Transfer sheet, method for producing transfer sheet, method for producing exterior member, and exterior member with release film

Abstract

To provide a transfer sheet which is excellent in visibility of a design without releasing a release film, can transfer a transfer layer having low glossy feeling and is used for manufacturing an exterior member.SOLUTION: A transfer sheet has a release film 1, and a transfer layer arranged on one surface of the release film, wherein the transfer layer has a first protective layer 2 and a second protective layer 3 in this order in a thickness direction from the release film side, the first protective layer contains a cured product of a first curable resin composition and a weather-resistant agent, the second protective layer contains a cured product of a second curable resin composition and a weather-resistant agent, the release film has a first surface S1 positioned opposite to the transfer layer side and a second surface S2 positioned on the transfer layer side, a 60° gross value of the first surface is 90 or more, a 60° gross value of the second surface is 40 or less, and indentation hardness in the cross section of the first protective layer is 150 MPa or more and 300 MPa or less.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a transfer sheet, a method for producing a transfer sheet, a method for producing an exterior member, and an exterior member with a release film. [Background technology]

[0002] It is known to decorate a base such as a metal member or a resin member by transferring a transfer layer (a layer transferred from the transfer sheet) of a transfer sheet to the base. For example, Patent Document 1 discloses a design transfer sheet including a release layer and a design transfer layer removably attached to the release layer, the design transfer layer including, from the release layer side, a first surface layer capable of being heat-bonded and a second surface layer capable of being heat-bonded, in this order. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2016-120643 A Summary of the Invention [Problem to be solved by the invention]

[0004] The transfer sheet has, for example, a release film and a transfer layer. In recent years, with the increasing trend of customers toward luxury goods, the transfer layer transferred to the substrate is required to have a low gloss. In addition, the transfer sheet is required to have excellent visibility of the design without peeling off the release film.

[0005] The present disclosure has been made in consideration of the above-mentioned situation, and has as its main object to provide a transfer sheet used in the manufacture of exterior components, which is capable of transferring a transfer layer having excellent visibility of a design and a low gloss appearance without peeling off a release film. [Means for solving the problem]

[0006] The present disclosure provides a transfer sheet used in the manufacture of an exterior member, the transfer sheet having a release film and a transfer layer disposed on one side of the release film, the transfer layer having a first protective layer and a second protective layer in this order in the thickness direction from the release film side, the first protective layer containing a cured product of a first curable resin composition and a weather resistance agent, the second protective layer containing a cured product of a second curable resin composition and a weather resistance agent, the release film having a first surface located on the opposite side to the transfer layer side and a second surface located on the transfer layer side, the 60° gloss value of the first surface is 90 or more, the 60° gloss value of the second surface is 40 or less, and the indentation hardness of the cross section of the first protective layer is 150 MPa or more and 300 MPa or less.

[0007] The present disclosure also provides a transfer sheet used in the manufacture of an exterior member, the transfer sheet having a release film and a transfer layer arranged on one side of the release film, the transfer layer having a first protective layer and a second protective layer in this order in the thickness direction from the release film side, the first protective layer containing a cured product of a first curable resin composition and a weather resistance agent, the second protective layer containing a cured product of a second curable resin composition and a weather resistance agent, the release film having a first surface located on the opposite side to the transfer layer side and a second surface located on the transfer layer side, the maximum height Rz of the first surface is 0.8 μm or less, the maximum height Rz of the second surface is 2.0 μm or more, and the indentation hardness of the cross section of the first protective layer is 150 MPa or more and 300 MPa or less.

[0008] The present disclosure provides a method for producing the above-mentioned transfer sheet, comprising: a first protective layer forming step of applying a first composition containing the first curable resin composition and the weather resistance agent to the second surface of the release film, and curing the composition to form the first protective layer; and a second protective layer forming step of applying a second composition containing the second curable resin composition and the weather resistance agent to the surface of the first protective layer opposite the release film, and curing the composition to form the second protective layer.

[0009] The present disclosure provides a method for manufacturing an exterior member, the method including a preparation step of preparing the above-mentioned transfer sheet, and a bonding step of opposing the surface of the transfer sheet facing the second protective layer to a substrate and bonding the two together.

[0010] The present disclosure provides an exterior member with a release film, which has, in this order in the thickness direction, a release film, a first protective layer, a second protective layer, and a substrate, wherein the first protective layer contains a cured product of a first curable resin composition and a weathering agent, and the second protective layer contains a cured product of a second curable resin composition and a weathering agent, the release film has a first surface located opposite to the first protective layer side and a second surface located on the first protective layer side, the 60° gloss value of the first surface is 90 or more, the 60° gloss value of the second surface is 40 or less, and the indentation hardness of the cross section of the first protective layer is 150 MPa or more and 300 MPa or less.

[0011] The present disclosure also provides an exterior member with a release film, which has, in this order in the thickness direction, a release film, a first protective layer, a second protective layer, and a substrate, wherein the first protective layer contains a cured product of a first curable resin composition and a weathering agent, and the second protective layer contains a cured product of a second curable resin composition and a weathering agent, the release film has a first surface located on the side opposite to the first protective layer and a second surface located on the first protective layer side, the maximum height Rz of the first surface is 0.8 μm or less, the maximum height Rz of the second surface is 2.0 μm or more, and the indentation hardness of a cross section of the first protective layer is 150 MPa or more and 300 MPa or less. Effect of the Invention

[0012] The present disclosure has the effect of providing a transfer sheet used in the manufacture of exterior components, which has excellent visibility of the design even without peeling off a release film and is capable of transferring a transfer layer having a low gloss. [Brief description of the drawings]

[0013] [Figure 1] 1 is a schematic cross-sectional view illustrating a transfer sheet according to the present disclosure. [Diagram 2] 1 is a schematic cross-sectional view illustrating a release film in the present disclosure. [Diagram 3] 1A to 1C are schematic cross-sectional views illustrating a method for producing a transfer sheet in the present disclosure. [Figure 4] 1A to 1C are schematic cross-sectional views illustrating a method for manufacturing an exterior member in the present disclosure. [Diagram 5] 1 is a schematic cross-sectional view illustrating an example of an exterior member with a release film in the present disclosure. [Figure 6] 1 is a schematic cross-sectional view showing an example of an exterior member according to the present disclosure. [Figure 7] FIG. 1 is a schematic cross-sectional view showing an example of a conventional transfer sheet. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The following describes the embodiments with reference to the drawings. However, the present disclosure can be implemented in many different forms and should not be limited to the description of the embodiments exemplified below. In addition, the drawings may show the width, thickness, and shape of each part in a schematic manner compared to the actual form in order to make the description clearer, but this is merely an example and should not be interpreted as being limiting.

[0015] In this specification, when describing a mode in which another component is disposed on a certain component, the term "above" or "below" includes both cases in which another component is disposed directly above or below the certain component so as to be in contact with the component, and cases in which another component is disposed above or below the certain component with another component interposed therebetween, unless otherwise specified. In addition, in this specification, when describing a mode in which another component is disposed on the surface of a certain component, the term "on the surface" includes both cases in which another component is disposed directly above or below the certain component so as to be in contact with the component, and cases in which another component is disposed above or below the certain component with another component interposed therebetween, unless otherwise specified.

[0016] The transfer sheet, the method for producing the transfer sheet, the method for producing an exterior member, and the exterior member with a release film according to the present disclosure will be described in detail below.

[0017] A. Transfer sheet The transfer sheet in the present disclosure has two embodiments, which will be described below separately.

[0018] I. Transfer sheet of the first embodiment 1(a) is a schematic cross-sectional view illustrating a transfer sheet in this embodiment. As shown in FIG. 1(a), a transfer sheet 10 has a release film 1 and a transfer layer X arranged on one surface of the release film 1. The transfer layer X is a first protective layer 2 and a second protective layer 3 from the release film 1 side in a thickness direction D. T 1(b), the transfer sheet 10 may have an adhesive layer 4 on the surface of the second protective layer 3 opposite to the first protective layer 2. As shown in FIG. 1(c), the transfer sheet 10 may have a design layer 5 on the surface of the second protective layer 3 opposite to the first protective layer 2. In FIG. 1(c), the design layer 5 is disposed between the adhesive layer 4 and the second protective layer 3.

[0019] In this embodiment, the first protective layer 2 contains a cured product of a first curable resin composition and a weather resistant agent, and the second protective layer 3 contains a cured product of a second curable resin composition and a weather resistant agent.

[0020] In addition, in this embodiment, the release film 1 has a first surface S1 located on the side opposite to the transfer layer X side, and a second surface S2 located on the transfer layer X side, the 60° gloss value of the first surface S1 is within a predetermined range, the 60° gloss value of the second surface S2 is within a predetermined range, and the indentation hardness of the cross section of the first protective layer 2 is within a predetermined range.

[0021] As described above, the transfer layer transferred to the substrate is required to have a low gloss. For this reason, a matte film containing, for example, a resin and a matte agent such as silica particles may be used as the release film of the transfer sheet. FIG. 7 is a schematic cross-sectional view showing an example of a transfer sheet using a matte film as the release film. The transfer sheet 200 shown in FIG. 7 has a matte film 21 as a release film and a transfer layer X arranged on one side of the matte film 21. The transfer layer X is formed by separating the first protective layer 22, the second protective layer 23, the design layer 25, and the adhesive layer 24 from the matte film 21 side in the thickness direction D. T In this order:

[0022] The transfer sheet 200 uses the matte film 21 as a release film, which imparts unevenness to the surface of the transfer layer X after the release film 21 is peeled off, and is thought to provide a low gloss feeling. However, when the transfer sheet 200 is observed from the matte film 21 side, diffuse reflection of light occurs on the surface of the matte film 21 opposite the transfer layer X, reducing the visibility of the design. Therefore, in order to visually recognize the design, it is necessary to peel off the matte film. In addition, when the transfer layer X has a low gloss feeling, the exterior member (member for outdoor use) is exposed to a harsh environment, and therefore there is a tendency for the gloss change due to deterioration of the resin to become significant.

[0023] In this specification, the visibility of the design refers to, for example, the visibility of the design that is expressed by a layer (for example, a design layer) inside the transfer layer.

[0024] On the other hand, the transfer sheet in this embodiment has a high 60° gloss value of the first surface of the release film within a predetermined range, and therefore the transfer sheet has excellent visibility of the design even without peeling off the release film. Therefore, it is possible to inspect for defects without peeling off the release film, improving workability. In addition, since the release film can be used as a masking film as it is, it is possible to reduce the amount of plastic used. Furthermore, since the 60° gloss value of the second surface is low within a predetermined range, the transfer layer after peeling off the release film has a low gloss feeling. In addition, the present inventors have found that since the 60° gloss value of the second surface is low within a predetermined range, the adhesion between the first protective layer and the release film is increased, and therefore the release film tends to be difficult to peel off. And, it has been found that since the indentation hardness at the cross section of the first protective layer is within a predetermined range, it is possible to easily peel off the release film.

[0025] In addition, exterior members (outdoor members) are required to have higher weather resistance than interior members (indoor members). For example, when manufacturing an exterior member using a decorative sheet, a transparent resin layer may be provided on the decorative sheet for the purpose of improving strength. In this case, since the transparent resin layer is a relatively thick layer, for example, high weather resistance is imparted by adding a sufficient amount of weather resistance agent to the transparent resin layer. In contrast, it is technically difficult to impart high weather resistance to a transfer sheet that does not have a layer corresponding to the transparent resin layer. In this embodiment, usually, both the first protective layer and the second protective layer contain a weather resistance agent. This makes it possible to impart high weather resistance while maintaining the properties required for the first protective layer (for example, surface properties such as scratch resistance and abrasion resistance) and the properties required for the second protective layer (for example, adhesion).

[0026] Furthermore, since the first protective layer contains a weather resistance agent, even when the surface of the transfer layer X has a low glossiness as in this embodiment, changes in glossiness due to deterioration of the resin are suppressed.

[0027] 1. Release film The transfer sheet in this embodiment has a release film. As shown in Fig. 1, the release film 1 in this embodiment has a first surface S1 located on the side opposite to the transfer layer X side, and a second surface S2 located on the transfer layer X side. The first surface S1 and the second surface S2 of the release film 1 face each other. As shown in Fig. 1, the release film 1 and the first protective layer 2 are preferably arranged so as to be in direct contact with each other.

[0028] (1) 60° gloss value In this embodiment, the 60° gloss value of the first surface of the release film is usually 90 or more, and may be 100 or more, or may be 110 or more. If the 60° gloss value of the first surface S1 is low, diffuse reflection due to surface unevenness tends to increase, and the visibility of the design may decrease. On the other hand, the 60° gloss value of the first surface of the release film is, for example, 200 or less, and may be 160 or less, or may be 140 or less.

[0029] In this embodiment, the 60° gloss value of the first surface of the release film is a value measured by the following method. The release film peeled off from the transfer sheet is placed on a non-glossy black mount with the first side facing up, and the 60° specular gloss is measured using a gloss meter ("Micro Trigloss (model name)", manufactured by BYK Gardner) in accordance with Method 3 of JIS Z 8741:1997.

[0030] In this embodiment, the 60° gloss value of the second surface S2 of the release film is usually 40 or less, may be 35 or less, or may be 30 or less. If the 60° gloss value of the second surface of the release film is high, the transfer layer after the release film is peeled off is less likely to exhibit a low gloss feeling. On the other hand, the 60° gloss value of the second surface S2 is, for example, 3.0 or more, may be 5.0 or more, or may be 10 or more. If the 60° gloss value of the second surface is low, the resin of the first protective layer may enter into a fine matte shape, making peeling difficult. In addition, it may not be possible to form the desired shape.

[0031] In this embodiment, the 60° gloss value of the second surface of the release film is a value measured by the following method. The release film peeled off from the transfer sheet is placed on a non-glossy black mount with the second side facing up, and the 60° specular gloss is measured using a gloss meter ("Micro Trigloss (model name)", manufactured by BYK Gardner) in accordance with Method 3 of JIS Z 8741:1997.

