Transfer sheet, method for manufacturing exterior member, and exterior member

Abstract

To provide a transfer sheet including a protective layer having three-dimensional processing property and scratch resistance in good balance.SOLUTION: A transfer sheet 10 used in manufacturing an exterior member including a substrate includes a release film 1 and a transfer layer placed on one surface of the release film. The transfer sheet is characterized by that the transfer layer includes, from the side of the release film, a first protective layer 2 and a second protective layer 3 in this order in a thickness direction; and in a case where a laminate is prepared by transferring the transfer layer in the transfer sheet to a substrate for evaluation via an adhesive layer, followed by peeling the release film, Erichsen indentation depth of the laminate is 7 mm or over and 11 mm or under.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This disclosure relates to a transfer sheet, a method for manufacturing an exterior component, and an exterior component. [Background technology]

[0002] It is known that a substrate, such as a metal member or a resin member, can be decorated by transferring a transfer layer (a layer transferred from a transfer sheet) onto the substrate. For example, Patent Document 1 discloses a rain gutter in which an oxide film layer is disposed on the outer surface of an aluminum substrate, a decorative layer is disposed on the outer surface of the oxide film layer, and a pattern is applied to the surface of the decorative layer. Specifically, Patent Document 1 discloses forming a decorative layer on the outer surface of an anodized aluminum substrate by hydrographic transfer. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-12283 [Overview of the project] [Problems that the invention aims to solve]

[0004] When transferring a transfer layer with a protective layer onto a substrate, cracks may occur in the protective layer, for example, if the protective layer cannot conform to the shape of the substrate. Furthermore, since exterior components (components for outdoor use) are exposed to harsh environments, cracks in the protective layer lead to a significant decrease in weather resistance and stain resistance. Therefore, a transfer sheet with a protective layer that has good three-dimensional processability is desired. On the other hand, if we focus solely on improving the three-dimensional processability of the protective layer, increasing the flexibility of the protective layer is effective, but increasing the flexibility of the protective layer may reduce its scratch resistance.

[0005] This disclosure is made in view of the above circumstances, and its main purpose is to provide a transfer sheet having a protective layer that achieves both three-dimensional processability and scratch resistance. [Means for solving the problem]

[0006] This disclosure provides a transfer sheet used in the manufacture of an exterior component having a substrate, wherein the transfer sheet comprises 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, and when the transfer layer of the transfer sheet is transferred to an evaluation substrate via an adhesive layer, the release film is peeled off, and a laminate is produced, the Erichsen indentation depth of the laminate is 7 mm or more and 11 mm or less.

[0007] Furthermore, this disclosure provides a method for manufacturing an exterior member having a substrate, comprising: a preparation step of preparing the above-mentioned transfer sheet; and an adhesion step of arranging the surface of the transfer sheet on the second protective layer side and the substrate facing each other, and bringing the transfer sheet and the substrate into close contact.

[0008] Furthermore, this disclosure provides an exterior component having a first protective layer, a second protective layer, an adhesive layer, and a substrate in this order in the thickness direction, and having an Erichsen indentation depth of 7 mm or more and 11 mm or less. [Effects of the Invention]

[0009] This disclosure offers the advantage of providing a transfer sheet having a protective layer that achieves both three-dimensional processability and scratch resistance. [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic cross-sectional view illustrating a transfer sheet in this disclosure. [Figure 2] This is a schematic cross-sectional view illustrating the method for forming the laminate in this disclosure. [Figure 3] This is a schematic cross-sectional view illustrating a method for manufacturing exterior components in this disclosure. [Modes for carrying out the invention]

[0011] The embodiments will be described below with reference to the drawings and other figures. However, this disclosure can be implemented in many different ways and should not be limited to the embodiments described below. In addition, the drawings may schematically represent the width, thickness, and shape of each part compared to the actual form in order to make the explanation clearer, but this is merely an example and should not be interpreted as limiting.

[0012] In this specification, when describing a manner in which one member is placed on another member, the term "above" or "below" includes, unless otherwise specified, both cases: when the other member is placed directly above or directly below the member so as to be in contact with it, and when the other member is placed above or below the member via yet another member. Similarly, in this specification, when describing a manner in which one member is placed on the surface of a member, the term "on the surface" includes, unless otherwise specified, both cases: when the other member is placed directly above or directly below the member so as to be in contact with it, and when the other member is placed above or below the member via yet another member.

[0013] The following describes in detail the manufacturing method of the transfer sheet and exterior component, and the exterior component as described in this disclosure.

[0014] A. Transfer sheet Figure 1(a) is a schematic cross-sectional view illustrating a transfer sheet in this disclosure. As shown in Figure 1(a), the transfer sheet 10 has a release film 1 and a transfer layer X disposed on one side of the release film 1. The transfer layer X has a first protective layer 2 and a second protective layer 3 from the release film 1 side, in the thickness direction D T In this order, they are present. Also, as shown in Figure 1(b), the transfer sheet 10 may have a design layer 4 on the side of the second protective layer 3 opposite to the first protective layer 2.

[0015] Further, as shown in Fig. 2(a), the transfer layer X on the transfer sheet 10 is transferred onto the evaluation substrate 22 via the adhesive layer 21, and the release film 1 is peeled off. As a result, as shown in Fig. 2(b), a laminate L having the transfer layer X, the adhesive layer 21, and the evaluation substrate 22 in this order in the thickness direction D T is obtained. In the present disclosure, the Erichsen indentation depth of the laminate L is within a predetermined range.

[0016] According to the present disclosure, since the Erichsen indentation depth of the laminate produced under predetermined conditions is within a predetermined range, a transfer sheet having a protective layer that achieves both three-dimensional processability and scratch resistance is obtained. As described above, when transferring a transfer layer having a protective layer onto a substrate, for example, cracks may occur in the protective layer because the protective layer cannot follow the shape of the substrate. In particular, when the substrate has a three-dimensional shape, the possibility of cracks occurring in the protective layer increases. In addition, since the exterior member (outdoor member) is exposed to a harsh environment, if cracks occur in the protective layer, the weather resistance and stain resistance will be significantly reduced. Regarding weather resistance, when the protective layer cracks, the underlying layer is exposed, and sufficient weather resistance cannot be maintained. Regarding stain resistance, when the protective layer cracks, contaminants penetrate into the transfer layer, and sufficient stain resistance cannot be maintained. In addition, when the protective layer cracks, that part may turn white and the design property may deteriorate. Therefore, a transfer sheet provided with a protective layer having good three-dimensional processability is desired. On the other hand, if only attention is paid to improving the three-dimensional processability of the protective layer, it is effective to increase the flexibility of the protective layer, but when the flexibility of the protective layer is increased, the scratch resistance of the protective layer may decrease. In the present disclosure, by adjusting the Erichsen indentation depth of the laminate produced under predetermined conditions to be within a predetermined range, a transfer sheet having a protective layer that achieves both three-dimensional processability and scratch resistance is obtained.

