Thermosetting resin sheet, vehicle and vehicle parts and method for manufacturing vehicle and vehicle parts

Abstract

To provide a thermosetting resin sheet capable of suppressing the occurrence of foaming during curing and heating, a vehicle and vehicle parts coated with the thermosetting resin sheet and a method for manufacturing a vehicle and vehicle parts.SOLUTION: There is provided a thermosetting resin sheet comprising a resin layer composed of a thermosetting resin composition and a transfer layer, wherein the total outgassing amount is 40000 ppm or less, as measured by gas chromatography-mass spectrometry (GC-MS) at the peak top temperature (T1) of endothermic or exothermic peaks obtained from differential scanning calorimetry of the resin layer of the thermosetting resin sheet. There are provided a vehicle and vehicle parts coated with the thermosetting resin sheet. There is provided a method for manufacturing a vehicle and vehicle parts which comprises a step of coating with the thermosetting resin sheet.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a thermosetting resin sheet, a vehicle and vehicle parts coated using the thermosetting resin sheet, and a method for manufacturing a vehicle and vehicle parts.

Background Art

[0002] For furniture, steel plates, vehicle bodies, etc., painting and decoration are performed from the viewpoints of design and durability. It is known that decoration is performed using a film such as a decorative film. As such a decorative film, for example, a thermosetting coating sheet mainly composed of an acrylic resin having a plurality of functional groups, a monomer having a plurality of functional groups as a crosslinking agent that reacts with an isocyanate group, and a blocked isocyanate is known as a conventional technique (see Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Generally, the paint layer constituting the decorative film is formed from a thermosetting resin composition, and after being bonded to an object as described above, it is often heated and cured. In addition, as the curing agent for the paint layer constituting the decorative film, a substance that generates gas during curing heating, such as blocked isocyanate, may be used. In that case, the generated gas may cause blistering on the decorative film.

[0005] Therefore, an object of the present invention is to provide a thermosetting resin sheet capable of suppressing the generation of blisters during curing heating, a vehicle and vehicle parts coated using the thermosetting resin sheet, and a method for manufacturing a vehicle and vehicle parts.

Means for Solving the Problems

[0006] As a result of intensive studies, the present inventor has found that the above problems can be solved by making the total outgas amount at the peak top temperature of endotherm or exotherm obtained from the differential scanning calorimetry of the resin layer of the thermosetting resin sheet equal to or less than a predetermined value. That is, the present invention provides the following [1] to

[12] . [1] A thermosetting resin sheet including a resin layer made of a thermosetting resin composition and a transfer layer, wherein the total outgas amount measured by gas chromatography-mass spectrometry (GC-MS method) at the peak top temperature (T1) of endotherm or exotherm obtained from the differential scanning calorimetry of the resin layer of the thermosetting resin sheet is 40,000 ppm or less. [2] The thermosetting resin sheet according to [1] above, wherein the total outgas amount measured by the GC-MS method at the peak top temperature (T1) of the resin layer of the thermosetting resin sheet is 1,000 ppm or more. [3] The thermosetting resin sheet according to [1] or [2] above, wherein the thermosetting resin composition contains a blocked isocyanate. [4] The thermosetting resin sheet according to [3] above, wherein the blocking agent of the blocked isocyanate is at least one compound selected from the group consisting of pyrazole-based compounds and malonic esters. [5] The thermosetting resin sheet according to [3] or [4] above, wherein the thermosetting resin composition contains a polyol resin, and the content of the blocked isocyanate in the resin layer is 40 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the polyol resin. [6] The thermosetting resin sheet according to any one of [1] to [5] above, wherein the thermosetting resin composition contains a polyol resin having a weight average molecular weight of 50,000 or more and 1,000,000 or less. [7] The thermosetting resin sheet according to [6] above, wherein the polyol resin is (meth)acrylic polyol. [8] The thermosetting resin composition further contains a colorant, The thermosetting resin sheet according to any one of [1] to [7] above, wherein the resin layer is a colored resin layer. [9] A vehicle painted using the thermosetting resin sheet according to any one of [1] to [8] above.

[10] A vehicle part painted using the thermosetting resin sheet according to any one of [1] to [8] above.

[11] A method for manufacturing a vehicle, including a step of painting using the thermosetting resin sheet according to any one of [1] to [8] above.

[12] A method for manufacturing a vehicle part, including a step of painting using the thermosetting resin sheet according to any one of [1] to [8] above. [Effect of the Invention]

[0007] According to the present invention, it is possible to provide a thermosetting resin sheet capable of suppressing the occurrence of warping during curing heating, a vehicle and a vehicle part painted using the thermosetting resin sheet, and a method for manufacturing a vehicle and a vehicle part. [Embodiments for Carrying Out the Invention]

[0008] [Thermosetting Resin Sheet] The thermosetting resin sheet of the present invention includes a resin layer made of a thermosetting resin composition and a transfer layer. And the total outgas amount measured by gas chromatography-mass spectrometry (GC-MS method) at the peak top temperature (T1) of endothermic or exothermic obtained from the differential scanning calorimetry of the resin layer of the thermosetting resin sheet is 40,000 ppm or less. Thereby, the occurrence of warping during curing heating of the thermosetting resin sheet can be suppressed.

[0009] (Total Outgas Amount) The total outgassing amount measured by gas chromatography-mass spectrometry (GC-MS method) at the peak top temperature (T1) of endotherm or exotherm obtained from the differential scanning calorimetry of the resin layer of the thermosetting resin sheet of the present invention is 40,000 ppm or less. If the total outgassing amount is greater than 40,000 ppm, a leak may occur during the curing heating of the thermosetting resin sheet. Also, when a base layer is formed on the object to be coated and then the thermosetting resin sheet is attached to the object to be coated, the base layer may peel off from the object to be coated. From such viewpoints, the total outgassing amount is preferably 35,000 ppm or less, more preferably 30,000 ppm or less, and even more preferably 25,000 ppm or less. The peak top temperature of endotherm or exotherm obtained from the differential scanning calorimetry of the resin layer of the thermosetting resin sheet and the total outgassing amount of the thermosetting resin sheet are preferably measured in the state of the resin layer after peeling the transfer layer from the thermosetting resin sheet. It may also be measured in a state where a transfer layer is laminated on one surface of the resin layer. Further, for example, when other layers such as a protective layer are laminated on the other surface of the resin layer, it is preferable to measure in a state where the other layer such as the protective layer is peeled off and the other surface of the resin layer is exposed. The detailed measurement method may be carried out as described in the examples below. The total outgassing amount of the thermosetting resin sheet can be adjusted by the type of blocking agent in the blocked isocyanate contained in the thermosetting resin composition. Also, when drying the curable resin composition when forming the resin layer, it can be adjusted by the drying temperature and drying time. Further, it can also be adjusted by dilution with a solvent component.

