JP7613493B2 - Transfer sheet, method for producing transfer sheet, method for producing exterior member, and exterior member with release film - Google Patents

Description

This disclosure relates to a transfer sheet, a method for manufacturing a transfer sheet, a method for manufacturing an exterior member, and an exterior member with a release film.

It is known to decorate a substrate such as a metal or resin member by transferring a transfer layer (a layer transferred from the transfer sheet) of a transfer sheet to the substrate. For example, Patent Document 1 discloses a design transfer sheet that includes 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 that can be heat-bonded and a second surface layer that can be heat-bonded, in that order.

JP 2016-120643 A

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

The present disclosure has been made in consideration of the above-mentioned circumstances, and has as its main object to provide a transfer sheet for use in the manufacture of exterior components, which is capable of transferring a transfer layer that has excellent visibility of the design and a low gloss appearance without the need to peel off a release film.

In the present disclosure, there is provided a transfer sheet used in the manufacture of exterior members, 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 weathering agent, the second protective layer containing a cured product of a second curable resin composition and a weathering 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.

The present disclosure also provides a transfer sheet used in the manufacture of exterior members, 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 weathering agent, the second protective layer containing a cured product of a second curable resin composition and a weathering 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 being 0.8 μm or less, the maximum height Rz of the second surface being 2.0 μm or more, and the indentation hardness of the cross section of the first protective layer being 150 MPa or more and 300 MPa or less.

The present disclosure provides a method for producing the above-mentioned transfer sheet, which includes a first protective layer forming step of applying a first composition containing the first curable resin composition and the weathering agent to the second surface of the release film, 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 weathering agent to the surface of the first protective layer opposite the release film, curing the composition to form the second protective layer.

The present disclosure provides a method for manufacturing an exterior member, which includes a preparation step of preparing the transfer sheet described above, 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.

In the present disclosure, an exterior member with a release film is provided, which has, in this order in the thickness direction, a release film, a first protective layer, a second protective layer, and a substrate, the first protective layer containing a cured product of a first curable resin composition and a weathering agent, the second protective layer containing a cured product of a second curable resin composition and a weathering agent, the release film having 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, and the indentation hardness of the cross section of the first protective layer is 150 MPa or more and 300 MPa or less.

The present disclosure also provides an exterior member with a release film, which 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 weathering agent, 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 the cross section of the first protective layer is 150 MPa or more and 300 MPa or less.

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 without the need to peel off the release film and can transfer a transfer layer having a low gloss.

1 is a schematic cross-sectional view illustrating a transfer sheet according to the present disclosure. 1 is a schematic cross-sectional view illustrating a release film in the present disclosure. 1A to 1C are schematic cross-sectional views illustrating a method for producing a transfer sheet in the present disclosure. 1A to 1C are schematic cross-sectional views illustrating a method for manufacturing an exterior member in the present disclosure. 1 is a schematic cross-sectional view illustrating an example of an exterior member with a release film in the present disclosure. 1 is a schematic cross-sectional view showing an example of an exterior member according to the present disclosure. FIG. 1 is a schematic cross-sectional view showing an example of a conventional transfer sheet.

Below, an embodiment will be described with reference to the drawings. However, this disclosure can be implemented in many different forms and should not be limited to the description of the embodiment exemplified below. Also, in order to make the explanation clearer, the drawings may show the width, thickness, and shape of each part in a schematic manner compared to the actual form, but this is merely an example and should not be interpreted as limiting.

In this specification, when describing a mode in which another component is placed on a certain component, the term "above" or "below" includes both cases in which another component is placed directly above or below the certain component, so as to be in contact with the component, and cases in which another component is placed above or below the certain component, with another component in between. In addition, in this specification, when describing a mode in which another component is placed on the surface of a certain component, the term "on the surface" includes both cases in which another component is placed directly above or below the certain component, so as to be in contact with the component, and cases in which another component is placed above or below the certain component, with another component in between.

The transfer sheet, the method for manufacturing the transfer sheet, the method for manufacturing the exterior member, and the exterior member with release film in this disclosure are described in detail below.

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

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

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

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.

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 has, from the matte film 21 side, a first protective layer 22, a second protective layer 23, a design layer 25, and an adhesive layer 24 in this order in the thickness direction D _T.

The transfer sheet 200 uses the matte film 21 as a release film, which imparts irregularities to the surface of the transfer layer X after the release film 21 is peeled off, resulting in a low gloss appearance. 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 view the design, it is necessary to peel off the matte film. Furthermore, when the transfer layer X has a low gloss appearance, exterior components (components for outdoor use) are exposed to harsh environments, and therefore tend to experience significant changes in gloss due to deterioration of the resin.

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

On the other hand, the transfer sheet in this embodiment has a high 60° gloss value on the first side of the release film 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 it is as a masking film, it is possible to reduce the amount of plastic used. Furthermore, since the 60° gloss value on the second side is low within a predetermined range, the transfer layer after peeling off the release film has a low gloss feel. In addition, the inventors have found that since the 60° gloss value on the second side is low within a predetermined range, the adhesion between the first protective layer and the release film is increased, so that the release film tends to be difficult to peel off. And, it has been found that since the indentation hardness on the cross section of the first protective layer is within a predetermined range, it is possible to easily peel off the release film.

