Layered sheet, vehicle, method for using layered sheet, and method for manufacturing layered sheet

Abstract

A layered sheet (1) according to the present invention has a transfer layer (10), and a coating material layer (20) that comprises a heat-curable resin composition or a moisture-curable resin composition, wherein the bending resistance of the transfer layer (10) is 20-120 mm. A vehicle according to the present invention is coated using this layered sheet. The present invention is thus able to provide a layered sheet that can minimize peeling marks remaining in the coating material layer when the transfer layer is peeled away and the coating material layer is transferred to an adherend, and can suppress the occurrence of wrinkling in the layered sheet when the layered sheet is adhered to the adherend.

Description

Laminated sheet, vehicle, method of using laminated sheet, and method of manufacturing laminated sheet

[0001] The present invention relates to a laminate sheet used for painting, a vehicle painted using the laminate sheet, a method for using the laminate sheet, and a method for manufacturing the laminate sheet.

[0002] Conventionally, various products such as furniture, steel plates, and vehicle bodies have been painted to impart functions such as design, durability, weather resistance, and scratch resistance. When industrially painting products having three-dimensional shapes, the paint is generally sprayed by air or electrostatic force. Spray painting has the following drawbacks: loss during painting, CO2 emissions from factories, etc. ２ In view of the need for large-scale capital investment, replacement with decorative technology using resin films has been considered recently.

[0003] Decorative technology is a technique used in various fields, such as household electrical appliances, automotive interior parts, and miscellaneous goods, to decorate the surface of a product by attaching a resin film (decorative film) printed with letters or pictures in white, black, or color ink to the product surface, thereby achieving high functionality and design. For example, Patent Document 1 describes a thermosetting coating sheet as a decorative film that is ductile, flexible, and easy to work with before curing, and also has excellent dispersibility for pigments and other additives, is easy to manufacture, and can form a uniform and hard cured film upon curing by heat. This thermosetting coating sheet may be provided with a support layer, and the support layer is peeled off from the thermosetting coating sheet after the thermosetting coating sheet is attached to an article, and the thermosetting coating sheet is then cured.

[0004] Japanese Patent Application Publication No. 4-11680

[0005] After attaching the thermosetting coating sheet to an adherend, the support layer can be peeled off to transfer the thermosetting coating sheet to the adherend, and the support layer can be used as a transfer layer. During the process of transferring the thermosetting coating sheet to the adherend, it is necessary to peel off the transfer layer without damaging the surface of the thermosetting coating sheet. However, conventional thermosetting coating sheets have had problems such as leaving peel marks on the thermosetting coating sheet when the transfer layer is peeled off, and wrinkles occurring in the thermosetting coating sheet when the thermosetting coating sheet is attached to the adherend.

[0006] Therefore, the present invention aims to provide a laminate sheet that can prevent peeling traces from remaining on the paint layer when the transfer layer is peeled off and the paint layer is transferred to the substrate, and that can prevent wrinkles from occurring in the laminate sheet when the laminate sheet is attached to the substrate, a vehicle painted using the laminate sheet, a method for using the laminate sheet, and a method for manufacturing the laminate sheet.

[0007] After extensive research, the present inventors discovered that the above-mentioned problems can be solved by adjusting the bending resistance of the transfer layer, and thus completed the present invention. The gist of the present invention is as follows: [1] A laminate sheet having a transfer layer and a coating layer made of a thermosetting resin composition or a moisture-curable resin composition, wherein the bending resistance of the transfer layer is 20 to 120 mm. [2] The laminate sheet according to [1] above, wherein the coating layer has a modulus of elasticity measured from the transfer layer side of 1.0 to 1500 MPa. [3] The laminate sheet according to [1] or [2] above, wherein the thermosetting resin composition contains a polymer component having a functional group reactive with an isocyanate group and a heat-reactive isocyanate. [4] The laminate sheet according to [3] above, wherein the polymer component having a functional group reactive with an isocyanate group contains a hydroxyl group. [5] The thermosetting resin sheet according to [3] or [4] above, wherein the polymer component having a functional group reactive with an isocyanate group is at least one resin selected from the group consisting of a (meth)acrylic resin, a polycarbonate resin, a polyester resin, and an epoxy resin. [6] The laminate sheet according to any one of [3] to [5] above, wherein the weight-average molecular weights of the polymer components having functional groups reactive with isocyanate groups are from 50,000 to 1,000,000. [7] The laminate sheet according to any one of [3] to [6] above, wherein the content of the polymer components having functional groups reactive with isocyanate groups in the thermosetting resin composition is from 20% by mass to 90% by mass. [8] The laminate sheet according to any one of [1] to [7] above, wherein the paint layer has a first resin layer made of a first thermosetting resin composition and a second resin layer made of a second thermosetting resin composition, wherein the first thermosetting resin composition contains a first polymer component having functional groups reactive with isocyanate groups and first thermoreactive isocyanates, and the second thermosetting resin composition contains a second polymer component having functional groups reactive with isocyanate groups, second thermoreactive isocyanates, and a colorant. [9] The laminate sheet according to the above [8], wherein the content of the first thermoreactive isocyanates in the thermosetting resin composition is 10% by mass or more and 70% by mass or less.

[10] The laminate sheet according to [1] above, wherein the moisture-curable resin composition contains a resin containing an isocyanate group.

[11] The laminate sheet according to [1] or

[10] above, wherein the moisture-curable resin composition contains a polymer having a weight-average molecular weight of 20,000 or more and 1,000,000 or less.

[12] The laminate sheet according to any one of [1] to

[11] above, wherein the transfer layer has a thickness of 10 μm or more and 1,000 μm or less.

[13] A vehicle painted using the laminate sheet according to any one of [1] to

[12] above.

[14] A method for using the laminate sheet according to any one of [1] to

[12] above, by attaching the laminate sheet according to any one of [1] to

[12] above to an adherend.

[15] A method for producing a laminate sheet in which a paint layer is made of a thermosetting resin composition and the paint layer has a first resin layer and a second resin layer, the method comprising: applying a first paint containing a first thermosetting resin composition containing a first polymer component and a thermoreactive isocyanate to a transfer layer and drying the paint to produce a first laminate comprising the transfer layer and the first resin layer formed on the transfer layer and made of the first thermosetting resin composition; applying a second paint containing a second thermosetting resin composition containing a second polymer component, a second thermoreactive isocyanate, and a colorant to a substrate and drying the paint to produce a second laminate comprising the substrate and the second resin layer formed on the substrate and made of the second thermosetting resin composition; and laminating the first laminate and the second laminate together so that the first resin layer and the second resin layer face each other.

[0008] According to the present invention, it is possible to provide a laminate sheet that can prevent peeling traces from remaining on the paint layer when the transfer layer is peeled off and the paint layer is transferred to the substrate, and that can prevent wrinkles from occurring in the laminate sheet when the laminate sheet is attached to the substrate, a vehicle painted using the laminate sheet, a method for using the laminate sheet, and a method for manufacturing the laminate sheet.

[0009] Fig. 1 is a schematic cross-sectional view of a laminate sheet according to one embodiment of the present invention. Fig. 2 is a schematic cross-sectional view of a laminate sheet according to another embodiment of the present invention. Fig. 3 is a schematic cross-sectional view of a laminate sheet according to another embodiment of the present invention. Fig. 4 is a schematic cross-sectional view of a laminate sheet according to another embodiment of the present invention.

[0010] [Thermosetting Resin Sheet] A laminate sheet according to one embodiment of the present invention will be described with reference to the drawings. As shown in Fig. 1, a laminate sheet 1 according to one embodiment of the present invention has a transfer layer 10 and a paint layer 20 in this order.

[0011] (Transfer Layer) The bending resistance of the transfer layer 10 in the laminate sheet 1 of one embodiment of the present invention is 20 to 120 mm. If the bending resistance of the transfer layer 10 is less than 20 mm, wrinkles may occur in the laminate sheet when the laminate sheet 1 is attached to an adherend. Furthermore, if the bending resistance of the transfer layer 10 is less than 20 mm, when the laminate sheet is pressed onto the surface with a squeegee or the like, pressure may concentrate at the area where the squeegee is applied, causing the laminate sheet to become warped. The warped portion may then adhere to the adherend discontinuously, resulting in wrinkles. Furthermore, if the bending resistance of the transfer layer 10 is greater than 120 mm, peeling marks may remain on the paint layer 20 when the transfer layer 10 is peeled off and the paint layer 20 is transferred to the adherend. From this perspective, the bending resistance of the transfer layer 10 in the laminate sheet 1 of one embodiment of the present invention is preferably 30 to 110 mm, more preferably 40 to 100 mm, even more preferably 50 to 90 mm, and even more preferably 60 to 80 mm. The bending resistance of the transfer layer 10 can be measured by the method described in the Examples below. The bending resistance of the transfer layer 10 can be adjusted by the material of the transfer layer 10, the thickness of the transfer layer 10, the stretching ratio and crystallinity of the resin film constituting the transfer layer 10, etc. More specifically, the higher the glass transition temperature (Tg) of the material of the transfer layer 10, the higher the bending resistance can be. Separately, the bending resistance of the transfer layer can also be increased by increasing the thickness, stretching ratio and crystallinity of the transfer layer. In this way, even if a soft material is used as the material of the transfer layer, the bending resistance can be adjusted by increasing the thickness, stretching ratio, crystallinity, etc.