[0032] As an example of a release film having the first and second surfaces as described above, there is a release film having a film layer including the first surface and a matte layer including the second surface, as described later. In this case, the 60° gloss value of the first surface can be adjusted by selecting the type of film layer. In addition, when the matte layer is the first matte layer described later, the 60° gloss value of the second surface can be adjusted by selecting the type of particles contained in the matte layer or adjusting the average particle size and content of the particles. Specifically, by increasing the content of the particles, the 60° gloss value of the second surface can be reduced. In addition, by increasing the average particle size of the particles, the 60° gloss value of the second surface can be reduced. In the case where the matte layer is the second matte layer described later, the 60° gloss value of the second surface can be adjusted by adjusting the content of the wrinkle formation stabilizer, the average particle size of the wrinkle formation stabilizer, the type of polymerizable monomer or polymerizable oligomer, the number of functional groups, the integrated amount of ultraviolet light, the output density, etc.

[0033] (2) Maximum height Rz The release film in this embodiment has a maximum height Rz of the first surface of, for example, 0.8 μm or less, or may be 0.6 μm or less, or may be 0.4 μm or less, while the maximum height Rz of the first surface of, for example, 0.1 μm or more, or may be 0.2 μm or more.

[0034] In this embodiment, the maximum height Rz of the first surface is a value measured by a method similar to the method for measuring the maximum height Rz of the first surface of the release film in the transfer sheet of the second embodiment described later.

[0035] In the embodiment, the release film has a second surface having a maximum height Rz of, for example, 2.0 μm or more, or may be 3.0 μm or more, or may be 4.0 μm or more, while the second surface has a maximum height Rz of, for example, 6.0 μm or less, or may be 5.0 μm or less.

[0036] In this embodiment, the maximum height Rz of the second surface is a value measured by a method similar to the method for measuring the maximum height Rz of the second surface of the release film in the transfer sheet of the second embodiment described later.

[0037] (3) Haze value As described above, the release film in this embodiment has a low 60° gloss value of the second surface within a predetermined range. Therefore, the external haze (haze caused by the surface shape) of the release film tends to be high. The haze value H1 of the release film is, for example, 40% or more, may be 60% or more, or may be 80% or more.

[0038] The above haze value H1 of the release film is the average value of three measurements made in accordance with JIS K7136:2000, with the light incident surface facing the second surface and a haze meter (HM-150L2N, manufactured by Murakami Color Research Laboratory) used as the measuring device.

[0039] On the other hand, when a tape application test is performed in which tape is applied to the second surface, the surface irregularities of the second surface are filled in, and the external haze decreases. In the release film of this embodiment, the difference ΔH (=H1-H2) between the haze value H2 after an adhesive tape ("Cellotape (registered trademark)" manufactured by Nichiban Co., Ltd.) is applied to the second surface and the haze value H1 before the tape is applied is preferably 20% or more. The difference (ΔH) in the haze values ​​is more preferably 30% or more, and even more preferably 40% or more.

[0040] The haze value H2 of the release film is the average value of three measurements made in accordance with JIS K7136:2000 using a haze meter (HM-150L2N, manufactured by Murakami Color Research Laboratory) with the light incident surface facing the tape.

[0041] (4) Composition The release film in this embodiment is not particularly limited as long as it has the first and second surfaces having the above-mentioned characteristics, and may be a single layer or may have a multi-layer structure. Fig. 2 is a schematic cross-sectional view showing an example of the release film in the embodiment. As shown in Fig. 2, the release film 1 has, for example, a film layer 1a including the above-mentioned first surface S1, and a matte layer 1b arranged on the transfer layer side surface of the film layer 1a and including the above-mentioned second surface S2.

[0042] (i) Film Layer The film layer is not particularly limited as long as it has the above-mentioned first surface, but is preferably a resin film. Examples of the resin contained in the resin film include ester resins, olefin resins, styrene resins, vinyl resins, (meth)acrylic resins, amide resins, imide resins, and carbonate resins.

[0043] The film layer preferably contains an ester-based resin or an olefin-based resin. Examples of ester-based resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polyethylene terephthalate-isophthalate copolymers. Among these, PET or PBT is preferred, and PET is more preferred, from the viewpoint of being less susceptible to thermal shrinkage during the production of the transfer sheet and shrinkage due to irradiation with ionizing radiation.

[0044] Examples of olefin resins include polyethylene, polypropylene, polybutene, ethylene-propylene copolymer, and ethylene-propylene-butene copolymer. Among these, polypropylene is preferred from the viewpoint of being less susceptible to thermal shrinkage during the production of the transfer sheet and shrinkage due to irradiation with ionizing radiation.

[0045] The film layer may be a stretched film or an unstretched film. The stretching ratio in the machine direction (MD) of the stretched film is, for example, 5 to 30 times. The stretching ratio in the width direction (TD) of the stretched film is, for example, 5 to 30 times. The thickness of the film layer is, for example, 10 μm to 200 μm, may be 15 μm to 150 μm, or may be 20 μm to 100 μm.

[0046] (ii) Matte layer The mat layer is not particularly limited as long as it has the above-mentioned second surface, and may contain, for example, a resin component and particles as a matting agent. Hereinafter, a matting layer containing a resin component and particles as a matting agent is referred to as a first matting layer. The resin component in the first matting layer is typically a cured product (crosslinked structure) of a curable resin. On the other hand, the resin component may be a thermoplastic resin. In particular, the first matting layer preferably contains a cured product of a curable resin. When the first matting layer contains a cured product of a curable resin, the releasability from the first protective layer is improved.

[0047] When the second surface of the release film is the surface of the first matte layer, the above-mentioned 60° gloss value and maximum height Rz can be adjusted by selecting the type of particles, adjusting the average particle size and content, and the like.

[0048] Examples of the curable resin include ionizing radiation curable resins and thermosetting resins. Examples of the ionizing radiation curable resin include electron beam curable resins and ultraviolet ray curable resins.

[0049] The ionizing radiation curable resin (ionizing radiation curable compound) is not limited as long as it undergoes a crosslinking polymerization reaction upon irradiation with ionizing radiation and changes into a three-dimensional polymer structure. Examples of the ionizing radiation curable resin include prepolymers, oligomers, and monomers having polymerizable unsaturated bonds or epoxy groups in the molecule that can be crosslinked upon irradiation with ionizing radiation. In the present embodiment, only one type of ionizing radiation curable resin may be used, or two or more types may be used. Among them, it is preferable to use at least one of a polyfunctional monomer and an oligomer as the ionizing radiation curable resin.

[0050] Examples of ionizing radiation curable resins include (meth)acrylate-based resins such as urethane (meth)acrylate, ester (meth)acrylate, and epoxy (meth)acrylate; silicon-based resins such as siloxane; ester-based resins; and epoxy-based resins. (Meth)acrylate-based resins refer to acrylate-based resins or methacrylate-based resins.

[0051] The weight average molecular weight of the ionizing radiation curable resin is, for example, from 500 to 80,000, and may be from 1,000 to 50,000. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

[0052] The ionizing radiation curable resin preferably contains at least a polyfunctional monomer or oligomer having a weight average molecular weight of at least 500. Examples of such polyfunctional monomers or oligomers include (meth)acrylate-based resins such as dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, urethane (meth)acrylate, ester (meth)acrylate, and epoxy (meth)acrylate.

[0053] On the other hand, examples of thermosetting resins include unsaturated ester resins, urethane resins (including two-component curing polyurethanes), epoxy resins, aminoalkyd resins, phenolic resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine urea co-condensation resins, silicon resins, and siloxane resins.

[0054] Examples of the particles include inorganic particles and synthetic resin particles. Examples of the inorganic particles include silica, alumina, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, and kaolin. Examples of the synthetic resin particles include acrylic beads, urethane beads, nylon beads, silicone beads, silicone rubber beads, polycarbonate beads, and polyolefin wax (e.g., polypropylene wax, polyethylene wax).

[0055] The average particle size of the particles is preferably 1.0 μm or more and 10 μm or less, and more preferably 2.0 μm or more and 8.0 μm or less.

[0056] The content of the particles in the first mat layer is preferably 3 parts by mass or more and 80 parts by mass or less, and more preferably 5 parts by mass or more and 60 parts by mass or less, based on 100 parts by mass of the resin component.

[0057] The first matte layer may contain additives such as a release agent, an ultraviolet absorber, an infrared absorber, a light stabilizer, a polymerization inhibitor, a crosslinking agent, an antistatic agent, an antioxidant, a leveling agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a thermal radical generator, an aluminum chelating agent, etc. The thickness of the first matte layer is not particularly limited, but is, for example, 0.1 μm or more and 10 μm or less.

[0058] The first matte layer can be obtained, for example, by applying a matte layer-forming ink containing a curable resin onto one surface of the film layer and curing the ink.

[0059] As the matte layer, for example, one side has an uneven shape formed by irregular wrinkles. Hereinafter, a layer having an uneven shape formed by irregular wrinkles on one side is referred to as a second matte layer. As the material and forming method of such a second matte layer, the material and forming method of the release layer described in JP 2022-149930 A can be adopted.

[0060] The second matte layer preferably contains a wrinkle formation stabilizer. As the wrinkle formation stabilizer, for example, organic particles or inorganic particles can be used. Examples of organic substances constituting the organic particles include polymethyl methacrylate, acrylic-styrene copolymer resin, melamine resin, polycarbonate, polystyrene, polyvinyl chloride resin, benzoguanamine-melamine-formaldehyde condensate, silicone, fluorine-based resin, and polyester-based resin. Examples of inorganic substances constituting the inorganic particles include silica, alumina, calcium carbonate, aluminosilicate, and barium sulfate, and among these, silica, which has excellent transparency, is preferred. The shape of the wrinkle formation stabilizer is not particularly limited, and examples thereof include spherical, polyhedral, scaly, and amorphous.

[0061] The average particle size of the wrinkle formation stabilizer is preferably 20 μm or less, more preferably 10 μm or less. On the other hand, it is preferably 1 nm or more, more preferably 3 nm or more. The average particle size of the wrinkle formation stabilizer is measured as the mass average value d50 in particle size distribution measurement by laser light diffraction method.

[0062] The content of the wrinkle formation stabilizer is, for example, 0.5 parts by mass or more and 6.0 parts by mass or less with respect to 100 parts by mass of the resin forming the second matte layer.

[0063] The irregular wrinkles are preferably composed of a plurality of convex portions formed by a plurality of protrusions and a concave portion formed by being surrounded by the plurality of protrusions, and the protrusions preferably have linear protrusions. More preferably, the irregular wrinkles are composed of a plurality of convex portions formed by a plurality of linear protrusions and a concave portion formed by being surrounded by the plurality of linear protrusions.

[0064] Examples of the resin forming the second mat layer include ionizing radiation curable resins. Examples of the ionizing radiation curable resin include electron beam curable resins and ultraviolet curable resins, and among these, ultraviolet curable resins are preferred. Specifically, the ionizing radiation curable resin can be appropriately selected from polymerizable monomers and polymerizable oligomers that have been conventionally used as ionizing radiation curable resins. As the polymerizable monomer, a (meth)acrylate-based monomer having a radical polymerizable unsaturated group in the molecule is preferred, and among these, a polyfunctional (meth)acrylate monomer is preferred. Here, "(meth)acrylate" means "acrylate or methacrylate". Examples of the polyfunctional (meth)acrylate monomer include a (meth)acrylate monomer having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth)acryloyl group as the functional group. The number of functional groups of the polyfunctional (meth)acrylate monomer is preferably 2 to 8, more preferably 2 to 6, even more preferably 2 to 4, and even more preferably 2 to 3. These polyfunctional (meth)acrylates may be used alone or in combination of two or more kinds.

[0065] The resin for forming the second matte layer is preferably a combination of the above polymerizable oligomer and polymerizable monomer. In this case, the content of the polymerizable oligomer is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, based on 100 parts by mass of the total of the polymerizable oligomer and the polymerizable monomer. On the other hand, it is preferably 90 parts by mass or less, more preferably 80 parts by mass or less.

[0066] The method for forming the second matte layer preferably includes a step of forming a coating layer by applying a resin composition for forming the second matte layer to one main surface side of the film layer, and a step of forming a second matte layer by irradiating the coating layer with light having a wavelength of at least 100 nm or more and less than 200 nm to harden the coating layer to form the second matte layer. In addition, when the resin composition contains a solvent, a solvent drying step may be included after the step of forming the coating layer. By irradiating the resin composition for forming the second matte layer with ultraviolet light having such a low wavelength, the formation of wrinkles on the surface (second surface) of the second matte layer is stabilized. By this irradiation, the energy of the ultraviolet light penetrates only the surface portion, and the energy does not reach the layer below it, so that only the surface portion of the resin composition begins to harden, and the formation of wrinkles is stabilized by the occurrence of hardening shrinkage only on the surface, and the surface layer of the resin composition becomes a cured product having wrinkles. Then, the curing proceeds from the surface vicinity portion where the curing proceeds slowly to the deep portion distant in the depth direction, and the resin composition is cured over the entire thickness thereof, forming a second matte layer having wrinkles on the surface that exhibit a light diffusion effect. From the viewpoint of promoting the curing proceeding to the deep portion, it is preferable to perform another irradiation treatment after irradiating with light having a wavelength of 100 nm or more and less than 200 nm, as described later.

[0067] As the light having a wavelength of at least 100 nm and less than 200 nm, for example, rare gases such as Ar, Kr, Xe, Ne, and halides of rare gases such as halogens such as F, Cl, I, Br, and the like, or excited dimers formed by discharging a mixed gas of these, that is, "excimer light" including light in the ultraviolet wavelength region from excimers. As the wavelength of the excimer light and the excimer serving as the light source, for example, light having a wavelength of 126 nm radiated from the excimer of Ar2 (hereinafter abbreviated as "126 nm (Ar2)"), 146 nm (Kr2), 157 nm (F2), 172 nm (Xe2), 193 nm (ArF), and the like can be preferably adopted. As the excimer light, either spontaneous emission light or laser light with high coherence (coherence) due to stimulated emission can be used, but it is usually sufficient to use spontaneous emission light. Incidentally, a discharge lamp that emits the light (ultraviolet light) is also called an "excimer lamp". Excimer light has a single wavelength peak and is characterized by a narrower half-width wavelength than ordinary ultraviolet light (e.g., ultraviolet light emitted from metal halide lamps, mercury lamps, etc.) By using such excimer light, wrinkle formation is stabilized, and the visibility and texture of the matte effect are stably improved.