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, high weather resistance can be imparted by, for example, 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).

In addition, because the first protective layer contains a weathering agent, changes in gloss due to deterioration of the resin are suppressed even when the surface of the transfer layer X has a low gloss, as in this embodiment.

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.

(1) 60° Gloss Value In this embodiment, the 60° gloss value of the first surface of the release film is usually 90 or more, 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, may be 160 or less, or may be 140 or less.

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.

In this embodiment, the 60° gloss value of the second surface S2 of the release film is usually 40 or less, and 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 feel. On the other hand, the 60° gloss value of the second surface S2 is, for example, 3.0 or more, and 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 penetrate into the fine matte shape, making peeling difficult. In addition, it may not be possible to form the desired shape.

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.

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 particle content, 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.

(2) Maximum height Rz
In the release film in this embodiment, the maximum height Rz of the first surface is, for example, 0.8 μm or less, or may be 0.6 μm or less, or may be 0.4 μm or less. On the other hand, the maximum height Rz of the first surface is, for example, 0.1 μm or more, or may be 0.2 μm or more.

In this embodiment, the maximum height Rz of the first surface is a value measured using 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 below.

In the embodiment, the release film has a maximum height Rz of the second surface of, for example, 2.0 μm or more, or may be 3.0 μm or more, or 4.0 μm or more. On the other hand, the maximum height Rz of the second surface of, for example, 6.0 μm or less, or may be 5.0 μm or less.

In this embodiment, the maximum height Rz of the second surface is a value measured using 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 below.

(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 due to 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.

The above haze value H1 of the release film is the average value of three measurements taken 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 second surface.

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 this embodiment, the release film preferably has a difference ΔH (=H1-H2) between the haze value H2 after 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, that is, 20% or more. It is more preferable that the difference in haze values (ΔH) is 30% or more, and even more preferable that it is 40% or more.

The above haze value H2 of the release film is the average value of three measurements taken in accordance with JIS K7136:2000, with the light incident surface facing the tape and a haze meter (HM-150L2N, manufactured by Murakami Color Research Laboratory) as the measuring device.

(4) Configuration 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. Figure 2 is a schematic cross-sectional view showing an example of a release film in an embodiment. As shown in Figure 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.

(i) Film layer The film layer is not particularly limited as long as it has the first surface described above, 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.

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 are preferred, with PET being more preferred, from the viewpoint of being less susceptible to thermal shrinkage during the production of the transfer sheet and shrinkage due to exposure to ionizing radiation.

Examples of olefin-based 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 to shrinkage due to exposure to ionizing radiation.

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

(ii) Matte layer The matte 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 matte agent. Hereinafter, a matte layer containing a resin component and particles as a matte agent is referred to as a first matte layer. The resin component in the first matte layer is typically a cured product (crosslinked structure) of a curable resin. On the other hand, the resin component may be a thermoplastic resin. Among them, it is preferable that the first matte layer contains a cured product of a curable resin. When the first matte layer contains a cured product of a curable resin, the releasability from the first protective layer is improved.

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, etc.

Examples of curable resins include ionizing radiation curable resins and thermosetting resins. Examples of ionizing radiation curable resins include electron beam curable resins and ultraviolet light curable resins.

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 this embodiment, only one type of ionizing radiation curable resin may be used, or two or more types may be used. Among these, it is preferable to use at least one of a polyfunctional monomer and an oligomer as the ionizing radiation curable resin.

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.

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

The ionizing radiation curable resin preferably contains at least a polyfunctional monomer or oligomer having a weight average molecular weight of 500 or more. 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.

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.

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).

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.

The particle content in the first matte 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, per 100 parts by mass of the resin component.

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, and an aluminum chelating agent, as necessary. 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.

The first matte layer can be obtained, for example, by applying a matte layer-forming ink containing a curable resin to one side of the film layer and curing it.

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

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. There are no particular restrictions on the shape of the wrinkle formation stabilizer, but examples include spherical, polyhedral, scaly, and amorphous shapes.

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.

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 per 100 parts by mass of the resin forming the second matte layer.

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 it is preferable that the protrusions have linear protrusions. More preferable 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.

Examples of resins forming the second mat layer include ionizing radiation curable resins. Examples of ionizing radiation curable resins 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". As the polyfunctional (meth)acrylate monomer, 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 is given. 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.

As the resin for forming the second mat layer, it is preferable to use a combination of the above-mentioned polymerizable oligomer and polymerizable monomer. In this case, the content of the polymerizable oligomer relative to a total of 100 parts by mass of the polymerizable oligomer and the polymerizable monomer is preferably 40 parts by mass or more, more preferably 50 parts by mass or more. On the other hand, it is preferably 90 parts by mass or less, more preferably 80 parts by mass or less.

As a method for forming the second matte layer, it is preferable to have 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, if 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 such low-wavelength ultraviolet light, 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 hardened product having wrinkles. Then, the curing proceeds from the surface area where the curing proceeds slowly to the deep area away in the depth direction, and the resin composition is cured throughout the entire thickness, 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 area, it is preferable to perform another irradiation process after irradiating with light having a wavelength of 100 nm or more and less than 200 nm, as described below.

