Transfer sheets and weather-resistant items

Abstract

To suppress lowering of adhesion between a surface protective layer and a primer layer for a long period of time in a transfer layer transferred onto a transferred body from a transfer sheet having the surface protective layer and the primer layer.SOLUTION: A transfer sheet has a releasable base material and a transfer layer, wherein the transfer layer has a surface protective layer and a primer layer, the surface protective layer is positioned between the releasable base material and the primer layer, and the surface protective layer contains a curable resin, a first ultraviolet absorber having an absorption peak at a first wavelength, a second ultraviolet absorber having an absorption peak at a second wavelength longer than the first wavelength, and a third ultraviolet absorber having an absorption peak at a third wavelength longer than the second wavelength.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to transfer sheets and weather-resistant articles. [Background technology]

[0002] Conventionally, a surface protective layer has been provided on the surface of an article such as an interior or exterior material for a building, furniture, fixtures, or home appliances in order to impart scratch resistance, stain resistance, etc. The surface protective layer is formed, for example, by coating or by using a transfer sheet (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-345228 Summary of the Invention [Problem to be solved by the invention]

[0004] For example, exterior materials used outdoors are often exposed to direct sunlight, so excellent weather resistance is desirable. However, when a surface protective layer is provided on the surface of a transferee using the above-mentioned transfer sheet, the weather resistance tends to be insufficient, such as peeling of the surface protective layer. The transfer sheet usually includes a transfer layer including a surface protective layer and a primer layer. The present inventors have found that the reason for the insufficient weather resistance is that the adhesion between the surface protective layer and the primer layer is insufficient after being left in an environment exposed to direct sunlight for a long period of time.

[0005] One object of the present disclosure is to suppress a decrease in adhesion between a surface protective layer and a primer layer for a long period of time in a transfer layer transferred to a receiving body from a transfer sheet having a transfer layer including a surface protective layer and a primer layer. [Means for solving the problem]

[0006] The transfer sheet of the present disclosure comprises a releasable substrate and a transfer layer, the transfer layer comprising a surface protective layer and a primer layer, the surface protective layer being located between the releasable substrate and the primer layer, and the surface protective layer containing a cured resin, a first ultraviolet absorber having an absorption peak at a first wavelength, a second ultraviolet absorber having an absorption peak at a second wavelength longer than the first wavelength, and a third ultraviolet absorber having an absorption peak at a third wavelength longer than the second wavelength. [Effects of the Invention]

[0007] According to the present disclosure, in a transfer layer transferred to a transfer recipient from a transfer sheet having a transfer layer including a surface protection layer and a primer layer, it is possible to suppress for a long period of time a decrease in adhesion between the surface protection layer and the primer layer, for example, in an environment exposed to direct sunlight. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic cross-sectional view of one embodiment of the transfer sheet of the present disclosure. [Figure 2] FIG. 2 is a schematic cross-sectional view of one embodiment of the transfer sheet of the present disclosure. [Figure 3] FIG. 3 is a schematic cross-sectional view of one embodiment of a weather-resistant article of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, embodiments of the present disclosure will be described in detail. The present disclosure can be implemented in many different forms, and should not be construed as being limited to the description of the embodiments exemplified below. For clarity of explanation, the drawings may show the width, thickness, shape, etc. of each layer more schematically than in the embodiments, but these are merely examples and do not limit the interpretation of the present disclosure. In this specification and each drawing, elements similar to those already described with reference to the previous drawings are designated by the same reference numerals, and detailed description may be omitted as appropriate.

[0010] Films and sheets may be referred to as films and sheets in the order of their relative thickness, but in the present disclosure, unless otherwise specified, sheets encompass films.

[0011] In the following description, unless otherwise specified, each of the components (for example, resin components, ultraviolet absorbers, light stabilizers, colorants, and additives) that appear may be used alone or in combination of two or more.

[0012] The transfer sheet of the present disclosure comprises a releasable substrate and a transfer layer. The transfer layer is provided releasably on a releasable substrate. The transfer layer comprises a surface protective layer and a primer layer. The surface protective layer is located between the releasable substrate and the primer layer. The surface protective layer, for example, constitutes the surface layer on the releasable substrate side of the transfer layer. The transfer layer may further comprise an adhesive layer. The adhesive layer, for example, constitutes the surface layer on the side of the transfer layer opposite to the releasable substrate side. Therefore, the transfer layer may comprise the surface protective layer, primer layer, and adhesive layer in this order.

[0013] In the transfer sheet of the present disclosure, the transfer layer may further include other layers different from the surface protective layer, primer layer, and adhesive layer. As the other layers, for example, known layers such as a design layer can be appropriately selected and used.

[0014] The surface protective layer contains a cured resin, a first ultraviolet absorber having an absorption peak at a first wavelength, a second ultraviolet absorber having an absorption peak at a second wavelength longer than the first wavelength, and a third ultraviolet absorber having an absorption peak at a third wavelength longer than the second wavelength. Details of these ultraviolet absorbers will be described later. A weather-resistant article obtained by transferring a transfer layer from the transfer sheet of the present disclosure to a transfer recipient can suppress a decrease in adhesion between the surface protective layer and the primer layer in an environment exposed to direct sunlight, and can maintain weather resistance for a long period of time in such an environment.

[0015] In a weather-resistant article having a primer layer and a surface protective layer, in order to maintain weather resistance over a long period of time, it is necessary to suppress deterioration of the primer layer. Therefore, it is important to determine to what extent the surface protective layer can absorb ultraviolet rays, which are considered to be one of the causes of primer layer deterioration. The present inventors have found that a surface protective layer containing one or two ultraviolet absorbers may be able to suppress ultraviolet-induced deterioration of the primer layer in the short term, but may not be able to sufficiently suppress ultraviolet-induced deterioration in the long term. This is presumably due to the following reasons. One of the factors that contribute to the adhesion between the primer layer and the surface protective layer is the polymer component contained in the primer layer. When this polymer component is degraded by ultraviolet light, the primer layer itself becomes brittle, weakening the adhesion between the primer layer and the surface protective layer, which is thought to cause peeling at the interface between the primer layer and the surface protective layer. This reduces the weather resistance of the article. For example, when the article is exposed to ultraviolet light for a long period of time, the polymer component contained in the primer layer gradually deteriorates. Here, for example, when one or two types of ultraviolet absorbers are added in large amounts to the surface protective layer, ultraviolet rays can be sufficiently absorbed, but in this case, problems such as bleed-out of the ultraviolet absorber, deterioration in adhesion between the surface protective layer and the primer layer, and deterioration in transparency of the surface protective layer may arise. In response to these problems, the present inventors have discovered that the long-term weather resistance of the article can be improved by incorporating at least three types of ultraviolet absorbers into the surface protective layer, each with a different absorption peak wavelength. This is presumably due to the following reasons: By using three or more types of ultraviolet absorbers in combination, a wide range of ultraviolet wavelengths can be covered. This allows the ultraviolet absorbers to adequately absorb ultraviolet rays across a wide wavelength range. Therefore, deterioration of the primer layer due to ultraviolet rays can be suppressed for a long period of time. As a result, the article can maintain its weather resistance for a sufficiently long period of time even in an environment exposed to direct sunlight. Furthermore, because deterioration of the transfer object itself can also be suppressed, the transfer sheet of the present disclosure can be applied to a variety of transfer objects.

[0016] The configuration of one embodiment of the transfer sheet of the present disclosure is shown in FIGS. The transfer sheet 1 shown in Fig. 1 comprises a releasable substrate 10 and a transfer layer 20 releasably provided on the releasable substrate 10. The transfer layer 20 comprises a surface protective layer 22 and a primer layer 24 in this order in the thickness direction from the side of the releasable substrate 10. That is, the releasable substrate 10, the surface protective layer 22, and the primer layer 24 are stacked in the thickness direction, which is the vertical direction on the paper surface of Fig. 1.

[0017] The transfer layer 20 in the transfer sheet 1 shown in Fig. 2 further includes an adhesive layer 26. The transfer layer 20 includes a surface protective layer 22, a primer layer 24, and an adhesive layer 26, in this order in the thickness direction from the side of the releasable substrate 10. That is, the releasable substrate 10, the surface protective layer 22, the primer layer 24, and the adhesive layer 26 are stacked in the thickness direction, which is the vertical direction on the paper surface of Fig. 2.

[0018] The configuration of the transfer sheet of the present disclosure will be described in detail below.