[0010] The total outgassing amount measured by gas chromatography-mass spectrometry (GC-MS method) at the peak top temperature (T1) of endothermic or exothermic obtained from differential scanning calorimetry of the resin layer of the thermosetting resin sheet of the present invention is preferably 1000 ppm or more. When the total outgassing amount is 1000 ppm or more, the glossiness of the thermosetting resin sheet can be further increased. In particular, in the painting of automobiles, glossiness is important from the perspective of design. From such a perspective, the total outgassing amount is more preferably 1000 ppm or more, still more preferably 6000 ppm or more, and even more preferably 10000 ppm or more.

[0011] The peak top temperature (T1) is preferably 100°C or more and 175°C or less. When the peak top temperature is 100°C or more, it is possible to prevent the resin layer from curing before the curing step (for example, the second step described later). Also, when the peak top temperature is 175°C or less, when a base layer is formed on the object to be painted and then the thermosetting resin sheet is attached to the object to be painted, it is possible to suppress the peeling of the base layer from the object to be painted. From such a perspective, the peak top temperature (T1) is more preferably 110°C or more and 145°C or less, and still more preferably 115°C or more and 125°C or less.

[0012] (Resin layer) The resin layer is made of a thermosetting resin composition. The thermosetting resin composition preferably contains a polyol resin. Also, the thermosetting resin composition preferably contains a blocked isocyanate.

[0013] <Polyol resin> Examples of the polyol resin include (meth)acrylic polyol resin, polycarbonate polyol resin, polyester polyol resin, epoxy resin-modified polyol resin, etc. Among them, (meth)acrylic polyol resin is preferred. In the polyol resin, the number of hydroxyl groups is not particularly limited as long as it is 2 or more. Further, the polyol resin may have functional groups other than hydroxyl groups. Examples of the functional groups other than hydroxyl groups include an amino group, a carboxyl group, and the like.

[0014] The polyol resin preferably contains a (meth)acrylic resin having a plurality of functional groups, particularly a plurality of hydroxyl groups. (The (meth)acrylic resin may have functional groups other than hydroxyl groups. Examples of the functional groups other than hydroxyl groups include an amino group, a carboxyl group, and the like.

[0015] (The (meth)acrylic resin is preferably an acrylic polymer obtained by polymerizing a monomer mixture containing a (meth)acrylate monomer having no functional group and a functional group-containing monomer having a hydroxyl group. In such an alkyl polymer, a hydroxyl group-containing monomer can be used to incorporate a hydroxyl group into the acrylic polymer. Note that (meth)acrylic means methacrylic or acrylic, and the same applies to other similar terms.

[0016] Examples of the (meth)acrylate monomer include (meth)acrylate monomers having no functional group, such as alkyl (meth)acrylates having 1 to 18 carbon atoms in the alkyl group, such as methyl (meth)acrylate and ethyl (meth)acrylate, (meth)acrylates having an aromatic ring, such as benzyl (meth)acrylate and phenoxydiethylene glycol (meth)acrylate, and 2-ethoxyethyl (meth)acrylate.

[0017] The hydroxyl group-containing monomer is not particularly limited, and examples thereof include (meth)acrylate monomers having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate.

[0018] Further, the monomer mixture may include monomers containing functional groups other than hydroxyl groups, the above-mentioned (meth)acrylate monomers such as styrene derivative monomers, and those other than hydroxyl group-containing monomers. By using monomers containing functional groups other than hydroxyl groups, such as amino groups and carboxyl groups, in addition to hydroxyl group-containing monomers, functional groups other than hydroxyl groups can be introduced into the (meth)acrylic resin in addition to hydroxyl groups. The amino group-containing monomer is not particularly limited, and examples include (meth)acrylate monomers having an amino group, such as 2-aminoethyl (meth)acrylate. The carboxyl group-containing monomer is not particularly limited, and examples include (meth)acrylic acid. The styrene derivative monomer is not particularly limited, and examples include styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-ethoxystyrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, and the like.

[0019] Further, as the (meth)acrylic resin, a copolymer obtained by block or graft polymerization of the above-mentioned acrylic polymer and another monomer or polymer may be used. In this case, examples of the other monomer or polymer include acrylic-based, styrene-based, maleic acid-based, imide-based, silicone-based, fluorine-based monomers, or polymers of these monomers.

[0020] The thermosetting resin composition preferably contains a polyol resin (hereinafter also referred to as a high molecular weight polyol resin) having a weight average molecular weight of 50,000 or more and 1,000,000 or less. By including a polyol resin having a weight average molecular weight of 50,000 or more and 1,000,000 or less in the thermosetting resin composition, it becomes easier to balance and improve the coatability, curability, tackiness, stretchability, etc. of the resin layer. From such a viewpoint, the weight average molecular weight of the high molecular weight polyol resin is more preferably 60,000 or more and 800,000 or less, still more preferably 70,000 or more and 600,000 or less, and even more preferably 80,000 or more and 300,000 or less. In the present specification, the weight average molecular weight is measured by gel permeation chromatography (GPC) and is determined as a standard polystyrene conversion value.

[0021] The hydroxyl value of the high molecular weight polyol resin is preferably 10 mgKOH / g or more and 300 mgKOH / g or less. When the hydroxyl value of the polyol resin is 10 mgKOH / g or more, the hardness of the resin layer can be further increased. When the hydroxyl value of the polyol resin is 300 mgKOH / g or less, the adhesive strength of the resin layer can be further increased. From such a viewpoint, the hydroxyl value of the polyol resin is more preferably 30 mgKOH / g or more and 200 mgKOH / g or less, and still more preferably 60 mgKOH / g or more and 170 mgKOH / g or less. In the case where the high molecular weight polyol resin in the resin layer contains a plurality of types of polyol resins, the hydroxyl value of the high molecular weight polyol resin is the weighted average value of the hydroxyl values of the polyol resins contained in the resin layer. For example, when two types of polyol resins, polyol resin (d1) and polyol resin (d2), are used as the polyol resin, if the hydroxyl value of polyol resin (d1) is X1, the blending ratio is m1, the hydroxyl value of polyol resin (d2) is X2, and the blending ratio is m2, the weighted average value of the hydroxyl value is represented by the following formula. The blending ratio is based on mass. The same applies to the hydroxyl groups in the plasticizing resin described later. Weighted average value of hydroxyl value (mgKOH / g) = X1 × (m1 / (m1 + m2)) + X2 × (m2 / (m1 + m2)) In addition, the hydroxyl value can be measured in accordance with JIS K 1557-1:2007.