[0068] From the viewpoint of stabilizing wrinkle formation and stably imparting a low gloss feeling to the transfer layer, the wavelength is preferably 120 nm or more, more preferably 140 nm or more, and even more preferably 150 nm or more, with the upper limit being less than 200 nm, and particularly preferably 172 nm (Xe2).

[0069] The integrated light amount of the wavelength light is preferably 1 mJ / cm from the viewpoint of stabilizing the formation of wrinkles and stably imparting a low gloss feeling to the transfer layer. 2 More preferably, 10 mJ / cm 2 The upper limit is, for example, 1,000 mJ / cm 2 Less than or equal to 500 mJ / cm 2From the same viewpoint, the ultraviolet light output density is preferably 0.01 W / cm or more, more preferably 0.1 W / cm or more, and the upper limit is, for example, 10 W / cm or less, more preferably 5 W / cm or less.

[0070] In addition, the oxygen concentration during irradiation with light of the above wavelengths is preferably as low as possible, preferably 1,000 ppm or less, and more preferably 750 ppm or less.

[0071] In the second mat layer forming step, in addition to the irradiation with the above-mentioned wavelength light of 100 nm or more and less than 200 nm, other treatments that contribute to the curing of the resin composition for forming the second mat layer may be performed. For example, from the viewpoint of stabilizing the formation of wrinkles due to the difference in the degree of curing progress between the surface portion and the deep portion distant from the surface in the depth direction and promoting the progress of curing to the deep portion, the resin composition for forming the second mat layer may be pre-cured as a whole by irradiating with, for example, wavelength light of 200 nm or more, for example, wavelength light of 380 nm or more, preferably wavelength light of about 385 nm or more and 400 nm or less, and then irradiated with wavelength light of 100 nm or more and less than 200 nm, or post-curing may be performed to further cure the resin composition after irradiation with wavelength light of 100 nm or more and less than 200 nm. The above-mentioned wavelength light belongs to ultraviolet light, but it is also possible to use other ionizing radiations other than ultraviolet light, such as electron beams. For example, in the post-curing, electron beams may be preferably used to improve the durability of the second mat layer.

[0072] The first matte layer and the second matte layer may be formed on the entire surface of one side of the film layer, or may be formed on a partial area of ​​one side of the film layer. The entire surface of one side of the film layer refers to 90% or more of the area of ​​one side of the film layer. The matte layer may be arranged so as to cover 95% or more of one side of the film layer, or may be arranged so as to cover 100%. On the other hand, the matte layer may be arranged so as to cover 50% or less of one side of the film layer, or may be arranged so as to cover 40% or less, or may be arranged so as to cover 30% or less.

[0073] 2.First protective layer The transfer sheet in this embodiment has a first protective layer, which contributes to improving the surface properties (such as scratch resistance and abrasion resistance) of the exterior member.

[0074] (1) Indentation hardness In this embodiment, the indentation hardness in the cross section of the first protective layer is usually 150 MPa or more, may be 180 MPa or more, or may be 190 MPa or more. If the indentation hardness in the cross section of the first protective layer is low, the release film may not be easily peeled off. Also, if the indentation hardness in the cross section of the first protective layer is low, good scratch resistance and abrasion resistance may not be obtained. On the other hand, the indentation hardness in the cross section of the first protective layer is usually 300 MPa or less, may be 280 MPa or less, or may be 250 MPa or less. If the indentation hardness in the cross section of the first protective layer is high, the first protective layer is likely to become hard and brittle, and weather resistance may decrease. Also, in an environment where temperature changes are repeated, the weather-resistant adhesion between the first protective layer and the second protective layer may decrease.

[0075] Exterior members are usually exposed to harsh environments. Therefore, the first protective layer and the second protective layer constituting the transfer layer in the transfer sheet used in the manufacture of the exterior member are required to have good weather-resistant adhesion. According to this embodiment, the indentation hardness of the cross section of the first protective layer is set to the above-mentioned range, and the indentation hardness of the cross section of the second protective layer is set to the below-mentioned range, thereby improving the weather-resistant adhesion and weather resistance.

[0076] The indentation hardness of the cross section of the first protective layer can be adjusted, for example, by the number of functional groups of the curable resin in the first curable resin composition for producing the first protective layer. For example, by reducing the number of functional groups of the ionizing radiation curable compound, the number of crosslinking points in the cured product of the first curable resin composition can be reduced, resulting in a more flexible structure and a lower indentation hardness.

[0077] The indentation hardness of the cross section of the first protective layer is a value measured by the following method. (Preparation of measurement samples) The transfer sheet is cut to an arbitrary size to prepare a cut sample. The cut sample is embedded in resin (a room temperature curing type epoxy two-part curing resin) and left at room temperature for 24 hours or more to harden, thereby preparing an embedded sample in which the cut sample is embedded in resin. The embedded sample is cut vertically using a microtome to expose the cross section of the layer to be measured, thereby preparing a sample for indentation hardness measurement. Specifically, a cross section is prepared in an environment of -120°C by using an ultramicrotome (Leica EM UC6, manufactured by Leica Microsystems) equipped with a freezing cutting system (Leica EM FC6, manufactured by Leica Microsystems) and a diamond knife, exposing the cross section of the layer to be measured. Compared to a cross section cut in an environment of room temperature, cross section roughness can be suppressed, and a cross section suitable for indentation testing can be obtained. In particular, cross section roughness can be suppressed in the case of soft materials.

[0078] (Method of measuring indentation hardness) In this specification, the "indentation hardness" is measured by the nanoindentation method, which is a method for continuously measuring the load and displacement during the process of pressing an indenter into the surface of a sample and unloading it, and calculating the mechanical quantity from the obtained load-displacement curve.

[0079] Specifically, the indentation hardness in the cross section of the first protective layer is measured by pressing a Berkovich indenter (material: diamond triangular pyramid) perpendicularly into the cut surface of the above-mentioned measurement sample using the following nanoindenter. The measurement device and measurement conditions are as follows. Here, the position where the Berkovich indenter is pressed is preferably approximately the center in the thickness direction of the first protective layer. Approximately the center means that when the thickness of the first protective layer is defined as T [μm], the deviation from the center in the thickness direction of the first protective layer is within ±0.1 T. In addition, when fine particles such as a filler (e.g., silica) are contained in the layer, the Berkovich indenter is pressed into a position that avoids the fine particles.

[0080] Equipment used: Nanoindenter (TI 950 TriboIndenter, manufactured by BRUKER) Indenter used: Berkovich indenter (model number: TI-0039, manufactured by BRUKER) Push-in control method: Displacement control method (no lift operation) Maximum indentation depth: 100nm Push rate: 10nm / sec Loading time: 10 seconds (pushing from 0 to 100 nm) ·Holding time: 5 seconds (100nm constant) Unloading time: 10 seconds (100 nm → return to 0) Number of measurements: 5

[0081] The indentation hardness of the cross section of the first protective layer can be calculated as follows. First, the indentation depth h (nm) corresponding to the indentation load P (N) is continuously measured, and a load-displacement curve is created. The created load-displacement curve is analyzed to determine the maximum indentation load P max (N) is expressed as the projected area A (mm 2 ) is the indentation hardness H IT can be calculated (formula (1) below). H IT =P max / A …(1) Here, A is the contact projected area obtained by correcting the indenter tip shape using a standard sample of fused quartz in a standard manner.

[0082] In this specification, the indentation hardness at the cross section of the first protective layer is the arithmetic average value of five measurements of the same sample, with the position shifted. Each measurement is measured with a shift of 5 μm or more. During the measurement, in order to confirm that the correction of the indenter shape is correctly performed and that there are no problems with the operation and measurement of the device, it is preferable to confirm that the measurement is performed within ±5% of the reference value using fused quartz, which is the standard sample of the device manufacturer. The indentation hardness is measured in an atmosphere with a temperature of 23°C ±5°C and a humidity of 40% to 65%.

[0083] The first protective layer is preferably a layer having lower flexibility than the second protective layer. In other words, the indentation hardness of the first protective layer is preferably higher than the indentation hardness of the second protective layer. This is because it is possible to effectively impart surface properties such as scratch resistance and abrasion resistance to the exterior member.

[0084] (2) Resin component The first protective layer contains a cured product (crosslinked structure) of the first curable resin composition as a resin component. The proportion of the cured product of the first curable resin composition is, for example, 70% by mass or more, or may be 90% by mass or more, or may be 95% by mass or more, or may be 100% by mass, based on the total resin components constituting the first protective layer.

[0085] The cured product of the first curable resin composition may be, for example, a cured product of an ionizing radiation curable resin composition. The ionizing radiation curable resin composition may be, for example, an electron beam curable resin composition or an ultraviolet ray curable resin composition. Among these, an electron beam curable resin composition is preferred because it does not require a polymerization initiator, has little odor, and is less likely to cause coloring.

[0086] The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter also referred to as "ionizing radiation curable compound"). The ionizing radiation curable functional group is a group that crosslinks and cures when irradiated with ionizing radiation, and examples of such functional groups include functional groups having an ethylenic double bond, such as a (meth)acryloyl group, a vinyl group, and an allyl group. In the present disclosure, the (meth)acryloyl group refers to an acryloyl group or a methacryloyl group. In the present disclosure, the (meth)acrylate refers to an acrylate or a methacrylate.

[0087] Ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Examples of ionizing radiation include electron beams (EB) and ultraviolet rays (UV). Other examples of ionizing radiation include electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams.

[0088] The ionizing radiation curable compound preferably contains at least one selected from, for example, urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polycarbonate (meth)acrylate, and acrylic (meth)acrylate. Among them, the ionizing radiation curable compound preferably contains at least urethane (meth)acrylate. The urethane (meth)acrylate is preferably a caprolactone-based urethane acrylate.

[0089] When the ionizing radiation curable compound contains a caprolactone-based urethane acrylate, the caprolactone-based urethane acrylate preferably has 2 or more and 4 or less functional groups, and more preferably has 2 or more and 3 or less functional groups.

[0090] The ionizing radiation curable compound may contain a caprolactone-based urethane acrylate and a urethane (meth)acrylate that is not modified with caprolactone. In this case, the content of the caprolactone-based urethane acrylate contained in the first protective layer is M CLUAThe content of urethane (meth)acrylate not modified with caprolactone is M UA Let us assume that UA and M. CLUA M for the sum of CLUA Mass ratio (M CLUA / (M UA +M CLUA )) is, for example, 40% by mass or more and 90% by mass or less, alternatively 45% by mass or more and 80% by mass or less, or 50% by mass or more and 70% by mass or less.

[0091] Caprolactone-based urethane acrylate can usually be obtained by reacting caprolactone-based polyol, organic isocyanate, and hydroxy(meth)acrylate. For example, the synthesis method includes reacting polycaprolactone-based polyol with organic polyisocyanate to generate a polyurethane prepolymer containing -NCO groups (isocyanate groups) at both ends, and then reacting it with hydroxy(meth)acrylate.

[0092] As the caprolactone-based polyol, commercially available products can be used, preferably those having two hydroxyl groups and a number average molecular weight of preferably 500 to 3000, more preferably 750 to 2000. In addition, polyols other than caprolactone-based polyols, such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, etc., can be used by mixing one or more polyols at any ratio. As the organic polyisocyanate, diisocyanates having two isocyanate groups are preferred, and from the viewpoint of suppressing yellowing, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, trimethylhexamethylene diisocyanate, etc. are preferred. As the hydroxy(meth)acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, caprolactone-modified 2-hydroxyethyl acrylate, etc. are preferred.

[0093] When the ionizing radiation curable resin composition contains a caprolactone-based polyol, the caprolactone-based urethane acrylate is preferably a caprolactone diol-based urethane acrylate. The caprolactone diol-based urethane acrylate refers to a urethane acrylate having a diethylene glycol terminal among the caprolactone-based urethane acrylates. By using the caprolactone diol-based urethane acrylate, it is possible to suppress the occurrence of cracks and whitening in the first protective layer.

[0094] The number average molecular weight of the ionizing radiation curable compound is, for example, from 300 to 10,000, may be from 1,000 to 10,000, or may be from 2,000 to 10,000. The number average molecular weight is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

[0095] For example, when the ionizing radiation curable compound is an ultraviolet ray curable compound, the ionizing radiation curable compound preferably contains at least one of a photopolymerization initiator and a photopolymerization accelerator. Examples of the photopolymerization initiator include acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α-acyloxime ester, acylphosphine oxide, and thioxanthones. Examples of the photopolymerization accelerator include p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester.

[0096] The first curable resin composition may be a thermosetting resin composition. Details of the thermosetting resin composition are the same as those described in "3. Second Protective Layer" below.

[0097] (3) Weatherproofing agent The first protective layer usually contains a weathering agent. By having the first protective layer contain a weathering agent, even if the surface of the transfer layer has a low gloss as in the present embodiment, gloss change due to deterioration of the resin is suppressed. Examples of weathering agents include ultraviolet absorbers and light stabilizers. The first protective layer preferably contains at least one of an ultraviolet absorber and a light stabilizer. The first protective layer may contain one or more ultraviolet absorbers. Similarly, the first protective layer may contain one or more light stabilizers.

[0098] Examples of the ultraviolet absorbing agent contained in the first protective layer include organic ultraviolet absorbing agents such as triazine-based ultraviolet absorbing agents, benzotriazole-based ultraviolet absorbing agents, benzophenone-based ultraviolet absorbing agents, oxybenzophenone-based ultraviolet absorbing agents, salicylic acid ester-based ultraviolet absorbing agents, and cyano(meth)acrylate-based ultraviolet absorbing agents, and inorganic ultraviolet absorbing agents such as titanium dioxide, cerium oxide, and zinc oxide. Among these, triazine-based ultraviolet absorbing agents are more preferable.

