Laminate including base material and adhesive layer

Abstract

To provide a laminate that can contribute to environmental protection and the reduction of petroleum resource consumption, and that has excellent performance such as weather resistance. [Solution] A laminate according to one embodiment of the present disclosure comprises a substrate containing a first copolymer comprising structural units derived from a carboxyl group-containing monomer, a second copolymer comprising structural units 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 about 800,000 or less and a glass transition temperature of less than about 0°C, and 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 more, and at least one of the first copolymer and the second copolymer contains structural units derived from a (meth)acrylate monomer containing carbon atoms of biological origin.

Description

[Technical Field]

[0001] This disclosure relates to a laminate comprising a substrate and an adhesive layer. [Background technology]

[0002] In recent years, laminates have been developed, such as decorative films with polyvinyl chloride resin layers and adhesive tapes with adhesive layers formed using bio-derived materials instead of petroleum-derived materials.

[0003] Patent Document 1 (Japanese Patent Publication No. 2018-034488) describes a decorative film having a polyvinyl chloride resin layer and a colorless, transparent coating layer, wherein the coating layer is made of a cured product of an ultraviolet-curable resin composition containing a polymerization initiator having an acylphosphine oxide group.

[0004] Patent Document 2 (Japanese Patent No. 7474537) describes a biodegradable laminate having a first layer and a second layer, wherein each of the first and second layers contains a biodegradable resin such as polylactic acid and an inorganic substance powder in a mass ratio of 70:30 to 10:90, the first layer further contains 0.1% to 5.0% by mass of one or more first additives selected from the group consisting of glycerin acetate fatty acid ester and tributyl acetyl citrate, and the second layer further contains 0.1% to 5.0% by mass of one or more second additives selected from the group consisting of isocyanate compounds, epoxy compounds and carbodiimide compounds. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2018-034488 [Patent Document 2] Patent No. 7474537 [Overview of the project] [Problems that the invention aims to solve]

[0006] Polyvinyl chloride (PVC) film was sometimes used to impart properties such as weather resistance to laminates. However, the use of PVC film was sometimes restricted from an environmental perspective. In addition, to reduce the use of petroleum resources, laminates were sometimes prepared using bio-derived materials such as polylactic acid resin instead of petroleum-derived materials. However, because polylactic acid resin is a biodegradable material, it was difficult to achieve long-term performance such as weather resistance.

[0007] This disclosure provides a laminate that can contribute to environmental protection and the reduction of petroleum resource consumption, and that has excellent performance such as weather resistance. [Means for solving the problem]

[0008] According to one embodiment of the present disclosure, a laminate is provided comprising a substrate containing a first copolymer containing structural units derived from a carboxyl group-containing monomer, a second copolymer containing structural units 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 about 800,000 or less and a glass transition temperature of less than about 0°C, and 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 more, and at least one of the first copolymer and the second copolymer contains structural units derived from a (meth)acrylate monomer containing carbon atoms of biological origin. [Effects of the Invention]

[0009] According to this disclosure, it is possible to provide a laminate that can contribute to environmental issues and the reduction of petroleum resource consumption, and that has excellent performance such as weather resistance.

[0010] The foregoing description shall not be deemed to disclose all embodiments of the present invention and all advantages relating to the present invention. [Modes for carrying out the invention]

[0011] Hereinafter, the present invention will be described in more detail for the purpose of exemplifying typical embodiments of the present invention, but the present invention is not limited to these embodiments.

[0012] In the present disclosure, for example, the "above" in the "adhesive layer disposed above the release liner" means that the adhesive layer is directly disposed above the release liner, or the adhesive layer is indirectly disposed above the release liner through another layer.

[0013] In the present disclosure, for example, the "below" in the "adhesive layer disposed below the substrate" means that the adhesive layer is directly disposed below the substrate, or the adhesive layer is indirectly disposed below the substrate through another layer.

