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

Abstract

A laminated sheet (1) according to the present invention has a transfer layer (10) and a coating layer (20) formed from a thermosetting resin composition or a moisture-curable resin composition, the transfer layer having a stiffness of 20-120 mm. A vehicle according to the present invention is obtained by coating the laminated sheet according to the present invention. According to the present invention, it is possible to provide a laminated sheet in which peeling marks can be prevented from remaining on a coating layer when a transfer layer is peeled and the coating layer is transferred to an adherend, and wrinkles can be prevented from occurring in the laminated sheet when the laminated sheet is attached to the adherend.

Description

Technical Field

[0001] This invention relates to a laminate for coating, a vehicle coated using the laminate, a method of using the laminate, and a method of manufacturing the laminate. Background Technology

[0002] Traditionally, coatings have been used to impart aesthetic appeal, durability, weather resistance, and scratch resistance to various products such as furniture, steel sheets, and vehicle bodies. Industrial coating of three-dimensional products is typically performed using air or electrostatic spraying. However, considering the losses during spraying, CO2 emissions from factories, and the large-scale equipment investment involved, research has recently been conducted on a shift towards resin film finishing techniques.

[0003] Decorative technology refers to the technique of applying resin films (decorative films) printed with text or patterns using white, black, or colored inks to the surface of products in various fields such as household appliances, automotive interiors, and general merchandise, thereby achieving high functionality and aesthetic design. For example, Patent Document 1 describes a thermosetting coating sheet as a decorative film. Before curing, this sheet exhibits excellent extensibility, flexibility, and workability. Furthermore, it demonstrates excellent dispersibility of pigments and other additives, is easy to manufacture, and during curing, it can form a uniform and highly rigid cured film through heat. Alternatively, a support layer can be provided on this thermosetting coating sheet. After the thermosetting coating sheet is applied to an article, the support layer is peeled off, and then the thermosetting coating sheet is cured.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 4-11680 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] By peeling off the support layer after attaching the thermosetting cover sheet to the substrate, the thermosetting cover sheet can be transferred onto the substrate, and the support layer can be used as a transfer layer. During the transfer of the thermosetting cover sheet to the substrate, the transfer layer needs to be peeled off to avoid damaging the surface of the thermosetting cover sheet. However, conventional thermosetting cover sheets have problems such as leaving peeling marks on the thermosetting cover sheet when peeling off the transfer layer, or wrinkles appearing on the thermosetting cover sheet when it is attached to the substrate.

[0009] Therefore, the objective of this invention is to provide a laminate, a vehicle coated using the laminate, a method of using the laminate, and a method of manufacturing the laminate, wherein when the laminate is peeled off to transfer the coating layer onto the substrate, peeling marks are suppressed from remaining on the coating layer, and wrinkles are suppressed from forming on the laminate when it is attached to the substrate.

[0010] Problem-solving methods

[0011] Through in-depth research, the inventors discovered that adjusting the stiffness and softness of the transfer layer can solve the aforementioned problems, thus completing this invention. The key points of this invention are as follows.

[0012] [1]. A laminate having a transfer layer and a coating layer formed of a thermosetting resin composition or a moisture-curing resin composition, wherein the stiffness of the transfer layer is 20 to 120 mm.

[0013] [2]. As described in [1] above, the elastic modulus of the coating layer measured from the transfer layer side is 1.0 to 1500 MPa.

[0014] [3]. As described in [1] or [2] above, the thermosetting resin composition contains a polymeric component having functional groups that are reactive to isocyanate groups and a thermo-reactive isocyanate.

[0015] [4]. As described in [3] above, the polymeric component having a functional group that is reactive to isocyanate groups has hydroxyl groups.

[0016] [5]. The thermosetting resin sheet as described in [3] or [4] above, wherein the polymeric component having a functional group that is reactive to isocyanate groups is at least one resin selected from (meth)acrylic resin, polycarbonate resin, polyester resin and epoxy resin.

[0017] [6]. The laminate as described in any one of [3] to [5] above, wherein the weight-average molecular weight of the polymeric component having a functional group that is reactive to isocyanate groups is 50,000 or more and 1,000,000 or less.

[0018] [7]. The laminate as described in any one of [3] to [6] above, wherein the content of the polymer component having a functional group that is reactive to isocyanate groups in the thermosetting resin composition is 20% by mass or more and 90% by mass or less.

[0019] [8]. The laminate as described in any one of [1] to [7] above, wherein the coating layer has a first resin layer formed of a first thermosetting resin composition and a second resin layer formed of a second thermosetting resin composition.

[0020] The first thermosetting resin composition contains a first polymeric component having functional groups reactive to isocyanate groups and a first thermoreactive isocyanate.

[0021] The second thermosetting resin composition contains a second polymeric component having functional groups reactive to isocyanate groups, a second thermally reactive isocyanate, and a colorant.

[0022] [9]. The laminated sheet as described in [8] above, 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.

[0023]

[10] . The laminate as described in [1] above, characterized in that the moisture-curing resin composition contains a resin having an isocyanate group.

[0024]

[11] . The laminate as described in [1] or

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

[0025]

[12] . The laminate as described in any one of [1] to

[11] above, wherein the thickness of the transfer layer is 10 μm or more and 1000 μm or less.

[0026]

[13] . A vehicle that is painted using any of the laminates described in any one of [1] to

[12] .

[0027]

[14] . A method of using a laminated sheet, wherein the laminated sheet described in any one of [1] to

[12] above is attached to the substrate for use.

[0028]

[15] . A method for manufacturing a laminated sheet, wherein the coating layer of the laminated sheet is formed of a thermosetting resin composition, the coating layer having a first resin layer and a second resin layer, the manufacturing method comprising the following steps:

[0029] The process of applying a first coating containing a first thermosetting resin composition onto a transfer layer and drying it to produce a first laminate having the transfer layer and the first resin layer formed of the first thermosetting resin composition disposed on the transfer layer, is described above.

[0030] The steps of applying a second coating containing a second thermosetting resin composition to a substrate and drying it, and fabricating a second laminate having the substrate and a second resin layer formed of the second thermosetting resin composition disposed on the substrate, and...

[0031] The process of bonding the first laminate and the second laminate together with the first resin layer and the second resin layer facing each other.

[0032] The first thermosetting resin composition contains a first polymeric component and a thermo-reactive isocyanate, and the second thermosetting resin composition contains a second polymeric component, a second thermo-reactive isocyanate, and a colorant.

[0033] Invention Effects

[0034] According to the present invention, a laminate can be provided that can suppress the presence of peeling marks on the coating layer when the coating layer is transferred to the substrate by peeling off the transfer layer, and can suppress the formation of wrinkles on the laminate when the laminate is attached to the substrate. Furthermore, a vehicle painted using the laminate, a method of using the laminate, and a method of manufacturing the laminate are also provided. Attached Figure Description

[0035] Figure 1 This is a schematic cross-sectional view of a laminated sheet according to one embodiment of the present invention.

[0036] Figure 2 This is a schematic cross-sectional view of a laminated sheet according to another embodiment of the present invention.

[0037] Figure 3 This is a schematic cross-sectional view of a laminated sheet according to another embodiment of the present invention.

[0038] Figure 4 This is a schematic cross-sectional view of a laminated sheet according to another embodiment of the present invention. Detailed Implementation

[0039] [Thermosetting resin sheets]

[0040] A laminated sheet according to one embodiment of the present invention will be described with reference to the accompanying drawings. Figure 1 As shown, in one embodiment of the present invention, the laminate 1 has a transfer layer 10 and a coating layer 20 in sequence.

[0041] (Transfer layer)

[0042] In one embodiment of the present invention, the stiffness of the transfer layer 10 in the laminate 1 is 20 to 120 mm. If the stiffness of the transfer layer 10 is less than 20 mm, wrinkles may sometimes occur in the laminate 1 when it is attached to the substrate. Furthermore, if the stiffness of the transfer layer 10 is less than 20 mm, when pressing the laminate from above with a rubber roller (squeegee) or similar device, the pressure is concentrated on the area acted upon by the rubber roller, sometimes causing twisting on the laminate. If it is discontinuously attached to the substrate in such a twisted state, there is a risk of wrinkles. Additionally, if the stiffness of the transfer layer 10 is greater than 120 mm, peeling marks may sometimes remain on the coating layer 20 when the transfer layer 10 is peeled off and the coating layer 20 is transferred to the substrate. From this perspective, the stiffness of the transfer layer 10 in the laminate 1 of one embodiment of the present invention is preferably 30-110 mm, more preferably 40-100 mm, further preferably 50-90 mm, and even more preferably 60-80 mm. The stiffness of the transfer layer 10 can be measured by the method described in the embodiments described later. The stiffness 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 of the resin film constituting the transfer layer 10, the crystallinity, etc. More specifically, as the material of the transfer layer 10, the higher the glass transition temperature (Tg), the more the stiffness can be improved. In addition, the stiffness of the transfer layer can also be improved 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 stiffness can be adjusted by increasing the thickness, stretching ratio, crystallinity, etc.