[0022] In addition to the high molecular weight polyol resin, the thermosetting resin composition may contain a plasticizing resin having a weight average molecular weight of less than 50,000. The plasticizing resin is preferably liquid at normal temperature and normal pressure. By containing a plasticizing resin having a low weight average molecular weight, the thermosetting resin composition can easily balance and improve the coatability, curability, tackiness, stretchability, etc. of the resin layer. In addition, the wettability to the object to be coated can be improved, and the adhesive strength of the resin layer to the object to be coated can be increased. The plasticizing resin is preferably a polyol resin having a weight average molecular weight of less than 50,000. The weight average molecular weight of the polyol resin used as the plasticizing resin is preferably 200 or more and 8000 or less, more preferably 300 or more and 6000 or less, and still more preferably 400 or more and 4000 or less.

[0023] The polyol resin used as the plasticizing resin is preferably (meth)acrylic polyol and polycarbonate polyol, and more preferably polycarbonate polyol.

[0024] The glass transition temperature of the polyol resin used as the plasticizing resin is preferably 10°C or lower, and more preferably -80°C or higher and 0°C or lower.

[0025] The hydroxyl value of the polyol resin used as the plasticizing resin is preferably 20 mgKOH / g or more and 350 mgKOH / g or less, more preferably 40 mgKOH / g or more and 300 mgKOH / g, and still more preferably 60 mgKOH / g or more and 250 mgKOH / g.

[0026] In a thermosetting resin composition, when a polyol resin is included as a plasticizing resin, the content of the polyol resin used as the plasticizing resin in the polyol resin is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and still more preferably 15% by mass or more and 30% by mass or less. Also, in this case, the content of the polyol resin having a weight average molecular weight of 50,000 or more and 1,000,000 or less in the polyol resin contained in the thermosetting resin composition is preferably 40% by mass or more and 80% by mass or less, more preferably 50% by mass or more and 70% by mass or less, and still more preferably 55% by mass or more and 65% by mass or less. Here, the content in the thermosetting resin composition means the content of each component in the whole thermosetting resin composition. For example, when the resin layer is multilayered, it means the content of each component of the thermosetting resin composition in the whole resin layer constituted by the whole multilayer. The same applies to the following regulations. The same also applies to the regulations on the hydroxyl value described above.

[0027] The content of the polyol resin in the thermosetting resin composition is preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 75% by mass or less, and still more preferably 35% by mass or more and 70% by mass or less. Note that the thermosetting resin composition for forming the resin layer may be diluted with volatile components such as a solvent as described later. In this specification, the content (mass%) of each component in the thermosetting resin composition means the value based on the solid content excluding the volatile components.

[0028] Within a range that does not inhibit the effects of the present invention, the thermosetting resin composition may contain a thermosetting resin other than the polyol resin. Examples of the thermosetting resin other than the polyol resin include (meth)acrylic resins other than the polyol resin, polycarbonate resins other than the polyol resin, polyester resins other than the polyol resin, epoxy resins other than the polyol resin, and the like. These thermosetting resins can be used alone or in combination of two or more.

[0029] The thermosetting resin other than the polyol resin may be a plasticized resin having a weight average molecular weight of less than 50,000, or a resin having a weight average molecular weight of 50,000 or more.

[0030] <Blocked isocyanate> The thermosetting resin composition preferably contains a blocked isocyanate. The blocked isocyanate is a compound in which the isocyanate group is blocked by a protecting group. When exposed to a high temperature, the protecting group (blocking agent) undergoes thermal dissociation and detaches, and a curing reaction occurs between the generated isocyanate group and the hydroxyl group of the above-mentioned polyol. The blocked isocyanate can be obtained, for example, by reacting a blocking agent with an isocyanate compound having two or more isocyanate groups in one molecule.

[0031] The isocyanate compound having two or more isocyanate groups in one molecule is not particularly limited. Examples thereof include 4,4'-diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), m-xylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), bis(isocyanatomethyl)cyclohexane (H6XDI), and modified products thereof. The modified product is not particularly limited, and examples thereof include adduct products, burette products, and isocyanurate products. The blocking agent of the blocked isocyanate is not particularly limited as long as the total outgas amount can be made 40,000 ppm or less. However, from the viewpoint of reducing the total outgas amount by lowering the heating temperature during the curing heating of the thermosetting resin sheet, the blocked isocyanate is preferably a blocked isocyanate in which the blocking agent is at least one compound selected from the group consisting of pyrazole-based compounds and malonic esters.

[0032] Examples of pyrazole compounds that can be used as blocking agents for blocked isocyanates include pyrazole, 3,5-dimethylpyrazole (DMP), 3,5-diisopropylpyrazole, 3,5-diphenylpyrazole, 3,5-di-t-butylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, 3-methyl-5-phenylpyrazole, and the like. These pyrazole compounds can be used alone or in combination of two or more. Among these, pyrazole and 3,5-dimethylpyrazole (DMP) are preferred.

[0033] Examples of malonic esters that can be used as blocking agents for blocked isocyanates include dialkyl malonates such as di-n-butyl malonate, di-t-butyl malonate, di-2-ethylhexyl malonate, methyl n-butyl malonate, ethyl n-butyl malonate, methyl s-butyl malonate, ethyl s-butyl malonate, methyl t-butyl malonate, ethyl t-butyl malonate, diethyl methylmalonate, dibenzyl malonate, diphenyl malonate, benzyl methyl malonate, ethyl phenyl malonate, t-butyl phenyl malonate, and isopropylidene malonate. These malonic esters can be used alone or in combination of two or more. Among these, diethyl methylmalonate is preferred.

[0034] The content of blocked isocyanate in the thermosetting resin composition is preferably adjusted so that the number of functional groups in the polyol resin is 0.4 or more and 1.8 or less, more preferably 0.6 or more and 1.5 or less, relative to the number of isocyanate groups in the blocked isocyanate.

