Coated articles and methods for manufacturing the same

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

Technical Field

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

Background Art

[0002] In recent years, as an alternative to transparent plate glass, it has become widespread to use a transparent material that is non-shattering or has greater shatter resistance than glass. For example, plastic substrates, particularly polycarbonate resins, etc., are excellent in transparency, impact resistance, heat resistance, etc., and are currently used in various applications such as for windows of buildings and vehicles, instrument covers, etc. as structural members to replace glass. However, since the surface properties such as scratch resistance and weather resistance are inferior to those of glass, it is eagerly desired to improve 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, in Patent Document 1, a protective film is provided with a siloxane-based hard coat paint, and further, the surface of the protective film is modified with vacuum ultraviolet light to form a photo-modified film. On the other hand, when the resin molded product is placed at a high temperature, the photo-modified film cannot follow the thermal expansion of the resin and is likely to crack, and there are problems with heat resistance and weather resistance.

[0004] In Patent Documents 2 and 3, a mesh mask is placed on a siloxane-based hard coat layer, and light is irradiated from above the mesh mask to expose the hard coat layer to light through the openings of the mesh mask, and the photo-modified layer and the siloxane-based hard coat layer are alternately formed on the surface of the resin substrate in a shape corresponding to the opening shape of the mesh mask, thereby relaxing the stress received by the photo-modified layer 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 the heat resistance when heated to 80°C is improved by either making the thickness of the primer layer containing an acrylic polymer 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 photomodified layer on top of it. On the other hand, when the primer layer is made thicker or a large amount of silica particles are added, cracks, premature peeling, and whitening of the coating are more likely to occur during weathering tests, posing challenges to weather resistance. In addition, polycarbonate resins are sometimes required to withstand temperatures exceeding 100°C. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Patent No. 4536824 [Patent Document 2] Patent No. 6585758 [Patent Document 3] International Publication No. 2020-044705 [Patent Document 4] Japanese Patent Publication No. 2016-030392 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] This invention has been made in view of the above circumstances, and aims to provide a coated article that has scratch resistance comparable to glass, as well as excellent heat resistance and weather resistance. [Means for solving the problem]

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

[0009] In other words, the present invention is 1. The material comprises a resin substrate, a primer layer provided on the resin substrate, a hard coat layer provided on the primer layer, and a photomodified layer formed on the surface of the hard coat layer. The primer layer (A) Vinyl-based (co)polymer: 100 parts by mass, and (B) Inorganic particles with a median diameter of 1 to 100 nm, measured by dynamic light scattering: 1 to 19 parts by mass A cured film of a primer composition comprising (A) vinyl (co)polymer, wherein (A-1) vinyl (co)polymer having an alkoxysilyl group, and the thickness of the primer layer is 1 to 20 μm. The aforementioned hard coat layer (a) Formula (1) below: R 1 m Si(OR 2 ) 4-m (1) (In the formula, R 1 Each is independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and multiple R 1 They may be bonded to each other to form a linking group, R 2 Each of these is an alkyl group having 1 to 3 carbon atoms, and m is 0, 1, or 2. A silicone resin obtained by (co)hydrolysis and condensation of at least one selected from alkoxysilanes represented by and their (partial) hydrolysis condensates, (b) Colloidal silica, (c) UV absorber A cured film of a silicone composition, and a coated article wherein the film thickness of the hard coat layer is 1 to 15 μm, 2. The coated article according to 1, wherein the light modifying layer contains silicon dioxide. 3. The coated article according to 1 or 2, wherein the (c) ultraviolet absorber contains a reactive ultraviolet absorber represented by the following general formula (2) and its (partial) hydrolysis condensate. [Chemical formula] [In the formula, R 3 is 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), provided that at least one of R 3 is a group represented by the following general formula (3). *-O-(CH2) 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. The asterisk * represents a bond with an adjacent atom.)] 4. The coated article according to any one of 1 to 3, wherein the surface hardness of the hard coat layer measured by nanoindentation is 0.10 to 0.50 GPa. 5. The coated article according to any one of 1 to 4, wherein the (B) inorganic particles contain 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 contains a vinyl copolymer having an (A-1) alkoxysilyl group and an ultraviolet absorbing group. 7. The coated article according to any one of 1 to 6, wherein the primer composition further contains one or more ultraviolet absorbers selected from (C) triazine derivatives and benzophenone derivatives. 8. The coated article according to any one of 1 to 7, wherein the primer composition further contains a (D) hindered amine light stabilizer. 9. A coated article according to any one of 1 to 8, wherein the thickness of the primer layer is 3 to 15 μm and the thickness of the hard coat layer is 3 to 13 μm. 10. A method for manufacturing a coated article as described in any of 1 to 9, A method for manufacturing a coated article, which includes the step of irradiating the surface of a hard coat layer with light with a wavelength of 300 nm or less to form a photomodified layer on the surface of the hard coat layer. To provide. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a coated article that has scratch resistance comparable to glass, as well as excellent heat resistance and weather resistance. Furthermore, according to the present invention, no special operations or equipment are required when photomodifying the hard coat layer, nor is any special post-treatment required after photomodification. Therefore, excellent scratch resistance, heat resistance, and weather resistance can be imparted to resin substrates of various shapes more easily. [Modes for carrying out the invention]

[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 photomodified layer formed on the surface of the hard coat layer. The primer layer is a cured film of a primer composition containing a vinyl (co)polymer having an alkoxysilyl group. The hard coat layer is a coated article in which the hard coat layer is a cured film of a silicone composition containing (a) silicone resin, (b) colloidal silica, and (c) an ultraviolet absorber.

[0012] One feature of the coated article of the present invention is that it contains an ultraviolet absorber in the hard coat layer. As described later, the inclusion of an ultraviolet absorber in the hard coat layer prevents light from reaching the primer layer during photomodification by light irradiation of the hard coat layer, thereby suppressing deterioration of scratch resistance caused by peeling of the coating or a decrease in adhesion.

[0013] Furthermore, by providing a primer layer containing a vinyl (co)polymer with alkoxysilyl groups in its molecular structure, the alkoxysilyl groups contained in the primer layer and / or silanol groups generated by their hydrolysis impart reactivity with the siloxane in the siloxane-based hard coat layer. This improves the adhesion between the substrate and the hard coat layer via the primer layer, and the crosslinking of the alkoxysilyl groups and / or silanol groups generated by their hydrolysis improves heat resistance, resulting in excellent scratch resistance and weather resistance.

[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, polycondensate of halogenated bisphenol A and ethylene glycol, acrylic urethane resin, aryl halide-containing acrylic resin, sulfur-containing resin, and the like. Among these, polycarbonate resin is preferred. Furthermore, these resin substrates may have their surfaces treated, specifically by chemical conversion treatment, corona discharge treatment, plasma treatment, or treatment with acid or alkaline solutions. Laminates in which the surface layer is made of a different type of resin than the main substrate can also be used. Specific examples of laminates include laminates having an acrylic resin layer or a urethane resin layer on the surface of a polycarbonate resin substrate manufactured by co-extrusion or lamination, and laminates having an acrylic resin layer on the surface of a polyester resin substrate.

