WO2023190478A1 - 転写シート及び耐候性物品 - Google Patents

転写シート及び耐候性物品 Download PDF

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Publication number
WO2023190478A1
WO2023190478A1 PCT/JP2023/012439 JP2023012439W WO2023190478A1 WO 2023190478 A1 WO2023190478 A1 WO 2023190478A1 JP 2023012439 W JP2023012439 W JP 2023012439W WO 2023190478 A1 WO2023190478 A1 WO 2023190478A1
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WIPO (PCT)
Prior art keywords
layer
transfer
mass
less
ultraviolet absorber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2023/012439
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English (en)
French (fr)
Japanese (ja)
Inventor
哲 古田
夏生 杉田
沙織 宮崎
泰宏 秋田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dai Nippon Printing Co Ltd
Original Assignee
Dai Nippon Printing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dai Nippon Printing Co Ltd filed Critical Dai Nippon Printing Co Ltd
Priority to CN202380022583.5A priority Critical patent/CN118715125A/zh
Priority to US18/841,457 priority patent/US20250162299A1/en
Priority to EP23780487.7A priority patent/EP4506164A4/en
Publication of WO2023190478A1 publication Critical patent/WO2023190478A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/04—4 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes

Definitions

  • the present disclosure relates to transfer sheets and weather-resistant articles.
  • a surface protective layer has been provided on the surface of the articles. It is being done.
  • the surface protective layer is formed, for example, by coating or using a transfer sheet (see, for example, Patent Document 1).
  • the transfer sheet usually includes a transfer layer including a surface protection layer and a primer layer. The present disclosers believe that the cause of insufficient weather resistance is due to insufficient adhesion between the surface protective layer and the primer layer after being exposed to direct sunlight for a long period of time. I found out.
  • One of the problems of the present disclosure is to suppress the decrease in adhesion between the surface protective layer and the primer layer for a long period of time in a transfer layer that is transferred from a transfer sheet having a transfer layer including a surface protective layer and a primer layer to an object to be transferred. It's about doing.
  • the transfer sheet of the present disclosure includes a releasable base material and a transfer layer, the transfer layer includes a surface protective layer and a primer layer, and the surface protective layer is located between the releasable base material and the primer layer.
  • the surface protective layer includes a cured resin, a first ultraviolet absorber having an absorption peak at a first wavelength, and 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 that is longer than the second wavelength.
  • the surface protection layer and the primer layer are separated in an environment exposed to direct sunlight. Decrease in adhesion can be suppressed for a long period of time.
  • FIG. 1 is a schematic cross-sectional view of an embodiment of a transfer sheet of the present disclosure.
  • FIG. 2 is a schematic cross-sectional view of an embodiment of the transfer sheet of the present disclosure.
  • FIG. 3 is a schematic cross-sectional view of one embodiment of the weather-resistant article of the present disclosure.
  • Films and sheets are sometimes referred to as films and sheets in descending order of thickness. However, in this disclosure, unless otherwise specified, sheet includes film.
  • the numerical range of the parameter is between any one upper limit value candidate and any one lower limit value candidate. It may also be configured by combining candidates. Examples of the above-mentioned parameters include physical property values, component contents, and layer thicknesses. As an example, "Parameter B is preferably A1 or more, more preferably A2 or more, even more preferably A3 or more. Parameter B is preferably A4 or less, more preferably A5 or less, and still more preferably A6 or less.” ” will be explained.
  • the numerical range of parameter B may be A1 or more and A4 or less, A1 or more and A5 or less, A1 or more and A6 or less, A2 or more and A4 or less, A2 or more and A5 or less, A2 or more and A6 or less. It may be A3 or more and A4 or less, A3 or more and A5 or less, or A3 or more and A6 or less.
  • each component that appears for example, a resin component, an ultraviolet absorber, a light stabilizer, a coloring agent, and an additive
  • a resin component for example, an ultraviolet absorber, a light stabilizer, a coloring agent, and an additive
  • the transfer sheet of the present disclosure includes a releasable base material and a transfer layer.
  • the transfer layer is releasably provided on the releasable base material.
  • the transfer layer includes a surface protection layer and a primer layer.
  • the surface protective layer is located between the releasable base material and the primer layer.
  • the surface protective layer constitutes, for example, the surface layer of the transfer layer on the side of the releasable base material.
  • the transfer layer may further include an adhesive layer.
  • the adhesive layer constitutes, for example, the surface layer of the transfer layer on the side opposite to the releasable base material side. Therefore, the transfer layer may include a surface protection layer, a primer layer, and an adhesive layer in this order.
  • the transfer layer may further include a layer different from the surface protection layer, primer layer, and adhesive layer.
  • a layer different from the surface protection layer, primer layer, and adhesive layer As other layers, well-known layers such as a design layer can be appropriately selected and used.
  • the surface protective layer includes 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 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 wavelength. Details of these ultraviolet absorbers will be described later.
  • the weather-resistant article obtained by transferring the transfer layer from the transfer sheet of the present disclosure to a transfer target can suppress the 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 time under conditions.
  • a weather-resistant article that includes a primer layer and a surface protection layer
  • the polymer component contained in the primer layer One of the factors contributing to the adhesion between the primer layer and the surface protective layer is the polymer component contained in the primer layer. It is thought that when this polymer component deteriorates due to ultraviolet rays, the primer layer itself becomes brittle, the adhesion between the primer layer and the surface protective layer becomes weak, and peeling occurs at the interface between the primer layer and the surface protective layer. This reduces the weather resistance of the article. For example, if the article is exposed to ultraviolet rays for a long period of time, the polymer component contained in the primer layer gradually deteriorates.
  • ultraviolet rays can be sufficiently absorbed.
  • the present disclosure has discovered that the long-term weather resistance of the above article can be improved by making the surface protective layer contain at least three types of ultraviolet absorbers each having a different absorption peak wavelength. Ta. This is presumed to be based on the following reasons. By using three or more of the above ultraviolet absorbers in combination, a wide range of ultraviolet wavelengths can be covered. This allows the ultraviolet absorber to sufficiently absorb ultraviolet rays in a wide range of wavelengths. Therefore, deterioration of the primer layer due to ultraviolet rays can be suppressed over a long period of time. As a result, the article can remain weather resistant for a sufficiently long period of time in an environment exposed to direct sunlight. Further, since deterioration of the transfer object itself can be suppressed, the transfer sheet of the present disclosure can be applied to various transfer objects.
  • the configuration of an embodiment of the transfer sheet of the present disclosure is shown in FIGS. 1 and 2.
  • the transfer sheet 1 shown in FIG. 1 includes a releasable base material 10 and a transfer layer 20 releasably provided on the releasable base material 10.
  • the transfer layer 20 includes a surface protection layer 22 and a primer layer 24 in this order in the thickness direction from the releasable base material 10 side. That is, the releasable base material 10, the surface protection layer 22, and the primer layer 24 are stacked in the thickness direction, which is the vertical direction in the plane of the paper in FIG.