[0019] The transfer sheet of the present disclosure comprises a releasable substrate. As the release substrate, for example, a film composed of a resin component (hereinafter also referred to as "resin film") can be used. Examples of the resin component include polyester, polyolefin, polystyrene, vinyl resin, (meth)acrylic resin, polyamide, polyimide, and polycarbonate. In the present disclosure, "(meth)acrylic" includes both "acrylic" and "methacrylic," and "(meth)acrylate" includes both "acrylate" and "methacrylate."

[0020] The releasable substrate is preferably a polyester film or a polyolefin film, since by using these films as the releasable substrate, for example, a surface protective layer can be easily formed on the film.

[0021] Examples of polyesters include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polyethylene terephthalate-isophthalate copolymers. Among these, PET and PBT are preferred, with PET being more preferred, from the viewpoint of being less susceptible to thermal shrinkage during production of the transfer sheet and shrinkage due to irradiation with ionizing radiation.

[0022] Examples of polyolefins include polyethylene, polypropylene, polybutene, ethylene-propylene copolymer, and ethylene-propylene-butene copolymer. Among these, polypropylene is preferred from the viewpoint of being less susceptible to thermal shrinkage during production of the transfer sheet and shrinkage due to irradiation with ionizing radiation.

[0023] The resin film may be a stretched film or an unstretched film, but is preferably a stretched film. The stretched film has a stretching ratio of, for example, 5 to 30 times in the machine direction (MD) and / or transverse direction (TD). When the resin film is a stretched film, for example, thermal shrinkage of the resin film caused by heating treatment during production of the transfer sheet and shrinkage of the resin film caused by crosslinking treatment due to irradiation with ionizing radiation can be suppressed, thereby improving the dimensional stability of the transfer sheet.

[0024] The stretched film may be a uniaxially stretched film or a biaxially stretched film, with a biaxially stretched film being preferred from the viewpoint of being less susceptible to thermal shrinkage during production of the transfer sheet and shrinkage due to irradiation with ionizing radiation.

[0025] The releasable substrate may have a single-layer structure or a multi-layer structure. The releasable substrate may be, for example, a single-layer resin film or a laminate of resin films. The laminate of resin films can be produced by, for example, dry lamination, wet lamination, or extrusion.

[0026] The surface of the releasable substrate on which the surface protective layer is provided may be subjected to a known release treatment as necessary, or may be provided with a release layer such as a silicone resin, which can improve the releasability between the surface protective layer and the releasable substrate during transfer, for example.

[0027] The thickness of the releasable substrate is preferably 5 μm or more, more preferably 10 μm or more, and is preferably 200 μm or less, more preferably 150 μm or less. When the releasable substrate has a multilayer structure, it is preferable that the thickness of the entire multilayer structure is within the above range.

[0028] In the transfer sheet of the present disclosure, the transfer layer includes a surface protective layer. The surface protective layer is a layer that constitutes the surface layer of a weather-resistant article obtained by transferring a transfer layer onto a transfer-receiving body, optionally via an adhesive layer. The surface protective layer is, for example, a layer that imparts weather resistance to the transfer-receiving body, and may also be a layer that imparts scratch resistance and stain resistance. The surface protective layer is preferably in contact with the releasable substrate.

[0029] The surface protective layer is provided on a releasable substrate. In other words, the surface protective layer is overlapped with the releasable substrate in the thickness direction. In one embodiment, the surface protective layer is provided on the entire surface of the releasable substrate.

[0030] The surface protective layer contains a cured resin. The cured resin functions, for example, as a binder in the surface protective layer. Examples of the cured resin include a cured product of a curable compound. Examples of the cured product of a curable compound include a cured product of an ionizing radiation curable compound and a cured product of a thermosetting resin. The surface protective layer may contain two or more of these cured resins.

[0031] Examples of thermosetting resins include unsaturated group-containing (meth)acrylic resins, unsaturated polyesters, urethane resins, epoxy resins, phenolic resins, aminoalkyd resins, urea resins, melamine resins, melamine-urea co-condensation resins, guanamine resins, diallyl phthalate resins, and silicone resins.

[0032] A curing agent is used together with the thermosetting resin as needed. In the case of unsaturated group-containing (meth)acrylic resin and unsaturated polyester, for example, a peroxide such as methyl ethyl ketone peroxide or a radical initiator such as azoisobutylnitrile is used. In the case of urethane resin, for example, an isocyanate-based curing agent is used. In the case of epoxy resin, for example, an organic amine-based curing agent is used.

[0033] Examples of thermosetting resins include two-component curing urethane resins that use a polyol as a base resin and an isocyanate compound as a curing agent. Examples of polyols include (meth)acrylic polyols, polyether polyols, polyester polyols, polyethylene glycols, and polypropylene glycols. The isocyanate compounds are polyvalent isocyanates having two or more isocyanate groups, such as aromatic isocyanates such as 4,4-diphenylmethane diisocyanate; and aliphatic (or alicyclic) isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate.

[0034] In one embodiment, the surface protective layer contains a cured product of a thermosetting resin as the curable resin, for example, a crosslinked cured product of a (meth)acrylic polyol with an isocyanate-based curing agent.

[0035] The ionizing radiation-curable compound refers to a compound that crosslinks and cures upon exposure to ionizing radiation and has an ionizing radiation-curable functional group. The ionizing radiation-curable functional group is a group that crosslinks upon exposure to ionizing radiation, and examples thereof include functional groups (ethylenically unsaturated groups) having an ethylenic double bond, such as (meth)acryloyl, vinyl, and allyl groups. The ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules. Examples of ionizing radiation include electron beams (EB) and ultraviolet rays (UV), as well as electromagnetic waves such as X-rays and gamma rays; and charged particle beams such as alpha rays and ion beams. From the viewpoint of incorporating an ultraviolet absorber into the surface protective layer, electron beams are preferred as the ionizing radiation.

[0036] Examples of the ionizing radiation curable compound include polymerizable monomers and polymerizable oligomers that have been conventionally used as ionizing radiation curable compounds. The polymerizable monomer is preferably a (meth)acrylate monomer having a (meth)acryloyl group in the molecule, more preferably a polyfunctional (meth)acrylate monomer having two or more (meth)acryloyl groups in the molecule. The number of (meth)acryloyl groups in the polyfunctional (meth)acrylate monomer is 2 or more, preferably 8 or less, more preferably 6 or less.

[0037] Examples of the polymerizable monomer include bifunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A tetraethoxy di(meth)acrylate, and bisphenol A tetrapropoxy di(meth)acrylate; trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, Examples of the (meth)acrylate include tri- or higher functional (meth)acrylates such as pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; and ethylene oxide-modified, propylene oxide-modified, caprolactone-modified, isocyanuric acid-modified, or propionic acid-modified products of these (meth)acrylates.

[0038] Examples of the polymerizable oligomer include (meth)acrylate oligomers having two or more (meth)acryloyl groups in the molecule. Examples of the (meth)acrylate oligomer include urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polycarbonate (meth)acrylate, polycaprolactone urethane (meth)acrylate, polycaprolactone diol urethane (meth)acrylate, and acrylic (meth)acrylate. The number of (meth)acryloyl groups in the polymerizable oligomer is two or more, preferably eight or less, and more preferably six or less.

[0039] Other examples of the polymerizable oligomer include highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acryloyl groups in the side chains of polybutadiene oligomers, and silicone (meth)acrylate oligomers having polysiloxane bonds in the main chains.

[0040] The weight average molecular weight of the polymerizable oligomer may be 500 or more, 1,000 or more, 2,000 or more, or 10,000 or less, 8,000 or less, or 6,000 or less. The weight average molecular weight is an average molecular weight measured by gel permeation chromatography (GPC) analysis and converted into standard polystyrene.

[0041] As the ionizing radiation curable compound, a monofunctional (meth)acrylate may be used in combination with a polyfunctional (meth)acrylate, for the purpose of reducing the viscosity of the curable composition during coating, etc. Examples of the monofunctional (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and isobornyl (meth)acrylate.

[0042] When the ionizing radiation curable compound is an ultraviolet curable compound, it is preferable to use at least one selected from a photopolymerization initiator and a photopolymerization accelerator together with the ultraviolet curable compound.

[0043] From the viewpoint of achieving excellent heat resistance, scratch resistance, and contamination resistance, the surface protective layer preferably contains a cured product of a curable compound, and more preferably contains a cured product of an ionizing radiation curable compound. Among ionizing radiation curable compounds, electron beam curable compounds are preferred as components for forming the surface protective layer because they can be made solvent-free, do not require a photopolymerization initiator, and provide stable curing properties. Among ionizing radiation curable compounds, polymerizable oligomers are preferred, (meth)acrylate oligomers having two or more (meth)acryloyl groups in the molecule are more preferred, and urethane (meth)acrylates are even more preferred.