[0035] The content of the blocked isocyanate in the thermosetting resin composition is preferably 40 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the polyol resin. When the content of the blocked isocyanate is 40 parts by mass or more with respect to 100 parts by mass of the polyol resin, the thermosetting resin composition can be cured more sufficiently. When the content of the blocked isocyanate is 90 parts by mass or less with respect to 100 parts by mass of the polyol resin, the total outgas amount of the thermosetting resin sheet can be further reduced. From such a viewpoint, the content of the blocked isocyanate is more preferably 50 parts by mass or more and 90 parts by mass or less, and still more preferably 55 parts by mass or more and 75 parts by mass or less with respect to 100 parts by mass of the polyol resin. Note that the thermosetting resin composition for forming the resin layer may be diluted with volatile components such as a solvent as described later. In this specification, the content (mass%) of each component in the thermosetting resin composition means a value based on the solid content excluding the volatile components.

[0036] In addition to the thermosetting resin and the curing agent, the thermosetting resin composition may appropriately contain components according to the performance required for the coating formed from the resin layer. For example, when the coating formed by the resin layer is a colored coating, colorants such as pigments, dyes, and brightening materials may be contained in the thermosetting resin composition. In this case, the resin layer becomes a colored resin layer. Also, when the coating formed by the resin layer is a heat-insulating coating, a heat-insulating material may be contained in the thermosetting resin composition. Further, the thermosetting resin composition may contain components other than those described above. For example, it may contain additives other than those described above. Examples of the additives include crosslinking agents, dispersants, inorganic fillers other than pigments and brightening materials, anti-aging agents, antioxidants, and rust preventives. Furthermore, the resin layer may be composed of a clear layer described later. Among these, it is preferable that the thermosetting resin composition contains at least a colorant.

[0037] Examples of pigments used as colorants include metal oxide pigments such as titanium oxide and iron oxide, inorganic pigments such as carbon black, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white, and organic pigments such as azo pigments, quinacridone pigments, diketopyrrolopyrrole pigments, perylene pigments, perinone pigments, benzimidazolone pigments, vat pigments, isoindoline pigments, isoindolinone pigments, metal chelate azo pigments, phthalocyanine pigments, indanthrone pigments, dioxane pigments, and indigo pigments, but are not limited thereto. As the dye, known dyes can be used, and examples include azo dyes, anthraquinone dyes, indigoid dyes, and stilbene dyes. The brightening agent is a compound capable of imparting brightness to the resin layer and a compound capable of imparting the property of showing gloss when observed from multiple directions. The brightening agent is not particularly limited, and examples include compounds having a titanium oxide layer provided on the surface of natural mica, synthetic mica, alumina flakes, glass flakes, etc. The thermosetting resin composition more preferably contains at least one of a pigment or a brightening agent as a colorant, and further preferably contains a pigment. Also, it is preferable for the thermosetting resin composition to contain both a pigment and a brightening agent. The content of the colorant in the thermosetting resin composition is not particularly limited, but is, for example, about 0.05 to 20% by mass, preferably 0.1 to 15% by mass, and more preferably 0.3 to 10% by mass. In addition to the above-mentioned additives such as colorants and heat insulating materials, the thermosetting resin composition may appropriately contain additives such as inorganic fillers, curing catalysts, curing accelerators, surface modifiers, defoaming agents, crosslinking agents, dispersants, anti-aging agents, and antioxidants.

[0038] The resin layer may consist of a single layer or may have a multilayer structure of two or more layers, but a multilayer structure is preferred. By having a multilayer structure, various functions can be imparted to the coating formed from the resin layer. When the resin layer has a multilayer structure, it suffices that the entire resin layer satisfies the above requirements, and it is not necessary for a part of the layers constituting the resin layer to satisfy the above requirements.

[0039] When the resin layer is a single layer, the resin layer preferably consists of a thermosetting resin composition containing a polyol resin and a blocked isocyanate. Further, the thermosetting resin composition may contain a colorant and other additives in addition to these.

[0040] When the resin layer has a multilayer structure, each layer preferably consists of a thermosetting resin composition containing a polyol resin and a blocked isocyanate. Further, each layer may contain a colorant as described above to form a colored resin layer, may contain a heat insulating material to form a heat insulating layer, or may be a clear layer without substantially containing a colorant.

[0041] When the resin layer has a multilayer structure, it preferably has at least a colored resin layer and a clear layer. When having a colored resin layer and a clear layer, the clear layer and the colored resin layer are preferably arranged in this order from the transfer layer side. With such a layer configuration, when the thermosetting resin sheet is attached to the object to be coated, the colored resin layer and the clear layer are arranged in this order from the object to be coated side. By having a colored resin layer, the object to be coated can be colored by the coating formed from the resin layer. Further, by providing a clear layer in addition to the colored resin layer, the colored resin layer can be protected or gloss can be imparted to the colored resin layer. The colored resin layer preferably contains a pigment as a colorant, and therefore, it is particularly preferable that the resin layer includes a clear layer and a pigment layer.

[0042] The colored resin layer and the clear layer are each preferably made of a thermosetting resin composition containing a polyol resin and a blocked isocyanate. The thermosetting resin composition for the colored resin layer may further contain a colorant as described above. The content of the colorant in the thermosetting resin composition for the colored resin layer is not particularly limited, but is, for example, about 0.1 to 25% by mass, preferably 0.3 to 20% by mass, more preferably 0.5 to 12% by mass.

[0043] The thermosetting resin composition for the colored resin layer preferably contains a polyol resin having a weight average molecular weight of 50,000 or more and 1,000,000 or less as described above, and preferably contains a plasticizing resin in addition to the polyol resin. As the plasticizing resin, a polyol resin having a weight average molecular weight of less than 50,000 is preferable as described above. The content of the polyol resin used as the plasticizing resin in the polyol resin of the thermosetting resin composition for the colored resin layer is preferably 20% by mass or more and 60% by mass or less, more preferably 30% by mass or more and 50% by mass or less, and still more preferably 35% by mass or more and 45% by mass or less. Also, in this case, the content of the polyol resin having a weight average molecular weight of 50,000 or more and 1,000,000 or less in the polyol resin of the thermosetting resin composition for the colored resin layer is preferably 40% by mass or more and 80% by mass or less, more preferably 50% by mass or more and 70% by mass or less, and still more preferably 55% by mass or more and 65% by mass or less.