[0015] <Primer layer> The primer layer in the coated article of the present invention consists of a cured film of a primer composition containing the following components (A) and (B). (A) Vinyl(co)polymer (B) Inorganic particles with a median diameter of 100 nm or less, as measured by dynamic light scattering.

[0016] [(A) Vinyl-based (co)polymer] (1)(A-1) Vinyl(co)polymer having an alkoxysilyl group The vinyl (co)polymer of component (A) includes the vinyl (co)polymer having an alkoxysilyl group (A-1). Examples of the vinyl (co)polymer having an alkoxysilyl group of component (A-1) include vinyl (co)polymers in which the alkoxysilyl group is bonded to the main chain via a Si-C bond. Examples of such (co)polymers include polymers of vinyl monomers in which the alkoxysilyl group is bonded via a Si-C bond, or copolymers of vinyl monomers in which the alkoxysilyl group is bonded via a Si-C bond with other vinyl monomers.

[0017] Here, any vinyl monomer in which an alkoxysilyl group is bonded via a 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 polymerizable functional groups include organic groups having 2 to 12 carbon atoms, such as vinyl, vinyloxy, (meth)acrylooxy, and (α-methyl)styryl groups. Specific examples include vinyl, 5-hexenyl, 9-decenyl, vinyloxymethyl, 3-vinyloxypropyl, (meth)acrylooxymethyl, 3-(meth)acrylooxypropyl, 11-(meth)acrylooxyundecyl, vinylphenyl(styryl), isopropenylphenyl(α-methylstyryl), and vinylphenylmethyl group (vinylbenzyl group). Among these, the (meth)acrylooxypropyl group is preferred due to its reactivity and availability. In this invention, (meth)acrylooxy means acrylic and / or methacrylic.

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

[0020] Other substituents that can bond to silicon atoms besides the alkoxy group mentioned above include alkyl groups such as methyl, ethyl, n-propyl, n-hexyl, and n-decyl groups, and aryl groups such as phenyl groups. Among these, the methyl group is preferred due to its availability.

[0021] Examples of vinyl monomers in which an alkoxysilyl group is bonded via a Si-C bond include, Methacryloxymethyltrimethoxysilane, Methacryloxypropyltrimethoxysilane, Methacryloxyundecyltrimethoxysilane, Methacryloxypropylmethyldimethoxysilane, Methacryloxypropyldimethylmethoxysilane, Methacryloxypropyltriethoxysilane, Acryloxypropyltrimethoxysilane, Acryloxypropylmethyldimethoxysilane, Acryloxypropyldimethylmethoxysilane, Acryloxypropyltriethoxysilane, Acryloxymethyltrimethoxysilane, Acryloxyundecyltrimethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, Vinylmethyldimethoxysilane, allyltrimethoxysilane, Styryltrimethoxysilane, Styrylmethyldimethoxysilane, Styryltriethoxysilane These are some examples. Among these, in terms of availability, handling, crosslinking density, reactivity, etc., Methacryloxypropyltrimethoxysilane, Methacryloxypropylmethyldimethoxysilane, Methacryloxypropyldimethylmethoxysilane, Acryloxypropyltrimethoxysilane, Acryloxypropylmethyldimethoxysilane It is preferable.

[0022] The amount of alkoxysilyl groups in component (A) is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, and even more preferably 3 to 15% by mass, relative to the total amount of component (A), for example, when the alkoxysilyl groups are trimethoxysilane. If it is 1% by mass or more, sufficient siloxane network formation by crosslinking with the vinyl (co)polymers or inorganic fillers is achieved, the coefficient of linear expansion of the coating becomes lower, and the heat resistance and durability are further improved. Furthermore, the reaction with siloxane in the hard coat layer further improves adhesion to the hard coat layer and weather resistance. Also, if 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 it is possible to suppress the occurrence of cracks in the coating due to post-crosslinking of unreacted alkoxysilyl groups over time.

[0023] Other vinyl monomers copolymerizable with the vinyl monomers in which the above-mentioned alkoxysilyl groups are bonded via Si-C bonds are not particularly limited as long as they are copolymerizable vinyl monomers, but examples 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 their derivatives 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; (Meth)acrylic acid esters of alkoxy(poly)alkylene glycols such as 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), and methoxypolypropylene glycol (meth)acrylate (the number of propylene glycol units is preferably, for example, 2 to 20); Mono(meth)acrylic acid esters of monohydric or polyhydric alcohols 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); Poly(meth)acrylic acid esters of polyhydric alcohols such as 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), and polypropylene glycol di(meth)acrylate (the number of propylene glycol units is preferably, for example, 2 to 20); (Poly)esters of non-polymerizable polybasic acids such as mono[2-(meth)acryloyloxyethyl] succinate, di[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acryloyloxyethyl] adipic acid, di[2-(meth)acryloyloxyethyl] adipic acid, mono[2-(meth)acryloyloxyethyl] phthalate, and di[2-(meth)acryloyloxyethyl] phthalate with hydroxyalkyl (meth)acrylates; (meth)acrylic acid esters containing amino groups, 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; Epoxy group-containing (meth)acrylic acid esters such as glycidyl (meth)acrylate These are some examples.

[0025] Furthermore, specific examples of derivatives of (meth)acrylonitrile include α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-trifluoromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, and vinylidene cyanide. Specific examples of derivatives of (meth)acrylamide 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, and hexyl vinyl ether. Specific examples of alkyl vinyl esters include vinyl formate, vinyl acetate, vinyl acrylate, vinyl butyrate, vinyl caproate, and vinyl stearate. Specific examples of styrene and its derivatives include styrene, α-methylstyrene, and vinyltoluene.

[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, and methyl (meth)acrylate and glycidyl (meth)acrylate being even more preferred. These monomers can be used individually or in combination of two or more.

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

[0029] [ka]

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

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

[0032] Specific examples of benzotriazole compounds represented by the above general formula (4) include, for example, 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, 2-[2'-hydroxy-3'-methyl-5'-(8-(meth)acryloxyoctyl)phenyl]-2H-benzotriazole These are some examples.

[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). A concentration of 1% by mass or more of the UV-absorbing groups is preferable because it results in good UV absorption properties and good weather resistance. A concentration of 20% by mass or less is preferable because it prevents whitening of the coating and provides good crack resistance. (A-1) Component may be used alone or in combination of two or more types.

[0034] (A-1) Component is particularly preferably one having the following constituent units (i) to (iii). In addition, vinyl copolymers having alkoxysilyl groups and ultraviolet absorbing groups can also be preferably used, and those containing the following constituent units (i) to (iv) are more preferably used. The order of the constituent units in component (A-1) is arbitrary, and component (A-1) may be an alternating copolymer, a random copolymer, or a block copolymer.

[0035] [ka] (In the formula, an asterisk * indicates a connection to an adjacent constituent unit.)

[0036] Component (A-1) is 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 monomer, and carrying out a polymerization reaction under heating (for example, 50 to 150°C, especially 70 to 120°C for 1 to 10 hours, especially 3 to 8 hours).