[0012] The transfer layer 10 is a member that protects the paint layer 20 from scratches and foreign matter adhesion. As described below, the transfer layer 10 also serves as a support when attaching the paint layer 20 to an adherend, typically serving as a support when transferring the paint layer 20 of the laminate sheet 1 to an adherend. The transfer layer 10 is preferably formed from a resin film. Examples of resins used for the resin film include thermoplastic resins. Specific examples of resins used for the resin film include polyolefin resins such as cyclic polyolefin resins, polyethylene resins, polypropylene resins, ethylene-vinyl acetate copolymer resins, polymethylpentene resins, and polystyrene resins; polyester resins such as polybutylene terephthalate and polyethylene terephthalate; polyamide resins, polycarbonate resins, polyimide resins, polyarylate resins, acrylic resins, fluororesins, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl alcohol resins, polyvinyl butyral resins, nylon resins, polyether ether ketone resins, polysulfone resins, polyethersulfone resins, and tetrafluoroethylene resins. Among these, polyolefin resins are preferred from the viewpoint of conformability, which will be described later, and polyester resins are preferred from the viewpoint of easily improving bending resistance. Furthermore, preferred polyolefin resins include polyethylene resins, polypropylene resins, and ethylene-vinyl acetate copolymer resins, and preferred polyester resins include polyethylene terephthalate.

[0013] The resin film may be a single-layer film consisting of one single layer, or a multilayer film consisting of two or more layers. Furthermore, in the resin film constituting the release layer, the resin contained in the resin film may be used alone, or two or more types may be used in combination. When two or more types of resins are used in combination, different types of resins may be used for each layer to form a multilayer film. Furthermore, a single-layer film may be formed from a mixture of two or more resins, or one or more layers of a multilayer film may be formed from a mixture of two or more resins. Examples of multilayer films include multilayer films in which a layer composed of a cyclic polyolefin resin or a polyolefin resin and a layer composed of a polyester resin are laminated together. For example, a multilayer film in which a polyester resin layer, a polyolefin resin layer, and a polyester resin layer are laminated together in this order may be used. Furthermore, the multilayer film may be a multilayer film in which each layer is composed of a polyolefin resin. Specific examples include a multilayer film in which a polyethylene resin, an ethylene-vinyl acetate copolymer resin, and a polyethylene resin are laminated together in this order, and a multilayer film in which a polypropylene resin, an ethylene-vinyl acetate copolymer resin, and a polypropylene resin are laminated together in this order.

[0014] Each layer in the transfer layer 10 may contain additives in addition to the resin. Known additives that are typically incorporated into resin films may be used. Specific examples of the additives include nucleating agents, fluorescent whitening agents, antioxidants, stabilizers, UV absorbers, surfactants, lubricants, fillers, crosslinking agents, crosslinking accelerators, antistatic agents, flame retardants, dispersants, pigments, dyes, and processing aids.

[0015] The resin film may be a stretched resin film or a non-stretched resin film, but is preferably a non-stretched resin film. Therefore, the resin film is preferably a non-stretched polyester film, more preferably a non-stretched polyethylene terephthalate film. The non-stretched resin film may also be a multilayer film, for example, a multilayer film having a polyolefin resin layer in addition to a polyester resin layer as described above.

[0016] The transfer layer 10 may have at least one surface that has been release-treated with a release agent such as a silicone-based release agent or a fluorine-based release agent. When the transfer layer 10 is release-treated, it is preferable that the release-treated surface constitutes the surface on the paint layer side. The release treatment of the transfer layer 10 makes it easier to peel the transfer layer 10 from the paint layer 20. However, the transfer layer 10 does not need to be release-treated as long as it can be peeled from the paint layer 20. The thickness of the transfer layer 10 is not particularly limited, but is, for example, 10 μm or more and 1000 μm or less, preferably 20 μm or more and 500 μm or less, and more preferably 30 μm or more and 300 μm or less.

[0017] (Paint Layer) The paint layer used in the present invention is made of a thermosetting resin composition that can be cured by heat. The curable resin composition preferably contains a polymer component containing a functional group that can be cured by reacting with the resin itself or a curing agent by heat. Examples of polymer components used in thermosetting resin compositions include curable resins, specifically (meth)acrylic resins, polycarbonate resins, polyester resins, and epoxy resins, with (meth)acrylic resins being preferred. By lowering the tack value of the paint layer, it becomes less likely to adhere discontinuously to the substrate and less likely to wrinkle. However, if the tack value is too low, it will not be possible to press the adherend, so it is necessary to set it within an appropriate range.

[0018] The thermosetting resin composition preferably contains a thermoreactive isocyanate as a curing agent. The thermoreactive isocyanate is a compound having an isocyanate group, and details thereof will be described later. By containing the thermoreactive isocyanate, the thermosetting resin composition can be easily cured by heat.

[0019] The thermosetting resin composition preferably contains a functional group reactive with the isocyanate group contained in the curing agent, specifically a hydroxyl group, an amino group, a carboxyl group, etc., and among these, a hydroxyl group is preferred. The functional group reactive with the isocyanate group is usually contained in the polymer component.

[0020] The weight-average molecular weight of the polymer component having a functional group reactive with an isocyanate group (hereinafter sometimes simply referred to as the "polymer component") is preferably 50,000 or more and 1,000,000 or less. When the weight-average molecular weight of the polymer component is 50,000 or more and 1,000,000 or less, the coating properties, curing properties, tackiness, extensibility, etc. of the coating layer are easily balanced and favorable. Furthermore, the laminate sheet having the coating layer can be properly maintained in its sheet shape. From this viewpoint, the weight-average molecular weight of the polymer component is more preferably 80,000 or more and 800,000 or less, even more preferably 100,000 or more and 600,000 or less, and even more preferably 150,000 or more and 500,000 or less. In this specification, the weight-average molecular weight is measured by gel permeation chromatography (GPC) and is calculated as a value converted into standard polystyrene.

[0021] (Elastic Modulus) In the laminate sheet, the elastic modulus measured from the transfer layer side of the paint layer is preferably 1.0 to 1500 MPa. When the elastic modulus measured from the transfer layer side of the paint layer is 1.0 to 1500 MPa, when the transfer layer is peeled off and the paint layer is transferred to the adherend, it is possible to further suppress the leaving of peeling marks on the paint layer, and the conformability to the surface of the adherend is further improved. From this viewpoint, the elastic modulus measured from the transfer layer side of the paint layer is more preferably 5.0 to 1000 MPa, even more preferably 10 to 600 MPa, and even more preferably 100 to 250 MPa. The elastic modulus measured from the transfer layer side of the paint layer is measured using a nanoindenter, and specifically, can be measured by the method described in the Examples below. The elastic modulus measured from the transfer layer side of the paint layer can be adjusted by the glass transition temperature, hydroxyl value and content of the polymer component in the thermosetting resin composition constituting the paint layer, the hydroxyl value and content of the plasticizing resin, the thickness of the paint layer, etc. The elastic modulus is greatly influenced by the resin layer in contact with the transfer layer (i.e., the first resin layer described below), and therefore can be easily adjusted by appropriately changing the polymer component and plasticizing resin of the first resin layer.

[0022] The laminate sheet 1 of one embodiment of the present invention is a preferred embodiment of the laminate sheet 1 of the present invention. Note that the laminate sheet 1 of one embodiment of the present invention is an example of the laminate sheet of the present invention and does not limit the laminate sheet of the present invention. The laminate sheet 1 of a preferred embodiment of the present invention has first and second resin layers 21, 22, and the resin layer on the opposite side to the transfer layer 10 side (the second resin layer 22) is a colored layer. The laminate sheet 1 of a preferred embodiment of the present invention will be described in detail below. The laminate sheet 1 of a preferred embodiment of the present invention has, in this order from the transfer layer 10 side, a first resin layer 21 made of a first thermosetting resin composition and a second resin layer 22 made of a second thermosetting resin composition, and the second resin layer 22 is a colored layer.

[0023] (Thermosetting Resin Composition) The first thermosetting resin composition contains a first polymer component, and the second thermosetting resin composition contains a second polymer component. The first polymer component contained in the first thermosetting resin composition may be the same as or different from the second polymer component contained in the second thermosetting resin composition.

[0024] <Polymer Component> The first polymer component and the second polymer component may each be selected from (meth)acrylic resin, polycarbonate resin, polyester resin, and epoxy resin, as described above, but both are preferably (meth)acrylic resin. Furthermore, the first and second polymer components may contain functional groups reactive with the functional groups (isocyanate groups) contained in thermally reactive isocyanates, specifically hydroxyl groups, amino groups, carboxyl groups, etc., with hydroxyl groups being preferred. The first polymer component and the second polymer component may each have one hydroxyl group, but preferably two or more. Therefore, both the first polymer component and the second polymer component are preferably (meth)acrylic polyol resins. The weight-average molecular weights of the first polymer component and the second polymer component are as described above. The weight-average molecular weights of the first polymer component and the second polymer component may be the same or different from each other.