  • 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 protection layer 22, a primer layer 24, and an adhesive layer 26 in this order in the thickness direction from the releasable base material 10 side. That is, the releasable base material 10, the surface protection layer 22, the primer layer 24, and the adhesive layer 26 are stacked in the thickness direction, which is the vertical direction in the plane of the paper of FIG.
  • the transfer sheet of the present disclosure includes a releasable base material.
  • a releasable base material for example, a film composed of a resin component (hereinafter also referred to as "resin film”) can be used.
  • the resin component include polyester, polyolefin, polystyrene, vinyl resin, (meth)acrylic resin, polyamide, polyimide, and polycarbonate.
  • (meth)acrylic includes both “acrylic” and “methacrylic”
  • (meth)acrylate” includes both “acrylate” and “methacrylate.”
  • polyester films and polyolefin films are preferred.
  • a surface protective layer or the like can be easily formed on the film.
  • polyester examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polyethylene terephthalate-isophthalate copolymer.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • PET and PBT are preferred, and PET is more preferred, from the viewpoint that thermal shrinkage during production of a transfer sheet and shrinkage due to irradiation with ionizing radiation are less likely to occur.
  • polystyrene resin examples include polyethylene, polypropylene, polybutene, ethylene-propylene copolymer, and ethylene-propylene-butene copolymer.
  • polypropylene is preferred from the viewpoint of being less likely to undergo thermal shrinkage during production of the transfer sheet or shrinkage due to irradiation with ionizing radiation.
  • the resin film may be a stretched film or an unstretched film, but is preferably a stretched film.
  • the stretching ratio in the machine direction (MD) and/or the width direction (TD) of the stretched film is, for example, 5 times or more and 30 times or less. Since the resin film is a stretched film, it is possible to suppress, for example, thermal shrinkage of the resin film caused by heat treatment when manufacturing the transfer sheet, and shrinkage of the resin film caused by crosslinking treatment due to irradiation with ionizing radiation. The dimensional stability of the sheet can be improved.
  • the stretched film may be a uniaxially stretched film or a biaxially stretched film.
  • a biaxially stretched film is preferred from the viewpoint of being less likely to undergo thermal shrinkage during production of the transfer sheet or shrinkage due to irradiation with ionizing radiation.
  • the releasable base material may have a single layer structure or a multilayer structure.
  • the releasable base material may be, for example, a single layer of resin film or a laminate of resin films.
  • the resin film laminate can be produced, for example, by using a dry lamination method, a wet lamination method, or an extrusion method.
  • the surface of the releasable base material on which the surface protective layer is provided may be subjected to a known mold release treatment, or may be provided with a mold release layer such as a silicone resin, if necessary. Thereby, for example, the releasability between the surface protective layer and the releasable base material during transfer can be improved.
  • the thickness of the releasable base material is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, for example, 5 ⁇ m or more and 200 ⁇ m or less.
  • the thickness of the entire multilayer structure is preferably within the above range.
  • the transfer layer includes a surface protection layer.
  • the surface protective layer is a layer constituting the surface layer of a weather-resistant article obtained by transferring a transfer layer onto a transfer target, optionally via an adhesive layer.
  • the surface protective layer is, for example, a layer that imparts weather resistance to the transfer target, and may also be a layer that imparts scratch resistance and stain resistance.
  • the surface protective layer is preferably in contact with the releasable base material.
  • the surface protective layer is provided on the releasable base material.
  • the surface protective layer is stacked on the releasable base material in the thickness direction.
  • the surface protective layer is provided on the entire surface of the releasable base material.
  • 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 cured products of curable compounds.
  • examples of cured products of curable compounds include cured products of ionizing radiation-curable compounds and cured products of thermosetting resins.
  • the surface protective layer may contain two or more of these cured resins.
  • thermosetting resins include (meth)acrylic resins containing unsaturated groups, unsaturated polyesters, urethane resins, epoxy resins, phenol resins, aminoalkyd resins, urea resins, melamine resins, melamine-urea cocondensation resins, and guanamine. resins, diallyl phthalate resins and silicone resins.
  • thermosetting resin Along with the thermosetting resin, a curing agent is used as necessary.
  • unsaturated group-containing (meth)acrylic resins and unsaturated polyesters for example, peroxides such as methyl ethyl ketone peroxide, or radical initiators such as azoisobutyl nitrile are used.
  • peroxides such as methyl ethyl ketone peroxide
  • radical initiators such as azoisobutyl nitrile
  • urethane resin for example, an isocyanate-based curing agent is used.
  • epoxy resin for example, an organic amine curing agent is used.
  • thermosetting resins include two-component curable urethane resins containing polyol as a main ingredient and an isocyanate compound as a curing agent.
  • the polyol include (meth)acrylic polyol, polyether polyol, polyester polyol, polyethylene glycol, and polypropylene glycol.
  • the isocyanate compound is a polyvalent isocyanate having two or more isocyanate groups, such as aromatic isocyanates such as 4,4-diphenylmethane diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc.
  • aromatic isocyanates such as 4,4-diphenylmethane diisocyanate
  • hexamethylene diisocyanate isophorone diisocyanate
  • hydrogenated tolylene diisocyanate hydrogenated diphenylmethane diisocyanate
  • the surface protective layer contains a cured product of a thermosetting resin as the cured resin, for example, a crosslinked cured product of (meth)acrylic polyol using an isocyanate-based curing agent.
  • An ionizing radiation-curable compound means a compound that crosslinks and cures by irradiation with ionizing radiation, and has an ionizing radiation-curable functional group.
  • An ionizing radiation-curable functional group is a group that crosslinks when irradiated with ionizing radiation, and includes, for example, a functional group having an ethylenic double bond (ethylenic unsaturated group) such as a (meth)acryloyl group, a vinyl group, and an allyl group. ).
  • Ionizing radiation refers to electromagnetic waves or charged particle beams that have energy quanta that can polymerize or crosslink molecules.
  • ionizing radiation examples include electron beams (EB) and ultraviolet (UV), electromagnetic waves such as X-rays and gamma rays; and charged particle beams such as alpha rays and ion beams. From the viewpoint of including an ultraviolet absorber in the surface protective layer, an electron beam is preferable as the ionizing radiation.
  • Examples of the ionizing radiation-curable compound include polymerizable monomers and polymerizable oligomers that are conventionally used as ionizing radiation-curable compounds.
  • a (meth)acrylate monomer having a (meth)acryloyl group in the molecule is preferable, and a polyfunctional (meth)acrylate monomer having two or more (meth)acryloyl groups in the molecule is more preferable.
  • 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.
  • polymerizable monomers examples include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and bisphenol A.
