Coated article and production method therefor

Abstract

Provided is a coated article comprising a resinous base, a primer layer disposed on the resinous base, a hardcoat layer disposed on the primer layer, and an optically modified layer formed on a surface-layer portion of the hardcoat layer, wherein the primer layer is a cured coating film formed from a primer composition comprising (A) a vinyl-based (co)polymer and (B) inorganic particles having a given median diameter, the vinyl-based (co)polymer (A) including (A-1) a vinyl-based (co)polymer having an alkoxysilyl group and the primer layer having a thickness of 1-20 μm, and the hardcoat layer is a cured coating film formed from a silicone composition comprising (a) a silicone resin, (b) colloidal silica, and (c) an ultraviolet absorber, the hardcoat layer having a thickness of 1-15 μm.

Description

Coated article and method of manufacturing same

[0001] The present invention relates to a coated article and a method for manufacturing the same, and more specifically to a coated article having an organic resin substrate such as a plastic substrate, a primer layer provided on the substrate, a hard coat layer provided on the primer layer, and a photo-modifying layer formed on the surface of the hard coat layer, and a method for manufacturing the same.

[0002] In recent years, transparent materials that are non-shatterproof or more shatter-resistant than glass have become widely used as replacements for transparent plate glass. For example, plastic substrates, particularly polycarbonate resins, are excellent in transparency, impact resistance, heat resistance, etc., and are currently used as structural replacements for glass in a variety of applications, such as windows for buildings and vehicles, and instrument covers. However, because polycarbonate resins are inferior to glass in surface properties such as scratch resistance and weather resistance, there is a strong demand for improving the surface properties of polycarbonate resin molded products.

[0003] As a means for imparting scratch resistance equivalent to that of glass to the surface of a resin molded product, Patent Document 1 proposes a method of forming a photo-modified film by providing a protective coating with a siloxane-based hard coat paint and then modifying the surface of the protective coating with vacuum ultraviolet light. However, when the resin molded product is placed under high temperatures, the photo-modified film cannot keep up with the thermal expansion of the resin, and is prone to cracking, resulting in problems with heat resistance and weather resistance.

[0004] Patent Documents 2 and 3 propose a method in which a mesh mask is placed on a siloxane-based hard coat layer, and light is irradiated from above the mesh mask, so that the light is directed onto the hard coat layer through the openings in the mesh mask, and photo-modified layers and siloxane-based hard coat layers are alternately formed on the surface of the resin substrate in a shape that corresponds to the opening shape of the mesh mask, thereby alleviating the stress that the photo-modified layer receives due to the expansion of the resin substrate and improving heat resistance. However, a simpler manufacturing method is desired.

[0005] Furthermore, Patent Document 4 reports that heat resistance when heated to 80°C is improved by increasing the thickness of a primer layer containing an acrylic polymer to 10 μm or more, or by forming a primer layer containing 20 to 60 parts by mass of silica particles per 100 parts by mass of acrylic polymer, and then forming a siloxane-based hard coat layer and a photo-modified layer on top of the primer layer. On the other hand, if the primer layer is made thicker or a large amount of silica particles is added, cracks, early peeling, whitening of the coating film, etc. are likely to occur during weather resistance tests, posing issues with weather resistance. In addition, polycarbonate resins are sometimes required to have heat resistance at temperatures above 100°C.

[0006] Japanese Patent No. 4536824 Japanese Patent No. 6585758 International Publication No. 2020-044705 Japanese Patent Application Laid-Open No. 2016-030392

[0007] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a coated article having scratch resistance comparable to that of glass, as well as excellent heat resistance and weather resistance.

[0008] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that a coated article having, on a resin substrate, a predetermined primer layer containing a vinyl-based (co)polymer having an alkoxysilyl group in its molecular structure, a predetermined siloxane-based hard coat layer provided on the primer layer, and a photo-modified layer formed on the surface portion of the hard coat layer, has scratch resistance comparable to that of glass, as well as excellent heat resistance and weather resistance, and have completed the present invention.

[0009] That is, the present invention provides: 1. a cured coating film of a primer composition comprising a resin substrate, a primer layer provided on the resin substrate, a hard coat layer provided on the primer layer, and a photo-modified layer formed on a surface layer portion of the hard coat layer, wherein the primer layer is a cured coating film of a primer composition comprising: (A) 100 parts by mass of a vinyl (co)polymer; and (B) 1 to 19 parts by mass of inorganic particles having a median diameter of 1 to 100 nm measured by a dynamic light scattering method, wherein the (A) vinyl (co)polymer comprises (A-1) a vinyl (co)polymer having an alkoxysilyl group, and the primer layer has a thickness of 1 to 20 μm, and the hard coat layer is a cured coating film of a primer composition comprising: (a) a vinyl (co)polymer represented by the following formula (1): R 1 m Si(OR 2 ) 4-m (1) (wherein, R 1 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and a plurality of R 1 may be bonded to each other to form a linking group, and R 2 are each independently an alkyl group having 1 to 3 carbon atoms, and m is 0, 1, or 2.) A coated article which is a cured coating of a silicone composition comprising: (a) a silicone resin obtained by (co)hydrolyzing and condensing at least one selected from alkoxysilanes represented by the formula (I) and their (partial) hydrolysis condensates, (b) colloidal silica, and (c) an ultraviolet absorber, wherein the hard coat layer has a thickness of 1 to 15 μm; 2. The coated article according to 1, wherein the photo-modified layer comprises silicon dioxide; 3. The coated article according to 1 or 2, wherein the (c) ultraviolet absorber comprises a reactive ultraviolet absorber represented by the following general formula (2) and its (partial) hydrolysis condensate; [In the formula, R 3 are each independently a hydrogen atom, a hydroxy group, an alkyl group having 1 to 5 carbon atoms, or a group represented by the following general formula (3), 3 At least one of the groups is a group represented by the following general formula (3): *—O—(CH2) j -SiR 4 k (OR 5 ) 3-k (3) (wherein, R 4 and R5 are each independently an alkyl group having 1 to 5 carbon atoms, j is an integer of 1 to 8, and k is an integer of 0 to 2. An asterisk * represents a bond to an adjacent atom.) 4. The coated article according to any one of 1 to 3, wherein the hard coat layer has a surface hardness of 0.10 to 0.50 GPa as measured by a nanoindentation method, 5. The coated article according to any one of 1 to 4, wherein the (B) inorganic particles comprise one or more particles selected from silica, zinc oxide, titanium oxide, and cerium oxide, 6. The coated article according to any one of 1 to 5, wherein the primer composition comprises (A-1) a vinyl copolymer having an alkoxysilyl group and an ultraviolet absorbing group, 7. The coated article according to any one of 1 to 6, wherein the primer composition further comprises (C) one or more ultraviolet absorbers selected from triazine derivatives and benzophenone derivatives, 8. The coated article according to any one of 1 to 7, wherein the primer composition further comprises (D) a hindered amine light stabilizer, 9. 10. A method for producing a coated article according to any one of 1 to 9, wherein the primer layer has a thickness of 3 to 15 μm and the hard coat layer has a thickness of 3 to 13 μm, the method including a step of irradiating the surface of the hard coat layer with light having a wavelength of 300 nm or less to form a photo-modified layer on the surface of the hard coat layer.

[0010] According to the present invention, a coated article can be provided that has scratch resistance comparable to that of glass, as well as excellent heat resistance and weather resistance. Furthermore, according to the present invention, no special operations or tools are required for photo-modification of the hard coat layer, and no special post-treatment is required after photo-modification. Therefore, excellent scratch resistance, heat resistance, and weather resistance can be more easily imparted to resin substrates of various shapes.

[0011] The present invention will be described in detail below. The coated article of the present invention comprises a resin substrate, a primer layer provided on the resin substrate, a hard coat layer provided on the primer layer, and a photo-modified layer formed on the surface of the hard coat layer, wherein the primer layer is a cured coating of a primer composition containing a vinyl (co)polymer having an alkoxysilyl group, and the hard coat layer is a cured coating of a silicone composition containing (a) a silicone resin, (b) colloidal silica, and (c) an ultraviolet absorber.

[0012] One of the features of the coated article of the present invention is that the hard coat layer contains an ultraviolet absorber, which prevents light from reaching the primer layer during photo-modification by irradiating the hard coat layer with light, as described below, and suppresses peeling of the coating or deterioration of scratch resistance due to reduced adhesion.

[0013] Furthermore, by providing a primer layer containing a vinyl-based (co)polymer containing an alkoxysilyl group in its molecular structure, the alkoxysilyl group contained in the primer layer and / or the silanol group generated by its hydrolysis imparts reactivity with the siloxane in the siloxane-based hard coat layer, improving adhesion between the substrate and the hard coat layer via the primer layer, and also improving heat resistance and exhibiting excellent scratch resistance and weather resistance due to crosslinking of the alkoxysilyl group and / or the silanol group generated by its hydrolysis.

[0014] <Resin Substrate> The resin substrate in the coated article of the present invention is not particularly limited, but various organic resin substrates are suitably used. Specific examples include polycarbonate resin, polystyrene resin, acrylic resin, modified acrylic resin, urethane resin, thiourethane resin, polycondensation product of halogenated bisphenol A and ethylene glycol, acrylic urethane resin, halogenated aryl group-containing acrylic resin, sulfur-containing resin, etc. Among these, polycarbonate resin is preferred. Furthermore, examples of the resin substrates whose surfaces have been treated, specifically, those that have been subjected to chemical conversion treatment, corona discharge treatment, plasma treatment, treatment with an acid or alkali solution, etc., can also be used. Furthermore, laminates in which the surface layer is formed of a resin different from that of the substrate body can also be used. Specific examples of laminates include laminates produced by co-extrusion or lamination, in which an acrylic resin layer or urethane resin layer is provided on the surface of a polycarbonate resin substrate, and laminates in which an acrylic resin layer is provided on the surface of a polyester resin substrate.