[0017] Also, for example, assume a case where the substrate is a metal member and a decorative sheet is attached to the metal member. In this case, since the metal (inorganic material) contained in the metal member and the resin (organic material) contained in the decorative sheet are dissimilar materials, it is difficult to separate the decorative member formed by bonding these materials during recycling. When a transfer sheet is used instead of the decorative sheet, the resin content contained in the sheet can be reduced. By reducing the resin content contained in the sheet, recycling becomes possible without separating the metal and the resin, thus reducing the environmental load. That is, when the substrate is a metal member, it becomes a transfer sheet capable of obtaining an exterior member with a low environmental load.

[0018] In addition, exterior members (members for outdoor use) are required to have higher weather resistance than interior members (members for indoor use). 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, for example, by adding a sufficient amount of a weathering agent to the transparent resin layer. On the other hand, it is highly technically difficult to impart high weather resistance to a transfer sheet that does not have a layer corresponding to the transparent resin layer. In the present disclosure, it is preferable that both the first protective layer and the second protective layer contain a weathering agent. Thereby, high weather resistance can be imparted while maintaining the characteristics required for the first protective layer (such as surface characteristics such as scratch resistance) and the characteristics required for the second protective layer (such as adhesion).

[0019] Furthermore, in the case of transfer sheets, the adhesion between the first and second protective layers tends to be insufficient. In the case of decorative sheets, a design layer is usually formed on a base layer, then a second protective layer is formed on the design layer, and then a first protective layer is formed on the second protective layer. The first protective layer is typically produced by curing a composition for forming the first protective layer that is formed on the second protective layer, so the adhesion between the first and second protective layers is good. In contrast, in the case of transfer sheets, a first protective layer is usually formed on a release film, then a second protective layer is formed on the first protective layer, and then a design layer is formed on the second protective layer. The first protective layer is typically produced by curing a composition for forming the first protective layer on a release film. Since the second protective layer is formed on the cured first protective layer, the adhesion between the first and second protective layers tends to be insufficient. In this disclosure, it is preferable that the second protective layer is a layer with higher flexibility than the first protective layer. This makes it possible to improve the adhesion between the first and second protective layers.

[0020] In this disclosure, when a transfer layer from a transfer sheet is transferred to an evaluation substrate via an adhesive layer, and a release film is peeled off to produce a laminate, the Erichsen indentation depth of the laminate is within a predetermined range. The material and shape of the evaluation substrate do not fundamentally affect the Erichsen indentation depth, so any evaluation substrate can be used. The evaluation substrate is, for example, a metal member. The evaluation substrate may also be an aluminum member. On the other hand, the shape of the evaluation substrate is not particularly limited, but it usually has a flat surface. In this disclosure, the Erichsen indentation depth of the transfer layer transferred to the flat surface of the evaluation substrate is usually within a predetermined range. Furthermore, by bringing the transfer layer and the evaluation substrate into close contact via an adhesive layer, they adhere firmly to each other, and the Erichsen indentation depth can be determined with high accuracy. The conditions for producing the laminate and the method for measuring the Erichsen indentation depth will be described in detail in the examples described later.

[0021] The Erichsen indentation depth of the laminate is typically 7 mm or more, and may be 8 mm or more. If the Erichsen indentation depth is too small, sufficient three-dimensional machinability may not be achieved. On the other hand, the Erichsen indentation depth of the laminate is typically 11 mm or less, and may be 10 mm or less. If the Erichsen indentation depth is too large, sufficient scratch resistance may not be achieved.

[0022] The Erichsen indentation depth of the laminate can be controlled, for example, by adjusting the type of resin (e.g., a curable compound) used to produce the first protective layer. For example, if the number of functional groups (curable functional groups) in the resin is large, a first protective layer with low three-dimensional processability is likely to be obtained. Therefore, it is preferable that the resin composition used to produce the first protective layer contains a bifunctional or trifunctional resin as the main component by mass. Furthermore, if the ratio of the polymerized average molecular weight to the number of functional groups (polymerized average molecular weight / number of functional groups) is small, a first protective layer with low three-dimensional processability is likely to be obtained, and if the above ratio (polymerized average molecular weight / number of functional groups) is large, a first protective layer with low scratch resistance is likely to be obtained. Therefore, in the resin composition used to produce the first protective layer, the above ratio of the main component resin by mass (polymerized average molecular weight / number of functional groups) is preferably, for example, 200 to 3000, and more preferably 300 to 1500.

[0023] The transfer sheet in this disclosure comprises 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 the first protective layer and the second protective layer, or it may further have other layers. Examples of other layers include a design layer. Preferably, the transfer layer has a design layer on the side of the second protective layer opposite to the first protective layer.

[0024] The thickness of the transfer layer is, for example, 8 μm or more, but may be 10 μm or more, 12 μm or more, or 14 μm or more. If the transfer layer is too 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, but may be 40 μm or less, or 30 μm or less. If the transfer layer is too thick, it becomes necessary to separate the metal and resin during recycling.

[0025] 1.1st protective layer The transfer sheet in this disclosure has a first protective layer. The first protective layer contributes to improving the surface properties (e.g., scratch resistance) of the exterior component. The first protective layer and the release film may be arranged in direct contact or with other layers in between.

[0026] The first protective layer preferably contains a cured product (crosslinked structure) of a curable resin composition as a resin component. The proportion of the cured product of the curable resin composition is, for example, 70% by mass or more, may be 90% by mass or more, 95% by mass or more, or 100% by mass, relative to the total resin components constituting the first protective layer.