  • Bifunctional (meth)acrylates such as tetraethoxydi(meth)acrylate and bisphenol A tetrapropoxydi(meth)acrylate; trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate , trifunctional or higher functional (meth)acrylates such as dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate; Examples include ethylene oxide-modified products, propylene oxide-modified products, caprolactone-modified products, isocyanuric acid-modified products, and propionic acid-modified products of (meth)acrylates.
  • Examples of the polymerizable oligomer include (meth)acrylate oligomers having two or more (meth)acryloyl groups in the molecule.
  • Examples of (meth)acrylate oligomers include urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polycarbonate (meth)acrylate, polycaprolactone urethane (meth)acrylate, and polyester (meth)acrylate.
  • Examples include caprolactone diol urethane (meth)acrylate and acrylic (meth)acrylate.
  • the number of (meth)acryloyl groups in the polymerizable oligomer is 2 or more, preferably 8 or less, more preferably 6 or less.
  • polymerizable oligomers include highly hydrophobic polybutadiene (meth)acrylate oligomers that have (meth)acryloyl groups in their side chains, and silicone (meth)acrylate oligomers that have polysiloxane bonds in their main chains. Can be mentioned.
  • the weight average molecular weight of the polymerizable oligomer may be 500 or more, 1,000 or more, 2,000 or more, 10,000 or less, 8,000 or less, 6,000 or less, for example. It may be 500 or more and 10,000 or less.
  • the weight average molecular weight is the average molecular weight measured by gel permeation chromatography (GPC) analysis and converted to standard polystyrene.
  • a monofunctional (meth)acrylate may be appropriately used in combination with a polyfunctional (meth)acrylate for the purpose of reducing the viscosity of the curable composition during coating.
  • monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, and cyclohexyl (meth)acrylate.
  • the ionizing radiation-curable compound is an ultraviolet-curable compound
  • 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, from the viewpoint of having excellent heat resistance, scratch resistance, and stain resistance.
  • ionizing radiation-curable compounds electron beam-curable compounds can be made solvent-free, do not require photopolymerization initiators, and provide stable curing properties, so they are recommended as components for forming the surface protective layer.
  • 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.
  • the content of the cured resin is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 90% by mass or more, based on the total resin components contained in the surface protective layer. be.
  • the surface protective layer includes 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 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 the third wavelength.
  • Each absorption peak is based on an absorbance spectrum measured using a UV-VIS near-infrared spectrophotometer.
  • the first ultraviolet absorber has an absorption peak at the first wavelength.
  • the first wavelength is preferably in the range of 270 nm or more and 300 nm or less, more preferably in the range of 270 nm or more and 290 nm or less, and even more preferably in the range of 270 nm or more and 280 nm or less.
  • the second ultraviolet absorber has an absorption peak at the second wavelength.
  • the second wavelength is preferably in the range of 310 nm or more and 330 nm or less, and more preferably in the range of 310 nm or more and 325 nm or less.
  • the third ultraviolet absorber has an absorption peak at the third wavelength.
  • the third wavelength is preferably in the range of 340 nm or more and 370 nm or less, and more preferably in the range of 345 nm or more and 365 nm or less.
  • the above absorption peak preferably means the maximum absorption peak in the wavelength range of 270 nm or more and 380 nm or less.
  • the maximum absorption peak is in the range of 270 nm or more and 300 nm or less.
  • 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 preferably 60 nm or less, more preferably 55 nm or less, even more preferably 50 nm or less,
  • the thickness is 10 nm or more and 60 nm or less.
  • 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 preferably 60 nm or less, more preferably 55 nm or less, even more preferably 50 nm or less,
  • the thickness is 10 nm or more and 60 nm or less.
  • 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 preferably 100 nm or less, more preferably 95 nm or less, even more preferably 90 nm or less, For example, it is 40 nm or more and 100 nm or less.
  • Examples of the first to third ultraviolet absorbers include triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers, which have excellent weather resistance and excellent absorbance and wavelength selectivity. From this point of view, triazine-based ultraviolet absorbers are preferred.
  • hydroxyphenyltriazine-based UV absorbers are preferred from the viewpoint of weather resistance.
  • examples of the hydroxyphenyltriazine ultraviolet absorber include a compound represented by formula (1), a compound represented by formula (2), and a compound represented by formula (3).
  • R 11 is a divalent organic group
  • R 13 and R 14 are each independently 1 It is a valent organic group
  • R 15 is a hydrogen atom or a monovalent organic group
  • n 11 and n 12 are each independently an integer of 0 to 5.
  • each R 13 may be the same or different.
  • each R 14 may be the same or different.
  • Examples of the divalent organic group for R 11 include aliphatic hydrocarbon groups such as an alkylene group and an alkenylene group, and an alkylene group is preferable 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, preferably 16 or less, more preferably 12 or less, still more preferably 8 or less, and particularly preferably 4. or less, for example, 1 or more and 16 or less.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic, and from the viewpoint of weather resistance, linear or branched is preferable, and linear is more preferable.
  • Examples of monovalent organic groups for R 13 and R 14 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 aromatic ring-containing hydrocarbon group is preferred, an aryl group is more preferred, and a phenyl group is particularly preferred.
  • each of n 11 and n 12 is preferably 0.
  • R 15 is preferably a monovalent organic group.
  • monovalent organic groups 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. , aliphatic hydrocarbon groups are preferred, and alkyl groups are more preferred.
  • 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, still more preferably 10 or less, for example 2 16 or less.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic, and from the viewpoint of weather resistance, linear or branched is preferable.
  • R 21 is a hydrogen atom or a monovalent organic group
  • R 22 and R 23 are each independently a hydroxyl group or a monovalent organic group
  • n 21 , n 22 and n 23 are each They are independently integers from 1 to 5.
  • each R 21 may be the same or different.
  • each R 22 may be the same or different.
  • each R 23 may be the same or different.
  • R 24 is a divalent organic group
  • R 25 is a monovalent organic group.
  • Examples of monovalent organic groups for R 22 and R 23 include the groups exemplified as monovalent organic groups for R 13 and R 14 in formula (1), and from the viewpoint of weather resistance, aromatic ring-containing hydrocarbons A group is preferable, an aryl group is more preferable, and a phenyl group is particularly preferable.
  • Examples of the divalent organic group for R 24 include the groups exemplified as the divalent organic group for R 11 in formula (1), and from the viewpoint of weather resistance, an aliphatic hydrocarbon group is preferable, and an alkylene group is preferable. 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, preferably 16 or less, more preferably 12 or less, still more preferably 8 or less, and particularly preferably 4. or less, for example, 1 or more and 16 or less.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic, and from the viewpoint of weather resistance, linear or branched is preferable, and linear is more preferable.
  • Examples of the monovalent organic group for R 25 include the groups exemplified as the monovalent organic group for R 15 in formula (1), and from the viewpoint of weather resistance, an aliphatic hydrocarbon group is preferable, and an alkyl group is preferable. 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, still more preferably 10 or less, for example 2 16 or less.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic, and from the viewpoint of weather resistance, linear or branched is preferable.