[0044] On the other hand, the clear layer is a transparent layer and may have transparency such that the color of the colored resin layer can be visually recognized from the outside through the clear layer. For example, the transmittance of light with a wavelength of 450 nm is preferably 80% or more. The clear layer is preferably a coating film that does not contain a colorant, but may contain a small amount of a colorant as long as its function is not impaired. The content of the colorant in the thermosetting resin composition for the clear layer is not particularly limited, but is, for example, 0 to 2% by mass, preferably 0 to 0.5% by mass, more preferably 0 to 0.1% by mass. The thermosetting resin composition for the clear layer preferably contains a polyol resin having a weight average molecular weight of 50,000 or more and 1,000,000 or less as described above, but may or may not contain a plasticizing resin in addition to the polyol resin. When a plasticizing resin is contained, it is preferable to use a polyol resin having a weight average molecular weight of less than 50,000 as the plasticizing resin. However, the content of the polyol resin as the plasticizing resin in the polyol resin of the thermosetting resin composition for the clear layer is preferably less than the content of the polyol resin as the plasticizing resin in the polyol resin of the thermosetting resin composition for the colored resin layer.

[0045] The content of the polyol resin having a weight average molecular weight of 50,000 or more and 1,000,000 or less in the polyol resin of the thermosetting resin composition for the clear layer is preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and still more preferably 90% by mass or more and 100% by mass or less. Also, the content of the polyol resin as the plasticizing resin in the polyol resin of the thermosetting resin composition for the clear layer is preferably 0% by mass or more and 30% by mass or less, more preferably 0% by mass or more and 20% by mass or less, and still more preferably 0% by mass or more and 10% by mass or less.

[0046] The content of the blocked isocyanate in the thermosetting resin composition for the clear layer and the colored resin layer is the same as that in the above-described thermosetting resin composition, and the description thereof is omitted. Further, the thermosetting resin composition for the clear layer and the colored resin layer may contain additives as appropriate in addition to the colorant.

[0047] Of course, when the resin layer has a multilayer structure, it is not limited to a two-layer structure of a clear layer and a colored resin layer, and it can have various laminated structures. It is also possible to provide two or more colored resin layers and one or more clear layers to form a structure of three or more layers, or it may consist of two colored resin layers with the clear layer omitted. Also, two or more clear layers may be provided. Further, a heat shielding layer or the like may be provided between the clear layer and the colored resin layer to form a structure of three or more layers.

[0048] The thickness of the resin layer is not particularly limited, but for example, it is 20 μm or more and 200 μm or less, preferably 30 μm or more and 100 μm or less. Also, when a colored resin layer and a clear layer are provided in the resin layer, the thickness of the colored resin layer is not particularly limited, but for example, it is 10 μm or more and 100 μm or less, preferably 15 μm or more and 50 μm or less. Also, the thickness of the clear layer is not particularly limited, but for example, it is 10 μm or more and 100 μm or less, preferably 15 μm or more and 50 μm or less.

[0049] (Transfer layer) The transfer layer protects the resin layer from damage and adhesion of foreign substances, and also serves as a support when attaching the resin layer to the object to be coated. The transfer layer is preferably capable of being formed by vacuum forming and is preferably capable of being processed by cutting.

[0050] The transfer layer is preferably formed from a resin film. Examples of the resin used for the resin film include polyolefin resins such as polyethylene resin and polypropylene resin, and polyimide resin. Among these, from the viewpoints of production cost and handleability, it is more preferable to contain polypropylene resin or polyethylene resin, and from the viewpoint of heat resistance, it is more preferable to contain polypropylene resin or polyimide resin.

[0051] As the polypropylene resin, homopolypropylene may be used, or a copolymer of propylene such as random polypropylene and a small amount (for example, 10% by mass or less) of other α-olefins may be used. Examples of the other α-olefins include linear α-olefins having 1 to 12 carbon atoms such as ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, and 1-decene. As the polyethylene resin, low-density polyethylene (LDPE, density: less than 0.930 g / cm 3 , medium-density polyethylene (MDPE, density: 0.930 g / cm 3 or more and less than 0.942 g / cm 3 ), high-density polyethylene (HDPE, density: 0.942 g / cm 3 or more), linear low-density polyethylene (LLDPE), etc. may be mentioned.

[0052] The resin film constituting the transfer layer may be a single-layer film composed of a single layer, or a multilayer film of two or more layers. Further, in the resin film constituting the transfer layer, the resin contained in the resin film may be used alone or in combination of two or more. When two or more resins are used in combination, different types of resins may be used for each layer to form a multilayer film. Further, a single-layer film may be formed by mixing two or more resins, or one or two or more layers in the multilayer film may be formed.

[0053] The transfer layer may be a release agent such as a silicone-based release agent or a fluorine-based release agent, and at least one surface thereof may be release-treated. When the transfer layer is release-treated, the release-treated surface preferably constitutes the surface on the resin layer side. The transfer layer is easily made to have good peelability from the resin layer by being release-treated. However, the transfer layer does not necessarily need to be release-treated as long as it can be peeled from the resin layer.

[0054] The thickness of the transfer layer is not particularly limited, but for example, it is 10 μm or more and 1000 μm or less, preferably 30 μm or more and 700 μm or less, more preferably 50 μm or more and 500 μm or less. When the thickness of the transfer layer is below the above upper limit value, the air permeability value is likely to be below a certain level, and it becomes easier to vent the gas generated from the resin layer. Also, when the thickness of the transfer layer is above the above lower limit value, a certain strength can be imparted to the transfer layer.

[0055] (Protective layer) The thermosetting resin sheet may be provided with a protective layer. The protective layer is a member that protects the resin layer from being damaged and from adhering foreign substances. The protective layer is preferably formed from a resin film. Examples of the resin used for the resin film for the protective layer include thermoplastic resins. Also, it is preferable to use a resin whose elongation at break can be adjusted within the above-mentioned desired range. The protective layer is preferably capable of being formed by vacuum forming and is preferably capable of being processed by cutting. Specific examples of the resin used for the resin film include polyolefin resins, polyester resins such as polybutylene terephthalate and polyethylene terephthalate, polyamide resins, polycarbonate resins, acrylic resins, fluororesins, soft vinyl chloride resins, polymethylpentene resins, tetrafluoroethylene resins, etc. When using a polyolefin resin, the same one as the above transfer layer can be used. Among the above, polyester resins are preferred.