[0027] Examples of cured products of curable resin compositions include cured products of ionizing radiation-curable resin compositions. Examples of ionizing radiation-curable resin compositions include electron beam-curable resin compositions and ultraviolet-curable resin compositions. Among these, electron beam-curable resin compositions are preferred because they do not require polymerization initiators, have less odor, and are less prone to discoloration.

[0028] An 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"). An ionizing radiation-curable functional group is a group that crosslinks and hardens upon irradiation with ionizing radiation, and examples include functional groups having an ethylenically double bond, such as a (meth)acryloyl group, a vinyl group, or an allyl group. In this disclosure, a (meth)acryloyl group means an acryloyl group or a metacloyl group. In this disclosure, a (meth)acrylate means an acrylate or a methacrylate.

[0029] Ionizing radiation refers to electromagnetic waves or charged particle beams that have energy quanta 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 γ-rays, and charged particle beams such as α-rays and ion beams.

[0030] The ionizing radiation curable compound preferably contains at least one selected from urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polycarbonate (meth)acrylate, and acrylic (meth)acrylate. Among them, the ionizing radiation curable compound preferably contains at least urethane (meth)acrylate. The urethane (meth)acrylate is preferably caprolactone-based urethane acrylate.

[0031] When the ionizing radiation curable compound contains 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.

[0032] Also, the ionizing radiation curable compound may contain caprolactone-based urethane acrylate and urethane (meth)acrylate that is not caprolactone-modified. In this case, the content of caprolactone-based urethane acrylate contained in the first protective layer is M CLUA and the content of urethane (meth)acrylate that is not caprolactone-modified is M UA Let it be. M UA And M CLUA The mass ratio of M CLUA to the total of M CLUA / (M UA +M CLUA )) is, for example, 40% by mass or more and 90% by mass or less, and may be 45% by mass or more and 80% by mass or less, or may be 50% by mass or more and 70% by mass or less.

[0033] Caprolactone-based urethane acrylates can usually be obtained by reacting a caprolactone-based polyol with an organic isocyanate and a hydroxy(meth)acrylate. One example of a synthesis method is to react a polycaprolactone-based polyol with an organic polyisocyanate to produce a polyurethane prepolymer containing -NCO groups (isocyanate groups) at both ends, and then react it with a hydroxy(meth)acrylate.

[0034] As the caprolactone-based polyol, commercially available polyols 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, and 1,6-hexanediol, can be used in any proportion by mixing one or more types. As the organic polyisocyanate, diisocyanates having two isocyanate groups are preferred, and from the viewpoint of suppressing yellowing, isophorone diisocyanate, hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, trimethylhexamethylene diisocyanate, etc. are preferred. As the hydroxy(meth)acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, caprolactone-modified 2-hydroxyethyl acrylate, etc. are preferred.

[0035] When an ionizing radiation-curable resin composition contains a caprolactone-based polyol, the caprolactone-based urethane acrylate is preferably a caprolactone diol-based urethane acrylate. A caprolactone diol-based urethane acrylate refers to a urethane acrylate among caprolactone-based urethane acrylates in which the terminal end is diethylene glycol. By using a caprolactone diol-based urethane acrylate, cracking and whitening of the first protective layer can be suppressed.

[0036] The number-average molecular weight of the ionizing radiation-curable compound is, for example, between 300 and 10,000, may be between 1,000 and 10,000, or between 2,000 and 10,000. The number-average molecular weight is measured by GPC analysis and converted to the average molecular weight in terms of standard polystyrene.

[0037] For example, if the ionizing radiation-curable compound is an ultraviolet-curable compound, it is preferable that the ionizing radiation-curable compound contains at least one of a photopolymerization initiator and a photopolymerization accelerator. Examples of photopolymerization initiators include acetophenone, benzophenone, α-hydroxyalkylphenone, Michler ketone, benzoin, benzyldimethyl ketal, benzoyl benzoate, α-acyloxime ester, acylphosphine oxide, and thioxanthones. Examples of photopolymerization accelerators include isoamyl p-dimethylaminobenzoate and ethyl p-dimethylaminobenzoate.

[0038] The first protective layer preferably contains a weather-resistant agent. Examples of weather-resistant agents include ultraviolet absorbers and light stabilizers. The first protective layer preferably contains at least one of the ultraviolet absorbers and light stabilizers. The first protective layer may contain one or more ultraviolet absorbers. Similarly, the first protective layer may contain one or more light stabilizers.

[0039] Examples of UV absorbers included in the first protective layer include organic UV absorbers such as triazine-based UV absorbers, benzotriazole-based UV absorbers, benzophenone-based UV absorbers, oxybenzophenone-based UV absorbers, salicylic acid ester-based UV absorbers, and cyano(meth)acrylate-based UV absorbers, as well as inorganic UV absorbers such as titanium dioxide, cerium oxide, and zinc oxide. Among these, triazine-based UV absorbers are more preferred.

[0040] Examples of triazine-based UV absorbers include hydroxyphenyltriazine-based UV absorbers. Examples of hydroxyphenyltriazine-based UV 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, and 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine. Examples include 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-triazine-2-yl)-5[2-(2-ethylhexanoyloxy)ethoxy]phenol.

[0041] The amount of ultraviolet absorber contained in the first protective layer is, for example, 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the ionizing radiation-curable compound, and may be 0.8 parts by mass or more and 8 parts by mass or 1 part by mass or more and 5 parts by mass. If the amount of ultraviolet absorber is too high, bleed-out of the ultraviolet absorber may occur, and if the amount of ultraviolet absorber is too low, sufficient ultraviolet absorption performance may not be obtained.

[0042] Examples of light stabilizers included in the first protective layer include hindered amine light stabilizers. Examples of hindered amine light stabilizers 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-tetramethylpiperidine-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine).

[0043] The amount of light stabilizer contained in the first protective layer is, for example, 1 to 10 parts by mass per 100 parts by mass of the ionizing radiation-curable compound, and may be 1.5 to 8 parts by mass, or 2 to 5 parts by mass. If the amount of light stabilizer is too high, bleed-out of the light stabilizer may occur, and if the amount of light stabilizer is too low, sufficient photostability may not be obtained.

