Laminate including substrate and adhesive layer

Abstract

A laminate of one embodiment of the present disclosure includes a substrate including a first copolymer including a constituent unit derived from a carboxyl group-containing monomer, a second copolymer including a constituent unit derived from an amino group-containing monomer, and a cured product of a crosslinking agent, and an adhesive layer. The first copolymer has a weight average molecular weight of about 800,000 or less and a glass transition temperature of lower than about 0°C. The second copolymer has a weight average molecular weight of about 30,000 or more and about 100,000 or less and a glass transition temperature of about 0°C or higher. At least one of the first copolymer or the second copolymer includes a constituent unit derived from a (meth)acrylate monomer containing a biologically derived carbon atom.

Description

LAMINATE INCLUDING SUBSTRATE AND ADHESIVE LAYERTechnical Field

[0001] The present disclosure relates to a laminate including a substrate and an adhesive layer.Background Art

[0002] In recent years, a laminate such as a decorative film including a polyvinyl chloride-based resin layer and an adhesive tape including an adhesive layer formed using a biologically derived material in place of a petroleum -derived material has been developed.

[0003] Patent Document 1 (JP 2018-034488 A) describes a decorative film including a polyvinyl chloride-based resin layer and a colorless and transparent coating layer, the coating layer including a cured product of an ultraviolet curable resin composition containing a polymerization initiator having an acylphosphine oxide group.

[0004] Patent Document 2 (JP 7474537 B) discloses a biodegradable laminate including a first layer and a second layer, in which each of the first layer and the second layer contains a biodegradable resin such as polylactic acid and an inorganic substance powder at a mass ratio of from 70:30 to 10:90, the first layer further contains 0. 1 mass% or more and 5.0 mass% or less of one or more first additives selected from the group consisting of a glycerin acetic acid fatty acid ester and tributyl acetylcitrate, and the second layer further contains 0.1 mass% or more and 5.0 mass% or less of one or more second additives selected from the group consisting of an isocyanate compound, an epoxy compound, and a carbodiimide compound.Citation ListPatent Documents

[0005] Patent Document 1: JP 2018-034488 APatent Document 2: JP 7474537 BSummary of InventionTechnical Problem

[0006] In order to impart performance such as weather resistance to the laminate, a polyvinyl chloride film may be used. However, the use of a polyvinyl chloride film is sometimes restricted from the viewpoint of environmental problems and the like. For the purpose of reducing an amount of petroleum resources used, a laminate may be prepared using a biologically derived material such as a polylactic acid resin instead of a petroleum -derived material. However, since the polylactic acid resin is a biodegradable material, it has been difficult to exhibit performance such as weather resistance for a long period of time.

[0007] The present disclosure provides a laminate that can contribute to environmental problems and reduction in the amount of petroleum resources used, and is excellent in performance such as weather resistance.Solution to Problem

[0008] According to one embodiment of the present disclosure, provided is a laminate including: a substrate including a first copolymer including a constituent unit derived from a carboxyl group- containing monomer, a second copolymer including a constituent unit derived from an amino group- containing monomer, and a cured product of a crosslinking agent; and an adhesive layer, in which the first copolymer has a weight average molecular weight of about 800,000 or less and a glass transition temperature of lower than about 0°C, the second copolymer has a weight average molecular weight of about 30,000 or more and about 100,000 or less and a glass transition temperature of about 0°C or higher, and at least one of the first copolymer or the second copolymer includes a constituent unit derived from a (meth)acrylate monomer containing a biologically derived carbon atom.Advantageous Effects of Invention

[0009] According to the present disclosure, it is possible to provide a laminate that can contribute to environmental problems and a reduction in an amount of petroleum resources used and is excellent in performance such as weather resistance.

[0010] The above description is not to be construed as having disclosed all the embodiments of the present invention nor all the advantages related to the present invention.Description of Embodiments

[0011] The present invention will be described in further detail hereinafter with the purpose of illustrating representative embodiments of the present invention, but the present invention is not limited to these embodiments.

[0012] In the present disclosure, the term “on” used, for example, in the phrase “an adhesive layer disposed on a release liner” means that the adhesive layer is disposed directly on the upper side of the release liner, or, that the adhesive layer is indirectly disposed on the upper side of the release liner via another layer.

[0013] In the present disclosure, the term “under”, for example, in “adhesive layer disposed under a substrate” means that the adhesive layer is disposed directly below the substrate, or that the adhesive layer is indirectly disposed below the substrate via another layer.

[0014] In the present disclosure, “transparent” refers to an average transmittance in a visible light region (wavelength of 400 nm to 700 nm) measured in accordance with JIS K 7375 of approximately 80% or more, and the average transmittance may be desirably approximately 85% or more, or approximately 90% or more. The upper limit of the average transmittance is not particularly limited, and can be, for example, approximately less than 100%, approximately 99% or less, or approximately 98% or less.

[0015] In the present disclosure, the term “translucent” refers to an average transmittance in a visible light region (wavelength of 400 nm to 700 nm) measured in accordance with JIS K 7375 of approximately less than 80%, and the average transmittance may be desirably approximately 75% or less, and “translucent” is intended to mean that an underlying layer or the like is not completely hidden.

[0016] In the present disclosure, the term “film” encompasses articles referred to as “sheets”.

[0017] In the present disclosure, “(meth)acrylic” means acrylic or methacrylic, “(meth)acrylate” means acrylate or methacrylate, and “(meth)acryloyl” means acryloyl or methacryloyl.

[0018] A laminate according to an embodiment of the present disclosure includes a substrate and an adhesive layer. In addition, the laminate of the present disclosure may include any layer (for example, cover layer, decorative layer, and release liner) described later.

[0019] In some embodiments, the laminate of the present disclosure exhibits weather resistance. The weather resistance can be evaluated by a color difference based on a weather resistance test described later. In some embodiments, the laminate of the present disclosure exhibits a color difference of less than about 20, about 15 or less, about 10 or less, less than about 10, about 8.0 or less, or about 5.0 or less after exposure for 500 hours according to JIS K 5600-7-7:2008. The lower limit of such color difference is not particularly limited, and may be, for example, about 0 or more, more than about 0, or about 0.1 or more.

[0020] In some embodiments, the laminate of the present disclosure exhibits elongation properties. Such elongation properties can be evaluated by a yield point evaluation test, an elongation test, and a tensile strength test described later. In some embodiments, the laminate of the present disclosure can exhibit a yield point of about 3.0 N / 25 mm or more, about 4.0 N / 25 mm or more, or about 5.0 N / 25 mm or more, about 50 N / 25 mm or less, about 45 N / 25 mm or less, about 40 N / 25 mm or less, about 35 N / 25 mm or less, or about 30 N / 25 mm or less, can exhibit an elongation of about 20% or more, about 25% or more, or about 30% or more, about 500% or less, about 400% or less, about 300% or less, about 270% or less, about 250% or less, or about 230% or less, and can exhibit a 2% tensile strength of about 2.0 N / 25 mm or more, about 2.5 N / 25 mm or more, or about 3.0 N / 25 mm or more, about 50 N / 25 mm or less, about 40 N / 25 mm or less, about 30 N / 25 mm or less, or about 20 N / 25 mm or less. In some embodiments, the substrate included in the laminate of the present disclosure may also exhibit such elongation properties.

[0021] In some embodiments, the laminate of the present disclosure can exhibit a breaking strength of about 5.0 N / 25 mm or more, about 6.0 N / 25 mm or more, or about 7.0 N / 25 mm or more, about 50 N / 25 mm or less, about 45 N / 25 mm or less, about 40 N / 25 mm or less, about 35 N / 25 mm or less, or about 30 N / 25 mm or less. The breaking strength can be determined by a breaking strength test described later. In some embodiments, the substrate included in the laminate of the present disclosure may also exhibit such breaking strength.

[0022] In some embodiments, the laminate of the present disclosure can exhibit a tear strength of about 10 N / mm or more, about 15 N / mm or more, or about 20 N / mm or more, about 100 N / mm or less, about 80 N / mm or less, about 50 N / mm or less, or about 40 N / mm or less. The tear strength can be determined by a tear strength test described later. In some embodiments, the substrate included in the laminate of the present disclosure may also exhibit such tear strength.

[0023] In some embodiments, the laminate of the present disclosure exhibits heat resistance. Such heat resistance can be evaluated by a heat shrinkage test described later. In some embodiments, a maximum width of opening (mouth opening) of a cut after the heat shrinkage test of the laminate of the present disclosure can achieve about 0.50 mm or less, about 0.40 mm or less, about 0.30 mm or less, or about 0.25 mm or less. The lower limit of such width is not particularly limited, and can be, for example, about 0 mm or more.

[0024] In some embodiments, the laminate of the present disclosure can exhibit an adhesive force of about 5.0 N / 25 mm or more, about 6.0 N / 25 mm or more, about 7.0 N / 25 mm or more, or about 8.0 N / 25 mm or more under a room temperature environment when a melamine-coated plate is used as an adherend to which an adhesive layer is applied. The upper limit of the adhesive force can be, for example, about 40.0 N / 25 mm or less, about 35.0 N / 25 mm or less, about 30.0 N / 25 mm or less, about 25.0 N / 25 mm or less, or about 20.0 N / 25 mm or less. Here, the “room temperature” in the present disclosure is intended to be a temperature in a room in which a test is performed, and specifically may be intended to be, for example, about 23°C ± about 5°C or about 23°C ± about 3°C.

[0025] The laminate of the present disclosure includes a substrate containing a cured product of a first copolymer, a second copolymer, and a crosslinking agent. Since these copolymers are polymers that can be further crosslinked with the crosslinking agent, the first copolymer and the second copolymer before being crosslinked with the crosslinking agent can also be referred to as “first partial polymer” and “second partial polymer”. In the present disclosure, the “cured product” is not limited to a crosslinking reactant in which a crosslinking reactive site in the first copolymer and / or the second copolymer is completely subjected to a crosslinking reaction, and may include a crosslinking reactant in which a part of the crosslinking reactive site remains without being subjected to the crosslinking reaction. In the present disclosure, the “substrate” is intended to be an underlying layer on which an adhesive is directly or indirectly stacked.

