Transfer sheet, method for manufacturing a component using the transfer sheet, and component

Abstract

To provide a surface protective transfer sheet which can suppress deterioration in adhesion between a layer and a layer constituting a transfer layer even in outdoor use, is excellent in resistance under an acidic environment, and has excellent weather resistance, and a member using the transfer sheet.SOLUTION: A transfer sheet has a transfer layer on a release film, wherein the transfer layer has a surface protective layer, a primer layer and an adhesive layer in this order from the side of the release film, the surface protective layer contains a cured product of an ionizing radiation-curable resin composition, a contact angle of water on a surface opposite to the primer layer of the surface protective layer is 60° or more, and a change rate of a ratio of an oxygen atom of the surface protective layer is 20% or more.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a weather-resistant surface protection transfer sheet, a method for manufacturing a component using the transfer sheet, and the component. [Background technology]

[0002] BACKGROUND ART So-called transfer sheets have been used conventionally as articles for decorating and protecting the surfaces of interior and exterior building materials, fixtures, furniture, interior and exterior vehicle materials, and the like. A transfer sheet has, for example, a release film and a transfer layer made up of a surface protection layer, a design layer, an adhesive layer, etc. This transfer sheet is adhered to the surface of a substrate such as a member, and then the release film is peeled off to transfer only the transfer layer to the surface of the substrate, thereby imparting a desired function to the surface of the substrate. In order to impart a desired function to the surface of the substrate, the transfer sheet is required to have various properties such as surface properties such as scratch resistance, contamination resistance, and weather resistance, as well as adhesion to the substrate and processability.

[0003] For example, Patent Document 1 proposes a design transfer sheet that includes a design transfer layer releasably attached to a release layer as a transfer sheet for decorating the surface of a substrate. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-120643 Summary of the Invention [Problem to be solved by the invention]

[0005] Typically, a transfer sheet is produced by forming a transfer layer in which a surface protective layer, an adhesive layer, etc. are laminated on a release film. Therefore, each layer constituting the transfer layer must be cured before the next layer is formed. In particular, the so-called surface protective layer, which imparts scratch resistance, weather resistance, etc. to the transfer layer, must be sufficiently cured to prevent the bleed-out of additives such as weathering agents contained in the surface protective layer and to impart sufficient scratch resistance and weather resistance to the surface of the transfer layer after transfer.

[0006] However, in the transfer sheet of Patent Document 1, when a surface protective layer is formed, it is necessary to harden the surface protective layer, which makes it impossible to ensure sufficient adhesion between the surface protective layer and the layer to be laminated next, and this can cause a problem that the adhesion between the layers constituting the transfer layer weakens over time, particularly when used in exterior components, etc. Furthermore, the transfer sheet of Patent Document 1 has poor resistance in acidic environments, and therefore can cause a problem of insufficient weather resistance, particularly in environments where the pH changes significantly, such as when exposed to acid rain.

[0007] The present disclosure has been made in consideration of these circumstances, and aims to provide a surface protection transfer sheet that can suppress a decrease in adhesion between the layers that make up the transfer layer even when used outdoors, has excellent resistance to acidic environments, and has excellent weather resistance, as well as a method for manufacturing a component and a component using the transfer sheet. [Means for solving the problem]

[0008] In order to solve the above problems, the present disclosure provides the following [1] to [6]. [1] A transfer sheet having a transfer layer on a release film, the transfer layer having a surface protection layer, a primer layer, and an adhesion layer in this order from the release film side, the surface protection layer containing a cured product of an ionizing radiation curable resin composition, the surface protection layer having a water contact angle of 60° or more on the surface opposite to the primer layer, and the surface protection layer having a rate of change in the proportion of oxygen atoms of 20% or more as measured by the following method. <Change in ratio of oxygen atoms> After the transfer layer of the transfer sheet and the substrate are adhered to each other, the release film is peeled off to obtain a member, and the surface of the surface protective layer of the member is subjected to a corona treatment. The proportion of oxygen atoms determined by X-ray photoelectron spectroscopy is A O The proportion of oxygen atoms determined by X-ray photoelectron spectroscopy after corona treatment of the surface of the surface protection layer of the member is B O When [Change in the proportion of oxygen atoms (%)] = (B O -A O )×100 / A O [2] The transfer sheet according to [1], wherein the ionizing radiation curable resin composition contains a urethane acrylate oligomer. [3] The transfer sheet according to [1] or [2], wherein the functional group equivalent of the ionizing radiation curable functional group of the ionizing radiation curable compound contained in the ionizing radiation curable resin composition is 50 g / mol or more and 5000 g / mol or less. [4] A method for manufacturing a member, comprising the following steps (1) and (2) in order: Step (1) A step of bringing the surface of the transfer layer side of the transfer sheet according to any one of [1] to [3] into close contact with a substrate. Step (2) is a step of peeling off the release film of the transfer sheet from the closely attached transfer sheet and substrate. [5] A member having a transfer layer on a substrate, the transfer layer having, from the substrate side, an adhesion layer, a primer layer, and a surface protection layer in this order, the surface protection layer containing a cured product of an ionizing radiation curable resin composition, the surface of the surface protection layer having a water contact angle of 60° or more before corona treatment, and the rate of change in the proportion of oxygen atoms determined by X-ray photoelectron spectroscopy after the surface of the surface protection layer of the member is corona treated is 20% or more. [Effects of the Invention]

[0009] According to the present disclosure, it is possible to provide a surface protection transfer sheet and a component using the transfer sheet that can suppress a decrease in adhesion between the layers that make up the transfer layer even when used outdoors, and that has excellent weather resistance and resistance in acidic environments. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a cross-sectional view showing one embodiment of a transfer sheet of the present disclosure. [Figure 2] FIG. 1 is a cross-sectional view of one embodiment of a member of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0011] [Transfer sheet] The transfer sheet of the present disclosure has a transfer layer on a release film, and the transfer layer has, from the release film side, a surface protection layer, a primer layer, and an adhesion layer in this order, the surface protection layer is a transfer sheet containing a cured product of an ionizing radiation curable resin composition, the surface protection layer has a water contact angle of 60° or more on the surface opposite to the primer layer, and the surface protection layer has a rate of change in the proportion of oxygen atoms of 20% or more as measured by the following method. <Change in ratio of oxygen atoms> After the transfer layer of the transfer sheet and the substrate are adhered to each other, the release film is peeled off to obtain a member, and the surface of the surface protective layer of the member is subjected to a corona treatment. The proportion of oxygen atoms determined by X-ray photoelectron spectroscopy is A O The proportion of oxygen atoms determined by X-ray photoelectron spectroscopy after corona treatment of the surface of the surface protection layer of the member is B O When [Change in the proportion of oxygen atoms (%)] = (B O -A O )×100 / A O

[0012] Fig. 1 is a cross-sectional view showing one embodiment of a transfer sheet according to the present disclosure. The transfer sheet 10 of Fig. 1 has a transfer layer 11 on a release film 1. The transfer layer 11 has, in order from the side in contact with the release film 1, a surface protection layer 2, a primer layer 3, and an adhesion layer 4. Although not shown in Fig. 1, the transfer sheet 10 may further have a second release film on the surface of the adhesion layer 4 opposite the release film 1, if necessary. Furthermore, although not shown in Fig. 1, the transfer layer 11 of the transfer sheet 10 may further have other functional layers, if necessary.