[0014] In the present disclosure, "transparent" means that the average transmittance in the visible light region (wavelength 400 nm to 700 nm) measured in accordance with JIS K 7375 is about 80% or more, desirably about 85% or more, or about 90% or more. There is no particular limitation on the upper limit value of the average transmittance, but for example, it can be less than about 100%, about 99% or less, or about 98% or less.

[0015] In the present disclosure, "translucent" means that the average transmittance in the visible light region (wavelength 400 nm to 700 nm) measured in accordance with JIS K 7375 is less than about 80%, desirably about 75% or less, and is intended not to completely conceal the base layer or the like.

[0016] In the present disclosure, the "film" includes a member called a "sheet".

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

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

[0019] In some embodiments, the laminates of the present disclosure exhibit weather resistance. Weather resistance can be evaluated by color difference based on weather resistance tests described later. In some embodiments, the laminates of the present disclosure exhibit a color difference of less than about 20, less than or equal to about 15, less than or equal to about 10, less than or equal to about 10, less than or equal to about 8.0, or less than or equal to about 5.0 after 500 hours of exposure according to JIS K 5600-7-7:2008. There is no particular limit to the lower limit of such color difference, and for example, it can be about 0 or more, greater than about 0, or about 0.1 or more.

[0020] In some embodiments, the laminates of the present disclosure exhibit elongation properties. Such elongation properties can be evaluated by yield strength tests, elongation tests, and tensile strength tests, as described later. In some embodiments, the laminates of the present disclosure can exhibit yield strengths of approximately 3.0 N / 25 mm or more, approximately 4.0 N / 25 mm or more, or approximately 5.0 N / 25 mm or more, approximately 50 N / 25 mm or less, approximately 45 N / 25 mm or less, approximately 40 N / 25 mm or less, approximately 35 N / 25 mm or less, or approximately 30 N / 25 mm or less, and approximately 20% or more, approximately 25% or more, or approximately 30% or more, approximately 500 The laminates can exhibit elongations of less than %, approximately 400% or less, approximately 300% or less, approximately 270% or less, approximately 250% or less, or approximately 230% or less, and can exhibit 2% tensile strengths of approximately 2.0 N / 25 mm or more, approximately 2.5 N / 25 mm or more, or approximately 3.0 N / 25 mm or more, approximately 50 N / 25 mm or less, approximately 40 N / 25 mm or less, approximately 30 N / 25 mm or less, or approximately 20 N / 25 mm or less. In some embodiments, the substrates constituting the laminates of the present disclosure may similarly exhibit such elongation characteristics.

[0021] In some embodiments, the laminates of the present disclosure can exhibit a breaking strength of approximately 5.0 N / 25 mm or more, approximately 6.0 N / 25 mm or more, or approximately 7.0 N / 25 mm or more, approximately 50 N / 25 mm or less, approximately 45 N / 25 mm or less, approximately 40 N / 25 mm or less, approximately 35 N / 25 mm or less, or approximately 30 N / 25 mm or less. Such breaking strengths can be determined by breaking strength tests described later. In some embodiments, the substrates constituting the laminates of the present disclosure may similarly exhibit such breaking strengths.

[0022] In some embodiments, the laminates of the present disclosure can exhibit tear strengths of approximately 10 N / mm or more, approximately 15 N / mm or more, or approximately 20 N / mm or more, approximately 100 N / mm or less, approximately 80 N / mm or less, approximately 50 N / mm or less, or approximately 40 N / mm or less. Such tear strengths can be determined by tear strength tests described later. In some embodiments, the substrates constituting the laminates of the present disclosure may similarly exhibit such tear strengths.

[0023] In some embodiments, the laminates of the present disclosure exhibit heat resistance. Such heat resistance can be evaluated by a heat shrinkage test described later. In some embodiments, the laminates of the present disclosure can achieve a maximum gap width (opening) of approximately 0.50 mm or less, approximately 0.40 mm or less, approximately 0.30 mm or less, or approximately 0.25 mm or less after a heat shrinkage test. There is no particular limit to the lower limit of such a width; for example, it can be approximately 0 mm or more.