[0026] The first copolymer included in the substrate includes a constituent unit derived from a carboxyl group-containing monomer, and has a weight average molecular weight of about 800,000 or less and a glass transition temperature of lower than about 0°C.

[0027] The weight average molecular weight of the first copolymer can be about 700,000 or less, about 600,000 or less, about 500,000 or less, about 450,000 or less, about 430,000 or less, about 400,000 or less, about 380,000 or less, or about 350,000 or less, and can be about 100,000 or more, about 150,000 or more, about 200,000 or more, or about 210,000 or more. The “weight average molecular weight” and the “molecular weight distribution” represented by weight average molecular weight (Mw)Znumber average molecular weight (Mn) in the present disclosure can be measured by a GPC method (gel permeation chromatography method). For example, the following conditions can be adopted as the measurement conditions:Apparatus: HP- 1090 Series II (available from Hewlett-Packard Company) Solvent: tetrahydrofuranColumn: Plgel MIXED-Bx2 (300 mm, outer diameter: 7.5 mm, inner diameter: 5 mm) Flow rate: 1. 0 mL / minDetecting means : refractive index Sample concentration: 0. 1 wt.% Calibration standard: polystyrene

[0028] In some embodiments, the molecular weight distribution of the first copolymer is about 10 or less. Such a molecular weight distribution can be about 8.0 or less, about 7.0 or less, about 6.0 or less, or about 5.0 or less. The lower limit of the molecular weight distribution is not particularly limited, and can be about 0 or more, about 1.0 or more, about 2.0 or more, or about 3.0 or more. When such a first copolymer having a narrow molecular weight distribution is used, a solid content of a substrate composition can be increased. When the substrate composition having a high solid content can be used, for example, energy required for drying the substrate can be reduced, and as a result, it is possible to suitably contribute to an environmental problem.

[0029] The glass transition temperature of the first copolymer can be about -5 °C or lower, about - 10°C or lower, about -20°C or lower, about -30°C or lower, about -40°C or lower, about -43°C or lower, about -45 °C or lower, about -47°C or lower, or about -50°C or lower, and can be about -100°C or higher, about -80°C or higher, about -70°C or higher, about -65°C or higher, or about -60°C or higher. The “glass transition temperature (Tg)” of the present disclosure can be determined as a calculated glass transition temperature by using the following Fox formula (Fox, T. G., Bull. Am. Phys. Soc., 1 (1956), p. 123) when the polymer is formed by copolymerization of n types of monomers:[Math. 1]T# d- 273.15In the equation, Tgi represents the glass transition temperature (°C) of a homopolymer of a component i, Xi represents the mass fraction of the monomer of the component i added during polymerization, and i is a natural number of 1 to n, and [Math. 2]

[0030] The first copolymer including a constituent unit derived from a carboxyl group-containing monomer can be obtained by copolymerization of a monoethylenically unsaturated monomer and a carboxy group-containing unsaturated monomer.

[0031] The monoethylenically unsaturated monomer typically includes (meth)acylates represented by the formula CH2=CR1COOR2(in the formula, R1is hydrogen or a methyl group, and R2is a linear, branched, or cyclic alkyl group, a phenyl group, an alkoxyalkyl group, a phenoxyalkyl group, a hydroxyalkyl group, or a cyclic ether group), and additionally, aromatic vinyl monomers such as styrene, a-methylstyrene, and vinyl toluene, vinyl esters such as vinyl acetate, and unsaturated nitriles such as acrylonitrile and methacrylonitrile. Examples of the monoethylenically unsaturated monomer represented by CH2=CR1COOR2can include linear alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl(meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-decyl (meth)acrylate, and n-dodecyl (meth)acrylate; branched alkyl (meth)acrylates such as isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, and isononyl (meth)acrylate; alicyclic (meth)acrylates such as cyclohexyl (meth)acrylate and isobomyl (meth)acrylate; phenyl (meth)acrylates; alkoxyalkyl (meth)acrylates such as methoxypropyl (meth)acrylate and 2-methoxybutyl (meth)acrylate; phenoxyalkyl (meth)acrylates such as phenoxyethyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2- hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and cyclic ether-containing (meth)acrylates such as glycidyl (meth)acrylate and tetrahydrofurfuryl (meth)acrylate. Among them, n-butyl (meth)acrylate is preferable from the viewpoint of compatibility with the second copolymer described later, weather resistance, followability, and the like. The monoethylenically unsaturated monomers can be used alone, or two or more types thereof can be used in combination.

[0032] As the monoethylenically unsaturated monomer, a (meth)acrylate monomer containing a biologically derived carbon atom may be used. The (meth)acrylate monomer containing a biologically derived carbon atom may be used alone or two or more types thereof may be used in combination. The present inventor has found that by adopting a specific first copolymer and a specific second copolymer described later, even if at least one of these copolymers includes a constituent unit derived from a (meth)acrylate monomer containing a biologically derived carbon atom, weatherability equivalent to that of a substrate prepared using a polyvinyl chloride can be exhibited. From the viewpoint of weather resistance and the like, the first copolymer preferably includes a constituent unit derived from a (meth)acrylate monomer containing a biologically derived carbon atom (hereinafter, the constituent unit is sometimes referred to as a “biologically derived constituent unit”), and in addition to the biologically derived constituent unit, it is more preferable that the first copolymer also includes a constituent unit derived from the above-described monoethylenically unsaturated monomer other than the biologically derived constituent unit, that is, the first copolymer is a terpolymer or higher order polymer (for example, a terpolymer). When the first copolymer also includes a constituent unit derived from the abovedescribed monoethylenically unsaturated monomer other than the biologically derived constituent unit, it is possible to adjust the performance such as compatibility with the second copolymer described later and, when present, a fifth copolymer described later, so that it is easy to exhibit desired physical properties in the substrate, and it is also possible to improve the adhesion to the adhesive layer. From the viewpoint of improving the performance such as the compatibility with the second copolymer described later and the fifth copolymer when present, the first copolymer preferably contains the same or the same kind of constituent unit as the constituent unit derived from the monoethylenically unsaturated monomer included in the second copolymer and / or the fifth copolymer. In the present disclosure, the “same kind of constituent unit” is intended to be a constituent unit containing monomers having the same main skeleton, such as n-butyl acrylate and n-butyl methacrylate.

[0033] The biologically derived carbon atom contains a certain percentage of a radioactive isotope (C- 14), whereas a petroleum-derived carbon atom contains a few radioactive isotopes C-14. Thus, the content of the biologically derived carbon atom can be calculated by measuring the concentration of C-14contained in each layer (for example, a substrate and an adhesive layer) included in the laminate or the composition capable of forming each layer. Specifically, the concentration can be measured according to ASTM D6866 of a standard used in the bioplastic industry.

[0034] As the (meth)acrylate monomer containing a biologically derived carbon atom, a (meth)acrylate monomer containing a plant-derived carbon atom is preferable from the viewpoints of weather resistance and the like. Examples of such plants include palm oil and coconut oil. From the viewpoint of weather resistance and the like, the (meth)acrylate monomer is preferably a (meth)acrylate monomer having an alkyl group having 4 or more, 5 or more, or 6 or more and 12 or less, 10 or less, or 8 or less carbon atoms, and more preferably at least one selected from the group consisting of n-octyl (meth)acrylate and 2-octyl (meth)acrylate.

[0035] When the first copolymer does not include the biologically derived constituent unit, a proportion of the constituent unit derived from the above-described monoethylenically unsaturated monomer other than the biologically derived constituent unit can be, for example, about 85 mass% or more, about 90 mass% or more, or about 92 mass% or more, and about 99.5 mass% or less, about 99 mass% or less, or about 98 mass% or less relative to the first copolymer. When the first copolymer contains the biologically derived constituent unit, the proportion of such a constituent unit can be, for example, about 40 mass% or more, about 50 mass% or more, about 55 mass% or more, or about 60 mass% or more, and about 99.5 mass% or less, about 95 mass% or less, about 90 mass% or less, about 80 mass% or less, about 75 mass% or less, about 70 mass% or less, or about 65 mass% or less relative to the first copolymer, and when the biologically derived constituent unit is present, the proportion of the constituent unit derived from the above-described monoethylenically unsaturated monomer other than the biologically derived constituent unit can be, for example, about 10 mass% or more, about 15 mass% or more, about 20 mass% or more, about 25 mass% or more, or about 30 mass% or more, about 50 mass% or less, about 45 mass% or less, about 40 mass% or less, or about 35 mass% or less relative to the first copolymer.

[0036] Examples of the carboxy group-containing unsaturated monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; unsaturated dicarboxylic acids such as itaconic acid, fumaric acid, citraconic acid, and maleic acid; co-carboxy polycaprolactone monoacrylate, phthalic acid monohydroxyethyl (meth)acrylate, [3-carboxyethyl acrylate, 2-(meth)acryloyl oxyethyl succinate, and 2-(meth)acryloyl oxyethyl hexahydrophthalate. The carboxy group-containing unsaturated monomers can be used alone, or two or more types thereof can be used in combination.

[0037] A proportion of the constituent unit derived from the carboxy group-containing unsaturated monomer can be about 0.5 mass% or more, about 1 mass% or more, or about 2 mass% or more, and about 15 mass% or less, about 10 mass% or less, or about 8 mass% or less relative to the first copolymer.

[0038] The second copolymer included in the substrate includes a constituent unit derived from an amino group-containing monomer, and has a weight average molecular weight of about 30,000 or more and about 100,000 or less and a glass transition temperature of about 0°C or higher.