  • n 21 may be 2 or more, and n 22 and n 23 may each be 1.
  • one of the plurality of R 21 may be a hydrogen atom, and when R 22 and R 23 are monovalent organic groups, they may be the same organic group.
  • 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. be.
  • each R 31 may be the same or different.
  • each R 31 may be the same or different.
  • each R 31 may be the same or different.
  • each R 31 may be the same or different.
  • R 34 is a divalent organic group
  • R 35 is a monovalent organic group.
  • Examples of the divalent organic group for R 34 include the groups exemplified as the divalent organic group for R 11 in formula (1), and from the viewpoint of weather resistance, an aliphatic hydrocarbon group is preferable, and an alkylene group is preferable. 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, preferably 16 or less, more preferably 12 or less, still more preferably 8 or less, and particularly preferably 4. or less, for example, 1 or more and 16 or less.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic, and from the viewpoint of weather resistance, linear or branched is preferable, and linear is more preferable.
  • Examples of the monovalent organic group for R 35 include the groups exemplified as the monovalent organic group for R 15 in formula (1), and from the viewpoint of weather resistance, an aliphatic hydrocarbon group is preferable, and an alkyl group is preferable. 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, still more preferably 10 or less, for example 2 16 or less.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic, and from the viewpoint of weather resistance, linear or branched is preferable.
  • Each of n 31 , n 32 and n 33 may be 2 or more.
  • one of the plurality of R 31s may be a hydrogen atom
  • one of the plurality of R 32s may be a hydrogen atom
  • one of the plurality of R 33s may be a hydrogen atom.
  • the hydroxyphenyltriazine ultraviolet absorber includes 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3 ,5-triazine, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5 -triazine, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy- 3-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-ethylhe
  • the total content of the first ultraviolet absorber, the second ultraviolet absorber, and the third ultraviolet absorber with respect to 100 parts by mass of the cured resin is preferably 0.5 parts by mass or more, more preferably is 1 part by mass or more, more preferably 2 parts by mass or more, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, for example 0.5 parts by mass or more and 10 parts by mass. below.
  • the total content of ultraviolet absorbers is at least the lower limit, the weather resistance of the transfer layer tends to be improved.
  • the total content of ultraviolet absorbers is below the upper limit, it tends to be possible to suppress a decrease in the adhesion between the surface protective layer and the primer layer due to bleed-out of the ultraviolet absorbers.
  • 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, and even more preferably 0.3 parts by mass or more. It is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, still more preferably 1.5 parts by mass or less, for example 0.1 parts by mass or more and 3 parts by mass or less. This tends to improve weather resistance, for example.
  • 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, and still more preferably 1 part by mass or more. , preferably 8 parts by mass or less, more preferably 6 parts by mass or less, still more preferably 5 parts by mass or less, for example 0.1 parts by mass or more and 8 parts by mass or less. This tends to improve weather resistance, for example.
  • 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, and even more preferably 0.3 parts by mass or more. It is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, still more preferably 1.5 parts by mass or less, for example 0.1 parts by mass or more and 3 parts by mass or less. This tends to improve weather resistance, for example.
  • the content of the second ultraviolet absorber is greater than the content of the first ultraviolet absorber, and is greater than the content of the third ultraviolet absorber. This allows the surface protective layer to absorb a wide range of wavelengths, which tends to further improve weather resistance, for example.
  • the surface protective layer may contain a light stabilizer from the viewpoint of weather resistance.
  • light stabilizers include aromatic light stabilizers, amine light stabilizers, organic acid light stabilizers, catechin light stabilizers, and hindered amine light stabilizers.
  • hindered amine light stabilizers include Agents are preferred.
  • the hindered amine light stabilizer is, for example, a compound having a structure containing a 2,2,6,6-tetramethylpiperidine skeleton in the molecule.
  • the light stabilizer examples include a reactive light stabilizer having an ethylenic double bond that can be polymerized with a curable compound that can form a cured resin of the surface protective layer, and an ethylenic double bond that can be polymerized with the curable compound. Mention may be made of non-reactive light stabilizers that do not have double bonds. Ethylenic double bonds are present in functional groups such as (meth)acryloyl groups, vinyl groups, and allyl groups.
  • the surface protective layer may contain at least one selected from a reactive light stabilizer and a non-reactive light stabilizer, and may also contain a reactive light stabilizer and a non-reactive light stabilizer.
  • Reactive light stabilizers are usually incorporated into the cured resin system when forming the surface protective layer and are immobilized, so they can exhibit long-term effects. Since the non-reactive light stabilizer can migrate in the surface protective layer, it can exhibit immediate effect.
  • the number of ethylenic double bonds in the reactive light stabilizer may be one or two or more.
  • Examples of the reactive light stabilizer 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-penta Methylpiperidine, 4-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, a compound with CAS number 1010692-24-6 and a compound with CAS number 1010692-21-3.
  • Examples of the reactive light stabilizer having two or more ethylenic double bonds include 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, ) Acryloyl-4-cyano-4-(meth)acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotoyloxy-2,2,6,6-tetramethylpiperidine, CAS Mention may be made of the compound with number 1954659-42-7 and the compound with CAS number 1010692-23-5.
  • non-reactive light stabilizers 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, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2) , 2,6,6-tetramethyl-4-piperidinyl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine), tetrakis(1,2,2,6,6-pentamethyl-4 -piperidyl)-1
  • the content of the light stabilizer per 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 It is 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, for example 0.5 parts by mass or more and 10 parts by mass or less.
  • the surface protective layer may contain only the above-mentioned reactive light stabilizer as a light stabilizer, may contain only the above-mentioned non-reactive light stabilizer, or may contain the above-mentioned reactive light stabilizer and the above-mentioned non-reactive light stabilizer. It may also contain a light stabilizer.
  • the mass-based compounding ratio of the reactive light stabilizer and the non-reactive light stabilizer in the surface protective layer is, for example, 10:0 to 2:8. But that's fine.
  • the surface protective layer may contain additives, such as antioxidants, wear resistance improvers, infrared absorbers, antistatic agents, leveling agents, thixotropic agents, and coupling agents. , defoamers, flame retardants, plasticizers, particles and antiblocking agents.
  • the surface protective layer does not substantially contain polyolefin. This tends to improve the weather resistance of the surface protective layer, for example.
  • “Substantially not containing polyolefin” means that the content of polyolefin is 1% by mass or less, preferably 0.1% by mass or less, and more preferably 0.1% by mass or less, based on the total resin components contained in the surface protective layer. Preferably it is 0.01% by mass or less, more preferably 0% by mass.
  • the surface protective layer has an absorbance A1 of 0.3 or more at wavelengths of 270 nm or more and 300 nm or less, an absorbance A2 of 0.6 or more at wavelengths of 310 nm or more and 330 nm or less, and It is preferable that the absorbance A3 is 0.2 or more.