[0024] In some embodiments, the laminates of the present disclosure can exhibit adhesive strengths of approximately 5.0 N / 25 mm or more, approximately 6.0 N / 25 mm or more, approximately 7.0 N / 25 mm or more, or approximately 8.0 N / 25 mm or more at room temperature when a melamine-coated board is used as the substrate to which the adhesive layer is applied. The upper limit of such adhesive strength can be, for example, approximately 40.0 N / 25 mm or less, approximately 35.0 N / 25 mm or less, approximately 30.0 N / 25 mm or less, approximately 25.0 N / 25 mm or less, or approximately 20.0 N / 25 mm or less. Here, "room temperature" in the present disclosure refers to the temperature inside the room in which the test is conducted, and specifically, for example, it may refer to approximately 23°C ± approximately 5°C, or approximately 23°C ± approximately 3°C.

[0025] The laminate of this disclosure includes a substrate comprising a first copolymer, a second copolymer, and a cured product of 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 crosslinking with the crosslinking agent may also be referred to as the "first partial polymer" and the "second partial polymer," respectively. In this disclosure, "cured product" is not limited to a crosslinked product in which the crosslinking reactive sites in the first copolymer and / or the second copolymer have completely crosslinked, but may also include a crosslinked product in which some of the crosslinking reactive sites remain uncrosslinked. In this disclosure, "substrate" may refer to a layer that serves as a base to which an adhesive is directly or indirectly laminated.

[0026] The first copolymer constituting the substrate contains constituent units derived from carboxyl group-containing monomers, has a weight-average molecular weight of approximately 800,000 or less, and a glass transition temperature of approximately 0°C or less.

[0027] The weight-average molecular weight of the first copolymer can be approximately 700,000 or less, approximately 600,000 or less, approximately 500,000 or less, approximately 450,000 or less, approximately 430,000 or less, approximately 400,000 or less, approximately 380,000 or less, or approximately 350,000 or less, and can be approximately 100,000 or more, approximately 150,000 or more, approximately 200,000 or more, or approximately 210,000 or more. The "weight-average molecular weight" and the "molecular weight distribution" expressed as weight-average molecular weight (Mw) / number-average molecular weight (Mn) in this disclosure can be measured by GPC (gel permeation chromatography). For example, the following conditions can be used as measurement conditions: Equipment: HP-1090 Series II (manufactured by Hewlett-Packard) Solvent: tetrahydrofuran Column: Plgel MIXED-Bx2 (300mm, outer diameter 7.5mm, inner diameter 5mm) Flow rate: 1.0 mL / min Detection 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 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. There is no particular limit to the lower limit of the molecular weight distribution, and it can be about 0 or more, about 1.0 or more, about 2.0 or more, or about 3.0 or more. Using a first copolymer with such a narrow molecular weight distribution can increase the solid content of the substrate composition. Using a substrate composition with high solid content can, for example, reduce the energy required to dry the substrate, and as a result, can make a favorable contribution to environmental issues.

[0029] The glass transition temperature of the first copolymer can be approximately -5°C or lower, approximately -10°C or lower, approximately -20°C or lower, approximately -30°C or lower, approximately -40°C or lower, approximately -43°C or lower, approximately -45°C or lower, approximately -47°C or lower, or approximately -50°C or lower, and can be approximately -100°C or higher, approximately -80°C or higher, approximately -70°C or higher, approximately -65°C or higher, or approximately -60°C or higher. The "glass transition temperature (Tg)" in this disclosure can be determined as the glass transition temperature calculated using the following FOX formula (Fox, TG, Bull. Am. Phys. Soc., 1 (1956), p. 123), assuming that each polymer is copolymerized from n types of monomers:

number

number

[0030] A first copolymer containing constituent units derived from a carboxyl group-containing monomer can be obtained by copolymerizing a monoethylene unsaturated monomer with a carboxyl group-containing unsaturated monomer.

