JP2023147702A - Transfer sheet, manufacturing method of exterior member, and exterior member - Google Patents

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

The present disclosure relates to a transfer sheet, a method for manufacturing an exterior member, and an exterior member.

It is known to decorate a base such as a metal member or a resin member by transferring a transfer layer in a transfer sheet (a layer transferred from the transfer sheet) to the base. For example, Patent Document 1 discloses a rain gutter in which an oxide film layer is disposed on the outer surface of an aluminum base material, a decorative layer is disposed on the outer surface, and a pattern is applied to the surface of the decorative layer. ing. Specifically, Patent Document 1 discloses forming a decorative layer on the outer surface of an alumite-treated aluminum base material by a hydraulic transfer process.

JP 2020-12283 Publication

When transferring a transfer layer having a protective layer onto a substrate, cracks may occur in the protective layer because, for example, the protective layer cannot follow the shape of the substrate. Furthermore, since the exterior member (outdoor member) is exposed to harsh environments, if the protective layer is cracked, the weather resistance and stain resistance will be significantly reduced. Therefore, a transfer sheet provided with a protective layer having good three-dimensional processability is desired. On the other hand, if we focus only 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 the scratch resistance of the protective layer. .

The present disclosure has been made in view of the above circumstances, and its main purpose is to provide a transfer sheet having a protective layer that has both three-dimensional processability and scratch resistance.

In the present disclosure, there is provided a transfer sheet used for manufacturing an exterior member having a base, and the transfer sheet includes 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 in the thickness direction from the release film side, and the transfer layer in the transfer sheet is evaluated via an adhesive layer. Provided is a transfer sheet in which, when a laminate is produced by transferring the laminate onto a substrate and peeling off the release film, the Erichsen indentation depth of the laminate is 7 mm or more and 11 mm or less.

The present disclosure also provides a method for manufacturing an exterior member having a base, including a preparation step of preparing the transfer sheet described above, and a surface of the transfer sheet on the second protective layer side facing the base. The present invention provides a method for manufacturing an exterior member, comprising a step of placing the transfer sheet and the substrate in close contact with each other.

Further, the present disclosure provides an exterior member having a first protective layer, a second protective layer, an adhesive layer, and a base in this order in the thickness direction, and having an Erichsen indentation depth of 7 mm or more and 11 mm or less. provide.

The present disclosure has the advantage that it is possible to provide a transfer sheet having a protective layer that has both three-dimensional processability and scratch resistance.

FIG. 1 is a schematic cross-sectional view illustrating a transfer sheet in the present disclosure. FIG. 2 is a schematic cross-sectional view illustrating a method for forming a laminate according to the present disclosure. It is a schematic sectional view illustrating the manufacturing method of the exterior member in this indication.

Embodiments will be described below with reference to the drawings and the like. However, the present disclosure can be implemented in many different ways and should not be limited to what is described in the embodiments illustrated below. In addition, in order to make the explanation clearer, the drawings may schematically represent the width, thickness, and shape of each part compared to the actual form, but this is only an example and should be interpreted in a limited manner. isn't it.

In this specification, when expressing the manner in which another member is placed on a certain member, when it is simply expressed as “above” or “below”, unless otherwise specified, the term “above” or “below” means directly above a certain member so as to be in contact with it. Alternatively, it includes both a case where another member is placed directly below a certain member, and a case where another member is placed above or below a certain member via another member. In addition, in this specification, when expressing the manner in which another member is placed on the surface of a certain member, when it is simply written as "on the surface", unless otherwise specified, it means that it is placed directly above or in contact with a certain member. This includes both a case where another member is placed directly below a certain member, and a case where another member is placed above or below a certain member via another member.

Hereinafter, the transfer sheet, the method for manufacturing the exterior member, and the exterior member in the present disclosure will be described in detail.

A. Transfer Sheet FIG. 1(a) is a schematic cross-sectional view illustrating a transfer sheet in the present disclosure. As shown in FIG. 1(a), the transfer sheet 10 includes a release film 1 and a transfer layer X disposed on one surface of the release film 1. The transfer layer X has a first protective layer 2 and a second protective layer 3 in this order from the release film 1 side in the thickness direction _DT . Further, as shown in FIG. 1(b), the transfer sheet 10 may have a design layer 4 on the surface of the second protective layer 3 opposite to the first protective layer 2.

Further, as shown in FIG. 2A, the transfer layer X on the transfer sheet 10 is transferred to the evaluation substrate 22 via the adhesive layer 21, and the release film 1 is peeled off. Thereby, 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 _DT is obtained. In the present disclosure, the Erichsen indentation depth of the laminate L is within a predetermined range.

According to the present disclosure, since the Erichsen indentation depth of the laminate produced under predetermined conditions is within a predetermined range, the transfer sheet has a protective layer that is compatible with three-dimensional processability and scratch resistance. As described above, when transferring a transfer layer having a protective layer onto a substrate, cracks may occur in the protective layer, for example, because the protective layer cannot follow the shape of the substrate. In particular, when the substrate has a three-dimensional shape, the possibility that cracks will occur in the protective layer increases. Furthermore, since the exterior member (outdoor member) is exposed to harsh environments, if the protective layer is cracked, the weather resistance and stain resistance will be significantly reduced. Regarding weather resistance, if the protective layer cracks, the underlying layer is exposed, making it impossible to maintain sufficient weather resistance. Regarding stain resistance, when the protective layer cracks, contaminants penetrate into the transfer layer, making it impossible to maintain sufficient stain resistance. Furthermore, when the protective layer is cracked, the cracked portion may turn white, resulting in a decrease in design. Therefore, a transfer sheet provided with a protective layer having good three-dimensional processability is desired. On the other hand, if we focus only 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 the scratch resistance of the protective layer. . In the present disclosure, by adjusting the Erichsen indentation depth of the laminate produced under predetermined conditions to a predetermined range, a transfer sheet having a protective layer that has both three-dimensional processability and scratch resistance can be obtained.