[0013] Among the functional layers constituting the transfer layer, the surface protective layer is a layer that imparts functions such as scratch resistance and weather resistance to the member, and is therefore preferably formed on the outermost surface of the member. Since the transfer sheet is usually produced by forming a transfer layer in which several layers are laminated on a release film, it is preferable that the surface protective layer in the transfer layer is formed in contact with the release film. Then, other layers such as a primer layer are formed on the formed surface protective layer.

[0003] Here, the surface protective layer needs to be sufficiently cured to prevent the bleed-out of additives such as weathering agents contained in the surface protective layer and to impart resistance to acidic environments, scratch resistance, and weather resistance to the surface of the member. Therefore, when the surface protective layer contains a cured product of an ionizing radiation-curable resin composition, the chemical and physical interactions between the surface protective layer and a layer such as a primer layer formed on the surface protective layer tend to be weaker, resulting in poor interlayer adhesion. In particular, when the ionizing radiation-curable resin composition is an electron beam-curable resin composition, the curing of the surface protective layer proceeds more easily than when it is an ultraviolet-curable resin composition, resulting in a significant tendency for poor interlayer adhesion.

[0014] When the transfer sheet of the present disclosure is adhered to the transfer layer side of the transfer sheet and a substrate, and then the release film is peeled off to form a component, the change rate in the proportion of oxygen atoms determined by X-ray photoelectron spectroscopy after corona treatment of the surface of the surface protection layer of the component is 20% or more, thereby improving the adhesion between the surface protection layer and the primer layer. The chemical composition of the surface protective layer is generally the same within the layer. Therefore, the change rate of the oxygen atom ratio on the surface of the surface protective layer of a member using the transfer sheet of the present disclosure is generally the same as the change rate of oxygen atoms on the surface of the primer layer side of the surface protective layer before forming the primer layer of the transfer sheet. Therefore, satisfying the change rate of the oxygen atom ratio of the present disclosure allows for the formation of more polar groups on the surface of the surface protective layer of the transfer sheet on the side where the primer layer is to be formed by performing corona treatment before forming the primer layer. Therefore, the so-called wettability of the surface of the surface protective layer can be improved, which improves the adhesion between the surface protective layer and the primer layer and improves the weather resistance of the transfer layer. On the other hand, if the rate of change in the proportion of oxygen atoms is too high, the crosslink density of the surface protective layer tends to decrease, which reduces the hardness of the surface protective layer and the durability of the transfer layer. Therefore, when the transfer sheet of the present disclosure is used as a component, the rate of change in the proportion of oxygen atoms determined by X-ray photoelectron spectroscopy after corona treatment of the surface of the surface protection layer of the component is preferably 23% or more and 70% or less, more preferably 25% or more and 60% or less, even more preferably 28% or more and 55% or less, and even more preferably 30% or more and 50% or less.

[0015] In the present disclosure, the proportions of oxygen atoms and carbon atoms in the surface protective layer can be determined by X-ray photoelectron spectroscopy according to the following procedures (1) to (3). (1) The peak area of ​​each atom was calculated from the peak of each atom obtained by X-ray photoelectron spectroscopy. (2) The peak area of ​​each atom was multiplied by the sensitivity coefficient specific to each atom to determine the abundance of each atom as a relative value. (3) The sum of the relative abundance values ​​of each atom was set to 100, and the proportions of oxygen atoms and carbon atoms were calculated.

[0016] In the transfer sheet of the present disclosure, the rate of change in the proportion of oxygen atoms in the surface protective layer can also be adjusted by the conditions of the corona treatment. For example, in the corona treatment, increasing the corona output tends to increase the rate of change in the proportion of oxygen atoms in the surface protective layer. Also, decreasing the line speed during the corona treatment tends to increase the proportion of oxygen atoms in the surface protective layer.

[0017] Furthermore, the transfer sheet of the present disclosure has a water contact angle of 60° or more on the surface of the surface protective layer opposite the primer layer. In the present disclosure, since the water contact angle of the surface protective layer opposite the primer layer is 60° or more, the surface of the surface protective layer is hydrophobic and has few polar groups such as OH groups. Therefore, even when exposed to an environment where the pH changes significantly due to the adhesion of acid, deterioration of the surface can be suppressed, thereby imparting resistance to acidic environments to the surface protective layer. Furthermore, the surface protective layer can be imparted with contamination resistance and solvent resistance. Therefore, a member using the transfer sheet of the present disclosure can exhibit excellent weather resistance even in an environment where the pH changes significantly, such as when exposed to acid rain. The contact angle of the surface of the surface protection layer in the transfer sheet of the present disclosure opposite the primer layer is preferably 65° or more, more preferably 70° or more, and even more preferably 75° or more, in order to make the surface of the surface protection layer hydrophobic, improve resistance in acidic environments, and further improve contamination resistance and solvent resistance. On the other hand, since the physical properties of the surface protective layer are generally the same within the layer, the contact angle of the surface protective layer before the primer layer of the transfer sheet is formed is generally the same as the contact angle of the surface opposite the primer layer. Therefore, it is preferable that the contact angle of the surface opposite the primer layer of the surface protective layer is easily reduced after corona treatment in order to improve the adhesion between the surface of the surface protective layer in contact with the primer layer and the primer layer, and to improve the weather resistance of the transfer sheet and the member. Therefore, the upper limit of the water contact angle of the surface protective layer opposite the primer layer in the transfer sheet of the present disclosure is preferably 100° or less, more preferably 95° or less, even more preferably 90° or less, and even more preferably 85° or less.

[0018] In the transfer sheet of the present disclosure, on the side of the surface protection layer opposite the primer layer, the contact angle after corona treatment is preferably less than 60°, more preferably 58° or less, and even more preferably 55° or less. Since the physical properties of the surface protective layer are generally the same within the layer, the contact angle of the surface protective layer before the primer layer of the transfer sheet is formed is generally the same as the contact angle of the surface opposite the primer layer. Therefore, by making the contact angle of the surface protective layer opposite the primer layer after corona treatment less than 60°, it is possible to easily improve the adhesion between the surface of the surface protective layer that comes into contact with the primer layer and the primer layer.

[0019] The water contact angle in this disclosure refers to the static contact angle measured by the θ / 2 method after 2 seconds of dropping 1.5 μL of pure water onto the surface protection layer.

[0020] <Release film> The release film is a layer that is releasably laminated on the transfer layer among the layers that make up the transfer sheet, and is peeled off from the transfer layer after the transfer layer is transferred to the surface of the substrate.

[0021] The release film is preferably a heat-resistant plastic film that can be peelably laminated to the transfer layer in order to improve the processability of the transfer sheet in the transfer step. Examples of plastic films used as release films include polyester films such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polyamide films such as nylon 6 and nylon 66; and polyimide films. Of these, polyester films are preferred, and among polyester films, polyethylene terephthalate is more preferred.

[0022] The thickness of the release film is not particularly limited, but in order to improve the handleability of the transfer sheet, it is preferably from 10 μm to 200 μm, more preferably from 15 μm to 150 μm, and even more preferably from 20 μm to 100 μm.

[0023] <Transfer layer> In the present disclosure, the transfer layer is a layer that is transferred onto the surface of a substrate, and has the role of imparting a predetermined function to the surface of the substrate. The transfer layer of the transfer sheet of the present disclosure has at least a surface protection layer, a primer layer, and an adhesion layer in this order from the release film side.

[0024] The transfer layer may further include other functional layers, such as an adhesive layer, an antiglare layer, an antifouling layer, a stress relaxation layer, an antistatic layer, a gas barrier layer, an antifogging layer, and a transparent conductive layer.