[0099] Examples of triazine-based ultraviolet absorbers include hydroxyphenyl triazine-based ultraviolet absorbers. Examples of hydroxyphenyl triazine-based ultraviolet absorbers include 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, azine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5[2-(2-ethylhexanoyloxy)ethoxy]phenol.

[0100] The content of the ultraviolet absorber in the first protective layer is, for example, 0.5 parts by mass to 10 parts by mass, alternatively 0.8 parts by mass to 8 parts by mass, or alternatively 1 part by mass to 5 parts by mass, relative to 100 parts by mass of the ionizing radiation curable compound. If the content of the ultraviolet absorber is high, bleeding out of the ultraviolet absorber may occur, whereas if the content of the ultraviolet absorber is low, sufficient ultraviolet absorbing performance may not be obtained.

[0101] The light stabilizer contained in the first protective layer may be, for example, a hindered amine light stabilizer. Examples of the hindered amine light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, and 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine).

[0102] The content of the light stabilizer in the first protective layer is, for example, 1 part by mass to 10 parts by mass, or may be 1.5 parts by mass to 8 parts by mass, or may be 2 parts by mass to 5 parts by mass, relative to 100 parts by mass of the ionizing radiation curable compound. If the content of the light stabilizer is high, bleeding out of the light stabilizer may occur, and if the content of the light stabilizer is low, sufficient light stability may not be obtained.

[0103] (4) Additives The first protective layer may contain particles. By containing particles in the first protective layer, the low gloss of the transfer layer is further improved. Examples of the types of particles contained in the first protective layer include the same types of particles as those exemplified in the first matte layer.

[0104] The average particle size of the particles contained in the first protective layer is preferably 2.0 μm or more and 10 μm or less, and more preferably 3.0 μm or more and 7.0 μm or less. The average particle size refers to D50 based on the volume-based particle size distribution measured by a laser diffraction scattering method.

[0105] The first protective layer may contain additives such as a silicone compound, a polymerization inhibitor, a crosslinking agent, an antistatic agent, an adhesion improver, an antioxidant, a leveling agent, a thixotropy imparting agent, a coupling agent, a plasticizer, an antifouling agent, an antifoaming agent, a filler, an anti-wear agent, an antibacterial agent, an antiviral agent, and an antifungal agent.

[0106] (5) First protective layer The thickness of the first protective layer is, for example, from 2 μm to 20 μm, or may be from 3 μm to 15 μm, or may be from 4 μm to 10 μm. If the first protective layer is too thin, sufficient weather resistance may not be obtained, and if the first protective layer is too thick, cracks may easily occur in the first protective layer, and good adhesion may not be obtained.

[0107] 3.Second protective layer The transfer sheet in this embodiment has a second protective layer. The second protective layer and the first protective layer may be disposed so as to be in direct contact with each other, or may be disposed via another layer.

[0108] (1) Resin component The second protective layer contains a cured product of the second curable resin composition (particularly, a cured product of a thermosetting resin composition) as a resin component. The proportion of the cured product of the second curable resin composition is, for example, 70% by mass or more, 90% by mass or more, 95% by mass or more, or 100% by mass, based on the total resin components constituting the second protective layer.

[0109] The thermosetting resin composition is a composition that contains at least a thermosetting resin and is cured by heating. Examples of the thermosetting resin include (meth)acrylic resins, urethane resins, urethane acrylic resins, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. The thermosetting resin composition may be a resin to which a curing agent such as an isocyanate curing agent or an epoxy curing agent has been added.

[0110] The cured product of the thermosetting resin composition is preferably a cured product of a thermosetting resin composition containing a (meth)acrylic resin, a urethane resin or a urethane acrylic resin, and more preferably a cured product of a thermosetting resin composition containing a urethane acrylic resin. In addition, the thermosetting resin composition preferably contains an isocyanate-based curing agent or an epoxy-based curing agent, and more preferably contains an isocyanate-based curing agent, in order to make the structure of the cured product more rigid.

[0111] In addition, when the second protective layer contains a urethane acrylic resin, the urethane acrylic resin is preferably a urethane acrylic copolymer, more preferably a polycarbonate-based urethane acrylic copolymer. The polycarbonate-based urethane acrylic copolymer is a resin obtained by radically polymerizing an acrylic monomer with a polycarbonate-based polyurethane polymer obtained by reacting a polycarbonate diol with a (di)isocyanate.

[0112] Examples of the (di)isocyanate include aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 1,5-naphthalene diisocyanate, n-isocyanate phenylsulfonyl isocyanate, o-isocyanate phenylsulfonyl isocyanate, and p-isocyanate phenylsulfonyl isocyanate; aliphatic isocyanates such as 1,6-hexamethylene diisocyanate; and alicyclic isocyanates such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate.

[0113] Examples of acrylic monomers include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate.

[0114] In the polycarbonate-based urethane acrylic copolymer, the mass ratio of the urethane component to the total of the acrylic component and the urethane component ([urethane component] / ([acrylic component]+[urethane component]) is, for example, 70% by mass or more and 95% by mass or less, or alternatively 75% by mass or more and 95% by mass or less, or 80% by mass or more and 90% by mass or less. By setting the mass ratio to 70% by mass or more, the proportion of the polycarbonate structure in the polycarbonate-based urethane acrylic copolymer can be increased, making the structure of the polycarbonate-based urethane acrylic copolymer more rigid. As a result, deformation due to temperature changes can be reduced. Furthermore, by setting the mass ratio to 95% by mass or less, it is easier to ensure the flexibility of the second protective layer and improves adhesion to the design layer.

[0115] (2) Indentation hardness In this embodiment, the indentation hardness of the cross section of the second protective layer is, for example, 2 MPa or more, may be 5 MPa or more, or may be 10 MPa or more. If the indentation hardness of the cross section of the second protective layer is low, the movement of the second protective layer becomes large in an environment where temperature changes are repeated, and a gap occurs between the second protective layer and the first protective layer, and good weather-resistant adhesion may not be obtained. On the other hand, the indentation hardness of the cross section of the second protective layer is, for example, 50 MPa or less, may be 40 MPa or less, or may be 30 MPa or less. If the indentation hardness of the cross section of the second protective layer is high, the adhesion (especially initial adhesion) with the first protective layer may be low. The method for measuring the indentation hardness of the cross section of the second protective layer is the same as the method for measuring the indentation hardness of the cross section of the first protective layer described above.

[0116] (3) Weatherproofing agent The second protective layer usually contains a weathering agent. Examples of weathering agents include an ultraviolet absorber and a light stabilizer. The second protective layer preferably contains at least one of an ultraviolet absorber and a light stabilizer. The preferred types and modes of the weathering agent are the same as those described in "2. First Protective Layer" above, and therefore will not be described here. In particular, the second protective layer preferably contains a triazine-based ultraviolet absorber. The second protective layer preferably contains a hindered amine-based light stabilizer.

[0117] The content of the ultraviolet absorber in the second protective layer is, for example, 0.1 parts by mass or more and 50 parts by mass or less, or may be 3 parts by mass or more and 40 parts by mass or less, or may be 10 parts by mass or more and 35 parts by mass or less, relative to 100 parts by mass of the resin component. The content of the ultraviolet absorber in the second protective layer (content relative to 100 parts by mass of the resin component) may be greater than the content of the ultraviolet absorber in the first protective layer (content relative to 100 parts by mass of the resin component).

[0118] The content of the light stabilizer in the second protective layer is, for example, 0.1 to 15 parts by mass, or 1 to 15 parts by mass, or 3 to 10 parts by mass, relative to 100 parts by mass of the resin component. The content of the light stabilizer in the second protective layer (content relative to 100 parts by mass of the resin component) may be greater than the content of the light stabilizer in the first protective layer (content relative to 100 parts by mass of the resin component).

[0119] (4) Additives The second protective layer may contain additives such as a silicone compound, a polymerization inhibitor, a crosslinking agent, an antistatic agent, an adhesion improver, an antioxidant, a leveling agent, a thixotropy imparting agent, a coupling agent, a plasticizer, an antifouling agent, an antifoaming agent, a filler, and an antiblocking agent.

[0120] (5)Second protective layer The thickness of the second protective layer is, for example, 2 μm to 10 μm, may be 3 μm to 8 μm, or may be 3 μm to 5 μm. If the second protective layer is thin, the adhesion (particularly initial adhesion) with the first protective layer may be low. On the other hand, if the second protective layer is thick, the movement of the second protective layer may be large in an environment where temperature changes are repeated, and good weather-resistant adhesion may not be obtained.

[0121] 4. Transfer layer The transfer sheet in this embodiment has a release film and a transfer layer disposed on one side of the release film. The transfer layer has at least a first protective layer and a second protective layer in order from the release film side. The transfer layer may have a first protective layer and a second protective layer, and may further have other layers. Examples of the other layers include a design layer and an adhesive layer. The transfer layer may have an adhesive layer on the surface of the second protective layer opposite to the first protective layer. The transfer layer may also have a design layer on the surface of the second protective layer opposite to the first protective layer.

[0122] The thickness of the transfer layer is, for example, 8 μm or more, may be 10 μm or more, may be 12 μm or more, may be 14 μm or more. If the transfer layer is thin, there is a possibility that sufficient weather resistance cannot be obtained. On the other hand, the thickness of the transfer layer is, for example, 50 μm or less, may be 40 μm or less, may be 30 μm or less.

[0123] (1) Adhesive layer The transfer sheet in this embodiment may or may not have an adhesive layer on the surface of the second protective layer opposite to the first protective layer. The adhesive layer is preferably a layer constituting the transfer layer in the transfer sheet that contacts the substrate. In this case, the adhesive layer is disposed to improve adhesion between the transfer layer and the substrate. The adhesive layer may contain a component having adhesive properties. Examples of the adhesive component include (meth)acrylic resins, vinyl chloride-vinyl acetate copolymers, vinyl acetate resins, ester resins, epoxy resins, imide resins, and rubber resins.

[0124] The adhesive layer may be a so-called pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer has adhesiveness at room temperature. Examples of the resin contained in the pressure-sensitive adhesive layer include (meth)acrylic resins, silicone resins, vinyl resins, ester resins, urethane resins, amide resins, epoxy resins, rubber resins, and ionomer resins.

[0125] The adhesive layer may be a so-called heat seal layer. The heat seal layer exhibits adhesion by heat. Examples of the resin contained in the heat seal layer include thermoplastic resins. Examples of the thermoplastic resin include acrylic resins, polyacrylic polyols, urethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, styrene-acrylic copolymers, acrylic-vinyl acetate copolymers, polyester resins, amide resins, cyanoacrylate resins, and epoxy resins, and these can be used alone or in combination of two or more kinds. Among these, it is preferable to use at least one of acrylic resins, polyacrylic polyols, and urethane resins in order to improve the processability during the manufacture of the exterior member and the adhesion between the transfer layer and the substrate. In particular, acrylic resins are preferable.

[0126] The indentation hardness of the adhesive layer in the cross section is not particularly limited, but may be, for example, 100 MPa or more and 300 MPa or less, or may be 120 MPa or more and 270 MPa or less, or may be 140 MPa or more and 250 MPa or less. If the indentation hardness of the adhesive layer in the cross section is in the above range, for example, good weather-resistant adhesion can be obtained between the adhesive layer and the design layer.

[0127] The thickness of the adhesive layer is, for example, 1 μm or more and 30 μm or less, or may be 2 μm or more and 15 μm or less, or 3 μm or more and 10 μm or less, or may be 3 μm or more and 8 μm or less. When the thickness of the adhesive layer is within the above range, it is easy to improve the adhesion between the adhesive layer and the base when producing the exterior member.

[0128] In the present embodiment, the adhesive layer may contain a colorant. When the adhesive layer contains a colorant, it is possible to impart design to the transfer layer. In other words, the adhesive layer may share the function of the design layer described later.

[0129] (2) Design layer The transfer sheet in this embodiment may or may not have a design layer on the side of the second protective layer opposite to the first protective layer. By providing a design layer, the design of the exterior member is improved. The design layer and the second protective layer may be arranged so as to be in direct contact with each other, or may be arranged via another layer.

[0130] Examples of the design layer include a solid layer (a layer coated with ink) and a pattern layer (a layer printed with ink). The transfer sheet may have a pattern layer and a solid layer in this order from the release film side as the design layer. Examples of the pattern in the pattern layer include wood grain, stone grain, sand grain, tiled pattern, brickwork pattern, cloth grain pattern, leather-squeezed pattern, geometric figures, letters, symbols, abstract patterns, and floral patterns.

[0131] The design layer usually contains a colorant and a binder resin. Examples of the colorant include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue, organic pigments (including dyes) such as quinacridone red, isoindolinone yellow, nickel azo complex, phthalocyanine blue, and azomethine azo black, metal pigments such as aluminum and brass, and pearl pigments such as titanium dioxide-coated mica and basic lead carbonate.

[0132] Examples of the binder resin include urethane resin, acrylic polyol resin, (meth)acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane acrylic copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-acrylic copolymer, chlorinated propylene resin, nitrocellulose resin, and cellulose acetate resin. Among them, it is more preferable to use an acrylic polyol resin in combination with a urethane resin.

[0133] The indentation hardness of the cross section of the design layer is not particularly limited, but may be, for example, 100 MPa or more and 300 MPa or less, or may be 120 MPa or more and 270 MPa or less, or may be 140 MPa or more and 250 MPa or less. If the indentation hardness of the cross section of the design layer is within the above range, for example, good weather-resistant adhesion can be obtained between the design layer and the adhesive layer or the second protective layer.

[0134] The design layer may contain additives such as ultraviolet absorbers, light stabilizers, hardeners, plasticizers, catalysts, etc., as necessary. The thickness of the design layer is, for example, 0.5 μm or more and 20 μm or less, or may be 1 μm or more and 10 μm or less, or may be 2 μm or more and 5 μm or less.