[0043] The transfer layer 10 is a component that protects the coating layer 20 from damage and foreign matter adhesion. Furthermore, as described later, the transfer layer 10 serves as a support when the coating layer 20 is attached to the substrate, typically as a support when the coating layer 20 of the laminate 1 is transferred to the substrate. The transfer layer 10 is preferably formed of a resin film. Thermoplastic resins can be listed as resins used in resin films.

[0044] Specifically, resins used in resin films can include cyclic polyolefin resins, polyethylene resins, polypropylene resins, ethylene-vinyl acetate copolymer resins, polymethylpentene resins, polystyrene resins, and other polyolefin resins; polyester resins such as polybutylene terephthalate and polyethylene terephthalate; polyamide resins, polycarbonate resins, polyimide resins, polyarylate resins, acrylic resins, fluorine resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl alcohol resins, polyvinyl butyral resins, nylon resins, polyetheretherketone resins, polysulfone resins, polyethersulfone resins, and tetrafluoroethylene resins. From the perspective of following suit (described later), polyolefin resins are preferred; from the perspective of easily improving rigidity and flexibility, polyester resins are preferred.

[0045] In addition, polyethylene resin, polypropylene resin, and ethylene-vinyl acetate copolymer resin are preferred as polyolefin resins, and polyethylene terephthalate is preferred as polyester resins.

[0046] The resin film can be a single-layer film consisting of one 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 can be a single type or a combination of two or more types. When using two or more resins, different types of resins can be used in each layer to form a multilayer film. Alternatively, a single-layer film can be formed by mixing two or more resins, or one or more layers of a multilayer film can be formed.

[0047] Among multilayer films, examples include multilayer films composed of layers made of cyclic polyolefin resin or polyolefin resin and layers made of polyester resin, and multilayer films in which polyester resin layers, polyolefin resin layers and polyester resin layers are stacked sequentially.

[0048] In addition, as a multilayer film, it can also be a multilayer film in which each layer is composed of polyolefin resin. Specifically, examples include multilayer films composed of polyethylene resin, ethylene-vinyl acetate copolymer resin and polyethylene resin stacked in sequence, and multilayer films composed of polypropylene resin, ethylene-vinyl acetate copolymer resin and polypropylene resin stacked in sequence.

[0049] In addition to resin, each layer in transfer layer 10 may also contain additives. Known additives that are blended into the resin film can be used as additives. Specific additives include crystallizing nucleating agents, fluorescent whitening agents, antioxidants, stabilizers, ultraviolet absorbers, surfactants, lubricants, fillers, crosslinking agents, crosslinking accelerators, antistatic agents, flame retardants, dispersants, pigments, dyes, and processing aids.

[0050] The resin film can be a stretched resin film or an unstretched resin film, but an unstretched resin film is preferred. Therefore, an unstretched polyester film is preferred as the resin film, and an unstretched polyethylene terephthalate film is more preferred. In addition, the unstretched resin film can also be a multilayer film, for example, as described above, it can also be a multilayer film having a polyolefin resin layer in addition to a polyester resin layer.

[0051] The transfer layer 10 can also be formed by demolding at least one surface with a release agent such as a siloxane-based release agent or a fluorine-based release agent. When the transfer layer 10 is demolded, it is preferable that the demolded surface forms the coating layer side. Demolding the transfer layer 10 facilitates good peelability from the coating layer 20. However, if the transfer layer 10 can be peeled from the coating layer 20, demolding may not be necessary.

[0052] There is no particular limitation on the thickness of the transfer layer 10, for example, it is 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.

[0053] (Coating layer)

[0054] The coating layer used in this invention is formed from a thermosetting resin composition capable of curing by heat. The curable resin composition may contain a polymeric component having functional groups that allow the resin to cure itself by heat or to cure by reacting with a curing agent. Examples of the polymeric component used in the thermosetting resin composition include curable resins, specifically (meth)acrylic resins, polycarbonate resins, polyester resins, and epoxy resins, with (meth)acrylic resins being preferred. As a coating layer, by reducing the tack value, it is difficult to adhere discontinuously to the substrate, and wrinkles are less likely to occur. However, if the tack value is too low, it cannot be pressed onto the substrate; therefore, the tack value needs to be within an appropriate range.

[0055] Thermosetting resin compositions preferably contain heat-reactive isocyanates as curing agents. Heat-reactive isocyanates are compounds having isocyanate groups, as detailed below. Because the thermosetting resin composition contains heat-reactive isocyanates, it can be easily cured by heat.

[0056] Furthermore, the thermosetting resin composition may contain functional groups that are reactive to the isocyanate groups contained in the curing agent. Specifically, examples include hydroxyl, amino, and carboxyl groups, with hydroxyl groups being preferred. Functional groups reactive to isocyanate groups are typically found in polymer components.

[0057] The weight-average molecular weight of the polymer component (hereinafter sometimes simply referred to as "polymer component") having functional groups reactive to isocyanate groups 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, it is easier to achieve a good balance in the coatability, curing properties, tack, and elongation of the coating layer. In addition, it is possible to properly maintain the laminated sheet with the coating layer in a sheet shape. From this point of view, the weight-average molecular weight of the polymer component is more preferably 80,000 or more and 800,000 or less, 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 addition, the weight-average molecular weight in this specification is determined by gel permeation chromatography (GPC) and is obtained as a conversion value for standard polystyrene.

[0058] (Elastic modulus)

[0059] Regarding the laminate, the elastic modulus of the coating layer, measured from the transfer layer side, is preferably 1.0 to 1500 MPa. If the elastic modulus of the coating layer, measured from the transfer layer side, is 1.0 to 1500 MPa, then when the transfer layer is peeled off and transferred to the substrate, residual peeling marks on the coating layer can be further suppressed, and the conformability to the substrate surface becomes better. From this viewpoint, the elastic modulus of the coating layer, measured from the transfer layer side, is more preferably 5.0 to 1000 MPa, more preferably 10 to 600 MPa, and even more preferably 100 to 250 MPa. The elastic modulus of the coating layer, measured from the transfer layer side, is the elastic modulus measured using a nanoindenter; specifically, it can be measured using the method described in the examples below.

[0060] The elastic modulus of the coating layer, measured from the transfer layer side, can be adjusted by factors such as the glass transition temperature, hydroxyl value and content of the polymer components in the thermosetting resin composition constituting the coating layer, the hydroxyl value and content of the plasticizer, and the thickness of the coating layer. Furthermore, since the elastic modulus is greatly influenced by the resin layer in contact with the transfer layer (i.e., the first resin layer described later), it can be easily adjusted by appropriately changing the polymer components or plasticizer of the first resin layer.

[0061] The laminate 1 of one embodiment of the present invention is a preferred embodiment of the laminate 1 of the present invention. Furthermore, the laminate 1 of one embodiment of the present invention is an example of the laminate 1 of the present invention and is not limited to the laminate 1 of the present invention. The laminate 1 of the preferred embodiment of the present invention has first and second resin layers 21, 22, and the resin layer (second resin layer 22) on the side opposite to the transfer layer 10 side becomes a coloring layer. Hereinafter, the laminate 1 of the preferred embodiment of the present invention will be described in detail.

[0062] The laminate 1 of the preferred embodiment of the present invention has, starting from the transfer layer 10 side, a first resin layer 21 formed of a first thermosetting resin composition and a second resin layer 22 formed of a second thermosetting resin composition, wherein the second resin layer 22 is a coloring layer.

[0063] (Thermosetting resin composition)

[0064] The first thermosetting resin composition contains a first polymeric component, and the second thermosetting resin composition contains a second polymeric component. Furthermore, the first polymeric component in the first thermosetting resin composition and the second polymeric component in the second thermosetting resin composition may be the same or different.

[0065] <Polymer Components>

[0066] As described above, the first and second polymeric components can be selected from (meth)acrylic resins, polycarbonate resins, polyester resins, and epoxy resins, but (meth)acrylic resins are preferred. Furthermore, the first and second polymeric components may contain functional groups reactive to the functional groups (isocyanate groups) found in thermally reactive isocyanates; specifically, hydroxyl, amino, and carboxyl groups are examples, with hydroxyl groups being preferred. The first and second polymeric components may have one hydroxyl group, but two or more are preferred. Therefore, both the first and second polymeric components are preferably (meth)acrylic polyol resins.

[0067] Furthermore, the weight-average molecular weights of the first and second polymeric components are as described above. The weight-average molecular weights of the first and second polymeric components may be the same or different.

[0068] The glass transition temperature (Tg) of the first polymer component is, for example, 20–100°C, preferably 30–90°C, more preferably 40–80°C, and even more preferably 50–70°C. By keeping the glass transition temperature (Tg) of the first polymer component within the above range, the elastic modulus of the transfer layer side of the coating layer can be easily adjusted to the desired range.

[0069] On the other hand, there is no particular limitation on the glass transition temperature of the second polymer component, for example, it is -50 to 80°C, preferably -20 to 60°C, and more preferably 10 to 50°C.

[0070] In addition, in this specification, the glass transition temperature is a value determined by differential scanning calorimetry (DSC) according to JIS K 7121.