[0025] The glass transition temperature (Tg) of the first polymer component is, for example, 20 to 100°C, preferably 30 to 90°C, more preferably 40 to 80°C, and even more preferably 50 to 70°C. By setting the glass transition temperature (Tg) of the first polymer component within the above range, it becomes easier to adjust the elastic modulus of the transfer layer side of the paint layer within the desired range described above. On the other hand, the glass transition temperature of the second polymer component is not particularly limited and is, for example, -50 to 80°C, preferably -20 to 60°C, and more preferably 10 to 50°C. In this specification, the glass transition temperature is a value determined by differential scanning calorimetry (DSC) in accordance with JIS K 7121.

[0026] The hydroxyl value of the first polymer component is preferably 20 mgKOH / g or more and 200 mgKOH / g or less, more preferably 60 mgKOH / g or more and 180 mgKOH / g or less, and even more preferably 100 mgKOH / g or more and 150 mgKOH / g or less. By setting the hydroxyl value of the first polymer component within the above range, the curability is improved, and it is easy to achieve high hardness of the paint layer after curing. On the other hand, the hydroxyl value of the second polymer component is preferably 20 mgKOH / g or more and 200 mgKOH / g or less, more preferably 50 mgKOH / g or more and 160 mgKOH / g or less, and even more preferably 80 mgKOH / g or more and 110 mgKOH / g or less. By setting the hydroxyl value of the second polymer component within the above range, the adhesion to the painted plate is improved, and it is easy to achieve high adhesion of the paint layer after curing. In addition, when the first thermosetting resin composition and the second thermosetting resin composition contain a plurality of polymer components, the hydroxyl value of the first polymer component and the hydroxyl value of the second polymer component are weighted average values ​​of the hydroxyl values ​​of the polymer components contained in each thermosetting resin composition. For example, when two types of polymer components, polymer component (d1) and polymer component (d2), are used as the polymer components, the hydroxyl value of polymer component (d1) is set to X １ , the blending ratio is m １ , the hydroxyl value of the polymer component (d2) is X ２ , the blending ratio is m ２ Then, the weighted average value of the hydroxyl value is expressed by the following formula. The blending ratio is based on mass. Weighted average value of the hydroxyl value (mgKOH / g) = X１ × (m １ / (m １ +m ２ )) + X ２ × (m ２ / (m １ +m ２ )) The hydroxyl value can be measured in accordance with JIS K 1557-1:2007.

[0027] The (meth)acrylic resin is preferably an acrylic polymer obtained by polymerizing a monomer mixture containing a (meth)acrylic acid ester monomer and a functional group-containing monomer having a hydroxyl group. Such an alkyl polymer can incorporate hydroxyl groups into the acrylic polymer by the hydroxyl group-containing monomer. Note that (meth)acrylic means methacrylic or acrylic, and the same applies to other similar terms.

[0028] Examples of the (meth)acrylic acid ester monomer include (meth)acrylic acid ester monomers having no functional group, such as alkyl (meth)acrylates having an alkyl group with about 1 to 18 carbon atoms, such as methyl (meth)acrylate and ethyl (meth)acrylate, (meth)acrylates having an aromatic ring, such as benzyl (meth)acrylate and phenoxydiethylene glycol (meth)acrylate, and 2-ethoxyethyl (meth)acrylate.

[0029] The hydroxyl group-containing monomer is not particularly limited, and examples thereof include (meth)acrylic acid ester monomers having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate.

[0030] The monomer mixture may also contain monomers other than the above-mentioned (meth)acrylic acid ester monomers and hydroxyl group-containing monomers, such as monomers containing functional groups other than hydroxyl groups, and styrene derivative monomers. By using a monomer containing a functional group other than hydroxyl groups, such as an amino group or a carboxyl group, in addition to the hydroxyl group-containing monomer, it is possible to introduce functional groups other than hydroxyl groups into the (meth)acrylic resin in addition to hydroxyl groups. The amino group-containing monomer is not particularly limited, and examples thereof include (meth)acrylic acid ester monomers having an amino group, such as 2-aminoethyl (meth)acrylate. The carboxyl group-containing monomer is not particularly limited, and examples thereof include (meth)acrylic acid. The styrene derivative monomer is not particularly limited, and examples thereof include styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-ethoxystyrene, p-chlorostyrene, m-chlorostyrene, and o-chlorostyrene.

[0031] The (meth)acrylic resin may also be a copolymer obtained by block or graft polymerization of the above-mentioned acrylic polymer with another monomer or polymer. In this case, the other monomer or polymer may be an acrylic, styrene, maleic acid, imide, silicone, or fluorine-based monomer, or a polymer of these monomers. Furthermore, the functional group of an acrylic polymer obtained by polymerizing a monomer mixture containing a (meth)acrylic acid ester monomer and a functional group-containing monomer may be reacted with a (meth)acryloyl group-containing compound having a reactive group capable of reacting with the functional group and a (meth)acryloyl group, thereby incorporating the (meth)acryloyl group into the acrylic polymer.

[0032] The content of the first polymer component in the first thermosetting resin composition and the content of the second polymer component in the second thermosetting resin composition are each preferably 20% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 80% by mass or less, and even more preferably 40% by mass or more and 70% by mass or less. The content of the first polymer component in the first thermosetting resin composition may be the same as or different from the content of the second polymer component in the second thermosetting resin composition. The thermosetting resin composition may be diluted with a volatile component such as a solvent as described below. In this specification, the content (mass%) of each component in the thermosetting resin composition means a value based on the solids content excluding the volatile component.

[0033] Within the scope of not impairing the effects of the present invention, when the first thermosetting resin composition uses a (meth)acrylic resin as the first polymer component, it may contain a thermosetting resin other than a (meth)acrylic resin, and when the second thermosetting resin composition uses a (meth)acrylic resin as the second polymer component, it may contain a thermosetting resin other than a (meth)acrylic resin. Examples of thermosetting resins other than a (meth)acrylic resin include polycarbonate resins, polyester resins, and epoxy resins. These thermosetting resins may be used alone or in combination of two or more.

[0034] <Thermal Reactive Isocyanates> It is preferred that the first thermosetting resin composition contains thermally reactive isocyanates (hereinafter, sometimes referred to as first thermally reactive isocyanates), and the second thermosetting resin composition contains thermally reactive isocyanates (hereinafter, sometimes referred to as second thermally reactive isocyanates).

[0035] Although known isocyanate compounds used as curing agents may be used as thermally reactive isocyanates, it is preferable to use blocked isocyanates. Blocked isocyanates are compounds in which an isocyanate group is blocked with a protecting group. When exposed to high temperatures, the protecting group (blocking moiety) thermally dissociates and is removed, causing a curing reaction between the resulting isocyanate group and a functional group (typically a hydroxyl group) in the polymer component. Blocked isocyanates can be obtained, for example, by reacting an isocyanate compound having two or more isocyanate groups per molecule with a blocking agent. The isocyanate compound having two or more isocyanate groups per molecule is not particularly limited, and examples thereof include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and modified products thereof. Examples of blocking agents include pyrazoles, phenols, oximes, lactams, and malonic acid esters. The first and second heat-reactive isocyanates may be used singly or in combination of two or more. The first and second heat-reactive isocyanates may be the same or different.

[0036] The thermal dissociation temperatures of the first and second thermally reactive isocyanates are preferably 180°C or lower. The thermal dissociation temperature is the temperature at which the thermally reactive isocyanates dissociate to generate isocyanate groups. It is preferable that the thermal dissociation temperatures of the first and second thermally reactive isocyanates are 180°C or lower, since this allows the thermosetting resin sheet to be cured at a relatively low temperature. From the viewpoint of curing the paint layer at a low temperature, the thermal dissociation temperatures of the first and second thermally reactive isocyanates are more preferably 160°C or lower, and even more preferably 140°C or lower. Furthermore, from the viewpoint of the storage stability of the thermosetting resin sheet, the thermal dissociation temperatures of the first and second thermally reactive isocyanates are preferably 40°C or higher, and more preferably 60°C or higher. The thermal dissociation temperature can be measured by, for example, mixing a resin highly reactive with isocyanate, such as a polymer component, in an amount equivalent to that of the blocked isocyanate, stirring at a predetermined temperature for 6 hours, and then evaluating the gel fraction.

[0037] The content of the first thermoreactive isocyanates in the first thermosetting resin composition and the content of the second thermoreactive isocyanates in the second thermosetting resin composition are preferably adjusted so that the ratio of the number of functional groups in the thermosetting resin to the number of isocyanate groups in the thermoreactive isocyanates is preferably 0.4 or more and 1.8 or less, more preferably 0.6 or more and 1.5 or less.

[0038] The contents of the first thermoreactive isocyanates in the first thermosetting resin composition and the second thermoreactive isocyanates in the second thermosetting resin composition are not particularly limited as long as they are adjusted so that the ratio of the number of functional groups to the number of isocyanate groups falls within the above-mentioned range, but are each preferably 10% by mass or more and 70% by mass or less, more preferably 20% by mass or more and 60% by mass or less, and even more preferably 30% by mass or more and 50% by mass or less. The content of the first thermoreactive isocyanates in the first thermosetting resin composition may be the same as or different from the content of the second thermoreactive isocyanates in the second thermosetting resin composition.