[0039] The weight average molecular weight of the second copolymer can be about 35,000 or more, about 40,000 or more, about 45,000 or more, about 50,000 or more, about 55,000 or more, or about60,000 or more, and can be about 90,000 or less, about 85,000 or less, about 80,000 or less, about 75,000 or less, or about 70,000 or less.

[0040] In some embodiments, the molecular weight distribution of the second copolymer is about 10 or less. Such a molecular weight distribution can be about 8.0 or less, about 7.0 or less, about 6.0 or less, or about 5.0 or less. The lower limit of the molecular weight distribution is not particularly limited, and can be about 0 or more, about 1.0 or more, about 2.0 or more, or about 3.0 or more. When such a second copolymer having a narrow molecular weight distribution is used, the solid content of the substrate composition can be increased. When the substrate composition having a high solid content can be used, for example, energy required for drying the substrate can be reduced, and as a result, it is possible to suitably contribute to an environmental problem.

[0041] The glass transition temperature of the second copolymer can be about 10°C or higher, about 20°C or higher, about 30°C or higher, about 40°C or higher, about 45°C or higher, about 50°C or higher, about 55°C or higher, or about 60°C or higher, and can be about 100°C or lower, about 90°C or lower, about 80°C or lower, about 75°C or lower, about 70°C or lower, or about 65°C or lower.

[0042] The second copolymer including a constituent unit derived from an amino group-containing monomer can be obtained by copolymerization of a monoethylenically unsaturated monomer and an amino group-containing unsaturated monomer.

[0043] As the monoethylenically unsaturated monomer, the monoethylenically unsaturated monomer in the first copolymer described above can be similarly used. Among them, methyl (meth)acrylate and n- butyl (meth)acrylate are preferable from the viewpoint of compatibility with the first copolymer described above, weather resistance, and the like. The monoethylenically unsaturated monomers can be used alone, or two or more types thereof can be used in combination. From the viewpoint of improving the performance such as the compatibility with the first copolymer described above and the fifth copolymer when present, the second copolymer preferably contains the same or the same kind of constituent unit as the constituent unit derived from the monoethylenically unsaturated monomer included in the first copolymer and / or the fifth copolymer.

[0044] Also in the second copolymer, similarly to the first copolymer, a (meth)acrylate monomer containing a biologically derived carbon atom may be used. As such a monomer, those described above can be similarly employed.

[0045] When the second copolymer does not contain the biologically derived constituent unit, the proportion of the constituent unit derived from the monoethylenically unsaturated monomer other than the biologically derived constituent unit can be, for example, about 85 mass% or more, about 90 mass% or more, or about 92 mass% or more, and about 99.5 mass% or less, about 99 mass% or less, or about 98 mass% or less relative to the second copolymer. When the second copolymer contains the biologically derived constituent unit, the proportion of such a constituent unit can be, for example, about 40 mass% or more, about 50 mass% or more, about 55 mass% or more, or about 60 mass% or more, and about 99.5 mass% or less, about 95 mass% or less, about 90 mass% or less, about 80 mass% or less, about 75 mass% or less, about 70 mass% or less, or about 65 mass% or less relative to the second copolymer, and when the biologically derived constituent unit is present, the proportion of the constituent unit derived from themonoethylenically unsaturated monomer other than the biologically derived constituent unit can be, for example, about 10 mass% or more, about 15 mass% or more, about 20 mass% or more, about 25 mass% or more, or about 30 mass% or more, about 50 mass% or less, about 45 mass% or less, about 40 mass% or less, or about 35 mass% or less relative to the second copolymer.

[0046] Examples of the amino group-containing unsaturated monomer include dialkylaminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl acrylate (DMAEA) and N,N-dimethylaminoethyl methacrylate (DMAEMA); dialkylaminoalkyl (meth)acrylamides such as N,N-dimethylaminopropyl acrylamide (DMAPAA) and N,N-dimethylaminopropyl methacrylamide; dialkylaminoalkyl vinyl ethers such as N,N-dimethylaminoethyl vinyl ether and N,N-diethylaminoethyl vinyl ether; and monomers having a tertiary amino group, e.g., vinyl monomers having a nitrogen-containing heterocycle such as vinylimidazole. The amino group-containing unsaturated monomers can be used alone, or two or more types thereof can be used in combination.

[0047] A proportion of the constituent unit derived from the amino group-containing monomer can be about 0.5 mass% or more, about 1 mass% or more, or about 2 mass% or more, and about 15 mass% or less, about 10 mass% or less, or about 8 mass% or less relative to the second copolymer.

[0048] The first and second copolymers (partial polymers) can be prepared using, for example, radical polymerization, and can be prepared by known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization. Examples of the initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide, and bis(4-tert-butylcyclohexyl) peroxy dicarbonate, and azo-based polymerization initiators such as 2,2'- azobisisobutyronitile, 2, 2'-azobis(2 -methylbutyronitrile), dimethyl 2, 2'-azobis(2 -methylpropionate), 4,4'- azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile) (AVN). An amount of the initiator used can be, for example, about 0.01 parts by mass or more or about 0.05 parts by mass or more, and about 5 parts by mass or less or about 3 parts by mass or less, relative to 100 parts by mass of the monomer mixture.

[0049] The substrate of the present disclosure can be prepared using a substrate composition containing the first and second copolymers (partial polymers) and a crosslinking agent. By using a composition containing a crosslinking agent, the substrate containing a cured product of the copolymer and the crosslinking agent can have a crosslinked structure. As the crosslinking agent, for example, a thermal crosslinking agent and a radiation crosslinking agent (for example, an ultraviolet crosslinking agent) can be used, and specifically, an epoxy crosslinking agent, a bisamide crosslinking agent, an aziridine crosslinking agent, a carbodiimide crosslinking agent, and the like can be used. The crosslinking agents can be used alone, or two or more types thereof can be used in combination.

[0050] Examples of the epoxy crosslinking agents include N,N,N',N'-tetraglycidyl-l,3- benzenedi(methanamine) (product name: TETRAD-X (Mitsubishi Gas Chemical Company Inc., Chiyoda-ku, Tokyo, Japan), E-AX, E-5XM (Soken Chemical & Engineering Co., Ltd., Toshima-ku, Tokyo, Japan)); and N,N'-(cyclohexane-l,3-diylbismethylene)bis(diglycidylamine) (product name: TETRAD-C (Mitsubishi Gas Chemical Company Inc., Chiyoda-ku, Tokyo, Japan), E-5C (Soken Chemical & Engineering Co., Ltd., Toshima-ku, Tokyo, Japan)). Examples of the bisamide crosslinkingagent include l,l'-(l,3-phenylenedicarbonyl)bis(2-methylaziridine), 1,4- bis(ethyleneiminocarbonylamino)benzene, 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane, and l,8-bis(ethyleneiminocarbonylamino)octane. Examples of the aziridine crosslinking agents include CHEMITITE PZ33 (Nippon Shokubai Co., Ltd., Osaka-shi, Osaka, Japan), and NeoCryl CX-100 (DSM Coating Resins, LLC., Zwolle, Provincie Overijssel, Netherlands). Examples of carbodiimide crosslinking agents include Carbodilite V-03, V-05, and V-07 (Nisshinbo Chemical Inc., Chuo-ku, Tokyo, Japan).

[0051] An amount of the crosslinking agent used can be about 0.01 parts by mass or more, about 0.05 parts by mass or more, or about 0.1 parts by mass or more, and about 5 parts by mass or less, about 3 parts by mass or less, or about 2 parts by mass or less, relative to 100 parts by mass of the second copolymer including a constituent unit derived from an amino group-containing monomer.

[0052] By changing a blending ratio of the first copolymer including a constituent unit derived from a carboxyl group-containing monomer and the second copolymer including a constituent unit derived from an amino group-containing monomer, desired performance (for example, weather resistance and followability) can be imparted to the laminate. In one embodiment, the blending ratio of the first copolymer is about 25 parts by mass or more, about 30 parts by mass or more, about 35 parts by mass or more, about 40 parts by mass or more, about 45 parts by mass or more, or about 50 parts by mass or more, and about 400 parts by mass or less, about 300 parts by mass or less, about 200 parts by mass or less, or about 150 parts by mass or less relative to 100 parts by mass of the second copolymer. The substrate containing the first copolymer in such a ratio can improve not only weather resistance but also performance such as followability.

[0053] A total content of the first copolymer, the second copolymer, and an optional fifth copolymer described later in the substrate or the substrate composition (solid content) can be, for example, about 25 mass% or more, about 30 mass% or more, about 35 mass% or more, about 40 mass% or more, about 45 mass% or more, about 50 mass% or more, about 55 mass% or more, or about 60 mass% or more, and 100 mass% or less, about 95 mass% or less, about 90 mass% or less, or about 80 mass% or less.

[0054] The substrate composition for forming a substrate may optionally contain other components alone or in combination of two or more as long as the effects of the present disclosure are not adversely affected. Examples of such optional components can include other resins (for example, thermoplastic resins and the fifth copolymer described later) other than the first and second copolymers described above, fillers, conductive agents, thermal conductivity imparting agents, antioxidants, UV absorbing agents, light stabilizers, heat stabilizers, dispersants, plasticizers, lubricants, surfactants, leveling agents, silane coupling agents, catalysts, pigments, dyes, and solvents.

[0055] The substrate may have a single layer structure or a multilayered structure. The substrate may have a three-dimensional uneven shape such as an embossed pattern on the entirety or part of the surface thereof.

[0056] The substrate can be formed by coating the adhesive layer with a substrate composition directly or via an arbitrary layer such as a bonding layer or a decorative layer. Alternatively, the substrate composition may be coated on the release liner directly or via an arbitrary layer such as a cover layer toform a substrate, and then the substrate may be laminated on the adhesive layer. The substrate can be formed by coating a release liner or the like with a substrate composition by knife coating, bar coating, blade coating, doctor coating, roll coating, cast coating, or the like, and performing radiation (for example, ultraviolet rays) irradiation treatment or heat treatment as necessary.