[0044] The content of the cured resin relative to all resin components contained in the surface protective layer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

[0045] The surface protective layer contains a first ultraviolet absorber having an absorption peak at a first wavelength, a second ultraviolet absorber having an absorption peak at a second wavelength longer than the first wavelength, and a third ultraviolet absorber having an absorption peak at a third wavelength longer than the second wavelength. Each absorption peak is based on an absorbance spectrum measured using a UV-Vis-NIR spectrophotometer.

[0046] The first ultraviolet absorber has an absorption peak at a first wavelength, which is preferably in the range of 270 nm to 300 nm, more preferably in the range of 270 nm to 290 nm, and even more preferably in the range of 270 nm to 280 nm.

[0047] The second ultraviolet absorber has an absorption peak at a second wavelength, which is preferably in the range of 310 nm to 330 nm, and more preferably in the range of 310 nm to 325 nm.

[0048] The third ultraviolet absorber has an absorption peak at a third wavelength, which is preferably in the range of 340 nm to 370 nm, and more preferably in the range of 345 nm to 365 nm.

[0049] The absorption peak preferably means the maximum absorption peak in the wavelength range of 270 nm to 380 nm. For example, when the first ultraviolet absorber has multiple absorption peaks in the wavelength range, the maximum absorption peak is preferably in the range of 270 nm to 300 nm.

[0050] The difference between the second wavelength and the first wavelength is preferably 10 nm or more, more preferably 20 nm or more, even more preferably 30 nm or more, and is preferably 60 nm or less, more preferably 55 nm or less, even more preferably 50 nm or less.

[0051] The difference between the third wavelength and the second wavelength is preferably 10 nm or more, more preferably 20 nm or more, even more preferably 30 nm or more, and is preferably 60 nm or less, more preferably 55 nm or less, even more preferably 50 nm or less.

[0052] The difference between the third wavelength and the first wavelength is preferably 40 nm or more, more preferably 50 nm or more, even more preferably 60 nm or more, and is preferably 100 nm or less, more preferably 95 nm or less, even more preferably 90 nm or less.

[0053] Examples of the first to third ultraviolet absorbers include triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers, and triazine-based ultraviolet absorbers are preferred from the viewpoints of excellent weather resistance, absorbance, and wavelength selectivity.

[0054] Among the triazine-based ultraviolet absorbers, hydroxyphenyltriazine-based ultraviolet absorbers are preferred from the viewpoint of weather resistance. Examples of the hydroxyphenyltriazine-based ultraviolet absorber include compounds represented by formula (1), formula (2), and formula (3).

[0055] [ka]

[0056] In formula (1), R 11 is a divalent organic group, and R 12 is -OC(=O)R 15 is an acyloxy group represented by R 13 and R 14 are each independently a monovalent organic group, and R 15is a hydrogen atom or a monovalent organic group, and n 11 and n 12 are each independently an integer between 0 and 5. 13 If there are multiple R 13 may be the same or different. 14 If there are multiple R 14 may be the same or different.

[0057] R 11 Examples of the divalent organic group include aliphatic hydrocarbon groups such as alkylene groups and alkenylene groups, with alkylene groups being preferred from the viewpoint of weather resistance. From the viewpoint of weather resistance, the number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 or more, more preferably 2 or more, and preferably 16 or less, more preferably 12 or less, even more preferably 8 or less, and particularly preferably 4 or less. The aliphatic hydrocarbon group may be linear, branched, or cyclic, with linear or branched being preferred from the viewpoint of weather resistance, and linear being more preferred.

[0058] R 13 and R 14 Examples of the monovalent organic group include aliphatic hydrocarbon groups such as alkyl groups, alkenyl groups, and cycloalkyl groups, and aromatic ring-containing hydrocarbon groups such as aryl groups and arylalkyl groups. From the viewpoint of weather resistance, aromatic ring-containing hydrocarbon groups are preferred, aryl groups are more preferred, and phenyl groups are particularly preferred.

[0059] From the viewpoint of weather resistance, 11 and n 12 are each preferably 0.

[0060] R 15is preferably a monovalent organic group from the viewpoint of weather resistance. Examples of the monovalent organic group include aliphatic hydrocarbon groups such as alkyl groups, alkenyl groups, and cycloalkyl groups, and aromatic ring-containing hydrocarbon groups such as aryl groups and arylalkyl groups. From the viewpoint of weather resistance, an aliphatic hydrocarbon group is preferred, and an alkyl group is more preferred. From the viewpoint of weather resistance, the number of carbon atoms in the aliphatic hydrocarbon group is preferably 2 or more, more preferably 4 or more, and preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. The aliphatic hydrocarbon group may be linear, branched, or cyclic, and from the viewpoint of weather resistance, a linear or branched one is preferred.

[0061] [ka]

[0062] In formula (2), R 21 is a hydrogen atom or a monovalent organic group, and R 22 and R 23 are each independently a hydroxyl group or a monovalent organic group, and n 21 , n 22 and n 23 are each independently an integer of 1 to 5. 21 If there are multiple R 21 may be the same or different. 22 If there are multiple R 22 may be the same or different. 23 If there are multiple R 23 may be the same or different.

[0063] R 21 The monovalent organic group is R 13 and R 14 The monovalent organic group includes the groups exemplified above, and also includes -R 24 -C(=O)OR 25 Examples of such groups include groups represented by R 24 is a divalent organic group, and R 25 is a monovalent organic group. 22 and R 23The monovalent organic group is R 13 and R 14 From the viewpoint of weather resistance, aromatic ring-containing hydrocarbon groups are preferred, aryl groups are more preferred, and phenyl groups are particularly preferred.

[0064] R 24 The divalent organic group is R in formula (1). 11 Examples of the divalent organic group include those exemplified above, and from the viewpoint of weather resistance, an aliphatic hydrocarbon group is preferred, and an alkylene group is more preferred. From the viewpoint of weather resistance, the number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 or more, more preferably 2 or more, and preferably 16 or less, more preferably 12 or less, even more preferably 8 or less, and particularly preferably 4 or less. The aliphatic hydrocarbon group may be linear, branched, or cyclic, and from the viewpoint of weather resistance, a linear or branched group is preferred, and a linear group is more preferred.

[0065] R 25 The monovalent organic group is R 15 Examples of the monovalent organic group include the groups exemplified above, and from the viewpoint of weather resistance, an aliphatic hydrocarbon group is preferred, and an alkyl group is more preferred. From the viewpoint of weather resistance, the number of carbon atoms in the aliphatic hydrocarbon group is preferably 2 or more, more preferably 4 or more, and preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. The aliphatic hydrocarbon group may be linear, branched, or cyclic, and from the viewpoint of weather resistance, a linear or branched group is preferred.

[0066] n 21 can be 2 or more, and n 22 and n 23 may each be 1. In this case, multiple R 21 One of the groups may be a hydrogen atom, and R 22 and R 23 When is a monovalent organic group, it may be the same organic group.

[0067] [ka]

[0068] In formula (3), R 31 , R 32 and R 33 are each independently a hydrogen atom or a monovalent organic group, and n 31 , n 32 and n 33 are each independently an integer of 1 to 5. 31 If there are multiple R 31 may be the same or different. 32 If there are multiple R 31 may be the same or different. 33 If there are multiple R 31 may be the same or different.

[0069] R 31 , R 32 and R 33 The monovalent organic group is R 13 and R 14 The monovalent organic group includes the groups exemplified above, and also includes -R 34 -C(=O)OR 35 Examples of such groups include groups represented by R 34 is a divalent organic group, and R 35 is a monovalent organic group.

[0070] R 34 The divalent organic group is R in formula (1). 11 Examples of the divalent organic group include those exemplified above, and from the viewpoint of weather resistance, an aliphatic hydrocarbon group is preferred, and an alkylene group is more preferred. From the viewpoint of weather resistance, the number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 or more, more preferably 2 or more, and preferably 16 or less, more preferably 12 or less, even more preferably 8 or less, and particularly preferably 4 or less. The aliphatic hydrocarbon group may be linear, branched, or cyclic, and from the viewpoint of weather resistance, a linear or branched group is preferred, and a linear group is more preferred.