[0056] The resin film forming the protective layer may be a single-layer film composed of a single layer, or may be a multilayer film of two or more layers. Also, in the resin film constituting the protective layer, the resin contained in the resin film may be used alone or two or more kinds may be used in combination. The resin film used for the protective layer may be a stretched resin film or an unstretched resin film that has not been stretched, but an unstretched resin film is preferred. The protective layer may be a release agent such as a silicone-based release agent or a fluorine-based release agent, and at least one of its surfaces may be subjected to a release treatment. When the protective layer is subjected to a release treatment, the release-treated surface preferably constitutes the surface on the resin layer side. By subjecting the protective layer to a release treatment, it becomes easier to improve the peelability from the resin layer. However, as long as the protective layer can be peeled from the resin layer, it may not be subjected to a release treatment. The thickness of the protective layer is not particularly limited, but for example, it is 10 μm or more and 1000 μm or less, preferably 30 μm or more and 700 μm or less, more preferably 50 μm or more and 500 μm or less.

[0057] (Method for manufacturing a thermosetting resin sheet) The method for manufacturing the thermosetting resin sheet is not particularly limited, but it can be manufactured by a known method. For example, a thermosetting resin composition is prepared, and the prepared thermosetting resin composition is applied onto the transfer layer and dried as necessary to form a resin layer. Further, when the thermosetting resin sheet includes a protective layer, the thermosetting resin composition is applied onto the protective layer and dried as necessary to form a resin layer, and a transfer layer may be further laminated onto the resin layer formed on the obtained protective layer to obtain a thermosetting resin sheet. When applying the thermosetting resin composition onto the transfer layer or the protective layer, the thermosetting resin composition may be appropriately diluted with a solvent or the like. Examples of the solvent include ethyl acetate, butyl acetate, and toluene. Further, when the resin layer is multilayered, it may be formed by sequentially forming and laminating each layer. For example, when having a clear layer and a colored resin layer, the clear layer and the colored resin layer may be laminated in this order onto the transfer layer. Further, when the thermosetting resin sheet includes a protective layer, a thermosetting resin sheet may be obtained by laminating the colored resin layer formed on the protective layer and the clear layer formed on the transfer layer.

[0058] [Coating method] Hereinafter, a coating method for coating an object to be coated using the thermosetting resin sheet of the present invention is provided. The coating method according to an embodiment of the present invention includes the following first and second steps. Step 1: A step of attaching a thermosetting resin sheet to an object to be coated Step 2: A step of heat-curing the thermosetting resin sheet

[0059] (Step 1) The first step is a step of attaching a thermosetting resin sheet to an object to be coated. The object to be coated to which the thermosetting resin sheet is attached is not particularly limited, and examples include vehicles such as electrical appliances, automobiles, and transportation equipment other than automobiles, vehicle parts of vehicles such as automobiles and transportation equipment other than automobiles, miscellaneous goods, heavy machinery, ships, aircraft, etc., exterior materials of houses, exterior walls or roof materials of buildings, bridges, steel structures, plants, wind power generation blades, etc. Vehicle parts include, for example, interior materials for vehicles and exterior materials for vehicles. Among these, vehicles and vehicle parts are preferred, vehicle parts are more preferred, and exterior materials for vehicles are even more preferred. Examples of exterior materials for vehicles include hoods, roofs, door panels, bumpers, fuel filler panels, trunk lids, rear gates, etc. When the thermosetting resin sheet is attached to an exterior material for a vehicle, it may be attached to an exterior material attached to the vehicle body or to an exterior material before being attached to the vehicle body. Also, the material of the object to be coated is not particularly limited, and it may be any of resin materials, inorganic materials such as ceramics, and metal materials such as steel materials, but among these, metal materials such as steel materials are preferred.

[0060] The thermosetting resin sheet used in the first step is a sheet for forming a coating on an object to be coated. The thermosetting resin sheet includes a resin layer and a transfer layer formed on one surface of the resin layer. The resin layer is made of a thermosetting resin composition and can be cured by heating. The resin layer constitutes a part of the coating formed on the object to be coated.

[0061] Before being attached to the object to be coated, a protective layer may be laminated on the other surface of the resin layer in the thermosetting resin sheet. When the protective layer is laminated, the transfer-type thermosetting resin may be attached to the object to be coated after peeling the protective layer from the resin layer to expose the resin layer. The method of peeling the protective layer is not particularly limited and may be peeled by a peeling device or manually. Of course, in the thermosetting resin sheet, the protective layer may be omitted.

[0062] In this step, it is preferable to attach the thermosetting resin sheet with the resin layer exposed to the object to be coated so that the resin layer is in contact therewith. At this time, the attachment of the thermosetting resin sheet to the object to be coated is not particularly limited and may be performed by manual attachment using a squeegee or the like, or may be performed using a laminating device. Since the resin layer is made of a thermosetting resin composition and is uncured at the time of attachment, it is easy to ensure a certain degree of flexibility. Therefore, the resin layer can be properly adhered to the object to be coated and temporarily fixed to the object to be coated with an appropriate adhesive strength.

[0063] The thermosetting resin sheet may be preformed by vacuum forming, press forming, pressure air forming, etc., and shaped into a shape corresponding to the shape of the object to be coated, and the shaped thermosetting resin sheet may be attached to the object to be coated. The preforming may be performed before peeling the protective layer from the resin layer when the thermosetting resin sheet has a protective layer, or may be performed after peeling the protective layer from the resin layer. By performing the preforming, even if the object to be coated has a complex shape, the thermosetting resin sheet can be easily adhered and attached to the object to be coated. Among the above, the preforming is preferably performed by vacuum forming. The preforming is preferably performed by pressing the coating sheet against a jig or a mold by vacuum forming and shaping the thermosetting resin sheet into a shape corresponding to the surface shape of the object to be coated while stretching the thermosetting resin sheet by the jig or the mold. Here, the vacuum forming is preferably TOM forming. TOM is "Three dimension Overlay Method", and when TOM forming is applied, it is possible to shape into a complex shape.

[0064] Before attaching the thermosetting resin sheet to the object to be painted, a base layer may be formed on the surface of the object to be painted. By attaching the thermosetting resin sheet to the object to be painted through the base layer, the adhesive force between the thermosetting resin sheet and the object to be painted can be further increased. The base layer can be formed, for example, by applying a paint for the base layer to the object to be painted. The painting method for the base layer is not particularly limited, and examples thereof include brush painting, roll brush painting, tampo painting, spray painting, roller painting, curtain flow painting, flow painting, dipping painting, spatula painting, etc.

