanol = 80 / 20, and the ratio (X) of the number of moles of hydroxyl groups contained in the emulsion particles to the number of moles of isocyanate groups contained in the block polyisocyanate was 0.6. Various evaluations were performed on the coating composition, substrate with adhesive layer, and laminate of Example 9. The results are shown in Table 1.

[0251] [Example 10] A water-based paint composition, a substrate with an adhesive layer, and a laminate were obtained in the same manner as in Example 1, except that the solvent composition (parts by mass) in the water-based paint composition was changed from water / isopropanol = 80 / 10 to 60 / 40. The solid content concentration of the water-based paint composition was 9% by mass. The solid content ratio (parts by mass) of each component in the water-based paint composition was composite particles / block polyisocyanate / Tinuvin400 / Tinuvin123 = 100 / 26.8 / 8 / 1.5, and the ratio (X) of the number of moles of hydroxyl groups contained in the emulsion particles to the number of moles of isocyanate groups contained in the block polyisocyanate was 0.6. Various evaluations were performed on the coating composition, substrate with adhesive layer, and laminate of Example 10. The results are shown in Table 2.

[0252] [Example 11] A water-based paint composition, a substrate with an adhesive layer, and a laminate were obtained in the same manner as in Example 1, except that the solvent composition (parts by mass) in the water-based paint composition was changed from water / isopropanol = 80 / 10 to 90 / 10. The solid content concentration of the water-based paint composition was 9% by mass. The solid content ratio (parts by mass) of each component in the water-based paint composition was composite particles / block polyisocyanate / Tinuvin400 / Tinuvin123 = 100 / 26.8 / 8 / 1.5, and the ratio (X) of the number of moles of hydroxyl groups contained in the emulsion particles to the number of moles of isocyanate groups contained in the block polyisocyanate was 0.6. Various evaluations were performed on the coating composition, substrate with adhesive layer, and laminate of Example 11. The results are shown in Table 2.

[0253] [Example 12] Solution A was obtained by mixing 56.0 g of a composite particle aqueous dispersion as a composite of emulsion particles and inorganic oxide, 5.0 g of water-dispersible block polyisocyanate (manufactured by Asahi Kasei Corporation, product name WS50-30W) as a curing agent, and 20.0 g of water under room temperature conditions. Next, solution B was obtained by mixing 0.54 g of Tinuvin® 400 (trade name, manufactured by BASF Japan Ltd.) as an organic UV absorber, 0.10 g of Tinuvin® 123 (trade name, manufactured by BASF Japan Ltd.) as a light stabilizer, 0.10 g of sodium dodecylbenzenesulfonate as a surfactant, and 18.3 g of isopropanol as a water-soluble organic solvent under room temperature conditions. A water-based paint composition was obtained by stirring liquid A and then adding liquid B dropwise over 5 minutes at room temperature and mixing. The solid content concentration of the water-based paint composition was 9% by mass. The solid content ratio (parts by mass) of each component in the water-based paint composition was composite particles / block polyisocyanate / Tinuvin400 / Tinuvin123 = 100 / 26.8 / 8 / 1.5. The solvent composition (parts by mass) in the paint composition was water / isopropanol = 80 / 20, and the ratio (X) of the number of moles of hydroxyl groups in the emulsion particles to the number of moles of isocyanate groups in the block polyisocyanate was 0.6. Next, the aqueous coating composition of Example 12 was applied onto a polycarbonate substrate using a bar coater and dried at 130°C for 2 hours to form an adhesive layer with a thickness of 5.0 μm on the polycarbonate substrate. In this way, the substrate with the adhesive layer of Example 12 was obtained. Furthermore, the hard coat layer composition was applied to the adhesive layer substrate of Example 12 using a bar coater, and then dried at 130°C for 2 hours to obtain a laminate having a hard coat layer with a thickness of 3.0 μm. Various evaluations were performed on the coating composition, substrate with adhesive layer, and laminate of Example 12. The results are shown in Table 2.