[0071] R 35 The monovalent organic group is R 15Examples of the monovalent organic group include the groups exemplified above, and from the viewpoint of weather resistance, an aliphatic hydrocarbon group is preferred, and an alkyl group is more preferred. From the viewpoint of weather resistance, the number of carbon atoms in the aliphatic hydrocarbon group is preferably 2 or more, more preferably 4 or more, and preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less. The aliphatic hydrocarbon group may be linear, branched, or cyclic, and from the viewpoint of weather resistance, a linear or branched group is preferred.

[0072] n 31 , n 32 and n 33 may be 2 or more. In this case, multiple R 31 One of the R may be a hydrogen atom, and multiple R 32 One of the R may be a hydrogen atom, and multiple R 33 One of the groups may be a hydrogen atom.

[0073] Specific examples of the hydroxyphenyltriazine-based ultraviolet absorber 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-[ Examples thereof include 4-[(2-hydroxy-3-tridecyloxypropyl)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, 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and compounds represented by the following formula:

[0074] [ka]

[0075] In the surface protective layer, the total content of the first ultraviolet absorber, the second ultraviolet absorber, and the third ultraviolet absorber relative to 100 parts by mass of the cured resin is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 6 parts by mass or less. When the total content of the ultraviolet absorbers is equal to or greater than the lower limit, the weather resistance of the transfer layer tends to be improved. When the total content of the ultraviolet absorbers is equal to or less than the upper limit, the deterioration of adhesion between the surface protective layer and the primer layer due to bleed-out of the ultraviolet absorbers tends to be suppressed.

[0076] In the surface protective layer, the content of the first ultraviolet absorber relative to 100 parts by mass of the cured resin is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, even more preferably 0.3 parts by mass or more, and is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, even more preferably 1.5 parts by mass or less. This tends to further improve, for example, weather resistance.

[0077] In the surface protective layer, the content of the second ultraviolet absorber relative to 100 parts by mass of the cured resin is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, and is preferably 8 parts by mass or less, more preferably 6 parts by mass or less, even more preferably 5 parts by mass or less. This tends to further improve, for example, weather resistance.

[0078] In the surface protective layer, the content of the third ultraviolet absorber relative to 100 parts by mass of the cured resin is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, even more preferably 0.3 parts by mass or more, and is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, even more preferably 1.5 parts by mass or less. This tends to further improve, for example, weather resistance.

[0079] In one embodiment, the content of the second ultraviolet absorber in the surface protective layer is greater than the content of the first ultraviolet absorber and greater than the content of the third ultraviolet absorber, which allows the surface protective layer to absorb a wide range of wavelengths and tends to further improve, for example, weather resistance.

[0080] The surface protective layer may contain a light stabilizer from the viewpoint of weather resistance. Examples of light stabilizers include aromatic light stabilizers, amine light stabilizers, organic acid light stabilizers, catechin light stabilizers, and hindered amine light stabilizers, and among these, hindered amine light stabilizers are preferred. Hindered amine light stabilizers are compounds having a structure containing a 2,2,6,6-tetramethylpiperidine skeleton in the molecule.

[0081] Examples of light stabilizers include reactive light stabilizers having an ethylenic double bond polymerizable with a curable compound capable of forming a cured resin of the surface protective layer, and non-reactive light stabilizers having no ethylenic double bond polymerizable with the curable compound. The ethylenic double bond is possessed by functional groups such as (meth)acryloyl groups, vinyl groups, and allyl groups. The surface protective layer may contain at least one selected from reactive light stabilizers and non-reactive light stabilizers, or may contain both reactive and non-reactive light stabilizers.

[0082] Reactive light stabilizers are usually incorporated into the cured resin system during the formation of the surface protective layer and are therefore fixed, providing a long-term effect, whereas non-reactive light stabilizers are mobile within the surface protective layer and therefore provide an immediate effect.

[0083] The number of ethylenic double bonds in the reactive light stabilizer may be one or two or more.

[0084] Examples of reactive light stabilizers having one ethylenic double bond include 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-(meth)acryloyloxy ... -cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, pentamethylpiperidinyl (meth)acrylate, the compound with CAS number 1010692-24-6 and the compound with CAS number 1010692-21-3. Examples of reactive light stabilizers having two or more ethylenic double bonds include 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotoyloxy-2,2,6,6-tetramethylpiperidine, the compound with CAS number 1954659-42-7, and the compound with CAS number 1010692-23-5.

[0085] Examples of the non-reactive light stabilizer include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, and methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate. tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, and bis-(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxy-benzyl)-2-n-butylmalonate.

[0086] In the surface protective layer, the content of the light stabilizer relative to 100 parts by mass of the cured resin is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 1.5 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 6 parts by mass or less.

[0087] The surface protective layer may contain, as the light stabilizer, only the reactive light stabilizer, only the non-reactive light stabilizer, or both the reactive light stabilizer and the non-reactive light stabilizer. The blending ratio by mass of the reactive light stabilizer and the non-reactive light stabilizer in the surface protective layer (reactive light stabilizer:non-reactive light stabilizer) may be, for example, 10:0 to 2:8.

[0088] The surface protective layer may contain additives. Examples of the additives include antioxidants, abrasion resistance improvers, infrared absorbers, antistatic agents, leveling agents, thixotropy-imparting agents, coupling agents, antifoaming agents, flame retardants, plasticizers, particles, and antiblocking agents.

[0089] It is preferable that the surface protective layer is substantially free of polyolefin. This tends to improve, for example, the weather resistance of the surface protective layer. "Substantially free of polyolefin" means that the content of polyolefin relative to the total resin components contained in the surface protective layer is 1% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, and even more preferably 0% by mass.

[0090] In the transfer sheet of the present disclosure, the surface protection layer preferably has an absorbance A1 of 0.3 or more at a wavelength of 270 nm or more and 300 nm or less, an absorbance A2 of 0.6 or more at a wavelength of 310 nm or more and 330 nm or less, and an absorbance A3 of 0.2 or more at a wavelength of 340 nm or more and 370 nm or less.

[0091] As described above, from the viewpoint of long-term weather resistance, by taking into consideration the absorbance A2 at a wavelength of 310 nm or more and 330 nm or less and the absorbance A3 at a wavelength of 340 nm or more and 370 nm or less in addition to the absorbance A1 at a wavelength of 270 nm or more and 300 nm or less, the surface protection layer can efficiently block ultraviolet rays, and the weather resistance of the transfer layer in an environment exposed to direct sunlight can be further improved.

[0092] The absorbance A1 is preferably 0.3 or more, more preferably 0.35 or more, and may be, for example, 0.5 or more, or 0.7 or more. The upper limit of the absorbance A1 is not particularly limited, but may be, for example, 1.5.

[0093] The absorbance A2 is preferably 0.6 or more, more preferably 0.7 or more, and may be, for example, 1.0 or more, or 1.2 or more. The upper limit of the absorbance A2 is not particularly limited, but may be, for example, 3.0.

[0094] The absorbance A3 is preferably 0.2 or more, more preferably 0.25 or more, and may be, for example, 0.5 or more, or 0.7 or more. The upper limit of the absorbance A3 is not particularly limited, but may be, for example, 1.5.

[0095] The absorbances A1, A2, and A3 can be adjusted, for example, by the contents of the first to third ultraviolet absorbents in the surface protective layer and the thickness of the surface protective layer. For example, the absorbance can be easily adjusted by the surface protective layer containing the first to third ultraviolet absorbents, respectively.

[0096] In one embodiment, the absorbance of the surface protective layer in the wavelength region of 270 nm or more and 370 nm or less has a maximum value in the range of 300 nm or more and 340 nm or less, which tends to further improve the long-term weather resistance of the transfer layer, for example.

[0097] Each absorbance is measured as follows. The average absorbance of the surface protective layer at wavelengths of 270 nm to 300 nm in accordance with JIS K0115:2004 is defined as absorbance A1, which is the average value obtained by measuring the absorbance at 1 nm intervals at wavelengths of 270 nm to 300 nm inclusive. The average absorbance A2 of the surface protective layer at wavelengths of 310 nm to 330 nm in accordance with JIS K0115:2004 is the average value of absorbance measurements taken at 1 nm intervals at wavelengths of 310 nm to 330 nm inclusive. The average absorbance A3 of the surface protective layer at wavelengths of 340 nm to 370 nm in accordance with JIS K0115:2004 is the average value of absorbance measurements taken at 1 nm intervals at wavelengths of 340 nm to 370 nm inclusive.