[0025] (Surface protective layer) The transfer sheet of the present disclosure has a surface protective layer on the transfer layer. The surface protective layer in the present disclosure is a layer formed to impart durability to the transfer layer, such as resistance to an acidic environment, scratch resistance, weather resistance, etc. Other durability required of the surface protective layer includes resistance to contamination by various substances such as mud.

[0026] In the present disclosure, the surface protective layer preferably contains a cured product of a curable resin composition as a resin component to improve resistance in an acidic environment and improve scratch resistance. The proportion of the cured product of the curable resin composition is preferably 70% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass, based on the total resin components constituting the surface protective layer.

[0027] As the cured product of the curable resin composition, a cured product of an ionizing radiation curable resin composition is used in order to improve the resistance of the surface protective layer in an acidic environment, the scratch resistance, and the weather resistance, as well as the processability of the transfer sheet. Examples of ionizing radiation curable resin compositions include electron beam curable resin compositions and ultraviolet curable resin compositions, and among these, electron beam curable resin compositions are preferred because they do not require a polymerization initiator, have less odor, and are less likely to be discolored. Furthermore, when the surface protective layer contains an ultraviolet absorber, electron beam curable resin compositions are preferred because they tend to increase the crosslink density of the cured product layer and tend to improve scratch resistance and contamination resistance.

[0028] 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 undergoes crosslinking and curing upon irradiation with ionizing radiation, and preferred examples include functional groups having an ethylenic double bond, such as a (meth)acryloyl group, a vinyl group, and an allyl group. In this specification, the term "(meth)acryloyl group" refers to an acryloyl group or a methcroyl group. In addition, in this specification, the term "(meth)acrylate" refers to an acrylate or a methacrylate. Furthermore, ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Typically, ultraviolet (UV) rays or electron beams (EB) are used, but it also includes other electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams. Specifically, the ionizing radiation curable compound can be appropriately selected from polymerizable monomers and polymerizable oligomers that have been conventionally used as ionizing radiation curable resins.

[0029] As the polymerizable monomer, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferred, and among them, a polyfunctional (meth)acrylate monomer is preferred. Here, "(meth)acrylate" means "acrylate or methacrylate." Examples of polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule, and having at least a (meth)acryloyl group as the functional group.

[0030] Examples of polymerizable oligomers include (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule, and having at least a (meth)acryloyl group as the functional group, such as urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers. Further examples of polymerizable oligomers include highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain, aminoplast resin (meth)acrylate oligomers obtained by modifying aminoplast resins having many reactive groups in a small molecule, and oligomers having cationically polymerizable functional groups in the molecule, such as novolac epoxy resins, bisphenol epoxy resins, aliphatic vinyl ethers, and aromatic vinyl ethers.

[0031] These polymerizable oligomers may be used alone or in combination of two or more. In order to improve the processing characteristics of the transfer sheet and the scratch resistance and weather resistance of the surface protective layer, one or more selected from urethane (meth)acrylate oligomer, epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer, polyether (meth)acrylate oligomer, polycarbonate (meth)acrylate oligomer, and acrylic (meth)acrylate oligomer are preferred, one or more selected from urethane (meth)acrylate oligomer and polycarbonate (meth)acrylate oligomer are more preferred, urethane (meth)acrylate oligomer is even more preferred, and it is even more preferred that the polymerizable oligomer contains a urethane acrylate oligomer.

[0032] In the present disclosure, the weight-average molecular weight (Mw) of the ionizing radiation-curable compound is preferably 1,000 or more and 10,000 or less, and more preferably 2,000 or more and 10,000 or less. That is, the ionizing radiation-curable compound is preferably an oligomer. When the weight-average molecular weight is within the above range, the composition for forming the surface protective layer has appropriate thixotropy, which makes it easy to form the surface protective layer with excellent processability. Furthermore, the surface protective layer can be easily improved in resistance to acidic environments, scratch resistance, and weather resistance. In this specification, the weight average molecular weight is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

[0033] In the present disclosure, the number of functional groups of the ionizing radiation-curable compound is preferably 2 to 20, more preferably 2 to 18, and even more preferably 2 to 15. By making the number of functional groups of the ionizing radiation-curable compound 2 or more, the resistance in acidic environments, scratch resistance, and weather resistance of the surface protective layer can be easily improved. Furthermore, by making the number of functional groups of the ionizing radiation-curable compound 20 or less, it is possible to prevent the surface protective layer from having too many crosslinking points, which makes it easier to increase the proportion of carbon-carbon single bonds contained in the surface protective layer and facilitates the introduction of oxygen atoms into the surface protective layer by corona treatment. As a result, it is easier to improve the adhesion between the surface protective layer and the primer layer, and it is easier to improve the weather resistance of the resulting transfer sheet and member.

[0034] In the present disclosure, the functional group equivalent weight of the ionizing radiation-curable functional group of the ionizing radiation-curable compound is preferably 50 g / mol or more and 5000 g / mol or less, more preferably 100 g / mol or more and 4500 g / mol or less, even more preferably 200 g / mol or more and 4000 g / mol or less, and still more preferably 300 g / mol or more and 3000 g / mol or less. A functional group equivalent of 50 g / mol or more can prevent the surface protective layer from having too many crosslinking points, which can increase the proportion of carbon-carbon single bonds contained in the surface protective layer and facilitate the introduction of oxygen atoms into the surface protective layer by corona treatment. This can facilitate improving the adhesion between the surface protective layer and the primer layer, and can facilitate improving the weather resistance of the resulting transfer sheet and member. Furthermore, a functional group equivalent of 5000 g / mol or less can facilitate improving the resistance, scratch resistance, and weather resistance of the surface protective layer in an acidic environment. In the present disclosure, the functional group equivalent of the ionizing radiation-curable functional group of the ionizing radiation-curable compound is determined by dividing the molecular weight or weight-average molecular weight of the ionizing radiation-curable compound by the number of ionizing radiation-curable functional groups per molecule.

[0035] When the ionizing radiation curable compound is an ultraviolet curable compound, it is preferable to contain additives such as a photopolymerization initiator and a photopolymerization accelerator. The photopolymerization initiator may be one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzil dimethyl ketal, benzoyl benzoate, α-acyloxime ester, acylphosphine oxide, thioxanthones, and the like. The photopolymerization accelerator can reduce polymerization inhibition caused by air during curing and increase the curing rate, and examples thereof include one or more selected from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc.

[0036] The surface protective layer may contain other additives as needed, as long as the effects of the present disclosure are not impaired. Examples of other additives that can be used include ultraviolet absorbers, light stabilizers, antioxidants, organic particles, and inorganic particles.

[0037] As the ultraviolet absorber contained in the surface protective layer, a triazine-based ultraviolet absorber is preferred, and a hydroxyphenyltriazine-based ultraviolet absorber is preferred, since it is easy to prevent the ultraviolet absorber from bleeding out from the surface protective layer and can impart long-term weather resistance to the transfer layer of the transfer sheet. Examples of hydroxyphenyltriazine-based ultraviolet absorbers include 2-(2-hydroxyphenyltriazine) 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-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine ]-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-1,3,5-triazin-2-yl)-5[2-(2-ethylhexanoyloxy)ethoxy]phenol, and the like are preferably exemplified, and these may be used alone or in combination of two or more.