Further, for example, assume that the base is a metal member and a decorative sheet is attached to the metal member. In this case, the metal (inorganic material) contained in the metal component and the resin (organic material) contained in the decorative sheet are different materials, so it is difficult to separate the decorative component when recycling them. be. When a transfer sheet is used instead of a decorative sheet, the resin content contained in the sheet can be reduced. By reducing the resin content contained in the sheet, it becomes possible to recycle the metal and resin without separating them, thereby reducing the environmental burden. That is, when the base is a metal member, the transfer sheet can provide an exterior member with less environmental load.

Furthermore, 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, for example, by adding a sufficient amount of weathering agent to the transparent resin layer. On the other hand, 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 the present disclosure, it is preferred that both the first protective layer and the second protective layer contain a weathering agent. This makes it possible to provide high weather resistance while maintaining the characteristics required for the first protective layer (e.g. surface characteristics such as scratch resistance) and the characteristics required for the second protective layer (e.g. adhesion). can.

Further, in the case of a transfer sheet, the adhesion between the first protective layer and the second protective layer is likely to be insufficient. Here, in the case of a decorative sheet, a design layer is usually formed on the 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. Form. The first protective layer is typically produced by curing a composition for forming the first protective layer formed on the second protective layer, so that the first protective layer and the second protective layer are closely bonded. sex becomes better. On the other hand, in the case of a transfer sheet, 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 second protective layer is formed on the second protective layer. A design layer is formed on the surface. The first protective layer is typically produced by curing a composition for forming the first protective layer on the release film. Since the second protective layer is formed on the cured first protective layer, the adhesion between the first protective layer and the second protective layer is likely to be insufficient. In the present disclosure, the second protective layer is preferably a layer with higher flexibility than the first protective layer. Thereby, the adhesion between the first protective layer and the second protective layer can be increased.

In the present disclosure, when a laminate is produced by transferring a transfer layer on a transfer sheet to an evaluation substrate via an adhesive layer and peeling off a release film, the Erichsen indentation depth of the laminate is determined to be a predetermined depth. within the range of Since the material and shape of the evaluation substrate basically do not affect the Erichsen indentation depth, any evaluation substrate can be used. The evaluation board is, for example, a metal member. The evaluation board may be an aluminum member. On the other hand, the shape of the evaluation substrate is not particularly limited, but usually has a flat portion. In the present disclosure, the Erichsen indentation depth of the transfer layer transferred onto the flat surface of the evaluation substrate is usually within a predetermined range. In addition, by bringing the transfer layer and the evaluation substrate into close contact with each other via the adhesive layer, they are firmly adhered 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 Examples described later.

The Erichsen indentation depth of the laminate is usually 7 mm or more, and may be 8 mm or more. If the Erichsen indentation depth is small, sufficient three-dimensional workability may not be obtained. On the other hand, the Erichsen indentation depth of the laminate is usually 11 mm or less, and may be 10 mm or less. If the Erichsen indentation depth is large, sufficient scratch resistance may not be obtained.

The Erichsen indentation depth of the laminate can be controlled, for example, by adjusting the type of resin (eg, curable compound) for producing the first protective layer. For example, when 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, the resin composition used for producing the first protective layer preferably contains a bifunctional or trifunctional resin as a main component on a mass basis. Furthermore, if the ratio of the polymerization average molecular weight to the number of functional groups (polymerization 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 (polymerization average molecular weight/number of functional groups) is large, , it is easy to obtain a first protective layer with low scratch resistance. Therefore, in the resin composition used for producing the first protective layer, the ratio (polymerization average molecular weight/number of functional groups) of the main component resin on a mass basis is preferably, for example, 200 or more and 3000 or less. , more preferably 300 or more and 1500 or less.

The transfer sheet in the present disclosure includes a release film and a transfer layer disposed on one surface 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 other layers include a design layer. The transfer layer preferably has 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, may be 10 μm or more, may be 12 μm or more, or may be 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, may be 40 μm or less, or may be 30 μm or less. If the transfer layer is thick, it becomes necessary to separate metal and resin during recycling.

1. First Protective Layer The transfer sheet in the present disclosure has a first protective layer. The first protective layer contributes to improving the surface characteristics (eg, scratch resistance) of the exterior member. The first protective layer and the release film may be arranged so as to be in direct contact with each other, or may be arranged with another layer interposed therebetween.

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, and may be 95% by mass or more, based on the total resin components constituting the first protective layer. The content may be 100% by mass.

Examples of the cured product of the curable resin composition include a cured product of an ionizing radiation-curable resin composition. Examples of the ionizing radiation curable resin composition include electron beam curable resin compositions and ultraviolet ray curable resin compositions. Among these, electron beam curable resin compositions are preferred because they do not require a polymerization initiator, have little odor, and are less likely to be colored.