[0057] The heat treatment can be performed using, for example, a heater such as an infrared heater, hot air, an oven, or the like. The heat treatment can be performed batchwise or continuously using a belt conveyor or the like, but is preferably performed continuously from the viewpoint of productivity or the like. A heating temperature (set temperature) can be, for example, about 70°C or higher, about 80°C or higher, or about 90°C or higher. An upper limit of the heating temperature is not particularly limited, and can be, for example, about 160°C or lower, about 140°C or lower, or about 120°C or lower.

[0058] The ultraviolet irradiation, which is a type of radiation irradiation, can be performed using, for example, a low-pressure mercury lamp, moderate-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, metal halide lamp, electrode-free lamp, UV-LED, or the like as a light source. The ultraviolet irradiation can be performed batchwise or continuously using a belt conveyor or the like, but is preferably performed continuously from the viewpoint of productivity or the like. An irradiation dose of ultraviolet rays (UV-C) can be, for example, about 1 mJ / cm2or more, about 50 mJ / cm2or more, or about 100 mJ / cm2or more. An upper limit of the irradiation dose of ultraviolet rays is not particularly limited, and can be, for example, about 500 mJ / cm2or less or about 450 mJ / cm2or less.

[0059] As the substrate, a substrate formed in a film shape in advance by extrusion, stretching, or the like may be used. Such a film can be laminated on the adhesive layer.

[0060] The substrate composition can typically be produced by mixing the above-described first copolymer, second copolymer, crosslinking agent, and optional components as necessary.

[0061] In some embodiments, when a pigment is added to the substrate composition, it is preferable that (1) at least one selected from the group consisting of the second copolymer and the fifth copolymer including a constituent unit derived from an amide group-containing monomer is mixed with a pigment to prepare a pigment mixture, and the pigment mixture is mixed with a mixture containing the first copolymer and a crosslinking agent to produce the substrate composition, or it is preferable that (2) at least one selected from the group consisting of the second copolymer and the fifth copolymer including a constituent unit derived from an amide group-containing monomer, a crosslinking agent, and a pigment are mixed to prepare a pigment mixture, and the pigment mixture is mixed with the first copolymer to produce the substrate composition. By producing the substrate composition in this manner, a substrate composition having excellent pigment dispersibility can be obtained.

[0062] The fifth copolymer including a constituent unit derived from an amide group-containing monomer can be obtained by copolymerizing an amide group-containing monomer with at least one selected from the group consisting of the above-described monoethylenically unsaturated monomer, a (meth)acrylate monomer containing a biologically derived carbon atom, and a carboxy group-containing unsaturated monomer. From the viewpoint of pigment dispersibility and the like, vinyl acetate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferable as the monoethylenically unsaturated monomer, and (meth)acrylic acid is preferable as the carboxy group-containing unsaturated monomer.From the viewpoint of improving the performance such as the compatibility with the first copolymer and the second copolymer described above, the fifth copolymer preferably contains the same or the same kind of constituent unit as the constituent unit derived from the monoethylenically unsaturated monomer included in the first copolymer and / or the second copolymer.

[0063] Examples of the amide group-containing monomer include N-vinylcaprolactam, N- vinylpyrrolidone, (meth)acrylamide, N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, and N-octyl (meth)acrylamide. Among them, (meth)acrylamide is preferable from the viewpoint of pigment dispersibility and the like. The amide group-containing monomers can be used alone, or two or more types thereof can be used in combination.

[0064] A proportion of the constituent unit derived from the amide group-containing monomer can be about 0.01 mass% or more, about 0.05 mass% or more, or about 0.1 mass% or more, and about 5 mass% or less, about 1 mass% or less, or about 0.5 mass% or less relative to the fifth copolymer.

[0065] In some embodiments, when the fifth copolymer does not include the biologically derived constituent unit, the proportion of the constituent unit derived from the above-described monoethylenically unsaturated monomer other than the biologically derived constituent unit can be, for example, about 85 mass% or more, about 90 mass% or more, or about 92 mass% or more, and about 99.5 mass% or less, about 99 mass% or less, or about 98 mass% or less relative to the fifth copolymer. When the fifth copolymer contains the biologically derived constituent unit, the proportion of such a constituent unit can be, for example, about 40 mass% or more, about 50 mass% or more, about 55 mass% or more, or about 60 mass% or more, and about 95 mass% or less, about 90 mass% or less, about 80 mass% or less, about 75 mass% or less, about 70 mass% or less, or about 65 mass% or less relative to the fifth copolymer, and when the biologically derived constituent unit is present, the proportion of the constituent unit derived from the above-described monoethylenically unsaturated monomer other than the biologically derived constituent unit can be, for example, about 10 mass% or more, about 15 mass% or more, about 20 mass% or more, about 25 mass% or more, or about 30 mass% or more, about 50 mass% or less, about 45 mass% or less, about 40 mass% or less, or about 35 mass% or less relative to the fifth copolymer.

[0066] In some embodiments, a proportion of the constituent unit derived from the carboxy group- containing unsaturated monomer can be about 0.5 mass% or more, about 1 mass% or more, or about 2 mass% or more, and about 15 mass% or less, about 10 mass% or less, or about 8 mass% or less relative to the fifth copolymer.

[0067] When the substrate composition and the substrate formed from the composition contain the fifth copolymer including a constituent unit derived from an amide group-containing monomer, in one embodiment, a blending ratio of the fifth copolymer is about 1 part by mass or more, about 2 parts by mass or more, or about 3 parts by mass or more, and about 30 parts by mass or less, about 25 parts by mass or less, about 20 parts by mass or less, about 15 parts by mass or less, or about 10 parts by mass or less, relative to 100 parts by mass of the second copolymer. The substrate containing the fifth copolymer in such a ratio can improve performance such as pigment dispersibility.

[0068] The pigment that can be blended in the substrate is not particularly limited, and an inorganic pigment or an organic pigment that has been known as a pigment can be used. The pigment may besurface-treated with silicon oxide, aluminum oxide, or the like. The pigment may be used alone or in combination of two or more types.

[0069] Examples of the inorganic pigment include white pigments such as zinc carbonate, zinc oxide, zinc sulfide, and titanium dioxide (titanium oxide); colored pigments such as black iron oxide, yellow iron oxide, red iron oxide, ultramarine blue, Prussian blue, cobalt blue, titanium yellow, turquoise, and molybdenum orange; and carbon blacks such as furnace black, channel black, thermal black, and acetylene black.

[0070] Examples of the organic pigment include C.I. Pigment White 6, C.I. Pigment Black 7, C.I. Pigment Red 122, 202, 254, and 255, C.I. Pigment Orange 43, C.I. Pigment Violet 19 and 23, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, and 15: 4, and C.I. Pigment Brown 23 and 25, C.I. Pigment Yellow 74, 109, 110, and 128, and C.I. Pigment Green 7 and 36.

[0071] A blending amount of the pigment can be, for example, about 0.1 mass% or more, about 1 mass% or more, or about 5 mass% or more, and about 55 mass% or less, about 50 mass% or less, about 20 mass% or less, or about 10 mass% or less relative to the entire substrate composition (solid content) or substrate.

[0072] In some embodiments, the substrate composition of the present disclosure has a solid content of about 45% or more. The solid content of the substrate composition can be about 48% or more, about 50% or more, about 52% or more, or about 55% or more, and can be about 80% or less, about 70% or less, about 65% or less, or about 60% or less. When the substrate composition having a high solid content can be used, for example, energy required for drying the substrate can be reduced, and as a result, it is possible to suitably contribute to an environmental problem.

[0073] The substrate may be wholly or partially translucent or opaque. However, when the laminate includes, for example, a decorative layer, a colored layer, or the like, the substrate is preferably transparent from the viewpoint of visibility of such a layer and the like. The substrate may be colored as long as the definition of "transparent" or "translucent" described above is satisfied.

[0074] The thickness of the substrate may vary, and, for example, may be about 1 micrometer or more, about 5 micrometers or more, about 10 micrometers or more, about 20 micrometers or more, about 30 micrometers or more, about 40 micrometers or more, or about 50 micrometers or more, and may be about 200 micrometers or less, about 150 micrometers or less, about 100 micrometers or less, or about 90 micrometers or less.

[0075] The laminate of the present disclosure includes an adhesive layer. For the adhesive layer, for example, a typically used adhesive can be used, such as a solvent, emulsion, pressure-sensitive, heatsensitive, thermosetting, or ultraviolet-curable adhesive of (meth)acrylic, polyolefin, polyurethane, polyester, or rubber. The adhesive layer may be applied by a well-known coating method or the like.

[0076] In some embodiments, the adhesive layer of the present disclosure includes a pressuresensitive adhesive layer including a third copolymer including a constituent unit derived from a carboxyl group-containing monomer, a fourth copolymer including a constituent unit derived from an amino group-containing monomer, and a cured product of a crosslinking agent, in which the third copolymer has a weight average molecular weight of about 800,000 or less and a glass transition temperature oflower than about 0°C, and the fourth copolymer has a weight average molecular weight of about 30,000 or more and about 100,000 or less and a glass transition temperature of about 0°C or higher. As the third copolymer, a copolymer similar to the first copolymer included in the substrate described above can be adopted, and as the fourth copolymer, a copolymer similar to the second copolymer included in the substrate described above can be adopted. When such an adhesive layer is used, a laminate which is more excellent in performance such as weather resistance and followability can be obtained. Such an adhesive layer can also be prepared to a pressure-sensitive adhesive layer (for example, a layer that exhibits pressure sensitive adhesion at room temperature (for example, about 20°C) and can adhere to surfaces of various adherends with relatively light pressure), a heat-sensitive adhesive layer (for example, a layer that does not exhibit the pressure sensitive adhesion at room temperature (for example, about 20°C) and exhibits the pressure sensitive adhesion at a high temperature (for example, 50°C)), or the like. When the same copolymer is adopted for the substrate and the adhesive layer, it is possible to suitably contribute to cost, adhesiveness of both layers, and the like. It is also possible to impart desired performance as a substrate and an adhesive layer by adjusting a blending amount of the copolymer used for the substrate and the adhesive layer and / or other conditions.