[0039] <Plasticizing Resin> The first thermosetting resin composition preferably contains, as a resin, a resin having a weight-average molecular weight of less than 50,000 (hereinafter also referred to as plasticizing resin (A2)) in addition to the (meth)acrylic resin (A1). The second thermosetting resin composition preferably contains, as a resin, a resin having a weight-average molecular weight of less than 50,000 (hereinafter also referred to as plasticizing resin (A2)) in addition to the (meth)acrylic resin (A1). The first thermosetting resin composition contains, as a resin, a plasticizing resin (A2) having a low weight-average molecular weight in addition to the high molecular weight (meth)acrylic resin (A1), which makes it easier to lower the glass transition temperature of the first thermosetting resin composition. Furthermore, it makes it easier to achieve a good balance between the coatability, curability, tackiness, extensibility, etc. of the first thermosetting resin composition. Furthermore, the second thermosetting resin composition also contains a plasticizing resin (A2) having a low weight-average molecular weight in addition to a high-molecular-weight (meth)acrylic resin (A1), which facilitates lowering the glass transition temperature of the second thermosetting resin composition. Furthermore, the second thermosetting resin composition is more likely to have a well-balanced coating property, curability, tackiness, extensibility, and the like. Furthermore, the wettability of the second thermosetting resin composition to an adherend can be improved, thereby enhancing adhesion to the adherend. The plasticizing resin (A2) is preferably compatible with the (meth)acrylic resin (A1) and, like the (meth)acrylic resin (A1), has a thermosetting functional group. Resins used for the plasticizing resin (A2) include (meth)acrylic resins, polycarbonate resins, polyester resins, and epoxy resins, with (meth)acrylic resins or polycarbonate resins being preferred. Examples of the (meth)acrylic resin used as the plasticizing resin (A2) include oligomers having functional groups such as hydroxyl groups, amino groups, and carboxyl groups. Examples of the (meth)acrylic resin used as the plasticizing resin (A2) include those described above for the (meth)acrylic resin, and preferably a (meth)acrylic polyol having multiple hydroxyl groups is used. Poly(meth)acrylates having carboxyl groups are also preferred. Polycarbonate resins are preferably polycarbonate polyols.

[0040] The weight average molecular weight of the plasticized resin (A2) is preferably 50 or more and 10,000 or less, more preferably 100 or more and 5,000 or less, and even more preferably 300 or more and 3,000 or less.

[0041] The plasticized resin (A2) is desirably a liquid at room temperature and normal pressure. The plasticized resin (A2) may or may not have a glass transition temperature. When the plasticized resin (A2) has a glass transition temperature, the glass transition temperature is not particularly limited, but is preferably less than 0°C, more preferably -20°C or lower, and even more preferably -40°C or lower. The lower limit of the glass transition temperature is not particularly limited, but is, for example, -120°C or higher, preferably -100°C or higher. By setting the glass transition temperature of the plasticized resin (A2) within the above range, tackiness is easily exhibited.

[0042] The hydroxyl value of the plasticized resin (A2) is preferably 20 mgKOH / g or more and 350 mgKOH / g or less, more preferably 50 mgKOH / g or more and 300 mgKOH / g or less, and even more preferably 80 mgKOH / g or more and 250 mgKOH / g or less.

[0043] The plasticizer resin (A2) is not limited to (meth)acrylic resins and polycarbonate resins, and any short-molecular-weight component can be used as the plasticizer resin (A2). Examples of plasticizer resins other than (meth)acrylic resins and polycarbonate resins include organic ester plasticizer resins such as monobasic organic acid esters and polybasic organic acid esters, phosphate plasticizer resins such as organic phosphoric acids and organic phosphorous acids, and glycol-based plasticizer resins.

[0044] When the first thermosetting resin composition contains a plasticizing resin, the content of the plasticizing resin in the first thermosetting resin composition is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 3 parts by mass or more and 30 parts by mass or less, and even more preferably 5 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total content of the polymer component, the thermoreactive isocyanates, and the plasticizing resin. In the paint layer, when the first thermosetting resin composition contains a plasticizing resin, the elastic modulus measured from the transfer layer side of the paint layer can be easily adjusted to a desired range by appropriately adjusting the content of the plasticizing resin in the first thermosetting resin composition. Furthermore, when the second thermosetting resin composition contains a plasticizing resin, the content of the plasticizing resin in the second thermosetting resin composition is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 3 parts by mass or more and 35 parts by mass or less, and even more preferably 5 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total content of the polymer component, the thermoreactive isocyanates, and the plasticizing resin.

[0045] The plasticizing resin in the first thermosetting resin composition may be the same as or different from the plasticizing resin in the second thermosetting resin composition, and the content of the plasticizing resin in the first thermosetting resin composition may be the same as or different from the content of the plasticizing resin in the second thermosetting resin composition.

[0046] <Colorant> The second thermosetting resin composition preferably contains a colorant. By including a colorant in the second thermosetting resin composition, the second resin layer can be a colored layer, thereby improving the design of the paint layer 20. Examples of colorants include pigments, dyes, and luster pigments. Examples of pigments include metal oxide pigments such as titanium oxide and iron oxide, inorganic pigments such as carbon black, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white, and organic pigments such as azo pigments, quinacridone pigments, diketopyrrolopyrrole pigments, perylene pigments, perinone pigments, benzimidazolone pigments, vat pigments, isoindoline pigments, isoindolinone pigments, metal chelate azo pigments, phthalocyanine pigments, indanthrone pigments, dioxane pigments, and indigo pigments. Examples of dyes include azo dyes, anthraquinone dyes, indigoid dyes, stilbene dyes, etc. Examples of glittering materials include compounds in which a titanium oxide layer is provided on the surface of natural mica, synthetic mica, alumina flakes, glass flakes, etc. These colorants can be used alone or in combination of two or more.

[0047] The content of the active components of the colorant in the second thermosetting resin composition, i.e., the content of the colorant excluding the binder resin, dispersant, and additives, varies depending on the colorant color. For example, the content of a white colorant required to impart hiding power to the second thermosetting resin composition is much larger than the content of a black colorant. For example, when the colorant is a black colorant such as carbon black, the content of the colorant is, for example, 0.5 parts by mass or more, preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, per 100 parts by mass of the total content of the second polymer component, the second thermoreactive isocyanate, and the plasticizing resin.

[0048] <Other Components> The first thermosetting resin composition and the second thermosetting resin composition may each contain components other than those described above, for example, additives other than those described above. Examples of additives include surface conditioners, antifoaming agents, urethanization catalysts, crosslinking agents, plasticizers, thickeners, adhesion promoters, fluorescent brighteners, stabilizers, ultraviolet absorbers, surfactants, flame retardants, antistatic agents, dispersants, inorganic fillers other than pigments and luster materials, antioxidants, antioxidants, and rust inhibitors.

[0049] The first thermosetting resin composition may contain a colorant in addition to the first polymer component and the first thermoreactive isocyanate. However, it is sufficient if the first resin layer 21 does not contain a colorant, or if it does contain a colorant, the amount is such that it does not impair transparency. It is preferable that the first resin layer 21 be a so-called clear layer. The clear layer is a transparent layer, and "transparent" means that the transmittance of light with a wavelength of 450 nm is 80% or more. On the other hand, since the second thermosetting resin composition contains a colorant, the second resin layer is preferably a colored resin layer and an opaque layer.

[0050] The thickness of the first resin layer 21 is not particularly limited, but is, for example, 5 μm to 150 μm, preferably 10 μm to 50 μm. The thickness of the second resin layer 22 is not particularly limited, but is, for example, 5 μm to 150 μm, preferably 10 μm to 50 μm.

[0051] The paint layer 20 in the laminate sheet 1 of a preferred embodiment of the present invention had two resin layers (a first resin layer 21 and a second resin layer 22). However, the number of resin layers constituting the paint layer in the laminate sheet of an embodiment of the present invention is not limited to two. For example, the paint layer 20A may be composed of a single resin layer (a first resin layer) as in the laminate 1A shown in FIG. 2. When composed of a single resin layer, the paint layer 20A is preferably a colored layer. The colored paint layer 20A may have the same configuration as the first thermosetting resin composition described above, except that it contains a colorant. The type and content of the colorant may be the same as those described for the second thermosetting resin composition described above.

[0052] Furthermore, as shown in FIG. 3, the paint layer 20B may be composed of three resin layers (21-23). ​​In this case, the resin layer 21 closest to the transfer layer is preferably the first resin layer described above, and the resin layer 22 furthest from the transfer layer is preferably the second resin layer described above. The resin layer 23 between the two resin layers 21 and 22 may be made of the same material as the resin layers 21 and 22. The resin layer 23 preferably contains, for example, a polymer component and a heat-reactive isocyanate. This configuration increases the peel strength between the resin layers 21 and 22, preventing interfacial peeling between the resin layers. The resin layer 23 may contain a colorant in addition to the polymer component and the heat-reactive isocyanate. The design of the paint layer 20B can be further enhanced by combining a resin layer 23 containing a colorant with another resin layer 23 containing a colorant. Furthermore, although not shown, the paint layer may be composed of four or more resin layers. In this case, the resin layer closest to the transfer layer is preferably the first resin layer described above, and the resin layer farthest from the transfer layer is preferably the second resin layer described above.