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 is crosslinked and cured by irradiation with ionizing radiation, and includes, for example, a functional group having an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, and an allyl group. Note that in the present disclosure, a (meth)acryloyl group refers to an acryloyl group or a methacryloyl group. Furthermore, in the present disclosure, (meth)acrylate refers to acrylate or methacrylate.

Ionizing radiation refers to electromagnetic waves or charged particle beams that have energy quanta that can polymerize or crosslink molecules. Ionizing radiation includes, for example, electron beams (EB) and ultraviolet light (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.

The ionizing radiation-curable compound is, for example, one selected from urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polycarbonate (meth)acrylate, and acrylic (meth)acrylate. It is preferable to include the above. Among these, it is preferable that the ionizing radiation-curable compound contains at least urethane (meth)acrylate. The urethane (meth)acrylate is preferably a caprolactone-based urethane acrylate.

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

Further, the ionizing radiation-curable compound may include caprolactone-based urethane acrylate and urethane (meth)acrylate that is not modified with caprolactone. In this case, the content of caprolactone-based urethane acrylate contained in the first protective layer is defined as M _CLUA , and the content of urethane (meth)acrylate that is not modified with caprolactone is defined as M _UA . The mass ratio of M _CLUA to the total of M _UA and M _CLUA (M _CLUA / ( _MUA + M _CLUA )) is, for example, 40 mass % or more and 90 mass % or less, and 45 mass % or more and 80 mass % or less, and It may be 50% by mass or more and 70% by mass or less.

Caprolactone-based urethane acrylate can usually be obtained by reacting caprolactone-based polyol, organic isocyanate, and hydroxy (meth)acrylate. As a synthesis method, for example, a polycaprolactone polyol and an organic polyisocyanate are reacted to produce a polyurethane prepolymer containing -NCO groups (isocyanate groups) at both ends, and then hydroxy (meth)acrylate and Examples include a method of reacting.

As the caprolactone polyol, commercially available ones can be used, preferably those having two hydroxyl groups and a number average molecular weight of preferably 500 to 3,000, more preferably 750 to 2,000. Further, polyols other than caprolactone-based polyols, such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, etc., may be used alone or in a mixture of a plurality of polyols in any ratio. The organic polyisocyanate is preferably a diisocyanate having two isocyanate groups, and from the viewpoint of suppressing yellowing, preferred examples include isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, trimethylhexamethylene diisocyanate, etc. . Preferred examples of the hydroxy(meth)acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and caprolactone-modified 2-hydroxyethyl acrylate.

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 whose terminal end is diethylene glycol among caprolactone-based urethane acrylates. By using caprolactone diol-based urethane acrylate, cracking and whitening can be suppressed from occurring in the first protective layer.

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

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

The first protective layer preferably contains a weathering agent. Examples of weathering agents include ultraviolet absorbers and light stabilizers. Preferably, 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 types of ultraviolet absorbers. Similarly, the first protective layer may contain one or more light stabilizers.

Examples of the ultraviolet absorbent contained in the first protective layer include triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, oxybenzophenone-based ultraviolet absorbers, salicylic acid ester-based ultraviolet absorbers, and cyano ( Examples include organic ultraviolet absorbers such as meth)acrylate 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 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, 2-[4-[(2-hydroxy-3-triazine) decyloxypropyl)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, 2-(4,6-diphenyl-1,3, Examples include 5-triazin-2-yl)-5[2-(2-ethylhexanoyloxy)ethoxy]phenol.

The content of the 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, and 0.8 parts by mass or more and 8 parts by mass, based on 100 parts by mass of the ionizing radiation-curable compound. The amount may be 1 part by mass or more and 5 parts by mass or less. If the content of the ultraviolet absorber is high, bleed-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 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, 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxy (ethylamine)-1,3,5-triazine).

The content of the light stabilizer contained in the first protective layer is, for example, 1 part by mass or more and 10 parts by mass or less, and 1.5 parts by mass or more and 8 parts by mass or less, based on 100 parts by mass of the ionizing radiation-curable compound. The amount may be 2 parts by mass or more and 5 parts by mass or less. If the content of the photostabilizer is high, bleed-out of the photostabilizer may occur, and if the content of the photostabilizer is low, sufficient photostability may not be obtained.

The first protective layer contains a silicone compound, a polymerization inhibitor, a crosslinking agent, an antistatic agent, an adhesion improver, an antioxidant, a leveling agent, a thixotropic agent, a coupling agent, a plasticizer, an antifouling agent, and an antifoaming agent. It may contain additives such as agents and fillers. Further, the thickness of the first protective layer may be, for example, 2 μm or more and 20 μm or less, 3 μm or more and 15 μm or less, or 4 μm or more and 10 μm or less. If the first protective layer is thin, sufficient weather resistance may not be obtained; if the first protective layer is thick, cracks may easily occur in the first protective layer, and good adhesion may not be obtained. There is.

2. Second Protective Layer The transfer sheet in the present disclosure has a second protective layer. The second protective layer is typically a softer layer than the first protective layer. Moreover, the second protective layer and the first protective layer may be arranged so as to be in direct contact with each other, or may be arranged with another layer interposed therebetween.

The second protective layer contains 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 includes a cured product (crosslinked structure) of the above resin.