[0077] The glass transition temperature and the weight average molecular weight of the third copolymer and the fourth copolymer can be appropriately adjusted from the ranges described in the first copolymer and the second copolymer described above so as to obtain desired adhesion performance. The molecular weight distribution of the third copolymer and the fourth copolymer can also appropriately adjusted from the ranges described in the first copolymer and the second copolymer described above. The use of the third copolymer and / or the fourth copolymer having a narrow molecular weight distribution can reduce the proportion of the low-molecular-weight copolymer that causes the decrease in adhesive force, and thus can improve performance such as adhesive force as compared with an adhesive layer prepared using a copolymer having a wide molecular weight distribution.

[0078] In some embodiments, in the adhesive layer of the present disclosure, at least one of the third copolymer or the fourth copolymer contains a constituent unit derived from a (meth)acrylate monomer containing a biologically derived carbon atom. As the (meth)acrylate monomer, a monomer used in the substrate described above can be similarly employed. Such an adhesive layer can further contribute to a reduction in the amount of petroleum resources used.

[0079] By changing a blending ratio of the third copolymer including a constituent unit derived from a carboxyl group-containing monomer and the fourth copolymer including a constituent unit derived from an amino group-containing monomer, desired performance (for example, pressure-sensitive type, heat-sensitive type, adhesive force, heat shrinkage resistance, reworkability, and followability) can be imparted to the laminate. In one embodiment, the blending ratio of the fourth copolymer is less than about 20 parts by mass, about 15 parts by mass or less, about 10 parts by mass or less, or about 7 parts by mass or less, and is about 1 part by mass or more, about 2 parts by mass or more, or about 3 parts by mass or more relative to 100 parts by mass of the third copolymer. The adhesive layer containing the fourth copolymer in such a ratio can improve performance such as adhesive force, heat shrinkage resistance, reworkability, and followability. The third copolymer having a weight average molecularweight of about 800,000 or less has a molecular weight lower than that of a known copolymer and is easily wetted, so that it has been difficult to obtain significant performance in terms of reworkability. Under such circumstances, the present inventor has found that the wettability is changed only by blending the fourth copolymer in a low amount, and the reworkability can be unexpectedly improved.

[0080] In some embodiments, the adhesive layer of the present disclosure can also be formed using a composition for forming an adhesive layer containing the third copolymer, the fourth copolymer, and a crosslinking agent, similarly to the substrate described above. By using a composition containing a crosslinking agent, the adhesive layer containing a cured product of the third copolymer, the fourth copolymer, and the crosslinking agent can have a crosslinked structure.

[0081] In some embodiments, the adhesive layer of the present disclosure and the substrate described above have a portion that is directly applied. The portion directly applied may be the entire surface of the adhesive layer or the substrate, or may be a part thereof. When the adhesive layer contains the same kind of component as the substrate, the adhesion between both layers can be further improved if such a portion directly applied is present.

[0082] Also in the adhesive layer, the crosslinking agent, the colorant, the fifth copolymer, other optional components other than these, and the like can be used. These components and the blending amounts thereof may be the same as those of the above -de scribed substrate. For example, the type of the adhesive layer can be adjusted to a pressure-sensitive type or a heat-sensitive type depending on the type or blending ratio of the crosslinking agent.

[0083] The total content of the third copolymer, the fourth copolymer, and, when present, the abovedescribed fifth copolymer in the adhesive layer or the composition for forming an adhesive layer (solid content) can be, for example, about 25 mass% or more, about 30 mass% or more, about 35 mass% or more, about 40 mass% or more, about 45 mass% or more, about 50 mass% or more, about 55 mass% or more, about 60 mass% or more, about 80 mass% or more, or about 90 mass% or more, 100 mass% or less, 99.9 mass% or less, about 99 mass% or less, about 95 mass% or less, about 90 mass% or less, about 80 mass% or less, about 70 mass% or less, about 60 mass% or less, about 55 mass% or less, or about 50 mass% or less.

[0084] The adhesive layer of the present disclosure can be obtained, for example, by applying the composition for forming an adhesive layer containing the third copolymer, the fourth copolymer, the crosslinking agent, and optional components (for example, the fifth copolymer, colorant) as necessary to a release liner described later or the like, and then subjecting the composition to a heat treatment and / or a radiation (for example, ultraviolet rays) irradiation treatment. Here, for the heat treatment and / or the radiation (for example, ultraviolet rays) irradiation treatment, the treatment in the substrate described above can be similarly adopted. When a pigment is blended in the adhesive composition, the adhesive composition can be prepared in the same manner as the substrate composition described above.

[0085] A thickness of the adhesive layer of the present disclosure may be appropriately set in consideration of the required adhesive force and the like. Such a thickness can be, for example, about 10 micrometers or more, about 20 micrometers or more, or about 30 micrometers or more, and can be about 300 micrometers or less, about 200 micrometers or less, or about 100 micrometers or less.

[0086] In some embodiments, the laminate of the present disclosure optionally includes an additional layer. Examples of such an additional layer can include at least one selected from the group consisting of cover layers, decorative layers (e.g., color layers, pattern layers, and relief layers), brightening layers, bonding layers, middle fdm layers, and release liners. The additional layer may be applied to the entire surface or a part of the surface of the laminate. The additional layer may have a three-dimensional shape such as an embossed pattern on its surface. A laminate including a layer capable of exhibiting decorative properties (e.g., a decorative layer) can also be referred to as “decorative laminate”. In the case of exhibiting protective performance, for example, performance capable of preventing chipping due to pebbles or the like, it can also be referred to as “protective laminate”.

[0087] The material of the cover layer is not particularly limited, and for example, one type of or a blend of two or more types of (meth)acrylic resins containing polymethyl methacrylate (PMMA) and (meth)acrylic copolymers, resins having a urethane bond (e.g., polyurethane), silicone resin, polycarbonate (PC), polyolefins such as polyethylene (PE) and polypropylene (PP), polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamides such as nylon, and copolymers such as ethylene / acrylic acid copolymers (EAA) and ionomers thereof, ethylene -ethyl acrylate copolymers, ethylene-vinyl acetate copolymers, and ethylene-vinyl alcohol copolymers (EV OH) can be used. The cover layer may have a multilayer structure. For example, the cover layer may be a laminate of fdms formed from the resins described above, or may be a multilayer coating of the resins described above. The cover layer may have a three-dimensional uneven shape such as an embossed pattern on the entirety or part of the surface thereof. Here, in the present disclosure, the term “resins having urethane bonds” may include, for example, a resin prepared using at least one selected from urethane (meth)acrylate and urethane (meth)acrylate oligomer besides a urethane resin, and the urethane resin can also include a (meth)acrylic urethane resin, and the like.

[0088] The cover layer can be formed by coating the substrate with a resin composition directly or via the bonding layer or the like. The coating of the cover layer can be performed before application or after application of the laminate to an adherend (e.g., support member described later). Alternatively, the release liner may be coated with the resin composition to form the cover layer. For example, the cover layer can be formed by coating a release liner or the like with a resin material such as a curable (meth)acrylic resin composition or a urethane composition by knife coating, bar coating, blade coating, doctor coating, roll coating, cast coating, or the like, and performing radiation (for example, ultraviolet rays) irradiation treatment or heat treatment as necessary.

[0089] For the cover layer, a material formed into a film form in advance by extrusion, drawing, or the like may be used. Such a film can be laminated on the substrate with a bonding layer interposed therebetween. By using a film with high flatness as such a film, an article (structure) can be given an appearance of higher surface flatness. The cover layer can be formed by multilayer extrusion with other layers. For example, a (meth)acrylic film can be used as the other layer. For example, a resin containing polymethyl methacrylate (PMMA), butyl polyacrylate, (meth)acrylic copolymer, ethylene / acrylic copolymer, ethylene vinyl acetate / acrylic copolymer can be formed into a film and used as the (meth)acrylic film.

[0090] The cover layer of the present disclosure can contain, for example, fillers, antioxidants, UV absorbing agents, light stabilizers, heat stabilizers, hard coat material, gloss-imparting agent, dispersants, plasticizers, flow improvers, surfactants, leveling agents, silane coupling agents, catalysts, pigments, and dyes as optional components in a range that does not impair the performance (e.g., protecting performance) based on the purpose.

[0091] The cover layer may be wholly or partially translucent or opaque. However, when the laminate includes, for example, a decorative layer or the like, the cover layer is preferably transparent from the viewpoint of visibility of such a layer and the like. The cover layer may be colored as long as the definition of “transparent” or “translucent” described above is satisfied.

[0092] Various thicknesses can be employed for the cover layer and, for example, the thickness may be approximately 1 micrometer or more, approximately 5 micrometers or more, or approximately 10 micrometers or more, and approximately 200 micrometers or less, approximately 100 micrometers or less, or approximately 80 micrometers or less.

[0093] Examples of the decorative layer include, but are not limited to, a color layer that exhibits a paint color, for example, a light color, such as white and yellow, and a strong color, such as red, brown, green, blue, gray, and black; a pattern layer that imparts a design pattern (such as a wood grain, a stone grain, a geometric pattern, or a leather pattern), a logo, a picture pattern, or the like to an article; a relief (embossed pattern) layer in which an uneven shape is provided on the surface; and combinations of these layers.