[0015] <Primer Layer> The primer layer in the coated article of the present invention comprises a cured coating of a primer composition containing the following components (A) and (B): (A) a vinyl (co)polymer; and (B) inorganic particles having a median diameter of 100 nm or less as measured by dynamic light scattering.

[0016] [(A) Vinyl (co)polymer] (1) (A-1) Vinyl (co)polymer having an alkoxysilyl group The vinyl (co)polymer of component (A) includes (A-1) a vinyl (co)polymer having an alkoxysilyl group. Examples of the vinyl (co)polymer of component (A-1) having an alkoxysilyl group include a vinyl (co)polymer in which the alkoxysilyl group is bonded to the main chain via an Si—C bond. Examples of such a (co)polymer include a polymer of a vinyl monomer in which an alkoxysilyl group is bonded via an Si—C bond, and a copolymer of a vinyl monomer in which an alkoxysilyl group is bonded via an Si—C bond with another vinyl monomer.

[0017] Here, any vinyl monomer having an alkoxysilyl group bonded via an Si-C bond can be used as long as it contains one vinyl polymerizable functional group and one or more alkoxysilyl groups in one molecule.

[0018] Examples of vinyl-based polymerizable functional groups include organic groups having 2 to 12 carbon atoms, such as vinyl, vinyloxy, (meth)acryloxy, and (α-methyl)styryl groups. Specific examples include vinyl, 5-hexenyl, 9-decenyl, vinyloxymethyl, 3-vinyloxypropyl, (meth)acryloxymethyl, 3-(meth)acryloxypropyl, 11-(meth)acryloxyundecyl, vinylphenyl(styryl), isopropenylphenyl(α-methylstyryl), and vinylphenylmethyl groups (vinylbenzyl groups). Among these, the (meth)acryloxypropyl group is preferred in terms of reactivity and availability. In the present invention, (meth)acryl means acrylic and / or methacrylic.

[0019] Examples of the alkoxy group in the alkoxysilyl group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, etc. Among these, methoxy and ethoxy groups are preferred because of ease of control of hydrolysis and ease of availability.

[0020] Examples of the substituent bonded to the silicon atom other than the alkoxy group include alkyl groups such as methyl, ethyl, n-propyl, n-hexyl, and n-decyl groups, and aryl groups such as phenyl groups. Of these, the methyl group is preferred because of its availability.

[0021] Examples of vinyl monomers in which an alkoxysilyl group is bonded via an Si—C bond include methacryloxymethyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxyundecyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyldimethylmethoxysilane, methacryloxypropyltriethoxysilane, acryloxypropyltrimethoxysilane, acryloxypropylmethyldimethoxysilane, acryloxypropyldimethylmethoxysilane, acryloxypropyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxyundecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, allyltrimethoxysilane, styryltrimethoxysilane, styrylmethyldimethoxysilane, and styryltriethoxysilane. Among these, methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyldimethylmethoxysilane, acryloxypropyltrimethoxysilane, and acryloxypropylmethyldimethoxysilane are preferred in terms of availability, ease of handling, crosslinking density, reactivity, and the like.

[0022] The amount of alkoxysilyl groups in component (A), for example, when the alkoxysilyl groups are trimethoxysilane, is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, and even more preferably 3 to 15% by mass, based on the total amount of component (A). When the amount is 1% by mass or more, sufficient siloxane network formation occurs due to crosslinking between the vinyl (co)polymers themselves or with inorganic fillers, etc., resulting in a lower linear expansion coefficient of the coating and improved heat resistance and durability. Furthermore, reaction with siloxanes in the hard coat layer further improves adhesion to the hard coat layer and weather resistance. Furthermore, when the amount of alkoxysilyl groups in component (A) is 50% by mass or less, the crosslinking density does not become too high, suppressing a decrease in adhesion due to excessive hardness and preventing cracking of the coating due to post-crosslinking of unreacted alkoxysilyl groups over time.

[0023] The other vinyl-based monomer copolymerizable with the vinyl-based monomer having an alkoxysilyl group bonded via an Si—C bond is not particularly limited as long as it is a copolymerizable vinyl-based monomer, and examples thereof include (meth)acrylic monomers, (meth)acrylic acid esters, (meth)acrylonitrile, (meth)acrylamide, alkyl vinyl ethers, alkyl vinyl esters, styrene, and derivatives thereof.

[0024] Specific examples of (meth)acrylic acid esters and derivatives thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, n-hexyl (meth)acrylate, isohexyl (meth)acrylate, n-heptyl (meth)acrylate, isoheptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, (Meth)acrylic acid esters of monohydric alcohols such as n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-undecyl (meth)acrylate, n-dodecyl (meth)acrylate, lauryl (meth)acrylate, palmityl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-methylcyclohexyl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and benzyl (meth)acrylate; 2-methoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 2-methoxybutyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate (the number of ethylene glycol units is preferably, for example, 2 to 20), methoxypolypropylene glycol (meth)acrylate (the number of propylene glycol units is preferably, for example, 2 to 20).(meth)acrylic acid esters of alkoxy (poly)alkylene glycols such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerin mono(meth)acrylate, pentaerythritol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate (the number of ethylene glycol units is preferably, for example, 2 to 20), and polypropylene glycol mono(meth)acrylate (the number of propylene glycol units is preferably, for example, 2 to 20); Ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, glycerin di(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate (the number of ethylene glycol units is preferably, for example, 2 to 20), polypropylene glycol di(meth)acrylate (the number of propylene glycol units is preferably, for example, 2 to 20).(meth)acrylic acid esters of polyhydric alcohols such as mono[2-(meth)acryloyloxyethyl] succinate, di[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] adipate, di[2-(meth)acryloyloxyethyl] adipate, mono[2-(meth)acryloyloxyethyl] phthalate, di[2-(meth)acryloyloxyethyl] phthalate, (poly)esters of non-polymerizable polybasic acids with hydroxyalkyl (meth)acrylates such as mono[2-(meth)acryloyloxyethyl] succinate, di[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] adipate, mono[2-(meth)acryloyloxyethyl] phthalate, and di[2-(meth)acryloyloxyethyl] phthalate; Examples thereof include amino group-containing (meth)acrylic acid esters such as 2-aminoethyl (meth)acrylate, 2-(N-methylamino)ethyl (meth)acrylate, 2-(N,N-dimethylamino)ethyl (meth)acrylate, 2-(N-ethylamino)ethyl (meth)acrylate, 2-(N,N-diethylamino)ethyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, and 4-(N,N-dimethylamino)butyl (meth)acrylate; and epoxy group-containing (meth)acrylic acid esters such as glycidyl (meth)acrylate.

[0025] Specific examples of the derivatives of (meth)acrylonitrile include α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-trifluoromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, and vinylidene cyanide. Specific examples of the (meth)acrylamide derivative include N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-ethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-methoxy(meth)acrylamide, N,N-dimethoxy(meth)acrylamide, N-ethoxy(meth)acrylamide, N,N-diethoxy(meth)acrylamide, diacetone(meth)acrylamide, N-methylol(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N,N-dimethylaminomethyl(meth)acrylamide, N-(2-dimethylamino)ethyl(meth)acrylamide, N,N'-methylenebis(meth)acrylamide, and N,N'-ethylenebis(meth)acrylamide.

[0026] Specific examples of alkyl vinyl ethers include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, etc. Specific examples of alkyl vinyl esters include vinyl formate, vinyl acetate, vinyl acrylate, vinyl butyrate, vinyl caproate, vinyl stearate, etc. Specific examples of styrene and its derivatives include styrene, α-methylstyrene, vinyltoluene, etc.

[0027] Of these monomers, (meth)acrylic acid esters are preferred, with methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, 4-methylcyclohexyl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and glycidyl (meth)acrylate being even more preferred, with methyl (meth)acrylate and glycidyl (meth)acrylate being even more preferred. These monomers can be used alone or in combination of two or more.

[0028] Furthermore, the component (A-1) may be a vinyl copolymer to which the ultraviolet absorber (C), described below, is chemically bonded. In this case, the polymer may be obtained, for example, by copolymerizing a (meth)acrylic monomer having an ultraviolet-absorbing group in the molecule. Examples of the (meth)acrylic monomer having an ultraviolet-absorbing group include benzotriazole compounds represented by the following general formula (4):

[0029]

[0030] In the formula, X is a hydrogen atom or a chlorine atom, and R 6 is a hydrogen atom, a methyl group, or a tertiary alkyl group having 4 to 8 carbon atoms, and R 7is a single bond or a linear or branched alkylene group having 2 to 10 carbon atoms, and R 8 represents a hydrogen atom or a methyl group.

[0031] In the above general formula (4), R 6 Examples of the tertiary alkyl group having 4 to 8 carbon atoms include tert-butyl, tert-pentyl, tert-hexyl, tert-heptyl, tert-octyl, and di-tert-octyl groups. 7 The alkylene group having 2 to 10 carbon atoms may be either linear or branched, and examples thereof include ethylene, trimethylene, propylene, tetramethylene, 1,1-dimethyltetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene groups.

[0032] Specific examples of the benzotriazole-based compound represented by the general formula (4) include 2-(2'-hydroxy-5'-(meth)acryloxyphenyl)-2H-benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-(meth)acryloxymethylphenyl)-2H-benzotriazole, 2-[2'-hydroxy-5'-(2-(meth)acryloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'-(2-(meth)acryloxyethyl)phenyl]-5-chloro-2H-benzotriazole, and 2-[2'-hydroxy-3'-methyl-5'-(8-(meth)acryloxyoctyl)phenyl]-2H-benzotriazole.

[0033] The amount of UV-absorbing groups bonded to the vinyl copolymer is preferably 1 to 20% by mass, more preferably 5 to 15% by mass, in the vinyl copolymer of component (A-1). When the UV-absorbing groups are contained in an amount of 1% by mass or more, the UV absorption characteristics and weather resistance are improved, which is preferred. When the UV-absorbing groups are contained in an amount of 20% by mass or less, whitening of the coating can be prevented and crack resistance is improved, which is preferred. The component (A-1) may be used alone or in combination of two or more types.

