Laminate, and a secondary decorative molded product comprising the above laminate.

Abstract

To provide a laminate that can form a secondary decorative molded product with excellent adhesion between the molded product and the laminate at a low temperature. [Solution] A laminate comprising, in that order, a support substrate (A), a hard coat layer (B), a primer layer (C), a coating layer (D1) containing a vapor-deposited aluminum pigment or a vapor-deposited indium pigment, and at least one metallic design layer (D) selected from a vapor-deposited metal layer (D2) on which at least one metal selected from indium, tin, and aluminum is vapor-deposited, and an adhesive layer (E), wherein the hard coat layer (B) comprises an active energy ray curable coating composition containing an active energy ray curable compound (b1), and the adhesive layer (E) comprises an adhesive coating composition containing a resin (e1) having a glass transition temperature in the range of -60 to +20°C.

Description

Technical Field

[0001] The present disclosure relates to a laminate and a secondary decorated molded article including the laminate.

Background Art

[0002] Studies have been conducted on laminates for decorating three-dimensional molded articles and secondary decorated molded articles using such laminates. For example, Patent Document 1 discloses a laminated film for decorating a three-dimensional molded article, which aims to provide a decorated molded article with excellent appearance durability. The laminated film for decorating a three-dimensional molded article according to Patent Document 1 sequentially includes a molding film layer (A), a clear coating film layer (B) made of an energy ray-curable coating film, a protective layer (C) for laminating a metal vapor deposition surface, a metal vapor deposition layer (D) made of indium or tin, and an adhesive layer (E). The protective layer (C) and the adhesive layer (E) contain a reactive resin, and the protective layer (C) contains two or more types of curing agents having different curabilities.

[0003] In paragraph

[0086] of Patent Document 1, it is disclosed that "as the adhesive resin contained in the adhesive layer (E), at least one adhesive resin selected from the group consisting of urethane resin, acrylic resin, olefin resin, vinyl chloride-vinyl acetate resin, epoxy resin, and butyral resin and having a softening temperature of 20 to 100°C is preferably contained." In paragraph

[0096] of Patent Document 1, it is disclosed that "from the above viewpoints, the present invention is particularly preferably used for imparting design properties to a metal substrate. Further, in fields where the shape is complex and problems due to deformation are likely to occur, such as automotive wheels, the above-described effects are more remarkable."

[0004] Paragraph

[0193] of Patent Document 1 states that it is preferable to pressurize the compressed air with compressed air of 130 kPa or more, and to set the temperature (T4) of the laminated film after decoration to 80°C to 170°C, and that this allows sufficient curing by the curing agent (IB), which has a higher curing temperature, among the two or more curing agents (IA) and curing agent (IB) containing the protective layer (C), which have different curing properties. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2022-100644 [Overview of the project] [Problems that the invention aims to solve]

[0006] The laminated film for decorating a three-dimensional molded body according to Patent Document 1 contains two or more curing agents with different curing properties in the protective layer (C). Therefore, in order to cure the curing agent (IB) which has a high curing temperature, it is necessary to heat the laminated film to a high temperature after compressed air is applied, and the material of the molded body to be decorated is limited to a metal substrate as described in paragraph

[0193] . Furthermore, in the case of the laminated film for decorating three-dimensional molded bodies described in Patent Document 1, if the laminated film is not heated to a high temperature after decoration following compressed air application, the adhesive resin contained in the adhesive layer (E) has a softening point of 20 to 100°C, resulting in poor adhesion between the laminated film for decorating three-dimensional molded bodies and the molded body to be decorated.

[0007] Therefore, the present disclosure aims to provide a laminate that can form a secondary decorative molded product with excellent adhesion between the molded product and the laminate at a low temperature. [Means for solving the problem]

[0008] The Disclosers have found a laminate comprising, in that order, a support substrate (A), a hard coat layer (B), a primer layer (C), a coating layer (D1) containing a vapor-deposited aluminum pigment or a vapor-deposited indium pigment, and at least one metallic design layer (D) selected from a vapor-deposited metal layer (D2) on which at least one metal selected from indium, tin, and aluminum is vapor-deposited, and an adhesive layer (E), wherein the hard coat layer (B) comprises an active energy ray curable coating composition containing an active energy ray curable compound (b1), and the adhesive layer (E) comprises an adhesive coating composition containing a resin (e1) having a glass transition temperature in the range of -60 to +20°C. [Effects of the Invention]

[0009] The laminate according to this disclosure can form a secondary decorative molded product with excellent adhesion between the molded product and the laminate at a low temperature. [Modes for carrying out the invention]

[0010] This disclosure relates to the following: (1) Support base material (A) Hard court layer (B), Primer layer (C), A coating layer (D1) containing vapor-deposited aluminum pigment or vapor-deposited indium pigment, and at least one metallic design layer (D) selected from a vapor-deposited metal layer (D2) on which at least one metal selected from indium, tin, and aluminum is vapor-deposited, Adhesive layer (E), A laminate having the following in that order, The hard coat layer (B) above comprises an active energy ray curable coating composition containing an active energy ray curable compound (b1), The above adhesive layer (E) is composed of an adhesive coating composition containing a resin (e1) having a glass transition temperature in the range of -60 to +20°C. Laminated structure.

[0011] (2) The laminate according to (1), wherein the tensile modulus of the support base material (A) is in the range of 3 to 650 MPa at 100°C. (3) The above active energy ray curable compound (b1) is a polymerizable unsaturated group-containing acrylic resin (b 11 A laminate according to (1) or (2), including ). (4) The polymerizable unsaturated group-containing acrylic resin (b 11 The laminate according to (3), wherein the polymerizable unsaturated group equivalent of ) is in the range of 300 to 600 g / eq.

[0012] (5) The polymerizable unsaturated group-containing acrylic resin (b 11 The laminate according to (3) or (4), wherein the weight-average molecular weight of the material is in the range of 10,000 to 60,000. (6) The above active energy ray curable compound (b1) is a (meth)acrylate compound (b) having 6 or more functional groups per molecule. 12 A laminate according to any one of (1) to (5), further including the above. (7) The laminate according to any one of (1) to (6), wherein the active energy ray curable coating composition further contains particles (b3).

[0013] (8) The laminate according to any one of (1) to (7), wherein the active energy ray curable coating composition further comprises an unsaturated resin that does not have polymerizable unsaturated groups. (9) The laminate according to any one of (1) to (8), wherein the active energy ray curable coating composition contains the unsaturated group-free resin in a solid content ratio of more than 0.0% and 10.0% by mass or less, based on the active energy ray curable coating composition. (10) A secondary decorative molded product comprising a molded product and a laminate covering the molded product, The above laminate is a laminate described in any one of items (1) to (9). Secondary decorative molded product. (11) The secondary decorated molded article according to (10), wherein the active energy ray curable coating composition of the hard coat layer (B) has been cured.

[0014] The laminate relating to this disclosure and the secondary decorative molded product having the laminate described above will be described in detail below. The laminate according to this disclosure comprises, in that order, a support substrate (A), a hard coat layer (B), a primer layer (C), a coating layer (D1) containing a vapor-deposited aluminum pigment or a vapor-deposited indium pigment, and at least one metallic design layer (D) selected from a vapor-deposited metal layer (D2) on which at least one metal selected from indium, tin, and aluminum is vapor-deposited, and an adhesive layer (E).

[0015] The laminate according to this disclosure is a laminate for secondary decoration methods, specifically for TOM (Three-Dimensional Overlay Method) molding. Furthermore, the laminate according to this disclosure can be used in both out-mold forming (OMF) and out-mold release (OMR) methods, and is particularly suitable for out-mold release (OMR).

[0016] Secondary decoration methods are decorative molding methods in which decoration is performed after the molded product has been formed. For example, TOM (Three-Dimensional Overlay Method) molding is a well-known example. TOM molding is generally performed using a TOM molding machine that has an upper box equipped with a heater, a depressurizing device and a compressed air device, and a lower box equipped with a lifting device and a depressurizing device.

[0017] In TOM molding using the bonding method (OMF), (i) the molded product is placed on the lifting equipment of the TOM molding machine and the laminate is placed between the upper box and the lower box, (ii) the upper box and the lower box are reduced in pressure and the laminate is heated and softened using a heater, (iii) the molded product is raised to the upper box together with the lifting equipment and the upper box is compressed air, thereby covering the molded product with the laminate, (iv) the upper box and the lower box are returned to atmospheric pressure, and (v) the excess laminate is trimmed to form a secondary decorated molded product.

[0018] In TOM molding using the transfer molding method (OMR), a secondary decorated molded product can be formed by (i) placing the molded product on the lifting equipment of the TOM molding machine and arranging a laminate between the upper box and the lower box, (ii) reducing the pressure in the upper box and heating and softening the laminate using a heater, (iii) raising the molded product together with the lifting equipment to the upper box and applying compressed air to the upper box to cover the molded product with the laminate, (iv) returning the upper box and the lower box to atmospheric pressure, and (v) peeling the support base material from the molded product.

[0019] Compared to vacuum forming, which uses only atmospheric pressure and no compressed air, TOM forming has advantages such as being able to make the laminate conform to the three-dimensional shape of the molded product and being able to handle molded products with large irregularities. In addition, TOM forming using the transfer method (OMR) has the advantage of eliminating the need for a trimming process of excess laminate.

[0020] [Supporting base material (A)] The support substrate (A) functions as a carrier when forming the laminate, specifically when forming the hard coat layer (B), primer layer (C), metallic design layer (D), and adhesive layer (E), and also has a protective function that protects the hard coat layer (B) which will constitute the outer surface of the secondary decorative molded product.

[0021] Examples of conventionally known films for the supporting substrate (A) include polyolefin films (e.g., polyethylene films, polypropylene films), polyester films (e.g., polyethylene terephthalate films), polycarbonate films, acrylic resin films, flexible polyvinyl chloride films, fluorine films, etc., with polyolefin films being preferred. The above film can be an unoriented type, for example, an unoriented polypropylene (CPP) film.

[0022] The support substrate (A) has a tensile modulus of elasticity of preferably 1 MPa or more, more preferably 3 MPa or more, and even more preferably 8 MPa or more at 100°C. Furthermore, the support substrate (A) has a tensile modulus of elasticity of preferably 800 MPa or less, more preferably 650 MPa or less, and even more preferably 630 MPa or less at 100°C. Having a tensile modulus of elasticity in the range of 1 MPa to 800 MPa results in excellent moldability of the laminate. Having a tensile modulus of elasticity in the range of 3 to 650 MPa results in excellent drawdown resistance (resistance to uneven thickness) and stretchability of the laminate, and excellent moldability.

[0023] The above tensile modulus can be measured as follows. (1) Prepare the sample by cutting the support substrate to a length of 70 mm and a width of 10 mm. (2) The sample is set in a tensile testing machine (Tensilon RTG-1210, manufactured by A&D Company, Ltd., equipped with a constant temperature and humidity testing device) with a chuck distance of 10 mm, and a tensile test is performed under the conditions of a temperature of 100°C and a tensile speed of 10 mm / min. (3) Measure the slope of the obtained initial elastic region. (4) Tensile tests are performed a total of five times on different samples, and the average value of the slope is adopted as the tensile modulus.

[0024] Furthermore, the tensile modulus of the support substrate (A) can be adjusted by the type of material used for the support substrate (A), the stretching of the film constituting the support substrate (A), etc.

[0025] The support substrate (A) preferably has a thickness of 0.01 mm or more, more preferably 0.02 mm or more, and preferably 0.5 mm or less, more preferably 0.3 mm or less. This provides excellent carrier and protective functions, and makes it less likely to inhibit the hardening of the hard coat layer (B) described later.

[0026] In this specification, the thickness of each of the laminations—the support substrate (A), hard coat layer (B), primer layer (C), metallic design layer (D), and adhesive layer (E)—is measured by observing the cross-section of the lamination using a benchtop electron microscope (Phenom ProX, Thermo Fisher Scientific).