[0094] The decorative layer can be applied to, but not limited to, the entirety or part of the surface of a layer included in the laminate, such as the substrate and / or the adhesive layer, directly or via a bonding layer and the like.

[0095] The material for the color layer is not limited to the following, but for example, a material obtained by dispersing a pigment in a binder resin, such as a (meth)acrylic resin or a resin having a urethane bond, can be used. Examples of the pigment include inorganic pigments, such as carbon black, chrome yellow, yellow iron oxide, colcothar, or red iron oxide; or organic pigments, such as a phthalocyanine pigment such as phthalocyanine blue or phthalocyanine green, an azo lake pigment, an indigo pigment, a perinone pigment, a perylene pigment, a quinophthalone pigment, a dioxazine pigment, and a quinacridone pigment such as quinacridone red.

[0096] The color layer can be formed using such a material, for example, by a coating method, such as gravure coating, roll coating, die coating, bar coating, or knife coating.

[0097] As a pattern layer, although not limited to the following, pattern layers obtained by printing a pattern such as a pattern, logo, or design directly on the substrate and / or the adhesive layer using a printing method such as gravure direct printing, gravure offset printing, inkjet printing, laser printing, or screen printing may be employed, or a film, sheet, or the like having a pattern, logo, design, or the like formed by coating such as gravure coating, roll coating, die coating, bar coating, or knife coating, punching, etching, or the like also can be used. For example, a material similar to those used in the color layer can be used for the pattern layer.

[0098] For the relief layer, a thermoplastic resin film having an uneven shape on the surface may be used, the uneven shape being obtained by a well-known method in the art, such as, for example, emboss finishing, scratch processing, laser processing, dry etching processing, or hot press processing. The relief layer may be also formed by applying a thermosetting or radiation-curable resin, such as a curable (meth)acrylic resin, on a release liner having an uneven shape, curing the resin by heat or radiation, and removing the release liner.

[0099] The thermoplastic resin, thermosetting resin, and radiation-curable resin used in the relief layer are not particularly limited but, for example, a polyester resin such as PET or PEN, a (meth)acrylic resin, a polyolefin resin such as polyethylene or polypropylene, a thermoplastic elastomer, polycarbonate, polyamide, an ABS resin, an acrylonitrile -styrene resin, polystyrene, vinyl chloride, or a resin having a urethane bond can be used. The relief layer may contain at least one of the pigments used in the color layer.

[0100] The decorative layer of the present disclosure can contain, for example, fillers, reinforcing agents, antioxidants, UV absorbing agents, light stabilizers, heat stabilizers, dispersants, plasticizers, flow improvers, surfactants, leveling agents, silane coupling agents, and catalysts as optional components in a range that does not negatively affect the effect of the present disclosure.

[0101] A thickness of the decorative layer may be appropriately adjusted according to the required decorativeness or the like and is not particularly limited. Such a thickness can be, for example, about 1 micrometer or more, about 3 micrometers or more, or about 5 micrometers or more, and can be about 50 micrometers or less, about 40 micrometers or less, or about 30 micrometers or less.

[0102] Examples of the brightening layer may include, but are not limited to, layers constituting the laminate, for example, layers containing a metal selected from aluminum, nickel, gold, silver, copper, platinum, chromium, iron, tin, indium, titanium, lead, zinc, and germanium, or an alloy or compound thereof, formed by vacuum deposition, sputtering, ion plating, plating, or the like on the entire surface or a part of the substrate and / or the adhesive layer. The thickness of the brightening layer may be appropriately set in accordance with the required decorativeness and the like.

[0103] In the laminate of the present disclosure, a bonding layer (sometimes referred to as "primer layer", for example) can be used to bond an additional layer in the laminate. As the bonding layer, a generally used adhesive agent such as a solvent-type, emulsion-type, pressure-sensitive type, heatsensitive type, and heat-curable or ultraviolet-curable type adhesive agent, including (meth)acrylics, polyolefins, polyurethanes, polyesters, rubbers, and the like can be used. The bonding layer may be applied by a well-known coating method or the like.

[0104] The laminate of the present disclosure may include a middle film layer. As the middle film layer, for example, resin films of resins having a urethane bond, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, or (meth)acrylic polymers can be used.

[0105] A thickness of the middle film layer can be, for example, about 5 micrometers or more, about 10 micrometers or more, or about 15 micrometers or more, and about 200 micrometers or less, about 100 micrometers or less, or about 50 micrometers or less.

[0106] In the laminate of the present disclosure, a release liner can be typically applied to the adhesive layer. Examples of the release liner include paper; a plastic material such as polyethylene, polypropylene, polyester (e.g., PET), and cellulose acetate; and paper coated with such a plastic material. These liners may have a surface that has been subjected to release treatment with a release agent such as silicone.

[0107] A thickness of the release liner, generally, can be about 5 micrometers or more, about 15 micrometers or more, or about 25 micrometers or more, and can be about 500 micrometers or less, about 300 micrometers or less, about 100 micrometers or less, or about 50 micrometers or less.

[0108] The laminate of the present disclosure may be, for example, a sheet-like article, a rolled body winded in a roll shape, or an article with a three-dimensional shape.

[0109] The following production method will be described as an example, but a method for producing the laminate of the present disclosure is not limited thereto.

[0110] For example, in the case of a laminate having a structure in which a cover layer, a substrate, an adhesive layer, and a release liner are provided in this order, a composition for a cover layer is coated on a first release liner, and a drying step and a curing step are applied as necessary to form a cover layer. Subsequently, the substrate composition is coated on the cover layer, and the drying step and the curing step are applied as necessary to form a substrate. The adhesive composition is coated on the second release liner, and the drying step and the curing step are applied as necessary to form an adhesive layer. The substrate and the adhesive layer are bonded together, and the first release liner can be removed to form a laminate.

[0111] In some embodiments, the above-described laminate of the present disclosure is disposed on an adherend via the adhesive layer, and an article including the laminate is provided.

[0112] A material for the adherend to which the laminate can be applied is not particularly limited. Examples of such a material include resin materials (e.g., polyolefin resins, polyester resins, (meth)acrylic resins, polycarbonate resins, resins having a urethane bond, and acrylonitrile-butadiene- styrene copolymers), inorganic materials (e.g., glass, ceramic, concrete, gypsum, calcium silicate, natural stone, and asphalt), rubber materials, cloth materials (e.g., woven fabrics, knitted fabrics, and nonwoven fabrics), metal or metal alloy materials (e.g., iron, aluminum, and stainless steel), and woody materials including paper and the like.

[0113] A shape or structure of the adherend is not particularly limited. The shape may be, for example, a plane shape (e.g., film shape or plate shape), curved surface shape, deformed shape, or three- dimensional shape, and the structure may be a single-layer structure, a laminated structure, or a composite structure in which a plurality of members having different shapes or materials are combined.

[0114] The laminate of the present disclosure can be used in a variety of applications. Examples of such purposes include signboards (e.g., internally illuminated signboards and externally illuminated signboards); signs (e.g., internally illuminated signs and externally illuminated signs); various interior or exterior articles such as interior or exterior articles for vehicles, such as automobiles, railways, aircrafts, and ships (e.g., roof members; pillar members; door trim members; instrument panel members; front members, such as hoods; bumper members; fender members; side sill members; and interior panelmembers); and interior or exterior articles of buildings (e.g., window glass, doors, sashes, roof members such as tiling, outer wall members, and wall papers); electrical appliances, such as personal computers, smartphones, cellular phones, refrigerators, and air conditioners; stationery; furniture; desks; and various containers such as cans. Since the laminate of the present disclosure is excellent in weather resistance, it can be suitably used as exterior uses, more specifically for exterior uses of vehicles (e.g., automobiles) and for exterior uses of buildings (e.g., exterior wall members). In some embodiments, the laminate of the present disclosure is also excellent in followability, and thus can be suitably used for a rough surface. For example, the laminate of the present disclosure can be suitably used for a rough surface (e.g., wall surface) having irregularities with a maximum height from a protrusion to a bottom of about 1 mm or more or about 1.5 mm or more, 1 cm or less, 7 mm or less, 5 mm or less, 3 mm or less, 2.5 mm or less, or 2 mm or less.

[0115] A method of applying the laminate of the present disclosure to the adherend (support member) constituting the article is not particularly limited, and a known method can be appropriately used. Examples of such a method can include hand application, injection molding methods such as an insert injection molding method, an in-molding method, an over-molding method, a two-color injection molding method, a core back injection molding method, and a sandwich injection molding method, a lamination method, and a three-dimensional heat stretch blow molding method (TOM).Examples

[0116] In the following examples, specific embodiments of the present disclosure are illustrated, but the present invention is not limited to these embodiments. All ‘part’ and ‘percent’ are based on mass unless otherwise specified. A numerical value essentially includes an error resulting from a measurement principle and a measuring device. The numerical value is generally indicated by a significant digit that is rounded.

[0117] Table 1 shows various materials used. In the table, the “Mw” and “Tg” mean “weight average molecular weight” and “glass transition temperature”, respectively. Regarding the polymers of API to AP9 and ADH1 to ADH3, copolymer-containing solutions were each prepared by polymerizing a polymerizable composition, obtained by mixing each monomer component, a chain transfer agent (such as isooctylthioglycolate), a polymerization initiator (such as 2,2'-azobis (2,4-dimethylvaleronitrile)), and a solvent (such as ethyl acetate), by a known polymerization method so as to have a mass ratio of a constituent unit derived from the monomer (for example, NOAA (n-octyl acrylate), BA (n-butyl acrylate), and AA (acrylic acid)) described in the table. Here, NOAA (n-octyl acrylate) and 2OA (2-octyl acrylate) correspond to a (meth)acrylate monomer containing a biologically derived carbon atom.