  • absorbance A1 at wavelengths of 270 nm to 300 nm absorbance A2 at wavelengths of 310 nm to 330 nm and absorbance A3 at wavelengths of 340 nm to 370 nm are taken into account.
  • absorbance A2 at wavelengths of 310 nm to 330 nm and absorbance A3 at wavelengths of 340 nm to 370 nm are taken into account.
  • the absorbance A1 is preferably 0.3 or more, more preferably 0.35 or more, for example, it may be 0.5 or more, or it may be 0.7 or more.
  • the upper limit of the absorbance A1 is not particularly limited, but may be, for example, 1.5.
  • the absorbance A2 is preferably 0.6 or more, more preferably 0.7 or more, for example, it may be 1.0 or more, or it may be 1.2 or more.
  • the upper limit of the absorbance A2 is not particularly limited, but may be, for example, 3.0.
  • the absorbance A3 is preferably 0.2 or more, more preferably 0.25 or more, for example, it may be 0.5 or more, or it may be 0.7 or more.
  • the upper limit of the absorbance A3 is not particularly limited, but may be, for example, 1.5.
  • the absorbances A1, A2, and A3 can be adjusted, for example, by the content of the first to third ultraviolet absorbers in the surface protective layer and the thickness of the surface protective layer. For example, if the surface protective layer contains each of the first to third ultraviolet absorbers, the absorbance can be easily adjusted.
  • the absorbance of the surface protective layer in the wavelength range of 270 nm or more and 370 nm or less includes a maximum value in the range of 300 nm or more and 340 nm or less. This tends to further improve the long-term weather resistance of the transfer layer, for example.
  • absorbance A1 The average value of the absorbance of the surface protective layer at a wavelength of 270 nm or more and 300 nm or less in accordance with JIS K0115:2004 is defined as absorbance A1.
  • the average value is the average value obtained when the absorbance is measured every 1 nm for a wavelength of 270 nm or more and 300 nm or less.
  • the average value of the absorbance of the surface protective layer in a wavelength range of 310 nm or more and 330 nm or less, based on JIS K0115:2004, is defined as absorbance A2.
  • the average value is the average value obtained when the absorbance is measured every 1 nm for a wavelength of 310 nm or more and 330 nm or less.
  • the average value of the absorbance of the surface protective layer in a wavelength range of 340 nm or more and 370 nm or less, based on JIS K0115:2004, is defined as absorbance A3.
  • the average value is the average value obtained when the absorbance is measured every 1 nm for a wavelength of 340 nm or more and 370 nm or less.
  • the absorbance of the surface protective layer included in the transfer sheet can be measured as follows.
  • the layers outside the surface protective layer of the transfer layer of the transfer sheet (for example, the primer layer and the adhesive layer) are removed by cutting or using a solvent, and the absorbance of the remaining laminate is measured. Thereafter, the absorbance of the releasable base material alone is measured.
  • the absorbance of the surface protective layer can be obtained by subtracting the absorbance of the releasable base material alone from the absorbance of the remaining laminate.
  • the surface protective layer is formed by preparing a curable composition, applying the composition to a releasable base material to form an uncured resin layer, and crosslinking and curing the uncured resin layer.
  • the mode of crosslinking and curing is, for example, curing by heat treatment when using a thermosetting resin, and curing by irradiation with ionizing radiation such as an electron beam and ultraviolet rays when using an ionizing radiation-curable compound.
  • the irradiation dose is, for example, 5 kGy or more and 300 kGy or less (0.5 Mrad or more and 30 Mrad or less), preferably 10 kGy or more and 100 kGy or less (1 Mrad or more and 10 Mrad or less).
  • ultraviolet light a light beam containing ultraviolet light with a wavelength of 190 nm or more and 380 nm or less may be emitted.
  • the thickness of the surface protective layer is preferably 1 ⁇ m or more, more preferably 1.5 ⁇ m or more, even more preferably 2 ⁇ m or more, and preferably 20 ⁇ m or less, from the viewpoint of the balance between processability, scratch resistance, and weather resistance. Preferably it is 15 ⁇ m or less, more preferably 10 ⁇ m or less, for example 1 ⁇ m or more and 20 ⁇ m or less.
  • the transfer layer includes a primer layer.
  • the primer layer can be provided, for example, for the purpose of improving the adhesion between the surface protection layer and the adhesive layer.
  • the primer layer contains a resin component.
  • resin components include vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-(meth)acrylic copolymer, chlorinated polyethylene, chlorinated polypropylene, urethane resin, (meth)acrylic resin, (meth) Examples include acrylic polyol resins, polystyrene, polyesters, polyamides, butyral resins, 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 above-mentioned two-component curable urethane resin.
  • urethane resin from the viewpoint of weather resistance and durability, a urethane resin having a (meth)acrylic skeleton in the polyurethane polymer chain is preferable.
  • urethane resins having a (meth)acrylic skeleton in the polyurethane polymer chain include urethane-(meth)acrylic copolymers, which are copolymers of urethane components and (meth)acrylic components, and polyols constituting polyurethane.
  • examples include resins in which a (meth)acrylic resin having a hydroxyl group or an isocyanate group is used as a component or a polyisocyanate component.
  • urethane-(meth)acrylic copolymers are preferred, and as the urethane-(meth)acrylic copolymers, for example, urethane-(meth)acrylic block copolymers are preferred.
  • the urethane-(meth)acrylic copolymer may further have a polycarbonate skeleton or a polyester skeleton in the polyurethane polymer chain.
  • 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 urethanes.
  • a polyester-based urethane-(meth)acrylic copolymer, which is a copolymer of a component and a (meth)acrylic component, can be mentioned.
  • Urethane-(meth)acrylic copolymers can be produced, for example, by a method in which a (meth)acrylic resin having at least two hydroxy groups in one molecule is reacted with a polyol and a polyisocyanate (see JP-A-6-100653, etc.). Alternatively, it can be obtained by a method in which a urethane prepolymer having unsaturated double bonds at both ends is reacted with a (meth)acrylic monomer (see JP-A No. 10-1524, etc.).
  • urethane prepolymers examples include polycarbonate-based urethane prepolymers obtained by reacting polycarbonate diol and diisocyanate, and polyester-based urethane prepolymers obtained by reacting polyester diol and diisocyanate.
  • diisocyanates include aliphatic isocyanates such as hexamethylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate and hydrogenated xylylene diisocyanate.
  • the (meth)acrylic monomer examples include (meth)acrylic acid and (meth)acrylic acid alkyl esters in which the alkyl group has 1 to 6 carbon atoms.
  • the urethane resins include polycarbonate urethane-(meth)acrylic copolymers, polyester urethane-(meth)acrylic copolymers, polyether urethane-(meth)acrylic copolymers, and caprolactone-based urethane-(meth)acrylic copolymers.
  • examples include urethane-(meth)acrylic copolymers.
  • the urethane component/(meth)acrylic component 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 95/1 or less. 5 or less.