[0034] As the component (A-1), those having the following structural units (i) to (iii) are particularly preferred. Vinyl copolymers having an alkoxysilyl group and an ultraviolet-absorbing group can also be preferably used, and those containing the following structural units (i) to (iv) are more preferred. The structural units contained in the component (A-1) may be arranged in any order, and the component (A-1) may be an alternating copolymer, a random copolymer, or a block copolymer.

[0035] (wherein the asterisk * indicates a bond to an adjacent building block.)

[0036] The component (A-1) can be obtained by adding a radical polymerization initiator selected from peroxides such as dicumyl peroxide and benzoyl peroxide, and azo compounds such as azobisisobutyronitrile to a solution containing the above-mentioned monomers, and carrying out a polymerization reaction under heating (for example, at 50 to 150°C, particularly 70 to 120°C, for 1 to 10 hours, particularly 3 to 8 hours).

[0037] The weight average molecular weight of the vinyl (co)polymer of component (A-1), as measured by gel permeation chromatography (GPC) in terms of polystyrene, is preferably 50,000 to 1,000,000, and more preferably 60,000 to 800,000. When the molecular weight is 1,000,000 or less, the viscosity does not become too high and handling is excellent, while when the molecular weight is 50,000 or more, poor appearance such as whitening of the coating is suppressed and better adhesion, durability, and weather resistance are obtained.

[0038] (2) (A-2) Alkoxysilyl Group-Free Vinyl (Co)polymer The primer composition of the present invention may also contain (A-2) an alkoxysilyl group-free vinyl copolymer. The alkoxysilyl group-free vinyl (co)polymer is not particularly limited, but can be obtained by (co)polymerizing a monomer other than the vinyl monomer to which the alkoxysilyl group is bonded via an Si—C bond.

[0039] Examples of monomers other than vinyl monomers having an alkoxysilyl group bonded via an Si-C bond, which serve as raw materials for component (A-2), include the same monomers as those exemplified as copolymerizable other monomers other than vinyl monomers having an alkoxysilyl group bonded via an Si-C bond for component (A-1), and specific examples thereof also include the same.The vinyl monomers used as raw materials for component (A-2) may be used alone or in combination of two or more.

[0040] Among these, (meth)acrylic acid esters are preferred, and methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, 4-methylcyclohexyl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and the like are more preferred, with methyl (meth)acrylate being even more preferred.

[0041] The polymerization conditions, such as reaction temperature, time, and polymerization initiator, are not particularly limited, and may be carried out under known conditions. For example, the polymerizable monomer can be easily obtained by using a radical polymerization initiator selected from peroxides such as dicumyl peroxide and benzoyl peroxide, and azo compounds such as azobisisobutyronitrile, and reacting the monomers at 50 to 150°C, particularly 70 to 120°C, for 1 to 10 hours, particularly 3 to 8 hours.

[0042] As the component (A-2), a commercially available product may be used, and specific examples thereof include (meth)acrylic acid ester resins such as DIANAL (registered trademark) BR-85, BR-88, and LR-1065 manufactured by Mitsubishi Rayon Co., Ltd. The component (A-2) may be used alone or in combination of two or more types.

[0043] The weight average molecular weight of component (A-2) as calculated as polystyrene by GPC is preferably 50,000 to 1,000,000, and more preferably 60,000 to 800,000. If the molecular weight is too large, the viscosity may become too high, making synthesis and handling difficult, while if the molecular weight is too small, poor appearance such as whitening of the coating may occur, and sufficient adhesion, durability, and weather resistance may not be obtained.

[0044] When the component (A-1) and the component (A-2) are used in combination, the weight average molecular weight of the entire component (A-1) and the component (A-2) in terms of polystyrene as determined by GPC is preferably 6,000 to 1,000,000, and more preferably 50,000 to 800,000. If the molecular weight is too large, the viscosity may become too high, making synthesis or handling difficult, while if the molecular weight is too small, poor appearance such as whitening of the coating may occur, and sufficient adhesion, durability, and weather resistance may not be obtained.

[0045] Furthermore, when components (A-1) and (A-2) are used in combination, the mass mixing ratio of components (A-1) and (A-2) is preferably (A-1):(A-2) = 3:1 to 1:3, more preferably (A-1):(A-2) = 2:1 to 1:2, and even more preferably (A-1):(A-2) = 3:2 to 2:3. If the amount of (A-1) is too large, it may cause poor appearance such as whitening of the coating, or may not provide sufficient adhesion, durability, or weather resistance, whereas if the amount of (A-2) is too large, the viscosity may become too high, making it difficult to handle, and the adhesion, durability, and weather resistance of the coating may be insufficient.

[0046] [(B) Inorganic Particles] Component (B) is inorganic particles having a median diameter of 1 to 100 nm as measured by dynamic light scattering. Examples of the inorganic particles include particles of known inorganic oxides such as silica, alumina, cerium oxide, zirconium oxide, zinc oxide, and titanium oxide, which can be used singly or in combination. Among these, silica, zinc oxide, titanium oxide, and cerium oxide particles are preferred. Use of these particles can enhance the hardness and scratch resistance of the coating. Additionally, use of particles such as cerium oxide, zirconium oxide, zinc oxide, and titanium oxide can further enhance the UV-shielding ability. Among these particles, silica particles and / or zinc oxide particles are particularly preferred because they provide excellent coating appearance and weather resistance.

[0047] The inorganic particles have a median diameter of 1 to 100 nm, preferably 3 to 50 nm, and more preferably 5 to 40 nm, in the volume particle size distribution measured by dynamic light scattering. If the median diameter exceeds 100 nm, the transparency of the coating film will be insufficient due to light scattering in the visible region, and if it is less than 1 nm, the hardness, scratch resistance, and weather resistance of the coating film will be poor. In the present invention, an apparatus such as the Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) can be used for measurements by dynamic light scattering.

[0048] The amount of the inorganic particles to be added is 1 to 19 parts by mass, preferably 3 to 16 parts by mass, and more preferably 5 to 15 parts by mass, per 100 parts by mass of the vinyl (co)polymer of component (A). If the amount is less than 1 part by mass, weather resistance is insufficient, while if the amount exceeds 19 parts by mass, the coating adhesion decreases, and coating appearance deteriorates, such as whitening, and cracks are more likely to occur during weather resistance testing, resulting in poor weather resistance.

[0049] The primer composition preferably contains (C) an ultraviolet absorber and (D) a hindered amine light stabilizer as an ultraviolet stabilizer, for the purpose of preventing yellowing and surface deterioration of the resin substrate.

[0050] [(C) Ultraviolet Absorber] The ultraviolet absorber of component (C) may be contained in the vinyl (co)polymer of component (A-1) in a form chemically bonded thereto as described above, or may be contained as an additive. When introduced as an additive, preferred examples include benzophenone derivatives, benzotriazole derivatives, cyanoacrylate derivatives, and triazine derivatives. Specific examples include 2,4-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-benzyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-diethoxybenzophenone, 2,2'-dihydroxy-4,4'-dipropoxybenzophenone, 2,2'-dihydroxy-4,4'-dibutoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-propoxybenzophenone, 2,2'-dihydroxy

[0039] Examples of suitable hydroxybenzophenones include hydroxy-4-methoxy-4'-butoxybenzophenone, 2,3,4-trihydroxybenzophenone; 2-(2-hydroxy-5-t-butylphenyl)benzotriazole, 2-(2-hydroxy-5-t-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-t-butylphenyl)benzotriazole; (2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, Tinuvin 400 (manufactured by BASF), Tinuvin 405 (manufactured by BASF), Tinuvin 460 (manufactured by BASF), Tinuvin 477 (manufactured by BASF), Tinuvin 479 (manufactured by BASF), Tinuvin 1577ED (manufactured by BASF), and Tinuvin 1600 (manufactured by BASF). These organic ultraviolet absorbers may be used alone or in combination of two or more, but it is preferable to use two or more in combination, and it is particularly preferable to use a triazine derivative and a benzophenone derivative in combination.

[0051] When an ultraviolet absorber is used, the blending amount is preferably 2 to 50 parts by mass, and more preferably 10 to 30% by mass, in total, per 100 parts by mass of component (A). When the blending amount is 2 parts by mass or more, weather resistance is further improved, and when the blending amount is 50 parts by mass or less, deterioration in adhesion of the coating and defects in appearance of the coating such as whitening can be suppressed.

[0052] When a triazodine derivative is used as the UV absorber, the amount is preferably 1 to 10 parts by mass, more preferably 2 to 5 parts by mass, per 100 parts by mass of component (A). When the triazodine derivative is contained in an amount of 1 part by mass or more, the UV absorption properties and weather resistance are improved, which is preferred. When the triazodine derivative is contained in an amount of 10 parts by mass or less, the whitening of the coating film can be prevented and the crack resistance is improved, which is preferred. When a benzophenone derivative is used as the UV absorber, the amount is preferably 7 to 40 parts by mass, more preferably 10 to 25 parts by mass, per 100 parts by mass of component (A). When the benzophenone derivative is contained in an amount of 7 parts by mass or more, the UV absorption properties and weather resistance are improved, which is preferred. When the benzophenone derivative is contained in an amount of 40 parts by mass or less, the whitening of the coating film can be prevented and the crack resistance is improved, which is preferred.