[0031] Monoethylenically unsaturated monomers are generally represented by the formula CH2=CR 1 COOR 2 (R in the formula 1 R is a hydrogen or methyl group, 2 In addition to (meth)acrylates represented by the formula CH2=CR (where CH2 is a linear, branched, or cyclic alkyl group, phenyl group, alkoxyalkyl group, phenoxyalkyl group, hydroxyalkyl group, or cyclic ether group), the formula also includes aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluene, vinyl esters such as vinyl acetate, and unsaturated nitriles such as acrylonitrile and methacrylonitrile. 1 COOR 2Examples of monoethylene unsaturated monomers represented by 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; and alicyclic(meth)acrylates such as cyclohexyl(meth)acrylate and isobornyl(meth)acrylate. Examples include phenyl (meth)acrylate; 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 these, n-butyl (meth)acrylate is preferred from the viewpoint of compatibility with the second copolymer described later, weather resistance, and conformability. Monoethylene unsaturated monomers can be used alone or in combination of two or more.

[0032] As the monoethylene unsaturated monomer, a (meth)acrylate monomer containing bio-derived carbon atoms may be used. The (meth)acrylate monomer containing bio-derived carbon atoms can be used alone or in combination of two or more types. The inventors have found that by employing a specific first copolymer and a specific second copolymer described later, even if at least one of them contains structural units derived from a (meth)acrylate monomer containing bio-derived carbon atoms, it is possible to achieve weather resistance equivalent to that of a substrate prepared using polyvinyl chloride. From the viewpoint of weather resistance, etc., the first copolymer preferably contains structural units derived from a (meth)acrylate monomer containing bio-derived carbon atoms (hereinafter sometimes referred to as "bio-derived structural units"), and more preferably, in addition to such bio-derived structural units, it also contains structural units derived from the monoethylene unsaturated monomer other than the bio-derived structural units described above, i.e., it is a ternary copolymer (for example, a ternary copolymer). If the first copolymer also contains constituent units derived from the monoethylene unsaturated monomers described above, in addition to the biologically derived constituent units, it is possible to adjust the properties such as compatibility with the second copolymer and, if present, the fifth copolymer, also described later. As a result, it becomes easier to achieve the desired physical properties in the substrate, and the adhesion to the adhesive layer can also be improved. From the viewpoint of improving the properties such as compatibility with the second copolymer and, if present, the fifth copolymer, it is preferable that the first copolymer contains the same or similar constituent units as the constituent units derived from the monoethylene unsaturated monomers that constitute the second copolymer and / or the fifth copolymer. In this disclosure, "same constituent units" may refer to constituent units composed of monomers having the same main skeleton, such as n-butyl acrylate and n-butyl methacrylate.

[0033] While bio-derived carbon atoms contain a certain percentage of the radioactive isotope C-14, petroleum-derived carbon atoms contain almost no C-14. Therefore, the content of bio-derived carbon atoms can be calculated by measuring the concentration of C-14 in each layer constituting the laminate (e.g., substrate, adhesive layer) or in the composition that can form each layer. Specifically, it can be measured in accordance with ASTM D6866, a standard used in the bioplastics industry.

[0034] As (meth)acrylate monomers containing carbon atoms of biological origin, plant-derived (meth)acrylate monomers containing carbon atoms are preferred from the viewpoint of weather resistance and other factors. Examples of such plants include palm oil and coconut oil. From the viewpoint of weather resistance and other factors, (meth)acrylate monomers having alkyl groups with 4 or more, 5 or more, 6 or more, 12 or less, 10 or less, or 8 or less carbon atoms are preferred, and at least one selected from the group consisting of n-octyl (meth)acrylate and 2-octyl (meth)acrylate is more preferred.