[0071] The hydroxyl value of the first polymer component is preferably 20 mg KOH / g or more and 200 mg KOH / g or less, more preferably 60 mg KOH / g or more and 180 mg KOH / g or less, and even more preferably 100 mg KOH / g or more and 150 mg KOH / g or less. By ensuring the hydroxyl value of the first polymer component is within the above range, good curing properties are achieved, making it easy for the coating layer to form a high-hardness layer after curing. On the other hand, the hydroxyl value of the second polymer component is preferably 20 mg KOH / g or more and 200 mg KOH / g or less, more preferably 50 mg KOH / g or more and 160 mg KOH / g or less, and even more preferably 80 mg KOH / g or more and 110 mg KOH / g or less. By ensuring the hydroxyl value of the second polymer component is within the above range, good adhesion to the coated board is achieved, making it easy for the coating layer to achieve a high-density bond after curing.

[0072] Furthermore, when the first thermosetting resin composition and the second thermosetting resin composition contain multiple polymeric components, the hydroxyl value of the first polymeric component and the hydroxyl value of the second polymeric component are the weighted average of the hydroxyl values ​​of the polymeric components contained in their respective thermosetting resin compositions. For example, if two polymeric components (d1) and (d2) are used as polymeric components, and the hydroxyl value of polymeric component (d1) is denoted as X1, the mixing ratio of polymeric component (d1) is denoted as m1, the hydroxyl value of polymeric component (d2) is denoted as X2, and the mixing ratio of polymeric component (d2) is denoted as m2, then the weighted average of the hydroxyl values ​​is expressed by the following formula. Additionally, the mixing ratio is based on mass.

[0073] The weighted average of hydroxyl values ​​(mgKOH / g) = X1 × (m1 / (m1+m2)) + X2 × (m2 / (m1+m2))

[0074] In addition, the hydroxyl value can be determined according to JISK1557-1:2007.

[0075] (Meth)acrylic resins are preferably acrylic polymers obtained by polymerizing a mixture of monomers containing "(meth)acrylate monomers" and "monomers containing functional groups having hydroxyl groups". Such alkyl polymers can incorporate hydroxyl groups into the acrylic polymer using hydroxyl-containing monomers. Furthermore, (meth)acrylic acid refers to methacrylic acid or acrylic acid, and other similar terms are also acceptable.

[0076] As for the aforementioned (meth)acrylate monomers, examples of (meth)acrylate monomers without functional groups include, for example, (meth)acrylate alkyl esters with an alkyl group having 1 or more and about 18 carbon atoms, such as (meth)acrylate methyl acrylate and (meth)acrylate ethyl acrylate; (meth)acrylates with aromatic rings, such as (meth)acrylate 2-ethoxyethyl acrylate; and so on.

[0077] As for the aforementioned hydroxyl-containing monomers, there are no particular limitations; examples include (meth)acrylate monomers with hydroxyl groups, such as 2-hydroxyethyl (meth)acrylate.

[0078] Furthermore, the monomer mixture may contain monomers other than the aforementioned (meth)acrylate monomers and hydroxyl-containing monomers, such as monomers containing functional groups other than hydroxyl groups, styrene derivative monomers, etc. In addition to hydroxyl-containing monomers, by using monomers containing functional groups other than hydroxyl groups, such as amino groups and carboxyl groups, functional groups other than hydroxyl groups can be introduced into (meth)acrylate resins. There are no particular limitations on amino-containing monomers; examples include (meth)acrylate monomers containing amino groups, such as 2-aminoethyl (meth)acrylate. There are no particular limitations on carboxyl-containing monomers; examples include (meth)acrylic acid.

[0079] As monomers of styrene derivatives, there are no particular limitations, and examples include styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-ethoxystyrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, etc.

[0080] Alternatively, copolymers obtained by block or graft polymerization of the aforementioned acrylic polymer with other monomers or polymers can also be used as (meth)acrylic resins. Examples of other monomers or polymers include acrylic, styrene, maleic acid, imide, siloxane, and fluorine monomers or polymers of these monomers. Furthermore, a (meth)acrylyl group-containing compound having reactive groups capable of reacting with the functional groups and (meth)acrylyl groups can be reacted onto the functional groups of an acrylic polymer obtained by polymerizing a mixture of (meth)acrylic ester monomers and functional group-containing monomers, thereby containing (meth)acrylyl groups in the acrylic polymer.

[0081] The content of the first polymeric component in the first thermosetting resin composition and the content of the second polymeric component in the second thermosetting resin composition are 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. Furthermore, the content of the first polymeric component in the first thermosetting resin composition may be the same as or different from the content of the second polymeric component in the second thermosetting resin composition.

[0082] In addition, thermosetting resin compositions may sometimes be diluted with volatile components such as solvents, as described below. However, in this specification, the content (mass%) of each component in the thermosetting resin composition refers to the value based on the solid content after removing volatile components.

[0083] To the extent that it does not impair the effects of the present invention, when the first thermosetting resin composition uses a (meth)acrylic resin as the first polymer component, it may also contain a thermosetting resin other than a (meth)acrylic resin; similarly, when the second thermosetting resin composition uses a (meth)acrylic resin as the second polymer component, it may also contain a thermosetting resin other than a (meth)acrylic resin. Examples of thermosetting resins other than (meth)acrylic resins include, for example, polycarbonate resins, polyester resins, and epoxy resins. These thermosetting resins may be used alone or in combination of two or more.

[0084] <Thermoreactive Isocyanates>

[0085] Preferably, the first thermosetting resin composition contains a heat-reactive isocyanate (hereinafter sometimes referred to as the first heat-reactive isocyanate), and the second thermosetting resin composition contains a heat-reactive isocyanate (hereinafter sometimes referred to as the second heat-reactive isocyanate).

[0086] As a thermally reactive isocyanate, known isocyanate compounds used as curing agents can be used, but terminal isocyanates are preferred. Terminal isocyanates are compounds in which isocyanate groups are terminally capped by protecting groups. When exposed to high temperatures, the protecting groups (terminated portions) thermally dissociate and detach, and the resulting isocyanate groups undergo a curing reaction with the functional groups (typically hydroxyl groups) in the aforementioned polymer components.

[0087] End-capped isocyanates can be obtained, for example, by reacting an end-capping agent with an isocyanate compound having two or more isocyanate groups in one molecule.

[0088] There are no particular limitations on isocyanate compounds having two or more isocyanate groups in one of the above-mentioned molecule, and examples include toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, hydrogenated phenylene diisocyanate, and their modified forms.

[0089] Examples of capping agents include pyrazoles, phenols, oximes, lactams, and malonic acid esters.

[0090] Furthermore, one of the first and second thermally reactive isocyanates may be used alone, or two or more may be used in combination. Additionally, the first and second thermally reactive isocyanates may be the same or different.

[0091] The thermal dissociation temperatures of both the first and second thermally reactive isocyanates are preferably below 180°C. Thermal dissociation temperature refers to the temperature at which the thermally reactive isocyanate dissociates to form isocyanate groups. If the thermal dissociation temperatures of both the first and second thermally reactive isocyanates are below 180°C, the thermosetting resin sheet can be cured at a relatively low temperature, which is therefore preferable. From the viewpoint of curing the coating layer at a low temperature, the thermal dissociation temperatures of both the first and second thermally reactive isocyanates are more preferably below 160°C, and even more preferably below 140°C. Furthermore, from the viewpoint of the storage stability of the thermosetting resin sheet, the thermal dissociation temperatures of both the first and second thermally reactive isocyanates are preferably above 40°C, and more preferably above 60°C. In addition, the thermal dissociation temperature can be determined, for example, by mixing the capped isocyanate with an equivalent amount of a resin, such as a polymer component, that is highly reactive to isocyanate, and stirring at a specified temperature for 6 hours, followed by an evaluation of the gel fraction.

[0092] The content of the first thermoreactive isocyanate in the first thermosetting resin composition and the content of the second thermosetting resin composition can be adjusted such that, relative to the number of isocyanate groups in the thermosetting resin, the number of functional groups in the thermosetting resin is preferably 0.4 or more and 1.8 or less, more preferably 0.6 or more and 1.5 or less.

[0093] The content of the first thermoreactive isocyanate in the first thermosetting resin composition and the content of the second thermosetting resin composition are not particularly limited as long as the ratio of the number of functional groups to the number of isocyanate groups is within the above-mentioned range, but are 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 isocyanate in the first thermosetting resin composition may be the same as or different from the content of the second thermoreactive isocyanate in the second thermosetting resin composition.

[0094] <Plasticized Resin>

[0095] The first thermosetting resin composition is preferably a resin containing, in addition to (meth)acrylic resin (A1), a resin with a weight average molecular weight of less than 50,000 (hereinafter also referred to as plasticizing resin (A2)). The second thermosetting resin composition is also preferably a resin containing, in addition to (meth)acrylic resin (A1), a resin with a weight average molecular weight of less than 50,000 (hereinafter also referred to as plasticizing resin (A2)).