[0037] Furthermore, the polystyrene-equivalent weight-average molecular weight of the vinyl (co)polymer component (A-1) determined by gel permeation chromatography (GPC) 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, resulting in better handling. When it is 50,000 or more, appearance defects such as whitening of the coating are suppressed, and better adhesion, durability, and weather resistance are obtained.

[0038] (2)(A-2) Vinyl(co)polymers that do not contain alkoxysilyl groups Furthermore, the primer composition of the present invention may also contain a vinyl copolymer that does not contain (A-2) alkoxysilyl groups. The vinyl-based (co)polymer that does not contain the alkoxysilyl group is not particularly limited, but can be obtained by (co)polymerizing a monomer other than a vinyl-based monomer in which the alkoxysilyl group is bonded via a Si-C bond.

[0039] Examples of monomers other than vinyl monomers in which alkoxysilyl groups are bonded via Si-C bonds, which serve as raw materials for component (A-2), include those similar to those exemplified in component (A-1) as other copolymerizable monomers other than vinyl monomers in which alkoxysilyl groups are bonded via Si-C bonds, and specific examples are also similar. (A-2) The vinyl monomers that serve as raw materials for component (A-2) may be used individually or in combination of two or more.

[0040] Among these, (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, and dicyclopentenyloxyethyl (meth)acrylate being even more preferred, and methyl (meth)acrylate being even more preferred.

[0041] Polymerization conditions such as reaction temperature, time, and polymerization initiator are not particularly limited and can be carried out under known conditions. For example, it 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 at, for example, 50 to 150°C, particularly 70 to 120°C, for 1 to 10 hours, and especially 3 to 8 hours.

[0042] (A-2) As for the component, commercially available products may be used, and specific examples include (meth)acrylic acid ester resins such as Dianal® BR-85, BR-88, and LR-1065 manufactured by Mitsubishi Rayon Co., Ltd. (A-2) Component (A-2) may be used alone or in combination of two or more components.

[0043] The weight-average molecular weight of component (A-2) in polystyrene equivalent, calculated by GPC, is preferably 50,000 to 1,000,000, and more preferably 60,000 to 800,000. If the molecular weight is too high, the viscosity may become too high, making synthesis difficult or handling difficult. If it is too low, it may cause appearance defects such as whitening of the coating, or may not provide sufficient adhesion, durability, or weather resistance.

[0044] When using components (A-1) and (A-2) in combination, the weight-average molecular weight of the combined components (A-1) and (A-2) in polystyrene equivalent, calculated by GPC, is preferably 6,000 to 1,000,000, and more preferably 50,000 to 800,000. If the molecular weight is too high, the viscosity may become too high, making synthesis difficult or handling difficult. If it is too low, it may cause appearance defects such as whitening of the coating, or may not provide sufficient adhesion, durability, or weather resistance.

[0045] Furthermore, when using components (A-1) and (A-2) in combination, the mass mixing ratio of components (A-1):(A-2) = 3:1 to 1:3 is preferred, (A-1):(A-2) = 2:1 to 1:2 is more preferred, and (A-1):(A-2) = 3:2 to 2:3 is even more preferred. If the amount of (A-1) is too high, it may cause appearance defects such as whitening of the coating, or insufficient adhesion, durability, and weather resistance may not be obtained. If the amount of (A-2) is too high, 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 with a median diameter of 1 to 100 nm as measured by dynamic light scattering. As the inorganic particles, for example, known inorganic oxides such as silica, alumina, cerium oxide, zirconium oxide, zinc oxide, and titanium oxide can be used individually or in combination of two or more. Among these, silica, zinc oxide, titanium oxide, and cerium oxide particles are preferred. By using the above-mentioned particles, the hardness and scratch resistance of the coating can be improved. In addition, by using particles such as cerium oxide, zirconium oxide, zinc oxide, and titanium oxide, the ultraviolet shielding ability can be further enhanced. Among the above-mentioned particles, silica particles and / or zinc oxide particles are particularly preferred because they result in good coating appearance and weather resistance.

[0047] The inorganic particles described above have a median diameter of 1 to 100 nm in the volume particle size distribution measured by dynamic light scattering, preferably 3 to 50 nm, and more preferably 5 to 40 nm. If the median diameter exceeds 100 nm, the transparency of the coating 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 will be poor. In this invention, a device such as the NanoTrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.) can be used for dynamic light scattering measurements.

[0048] The amount of inorganic particles to be blended is 1 to 19 parts by mass per 100 parts by mass of the vinyl-based (co)polymer of component (A), preferably 3 to 16 parts by mass, and more preferably 5 to 15 parts by mass. If the amount is less than 1 part by mass, the weather resistance will be insufficient, and if it exceeds 19 parts by mass, poor film appearance such as reduced adhesion and whitening will occur, cracks will be more likely to occur during weather resistance tests, and the weather resistance will deteriorate.

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

[0050] [(C) UV absorber] The ultraviolet absorber of component (C) may be included in the form of chemical bonding to the vinyl (co)polymer of component (A-1) as described above, or it may be included as an additive. When introduced as an additive, benzophenone derivatives, benzotriazole derivatives, cyanoacrylate derivatives, triazine derivatives, etc. are preferred. 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-bendyloxybenzophenone, 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, and 2,2'-dihydroxy Examples include droxy-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-triazine-2-yl)-5-(hexyloxy)phenol, Tinuvin 400 (BASF), Tinuvin 405 (BASF), Tinuvin 460 (BASF), Tinuvin 477 (BASF), Tinuvin 479 (BASF), Tinuvin 1577ED (BASF), and Tinuvin 1600 (BASF). These organic UV absorbers may be used individually or in combination of two or more, but it is preferable to use two or more in combination, and in particular, it is preferable to use a triazine derivative and a benzophenone derivative in combination.

[0051] When using an ultraviolet absorber, the amount added is preferably 2 to 50 parts by mass, and more preferably 10 to 30% by mass, per 100 parts by mass of component (A). At 2 parts by mass or more, weather resistance is further improved, and at 50 parts by mass or less, deterioration of the film's appearance, such as reduced adhesion and whitening, can be suppressed.

[0052] When using a triazodine derivative as an ultraviolet absorber, 1 to 10 parts by mass, and more preferably 2 to 5 parts by mass, are preferred per 100 parts by mass of component (A). Including 1 part by mass or more of the triazodine derivative is preferable because it results in good ultraviolet absorption characteristics and good weather resistance. Including 10 parts by mass or less is preferable because it prevents whitening of the coating and improves crack resistance. When using a benzophenone derivative as an ultraviolet absorber, the amount is preferably 7 to 40 parts by mass, and more preferably 10 to 25 parts by mass, per 100 parts by mass of component (A). Including 7 parts by mass or more of the benzophenone derivative is preferable because it results in good ultraviolet absorption characteristics and good weather resistance. Including 40 parts by mass or less is preferable because it prevents whitening of the coating and improves crack resistance.