[0135] (3) Second release film The transfer sheet in this embodiment may have a second release film on the surface of the second protective layer opposite to the first protective layer. For example, when the transfer sheet is wound into a roll, the occurrence of blocking can be suppressed. The second release film is usually peeled off from the transfer sheet before the adhesion process described below. Details of the second release film are the same as those described for the first release film above, so the description here is omitted.

[0136] II. Transfer sheet of the second embodiment 1(a) is a schematic cross-sectional view illustrating a transfer sheet in this embodiment. As shown in FIG. 1(a), a transfer sheet 10 has a release film 1 and a transfer layer X arranged on one surface of the release film 1. The transfer layer X is a first protective layer 2 and a second protective layer 3 from the release film 1 side in a thickness direction D. T 1(b), the transfer sheet 10 may have an adhesive layer 4 on the surface of the second protective layer 3 opposite to the first protective layer 2. As shown in FIG. 1(c), the transfer sheet 10 may have a design layer 5 on the surface of the second protective layer 3 opposite to the first protective layer 2. In FIG. 1(c), the design layer 5 is disposed between the adhesive layer 4 and the second protective layer 3.

[0137] In this embodiment, the first protective layer 2 contains a cured product of a first curable resin composition and a weather resistant agent, and the second protective layer 3 contains a cured product of a second curable resin composition and a weather resistant agent.

[0138] In this embodiment, the release film 1 has a first surface S1 located on the side opposite to the transfer layer X side and a second surface S2 located on the transfer layer X side, the maximum height Rz of the first surface S1 is within a predetermined range, the maximum height Rz of the second surface S2 is within a predetermined range, and the indentation hardness in a cross section of the first protective layer 2 is within a predetermined range.

[0139] In the transfer sheet of this embodiment, the maximum height Rz of the first surface of the release film is low within a predetermined range, so that the transfer sheet has excellent visibility of the design even without peeling off the release film. Therefore, it is possible to inspect for defects without peeling off the release film, improving workability. In addition, since the release film can be used as a masking film as it is, it is possible to reduce the amount of plastic used. Furthermore, since the maximum height Rz of the second surface is high within a predetermined range, the transfer layer after peeling has a low gloss feeling. In addition, the present inventors have found that the release film tends to be difficult to peel off because the adhesion between the first protective layer and the release film is increased by the maximum height Rz of the second surface being high within a predetermined range. And, it has been found that the indentation hardness in the cross section of the first protective layer is within a predetermined range, so that the release film can be easily peeled off.

[0140] In addition, exterior members (outdoor members) are required to have higher weather resistance than interior members (indoor members). For example, when manufacturing an exterior member using a decorative sheet, a transparent resin layer may be provided on the decorative sheet for the purpose of improving strength. In this case, since the transparent resin layer is a relatively thick layer, for example, high weather resistance is imparted by adding a sufficient amount of weather resistance agent to the transparent resin layer. In contrast, it is technically difficult to impart high weather resistance to a transfer sheet that does not have a layer corresponding to the transparent resin layer. In this embodiment, usually, both the first protective layer and the second protective layer contain a weather resistance agent. This makes it possible to impart high weather resistance while maintaining the properties required for the first protective layer (for example, surface properties such as scratch resistance and abrasion resistance) and the properties required for the second protective layer (for example, adhesion).

[0141] Furthermore, since the first protective layer contains a weather resistance agent, even when the surface of the transfer layer has a low gloss as in this embodiment, changes in gloss due to deterioration of the resin are suppressed.

[0142] 1. Release film The transfer sheet in this embodiment has a release film. As shown in Fig. 1, the release film in this embodiment has a first surface S1 located on the side opposite to the transfer layer X side, and a second surface S2 located on the transfer layer X side. As shown in Fig. 1, the release film 1 and the first protective layer 2 are preferably arranged so as to be in direct contact with each other.

[0143] (1) Maximum height Rz In the release film in this embodiment, the maximum height Rz of the first surface is usually 0.8 μm or less, may be 0.6 μm or less, or may be 0.4 μm or less. Rz (maximum height) is one of the peak and height parameters of the profile curve defined in JIS B0601:2013, and is the sum of the height of the highest peak and the depth of the deepest valley in the profile curve in the reference length. Therefore, when Rz (maximum height) is in the above range, diffuse reflection of light is suppressed, and the visibility of the design is improved. On the other hand, the maximum height Rz of the first surface is, for example, 0.1 μm or more, and may be 0.2 μm or more.

[0144] In this embodiment, the maximum height Rz of the first surface is a value measured using the following measuring device and conditions in a rectangular (1024 μm×768 μm) measurement area at any location on the first surface of the release film. Measurement equipment: Shape analysis laser microscope (VK-X1000, manufactured by Keyence Corporation) Objective lens: 50x Measurement mode: Shape measurement mode Measurement pitch: 12μm Measurement quality: High speed mode Scan mode: Laser confocal

[0145] In this specification, Rz (maximum height) is the average value of measurements taken at any ten points.

[0146] In the present embodiment, the release film has a maximum height Rz of the second surface of usually 2.0 μm or more, may be 3.0 μm or more, or may be 4.0 μm or more. If the maximum height Rz of the second surface is low, the transfer layer after the release film is peeled off is unlikely to exhibit a low gloss feeling. On the other hand, the maximum height Rz of the second surface is, for example, 6.0 μm or less, and may be 5.0 μm or less.

[0147] In this embodiment, the maximum height Rz of the second surface is a value measured for the second surface of the release film in the same manner as the measuring method for the maximum height Rz of the first surface described above.

[0148] As an example of a release film having the first and second surfaces as described above, there may be mentioned a release film having a film layer including the first surface and a matte layer including the second surface as described above. In this case, the maximum height Rz of the first surface can be adjusted by selecting the type of film layer. In addition, when the matte layer is the first matte layer described below, the maximum height Rz of the second surface can be adjusted by selecting the type of particles contained in the matte layer or adjusting the average particle diameter and content of the particles. Specifically, by increasing the content of the particles, the maximum height Rz of the second surface can be increased. In addition, by increasing the average particle diameter of the particles, the maximum height Rz of the second surface can be increased. In the case where the matte layer is the second matte layer described below, the maximum height Rz can be adjusted by adjusting the content of the wrinkle formation stabilizer, the average particle diameter of the wrinkle formation stabilizer, the type of polymerizable monomer or polymerizable oligomer, the number of functional groups, the integrated light amount of ultraviolet light, the output density, and the like.

[0149] (2)Other The haze and configuration of the release film can be similar to those of the release film in the first embodiment described above.

[0150] 2.First protective layer The first protective layer may be the same as the first protective layer in the first embodiment described above.

[0151] 3.Second protective layer The second protective layer may be the same as the second protective layer in the first embodiment described above.

[0152] 4. Transfer layer The transfer layer may be the same as the transfer layer in the first embodiment described above.

[0153] B. Method of manufacturing transfer sheet FIG. 3 is a schematic cross-sectional view illustrating a method for producing a transfer sheet in the present disclosure. First, as shown in FIG. 3(a), a release film 1 is prepared. Next, as shown in FIG. 3(b), a first composition containing a first curable resin composition and a weather resistance agent is applied to the second surface S2 of the release film 1 and cured to form a first protective layer 2. Next, as shown in FIG. 3(c), a second composition containing a second curable resin composition and a weather resistance agent is applied to the surface of the first protective layer 2 opposite to the release film 1 and cured to form a second protective layer 3. Thereby, the release film 1, the first protective layer 2, and the second protective layer 3 are arranged in a thickness direction D. T 3, the transfer sheet 10 having the above-mentioned steps in this order is obtained. In FIG.

[0154] 3 may be the release film in the above-mentioned first embodiment, or the release film in the above-mentioned second embodiment. In addition, the indentation hardness of the cross section of the first protective layer is within a predetermined range.

[0155] According to the present disclosure, for the reasons described above, a transfer sheet for use in the manufacture of exterior components, which has excellent visibility of a design even without peeling off a release film and is capable of transferring a transfer layer having a low gloss feeling, can be obtained. Each step will be described in detail below.

[0156] 1. First protective layer formation process The first protective layer forming step in the present disclosure is a step of applying a first composition containing the first curable resin composition and a weathering agent to the second surface of the release film, curing the composition, and forming the first protective layer. The first composition is a composition for forming the first protective layer. The first curable resin composition and the weathering agent are the same as those described in "A. Transfer sheet" above, so the description here is omitted.

[0157] Examples of the method for applying the first composition include gravure printing, bar coating, roll coating, reverse roll coating, and comma coating. The first coating layer is obtained by applying the first composition. Examples of the method for curing the first coating layer include a method of irradiating with ionizing radiation such as electron beams and ultraviolet rays, and a method of applying heat.

[0158] 2.Second protective layer formation process The second protective layer forming step in the present disclosure is a step of applying a second composition containing the second curable resin composition and a weathering agent to the surface of the first protective layer opposite to the release film, and curing the composition to form the second protective layer. The second composition is a composition for forming the second protective layer. The second curable resin composition and the weathering agent are the same as those described in "A. Transfer sheet" above, so the description here is omitted.

[0159] Examples of the method for applying the second composition include gravure printing, bar coating, roll coating, reverse roll coating, and comma coating. By applying the second composition, a second coating layer is obtained. Examples of the method for curing the second coating layer include a method of applying heat.

[0160] 3.Other processes The method for producing a transfer sheet in the present disclosure may include a step of forming a layer belonging to the above-mentioned transfer layer in addition to the first protective layer forming step and the second protective layer forming step.For example, the method for producing a transfer sheet in the present disclosure may include an adhesive layer forming step of forming an adhesive layer on the surface of the second protective layer opposite to the first protective layer.As a method for forming an adhesive layer, the composition for forming the adhesive layer is coated by a known method such as gravure printing, bar coating, roll coating, reverse roll coating, comma coating, etc., and dried and cured as necessary.

[0161] For example, the method for producing a transfer sheet in the present disclosure may include a design layer forming step of forming a design layer on the surface of the second protective layer opposite to the first protective layer. For example, a method of forming a design layer may include a method of applying an ink containing a colorant, a binder resin, and a solvent to the surface of the second protective layer opposite to the first protective layer. In addition, the transfer sheet obtained by each of the above-mentioned steps is the same as the contents described in "A. Transfer sheet" above, so the description here is omitted.

[0162] C. Manufacturing method of exterior components 4 is a schematic cross-sectional view illustrating a method for producing an exterior member according to the present disclosure. First, as shown in FIG. 4(a), a transfer sheet 10 is prepared. The transfer sheet 10 shown in FIG. 4(a) is a sheet in which a release film 1, a first protective layer 2, a second protective layer 3, a design layer 5, and an adhesive layer 4 are arranged in a thickness direction D. T 4(b), the surface of the transfer sheet 10 facing the second protective layer 3 is placed opposite the substrate 20 and brought into close contact with the substrate 20. The "surface of the transfer sheet 10 facing the second protective layer 3" refers to the surface of the transfer sheet 10 that is located on the second protective layer 3 side when the release film 1 is used as a reference. Since the transfer sheet 10 shown in FIG. 4(a) has the design layer 5 and the adhesive layer 4, the "surface of the transfer sheet 10 facing the second protective layer 3" corresponds to the surface of the adhesive layer 4.

[0163] In the method for producing an exterior member according to the present disclosure, after the above-mentioned adhesion step, the release film 1 may be peeled off from the transfer sheet 10 as shown in Fig. 4(c). This allows the first protective layer 2, the second protective layer 3, the design layer 5, the adhesive layer 4, and the base 20 to be separated in the thickness direction D T In this order, the exterior member 100 is obtained.

[0164] According to the present disclosure, by using the transfer sheet described above, an exterior member having good weather-resistant adhesion can be obtained.

[0165] 1. Preparation process The preparation step in this disclosure is a step of preparing the transfer sheet of the first embodiment described above or the transfer sheet of the second embodiment described above. The transfer sheet of the first embodiment or the transfer sheet of the second embodiment is the same as that described in "A. Transfer sheet" above, so the description here is omitted.

[0166] 2. Adhesion process The adhesion step in the present disclosure is a step of placing the surface of the transfer sheet on the second protective layer side against a substrate and adhering them together. When placing the transfer sheet against the substrate, they may be placed so as to be in direct contact with each other, or may be placed between them via another layer. For example, when the transfer sheet does not have an adhesive layer, an adhesive layer is placed.

[0167] The material for the substrate in the present disclosure is not particularly limited, and can be appropriately selected from among resins, wood, metals, nonmetallic inorganic materials, paper, nonwoven fabrics, woven fabrics, and the like depending on the application.

[0168] An example of the substrate in the present disclosure is a resin member. Examples of resins used in the resin member include vinyl chloride resins, (meth)acrylic resins, ester resins, styrene resins, olefin resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), phenolic resins, cellulose resins, rubber, polycarbonate resins, and melamine resins. The resin member may contain fibers such as carbon fibers, glass fibers, aramid fibers, Zylon fibers, boron fibers, and polyethylene fibers. The strength of the resin member can be improved by containing fibers. Another example of the substrate is a wood member. Examples of the wood member include a wood veneer, wood plywood, particle board, and wood fiber board. Examples of wood used in the wood member include cedar, cypress, pine, and lauan.

[0169] Another example of the substrate is a metal member. Examples of metals used for the metal member include iron and aluminum. Another example of the substrate is a ceramic member. The material of the ceramic member may be ceramics such as glass or porcelain, a non-cement ceramic material such as gypsum, or a non-ceramic ceramic material such as ALC (aerated lightweight concrete). A calcium silicate board may also be used as the ceramic member.

[0170] The substrate may be surface-treated to improve adhesion to the transfer sheet. When the substrate is an aluminum member, examples of the surface treatment include anodizing, chemical conversion treatment, plating, painting, blasting, and polishing. When the substrate is a ceramic member, examples of the surface treatment include UV coating and painting.