[0096] The first thermosetting resin composition, by containing a low weight-average molecular weight plasticizer (A2) in addition to a high molecular weight (meth)acrylic resin (A1), readily lowers the glass transition temperature of the first thermosetting resin composition. Furthermore, it readily achieves a good balance in the coating properties, curing properties, tackiness, and elongation of the first thermosetting resin composition. Similarly, the second thermosetting resin composition, by containing a low weight-average molecular weight plasticizer (A2) in addition to a high molecular weight (meth)acrylic resin (A1), readily lowers the glass transition temperature of the second thermosetting resin composition. Furthermore, it readily achieves a good balance in the coating properties, curing properties, tackiness, and elongation of the second thermosetting resin composition. Consequently, it can improve the wettability of the second thermosetting resin composition to the substrate and improve its adhesion to the substrate.

[0097] As the plasticizing resin (A2), the plasticizing resin (A2) is selected to be compatible with (meth)acrylic resin (A1), and is the same as (meth)acrylic resin (A1), preferably having functional groups that can be thermosetting. Examples of resins used as the plasticizing resin (A2) include (meth)acrylic resins, polycarbonate resins, polyester resins, and epoxy resins, with (meth)acrylic resins or polycarbonate resins being preferred.

[0098] As the (meth)acrylic resin used as the plasticizing resin (A2), oligomers having functional groups such as hydroxyl, amino, and carboxyl groups can be listed. As the (meth)acrylic resin used as the plasticizing resin (A2), a (meth)acrylic polyol having multiple hydroxyl groups, as described above, is preferably used. Additionally, poly(meth)acrylates having carboxyl groups are also preferred. Furthermore, polycarbonate polyols are preferred as the polycarbonate resin.

[0099] The weight-average molecular weight of the plasticizing 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.

[0100] The plasticizer (A2) is preferably a liquid at room temperature and pressure. The plasticizer (A2) may or may not have a glass transition temperature. If the plasticizer (A2) does have a glass transition temperature, there is no particular limitation on the glass transition temperature; it is preferably below 0°C, more preferably below -20°C, and even more preferably below -40°C. Furthermore, there is no particular limitation on the lower limit of the glass transition temperature; for example, it is above -120°C, preferably above -100°C.

[0101] By keeping the glass transition temperature of the plasticizer (A2) within the above range, it is easy to exhibit viscosity.

[0102] The hydroxyl value of the plasticizing resin (A2) is preferably 20 mg KOH / g or more and 350 mg KOH / g or less, more preferably 50 mg KOH / g or more and 300 mg KOH / g, and even more preferably 80 mg KOH / g or more and 250 mg KOH / g.

[0103] Furthermore, plasticizing resin (A2) is not limited to (meth)acrylic resins or polycarbonate resins; any short molecular weight component can be used as plasticizing resin (A2). Examples of plasticizing resins other than (meth)acrylic resins and polycarbonate resins include organic acid ester plasticizing resins such as monobasic and polybasic organic acid esters, phosphoric acid plasticizing resins such as organic phosphoric acid and organic phosphorous acid, and glycol plasticizing resins.

[0104] When the first thermosetting resin composition contains a plasticizer, the content of the plasticizer 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 a total of 100 parts by mass of the polymer, thermoreactive isocyanate, and plasticizer. For the coating layer, when the first thermosetting resin composition contains a plasticizer, by appropriately adjusting the content of the plasticizer in the first thermosetting resin composition, the elastic modulus of the coating layer measured from the transfer layer side can be easily adjusted to a desired range.

[0105] Furthermore, when the second thermosetting resin composition contains a plasticizer, the content of the plasticizer in the second thermosetting resin composition is preferably 1 part or more and 50 parts or less, more preferably 3 parts or more and 35 parts or less, and even more preferably 5 parts or more and 20 parts or less, relative to a total of 100 parts by mass of the polymer, the thermally reactive isocyanate and the plasticizer.

[0106] The plasticizer in the first thermosetting resin composition may be the same as or different from the plasticizer in the second thermosetting resin composition. Furthermore, the content of the plasticizer in the first thermosetting resin composition may be the same as or different from the content of the plasticizer in the second thermosetting resin composition.

[0107] <Coloring agent>

[0108] The second thermosetting resin composition preferably contains a colorant. By containing a colorant in the second thermosetting resin composition, the second resin layer can become a colored layer, improving the appearance of the coating layer 20. Examples of colorants include pigments, dyes, and gloss materials. Examples of pigments include: metal oxide pigments such as titanium dioxide and iron oxide; inorganic pigments such as carbon black, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white; azo pigments; quinacridone pigments; diketopyrrolopyrrole pigments; perylene pigments; perinone pigments; benzimidazolone pigments; vat pigments; isoindoline pigments; isoindolineone pigments; metal chelate azo pigments; phthalocyanine pigments; indanthrene pigments; dioxane pigments; and indigo pigments, among other organic pigments. Examples of dyes include azo dyes, anthraquinone dyes, indigo dyes, and stilbene dyes. Examples of glossy materials include compounds with a titanium dioxide layer formed on the surface of natural mica, synthetic mica, alumina flakes, and glass flakes. These colorants can be used alone or in combination of two or more.

[0109] The effective component of the colorant in the second thermosetting resin composition, i.e., the content of the colorant other than the binder resin, dispersant, and additives, varies depending on the color of the colorant. For example, the content of white colorant required to impart concealment to the second thermosetting resin composition becomes very large compared to the content of 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, relative to the total content of the second polymer component, the second thermally reactive isocyanate, and the plasticizer resin, which is 100 parts by mass.

[0110] <Other Ingredients>

[0111] The first thermosetting resin composition and the second thermosetting resin composition may each contain components other than those described above, such as additives other than those described above. Examples of additives include surface conditioners, defoamers, urethane esterification catalysts, crosslinking agents, plasticizers, thickeners, adhesion promoters, fluorescent whitening agents, stabilizers, ultraviolet absorbers, surfactants, flame retardants, antistatic agents, dispersants, inorganic fillers other than pigments and glossy materials, anti-aging agents, antioxidants, rust inhibitors, etc.

[0112] In the first thermosetting resin composition, in addition to the first polymer component and the first thermally reactive isocyanate, a colorant may be included, but it may also be absent, or even if it contains a colorant, the amount may be such that it does not impair transparency. The first resin layer 21 is preferably a so-called clear layer. A clear layer is a transparent layer, and transparency 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 a colored resin layer, and is preferably an opaque layer.

[0113] The thickness of the first resin layer 21 is not particularly limited, for example, it is 5 μm or more and 150 μm or less, preferably 10 μm or more and 50 μm or less. Similarly, the thickness of the second resin layer 22 is not particularly limited, for example, it is 5 μm or more and 150 μm or less, preferably 10 μm or more and 50 μm or less.

[0114] In a preferred embodiment of the present invention, the coating layer 20 of the laminate 1 has two resin layers (a first resin layer 21 and a second resin layer 22). However, the number of resin layers constituting the coating layer in the laminate of the embodiment of the present invention is not limited to two. For example, it may also be as follows: Figure 2 As shown in the laminate 1A, the coating layer 20A is composed of a single resin layer (first resin layer).

[0115] In the case where it consists of a single resin layer, the coating layer 20A is preferably a coloring layer. The coating layer 20A, as a coloring layer, may contain a colorant and may have the same composition as the first thermosetting resin composition described above. Furthermore, the type and content of the colorant can be as described in the second thermosetting resin composition above.

[0116] Alternatively, it can be like Figure 3As shown in the laminate 1B, the coating layer 20B is composed of three resin layers (21-23). ​​In this case, the resin layer 21 on the transfer layer side 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, present between the two resin layers 21 and 22, can be made of the same type of material as the resin layers 21 and 22; for example, the resin layer 23 preferably contains a polymer component and a heat-reactive isocyanate. In this manner, even with the resin layer 23 between the resin layers 21 and 22, the peel strength between each resin layer can be improved, and interfacial peeling between the resin layers can be prevented. In addition to the polymer component and the heat-reactive isocyanate, the resin layer 23 may also contain a colorant. The combination of a resin layer 23 containing a colorant and a resin layer 23 containing a colorant further improves the appearance design of the coating layer 20B. Furthermore, although not shown, the coating layer may also be composed of four or more resin layers. At this time, 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.

[0117] In the above description, the coating layer was described under the premise that it has a colored layer for the purpose of improving the appearance design. However, the coating layer can be given various functions and does not necessarily need to contain a colored layer. The coating layer can also be a transparent layer. For example, in the laminate 1A, the coating layer 20A can also be formed from a first thermosetting resin composition without colorant.

[0118] In addition to providing protection or enhancing the appearance of the bonded object, coating layers can also impart various other functions. For example, a coating layer can serve as a heat-insulating coating; in this case, the coating layer can be a heat-insulating layer containing heat-insulating materials. Furthermore, by creating surface irregularities in the coating layer, a surface texture similar to felt or embossing can be imparted. Moreover, functions such as rust prevention, mildew prevention, heat insulation, and antistatic properties can also be achieved by blending desired components into the curing resin composition.