As the wavelength light of at least 100 nm or more and less than 200 nm, for example, rare gases such as Ar, Kr, Xe, Ne, halogenated rare gases such as F, Cl, I, Br, or 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 with a wavelength of 126 nm radiated from the excimer of Ar ₂ (hereinafter abbreviated as "126 nm (Ar ₂ )"), 146 nm (Kr ₂ ), 157 nm (F ₂ ), 172 nm (Xe ₂ ), 193 nm (ArF), etc. can be preferably used. 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. Discharge lamps that emit this light (ultraviolet light) are also called "excimer lamps." Excimer light has a single wavelength peak and is characterized by a narrower half-width wavelength than normal 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.

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 ).

The integrated light amount of the wavelength light is preferably 1 mJ/cm2 ^{or more} , more preferably 10 mJ/cm2 ^{or more} , from the viewpoint of stabilizing the formation of wrinkles and stably imparting a low gloss feeling to the transfer layer. The upper limit is, for example, 1,000 mJ/cm2 ^or less, more preferably 500 mJ/cm2 or less. From the same viewpoint, the ultraviolet light output density is preferably 0.01 W/cm2 or more, more preferably 0.1 W/cm2 or ^more , and the upper limit is, for example, 10 W/cm2 or less, more preferably 5 W/cm2 or less.

In addition, it is preferable that the oxygen concentration when irradiating the above wavelength light is lower, preferably 1,000 ppm or less, and more preferably 750 ppm or less.

In the second mat layer forming step, in addition to the irradiation with the above-mentioned 100 nm or more and less than 200 nm wavelength light, 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, 200 nm or more wavelength light, for example, 380 nm or more, preferably 385 nm or more and 400 nm or less, and then irradiated with 100 nm or more and less than 200 nm wavelength light, or after irradiation with 100 nm or more and less than 200 nm wavelength light, post-curing may be performed to further cure the resin composition. The above-mentioned wavelength light belongs to ultraviolet rays, but it is also possible to use other ionizing radiations other than ultraviolet rays, 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.

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.

2. First Protective Layer The transfer sheet in this embodiment has a first protective layer. The first protective layer contributes to improving the surface properties (e.g., scratch resistance, abrasion resistance, etc.) of the exterior member.

(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. In addition, 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. In addition, in an environment where temperature changes are repeated, the weather resistance adhesion between the first protective layer and the second protective layer may decrease.

Exterior components are usually exposed to harsh environments. For this reason, the first protective layer and the second protective layer that constitute the transfer layer in the transfer sheet used in the manufacture of the exterior components 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 range described below, thereby improving the weather-resistant adhesion and weather resistance.

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 used to produce 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.

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 frozen 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.

(Method of measuring indentation hardness)
In this specification, "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.

Specifically, the indentation hardness of the cross section of the first protective layer is measured by pressing a Berkovich indenter (material: diamond triangular pyramid) vertically into the cut surface of the measurement sample described above using the nanoindenter described below. The measurement device and measurement conditions are as follows. Here, it is preferable that the position where the Berkovich indenter is pressed is 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. Furthermore, 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.

Equipment used: Nanoindenter (TI 950 TriboIndenter, manufactured by BRUKER)
Indenter used: Berkovich indenter (model number: TI-0039, manufactured by BRUKER)
・Push control method: Displacement control method (lift operation not used)
Maximum indentation depth: 100 nm
Push-in rate: 10 nm/sec Loading time: 10 sec (pushing from 0 to 100 nm)
・Holding time: 5 seconds (100 nm constant)
Unloading time: 10 seconds (return from 100 nm to 0)
Number of measurements: 5

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, and the indentation hardness HIT can be calculated as the maximum indentation load _{P max} (N) divided by the projected area A (mm ² ) of contact between the indenter and the cross section of the first protective layer at that time (the following formula (1)).
_HIT = _Pmax /A...(1)
Here, A is the contact projected area obtained by correcting the shape of the indenter tip using a standard sample of fused quartz in a standard manner.

In this specification, the indentation hardness of the cross section of the first protective layer is the arithmetic average value of five measurements taken on the same sample at different positions. Each measurement was taken with a shift of 5 μm or more. When taking measurements, it is preferable to use fused quartz, the standard sample of the device manufacturer, to confirm that measurements can be taken within ±5% of the reference value in order to confirm that the indenter shape has been correctly corrected and that there are no problems with the operation and measurement of the device. The indentation hardness is measured in an atmosphere with a temperature of 23°C ±5°C and a humidity of 40% to 65%.

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.

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

An example of a cured product of the first curable resin composition is a cured product of an ionizing radiation curable resin composition. Examples of ionizing radiation curable resin compositions include an electron beam curable resin composition and 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 coloration.

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 this disclosure, a (meth)acryloyl group refers to an acryloyl group or a methacryloyl group. In this disclosure, a (meth)acrylate refers to an acrylate or a methacrylate.

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.

The ionizing radiation curable compound preferably contains one or more compounds selected from, for example, urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polycarbonate (meth)acrylate, and acrylic (meth)acrylate. Of these, the ionizing radiation curable compound preferably contains at least urethane (meth)acrylate. The urethane (meth)acrylate is preferably a caprolactone-based urethane acrylate.

When the ionizing radiation curable compound contains a caprolactone-based urethane acrylate, the number of functional groups of the caprolactone-based urethane acrylate is preferably 2 or more and 4 or less, and more preferably 2 or more and 3 or less.