[0035] If the first copolymer does not contain biologically derived structural units, the proportion of structural units derived from the monoethylene unsaturated monomers other than the biologically derived structural units can be, for example, about 85% by mass or more, about 90% by mass or more, or about 92% by mass or more, about 99.5% by mass or less, about 99% by mass or less, or about 98% by mass or less, relative to the first copolymer. If the first copolymer contains biologically derived constituent units, the proportion of such constituent units can be, for example, about 40% by mass or more, about 50% by mass or more, about 55% by mass or more, or about 60% by mass or more, about 99.5% by mass or less, about 95% by mass or less, about 90% by mass or less, about 80% by mass or less, about 75% by mass or less, about 70% by mass or less, or about 65% by mass or less, relative to the first copolymer. If present, the proportion of constituent units derived from the above-mentioned monoethylene unsaturated monomers other than the biologically derived constituent units can be, for example, about 10% by mass or more, about 15% by mass or more, about 20% by mass or more, about 25% by mass or more, or about 30% by mass or more, about 50% by mass or less, about 45% by mass or less, about 40% by mass or less, or about 35% by mass or less, relative to the first copolymer.

[0036] Examples of carboxyl group-containing unsaturated monomers 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; ω-carboxypolycaprolactone monoacrylate, monohydroxyethyl (meth)acrylate phthalate, β-carboxyethyl acrylate, 2-(meth)acryloyloxyethyl succinic acid, and 2-(meth)acryloyloxyethyl hexahydrophthalic acid. Carboxyl group-containing unsaturated monomers can be used alone or in combination of two or more.

[0037] The proportion of constituent units derived from carboxyl group-containing unsaturated monomers can be approximately 0.5% by mass or more, approximately 1% by mass or more, or approximately 2% by mass or more, approximately 15% by mass or less, approximately 10% by mass or less, or approximately 8% by mass or less, relative to the first copolymer.

[0038] The second copolymer constituting the substrate contains constituent units derived from amino group-containing monomers, has a weight-average molecular weight of approximately 30,000 to approximately 100,000, and a glass transition temperature of approximately 0°C or higher.

[0039] The weight-average molecular weight of the second copolymer can be approximately 35,000 or more, approximately 40,000 or more, approximately 45,000 or more, approximately 50,000 or more, approximately 55,000 or more, or approximately 60,000 or more, and can be approximately 90,000 or less, approximately 85,000 or less, approximately 80,000 or less, approximately 75,000 or less, or approximately 70,000 or less.

[0040] In some embodiments, the molecular weight distribution of the second copolymer is about 10 or less. Such 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. There is no particular limit to the lower limit of the molecular weight distribution, and it can be about 0 or more, about 1.0 or more, about 2.0 or more, or about 3.0 or more. Using a second copolymer with such a narrow molecular weight distribution can increase the solid content of the substrate composition. Using a substrate composition with high solid content can, for example, reduce the energy required to dry the substrate, and as a result, can make a favorable contribution to environmental issues.

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

[0042] A second copolymer containing constituent units derived from an amino group-containing monomer can be obtained by copolymerizing a monoethylene unsaturated monomer with an amino group-containing unsaturated monomer.

[0043] As the monoethylene unsaturated monomer, the monoethylene unsaturated monomers in the first copolymer described above can be used in the same way. Among these, methyl (meth)acrylate and n-butyl (meth)acrylate are preferred from the viewpoint of compatibility with the first copolymer described above, weather resistance, etc. The monoethylene unsaturated monomer can be used alone or in combination of two or more. From the viewpoint of improving performance such as compatibility with the first copolymer described above and the fifth copolymer if present, it is preferable that the second copolymer contains the same or the same type of constituent units as those derived from the monoethylene unsaturated monomers constituting the first copolymer and / or the fifth copolymer.

[0044] In the second copolymer, as in the first copolymer, a (meth)acrylate monomer containing bio-derived carbon atoms may be used. The monomers described above can be used in the same manner.

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

[0046] Examples of amino group-containing unsaturated monomers 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 tertiary amino groups, such as vinyl monomers having nitrogen-containing heterocycles, such as vinylimidazole. Amino group-containing unsaturated monomers can be used alone or in combination of two or more.

[0047] The proportion of constituent units derived from amino group-containing monomers can be approximately 0.5% by mass or more, approximately 1% by mass or more, or approximately 2% by mass or more, approximately 15% by mass or less, approximately 10% by mass or less, or approximately 8% by mass or less, relative to the second copolymer.