[0027] [Hard coat layer (B)] The hard coat layer (B) is a layer that constitutes the outer surface of a secondary decorative molded product and protects the outer surface of the secondary decorative molded product, in a secondary decorative molded product comprising a molded product and a laminate covering the molded product. The hard coat layer (B) contains an active energy ray curable coating composition containing an active energy ray curable compound (b1).

[0028] The active energy ray curable coating composition constituting the hard coat layer (B) can be cured by active energy rays before the laminate covers the molded product or after the laminate covers the molded product, but it is preferable to cure it by active energy rays after the laminate covers the molded product.

[0029] <Active energy ray curable coating composition> <Activated energy ray-curable compound (b1)> Active energy ray curable compound (b1) refers to a compound that can be cured by active energy rays. Active energy ray curable compound (b1) can be any compound known in the art as curable by active energy rays, without any particular limitations, and may, for example, contain an unsaturated group that can be polymerized by active energy rays. Examples of the above-mentioned active energy rays include ultraviolet light, visible light, laser light (near-infrared laser, visible light laser, ultraviolet laser, etc.), microwaves, electron beams, electromagnetic waves, etc., with ultraviolet light being preferred.

[0030] The active energy ray curable compound (b1) is a polymerizable unsaturated group-containing acrylic resin (b 11It is preferable that the hard coat layer (B) has an excellent appearance during coating, and the laminate, especially the hard coat layer (B), can be easily stretched by heating. In addition, the hard coat layer (B) can be made less prone to blocking.

[0031] Polymerizable unsaturated group-containing acrylic resin (b 11 Examples of such materials include acrylic resins having (meth)acryloyl groups in their molecules. Acrylic resins having (meth)acryloyl groups in their molecules can be obtained, for example, by: 1) an addition reaction of epoxy group-containing acrylic resin with carboxyl group-containing (meth)acrylate; 2) an addition reaction of carboxyl group-containing acrylic resin with epoxy group-containing (meth)acrylate; 3) an addition reaction of hydroxyl group-containing acrylic resin with isocyanate group-containing (meth)acrylate; or 4) an addition reaction of isocyanate group-containing acrylic resin with hydroxyl group-containing (meth)acrylate.

[0032] The addition reaction between functional group-containing acrylic resins such as epoxy group-containing acrylic resins, carboxyl group-containing acrylic resins, and hydroxyl group-containing acrylic resins, and carboxyl group-containing (meth)acrylates, epoxy group-containing (meth)acrylates, isocyanate group-containing (meth)acrylates, hydroxyl group-containing (meth)acrylates, etc., can be carried out, for example, in an organic solvent at 40 to 160°C, using a catalyst as necessary.

[0033] Examples of the carboxyl group-containing (meth)acrylates mentioned above include (meth)acrylic acid. Examples of epoxy group-containing (meth)acrylates include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and 3,4-epoxycyclohexylethyl (meth)acrylate.

[0034] Examples of the above-mentioned isocyanate group-containing (meth)acrylates include isocyanate methyl (meth)acrylate, isocyanate ethyl (meth)acrylate, isocyanate propyl (meth)acrylate, isocyanate octyl (meth)acrylate, p-methacryloxy-α,α'-dimethylbenzyl isocyanate, and m-acryloxy-α,α'-dimethylbenzyl isocyanate. Furthermore, examples include polyisocyanate compounds in which a portion of the isocyanate is reacted with a hydroxyl group-containing (meth)acrylate.

[0035] Examples of the hydroxyl group-containing (meth)acrylates mentioned above include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropene glycol mono(meth)acrylate, and ring-opening reaction products of (meth)acrylate compounds and ε-caprolactone compounds. Other examples include trimethylolpropanedi(meth)acrylate and pentaerythritol tri(meth)acrylate.

[0036] The functional group-containing acrylic resins, such as the carboxyl group-containing acrylic resin, epoxy group-containing acrylic resin, and hydroxyl group-containing acrylic resin, can be produced by various methods. The simplest and most preferred method involves copolymerizing a polymerizable unsaturated monomer selected from among the carboxyl group-containing (meth)acrylate, epoxy group-containing (meth)acrylate, isocyanate group-containing (meth)acrylate, and hydroxyl group-containing (meth)acrylate to obtain the desired functional group-containing acrylic resin, with other polymerizable unsaturated monomers as needed, in an organic solvent.

[0037] Examples of other polymerizable unsaturated monomers include the following: Alkyl methacrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethyloctyl (meth)acrylate, dodecyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, etc.

[0038] Alkyl carbitols (meth)acrylates such as benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and ethyl carbitol (meth)acrylate; and other (meth)acrylate esters such as isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate.

[0039] Hydrolyzable silyl group-containing polymerizable unsaturated monomers such as γ-(meth)acryloyloxypropyltrimethoxysilane, γ-(meth)acryloyloxypropyltriethoxysilane, and γ-(meth)acryloyloxypropylmethyldimethoxysilane. Fluorine-containing α-olefin compounds such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene, and hexafluoropropylene.

[0040] • Perfluoroalkyl-perfluorovinyl ethers or (per)fluoroalkyl vinyl ethers (where the alkyl group has 1 to 18 carbon atoms), such as trifluoromethyltrifluorovinyl ether, pentafluoroethyltrifluorovinyl ether, and heptafluoropropyltrifluorovinyl ether (where the alkyl group has 1 to 18 carbon atoms), and other fluorine-containing vinyl polymerizable unsaturated monomers.

[0041] Mono- or diester compounds of various polymerizable unsaturated monomers containing polyvalent carboxyl groups, such as fumaric acid, maleic acid, and itaconic acid, and monoalkyl alcohols having 1 to 18 carbon atoms; aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, and p-tert-butylstyrene. • Amino group-containing amide polymerizable unsaturated monomers such as (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, Nn-propyl(meth)acrylamide, and diacetone(meth)acrylamide.

[0042] Dialkylaminoalkyl compounds such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate; nitrogen-containing polymerizable unsaturated monomers such as tert-butylaminoethyl (meth)acrylate, tert-butylaminopropyl (meth)acrylate, aziridinyl ethyl (meth)acrylate, pyrrolidinyl ethyl (meth)acrylate, piperidinyl ethyl (meth)acrylate, (meth)acryloylmorpholine, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, N-vinyloxazoline, and (meth)acrylonitrile.

[0043] • Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, branched aliphatic vinyl carboxylates with 9 carbon atoms, branched aliphatic vinyl carboxylates with 10 carbon atoms, branched aliphatic vinyl carboxylates with 11 carbon atoms, vinyl stearate, and other aliphatic vinyl carboxylates. • Vinyl ester compounds of cyclic carboxylic acids such as vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate, and p-tert-butylbenzoate vinyl.

[0044] Alkyl vinyl ether compounds such as ethyl vinyl ether, hydroxyethyl vinyl ether, hydroxy-n-butyl vinyl ether, hydroxyisobutyl vinyl ether, cyclohexyl vinyl ether, and lauryl vinyl ether. • Halogenated olefin compounds other than the above-mentioned fluoroolefin compounds, such as vinyl chloride and vinylidene chloride; • α-olefin compounds such as ethylene, propylene, and butene-1

[0045] Furthermore, in the preparation of the epoxy group-containing acrylic resin described above, carboxyl group-containing polymerizable unsaturated monomers, isocyanate group-containing polymerizable unsaturated monomers, and hydroxyl group-containing polymerizable unsaturated monomers are treated as other polymerizable unsaturated monomers. In the preparation of carboxyl group-containing acrylic resin, epoxy group-containing polymerizable unsaturated monomers, isocyanate group-containing polymerizable unsaturated monomers, and hydroxyl group-containing polymerizable unsaturated monomers are treated as other polymerizable unsaturated monomers. In the preparation of hydroxyl group-containing acrylic resin, carboxyl group-containing polymerizable unsaturated monomers, epoxy group-containing polymerizable unsaturated monomers, and isocyanate group-containing polymerizable unsaturated monomers are treated as other polymerizable unsaturated monomers.

[0046] In this specification, "(meth)acrylate" means acrylate and / or methacrylate, and "(meth)acrylic acid" means acrylic acid and / or methacrylic acid. Also, "(meth)acryloyl" means acryloyl and / or methacryloyl, and "(meth)acrylamide" means acrylamide and / or methacrylamide.

[0047] Examples of radical polymerization initiators used in the preparation of functional group-containing acrylic resins such as the carboxyl group-containing acrylic resin, epoxy group-containing acrylic resin, hydroxyl group-containing acrylic resin, and isocyanate group-containing acrylic resin include 2,2'-azobisisobutyronitrile, 2,2'-azobis-methylbutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis-cyclohexanecarbonitride, and dimethyl-2, Azo compounds such as 2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis-(2-amidinopropene)2-hydrochloride, 2-tert-butylazo-2-cyanopropane, 2,2'-azobis(2-methyl-propionamide)2-hydrate, 2,2'-azobis[2-(2-imidazolin-2-yl)propene], and 2,2'-azobis(2,2,4-trimethylpentane); benzoyl peroxide, methyl ethyl acetate Examples include ketone peroxide compounds such as ton peroxide, cumene hydroperoxide, potassium persulfate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, 1,1-bis-tert-butyl peroxy-3,3,5-trimethylcyclohexane, tert-butyl peroxylaurate, tert-butyl peroxyisophthalate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, dicumyl peroxide, and di-tert-butyl peroxide; peroxyketal compounds; hydroperoxide compounds; dialkyl peroxide compounds; diacyl peroxide compounds; peroxyester compounds; peroxydicarbonate compounds; and hydrogen peroxide.

[0048] Furthermore, the organic solvents used in the preparation of the above-mentioned functional group-containing acrylic resin include, for example, alkyl alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, and isopentanol; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, and propylene glycol diethyl ether; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; and aromatic hydrocarbon-containing solvents such as Exxon Aromatic Naphtha No. 2 (Exxon Corporation, USA). Examples of organic solvents include: mixed hydrocarbon solvents; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and n-octane; mixed hydrocarbon solvents containing aliphatic hydrocarbons such as Isopar C, Isopar E, Exol DSP100 / 140, Exol D30 (all from Exxon Corporation, USA), and IP Solvent 1016 (Idemitsu Petrochemical Co., Ltd.); alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; ether solvents such as tetrahydrofuran, dioxane, diisopropyl ether, and di-n-butyl ether; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, hexyl acetate, ethyl propionate, and butyl propionate. Small amounts of water can also be used in combination with these organic solvents.

[0049] Furthermore, when preparing the functional group-containing acrylic resin described above, a chain transfer agent may be used as needed. Examples of chain transfer agents include dodecyl mercaptan, lauryl mercaptan, thioglycolate ester, mercaptoethanol, and α-methylstyrene dimer.

[0050] The acrylic resin (b) containing a polymerizable unsaturated group 11 ) preferably has a polymerizable unsaturated group equivalent of 150 g / eq or more, more preferably 300 g / eq or more, and even more preferably 360 g / eq or more. Further, the acrylic resin (b 11 ) preferably has a polymerizable unsaturated group equivalent of 800 g / eq or less, more preferably 600 g / eq or less, and even more preferably 500 g / eq or less. When the polymerizable unsaturated group equivalent is in the range of 150 to 800 g / eq, it becomes easier to form the laminate. Further, when the polymerizable unsaturated group equivalent is in the range of 300 to 600 g / eq, the hard coat layer (B) is excellent in blocking resistance and abrasion resistance.