[0053] The above explanation assumes that the paint layer has a colored layer for the purpose of improving design. However, the paint layer can be imparted with various functions and does not necessarily need to contain a colored layer. The paint layer can also be a clear layer. For example, in the laminate sheet 1A, the paint layer 20A can be made of a first thermosetting resin composition that does not contain a colorant. Furthermore, the paint layer can be imparted with various functions other than protecting the substrate or improving design. For example, the paint layer can function as a heat-shielding coating. In this case, the paint layer can be a heat-shielding layer containing a heat-shielding material. Furthermore, by providing surface irregularities to the paint layer, surface properties such as matte or grained finishes can be imparted. Furthermore, functions such as rust prevention, mildew prevention, insulation, and antistatic properties can be achieved by incorporating appropriate components into the curable resin composition. In either embodiment, the paint layer 20 preferably has at least a first resin layer made of a first thermosetting resin composition in contact with the transfer layer 10. The details of the first thermosetting resin composition are as described above, but it may contain appropriate components according to the purpose, if necessary.

[0054] As shown in FIG. 4 , the laminate sheet 1C of the present invention may further include a substrate 30 provided on the side of the paint layer 20 opposite the transfer layer side. The substrate 30 used in the laminate sheet 1C is a member that protects the paint layer 20 from scratches and foreign matter adhesion, and is preferably peeled off from the paint layer 20 before the paint layer 20 is bonded to the substrate. The substrate 30 is preferably formed from a resin film. Examples of resins used in the resin film include thermoplastic resins. Specific examples of thermoplastic resins used in the substrate 30 are the same as those that can be used in the transfer layer 10, with polyester resin being preferred. The substrate may be provided on the side of the paint layer opposite the transfer layer side not only in the laminate sheet 1C but also in any laminate sheet configuration.

[0055] The resin film may be a single-layer film consisting of one single layer, or may be a multilayer film consisting of two or more layers. Furthermore, in the resin film constituting the release layer, the resin contained in the resin film may be used alone, or two or more types may be used in combination. When two or more types of resins are used in combination, a multilayer film may be formed by using different types of resins in each layer. Furthermore, a single-layer film may be formed by mixing two or more types of resins, or one or more layers in a multilayer film may be formed. Each layer in the substrate 30 may contain additives in addition to the resin. Specific examples of additives are as described for the transfer layer.

[0056] The resin film in the substrate 30 may be a stretched resin film or a non-stretched resin film, but a stretched resin film is preferred. Therefore, a stretched polyester resin film is preferred as the resin film. The substrate 30 may have at least one surface that has been release-treated with a release agent such as a silicone-based release agent or a fluorine-based release agent. If the substrate 30 is release-treated, it is preferred that the release-treated surface constitutes the surface on the paint layer side. The release treatment of the substrate 30 facilitates easy releasability from the paint layer 20. However, the substrate 30 does not need to be release-treated as long as it can be releasable from the paint layer 20. The thickness of the substrate 30 is not particularly limited, but is, for example, 10 μm to 1000 μm, preferably 30 μm to 700 μm, and more preferably 50 μm to 500 μm.

[0057] (Moisture-curable resin composition) The coating layer used in the present invention may be made of a moisture-curable resin composition that can be cured by moisture. The moisture-curable resin composition contains a moisture-curable resin. Examples of the moisture-curable resin include prepolymers having an isocyanate group. Examples of prepolymers having an isocyanate group include prepolymers having an isocyanate group at the terminal. Examples of prepolymers having an isocyanate group at the terminal include those obtained by reacting a polyisocyanate with an active hydrogen-containing compound and / or an active hydrogen-containing polymer. Examples of polyisocyanates that can be used to prepare prepolymers having isocyanate groups at their terminals include tolylene diisocyanate, crude tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, carbazimidated diphenylmethane diisocyanate, phenylene diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate, with polymethylene polyphenyl isocyanate being preferred. The weight-average molecular weight of the prepolymer is preferably 20,000 or more and 1,000,000 or less. The weight-average molecular weight is measured by gel permeation chromatography (GPC) and is calculated as a value converted into standard polystyrene.

[0058] Examples of the active hydrogen-containing compound and active hydrogen-containing polymer that can be used include: active hydrogen-containing compounds such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolethane, trimethylolpropane, castor oil, diglycerin, sorbitol, pentaerythritol, and dipentaerythritol; and active hydrogen-containing polymers having two or more terminal hydroxyl groups, an average molecular weight of 3,000 or less, an average functionality of 2 or more, preferably an average molecular weight of 200 to 1,000, and an average functionality of 2 to 2.5, which are obtained by addition polymerization of the above-mentioned active hydrogen-containing compounds with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and tetrahydrofuran, either alone or in combination. Other active hydrogen-containing polymers that can be used in combination include polyester polyols, oil-modified polyester polyols, poly-ε-caprolactone polyols, polycarbonate diols, acrylic polyols, polyamines, polyamides, urea resins, and melamine resins, which have an average molecular weight of 3,000 or less and an average functionality of 1.5 or more, preferably an average molecular weight of 200 to 1,000 and an average functionality of 2 to 2.5. Prepolymers having terminal isocyanate groups have, for example, an effective NCO content of 1 to 15% by mass, preferably 8 to 13% by mass. Of the above, urethane prepolymers having terminal isocyanate groups are preferred.

[0059] The prepolymer having a terminal isocyanate group can be synthesized by carrying out a urethanization reaction of the above polyisocyanate and a conventional polyol containing the above active hydrogen-containing polymer under conditions of excess isocyanate at a temperature of 40°C to 90°C, preferably 55°C to 75°C, in a moisture-free system.

[0060] The urethanization reaction is usually carried out in an organic solvent, and examples of such solvents include ketone solvents such as methyl ethyl ketone, ester solvents such as ethyl acetate, aromatic solvents such as toluene and xylene, and other solvents commonly used in paints. The urethanization reaction can also be carried out using a catalyst, such as a tertiary amine catalyst such as triethylamine or dimethylaniline, or a metal catalyst such as tin or zinc. These catalysts also function as catalysts when reacting with moisture in the air during coating film formation.

[0061] The content of the prepolymer in the moisture-curable resin composition may be, for example, 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more. The content of the prepolymer in the moisture-curable resin composition may be 100% by mass or less, but from the viewpoint of containing a certain amount or more of other components such as compound (B), it is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0062] (Compound (B)) In addition to the prepolymer described above, the moisture-curable resin composition preferably further contains a compound (B) (polyisocyanate compound) having an isocyanate group. The compound (B) may be any compound that is cured by moisture. By containing the compound (B), the moisture-curable resin composition can increase the hardness of the paint layer after curing, and therefore the mechanical strength and scratch resistance of the paint layer after curing can be improved. The compound (B) may have two or more isocyanate groups. Furthermore, the compound (B) may be a compound other than the prepolymer described above, and may be a compound that does not contain a polyacrylic skeleton or a polyurethane skeleton.

[0063] Examples of the compound (B) include polyisocyanates such as aliphatic diisocyanate compounds such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, isophorone diisocyanate (IPDI), xylylene diisocyanate, hydrogenated xylylene diisocyanate (H6XDI), hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, and dicyclohexylmethane diisocyanate; and aromatic diisocyanate compounds such as 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, and naphthalene-1,5-diisocyanate.

[0064] The compound (B) may be a modified product obtained by polymerizing the above-mentioned polyisocyanate, such as polymeric MDI, or may be a polyol-modified product (adduct) of a polyisocyanate such as a trimethylolpropane adduct of a polyisocyanate, a biuret of a polyisocyanate, an allophanate of a polyisocyanate, an isocyanurate of a polyisocyanate, or a condensate thereof, etc. Specific preferred examples include HDI adduct, HDI biuret, HDI allophanate, HDI isocyanurate, H6XDI isocyanurate, IPDI isocyanurate, IPDI adduct, etc. As the compound (B), it is preferable to select one that is flexible and has high adhesive strength in an uncured state, and from such a viewpoint, an aliphatic polyisocyanate or a modified product thereof is preferable, and among them, an adduct, a biuret, an allophanate, or an isocyanurate of an aliphatic polyisocyanate is more preferable, and an adduct, a biuret, an allophanate, or an isocyanurate of HDI or IPDI is even more preferable. The compound (B) may be used alone or in combination of two or more.

[0065] The molecular weight of compound (B) is not particularly limited, but is preferably 1000 or less. By reducing the molecular weight of compound (B), the adhesive strength of the paint layer before curing and the adhesion to the substrate after curing can be increased. The molecular weight of compound (B) is preferably 800 or less, more preferably 700 or less. The molecular weight of compound (B) is not particularly limited, but may be, for example, 160 or more, preferably 200 or more, more preferably 300 or more, and even more preferably 400 or more. The molecular weight of compound (B) is calculated from the structural formula. When two or more types of compound (B) are used in combination, the weight average molecular weight is used.

[0066] When compound (B) is used, the content of compound (B) in the moisture-curable resin composition is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, when the total of the prepolymer and compound (B) is 100 parts by mass. By making the content of compound (B) a certain amount or more, it becomes easier to increase the hardness of the resin layer after curing. Furthermore, the content of compound (B) may be, for example, 80 parts by mass or less, but is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 40 parts by mass or less. By making the content of compound (B) a certain value or less, it becomes easier to improve the surface condition of the resin layer while improving the adhesion strength of the paint layer before curing and the adhesion after curing.