[0119] Alternatively, in any embodiment, the coating layer 20 may have a first resin layer formed of at least the first thermosetting resin composition that is in contact with the transfer layer 10. Furthermore, details regarding the first thermosetting resin composition are as described above, but it may also contain suitable components as needed.

[0120] like Figure 4As shown, the laminate 1C of the embodiment of the present invention may also have a substrate 30 disposed on the opposite side of the transfer layer side of the coating layer 20. The substrate 30 used in the laminate 1C is a component that protects the coating layer 20 from damage and foreign matter adhesion, and it is preferable to peel off the coating layer 20 before bonding the coating layer 20 to the substrate. The substrate 30 is preferably formed of 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 used in the transfer layer 10 described above, wherein polyester resin is preferred. In addition, the substrate can be disposed not only on the laminate 1C, but also on the opposite side of the transfer layer side of the coating layer in a laminate of any structure.

[0121] The resin film can be a single-layer film consisting of one 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 can be a single type of resin, or two or more types can be used in combination. When two or more resins are used in combination, different types of resins can be used in each layer to form a multilayer film. Alternatively, a single-layer film can be formed by mixing two or more resins, or one or two or more layers of a multilayer film can be formed.

[0122] In addition to resin, each layer in substrate 30 may contain additives. Specific examples of additives are described in the section on transfer layers.

[0123] The resin film in the substrate 30 can be a stretched resin film or an unstretched resin film, but a stretched resin film is preferred. Therefore, a stretched polyester resin film is preferred as the resin film.

[0124] The substrate 30 may be a substrate on which at least one surface has been treated with a release agent such as a siloxane-based release agent or a fluorine-based release agent. When the substrate 30 is treated with a release agent, the treated surface preferably forms the surface of the coating layer. The substrate 30 exhibits good peelability, making it easy to separate from the coating layer 20 through the release treatment. However, if the substrate 30 can be peeled from the coating layer 20, a release treatment may not be necessary.

[0125] There is no particular limitation on the thickness of the substrate 30, for example, it is 10 μm or more and 1000 μm or less, preferably 30 μm or more and 700 μm or less, and more preferably 50 μm or more and 500 μm or less.

[0126] (Moisture-curing resin composition)

[0127] The coating layer used in this invention can also be formed from a moisture-curing resin composition capable of curing due to moisture. The moisture-curing resin composition contains a moisture-curing resin. Examples of moisture-curing resins include, for instance, prepolymers having isocyanate groups.

[0128] Examples of prepolymers having isocyanate groups include those with terminal isocyanate groups. Examples of prepolymers with terminal isocyanate groups include, for example, prepolymers obtained by reacting polyisocyanates with compounds containing active hydrogen and / or polymers containing active hydrogen.

[0129] As a polyisocyanate used in preparing prepolymers with terminal isocyanate groups, toluene diisocyanate, crude toluene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, carbodiimide diphenylmethane diisocyanate, phenyl diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethylene diisocyanate, hexamethylene diisocyanate, etc. can be used, with polymethylene polyphenyl isocyanate being preferred.

[0130] The weight-average molecular weight of the prepolymer is preferably 20,000 or more and 1,000,000 or less. Furthermore, the weight-average molecular weight is determined by gel permeation chromatography (GPC) and used as a conversion value for standard polystyrene.

[0131] The following substances can be used as the above-mentioned compounds or polymers containing active hydrogen.

[0132] Used in the following ways: A compound containing active hydrogen, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, trimethylolethane, trimethylolpropane, castor oil, diglycerol, sorbitol, pentaerythritol, dipentaerythritol, etc.; and an active hydrogen polymer obtained by additionally polymerizing the above-mentioned active hydrogen compounds with ethylene oxide, propylene oxide, butene oxide, styrene oxide, tetrahydrofuran, etc., alone or in mixtures, having an average molecular weight of 3000 or less, an average number of functional groups of 2 or more, preferably an average molecular weight of 200 to 1000, and an average number of functional groups of 2 to 2.5. It can also be used in combination with other polyester polyols, oil-modified polyester polyols, poly-ε-caprolactone polyols, polycarbonate diols, acrylic polyols, polyamines, polyamides, urea resins, and melamine resins, which are polymers containing active hydrogen with an average molecular weight of less than 3000 and an average number of functional groups of more than 1.5, preferably with an average molecular weight of 200 to 1000 and an average number of functional groups of 2 to 2.5.

[0133] Prepolymers with terminal isocyanate groups have an effective NCO content of 1 to 15% by mass, preferably 8 to 13% by mass.

[0134] Of the above, urethane prepolymers having terminal isocyanate groups are preferred.

[0135] Prepolymers having terminal isocyanate groups can be synthesized by urethane esterification of the above-mentioned polyisocyanate and a conventional polyol containing the above-mentioned polymer with active hydrogen under conditions of excess isocyanate at a temperature of 40°C to 90°C, preferably 55°C to 75°C, with moisture barrier.

[0136] The above-mentioned carbamate esterification reaction is usually carried out in an organic solvent. Suitable 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 coatings. The carbamate esterification reaction can also use a catalyst. Suitable catalysts include tertiary amine catalysts such as triethylamine and dimethylaniline, or metal catalysts such as tin and zinc. These catalysts also act as catalysts for the reaction of the coating film with moisture in the air.

[0137] The content of prepolymer in the moisture-curing resin composition is, 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 prepolymer in the moisture-curing resin composition is 100% by mass or less, and 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.

[0138] (Compound (B))

[0139] In addition to the aforementioned prepolymer, the moisture-curing resin composition preferably also contains a compound (B) (a polyisocyanate compound) having isocyanate groups. Compound (B) can be any compound capable of curing due to moisture. By containing compound (B), the moisture-curing resin composition can improve the hardness of the cured coating layer, thus resulting in good mechanical strength, damage resistance, and other properties of the cured coating layer. It is preferable that compound (B) has two or more isocyanate groups. Furthermore, compound (B) can be a compound other than the aforementioned prepolymer, and may be a compound that does not contain a polyacrylic acid backbone or a polyurethane backbone.

[0140] As compound (B), examples include aliphatic diisocyanate compounds such as hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, isophorone diisocyanate (IPDI), phenylene diisocyanate, hydrogenated phenylene diisocyanate (H6XDI), hydrogenated diphenylmethane diisocyanate, cyclohexane diisocyanate, bis(isocyanate methyl)cyclohexane, and dicyclohexylmethane diisocyanate, as well as aromatic diisocyanate compounds such as 4,4-diphenylmethane diisocyanate, toluene diisocyanate, and naphthalene-1,5-diisocyanate, and polyisocyanates.

[0141] Compound (B) can be a modified product of polymerized polyisocyanate, or polymerized MDI (polydiphenylmethane diisocyanate), or a polyol-modified polyisocyanate (adduct) such as a trimethylolpropane adduct of polyisocyanate, a biuret form of polyisocyanate, a urea form of polyisocyanate, an isocyanurate form of polyisocyanate, and their condensates. Preferred examples include HDI adducts, HDI biuret, HDI urea form, HDI isocyanurate, H6XDI isocyanurate, IPDI isocyanurate, and IPDI adducts.

[0142] As compound (B), it is preferable to select a compound that is soft and has high adhesion in the uncured state. From this point of view, aliphatic polyisocyanates or their modified forms are preferred, among which adducts, biuret bodies, urea carbamate bodies, and isocyanurates are more preferred, and adducts, biuret bodies, urea carbamate bodies, and isocyanurates of HDI or IPDI are even more preferred.

[0143] Compound (B) can be used alone or in combination of two or more.

[0144] The molecular weight of compound (B) is not particularly limited, but is preferably 1000 or less. Lowering the molecular weight of compound (B) can improve the adhesion of the coating layer before curing and its adhesion to the substrate after curing. 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; for example, 160 or more is acceptable, preferably 200 or more, more preferably 300 or more, and even more preferably 400 or more.

[0145] Furthermore, the molecular weight of compound (B) is calculated based on its structural formula. Additionally, when two or more compounds (B) are used together, the weight-average molecular weight is expressed.

[0146] When using compound (B), if the total amount of prepolymer and compound (B) is set to 100 parts by mass, the content of compound (B) in the moisture-curing 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. By ensuring that the content of compound (B) is at least a certain amount, the hardness of the cured resin layer can be easily improved. Furthermore, the content of compound (B) is, for example, 80 parts by mass or less, 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 ensuring that the content of compound (B) is at least a certain value, it is easy to improve the adhesion of the coating layer before curing and the adhesion after curing while maintaining a good surface condition of the resin layer.

[0147] The laminate of the present invention, when the coating layer is formed of a moisture-curing resin composition, may include a first resin layer and a second resin layer as described above. In the presence of the first and second resin layers, the first and second resin layers may be formed from a first moisture-curing resin composition containing a prepolymer or a first moisture-curing resin composition containing a prepolymer and compound (B), respectively. Furthermore, the first and second moisture-curing resin compositions may be appropriately selected from the aforementioned moisture-curing resin compositions.