[0044] The first protective layer may contain additives such as silicone compounds, polymerization inhibitors, crosslinking agents, antistatic agents, adhesion enhancers, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, antifouling agents, defoaming agents, and fillers. The thickness of the first protective layer may be, for example, 2 μm to 20 μm, 3 μm to 15 μm, or 4 μm to 10 μm. If the first protective layer is too thin, sufficient weather resistance may not be obtained, and if the first protective layer is too thick, cracks may easily form in the first protective layer, potentially resulting in poor adhesion.

[0045] 2.Second protective layer The transfer sheet in this disclosure has a second protective layer. The second protective layer is typically more flexible than the first protective layer. The second protective layer and the first protective layer may be in direct contact with each other, or they may be arranged with other layers in between.

[0046] The second protective layer contains a resin. Examples of the resin include (meth)acrylic resins, urethane resins, butyral resins, polyolefins, chlorinated polyolefins, vinyl chloride-vinyl acetate copolymers, and polyesters. Among these, urethane resins are preferred. The second protective layer preferably contains a cured product (crosslinked structure) of the above resin.

[0047] The second protective layer preferably contains a cured product of a curable resin composition (particularly a cured product of a thermosetting resin composition). The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a composition that hardens upon 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. The thermosetting resin composition may also be obtained by adding a curing agent such as an isocyanate curing agent or an epoxy curing agent to these resins.

[0048] 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. Furthermore, the thermosetting resin composition preferably contains an isocyanate-based curing agent or an epoxy-based curing agent to make the structure of the cured product more rigid, and more preferably contains an isocyanate-based curing agent.

[0049] Furthermore, if 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 radical polymerization of an acrylic monomer to a polycarbonate-based polyurethane polymer obtained by reacting a polycarbonate diol with a (di)isocyanate.

[0050] Examples of (di)isocyanates include aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4-tole 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.

[0051] Examples of acrylic monomers include alkyl esters of (meth)acrylate such as (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate.

[0052] In a polycarbonate-based urethane-acrylic copolymer, the mass ratio of the urethane component to the total of the acrylic and urethane components ([urethane component] / ([acrylic component]+[urethane component]) is, for example, 70% by mass or more and 95% by mass or less, and may also be 75% by mass or more and 95% by mass or less, or 80% by mass or more and 90% by mass or less. By setting the above mass ratio to 70% by mass or more, the proportion of the polycarbonate structure in the polycarbonate-based urethane-acrylic copolymer can be increased, making the structure of the polycarbonate-based urethane-acrylic copolymer more rigid. Therefore, deformation due to temperature changes can be reduced. In addition, by setting the above mass ratio to 95% by mass or less, it becomes easier to ensure the flexibility of the second protective layer and the adhesion with the design layer is improved.

[0053] The second protective layer preferably 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 forms of weather-resistant agents are the same as those described in "1. First Protective Layer" above, so they are omitted here. In particular, the second protective layer preferably contains a triazine-based ultraviolet absorber. Furthermore, the second protective layer preferably contains a hindered amine-based light stabilizer.

[0054] The amount of 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 per 100 parts by mass of resin component, and may be 3 parts by mass or more and 40 parts by mass or 10 parts by mass or more and 35 parts by mass or less. Furthermore, the amount of ultraviolet absorber contained in the second protective layer (per 100 parts by mass of resin component) may be greater than the amount of ultraviolet absorber contained in the first protective layer (per 100 parts by mass of resin component).

[0055] The amount of 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 per 100 parts by mass of resin component, and may be 1 part by mass or more and 15 parts by mass or 3 parts by mass or more and 10 parts by mass. Furthermore, the amount of light stabilizer contained in the second protective layer (amount per 100 parts by mass of resin component) may be greater than the amount of light stabilizer contained in the first protective layer (amount per 100 parts by mass of resin component).

[0056] The second protective layer may contain additives such as silicone compounds, polymerization inhibitors, crosslinking agents, antistatic agents, adhesion enhancers, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, antifouling agents, defoaming agents, and fillers. The thickness of the second protective layer may be, for example, 2 μm to 10 μm, 3 μm to 8 μm, or 3 μm to 5 μm. If the second protective layer is thin, the adhesion (especially the initial adhesion) to the relatively hard first protective layer may be low. On the other hand, if the second protective layer is thick, the movement of the second protective layer due to heat will be greater, making it easier for cracks to form in the first protective layer.

[0057] 3. Design layer The transfer sheet in this disclosure may or may not have a design layer on the side of the second protective layer opposite to the first protective layer. Providing a design layer improves the aesthetic appearance of the exterior component. The design layer and the second protective layer may be arranged in direct contact or arranged via other layers.

[0058] Examples of design layers include a solid color layer (a layer with solid ink coverage) and a pattern layer (a layer with printed ink). A transfer sheet may have a pattern layer and a solid color layer as design layers, in that order from the release film side. Examples of patterns (designs) in the pattern layer include wood grain, stone pattern, sand pattern, tile pattern, brick pattern, fabric pattern, leather pattern, geometric figures, letters, symbols, abstract patterns, and floral patterns.

[0059] The design layer typically contains a coloring agent and a binder resin. Examples of coloring agents include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, lead yellow, titanium yellow, reddish-brown, cadmium red, ultramarine, and cobalt blue; organic pigments (including dyes) such as quinacridone red, isoindolinone yellow, nickel azo complex, phthalocyanine blue, and azomethine azoblack; metallic pigments such as aluminum and brass; and pearl pigments such as titanium dioxide-coated mica and basic lead carbonate.

[0060] Examples of binder resins include urethane resins, acrylic polyol resins, (meth)acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-acrylic copolymers, chlorinated propylene resins, nitrocellulose resins, and cellulose acetate resins.

[0061] The design layer may contain additives such as ultraviolet absorbers, light stabilizers, curing agents, plasticizers, and catalysts, as needed. The thickness of the design layer may be, for example, 0.5 μm to 20 μm, 1 μm to 10 μm, or 2 μm to 5 μm.

[0062] 4. Release film The transfer sheet in this disclosure has a release film (first release film) on the side of the first protective layer opposite to the second protective layer. The release film and the first protective layer may be in direct contact or may be arranged with other layers in between.

[0063] The release film is preferably a resin film. Examples of resins included in the resin film include ester resins, olefin resins, styrene resins, vinyl resins, (meth)acrylic resins, amide resins, imide resins, and carbonate resins.