[0067] When the coating layer of the laminate sheet of the present invention is made of a moisture-curable resin composition, it may include a first resin layer and a second resin layer as described above. When the first resin layer and the second resin layer are present, the first resin layer and the second resin layer may be made of a first moisture-curable resin composition and a second moisture-curable resin composition, respectively, containing a prepolymer or containing a prepolymer and a compound (B). The first moisture-curable resin composition and the second moisture-curable resin composition may each be formulated as appropriate from the moisture-curable resin compositions described above.

[0068] As described below, when a first resin layer and a second resin layer are provided, the content of compound (B) in the first moisture-curable resin composition is more preferably 25 parts by mass or more, and the content of compound (B) in the second moisture-curable resin composition is more preferably less than 25 parts by mass.

[0069] In addition, when the first moisture-curing resin composition and the second moisture-curing resin composition contain the compound (B), the amount of compound (B) may be adjusted within the above range. However, when the total amount of the prepolymer and the compound (B) is 100 parts by mass, it is preferable to make the content of the compound (B) in the first moisture-curing resin composition greater than the content of the compound (B) in the second moisture-curing resin composition. In this case, when the total amount of the prepolymer and the compound (B) in the first moisture-curing resin composition is 100 parts by mass, the difference between the content of the compound (B) and the content of the prepolymer and the compound (B) in the second moisture-curing resin composition is 100 parts by mass is, for example, 2 parts by mass or more and 25 parts by mass or less, preferably 5 parts by mass or more and 20 parts by mass or less, more preferably 7 parts by mass or more and 15 parts by mass or less. In this way, by making the content of compound (B) in the second moisture-curable resin composition greater than the content of compound (B) in the first moisture-curable resin composition, it becomes easier to increase the above-mentioned elastic modulus while also improving the adhesion to the adherend.

[0070] It is also preferable that the second moisture-curing resin composition further contains a colorant. By containing a colorant in the second moisture-curing resin composition, the second resin layer can be made a colored layer, thereby improving the design of the paint layer 20. The type of colorant and the content of the colorant in the second moisture-curing resin composition are as described for the second thermosetting resin composition, but the standard for the content of the colorant is based on 100 parts by mass of the total content of the prepolymer and compound (B). On the other hand, the first moisture-curing resin composition may also contain a colorant, but it may not contain a colorant, or if it does contain a colorant, it may contain an amount that does not impair transparency, and the first resin layer is preferably a so-called clear layer as described above. Furthermore, when the paint layer is made of a moisture-curing resin composition and is a single resin layer, the paint layer may or may not be a colored layer. In the case of a colored layer, it is sufficient to contain a colorant as described above.

[0071] The moisture-curable resin composition (or the first moisture-curable resin composition and the second heat-and-moisture-curable resin composition) may each contain components other than those described above, for example, additives other than those described above. Examples of additives include moisture-cure accelerating catalysts. In addition to the moisture-cure accelerating catalyst, it is also possible to use the additives listed for the thermosetting resin composition as appropriate.

[0072] The structure of the paint layer when a moisture-curable resin composition other than those described above is the same as when a thermosetting resin composition is used, and therefore a description thereof will be omitted.

[0073] [Method for Manufacturing Laminate Sheet] The following description focuses on a method for manufacturing a laminate sheet in an embodiment in which the paint layer is made of a thermosetting resin composition and has a first resin layer and a second resin layer. This manufacturing method includes the following steps A, B, and C. (1) Step A: In step A, a first paint containing a first thermosetting resin composition containing a first polymer component and a thermoreactive isocyanate is applied to a transfer layer and dried to produce a first laminate including a transfer layer and a first resin layer formed on the transfer layer and made of the first thermosetting resin composition. Note that the first thermosetting resin composition, the transfer layer, and the first resin layer have already been described, so a description of the first thermosetting resin composition, the transfer layer, and the first resin layer will be omitted.

[0074] The first coating material may be made of the first thermosetting resin composition, but from the viewpoint of improving workability such as coating properties, it is preferable that the first thermosetting resin composition be diluted with a solvent, such as ethyl acetate, butyl acetate, methyl ethyl ketone, isopropyl alcohol, methyl methacrylate, or toluene.

[0075] Furthermore, the drying carried out after applying the first coating material to the transfer layer is preferably drying that includes at least the main drying step described below, and more preferably drying that involves the pre-drying step and the main drying step described below in this order.

[0076] The drying temperature in the pre-drying step is preferably 50°C or higher and 70°C or lower, more preferably 55°C or higher and 65°C or lower. The drying time in the pre-drying step is preferably 1 minute or higher and 30 minutes or lower, more preferably 2 minutes or higher and 15 minutes or lower. The drying temperature in the main drying step is preferably 75°C or higher and 130°C or lower, more preferably 80°C or higher and 120°C or lower. When the drying temperature is above these lower limits, the solvent is easily removed properly, preventing the solvent from evaporating and causing bubbles when the resin layer is cured. Furthermore, by setting the drying temperature below the above upper limit, the thermosetting resin composition can be prevented from curing more than necessary during drying. The drying time in the main drying step is preferably 1 minute or higher and 30 minutes or lower, more preferably 2 minutes or higher and 15 minutes or lower. Setting the drying time above the above lower limit makes it easy to remove the solvent properly, preventing the solvent from evaporating and causing bubbles when the resin layer is cured. Furthermore, by setting the drying temperature below the above upper limit, the thermosetting resin composition can be prevented from curing more than necessary during drying.

[0077] The dried resin layer may be subjected to initial curing as needed. Initial curing refers to curing the thermosetting resin composition constituting the resin layer to a semi-cured state. Initial curing can be performed by heating, and is preferably performed under conditions of a heating temperature of 90°C or higher and 150°C or lower for a heating time of approximately 2 minutes or higher and 5 minutes or lower.

[0078] (2) Step B In step B, a second coating material containing a second thermosetting resin composition containing a second polymer component, a second thermoreactive isocyanate, and a colorant is applied to a substrate and dried to produce a second laminate including a substrate and a second resin layer formed on the substrate and consisting of the second thermosetting resin composition. Note that the second thermosetting resin composition, the substrate, and the second resin layer have already been described, so description of the second thermosetting resin composition, the substrate, and the second resin layer will be omitted.

[0079] The second coating material may be made of a second thermosetting resin composition, but from the viewpoint of improving workability such as coating properties, it is preferable that the second thermosetting resin composition be diluted with a solvent, such as ethyl acetate, butyl acetate, methyl ethyl ketone, isopropyl alcohol, methyl methacrylate, or toluene.

[0080] Furthermore, the drying carried out after applying the second coating material to the substrate is preferably drying that includes at least the main drying step described below, similar to the drying carried out after applying the first coating material to the transfer layer, and more preferably drying that carries out the pre-drying step and main drying step described below in this order. Note that the pre-drying step and main drying step have been explained in the section "Step A," so explanation of the pre-drying step and main drying step will be omitted.

[0081] (3) Step C In step C, the first laminate and the second laminate are bonded together so that the first resin layer and the second resin layer face each other. As a result, a laminate sheet 1C having a laminate structure of transfer layer / first resin layer / second resin layer / substrate can be produced. By peeling the substrate from this laminate sheet, a laminate sheet consisting of the transfer layer, the first resin layer, and the second resin layer can be produced.

[0082] Furthermore, as described above, when another resin layer 23 is provided between the resin layers 21 and 22, the other resin layer is first formed on a separately provided release film or the like to produce a third laminate. Then, the third laminate is bonded to the first laminate to form the other resin layer on the first resin layer of the first laminate, or the third laminate is bonded to the second laminate to form the other resin layer on the second resin layer of the second laminate. Thereafter, the first and second laminates are bonded together as in step C described above to produce a laminate sheet 1B including the resin layer 21, the resin layer 22, and the other resin layer 23 provided between the resin layers 21 and 22. In this case, the release film may be peeled off after or before laminating the other resin layer 23 on the resin layer 22 or the resin layer 21. The release film may be a release polyethylene terephthalate film (release PET film) or the like.

[0083] Furthermore, when the paint layer 20 is made of a single resin layer 20A, it is possible to obtain a laminated sheet 1A in which the resin layer 20A is laminated on the transfer layer 10 by omitting steps B and C. Furthermore, a substrate 30 may be further laminated on the resin layer 20A laminated on the transfer layer 10.

[0084] It should be noted that the laminate sheet of the preferred embodiment of the present invention can also be manufactured by methods other than the above-described method for manufacturing the laminate sheet.

[0085] In addition, in the case of a laminate in which the paint layer is made of a moisture-curable resin composition, the laminate can be manufactured in a similar manner to the manufacturing method of the laminate sheet described above by using a paint containing a moisture-curable resin composition instead of a paint containing a thermosetting resin composition.