[0038] The content of the ultraviolet absorber in the surface protective layer is preferably 0.5 to 10 parts by mass, more preferably 0.8 to 8 parts by mass, and even more preferably 1 to 5 parts by mass, per 100 parts by mass of the ionizing radiation-curable compound. By including an ultraviolet absorber content of 0.5 parts by mass or more, the ultraviolet absorber is less likely to bleed out, sufficient ultraviolet absorption ability is more likely to be obtained, and the weather resistance of the surface protective layer can be improved. Furthermore, by including an ultraviolet absorber content of 10 parts by mass or less, the crosslink density of the surface protective layer is less likely to decrease, and durability can be more easily improved.

[0039] The light stabilizer contained in the surface protective layer is preferably a hindered amine light stabilizer. Examples of the hindered amine light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, and 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine).

[0040] The content of the light stabilizer in the surface protective layer is preferably from 1 to 10 parts by mass, more preferably from 1.5 to 8 parts by mass, and even more preferably from 2 to 5 parts by mass, relative to 100 parts by mass of the ionizing radiation-curable compound. If the content of the light stabilizer is within the above range, the light stabilizer does not bleed out and sufficient light stability is obtained, resulting in excellent weather resistance.

[0041] The thickness of the surface protective layer is preferably 2 μm or more and 20 μm or less, more preferably 3 μm or more and 18 μm or less, and even more preferably 4 μm or more and 16 μm or less, in order to improve the processability of the transfer sheet and the scratch resistance and weather resistance of the surface protective layer.

[0042] (primer layer) The transfer sheet of the present disclosure has a primer layer in the transfer layer. The primer layer is formed between the above-mentioned surface protective layer and the below-described adhesion layer. By forming the primer layer between the surface protective layer and the adhesion layer, it is possible to improve adhesion between the layers constituting the transfer layer, and to improve the weather resistance and durability of the transfer layer.

[0043] The primer layer preferably contains a cured product of a curable resin composition in order to improve the processability of the transfer sheet and the adhesion between the layers contained in the transfer layer. The cured product of the curable resin composition contained in the primer layer preferably contains a cured product of a thermosetting resin composition in order to improve adhesion between the layers contained in the transfer layer. A thermosetting resin composition is a composition containing at least a thermosetting resin and is a resin composition that cures when heated. Examples of thermosetting resins include acrylic resins, urethane resins, urethane acrylic resins, phenolic resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins, which can be used alone or in combination. In addition, the thermosetting resin composition may be one in which a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent is added to these resins.

[0044] As the cured product of the thermosetting resin composition contained in the primer layer, in order to improve the processability of the transfer sheet and the adhesion between the layers contained in the transfer layer, a cured product of a thermosetting resin composition containing an acrylic resin, a urethane resin, or a urethane acrylic resin is more preferable, and a cured product of a thermosetting resin composition containing a urethane acrylic resin is even more preferable. Furthermore, in order to improve the processability of the transfer sheet and the adhesion between the layers contained in the transfer layer, the cured product of the thermosetting resin composition contained in the primer layer preferably contains an isocyanate-based curing agent or an epoxy-based curing agent, and more preferably contains an isocyanate-based curing agent.

[0045] Furthermore, when the primer layer contains a urethane acrylic resin, the urethane acrylic resin is preferably an acrylic urethane copolymer, and more preferably a polycarbonate-based acrylic urethane copolymer. When the primer layer contains a polycarbonate-based acrylic urethane copolymer, adhesion between the layers constituting the transfer layer can be easily improved, and the weather resistance and durability of the transfer layer can be easily improved. The polycarbonate-based urethane acrylic copolymer is a resin obtained by radically polymerizing an acrylic monomer using a polycarbonate-based polyurethane polymer obtained by reacting a polycarbonate diol with a (di)isocyanate as a radical polymerization initiator.

[0046] Examples of (di)isocyanates include aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 1,5-naphthalene diisocyanate, n-isocyanatephenylsulfonyl isocyanate, o-isocyanatephenylsulfonyl isocyanate, and p-isocyanatephenylsulfonyl isocyanate; aliphatic isocyanates such as 1,6-hexamethylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate, as well as their adducts and polymers, which may be used alone or in combination of two or more. Among these, aliphatic isocyanates such as hexamethylene diisocyanate and alicyclic isocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate are preferred for improving the weather-resistant adhesion of the transfer layer.

[0047] Examples of acrylic monomers include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and other (meth)acrylic acid alkyl esters, which can be used alone or in combination of two or more.

[0048] In the present disclosure, when the primer layer contains a polycarbonate-based urethane acrylic copolymer, the mass ratio of the urethane component to the acrylic component of the polycarbonate-based urethane acrylic copolymer, [urethane component] / [acrylic component], is preferably 75 / 25 or more and 95 / 5 or less, and more preferably 80 / 20 or more and 90 / 10 or less. By keeping the [urethane component] / [acrylic component] within the above range, it is possible to easily improve the adhesion between the layers that make up the transfer layer, and it is easy to improve the weather resistance and durability of the transfer layer.

[0049] The primer layer may contain other additives as needed, as long as they do not impair the effects of the present invention. As other additives, for example, ultraviolet absorbers, antioxidants, light stabilizers, organic particles, inorganic particles, etc. are preferably used. As the ultraviolet absorber, the ultraviolet absorbers exemplified in the above-mentioned surface protective layer can be suitably used. Furthermore, as the light stabilizer, the light stabilizers exemplified in the above-mentioned surface protective layer can be suitably used.

[0050] The thickness of the primer layer is preferably 2 μm to 10 μm, more preferably 3 μm to 8 μm, and even more preferably 3 μm to 5 μm, in order to improve the processability of the transfer sheet and the weather-resistant adhesion of the transfer layer.

[0051] (adhesion layer) The transfer sheet of the present disclosure has an adhesion layer on the transfer layer. The adhesion layer is formed on the above-mentioned primer layer. The adhesion layer in the present disclosure is formed to improve adhesion between the substrate constituting the member and the transfer layer of the transfer sheet.

[0052] In the present disclosure, the adhesion layer preferably contains a cured product of a thermosetting resin composition or a thermoplastic resin, more preferably a thermoplastic resin, in order to improve adhesion between the substrate constituting the exterior component and the transfer layer.

[0053] The thermosetting resin is preferably one containing a composition that has the property of crosslinking due to a chemical reaction caused by heat, and examples thereof include two-component curing urethane resins, polyester urethane resins, polyether urethane resins, acrylic resins, polyester resins, polyamide resins, polyvinyl acetate resins, epoxy resins, rubber resins, etc. The urethane resin that constitutes the two-component curing urethane resin is a polyurethane that uses polyol (polyhydric alcohol) as the main component and isocyanate as the crosslinking agent (curing agent).

[0054] Examples of thermoplastic resins include acrylic resins, polyacrylic polyols, urethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, styrene-acrylic copolymers, acrylic-vinyl acetate copolymers, polyester resins, amide resins, cyanoacrylate resins, and epoxy resins. These can be used alone or in combination. Among these, acrylic resins, polyacrylic polyols, urethane resins, and vinyl chloride-vinyl acetate copolymers are preferred in order to improve the processability when forming a member using a transfer sheet, the adhesion between the transfer layer of the transfer sheet and the substrate, and the weather-resistant adhesion of the member. These resins can be used alone or as a mixed resin combining two or more types. Mixed resins of acrylic resin and vinyl chloride-vinyl acetate copolymer, and mixed resins of polyacrylic polyol and urethane resin are more preferred.