The ionizing radiation curable compound may contain a caprolactone-based urethane acrylate and a non-caprolactone-modified urethane (meth)acrylate. In this case, the content of the caprolactone-based urethane acrylate contained in the first protective layer is M _CLUA , and the content of the non-caprolactone-modified urethane (meth)acrylate is M _UA . The mass ratio of M _CLUA to the total of M _UA and M _CLUA (M _CLUA /(M _UA +M _CLUA )) is, for example, 40 mass% or more and 90 mass% or less, or may be 45 mass% or more and 80 mass% or less, or may be 50 mass% or more and 70 mass% or less.

Caprolactone-based urethane acrylates can usually be obtained by reacting caprolactone-based polyols, organic isocyanates, and hydroxy(meth)acrylates. For example, a synthesis method involves reacting polycaprolactone-based polyols with organic polyisocyanates to produce polyurethane prepolymers containing -NCO groups (isocyanate groups) at both ends, and then reacting the resulting polyurethane prepolymer with hydroxy(meth)acrylate.

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 also be used by mixing one or more polyols in any ratio. As the organic polyisocyanate, a diisocyanate having two isocyanate groups is preferable, and from the viewpoint of suppressing yellowing, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, trimethylhexamethylene diisocyanate, etc. are preferable. As the hydroxy(meth)acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, caprolactone-modified 2-hydroxyethyl acrylate, etc. are preferable.

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. Caprolactone diol-based urethane acrylate refers to a urethane acrylate having a diethylene glycol terminal among caprolactone-based urethane acrylates. By using caprolactone diol-based urethane acrylate, it is possible to suppress the occurrence of cracks and whitening in the first protective layer.

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

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 photopolymerization initiators include acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α-acyloxime ester, acylphosphine oxide, and thioxanthones. Examples of photopolymerization accelerators include p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester.

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.

(3) Weather Resistant The first protective layer usually contains a weather resistant agent. By having the first protective layer contain a weather resistant 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 weather resistant agents include ultraviolet absorbers and light stabilizers. It is preferable that the first protective layer 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.

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

Examples of triazine-based ultraviolet absorbers include hydroxyphenyltriazine-based ultraviolet absorbers. Examples of hydroxyphenyltriazine-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.

The content of the ultraviolet absorber in the first protective layer is, for example, 0.5 parts by mass or more and 10 parts by mass or less, or may be 0.8 parts by mass or more and 8 parts by mass or less, or may be 1 part by mass or more and 5 parts by mass or less, 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, and if the content of the ultraviolet absorber is low, sufficient ultraviolet absorption performance may not be obtained.

Examples of the light stabilizer contained in the first protective layer include hindered amine light stabilizers. 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).

The content of the light stabilizer in the first protective layer is, for example, 1 part by mass or more and 10 parts by mass or less, or may be 1.5 parts by mass or more and 8 parts by mass or less, or may be 2 parts by mass or more and 5 parts by mass or less, 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.

(4) Additives The first protective layer may contain particles. By containing particles in the first protective layer, the low gloss feeling 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.

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.

The first protective layer may contain additives such as silicone compounds, polymerization inhibitors, crosslinking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, antifouling agents, defoaming agents, fillers, anti-wear agents, antibacterial agents, antiviral agents, and antifungal agents.

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

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.

(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.

Thermosetting resin compositions are compositions that contain at least a thermosetting resin and are cured by heating. Examples of thermosetting resins include (meth)acrylic resins, urethane resins, urethane acrylic resins, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. Thermosetting resin compositions may also be those in which a curing agent such as an isocyanate curing agent or an epoxy curing agent has been added to these resins.

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.

When the second protective layer contains a urethane acrylic resin, the urethane acrylic resin is preferably a urethane acrylic copolymer, and 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.

(Di)isocyanates include, for example, 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.

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, and other (meth)acrylic acid alkyl esters.

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 may be 75% by mass or more and 95% by mass or less, or may be 80% by mass or more and 90% by mass or less. By making the mass ratio 70% by mass or more, the proportion of the polycarbonate structure in the polycarbonate-based urethane acrylic copolymer can be increased, and the structure of the polycarbonate-based urethane acrylic copolymer becomes more rigid. Therefore, deformation due to temperature changes can be reduced. Furthermore, by making the mass ratio 95% by mass or less, it becomes easier to ensure the flexibility of the second protective layer, and adhesion to the design layer is improved.

(2) Indentation hardness In this embodiment, the indentation hardness in 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 in 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 in 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 in 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 in the cross section of the second protective layer is the same as the method for measuring the indentation hardness in the cross section of the first protective layer described above.

(3) Weather Resistant The second protective layer usually contains a weather resistant agent. Examples of weather resistant agents include ultraviolet absorbers and light stabilizers. The second protective layer preferably contains at least one of an ultraviolet absorber and a light stabilizer. The preferred types and modes of the weather resistant 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. In addition, the second protective layer preferably contains a hindered amine-based light stabilizer.

The content of the ultraviolet absorber contained 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 10 parts by mass or more and 35 parts by mass or less, relative to 100 parts by mass of the resin component. In addition, the content of the ultraviolet absorber contained 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 contained in the first protective layer (content relative to 100 parts by mass of the resin component).