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 is cured by heating. Examples of thermosetting resins include (meth)acrylic resins, urethane resins, urethane acrylic resins, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. . Further, the thermosetting resin composition may be one in which a curing agent such as an isocyanate curing agent or an epoxy curing agent is 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 a thermosetting resin containing a urethane acrylic resin. A cured product of the composition is more preferred. Further, in order to make the structure of the cured product more rigid, the thermosetting resin composition preferably contains an isocyanate curing agent or an epoxy curing agent, and more preferably contains an isocyanate curing agent.

Moreover, 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. A polycarbonate-based urethane-acrylic copolymer is a resin obtained by radically polymerizing an acrylic monomer to a polycarbonate-based polyurethane polymer obtained by reacting a polycarbonate diol and a (di)isocyanate.

Examples of the (di)isocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 1,5-naphthalene diisocyanate, n-isocyanate phenylsulfonyl isocyanate, o-isocyanate phenylsulfonyl isocyanate, p-isocyanate phenyl Examples include aromatic isocyanates such as sulfonyl 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, and (meth)acrylate. Examples include alkyl (meth)acrylates such as n-butyl and isobutyl (meth)acrylate.

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, and may 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, polycarbonate-based urethane acrylic Since the proportion of the polycarbonate structure in the polymer can be increased, the structure of the polycarbonate-based urethane-acrylic copolymer becomes more rigid.Therefore, deformation due to temperature changes can be reduced.In addition, the above mass ratio can be set to 95% by mass or less. By doing so, it becomes easier to ensure the flexibility of the second protective layer, and the adhesion with the design layer is improved.

The second protective layer preferably contains a weathering agent. Examples of weathering agents include ultraviolet absorbers and light stabilizers. The second protective layer preferably contains at least one of an ultraviolet absorber and a light stabilizer. Since the preferable types and embodiments of the weathering agent are the same as those described in "1. First Protective Layer" above, their description is omitted here. In particular, the second protective layer preferably contains a triazine-based ultraviolet absorber. Further, the second protective layer preferably contains a hindered amine 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, and 3 parts by mass or more and 40 parts by mass or less, based on 100 parts by mass of the resin component. The amount may be 10 parts by mass or more and 35 parts by mass or less. The content of the ultraviolet absorber contained in the second protective layer (content based on 100 parts by mass of the resin component) is the content of the ultraviolet absorbent contained in the first protective layer (content based on 100 parts by mass of the resin component). There may be more.

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, and 1 part by mass or more and 15 parts by mass or less, based on 100 parts by mass of the resin component. The amount may be 3 parts by mass or more and 10 parts by mass or less. The content of the light stabilizer contained in the second protective layer (content based on 100 parts by mass of the resin component) is the content of the light stabilizer contained in the first protective layer (content based on 100 parts by mass of the resin component). There may be more.

The second protective layer contains a silicone compound, a polymerization inhibitor, a crosslinking agent, an antistatic agent, an adhesion improver, an antioxidant, a leveling agent, a thixotropic agent, a coupling agent, a plasticizer, an antifouling agent, and an antifoaming agent. It may contain additives such as agents and fillers. Further, the thickness of the second protective layer may be, for example, 2 μm or more and 10 μm or less, 3 μm or more and 8 μm or less, or 3 μm or more and 5 μm or less. If the second protective layer is thin, the adhesion (especially initial adhesion) with 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 increases, making it easier for cracks to occur in the first protective layer.

3. Design Layer The transfer sheet in the present disclosure may or may not have a design layer on the surface of the second protective layer opposite to the first protective layer. Providing the design layer improves the design of the exterior member. 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 with another layer interposed therebetween.

Examples of the design layer include a solid layer (a layer coated with ink) and a pattern layer (a layer printed with ink). The transfer sheet may have a pattern layer and a solid layer as design layers in order from the release film side. The patterns in the pattern layer include, for example, wood grain patterns, stone grain patterns, sand grain patterns, tiling patterns, brickwork patterns, cloth grain patterns, leather tie patterns, geometric figures, characters, symbols, abstract patterns, and flowers. One example is the pattern.

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

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

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

4. Release Film The transfer sheet in the present disclosure has a release film (first release film) on the surface of the first protective layer opposite to the second protective layer. The release film and the first protective layer may be arranged so as to be in direct contact with each other, or may be arranged with another layer interposed therebetween.

The release film 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 release film preferably contains an ester resin or an olefin resin. Examples of the ester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polyethylene terephthalate-isophthalate copolymer. Among these, PET or PBT is preferable, and PET is more preferable, from the viewpoint that thermal shrinkage during production of a transfer sheet and shrinkage due to irradiation with ionizing radiation are less likely to occur.

Examples of the olefin resin include polyethylene, polypropylene, polybutene, ethylene-propylene copolymer, and ethylene-propylene-butene copolymer. Among these, polypropylene is preferred from the viewpoint of being less likely to shrink due to heat shrinkage during production of the transfer sheet and shrinkage due to irradiation with ionizing radiation.

The release film may be a stretched film or an unstretched film. The stretching ratio in the machine direction (MD) of the stretched film is, for example, 5 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. Further, the thickness of the release film may be, for example, 10 μm or more and 200 μm or less, 15 μm or more and 150 μm or less, or 20 μm or more and 100 μm or less.

5. Transfer Sheet The transfer sheet in the present disclosure includes a release film and a transfer layer (at least a first protective layer and a second protective layer).

The transfer sheet in the present disclosure 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 manufactured by winding it up 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 step described below. The details of the second release film are the same as those described for the first release film described above, and therefore will not be described here.