[0118] Table 1BA: n-butyl acrylate, AA: acrylic acid, 2EHA: 2-ethylhexyl acrylate, MMA: methyl methacrylate, BMA: n-butyl methacrylate, DMAEMA: 2-(dimethylamino)ethyl methacrylateNOAA: n-octyl acrylate, 20 A: 2-octyl acrylate, Vac: vinyl acetate, ACM: acrylamide, AN: acrylonitrile

[0119] Table 2 shows pigment mixtures used in preparing a composition for a colored substrate and a composition for a colored adhesive layer containing a colorant, Table 3 shows each component amount (parts by mass) and the solid content (%) of the composition for a colored adhesive layer (ADI, AD2, and AD5 to 7) prepared using the pigment mixture and the compositions for a transparent adhesive layer (AD3 and AD4) prepared without using the pigment mixture, and Table 4 shows each component amount (parts by mass) and the solid content (%) of each component and the solid content (%) of the composition for a colored substrate prepared using the pigment mixture. Here, each component amount in Tables 3 and 4 is a value based on the nonvolatile content.

[0120] Table 2

[0121] Table 3

[0122] Table d

[0123] Example 1A 50 micrometer-thick polyester backing liner coated with a release layer was coated with a cover layer forming solution TCI using a knife coater. The coating layer was dried at 155°C for 15 seconds to obtain a 3 micrometer-thick transparent cover layer.

[0124] A substrate composition was prepared by mixing the second copolymer (API) including a constituent unit derived from an amino group-containing monomer, the first copolymer (AP2) including a constituent unit derived from a carboxyl group-containing monomer, and the crosslinking agent (CL1) such that a mass ratio of the second copolymer (API), the first copolymer (AP2), and the crosslinking agent (CL1) was 100: 110: 0.2 based on the nonvolatile content. The composition was coated on the cover layer with a knife coater. The obtained coating layer was dried at 95°C for 5 minutes to obtain a 53 micrometer-thick substrate (FL1).

[0125] A liner of polyethylene laminated paper including a silicone release layer on one side was coated with a white composition for an adhesive layer (ADI) using a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain a 40 micrometer-thick adhesive layer. The adhesive layer was laminated on a substrate, and then the polyester backing liner on the cover layer side was peeled off to obtain a laminate of Example 1. Here, in the composition for an adhesive layer (ADI), API corresponds to the fourth copolymer containing a constituent unit derived from an amino group-containing monomer, and ADH1 corresponds to the third copolymer containing a constituent unit derived from a carboxyl group-containing monomer.

[0126] Example 2A cover layer was obtained in the same manner as in Example 1. Next, API, AP2, and CL1 were mixed such that a mass ratio of API, AP2, and CL1 was 100:75: 1 based on the nonvolatile content, thereby preparing a substrate composition having a solid content of 43%. The composition was coated on the cover layer with a knife coater. The obtained coating layer was dried at 95°C for 5 minutes to obtain a 58 micrometer-thick substrate (FL2).

[0127] A liner of polyethylene laminated paper including a silicone release layer on one side was coated with a white composition for an adhesive layer (AD2) using a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain a 30 micrometer-thick adhesive layer. The adhesive layer was laminated on a substrate, and then the polyester backing liner on the cover layer side was peeled off to obtain a laminate of Example 2.

[0128] Example 3A cover layer, a substrate, and an adhesive layer were obtained in the same manner as in Example 2. Next, Latex gen3 magenta ink was printed on the substrate with an HP Latex 365 printer (available from HP Development Company, L.P. (Minato-ku, Tokyo, Japan)). A printing layer and the adhesive layer were laminated, and the polyester backing liner on the cover layer side was peeled off to obtain a laminate of Example 3.

[0129] Examples 4 to 6Laminates of Examples 4 to 6 were obtained in the same manner as in Example 3 according to the configuration shown in Table 5.

[0130] Example 7API, AP2, and CL1 were mixed such that the mass ratio of API, AP2, and CL1 was 100: 110:0.2 based on the nonvolatile content, thereby preparing a substrate composition having a solid content of 43%. The composition was coated on a 50 micrometer-thick polyester backing liner, coated with a release layer, with a knife coater. The obtained coating layer was dried at 95°C for 5 minutes to obtain a 42 micrometer-thick substrate (FL3).

[0131] A laminate of Example 7 was obtained in the same manner as in Example 1 according to the configuration shown in Table 5.

[0132] Example 8A laminate of Example 8 was obtained in the same manner as Example 7, except that AP2 was changed to AP4, and the substrate thickness was changed to 41 micrometers. In Table 5, the substrate of the laminate is denoted as FL4.

[0133] Example 9A laminate of Example 9 was obtained in the same manner as Example 7, except that AP2 was changed to AP5, and the substrate thickness was changed to 43 micrometers. In Table 5, the substrate of the laminate is denoted as FL5.

[0134] Example 10On a 50 micrometer-thick polyester backing liner coated with a release layer, the substrate composition of FL6 in Table 4 was coated with a knife coater. The obtained coating layer was dried at 95 °C for 5 minutes to obtain a 40 micrometer-thick yellow substrate (FL6).

[0135] An adhesive layer prepared in the same manner as in Example 1 was laminated on a substrate, and then the polyester backing liner was peeled off to obtain a laminate of Example 10.

[0136] Example 11On a 50 micrometer-thick polyester backing liner coated with a release layer, the substrate composition of FL7 in Table 4 was coated with a knife coater. The obtained coating layer was dried at 95 °C for 5 minutes to obtain a 40 micrometer-thick red substrate (FL7).

[0137] In the same manner as in Example 1, an adhesive layer prepared using the composition for an adhesive layer (ADI) was laminated on a substrate, and then the polyester backing liner was peeled off to obtain a laminate of Example 11.

[0138] Example 12A laminate of Example 12 was obtained in the same manner as in Example 10 except that ADI was changed to AD3.

[0139] Example 13A laminate of Example 13 was obtained in the same manner as in Example 11 except that ADI was changed to AD3.

[0140] Example 14API, AP2, and CL1 were mixed such that the mass ratio of API, AP2, and CL1 was 100:90: 1 based on the nonvolatile content, thereby preparing a substrate composition having a solid content of 43%. The composition was coated on a 50 micrometer-thick polyester backing liner, coated with a release layer,with a knife coater. The obtained coating layer was dried at 95°C for 5 minutes to obtain a 25 micrometer-thick substrate (FL8).

[0141] In the same manner as in Example 2, an adhesive layer prepared using the composition for an adhesive layer (AD2) was laminated on a substrate, and then the polyester backing liner was peeled off to obtain a laminate of Example 14.

[0142] Example 15A laminate of Example 15 was obtained in the same manner as Example 14, except that AD2 was changed to AD4, and the substrate thickness was changed to 38 micrometers.

[0143] Example 16A laminate of Example 16 was obtained in the same manner as in Example 14, except that a substrate was prepared, and then the substrate was printed with SS21 black ink using a Mimaki JV330 printer (available from Mimaki Engineering Co., Ltd. (Tomi-shi, Nagano, Japan)).

[0144] Example 17A laminate of Example 17 was obtained in the same manner as in Example 15, except that a substrate was prepared, and then the substrate was printed with SS21 black ink using a Mimaki JV330 printer (available from Mimaki Engineering Co., Ltd. (Tomi-shi, Nagano, Japan)).

[0145] Example 18API, AP6, and CL1 were mixed such that a mass ratio of API, AP6, and CL1 was 100:50: 1 based on the nonvolatile content, thereby preparing a substrate composition having a solid content of 39%. The composition was coated on a 50 micrometer-thick polyester backing liner, coated with a release layer, with a knife coater. The obtained coating layer was dried at 95°C for 5 minutes to obtain a 51 micrometer-thick substrate (FL9).

[0146] A liner of polyethylene laminated paper including a silicone release layer on one side was coated with a composition for an adhesive layer (AD5) using a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain a 33 micrometer-thick adhesive layer. The adhesive layer was laminated on a substrate, and then the polyester backing liner was peeled off to obtain a laminate of Example 18.

[0147] Example 19A laminate of Example 19 was obtained in the same manner as Example 18, except that AD5 was changed to AD6, and the thickness of the adhesive layer was changed to 32 micrometers.

[0148] Example 20A liner of polyethylene laminated paper including a silicone release layer on one side was coated with a white composition for an adhesive layer (AD7) using a knife coater. The coating layer was dried at 95 °C for 5 minutes to obtain a 30 micrometer-thick adhesive layer.

[0149] A substrate (FL 10) was obtained in the same manner as Example 7, except that AP2 was changed to AP7, and the substrate thickness was changed to 38 micrometers.

[0150] The adhesive layer was laminated on a substrate, and then the polyester backing liner was peeled off to obtain a laminate of Example 20.

[0151] Example 21A laminate of Example 21 was obtained in the same manner as Example 20, except that AP7 was changed to AP8, and the substrate thickness was changed to 40 micrometers.

[0152] In Reference Examples 1 to 6 below, a laminate of a test sample was prepared using a known petroleum -derived material.

[0153] Reference Example 1A 50 micrometer-thick polyester backing liner coated with a release layer was coated with a cover layer forming solution TC2 using a knife coater. The coating layer was dried at 155°C for 15 seconds to obtain a 3 micrometer-thick transparent cover layer.

[0154] API, AP3, and CL1 were mixed such that a mass ratio of API, AP3, and CL1 was 100: 110:0.2 based on the nonvolatile content, thereby preparing a substrate composition. The composition was coated on the cover layer with a knife coater. The obtained coating layer was dried at 95 °C for 5 minutes to obtain a 43 micrometer-thick substrate (FL 12).

[0155] A liner of polyethylene laminated paper including a silicone release layer on one side was coated with a white composition for an adhesive layer (ADI) using a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain a 40 micrometer-thick adhesive layer. The adhesive layer was laminated on a substrate, and then the polyester backing liner on the cover layer side was peeled off to obtain a laminate of Reference Example 1. Here, AP3 used in the substrate composition is a copolymer prepared using a known petroleum -derived material, and is not a copolymer prepared using a (meth)acrylate monomer containing a biologically derived carbon atom (for example, n-octyl acrylate or 2-octyl acrylate).