[0064] The release film preferably contains an ester resin or an olefin resin. Examples of ester resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polyethylene terephthalate-isophthalate copolymer. Among these, PET or PBT are preferred, and PET is more preferred, from the viewpoint of being less susceptible to thermal shrinkage during the manufacture of the transfer sheet and shrinkage due to irradiation with ionizing radiation.

[0065] Examples of olefin resins include polyethylene, polypropylene, polybutene, ethylene-propylene copolymer, and ethylene-propylene-butene copolymer. Among these, polypropylene is preferred from the viewpoint of being less susceptible to thermal shrinkage during the manufacture of the transfer sheet and shrinkage due to irradiation with ionizing radiation.

[0066] The release film may be a stretched film or an unstretched film. The stretching ratio in the mechanical direction (MD) of the stretched film is, for example, 5 times or more and 30 times or less. The stretching 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 release film is, for example, 10 μm or more and 200 μm or less, may be 15 μm or more and 150 μm or less, or 20 μm or more and 100 μm or less.

[0067] 5. Transfer sheet The transfer sheet in this disclosure comprises a release film and a transfer layer (at least a first protective layer and a second protective layer).

[0068] The transfer sheet in this disclosure may have a second release film on the side of the second protective layer opposite to the first protective layer. For example, when the transfer sheet is manufactured by winding it into a roll, the occurrence of blocking can be suppressed. The second release film is usually peeled off from the transfer sheet before the adhesion process described later. Details of the second release film are the same as those described for the first release film above, so they are omitted here.

[0069] 6. Method for forming a transfer sheet The method for forming the transfer sheet in this disclosure is not particularly limited, but for example, one method is to form a first protective layer on the surface of a release film, and then form a second protective layer on the surface of the first protective layer opposite to the release film. Furthermore, a design layer may be formed on the surface of the second protective layer opposite to the first protective layer.

[0070] One method for forming the first protective layer is to coat the surface of a release film with a composition for forming the first protective layer and then cure it. Examples of coating methods for the above composition include gravure printing, bar coating, roll coating, reverse roll coating, and comma coating. Examples of curing methods include irradiation with ionizing radiation such as electron beams and ultraviolet rays.

[0071] As a method for forming the second protective layer, for example, a composition for forming the second protective layer is applied to the side of the first protective layer opposite to the release film, and cured as necessary. As a method for applying the above composition, for example, gravure printing, bar coating, roll coating, reverse roll coating, and comma coating are used. As a curing method, for example, heat is used. Furthermore, as a method for forming the design layer, for example, an ink containing a colorant, a binder resin, and a solvent is applied to the side of the second protective layer opposite to the first protective layer.

[0072] B. Manufacturing method of exterior components Figure 3 is a schematic cross-sectional view illustrating a method for manufacturing an exterior component according to this disclosure. First, as shown in Figure 3(a), a transfer sheet 10 is prepared. The transfer sheet 10 consists of a release film 1, a first protective layer 2, and a second protective layer 3, with the thickness direction D T In this order, the components are present. Next, as shown in Figure 3(b), the adhesive layer 30 is placed between the side of the transfer sheet 10 facing the second protective layer 3 and the substrate 20, and the transfer sheet 10, the adhesive layer 30 and the substrate 20 are brought into close contact. The "side of the transfer sheet 10 facing the second protective layer 3" refers to the side of the transfer sheet 10 that is located on the side of the second protective layer 3 when the release film 1 is used as a reference. Next, as shown in Figure 3(c), the release film 1 is peeled off the transfer sheet 10. This separates the first protective layer 2, the second protective layer 3, the adhesive layer 30 and the substrate 20 in the thickness direction D T In this way, an exterior member 100 having these elements in this order is obtained.

[0073] According to this disclosure, by using the transfer sheet described above, an exterior component having a protective layer that achieves both three-dimensional processability and scratch resistance can be obtained.

[0074] 1. Preparation process The preparation step in this disclosure is the step of preparing the transfer sheet described above. The transfer sheet is the same as described in "A. Transfer Sheet" above, so its description is omitted here.

[0075] 2. Adhesion process The adhesion step in this disclosure is a step of arranging the surface of the transfer sheet facing the second protective layer and the substrate facing each other, and adhering the transfer sheet and the substrate to each other. In the adhesion step, the surface of the transfer sheet facing the second protective layer and the substrate may be in direct contact. Alternatively, in the adhesion step, an adhesive layer may be placed between the surface of the transfer sheet facing the second protective layer and the substrate.

[0076] (1) Base An example of a substrate in this disclosure is a metal member. Since the metal member and the resin contained in the transfer layer are dissimilar materials, their adhesion tends to be poor. In contrast, the adhesion between the substrate and the transfer layer can be improved by bonding them together, for example, via an adhesive layer. In particular, for exterior members (members for outdoor use), high adhesion between the substrate and the transfer layer is desirable because they are exposed to harsh environments.

[0077] Metal components are components containing a single metal or a metal alloy. Examples of metals used in metal components include aluminum, iron, steel, and copper. Aluminum components are preferable because they are lightweight, have excellent corrosion resistance, and are useful as a base for exterior components. Aluminum components are components containing aluminum or an aluminum alloy. It is preferable that aluminum components have an aluminum oxide film on their surface because this improves the corrosion resistance of the aluminum component. An example of a method for forming the aluminum oxide film is anodizing.

[0078] Other examples of substrates include resin components. Examples of resins used in resin components include polycarbonate resins, vinyl chloride resins, acrylic resins, ester resins, styrene resins, olefin resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), phenolic resins, cellulose resins, and rubber. Another example of a substrate is a wood component. Examples of wood components include wood veneer, wood plywood, particleboard, and wood fiberboard. Examples of wood used in wood components include cedar, cypress, pine, and lauan. Another example of a substrate is a ceramic component. The material of a ceramic component may be ceramics such as glass or porcelain, non-cement ceramic materials such as gypsum, or non-ceramic ceramic materials such as ALC (autoclaved lightweight concrete).