[0053] [(D) Hindered Amine Light Stabilizer] The primer composition preferably contains (D) a hindered amine light stabilizer. In particular, a hindered amine light stabilizer having one or more cyclic hindered amine structures in the molecule, good compatibility with the primer composition used in the present invention, and low volatility is preferred. Specific examples of hindered amine light stabilizers include 3-dodecyl-1-(2,2',6,6'-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, N-methyl-3-dodecyl-1-(2,2',6,6'-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, N-acetyl-3-dodecyl-1-(2,2',6,6'-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, bis(2,2') sebacate, and bis(2,2') sebacate. ,6,6'-tetramethyl-4-piperidyl), bis(1,2,2',6,6'-pentamethyl-4-piperidyl) sebacate, tetrakis(2,2',6,6'-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2',6,6'-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, Tinuvin 123 (manufactured by BASF), Tinuvin 249 ( BASF), Tinuvin 622-SF (BASF), Tinuvin 765 (BASF), condensation product of 1,2,3,4-butanetetracarboxylic acid, 2,2',6,6'-tetramethyl-piperidinol and tridecanol, 8-acetyl-3-dodecyl-7,7',9,9'-tetramethyl-1,3,8-triazaspiro[4,5]decane-2,4-dione, 1,2,3,4-butanetetracarboxylic acid and 1,2,6,6'- Examples thereof include a condensation product of pentamethyl-4-piperidinol and β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5']undecane)diethanol, and a condensation product of 1,2,3,4-butanetetracarboxylic acid, 2,2',6,6'-pentamethyl-4-piperidinol, and β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5']undecane)diethanol.Furthermore, for the purpose of immobilizing the light stabilizer, silylated light stabilizers as described in Japanese Patent Publication No. 61-56187 can be used, such as 2,2,6,6-tetramethylpiperidino-4-propyltrimethoxysilane, 2,2',6,6'-tetramethylpiperidino-4-propylmethyldimethoxysilane, 2,2',6,6'-tetramethylpiperidino-4-propyltriethoxysilane, 2,2',6,6'-tetramethylpiperidino-4-propylmethyldiethoxysilane, and (partial) hydrolysates thereof. These light stabilizers can be used alone or in combination of two or more. Among these, a neutral hindered amine light stabilizer (TINUVIN 249, manufactured by BASF Japan Ltd.) is preferred.

[0054] When a hindered amine light stabilizer is used, the amount thereof is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 1 to 5% by mass, per 100 parts by mass of component (A). An amount of 0.1 part by mass or more is preferred because weather resistance is improved, while an amount of 10 parts by mass or less is preferred because reduced adhesion of the coating and poor appearance of the coating such as whitening can be suppressed.

[0055] [(E) Solvent] The primer composition may contain a solvent. The solvent is not particularly limited as long as it dissolves or disperses the above components, but highly polar organic solvents are preferred. Specific examples of organic solvents include alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol, isobutanol, t-butanol, cyclohexanol, and diacetone alcohol; ketones such as methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol; ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate; and esters such as ethyl acetate, propyl acetate, butyl acetate, and cyclohexyl acetate. One or a mixture of two or more solvents selected from the group consisting of these can be used. Among these, ethers are preferred, and propylene glycol monomethyl ether is more preferred.

[0056] When a solvent is used, the amount of solvent added is preferably an amount that results in a solids concentration of the primer composition of 1 to 50% by mass, more preferably 5 to 30% by mass. Outside this range, defects may occur in the coating film obtained by curing the composition. That is, at a concentration below the above range, the coating film is prone to sagging, twisting, and mottling, and the desired hardness and scratch resistance may not be achieved. Furthermore, at a concentration above the above range, the coating film may be prone to blushing, whitening, and cracking.

[0057] [Other Components] The primer composition may contain, as necessary, a dispersant for the inorganic particle component (B), etc., within the range that does not impair the effects of the present invention. Examples of dispersants include cationic surfactants, anionic surfactants, nonionic surfactants, and various silane compounds or siloxane compounds that are reactive with particle surfaces, such as silane coupling agents.

[0058] The primer composition may absorb water during storage or use, resulting in hydrolysis of the alkoxysilyl groups in the vinyl (co)polymer (A), which may reduce its storage stability. To prevent this, a dehydrating agent may be added. Specific examples of dehydrating agents include orthocarboxylic acid esters such as methyl orthoformate, ethyl orthoformate, and ethyl orthoacetate; dialkylcarbodiimides such as dicyclohexylcarbodiimide; and solid adsorbents such as silica gel and molecular sieves.

[0059] To the above primer composition, a leveling agent, a metal powder, an antioxidant, a heat ray reflective / absorbent agent, a flexibility imparting agent, an antistatic agent, an antifouling agent, a water repellent agent, etc. may be added as needed, within the range that does not impair the effects of the present invention.

[0060] From the viewpoint of storage stability, the pH of the primer composition is preferably 2 to 8, more preferably 3 to 6. If the pH is outside this range, storage stability may decrease. The method for adjusting the pH is not particularly limited, but a pH adjuster can be added to adjust the pH to the above range. If the pH of the primer composition is outside the above range and is on the acidic side of this range, the pH can be adjusted by adding a basic compound such as ammonia or ethylenediamine, or if it is on the basic side, the pH can be adjusted by using an acidic compound such as hydrochloric acid, nitric acid, acetic acid, or citric acid.

[0061] The primer composition used in the present invention can be obtained by mixing the above-mentioned components in a conventional manner. The obtained primer composition can be applied to a resin substrate and cured to form a primer layer.

[0062] Examples of the method for applying the primer composition include various coating methods such as brush coating, spraying, dipping, flow coating, roll coating, curtain coating, spin coating, and knife coating.

[0063] The primer composition may be cured by leaving it in the air to dry or by heating. The curing temperature and time are not particularly limited, but it is preferably heated at a temperature equal to or lower than the heat resistance temperature of the substrate for 10 minutes to 2 hours, and more preferably heated at 80 to 135°C for 30 minutes to 2 hours.

[0064] The thickness of the primer layer must be 1 to 20 μm, preferably 3 to 15 μm, and more preferably 5 μm or more and less than 10 μm, in order to satisfy the requirements of hardness, scratch resistance, long-term stable adhesion, and no cracking of the coating. If the thickness is less than 1 μm, the ultraviolet ray shielding ability will be insufficient, and peeling of the coating will occur, and if the thickness exceeds 20 μm, cracking will occur in the coating.

[0065] <Hard Coat Layer> The coated article of the present invention has a hard coat layer formed on a primer layer. The hard coat layer in the coated article of the present invention is a cured coating of a silicone composition containing the following components (a) to (c): (a) a compound represented by the following formula (1): R 1 m Si(OR 2 ) 4-m (1) (wherein, R 1 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and R 2 each independently represents an alkyl group having 1 to 3 carbon atoms, and m is 0, 1, or 2.) A silicone resin obtained by (co)hydrolyzing and condensing at least one selected from alkoxysilanes represented by the following formula (I): and (ii) a (partial) hydrolyzed condensate thereof; (b) colloidal silica; and (c) an ultraviolet absorber.

[0066] [Component (a)] Component (a) is a silicone resin obtained by (co)hydrolyzing and condensing at least one selected from alkoxysilanes represented by the following general formula (1) and their (partial) hydrolysis and condensation products. 1 m Si(OR 2 ) 4-m (1)

[0067] In the formula, R 1are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R 1 may be bonded to each other to form a linking group, and R 2 are each independently an alkyl group having 1 to 3 carbon atoms, and m is 0, 1, or 2.

[0068] R 1 The monovalent hydrocarbon group R may be linear, branched, or cyclic, and examples thereof include an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms; a cycloalkyl group having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms; an alkenyl group having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 6 carbon atoms; and an aryl group having 6 to 12 carbon atoms, preferably 6 to 8 carbon atoms. 1 Specific examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl and allyl; and aryl groups such as phenyl. Some or all of the hydrogen atoms in these groups may be substituted with other substituents, specific examples of which include halogen-substituted hydrocarbon groups such as chloromethyl, γ-chloropropyl, and 3,3,3-trifluoropropyl; and (meth)acryloxy-, epoxy-, mercapto-, amino-, and isocyanate-substituted hydrocarbon groups such as γ-(meth)acryloxypropyl, γ-glycidoxypropyl, 3,4-epoxycyclohexylethyl, γ-mercaptopropyl, γ-aminopropyl, and γ-isocyanatopropyl. Another example is an isocyanurate group in which multiple isocyanate-substituted hydrocarbon groups are bonded together. Among these, alkyl groups are preferred when the compound is used in applications requiring scratch resistance and weather resistance, and epoxy, (meth)acryloxy, and isocyanurate-substituted hydrocarbon groups are preferred when toughness and dyeability are required.

[0069] R 2Examples of the alkyl group having 1 to 3 carbon atoms include methyl, ethyl, n-propyl, and isopropyl groups. Among these, the alkyl group having 1 to 3 carbon atoms is particularly preferred because of its high reactivity in hydrolysis and condensation and the high reactivity of the resulting alcohol R 2 Considering that OH has a high vapor pressure and is easily removed by distillation, a methyl group or an ethyl group is preferred.

[0070] In the above formula (1), when m=0, the general formula: Si(OR 2 Specific examples of the tetraalkoxysilane and its partial hydrolysis condensate (a-0) represented by formula (4) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, partial hydrolysis condensate of tetramethoxysilane (trade name "M Silicate 51" manufactured by Tama Chemicals Co., Ltd., trade name "MSI51" manufactured by Colcoat Co., Ltd., trade name "MS51" and "MS56" manufactured by Mitsubishi Chemical Corporation), partial hydrolysis condensate of tetraethoxysilane (trade name "Silicate 35" and "Silicate 45" manufactured by Tama Chemicals Co., Ltd., trade name "ESI40" and "ESI48" manufactured by Colcoat Co., Ltd.), and partial co-hydrolysis condensate of tetramethoxysilane and tetraethoxysilane (trade name "FR-3" manufactured by Tama Chemicals Co., Ltd., trade name "EMSi48" manufactured by Colcoat Co., Ltd.).

[0071] In the above formula (1), when m=1, the general formula: R 1 Si(OR 2Specific examples of trialkoxysilane (a-1) represented by the formula (3) and its partial hydrolysis condensate include hydrogentrimethoxysilane, hydrogentriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltriisopropoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-methyltriethoxy ... trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-(2-aminoethyl)aminopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane Examples of suitable silanes include tris(3-trimethoxysilylpropyl)isocyanurate and tris(3-triethoxysilylpropyl)isocyanurate in which isocyanate groups are bonded together, partial hydrolysis condensates of methyltrimethoxysilane (trade names "KC-89S" and "X-40-9220", manufactured by Shin-Etsu Chemical Co., Ltd.), and partial hydrolysis condensates of methyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane (trade name "X-41-1056", manufactured by Shin-Etsu Chemical Co., Ltd.).