[0055] In addition, when a thermoplastic resin is used for the adhesive layer, it is preferable that the adhesive layer further contains a curing agent. By containing a curing agent, the crosslink density of the adhesive layer can be increased, which makes it easier to improve the interlayer adhesion and weather resistance of the transfer layer, and makes it easier to improve the weather-resistant adhesion of the member. When a thermoplastic resin is used, the curing agent is preferably an isocyanate-based curing agent, such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, or trimethylhexamethylene diisocyanate. When a thermoplastic resin is used, the content of the curing agent is preferably 5 parts by mass or more and 60 parts by mass or less, and more preferably 15 parts by mass or more and 45 parts by mass or less, per 100 parts by mass of the thermoplastic resin. By setting the content of the curing agent to 5 parts by mass or more, the crosslink density of the adhesion layer can be increased, which makes it easier to improve the weather-resistant adhesion of the member. Furthermore, by setting the content of the curing agent to 60 parts by mass or less, the flexibility of the adhesion layer can be ensured, which makes it easier to improve the adhesion between the transfer layer of the member and the substrate, which makes it easier to improve the weather-resistant adhesion of the member. Furthermore, it makes it easier to suppress the occurrence of blocking when winding up the transfer sheet.

[0056] The weight-average molecular weight of the thermoplastic resin is preferably 10,000 or more and 200,000 or less, preferably 20,000 or more and 150,000 or less, and more preferably 30,000 or more and 120,000 or less. When the weight-average molecular weight of the thermoplastic resin composition is within the above range, the coating suitability is improved, and it is easy to form an adhesive layer in a good condition. Furthermore, when an exterior component is manufactured using the exterior transfer sheet of the present disclosure, it is easy to improve the adhesion between the adhesive layer and the substrate, and it is easy to improve the durability of the component.

[0057] In the present disclosure, the adhesion layer may further contain a colorant. When the adhesion layer contains a colorant, it is possible to impart design properties to the transfer layer. The colorant is not particularly limited, and examples thereof include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, nickel azo complex, phthalocyanine blue, and azomethine azo black; metal pigments such as flaky flakes of aluminum, brass, and the like; and pearlescent pigments such as flaky flakes of titanium dioxide-coated mica and basic lead carbonate, and the like.

[0058] When the adhesive layer contains a colorant, the content of the colorant is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and even more preferably 20 parts by mass or more and 70 parts by mass or less, relative to 100 parts by mass of the resin constituting the adhesive layer. When the content of the colorant is 5 parts by mass or more, the design property of the member can be further improved when forming the member. Further, when the content of the colorant is 90 parts by mass or less, it is easy to suppress the decrease in the adhesion between the adhesion layer and the base material due to the colorant, and when forming the member, it is easy to form a more durable transfer layer.

[0059] Further, the adhesion layer may contain other additives as necessary as long as the effects of the present disclosure are not impaired. Examples of other additives include extender pigments, solvents, ultraviolet absorbers, antioxidants, light stabilizers, and the like. Further, as the ultraviolet absorber, the ultraviolet absorber presented in the above surface protection layer can be preferably used. Further, as the light stabilizer, the light stabilizer presented in the above surface protection layer can be preferably used.

[0060] The thickness of the adhesion layer is preferably 2 μm or more and 10 μm or less, more preferably 3 μm or more and 8 μm or less, and still more preferably 3 μm or more and 7 μm or less. When the thickness of the adhesion layer is 2 μm or more, the adhesion between the transfer layer and the base material can be improved when forming the member. Further, when the thickness of the adhesion layer is 10 μm or less, it is easy to suppress the strain of the transfer layer caused by the softening of the adhesion layer under a high temperature environment, so it is easy to prevent the weather resistance adhesion from decreasing.

[0061] <Second release film> The transfer sheet of the present disclosure may further have a second release film on the surface opposite to the release film of the transfer layer. By having the second release film on the transfer sheet of the present disclosure, it is easy to prevent blocking when winding the transfer sheet into a roll during production, and it is easy to prevent the transfer sheet from accidentally sticking to other objects.

[0062] When the peel strength between the release film and the transfer layer is defined as P1 and the peel strength between the second release film and the transfer layer is defined as P2, it is preferable that P2 < P1. By P2 < P1, it is easy to peel the second release film before the release film. In this specification, the peel strength can be measured in accordance with the 180-degree peel test of JIS Z 0237:2009.

[0063] The second release film is not particularly limited as long as it can be peeled from the transfer layer, and a plastic film is preferably used. The plastic film used as the second release film can be the same as those exemplified for the release film described above. Among the plastic films exemplified above, polyester films are preferred to improve the handleability of the transfer sheet, and among polyester films, polyethylene terephthalate films are particularly preferred.

[0064] The surface of the second release film that comes into contact with the transfer layer is preferably treated with a release agent or the like. As the release agent, known release agents such as fluorine-based release agents and silicone-based release agents can be used. By treating the second release film with a release agent or the like, the relationship between the peel strength P1 and the peel strength P2 can be adjusted to P2. <P1にしやすくできる。

[0065] The thickness of the second release film is not particularly limited, but in order to improve the handleability of the transfer sheet, it is preferably 10 μm or more and 200 μm or less, more preferably 15 μm or more and 150 μm or less, and even more preferably 20 μm or more and 100 μm or less.

[0066] <Transfer sheet manufacturing method> The method for producing a transfer sheet according to the present disclosure includes at least a surface protection layer forming step, a primer layer forming step, and an adhesion layer forming step.

[0067] (Surface protective layer formation process) The surface protective layer forming step is a step of forming a surface protective layer on a release film. The surface protective layer can be formed by applying a composition for forming the surface protective layer by a known method such as gravure printing, bar coating, roll coating, reverse roll coating, or comma coating, drying the applied composition as needed, and curing the applied composition by irradiating it with ionizing radiation such as an electron beam. Furthermore, before forming the primer layer in the primer layer forming step described below, it is preferable to subject the surface of the formed surface protective layer to a corona treatment in order to improve adhesion between the surface protective layer and the primer layer.

[0068] (Primer layer formation process) The primer layer forming step is a step of forming a primer layer on the surface protective layer formed in the surface protective layer forming step. The primer layer can be formed by applying a composition for forming the primer layer by a known method such as gravure printing, bar coating, roll coating, reverse roll coating, or comma coating, and then drying and curing the composition as necessary.

[0069] (Adhesion layer formation process) The adhesion layer forming step is a step of forming an adhesion layer on the primer layer formed in the primer layer forming step. The adhesion layer can be formed by applying a composition for forming the adhesion layer by a known method such as gravure printing, bar coating, roll coating, reverse roll coating, or comma coating, and drying and curing the applied composition as necessary.

[0070] (Second release film forming step) The second release film forming step is a step of forming a second release film on the surface of the transfer layer opposite to the release film, and can be performed by, for example, a known lamination method. Furthermore, the method may include a step of subjecting one surface of the second release film to a release treatment prior to the second release film forming step. The release treatment can be performed using a known coating method, such as gravure coating.

[0071] <Mechanism of manufacturing components> A member using the transfer sheet of the present disclosure can be produced by using the transfer sheet of the present disclosure and transferring the transfer layer of the transfer sheet to a substrate.