[0053] [(D) Hindered amine-based light stabilizers] The above primer composition preferably contains (D) a hindered amine-based light stabilizer. In particular, it is preferable that the stabilizer has one or more cyclic hindered amine structures in its molecule, has good compatibility with the primer composition used in the present invention, and has low volatility. Specific examples of hindered amine-based 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, 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), condensate of 1,2,3,4-butanetetracarboxylic acid and 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 include a condensate of pentamethyl-4-piperidinol with β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5']undecane)diethanol, and a condensate of 1,2,3,4-butanetetracarboxylic acid with 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 such as those described in Japanese Patent Publication No. 61-56187, for example, 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 are also used. These light stabilizers can be used individually or in combination of two or more. Among these, a neutral hindered amine-based light stabilizer (TINUVIN249, manufactured by BASF Japan Ltd.) is preferred.

[0054] When using a hindered amine-based light stabilizer, the amount added 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 parts by mass or more is preferred because it provides good weather resistance, and an amount of 10 parts by mass or less is preferred because it suppresses defects in the appearance of the coating, such as reduced adhesion and whitening.

[0055] [(E) Solvent] The above primer composition may contain a solvent. The solvent is not particularly limited as long as it dissolves or disperses the above components, but a highly polar organic solvent is 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 acetate, and esters such as ethyl acetate, propyl acetate, butyl acetate, and cyclohexyl acetate. One or more solvents selected from this group can be used. Among these, ethers are preferred, and propylene glycol monomethyl ether is more preferred.

[0056] When using a solvent, the amount used is preferably such that the solid content concentration of the primer composition is 1 to 50% by mass, more preferably 5 to 30% by mass. Outside this range, defects may occur in the cured film of the composition. Specifically, at concentrations below the above range, the film is prone to sagging, wrinkling, and mottling, and the desired hardness and scratch resistance may not be obtained. Furthermore, at concentrations exceeding the above range, the film is prone to brushing, whitening, and cracking.

[0057] [Other ingredients] The above primer composition may optionally contain (B) a dispersant for inorganic particulate components, etc., to the extent that it does not inhibit 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 the particle surface, such as silane coupling agents.

[0058] The above primer composition may absorb water during storage or use, causing 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] The above primer composition may optionally contain leveling agents, metal powders, antioxidants, heat reflectors / absorbers, flexibility enhancers, antistatic agents, antifouling agents, water-repellent agents, etc., to the extent that they do not impair the effects of the present invention.

[0060] For optimal storage stability, the pH of the above-mentioned primer composition is preferably 2 to 8, more preferably 3 to 6. If the pH is outside this range, the storage life may be reduced. The method for adjusting the pH is not particularly limited, but it can also be adjusted to the above range by adding a pH adjusting agent. If the pH of the primer composition is outside the above range, if it is on the acidic side, the pH can be adjusted by adding a basic compound such as ammonia or ethylenediamine, and if it is on the basic side, the pH can be adjusted 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 components in accordance with conventional methods. Furthermore, the obtained primer composition can be applied to a resin substrate and cured to form a primer layer.

[0062] Examples of application methods for the primer composition include brush application, 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 air dry or by heating. The curing temperature and curing time are not particularly limited, but for example, it is preferable to heat it at a temperature below the heat resistance temperature of the substrate for 10 minutes to 2 hours, and more preferably 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 film hardness, scratch resistance, long-term stable adhesion, and crack prevention. If the film thickness is less than 1 μm, the UV shielding ability will be insufficient, and peeling of the film may occur, while if the film thickness exceeds 20 μm, cracks will occur in the film.

[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 film of a silicone composition containing the following components (a) to (c). (a) Formula (1) below: R 1 m Si(OR 2 ) 4-m (1) (In the formula, R 1 Each is independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, R 2 Each of these is an alkyl group having 1 to 3 carbon atoms, and m is 0, 1, or 2. A silicone resin obtained by (co)hydrolysis and condensation of at least one selected from alkoxysilanes represented by and their (partial) hydrolysis condensates, (b) Colloidal silica, (c) UV absorber

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

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

[0068] R 1 The monovalent hydrocarbon group may be linear, branched, or cyclic, and examples include alkyl groups having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms; cycloalkyl groups having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms; alkenyl groups having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms; and aryl groups having 6 to 12 carbon atoms, preferably 6 to 8 carbon atoms. R 1 Specific examples of monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl and allyl groups; and aryl groups such as phenyl groups. Furthermore, some or all of the hydrogen atoms of these groups may be substituted with other substituents. Specific examples 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-isocyanatetopropyl. Additionally, isocyanurate groups formed by the bonding of multiple isocyanate-substituted hydrocarbon groups can also be cited. Among these, alkyl groups are preferred when scratch resistance and weather resistance are required, while epoxy, (meth)acryloxy, and isocyanurate-substituted hydrocarbon groups are preferred when toughness and dyeability are required.

[0069] R 2 Examples of alkyl groups with 1 to 3 carbon atoms include methyl, ethyl, n-propyl, and isopropyl groups. Among these, those with high reactivity in hydrolysis and condensation, and the resulting alcohol R 2 Considering that the vapor pressure of the OH group is high and it is easily removed by distillation, methyl and ethyl groups are preferred.

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

[0071] In equation (1) above, when m=1, the general formula is: R 1 Si(OR 2Specific examples of trialkoxysilane (a-1) represented by )3 and its partial hydrolysis condensates 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-chloropropyltrimethyl Toxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-(2-aminoethyl)aminopropyltrimethoxysilane, γ-isocyanatetopropyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane Examples include tris(3-trimethoxysilylpropyl) isocyanurate, tris(3-triethoxysilylpropyl) isocyanurate, a partially hydrolyzed condensate of methyltrimethoxysilane (product names "KC-89S" and "X-40-9220", manufactured by Shin-Etsu Chemical Co., Ltd.), and a partially hydrolyzed condensate of methyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane (product name "X-41-1056", manufactured by Shin-Etsu Chemical Co., Ltd.).

[0072] In the above equation (1), when m=2, the general formula is: R 1 2Si(OR 2Specific examples of the dialkoxysilane represented by (a-2) and its (partial) hydrolysis 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, N-(2-aminoethyl)aminopropylmethyldimethoxysilane, etc.

[0073] The silicone resin of component (a) can be prepared by using components (a-0), (a-1), and (a-2) in any proportion. However, to further improve storage stability, scratch resistance, and crack resistance, it is preferable to use (a-0), (a-1), and (a-3) in a ratio of 0-50% silicon atoms from (a-0), 50-100% silicon atoms from (a-1), and 0-50% silicon atoms from (a-2) relative to the total number of Si atoms of (a-0), (a-1), and (a-3). It is even more preferable to use (a-0), (a-1), and (a-2) in a ratio of 0-30% silicon atoms from (a-0), 70-100% silicon atoms from (a-1), and 0-30% silicon atoms from (a-2). In this case, it is preferable that the main component (a-1) is 50% or more, as this results in good curability and an appropriate hardness for the cured film.