[0086] [Method of Use of Laminate Sheet] A preferred embodiment of the present invention is a laminate sheet for forming a decorative body, such as a coating, on various articles (adherends), and is used by being attached to the adherend. Specifically, in a preferred embodiment of the present invention, the laminate sheet is prepared by peeling off the substrate, peeling off the transfer layer, attaching the paint layer to the adherend, and heating the paint layer attached to the adherend. The method for peeling off the substrate is not particularly limited, and peeling may be performed using a peeling device or manually. The attachment of the paint layer to the adherend is not particularly limited, and may be performed by hand using a squeegee or a laminating device. Furthermore, when the paint layer is made of a thermosetting resin composition, the paint layer is cured by heating, and the cured paint layer forms a decorative body. Furthermore, when the paint layer is made of a moisture-curing resin composition, the paint layer attached to the adherend is left, for example, in an atmospheric environment or a high-humidity environment, whereby the paint layer is moisture-cured, and the cured paint layer forms a decorative body.

[0087] The transfer layer is peeled off and removed after the substrate is peeled off. Typically, after the transfer layer is peeled off, the paint layer is heated or left to stand as described above to harden the paint layer. The transfer layer is preferably peeled off from the paint layer after the laminate sheet is attached to the adherend via the paint layer. This allows the transfer layer to serve as a support for the paint layer when the paint layer is attached to the adherend. The method for peeling off the transfer layer is not particularly limited, and it may be peeled off using a peeling device or by hand. The transfer layer may be peeled off at room temperature or a temperature around that temperature (approximately 15 to 35°C), or it may be peeled off after the paint layer has cooled.

[0088] The laminate sheet of one embodiment of the present invention may be preformed by vacuum forming, press forming, compressed air forming, or the like to a shape corresponding to the shape of the adherend, and then bonded to the adherend. Preforming may be performed before or after peeling the substrate from the paint layer of the laminate sheet. Preforming allows the laminate sheet to be easily adhered to the adherend, even if the adherend has a complex shape. Among the above methods, preforming is preferably performed by vacuum forming. Preforming may involve pressing the laminate sheet against a jig or mold by vacuum forming, and stretching the laminate sheet using the jig or mold to form a shape corresponding to the surface shape of the adherend. Here, the vacuum forming is preferably TOM forming. TOM stands for "Three Dimension Overlay Method," and applying TOM forming allows for forming into complex shapes.

[0089] The adherend to which the laminate sheet of the present invention can be attached is not particularly limited, but includes vehicle interior materials such as electrical appliances, automobiles, and railroad vehicle interior materials; vehicle exterior materials such as automobiles and railroad vehicle exterior materials; exterior materials for miscellaneous goods, heavy machinery, ships, and aircraft; exterior wall or roof materials for houses and buildings; bridges, steel frames, plants, wind power generation blades, and the like. Among these, vehicle exterior materials such as automobile exterior materials are preferred. Examples of vehicle exterior materials include hoods, roofs, door panels, bumpers, fuel filler panels, trunk lids, and rear gates. When attached to vehicle exterior materials, the laminate sheet of the present invention may be attached to an exterior material attached to the vehicle body, or to an exterior material before attachment to the vehicle body. The material of the adherend is also not particularly limited, but may be any of resin materials, inorganic materials such as ceramics, and metal materials such as steel, with metal materials such as steel being preferred. Metallic materials such as steel are difficult to paint at the same time as molding the adherend using insert molding, and painting with a resin sheet is difficult, but by using the laminated sheet of the present invention, such materials can be easily painted.

[0090] [Vehicle] The vehicle of the present invention is painted using the laminate sheet of the present invention. As described above, by using the laminate sheet of the present invention, it is possible to prevent peeling traces from remaining on the paint layer when the transfer layer is peeled off and the paint layer is transferred to the adherend, and it is also possible to prevent wrinkles from occurring in the laminate sheet when the laminate sheet is attached to the adherend. Therefore, the vehicle of the present invention can have a painted surface that is free of peeling traces and wrinkles.

[0091] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0092] The measurement and evaluation methods in this example are as follows. (Bending resistance) The transfer layer was cut into strips measuring 20 mm wide x 200 mm long to prepare sample pieces. The bending resistance was measured based on bending resistance method A (45° cantilever method) described in JIS L 1084, and the minimum value was taken as the measured value. The measurement limit of the device was 150 mm, and values ​​exceeding this were recorded as "150<".

[0093] (Elastic modulus) The laminated sheet was bonded to a 50 μm thick polyethylene terephthalate film, and then the transfer layer was peeled off. The elastic modulus was measured from the first resin layer side of the paint layer using a nanoindenter. A "TI950" manufactured by Hysitron was used as the nanoindenter, and a Berkovich diamond indenter was attached. The indenter was pressed into the paint layer surface at a speed of 200 nm / sec for 5 seconds, and then the indenter was unloaded for 5 seconds to measure the elastic modulus. The elastic modulus measurement was performed at room temperature (25 ° C.).

[0094] (Remaining Peeling Traces) The laminate sheets of the Examples and Comparative Examples were cut to 50 mm x 50 mm and attached to a coated steel plate using a squeegee and water containing 0.5% surfactant. The transfer layer was then peeled off to transfer the paint layer to the coated steel plate. The appearance of the surface of the paint layer (the surface of the first resin layer) after peeling off the transfer layer was observed, and the laminate sheets of the Examples and Comparative Examples were evaluated according to the following evaluation criteria. <Evaluation Criteria> A: The transfer layer was easy to peel off, and there were no rough spots or linear peeling traces on the surface of the first resin layer after peeling off the transfer layer. B: The transfer layer was easy to peel off, and there were dot-like peeling traces on the surface of the first resin layer after peeling off the transfer layer, but no rough spots or linear peeling traces. C: The transfer layer was difficult to peel off, and there were no linear peeling traces on the surface of the first resin layer after peeling off the transfer layer. D: Rough spots or linear peeling traces were observed on the surface of the first resin layer after peeling off the transfer layer.

[0095] (Evaluation of Adhesion) The laminate sheets of the Examples and Comparative Examples were cut to 50 mm x 100 mm and attached to a coated steel plate using a squeegee and water containing 0.5% surfactant, and the laminate sheets of the Examples and Comparative Examples were evaluated according to the following evaluation criteria. <Evaluation criteria> A: No wrinkles were observed in the laminate sheet that was attached to the coated steel plate even once out of 10 times. B: Wrinkles were observed in the laminate sheet that was attached to the coated steel plate once or more out of 10 times.

[0096] (Evaluation of Conformability) Adherends having a 10 mm step and an adherend having a curved surface with R = 150 mm were prepared, and the laminate sheets of the Examples and Comparative Examples were attached to these adherends, and the laminate sheets of the Examples and Comparative Examples were evaluated according to the following evaluation criteria. <Evaluation criteria> A: The laminate sheet was able to conform to the 10 mm step. B: The laminate sheet was unable to conform to the 10 mm step, but was able to conform to the curved surface with R = 150 mm. C: The laminate sheet was unable to conform to the 10 mm step, and was unable to conform to the curved surface with R = 150 mm.

[0097] The components of the film for transfer layer, the film for substrate, and the resin layer used in the examples and comparative examples are as follows.<Film for transfer layer> Film A: polyethylene terephthalate film, "NS Separator MXA" manufactured by Nakamoto Pax Co., Ltd., thickness 75 μm, with release treatment using a silicone-based release agent Film B: polyethylene terephthalate film, "NS Separator MXA" manufactured by Nakamoto Pax Co., Ltd., thickness 50 μm, with release treatment using a silicone-based release agent Film C: polyethylene terephthalate film, "NS Separator MXA" manufactured by Nakamoto Pax Co., Ltd., thickness 25 μm, with release treatment using a silicone-based release agent Film D: polyethylene terephthalate film, "NS-38-F-100N" manufactured by Nakamoto Pax Co., Ltd., thickness 38 μm, with release treatment using a silicone-based release agent Film E: polypropylene / EVA / polypropylene multilayer film, "Convenience store film PP type transparent" manufactured by Okamoto Corporation, thickness 100 μm, without release treatment Film F: Polypropylene / EVA / polypropylene multilayer film, Okamoto Corporation's "Convenience Store Film PP Type Transparent", thickness 300 μm, no release treatment. Film G: Polyethylene / EVA / polyethylene multilayer film, Okamoto Corporation's "Convenience Store Film PE Type Transparent", thickness 100 μm, no release treatment. Film H: Polyethylene terephthalate film, Nippa Corporation's "Q2-ASI5", thickness 50 μm, with release treatment using a silicone-based release agent. Film I: Polyethylene terephthalate film, Nippa Corporation's "NM-ASI5", thickness 50 μm, with release treatment using a silicone-based release agent. Film J: Unstretched polyethylene terephthalate film, amorphous, Nakamoto Pax Co., Ltd.'s "A-PET-MXA", thickness 100 μm, with release treatment using a silicone-based release agent. Film K: Unstretched polyethylene terephthalate film, amorphous, "A-PET-MXA" manufactured by Nakamoto Pax Co., Ltd., thickness 200 μm, released with a silicone-based release agent. Film L: Polyethylene terephthalate film, "NS Separator MXA" manufactured by Nakamoto Pax Co., Ltd., thickness 12 μm, released with a silicone-based release agent. Film M: Unstretched polyethylene terephthalate film, amorphous, "A-PET-AU" manufactured by Nakamoto Pax Co., Ltd., thickness 400 μm, released with a silicone-based release agent.