The content of the light stabilizer contained in the second protective layer is, for example, 0.1 parts by mass or more and 15 parts by mass or less, or may be 1 part by mass or more and 15 parts by mass or less, or may be 3 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the resin component. In addition, the content of the light stabilizer contained 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 contained in the first protective layer (content relative to 100 parts by mass of the resin component).

(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.

(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.

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.

The thickness of the transfer layer is, for example, 8 μm or more, and may be 10 μm or more, 12 μm or more, or 14 μm or more. If the transfer layer is thin, sufficient weather resistance may not be obtained. On the other hand, the thickness of the transfer layer is, for example, 50 μm or less, and may be 40 μm or less, or 30 μm or less.

(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 that contacts the substrate and constitutes the transfer layer in the transfer sheet. 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.

The adhesive layer may be a so-called pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer has adhesiveness at room temperature. Examples of resins 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.

The adhesive layer may be a so-called heat seal layer. The heat seal layer exhibits adhesiveness by heat. Examples of the resin contained in the heat seal layer include thermoplastic resins. Examples of thermoplastic resins 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. 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.

The indentation hardness of the cross section of the adhesive 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 adhesive layer is within the above range, good weather-resistant adhesion can be obtained, for example, between the adhesive layer and the design layer.

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 3 μm or more and 8 μm or less. When the thickness of the adhesive layer is within the above range, it is easier to improve the adhesion between the adhesive layer and the substrate when manufacturing the exterior member.

In this embodiment, the adhesive layer may contain a colorant. By including a colorant in the adhesive layer, 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 below.

(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.

Examples of design layers include a solid layer (a layer coated with ink) and a picture layer (a layer printed with ink). The transfer sheet may have, in order from the release film side, a picture layer and a solid layer as design layers. Examples of pictures (patterns) in the picture layer include wood grain patterns, stone grain patterns, sand grain patterns, tile patterns, brickwork patterns, fabric patterns, leather-stained patterns, geometric shapes, letters, symbols, abstract patterns, and floral patterns.

The design layer usually contains a colorant and a binder resin. Examples of colorants 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.

Examples of binder resins include urethane-based resins, acrylic polyol-based resins, (meth)acrylic resins, ester-based resins, amide-based resins, butyral-based resins, styrene-based resins, urethane acrylic copolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-acrylic copolymers, chlorinated propylene-based resins, nitrocellulose-based resins, and cellulose acetate-based resins. Among these, it is more preferable to use a combination of acrylic polyol-based resins and urethane-based resins.

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, good weather-resistant adhesion can be obtained, for example, between the adhesive layer or the second protective layer.

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

(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 shape and manufactured, 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.

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

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

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 of the cross section of the first protective layer 2 is within a predetermined range.

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 it is as a masking, 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 inventors have found that since the maximum height Rz of the second surface is high within a predetermined range, the adhesion between the first protective layer and the release film is increased, so that 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.

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, high weather resistance can be imparted by, for example, 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).

In addition, because the first protective layer contains a weathering agent, changes in gloss due to deterioration of the resin are suppressed, even when the surface of the transfer layer has a low gloss, as in this embodiment.

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.

(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.

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 device: 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

In addition, in this specification, Rz (maximum height) is the average value of measurements taken at any 10 points.

In this embodiment, the release film has a maximum height Rz of the second surface that is typically 2.0 μm or more, and may be 3.0 μm or more, or 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 less likely to exhibit a low gloss appearance. 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.

In this embodiment, the maximum height Rz of the second surface is a value measured on the second surface of the release film using a method similar to the method for measuring the maximum height Rz of the first surface described above.

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 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 size 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 size 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 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.

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

2. First Protective Layer The first protective layer may be the same as the first protective layer in the first embodiment described above.

3. Second Protective Layer The second protective layer may be similar to the second protective layer in the first embodiment described above.

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

B. Manufacturing method of transfer sheet FIG. 3 is a schematic cross-sectional view illustrating a manufacturing method of 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 weathering 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 weathering 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. This results in a transfer sheet 10 having the release film 1, the first protective layer 2, and the second protective layer 3 in this order in the thickness direction D _T. In FIG. 3, the transfer layer X corresponds to the first protective layer 2 and the second protective layer 3.

The release film 1 shown in FIG. 3 may be the release film in the first embodiment described above, or the release film in the second embodiment described above. In addition, the indentation hardness of the cross section of the first protective layer is within a predetermined range.

According to the present disclosure, for the reasons described above, a transfer sheet for use in the manufacture of exterior components can be obtained, which allows for the transfer of a transfer layer having excellent visibility of the design and low gloss without the need to peel off the release film. Each step will be described in detail below.

1. First Protective Layer Forming Step 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.

Methods for applying the first composition include, for example, gravure printing, bar coating, roll coating, reverse roll coating, and comma coating. By applying the first composition, a first coating layer is obtained. Methods for curing the first coating layer include, for example, a method of irradiating with ionizing radiation such as electron beams or ultraviolet rays, and a method of applying heat.

2. Second Protective Layer Forming Step 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.

Methods for applying the second composition include, for example, gravure printing, bar coating, roll coating, reverse roll coating, and comma coating. By applying the second composition, a second coating layer is obtained. Methods for curing the second coating layer include, for example, applying heat.