[0254] [Example 13] Solution A was obtained by mixing 56.0 g of a composite particle aqueous dispersion as a composite of emulsion particles and inorganic oxides, 5.0 g of water-dispersible block polyisocyanate (manufactured by Asahi Kasei Corporation, WS50-30W (product name)) as a curing agent, 0.5 g of a 10% sodium dodecylbenzenesulfonate aqueous solution as a surfactant, and 19.6 g of water under room temperature conditions. Next, solution B was obtained by mixing 0.54 g of Tinuvin® 400 (trade name, manufactured by BASF Japan Ltd.) as an organic UV absorber, 0.10 g of Tinuvin® 123 (trade name, manufactured by BASF Japan Ltd.) as a light stabilizer, 0.05 g of sodium dodecylbenzenesulfonate as a surfactant, and 18.3 g of isopropanol as a water-soluble organic solvent under room temperature conditions. A water-based paint composition was obtained by stirring liquid A and then adding liquid B dropwise over 5 minutes at room temperature and mixing. The solid content concentration of the water-based paint composition was 9% by mass. The solid content ratio (parts by mass) of each component in the water-based paint composition was 100 / 26.8 / 8 / 1.5 for the composite particles / Tinuvin400 / blocked polyisocyanate / Tinuvin123. The solvent composition (parts by mass) in the paint composition was 80 / 20 for water / isopropanol, and the ratio (X) of the number of moles of hydroxyl groups in the emulsion particles to the number of moles of isocyanate groups in the blocked polyisocyanate was 0.6. Using the aqueous coating composition of Example 13, a substrate with an adhesive layer and a laminate were obtained in the same manner as in Example 1. Various evaluations were performed on the coating composition, substrate with adhesive layer, and laminate of Example 13. The results are shown in Table 2.

[0255] [Comparative Example 1] A water-based paint composition, a substrate with an adhesive layer, and a laminate were obtained in the same manner as in Example 1, except that ethanol (boiling point: 78°C) was used instead of isopropanol as the water-soluble organic solvent in the water-based paint composition. The solid content concentration of the water-based paint composition was 9% by mass. The solid content ratio (parts by mass) of each component in the water-based paint composition was composite particles / block polyisocyanate / Tinuvin400 / Tinuvin123 = 100 / 26.8 / 8 / 1.5. The solvent composition (parts by mass) in the water-based paint composition was water / ethanol = 80 / 20, and the ratio (X) of the number of moles of hydroxyl groups in the emulsion particles to the number of moles of isocyanate groups in the block polyisocyanate was 0.6. Various evaluations were performed on the water-based coating composition, substrate with adhesive layer, and laminate of Comparative Example 1. The results are shown in Table 2.

[0256] [Comparative Example 2] A water-based paint composition, a substrate with an adhesive layer, and a laminate were obtained in the same manner as in Example 1, except that propylene glycol monomethyl ether acetate (boiling point: 146.4°C) was used instead of isopropanol as the water-soluble organic solvent in the water-based paint composition. The solid content concentration of the water-based paint composition was 9% by mass. The solid content ratio (parts by mass) of each component in the water-based paint composition was composite particles / block polyisocyanate / Tinuvin400 / Tinuvin123 = 100 / 26.8 / 8 / 1.5. The solvent composition (parts by mass) in the water-based paint composition was water / propylene glycol monomethyl ether acetate = 80 / 20, and the ratio (X) of the number of moles of hydroxyl groups in the emulsion particles to the number of moles of isocyanate groups in the block polyisocyanate was 0.6. Various evaluations were performed on the water-based coating composition, substrate with adhesive layer, and laminate of Comparative Example 2. The results are shown in Table 2.

[0257] [Comparative Example 3] A paint composition, a substrate with an adhesive layer, and a laminate were obtained in the same manner as in Example 1, except that butyl acetate, a non-water-soluble organic solvent, was used instead of isopropanol, a water-soluble organic solvent. The solid content concentration of the paint composition was 9% by mass. The solid content ratio (parts by mass) of each component in the water-based paint composition was composite particles / block polyisocyanate / Tinuvin400 / Tinuvin123 = 100 / 26.8 / 8 / 1.5. The solvent composition (parts by mass) in the paint composition was water / butyl acetate = 80 / 20, and the ratio (X) of the number of moles of hydroxyl groups in the emulsion particles to the number of moles of isocyanate groups in the block polyisocyanate was 0.6. Various evaluations were performed on the paint composition, substrate with adhesive layer, and laminate of Comparative Example 3. The results are shown in Table 2.