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

Examples of the method for forming the first protective layer include a method of applying a composition for forming the first protective layer to the surface of the release film and curing the composition. Examples of methods for applying the composition include gravure printing, bar coating, roll coating, reverse roll coating, and comma coating. Examples of the curing method include methods of irradiating with ionizing radiation such as electron beams and ultraviolet rays.

As a method for forming the second protective layer, for example, a composition for forming the second protective layer is applied to the surface of the first protective layer opposite to the release film, and cured as necessary. There are several methods. Examples of methods for applying the composition include gravure printing, bar coating, roll coating, reverse roll coating, and comma coating. Examples of the curing method include heat. Further, as a method for forming the design layer, for example, a method of applying ink containing a colorant, a binder resin, and a solvent to the surface of the second protective layer opposite to the first protective layer can be mentioned.

B. Method for Manufacturing Exterior Member FIG. 3 is a schematic cross-sectional view illustrating a method for manufacturing an exterior member according to the present disclosure. First, as shown in FIG. 3(a), a transfer sheet 10 is prepared. The transfer sheet 10 has a release film 1, a first protective layer 2, and a second protective layer 3 in this order in the thickness direction _DT . Next, as shown in FIG. 3B, an adhesive layer 30 is placed between the surface of the transfer sheet 10 on the second protective layer 3 side and the base 20, and the transfer sheet 10 and the adhesive layer 30 are And the base body 20 is 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 with respect to the release film 1. Next, as shown in FIG. 3(c), the release film 1 is peeled off from the transfer sheet 10. As a result, an exterior member 100 having the first protective layer 2, the second protective layer 3, the adhesive layer 30, and the base 20 in this order in the thickness direction _DT is obtained.

According to the present disclosure, by using the above-described transfer sheet, an exterior member having a protective layer that has both three-dimensional workability and scratch resistance can be obtained.

1. Preparation Step The preparation step in the present disclosure is a step of preparing the above-mentioned transfer sheet. The details of the transfer sheet are the same as those described in "A. Transfer sheet" above, so a description thereof will be omitted here.

2. Close Contact Step The close contact step in the present disclosure is a step of arranging the surface of the transfer sheet on the second protective layer side and the base body so as to face each other, and bringing the transfer sheet and the base body into close contact with each other. In the adhesion step, the surface of the transfer sheet on the second protective layer side and the substrate may be brought into direct contact. On the other hand, in the adhesion step, an adhesive layer may be placed between the surface of the transfer sheet on the second protective layer side and the substrate.

(1) Substrate An example of the substrate in the present disclosure is a metal member. Since the metal member and the resin contained in the transfer layer are different materials, the adhesion between the two tends to be low. On the other hand, the adhesion between the substrate and the transfer layer can be improved by, for example, bringing the substrate and the transfer layer into close contact with each other via an adhesive layer. In particular, since exterior members (outdoor members) are exposed to harsh environments, it is desirable that the adhesion between the substrate and the transfer layer be high.

The metal member is a member containing a single metal or a metal alloy. Examples of metals used for the metal member include aluminum, iron, steel, and copper. Preferably, the metal member is an aluminum member. This is because aluminum members are lightweight and have excellent corrosion resistance, and are useful as bases for exterior members. The aluminum member is a member containing aluminum or an aluminum alloy. Preferably, the aluminum member has an aluminum oxide coating on its surface. This is because the corrosion resistance of the aluminum member is improved. An example of a method for forming the aluminum oxide film is alumite treatment.

Another example of the base is a resin member. Examples of resins used for resin members include polycarbonate resins, vinyl chloride resins, acrylic resins, ester resins, styrene resins, olefin resins, and acrylonitrile-butadiene-styrene copolymers (ABS resins). , phenolic resin, cellulose resin, and rubber. Further, another example of the base body is a wooden member. Examples of the wood member include wood veneer, wood plywood, particle board, and wood fiberboard. Examples of the wood used for the wooden member include cedar, cypress, pine, and lauan. Other examples of the base include ceramic members. The material of the ceramic components may be ceramics such as glass and china, non-cement ceramic materials such as gypsum, and non-ceramic ceramic materials such as ALC (lightweight aerated concrete). .

The shape of the substrate is not particularly limited, and examples thereof include a plate shape, a sheet shape, and a three-dimensional shape. The three-dimensional shape refers to a three-dimensional shape expressed by coordinates of the X, Y, and Z axes. In the adhesion step, it is preferable to cover the three-dimensional shaped portion (site having a three-dimensional shape) of the substrate with a transfer sheet. In the three-dimensional portion, the adhesion between the substrate and the transfer layer tends to be low, but by providing an adhesive layer, for example, the adhesion between the substrate and the transfer layer can be increased. In particular, since exterior members (outdoor members) are exposed to harsh environments, it is desirable that the adhesion between the substrate and the transfer layer be high.

The base body may have a flat portion, a curved portion, or both a flat portion and a curved portion. Further, the base body may have at least one of a corner, a convex part, a recess, a convex line, a concave line, a bellows part, and a penetrating part.

(2) Adhesive layer In the adhesion step, an adhesive layer may be placed between the surface of the transfer sheet on the second protective layer side and the substrate.