[0074] In the production of the silicone resin of component (a), components (a-0), (a-1), and (a-2) may be (co)hydrolyzed and condensed by known methods. For example, silicone resin can be obtained by (co)hydrolyzing and condensing alkoxysilanes of components (a-0), (a-1), and (a-2), or their (partial) hydrolyzed condensates, or mixtures thereof, with water having a pH of 1 to 7.5, preferably 2 to 7. In this case, water in which metal oxide fine particles such as silica sol are dispersed may be used. To adjust to this pH range and to 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 catalysts. Furthermore, during hydrolysis, metal oxide fine particles such as silica sol dispersed in water or an organic solvent may be included in the presence of the solution.

[0075] In the hydrolysis process, 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). Excessive use of water can not only reduce the efficiency of the apparatus, but also lead to a decrease in coating properties and drying properties in the final composition due to the effects of residual water. Furthermore, to improve storage stability, scratch resistance, and crack resistance, it is preferable to use 50 parts by mass or more and less than 150 parts by mass.

[0076] The hydrolysis step may involve adding or dropping water dropwise to an alkoxysilane or its (partial) hydrolysis condensate, or conversely, adding or dropping the alkoxysilane or its (partial) hydrolysis condensate dropwise to water. In this case, the reaction solvent may contain an organic solvent, but it is preferable that it does not contain an organic solvent. This is because the amount of organic solvent tends to decrease as the amount of organic solvent increases.

[0077] The condensation process can be carried out continuously following the hydrolysis process, and is usually performed at room temperature or under heating conditions below 100°C. At temperatures above 100°C, gelation may occur. Furthermore, condensation can be promoted by distilling off the alcohol produced by hydrolysis at 80°C or above under atmospheric or reduced pressure. Additionally, condensation catalysts such as basic compounds, acidic compounds, or metal chelate compounds may be added to further promote condensation. Before or during the condensation process, an organic solvent may be added to adjust the degree and concentration of condensation, or a dispersion of metal oxide fine particles such as silica sol in water or an organic solvent may be added. Generally, as condensation progresses, the molecular weight of the silicone resin increases and its solubility in water and the resulting alcohol decreases. Therefore, as the organic solvent to be added, a relatively polar organic solvent that dissolves the silicone resin well and has a boiling point of 80°C or higher is preferred. 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 acetate, 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 in GPC analysis is preferably 1,500 to 50,000, and more preferably 2,000 to 20,000. When the molecular weight is 1,500 or higher, the toughness of the coating is excellent and crack formation can be suppressed, while when the molecular weight is 50,000 or lower, the hardness may become too low and whitening of the coating due to phase separation of the resin in the coating can be suppressed.

[0079] [(b) Component] (b) Component 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 and organic-dispersed types can be used. Specifically, examples include Nissan Chemical Corporation's Snowtex-O, OS, O40, OL, methanol silica sol, IPA-ST, IBA-ST, PMA-ST, MEK-ST, etc. As for silica, those with a median diameter of 5 to 50 nm, as measured by dynamic light scattering, are preferred in terms 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, based on solid content, when component (a) is 100 parts by mass.

[0081] [(c) component] (c) Component is an ultraviolet absorber. Examples of ultraviolet absorbers for component (c) 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-bendyloxybenzophenone, 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, Examples include 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-triazine-2-yl)-5-(hexyloxy)phenol, Tinuvin 400 (BASF), Tinuvin 405 (BASF), Tinuvin 460 (BASF), Tinuvin 477 (BASF), Tinuvin 479 (BASF), Tinuvin 1577ED (BASF), Tinuvin 1600 (BASF), etc. In addition, silane coupling type reactive ultraviolet absorbers in which a portion of the above compounds are substituted with alkoxysilyl groups can be used. Among these, a silane coupling agent type reactive UV absorber in which a portion of the above compound is substituted with an alkoxysilyl group is preferred. By using the above reactive UV absorber, the UV-absorbing group is immobilized within the hard coat layer, and the bleed-out of the UV absorber over time is suppressed, which is effective in suppressing whitening and cracking.

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

[0083] [ka]

[0084] In the formula, R 3 Each of these is 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), but R 3 At least one of these is a group represented by the following general formula (3). *-O-(CH2) j -SiR 4 k (OR 5 ) 3-k (3) (In the formula, R 4 and R 5 Each of the elements is an alkyl group having 1 to 5 carbon atoms, j is an integer from 1 to 8, and k is an integer from 0 to 2. An asterisk (*) indicates a bond with an adjacent atom.

[0085] In equation (2) above, R 3 The alkyl group has 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and may be linear or branched. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, and isopentyl groups. Note, R 3 At least one of these groups is the group represented by the general formula (3) above. Having the group represented by the general formula (3) above allows the ultraviolet absorber to be immobilized within the hard coat layer, suppressing bleed-out over time, and thus effectively suppressing whitening and cracking of the hard coat layer. Also, R 3 It is preferable that at least one of them be a hydroxyl group, as this results in better UV absorption. 3 Of these, it is preferable that all but the group represented by the general formula (3) and the hydroxyl group are hydrogen atoms.

[0086] In the above equation (3), R 4 and R 5 The alkyl group having 1 to 5 carbon atoms is preferably 1 to 3 carbon atoms, and specific examples include R 3 Examples of groups similar to those exemplified above include R. 4 A methyl group or an ethyl group is preferred. Also, R 5 This is due to the high reactivity of hydrolysis and condensation, and the resulting alcohol R 5 Considering the high vapor pressure of the OH group and the ease of distillation removal, methyl and ethyl groups are preferred.

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

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

[0089] The amount of component (c) 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 above 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 curing catalysts include salts of 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), dicyandiamide, etc. Examples of base compounds include: 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 dibutylsuturethane laurate; and acidic compounds such as p-toluenesulfonic acid and trichloroacetic acid. Among these, sodium propionate, sodium acetate, sodium formate, trimethylbenzylammonium hydroside, tetramethylammonium hydroside, tetraethylammonium hydroside, tetrapropylammonium hydroside, tetrabutylammonium hydroside, tris(acetylacetonate)aluminum, and diisopropoxy(ethylacetoacetate)aluminum.

[0091] When a curing catalyst is used, the amount it is added should be sufficient to cure the silicone resin of component (a), and is not particularly limited. Specifically, it is preferably 0.0001 to 1% by mass, and more preferably 0.0005 to 0.1% by mass, relative to the solid content of the silicone resin. If it is 0.0001% by mass or more, sufficient curing will be achieved, and if it is 1% by mass or less, crack formation in the coating and a decrease in water resistance can be suppressed.

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

[0093] [Other ingredients] The above silicone composition may optionally contain pH adjusters, leveling agents, thickeners, pigments, dyes, metal oxide particles other than silica, metal powders, antioxidants, UV stabilizers, heat reflectance / absorption agents, flexibility agents, antistatic agents, antifouling agents, water-repellent agents, etc., to the extent that it does not impair the effects of the present invention.

[0094] The silicone composition used in the present invention can be obtained by mixing the above components in accordance with conventional methods. Furthermore, the obtained silicone composition can be applied to the primer layer and cured to form a hard coat layer. Methods for applying the silicone composition include those similar to those exemplified for the primer composition.