[0051] In this specification, the polymerizable unsaturated group equivalent means the molar mass per one unsaturated group. When the weight average molecular weight of the acrylic resin (b 11 ) is Mw and the number of unsaturated groups contained in one molecule of the acrylic resin (b 11 ) is σ, the polymerizable unsaturated group equivalent is represented by Mw / σ. The polymerizable unsaturated group equivalent can be measured by adding dodecyl mercaptan to the radically polymerizable unsaturated group and back-titrating the remaining dodecyl mercaptan with an iodine solution. The method for measuring the weight average molecular weight will be described later.

[0052] The acrylic resin (b 11 ) preferably has a weight average molecular weight of 5,000 or more, more preferably 10,000 or more, and even more preferably 15,000 or more. Thereby, the hard coat layer (B) is excellent in blocking resistance. Further, the acrylic resin (b 11 ) preferably has a weight average molecular weight of 100,000 or less, more preferably 60,000 or less, and even more preferably 40,000 or less. Thereby, the hard coat layer (B) is excellent in blocking resistance and abrasion resistance.

[0053] In this specification, the weight-average molecular weight is the value obtained by converting the weight-average molecular weight measured using gel permeation chromatography (GPC) to the molecular weight of standard polystyrene. Specifically, a total of four gel permeation chromatographs are used: one "TSKgel G4000HXL", two "TSKgel G3000HXL", and one "TSKgel G2000HXL" (Tosoh Corporation). Measurements can be performed under the conditions of tetrahydrofuran mobile phase, measurement temperature of 40°C, flow rate of 1 mL / min, and radioisotope detector (RI). Furthermore, commercially available "standard polystyrene," such as "TSK Standard Polystyrene" manufactured by Tosoh Corporation, can be used as the "standard polystyrene."

[0054] The above active energy ray curable coating composition may further contain an active energy ray polymerization initiator. Examples of active energy rays in the above active energy ray polymerization initiator are those described in the section on "active energy ray curable compound (b1)". A photopolymerization initiator (b2) is preferred as the above active energy ray polymerization initiator.

[0055] <Photopolymerization initiator (b2)> The photopolymerization initiator (b2) is an optional component that may be included in the above-mentioned active energy ray curable coating composition. Examples of photopolymerization initiators (b2) include photochemically activatable compounds (e.g., benzoin); combinations of chromophores and co-initiators (e.g., benzophenone and tertiary amines) and mixtures thereof; combinations of sensitizers and co-initiators (e.g., thioxanthone and tertiary amine) or chromophores (e.g., thioxanthone and aminoketone); redox systems such as combinations of H2O2 and iron(II) salts; and electron transport pairs such as dyes and borates and / or amines.

[0056] Examples of photopolymerization initiators (b2) include α-diketone compounds such as benzyl and diacetyl; acyloin compounds such as benzoin; acyloin ether compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and thioxanthone-4-sulfonic acid; benzophenone compounds such as benzophenone, o-methylbenzoylbenzoate, 4-methylbenzophenone, 4-phenylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone; Michler ketone compounds; acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, and α,α'-dimethoxyacetoxybenzophenone. Examples include acetophenone compounds such as 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, α-isohydroxyisobutylphenone, α,α'-dichloro-4-phenoxyacetophenone, and 1-hydroxycyclohexylphenyl ketone; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(acyl)phosphine oxide; quinone compounds such as anthraquinone and 1,4-naphthoquinone; halogen compounds such as phenacyl chloride, trihalomethylphenylsulfone, and tris(trihalomethyl)-s-triazine; and peroxides such as di-tert-butyl peroxide.

[0057] Examples of commercially available photopolymerization initiators (b2) include Omnirad-127, Omnirad-184, Omnirad-MBF, Omnirad-BP Flakes, Omnirad-500, Omnirad-369, Omnirad-651, Omnirad-754, Omnirad-819, Omnirad-907, Omnirad-2959, Omnirad-TPO H, Omnirad-1173 (all from IGM Resins); Kayacure-MBP, Kayacure-DETX-S, Kayacure-DMBI, Kayacure-EPA, Kayacure-OA (all from Nippon Kayaku Co., Ltd.); Vicure-10, Vicure-55 (both from Stauffer GmbH) Examples include: Trigonal P1 (manufactured by AKZO Co., LTD.); Sandoray 1000 (manufactured by Sandoz Co., LTD.); Deep (manufactured by APJOHN Co., LTD.); Quantacure-PDO, Quantacure-ITX, Quantacure-EPD (all manufactured by Ward Blekinsop Co., LTD.); Esacure KIP 150, Esacure ONE (Lamberti), etc.

[0058] <(meth)acrylate compound (b 12 )> Active energy ray curable compound (b1) is a (meth)acrylate compound (b) having 6 or more functional groups per molecule. 12 ) may further include. This results in the hard coat layer (B) having excellent abrasion resistance. From the viewpoint of the wear resistance of the hard coat layer (B), (meth)acrylate compound (b 12 The (meth)acrylate compound (b) has preferably 8 or more functional groups per molecule, and more preferably 10 or more. 12 The upper limit for the number of functional groups per molecule is 15, from the standpoint of ease of handling.

[0059] (meth)acrylate compound (b 12 From the viewpoint of adhesion between the hard coat layer (B) and the primer layer (C) in the secondary decorated molded product, the (meth)acrylate compound (b) preferably has a polymerizable unsaturated group equivalent of 90 g / eq or more, more preferably 160 g / eq or more, and even more preferably 250 g / eq or more. Furthermore, from the viewpoint of abrasion resistance of the hard coat layer (B), the (meth)acrylate compound (b) 12 The polymerizable unsaturated group equivalent is preferably 3,000 g / eq or less, more preferably 2,000 g / eq or less, and even more preferably 1,000 g / eq or less.

[0060] (meth)acrylate compound (b 12 The (meth)acrylate compound (b) has a weight-average molecular weight of preferably 500 or more, more preferably 1,000 or more, and even more preferably 1,500 or more, from the viewpoint of adhesion between the hard coat layer (B) and the primer layer (C) in the secondary decorated molded product. 12 From the viewpoint of handling properties (e.g., viscosity) and appearance of the laminate, (meth)acrylate compound (b 12 The material preferably has a weight-average molecular weight of 20,000 or less, more preferably 12,000 or less, and even more preferably 6,000 or less.

[0061] (meth)acrylate compound (b 12 As for the functional group, there are no particular restrictions as long as the number of functional groups per molecule is 6 or more, but it is preferably a urethane (meth)acrylate. Examples of the above urethane (meth)acrylate include the polyisocyanate compound (b) described later. 12 -1) and a hydroxyl group-containing (meth)acrylate (b) having a hydroxyl group and a (meth)acryloyl group in one molecule. 12 -2) and, if necessary, a polyol compound (b 12 -3) and / or chain elongation component of hydroxyl group-containing compounds (b 12 -4) Urethane (meth)acrylate obtained by reacting with the above polyol compound (b 12-3) and isocyanate group-containing (meth)acrylate (b) having an isocyanate group and a (meth)acryloyl group in one molecule as described below. 12 -5) and, if necessary, the above polyisocyanate compound (b 12 -1) and / or chain elongation component of hydroxyl group-containing compounds (b 12 -4) A urethane (meth)acrylate or the like obtained by reacting it with the other can be used.

[0062] <Polyisocyanate compounds (b 12 -1)> The above polyisocyanate compound (b 12 -1) is a compound having two or more isocyanate groups in one molecule. Polyisocyanate compounds (b 12 Examples of (-1) include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates and aromatic polyisocyanates, their derivatives, and any combination thereof.

[0063] Examples of the above aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and methyl 2,6-diisocyanatohexanoate (common name: ridi Examples include aliphatic diisocyanates such as diisocyanate, and aliphatic triisocyanates such as 2-isocyanatoethyl 2,6-diisocyanatohexanoate, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane.

[0064] Examples of the above alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name: isophorone diisocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3- or Alicyclic diisocyanates such as 1,4-bis(isocyanatomethyl)cyclohexane (common name: hydrogenated xylylene diisocyanate) or mixtures thereof, methylenebis(1,4-cyclohexanediyl)diisocyanate (common name: hydrogenated MDI) and norbornane diisocyanate, as well as 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, and 2-(3-isocyanatopropyl)-2,5-di(i (Socyanatomethyl)-bicyclo(2.2.1)heptane, 2-(3-isocyanatopropyl)-2,6-di(isocyanatomethyl)-bicyclo(2.2.1)heptane, 3-(3-isocyanatopropyl)-2,5-di(isocyanatomethyl)-bicyclo(2.2.1)heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane, 6-(2-isocyanatopropyl) Examples include alicyclic triisocyanates such as sodium ethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane, and 6-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane.

[0065] Examples of the above-mentioned aromatic aliphatic polyisocyanates include aromatic aliphatic diisocyanates such as methylenebis(1,4-phenylene) diisocyanate (common name: MDI), 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω,ω'-diisocyanato-1,4-diethylbenzene and 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (common name: tetramethylxylylene diisocyanate) or mixtures thereof, as well as aromatic aliphatic triisocyanates such as 1,3,5-triisocyanatomethylbenzene.

[0066] Examples of the above-mentioned aromatic polyisocyanates include m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate, 2,4- or 2,6-tolylenediisocyanate or mixtures thereof, aromatic diisocyanates such as 4,4'-toluidinediisocyanate and 4,4'-diphenyletherdiisocyanate, aromatic triisocyanates such as triphenylmethane-4,4',4''-triisocyanate, 1,3,5-triisocyanatobenzene and 2,4,6-triisocyanatotoluene, and aromatic tetraisocyanates such as 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate.

[0067] Examples of derivatives of the above polyisocyanate include dimers, trimers, biuretes, allophanates, uretodiones, uretoimines, isocyanurates, oxadiazinetriones, polymethylene polyphenyl polyisocyanates (crude MDI, polymeric MDI), and crude TDI.

[0068] <Hydroxyl group-containing (meth)acrylate (b 12 -2)> Hydroxyl group-containing (meth)acrylate (b 12 -2) is a compound having a hydroxyl group and a (meth)acryloyl group in one molecule. Hydroxyl group-containing (meth)acrylate (b 12Examples of (2) include monoesters of (meth)acrylic acid with a dihydric alcohol having 2 to 8 carbon atoms, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; ε-caprolactone modified forms of the monoesters of (meth)acrylic acid with a dihydric alcohol having 2 to 8 carbon atoms; N-hydroxymethyl (meth)acrylamide; allyl alcohol; and (meth)acrylates having polyoxyalkylene chains with hydroxyl groups at the molecular ends; di(meth)acrylate compounds such as glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol di(meth)acrylate; and tri(meth)acrylate compounds such as pentaerythritol tri(meth)acrylate.

[0069] <Polyol compounds (b) 12 -3)> Polyol compounds (b 12 -3) is the above hydroxyl group-containing (meth)acrylate (b 12 Compounds other than (-2) that have two or more hydroxyl groups in one molecule.

[0070] Polyol compounds (b 12-3) For example, ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,2-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-pentanediol, 1,5- Pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-4,3-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, tricyclodeca Examples include dihydric alcohols such as dimethanol, neopentyl glycol hydroxypivalate, hydrogenated bisphenol A, hydrogenated bisphenol F, and dimethylolpropionic acid; polylactone diols obtained by adding lactone compounds such as ε-caprolactone to these dihydric alcohols; ester diol compounds such as bis(hydroxyethyl) terephthalate; polyether diol compounds such as alkylene oxide adducts of bisphenol A, polyethylene glycol, polypropylene glycol, and polybutylene glycol; trihydric or higher alcohols such as glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tris(2-hydroxyethyl)isocyanuric acid, sorbitol, and mannitol; polylactone polyol compounds obtained by adding lactone compounds such as ε-caprolactone to these trihydric or higher alcohols; and fatty acid esters of glycerin.

[0071] <Hydroxygroup-containing compound chain elongation component (b 12 -4)> Chain elongation component of hydroxyl group-containing compounds (b 12-4) is a hydroxyl group-containing (meth)acrylate (b 12 -2) and polyol compounds (b 12 This compound can react with hydroxyl group-containing compounds such as (-3) to extend its molecular chain.