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

It is preferable that the adhesive layer 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 be 20 N/inch or more and 40 N/inch or less. The peel strength of the adhesive layer is measured by the method below. That is, an adhesive is applied to a 0.8 mm thick aluminum plate (anodized) to a thickness of 5 μm, and the adhesive is bonded to a polyester film (manufactured by Toyobo Co., Ltd., Toyobo Ester Film E5001, thickness 50 μm) using a roll laminator. . The obtained laminate is subjected to a 180° peel test based on JIS K6854-2:1999 to measure peel strength. Further, the hardness of the adhesive layer is not particularly limited, but preferably has a pencil hardness of B or higher. Further, the thickness of the adhesive layer is not particularly limited, but may be, for example, 2 μm or more and 100 μm or less, 2 μm or more and 50 μm or less, or 2 μm or more and 35 μm or less.

(3) Adhesion method In the adhesion step, it is preferable that an adhesive layer is disposed between the surface of the transfer sheet on the second protective layer side and the substrate, and the transfer sheet, the adhesive layer, and the substrate are brought into close contact. The adhesion step preferably includes an adhesive layer forming process for forming an adhesive layer, and an adhesion process for adhering the transfer sheet, the adhesive layer, and the substrate. Moreover, it is preferable that the adhesion process includes a supply process of supplying the transfer sheet from a roll of the transfer sheet before the adhesive layer forming process. A roll-shaped transfer sheet usually does not have an adhesive layer.

In the adhesive layer forming process, an adhesive layer coating liquid may be applied to the surface of the transfer sheet on the second protective layer side to form an adhesive layer. In this case, there is an advantage that the adhesive layer coating liquid can be uniformly applied to the transfer sheet. On the other hand, in the adhesive layer forming process, an adhesive layer coating liquid may be applied to the surface of the substrate to form an adhesive layer. In this case, there is an advantage that the influence of heat shrinkage of the adhesive is less likely to occur. For example, when applying a coating liquid for an adhesive layer to a transfer sheet, if the adhesive shrinks due to heat, wrinkles may occur on the transfer sheet. On the other hand, when an adhesive layer coating liquid is applied to a substrate, the substrate usually does not bend even if the adhesive shrinks due to heat.

In the contact treatment, a method for bringing the transfer sheet and the substrate into close contact includes, for example, a lamination method. In the lamination method, for example, a laminate having a transfer sheet and a substrate is heated and pressurized from the transfer sheet side. Examples of heating and pressurizing methods include a method using a roll transfer device. The roll temperature of the roll transfer device is, for example, 200°C or lower, and may be 180°C or lower. If the roll temperature is high, the transfer sheet may become softer than necessary. On the other hand, the roll temperature of the roll transfer device is, for example, 100°C or higher, may be 110°C or higher, or may be 120°C or higher.

The method for manufacturing an exterior member in the present disclosure may include a peeling step of peeling the release film from the first protective layer after the adhesion step.

3. Exterior Member The exterior member in the present disclosure includes a first protective layer, a second protective layer, an adhesive layer, and a base in this order in the thickness direction. The exterior member may be an exterior member with a release film that has a release film on the side opposite to the second protective layer of the first protective layer, or an exterior member that does not have a release film. There may be.

The exterior member in the present disclosure is normally used for exterior (outdoors). Exterior uses include, for example, building materials. The building materials are used, for example, in buildings such as houses, offices, stores, hospitals, and clinics. Applications of exterior members include, for example, exterior walls, roofs, soffits, louvers, door pockets, window frames, doors, door frames, handrails, fences, and drying racks.

C. Exterior Member The exterior member in the present disclosure has a first protective layer, a second protective layer, an adhesive layer, and a base in this order in the thickness direction, and has an Erichsen indentation depth of 7 mm or more and 11 mm or less.

According to the present disclosure, since the Erichsen indentation depth is within a predetermined range, the exterior member has a protective layer that has both three-dimensional workability and scratch resistance. The exterior member in the present disclosure is the same as that described in "B. Exterior member manufacturing method" above, so the description here will be omitted.

The present disclosure is not limited to the above embodiments. The above-mentioned embodiments are illustrative, and any configuration that has substantially the same technical idea as the technical idea stated in the claims of the present disclosure and has similar effects is disclosed in the present disclosure. covered within the technical scope of

[Example 1]
(1) Preparation of transfer sheet A polyester film (Toyobo Co., Ltd., trade name: Toyobo Ester Film E5001, thickness: 50 μm) that had not been subjected to easy-adhesion treatment was prepared as a release film. On one side of the release film, the following composition for forming a first protective layer was applied by gravure coating to form an uncured resin layer. Thereafter, 50 kGy of electron beam irradiation was performed at an accelerating voltage of 165 kV to cure the film, thereby forming a first protective layer with a thickness of 5 μm. Thereafter, corona irradiation was performed on the first protective layer.
<Composition for forming 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 = approximately 1200)
Trifunctional urethane acrylate: 70 parts by mass (weight average molecular weight/number of functional groups = approximately 800)
・Hydroxyphenyltriazine ultraviolet absorber: 2 parts by mass (product name: TINUVIN479, BASF)
・Light stabilizer having a reactive functional group: 2 parts by mass (product name: Sanol LS-3410, Nippon Nyukazai Co., Ltd.)