[0171] The shape of the substrate is not particularly limited, and may be, for example, a plate, a sheet, or a three-dimensional shape. The substrate may have a flat surface, a curved surface, or both a flat surface and a curved surface. The substrate may have at least one of a convex portion, a concave portion, a convex streak portion, a concave streak portion, and a through portion.

[0172] As the substrate in the present disclosure, among others, an acrylic plate, a polycarbonate plate, a non-combustible plate, a metal plate, a polyvinyl chloride plate, a melamine plate, or a carbon fiber reinforced plastic plate is preferable. As the non-combustible plate, for example, a fiber reinforced cement plate can be mentioned, among others, a calcium silicate plate is preferable.

[0173] In the adhesion step, the surface of the transfer sheet on the second protective layer side is opposed to the substrate, and the two are adhered to each other. Examples of the method for adhering the two include a lamination method. In the lamination method, for example, the laminate of the transfer sheet and the substrate is heated and pressed from the transfer sheet side. Examples of the method for heating and pressing include a method using a roll transfer device. The roll temperature of the roll transfer device is, for example, 200°C or less, and may be 180°C or less. If the roll temperature is high, there is a possibility that the transfer sheet will be softened more than necessary. On the other hand, the roll temperature of the roll transfer device is, for example, 100°C or more, and may be 110°C or more, or may be 120°C or more.

[0174] Furthermore, the method for producing an exterior member according to the present disclosure may include, after the adhesion step, a peeling step of peeling the release film from the first protective layer.

[0175] 3. Exterior materials The exterior member in the present disclosure has a first protective layer, a second protective layer, and a substrate in this order in the thickness direction. The exterior member may be an exterior member with a release film having a release film on the surface of the first protective layer opposite to the second protective layer, or may be an exterior member without a release film after the release film is peeled off.

[0176] In the exterior member after the release film is peeled off, the 60° gloss value of the surface of the first protective layer opposite the second protective layer is, for example, 30 or less, and may be 20 or less. On the other hand, it may be, for example, 0.1 or more, and may be 1.0 or more. Furthermore, in the exterior member after the release film is peeled off, the maximum height Rz of the surface of the first protective layer opposite to the second protective layer is, for example, 1.5 μm or more and may be 2.0 μm or more, while it may be, for example, 6.0 μm or less and 5.0 μm or less.

[0177] The exterior member in the present disclosure is, for example, a building material (an exterior member of an architectural structure). The building material is used, for example, in houses, offices, stores, hospitals, clinics, general roads and highways, agricultural houses, and the like. Examples of uses of the exterior member include exterior walls, roofs, eaves ceilings, door pockets, window frames, doors, door frames, handrails, fences, drying racks, partition boards, and the like. Specific uses of the exterior member include soundproof walls or windbreak walls on general roads and highways, balcony partition boards, fences, roof members for terraces or carports, transparent members constituting agricultural houses, and the like.

[0178] In addition, the exterior member in the present disclosure is used as, for example, exterior members of vehicles, ships and aircraft, exterior members of industrial machines, and exterior members of various lenses, in addition to building materials (exterior members of architectural structures). Exterior members of vehicles include, for example, window materials such as side windows, rear windows, roof windows, front windows and quarter windows; headlight covers, turn signal lamp lenses, reflectors; and pillars. Exterior members of vehicles include, for example, automobiles, railroad cars, construction machines, and light vehicles such as golf carts. Exterior materials of industrial machines include, for example, window materials for visibility in machine tools. Exterior lenses include, for example, traffic light lenses.

[0179] D. Exterior parts with release film The exterior member with a release film in the present disclosure has two embodiments, which will be described below separately.

[0180] I. Exterior member with release film according to the first embodiment 5(a) is a schematic cross-sectional view illustrating an exterior member with a release film in this embodiment. The exterior member with a release film 50 in this embodiment is a release film 1, a first protective layer 2, a second protective layer 3, and a base 20 arranged in a thickness direction D T In this order:

[0181] 5(b), the exterior member 50 with a release film may have an adhesive layer 4 on the surface of the second protective layer 3 opposite to the first protective layer 2. Moreover, as shown in FIG. 5(c), the exterior member 50 with a release film may have a design layer 5 on the surface of the second protective layer 3 opposite to the first protective layer 2.

[0182] In this embodiment, the first protective layer 2 contains a cured product of a first curable resin composition and a weather resistant agent, and the second protective layer 3 contains a cured product of a second curable resin composition and a weather resistant agent.

[0183] In the present embodiment, the release film 1 has a first surface S1 located on the side opposite to the first protective layer 2 and a second surface S2 located on the first protective layer 2 side, the 60° gloss value of the first surface S1 is within a predetermined range, the 60° gloss value of the second surface S2 is within a predetermined range, and the indentation hardness of the cross section of the first protective layer 2 is within a predetermined range.

[0184] In the present embodiment, the release film-attached exterior member can use the release film as a masking agent. Furthermore, since the 60° gloss value of the second surface of the release film is low within a predetermined range, the surface of the first protective layer after the release film is peeled off has a low gloss. Since the indentation hardness of the cross section of the first protective layer is within a predetermined range, the release film can be easily peeled off. In addition, in the present disclosure, both the first protective layer and the second protective layer usually contain a weathering agent. This allows the first protective layer to have high weather resistance while maintaining the properties required for the first protective layer (for example, surface properties such as scratch resistance and abrasion resistance) and the properties required for the second protective layer (for example, adhesion). Furthermore, since the first protective layer contains a weathering agent, even if the surface of the first protective layer has a low gloss as in the present disclosure, the change in gloss due to deterioration of the resin is suppressed.

[0185] The release film in this embodiment is the same as the release film in the transfer sheet of the first embodiment described above in "A. Transfer sheet", so the description here is omitted. The first protective layer, second protective layer, design layer, and adhesive layer are the same as those described above in "A. Transfer sheet", so the description here is omitted. The base is the same as those described above in "C. Manufacturing method of exterior member", so the description here is omitted.

[0186] II. Exterior member with release film according to the second embodiment 5(a) is a schematic cross-sectional view illustrating an exterior member with a release film in this embodiment. The exterior member with a release film 50 in this embodiment is a release film 1, a first protective layer 2, a second protective layer 3, and a base 20 arranged in a thickness direction D T In this order:

[0187] 5(b), the exterior member 50 with a release film may have an adhesive layer 4 on the surface of the second protective layer 3 opposite to the first protective layer 2. Moreover, as shown in FIG. 5(c), the exterior member 50 with a release film may have a design layer 5 on the surface of the second protective layer 3 opposite to the first protective layer 2.

[0188] In this embodiment, the first protective layer 2 contains a cured product of a first curable resin composition and a weather resistant agent, and the second protective layer 3 contains a cured product of a second curable resin composition and a weather resistant agent.

[0189] In this embodiment, the release film 1 has a first surface S1 located on the side opposite to the transfer layer X side and a second surface S2 located on the transfer layer X side, the maximum height Rz of the first surface S1 is within a predetermined range, the maximum height Rz of the second surface S2 is within a predetermined range, and the indentation hardness in a cross section of the first protective layer 2 is within a predetermined range.

[0190] In the exterior member with a release film in this embodiment, the release film can be used as a masking. Furthermore, since the maximum height Rz of the second surface is high within a predetermined range, the surface of the first protective layer after the release film is peeled off has a low gloss. Since the indentation hardness in the cross section of the first protective layer is within a predetermined range, the release film can be easily peeled off. In addition, in this embodiment, both the first protective layer and the second protective layer usually contain a weathering agent. This makes it possible to impart high weather resistance while maintaining the characteristics required for the first protective layer (for example, surface characteristics such as scratch resistance and abrasion resistance) and the characteristics required for the second protective layer (for example, adhesion). Furthermore, since the first protective layer contains a weathering agent, even if the surface of the first protective layer has a low gloss as in this embodiment, the change in gloss due to deterioration of the resin is suppressed.

[0191] The release film in this embodiment is the same as the release film in the transfer sheet of the second embodiment described above in "A. Transfer sheet", so the description here is omitted. The first protective layer, second protective layer, design layer, and adhesive layer are the same as those described above in "A. Transfer sheet", so the description here is omitted. The base is the same as those described above in "C. Manufacturing method of exterior member", so the description here is omitted.

[0192] E. Exterior materials In the present disclosure, an exterior member after the release film is peeled off can be provided. Fig. 6 is a schematic cross-sectional view showing an example of an exterior member after the release film is peeled off. The exterior member 100 is a first protective layer 2, a second protective layer 3, and a base body 20 arranged in a thickness direction D. T in that order, the first protective layer 2 contains a cured product of the first curable resin composition and a weather resistant agent, the second protective layer 3 contains a cured product of the second curable resin composition and a weather resistant agent, and the indentation hardness of the cross section of the first protective layer 2 is 150 MPa or more and 300 MPa or less. As shown in Fig. 6, the exterior member 100 may have a base 20 and a transfer layer X bonded to each other via an adhesive layer 4 of the transfer layer X. In addition, a design layer 5 may be provided between the second protective layer 3 and the adhesive layer 4.

[0193] In the exterior member 100 after the release film has been peeled off, the 60° gloss value of the surface S3 of the first protective layer 2 opposite the second protective layer 3 may be, for example, 30 or less, or 20 or less. Alternatively, it may be, for example, 0.1 or more, or 1.0 or more. Furthermore, in the exterior member after the release film has been peeled off, the maximum height Rz of the surface S3 of the first protective layer 2 opposite the second protective layer 3 may be, for example, 1.5 μm or more, or 2.0 μm or more. Alternatively, it may be, for example, 6.0 μm or less, or 5.0 μm or less.

[0194] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present disclosure and exhibits similar effects is included in the technical scope of the present disclosure. EXAMPLES

[0195] [Example 1] (Preparation of release film 1) The following composition 1 for forming a matte layer (thermosetting resin composition) was applied to the corona-treated surface of a 50 μm-thick PET film (E5101, Toyobo Co., Ltd.) in an amount of 3 g / m after drying. 2The mixture was then cured in an oven at 40° C. for 5 days, thereby obtaining a release film 1 having a film layer and a first matte layer. <Composition 1 for forming matte layer> Polyester polyol resin: 100 parts by weight Hardener: 15 parts by weight (hexamethylene diisocyanate) Matting agent: 30 parts by weight (silica particles, average particle size 3 μm) Solvent: appropriate amount

[0196] Next, the following composition 1 for forming a first protective layer was applied to the second surface (matte layer surface) of the release film 1 in an amount of 5 g / m2 after drying. 2 Then, the coating was irradiated with an electron beam (applied voltage: 90 kV, 5 Mrad (50 kGy)) to form a first protective layer having a thickness of 5 μm. <Composition 1 for forming first protective layer> ·Ionizing radiation curable resin composition: 100 parts by mass (Caprolactone-based urethane acrylate: 30 parts by mass) (Pentaerythritol triacrylate (hydroxyl group-containing acrylate): 70 parts by mass) Triazine-based UV absorber: 2 parts by weight (Hydroxyphenyltriazine UV absorber (product name: TINUVIN479, BASF)) Light stabilizer having a reactive functional group: 2 parts by weight (Product name: Sanol LS-3410, Nippon Nyukazai Co., Ltd.) Solvent: appropriate amount

[0197] Next, the surface of the obtained first protective layer was subjected to a corona discharge treatment, and then the following composition 1 for forming a second protective layer was applied and dried to form a second protective layer having a thickness of 5 μm. <Composition 1 for forming second protective layer> Polycarbonate-based urethane acrylic copolymer: 100 parts by weight Hydroxyphenyltriazine UV absorber: 17 parts by weight (product name: TINUVIN 400, BASF) Hydroxyphenyltriazine UV absorber: 13 parts by weight (product name: TINUVIN 479, BASF) Hindered amine light stabilizer: 8 parts by weight (product name: TINUVIN 123, BASF) Anti-blocking agent: 9 parts by weight (silica particles, average particle size 3 μm) Hardener: 25 parts by weight (hexamethylene diisocyanate) Solvent: appropriate amount

[0198] Next, ink composition 1 containing a resin component and a pigment was applied to the surface of the obtained second protective layer by gravure coating and dried to form a design layer having a thickness of 3 to 5 μm including a pattern layer and a solid layer. <Ink composition 1> Resin components of ink Mixture of urethane resin and polyacrylic polyol (mass ratio 20:80) Pigments (including organic and inorganic pigments)

[0199] Adhesive composition 1, which contains an acrylic resin and a vinyl chloride-vinyl acetate copolymer in a mass ratio of 6:4, was applied by gravure coating to the surface of the obtained design layer, and dried to form an adhesive layer with a thickness of 2 μm. This resulted in a transfer sheet having a release film, a first protective layer, a second protective layer, a design layer, and an adhesive layer in that order in the thickness direction.

[0200] [Example 2] (Preparation of release film 2) A resin composition containing an acrylic resin and a urethane resin as binder resins was applied to one side of a PET film having a thickness of 100 μm and subjected to a corona discharge treatment, and then dried to form an easy-adhesion layer (thickness: 2 μm). Onto the easy-adhesion layer, the following composition 2 for forming a matte layer was applied by a gravure method (application amount: 5 g / m 2 (drying)), and then irradiated with ultraviolet light using a UV irradiation device consisting of LEDs (wavelength: 395 nm, ultraviolet light amount: 0.6 W / cm 2), and then irradiated with ultraviolet light using an excimer light irradiation device (wavelength: 172 nm (Xe2), ultraviolet light output density: 1 W / cm, cumulative light amount: 10 to 100 mJ / cm 2 The adhesive layer was placed in a nitrogen atmosphere (oxygen concentration 200 ppm or less), and then irradiated with ultraviolet light using a high-pressure mercury lamp (wavelength: 365 nm, ultraviolet output density: 200 W / cm) to form a second matte layer. By the above steps, a release film 2 having an easy-adhesion layer and a second matte layer on a support was obtained.