[0072] In the above formula (1), when m=2, the general formula: R 1 2Si(OR 2Specific examples of the dialkoxysilane represented by formula (a-2) and its (partially) hydrolyzed condensate (a-2) include methylhydrogendimethoxysilane, methylhydrogendiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, methylpropyldimethoxysilane, methylpropyldiethoxysilane, diisopropyldimethoxysilane, phenylmethyldimethoxysilane, vinylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, and N-(2-aminoethyl)aminopropylmethyldimethoxysilane.

[0073] The silicone resin of component (a) may be prepared by using the components (a-0), (a-1), and (a-2) in any proportion, but in order to further improve storage stability, scratch resistance, and crack resistance, it is preferable to use a ratio of 0 to 50% of the number of silicon atoms derived from (a-0), 50 to 100% of the number of silicon atoms derived from (a-1), and 0 to 50% of the number of silicon atoms derived from (a-2) relative to the total number of Si atoms in (a-0), (a-1), and (a-3), and it is more preferable to use a ratio of 0 to 30% of the number of silicon atoms derived from (a-0), 70 to 100% of the number of silicon atoms derived from (a-1), and 0 to 30% of the number of silicon atoms derived from (a-2). In this case, if the main component (a-1) is 50% or more, the curability is good and the hardness of the cured film is moderate, which is preferable.

[0074] To produce the silicone resin of component (a), components (a-0), (a-1), and (a-2) may be (co)hydrolyzed and condensed by a known method. For example, the silicone resin can be obtained by (co)hydrolyzing and condensing the alkoxysilanes of components (a-0), (a-1), and (a-2), or their (partially) hydrolyzed and condensed products, or a mixture thereof, in water having a pH of 1 to 7.5, preferably 2 to 7. In this case, a dispersion of metal oxide fine particles such as silica sol in water may be used. To adjust the pH to this range and promote hydrolysis, inorganic and organic acids such as hydrogen fluoride, hydrochloric acid, nitric acid, formic acid, acetic acid, propionic acid, oxalic acid, citric acid, maleic acid, benzoic acid, malonic acid, glutaric acid, glycolic acid, methanesulfonic acid, and toluenesulfonic acid, or solid acid catalysts such as cation exchange resins having carboxylic acid groups or sulfonic acid groups on their surface, or water-dispersed metal oxide fine particles such as acidic water-dispersed silica sol may be used as a catalyst. Furthermore, during the hydrolysis, metal oxide fine particles such as silica sol dispersed in water or an organic solvent may be present.

[0075] In the hydrolysis step, the amount of water used is preferably 20 to 3,000 parts by mass per 100 parts by mass of the total of components (a-0), (a-1), and (a-2). The use of excessive water not only reduces the efficiency of the apparatus, but may also cause a decrease in the coating and drying properties of the final composition due to the influence of the remaining water. Furthermore, in order to improve storage stability, scratch resistance, and crack resistance, the amount of water used is preferably 50 parts by mass or more but less than 150 parts by mass.

[0076] The hydrolysis step may involve dropping or pouring water into the alkoxysilane or its (partial) hydrolysis condensate, or conversely, dropping or pouring the alkoxysilane or its (partial) hydrolysis condensate into water. In this case, the reaction solvent may contain an organic solvent, but it is preferable not to contain an organic solvent. This is because the more organic solvent is contained, the smaller the molecular weight of the resulting silicone resin tends to be.

[0077] The condensation step may be carried out continuously following the hydrolysis step, and is usually carried out at room temperature or under heating at 100°C or less. Temperatures higher than 100°C may result in gelation. Furthermore, condensation can be promoted by distilling off the alcohol produced by hydrolysis at 80°C or higher under normal or reduced pressure. Furthermore, a condensation catalyst such as a basic compound, an acidic compound, or a metal chelate compound may be added to promote condensation. Before or during the condensation step, an organic solvent may be added to adjust the degree of condensation and the concentration, or a dispersion of metal oxide fine particles such as silica sol in water or an organic solvent may be added. Generally, as the condensation progresses, the silicone resin increases in molecular weight and its solubility in water and the produced alcohol decreases. Therefore, the organic solvent to be added is preferably an organic solvent that dissolves the silicone resin well and has a relatively high polarity and a boiling point of 80°C or higher. Specific examples of such organic solvents include alcohols such as isopropyl alcohol, n-butanol, isobutanol, t-butanol, cyclohexanol, and diacetone alcohol; ketones such as methyl propyl ketone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol; ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate; and esters such as propyl acetate, butyl acetate, and cyclohexyl acetate.

[0078] The polystyrene-equivalent weight average molecular weight of the obtained silicone resin as determined by GPC analysis is preferably 1,500 to 50,000, and more preferably 2,000 to 20,000. A molecular weight of 1,500 or more provides a coating with excellent toughness and can suppress the occurrence of cracks, while a molecular weight of 50,000 or less can suppress whitening of the coating due to excessively low hardness or phase separation of the resin in the coating.

[0079] [Component (b)] Component (b) is colloidal silica. The colloidal silica of component (b) is preferably in the form of silica colloidally dispersed in a medium such as water or an organic solvent, and commercially available water-dispersed or organic-dispersed types can be used. Specific examples include Snowtex-O, OS, O40, OL, methanol silica sol, IPA-ST, IBA-ST, PMA-ST, and MEK-ST, all manufactured by Nissan Chemical Industries, Ltd. Silica having a median diameter of 5 to 50 nm as measured by dynamic light scattering is preferred from the viewpoint of the transparency and hardness of the resulting hard coat layer.

[0080] The amount of colloidal silica blended is preferably 3 to 100 parts by mass, more preferably 6 to 50 parts by mass, and even more preferably 10 to 30 parts by mass, calculated as solid content, per 100 parts by mass of component (a).

[0081] [Component (c)] Component (c) is an ultraviolet absorber. Examples of the ultraviolet absorber of component (c) include benzophenone derivatives, benzotriazole derivatives, cyanoacrylate derivatives, and triazine derivatives. Specific examples thereof include 2,4-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-benzyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-diethoxybenzophenone, 2,2'-dihydroxy-4,4'-dipropoxybenzophenone, 2,2'-dihydroxy-4,4'-dibutoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-propoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-butoxybenzophenone, 2, 3,4-trihydroxybenzophenone; 2-(2-hydroxy-5-t-butylphenyl)benzotriazole, 2-(2-hydroxy-5-t-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-t-butylphenyl)benzotriazole; (2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, Tinuvin 400 (BASF) Examples of such reactive ultraviolet absorbers include Tinuvin 405 (manufactured by BASF), Tinuvin 460 (manufactured by BASF), Tinuvin 477 (manufactured by BASF), Tinuvin 479 (manufactured by BASF), Tinuvin 1577ED (manufactured by BASF), and Tinuvin 1600 (manufactured by BASF). In addition, reactive ultraviolet absorbers of the silane coupling agent type in which a portion of the above compound is substituted with an alkoxysilyl group can also be used. Among these, reactive ultraviolet absorbers of the silane coupling agent type in which a portion of the above compound is substituted with an alkoxysilyl group are preferred. By using such reactive ultraviolet absorbers, the ultraviolet-absorbing group is fixed within the hard coat layer, and bleeding out of the ultraviolet absorber over time is suppressed, which is effective in suppressing whitening and cracking.

[0082] The reactive ultraviolet absorber is preferably a benzophenone derivative having one or more alkoxysilyl groups, represented by the following general formula (2):

[0083]

[0084] In the formula, R 3 are each independently a hydrogen atom, a hydroxy group, an alkyl group having 1 to 5 carbon atoms, or a group represented by the following general formula (3), 3 At least one of the groups is a group represented by the following general formula (3): *—O—(CH2) j -SiR 4 k (OR 5 ) 3-k (3) (wherein, R 4 and R 5 are each independently an alkyl group having 1 to 5 carbon atoms, j is an integer of 1 to 8, and k is an integer of 0 to 2. An asterisk * represents a bond to an adjacent atom.

[0085] In the above formula (2), R 3 The alkyl group in R has 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and may be either linear or branched. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, and isopentyl groups. 3 At least one of the groups R is a group represented by the general formula (3). By having the group represented by the general formula (3), the ultraviolet absorber is fixed in the hard coat layer, and bleeding out over time is suppressed, which is effective in suppressing whitening and cracking of the hard coat layer. 3 At least one of R is preferably a hydroxy group, since this improves the ultraviolet absorption properties. 3 Among these, it is preferable that all of the groups other than the group represented by the general formula (3) and the hydroxy group are hydrogen atoms.

[0086] In the above formula (3), R 4 and R 5The alkyl group having 1 to 5 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and specific examples thereof include R 3 Among these, R 4 is preferably a methyl group or an ethyl group. 5 is highly reactive in hydrolysis and condensation, and the alcohol R 5 Considering the high vapor pressure of OH and the ease of distillation, a methyl group or an ethyl group is preferred.

[0087] j is an integer of 1 to 8, and from the viewpoint of easy availability of raw materials, an integer of 1 to 3 is preferred, with j = 3 being preferred. k is an integer of 0 to 2, and k = 0 is particularly preferred because it increases the reactivity of hydrolysis and condensation and improves the scratch resistance of the coating.

[0088] Among the benzophenone derivatives represented by the above general formula (2), 2-hydroxy-4-trimethoxysilylpropoxybenzophenone is preferred.

[0089] The amount of component (c) blended is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass, per 100 parts by mass of component (a).