Next, on the corona-irradiated first protective layer, the following composition for forming a second protective layer was applied by gravure coating and dried to form a second protective layer having a thickness of 3.5 μm.
<Composition for forming second protective layer>
・Polycarbonate-based urethane acrylic copolymer: 100 parts by mass ・Hydroxyphenyltriazine-based ultraviolet absorber: 17 parts by mass (product name: TINUVIN400, BASF)
・Hydroxyphenyltriazine ultraviolet absorber: 13 parts by mass (product name: TINUVIN479, BASF)
・Hindered amine light stabilizer: 8 parts by mass (product name: TINUVIN123, BASF)
・Anti-blocking agent: 9 parts by mass (silica particles, average particle size 3 μm)
・Curing agent: 25 parts by mass (hexamethylene diisocyanate)

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 ink for the design layer is a thermosetting resin containing an acrylic resin and a vinyl chloride-vinyl acetate copolymer, and the mass ratio of the acrylic resin and the vinyl chloride-vinyl acetate copolymer is 8:2. Ta. Thereby, a transfer sheet having a release film, a first protective layer, a second protective layer, and a design layer in this order in the thickness direction was obtained.

(2) Preparation of evaluation member Apply heat-sensitive adhesive (base resin: Aronmelt PES-320SK (Toagosei Co., Ltd.), curing agent: Coronate L (Tosoh Corporation), main resin: curing agent = 100 to the surface of the design layer side of the transfer sheet. :11, mass ratio) was applied and dried to form an adhesive layer with a thickness of 30 μm. Next, the transfer sheet on which the adhesive layer was formed was cured at 150° C. for 1 minute. An aluminum plate (thickness: 0.8 mm) was prepared as a base, and the surface was subjected to alumite treatment. The transfer sheet is placed so as to face the substrate via the adhesive layer, and passed between the rolls of a roll laminator (laminate temperature: 160°C, lamination pressure: 5 kgf/m ² ). A laminated member having an adhesive layer and a substrate was obtained. The release film was peeled off from the obtained laminated member. Thereby, an evaluation member (laminate) having the first protective layer, the second protective layer, the design layer, the adhesive layer, and the base in this order in the thickness direction was obtained.

[Example 2]
An evaluation member was obtained in the same manner as in Example 1 except that the following composition for forming the first protective layer was used.
<Composition for forming first protective layer>
- Ionizing radiation curable resin composition: 100 parts by mass Trifunctional caprolactone urethane acrylate: 20 parts by mass (weight average molecular weight/number of functional groups = approximately 1200)
Bifunctional urethane acrylate A: 60 parts by mass (weight average molecular weight/number of functional groups = approximately 300)
Bifunctional urethane acrylate B: 20 parts by mass (weight average molecular weight/number of functional groups = approximately 400)
・Hydroxyphenyltriazine ultraviolet absorber: 2 parts by mass (product name: TINUVIN479, BASF)
・Light stabilizer having a reactive functional group: 2 parts by mass (product name: Sanol LS-3410, Nippon Nyukazai Co., Ltd.)

[Example 3]
An evaluation member was obtained in the same manner as in Example 1 except that the following composition for forming the first protective layer was used.
<Composition for forming first protective layer>
- Ionizing radiation curable resin composition: 100 parts by mass Trifunctional caprolactone urethane acrylate: 20 parts by mass (weight average molecular weight/number of functional groups = approximately 1200)
Bifunctional urethane acrylate A: 70 parts by mass (weight average molecular weight/number of functional groups = approximately 300)
Bifunctional urethane acrylate B: 10 parts by mass (weight average molecular weight/number of functional groups = approximately 400)
・Hydroxyphenyltriazine ultraviolet absorber: 2 parts by mass (product name: TINUVIN479, BASF)
・Light stabilizer having a reactive functional group: 2 parts by mass (product name: Sanol LS-3410, Nippon Nyukazai Co., Ltd.)

[Example 4]
An evaluation member was obtained in the same manner as in Example 1 except that the following composition for forming the first protective layer was used.
<Composition for forming first protective layer>
- Ionizing radiation curable resin composition: 100 parts by mass Trifunctional caprolactone urethane acrylate: 50 parts by mass (weight average molecular weight/number of functional groups = approximately 1200)
Bifunctional urethane acrylate: 50 parts by mass (weight average molecular weight/number of functional groups = approximately 3000)
・Hydroxyphenyltriazine ultraviolet absorber: 2 parts by mass (product name: TINUVIN479, BASF)
・Light stabilizer having a reactive functional group: 2 parts by mass (product name: Sanol LS-3410, Nippon Nyukazai Co., Ltd.)

[Comparative example 1]
An evaluation member was obtained in the same manner as in Example 1 except that the following composition for forming the first protective layer was used.
<Composition for forming first protective layer>
- Ionizing radiation curable resin composition: 100 parts by mass Hexafunctional caprolactone-based urethane acrylate: 60 parts by mass (weight average molecular weight/number of functional groups = approximately 150)
Bifunctional caprolactone urethane acrylate: 40 parts by mass (weight average molecular weight/number of functional groups = approximately 2000)
・Hydroxyphenyltriazine ultraviolet absorber: 2 parts by mass (product name: TINUVIN479, BASF)
・Light stabilizer having a reactive functional group: 2 parts by mass (product name: Sanol LS-3410, Nippon Nyukazai Co., Ltd.)

[Comparative example 2]
An evaluation member was obtained in the same manner as in Example 1 except that the following composition for forming the first protective layer was used.
<Composition for forming 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 = approximately 3000)
・Hydroxyphenyltriazine ultraviolet absorber: 2 parts by mass (product name: TINUVIN479, BASF)
・Light stabilizer having a reactive functional group: 2 parts by mass (product name: Sanol LS-3410, Nippon Nyukazai Co., Ltd.)