[0201] <Composition 2 for forming matte layer> Multifunctional urethane acrylate oligomer (4 functional): 65 parts by weight Monofunctional acrylate monomer: 35 parts by weight Wrinkle formation stabilizer (silica particles, average particle size: 3 μm): 1.0 parts by weight Photopolymerization initiator (benzophenone type): 0.8 parts by weight

[0202] Next, the composition 1 for forming the first protective layer was applied to the second surface (matte layer surface) of the release film 2 in such a manner that the coating amount after drying was 5 g / m 2 Then, the coating was irradiated with an electron beam (applied voltage: 90 kV, 5 Mrad (50 kGy)) to form a first protective layer having a thickness of 5 μm.

[0203] Next, the surface of the obtained first protective layer was subjected to a corona discharge treatment, and then the above-mentioned composition 1 for forming the second protective layer was applied and dried to form a second protective layer having a thickness of 5 μm.

[0204] Next, the ink composition 1 containing a resin component and a pigment was applied to the surface of the obtained second protective layer by gravure coating and dried to form a design layer having a thickness of 3 to 5 μm including a pattern layer and a solid layer.

[0205] The adhesive composition 1 was applied to the surface of the obtained design layer by gravure coating and dried to form an adhesive layer having a thickness of 2 μm. This resulted in a transfer sheet having a release film, a first protective layer, a second protective layer, a design layer, and an adhesive layer in this order in the thickness direction.

[0206] [Example 3] (Preparation of release film 3) The following composition 3 for forming a matte layer (thermosetting resin composition) was applied to the corona-treated surface of a 50 μm-thick PET film (E5101, Toyobo Co., Ltd.) in an amount of 3 g / m after drying. 2 The mixture was then cured in an oven at 40° C. for 5 days, thereby obtaining a release film 3 having a film layer and a first matte layer. <Composition 3 for forming matte layer> Polyester polyol resin: 100 parts by weight Hardener: 15 parts by weight (hexamethylene diisocyanate) Matting agent: 15 parts by weight (silica particles, average particle size 3 μm) Solvent: appropriate amount

[0207] Next, the composition 1 for forming the first protective layer was applied to the second surface (matte layer surface) of the release film 3 in such a manner that the coating amount after drying was 5 g / m 2 Then, the coating was irradiated with an electron beam (applied voltage: 90 kV, 5 Mrad (50 kGy)) to form a first protective layer having a thickness of 5 μm.

[0208] Next, the surface of the obtained first protective layer was subjected to a corona discharge treatment, and then the above-mentioned composition 1 for forming the second protective layer was applied and dried to form a second protective layer having a thickness of 5 μm.

[0209] Next, the following ink composition 2 containing a resin component and a pigment was applied to the surface of the obtained second protective layer by gravure coating and dried to form a design layer having a thickness of 3 to 5 μm including a pattern layer and a solid layer. <Ink composition 2> -Mixed resin of acrylic resin and vinyl chloride-vinyl acetate copolymer (mass ratio 8:2) Pigments (including organic and inorganic pigments)

[0210] The adhesive composition 1 was applied to the surface of the obtained design layer by gravure coating and dried to form an adhesive layer having a thickness of 2 μm. This resulted in a transfer sheet having a release film, a first protective layer, a second protective layer, a design layer, and an adhesive layer in this order in the thickness direction.

[0211] [Example 4] (Preparation of release film 4) The following composition 4 for forming a matte layer (thermosetting resin composition) was applied to the corona-treated surface of a 50 μm-thick PET film (E5101, Toyobo Co., Ltd.) at a coating amount of 3 g / m after drying. 2 The mixture was then cured in an oven at 40° C. for 5 days, thereby obtaining a release film 4 having a film layer and a first matte layer. <Composition 4 for forming matte layer> Polyester polyol resin: 100 parts by weight Hardener: 15 parts by weight (hexamethylene diisocyanate) Matting agent: 10 parts by weight (silica particles, average particle size 2.5 μm) Solvent: appropriate amount

[0212] Next, the following composition 2 for forming a first protective layer was applied to the second surface (matte layer surface) of the release film 4 in an amount of 5 g / m2 after drying. 2 Then, the coating was irradiated with an electron beam (applied voltage: 90 kV, 5 Mrad (50 kGy)) to form a first protective layer having a thickness of 5 μm.

[0213] <Composition 2 for forming first protective layer> ·Ionizing radiation curable resin composition: 100 parts by mass (Caprolactone-based urethane acrylate: 60 parts by mass) (Urethane acrylate: 40 parts by weight) Hydroxyphenyltriazine-based UV absorber: 2 parts by weight (Product name: TINUVIN479, BASF) Light stabilizer having a reactive functional group: 2 parts by weight (Product name: Sanol LS-3410, Nippon Nyukazai Co., Ltd.) Matting agent: 5 parts by weight (silica particles, average particle size 3 μm) Solvent: appropriate amount

[0214] Next, the surface of the obtained first protective layer was subjected to a corona discharge treatment, and then the following composition 2 for forming a second protective layer was applied and dried to form a second protective layer having a thickness of 5 μm.

[0215] <Composition 2 for forming second protective layer> Polycarbonate-based urethane acrylic copolymer: 98 parts by weight Acrylic polyol: 2 parts by weight Hydroxyphenyltriazine UV absorber: 17 parts by weight (product name: TINUVIN 400, BASF) Hydroxyphenyltriazine UV absorber: 13 parts by weight (product name: TINUVIN 479, BASF) Hindered amine light stabilizer: 8 parts by weight (product name: TINUVIN 123, BASF) Anti-blocking agent: 9 parts by weight (silica particles, average particle size 3 μm) Hardener: 25 parts by weight (hexamethylene diisocyanate) Solvent: appropriate amount

[0216] Next, the following ink composition 3 containing a resin component and a pigment was applied to the surface of the obtained second protective layer by gravure coating and dried to form a design layer having a thickness of 3 to 5 μm including a pattern layer and a solid layer. <Ink composition 3> Acrylic polyol resin Pigments (including organic and inorganic pigments)

[0217] The adhesive composition 1 was applied to the surface of the obtained design layer by gravure coating and dried to form an adhesive layer having a thickness of 2 μm. This resulted in a transfer sheet having a release film, a first protective layer, a second protective layer, a design layer, and an adhesive layer in this order in the thickness direction.

[0218] [Comparative Example 1] A release film 5 (PET film E5001, manufactured by Toyobo Co., Ltd.) not containing a matting agent was prepared.

[0219] Next, the composition 1 for forming the first protective layer was applied to one surface of the release film 5 so that the coating amount after drying was 5 g / m 2 Then, the coating was irradiated with an electron beam (applied voltage: 90 kV, 5 Mrad (50 kGy)) to form a first protective layer having a thickness of 5 μm.

[0220] Next, the surface of the obtained first protective layer was subjected to a corona discharge treatment, and then the above-mentioned composition 1 for forming the second protective layer was applied and dried to form a second protective layer having a thickness of 5 μm.

[0221] Next, the ink composition 1 containing a resin component and a pigment was applied to the surface of the obtained second protective layer by gravure coating and dried to form a design layer having a thickness of 3 to 5 μm including a pattern layer and a solid layer.

[0222] The adhesive composition 1 was applied to the surface of the obtained design layer by gravure coating and dried to form an adhesive layer having a thickness of 2 μm. This resulted in a transfer sheet having a release film, a first protective layer, a second protective layer, a design layer, and an adhesive layer in this order in the thickness direction.

[0223] [Comparative Example 2] A release film 6 (PET film with a thickness of 50 μm, haze (Hz): 30%, total light transmittance (Tt): 85%) containing a matting agent was prepared.

[0224] Next, the composition 1 for forming the first protective layer was applied to one surface of the release film 6 in such a manner that the coating amount after drying was 5 g / m 2 Then, the coating was irradiated with an electron beam (applied voltage: 90 kV, 5 Mrad (50 kGy)) to form a first protective layer having a thickness of 5 μm.

[0225] Next, the surface of the obtained first protective layer was subjected to a corona discharge treatment, and then the above-mentioned composition 1 for forming the second protective layer was applied and dried to form a second protective layer having a thickness of 5 μm.

[0226] Next, the ink composition 1 containing a resin component and a pigment was applied to the surface of the obtained second protective layer by gravure coating and dried to form a design layer having a thickness of 3 to 5 μm including a pattern layer and a solid layer.

[0227] The adhesive composition 1 was applied to the surface of the obtained design layer by gravure coating and dried to form an adhesive layer having a thickness of 2 μm. This resulted in a transfer sheet having a release film, a first protective layer, a second protective layer, a design layer, and an adhesive layer in this order in the thickness direction.

[0228] [Comparative Example 3] A release film 7 (PET film with a thickness of 50 μm, haze (Hz): 83%, total light transmittance (Tt): 68%) with a matting agent mixed therein was prepared.

[0229] Next, the composition 1 for forming the first protective layer was applied to one surface of the release film 7 so that the coating amount after drying was 5 g / m 2 Then, the coating was irradiated with an electron beam (applied voltage: 90 kV, 5 Mrad (50 kGy)) to form a first protective layer having a thickness of 5 μm.

[0230] Next, the surface of the obtained first protective layer was subjected to a corona discharge treatment, and then the above-mentioned composition 1 for forming the second protective layer was applied and dried to form a second protective layer having a thickness of 5 μm.

[0231] Next, the ink composition 1 containing a resin component and a pigment was applied to the surface of the obtained second protective layer by gravure coating and dried to form a design layer having a thickness of 3 to 5 μm including a pattern layer and a solid layer.

[0232] The adhesive composition 1 was applied to the surface of the obtained design layer by gravure coating and dried to form an adhesive layer having a thickness of 2 μm. This resulted in a transfer sheet having a release film, a first protective layer, a second protective layer, a design layer, and an adhesive layer in this order in the thickness direction.

[0233] [Comparative Example 4] The release film 1 was used as the release film, and the following composition 3 for forming a first protective layer was applied to the second surface of the release film 1 in an amount of 5 g / m2 after drying. 2 Then, the coating was irradiated with an electron beam (applied voltage: 90 kV, 5 Mrad (50 kGy)) to form a first protective layer having a thickness of 5 μm.

[0234] <Composition 3 for forming first protective layer> ·Ionizing radiation curable resin composition: 100 parts by mass (Caprolactone-based urethane acrylate: 100 parts by mass) Hydroxyphenyltriazine-based UV absorber: 2 parts by weight (Product name: TINUVIN479, BASF) Light stabilizer having a reactive functional group: 2 parts by weight (Product name: Sanol LS-3410, Nippon Nyukazai Co., Ltd.)

[0235] Next, the surface of the obtained first protective layer was subjected to a corona discharge treatment, and then the above-mentioned composition 1 for forming the second protective layer was applied and dried to form a second protective layer having a thickness of 5 μm.

[0236] Next, the ink composition 1 containing a resin component and a pigment was applied to the surface of the obtained second protective layer by gravure coating and dried to form a design layer having a thickness of 3 to 5 μm including a pattern layer and a solid layer.

[0237] The adhesive composition 1 was applied to the surface of the obtained design layer by gravure coating and dried to form an adhesive layer having a thickness of 2 μm. This resulted in a transfer sheet having a release film, a first protective layer, a second protective layer, a design layer, and an adhesive layer in this order in the thickness direction.

[0238] [Measurement of 60° gloss value of release film] The release films used in the examples and comparative examples were placed on a non-glossy black mount with the first side facing up, and the 60° specular gloss of the first side was measured using a gloss meter ("Micro Trigloss (model name)", manufactured by BYK Gardner) in accordance with JIS Z 8741:1997, Method 3. Similarly, the release films were placed with the second side facing up, and the 60° specular gloss of the second side was measured.

[0239] [Measurement of maximum height Rz of release film] The maximum height Rz of the first surface of the release film used in the examples and comparative examples was measured using a rectangle (1024 μm × 768 μm) at any point on the first surface of the release film as the measurement area, with the following measurement device and under the following conditions. Similarly, the maximum height Rz of the second surface of the release film was measured using a rectangle (1024 μm × 768 μm) at any point on the second surface as the measurement area. Rz (maximum height) was the average value of the measured values ​​at any 10 points. Measurement equipment: Shape analysis laser microscope (VK-X1000, manufactured by Keyence Corporation) Objective lens: 50x Measurement mode: Shape measurement mode Measurement pitch: 12μm Measurement quality: High speed mode Scan mode: Laser confocal

[0240] [Haze value of release film] The haze value H1 of the release film used in the examples and comparative examples was measured in accordance with JIS K7136:2000 using a haze meter (HM-150L2N, manufactured by Murakami Color Research Laboratory) (before the tape application test). The light incident surface during haze measurement was the second surface side. In addition, an adhesive tape ("Cellotape (registered trademark)", manufactured by Nichiban Co., Ltd.) was applied to the second surface of the release film, and the haze value H2 was measured in the same manner as above (after the tape application test), and the difference ΔH (=H1-H2) in the haze value before and after the tape application test was calculated. The results are shown in Table 1.

[0241] [Indentation hardness measurement] The indentation hardness of the first protective layer of the obtained transfer sheet was measured by the method described above. The results are shown in Table 1.

[0242] [Evaluation of pattern visibility] Twenty random adults visually observed the obtained transfer sheet from the release film side. They answered the percentage of the pattern they could see, and the average of the answers of the 20 people was calculated and evaluated according to the following criteria. A: When viewed from the release film side, more than 70% of the pattern can be seen. B: When viewed from the release film side, 50% of the pattern can be seen C: When viewed from the release film side, less than 30% of the pattern can be seen.

[0243] [Evaluation of peelability] A 2 mm thick polycarbonate plate ("Carboglass / Polish", manufactured by AGC Inc.) was prepared as a substrate, and one side of the substrate was laminated opposite the transfer layer of the transfer sheet obtained above. Thereafter, a laminator was used to apply heat and pressure from the transfer sheet side under conditions of a lamination roll temperature of 170°C and a conveying speed of 2 m / min, thereby adhering the substrate and the transfer layer of the transfer sheet. The release film was peeled off from the adhered transfer sheet. The releasability of the release film at this time was evaluated according to the following evaluation criteria. (Evaluation Criteria) A: When the release film is peeled off by hand, it can be peeled off without breaking the PET film. B: When the release film was peeled off by hand, the PET film was partially torn or could not be peeled off.