[0072] Chain elongation component of hydroxyl group-containing compounds (b 12 Examples of (4) include lactone compounds such as ε-caprolactone and γ-valerolactone; and alkylene oxide compounds such as ethylene oxide and propylene oxide.

[0073] <Isocyanate group-containing (meth)acrylate (b 12 -5)> Isocyanate group-containing (meth)acrylate (b 12 -5) is a compound having an isocyanate group and a (meth)acryloyl group in one molecule.

[0074] Isocyanate group-containing (meth)acrylate (b 12 Examples of -5) include isocyanate methyl (meth)acrylate, isocyanate ethyl (meth)acrylate, isocyanate propyl (meth)acrylate, isocyanate butyl (meth)acrylate, isocyanate octyl (meth)acrylate, p-methacryloxy-α,α'-dimethylbenzyl isocyanate, m-acryloxy-α,α'-dimethylbenzyl isocyanate, m- or p-isopropenyl-α,α'-dimethylbenzyl isocyanate, 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate, and reaction products of 1 mole of hydroxyalkyl (meth)acrylate and 1 mole of diisocyanate compound. Specifically, examples include compounds obtained by equimolar addition reactions of compounds having two isocyanate groups with different reactivity, such as isophorone diisocyanate, with hydroxyl group-containing polymerizable unsaturated monomers such as 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate.

[0075] For details on the synthesis of the above-mentioned urethane acrylate, please refer to International Publication No. 2020 / 175664, and a further explanation is omitted herein.

[0076] <Particle (b3)> The active energy ray curing coating composition preferably further contains particles (b3). This results in the hard coat layer (B) having excellent abrasion resistance and blocking resistance. Furthermore, particles (b3) are reactive particles (b) that can react with the active energy ray curable compound (b1). 31 It is preferable that the hard coat layer (B) contains the following:

[0077] Silica particles are preferred as the particles (b3). This makes it possible to more reliably impart abrasion resistance and blocking resistance to the hard coat layer (B). Examples of the silica particles include dry silica particles, wet silica particles, silica gel particles, calcium ion exchange silica particles, colloidal silica particles, and the like.

[0078] From the viewpoint of imparting wear resistance to the hard coat layer (B), the above silica particles preferably have an average primary particle diameter of 1 nm or more, and more preferably 5 nm or more. Furthermore, from the viewpoint of transparency, the above silica particles preferably have an average primary particle diameter of 100 nm or less, and more preferably 60 nm or less.

[0079] The average primary particle diameter of the silica particles can be measured, for example, by observing particles using an electron microscope such as a transmission electron microscope (TEM). Alternatively, commercially available products with a specific particle diameter indicated may be used. In this invention, the average primary particle diameter of the silica particles is obtained by taking images with a transmission electron microscope, observing 20 particles on a randomly drawn straight line as primary particles, and calculating the measured value as the number average diameter of the largest diameter through image analysis. In this case, if the silica particles are not circular, the diameter equivalent to a circle of the same area is determined and this is taken as the diameter of the silica particles.

[0080] The silica particles described above may be those whose surfaces are not modified with organic matter, but from the viewpoint of abrasion resistance and transparency of the hard coat layer (B), it is preferable to include organically modified silica particles whose particle surfaces are modified with organic matter, and more preferably to include organically modified silica having unsaturated groups that can react with the active energy ray curable compound (b1). The above organic modification refers to a composite form in which an organic compound or organic group is introduced physically or chemically (preferably chemically) onto the surface of the silica particles. Examples of the above organic compound or organic group include those known in the art, but it is preferable that it be an unsaturated group that can react with the active energy ray curable compound (b1) in order to improve the silica particle content and obtain a hard coat layer (B) with excellent abrasion resistance while maintaining the transparency of the film obtained by active energy ray curing.

[0081] Unsaturated groups that can react with the active energy ray curable compound (b1) include functional groups having a carbon-carbon double bond (also called polymerizable double bond), such as vinyl groups, (meth)acryloyl groups, (meth)acrylamide groups, vinyl ether groups, allyl groups, etc., with (meth)acryloyl groups being preferred.

[0082] The silica particles may be dispersed in a dispersion medium, and examples of dispersion mediums include water; alcohol-based solvents such as methanol, ethanol, isopropanol, n-propanol, isobutanol, and n-butanol; polyhydric alcohol-based solvents such as ethylene glycol; polyhydric alcohol derivatives such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; and ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diacetone alcohol. Water and / or lower alcohol-based solvents having 3 or fewer carbon atoms are preferred as the dispersion medium.

[0083] Commercially available colloidal silica particles include methanol silica sol (average particle size 10-15 nm), MA-ST-M (average particle size 20-25 nm), IPA-ST (average particle size 10-15 nm), IPA-ST-L (average particle size 40-50 nm), IPA-ST-ZL (average particle size 70-100 nm), MEK-ST-40 (average particle size 10-15 nm), MEK-ST- L (average particle size 40~50nm), MEK-ST-ZL (average particle size 70~100nm), DMAC-ST (average particle size 10~15nm), NPC-ST-30 (average particle size 10~15nm) m), PGM-ST (average particle size 10~15nm), EAC-ST (average particle size 10~15nm), IPA-ST-UP (average particle size 9~15nm), ST-UP (average particle size 40~10nm), 0nm), ST-OUP (average particle size 40~100nm), ST-20L (average particle size 40~50nm), ST-30 (average particle size 10~15nm), ST-O-40 (average particle size 20~ 25nm), ST-N-40 (average particle size 20~25nm), ST-C (average particle size 10~15nm), ST-NS (average particle size 8~11nm), ST-O (average particle size 10~15nm) Examples include ST-50 (average particle size 20-25 nm), ST-OL (average particle size 40-50 nm), MEK-AC-2140Z (average particle size 10-15 nm), PGM-AC-2140Y (average particle size 10-15 nm), MEK-AC-4130Y (average particle size 40-50 nm), and MEK-AC-5140Z (average particle size 70-100 nm) (Nissan Chemical Industries, Ltd.).

[0084] If the active energy ray curable coating composition further contains particles (b3), the active energy ray curable coating composition contains particles (b3) in a solid content ratio of preferably more than 0% by mass, more preferably 20% by mass or more, and even more preferably 40% by mass or more, based on the active energy ray curable coating composition. Furthermore, if the active energy ray curable coating composition further contains particles (b3), the active energy ray curable coating composition contains particles (b3) in a solid content ratio of preferably 85% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less, based on the active energy ray curable coating composition. As a result, the hard coat layer (B) has excellent abrasion resistance and transparency.

[0085] The above active energy ray curable coating composition may contain other components. Examples of the above other components include polymerizable unsaturated group-containing acrylic resin (b 11 Other resins besides those mentioned above, crosslinking agents, matting agents, ultraviolet absorbers (UVA), light stabilizers (HALS), pigments, dyes, surface modifiers, defoamers, conductive fillers, solvents, etc. are also included.

[0086] Examples of the other resins mentioned above include unsaturated resins that do not contain polymerizable unsaturated groups. Examples of unsaturated resin types include acrylic resins, polyester resins, urethane resins, silicone resins, fluororesins, and modified resins thereof, as well as any combination thereof.

[0087] The above unsaturated group-free resin preferably has a glass transition temperature of 50°C or higher, more preferably 80°C or higher, and even more preferably 90°C or higher, and preferably 150°C or lower, more preferably 140°C or lower, and even more preferably 130°C or lower, from the viewpoint of improving the blocking resistance of the hard coat layer (B).

[0088] In this specification, the glass transition temperature refers to the static glass transition temperature. The static glass transition temperature can be determined, for example, by taking a sample in a measuring cup, removing the solvent by vacuum suction, and then measuring the change in heat quantity in the range of -100°C to 150°C at a heating rate of 3°C / min using a differential scanning calorimeter "DSC-50Q" (manufactured by Shimadzu Corporation, product name), and using this as the point of change at the first baseline on the low-temperature side.

[0089] The above unsaturated group-containing resin preferably has a weight-average molecular weight of 3,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more, and preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less, from the viewpoint of blocking resistance and appearance.

[0090] If the above-mentioned active energy ray-curable coating composition contains the above-mentioned unsaturated group-containing resin, the above-mentioned active energy ray-curable coating composition contains the above-mentioned unsaturated group-containing resin in a solid content ratio of preferably more than 0.0%, more preferably 0.1% by mass or more, even more preferably 1.0% by mass or more, and even more preferably 2.0% by mass or more, and preferably 10.0% by mass or less, more preferably 7.0% by mass or less, and even more preferably 5.0% by mass or less, from the viewpoint of blocking resistance and appearance.

[0091] Examples of the crosslinking agent include compounds having functional groups that can react with the functional groups of the resin contained in the active energy ray curable coating composition, such as melamine, benzoguanamine, polyamine, (blocked) polyisocyanate compounds, metal chelate compounds, and epoxy resins.

[0092] Examples of the matting agent mentioned above include organic particles and inorganic particles. Specific examples of the organic particles include spherical resin particles containing materials such as silicone resin, melamine resin, acrylic resin, polystyrene resin, styrene-acrylic copolymer, urethane resin, polyethylene resin, polycarbonate resin, and benzoguanamine resin. Examples of the inorganic particles include silica particles, alumina particles, zirconia particles, zircon particles, tin oxide particles, and magnesia particles.

[0093] The above-mentioned matting agent preferably has an average particle diameter of 0.5 μm or more, more preferably 0.8 μm or more, and preferably 10.0 μm or less, more preferably 5.0 μm or less. Due to its low cohesiveness, the average particle size of the above-mentioned matting agent is determined by using the median (D50) of the volume-averaged particle size measured by laser diffraction scattering (microtrac method).

[0094] The hard coat layer (B) preferably has a thickness of 3 μm or more, more preferably 5 μm or more, and preferably 30 μm or less, more preferably 20 μm or less. This provides excellent adhesion between the hard coat layer (B) and the primer layer (C) in the secondary decorated molded product.

[0095] [Primer layer (C)] The primer layer (C) is positioned between the hard coat layer (B) and the metallic design layer (D), and is a layer that suppresses the deterioration of the design properties of the metallic design layer (D) when the laminate according to this disclosure is stretched during TOM molding, due to the movement of the hard coat layer (B) before it is cured by the active energy rays. Furthermore, it can be difficult to form a metallic-looking design layer (D) on top of the hard coat layer (B) before it is cured by the active energy rays. By forming a primer layer (C) between the hard coat layer (B) and the metallic-looking design layer (D), it becomes easier to form the metallic-looking design layer (D).

[0096] Furthermore, the metallic-looking design layer (D) may have poor adhesion to other layers. For this reason, it is preferable to improve adhesion to other layers by forming a primer layer (C) made of a material with excellent adhesion to other materials and applying the primer layer (C) on the metallic-looking design layer (D).

[0097] The primer layer (C) may include resins that are not intended to react, such as acrylic resins, vinyl chloride-vinyl acetate copolymers, polyamide resins, polyester resins, urethane resins, epoxy resins, polyolefin resins, styrene resins, etc. Furthermore, the primer layer (C) may include a set of resins intended to react, such as a set of film-forming resin and a curing agent, or some or all of the reactants thereof.

[0098] The above-mentioned film-forming resin is a resin that hardens by reacting with a curing agent to form a crosslinked structure. Examples of the above-mentioned film-forming resin include resins having hydroxyl groups, such as acrylic resins, epoxy resins, polyurethane resins, vinyl chloride-vinyl acetate copolymers, polyamide resins, polyester resins, and styrene resins, and examples of the above-mentioned curing agents include isocyanate compounds and melamine resins.