3. Other steps 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. The adhesive layer can be formed by applying a composition for forming an adhesive layer by a known method such as gravure printing, bar coating, roll coating, reverse roll coating, or comma coating, and drying and curing as necessary.

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 the first protective layer. An example of a method for forming a design layer is a method of applying an ink containing a colorant, a binder resin, and a solvent to the surface of the second protective layer opposite the first protective layer. In addition, the transfer sheet obtained by each of the above-mentioned steps is the same as that described above in "A. Transfer sheet", so the description here is omitted.

C. Manufacturing method of exterior member FIG. 4 is a schematic cross-sectional view illustrating a manufacturing method of an exterior member in 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) has a release film 1, a first protective layer 2, a second protective layer 3, a design layer 5, and an adhesive layer 4 in this order in the thickness direction _DT . Next, as shown in FIG. 4(b), the surface of the transfer sheet 10 on the second protective layer 3 side is opposed to the substrate 20, and both are brought into close contact. The "surface of the transfer sheet 10 on the second protective layer 3 side" refers to the surface of the transfer sheet 10 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 a design layer 5 and an adhesive layer 4, the "surface of the transfer sheet 10 on the second protective layer 3 side" corresponds to the surface of the adhesive layer 4.

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 results in an exterior member 100 having the first protective layer 2, the second protective layer 3, the design layer 5, the adhesive layer 4, and the base 20 in this order in the thickness direction _DT .

According to the present disclosure, by using the transfer sheet described above, an exterior component with good weather-resistant adhesion can be obtained.

1. Preparation step 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.

2. Adhesion step 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 and the substrate against each other, they may be placed so as to be in direct contact with each other, or may be placed with another layer between them. For example, when the transfer sheet does not have an adhesive layer, an adhesive layer is placed.

The substrate material in this disclosure is not particularly limited, and may be selected appropriately depending on the application from among resin, wood, metal, nonmetallic inorganic material, paper, nonwoven fabric, woven fabric, etc.

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 fiber, glass fiber, aramid fiber, Zylon fiber, boron fiber, and polyethylene fiber. By containing fibers, the strength of the resin member can be improved. Another example of the substrate is a wood member. Examples of wood members include wood veneers, wood plywood, particle board, and wood fiber board. Examples of wood used in the wood members include cedar, cypress, pine, and lauan.

Another example of the substrate is a metal member. Metals used for the metal member include, for example, 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 (lightweight aerated concrete). Calcium silicate board may also be used as the ceramic member.

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.

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.

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.

In the adhesion step, the surface of the transfer sheet on the second protective layer side is placed opposite the substrate, and the two are brought into close contact with each other. For example, lamination is one method for bringing the two into close contact with each other. In lamination, the laminate of the transfer sheet and the substrate is heated and pressurized from the transfer sheet side. For example, a method using a roll transfer device is used. 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 soften 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.

The manufacturing method of the exterior member according to the present disclosure may also include a peeling step of peeling the release film from the first protective layer after the adhesion step.

The exterior member in the present disclosure has a first protective layer, a second protective layer, and a base 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.

In the exterior member after the release film is peeled off, the 60° gloss value of the surface of the first protective layer opposite to 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.

The exterior member in this disclosure is, for example, a building material (an exterior member of an architectural structure). Building materials are used, for example, in houses, offices, stores, hospitals, clinics, general roads and highways, agricultural greenhouses, etc. Examples of uses of the exterior member include exterior walls, roofs, eaves ceilings, door pockets, window frames, doors, door frames, handrails, fences, drying racks, partitions, etc. Specific uses of the exterior member include soundproof walls or windbreaks on general roads and highways, balcony partitions, fences, roofing members for terraces or carports, transparent members that constitute agricultural greenhouses, etc.

In addition to building materials (exterior members of architectural structures), the exterior members of the present disclosure are used, for example, as exterior members of vehicles, ships, and aircraft, exterior members of industrial machinery, and exterior members of various lenses. 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. Examples of vehicles include, for example, automobiles, railroad cars, construction machinery, and light vehicles such as golf carts. Exterior materials of industrial machinery include, for example, window materials for visibility in machine tools. Examples of lenses include, for example, traffic light lenses.

D. Exterior Member with Release Film The exterior member with release film in the present disclosure has two embodiments. Each embodiment will be described below separately.

I. Exterior member with release film of first embodiment Fig. 5 (a) is a schematic cross-sectional view illustrating an exterior member with release film in this embodiment. The exterior member with release film 50 in this embodiment has a release film 1, a first protective layer 2, a second protective layer 3, and a base 20 in this order in the thickness direction _DT .

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

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

In this 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.

In the present embodiment, the release film-attached exterior member can use the release film as a masking film. 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 makes it possible to impart high weather resistance while maintaining the characteristics required for the first protective layer (e.g., surface characteristics such as scratch resistance and abrasion resistance) and the characteristics required for the second protective layer (e.g., adhesion). Furthermore, since the first protective layer contains a weathering agent, even when the surface of the first protective layer has a low gloss as in the present disclosure, gloss changes due to deterioration of the resin are suppressed.

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 for exterior member", so the description here is omitted.