[0079] The shape of the substrate is not particularly limited, but examples include plate-like, sheet-like, and three-dimensional shapes. A three-dimensional shape refers to a three-dimensional shape expressed by coordinates on the X, Y, and Z axes. In the adhesion process, it is preferable to cover the three-dimensional part of the substrate (the part having a three-dimensional shape) with the transfer sheet. The adhesion between the substrate and the transfer layer tends to be low in the three-dimensional part, but the adhesion between the substrate and the transfer layer can be improved by, for example, providing an adhesive layer. In particular, since exterior members (members for outdoor use) are exposed to harsh environments, high adhesion between the substrate and the transfer layer is desirable.

[0080] The base may have flat sections, curved sections, or both. Furthermore, the base may have at least one of the following: corners, protrusions, recesses, ridges, concave sections, bellows sections, or through sections.

[0081] (2) Adhesive layer In the adhesion process, an adhesive layer may be placed between the second protective layer side of the transfer sheet and the substrate.

[0082] The adhesive used in the adhesive layer is not particularly limited, and any known adhesive can be used. Examples include heat-sensitive adhesives and pressure-sensitive adhesives. Examples of resins used in the adhesive include acrylic resins, urethane resins, vinyl chloride resins, vinyl acetate resins, ester resins, amide resins, vinyl chloride-vinyl acetate copolymers, and styrene-acrylic copolymers. In addition, two-component curing polyurethane adhesives and polyester adhesives using an isocyanate compound as a curing agent may be used as the adhesive. Furthermore, the adhesive is preferably a solvent-based adhesive or a polyurethane reactive (PUR) adhesive.

[0083] The adhesive layer preferably has high peel strength. The peel strength of the adhesive layer is, for example, 15 N / inch or more and 50 N / inch or less, and may also be 20 N / inch or more and 40 N / inch or less. The peel strength of the adhesive layer is measured by the following method. That is, an adhesive is applied to a 0.8 mm thick aluminum plate (anodized) to a thickness of 5 μm, and then bonded to a polyester film (Toyobo Ester Film E5001, manufactured by Toyobo Co., Ltd., 50 μm thick) using a roll laminator. The resulting laminate is subjected to a 180° peel test in accordance with JIS K6854-2:1999, and the peel strength is measured. The hardness of the adhesive layer is not particularly limited, but it is preferably a pencil hardness of B or higher. The thickness of the adhesive layer is not particularly limited, but for example, it is 2 μm or more and 100 μm or less, may also be 2 μm or more and 50 μm or less, or 2 μm or more and 35 μm or less.

[0084] (3) Method of adhesion In the adhesion process, it is preferable to place an adhesive layer between the second protective layer side of the transfer sheet and the substrate, thereby adhering the transfer sheet, adhesive layer, and substrate to each other. The adhesion process preferably includes an adhesive layer formation process to form the adhesive layer and an adhesion process to adhere the transfer sheet, adhesive layer, and substrate to each other. Furthermore, it is preferable that the adhesion process includes a supply process to supply the transfer sheet from the roll before the adhesive layer formation process. Roll-shaped transfer sheets usually do not have an adhesive layer.

[0085] In the adhesive layer formation process, an adhesive layer may be formed by applying an adhesive coating liquid to the second protective layer side of the transfer sheet. In this case, there is the advantage that the adhesive coating liquid can be uniformly applied to the transfer sheet. On the other hand, in the adhesive layer formation process, an adhesive layer may be formed by applying an adhesive coating liquid to the surface of the substrate. In this case, there is the advantage that the effects of thermal shrinkage of the adhesive are less likely to occur. For example, when the adhesive coating liquid is applied to the transfer sheet, if the adhesive shrinks due to heat, wrinkles may form on the transfer sheet. In contrast, when the adhesive coating liquid is applied to the substrate, even if the adhesive shrinks due to heat, the substrate usually does not bend.

[0086] In the adhesion process, one method for adhering the transfer sheet and the substrate is lamination. In lamination, for example, the laminate having the transfer sheet and the substrate is heated and pressurized from the transfer sheet side. One method for heating and pressurizing is to use a roll transfer device. The roll temperature of the roll transfer device is, for example, 200°C or less, and may be 180°C or less. If the roll temperature is too high, the transfer sheet may soften more than necessary. On the other hand, the roll temperature of the roll transfer device is, for example, 100°C or higher, and may be 110°C or higher, and may be 120°C or higher.

[0087] The method for manufacturing the exterior component in this disclosure may include a peeling step after the adhesion step in which a release film is peeled off from the first protective layer.

[0088] 3. Exterior components The exterior member in this disclosure has a first protective layer, a second protective layer, an adhesive layer, and a substrate in this order in the thickness direction. The exterior member may be an exterior member with a release film having a release film on the side of the first protective layer opposite to the second protective layer, or it may be an exterior member without a release film.

[0089] The exterior components described herein are typically used outdoors. Examples of exterior applications include building materials. Building materials are used in buildings such as houses, offices, shops, hospitals, and clinics. Examples of exterior component applications include exterior walls, roofs, eaves, louvers, door pockets, window frames, doors, door frames, handrails, fences, and clothes drying racks.

[0090] C. Exterior components The exterior member in this disclosure has a first protective layer, a second protective layer, an adhesive layer, and a substrate in this order in the thickness direction, and the Erichsen indentation depth is 7 mm or more and 11 mm or less.

[0091] According to this disclosure, since the Erichsen indentation depth is within a predetermined range, the exterior component has a protective layer that achieves both three-dimensional workability and scratch resistance. The exterior component in this disclosure is the same as described in "B. Method for Manufacturing the Exterior Component" above, so the description is omitted here.

[0092] This disclosure is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of this disclosure and achieves similar effects is included within the technical scope of this disclosure. [Examples]

[0093] [Example 1] (1) Preparation of the transfer sheet As a release film, an untreated polyester film (Toyobo Co., Ltd., product name: Toyobo Ester Film E5001, thickness: 50 μm) was prepared. The composition for forming the first protective layer described below was applied to one side of the release film by gravure coating to form an uncured resin layer. Subsequently, it was cured by electron beam irradiation at an accelerating voltage of 165 kV with 50 kGy, forming a first protective layer with a thickness of 5 μm. After that, corona irradiation was performed on the first protective layer. <Composition for forming the first protective layer> ·Ionizing radiation curable resin composition: 100 parts by mass Trifunctional caprolactone-based urethane acrylate: 30 parts by mass (Weight average molecular weight / Number of functional groups=approx. 1200) Trifunctional urethane acrylate: 70 parts by mass (Weight average molecular weight / number of functional groups = approx. 800) • Hydroxyphenyltriazine-based UV absorber: 2 parts by mass (Product name: TINUVIN479, BASF) • Light stabilizer having reactive functional groups: 2 parts by mass (Product name: Sanol LS-3410, Nippon Emulsifier Co., Ltd.)