[0148] As described below, when the first resin layer and the second resin layer are provided, the content of compound (B) in the first moisture-curing resin composition is more preferably 25 parts by mass or more, and the content of compound (B) in the second moisture-curing resin composition is more preferably less than 25 parts by mass.

[0149] Furthermore, when the first and second moisture-curing resin compositions contain compound (B), the mixing amount of compound (B) can be adjusted within the aforementioned range. Specifically, when the total amount of prepolymer and compound (B) is set to 100 parts by mass, it is preferable that the content of compound (B) in the first moisture-curing resin composition is greater than the content of compound (B) in the second moisture-curing resin composition. In this case, the difference between the content of compound (B) when the total amount of prepolymer and compound (B) in the first moisture-curing resin composition is set to 100 parts by mass and the content of compound (B) when the total amount of prepolymer and compound (B) in the second moisture-curing resin composition is set to 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, and more preferably 7 parts by mass or more and 15 parts by mass or less.

[0150] In this way, by making the content of compound (B) in the second moisture-curing resin composition greater than the content of compound (B) in the first moisture-curing resin composition, it is easy to improve the above-mentioned elastic modulus and the adhesion to the bonded body at the same time.

[0151] Furthermore, the second moisture-curing resin composition preferably also contains a colorant. By including a colorant in the second moisture-curing resin composition, the second resin layer can be made into a colored layer, thereby improving the appearance design of the coating layer 20.

[0152] In addition, regarding the type of colorant and the content of colorant in the second moisture-curing resin composition, as explained in the second thermosetting resin composition, the basis for the content of colorant is based on 100 parts by mass of the total content of prepolymer and compound (B).

[0153] On the other hand, the first moisture-curing resin composition may contain a colorant, or it may not contain a colorant, or even if it contains a colorant, it may contain only an amount that does not impair transparency. The first resin layer is preferably a so-called transparent layer as described above.

[0154] Furthermore, when the coating layer is formed from a moisture-curing resin composition and is a single resin layer, the coating layer may or may not be a colored layer. In the case of a colored layer, as described above, it can be any layer containing a colorant.

[0155] The moisture-curing resin composition (or the first moisture-curing resin composition and the second thermo-moisture-curing resin composition) may each contain components other than those described above, such as additives other than those described above. Moisture-curing accelerating catalysts are among the examples of additives. In addition to moisture-curing accelerating catalysts, additives listed in the thermosetting resin composition may also be appropriately used.

[0156] Furthermore, the composition of the coating layer when using moisture-curing resin compositions other than those described above is the same as when using thermosetting resin compositions, and its description is omitted.

[0157] [Manufacturing method of laminated wafers]

[0158] The following description focuses on a method for manufacturing a laminated sheet in which the coating layer is formed 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.

[0159] (1) Process A

[0160] In step A, a first coating containing "a first thermosetting resin composition containing a first polymeric component and a thermo-reactive isocyanate" is applied to a transfer layer and dried to produce a first laminate having a transfer layer and a first resin layer formed of the first thermosetting resin composition disposed on the transfer layer. Since the first thermosetting resin composition, the transfer layer, and the first resin layer have already been described, further explanation of these components is omitted.

[0161] The first coating may be formed from the first thermosetting resin composition, but from the viewpoint of improving coatability and other workability, it is preferable that the first thermosetting resin composition is diluted with a solvent. Examples of solvents include ethyl acetate, butyl acetate, methyl ethyl ketone, isopropanol, methyl methacrylate, and toluene.

[0162] Furthermore, the drying process after the first coating is applied to the transfer layer is preferably a drying process that includes at least the formal drying process described later, and more preferably a drying process that sequentially includes the pre-drying process described later and the formal drying process.

[0163] The drying temperature in the pre-drying process 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 process is preferably 1 minute or higher and 30 minutes or lower, more preferably 2 minutes or higher and 15 minutes or lower.

[0164] The drying temperature in the formal drying process is preferably 75°C or higher and 130°C or lower, more preferably 80°C or higher and 120°C or lower. If the drying temperature is above these lower limits, the solvent can be easily and properly removed, preventing the formation of bubbles due to the vaporization of the solvent during resin layer curing. In addition, by setting it below the above upper limits, it is possible to prevent the thermosetting resin composition from curing to an excessive degree during drying.

[0165] The drying time in the formal drying process is preferably 1 minute or more and 30 minutes or less, more preferably 2 minutes or more and 15 minutes or less. By setting the drying time to the lower limit or above, the solvent can be removed appropriately, preventing the formation of bubbles due to solvent vaporization during resin layer curing. In addition, by setting it to the upper limit or below, it is possible to prevent the thermosetting resin composition from curing to the necessary degree during drying.

[0166] Alternatively, the dried resin layer can be initially cured as needed. Initial curing refers to curing the thermosetting resin composition constituting the resin layer to a semi-cured state. Initial curing can be carried out by heating, under conditions of a heating temperature above 90°C and below 150°C, and a heating time of more than 2 minutes and less than 5 minutes.

[0167] (2) Process B

[0168] In step B, a second coating containing "a second thermosetting resin composition comprising a second polymeric component, a second thermally reactive isocyanate, and a colorant" is applied to a substrate and dried to produce a second laminate having a substrate and a second resin layer formed of the second thermosetting resin composition disposed on the substrate. Furthermore, since the second thermosetting resin composition, the substrate, and the second resin layer have already been described, further descriptions of these components are omitted.

[0169] The second coating can be formed from the second thermosetting resin composition, but from the viewpoint of improving coatability and other workability, it is preferable that the second thermosetting resin composition is diluted with a solvent. Examples of solvents include ethyl acetate, butyl acetate, methyl ethyl ketone, isopropanol, methyl methacrylate, and toluene.

[0170] Furthermore, the drying process after applying the second coating to the substrate is similar to the drying process after applying the first coating to the transfer layer, preferably including at least the formal drying step described later, and more preferably the drying process consisting of the pre-drying step and the formal drying step described later. Additionally, the pre-drying step and the formal drying step have already been described in item "Step A," therefore, the description of the pre-drying step and the formal drying step is omitted.

[0171] (3) Process C

[0172] In step C, the first and second resin layers are bonded together with the first and second resin layers facing each other. As a result, a laminate 1C having a laminate structure of transfer layer / first resin layer / second resin layer / substrate can be manufactured. By peeling the substrate from this laminate, a laminate consisting of a transfer layer, a first resin layer, and a second resin layer can be manufactured.

[0173] Furthermore, as described above, if other resin layers 23 are further provided between resin layers 21 and 22, a third laminate is first made by forming other resin layers on a separately provided release film, etc. Then, the third laminate is bonded to the first laminate, and other resin layers are formed on the first resin layer of the first laminate; or the third laminate is bonded to the second laminate, and other resin layers are formed on the second resin layer of the second laminate. Then, as in step C described above, by bonding the first laminate and the second laminate, a laminate sheet 1B having resin layers 21, 22, and other resin layers 23 provided between resin layers 21 and 22 can be manufactured. At this time, the release film can be peeled off after the other resin layers 23 are laminated onto resin layers 22 or 21, or peeled off before lamination. As the release film, a release polyethylene terephthalate film (release PET film), etc., can be used.

[0174] Furthermore, when the coating layer 20 is composed of a single resin layer 20A, by omitting steps B and C, a laminated sheet 1A with the resin layer 20A stacked on the transfer layer 10 can be obtained. Alternatively, a substrate 30 can be stacked on top of the resin layer 20A stacked on the transfer layer 10.

[0175] In addition, the laminated sheet of the preferred embodiment of the present invention can also be manufactured by methods other than the laminated sheet manufacturing method described above.

[0176] In addition, when the coating layer is a laminate formed from a moisture-curing resin composition, the laminate can be manufactured in the same way as the above-described laminate manufacturing method by using a coating containing a moisture-curing resin composition instead of a coating containing a thermosetting resin composition.

[0177] [How to use laminated films]

[0178] The laminated sheet of the preferred embodiment of the present invention is a sheet material used to form decorative bodies such as coatings on various articles (adhesive bodies), and is used by attaching it to the adhesive body. Specifically, in the laminated sheet of the preferred embodiment of the present invention, after peeling off the substrate, the transfer layer can be peeled off, the coating layer can be adhered to the adhesive body, and the coating layer adhered to the adhesive body can be heated. There is no particular limitation on the method of peeling off the substrate; it can be peeled off by a peeling device or manually. There is no particular limitation on the adhesion of the coating layer to the adhesive body; it can be done manually using a rubber roller or the like, or it can be done using a lamination device. In addition, when the coating layer is formed of a thermosetting resin composition, the coating layer is cured by heating, and the decorative body is formed by the cured coating layer. In addition, when the coating layer is formed of a moisture-curing resin composition, the coating layer adhered to the adhesive body is placed in, for example, an atmospheric environment or a high-humidity environment, whereby the coating layer is cured by moisture, and the decorative body is formed by the cured coating layer.

[0179] Furthermore, the transfer layer is peeled off after the substrate is removed, but typically, the coating layer can be heated or placed as described above after the transfer layer is peeled off to cure it. Alternatively, the transfer layer is preferably peeled off from the coating layer after the laminate is bonded to the substrate via the coating layer. Thus, the transfer layer acts as a support for the coating layer when it is bonded to the substrate. There are no particular limitations on the method of peeling off the transfer layer; it can be done using a peeling device or manually.