[Erichsen indentation depth measurement]
The Erichsen indentation depth of the evaluation member (laminate) obtained in each Example and each Comparative Example was determined. Specifically, using an Erichsen type film tester (manufactured by Toyo Seiki Seisakusho), the test material was applied to the base (aluminum plate) side of the evaluation member (size: 100 mm x 100 mm) in an environment of 23°C ± 5°C. When a spherical punch (diameter: 20 mm) was gradually pushed in (speed: 10 mm/min) and observed with an optical microscope (Keyence VHX-6000, magnification: 500 times), a crack occurred in the first protective layer. The travel distance of the punch (the depth of the indentation) was defined as the Erichsen indentation depth. The results are shown in Table 1.

[Evaluation of three-dimensional workability]
The three-dimensional workability of the evaluation members obtained in each Example and each Comparative Example was evaluated. Specifically, the evaluation member was subjected to a bending test at a bending angle of 1 mmR, the first protective layer at the bent portion was observed with a microscope, and evaluated based on the following criteria. The results are shown in Table 1.
A: No scratches or cracks were observed.
B: Very slight scratches or cracks were observed.
C: Scratches or cracks were clearly observed.

[Evaluation of scratch resistance]
The scratch resistance of the evaluation members obtained in each Example and each Comparative Example was evaluated. Specifically, the surface of the first protective layer in the evaluation member was rubbed 10 times with Bonstar steel wool #0000 under a load of 0.2 kg/cm ² . Thereafter, it was visually observed and evaluated based on the following criteria. The results are shown in Table 1.
A: No scratches were observed.
B: Minor scratches were observed.
C: Significant scratches were observed.

As shown in Table 1, in each Example, the Erichsen indentation depth was within a predetermined range, and the three-dimensional workability and scratch resistance were good. On the other hand, in Comparative Example 1, the Erichsen indentation depth was small and the three-dimensional workability was insufficient. Further, in Comparative Example 2, although the Erichsen indentation depth was large and the three-dimensional workability was good, the scratch resistance was insufficient. In this way, by setting the Erichsen indentation depth within a predetermined range, it was possible to achieve both three-dimensional workability and scratch resistance.

1... Release film 2... First protective layer 3... Second protective layer 4... Design layer 10... Transfer sheet 20... Base 100... Exterior member

Claims (17)

A transfer sheet used for manufacturing an exterior member having a base,
The transfer sheet includes 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 the thickness direction,
When the transfer layer in the transfer sheet is transferred to the evaluation substrate via the adhesive layer and the release film is peeled off to produce a laminate, the Erichsen indentation depth of the laminate is 7 mm or more. A transfer sheet that is 11 mm or less. The transfer sheet according to claim 1, wherein the base has a three-dimensional shape. The transfer sheet according to claim 1 or 2, wherein the base is a metal member. 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. The transfer sheet according to any one of claims 1 to 4, wherein the first protective layer contains a triazine-based ultraviolet absorber. 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. The transfer sheet according to any one of claims 1 to 6, wherein the second protective layer contains a triazine-based ultraviolet absorber. The transfer sheet according to any one of claims 1 to 7, wherein the first protective layer contains a cured product of an ionizing radiation-curable resin composition. The transfer sheet according to any one of claims 1 to 8, wherein the second protective layer contains a cured product of a thermosetting resin composition. The transfer sheet according to any one of claims 1 to 9, wherein the transfer sheet has a design layer on a surface of the second protective layer opposite to the first protective layer. A method for manufacturing an exterior member having a base, the method comprising:
A preparation step of preparing a transfer sheet according to any one of claims 1 to 10;
a contacting step of arranging the surface of the transfer sheet on the second protective layer side and the base body so as to face each other, and bringing the transfer sheet and the base body into close contact;
A method for manufacturing an exterior member, comprising: 12. The method for manufacturing an exterior member according to claim 11, wherein in the adhesion step, an adhesive layer is disposed between the surface of the transfer sheet on the second protective layer side and the base body. The adhesion step is
an adhesive layer forming process for forming the adhesive layer;
a contact treatment for bringing the transfer sheet, the adhesive layer, and the substrate into close contact;
The exterior member according to claim 12, wherein in the adhesive layer forming process, an adhesive layer coating liquid is applied to the surface of the transfer sheet on the second protective layer side to form the adhesive layer. manufacturing method. The adhesion step is
The method for manufacturing an exterior member according to claim 13, further comprising a supplying process of supplying the transfer sheet from a roll of the transfer sheet before the adhesive layer forming process. The adhesion step is
an adhesive layer forming process for forming the adhesive layer;
a contact treatment for bringing the transfer sheet, the adhesive layer, and the base into close contact;
13. The method for manufacturing an exterior member according to claim 12, wherein in the adhesive layer forming process, an adhesive layer coating liquid is applied to the surface of the base to form the adhesive layer. The method for manufacturing an exterior member according to any one of claims 12 to 15, wherein in the adhering step, the adhesive layer is formed using a heat-sensitive adhesive. having a first protective layer, a second protective layer, an adhesive layer and a base in this order in the thickness direction,
An exterior member having an Erichsen indentation depth of 7 mm or more and 11 mm or less.