[0095] The silicone composition may be left to air dry after application, or it may be heated. The curing temperature and curing time are not particularly limited, but for example, it is preferable to heat it at a temperature below the heat resistance temperature of the substrate for 10 minutes to 2 hours, 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 crack prevention, it is necessary to 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 UV shielding ability will be insufficient, the coating will peel off, and the hardness and scratch resistance of the coating will be insufficient. Also, if the film thickness exceeds 15 μm, cracks will occur in the coating.

[0097] [Hardness of the hard coat layer] The hard coat layer described above preferably has a surface hardness of 0.10 to 0.50 GPa, more preferably 0.20 to 0.40 GPa, and even more preferably 0.25 to 0.35 GPa, as measured by the nanoindentation method. Examples of devices for measuring the elastic modulus of such a coating include nanoindenters (Hyditron Triboindenter, manufactured by Bruker Japan Co., Ltd.; ENT-NEXUS, manufactured by Elionix Co., Ltd.). A surface hardness of 0.10 GPa or higher is preferable because it results in good abrasion resistance when the photomodified layer is formed. A surface hardness of 0.50 GPa or lower is also preferable because the siloxane-based hard coat layer can effectively mitigate the stress that the photomodified layer receives from the resin substrate during heat resistance and weather resistance tests, thereby improving crack resistance and resulting in good heat resistance and weather resistance of the coating.

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

[0099] <Photomodified layer> The coated article of the present invention has a photomodified layer formed on the surface of the hard coat layer. In the coated article of the present invention, the photomodified layer is preferably a hard thin film layer mainly composed of silicon dioxide, obtained by irradiating the surface of the hard coat layer with light with a wavelength of 300 nm or less. It is known that the energy of short-wavelength light below 300 nm can cleave the bonding chains of organic polymers, selectively cleaving the CH, 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 recombining these cleaved oxygen atoms with silicon atoms, thereby modifying a portion of the hard coat layer into a hard thin film layer mainly composed of silicon dioxide.

[0100] Examples of vacuum ultraviolet light sources with short wavelengths below 300 nm include excimer lasers, excimer lamps, and low-pressure mercury lamps. Examples of excimer lasers include Ar2 lasers with a wavelength of 126 nm, F2 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 vacuum ultraviolet light sources below 300 nm are Ar2 lasers, F2 lasers, ArF lasers, and KrF excimer lasers. Furthermore, excimer lamps exist with wavelengths of 126 nm (Ar2), 146 nm (Kr2), 165 nm (ArBr), 172 nm (Xe2), 175 nm (ArCl), 193 nm (ArF), 207 nm (KrBr), 222 nm (KrCl), 253 nm (XeCl), 283 nm (XeBr), and 308 nm (XeCl). In this invention, it is preferable to use an F2 laser or a Xe excimer lamp.

[0101] The method of ultraviolet irradiation is not particularly limited, but examples include irradiating the hard coat layer with ultraviolet light of a wavelength of 300 nm or less using the above-mentioned light source in the atmosphere or an inert gas atmosphere such as nitrogen or argon. The integrated light intensity is 0.1 J / cm². 2 The above is preferable, and 0.5 J / cm 2 The above is preferable.

[0102] The thickness of the photomodified 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 also 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 printed layer, a recording layer, a heat shielding layer, an adhesive layer, an inorganic vapor-deposited film layer, etc., on top of the above-mentioned photomodified layer.

[0104] One of the characteristics of the coated articles of the present invention is the visible light transmittance of the coating. This can be evaluated by the haze value of the coating. Since the haze value increases with increasing film thickness, in the present invention, a haze value of 2.0 or less is preferred, more preferably 1.5 or less, and even more preferably 1.0 or less for film thicknesses of 20 μm or less. The haze of the coating can be measured, for example, with a turbidimeter NDH2000 (manufactured by Nippon Denshoku Industries, Ltd.).

[0105] One of the characteristics of the coated articles of the present invention is the good adhesion between the coating and the substrate. This can be evaluated by a grid peel test in accordance with JIS K5400. Using a razor blade, 25 grids are created by making 6 vertical and 6 horizontal cuts at 2 mm intervals in the coating. After firmly attaching cellophane tape (registered trademark, manufactured by Nichiban Co., Ltd.), the tape is rapidly peeled off at a 90° angle. The number of squares (X) that remain without peeling the coating is expressed as X / 25. The closer the value of X to 25, the better the adhesion is considered to be. Furthermore, if a substrate with a cured coating is boiled in 100°C water for 2 hours and the same grid test is performed, it can be used as an indicator of water-resistant adhesion.

[0106] One of the features of the coated articles of the present invention is their excellent scratch resistance. This can be evaluated by the difference in haze (ΔHz) before and after the Taber abrasion test. In accordance with ASTM1044, the abrasion wheel CS-10F was mounted on a Taber abrasion tester and the test was performed under a load of 500gf. 10 When the ΔHz (% points) measured after 00 rotations is evaluated as (haze after test (%)) - (haze before test (%)), the ΔHz for 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 this field, it is common to judge that a haze difference (ΔHz) of 2 points or less in the above test has scratch resistance equivalent to or better than glass.

[0107] One of the features of the coated articles of the present invention is good heat resistance. An example of a heat resistance test is to store the articles in an oven at 110°C for 100 to 1000 hours and observe the appearance of the test pieces every 100 hours. Preferably, the coated articles of the present invention do not develop cracks or peeling in the coating after 200 hours of testing, more preferably after 500 hours of testing, and most preferably after 1000 hours of testing.

[0108] One of the characteristics of the coated articles of the present invention is good weather resistance. This can be determined by the change in the appearance of the coating during a weather resistance test. As an example of a weather resistance test, an Iwasaki Electric Co., Ltd. iSuper UV Tester W-151 was used, and ultraviolet irradiation (irradiation intensity 90 mW / cm²) was performed for 4 hours. 2 One evaluation method involves observing the condition of the test specimen every 12 hours (10 cycles) of a 12-hour cycle consisting of a black panel at 63°C and 70% humidity, followed by 4 hours of darkness (63°C and 90% humidity), and 4 hours of condensation (30°C and 95% humidity). Observation can be done visually or using a microscope. While there are no particular limitations on the type of microscope that can be used for this purpose, an example is a laser microscope (manufactured by Keyence Corporation, model name "VK-8710"). In the above weather resistance test, it is preferable that no cracks or peeling occur in the coating after 360 hours of testing, more preferably that no cracks or peeling occur in the coating after 480 hours of testing, and even more preferably that no cracks or peeling occur in the coating after 600 hours of testing.