[0180] Furthermore, the peeling of the transfer layer can be carried out at room temperature or a temperature near it (around 15-35°C), or it can be carried out after the coating layer has cooled down.

[0181] In one embodiment of the present invention, the laminate can also be pre-formed into a shape corresponding to the shape of the adherend through vacuum forming, compression molding, or air-forming, and then bonded to the adherend. When pre-forming is performed, it can be done before or after the substrate is peeled from the coating layer. By pre-forming, even if the adherend has a complex shape, the laminate can be easily and tightly adhered to the adherend. In the above, pre-forming is preferably performed by vacuum forming. Pre-forming can be achieved by pressing the laminate onto a jig or mold using vacuum forming, stretching the laminate using the jig or mold, and shaping it into a shape corresponding to the surface shape of the adherend.

[0182] Here, vacuum forming is preferably TOM forming. TOM stands for "Three Dimension Overlay Method". If TOM forming is applied, it is possible to shape complex shapes.

[0183] The substrate to which the laminated sheet of this invention is attached is not particularly limited, and can include, for example, interior materials for vehicles such as electrification products, automobile and railway vehicle interior materials, exterior materials for vehicles such as automobile and railway vehicle exterior materials, exterior materials for general merchandise, heavy machinery, ships, and aircraft, exterior wall or roof materials for residences and buildings, bridges, steel frames, factories, and wind turbine blades. Among these, exterior materials for vehicles, such as automobile exterior materials, are preferred. Examples of exterior materials for vehicles include, for example, hoods, roofs, door panels, bumpers, fuel filler panels, trunk lids, and rear doors. When the laminated sheet of this invention is attached to an exterior material for a vehicle, it can be attached to an exterior material installed on the vehicle body or to an exterior material installed in front of the vehicle body.

[0184] Furthermore, there are no particular limitations on the material of the bonded body; it can be any of resin materials, inorganic materials such as ceramics, or metallic materials such as steel, with metallic materials such as steel being preferred. It is difficult to coat metallic materials such as steel simultaneously with the molding of the bonded body using insert molding, and coating with resin sheets is also challenging. However, by using the laminated sheet of this invention, coating can be easily performed even with such materials.

[0185] 〔vehicle〕

[0186] The vehicle of the present invention is coated using the laminate sheet of the present invention. As described above, by using the laminate sheet of the present invention, when the paint layer is transferred onto the substrate by peeling off the transfer layer, it is possible to suppress residual peeling marks on the paint layer, and when the laminate sheet is attached to the substrate, it is possible to suppress the formation of wrinkles on the laminate sheet. Therefore, the vehicle of the present invention can have a painted surface without peeling marks or wrinkles.

[0187] Example

[0188] The present invention will now be described in more detail by way of examples, but the present invention is not limited by these examples.

[0189] The measurement and evaluation methods in this embodiment are as follows.

[0190] (Bending resistance)

[0191] The transfer layer was cut into strips measuring 20 mm wide and 200 mm long to serve as sample pieces. The stiffness was determined according to the stiffness-softness A method (45° cantilever method) described in JIS L1084, and the minimum value was taken as the measured value. Furthermore, the measurement limit of the device is 150 mm; values ​​exceeding this limit are recorded as "150 <".

[0192] (Elastic modulus)

[0193] After laminating the sheet to a 50 μm thick polyethylene terephthalate (PET) film, the transfer layer was peeled off, and the elastic modulus was measured from the first resin layer side of the coating layer using a nanoindenter. A Hysitron TI950 nanoindenter was used, equipped with a Berkovich-type diamond indenter. The indenter was pressed into the coating layer surface at a speed of 200 nm / sec for 5 seconds, and then the load was removed after 5 seconds to measure the elastic modulus. The elastic modulus was measured at room temperature (25°C).

[0194] (Residual traces of peeling)

[0195] The laminates of the examples and comparative examples were cut into 50mm × 50mm pieces and attached to the coated steel plate using a rubber roller and water containing 0.5% surfactant. Then, the transfer layer was peeled off, and the coating layer was transferred onto the coated steel plate. The appearance of the surface of the coating layer (the surface of the first resin layer) after the transfer layer was peeled off was observed. The laminates of the examples and comparative examples were evaluated using the following evaluation criteria.

[0196] <Evaluation Criteria>

[0197] A: The transfer layer is easy to peel off, and the surface of the first resin layer after peeling off the transfer layer is free of rough, dotted, and linear peeling marks.

[0198] B: The transfer layer is easy to peel off. On the surface of the first resin layer after the transfer layer is peeled off, there are dotted peeling marks, but no rough or linear peeling marks.

[0199] C: The transfer layer is difficult to peel off, but there are no linear peeling marks on the surface of the first resin layer after the transfer layer is peeled off.

[0200] D: Rough or linear peeling marks were observed on the surface of the first resin layer after the transfer layer was peeled off.

[0201] (Adhesion evaluation)

[0202] The laminated sheets of the examples and comparative examples were cut into 50mm × 100mm pieces and attached to the coated steel plate using a rubber roller and water containing 0.5% surfactant. The laminated sheets of the examples and comparative examples were evaluated according to the following evaluation criteria.

[0203] <Evaluation Criteria>

[0204] A: The film was applied 10 times to the coated steel plate, and none of the laminated sheets were wrinkled.

[0205] B: The film was applied 10 times to the coated steel plate, and the laminated film applied more than once had wrinkles.

[0206] (Follow-up evaluation)

[0207] Prepare a substrate with a 10mm step and a substrate with a curved surface of R=150mm. Attach the laminates of the embodiments and comparative examples to these substrates. Evaluate the laminates of the embodiments and comparative examples using the following evaluation criteria.

[0208] <Evaluation Criteria>

[0209] A: The laminated sheet can follow a 10mm step.

[0210] B: The laminated sheet cannot follow a 10mm step, but it can follow a curved surface with R=150mm.

[0211] C: The laminate cannot follow a 10mm step and cannot follow a surface with R=150mm.

[0212] The components of the transfer layer film, substrate film, and resin layer used in the examples and comparative examples are as follows.

[0213] <Transfer Layer Film>

[0214] Membrane A: Polyethylene terephthalate membrane, manufactured by Nakamoto Packs Co., Ltd., "NS SeparatorMXA", 75μm thick, and demolded using a siloxane-based release agent.

[0215] Membrane B: Polyethylene terephthalate membrane, manufactured by Nakamoto Packs Co., Ltd., "NS SeparatorMXA", 50 μm thick, and demolded using a siloxane-based release agent.

[0216] Membrane C: Polyethylene terephthalate membrane, manufactured by Nakamoto Packs Co., Ltd., "NS SeparatorMXA", 25μm thick, and demolded using a siloxane-based release agent.

[0217] Membrane D: Polyethylene terephthalate membrane, manufactured by Nakamoto Packs Co., Ltd., "NS-38-F-100N", 38μm thick, and released using a siloxane-based release agent.

[0218] Membrane E: A multilayer film of polypropylene / EVA / polypropylene, manufactured by Okamoto Co., Ltd., "Convenience store film (PP type, transparent)," 100μm thick, without mold release treatment.

[0219] Membrane F: Polypropylene / EVA / polypropylene multilayer film, manufactured by Okamoto Co., Ltd., "Convenience store film, PP type transparent", thickness 300μm, no demolding treatment.

[0220] Membrane G: Polyethylene / EVA / polyethylene multilayer film, manufactured by Okamoto Co., Ltd., "Convenience store film, PE type transparent", 100μm thick, no demolding treatment.

[0221] Membrane H: Polyethylene terephthalate membrane, manufactured by Nippa Corporation, "Q2-ASI5", 50 μm thick, with a release treatment using a siloxane-based release agent.

[0222] Membrane I: Polyethylene terephthalate membrane, manufactured by Nippa Corporation, "NM-ASI5", 50 μm thick, and released using a siloxane-based release agent.

[0223] Membrane J: Unstretched polyethylene terephthalate film, non-crystalline, manufactured by Nakamoto Packs Co., Ltd., "A-PET-MXA", 100μm thick, and released using a siloxane-based release agent.

[0224] Film K: Unstretched polyethylene terephthalate film, non-crystalline, manufactured by Nakamoto Packs Co., Ltd., "A-PET-MXA", 200μm thick, and released using a siloxane-based release agent.

[0225] Membrane L: Polyethylene terephthalate membrane, manufactured by Nakamoto Packs Co., Ltd., "NS SeparatorMXA", 12μm thick, and demolded using a siloxane-based release agent.

[0226] Membrane M: Unstretched polyethylene terephthalate film, non-crystalline, manufactured by Nakamoto Packs Co., Ltd., "A-PET-AU", 400μm thick, and released using a siloxane-based release agent.

[0227] <Film for Substrate Layer>

[0228] The polyethylene terephthalate film, manufactured by Nippa Corporation as "Q2-ASI5", has a thickness of 50 μm and was released using a siloxane-based release agent.