II. Exterior member with release film of second embodiment Fig. 5 (a) is a schematic cross-sectional view illustrating an exterior member with release film in this embodiment. The exterior member with release film 50 in this embodiment has a release film 1, a first protective layer 2, a second protective layer 3, and a base 20 in this order in the thickness direction _DT .

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

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

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 of the cross section of the first protective layer 2 is within a predetermined range.

In the present embodiment, the release film-attached exterior member can use the release film as a masking material. 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 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 embodiment, 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 characteristics required for the first protective layer (e.g., surface characteristics such as scratch resistance and abrasion resistance) and the characteristics required for the second protective layer (e.g., 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 embodiment, the change in gloss due to deterioration of the resin is suppressed.

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 for exterior member", so the description here is omitted.

E. Exterior member In the present disclosure, an exterior member after peeling off the release film can be provided. FIG. 6 is a schematic cross-sectional view showing an example of an exterior member after peeling off the release film. The exterior member 100 has a first protective layer 2, a second protective layer 3, and a base 20 in this order in the thickness direction D _T , the first protective layer 2 contains a cured product of the first curable resin composition and a weathering agent, the second protective layer 3 contains a cured product of the second curable resin composition and a weathering agent, and the indentation hardness in 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 the base 20 and the transfer layer X bonded via the 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.

After the release film is peeled off, the exterior member 100 has a 60° gloss value of the surface S3 of the first protective layer 2 opposite the second protective layer 3, which may be, for example, 30 or less, or 20 or less. On the other hand, it may be, for example, 0.1 or more, or 1.0 or more. Furthermore, after the release film is peeled off, the exterior member has a maximum height Rz of the surface S3 of the first protective layer 2 opposite the second protective layer 3, which may be, for example, 1.5 μm or more, or 2.0 μm or more. On the other hand, it may be, for example, 6.0 μm or less, or 5.0 μm or less.

This 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 ideas described in the claims of this disclosure and provides similar effects is included within the technical scope of this disclosure.

[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.) so that the coating amount after drying was 3 g/ ^m2 , and the mixture was aged in an oven at 40° C. for 5 days. As a result, a release film 1 having a film layer and a first matte layer was obtained.
<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

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 so that the coating amount after drying was 5 g/ ^m2 , and then dried. Thereafter, the composition 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 ultraviolet absorber: 2 parts by mass (hydroxyphenyltriazine-based ultraviolet absorber (product name: TINUVIN 479, BASF))
Light stabilizer having a reactive functional group: 2 parts by mass (product name: Sanol LS-3410, Nippon Nyukazai Co., Ltd.)
・Solvent: appropriate amount

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-based ultraviolet absorber: 17 parts by weight (product name: TINUVIN 400, BASF Corporation)
Hydroxyphenyltriazine-based ultraviolet absorber: 13 parts by mass (product name: TINUVIN 479, BASF)
Hindered amine light stabilizer: 8 parts by mass (product name: TINUVIN 123, BASF)
Antiblocking agent: 9 parts by weight (silica particles, average particle size 3 μm)
Hardener: 25 parts by mass (hexamethylene diisocyanate)
・Solvent: appropriate amount

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>
Ink resin component: Mixture of urethane resin and polyacrylic polyol (mass ratio 20:80)
・Pigments (including organic and inorganic pigments)

Adhesive composition 1, which contains an acrylic resin and a vinyl chloride-vinyl acetate copolymer in a ratio of 6:4 (mass ratio), was applied by gravure coating to the surface of the obtained design layer, and then 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.

[Example 2]
(Preparation of Release Film 2)
A resin composition containing an acrylic resin and a urethane resin as a binder resin was applied to one side of a PET film having a thickness of 100 μm and dried to form an easy-adhesion layer (thickness: 2 μm). The following composition 2 for forming a matte layer was applied to the easy-adhesion layer by a gravure method (amount applied: 5 g/m ² (when dried)), and then ultraviolet light was irradiated using a UV irradiation device composed of LEDs (wavelength: 395 nm, ultraviolet light amount: 0.6 W/cm ² ), and then ultraviolet light was irradiated using an excimer light irradiation device (wavelength: 172 nm (Xe ₂ ), ultraviolet light output density: 1 W/cm 2 , accumulated light amount: 10 to 100 mJ/cm ² , nitrogen atmosphere (oxygen concentration 200 ppm or less)), and then ultraviolet light was irradiated using a high-pressure mercury lamp (wavelength: 365 nm, ultraviolet light output density: 200 W/cm 2 ) to form a second matte layer. Through the above steps, a release film 2 having an easy-adhesion layer and a second matte layer on a support was obtained.

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

Next, the composition 1 for forming the first protective layer was applied to the second surface (matte layer surface) of the release film 2 so that the coating amount after drying was 5 g/ ^m2 , and then dried. Thereafter, the composition 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.

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.

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.

The adhesive composition 1 was applied to the surface of the obtained design layer by gravure coating 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 this order in the thickness direction.

[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.) so that the coating amount after drying was 3 g/ ^m2 , and the coating was aged in an oven at 40° C. for 5 days. As a result, a release film 3 having a film layer and a first matte layer was obtained.
<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

Next, the composition 1 for forming the first protective layer was applied to the second surface (matte layer surface) of the release film 3 so that the coating amount after drying was 5 g/ ^m2 , and then dried. Thereafter, the composition 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.

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.