[0156] Reference Example 2A cover layer was obtained in the same manner as in Example 1. Next, API, AP3, and CL1 were mixed such that the mass ratio of API, AP3, and CL1 was 100:75: 1 based on the nonvolatile content, thereby preparing a substrate composition having a solid content of 29%. The composition was coated on the cover layer with a knife coater. The obtained coating layer was dried at 95°C for 5 minutes to obtain a 52 micrometer-thick substrate (FL13).

[0157] A liner of polyethylene laminated paper including a silicone release layer on one side was coated with a white composition for an adhesive layer (AD2) using a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain a 30 micrometer-thick adhesive layer. The adhesive layer was laminated on a substrate, and then the polyester backing liner on the cover layer side was peeled off to obtain a laminate of Reference Example 2.

[0158] Reference Example 3A cover layer, a substrate, and an adhesive layer were obtained in the same manner as in Reference Example 2. Next, Latex gen3 magenta ink was printed on the substrate with an HP Latex 365 printer (available from HP Development Company, L.P. (Minato-ku, Tokyo, Japan)). A printing layer and the adhesive layer were laminated, and the polyester backing liner on the cover layer side was peeled off to obtain a laminate of Reference Example 3.

[0159] Reference Examples 4 to 6Laminates of Reference Examples 4 to 6 were obtained in the same manner as in Reference Example 3 except that the ink applied to the substrate was changed to a cyan ink, a yellow ink, or a black ink.

[0160] Evaluation testEach of the obtained test samples was evaluated according to the following test method. The results are indicated in Table 5.

[0161] (Weather resistance test)The test sample was cut to a width of 70 mm and a length of 40 mm to prepare a test piece, and the test piece was placed on an aluminum plate having a thickness of 1.5 mm. After the placement, the test piece was exposed in Xenon Ci5000 Weather-Ometer (trademark) available from ATRUS in accordance with JIS K 5600-7-7:2008.

[0162] L*, a*, and b* values were measured at an initial stage (before exposure) and after exposure for500 hours using a spectrophotometer (CM-3700d, available from Konica Minolta, Inc. (Chiyoda-ku, Tokyo, Japan)). The values of the test pieces at the initial stage were Li*, ai*, and bi*, and the values of the test pieces after exposure for 500 hours were L2*, a2*, and b2*. A color difference (AE) was calculated from the following Formula 1:• ' ' Formula 1Here, a sample having a color difference of less than 10 at the initial stage (before exposure) and after exposure for 500 hours was evaluated as “A”, a sample having a color difference of 10 or more and less than 20 was evaluated as “B”, and a sample having a color difference of 20 or more was evaluated as “C” Here, “A” was determined as “good”, “B” was determined as “unacceptable”, and “D” was determined as “poor”.

[0163] Yield point evaluation testA test piece was prepared by cutting a test sample into a width of 25 mm and a length of 150 mm. Under an atmosphere of 20°C, the tensile force and elongation of the test piece were measured using a Tensilon universal material testing machine (available from A&D Company, Limited (Toshima-ku, Tokyo, Japan)). The speed of the air jaw was 300 mm per minute, and an air jaw interval was 100 mm. The yield point was determined from a graph of the elongation (x-axis) and the tensile force (y-axis).

[0164] Breaking strength testA test piece was prepared by cutting a test sample into a width of 25 mm and a length of 150 mm. Under an atmosphere of 20°C, the breaking strength of the test piece was measured using a Tensilon universal material testing machine (available from A&D Company, Limited (Toshima-ku, Tokyo, Japan)). The speed of the air jaw was 300 mm per minute, and an air jaw interval was 100 mm.

[0165] Elongation testA test piece was prepared by cutting a test sample into a width of 25 mm and a length of 150 mm. Under an atmosphere of 20°C, the elongation of the test piece was measured using a Tensilon universal material testing machine (available from A&D Company, Limited (Toshima-ku, Tokyo, Japan)). The speed of the air jaw was 300 mm per minute, and an air jaw interval was 100 mm.

[0166] Tensile strength testA test piece was prepared by cutting a test sample into a width of 25 mm and a length of 150 mm. Under an atmosphere of 20°C, the tensile force and elongation of the test piece were measured using a Tensilon universal material testing machine (available from A&D Company, Limited (Toshima-ku, Tokyo, Japan)). The speed of the air jaw was 300 mm per minute, and an air jaw interval was 100 mm. The tensile force at 2% elongation was recorded as the tensile strength (2% tensile strength).

[0167] Tear strength testA test sample was prepared in accordance with JIS K-7128-3. Under an atmosphere of 20°C, the tear strength of the test piece was measured using a Tensilon universal material testing machine (available from A&D Company, Limited (Toshima-ku, Tokyo, Japan)). A speed of an air jaw was 200 mm per minute. The value in the table is an average value of numerical values obtained from five test pieces.

[0168] Adhesive force testA test piece was prepared by cutting a test sample into a width of 25 mm and a length of 150 mm. The test piece was applied to a melamine-coated plate (available from PALTEK CORPORATION (Hiratsuka-shi, Kanagawa, Japan)) under an atmosphere of 20°C according to JIS Z 0237 8.2.3. The test piece was left standing at 20°C for 48 hours, and then a 180 degree peel strength of the test piece was measured using a Tensilon universal material testing machine (available from A&D Company, Limited (Toshima-ku, Tokyo, Japan)). A speed of an air jaw was 300 mm per minute.

[0169] Heat shrinkage testA test piece was prepared by cutting a test sample into a width of 50 mm and a length of 100 mm. This test piece was attached to an aluminum plate and set at 23 °C for 24 hours, and then the test piece was cut into a cross shape. The test piece was left at 65°C for 48 hours. After heat aging, the value of the maximum width of the opening (mouth opening) of the cut was measured with a microscope.

[0170] Ink adhesion testLatex gen3 ink or SS21 ink was printed on a substrate of a test sample with an HP Latex 365 printer or a Mimaki JV330 printer to prepare a test piece. 100 cuts were made in a grid shape in a printing ink layer of the test piece, a cellophane tape (available from Nichiban Co., Ltd. (Bunkyo-ku, Tokyo, Japan)) was attached onto the ink layer with a squeeze and then peeled off at a high speed, and the number of squares remaining on the test piece was counted. A test piece having no ink transfer on a tape surface and 100 squares in close contact with the test piece was evaluated as having “good” ink adhesion. When the number of squares remaining on the test piece was from 90 to 99, the ink adhesion was evaluated as “acceptable”. When the number of squares remaining on the test piece was less than 90, the ink adhesion was evaluated as “poor”.

[0171] Ink quality te stA printed surface of the test piece prepared in the ink adhesion test was visually observed, and while the test piece in which banding, graininess, or image quality unevenness was not observed was evaluated as “good”, the test piece in which banding, graininess, or image quality unevenness was observed was evaluated as “poor”.

[0173] It is apparent for a person skilled in the art that various variations of the embodiments and examples described above can be made without departing from the basic principles of the present invention. In addition, it is apparent for a person skilled in the art that various modifications and variations of the present invention can be made without departing from the spirit and scope of the present invention.

Claims

ClaimsClaim 1A laminate comprising: a substrate including a first copolymer including a constituent unit derived from a carboxyl group-containing monomer, a second copolymer including a constituent unit derived from an amino group-containing monomer, and a cured product of a crosslinking agent; and an adhesive layer, wherein the first copolymer has a weight average molecular weight of 800,000 or less and a glass transition temperature of lower than 0°C, the second copolymer has a weight average molecular weight of 30,000 or more and 100,000 or less and a glass transition temperature of 0°C or higher, and at least one of the first copolymer or the second copolymer includes a constituent unit derived from a (meth)acrylate monomer containing a biologically derived carbon atom.Claim 2The laminate according to claim 1, wherein the adhesive layer includes a third copolymer including a constituent unit derived from a carboxyl group-containing monomer, a fourth copolymer including a constituent unit derived from an amino group-containing monomer, and a cured product of a crosslinking agent, the third copolymer has a weight average molecular weight of 800,000 or less and a glass transition temperature of lower than 0°C, the fourth copolymer has a weight average molecular weight of 30,000 or more and 100,000 or less and a glass transition temperature of 0°C or higher, and at least one of the third copolymer or the fourth copolymer includes a constituent unit derived from a (meth)acrylate monomer containing a biologically derived carbon atom.Claim 3The laminate according to claim 1 or 2, wherein the (meth)acrylate monomer has an alkyl group having 4 or more and 12 or less carbon atoms.Claim 4The laminate according to claim 1 or 2, wherein the (meth)acrylate monomer includes at least one selected from the group consisting of n-octyl (meth)acrylate and 2-octyl (meth)acrylate.Claim 5The laminate according to claim 1 or 2, wherein a proportion of the constituent unit derived from a (meth)acrylate monomer containing a biologically derived carbon atom is 40 mass% or more relative to the copolymer including the constituent unit.Claim 6The laminate according to claim 1 or 2, wherein the substrate has a 2% tensile strength of 2.0 N / 25 mm or more.Claim 7The laminate according to claim 1 or 2, wherein a content of the first copolymer is 25 parts by mass or more and 400 parts by mass or less relative to 100 parts by mass of the second copolymer.Claim 8The laminate according to claim 2, wherein a content of the fourth copolymer is 1 part by mass or more and less than 20 parts by mass relative to 100 parts by mass of the third copolymer.Claim 9The laminate according to claim 1 or 2, wherein at least one of the substrate or the adhesive layer further includes a pigment.Claim 10The laminate according to claim 1 or 2, further comprising a cover layer.

Images