[0090] [Curing Catalyst] The silicone composition preferably contains a curing catalyst that promotes the condensation reaction of condensable groups, such as silanol groups and alkoxy groups, contained in the silicone resin (a). Specific examples of the curing catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, sodium propionate, potassium propionate, sodium acetate, potassium acetate, sodium formate, potassium formate, trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium acetate, n-hexylamine, tributylamine, diazabicycloundecene (DBU), and salts of dicyandiamide. basic compounds; metal-containing compounds such as tetraisopropyl titanate, tetrabutyl titanate, titanium acetylacetonate, aluminum triisobutoxide, aluminum triisopropoxide, tris(acetylacetonate)aluminum, diisopropoxy(ethylacetoacetate)aluminum, aluminum perchlorate, aluminum chloride, cobalt octylate, cobalt acetylacetonate, iron acetylacetonate, tin acetylacetonate, dibutyltin octylate, and dibutyltin laurate; and acidic compounds such as p-toluenesulfonic acid and trichloroacetic acid. Among these, particularly preferred are sodium propionate, sodium acetate, sodium formate, trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tris(acetylacetonate)aluminum, and diisopropoxy(ethylacetoacetate)aluminum.

[0091] When a curing catalyst is used, its amount is not particularly limited as long as it is an amount effective for curing the silicone resin of component (a), but specifically, it is preferably 0.0001 to 1 mass % of the solid content of the silicone resin, and more preferably 0.0005 to 0.1 mass %. If it is 0.0001 mass % or more, curing will be sufficient, and if it is 1 mass % or less, cracking of the coating and a decrease in water resistance can be suppressed.

[0092] [Solvent] The silicone composition preferably contains a solvent. Examples of the solvent include the same solvents as those used in the primer composition. When a solvent is used, the amount of solvent added is such that the solids concentration of the silicone composition is preferably 5 to 40 mass %, more preferably 10 to 35 mass %.

[0093] [Other Components] The silicone composition may contain, as necessary, pH adjusters, leveling agents, thickeners, pigments, dyes, metal oxide particles other than silica, metal powders, antioxidants, ultraviolet stabilizers, heat ray reflecting / absorbing agents, flexibility imparting agents, antistatic agents, antifouling agents, water repellency imparting agents, and the like, provided the effects of the present invention are not impaired.

[0094] The silicone composition used in the present invention can be obtained by mixing the above-mentioned components in accordance with a conventional method. The obtained silicone composition can be applied to the above-mentioned primer layer and cured to form a hard coat layer. The application method of the silicone composition can be the same as the method exemplified for the primer composition.

[0095] The silicone composition may be cured by leaving it in the air to dry, or by heating. The curing temperature and time are not particularly limited, but it is preferable to heat it for 10 minutes to 2 hours at a temperature equal to or lower than the heat resistance temperature of the substrate, and more preferably at 80 to 135°C for 30 minutes to 2 hours.

[0096] The thickness of the resulting hard coat layer is not particularly limited, but in order to satisfy the requirements of hardness, scratch resistance, long-term stable adhesion, and no cracking of the coating, it must be 1 to 15 μm, preferably 3 to 13 μm, and more preferably 5 to 10 μm. If the thickness is less than 1 μm, the ultraviolet shielding ability will be insufficient, peeling of the coating will occur, and the hardness and scratch resistance of the coating will be insufficient. Furthermore, if the film thickness exceeds 15 μm, cracks will occur in the coating.

[0097] [Hardness of Hard Coat Layer] The surface hardness of the hard coat layer, as measured by nanoindentation, is preferably 0.10 to 0.50 GPa, more preferably 0.20 to 0.40 GPa, and even more preferably 0.25 to 0.35 GPa. Examples of devices for measuring the elastic modulus of such coatings include nanoindenters (Hygitron Tribo Indenter, manufactured by Bruker Japan Co., Ltd.; ENT-NEXUS, manufactured by Elionix Co., Ltd.). A surface hardness of 0.10 GPa or more is preferable because the abrasion resistance of the photo-modified layer formed is good. A surface hardness of 0.50 GPa or less is preferable because the siloxane-based hard coat layer can effectively alleviate the stress that the photo-modified layer receives from the resin substrate during heat resistance tests and weather resistance tests, improving crack resistance and improving the heat resistance and weather resistance of the coating.

[0098] In the present invention, the hardness is a value obtained by analyzing data obtained when a Berkovich-type indenter is pressed into the surface of a siloxane-based hard coat layer at a load of 0.5 mN using a nanoindenter (ENT-NEXUS, manufactured by Elionix Co., Ltd.) at room temperature of 23°C, using dedicated software.

[0099] <Photo-modified layer> The coated article of the present invention has a photo-modified layer formed on the surface of the hard coat layer. The photo-modified layer in the coated article of the present invention is preferably a hard thin film layer composed primarily of silicon dioxide, obtained by irradiating the surface of the hard coat layer with light having a wavelength of 300 nm or less. It is known that the energy of short-wavelength light having a wavelength of 300 nm or less can cleave the bonding chains of organic polymers, sequentially and selectively cleave the C-H, Si-C, and Si-O-Si bonds that constitute the side-chain functional groups in the hard coat layer formed on the substrate, and further recombine the cleaved oxygen atoms with silicon atoms, thereby modifying a portion of the hard coat layer into a hard thin film layer composed primarily of silicon dioxide.

[0100] Examples of light sources for vacuum ultraviolet rays with a short wavelength of 300 nm or less include excimer lasers, excimer lamps, low-pressure mercury lamps, etc. Examples of excimer lasers include Ar lasers with a wavelength of 126 nm, F lasers with a wavelength of 157 nm, ArF excimer lasers with a wavelength of 193 nm, KrF excimer lasers with a wavelength of 248 nm, and XeCl excimer lasers with a wavelength of 307 nm. Of these, the light sources for vacuum ultraviolet rays with a wavelength of 300 nm or less are Ar lasers, F lasers, ArF lasers, and KrF excimer lasers. Excimer lamps are available with wavelengths of 126 nm (Ar), 146 nm (Kr), 165 nm (ArBr), 172 nm (Xe), 175 nm (ArCl), 193 nm (ArF), 207 nm (KrBr), 222 nm (KrCl), 253 nm (XeCl), 283 nm (XeBr), and 308 nm (XeCl). In the present invention, it is preferable to use an F laser or a Xe excimer lamp.

[0101] The ultraviolet irradiation method is not particularly limited, but examples thereof include a method in which the hard coat layer is irradiated with ultraviolet light having a wavelength of 300 nm or less using the above-mentioned light source in an atmosphere of air or an inert gas such as nitrogen or argon. 2 More than 0.5 J / cm is preferable. 2 The above is more preferable.

[0102] The thickness of the photo-modified layer is preferably 0.1 to 1.0 μm, more preferably 0.2 to 0.8 μm, and even more preferably 0.3 to 0.6 μm. A thickness of 0.1 μm or more is preferable because it provides good abrasion resistance. A thickness of 1.0 μm or less is preferable because it provides good heat resistance and weather resistance.

[0103] <Other Layers> The coated article of the present invention may further have an ultraviolet absorbing layer, a printing layer, a recording layer, a heat ray shielding layer, an adhesive layer, an inorganic vapor deposition film layer, etc. on the above-mentioned photo-modifying layer.

[0104] One of the characteristics of the coated article of the present invention is the visible light transmittance of the coating. This can be evaluated by the haze value of the coating. The haze increases as the coating thickness increases, so in the present invention, the haze at a coating thickness of 20 μm or less is preferably 2.0 or less, more preferably 1.5 or less, and even more preferably 1.0 or less. The haze of the coating can be measured, for example, using a turbidity meter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.).

[0105] One of the characteristics of the coated article of the present invention is good adhesion between the coating and the substrate. This can be evaluated as an index by a checkerboard peel test in accordance with JIS K5400. Using a razor blade, 25 checkerboard patterns were created by cutting six vertical and six horizontal cuts at 2 mm intervals in the coating. Cellotape (registered trademark, manufactured by Nichiban Co., Ltd.) was then firmly adhered to the grid, and the grid was rapidly peeled off at a 90° angle toward the user. The number of grids (X) remaining without peeling of the coating was expressed as X / 25. The closer the number of grids (X) was to 25, the better the adhesion. Alternatively, a substrate bearing a cured coating can be boiled in water at 100° C. for 2 hours and subjected to a similar checkerboard peel test, providing an index of water-resistant adhesion.

[0106] One of the characteristics of the coated article of the present invention is its excellent scratch resistance. This can be evaluated as an index of the difference in haze (ΔHz) before and after the test in a Taber abrasion test. According to ASTM 1044, a Taber abrasion tester is used to measure the haze after 500 revolutions under a load of 500 gf using a CS-10F abrasion wheel. When the haze is measured using this tester and ΔHz (% points) is calculated as (haze (%) after the test) - (haze (%) before the test), ΔHz at a film thickness of 20 μm or less is preferably 10 points or less, more preferably 5 points or less, and even more preferably 2 points or less. In the art, it is common to judge a film to have scratch resistance equal to or greater than that of glass when the haze difference (ΔHz) in the above test is 2 points or less.

[0107] One of the characteristics of the coated article of the present invention is good heat resistance. One example of a heat resistance test is a method in which the test piece is stored in an oven at 110°C for 100 to 1000 hours and the appearance of the test piece is observed every 100 hours. Preferably, the coated article of the present invention exhibits no cracks or peeling in the coating even after a 200-hour test, more preferably no cracks or peeling in the coating even after a 500-hour test, and most preferably no cracks or peeling in the coating even after a 1000-hour test.