[0099] As for the combination of the above-mentioned film-forming resin and curing agent, a combination of a hydroxyl-containing acrylic resin (c1) containing hydroxyl groups and an isocyanate compound (c2) is preferred. When the primer layer (C) contains the hydroxyl-containing acrylic resin (c1), the metallic-looking design layer (D) exhibits excellent metallic properties, and consequently, the secondary decorated molded product exhibits excellent metallic properties. Furthermore, when the primer layer (C) contains the isocyanate compound (c2), the metallic-looking design layer (D) exhibits excellent metallic properties, and consequently, the secondary decorated molded product exhibits excellent metallic properties. In addition, the primer layer (C) exhibits excellent solvent resistance.

[0100] <Hydroxygroup-containing acrylic resin (c1)> Hydroxyl group-containing acrylic resin (c1) is polymerizable unsaturated group-containing acrylic resin (b 11 You can adopt the method explained in the section marked with ). The hydroxyl group-containing acrylic resin (c1) preferably has a hydroxyl value of more than 0 mgKOH / g, more preferably 20 mgKOH / g or more, and even more preferably 40 mgKOH / g or more. Furthermore, the hydroxyl group-containing acrylic resin (c1) preferably has a hydroxyl value of 200 mgKOH / g or less, more preferably 160 mgKOH / g or less, and even more preferably 120 mgKOH / g or less. If the hydroxyl value of the hydroxyl group-containing acrylic resin (c1) exceeds 200 mgKOH / g, the secondary decorated molded product may have poor adhesion between the primer layer (C) and the metallic design layer (D).

[0101] In this specification, the hydroxyl value may be measured in accordance with JIS K 0070:1992, "Test methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponifiable matter of chemical products."

[0102] The hydroxyl group-containing acrylic resin (c1) preferably has a glass transition temperature of 30°C or higher, more preferably 40°C or higher, and even more preferably 60°C or higher. This results in a secondary decorated molded product with excellent solvent resistance and metallic appearance, and excellent adhesion between the primer layer (C) and the metallic design layer (D). Alternatively, the hydroxyl group-containing acrylic resin (c1) may have a glass transition temperature of 120°C or lower, more preferably 110°C or lower, and even more preferably 100°C or lower. This results in excellent adhesion between the primer layer (C) and the metallic design layer (D) of the secondary decorated molded product.

[0103] In this specification, the glass transition temperature can be measured, for example, by taking a sample in a measuring cup, completely removing the solvent by vacuum suction, and then measuring the change in heat quantity in the range of -100°C to 150°C at a heating rate of 3°C / min using a differential scanning calorimeter "DSC-50Q" (Shimadzu Corporation), and adopting the point of change at the first baseline on the low-temperature side as the glass transition temperature.

[0104] <Isocyanate compound (c2)> Examples of isocyanate compounds (c2) include isocyanate monomers, polyisocyanates, and blocked isocyanates, with polyisocyanates being preferred from the viewpoint of ease of use. Examples of the above-mentioned polyisocyanates include linear aliphatic isocyanates, alicyclic isocyanates, and aromatic aliphatic isocyanates.

[0105] Examples of the above-mentioned linear (linear or branched) aliphatic isocyanates include ethylene diisocyanate, trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, dodecamethylene diisocyanate, and other aliphatic diisocyanates.

[0106] Examples of the alicyclic isocyanates mentioned above include 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, or mixtures thereof (hydrogenated XDI). Examples of aromatic aliphatic isocyanates having a primary isocyanate group include 1,3- or 1,4-xylylene diisocyanate, or mixtures thereof (XDI).

[0107] Examples of the above-mentioned isocyanates include Desmodule N3800 (Sumika Covestro Urethane Co., Ltd.), Takenate D-178NL, Takenate D-110N, Stabio D-370N, D-376N (Mitsui Chemicals, Inc.), Desmodule H, N75MPA / X, N3200, N3300, N3390EA, N3400, N3600, N3790BA, N3800, N3900, XP2580, XP2840, Sumijoule HT (manufactured by Sumika Covestro Urethane Co., Ltd.), Duranate 24A-100, 22A-75P, TPA-100, TKA-100, P301-75E, D101, D201 (Asahi Kasei Corporation), etc.

[0108] In a combination of a hydroxyl group-containing acrylic resin (c1) and an isocyanate compound (c2), the molar ratio (NCO / OH ratio) of isocyanate groups (NCO) in the isocyanate compound (c2) to the hydroxyl groups (OH) in the hydroxyl group-containing acrylic resin (c1) is preferably 0.10 or higher, more preferably 0.15 or higher, and even more preferably 0.20 or higher. This results in excellent solvent resistance of the primer layer (C). Furthermore, the above molar ratio (NCO / OH ratio) is preferably 0.80 or lower, more preferably 0.70 or lower, and even more preferably 0.60 or lower. This results in excellent stretchability of the laminate and excellent adhesion between the primer layer (C) and the metallic design layer (D) of the secondary decorated molded product.

[0109] A curing catalyst can be added when reacting a hydroxyl group-containing acrylic resin (c1) and an isocyanate compound (c2). Examples of the curing catalyst include tin catalysts, amine catalysts, and lead catalysts, with organotin compounds being preferred. Examples of the organotin compounds include dibutyltin dilaurate (DBTL), dibutyltin oxide, and tetra-n-butyl-1,3-diacetoxystanoxane.

[0110] The primer layer (C) preferably has a thickness of 0.1 μm or more, more preferably 0.2 μm or more. This results in a secondary decorated molded product with excellent metallic appearance. Alternatively, the primer layer (C) preferably has a thickness of 10.0 μm or less, more preferably 2.0 μm or less. This results in a secondary decorated molded product with excellent metallic appearance.

[0111] [Metallic design layer (D)] At least one metallic-looking design layer (D) is selected from a coating layer (D1) containing a vapor-deposited aluminum pigment or a vapor-deposited indium pigment, and a vapor-deposited metal layer (D2) on which at least one metal selected from indium, tin, and aluminum is vapor-deposited. By including the coating layer (D1) in at least one metallic-looking design layer (D), a metallic-looking design layer (D) having a mirror-like appearance similar to a metal surface can be provided. Furthermore, by including the vapor-deposited metal layer (D2) in at least one metallic-looking design layer (D), the metallic-looking design layer (D) has excellent stretchability, and when the laminate follows the three-dimensional shape of the molded product during TOM molding, whitening, cracking, etc., are less likely to occur in the metallic-looking design layer (D).

[0112] In this specification, a coating layer (D1) containing a vapor-deposited aluminum pigment or a vapor-deposited indium pigment may be simply referred to as "coating layer (D1)," and a vapor-deposited metal layer (D2) on which at least one metal selected from indium, tin, and aluminum is vapor-deposited may be simply referred to as "vapor-deposited metal layer (D2)."

[0113] <Coating layer (D1)> In the coating layer (D1), vapor-deposited aluminum pigment refers to pigment obtained by shredding a vapor-deposited aluminum film into flakes, and vapor-deposited indium pigment refers to pigment obtained by shredding a vapor-deposited indium film into flakes.

[0114] Examples of commercially available vapor-deposited aluminum pigments include Metasheen71-0010 (BASF), Metalure C-21007AE, Metalure L55700, Metalure L51016MA, Metalure A61006 (all from Eckart), and Starbrite 2100-EAC (Silverline).

[0115] The coating layer (D1) may include, in addition to vapor-deposited aluminum pigment and / or vapor-deposited indium pigment, at least one of a set of resins not intended to react and a set of resins intended to react. The set of resins not intended to react and resins intended to react can be any resin known in the art as constituting a coating film, without any particular limitations, and examples include those described in the primer layer (C). The coating layer (D1) is a set of resins intended to react, for example, a film-forming resin (d 11 ) and hardening agent (d 12 Preferably, the reactants include ), or some or all of them.

[0116] <Vapour-deposited metal layer (D2)> Regarding the vapor-deposited metal layer (D2), vapor deposition is a method of forming a thin film by heating a vapor deposition material selected from at least one metal selected from indium, tin, and aluminum in a reduced-pressure container, vaporizing it, and depositing it onto the surface of a substrate placed at a distance. -3 ~10 -4 A vacuum level of approximately Pa is required.

[0117] The formation of a vapor-deposited metal layer (D2) on a primer layer (C) is carried out, for example, by (1) setting a laminated film comprising a support substrate (A), a hard coat layer (B), and a primer layer (C), and a target metal in a chamber, (2) reducing the pressure inside the chamber, (3) heating the target metal to generate steam and deposit the target metal onto the primer layer (C), and (4) returning the chamber to atmospheric pressure.

[0118] The vapor-deposited metal layer (D2) preferably has an optical density of 0.6 to 1.4. This prevents the gloss of the stretched portion of the laminate from weakening as the laminate conforms to the three-dimensional shape of the molded product during TOM molding, and also prevents whitening due to microcracks from occurring in the stretched portion of the laminate.

[0119] In this specification, the optical density of the vapor-deposited metal layer (D2) can be measured using a color transmission densitometer (Dainippon Screen Mfg. Co., Ltd., DM-500).

[0120] The coating layer (D1) preferably has a thickness of 0.01 μm or more, more preferably 0.1 μm, and preferably 5.0 μm or less, and more preferably 3.0 μm or less. This makes it easier to obtain a secondary decorated molded product with excellent metallic appearance.

[0121] The vapor-deposited metal layer (D2) preferably has a thickness of 10 nm or more, more preferably 30 nm or more, and preferably 100 nm or less, more preferably 80 nm or less. This makes it easier to obtain a secondary decorated molded product with excellent metallic appearance, and also reduces the likelihood of whitening, cracking, etc., occurring in the metallic design layer (D) when the laminate is made to conform to the three-dimensional shape of the molded product during TOM molding.

[0122] [Adhesive layer (E)] <Adhesive coating composition> <Resin (e1)> The adhesive layer (E) is a layer used to bond the laminate to a molded product when decorating the molded product with the laminate. The adhesive layer (E) is composed of an adhesive coating composition containing a resin (e1) having a glass transition temperature in the range of -60 to +20°C. By including a resin (e1) having a glass transition temperature in the range of -60 to +20°C in the adhesive layer (E), the temperature at which a secondary decorated molded product with excellent adhesion between the molded product and the laminate can be formed can be lowered. Specifically, in TOM molding, the bonding temperature when coating the molded product with the laminate and bonding the laminate to the molded product can be lowered. By lowering the bonding temperature, for example, additional heating required to bond the laminate to the molded product can be omitted.

[0123] The bonding temperature is preferably 140°C or lower, more preferably 130°C or lower, and even more preferably 120°C or lower. Furthermore, the bonding temperature is preferably 80°C or higher, more preferably 90°C or higher, and even more preferably 100°C or higher.

[0124] The resin (e1) preferably has a glass transition temperature of 0°C or lower, more preferably -10°C or lower, even more preferably -20°C or lower, and even more preferably -30°C or lower. This makes it possible to form a secondary decorated molded product with superior adhesion between the molded product and the laminate at a low temperature.

[0125] Examples of resins (e1) include urethane resin, acrylic resin, olefin resin, vinyl chloride / vinyl acetate resin, epoxy resin, and butyral resin.

[0126] The adhesive layer (E) preferably has a thickness of 0.1 μm or more, more preferably 1.0 μm or more. This ensures that the laminate has excellent adhesion between the molded product and the laminate. Alternatively, the adhesive layer (E) preferably has a thickness of 20.0 μm or less, more preferably 10.0 μm or less. This ensures that the secondary decorated molded product has excellent metallic appearance.