[0072] (base material) The substrate is not particularly limited, and may be selected appropriately depending on the intended use from resin, paper, nonwoven or woven fabric, wood, metal, nonmetallic inorganic material, etc. When a resin is used as the substrate, physical or chemical surface treatment such as oxidation or roughening may be applied to one or both sides of the substrate as desired to improve adhesion between the transfer layer of the transfer sheet and the substrate. Metals used for the metal plate include metal materials such as iron, aluminum, and copper, which may be subjected to surface treatment such as hot-dip galvanizing or electrogalvanizing. The shape of the substrate is not particularly limited, and may be a flat plate such as a sheet, or may have a three-dimensional shape such as a curved plate or a polygonal pillar.

[0073] The substrate preferably has an adhesive layer on the surface thereof in order to improve adhesion between the transfer layer of the transfer sheet and the substrate. The resin contained in the adhesive layer of the substrate is exemplified by the same resins as those in the adhesion layer of the transfer sheet, and the preferred ranges are also the same. The resins used in the adhesive layer of the substrate and the design layer of the transfer layer may be the same or different resins, but it is preferable to use the same resin in order to easily improve the adhesion between the substrate and the transfer layer. In addition, when the substrate includes an adhesive layer, it is preferable to further include a primer layer between the substrate and the adhesive layer.By including the primer layer, it is possible to easily improve the adhesion between the substrate and the adhesive layer, and therefore it is possible to easily improve the durability and weather resistance of the member.Examples of the primer layer of the substrate include those similar to the primer layer of the transfer sheet described above, and the preferred range is also the same.

[0074] The method for producing a member according to the present disclosure includes the following steps (1) and (2) in this order. Step (1) is a step of bringing the transfer layer side of the transfer sheet of the present disclosure into close contact with a substrate. Step (2) is a step of peeling off the release film of the transfer sheet from the closely attached transfer sheet and substrate.

[0075] One embodiment of the above step (1) is, for example, a lamination method having the following steps (a1) and (a2) in order: (a1) A step of contacting and superposing the transfer layer side of the transfer sheet on a flat substrate. (a2) A step of applying heat and pressure from the release film side of the transfer sheet to bring the substrate on the flat plate and the transfer layer of the transfer sheet into close contact with each other.

[0076] The steps (a1) and (a2) can be carried out by a lamination method using heat and pressure in combination with a roll transfer device or the like.

[0077] In step (a2), the lamination roll temperature of the roll transfer device is preferably 200°C or lower, more preferably 180°C or lower. By setting the lamination roll temperature to 200°C or lower, it becomes easier to prevent the transfer layer of the transfer sheet from softening more than necessary, and the transfer layer can be transferred to the substrate in good condition. Furthermore, the lower limit of the lamination roll temperature of the roll transfer device in step (a2) is not particularly limited as long as the transfer layer of the transfer sheet and the substrate are in close contact, but is usually 100°C or higher, preferably 110°C or higher, and more preferably 120°C or higher.

[0078] Another embodiment of the above (1) is, for example, an in-mold molding method having the following steps (z1) to (z4) in order. (z1) A step of placing the transfer layer side of the transfer sheet described above facing the inside of the in-mold forming die. (z2) A step of injecting a resin into the in-mold molding die. (z3) A step of integrating the transfer sheet and the resin to bring the transfer layer of the transfer sheet and the resin into close contact with each other, thereby forming a resin molded body. (z4) A step of removing the resin molded body from the in-mold molding die.

[0079] Furthermore, when the above-mentioned adhesive layer or bonding layer contains a curing agent, it is preferable to have the following step (3) after the above step (2) in order to promote curing of the adhesive layer or bonding layer. (3) Aging step for a predetermined time at a certain temperature.

[0080] The aging temperature is preferably 70°C or lower, and more preferably 65°C or lower. By setting the temperature at 70°C or lower, the curing reaction of the adhesion layer or adhesive layer etc. proceeds slowly, and rapid shrinkage associated with the curing reaction can be prevented. The lower limit of the aging temperature varies depending on the configuration of the adhesion layer or adhesive layer etc., but is usually 40°C or higher in order to promote the curing reaction of the thermosetting resin composition etc. contained in the adhesion layer or adhesive layer. The aging time varies depending on the structure of the adhesive layer or the bonding layer, etc., or the temperature conditions for aging, but is usually 12 hours or more, preferably 18 hours or more, more preferably 24 hours or more, and even more preferably 36 hours or more.

[0081] In addition, the member of the present disclosure preferably has an adhesive layer between the transfer layer and the substrate to further improve adhesion between the transfer layer and the substrate. The adhesive layer may be formed in advance on the transfer layer of the transfer sheet, or on the surface of the substrate, or both. When an adhesive layer is formed on the surface of the substrate, it is preferable to further include the following step (o1) before the above step (1). (o1) A step of forming an adhesive layer on a substrate.

[0082] Furthermore, when the transfer sheet described above has a second release film on the surface of the transfer layer opposite to the release film side, it is preferable to have the following step (o2) before the above step (1). (o2) A step of peeling off the second release film from the transfer sheet to expose the transfer layer.

[0083] [Component] The member of the present disclosure is a member having a transfer layer on a substrate, and the transfer layer has, from the substrate side, an adhesion layer, a primer layer, and a surface protection layer in this order, the surface protection layer contains a cured product of an ionizing radiation curable resin composition, the surface of the surface protection layer has a water contact angle of 60° or more, and the rate of change in the proportion of oxygen atoms determined by X-ray photoelectron spectroscopy after corona treatment of the surface of the surface protection layer of the member is 20% or more.

[0084] FIG. 2 is a cross-sectional view showing one embodiment of a member of the present disclosure. The member 20 in FIG. 2 has a transfer layer 11 on a substrate 5. The transfer layer 11 has, in order from the side contacting the substrate 5, an adhesion layer 4, a primer layer 3, and a surface protection layer 2. Although not shown in FIG. 2, the member 20 may further have an adhesive layer between the adhesion layer 4 and the substrate 5, if necessary. Furthermore, although not shown in FIG. 2, if the member has an adhesive layer, a primer layer of the substrate may further be present between the adhesive layer and the substrate. Furthermore, although not shown in FIG. 2, the transfer layer 11 of the member 20 may further have other functional layers, if necessary.

[0085] As described above, in the member of the present disclosure, the change rate of the proportion of oxygen atoms measured by X-ray photoelectron spectroscopy after corona treatment of the surface of the surface protective layer is 20% or more, which improves the so-called wettability of the surface of the surface protective layer, thereby improving the adhesion between the surface protective layer and the primer layer and improving the weather resistance of the transfer layer. Therefore, the weather-resistant adhesion of the member of the present disclosure can be improved. The preferred range of the change rate of the proportion of oxygen atoms measured by X-ray photoelectron spectroscopy after corona treatment of the surface protective layer in the member of the present disclosure is the same as the change rate of the proportion of oxygen atoms in the surface protective layer of the transfer sheet of the present disclosure described above.

[0086] Furthermore, since the surface of the surface protective layer of the member of the present disclosure has a water contact angle of 60° or more, the surface of the surface protective layer is hydrophobic and has few polar groups such as OH groups, and therefore, even when exposed to an environment where the pH changes significantly due to the adhesion of acid, etc., surface deterioration can be suppressed, thereby imparting resistance to acidic environments to the surface protective layer. Therefore, the member of the present disclosure can exhibit excellent weather resistance even in an environment where the pH changes significantly, such as when exposed to acid rain. The preferred range of the water contact angle of the surface of the surface protective layer of the member of the present disclosure is the same as the water contact angle of the surface of the surface protective layer of the transfer sheet of the present disclosure on the side opposite the primer layer.