[0108] One of the characteristics of the coated article of the present invention is good weather resistance. An indicator of this can be determined by the change in the appearance of the coating in a weather resistance test. As an example of the weather resistance test, an Iwasaki Electric Co., Ltd. Eye Super UV Tester W-151 was used, and the coating was irradiated with ultraviolet light for 4 hours (irradiation intensity 90 mW / cm 2An example of a method for evaluating weather resistance is to observe the condition of the test piece every 120 hours, with 10 cycles consisting of 12 hours of darkness (black panel temperature 63°C, humidity 70%), 4 hours of darkness (black panel temperature 63°C, humidity 90%), and 4 hours of condensation (black panel temperature 30°C, humidity 95%). The observation method can be visual or using a microscope. The microscope that can be used for this purpose is not particularly limited, but an example includes a laser microscope (manufactured by Keyence Corporation, device name "VK-8710"). In the weather resistance test, it is preferable that no cracks or peeling occur in the coating even after 360 hours of testing, more preferably no cracks or peeling occur in the coating even after 480 hours of testing, and even more preferably no cracks or peeling occur in the coating even after 600 hours of testing.

[0109] In the above weather resistance test, one-third of the test time was spent on light irradiation, and the intensity was 900 W / m 2 900W / m 2 The cumulative energy when ultraviolet light of this intensity is irradiated for 1 hour is 0.9 kWh / m 2 However, according to the rules for converting derived units, this is equal to 3.24 MJ (megajoules). Therefore, the cumulative irradiation dose after 600 hours of the SUV test is 600 (test time) x 1 / 3 (light irradiation test rate) x 3.24 (MJ / m 2 ・h)≒648(MJ / m 2 The test conditions and environment for the weather resistance test in the present invention can be set arbitrarily, but the correlation between the test conditions and outdoor exposure can be easily estimated. For example, when the amount of ultraviolet light outdoors is measured using an ultraviolet illuminance meter (Eye ultraviolet illuminance meter UVP365-1, manufactured by Iwasaki Electric Co., Ltd.), the value is 1×101 W / m 2 (Measured at noon on the vernal equinox on a clear day in Matsuida-cho, Annaka-shi, Gunma Prefecture.) The average annual sunshine hours in Japan are about 2000 hours, so the cumulative annual irradiation in Japan is about 2000 (h / year) x 1 (year) x 10 (W / m 2 )=20(kWh / m 2 ) ≒ 72 (MJ / m 2Therefore, the cumulative irradiation amount after 600 hours of the SUV test is equivalent to the cumulative irradiation amount that the sample would receive if used outdoors in Japan for about 9 years, as calculated using the following formula: 648 (MJ / m 2 , cumulative irradiation amount after 600 hours of testing) / 72 (MJ / m 2 ・The annual amount of light exposure in Japan is approximately 9 (years). Because outdoor environments vary depending on latitude and climate, the test conditions can be adjusted appropriately depending on the environment in which the cured coating will be used.

[0110] The present invention will be specifically described below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. In the following examples, % means mass %, parts means parts by mass, and Me means methyl groups. The weight-average molecular weight was measured by gel permeation chromatography (GPC) using standard polystyrene as the reference.

[0111] [1] Synthesis of vinyl copolymer (A-1) [Synthesis Example 1] <Synthesis of vinyl copolymer (A-1-1) having ultraviolet absorbing group and alkoxysilyl group> A 2-liter flask equipped with a stirrer, a condenser, and a thermometer was charged with 126 g of isobutyl acetate and 126 g of isopropyl alcohol as solvents, and heated to 80°C under a nitrogen stream. To this was added dropwise a monomer mixture solution (a mixture of 90 g of γ-methacryloxypropyltrimethoxysilane, 270 g of methyl methacrylate, 22.5 g of glycidyl methacrylate, 67.5 g of RUVA-1 (2-[2'-hydroxy-5'-(2-methacryloxyethyl)phenyl]-2H-benzotriazole (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) as an ultraviolet absorbing group, and 1 g of 2,2'-azobis(2-methylbutyronitrile) as a polymerization initiator) that had been prepared in advance at 80 to 90°C over 1.5 hours, and the mixture was further stirred at 80 to 90°C for 5 hours. The mixture was then allowed to cool, and 367 g of diacetone alcohol was added to terminate the reaction. The obtained vinyl copolymer (A-1-1) having an ultraviolet absorbing group and an alkoxysilyl group had a proportion of ultraviolet absorbing groups of 10.2% by mass, a proportion of trimethoxysilyl groups of 10.2% by mass, and a weight average molecular weight of 87,800.

[0112] Synthesis Example 2 Synthesis of Vinyl Copolymer (A-1-2) Having Alkoxysilyl Groups Vinyl copolymer (A-1-2) having alkoxysilyl groups was obtained by the same procedure as in Synthesis Example 1, except that the composition was changed as shown in Table 1. The proportion of trimethoxysilyl groups in the obtained copolymer was 9.4 mass%, and the weight average molecular weight was 60,800.

[0113]

[0114] (Note) MPTMS: γ-methacryloxypropyltrimethoxysilane RUVA-1: 2-[2'-hydroxy-5'-(2-methacryloxyethyl)phenyl]-2H-benzotriazole (RUVA-93, manufactured by Otsuka Chemical Co., Ltd.) MMA: methyl methacrylate GMA: glycidyl methacrylate

[0115] [2] Synthesis of UV absorber [Synthesis Example 3] <Synthesis of reactive UV absorber (c-1)> In a reactor, 25.4 g (0.1 mol) of 4-allyloxy-2-hydroxybenzophenone (manufactured by Aldrich) was suspended in 70 mL of toluene. 0.05 g of platinum catalyst PL50-T (manufactured by Shin-Etsu Chemical Co., Ltd.) was added, the temperature was raised to 65°C, and 29.3 g (0.24 mol) of trimethoxysilane was added. After stirring at 80°C for 2 hours, the reaction mixture was cooled, and 5 g of Wakogel C-100 was added to adsorb the platinum catalyst. The mixture was then filtered, and the solvent was removed by vacuum concentration to obtain 34.8 g (0.092 mol) of a red oily substance. 1 The H-NMR spectrum was consistent with the structure of 2-hydroxy-4-trimethoxysilylpropoxybenzophenone. The resulting compound is abbreviated as reactive ultraviolet absorber (c-1).

[0116] [3] Preparation of Silicone Composition [Synthesis Example 4] <Preparation of Silicone Composition (HC-1)> 48 g of methyltrimethoxysilane and 1.2 g of the reactive UV absorber (c-1) obtained in Synthesis Example 3 were added to a 500-milliliter flask equipped with a stirrer, a condenser, and a thermometer, and the mixture was maintained at 20°C with stirring. 29.4 g of water-dispersed colloidal silica (Snowtex O, manufactured by Nissan Chemical Industries, Ltd., average particle size 15-20 nm, SiO2 content: 20%), 8.2 g of acetic acid, and 30 g of water were added and stirred. After stirring at 60°C for 3 hours, 45 g of n-butanol was added, and then a total of 72 g of by-produced methanol and a portion of the water was distilled off at normal pressure. The mixture was then diluted with isopropanol to a solids concentration of 30% by mass to obtain a solution. Next, to 30 g of the above solution, 0.02 g of polyether-modified silicone KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a leveling agent, and 0.1 g of a 10 mass % aqueous solution of tetrabutylammonium hydroxide was added as a curing catalyst. The mixture was stirred at room temperature for 1 hour, and the precipitate was removed by filtration using filter paper, yielding silicone composition (HC-1).

[0117] Comparative Synthesis Example 1 Preparation of UV-Absorbent-Free Silicone Composition (HC-2) The same procedure as in Synthesis Example 4 was carried out, except that the reactive UV absorber (c-1) was not added, to obtain a UV-absorbent-free silicone composition (HC-2).

[0118] [4] Preparation of Primer Compositions [Preparation Examples 1 to 8, Comparative Preparation Examples 1 to 6] Primer compositions were obtained by adding propylene glycol monomethyl ether (E-1) to a composition prepared according to a conventional method using the formulations (solids content, parts by mass) shown in Tables 2 and 3 to adjust the concentration to 5 mass% of the dehydrating agent ethyl orthoformate (F-1) and 500 mass ppm of the leveling agent LE-604 (G-1) in the composition, and a total solids concentration of 20 mass%. Note that among the abbreviations used in the Preparation Examples, Examples, and Comparative Examples, those not explained in the Synthesis Examples are as follows:

[0119] <Component (A-2)> A-2-1: Polymethyl methacrylate resin (Dianal BR-88, manufactured by Mitsubishi Rayon Co., Ltd., Mw: 576,900, Tg: 105°C) A-2-2: Polymethyl methacrylate resin (Dianal BR-85, manufactured by Mitsubishi Rayon Co., Ltd., Mw: 263,800, Tg: 105°C)

[0120] <(B) Inorganic Particles> B-1: Propylene glycol monomethyl ether dispersion of silica (PMA-ST, solid content concentration 30%, primary particle size 10 to 15 nm, manufactured by Nissan Chemical Industries, Ltd.) B-2: Alcohol dispersion of zinc oxide (ZNTANB15WT%-E34, solid content concentration 15%, primary particle size 10 to 15 nm, manufactured by CIK Nanotech Co., Ltd.)

[0121] <(C) Ultraviolet absorber> C-1: 2-[2-hydroxy-4-(1-octyloxycarbonylethoxy)phenyl]-4,6-bis(4-phenylphenyl)-1,3,5-triazine (TINUVIN 479, manufactured by BASF Japan Ltd.) C-2: 2,4-dihydroxybenzophenone (Seesorb 106, manufactured by Shipro Chemical Co., Ltd.)

[0122] <(D) Hindered amine light stabilizer> D-1: Neutral hindered amine light stabilizer (TINUVIN 249, manufactured by BASF Japan Ltd.)

[0123] <(E) Solvent> E-1: Propylene glycol monomethyl ether

[0124] <(F) Dehydrating Agent> F-1: Ethyl orthoformate

[0125] <(G) Leveling Agent> G-1: LE-604 (manufactured by Kyoeisha Chemical Co., Ltd.)