[0127] <Other resins (e2)> In the adhesive layer (E), the adhesive coating composition may include other resins (e2) in addition to the resin (e1). The other resin (e2) preferably has a glass transition temperature of over 20°C, more preferably 40°C or higher, and even more preferably 50°C or higher. This allows the adhesive layer (E) to be strengthened, and the secondary decorated molded product has excellent adhesion between the molded product and the laminate. Alternatively, the other resin (e2) preferably has a glass transition temperature of 120°C or lower, more preferably 110°C or lower, and even more preferably 90°C or lower. This makes it easier for the adhesive layer (E) of the laminate to adhere to the molded product during TOM molding, and the secondary decorated molded product has excellent adhesion between the molded product and the laminate.

[0128] Other resins (e2) include urethane resin, acrylic resin, olefin resin, vinyl chloride / vinyl acetate resin, epoxy resin, and butyral resin.

[0129] [Protective layer (F)] The laminate according to this disclosure may comprise a metallic design layer (D) and an adjacent protective layer (F). The presence of the protective layer (F) prevents damage to the metallic design layer (D) during processing when manufacturing the laminate. Furthermore, the presence of the protective layer (F) is expected to improve the adhesion between the metallic design layer (D) and the adhesive layer (E) of the secondary decorated molded product.

[0130] The protective layer (F) may include at least one of a set of resins that are not intended to react and a set of resins that are intended to react. The protective layer (F) may include a resin that is not intended to react and may not include a set of resins that are intended to react. This eliminates the need for post-heating processes to age the protective layer (F). The set of resins not intended to react and resins intended to react can be any resin known in the art as constituting a coating film, without any particular limitations, and examples include those described in the primer layer (C). The protective layer (F) preferably includes a resin that is not intended to react, such as a film-forming resin (f1).

[0131] [Secondary Decorated Molded Product] The secondary decorated molded product relating to this disclosure comprises a molded product and a laminate covering the molded product. The materials that make up the above-mentioned molded product are not particularly limited, and include plastics, metals, and the like. Examples of the above-mentioned plastics include acrylonitrile butadiene styrene (ABS), polycarbonate, polyphthalamide, polyoxymethylene, polymethyl methacrylate, polyolefin (e.g., polypropylene, polyethylene), polybutylene terephthalate, polyvinyl chloride, phenolic resin, and polyurethane. Examples of the above-mentioned metals include aluminum, iron, copper, and magnesium.

[0132] In the secondary decorated molded product relating to this disclosure, the material of the molded product is preferably the above-mentioned plastic. This is because the above-mentioned laminate allows for the formation of a secondary decorated molded product with excellent adhesion between the molded product and the laminate at a low temperature.

[0133] The above-mentioned molded products are not particularly limited and include, for example, automotive exterior parts such as wheels, bumpers, front under spoilers, rear under spoilers, side under skirts, side garnishes, and door mirrors; automotive interior parts such as instrument panels, center consoles, and door switch panels; housings for home appliances such as mobile phones, audio products, refrigerators, fan heaters, and lighting fixtures; and washbasins.

[0134] In the laminate of the secondary decorated molded product described above, it is preferable that the active energy ray curable coating composition constituting the hard coat layer (B) is cured by active energy rays. The statement that the active energy ray curable coating composition is cured by active energy rays means that the unsaturated groups polymerizable by active energy rays in the active energy ray curable compound (b1) within the active energy ray curable coating composition form a crosslinked structure. 12 ), reactive particles (b 31 ) etc., if the active energy ray curable compound (b1) contains an unsaturated group that can be polymerized by active energy rays and a (meth)acrylate compound (b 12 ) possesses an active energy ray that allows polymerization of unsaturated groups, and reactive particles (b 31 The active energy ray-curable compound (b1) possessed by the compound can form a cross-linked structure with an unsaturated group that can react with it. [Examples]

[0135] The present invention will be described in more detail below with reference to manufacturing examples, examples, and comparative examples. However, the present invention is not limited thereto. In each example, "parts" and "%" are based on mass unless otherwise specified. The film thickness of the coating is based on the cured film.

[0136] [Hard coat layer (B)] [polymerizable unsaturated group-containing acrylic resin (b 11 ) Manufacturing] [Manufacturing Example 1] In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and dropping device, 80 parts of methyl isobutyl ketone were charged and stirred at 100°C while blowing in nitrogen gas. A mixture of 58 parts of methyl methacrylate, 42 parts of glycidyl methacrylate, and 1.5 parts of 2,2'-azobisisobutyronitrile was added to the reaction vessel at a uniform rate over 3 hours, and the contents of the reaction vessel were further aged at the same temperature for 2 hours. Subsequently, a mixture of 10 parts of methyl isobutyl ketone and 0.5 parts of 2,2'-azobisisobutyronitrile was further added to the reaction vessel over 1 hour, and after the addition was complete, the contents of the reaction vessel were aged for 1 hour.

[0137] Next, after lowering the temperature of the reaction vessel contents to 80°C, 21 parts acrylic acid, 0.1 parts hydroquinone monomethyl ether, 30 parts butyl acetate, and 0.04 parts triphenylphosphine were added, and the temperature was maintained for 5 hours while blowing air into the reaction vessel. After cooling, a polymerizable unsaturated group-containing acrylic resin (b) with a solid content of 50% was obtained. 11 Solution No. 1 was obtained. Polymerizable unsaturated group-containing acrylic resin (b 11 The weight-average molecular weight (Mw) of No. 1 was 30,000, and the polymerizable unsaturated group equivalents derived from acrylic acid, calculated on a solid content basis, were 420 g / eq.

[0138] [Manufacturing Examples 2-6] Except for the composition shown in Table 1 below, the polymerizable unsaturated group-containing acrylic resin (b) is produced in the same manner as in Production Example 1. 11 ) Obtained No.2 to No.6.

[0139] [Table 1]

[0140] [Manufacturing of Active Energy Ray Curable Coating Compositions] [Manufacturing Example 7] The polymerizable unsaturated group-containing acrylic resin obtained in Production Example 1 (b 11 ) No.1 171.4 parts (solids 85.7 parts) and (meth)acrylate compounds (b) having 6 or more functional groups per molecule 12) as "Art Resin UN-904" (product name, manufactured by Negami Kogyo Co., Ltd., a urethane acrylate compound with 10 functional groups per molecule, solids concentration: 100%) 14.3 parts (solids 14.3 parts), and as a photopolymerization initiator (b2) "Omnirad 184" (product name, manufactured by IGM RESINS, an alkylphenone-based photopolymerization initiator, solids concentration: 100%) 14.3 parts (solids 14.3 parts), and reactive particles (b 31 257.1 parts (117.5 parts solids) of "MEK-AC-2140Z" (product name, manufactured by Nissan Chemical Corporation, organic dispersed colloidal silica having methacryloyl groups on its surface, average primary particle size: 13 nm, solid content concentration: 45.7%) were uniformly mixed, and methyl ethyl ketone was added to obtain an active energy ray curable coating composition (B') No. 1 with a solid content concentration of 33%.

[0141] [Manufacturing Examples 8-28] Active energy ray curable coating compositions (B') No. 2 to No. 22 were obtained in the same manner as in Production Example 7, except that the formulation composition was as shown in Tables 2-1 and 2-2 below. The amounts of each material in the table are expressed as solid content. Note that in Table 2, polymerizable unsaturated group-containing acrylic resin (b 11 ) simply means "acrylic resin (b 11 ) is written as, and (meth)acrylate compounds (b) have 6 or more functional groups per molecule. 12 ) simply means "(meth)acrylate compound (b 12 It is written as ")". Also, in Tables 2-1 and 2-2, the notation "Art Resin" is omitted for the Art Resin series manufactured by Negami Kogyo Co., Ltd.

[0142] [Table 2-1]

[0143] [Table 2-2]

[0144] The components listed in the table are as follows: [polymerizable unsaturated group-containing acrylic resin (b 11 )] (Note 1) SMP-250 Product name, manufactured by Kyoeisha Chemical Co., Ltd., unsaturated group equivalent: 250g / eq, weight average molecular weight: 35,000, solid content concentration: 50% (Note 2) SMP-360 Product name, manufactured by Kyoeisha Chemical Co., Ltd., unsaturated group equivalent: 360g / eq, weight average molecular weight: 35,000, solid content concentration: 50% (Note 3) SMP-550 Product name, manufactured by Kyoeisha Chemical Co., Ltd., unsaturated group equivalent: 550g / eq, weight average molecular weight: 35,000, solid content concentration: 50%

[0145] [(meth)acrylate compounds (b) that have 6 or more functional groups per molecule 12 )] (Note 4) Art Resin UN-3200HA Product name, manufactured by Negami Kogyo Co., Ltd., solid content concentration: 100% (Note 5) Art Resin UN-954 Product name, manufactured by Negami Kogyo Co., Ltd., solid content concentration: 60% [Photopolymerization initiator (b2)] (Note 6) Omnirad 1173 Product name: IGM RESINS, alkylphenone-based photopolymerization initiator, solids content: 100%

[0146] [reactive particles (b 31 )] (Note 7) MEK-AC-4130Y Product name: Nissan Chemical Corporation; Organic dispersed colloidal silica with methacryloyl groups on its surface; Average particle size: 45 nm; Solid content concentration: 30.8% [Particle (b3)] (Note 8) MEK-ST-40 Product name: Nissan Chemical Corporation, Organic Dispersed Colloidal Silica, Average Primary Particle Size: 12.5 nm, Solid Content Concentration: 40% (Note 9) MEK-ST-L Product name: Nissan Chemical Corporation, Organic Dispersed Colloidal Silica, Average Primary Particle Size: 45 nm, Solid Content Concentration: 30%

[0147] [Other ingredients] (Note 10) BYK-354 Product name: Big Chemie Japan Co., Ltd., Acrylic surface modifier, Solids content: 51% (Note 11) TINUVIN 384-2 Product name: BASF, Benzotriazole-based UV absorber, Solid content: 95% (Note 12) VALIFAST YELLOW 3175 Product name: Orient Chemical Industry Co., Ltd., Dye: CI Solvent Yellow 151, Solids content: 100%

[0148] (Note 13) Olestar Q713BA Product name: Mitsui Chemicals, Inc., Hydroxyl group-containing acrylic resin, Hydroxyl value: 50 mg KOH / g, Weight-average molecular weight: approx. 23,000, Glass transition temperature: 122°C, Solids content: 50%, Unsaturated group-free resin (Note 14) Elitel UE-9900 Product name: Unitika Corporation, Hydroxyl group-containing polyester resin, Hydroxyl value: 8 mg KOH / g, Weight-average molecular weight: approx. 15,000, Glass transition temperature: 101°C, Solids content: 100%, Unsaturated group-free resin (Note 15)MX-300 Product name: Soken Chemical Co., Ltd., Cross-linked acrylic resin monodisperse particles, average particle size 3 μm, spherical organic fine particles, solid content 100% by mass, matting agent.

[0149] [Primer layer (C)] [Manufacturing of hydroxyl group-containing acrylic resin (c1)] [Manufacturing Example 29] 90 parts of butyl acetate were placed in a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet, and the contents of the four-necked flask were heated to 110°C under nitrogen gas aeration. After the contents reached 110°C, the nitrogen gas aeration was stopped, and monomer mixture 1, having the composition of monomers and polymerization initiators shown below, was added dropwise to the four-necked flask over 5 hours.

[0150] [Monomer mixture 1] - Methyl methacrylate 56 parts - Hydroxyethyl methacrylate 44 parts - Perbutyl O 3.5 parts Perbutyl O (trade name) is t-butylperoxy-2-ethylhexanoate, sold by NOF Corporation.

[0151] Next, the contents of the four-necked flask were aged for 2 hours at 105°C while aeration with nitrogen gas. Then, a mixture of 0.5 parts perbutyl O and 10 parts toluene was added dropwise to the four-necked flask over 1 hour. After that, the contents of the four-necked flask were aged for 2 hours at approximately 105°C, and diluted with 5 parts toluene to obtain a hydroxyl group-containing acrylic resin (c1) No. 1 solution with a solid content of 50%. The hydroxyl value based on the solid content of the obtained acrylic resin was 190 mg KOH / g, the weight-average molecular weight was approximately 13,000, and the glass transition temperature was 81°C.