[0258] [Comparative Example 4] Except for the absence of an organic ultraviolet absorber and a light stabilizer, a water-based coating composition, a substrate with an adhesive layer, and a laminate were obtained in the same manner as in Example 1. The solid content concentration of the water-based coating composition was 9% by mass. The solvent composition (parts by mass) of the water-based coating composition was water / isopropanol = 80 / 20, and the ratio (X) of the number of moles of hydroxyl groups in the emulsion particles to the number of moles of isocyanate groups in the blocked polyisocyanate was 0.6. Various evaluations were performed on the paint composition, substrate with adhesive layer, and laminate of Comparative Example 4. The results are shown in Table 2.

[0259] [Comparative Example 5] A water-based paint composition was obtained by mixing 15g of E2050S aqueous dispersion (trade name, manufactured by Asahi Kasei Corporation, solid content concentration 46%) as an emulsion particle aqueous dispersion, 14g of spherical water-dispersible colloidal silica "Snowtex® C" (trade name, manufactured by Nissan Chemical Industries, Ltd., solid content 20% by mass, primary average particle size 15nm) as an inorganic oxide, 2.1g of Tinuvin® 400 (trade name, manufactured by BASF Japan Ltd.) as an organic ultraviolet absorber, 0.1g of Tinuvin® 123 (trade name, manufactured by BASF Japan Ltd.) as a light stabilizer, 33g of water, and 35g of ethanol (boiling point: 78℃) as a water-soluble organic solvent under room temperature conditions. The solid content concentration of the water-based paint composition was 12% by mass. The solid content ratio (parts by mass) of each component in the water-based paint composition was E2050S / Snowtex C / Tinuvin400 / Tinuvin123 = 100 / 40 / 30 / 2. Furthermore, the solvent composition (parts by mass) of the water-based paint composition was water / ethanol = 80 / 20. Using the aqueous coating composition of Comparative Example 5, a substrate with an adhesive layer and a laminate were obtained in the same manner as in Example 1. Various evaluations were performed on the water-based coating composition, substrate with adhesive layer, and laminate of Comparative Example 5. The results are shown in Table 2.

[0260] [Table 1]

[0261] [Table 2] [Industrial applicability]

[0262] The aqueous coating compositions, substrates with adhesive layers, laminates, and composition sets provided by the present invention are useful, for example, as hard coats for building materials, as well as automotive components, electronic devices, and electrical products.

Claims

1. A mixture of emulsion particles and an inorganic oxide, and / or a composite of said emulsion particles and an inorganic oxide, Blocked polyisocyanate and, Organic UV absorbers, Light stabilizer, A water-based paint composition comprising a solvent, The aforementioned solvent consists only of a water-soluble organic solvent having a boiling point of 80°C or higher and 140°C or lower, and soluble in water at a concentration of 10% or more, and water. The water-soluble organic solvent is at least one selected from the group consisting of alcohol compounds, glycol ether compounds, ether compounds, ketone compounds, and nitrile compounds. The content of the water-soluble organic solvent is 5% by mass or more and 40% by mass or less, based on 100% by mass of the water-based paint composition. The inorganic oxide includes silica in a spherical and / or linked structure. Water-based paint composition.

2. The water-based paint composition according to claim 1, wherein the water-soluble organic solvent is an alcohol compound.

3. The aqueous coating composition according to claim 1 or 2, wherein the average particle size of the mixture and / or the composite is 2 to 2000 nm.

4. A water-based paint composition according to any one of claims 1 to 3, further comprising a surfactant.

5. The aqueous coating composition according to claim 2, wherein the alcohol compound comprises isopropanol.

6. The aqueous coating composition according to any one of claims 1 to 5, wherein the organic ultraviolet absorber comprises one or more selected from the group consisting of benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, and benzophenone ultraviolet absorbers.

7. The aqueous coating composition according to any one of claims 1 to 6, wherein the light stabilizer comprises a hindered amine compound.

8. It comprises a base material and an adhesive layer disposed on the base material, A substrate with an adhesive layer, wherein the adhesive layer comprises a cured product of the water-based paint composition described in any one of claims 1 to 7.

9. The present invention comprises a substrate with an adhesive layer as described in claim 8, and a hard coat layer disposed on the adhesive layer in the substrate, The hard coat layer comprises polymer nanoparticles and a matrix component. The matrix component includes an inorganic oxide, Martens hardness HM of the polymer nanoparticles G And the Martens hardness HM of the matrix component. H HM H / HM G A laminate that satisfies the relationship >1.

10. The laminate according to claim 9, wherein the haze value H1 of the substrate with the adhesive layer is greater than the haze value H2 of the laminate.

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