[0087] In addition, the member of the present disclosure preferably has an adhesive layer between the transfer layer and the substrate as needed to improve adhesion between the transfer layer and the substrate. Examples of the adhesive layer include those similar to the adhesive layer of the transfer sheet described above, and the preferred range is also similar. In addition, when the member of the present disclosure has an adhesive layer, it is preferable to have a primer layer between the adhesive layer and the substrate as needed to improve the adhesion between the adhesive layer and the substrate. Examples of the primer layer of the substrate include those similar to the primer layer of the transfer sheet described above, and the preferred ranges are also similar. [Example]

[0088] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Each property value was measured and evaluated by the following methods.

[0089] 1. Measurement and evaluation methods 1-1. Measurement of the ratio of each atom by X-ray photoelectron spectroscopy (XPS) For the members obtained in the examples and comparative examples, the proportions of oxygen atoms and carbon atoms in the surface protective layer before corona treatment were measured using a scanning X-ray photoelectron spectrometer (model number: PHI 5000 VersaProbe III, manufactured by PHI) under the following measurement conditions. In addition, the surface protective layer of the members obtained in the examples and comparative examples was subjected to corona treatment under the following corona treatment conditions, and the proportions of oxygen atoms and carbon atoms in the surface protective layer after corona treatment were measured. <Measurement conditions> Incident X-ray: AlKα (monochromatic X-ray, hν=1486.6eV) X-ray output: 50W (15kV, 3.3mA) X-ray beam diameter: 200 μm X-ray scan: 600 μm x 200 μm Photoelectron capture angle: 45° Charge neutralization: electron neutralization gun, low acceleration Ar + ion irradiation <Corona treatment conditions> Corona output: 90kW Line speed: 15m / min

[0090] The change in the proportions of carbon atoms and oxygen atoms after corona treatment was calculated using the following formula from the proportions of carbon atoms and oxygen atoms measured above. The results are summarized in Table 1. [Percentage change in the proportion of each atom after corona treatment (%)] = ([Proportion of each atom after corona treatment] - [Proportion of each atom before corona treatment]) x 100 / [Proportion of each atom before corona treatment]

[0091] 1-2. Measurement of water contact angle A contact angle meter (model number: CA-X (model number), manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the contact angle between the surface protective layer and pure water before and after the corona treatment of the members obtained in the examples and comparative examples. Regarding the contact angle with water in this disclosure, 1.5 μL of pure water was dropped onto the surface protective layer, and the static contact angle was measured 2 seconds after the drop landed according to the θ / 2 method. The measurement results are summarized in Table 1.

[0092] 1-3. Measurement of Martens hardness The Martens hardness of the surface of the surface protection layer of the members obtained in the examples and comparative examples was measured using an ultra-microhardness tester (model number: Picodentor HM-500, manufactured by Fisher Instruments) under the following measurement conditions. The average indenter penetration depth was 0.5 μm. The measurement results are summarized in Table 1. <Measurement conditions> Indenter used: Vickers indenter (diamond, square pyramidal shape, model number: VV005, manufactured by Fisher Instruments) Push-in conditions: Maximum load Maximum push-in force: 20mN Load application time: 10 seconds Holding time: Hold for 5 seconds at maximum pressing load Load unloading time: 10 seconds Sample placement stage: Suction stage (Model: SP2130-AD, manufactured by SMC)

[0093] 1-4. Evaluation of resistance in acidic environments Gauze soaked in 10% hydrochloric acid was placed on the surface protective layer of the members obtained in the examples and comparative examples and left for 12 hours. After leaving, the appearance of the members was observed and evaluated according to the following criteria. The evaluation results are summarized in Table 1. <Evaluation criteria> A: There was no change in appearance. B: The gloss has changed significantly.

[0094] 1-5. Weather-resistant adhesion evaluation The components obtained in the examples and comparative examples were subjected to an accelerated weathering test using a metal halide lamp (MWOM) for 400 hours (a cycle consisting of 20 hours of ultraviolet irradiation under the irradiation conditions below, followed by 4 hours of condensation under the condensation conditions below, with this cycle being repeated). After the accelerated weathering test, the appearance of the components was visually observed and evaluated according to the following criteria. The evaluation results are summarized in Table 1. <Conditions for accelerated weathering test> (Test equipment) Manufactured by Daipla Wintes, product name "Daipla Metal Weather" (Irradiation conditions) Illuminance: 65mW / cm 2 Black panel temperature: 63°C, chamber humidity: 50%RH, time: 20 hours (Condensation conditions) Illuminance: 0mW / cm 2 , Humidity inside the tank: 98%RH, Time: 4 hours <Evaluation criteria> A: No peeling was observed. B: Partial peeling was observed. C: Most of the peeling was observed.

[0095] 2. Preparation of transfer sheet and components [Example 1] A 26 μm thick matte PET film (Diafoil E130-26, manufactured by Mitsubishi Chemical Corporation) was prepared as a release film. The following surface protection layer forming liquid 1 was applied to one side of the release film in a coating amount of 5 g / m2 after drying. 2 After drying at 70°C for 1 minute, the coating was irradiated with an electron beam (voltage: 175 keV, 5 Mrad (50 kGy)) to form a 5 μm thick protective layer. The surface of the protective layer was then corona treated at an output of 90 kW and a line speed of 15 m / min. <Surface protective layer forming liquid 1> Urethane acrylate: 100 parts by weight (Bifunctional urethane acrylate oligomer (Mw: 4000) / multifunctional urethane acrylate oligomer (number of functional groups: 12 to 18, Mw: 1000) = 50 / 50 (mass ratio)) UV absorber: 2 parts by weight ("Tinuvin 479" (BASF)) Light stabilizer: 2 parts by weight (LS-3410 (manufactured by Nippon Nyukazai Co., Ltd.)) Solvent: appropriate amount (methyl ethyl ketone)

[0096] Next, the following primer layer-forming liquid was applied to the formed surface protective layer in a coating amount of 3.5 g / m after drying. 2 The mixture was dried at 70°C for 1 minute to form a primer layer having a thickness of 3 µm. <Primer layer forming liquid> Polycarbonate-based urethane acrylic copolymer: 100 parts by weight (Urethane component / acrylic component = 70 / 30 (mass ratio)) UV absorber: 30 parts by weight (15 parts by weight of "Tinuvin 479" (manufactured by BASF), 15 parts by weight of "Tinuvin 400" (manufactured by BASF)) Light stabilizer: 6 parts by weight (6 parts by mass of "Tinuvin 123" (BASF)) Silica: 5 parts by weight Hexamethylene diisocyanate curing agent: 6 parts by mass Solvent: appropriate amount (methyl ethyl ketone)

[0097] Next, the adhesive layer forming liquid described below was applied to the formed primer layer in a coating amount of 5 g / m after drying. 2 The coating was dried at 70° C. for 1 minute to form an adhesive layer having a thickness of 5 μm, and then aged at 50° C. for 2 days to obtain a transfer sheet of Example 1. <Adhesion layer forming liquid> Mixed resin of acrylic resin and vinyl chloride-vinyl acetate copolymer: 100 parts by weight (acrylic resin / vinyl chloride-vinyl acetate copolymer = 80 / 20 (mass ratio), weight average molecular weight: 65,000) Pigment: 60 parts by weight Solvent: appropriate amount (methyl ethyl ketone)