[0098] The absorbance of the surface protective layer of the transfer sheet can be measured as follows. Layers (e.g., a primer layer and an adhesive layer) outside the surface protective layer of the transfer layer of the transfer sheet are removed by cutting or using a solvent, and the absorbance of the remaining laminate is measured. Thereafter, the absorbance of the releasable substrate alone is measured. The absorbance of the surface protective layer is obtained by subtracting the absorbance of the releasable substrate alone from the absorbance of the remaining laminate.

[0099] In one embodiment, the surface protective layer can be formed by preparing a curable composition, applying the composition to a releasable substrate to form an uncured resin layer, and curing the uncured resin layer by crosslinking. The crosslinking curing can be performed, for example, by curing through heat treatment when a thermosetting resin is used, or by curing through irradiation with ionizing radiation such as electron beams or ultraviolet rays when an ionizing radiation-curable compound is used.

[0100] When an electron beam is used as the ionizing radiation, the exposure dose is, for example, 5 kGy to 300 kGy (0.5 Mrad to 30 Mrad), preferably 10 kGy to 100 kGy (1 Mrad to 10 Mrad). When ultraviolet light is used as the ionizing radiation, light containing ultraviolet light with a wavelength of 190 nm to 380 nm may be emitted.

[0101] From the viewpoint of a balance between processability, scratch resistance, and weather resistance, the thickness of the surface protective layer is preferably 1 μm or more, more preferably 1.5 μm or more, and even more preferably 2 μm or more, and is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less.

[0102] In the transfer sheet of the present disclosure, the transfer layer includes a primer layer. The primer layer can be provided for the purpose of improving the adhesion between the surface protective layer and the adhesive layer, for example.

[0103] In one embodiment, the primer layer contains a resin component. Examples of the resin component include vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-(meth)acrylic copolymer, chlorinated polyethylene, chlorinated polypropylene, urethane resin, (meth)acrylic resin, (meth)acrylic polyol resin, polystyrene, polyester, polyamide, butyral resin, nitrocellulose, and cellulose acetate. The resin component may be a crosslinked cured product of these resins using a curing agent. The resin component may be, for example, a cured product of the two-component curing urethane resin described above.

[0104] From the viewpoint of weather resistance and durability, the urethane resin is preferably a urethane resin having a (meth)acrylic skeleton in the polyurethane polymer chain. Examples of the urethane resin having a (meth)acrylic skeleton in the polyurethane polymer chain include a urethane-(meth)acrylic copolymer, which is a copolymer of a urethane component and a (meth)acrylic component, and a resin using a (meth)acrylic resin having a hydroxy group or an isocyanate group as the polyol component or polyisocyanate component constituting the polyurethane. Among these, a urethane-(meth)acrylic copolymer is preferred, and a preferred example of the urethane-(meth)acrylic copolymer is a urethane-(meth)acrylic block copolymer.

[0105] From the viewpoint of adhesion between the primer layer and the surface protective layer, the urethane-(meth)acrylic copolymer may further have a polycarbonate skeleton or a polyester skeleton in the polyurethane polymer chain. Examples of such urethane-(meth)acrylic copolymers include polycarbonate-based urethane-(meth)acrylic copolymers, which are copolymers of a polycarbonate-based urethane component and a (meth)acrylic component, and polyester-based urethane-(meth)acrylic copolymers, which are copolymers of a polyester-based urethane component and a (meth)acrylic component.

[0106] The urethane-(meth)acrylic copolymer can be obtained, for example, by a method of reacting a (meth)acrylic resin having at least two hydroxy groups in one molecule with a polyol and a polyisocyanate (see, for example, JP-A-6-100653), or by a method of reacting a urethane prepolymer having unsaturated double bonds at both ends with a (meth)acrylic monomer (see, for example, JP-A-10-1524).

[0107] Examples of urethane prepolymers include polycarbonate-based urethane prepolymers obtained by reacting polycarbonate diol with diisocyanate, and polyester-based urethane prepolymers obtained by reacting polyester diol with diisocyanate. Examples of diisocyanates include aliphatic isocyanates such as hexamethylene diisocyanate, and alicyclic isocyanates such as isophorone diisocyanate and hydrogenated xylylene diisocyanate. Examples of (meth)acrylic monomers include (meth)acrylic acid and (meth)acrylic acid alkyl esters having an alkyl group with 1 to 6 carbon atoms.

[0108] Specific examples of urethane resins include polycarbonate-based urethane-(meth)acrylic copolymers, polyester-based urethane-(meth)acrylic copolymers, polyether-based urethane-(meth)acrylic copolymers, and caprolactone-based urethane-(meth)acrylic copolymers. These resin components are preferred from the viewpoints of improving weather resistance and further improving adhesion between the surface protective layer and the adhesive layer.

[0109] In the urethane resin, the urethane component / (meth)acrylic component (mass ratio) is preferably 20 / 80 or more and 99 / 1 or less, more preferably 50 / 50 or more and 95 / 5 or less, and even more preferably 70 / 30 or more and 95 / 5 or less. This can further improve, for example, weather resistance. The content of the (meth)acrylic component in the urethane resin is the proportion of monomer units constituting the (meth)acrylic skeleton per total mass of the urethane resin. The content of the (meth)acrylic component in the urethane resin is calculated by measuring the NMR spectrum of the urethane resin and determining the ratio of the peak area attributable to the (meth)acrylic component to the total peak area.

[0110] The weight-average molecular weight of the urethane resin may be 10,000 or more, or 30,000 or more, or 100,000 or less, or 80,000 or less. This can further improve weather resistance, for example. The weight-average molecular weight in this specification is determined by gel permeation chromatography (GPC) as a value converted into standard polystyrene.

[0111] The content of the resin component in the primer layer is, for example, 50% by mass or more.

[0112] The primer layer may contain an ultraviolet absorber such as the first to third ultraviolet absorbers described above. The primer layer may contain the light stabilizer described above. The primer layer may contain the additives described above.

[0113] When the primer layer contains an ultraviolet absorber, the content of the ultraviolet absorber in the primer layer may be 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 50 parts by mass or less, 45 parts by mass or less, or 40 parts by mass or less, per 100 parts by mass of the resin component contained in the primer layer.

[0114] When the primer layer contains a light stabilizer, the content of the light stabilizer in the primer layer may be 0.1 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, 10 parts by mass or less, 8 parts by mass or less, or 6 parts by mass or less, relative to 100 parts by mass of the resin component contained in the primer layer.

[0115] The thickness of the primer layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, and even more preferably 1 μm or more, and is preferably 10 μm or less, more preferably 8 μm or less, and even more preferably 6 μm or less.

[0116] To improve adhesion between the surface protective layer and the primer layer, the surface protective layer may be subjected to a surface treatment before the formation of the primer layer, such as a corona discharge treatment, a plasma treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, or an ozone / ultraviolet treatment.

[0117] In order to improve the adhesion between the surface protective layer and the primer layer, the crosslinking curing of the surface protective layer may be limited to a semi-cured state, and then the resin composition for the primer layer may be applied to the semi-cured surface protective layer, followed by irradiating the surface protective layer with ionizing radiation to completely cure the surface protective layer.

[0118] When a primer layer is formed by applying a resin composition for a primer layer onto a surface protective layer after curing the surface protective layer, it may be difficult to sufficiently increase the adhesion between the primer layer and the surface protective layer. In such cases, for example, if the primer layer deteriorates due to ultraviolet irradiation in an environment exposed to direct sunlight, peeling between the primer layer and the surface protective layer is likely to occur. In the present disclosure, since deterioration of the primer layer can be suppressed over the long term as described above, such peeling can be suppressed.

[0119] In the transfer sheet of the present disclosure, the transfer layer may include a design layer. The transfer layer may include a design layer between the primer layer and the adhesive layer. The design layer may be disposed on a part of the surface of the primer layer opposite the surface protective layer, or may be disposed on the entire surface. The design layer may be a layer that covers the entire surface of the primer layer opposite the surface protective layer, or may be a patterned layer including areas where a design is disposed and areas where a design is not disposed on the surface of the primer layer opposite the surface protective layer.

[0120] The design layer can be provided to display a design. The design layer has, for example, a pattern. Examples of patterns include wood grain patterns imitating tree rings or vessel grooves on the surface of a wooden board, stone grain patterns imitating the surface of rocks such as marble and granite, fabric patterns imitating cloth grain or cloth-like patterns, leather grain patterns imitating the surface of leather, pear-skin patterns, tile patterns, brickwork patterns, geometric patterns, and abstract patterns such as letters, figures, symbols, polka dots, and floral patterns. The pattern may be a single solid color (a so-called solid image). The pattern may also be a composite pattern containing two or more of these. The design layer may have two or more layers. For example, the design layer may have a colored first layer and a second layer provided on the first layer to form the pattern.