[0065] The paint for the base layer may be any paint generally used for painting building materials and vehicles.

[0066] (Second step) The second step is a step performed after the first step, and the resin layer of the thermosetting resin sheet is heated and cured. In this step, it is preferable to cure the resin layer sufficiently until it can be used as a coating.

[0067] Also, in the second step, the thermosetting resin sheet may be heated using a heating device such as an oven or an infrared heater in a state where it is attached to the object to be painted. The heating temperature is preferably 50°C or higher and 165°C or lower, more preferably 60°C or higher and 145°C or lower. Also, the heating time is, for example, 5 minutes or longer and 60 minutes or shorter, preferably 10 minutes or longer and 30 minutes or shorter.

[0068] In the painting method of the present invention, further, a step of peeling the transfer layer from the resin layer may be provided. The peeling of the transfer layer may be peeled by a peeling device or may be peeled manually. The peeling of the transfer layer may be performed before the above-described second step, after the second step, or during the second step, but it is preferably performed before the second step. By performing it before the second step, the generated trace amount of outgas can be released to the outside without being inhibited by the transfer layer, so that the foaming caused by the wake can be more effectively suppressed.

[0069] [Vehicle, vehicle parts, method for manufacturing a vehicle, method for manufacturing vehicle parts] The vehicle and vehicle parts of the present invention are coated using the thermosetting resin sheet of the present invention. Therefore, the method for manufacturing a vehicle and the method for manufacturing vehicle parts of the present invention include a step of coating using the thermosetting resin sheet of the present invention. Note that the coating step may be performed by the method described in the above coating method.

Example

[0070] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0071] The measurement method and evaluation method in this example are as follows. <Peak top temperature (T1)> The peak top temperature (T1) of the endothermic or exothermic peak obtained from the differential scanning calorimetry of the resin layer of the thermosetting resin sheet was measured as follows. Using a differential scanning calorimeter (manufactured by Seiko Instruments Inc., trade name "DSC7020"), under a nitrogen stream, at a heating rate of 10 ° C / min in the temperature range of 30 ° C to 200 ° C, 10 mg of the resin layer obtained by peeling the transfer layer from the thermosetting resin sheet was measured. The peak top temperature of the endothermic peak or exothermic peak with an absolute value of the endothermic amount or exothermic amount (J1) of 5 mj / mg or more was defined as the peak top temperature (T1) of the resin layer of the thermosetting resin sheet. When there are multiple peak top temperatures of the endothermic or exothermic peak with an absolute value of the endothermic amount or exothermic amount (J1) of 5 mj / mg or more, the peak top temperature of the lowest temperature was defined as the peak top temperature (T1) of the resin layer of the thermosetting resin sheet.

[0072] <Total outgas amount> The total outgassing amount was measured as follows. A thermosetting resin sheet composed of a transfer layer and a resin layer was cut into pieces of 5 mm × 5 mm. The transfer layer was peeled off from the cut thermosetting resin sheet to prepare a measurement sample composed of the resin layer. The total outgassing amount (ppm in toluene conversion: μg / g) of the measurement sample was measured using a thermal desorption GC-MS (thermal desorption device: manufactured by PerkinElmer, trade name "TurboMatrix 350", GC-MS device: manufactured by JEOL Ltd., trade name "JMS Q1500GC"). The detailed measurement conditions are as follows. (Measurement conditions) Device: Outgassing analysis Device: TurboMatrix 350 (manufactured by PerkinElmer) Heating: the above peak top temperature (T1), 30 min (20 mL / min) Secondary desorption: 350 °C Split: inlet 25 mL / min, outlet 25 mL / min, injection volume 2.5% GC / MS device: Agilent7890B&JMS-Q1500GC Column: EQUITY-1 (non-polar) 0.32 mm × 60 m × 0.25 μm Column temperature: 40 °C (4 min) → 10 °C / min → 300 °C (10 min) He flow rate: 1.5 mL / min (split ratio 1:30) MS temperature: ion source; 230 °C, interface; 250 °C MS measurement range: 29~600 Ionization method: EI method Measurement mode: scan Ionization voltage: 70 eV

[0073] (Foaming property) Using a construction liquid (manufactured by Lintec Corporation, product name "Real Paerfect"), a 5 cm × 5 cm thermosetting resin sheet was water - pasted onto a glass plate. After peeling off the transfer layer, it was baked at the peak top temperature (T1) for 40 minutes. Then, after cooling, the number of foaming sites in a 4 cm × 4 cm range centered on the center of the thermosetting resin sheet was visually measured. Note that the more the number of foaming sites, the easier it is for the thermosetting resin sheet to develop warping. (Evaluation Criteria) A: The number of foaming sites is 9 or less B: The number of foaming sites is 10 or more and 19 or less C: The number of foaming sites is 20 or more

[0074] (Adhesion of the base layer) Using a construction liquid (manufactured by Lintec Corporation, product name "Real Paerfect"), a 5 cm × 5 cm thermosetting resin sheet was water - pasted onto a glass plate. After peeling off the transfer layer, it was baked at the peak top temperature (T1) for 40 minutes. A cross - cut test was carried out at 2 mm intervals for 100 squares in accordance with the JIS standard (JIS K5600 - 5 - 6) and evaluated according to the following evaluation criteria. (Evaluation Criteria) A: No peeling or chipping B: No peeling, but chipping occurs C: One or more peelings occur

[0075] (Glossiness) Using a construction liquid (manufactured by Lintec Corporation, product name "Real Paerfect"), a 5 cm × 5 cm thermosetting resin sheet was water - pasted onto a glass plate. After peeling off the transfer layer, it was baked at the peak top temperature (T1) for 40 minutes. Then, after cooling, a gloss meter (manufactured by BYK, product name "micro - TRI - gloss") was used to measure the 60° glossiness in a 4 cm × 4 cm range centered on the center of the thermosetting resin sheet in accordance with JIS K 5600 - 4 - 7. (Evaluation Criteria) A: 60° glossiness is 80% or more B: 60° glossiness is 70% or more and less than 80% C: 60° glossiness is less than 70%