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>
- A mixed resin of acrylic resin and vinyl chloride-vinyl acetate copolymer (mass ratio 8:2)
・Pigments (including organic and inorganic pigments)

The adhesive composition 1 was applied to the surface of the obtained design layer by gravure coating 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 this order in the thickness direction.

[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.) so that the coating amount after drying was 3 g/ ^m2 , and the mixture was aged in an oven at 40° C. for 5 days. As a result, a release film 4 having a film layer and a first matte layer was obtained.
<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

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 so that the coating amount after drying was 5 g/ ^m2 , and then dried. Thereafter, the composition 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 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 mass)
Hydroxyphenyltriazine ultraviolet absorber: 2 parts by mass (product name: TINUVIN 479, 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

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

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

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)

The adhesive composition 1 was applied to the surface of the obtained design layer by gravure coating 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 this order in the thickness direction.

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

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/ ^m2 , and then dried. Thereafter, the composition 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.

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.

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.

The adhesive composition 1 was applied to the surface of the obtained design layer by gravure coating 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 this order in the thickness direction.

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

Next, the composition 1 for forming the first protective layer was applied to one surface of a release film 6 so that the coating amount after drying was 5 g/ ^m2 , and then dried. Thereafter, the composition 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.

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.

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.

The adhesive composition 1 was applied to the surface of the obtained design layer by gravure coating 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 this order in the thickness direction.

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

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/ ^m2 , and then dried. Thereafter, the composition 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.

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.

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.

The adhesive composition 1 was applied to the surface of the obtained design layer by gravure coating 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 this order in the thickness direction.

[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 so that the coating amount after drying was 5 g/ ^m2 , and then dried. Thereafter, the film 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 3 for forming first protective layer>
Ionizing radiation curable resin composition: 100 parts by mass (caprolactone-based urethane acrylate: 100 parts by mass)
Hydroxyphenyltriazine ultraviolet absorber: 2 parts by mass (product name: TINUVIN 479, BASF)
Light stabilizer having a reactive functional group: 2 parts by weight (product name: Sanol LS-3410, Nippon Nyukazai Co., Ltd.)

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.

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.

The adhesive composition 1 was applied to the surface of the obtained design layer by gravure coating 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 this order in the thickness direction.

[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.

[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 device: 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

[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 the 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.

[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.

[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 that they could see, and the average of the answers of the 20 people was calculated and evaluated according to the following evaluation criteria.
A: When viewed from the release film side, 70% or more 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, only 30% or less of the pattern can be seen.

[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 was peeled off by hand, the PET film was not broken and could be peeled off.
B: When the release film was peeled off by hand, partial breakage was confirmed in the PET film, or the film could not be peeled off.

[60° gloss value and maximum height Rz after release film peeling]
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.

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

[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.

The obtained evaluation components were subjected to the following accelerated weathering test using a metal halide lamp (MWOM) for 700 hours (a test in which one cycle is irradiated with ultraviolet light for 20 hours under the irradiation conditions below, followed by condensation for 4 hours under the condensation conditions below, and the cycle is repeated). After that, the weathering adhesion was evaluated as follows. The evaluation results are shown in Table 1.

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

Adhesive tape (Cellotape (registered trademark), manufactured by Nichiban Co., Ltd.) was applied to the evaluation member on which the accelerated weathering 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 peeled off at a 45° angle 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 weathering test.

<Evaluation criteria>
A: No peeling occurred between the transfer layers.
B: Peeling occurred between the layers of the transfer layer.

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, after being attached to a substrate and the release film was peeled off, it was confirmed that the surface of the transfer layer had a low gloss feel. 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 feel 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 pattern visibility was poor in Comparative Examples 2 and 3, which used PET films kneaded with a matte agent. In Comparative Example 4, the indentation hardness of the first protective layer was low, and it was difficult to peel off the release film.

Thus, the present disclosure provides, for example, the following inventions:

[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 [2], wherein the 60° gloss value of the second surface is 40 or less.

[4]
The transfer sheet described in any one of [1] to [3], 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 any one of [1] to [4], wherein the 60° gloss value of the second surface is 3.0 or more.

[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.

[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.

[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.

[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.

[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.

[11]
The transfer sheet according to any one of [1] to [10], wherein the second curable resin composition is a thermosetting resin composition.

[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.

[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:

[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:

[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 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.

[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.

[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.

[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 a surface of the first protective layer opposite to the second protective layer is 1.5 μm or more.

Reference Signs List 1: Release film S1: First surface S2: Second surface 2: First protective layer 3: Second protective layer 4: Adhesive layer 5: Design layer 10: Transfer sheet 20: Base 50: Exterior member with film 100: Exterior member

Claims (16)

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. 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. 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. The transfer sheet according to claim 1 or 2, wherein the release film has a film layer including the first surface, and a matte layer disposed on the surface of the film layer facing the transfer layer and including the second surface. 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. 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. 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. 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. The transfer sheet according to claim 1 or 2, wherein the first curable resin composition is an ionizing radiation curable resin composition. The transfer sheet according to claim 1 or 2, wherein the first curable resin composition is an electron beam curable resin composition. The transfer sheet according to claim 1 or 2, wherein the second curable resin composition is a thermosetting resin composition. 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. 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: 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 producing an exterior member comprising the steps of: 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. 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.