[0152] [Manufacturing Example 30] Eighty parts of butyl acetate were placed in a four-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet, and the contents of the four-necked flask were heated to 110°C under nitrogen gas aeration. After the contents reached 110°C, the nitrogen gas aeration was stopped, and monomer mixture 2, consisting of the monomer and polymerization initiator shown below, was added dropwise to the four-necked flask over 5 hours.

[0153] [Monomer mixture 2] - Methyl methacrylate 50 parts - Hydroxyethyl methacrylate 50 parts - Perbutyl O 1 part

[0154] Next, the contents of the four-necked flask were aged for 2 hours at 105°C while aeration with nitrogen gas. Then, a mixture of 0.5 parts perbutyl O and 10 parts toluene was added dropwise to the four-necked flask over 1 hour. After that, the contents of the four-necked flask were aged for 2 hours at approximately 105°C, and diluted with 10 parts toluene to obtain a hydroxyl group-containing acrylic resin (c1) No. 2 solution with a solid content of 50%. The hydroxyl value based on the solid content of the obtained acrylic resin was 216 mg KOH / g, the weight-average molecular weight was approximately 29,000, and the glass transition temperature was 78°C.

[0155] [Production of Primer Composition (C')] [Manufacturing Example 31] 181.8 parts (100.0 parts solids) of Acrydic AU-7005 (trade name, manufactured by DIC Corporation, hydroxyl group-containing acrylic resin, hydroxyl value: 65 mg KOH / g, weight-average molecular weight: approximately 12,000, glass transition temperature: 90°C, solids concentration: 55%) and 21.0 parts (15.8 parts solids) of Takenate D-110N (trade name, manufactured by Mitsui Chemicals, polyisocyanate compound, solids concentration: 75%) were uniformly mixed, and methyl ethyl ketone was added to obtain primer composition (C') No. 1 with a solids concentration of 20%.

[0156] [Manufacturing Examples 32-44] Primer compositions (C') No. 2 to No. 14 were obtained in the same manner as in Production Example 31, except that the formulation was as shown in Table 3 below. The amounts of each material in the table are expressed as solid content.

[0157] [Table 3]

[0158] The components listed in the table are as follows: (Note 16) Acrydic WXU-880-BA Product name: DIC Corporation, Hydroxyl group-containing acrylic resin, Hydroxyl value: 20 mg KOH / g, Weight-average molecular weight: approx. 26,000, Glass transition temperature: 90°C, Solids content: 50% (Note 17) ARUFON UHE-2012 Product name: Toagosei Co., Ltd., Hydroxyl group-containing acrylic resin, Hydroxyl value: 67 mg KOH / g, Weight-average molecular weight: approx. 5,800, Glass transition temperature: 20°C, Solids content: 100% (Note 18) Acrydic WAU-137-BA Product name: DIC Corporation, Hydroxyl group-containing acrylic resin, Hydroxyl value: 56 mg KOH / g, Weight-average molecular weight: Approximately 15,000, Glass transition temperature: 35°C, Solids content: 62%

[0159] (Note 19) Dianaal LR-2697 Product name: Mitsubishi Chemical Corporation, Hydroxyl group-containing acrylic resin, Hydroxyl value: 41 mg KOH / g, Weight-average molecular weight: Approximately 10,000, Glass transition temperature: 119°C, Solids content: 55% (Note 20) Solvine C Product name: Nisshin Chemical Industry Co., Ltd., Vinyl chloride / vinyl acetate copolymer resin, Solids content: 100%

[0160] [Metallic design layer (D)] [Manufacturing of metallic coating composition (D1')] [Manufacturing Example 45] Film-forming resin (d 11 ) as Olestar Q164BE (product name, manufactured by Mitsui Chemicals, hydroxyl group-containing acrylic resin, hydroxyl value: 60 mg KOH / g, weight-average molecular weight: approximately 22,000, glass transition temperature: 98°C, solids concentration: 45%) 222.1 parts (solids 100 parts) and curing agent (d 1239.1 parts of Takenate D-110N (29.3 parts solids) as a coating agent, 0.5 parts of Polyflow KL-100 (product name, manufactured by Kyoeisha Chemical Co., Ltd., organic modified silicone / special oligomer, solids concentration: 100%) (0.5 parts solids) as a surface modifier, and 125 parts of Leaf Powder 49CJ1120 (product name, manufactured by Oike Kogyo Co., Ltd., vapor-deposited indium flake pigment, solids concentration: 20%) (25 parts solids) were blended together, and a mixed solution of methyl ethyl ketone / propylene glycol monomethyl ether / ethylene glycol monobutyl ether = 45 / 50 / 5 was added and mixed uniformly to obtain a metallic coating composition (D1') No. 1 with a solids concentration of 27%.

[0161] [Manufacturing Example 46] Film-forming resin (d 11 ) as Olestar Q164BE 222.1 parts (solid content 100 parts) and hardener (d 12 39.1 parts of Takenate D-110N (29.3 parts solids) as a coating agent, 0.5 parts of Polyflow KL-100 (0.5 parts solids) as a surface modifier, and 250 parts of Matelure C-21007AE (trade name, manufactured by ECKALT, vapor-deposited aluminum flake pigment, solids concentration: 10%) (25 parts solids) were combined and a mixed solution of methyl ethyl ketone / propylene glycol monomethyl ether / ethylene glycol monobutyl ether = 45 / 50 / 5 was added and mixed uniformly to obtain a metallic coating composition (D1') No. 2 with a solids concentration of 27%.

[0162] [Adhesive layer (E)] [Manufacturing of adhesive composition (E')] [Manufacturing Example 47] 37.5 parts (37.5 parts solids) of ARUFON UP-1010 (trade name, manufactured by Toagosei Co., Ltd., acrylic resin, hydroxyl value: 0 mg KOH / g, weight-average molecular weight: approximately 1,700, glass transition temperature: -31°C, solids concentration: 100%) as a resin (e1) with a glass transition temperature in the range of -60 to +20°C, and 62.5 parts (62.5 parts solids) of Joncryl 819 (trade name, manufactured by BASF, carboxyl group-containing acrylic resin, acid value: 75 mg KOH / g, weight-average molecular weight: approximately 14,500, glass transition temperature: 57°C, solids concentration: 100%) were uniformly mixed, and then ethyl acetate / methyl ethyl ketone = 50 / 50 was added to obtain adhesive composition (E') No. 1 with a solids concentration of 30%.

[0163] [Manufacturing Examples 48-53] Adhesive compositions (E') No. 2 to No. 7 were obtained in the same manner as in Production Example 47, except that the compound composition was as shown in Table 4 below. The amounts of each material in the table are expressed as solid content. In Table 4, resin (e1) with a glass transition temperature in the range of -60 to +20°C is simply referred to as "resin (e1)".

[0164] [Table 4]

[0165] The components listed in the table are as follows: [Resin(e1) with a glass transition temperature in the range of -60 to +20°C] (Note 21) ARUFON UC-3510 Product name: Toagosei Co., Ltd., manufactured by Toagosei Co., Ltd., carboxyl group-containing acrylic resin, acid value: 70 mg KOH / g, weight-average molecular weight: approximately 2,000, glass transition temperature: -50°C, solid content concentration: 100% (Note 22) TEGO AddBond 1270 Product name: Evonik, manufactured by Evonik, hydroxyl group-containing polyester resin, hydroxyl value: 10 mg KOH / g, glass transition temperature: 20°C, solids content: 70%

[0166] [Other resins (e2)] (Note 23) Dianaal BR-117 Product name: Mitsubishi Chemical Corporation, acrylic resin, hydroxyl value: 0 mg KOH / g, weight-average molecular weight: approximately 140,000, glass transition temperature: 34°C, solids content: 100% (Note 24) Byron GK-830 Product name: Toyobo MC Co., Ltd., Hydroxyl group-containing polyester resin, Hydroxyl value: 7 mg KOH / g, Weight-average molecular weight: Approximately 32,000, Glass transition temperature: 25°C, Solids content: 100% (Note 25) ARUFON UP-1000 Product name: Acrylic resin, manufactured by Toagosei Co., Ltd., Hydroxyl value: 0 mg KOH / g, Weight-average molecular weight: approx. 3,000, Glass transition temperature: -77°C, Solids content: 100%

[0167] [Protective layer (F)] [Production of protective coating composition (F')] [Manufacturing Example 54] Acrydic AU-7005 (trade name, manufactured by DIC Corporation, hydroxyl group-containing acrylic resin, hydroxyl value: 65 mg KOH / g, weight-average molecular weight: approximately 12,000, glass transition temperature: 90°C, solids concentration: 55%) was mixed with ethyl acetate to obtain protective coating composition (F') No. 1 with a solids concentration of 20%.

[0168] [Manufacturing Example 55] Methyl ethyl ketone was added to 100 parts (100 parts solids) of Byron 882 (trade name, manufactured by Toyobo MC Co., Ltd., hydroxyl group-containing polyester resin, hydroxyl value: 3 mg KOH / g, weight-average molecular weight: approximately 15,000, glass transition temperature: 68°C, solids concentration: 100%) to obtain protective coating composition (F') No. 2 with a solids concentration of 20%.

[0169] [Laminated structure] [Fabrication of laminates] [Example 1] On a support substrate (A) No. 1 (Pyrene P1146, manufactured by Toyobo Co., Ltd., CPP film, thickness: 50 μm, tensile modulus: 34 MPa), the active energy ray curable coating composition (B') No. 1 obtained in Production Example 7 was applied using a bar coater to a dry film thickness of 10 μm, and dried at 100°C for 1 minute to form an uncured hard coat layer (B) No. 1. Next, on the uncured hard coat layer (B) No. 1, the primer composition (C') No. 1 obtained in Production Example 31 was applied using a bar coater to a dry film thickness of 1 μm, and dried at 100°C for 1 minute. After that, heat aging was performed at 40°C for 48 hours to form a primer layer (C).

[0170] Next, indium was deposited onto the primer layer (C) by vacuum deposition to form a vapor-deposited metal layer (D2) No. 1 made of indium (In) with a thickness of 40 nm. Then, protective coating composition (F') No. 1 obtained in Production Example 54 was applied to the vapor-deposited metal layer (D2) No. 1 using a bar coater to a dry film thickness of 1 μm, and dried at 100°C for 1 minute to form a protective layer (F). Next, adhesive composition (E') No. 1 obtained in Production Example 47 was applied to the protective layer (F) using a bar coater to a dry film thickness of 6 μm, and dried at 100°C for 1 minute to form an adhesive layer (E), thereby obtaining laminate No. 1.

[0171] [Examples 2-52 and Comparative Examples 1-5] Laminates No. 1 to 52 and Laminates No. 55 to 59 were prepared in the same manner as in Example 1, except that the combination of each layer and the dry film thickness of each layer were as shown in Tables 5-1 to 5-4 (hereinafter simply referred to as "Table 5").

[0172] [Example 53] Laminate No. 53 was obtained in the same manner as in Example 1, except that aluminum was deposited on the primer layer (C) by vacuum deposition instead of the deposited metal layer (D2) No. 1, forming a deposited metal layer (D2) No. 2 made of aluminum (Al) with a thickness of 50 nm. [Example 54] Laminate No. 54 was obtained in the same manner as in Example 1, except that tin was deposited on the primer layer (C) by vacuum deposition instead of the deposited metal layer (D2) No. 1, forming a deposited metal layer (D2) No. 3 consisting of tin (Sn) with a thickness of 21 nm.