[0121] The design layer can be formed, for example, by a printing method or a coating method. Examples of printing methods include gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, and inkjet printing. Examples of coating methods include gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, and reverse roll coating. Each of the other layers can also be formed, for example, by these methods.

[0122] In one embodiment, the design layer contains a resin component and a colorant. Examples of the resin component include vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-(meth)acrylic copolymer, chlorinated polyethylene, chlorinated polypropylene, urethane-(meth)acrylic copolymer, (meth)acrylic resin, (meth)acrylic polyol resin, polystyrene, polyurethane, polyester, polyamide, butyral resin, nitrocellulose, and cellulose acetate.

[0123] Examples of colorants include pigments and dyes. Specific examples include inorganic pigments such as carbon black, 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, phthalocyanine blue, azomethine azo black, and nickel azo complexes; metal pigments consisting of scaly flakes such as aluminum and brass; and pearlescent pigments consisting of scaly flakes such as titanium dioxide-coated mica and basic lead carbonate.

[0124] The content of colorant in the design layer may be 5 parts by mass or more, 15 parts by mass or more, 30 parts by mass or more, 200 parts by mass or less, 150 parts by mass or less, or 100 parts by mass or less, relative to 100 parts by mass of the resin component contained in the design layer.

[0125] The design layer may contain additives. Examples of additives include ultraviolet absorbers, light stabilizers, antioxidants, fillers, antifoaming agents, flame retardants, plasticizers, and lubricants. The design layer may contain weathering agents such as ultraviolet absorbers, light stabilizers, and antioxidants in order to improve weather resistance.

[0126] The thickness of the design layer is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more, and is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less. This can improve the design, for example.

[0127] The design layer may have a metal thin film. Examples of metals constituting the metal thin film include tin, indium, chromium, aluminum, nickel, iron, cobalt, copper, silver, gold, platinum, and zinc, as well as alloys containing at least one selected from these metals. Examples of alloys include brass, bronze, and stainless steel. Examples of methods for forming the metal thin film include vacuum deposition, sputtering, and ion plating. The thickness of the metal thin film is, for example, 0.1 μm or more and 1 μm or less. The adhesive layer may also serve as the design layer.

[0128] In the transfer sheet of the present disclosure, the transfer layer may include an adhesive layer. The adhesive layer has the function of adhering the transfer sheet to the surface of the transfer recipient. In one embodiment, the adhesive layer constitutes the surface layer of the transfer layer on the side opposite the releasable substrate side. The adhesive layer is the layer that comes into contact with the transfer recipient after transfer. This allows the transfer layer to be successfully transferred and attached to the transfer recipient.

[0129] In the present disclosure, the transfer sheet is attached to the object to be transferred so that the adhesive layer is in contact with the surface of the object to be transferred, and then the releasable substrate is peeled off, thereby allowing the transfer layer comprising the surface protection layer and the primer layer to be transferred from the transfer sheet onto the object to be transferred with good adhesion.

[0130] Preferred adhesive resins that can be used in the adhesive layer include heat-fusible resins such as (meth)acrylic resins, polyolefins, chlorinated polyolefins, vinyl chloride-vinyl acetate copolymers, polyamides, polyesters, chlorinated rubbers, urethane resins, epoxy resins, and styrene resins. Among these, (meth)acrylic resins such as polymethyl methacrylate resins are preferred from the viewpoint of improving weather resistance.

[0131] The content of the adhesive resin in the adhesive layer is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more.

[0132] The adhesive layer may contain additives, such as weathering agents such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropy-imparting agents, coupling agents, plasticizers, antifoaming agents, fillers, and colorants.

[0133] The adhesive layer may contain a weather resistant agent, the details of which are as described above. The content of the ultraviolet absorber in the adhesive layer may be 0.1 parts by mass or more, 1 part by mass or more, 3 parts by mass or more, 25 parts by mass or less, 20 parts by mass or less, or 15 parts by mass or less, relative to 100 parts by mass of the adhesive resin. The content of the light stabilizer in the adhesive layer may be 0.05 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, 7 parts by mass or less, or 5 parts by mass or less, relative to 100 parts by mass of the adhesive resin.

[0134] The thickness of the adhesive layer is preferably 1 μm or more, and preferably 12 μm or less, more preferably 6 μm or less, which allows, for example, the transfer layer to be well adhered to the transfer target and also ensures excellent transparency.

[0135] The thickness of the adhesive layer is preferably greater than the thickness of the primer layer.

[0136] The adhesive layer can be formed, for example, by applying a composition containing components constituting the adhesive layer (adhesive layer composition) onto the primer layer, and drying it as necessary.

[0137] The transfer sheet of the present disclosure may include a cover film (protective film) on the adhesive layer. Specifically, a cover film may be attached to the adhesive layer. This can effectively protect the surface of the adhesive layer, which is preferable for storing the transfer sheet. When using the transfer sheet, the cover film is peeled off from the adhesive layer to expose the adhesive layer, and the transfer sheet is attached to the transfer target via this adhesive layer.

[0138] The cover film is made of a resin component such as polyolefin.

[0139] The weather-resistant article of the present disclosure includes a transfer receiving body and a surface protective film provided on at least a portion of the surface of the transfer receiving body. The surface protective film is the transfer layer in the transfer sheet of the present disclosure, and the surface protective layer included in the transfer layer constitutes at least a portion of the surface layer of the weather-resistant article.

[0140] In one embodiment, as shown in Fig. 3, the weather-resistant article 2 comprises a transfer recipient 30 and a transfer layer 20 provided on the surface of the transfer recipient 30. In the embodiment of Fig. 3, the transfer layer 20 comprises an adhesive layer 26, a primer layer 24, and a surface protective layer 22, in this order from the transfer recipient 30 side. Therefore, the weather-resistant article 2 comprises the adhesive layer 26, the primer layer 24, and the surface protective layer 22, in this order, on the transfer recipient 30. The releasable substrate 10 only needs to be peeled off when the weather-resistant article 2 is used.

[0141] The recipient is an article to which the transfer layer of the transfer sheet of the present disclosure is transferred. The transfer layer of the transfer sheet of the present disclosure can be transferred to an exterior material, for example. The exterior material can maintain good weather resistance even after being exposed to harsh outdoor conditions.

[0142] Exterior materials are molded articles used outdoors, for example, molded articles for applications requiring weather resistance due to daily exposure to direct sunlight. The transfer layer of the transfer sheet of the present disclosure has excellent weather resistance and is therefore suitable for exterior material applications. The shape of the exterior material is not particularly limited, and examples thereof include plates such as flat plates and curved plates, three-dimensional shaped articles, sheets, and films. Examples of exterior materials include resin materials, wood materials, and inorganic materials.

[0143] Examples of resin members include sheets, plates, and three-dimensional articles made of polyolefin, vinyl chloride resin, styrene resin, (meth)acrylic resin, polyester, polycarbonate, polyamide, polyimide, cellulose resin, phenolic resin, rubber, etc.

[0144] Examples of wooden members include boards and three-dimensional articles made of wood fiberboards such as wood veneer, wood plywood, particle board, medium density fiberboard (MDF), and laminated wood.

[0145] Examples of inorganic members include metal members and other inorganic members. Metal members include sheets, plates, and three-dimensional articles made of iron, aluminum, copper, tin, titanium, and alloys containing at least one of these metals (e.g., carbon steel, stainless steel, duralumin, brass, and bronze). Other inorganic members include plates and three-dimensional articles made of glass, ceramics such as porcelain, non-cement ceramic materials such as gypsum, and lightweight aerated concrete (ALC) plates.

[0146] Examples of exterior materials include exterior materials for building structures, exterior materials for vehicles, ships, and aircraft, exterior materials for industrial machinery, and various lenses. Examples of exterior materials (building materials) for building structures include exterior walls, roofs, eaves ceilings, floors, fences, various doors such as entrance doors and gates, window materials, handrails, balcony partitions, roofing materials for terraces or carports, agricultural greenhouses, and soundproof or windbreak walls for general roads and expressways. Examples of exterior materials for vehicles include window materials such as side windows, rear windows, roof windows, front windows, and quarter windows; headlight covers, turn signal lamp lenses, reflectors; and pillars. Examples of vehicles include light vehicles such as automobiles, railroad cars, construction machinery, and golf carts. Examples of exterior materials for industrial machinery include visibility window materials for machine tools. Examples of lenses include traffic light lenses.