[0229] <Polymer Components>

[0230] Acrylic polyol resin (1): weight average molecular weight 290,000, hydroxyl value 80 mgKOH / g, glass transition temperature 20℃, solids content (NV) = 30% by mass (solvent: ethyl acetate, etc.)

[0231] Acrylic polyol resin (2): weight average molecular weight 250,000, hydroxyl value 80 mgKOH / g, glass transition temperature 40℃, solid content concentration (NV) = 30% by mass (solvent: ethyl acetate, etc.)

[0232] Acrylic polyol resin (3): weight average molecular weight 250,000, hydroxyl value 150 mgKOH / g, glass transition temperature 40℃, solid content concentration (NV) = 30% by mass (solvent: ethyl acetate, etc.)

[0233] Acrylic polyol resin (4): weight average molecular weight 260,000, hydroxyl value 110 mgKOH / g, glass transition temperature 60℃, solid content concentration (NV) = 30% by mass (solvent: ethyl acetate, etc.)

[0234] Acrylic polyol resin (5): weight average molecular weight 220,000, hydroxyl value 110 mgKOH / g, glass transition temperature 80℃, solid content concentration (NV) = 25% by mass (solvent: ethyl acetate, etc.)

[0235] <Plasticized Resin>

[0236] Polycarbonate diol, average molecular weight 500, manufactured by UBE Corporation, "ETERNACOLL PH-50", hydroxyl value 224 mgKOH / mg, solids content (NV) = 100% by mass

[0237] <Pigments (Colorants)>

[0238] Nikko-Bics' "NSP-UP841B" has an effective pigment concentration of 9% by mass and a solids content (NV) of 24% by mass.

[0239] <Glossy Materials (Colorants)>

[0240] Merck's "Xirallic T60-10 WNT Crystal Silver"

[0241] <Thermoreactive Isocyanates>

[0242] Hexamethylene diisocyanate-based end-capped isocyanate (HDI series), end-capping agent: 3,5-dimethylpyrazole (DMP), solids content (NV) = 70%, solvent: ethyl acetate.

[0243] The components used in the moisture-curing resin composition are as follows.

[0244] Carbamate prepolymer: Trade name "Acrylit 8PU-4015N", manufactured by Taisei Fine Chemical Co., Ltd., molecular weight 50,000

[0245] Polyisocyanate (1): Trade name "Takenate D-140N", manufactured by Mitsui Chemicals Co., Ltd., isophorone diisocyanate adduct, molecular weight 640

[0246] Polyisocyanate (2): Trade name "Desmodur N3200A", manufactured by Covestro, HDI biuret, molecular weight 480

[0247] Pigment (colorant): Nikko-Bics "NSP-UP 841B", effective pigment concentration = 9% by mass, solids content (NV) = 24% by mass

[0248] Brightening material (colorant): Merck's "Xirallic T60-10 WNT Crystal Silver"

[0249] [Preparation of thermosetting resin compositions A-G]

[0250] Thermosetting resin compositions A to G are prepared by adding each component according to the formula shown in Table 1, and adding ethyl acetate as a solvent to make the solid component concentration 30% by mass.

[0251] [Preparation of moisture-curing resin compositions H-J]

[0252] The components were mixed in the manner shown in Table 5, and ethyl acetate was added as a solvent to prepare a moisture-curing resin composition H-J coating with a solid component concentration of 30% by mass.

[0253] [Example 1]

[0254] A thermosetting resin composition D is applied to the surface of the transfer layer film B using an applicator. A pre-drying process is then performed at a drying temperature of 60°C for 20 minutes, followed by a formal 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.

[0255] Next, a thermosetting resin composition G is coated onto the surface of the substrate film using a coating machine. Then, a pre-drying process is performed at a drying temperature of 60°C and a drying time of 30 minutes. Finally, a formal drying process is performed at a drying temperature of 80°C and a drying time of 5 minutes to form a second resin layer with a thickness of 30 μm on the substrate.

[0256] The first resin layer on the transfer layer and the second resin layer on the substrate were laminated together at 25°C to obtain a laminated sheet in the order of transfer layer, first resin layer, second resin layer and substrate. The obtained laminated sheet was used for the above evaluation. The evaluation results are shown in Table 2.

[0257] [Examples 2-20, Comparative Examples 1-4]

[0258] Except for changing the transfer layer film used in the transfer layer as shown in Tables 2-4, and changing the composition of the thermosetting resin composition and the moisture-curing resin composition as shown in Tables 1 and 5, the procedure was carried out in the same manner as in Example 1. The evaluation results are shown in Tables 2-4 and 6.

[0259]

[0260] *Table 1 shows the basic amount of solid components in thermosetting resin compositions A to G. The total amount of solid components in acrylic polymers, plasticizers, and thermo-reactive isocyanates is set as 100 parts by mass.

[0261] *The effective component amount of the pigment is obtained by multiplying the value in Table 1 by 9 / 24.

[0262]

[0263]

[0264]

[0265]

[0266] *Table 1 is based on the solid content of each component in the moisture-curing resin compositions H to J. The total solid content of the urethane prepolymer, polyisocyanate (1) and polyisocyanate (2) is set as 100 parts by mass.

[0267] *The effective component amount of the pigment is obtained by multiplying the value in Table 1 by 9 / 24.

[0268]

[0269] Comparative Examples 1-20 and Comparative Examples 1-4 show that if the stiffness of the transfer layer is 20-120 mm, peeling marks on the coating layer can be suppressed when the transfer layer is peeled off and transferred to the substrate. Furthermore, if the stiffness of the transfer layer is 20-120 mm, wrinkling of the laminate can be suppressed when it is attached to the substrate.

[0270] Explanation of symbols in attached drawings

[0271] 1, 1A-1C laminated sheets

[0272] 10 transfer layers

[0273] 20, 20A, 20B Coating Layers

[0274] 21 First resin layer

[0275] 22 Second resin layer

[0276] 23 Other resin layers

[0277] 30 substrate

Claims

1. A laminate having a transfer layer and a coating layer formed of a thermosetting resin composition or a moisture-curing resin composition, wherein the stiffness of the transfer layer is 20 to 120 mm.

2. The laminate as claimed in claim 1, wherein the elastic modulus of the coating layer, measured from the transfer layer side, is 1.0 to 1500 MPa.

3. The laminate as claimed in claim 1 or 2, wherein the thermosetting resin composition contains a polymeric component having functional groups reactive to isocyanate groups and a thermo-reactive isocyanate.

4. The laminated sheet as claimed in claim 3, wherein the polymeric component having a functional group reactive to isocyanate groups has hydroxyl groups.

5. The thermosetting resin sheet as described in claim 3 or 4, wherein the polymeric component having a functional group reactive to isocyanate groups is at least one resin selected from (meth)acrylic resins, polycarbonate resins, polyester resins, and epoxy resins.

6. The laminate according to any one of claims 3 to 5, wherein the weight-average molecular weight of the polymeric component having a functional group reactive to isocyanate groups is 50,000 or more and 1,000,000 or less.

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

8. The laminate according to any one of claims 1 to 7, wherein the coating layer comprises a first resin layer formed of a first thermosetting resin composition and a second resin layer formed of a second thermosetting resin composition. The first thermosetting resin composition contains a first polymeric component having functional groups reactive to isocyanate groups and a first thermoreactive isocyanate. The second thermosetting resin composition contains a second polymeric component having functional groups reactive to isocyanate groups, a second thermally reactive isocyanate, and a colorant.

9. The laminate as claimed in 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 laminated sheet as claimed in claim 1, characterized in that, The moisture-curing resin composition contains a resin having isocyanate groups.

11. The laminate as claimed in claim 1 or 10, wherein the moisture-curing resin composition contains a polymer with a weight-average molecular weight of 20,000 or more and 1,000,000 or less.

12. The laminate according to any one of claims 1 to 11, wherein the thickness of the transfer layer is 10 μm or more and 1000 μm or less.

13. A vehicle painted using the laminated sheet according to any one of claims 1 to 12.

14. A method of using a laminated sheet, wherein the laminated sheet according to any one of claims 1 to 12 is attached to a substrate for use.

15. A method for manufacturing a laminated sheet, wherein the coating layer of the laminated sheet is formed from a thermosetting resin composition, the coating layer having a first resin layer and a second resin layer, the manufacturing method comprising the following steps: The process of applying a first coating containing a first thermosetting resin composition onto a transfer layer and drying it to produce a first laminate having the transfer layer and the first resin layer formed of the first thermosetting resin composition disposed on the transfer layer, is described above. The steps of applying a second coating containing a second thermosetting resin composition to a substrate and drying it, and fabricating a second laminate having the substrate and a second resin layer formed of the second thermosetting resin composition disposed on the substrate, and... The process of bonding the first laminate and the second laminate together with the first resin layer and the second resin layer facing each other. The first thermosetting resin composition contains a first polymeric component and a thermo-reactive isocyanate, and the second thermosetting resin composition contains a second polymeric component, a second thermo-reactive isocyanate, and a colorant.

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