[0173] The components listed in Table 5 are as follows: (Note 26) Supporting base material (A) No.2 M-6, manufactured by Tamapoly Co., Ltd., polyethylene film, tensile modulus: 2 MPa, thickness: 50 μm (Note 27) Supporting base material (A) No.3 CEL-9831A, manufactured by Sumitomo Bakelite Co., Ltd., polyethylene film, tensile modulus: 8 MPa, thickness: 100 μm (Note 28) Supporting base material (A) No.4 Lumirror S-10, manufactured by Toray Industries, Ltd., polyethylene terephthalate film, tensile modulus: 630 MPa, thickness: 100 μm (Note 29) Supporting base material (A) No.5 Cosmoshine A4160, manufactured by Toyobo Co., Ltd., polyethylene terephthalate film, tensile modulus: 660 MPa, thickness: 100 μm

[0174] Table 5 summarizes the composition of laminates No. 1 to No. 59. The adhesion, appearance, abrasion resistance, blocking resistance, and moldability of laminates No. 1 to No. 59 and secondary decorative molded products No. 1 to No. 59 were evaluated. The results are summarized in Table 5. The evaluation methods for adhesion, appearance, abrasion resistance, blocking resistance, and moldability are as follows. In Table 5, "Active energy ray curable coating composition (B')" is simply referred to as "Coating composition (B')".

[0175] [Preparation of secondary decorative molded parts for evaluation of appearance, adhesion, and wear resistance] An ABS plate measuring 200 mm in length, 100 mm in width, and 2 mm in thickness was placed on the table inside the lower chamber box of a compact TOM molding machine (NGF-T-0203, manufactured by Fuse Vacuum Co., Ltd.). After lowering the table, each of the laminates No. 1 to No. 59 was attached to the sheet clamp frame so that the adhesive layer (E) faced the sheet clamp frame. The upper chamber was closed, the pressure inside the chamber was reduced to 0.5 kPa or less, and the laminate was heated to 110°C using a near-infrared heater. The table was then raised to press the ABS plate and the laminate together. After that, compressed air at 300 kPa was introduced only into the upper box and held for 10 seconds. The upper and lower chambers were opened to the atmosphere, and a secondary decorated molded product covered with the laminate was obtained. Furthermore, after peeling off the support substrate (A), 140 W / cm² was applied. 2 Using a high-pressure mercury lamp, 500 mJ / cm² 2 The hard coat layer (B) was cured by irradiating it with ultraviolet light of a certain intensity, and secondary decorative molded products No. 1 to No. 59 were obtained for evaluation of appearance, adhesion, and abrasion resistance.

[0176] [Evaluation of adhesion] For each of the secondary decorated molded products No. 1 to No. 59, a grid pattern was cut into the laminate with a cutter so as to reach the base material (ABS plate), creating 100 1mm x 1mm lattice patterns. Subsequently, adhesive cellophane tape was applied to the surface of each test painted plate with cuts, and the adhesive cellophane tape was rapidly peeled off at a temperature of 23±2℃ and a relative humidity of 50±5%RH. The remaining state of the lattice pattern coating film after peeling was examined, and the adhesion was evaluated according to the following evaluation criteria. A, B, and C are considered acceptable. The evaluation results are shown in Table 5.

[0177] [Evaluation Criteria] A: 100 of the Goban-mesh coating remained, and there were no small chips or lifting of the coating at the edges of the cutter's notches. B: 100 small areas of the paint film remained, and small chips and lifting of the paint film were present at the edges of the cutter's notches. C: 90 to 99 Goban-type coatings remained. D: 70 to 89 Goban-type coatings remained. E: The number of remaining Goban-type coatings was 70 or less.

[0178] [Appearance Evaluation] Each of the secondary decorated molded products No. 1 to No. 59 was visually inspected, and their appearance was evaluated according to the following evaluation criteria. A, B, and C are considered acceptable. The evaluation results are shown in Table 5. [Evaluation Criteria] A: It had a good metallic appearance. B: Although the gloss is slightly lower, a metallic appearance was achieved. C: The metallic appearance was slightly damaged, but it was at a level that did not affect the product's functionality. D: The metallic appearance was damaged, indicating a product defect. E: No metallic appearance was achieved at all.

[0179] [Evaluation of abrasion resistance] Each surface of secondary decorated molded products No. 1 to No. 59 was subjected to a 200g load of #0000 steel wool being passed back and forth 10 times using a steel wool resistance tester. Subsequently, scratches on the surfaces were visually observed, and the abrasion resistance was evaluated according to the following evaluation criteria. A, B, and C are considered acceptable. The evaluation results are shown in Table 5.

[0180] [Evaluation Criteria] A: There were no scratches on the surface. B: The number of scratches on the surface was less than 5. C: Although there were more than 5 but less than 10 scratches on the surface, the level was not at a level that would cause any problems with the product. D: The number of surface scratches was between 10 and 20. E: More than 20 scratches were observed on the surface.

[0181] [Evaluation of blocking resistance] The blocking resistance of each of the laminates No. 1 to 59 was evaluated as follows. (1) An active energy ray curable coating composition (B') was applied to a support substrate (A). (2) The active energy ray curable coating composition (B') was dried to form an uncured hard coat layer (B). (3) A different support substrate (A) was laminated onto the uncured hard coat layer (B), and after being left for 24 hours under a pressure of 500g at a temperature of 40°C and a relative humidity of 50%RH, the degree of peeling (ease of peeling) between the uncured hard coat layer (B) and the other support substrate (A) was evaluated according to the following evaluation criteria. A, B, and C are considered acceptable. The evaluation results are shown in Table 5.

[0182] Furthermore, the significance of evaluating the blocking resistance of the laminate, as described above, is as follows: In forming the laminate, an active energy ray curable coating composition (B') is applied to a support substrate (A) to form a two-layer laminate consisting of the support substrate (A) and an uncured hard coat layer (B), and the two-layer laminate is sometimes wound onto a roll. In this case, the uncured hard coat layer (B) on the roll on which the two-layer laminate is wound may exhibit tackiness, causing it to adhere to another support substrate (A) and resulting in blocking. From the viewpoint of evaluating such blocking properties, the evaluation was performed as described above.

[0183] [Evaluation Criteria] A: There was no adhesion between the first and second samples, and they could be peeled off without resistance. B: There was some partial adhesion between the first and second samples, but they could be peeled apart without resistance. C: There was some partial adhesion between the first and second samples, and there was some resistance when peeling them apart. D: There was adhesion across the entire surface between the first and second samples, and resistance was encountered when peeling them apart. E: There was adhesion across the entire surface between the first and second samples, and strong resistance was encountered when peeling them apart.

[0184] [Evaluation of moldability] The laminates No. 1 to 59 were cut into a size of 20 mm (width) × 100 mm (length), and the formability was evaluated by a stretching test using a tensile testing machine (RTG-1210, manufactured by A&D Company Limited) under the conditions of a chuck distance of 40 mm, an ambient temperature of 110°C, and a stretching speed of 50 mm / min. Specifically, in the stretching test, the elongation rate at the time when whitening occurred or cracks appeared in the measurement sample was visually recorded, and the formability was evaluated based on the following evaluation criteria according to the elongation rate.

[0185] [Evaluation Criteria] A: The elongation rate was 51% or more. B: The elongation rate was 11% or more and less than 51%. C: The elongation rate was 6% or more and less than 11%. D: The elongation rate was 3% or more and less than 6%. E: The elongation rate was less than 3%.

[0186] [Evaluation of Inkjet Coating Suitability for Secondary Decorated Molded Products] Color printing was performed on the surfaces of each of the secondary decorated molded products No. 1 to No. 59 using an inkjet printer (UFJ7151, manufactured by Mimaki Engineering Co., Ltd.) with UV-curable ink for inkjet printing (LH100, manufactured by Mimaki Engineering Co., Ltd.) to form a color printing section. Next, the color printing section on the obtained laminate was cut into a grid pattern with a cutter so as to reach the laminate, and 100 grids with a size of 1 mm × 1 mm were formed. When evaluating the adhesion between the color printing section and the laminate (hard coat layer (B)), in all of the secondary decorated molded products No. 1 to No. 59, the remaining number / total number = 100 pieces / 100 pieces and there was no edge chipping.

[0187] [Table 5-1]

[0188] [Table 5-2]

[0189] [Table 5-3]

[0190] [Table 5-4]

[0191] [Example 55] Laminate No. 60 and secondary decorated molded product No. 60 were obtained in the same manner as in Example 1, except that instead of the vapor-deposited metal layer (D2) No. 1, the metallic coating composition (D1') No. 1 obtained in Production Example 45 was applied to the primer layer (C) with a bar coater to a dry film thickness of 5 μm, dried at 100°C for 1 minute, and then heat-aged at 40°C for 48 hours to form the coating layer (D1) No. 1.

[0192] [Example 56] Laminate No. 61 and secondary decorated molded product No. 61 were obtained in the same manner as in Example 1, except that instead of the vapor-deposited metal layer (D2) No. 1, the metallic coating composition (D1') No. 2 obtained in Production Example 46 was applied to the primer layer (C) with a bar coater to a dry film thickness of 5 μm, dried at 100°C for 1 minute, and then heat-aged at 40°C for 48 hours to form the coating layer (D1) No. 2.

[0193] [Comparative Examples 6-9] Laminates No. 62-65 and secondary decorated molded products No. 62-65 were obtained in the same manner as in Example 55, except that the combination of each layer and the dry film thickness of each layer were as shown in Table 6.

[0194] The adhesion, appearance, abrasion resistance, blocking resistance, and moldability of laminates No. 60 to No. 65 and secondary decorated molded products No. 60 to No. 65 were evaluated. The results are summarized in Table 6. Note that in Table 6, "Active energy ray curable coating composition (B')" is simply referred to as "Coating composition (B')".

[0195] Table 6

Claims

1. Support base material (A), Hard court layer (B), Primer layer (C), A coating layer containing vapor-deposited aluminum pigment or vapor-deposited indium pigment (D 1 ), and a deposited metal layer (D) having at least one metal selected from indium, tin, and aluminum deposited on it. 2 ) at least one metallic-looking design layer (D) selected from, Adhesive layer (E), A laminate having the following in that order, The hard coat layer (B) is made of an active energy ray curable compound (b 1 The active energy ray curable coating composition contains ) The adhesive layer (E) is made of a resin (e) having a glass transition temperature in the range of -60 to +20°C. 1 It consists of an adhesive coating composition containing ) Laminated structure.

2. The laminate according to claim 1, wherein the tensile modulus of the support substrate (A) is in the range of 3 to 650 MPa at 100°C.

3. The activated energy ray curable compound (b 1 ) is a polymerizable unsaturated group-containing acrylic resin (b 11 The laminate according to claim 1, including ).

4. The polymerizable unsaturated group-containing acrylic resin (b 11 The laminate according to claim 3, wherein the polymerizable unsaturated group equivalent of ) is in the range of 300 to 600 g / eq.

5. The polymerizable unsaturated group-containing acrylic resin (b 11 The laminate according to claim 3, wherein the weight-average molecular weight of the ) is in the range of 10,000 to 60,000.

6. The active energy ray-curable compound (b 1 ) further contains a (meth)acrylate compound (b 12 ) having 6 or more functional groups per molecule, and the laminate according to claim 1.

7. The active energy ray curable coating composition contains particles (b 3 The laminate according to claim 1, further containing ).

8. The laminate according to claim 1, further comprising an unsaturated resin that does not contain polymerizable unsaturated groups, wherein the active energy ray curable coating composition.

9. The laminate according to claim 8, wherein the active energy ray curable coating composition contains the unsaturated group-free resin in a solid content ratio of more than 0.0% and 10.0% by mass or less, based on the active energy ray curable coating composition.

10. A secondary decorative molded product comprising a molded product and a laminate covering the molded product, The laminate is the laminate according to any one of claims 1 to 9. Secondary decorative molded product.

11. The secondary decorative molded article according to claim 10, wherein the active energy ray curable coating composition of the hard coat layer (B) is cured.

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