[0109] In the above weather resistance test, one-third of the test time was spent on light irradiation, with an intensity of 900 W / m². 2 It is 900W / m 2 The cumulative energy obtained from irradiating with ultraviolet light of this intensity for one hour is 0.9 kWh / m². 2However, following the rules for converting units, this is equal to 3.24 MJ (megajoules). Therefore, the cumulative irradiation dose after 600 hours of the above SUV test is 600 (test time) × 1 / 3 (percentage of light irradiation test) × 3.24 (MJ / m 2 ·h)≈648(MJ / m 2 ) The test conditions and environment for the weather resistance test in this invention can be set arbitrarily, but the correlation between the test conditions and outdoor exposure can be easily estimated. For example, if the amount of ultraviolet light outdoors is measured using an ultraviolet irradiometer (i-UVP365-1, manufactured by Iwasaki Electric Co., Ltd.), the correlation is 1 × 10¹ W / m². 2 This can be seen (measured at noon on a clear day on the vernal equinox in Matsuida-cho, Annaka City, Gunma Prefecture). The average annual sunshine hours in Japan are approximately 2000 hours, so the cumulative radiation dose in Japan over one year is approximately 2000 (h / year) × 1 (year) × 10 (W / m²). 2 ) = 20 (kWh / m 2 ) ≈ 72 (MJ / m 2 ) can be roughly estimated as follows. Therefore, the cumulative irradiation dose after 600 hours of the above SUV test corresponds to the cumulative irradiation dose that the sample would receive if used outdoors in Japan for approximately 9 years, as shown by the following formula: 648 (MJ / m 2 (cumulative irradiation dose after 600 hours of testing) / 72(MJ / m 2 * (Annual light exposure in Japan) ≈ 9 (years). Since outdoor environments vary depending on latitude and climate, test conditions should be appropriately modified according to the usage environment of the cured coating. [Examples]

[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, % represents mass%, parts represents parts by mass, and Me represents a methyl group. The weight-average molecular weight was measured by gel permeation chromatography (GPC) based on standard polystyrene.

[0111] [1] Synthesis of vinyl copolymer (A-1) [Synthesis Example 1] <Synthesis of vinyl copolymer (A-1-1) having UV-absorbing groups and alkoxysilyl groups> In a 2-liter flask equipped with a stirrer, condenser, and thermometer, 126 g of isobutyl acetate and 126 g of isopropyl alcohol were charged as solvents and heated to 80°C under a nitrogen stream. A pre-prepared monomer mixture (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) was added dropwise over 1.5 hours at 80-90°C, and the mixture was stirred for another 5 hours at 80-90°C. After cooling, 367 g of diacetone alcohol was added to stop the reaction. In the obtained vinyl copolymer (A-1-1) having UV-absorbing groups and alkoxysilyl groups, the proportion of UV-absorbing groups was 10.2% by mass, the proportion of trimethoxysilyl groups was 10.2% by mass, and the weight-average molecular weight was 87,800.

[0112] [Synthesis Example 2] <Synthesis of vinyl copolymer (A-1-2) having alkoxysilyl groups> Except for the change in composition shown in Table 1, the same procedure as in Synthesis Example 1 was performed to obtain a vinyl copolymer (A-1-2) having alkoxysilyl groups. The proportion of trimethoxysilyl groups in the obtained copolymer was 9.4% by mass, and the weight-average molecular weight was 60,800.

[0113] [Table 1]

[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 absorbers [Synthesis Example 3] <Synthesis of reactive UV absorber (c-1)> 25.4 g (0.1 mol) of 4-alyloxy-2-hydroxybenzophenone (Aldrich) was suspended in 70 mL of toluene in a reactor. 0.05 g of platinum catalyst PL50-T (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, 5 g of Wako Gel C-100 was added to adsorb the platinum catalyst, and the mixture was filtered. The solvent was removed by vacuum concentration to obtain 34.8 g (0.092 mol) of a red oily substance. Main component 1 The 1H-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)> In a 500 ml flask equipped with a stirrer, condenser, and thermometer, 48 g of methyltrimethoxysilane and 1.2 g of the reactive ultraviolet absorber (c-1) obtained in Synthesis Example 3 were added and the mixture was kept at 20°C while stirring. Then, 29.4 g of water-dispersed colloidal silica (Snowtex O, manufactured by Nissan Chemical Corporation, average particle size 15-20 nm, SiO2: 20%), 8.2 g of acetic acid, and 30 g of water were added and the mixture was stirred. Furthermore, after stirring at 60°C for 3 hours, 45 g of n-butanol was added, and then 72 g of by-product methanol and some water was removed by distillation at atmospheric pressure. Subsequently, a solution was obtained by diluting with isopropanol to a solid content concentration of 30% by mass. Next, 0.02 g of polyether-modified silicone KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 30 g of the above solution as a leveling agent, and 0.1 g of a 10% by 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 through filter paper to obtain silicone composition (HC-1).

[0117] [Comparative Synthesis Example 1] <Preparation of a silicone composition (HC-2) that does not contain UV absorbers> The same procedure as in Synthesis Example 4 was followed, except that the reactive UV absorber (c-1) was not added, to obtain a UV absorber-free silicone composition (HC-2).

[0118] [4] Preparation of primer composition [Preparation Examples 1-8, Comparative Preparation Examples 1-6] Compositions were prepared according to conventional methods using the compositions shown in Tables 2 and 3 (based on solid content, parts by mass). To these compositions, ethyl orthoformate (F-1), a dehydrating agent, was added at 5% by mass, LE-604 (G-1), a leveling agent, was added at 500 ppm by mass, and propylene glycol monomethyl ether (E-1) was added to adjust the concentration to achieve a total solid content concentration of 20% by mass, thereby obtaining primer compositions. The abbreviations used in the preparation examples, examples, and comparative examples that are not explained in the synthesis examples are as follows:

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

[0120] <(B) Inorganic particles> B-1: Silica-based propylene glycol monomethyl ether dispersion (PMA-ST, solid content concentration 30%, primary particle size 10-15 nm, manufactured by Nissan Chemical Corporation) B-2: Zinc oxide alcohol dispersion (ZNTANB15WT%-E34, solid content concentration 15%, primary particle size 10-15nm, manufactured by CIK Nanotech Co., Ltd.)

[0121] <(C) UV absorber> C-1: 2-[2-hydroxy-4-(1-octyloxycarbonylethoxy)phenyl]-4,6-bis(4-phenylphenyl)-1,3,5-triazine (TINUVIN479, manufactured by BASF Japan Ltd.) C-2: 2,4-Dihydroxybenzophenone (C-Sorb 106, manufactured by Cipro Chemical Corporation)

[0122] <(D) Hindered amine-based light stabilizers> D-1: Neutral hindered amine-based photostabilizer (TINUVIN249, 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] Manufacturing of covering articles [Examples 1-8, Comparative Examples 1-4] Each primer composition obtained in the above preparation example and comparative preparation example was applied to a cleaned polycarbonate resin plate (5 mm thick, product name: Takiron PC Clear-1600, manufactured by Takiron CI Co., Ltd.) by dip coating to form a cured film of 5 to 10 μm thickness, and then heated and cured at 130°C for 90 minutes to form a primer layer. After the obtained test specimens were allowed to cool to room temperature, the silicone compositions described in Tables 2 and 3 (HC-1 or HC-2 prepared in Synthesis Example 4 or Comparative Synthesis Example 1) were applied to the primer layer by dip coating to form a cured film with a thickness of 5 μm or more and 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 type excimer lamp, the surface of the siloxane-based hard coat layer was irradiated with light at a dose of 2 J / cm² under an N2 atmosphere. 2 Light irradiation was performed to create a photomodified layer with a thickness of 0.1 to 0.4 μm.