  • the content of the (meth)acrylic component in the urethane resin is the ratio of monomer units constituting the (meth)acrylic skeleton to the 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 attributed to the (meth)acrylic component to the total peak area.
  • the weight average molecular weight of the urethane resin may be 10,000 or more, 30,000 or more, or 100,000 or less, 80,000 or less, for example, 10,000 or more and 100,000 or less. Thereby, for example, weather resistance can be further improved.
  • the weight average molecular weight in this specification is determined by gel permeation chromatography (GPC) as a standard polystyrene equivalent value.
  • the content ratio of the resin component in the primer layer is, for example, 50% by mass or more.
  • 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 mentioned above.
  • the primer layer may contain the above additives.
  • the content of the ultraviolet absorber in the primer layer may be 1 part by mass or more, or 5 parts by mass or more, based on 100 parts by mass of the resin component contained in the primer layer. It may be 10 parts by mass or more, 50 parts by mass or less, 45 parts by mass or less, 40 parts by mass or less, for example, 1 part by mass or more and 50 parts by mass or less.
  • the content of the light stabilizer in the primer layer may be 0.1 parts by mass or more, and 0.5 parts by mass, based on 100 parts by mass of the resin component contained in the primer layer. It may be more than 1 part by mass, it may be 10 parts by mass or less, it may be 8 parts by mass or less, it may be 6 parts by mass or less, for example, it may be 0.1 part by mass or more and 10 parts by mass or less.
  • the thickness of the primer layer is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, even more preferably 1 ⁇ m or more, and preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less, still more preferably 6 ⁇ m or less, for example. It is 0.1 ⁇ m or more and 10 ⁇ m or less.
  • the surface protective layer may be surface-treated before forming the primer layer.
  • surface treatment methods include corona discharge treatment, plasma treatment, chromium oxidation treatment, flame treatment, hot air treatment, and ozone/ultraviolet treatment.
  • the crosslinking of the surface protective layer is kept in a semi-cured state, and then the resin composition for the primer layer is applied to the semi-cured surface protective layer.
  • the surface protective layer may be completely cured by irradiating with ionizing radiation.
  • a primer layer When forming a primer layer by applying a primer layer resin composition onto the surface protection layer after the surface protection layer is cured, it may be difficult to sufficiently increase the adhesion between the primer layer and the surface protection layer. be. In such a case, if the primer layer deteriorates due to UV irradiation in an environment where it is exposed to direct sunlight, for example, the primer layer and the surface protective layer are likely to peel off. In the present disclosure, since deterioration of the primer layer can be suppressed over a long period of time as described above, such peeling can be suppressed.
  • 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 arranged on a part of the surface of the primer layer opposite to the surface protection layer, or may be arranged on the entire surface.
  • the design layer may be a layer that covers the entire surface of the primer layer opposite to the surface protection layer, and may include a pattern including a pattern placement area and a non-printing area on the surface of the primer layer opposite to the surface protection layer. It may be in the form of
  • a design layer can be provided to display a design.
  • the design layer has, for example, a pattern.
  • Patterns include, for example, wood grain patterns that imitate tree rings or conduit grooves on the surface of wood boards, stone grain patterns that imitate the surfaces of rocks such as marble and granite, fabric patterns that imitate cloth grain or cloth-like patterns, and leather surfaces. Examples include leather grain patterns, satin-like patterns, tiled patterns, brickwork patterns, geometric patterns, and abstract patterns such as letters, figures, symbols, polka dots, and floral patterns.
  • the pattern may be a solid color (so-called solid image).
  • the pattern may be a composite pattern including two or more of these types.
  • the design layer may have two or more layers.
  • the design layer may include a colored first layer and a second layer provided on the first layer to form a pattern.
  • the design layer can be formed, for example, by a printing method or a coating method.
  • printing methods include gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, and inkjet printing.
  • coating method include gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, and reverse roll coating.
  • Other layers can also be formed, for example, by these methods.
  • the design layer contains a resin component and a colorant.
  • the resin component include vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-(meth)acrylic copolymer, chlorinated polyethylene, chlorinated polypropylene, urethane-(meth)acrylic copolymer, and (meth)acrylic copolymer. ) acrylic resins, (meth)acrylic polyol resins, polystyrenes, polyurethanes, polyesters, polyamides, butyral resins, nitrocellulose and cellulose acetate.
  • colorants include pigments and dyes.
  • inorganic pigments such as carbon black, iron black, titanium white, antimony white, yellow lead, titanium yellow, Bengara, cadmium red, ultramarine blue, and cobalt blue; quinacridone red, isoindolinone yellow, phthalocyanine blue, and azomethine.
  • Organic pigments or dyes such as azo black and nickel azo complexes; metallic pigments consisting of flakes such as aluminum and brass; and pearlescent pigments consisting of flakes such as titanium dioxide coated mica and basic lead carbonate. ) pigments.
  • the content of the 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, or 200 parts by mass or less, based on 100 parts by mass of the resin component contained in the design layer. It may be 150 parts by mass or less, or 100 parts by mass or less, for example, 5 parts by mass or more and 200 parts by mass or less.
  • the design layer may contain additives.
  • 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 from the viewpoint of improving weather resistance.
  • the thickness of the design layer is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, even more preferably 2 ⁇ m or more, and preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, still more preferably 10 ⁇ m or less, for example 0. It is 5 ⁇ m or more and 20 ⁇ m or less. Thereby, for example, the design can be improved.
  • the design layer may include a metal thin film.
  • metals constituting the metal thin film include tin, indium, chromium, aluminum, nickel, iron, cobalt, copper, silver, gold, platinum, and zinc, and alloys containing at least one selected from these metals. Can be mentioned. Alloys include, for example, brass, bronze and stainless steel. Examples of methods for forming the metal thin film include vacuum evaporation, sputtering, and ion plating. The thickness of the metal thin film is, for example, 0.1 ⁇ m or more and 1 ⁇ m or less.
  • the adhesive layer may also serve as a design layer.
  • the transfer layer may include an adhesive layer.
  • the adhesive layer has a function of bringing the transfer sheet into close contact with the surface of the object to be transferred.
  • the adhesive layer constitutes the surface layer of the transfer layer on the side opposite to the releasable substrate side.
  • the adhesive layer is a layer that comes into contact with the object to be transferred after the transfer. Thereby, the transfer layer can be successfully transferred and attached to the object to be transferred.
  • a surface protective layer and a primer layer are provided from the transfer sheet by attaching the transfer sheet to a transfer object such that the adhesive layer is in contact with the surface of the transfer object, and then peeling off the releasable base material.
  • the transfer layer can be transferred onto the object to be transferred with good adhesion.
  • 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 still more preferably 70% by mass or more.
  • the adhesive layer may contain additives.
  • additives include weathering agents such as ultraviolet absorbers and light stabilizers, wear resistance improvers, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropic agents, coupling agents, Plasticizers, antifoaming agents, fillers as well as colorants may be mentioned.