[0076] The components of the film for the transfer layer, the film for the protective layer, and the resin layer used in the examples and comparative examples are as follows. <Film for Transfer Layer and Film for Protective Layer> Convenience store PE: Unstretched polyethylene / EVA multilayer film ("Convenience store PE" manufactured by Okamoto & Co., Ltd., thickness 200 μm)

[0077] <Polyol Resin> Acrylic polyol resin (1): Weight average molecular weight 250,000, hydroxyl value 80 mgKOH / g, glass transition temperature 40 °C, solid content concentration (NV) = 29.6 mass% (solvent: ethyl acetate) Acrylic polyol resin (2): Weight average molecular weight 250,000, hydroxyl value 150 mgKOH / g, glass transition temperature 40 °C, solid content concentration (NV) = 29.6 mass% (solvent: ethyl acetate) Polycarbonate diol: Weight average molecular weight 500, hydroxyl value 224 mgKOH / g, solid content concentration (NV) = 100 mass%, manufactured by UBE Industries, Ltd., "PH-50"

[0078] <Block Isocyanate> Block isocyanate (1): Hexamethylene diisocyanate (HDI)-based block isocyanate, manufactured by Mitsui Chemicals, Inc., blocking agent type: pyrazole-based compound blocking agent, effective NCO content 10.4 mass%, solid content concentration (NV) = 68 mass% (solvent: ethyl acetate) Block isocyanate (2): Hexamethylene diisocyanate (HDI)-based block isocyanate, manufactured by Asahi Kasei Corporation, "Duranate MF-K60B", blocking agent type: malonic ester, effective NCO content 8.0 mass%, solid content concentration (NV) = 60 mass% (solvent: butyl acetate and butanol) Block isocyanate (3): Hexamethylene diisocyanate (HDI)-based block isocyanate, manufactured by Mitsui Chemicals, Inc., "Takenate B-882N", blocking agent type: oxime-based blocking agent, effective NCO content 10.7 mass%, solid content concentration (NV) = 70 mass% (solvent: aromatic hydrocarbon solvent S100 and butyl acetate)

[0079] <Urethane-forming catalyst> 「XK-639」, manufactured by Kusumoto Chemicals, Ltd., solid content concentration (NV) = 100%

[0080] <Pigment (colorant)> 「NSP-RF 890B BLACK」 manufactured by Nichihiro Binks Co., Ltd., effective pigment concentration = 15% by mass, solid content concentration (NV) = 15% by mass, solvent is MEK

[0081] <Lustrous material (colorant)> 「Xirallic T60-10 WNT Crystal Silver」 manufactured by Merck, solid content concentration (NV) = 100% by mass

[0082] [Preparation of thermosetting resin compositions A to G] Each component was added in the formulation as shown in Table 1, and ethyl acetate was added as a solvent to prepare diluted solutions of thermosetting resin compositions A to G so that the solid content concentration was 40% by mass.

[0083]

Table 1

[0084] [Example 1] On the surface of the film for the protective layer, thermosetting resin composition A was applied with an applicator, and then the drying process was carried out under the conditions of a drying temperature of 60 °C and a drying time of 15 minutes to form a colored resin layer with a thickness of 20 μm on the protective layer. Next, on the surface of the film for the transfer layer, thermosetting resin composition D was applied with an applicator, and then the drying process was carried out under the conditions of a drying temperature of 60 °C and a drying time of 15 minutes to form a clear layer with a thickness of 20 μm on the transfer layer. The clear layer on the transfer layer and the colored resin layer on the protective layer were laminated at 25 °C, and then the protective layer was peeled off from the colored resin layer to obtain a thermosetting resin sheet laminated in the order of the transfer layer, the clear layer, and the colored resin layer. The evaluation results of the obtained thermosetting resin sheet are shown in Table 2.

[0085] [Examples 2, 3, Comparative Example 1] It was the same as Example 1, except that the thermosetting resin composition used to form the colored resin layer and the clear layer was changed as described in Table 2.

[0086] [Example 4] It was carried out in the same manner as Example 2, except that the drying temperature in the drying process was changed to 40°C.

[0087] [Example 5] It was carried out in the same manner as Example 2, except that the drying temperature in the drying process was changed to 80°C.

[0088]

Table 2

[0089] For the thermosetting resin sheets of Examples 1 to 5, since the total outgas amount at the peak top temperature (T1) of the resin layer was 40,000 ppm or less, the evaluation regarding foamability was good. On the other hand, for the thermosetting resin sheet of Comparative Example 1, since the total outgas amount at the peak top temperature (T1) of the resin layer was greater than 40,000 ppm, the evaluation regarding foamability was poor.

Claims

1. A thermosetting resin sheet comprising a resin layer made of a thermosetting resin composition and a transfer layer, wherein the total outgassing amount measured by gas chromatography-mass spectrometry (GC-MS method) at the peak top temperature (T1) of endotherm or exotherm obtained from differential scanning calorimetry of the resin layer of the thermosetting resin sheet is 40,000 ppm or less.

2. The thermosetting resin sheet according to claim 1, wherein the total outgassing amount measured by GC-MS method at the peak top temperature (T1) of the resin layer of the thermosetting resin sheet is 1000 ppm or more.

3. The thermosetting resin sheet according to claim 1 or 2, wherein the thermosetting resin composition contains a blocked isocyanate.

4. The thermosetting resin sheet according to claim 3, wherein the blocking agent of the blocked isocyanate is at least one compound selected from the group consisting of pyrazole-based compounds and malonic esters.

5. The thermosetting resin composition contains a polyol resin, and the content of the blocked isocyanate in the resin layer is 40 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the polyol resin. The thermosetting resin sheet according to claim 3.

6. The thermosetting resin sheet according to claim 1 or 2, wherein the thermosetting resin composition contains a polyol resin having a weight average molecular weight of 50,000 or more and 1,000,000 or less.

7. The thermosetting resin sheet according to claim 6, wherein the polyol resin is (meth)acrylic polyol.

8. The thermosetting resin composition further contains a colorant, and the resin layer is a colored resin layer. The thermosetting resin sheet according to claim 1 or 2.

9. A vehicle painted using the thermosetting resin sheet according to claim 1 or 2.

10. Vehicle parts painted using the thermosetting resin sheet according to claim 1 or 2.

11. A method for manufacturing a vehicle, comprising a step of painting using the thermosetting resin sheet according to claim 1 or 2.

12. A method for manufacturing vehicle parts, comprising a step of painting using the thermosetting resin sheet according to claim 1 or 2.

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