[0127] [Comparative Example 5] A specimen 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 was coated by a dip coating method to a thickness of 22 μm and the hard coat layer to a thickness of 16 μm.

[0128] [Comparative Example 6] A test specimen of Comparative Example 6 was obtained in the same manner as in Examples 1 to 8 and Comparative Examples 1 to 4, except that a photomodified layer was not formed.

[0129] [6] Physical property evaluation of coated articles The coated articles obtained in the above examples and comparative examples were used as test specimens, and various physical properties were evaluated. The results are shown in Tables 2 and 3.

[0130] (1) Surface hardness of the coating: The hardness of the coating in this invention was determined by a nanoindentation method using a nanoindenter (ENT-NEXUS, manufactured by Elionix Co., Ltd.). Specifically, a resin substrate having a siloxane-based hard coat layer on its outermost surface, prepared in the above examples and comparative examples, was cut to 15 mm x 15 mm. Instant adhesive (Aron Alpha Fast-Acting Multi-Purpose, manufactured by Toagosei Co., Ltd.) was applied to a dedicated sample fixing substrate (10 mm x 10 mm, 1 mm thick), and the substrate side of the sample was bonded to the fixing substrate to obtain a measurement sample. The obtained measurement samples were fixed to a dedicated sample holder with the siloxane-based hard coat layer side in contact with the indenter. A Berkovich-type indenter was pressed into the coating surface at room temperature (23°C) until a load of 0.5 mN was reached. The data obtained was then analyzed using dedicated software to determine the surface hardness of the coating. Surface hardness was determined by performing the same procedure on three different points in each sample, and the average value was calculated.

[0131] (2) Initial appearance of the coating: The appearance of the coating on the test specimens was observed visually.

[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, creating 25 grid squares with 6 vertical and 6 horizontal cuts at 2mm intervals. After firmly adhering commercially available cellophane adhesive tape to the grid, it was rapidly peeled off at a 90-degree angle towards the user. The number of squares (X) that remained without the coating peeling off was expressed as X / 25.

[0134] (5) Water resistance and water adhesion: After immersing the test specimen in boiling water for 2 hours, the adhesion test was performed in the same manner as in (4) above.

[0135] (6) Scratch resistance: In accordance with ASTM1044, the CS-10F abrasion wheel was mounted on a Taber abrasion tester, and the haze was measured after 1000 rotations under a load of 500gf. Scratch resistance ΔHz (% points) was expressed as (haze after test (%)) - (haze before test (%)).

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

[0137] (8) Weather resistance: SUV accelerated weathering test: Weather resistance was evaluated under the same conditions as described in International Publication No. 2020 / 066993. Specifically, an accelerated weathering tester, the Super UV Tester (SUV), manufactured by Iwasaki Electric Co., Ltd., was used, with 4 hours of irradiation (irradiation intensity 90 mW / cm²). 2 The test consisted of a 12-hour cycle consisting of a black panel temperature of 63°C and 70% humidity, 4 hours of darkness (black panel temperature 63°C and 90% humidity), and 4 hours of condensation (black panel temperature 30°C and 95% humidity). After 600 hours (50 cycles), the presence or absence of coating cracks and delamination was checked and evaluated according to the following criteria. [Weather-resistant coating cracking] The appearance of the coating after the weathering test was evaluated according to the following criteria. ○: No abnormalities ×: Crack present [Weather-resistant coating peeling] The condition of the coating after the weathering test was evaluated according to the following criteria. ○: No abnormalities ×: Peeling

[0138] [Table 2]

[0139] [Table 3]

[0140] As shown in Table 2, the coated articles of Examples 1 to 8, which satisfy the requirements of the present invention, exhibited good transparency of the coating and adhesion to the polycarbonate resin substrate, and a scratch resistance ΔHz of 2 points or less, demonstrating excellent scratch resistance. In addition, there were no cracks or peeling of the coating after heat resistance tests and SUV weather resistance tests, indicating that they possessed excellent heat resistance and weather resistance.

[0141] On the other hand, as shown in Table 3, when vinyl copolymers without alkoxysilyl groups were used, as in Comparative Example 1 and Comparative Example 2, cracks occurred after the heat resistance test, and the coating peeled off after the SUV weather resistance test. This suggests that vinyl copolymers having alkoxysilyl groups have the effect of improving the heat resistance and weather resistance of coated articles containing the photomodified layer.

[0142] Furthermore, even when using a vinyl copolymer having an alkoxysilyl group, as in Comparative Example 3, if the hard coat layer does not contain an ultraviolet absorber, heat resistance is good, but scratch resistance deteriorates, and peeling of the coating occurred after the SUV weathering test. This is thought to be because, because the hard coat layer does not contain an ultraviolet absorber, the irradiation light during photomodification reaches the primer layer, degrading the primer layer and worsening the adhesion of the coating.

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

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

Claims

1. The material comprises a resin substrate, a primer layer provided on the resin substrate, a hard coat layer provided on the primer layer, and a photomodified layer formed on the surface of the hard coat layer. The primer layer (A) Vinyl-based (co)polymer: 100 parts by mass, and (B) Inorganic particles with a median diameter of 1 to 100 nm as measured by dynamic light scattering: 1 to 19 parts by mass A cured film of a primer composition containing, wherein the (A) vinyl-based (co)polymer comprises (A-1) a vinyl-based (co)polymer having an alkoxysilyl group, and the film thickness of the primer layer is 1 to 20 μm. The aforementioned hard coat layer (a) The following formula (1): R 1 m Si(OR 2 ) 4-m (1) (In the formula, R 1 Each is independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group, and there are multiple R 1 They may be bonded to each other to form a linking group, R 2 Each of these is 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 and their (partial) hydrolysis condensates, (b) Colloidal silica, (c) UV absorber A cured film of a silicone composition containing, wherein the thickness of the hard coat layer is 1 to 15 μm. A coated article in which the photomodified layer is a layer with a thickness of 0.1 to 1.0 μm, mainly composed of silicon dioxide.

2. The coated article according to claim 1, wherein the (c) ultraviolet absorber comprises a reactive ultraviolet absorber represented by the following general formula (2) and a (partial) hydrolysis condensate thereof. 【Chemistry 1】 [wherein, R 3 is 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), provided that at least one of R 3 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 Each of the elements is an alkyl group having 1 to 5 carbon atoms, j is an integer from 1 to 8, and k is an integer from 0 to 2. An asterisk (*) indicates a bond with an adjacent atom.

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

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

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

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

7. The coated article according to claim 1, wherein the primer composition further comprises (D) a hindered amine-based light stabilizer.

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

9. A method for manufacturing a coated article according to any one of claims 1 to 8, The process involves applying the primer composition onto a resin substrate and curing it to form a primer layer. The steps include applying the silicone composition onto the primer layer and curing it to form a hard coat layer, and A method for manufacturing a coated article, comprising the step of irradiating the surface of a hard coat layer with light rays with a wavelength of 300 nm or less to form a photomodified layer on the surface of the hard coat layer.

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