[0147] The thickness of the exterior material may be selected appropriately depending on the application and material, and in one embodiment, may be 0.1 mm or more, 0.3 mm or more, 0.5 mm or more, 10 mm or less, 5 mm or less, or 3 mm or less.

[0148] The above-mentioned transfer object is not limited to exterior materials, but also includes, for example, interior materials for vehicles, ships and aircraft, interior materials for building structures, front panels of various display devices, convex mirrors, traffic signs and nameplates. The transfer object may be, for example, a decorative material such as a decorative board.

[0149] The weather-resistant article of the present disclosure can be obtained, for example, by using the transfer sheet of the present disclosure to transfer the transfer layer of the transfer sheet onto at least a portion of the surface of a transferee. In one embodiment, a method for producing a weather-resistant article of the present disclosure includes the steps of preparing the transfer sheet of the present disclosure and a transferee, placing the transfer sheet on the transferee so that the transfer layer of the transfer sheet faces the transferee, and peeling off the releasable substrate of the transfer sheet.

[0150] In one embodiment, a transfer sheet of the present disclosure having a transfer layer including a surface protection layer, a primer layer, and an adhesive layer, and a recipient are prepared, and the transfer sheet is placed on at least a portion of the surface of the recipient so that the adhesive layer of the transfer sheet contacts the surface of the recipient.

[0151] In one embodiment, a transfer sheet according to the present disclosure, which includes a transfer layer including a surface protective layer and a primer layer, and a transferee having an adhesive layer on its surface, are prepared, and the transfer sheet is placed on at least a portion of the surface of the transferee so that the transfer layer of the transfer sheet and the adhesive layer on the transferee are in contact with each other. Examples of the adhesive layer on the transferee include an adhesive layer that can be provided on the transfer layer of the transfer sheet.

[0152] The placement may be performed under heat and / or pressure. The releasable substrate of the transfer sheet is then peeled off from the transfer layer, specifically from the surface protective layer. In this manner, a weather-resistant article is obtained. Examples of transfer methods include thermal transfer methods such as roll transfer and press transfer, and in-mold molding.

[0153] The releasable substrate may be used as a protective film for the weather-resistant article without being immediately peeled off from the transfer layer, in which case the releasable substrate may be peeled off from the transfer layer before the weather-resistant article is used.

[0154] After the transfer sheet is placed on the surface of the transfer-receiving material, the resulting weather-resistant article may be further subjected to processing such as bending, etc. The processing may be carried out either before or after peeling off the releasable substrate.

[0155] The weather-resistant article of the present disclosure may be manufactured, for example, by simultaneously forming the transferee and placing a transfer sheet. For example, a resin is injected onto the adhesive layer of the transfer sheet to integrate the transfer sheet with a resin molded article (injection molded article) as the transferee. The releasable substrate is then peeled off from the transfer layer. In this case, examples of methods for forming the resin molded article include various injection molding methods such as in-mold molding, insert molding, simultaneous injection molding and decoration, blow molding, and gas injection molding.

[0156] The present disclosure relates to, for example, the following [1] to

[15] . [1] A transfer sheet comprising a releasable substrate and a transfer layer, the transfer layer comprising a surface protective layer and a primer layer, the surface protective layer being located between the releasable substrate and the primer layer, the surface protective layer containing a cured resin, a first ultraviolet absorber having an absorption peak at a first wavelength, a second ultraviolet absorber having an absorption peak at a second wavelength longer than the first wavelength, and a third ultraviolet absorber having an absorption peak at a third wavelength longer than the second wavelength. [2] The transfer sheet according to the above [1], wherein the difference between the second wavelength and the first wavelength is 10 nm or more, and the difference between the third wavelength and the second wavelength is 10 nm or more. [3] The transfer sheet according to [1] or [2] above, wherein the second wavelength is in the range of 310 nm or more and 330 nm or less. [4] The transfer sheet according to any one of the above [1] to [3], wherein the first wavelength is in the range of 270 nm or more and 300 nm or less. [5] The transfer sheet according to any one of the above [1] to [4], wherein the third wavelength is in the range of 340 nm or more and 370 nm or less. [6] A transfer sheet according to any one of [1] to [5] above, wherein the content of the second ultraviolet absorber in the surface protective layer is greater than the content of the first ultraviolet absorber and greater than the content of the third ultraviolet absorber. [7] The transfer sheet according to any one of the above [1] to [6], wherein the first ultraviolet absorber, the second ultraviolet absorber, and the third ultraviolet absorber are each independently a triazine-based ultraviolet absorber. [8] A transfer sheet according to any one of [1] to [7] above, wherein the surface protective layer contains a first ultraviolet absorber, a second ultraviolet absorber, and a third ultraviolet absorber in a total amount of 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the cured resin contained in the surface protective layer. [9] A transfer sheet according to any one of [1] to [8] above, wherein the surface protective layer contains, relative to 100 parts by mass of the cured resin contained in the surface protective layer, 0.1 parts by mass or more and 3 parts by mass or less of a first ultraviolet absorber, 0.1 parts by mass or more and 8 parts by mass or less of a second ultraviolet absorber, and 0.1 parts by mass or more and 3 parts by mass or less of a third ultraviolet absorber.

[10] The transfer sheet according to any one of the above [1] to [9], wherein the primer layer contains an ultraviolet absorber.

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

[10] , wherein the transfer layer further comprises a design layer.

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

[11] , wherein the transfer layer further comprises an adhesive layer as a surface layer on the side opposite to the releasable substrate side.

[13] The transfer sheet according to any one of the above [1] to

[12] , for transferring a transfer layer onto at least a part of the surface of an exterior material.

[14] A weather-resistant article comprising a transfer object and a surface protective film provided on at least a portion of the surface of the transfer object, wherein the surface protective film is a transfer layer in a transfer sheet described in any one of [1] to

[13] above, and the surface protective layer in the transfer layer constitutes at least a portion of the surface layer of the weather-resistant article.

[15] The weather-resistant article according to the above

[14] , wherein the transfer layer has an adhesive layer, or an adhesive layer is provided between the transfer layer and the object to be transferred. [Example]

[0157] The transfer sheet of the present disclosure will be described in more detail below based on examples, but the transfer sheet of the present disclosure is not limited to these examples in any way.

[0158] [Example 1] An untreated matte PET film (PET raw material Diafoil E130-26, Mitsubishi Chemical) was prepared as a release substrate. Approximately 5 g of the ionizing radiation-curable resin composition described below was applied to the release substrate to form an uncured resin layer. The uncured resin layer was then cured by irradiating it with an electron beam (acceleration voltage: 175 kV, exposure dose: 5 Mrad (50 kGy)) to form a 5 μm-thick surface protective layer. The surface protective layer was subjected to a corona discharge treatment. Approximately 2.5 g of the primer layer resin composition described below was applied to the corona discharge-treated surface protective layer by gravure printing and dried to form a 3.5 μm-thick primer layer. Approximately 5 g of a heat-sealable resin (polymethyl methacrylate resin (PMMA), molecular weight approximately 96,000) was applied to the primer layer to form a 4.5 μm-thick adhesive layer (heat seal layer), which was then aged at room temperature for 24 hours.

[0159] In this way, a transfer sheet was obtained. The transfer sheet had a PET film as a releasable substrate and a transfer layer provided on the PET film, and the transfer layer had a surface protective layer, a primer layer, and an adhesive layer.

[0160] <Ionizing radiation curable resin composition> 100 parts by weight of trifunctional urethane acrylate oligomer with a weight-average molecular weight of 4,000 First ultraviolet absorber: 0.5 parts by mass Hydroxyphenyltriazine ultraviolet absorbers, Product name: ADK STAB LA-46, ADEKA Corporation, Absorption peak wavelength: 275 nm Second UV absorber: 3 parts by weight Hydroxyphenyltriazine ultraviolet absorbers, Product name: TINUVIN 479, BASF Absorption peak wavelength: 322 nm Third UV absorber 0.5 parts by mass Hydroxyphenyltriazine ultraviolet absorbers, Product name: TINUVIN477, BASF Absorption peak wavelength: 356 nm Hindered amine reactive light stabilizer 3 parts by mass Product name: Sanol LS-3410, Nippon Nyukazai Co., Ltd. 1,2,2,6,6-Pentamethyl-4-piperidinyl methacrylate

[0161] <Resin composition for primer layer> Polycarbonate-based urethane-acrylic copolymer 100 parts by weight (Urethane component / acrylic component = 70 / 30 (mass ratio)) Hydroxyphenyltriazine ultraviolet absorber 30 parts by weight (trade name: Tinuvin 479 (2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, BASF) 15 parts by mass, Product name: Tinuvin 400 (2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, BASF) 15 parts by mass) Hindered amine light stabilizer 3.5 parts by mass (Trade name: Tinuvin 123 (BASF), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate)

[0162] [Comparative Example 1] A transfer sheet was obtained in the same manner as in Example 1, except that the first ultraviolet absorber in the ionizing radiation curable resin composition was not added, the amount of the second ultraviolet absorber (TINUVIN479) was changed to 1 part by mass, the amount of the third ultraviolet absorber (TINUVIN477) was changed to 3 parts by mass, and no hindered amine-based reactive light stabilizer was added.