[0098] Next, a 0.8 mm thick aluminum plate was prepared as a substrate, and the following hot melt adhesive was applied to one side of the substrate in an amount of 5 g / m 2 The adhesive layer was coated to a thickness of 5 μm. Next, the adhesive layer of the substrate and the adhesive layer of the transfer sheet obtained above were laminated facing each other. Thereafter, using a laminator (Desktop Roll Laminator B316A3, manufactured by Aco Brands Japan Co., Ltd.), heat and pressure were applied from the transfer sheet side under conditions of a lamination roll temperature of 160°C and a conveying speed of 2 m / min to adhere the substrate and the transfer layer of the transfer sheet, and the release film was peeled off from the adhered transfer sheet to obtain the member of Example 1. <Hot melt adhesive> Main ingredient: 100 parts by weight ("Aronmelt PES-320SK", manufactured by Toagosei Co., Ltd.) Hardener: 11 parts by weight ("Coronate L", manufactured by Tosoh Corporation)

[0099] [Example 2] A transfer sheet and a member of Example 2 were obtained in the same manner as in Example 1, except that the surface protective layer was formed using the following surface protective layer-forming liquid 2. <Surface protective layer forming liquid 2> Urethane acrylate: 100 parts by weight (Difunctional urethane acrylate oligomer (Mw: 4000) / multifunctional urethane acrylate oligomer (number of functional groups: 6 to 8, Mw: 3000) = 40 / 60 (mass ratio)) UV absorber: 2 parts by weight ("Tinuvin 479" (BASF)) Light stabilizer: 2 parts by weight (LS-3410 (manufactured by Nippon Nyukazai Co., Ltd.)) Solvent: appropriate amount (methyl ethyl ketone)

[0100] [Example 3] A transfer sheet and a member of Example 3 were obtained in the same manner as in Example 1, except that the surface protective layer was formed using the following surface protective layer-forming liquid 3. <Surface protective layer forming liquid 3> Urethane acrylate: 100 parts by weight (Trifunctional urethane acrylate oligomer (Mw: 4000) / trifunctional urethane acrylate oligomer (Mw: 2500) = 30 / 70 (mass ratio)) UV absorber: 2 parts by weight ("Tinuvin 479" (BASF)) Light stabilizer: 2 parts by weight (LS-3410 (manufactured by Nippon Nyukazai Co., Ltd.)) Solvent: appropriate amount (methyl ethyl ketone)

[0101] [Comparative Example 1] A transfer sheet and a member of Comparative Example 1 were obtained in the same manner as in Example 1, except that the surface protective layer was formed using the following surface protective layer-forming liquid 4. <Surface protective layer forming liquid 4> Urethane acrylate: 100 parts by weight (tetrafunctional acrylate monomer (molecular weight: 400)) UV absorber: 2 parts by weight ("Tinuvin 479" (BASF)) Light stabilizer: 2 parts by weight (LS-3410 (manufactured by Nippon Nyukazai Co., Ltd.)) Solvent: appropriate amount (methyl ethyl ketone)

[0102] Comparative Example 2 A transfer sheet and a member of Comparative Example 2 were obtained in the same manner as in Example 1, except that the surface protective layer was formed using the following surface protective layer-forming liquid 5. <Surface protective layer forming liquid 5> Urethane acrylate: 80 parts by weight (Trifunctional urethane acrylate oligomer (Mw: 4000) / trifunctional urethane acrylate oligomer (Mw: 2500) = 30 / 70 (mass ratio)) Quaternary ammonium UV-curable hydrophilic resin: 20 parts by weight UV absorber: 2 parts by weight ("Tinuvin 479" (BASF)) Light stabilizer: 2 parts by weight (LS-3410 (manufactured by Nippon Nyukazai Co., Ltd.)) Solvent: appropriate amount (methyl ethyl ketone)

[0103] [Table 1]

[0104] From the results in Table 1, it can be confirmed that Examples 1 to 3 having the characteristics of the present disclosure are excellent in resistance and weather-resistant adhesion in an acidic environment, and exhibit excellent weather resistance. On the other hand, in Comparative Examples 1 and 2, the rate of change in the proportion of oxygen atoms in the surface protective layer after corona treatment was lower than in Examples 1 to 3, or the contact angle of water on the surface protective layer was less than 60°, resulting in low resistance or weather-resistant adhesion in an acidic environment and poor weather resistance. [Industrial Applicability]

[0105] The transfer sheet of the present disclosure has excellent weather-resistant adhesion and is therefore suitable for use as interior building components such as walls, ceilings, and floors, or exterior building components such as exterior walls, roofs, eaves soffits, fences, and gates, as well as fittings or fixtures such as various doors such as window frames and entrance doors, handrails, baseboards, moldings, window frames, door frames, and moldings, as well as general furniture such as chests of drawers, shelves, and desks, kitchen furniture such as dining tables and sinks, surface decorative panels for cabinets of low-electrical appliances and office equipment, and interior or exterior vehicle components. Furthermore, components using the transfer sheet of the present disclosure are suitable for use in the above-mentioned various components, especially components used in environments exposed to direct sunlight. [Explanation of symbols]

[0106] 1 Release film 2 Surface protective layer 3 Primer layer 4 Adhesion layer 5 Base material 10 Transfer sheet 11 Transfer layer 20 Components

Claims

1. A transfer layer is provided on a release film, the transfer layer has a surface protection layer, a primer layer, and an adhesion layer in this order from the release film side; the surface protective layer is a transfer sheet containing a cured product of an ionizing radiation curable resin composition, the surface of the surface protective layer opposite to the primer layer has a water contact angle of 60° or more; A transfer sheet in which the change rate of the proportion of oxygen atoms in the surface protective layer is 20% or more as measured by the following method. <Change in ratio of oxygen atoms> After the transfer layer of the transfer sheet and the substrate are brought into close contact with each other, the release film is peeled off to obtain a member. The corona treatment conditions are a corona output of 90 kW and a line speed of 15 m / min. The surface of the surface protection layer of the member is subjected to a corona treatment under conditions of a corona output of 90 kW and a line speed of 15 m / min. The proportion of oxygen atoms determined by X-ray photoelectron spectroscopy before the corona treatment is A. Ｏ The proportion of oxygen atoms determined by X-ray photoelectron spectroscopy after the corona treatment of the surface of the surface protection layer of the member is B Ｏ When [Change in the proportion of oxygen atoms (%)] = (B Ｏ -A Ｏ ) x 100 / A Ｏ

2. The transfer sheet according to claim 1 , wherein the ionizing radiation curable resin composition contains a urethane acrylate oligomer.

3. 3. The transfer sheet according to claim 1, wherein the functional group equivalent of the ionizing radiation curable functional group of the ionizing radiation curable compound contained in the ionizing radiation curable resin composition is 50 g / mol or more and 5000 g / mol or less.

4. A method for manufacturing a member, comprising the following steps (1) and (2) in order: Step (1) A step of bringing the surface of the transfer layer side of the transfer sheet according to any one of claims 1 to 3 into close contact with a substrate. Step (2) A step of peeling off the release film of the transfer sheet from the tightly adhered transfer sheet and substrate.

5. A member having a transfer layer on a substrate, the transfer layer has an adhesion layer, a primer layer, and a surface protection layer in this order from the substrate side; the surface protective layer comprises a cured product of an ionizing radiation curable resin composition, the contact angle of water on the surface of the surface protection layer is 60° or more; A member, wherein the change rate of the proportion of oxygen atoms measured by X-ray photoelectron spectroscopy after the surface of the surface protection layer of the member is 20% or more under corona treatment conditions of a corona output of 90 kW and a line speed of 15 m / min.

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