[0094] Next, the composition for forming the second protective layer described below was applied to the corona-irradiated first protective layer by gravure coating and dried to form a second protective layer with a thickness of 3.5 μm. <Composition for forming the second protective layer> • Polycarbonate-based urethane-acrylic copolymer: 100 parts by mass • Hydroxyphenyltriazine-based UV absorber: 17 parts by mass (Product name: TINUVIN400, BASF) • Hydroxyphenyltriazine-based UV absorber: 13 parts by mass (product name: TINUVIN479, BASF) • Hindered amine light stabilizer: 8 parts by mass (product name: TINUVIN123, BASF) • Blocking inhibitor: 9 parts by mass (silica particles, average particle size 3 μm) • Hardener: 25 parts by mass (hexamethylene diisocyanate)

[0095] Next, a design layer ink 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. The resin component of the design layer ink was a thermosetting resin containing an acrylic resin and a vinyl chloride-vinyl acetate copolymer, with a mass ratio of 8:2 between the acrylic resin and the vinyl chloride-vinyl acetate copolymer. This resulted in a transfer sheet having the release film, the first protective layer, the second protective layer, and the design layer in this order in the thickness direction.

[0096] (2) Preparation of evaluation components A heat-sensitive adhesive (main component: Aronmelt PES-320SK (Toagosei Co., Ltd.), hardener: Coronate L (Tosoh Corporation), main component:hardener = 100:11, mass ratio) was applied to the design layer side of the transfer sheet and dried to form an adhesive layer 30 μm thick. Next, the transfer sheet with the adhesive layer was cured at 150°C for 1 minute. An aluminum plate (thickness 0.8 mm) was prepared as a substrate and anodized on its surface. The transfer sheet was positioned facing the substrate with the adhesive layer in between, and these were passed between the rolls of a roll laminator (lamination temperature: 160°C, lamination pressure: 5 kgf / m²). 2 A laminated member having a transfer sheet, an adhesive layer, and a substrate was obtained. The release film was peeled off the obtained laminated member. This resulted in obtaining an evaluation member (laminated body) having a first protective layer, a second protective layer, a design layer, an adhesive layer, and a substrate in this order in the thickness direction.

[0097] [Example 2] An evaluation member was obtained in the same manner as in Example 1, except that the composition for forming the first protective layer described below was used. <Composition for forming the first protective layer> ·Ionizing radiation curable resin composition: 100 parts by mass Trifunctional caprolactone-based urethane acrylate: 20 parts by mass (Weight average molecular weight / Number of functional groups=approx. 1200) Bifunctional urethane acrylate A: 60 parts by mass (Weight average molecular weight / Number of functional groups = approx. 300) Bifunctional urethane acrylate B: 20 ​​parts by mass (Weight average molecular weight / Number of functional groups = approx. 400) • Hydroxyphenyltriazine-based UV absorber: 2 parts by mass (Product name: TINUVIN479, BASF) • Light stabilizer having reactive functional groups: 2 parts by mass (Product name: Sanol LS-3410, Nippon Emulsifier Co., Ltd.)

[0098] [Example 3] An evaluation member was obtained in the same manner as in Example 1, except that the composition for forming the first protective layer described below was used. <Composition for forming the first protective layer> ·Ionizing radiation curable resin composition: 100 parts by mass Trifunctional caprolactone-based urethane acrylate: 20 parts by mass (Weight average molecular weight / Number of functional groups=approx. 1200) Bifunctional urethane acrylate A: 70 parts by mass (Weight average molecular weight / Number of functional groups = approx. 300) Bifunctional urethane acrylate B: 10 parts by mass (Weight average molecular weight / Number of functional groups = approx. 400) • Hydroxyphenyltriazine-based UV absorber: 2 parts by mass (Product name: TINUVIN479, BASF) • Light stabilizer having reactive functional groups: 2 parts by mass (Product name: Sanol LS-3410, Nippon Emulsifier Co., Ltd.)

[0099] [Example 4] An evaluation member was obtained in the same manner as in Example 1, except that the composition for forming the first protective layer described below was used. <Composition for forming the first protective layer> ·Ionizing radiation curable resin composition: 100 parts by mass Trifunctional caprolactone-based urethane acrylate: 50 parts by mass (Weight average molecular weight / Number of functional groups=approx. 1200) Bifunctional urethane acrylate: 50 parts by mass (Weight average molecular weight / number of functional groups = approx. 3000) • Hydroxyphenyltriazine-based UV absorber: 2 parts by mass (Product name: TINUVIN479, BASF) • Light stabilizer having reactive functional groups: 2 parts by mass (Product name: Sanol LS-3410, Nippon Emulsifier Co., Ltd.)

[0100] [Comparative Example 1] An evaluation member was obtained in the same manner as in Example 1, except that the composition for forming the first protective layer described below was used. <Composition for forming the first protective layer> ·Ionizing radiation curable resin composition: 100 parts by mass Hetafunctional caprolactone-based urethane acrylate: 60 parts by mass (Weight average molecular weight / Number of functional groups=approx. 150) Bifunctional caprolactone-based urethane acrylate: 40 parts by mass (Weight average molecular weight / number of functional groups = approx. 2000) • Hydroxyphenyltriazine-based UV absorber: 2 parts by mass (Product name: TINUVIN479, BASF) • Light stabilizer having reactive functional groups: 2 parts by mass (Product name: Sanol LS-3410, Nippon Emulsifier Co., Ltd.)

[0101] [Comparative Example 2] An evaluation member was obtained in the same manner as in Example 1, except that the composition for forming the first protective layer described below was used. <Composition for forming the first protective layer> ·Ionizing radiation curable resin composition: 100 parts by mass Bifunctional urethane acrylate: 100 parts by mass (Weight average molecular weight / number of functional groups = approx. 3000) • Hydroxyphenyltriazine-based UV absorber: 2 parts by mass (Product name: TINUVIN479, BASF) • Light stabilizer having reactive functional groups: 2 parts by mass (Product name: Sanol LS-3410, Nippon Emulsifier Co., Ltd.)