[0244] [60° gloss value and maximum height Rz after removing the release film] In the evaluation of the releasability, the 60° gloss value and maximum height Rz of the surface of the first protective layer after the release film was peeled off were measured by the above-mentioned method. The results are shown in Table 1.

[0245] [Luxury rating] In the evaluation of releasability, 20 random adults observed the surface design of the component after the release film was peeled off, and rated it as follows based on the number of people who answered that it had a luxurious feel. A: 16 or more people B: More than 11 people and less than 15 people C: More than 6 people and less than 10 people D: Less than 5 people

[0246] [Weather-resistant adhesion evaluation] In the evaluation of the releasability, the member from which the release film had been peeled off was used as the evaluation member.

[0247] The obtained evaluation members were subjected to the following accelerated weathering test using a metal halide lamp (MWOM) for 700 hours (a cycle of 20 hours of ultraviolet irradiation under the following irradiation conditions, followed by 4 hours of condensation under the following condensation conditions, and the cycle was repeated). The weathering adhesion was then evaluated as follows. The evaluation results are shown in Table 1.

[0248] <Conditions for accelerated weathering test> (Test Equipment) Manufactured by Daipla Wintes, product name "Daipla Metal Weather" (Irradiation conditions) Illuminance: 65mW / cm 2 , Black panel temperature: 63℃, chamber humidity: 50%RH, time: 20 hours (Condensation conditions) Illuminance: 0mW / cm 2 , Humidity inside the tank: 98%RH, Time: 4 hours

[0249] Adhesive tape ("Cellotape (registered trademark)" manufactured by Nichiban Co., Ltd.) was applied to the evaluation member on which the accelerated weather resistance test had been performed, over an area of ​​2.5 cm x 2.5 cm, so that it protruded about 5 cm from the edge. The protruding portion of the applied adhesive tape was then pinched and the adhesive tape was peeled off in a direction at 45° to the surface of the evaluation member to check the interlayer adhesion of the transfer layer, and the adhesion was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1. In addition, the initial interlayer adhesion was evaluated using the same method and evaluation criteria for evaluation members that had not been subjected to the accelerated weather resistance test.

[0250] <Evaluation criteria> A: No peeling occurred between the transfer layers. B: Peeling occurred between the transfer layers.

[0251] [Table 1]

[0252] As shown in Table 1, the transfer sheets of Examples 1 to 4 were confirmed to have good visibility of the pattern in the design layer. In addition, it was confirmed that the surface of the transfer layer had a low gloss feeling after being attached to a substrate and the release film was peeled off. In addition, the release film was easily peeled off. On the other hand, it was confirmed that the transfer layer did not have a low gloss feeling in Comparative Example 1, which used a PET film that did not have a matte layer and did not have a matte agent kneaded into it. In addition, it was confirmed that the visibility of the pattern was poor in Comparative Examples 2 and 3, which used a PET film kneaded with a matte agent. In addition, in Comparative Example 4, the indentation hardness of the first protective layer was low, and it was difficult to peel off the release film.

[0253] Thus, in the present disclosure, for example, the following inventions are provided:

[0254] [1] A transfer sheet used in the manufacture of an exterior member, The transfer sheet has a release film and a transfer layer disposed on one surface of the release film, The transfer layer has a first protective layer and a second protective layer in this order from the release film side in a thickness direction, the first protective layer contains a cured product of a first curable resin composition and a weather resistance agent; the second protective layer contains a cured product of a second curable resin composition and a weather resistance agent, the release film has a first surface located on the side opposite to the transfer layer side and a second surface located on the transfer layer side, The 60° gloss value of the first surface is 90 or more; the second surface has a 60° gloss value of 40 or less; A transfer sheet, wherein the indentation hardness of the cross section of the first protective layer is 150 MPa or more and 300 MPa or less.

[0255] [2] A transfer sheet used in the manufacture of an exterior member, The transfer sheet has a release film and a transfer layer disposed on one surface of the release film, The transfer layer has a first protective layer and a second protective layer in this order from the release film side in a thickness direction, the first protective layer contains a cured product of a first curable resin composition and a weather resistance agent; the second protective layer contains a cured product of a second curable resin composition and a weather resistance agent, the release film has a first surface located on the side opposite to the transfer layer side and a second surface located on the transfer layer side, The maximum height Rz of the first surface is 0.8 μm or less, The second surface has a maximum height Rz of 2.0 μm or more, A transfer sheet, wherein the indentation hardness of the cross section of the first protective layer is 150 MPa or more and 300 MPa or less.

[0256] [3] The 60° gloss value of the first surface is 90 or more; The transfer sheet according to [2], wherein the 60° gloss value of the second surface is 40 or less.

[0257] [4] The release film has a film layer including the first surface, and a matte layer arranged on the surface of the film layer facing the transfer layer and including the second surface. The transfer sheet described in any of [1] to [3].

[0258] [5] The 60° gloss value of the first surface is 200 or less; The transfer sheet according to any one of [1] to [4], wherein the 60° gloss value of the second surface is 3.0 or more.

[0259] [6] The maximum height Rz of the first surface is 0.1 μm or more, The transfer sheet according to any one of [1] to [5], wherein the second surface has a maximum height Rz of 6.0 μm or less.

[0260] [7] The transfer sheet according to any one of [1] to [6], wherein when a tape application test is performed in which a tape is applied to the second surface of the release film, the difference in haze value (ΔH) before and after the tape application test is 20% or more.

[0261] [8] The transfer sheet according to any one of [1] to [7], wherein the indentation hardness of the cross section of the second protective layer is 2 MPa or more and 50 MPa or less.

[0262] [9] The transfer sheet according to any one of [1] to [8], wherein the first curable resin composition is an ionizing radiation curable resin composition.

[0263]

[10] The transfer sheet according to any one of [1] to [9], wherein the first curable resin composition is an electron beam curable resin composition.

[0264]

[11] The transfer sheet according to any one of [1] to

[10] , wherein the second curable resin composition is a thermosetting resin composition.

[0265]

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

[11] , wherein the first protective layer and the second protective layer each contain at least one of an ultraviolet absorber and a light stabilizer as the weather resistance agent.

[0266]

[13] A method for producing a transfer sheet according to any one of [1] to

[12] , a first protective layer forming step of applying a first composition containing the first curable resin composition and the weather resistance agent to the second surface of the release film and curing the composition to form the first protective layer; a second protective layer forming step of applying a second composition containing the second curable resin composition and the weather resistance agent to a surface of the first protective layer opposite to the release film, and curing the composition to form the second protective layer; The method for producing a transfer sheet comprising the steps of:

[0267]

[14] A preparation step of preparing a transfer sheet according to any one of [1] to

[12] ; a bonding step of placing the second protective layer side of the transfer sheet against a substrate and bonding the two together; The method for producing an exterior member comprising the steps of:

[0268]

[15] The film has a release film, a first protective layer, a second protective layer, and a substrate, in this order in the thickness direction; the first protective layer contains a cured product of a first curable resin composition and a weather resistance agent; the second protective layer contains a cured product of a second curable resin composition and a weather resistance agent, the release film has a first surface located on the side opposite to the first protective layer and a second surface located on the first protective layer side, The 60° gloss value of the first surface is 90 or more; the second surface has a 60° gloss value of 40 or less; An exterior member with a release film, wherein the indentation hardness of the cross section of the first protective layer is 150 MPa or more and 300 MPa or less.

[0269]

[16] The film has a release film, a first protective layer, a second protective layer, and a substrate, in this order in the thickness direction; the first protective layer contains a cured product of a first curable resin composition and a weather resistance agent; the second protective layer contains a cured product of a second curable resin composition and a weather resistance agent, the release film has a first surface located on the side opposite to the first protective layer and a second surface located on the first protective layer side, The maximum height Rz of the first surface is 0.8 μm or less, The second surface has a maximum height Rz of 2.0 μm or more, An exterior member with a release film, wherein the indentation hardness of the cross section of the first protective layer is 150 MPa or more and 300 MPa or less.

[0270]

[17] A first protective layer, a second protective layer, and a substrate, in this order in a thickness direction, the first protective layer contains a cured product of a first curable resin composition and a weather resistance agent; the second protective layer contains a cured product of a second curable resin composition and a weather resistance agent, the indentation hardness of the first protective layer in a cross section is 150 MPa or more and 300 MPa or less; an exterior member, wherein a 60° gloss value of the surface of the first protective layer opposite to the second protective layer is 30 or less.

[0271]

[18] A first protective layer, a second protective layer, and a substrate, in this order in a thickness direction, the first protective layer contains a cured product of a first curable resin composition and a weather resistance agent; the second protective layer contains a cured product of a second curable resin composition and a weather resistance agent, the indentation hardness of the first protective layer in a cross section is 150 MPa or more and 300 MPa or less; an exterior member, wherein a maximum height Rz of the surface of the first protective layer opposite to the second protective layer is 1.5 μm or more. [Explanation of symbols]

[0272] 1 ... Release film S1...Side 1 S2...Side 2 2 … 1st protective layer 3…Second protective layer 4 … Adhesive layer 5 … Design layer 10 ... Transfer sheet 20 … Base 50 … Exterior material with film 100 … Exterior materials

Claims

1. A transfer sheet used in the manufacture of an exterior member, The transfer sheet has a release film and a transfer layer disposed on one surface of the release film, The transfer layer has a first protective layer and a second protective layer in this order from the release film side in a thickness direction, the first protective layer contains a cured product of a first curable resin composition and a weather resistance agent; the second protective layer contains a cured product of a second curable resin composition and a weather resistance agent, The release film has a first surface located on the side opposite to the transfer layer side and a second surface located on the transfer layer side, The 60° gloss value of the first surface is 90 or more; the 60° gloss value of the second surface is 40 or less; A transfer sheet, wherein the indentation hardness of the cross section of the first protective layer is 150 MPa or more and 300 MPa or less.

2. A transfer sheet used in the manufacture of an exterior member, The transfer sheet has a release film and a transfer layer disposed on one surface of the release film, The transfer layer has a first protective layer and a second protective layer in this order from the release film side in a thickness direction, the first protective layer contains a cured product of a first curable resin composition and a weather resistance agent; the second protective layer contains a cured product of a second curable resin composition and a weather resistance agent, The release film has a first surface located on the side opposite to the transfer layer side and a second surface located on the transfer layer side, The maximum height Rz of the first surface is 0.8 μm or less, The maximum height Rz of the second surface is 2.0 μm or more, A transfer sheet, wherein the indentation hardness of the cross section of the first protective layer is 150 MPa or more and 300 MPa or less.

3. The 60° gloss value of the first surface is 90 or more; The transfer sheet according to claim 2 , wherein the second surface has a 60° gloss value of 40 or less.

4. The transfer sheet according to claim 1 or claim 2, wherein the release film has a film layer including the first surface, and a matte layer arranged on the surface of the film layer facing the transfer layer and including the second surface.

5. The 60° gloss value of the first surface is 200 or less; The transfer sheet according to claim 1 or 3, wherein the second surface has a 60° gloss value of 3.0 or more.

6. The maximum height Rz of the first surface is 0.1 μm or more, The transfer sheet according to claim 2 , wherein the second surface has a maximum height Rz of 6.0 μm or less.

7. The transfer sheet according to claim 1 or 2, wherein, when a tape application test is performed in which a tape is applied to the second surface of the release film, the difference in haze value (ΔH) before and after the tape application test is 20% or more.

8. The transfer sheet according to claim 1 or 2, wherein the indentation hardness of the cross section of the second protective layer is 2 MPa or more and 50 MPa or less.

9. The transfer sheet according to claim 1 or 2, wherein the first curable resin composition is an ionizing radiation curable resin composition.

10. The transfer sheet according to claim 1 or 2, wherein the first curable resin composition is an electron beam curable resin composition.

11. The transfer sheet according to claim 1 or 2, wherein the second curable resin composition is a thermosetting resin composition.

12. The transfer sheet according to claim 1 or 2, wherein the first protective layer and the second protective layer each contain at least one of an ultraviolet absorbing agent and a light stabilizer as the weather resistance agent.

13. A method for producing the transfer sheet according to claim 1 or 2, comprising the steps of: a first protective layer forming step of applying a first composition containing the first curable resin composition and the weather resistance agent to the second surface of the release film and curing the composition to form the first protective layer; a second protective layer forming step of applying a second composition containing the second curable resin composition and the weather resistance agent to a surface of the first protective layer opposite to the release film, and curing the composition to form the second protective layer; The method for producing a transfer sheet comprising the steps of:

14. A preparation step of preparing the transfer sheet according to claim 1 or 2; a bonding step of placing the second protective layer side of the transfer sheet against a substrate and bonding the two together; The method for manufacturing an exterior member comprising the steps of:

15. The film has a release film, a first protective layer, a second protective layer, and a substrate, in this order in a thickness direction; the first protective layer contains a cured product of a first curable resin composition and a weather resistance agent; the second protective layer contains a cured product of a second curable resin composition and a weather resistance agent, The release film has a first surface located on the side opposite to the first protective layer and a second surface located on the first protective layer side, The 60° gloss value of the first surface is 90 or more; the 60° gloss value of the second surface is 40 or less; An exterior member with a release film, wherein the indentation hardness of the cross section of the first protective layer is 150 MPa or more and 300 MPa or less.

16. The film has a release film, a first protective layer, a second protective layer, and a substrate, in this order in a thickness direction; the first protective layer contains a cured product of a first curable resin composition and a weather resistance agent; the second protective layer contains a cured product of a second curable resin composition and a weather resistance agent, The release film has a first surface located on the side opposite to the first protective layer and a second surface located on the first protective layer side, The maximum height Rz of the first surface is 0.8 μm or less, The maximum height Rz of the second surface is 2.0 μm or more, An exterior member with a release film, wherein the indentation hardness of the cross section of the first protective layer is 150 MPa or more and 300 MPa or less.

Images