  • the adhesive layer may contain a weathering agent. Details of the weathering agent 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, and 25 parts by mass or less, based on 100 parts by mass of the adhesive resin. , 20 parts by mass or less, 15 parts by mass or less, for example 0.1 parts by mass or more and 25 parts by mass or less.
  • 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, and 7 parts by mass or less, based on 100 parts by mass of the adhesive resin. It may be 5 parts by mass or less, for example, 0.05 parts by mass or more and 7 parts by mass or less.
  • the thickness of the adhesive layer is preferably 1 ⁇ m or more, preferably 12 ⁇ m or less, more preferably 6 ⁇ m or less, for example, 1 ⁇ m or more and 12 ⁇ m or less.
  • the transfer layer can be bonded well to the object to be transferred, and excellent transparency can be ensured.
  • the thickness of the adhesive layer is preferably greater than the thickness of the primer layer.
  • the adhesive layer can be formed, for example, by applying a composition containing components constituting the adhesive layer (adhesive layer composition) on the primer layer, and drying the composition as necessary.
  • the transfer sheet of the present disclosure may include a cover film (protective film) on the adhesive layer.
  • a cover film may be attached on the adhesive layer. This allows the surface of the adhesive layer to be well protected and is preferable for storing 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 object to be transferred via this adhesive layer.
  • the cover film is made of a resin component such as polyolefin, for example.
  • the weather-resistant article of the present disclosure includes a transfer target and a surface protection film provided on at least a portion of the surface of the transfer target.
  • the surface protection film is a transfer layer in the transfer sheet of the present disclosure, and the surface protection layer included in the transfer layer constitutes at least a part of the surface layer of the weather-resistant article.
  • the weather-resistant article 2 includes a transfer target 30 and a transfer layer 20 provided on the surface of the transfer target 30.
  • the transfer layer 20 includes an adhesive layer 26, a primer layer 24, and a surface protection layer 22 in this order from the transfer target 30 side. Therefore, the weather-resistant article 2 includes the adhesive layer 26, the primer layer 24, and the surface protection layer 22 on the transfer target 30 in this order.
  • the releasable base material 10 only needs to be peeled off when the weather-resistant article 2 is used.
  • the transfer target is an article to which the transfer layer of the transfer sheet of the present disclosure is transferred.
  • Examples of the transfer target include an exterior material.
  • the exterior material to which the transfer layer of the transfer sheet of the present disclosure has been transferred can maintain good weather resistance even after being exposed to harsh outdoor conditions.
  • the exterior material is a molded product used outdoors, for example, a molded product for applications that require weather resistance because it is exposed to direct sunlight every day.
  • the transfer layer in the transfer sheet of the present disclosure has excellent weather resistance and is therefore suitable for use as an exterior material.
  • the shape of the exterior material is not particularly limited, and examples include plate materials such as flat plates and curved plates, three-dimensional articles, sheets, and films. Examples of the exterior material include resin members, wooden members, and inorganic members.
  • resin members include sheets, plates, or three-dimensional materials made of polyolefin, vinyl chloride resin, styrene resin, (meth)acrylic resin, polyester, polycarbonate, polyamide, polyimide, cellulose resin, phenolic resin, rubber, etc. Examples include shaped articles.
  • wood member examples include board materials or three-dimensional articles made of wood veneer, wood plywood, particle board, medium density fiberboard (MDF), wood fiberboard such as laminated wood, and the like.
  • MDF medium density fiberboard
  • Examples of the inorganic member include metal members and other inorganic members.
  • Examples of metal members include sheets and plates made of iron, aluminum, copper, tin, titanium, alloys containing at least one of these metals (e.g., carbon steel, stainless steel, duralumin, brass, and bronze), etc. Or three-dimensional shaped articles can be mentioned.
  • Examples of other inorganic members include plates or three-dimensional articles made of glass, ceramics such as china, non-cement ceramic materials such as gypsum, lightweight aerated concrete (ALC) plates, and the like.
  • Exterior materials include, for example, exterior materials for architectural structures, exterior materials for vehicles, ships, and aircraft, exterior materials for industrial machines, and various lenses.
  • Exterior materials (building materials) for architectural structures include, for example, exterior walls, roofs, eaves, floors, fences, various doors such as entrance doors and gates, window materials, handrails, partition boards for balconies, and roofs for terraces or carports. Examples include soundproof walls or windshield walls for members, agricultural houses, general roads, expressways, etc.
  • vehicle exterior materials 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 automobiles, railroad vehicles, construction machinery, and light vehicles such as golf carts.
  • Examples of exterior materials for industrial machines include visual window materials for machine tools.
  • the lens include a traffic light lens.
  • the thickness of the exterior material may be appropriately selected depending on the use and material, and in one embodiment, it may be 0.1 mm or more, 0.3 mm or more, 0.5 mm or more, 10 mm or less, It may be 5 mm, or 3 mm or less, for example, 0.1 mm or more and 10 mm or less.
  • the objects to be transferred are not limited to exterior materials, but include, for example, interior materials for vehicles, ships and aircraft, interior materials for architectural structures, front panels of various display devices, curved mirrors, traffic signs, and name plates. You can also do it.
  • the object to be transferred may be, for example, a decorative material such as a decorative board.
  • the weather-resistant article of the present disclosure can be obtained, for example, by using the transfer sheet of the present disclosure and transferring the transfer layer of the transfer sheet onto at least a portion of the surface of a transfer target.
  • the method for manufacturing a weather-resistant article of the present disclosure includes a step of preparing a transfer sheet and a transfer target of the present disclosure, and placing the transfer sheet on the transfer target, with the transfer layer of the transfer sheet facing the transfer target. and a step of peeling off the releasable base material on the transfer sheet.
  • a transfer sheet of the present disclosure including a transfer layer including a surface protective layer, a primer layer, and an adhesive layer and a transfer target are prepared, and the adhesive layer in the transfer sheet and the surface of the transfer target are in contact with each other.
  • the transfer sheet is placed on at least a portion of the surface of the object to be transferred.
  • a transfer sheet of the present disclosure including a transfer layer including a surface protective layer and a primer layer, and a transfer target whose surface is provided with an adhesive layer are prepared, and the transfer layer and the transfer target in the transfer sheet are prepared.
  • the transfer sheet is placed on at least a portion of the surface of the object to be transferred so that it is in contact with the adhesive layer provided thereon.
  • the adhesive layer provided on the transfer target include an adhesive layer that can be included in the transfer layer of a transfer sheet.
  • the above arrangement may be performed under heat and/or pressure.
  • the releasable base material in the transfer sheet is peeled off from the transfer layer, specifically from the surface protection layer. In this way, a weather-resistant article is obtained.
  • a thermal transfer method such as a roll transfer method and a press transfer method, or an in-mold molding method can be adopted.
  • the releasable base material may be used as a protective film for weather-resistant articles without being immediately peeled off from the transfer layer. In such a case, the releasable base material may be peeled off from the transfer layer before using the weather-resistant article.