[0126] [5] Production of Coated Articles [Examples 1 to 8, Comparative Examples 1 to 4] Each primer composition obtained in the above Preparation Examples and Comparative Preparation Examples was applied to a surface-cleaned polycarbonate resin plate (5 mm thick, product name: Takiron PC Clear-1600 Type, manufactured by Takiron C.I. Co., Ltd.) by dip coating to form a cured film of 5 to 10 μm, and then heated and cured at 130°C for 90 minutes to form a primer layer. After the obtained test piece was allowed to cool to room temperature, a silicone composition (HC-1 or HC-2 prepared in Synthesis Example 4 or Comparative Synthesis Example 1) described in Tables 2 and 3 was applied to the primer layer by dip coating to form a cured film of 5 μm or more but less than 10 μm, and then cured at 120°C for 60 minutes to form a siloxane-based hard coat layer. Next, using a 172 nm wavelength Xe2 excimer lamp, light was irradiated onto the surface of the siloxane-based hard coat layer in an N2 atmosphere at a light irradiation dose of 2 J / cm 2 The light irradiation was carried out so that a photo-modified layer having a film thickness of 0.1 to 0.4 μm was formed.

[0127] [Comparative Example 5] A test piece for Comparative Example 5 was obtained in the same manner as in Examples 1 to 8 and Comparative Examples 1 to 4, except that the primer layer and the hard coat layer were applied by dip coating so that the thickness of the primer layer was 22 μm and the thickness of the hard coat layer was 16 μm, respectively.

[0128] Comparative Example 6 A test piece for Comparative Example 6 was obtained in the same manner as in Examples 1 to 8 and Comparative Examples 1 to 4, except that no photo-modified layer was formed.

[0129] [6] Evaluation of Physical Properties of Coated Articles The coated articles obtained in the above Examples and Comparative Examples were used as test pieces to evaluate various physical properties. The results are shown in Tables 2 and 3.

[0130] (1) Surface Hardness of Coating: The hardness of the coating in the present invention was determined by nanoindentation using a nanoindenter (ENT-NEXUS, manufactured by Elionix Co., Ltd.). Specifically, the resin substrate having a siloxane-based hard coat layer on the outermost surface, as prepared in the above Examples and Comparative Examples, was cut to 15 mm x 15 mm, and a dedicated sample fixing substrate (10 mm x 10 mm, 1 mm thick) was coated with instant adhesive (Aron Alpha Fast-Acting Multipurpose, manufactured by Toagosei Co., Ltd.). The substrate side of the sample was adhered to the fixing substrate to obtain a measurement sample. The obtained measurement sample was fixed to a dedicated sample fixing table so that the siloxane-based hard coat layer side was in contact with the indenter. A Berkovich-type indenter was pressed into the coating surface at room temperature (23°C). The data obtained when the indenter was pressed until a load of 0.5 mN was reached was analyzed using dedicated software to determine the surface hardness of the coating. The same procedure was carried out on three different points on each sample to determine the surface hardness, and the average value was calculated.

[0131] (2) Initial Coating Appearance: The coating appearance of the test piece was visually observed.

[0132] (3) Transparency: The haze of the coating was measured using a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

[0133] (4) Primary Adhesion: In accordance with JIS K5400, a test piece was cut with a razor blade in six lines at 2 mm intervals vertically and horizontally to form 25 grids, and commercially available cellophane adhesive tape was firmly adhered to the grid. The tape was then rapidly peeled off at an angle of 90 degrees toward the user. The number of grids (X) that remained without peeling of the coating was represented as X / 25.

[0134] (5) Water Resistance and Water-Resistant Adhesion: After immersing the test piece in boiling water for 2 hours, an adhesion test was carried out in the same manner as in (4) above.

[0135] (6) Scratch resistance: According to ASTM 1044, a Taber abrasion tester was used with an abrasion wheel CS-10F attached, and the haze was measured after 1,000 revolutions under a load of 500 gf. The scratch resistance ΔHz (% points) was expressed as (haze after test (%)) - (haze before test (%)).

[0136] (7) Heat resistance: A test piece was placed in an oven at 110°C, and after 1000 hours, the appearance of the coating was observed and evaluated according to the following criteria: ○: No abnormality ×: Cracks in the coating

[0137] (8) Weather resistance: SUV accelerated weather resistance test: Weather resistance was evaluated under the same conditions as those described in WO 2020 / 066993. That is, using an accelerated weather resistance tester Super UV Tester (SUV) manufactured by Iwasaki Electric Co., Ltd., the test piece was subjected to 4 hours of irradiation (irradiation intensity 90 mW / cm 2 The test was carried out for 600 hours (50 cycles), with one cycle consisting of 12 hours in darkness (black panel temperature 63°C, humidity 70%), 4 hours in darkness (black panel temperature 63°C, humidity 90%), and 4 hours in condensation (black panel temperature 30°C, humidity 95%). After 600 hours (50 cycles), the presence or absence of coating cracks and coating peeling was confirmed and evaluated according to the following criteria. [Weather-resistant coating cracks] The appearance of the coating after the weather resistance test was evaluated according to the following criteria. ○: No abnormalities ×: Cracks present [Weather-resistant coating peeling] The condition of the coating after the weather resistance test was evaluated according to the following criteria. ○: No abnormalities ×: Peeling

[0138]

[0139]

[0140] As shown in Table 2, the coated articles of Examples 1 to 8, which satisfied the requirements of the present invention, had good coating transparency and adhesion to the polycarbonate resin substrate, and exhibited excellent scratch resistance, with a scratch resistance ΔHz of 2 points or less. In addition, there was no coating cracking or peeling even after the heat resistance test or SUV weather resistance test, demonstrating that the articles combined excellent heat resistance and weather resistance.

[0141] On the other hand, as shown in Table 3, when a vinyl copolymer without alkoxysilyl groups was used as in Comparative Examples 1 and 2, cracks occurred after the heat resistance test and peeling of the coating occurred after the SUV weather resistance test. This suggests that the vinyl copolymer with alkoxysilyl groups has the effect of improving the heat resistance and weather resistance of coated articles including a photo-modified layer.

[0142] Furthermore, even when a vinyl copolymer having an alkoxysilyl group was used as in Comparative Example 3, if no ultraviolet absorber was contained in the hard coat layer, the heat resistance was good, but the scratch resistance deteriorated, and peeling of the coating occurred after the SUV weather resistance test. This is thought to be because, since no ultraviolet absorber was contained in the hard coat layer, the irradiated light during photo-modification reached the primer layer, degrading the primer layer and thereby worsening the adhesion of the coating.

[0143] When a large amount of inorganic particles was introduced, as in Comparative Example 4, or when the film thickness was too thick, as in Comparative Example 5, the balance between the thermal expansion and stress relaxation properties of the primer layer was lost, resulting in poor adhesion and early cracking during heat resistance tests and weather resistance tests.

[0144] Furthermore, when a vinyl copolymer having an alkoxysilyl group was used as the primer component and a siloxane-based hard coat layer containing an ultraviolet absorber was laminated as in Comparative Example 6, heat resistance and SUV weather resistance were good, but scratch resistance was not good because there was no photo-modified layer. From the above results, it was clear that the coated articles of Examples 1 to 8, which satisfied the requirements of the present invention, had excellent coating transparency, scratch resistance, heat resistance, and weather resistance.

Claims

1. A resin substrate, a primer layer provided on the resin substrate, a hard coat layer provided on the primer layer, and a light-modifying layer formed on a surface portion of the hard coat layer, The primer layer is (A) vinyl-based (co)polymer: 100 parts by mass, and (B) Inorganic particles having a median diameter of 1 to 100 nm measured by dynamic light scattering: 1 to 19 parts by mass wherein the (A) vinyl (co)polymer comprises (A-1) a vinyl (co)polymer having an alkoxysilyl group, and the thickness of the primer layer is 1 to 20 μm; The hard coat layer is (a) The following formula (1): R 1 m Si(OR 2 ) 4-m (1) (In the formula, R 1 are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, 1 may be bonded to each other to form a linking group, 2 are each independently an alkyl group having 1 to 3 carbon atoms, and m is 0, 1, or 2. and (partial) hydrolysis and condensation products thereof. (b) colloidal silica; (c) Ultraviolet absorber wherein the hard coat layer has a thickness of 1 to 15 μm.

2. 10. The coated article of claim 1, wherein the photomodifying layer comprises silicon dioxide.

3. 2. The coated article according to claim 1, wherein the ultraviolet absorber (c) comprises a reactive ultraviolet absorber represented by the following general formula (2) and a (partial) hydrolysis condensate thereof: 【Chemistry 1】 [In the formula, R 3 are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or a group represented by the following general formula (3), 3 At least one of these is a group represented by the following general formula (3). *-O-(CH 2 ) j -SiR 4 k (OR 5 ) 3-k (3) (In the formula, R 4 and R 5 are each independently an alkyl group having 1 to 5 carbon atoms, j is an integer of 1 to 8, and k is an integer of 0 to 2. An asterisk * represents a bond to an adjacent atom.

4. 2. The coated article according to claim 1, wherein the surface hardness of the hard coat layer measured by a nanoindentation method is 0.10 to 0.50 GPa.

5. 2. The coated article according to claim 1, wherein the inorganic particles (B) comprise one or more particles selected from the group consisting of silica, zinc oxide, titanium oxide and cerium oxide.

6. 2. The coated article according to claim 1, wherein the primer composition comprises (A-1) a vinyl copolymer having an alkoxysilyl group and an ultraviolet absorbing group.

7. 2. The coated article according to claim 1, wherein the primer composition further comprises (C) one or more ultraviolet absorbers selected from the group consisting of triazine derivatives and benzophenone derivatives.

8. 2. The coated article of claim 1, wherein the primer composition further comprises (D) a hindered amine light stabilizer.

9. 2. The coated article according to claim 1, wherein the thickness of said primer layer is 3 to 15 μm, and the thickness of said hard coat layer is 3 to 13 μm.

10. A method for producing a coated article according to any one of claims 1 to 9, comprising the steps of: A method for producing a coated article, comprising the step of irradiating a surface of a hard coat layer with light having a wavelength of 300 nm or less to form a photo-modified layer on a surface portion of the hard coat layer.

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