[0102] [Erichsen indentation depth measurement] The Erichsen indentation depth was determined for the evaluation members (laminated structures) obtained in each example and comparative example. Specifically, using an Erichsen-type coating tester (manufactured by Toyo Seiki Seisakusho), a spherical punch (diameter: 20 mm) was gradually pressed into the base (aluminum plate) side of the evaluation member (size: 100 mm x 100 mm) at an environment of 23°C ± 5°C (speed: 10 mm / min). The distance the punch traveled (depth of the indentation) at which a crack occurred in the first protective layer when observed with an optical microscope (Keyence VHX-6000, magnification: 500x) was defined as the Erichsen indentation depth. The results are shown in Table 1.

[0103] [Evaluation of three-dimensional machinability] The three-dimensional processability of the evaluation members obtained in each example and comparative example was evaluated. Specifically, a bending test was performed on the evaluation members at a bending angle of 1 mmR, and the first protective layer of the bent portion was observed under a microscope and evaluated according to the following criteria. The results are shown in Table 1. A: No damage or cracks were found. B: Very minor scratches or cracks were found. C: Clear damage or cracks were observed.

[0104] [Evaluation of scratch resistance] The scratch resistance of the evaluation members obtained in each example and comparative example was evaluated. Specifically, the surface of the first protective layer of the evaluation member was treated with 0.2 kg / cm² of Bonstar steel wool #0000. 2 The device was rubbed back and forth 10 times under a load. Afterwards, it was visually observed and evaluated according to the following criteria. The results are shown in Table 1. A: No injuries were found. B: Minor injuries were found. C: Significant damage was found.

[0105] [Table 1]

[0106] As shown in Table 1, in each example, good three-dimensional machinability and scratch resistance were achieved when the Erichsen indentation depth was within a predetermined range. In contrast, in Comparative Example 1, the Erichsen indentation depth was small, resulting in insufficient three-dimensional machinability. In Comparative Example 2, the Erichsen indentation depth was large, resulting in good three-dimensional machinability but insufficient scratch resistance. Thus, by setting the Erichsen indentation depth within a predetermined range, it was possible to achieve both good three-dimensional machinability and scratch resistance. [Explanation of symbols]

[0107] 1… Release film 2 … 1st protective layer 3…Second protective layer 4. Design layer 10… Transfer sheet 20 … Base 100 ... Exterior components

Claims

1. A transfer sheet used in the manufacture of exterior components having a substrate, The transfer sheet comprises a release film and a transfer layer disposed on one side of the release film. The transfer layer has a first protective layer and a second protective layer in this order in the thickness direction, starting from the release film side. A transfer sheet wherein, when the transfer layer of the transfer sheet is transferred to an evaluation substrate (material: aluminum, thickness: 0.8 mm) via an adhesive layer, the release film is peeled off, and a laminate is produced, the Erichsen indentation depth of the laminate is 7 mm or more and 11 mm or less.

2. The transfer sheet according to claim 1, wherein the substrate has a three-dimensional shape.

3. The transfer sheet according to claim 1 or claim 2, wherein the substrate is a metal member.

4. The transfer sheet according to any one of claims 1 to 3, wherein the first protective layer contains at least one of an ultraviolet absorber and a light stabilizer.

5. The transfer sheet according to any one of claims 1 to 4, wherein the first protective layer contains a triazine-based ultraviolet absorber.

6. The transfer sheet according to any one of claims 1 to 5, wherein the second protective layer contains at least one of an ultraviolet absorber and a light stabilizer.

7. The transfer sheet according to any one of claims 1 to 6, wherein the second protective layer contains a triazine-based ultraviolet absorber.

8. The transfer sheet according to any one of claims 1 to 7, wherein the first protective layer comprises a cured product of an ionizing radiation-curable resin composition.

9. The transfer sheet according to any one of claims 1 to 8, wherein the second protective layer comprises a cured product of a thermosetting resin composition.

10. The transfer sheet according to any one of claims 1 to 9, wherein the transfer sheet has a design layer on the side of the second protective layer opposite to the first protective layer.

11. A method for manufacturing an exterior member having a base, A preparation step of preparing a transfer sheet according to any one of claims 1 to 10, The transfer sheet and the substrate are positioned facing each other, and the transfer sheet and the substrate are brought into close contact in a bonding step. A method for manufacturing an exterior component, comprising the same characteristics.

12. The method for manufacturing an exterior member according to claim 11, wherein in the adhesion step, an adhesive layer is placed between the surface of the transfer sheet on the second protective layer side and the substrate.

13. The aforementioned adhesion process is The adhesive layer forming process for forming the aforementioned adhesive layer, The process includes an adhesion treatment to bring the transfer sheet, the adhesive layer, and the substrate into close contact. The method for manufacturing an exterior member according to claim 12, wherein in the adhesive layer formation process, an adhesive layer coating liquid is applied to the second protective layer side of the transfer sheet to form the adhesive layer.

14. The aforementioned adhesion process is The method for manufacturing an exterior member according to claim 13, further comprising a supply process of supplying the transfer sheet from a roll of transfer sheets before the adhesive layer formation process.

15. The aforementioned adhesion process is The adhesive layer forming process for forming the aforementioned adhesive layer, The process includes an adhesion treatment to bring the transfer sheet, adhesive layer, and substrate into close contact. The method for manufacturing an exterior member according to claim 12, wherein in the adhesive layer formation process, an adhesive layer coating liquid is applied to the surface of the substrate to form the adhesive layer.

16. A method for manufacturing an exterior member according to any one of claims 12 to 15, wherein in the bonding step, the adhesive layer is formed using a heat-sensitive adhesive.

17. The first protective layer, the second protective layer, the adhesive layer, and the substrate are arranged in this order in the thickness direction. An exterior component wherein, when the first protective layer, the second protective layer, and the adhesive layer are arranged on an evaluation substrate (material: aluminum, thickness: 0.8 mm) to produce a laminate, the Erichsen indentation depth of the laminate is 7 mm or more and 11 mm or less.

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