[0098] <Film for base layer> Polyethylene terephthalate film, "Q2-ASI5" manufactured by Nippa Corporation, thickness 50 μm, release-treated with a silicone-based release agent

[0099] <Polymer Components> Acrylic polyol resin (1): weight average molecular weight 290,000, hydroxyl value 80 mg KOH / g, glass transition temperature 20°C, solid content (NV) = 30 mass% (solvent: ethyl acetate, etc.) Acrylic polyol resin (2): weight average molecular weight 250,000, hydroxyl value 80 mg KOH / g, glass transition temperature 40°C, solid content (NV) = 30 mass% (solvent: ethyl acetate, etc.) Acrylic polyol resin (3): weight average molecular weight 250,000, hydroxyl value 150 mg KOH / g, glass transition temperature 40°C, solid content (NV) = 30 mass% (solvent: ethyl acetate, etc.) Acrylic polyol resin (4): weight average molecular weight 260,000, hydroxyl value 110 mg KOH / g, glass transition temperature 60°C, solid content (NV) = 30 mass% (solvent: ethyl acetate, etc.) Acrylic polyol resin (5): weight average molecular weight 220,000, hydroxyl value 110 mgKOH / g, glass transition temperature 80°C, solid content (NV) = 25 mass% (solvent: ethyl acetate, etc.)

[0100] <Plasticized Resin> Polycarbonate diol, average molecular weight 500, "ETERNACOLL PH-50" manufactured by UBE Corporation, hydroxyl value 224 mg KOH / mg, solid content (NV) = 100% by mass

[0101] <Pigment (colorant)> "NSP-UP 841B" manufactured by Nikko Bix Co., Ltd., effective pigment concentration = 9 mass%, solid content concentration (NV) = 24 mass% <Glittering material (colorant)> "Xirallic T60-10 WNT Crystal Silver" manufactured by Merck

[0102] <Heat-reactive isocyanates> Hexamethylene diisocyanate-based blocked isocyanate (HDI-based), blocking agent type: 3,5-dimethylpyrazole (DMP), solid content (NV) = 70%, solvent: ethyl acetate

[0103] The components used in the moisture-curable resin composition were as follows. Urethane prepolymer: trade name "Acrylt 8PU-4015N", manufactured by Taisei Fine Chemical Co., Ltd., molecular weight 50,000 Polyisocyanate (1): trade name "Takenate D-140N", manufactured by Mitsui Chemicals, Inc., isophorone diisocyanate adduct, molecular weight 640 Polyisocyanate (2): trade name "Desmodur N3200A", manufactured by Covestro, HDI biuret, molecular weight 480 Pigment (colorant): "NSP-UP 841B" manufactured by Nikko Bix Co., Ltd., effective pigment concentration = 9 mass%, solid content concentration (NV) = 24 mass% Brilliant material (colorant): "Xirallic T60-10 WNT Crystal Silver" manufactured by Merck

[0104] [Preparation of Thermosetting Resin Compositions A to G] Each component was added in the proportions shown in Table 1, and ethyl acetate was added as a solvent to prepare coating materials of thermosetting resin compositions A to G so that the solid content concentration was 30 mass %.

[0105] [Preparation of Moisture-Curable Resin Compositions H to J] Each component was blended to obtain the solid content shown in Table 5, and ethyl acetate was added as a solvent to prepare coating materials of moisture-curable resin compositions H to J so that the solid content concentration was 30 mass%.

[0106] [Example 1] Thermosetting resin composition D was applied to the surface of film B for the transfer layer using an applicator, followed by a pre-drying process at a drying temperature of 60°C for 20 minutes, followed by a main drying process at a drying temperature of 80°C for 5 minutes, forming a first resin layer with a thickness of 30 μm on the transfer layer. Next, thermosetting resin composition G was applied to the surface of film for the substrate using an applicator, followed by a pre-drying process at a drying temperature of 60°C for 30 minutes, followed by a main drying process at a drying temperature of 80°C for 5 minutes, forming a second resin layer with a thickness of 30 μm on the substrate. The first resin layer on the transfer layer and the second resin layer on the substrate were bonded together and laminated at 25°C to obtain a laminate sheet in which the transfer layer, first resin layer, second resin layer, and substrate were laminated in this order. The obtained laminate sheet was used for the above evaluations. The evaluation results are shown in Table 2.

[0107] Examples 2 to 20, Comparative Examples 1 to 4 The same procedures as in Example 1 were carried out, except that the transfer layer film used for the transfer layer was changed as shown in Tables 2 to 4, and the compositions of the thermosetting resin composition and moisture-curable resin composition were changed as shown in Tables 1 and 5. The evaluation results are shown in Tables 2 to 4 and 6.

[0108] *Table 1 shows the amount of each component in thermosetting resin compositions A to G based on solid content, with the total solid content of the acrylic polymer component, plasticizing resin, and heat-reactive isocyanates taken as 100 parts by mass. *The amount of active ingredient in the pigment is the value in Table 1 multiplied by 9 / 24.

[0109]

[0110]

[0111]

[0112] *Table 1 shows the amount of each component in moisture-curing resin compositions H to J based on solid content, with the total solid content of urethane prepolymer, polyisocyanate (1), and polyisocyanate (2) being 100 parts by mass. *The amount of active ingredient of the pigment is the value in Table 1 multiplied by 9 / 24.

[0113]

[0114] By comparing Examples 1 to 20 and Comparative Examples 1 to 4, it was found that when the transfer layer has a bending resistance of 20 to 120 mm, it is possible to prevent peeling traces from remaining on the paint layer when the transfer layer is peeled off and the paint layer is transferred to the adherend. Furthermore, it was also found that when the transfer layer has a bending resistance of 20 to 120 mm, it is possible to prevent wrinkles from forming on the laminate sheet when the laminate sheet is attached to the adherend.

[0115] REFERENCE SIGNS LIST 1, 1A to 1C laminated sheet 10 transfer layer 20, 20A, 20B paint layer 21 first resin layer 22 second resin layer 23 other resin layer 30 substrate

Claims

1. A laminated sheet having a transfer layer and a coating layer made of a thermosetting resin composition or a moisture-curable resin composition, wherein the bending resistance of the transfer layer is 20 to 120 mm.

2. The laminate sheet according to claim 1, wherein the elastic modulus of the paint layer measured from the transfer layer side is 1.0 to 1500 MPa.

3. The laminate sheet according to claim 1 or 2, wherein the thermosetting resin composition contains a polymer component having a functional group reactive to an isocyanate group and a heat-reactive isocyanate.

4. The laminate sheet according to claim 3, wherein the polymer component having a functional group reactive with an isocyanate group has a hydroxyl group.

5. A thermosetting resin sheet according to claim 3 or 4, wherein the polymer component having a functional group reactive to an isocyanate group is at least one resin selected from the group consisting of (meth)acrylic resins, polycarbonate resins, polyester resins, and epoxy resins.

6. The laminate sheet according to any one of claims 3 to 5, wherein the weight average molecular weight of each of the polymer components having a functional group reactive to an isocyanate group is 50,000 or more and 1,000,000 or less.

7. A laminate sheet described in any one of claims 3 to 6, wherein the content of a polymer component having a functional group reactive to an isocyanate group in the thermosetting resin composition is 20% by mass or more and 90% by mass or less.

8. A laminate sheet according to any one of claims 1 to 7, wherein the paint layer has a first resin layer made of a first thermosetting resin composition and a second resin layer made of a second thermosetting resin composition, the first thermosetting resin composition contains a first polymer component having a functional group reactive to an isocyanate group and a first heat-reactive isocyanate, and the second thermosetting resin composition contains a second polymer component having a functional group reactive to an isocyanate group, a second heat-reactive isocyanate, and a colorant.

9. The laminate sheet according to claim 8, wherein the content of the first thermally reactive isocyanate in the thermosetting resin composition is 10% by mass or more and 70% by mass or less.

10. The laminate sheet according to claim 1, wherein the moisture-curable resin composition contains a resin containing an isocyanate group.

11. The laminate sheet according to claim 1 or 10, wherein the moisture-curable resin composition contains a polymer having a weight-average molecular weight of 20,000 or more and 1,000,000 or less.

12. The laminate sheet according to any one of claims 1 to 11, wherein the thickness of the transfer layer is from 10 µm to 1,000 µm.

13. A vehicle coated with the laminate sheet according to any one of claims 1 to 12.

14. A method for using a laminate sheet according to any one of claims 1 to 12, comprising attaching the laminate sheet to an adherend.

15. A method for producing a laminate sheet in which a paint layer is made of a thermosetting resin composition and the paint layer has a first resin layer and a second resin layer, comprising the steps of: applying a first paint containing a first thermosetting resin composition containing a first polymer component and a thermoreactive isocyanate to a transfer layer and drying the paint to produce a first laminate comprising the transfer layer and the first resin layer provided on the transfer layer and made of the first thermosetting resin composition; applying a second paint containing a second thermosetting resin composition containing a second polymer component, a second thermoreactive isocyanate, and a colorant to a substrate and drying the paint to produce a second laminate comprising the substrate and the second resin layer provided on the substrate and made of the second thermosetting resin composition; and laminating the first laminate and the second laminate together so that the first resin layer and the second resin layer face each other.

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