[0163] [Absorbance] A surface protective layer was formed on a PET film under the same conditions as above to prepare a test piece. Using an ultraviolet-visible-near-infrared spectrophotometer (Hitachi, Ltd., product name: UH-4150), the absorbance of the test piece in each wavelength range was measured in accordance with JIS K0115:2004. The absorbance of the PET film was subtracted from this absorbance to obtain the above-mentioned "absorbance A1," "absorbance A2," and "absorbance A3."

[0164] The absorbance of the surface protective layer corresponding to the transfer sheet of Example 1 was as follows. Absorbance A1:1.2 Absorbance A2:1.6 Absorbance A3:1.4

[0165] The absorbance of the surface protective layer corresponding to the transfer sheet of Comparative Example 1 was as follows. Absorbance A1:0.25 Absorbance A2:0.6 Absorbance A3:1.2

[0166] [Transcript] The transfer sheets obtained in the Examples and Comparative Examples and a 2 mm thick polycarbonate plate were prepared as the transfer recipient. No weathering agent was added to the polycarbonate plate. The transfer sheet was placed on one side of a polycarbonate plate heated to 130°C, with the adhesive layer of the transfer sheet in contact with the polycarbonate plate, and then pressed using a roll at 160°C. This resulted in a molded article with a releasable substrate, which in turn comprised a polycarbonate plate, adhesive layer, primer layer, surface protective layer, and releasable substrate. Next, the releasable substrate was peeled from the transfer layer of the transfer sheet to obtain a test specimen. The surface protective layer constituted the surface layer on one side of the test specimen.

[0167] [Weather resistance] Using the following ultra-accelerated weathering test equipment, the above test specimens were subjected to an ultra-accelerated weathering test (a test in which one cycle was repeated, consisting of 20 hours of ultraviolet irradiation under the following irradiation conditions, followed by 4 hours of condensation under the following condensation conditions) for 800 hours.

[0168] <Ultra-accelerated weathering test equipment> An ultra-accelerated weathering test device (product name: iSuper UV Tester SUV-W261, manufactured by Iwasaki Electric Co., Ltd.) equipped with a UV lamp (product name: M04-L21WB / SUV, manufactured by Iwasaki Electric Co., Ltd.), a lamp jacket (product name: WJ50-SUV, manufactured by Iwasaki Electric Co., Ltd.), and an illuminance meter (product name: UVD-365PD, manufactured by Iwasaki Electric Co., Ltd.). <Irradiation conditions> Black panel temperature: 63°C ·Illuminance: 100mW / cm 2 ·Battle humidity: 50%RH Duration: 20 hours <Condensation conditions> ·Illuminance: 0mW / cm 2 ·Battle humidity: 98%RH Duration: 4 hours

[0169] [Adhesion evaluation] After the weather resistance test was performed for 800 hours, the test specimens were subjected to a cellophane tape resistance test, and the presence or absence of peeling of the surface protective layer was visually observed and evaluated as follows: The cellophane tape resistance test was performed by attaching a cellophane adhesive tape (trade name: Cellotape®) manufactured by Nichiban Co., Ltd. to a test area of ​​1.5 cm × 1.5 cm on the surface of the test specimen on the surface protective layer side, and then pulling it forcefully toward the user at a 45-degree angle. ○: No peeling of the surface protective layer. Δ: Peeling of the surface protective layer occurred in an area of ​​less than 50% of the test area. ×: Peeling of the surface protective layer occurred in 50% or more of the test area. The results were as follows: Example 1: Comparative Example 1: △ [Explanation of symbols]

[0170] 1...Transfer sheet 2...Weather resistant articles 10…Releasable base material 20...Transfer layer 22…Surface protective layer 24...Primer layer 26...adhesive layer 30...transferred object (e.g., exterior material)

Claims

1. A transfer sheet comprising a releasable substrate and a transfer layer, the transfer layer includes a surface protective layer and a primer layer; the surface protective layer is located between the releasable substrate and the primer layer, the surface protective layer contains a cured resin, a first ultraviolet absorber having an absorption peak at a first wavelength, a second ultraviolet absorber having an absorption peak at a second wavelength longer than the first wavelength, and a third ultraviolet absorber having an absorption peak at a third wavelength longer than the second wavelength, the absorption peaks being based on an absorbance spectrum measured using an ultraviolet-visible-near-infrared spectrophotometer; the second wavelength is in the range of 310 nm or more and 330 nm or less, a difference between the second wavelength and the first wavelength is 10 nm or more; a difference between the third wavelength and the second wavelength is 10 nm or more; In the surface protective layer, the content of the second ultraviolet absorber is greater than the content of the first ultraviolet absorber and greater than the content of the third ultraviolet absorber; The transfer sheet, wherein the first ultraviolet absorber, the second ultraviolet absorber, and the third ultraviolet absorber are each independently a triazine-based ultraviolet absorber.

2. A transfer sheet comprising a releasable substrate and a transfer layer, the transfer layer includes a surface protective layer and a primer layer; the surface protective layer is located between the releasable substrate and the primer layer, the surface protective layer contains a cured resin, a first ultraviolet absorber having an absorption peak at a first wavelength, a second ultraviolet absorber having an absorption peak at a second wavelength longer than the first wavelength, and a third ultraviolet absorber having an absorption peak at a third wavelength longer than the second wavelength, the absorption peaks being based on an absorbance spectrum measured using an ultraviolet-visible-near-infrared spectrophotometer; the second wavelength is in the range of 310 nm or more and 330 nm or less, a difference between the second wavelength and the first wavelength is 10 nm or more; a difference between the third wavelength and the second wavelength is 10 nm or more; In the surface protective layer, the content of the second ultraviolet absorber is greater than the content of the first ultraviolet absorber and greater than the content of the third ultraviolet absorber; The transfer sheet, wherein the primer layer contains an ultraviolet absorber.

3. The transfer sheet according to claim 1 or 2, wherein the first wavelength is in the range of 270 nm to 300 nm.

4. The transfer sheet according to any one of claims 1 to 3, wherein the third wavelength is in the range of 340 nm or more and 370 nm or less.

5. The transfer sheet according to claim 2 , wherein the first ultraviolet absorber, the second ultraviolet absorber, and the third ultraviolet absorber are each independently a triazine-based ultraviolet absorber.

6. The transfer sheet according to any one of claims 1 to 5, wherein the surface protective layer contains the first ultraviolet absorber, the second ultraviolet absorber, and the third ultraviolet absorber in a total amount of 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the cured resin contained in the surface protective layer.

7. The transfer sheet according to any one of claims 1 to 6, wherein the surface protective layer contains, relative to 100 parts by mass of the cured resin contained in the surface protective layer, 0.1 parts by mass or more and 3 parts by mass or less of the first ultraviolet absorber, 0.1 parts by mass or more and 8 parts by mass or less of the second ultraviolet absorber, and 0.1 parts by mass or more and 3 parts by mass or less of the third ultraviolet absorber.

8. The transfer sheet according to any one of claims 1 to 7, wherein the transfer layer further comprises a design layer.

9. The transfer sheet according to any one of claims 1 to 8, wherein the transfer layer further comprises an adhesive layer as a surface layer on the side opposite to the releasable substrate.

10. The transfer sheet according to any one of claims 1 to 9, for transferring the transfer layer onto at least a part of the surface of an exterior material.

11. A transfer object; a surface protection film provided on at least a portion of the surface of the transfer object; A weather-resistant article comprising: The surface protective film is the transfer layer in the transfer sheet according to any one of claims 1 to 10, and the surface protective layer in the transfer layer constitutes at least a part of the surface layer of the weather-resistant article. Weather resistant articles.

12. the transfer layer comprises an adhesive layer, or The weather-resistant article according to claim 11 , further comprising an adhesive layer provided between the transfer layer and the transfer-receiving body.

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