  • the obtained weather-resistant article may be further subjected to processing such as bending.
  • the processing may be performed either before or after peeling off the releasable base material.
  • the weather-resistant article of the present disclosure may be manufactured, for example, by simultaneously forming the transfer target and arranging the transfer sheet. For example, a resin is injected onto the adhesive layer of the transfer sheet to integrate the transfer sheet and a resin molded body (injection molded body) as a transfer target. Next, the releasable base material is peeled off from the transfer layer.
  • methods for forming the resin molded body include various injection molding methods such as in-mold molding, insert molding, injection molding simultaneous decoration, blow molding, and gas injection molding.
  • a transfer sheet comprising a releasable base material and a transfer layer, where the transfer layer includes a surface protective layer and a primer layer, and the surface protective layer has a layer between the releasable base material and the primer layer.
  • the surface protective layer includes a cured resin, a first ultraviolet absorber having an absorption peak at a first wavelength, and 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 content of the second ultraviolet absorber is greater than the content of the first ultraviolet absorber and the content of the third ultraviolet absorber is greater than the content of the above [1] to [ 5].
  • the transfer sheet according to any one of 5]. [7] 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 triazine-based ultraviolet absorbers. transfer sheet. [8]
  • the surface protective layer contains a total of 0.5 parts of the first ultraviolet absorber, the second ultraviolet absorber, and the third ultraviolet absorber with respect to 100 parts by mass of the cured resin contained in the surface protection layer.
  • the surface protective layer contains 0.1 parts by mass or more and 3 parts by mass of the first ultraviolet absorber and 0.1 parts by mass or more and 8 parts by mass, based on 100 parts by mass of the cured resin contained in the surface protective layer.
  • a weather-resistant article which is a transfer layer in the transfer sheet according to claim 1, wherein a surface protective layer in the transfer layer constitutes at least a part of the surface layer of the weather-resistant article.
  • Example 1 As a releasable base material, an untreated matte PET film (PET original Diafoil E130-26, Mitsubishi Chemical) was prepared. Approximately 5 g of the following ionizing radiation curable resin composition was applied on a releasable base material to form an uncured resin layer, and irradiated with an electron beam (acceleration voltage: 175 kV, irradiation dose: 5 Mrad (50 kGy)). The uncured resin layer was cured to form a surface protective layer with a thickness of 5 ⁇ m. Corona discharge treatment was performed on the surface protective layer.
  • PET original Diafoil E130-26 Mitsubishi Chemical
  • a primer layer Approximately 2.5 g of the following resin composition for a primer layer was applied to the surface protective layer after the corona discharge treatment using a gravure printing method and dried to form a primer layer with a thickness of 3.5 ⁇ m. Approximately 5 g of heat-fusible resin (polymethyl methacrylate resin (PMMA), molecular weight approximately 96,000) is applied onto the primer layer to form an adhesive layer (heat seal layer) with a thickness of 4.5 ⁇ m, and the adhesive layer is left at room temperature for 24 hours. I took care of myself.
  • PMMA polymethyl methacrylate resin
  • the transfer sheet includes a PET film as a releasable base material, and a transfer layer provided on the PET film, and the transfer layer includes a surface protection layer, a primer layer, and an adhesive layer.
  • ⁇ Ionizing radiation curable resin composition > - 100 parts by mass of trifunctional urethane acrylate oligomer with a weight average molecular weight of 4,000 - 0.5 parts by mass of the first ultraviolet absorber Hydroxyphenyltriazine-based ultraviolet absorber, Product name: ADEKA STAB LA-46, ADEKA Co., Ltd.
  • Absorption peak wavelength 275nm ⁇ Second ultraviolet absorber 3 parts by mass hydroxyphenyltriazine ultraviolet absorber, Product name: TINUVIN479, BASF, Absorption peak wavelength: 322nm ⁇ Third ultraviolet absorber 0.5 part by mass hydroxyphenyltriazine ultraviolet absorber, Product name: TINUVIN477, BASF, Absorption peak wavelength: 356nm ⁇ Hindered amine-based 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
  • a test piece was prepared by forming a surface protective layer on a PET film under the same conditions as above. Using an ultraviolet-visible-near-infrared spectrophotometer (manufactured by Hitachi, Ltd., trade name: UH-4150), the absorbance of the test piece in each wavelength range was measured in accordance with JIS K0115:2004. By subtracting the absorbance of the PET film from this absorbance, the above-mentioned "absorbance A1", “absorbance A2", and "absorbance A3" were obtained.
  • the absorbances of the surface protective layer corresponding to the transfer sheet of Example 1 were as follows. Absorbance A1: 1.2 Absorbance A2: 1.6 Absorbance A3: 1.4
  • the absorbances of the surface protective layer corresponding to the transfer sheet of Comparative Example 1 were as follows. Absorbance A1: 0.25 Absorbance A2: 0.6 Absorbance A3: 1.2
  • Transfer sheets obtained in Examples and Comparative Examples and a polycarbonate plate with a thickness of 2 mm were prepared as a transfer target. No weathering agent is added to the polycarbonate board.
  • the above transfer sheet was superimposed on one side of a polycarbonate plate heated to 130°C so that the adhesive layer of the transfer sheet was in contact with the polycarbonate plate, and was pressure-bonded using a roll at 160°C. Thereby, a molded article with a releasable base material was obtained, which included a polycarbonate plate, an adhesive layer, a primer layer, a surface protective layer, and a releasable base material in this order.
  • the releasable base material was peeled off from the transfer layer of the transfer sheet to obtain a test piece.
  • the surface protective layer constitutes the surface layer on one side of the test piece.
  • ⁇ Super accelerated weather resistance test device 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 illumination meter (product name: UVD-365PD, manufactured by Iwasaki Electric Co., Ltd.)
  • Super accelerated weather resistance test equipment product name: ⁇ I Super UV Tester SUV-W261'', manufactured by Iwasaki Electric Co., Ltd.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Decoration By Transfer Pictures (AREA)
PCT/JP2023/012439 2022-03-28 2023-03-28 転写シート及び耐候性物品 Ceased WO2023190478A1 (ja)

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CN202380022583.5A CN118715125A (zh) 2022-03-28 2023-03-28 转印片和耐候性物品
US18/841,457 US20250162299A1 (en) 2022-03-28 2023-03-28 Transfer sheet and weather-resistant article
EP23780487.7A EP4506164A4 (en) 2022-03-28 2023-03-28 TRANSFER SHEET AND WEATHERPROOF ITEM

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US20250162299A1 (en) 2025-05-22
TW202402539A (zh) 2024-01-16
JP7792839B2 (ja) 2025-12-26
EP4506164A1 (en) 2025-02-12
JP2023178329A (ja) 2023-12-14
EP4506164A4 (en) 2026-04-01
CN118715125A (zh) 2024-09-27

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