[0048] The first and second copolymers (partial polymers) can be prepared, for example, using radical polymerization, or using known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization. As initiators, for example, organic peroxides such as benzoyl peroxide, lauroyl peroxide, and bis(4-tert-butylcyclohexyl) peroxydicarbonate, and azo polymerization initiators such as 2,2'-azobisisobutyronitrile, 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) can be used. The amount of initiator used can be, for example, about 0.01 parts by mass or more, or about 0.05 parts by mass or more, about 5 parts by mass or less, or about 3 parts by mass or less, per 100 parts by mass of the monomer mixture.

[0049] The substrates of this disclosure can be prepared using a substrate composition comprising a first and a second copolymer (partial polymer) and a crosslinking agent. By using a composition containing a crosslinking agent, the substrate comprising such copolymer and cured crosslinking agent can have a crosslinked structure. Examples of crosslinking agents include thermal crosslinking agents and radiation crosslinking agents (e.g., ultraviolet crosslinking agents), and specifically, epoxy crosslinking agents, bisamide crosslinking agents, aziridine crosslinking agents, and carbodiimide crosslinking agents can be used. The crosslinking agents can be used alone or in combination of two or more.

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

[0051] The amount of crosslinking agent used may 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, about 5 parts by mass or less, about 3 parts by mass or less, or about 2 parts by mass or less, per 100 parts by mass of the second copolymer containing constituent units derived from amino group monomers.

[0052] By changing the blending ratio of a first copolymer containing structural units derived from carboxyl group monomers and a second copolymer containing structural units derived from amino group monomers, desired performance (e.g., weather resistance, conformability) can be imparted to the laminate. In one embodiment, the blending ratio of the first copolymer is approximately 25 parts by mass or more, approximately 30 parts by mass or more, approximately 35 parts by mass or more, approximately 40 parts by mass or more, approximately 45 parts by mass or more, or approximately 50 parts by mass or more, approximately 400 parts by mass or less, approximately 300 parts by mass or less, approximately 200 parts by mass or less, or approximately 150 parts by mass or less, per 100 parts by mass of the second copolymer. A substrate containing the first copolymer in such proportions can improve performance such as conformability in addition to weather resistance.

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

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

[0055] The base material may have a single-layer structure or a multi-layer structure. The base material may have a three-dimensional concavo-convex shape such as an embossed pattern on the entire surface or a part of its surface.

[0056] The base material can be formed by coating a base material composition on an adhesive layer directly or through an arbitrary layer such as a bonding layer or a decorative layer. Alternatively, after forming a base material by coating a base material composition directly on a release liner or through an arbitrary layer such as a cover layer, the base material can be laminated on an adhesive layer. The base material can be formed by coating a base material composition on a release liner or the like by knife coating, bar coating, blade coating, doctor coating, roll coating, or cast coating, and performing radiation (e.g., ultraviolet rays) irradiation treatment or heat treatment as necessary.

[0057] The heat treatment can be performed using, for example, a heating heater such as an infrared heater, hot air, an oven, etc. The heat treatment can be performed batchwise or continuously using a belt conveyor or the like, but from the viewpoint of productivity, etc., it is preferably performed continuously. The heating temperature (set temperature) can be, for example, about 70 °C or higher, about 80 °C or higher, or about 90 °C or higher. There is no particular limitation on the upper limit value of the heating temperature, and it can be, for example, about 160 °C or lower, about 140 °C or lower, or about 120 °C or lower.

[0058] As ultraviolet irradiation, which is a kind of radiation irradiation, it can be performed using, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp, or a UV-LED as a light source. The ultraviolet irradiation can be performed batchwise or continuously using a belt conveyor or the like, but from the viewpoint of productivity, etc., it is preferably performed continuously. The irradiation amount of ultraviolet rays (UV-C) can be, for example, about 1 mJ / cm 2 or more, about 50 mJ / cm 2 or more, or about 100 mJ / cm 2 or more. There is no particular limitation on the upper limit value of the irradiation amount of ultraviolet rays, but for example, about 500 mJ / cm2 The following or approximately 450 mJ / cm² 2 The following is possible:

[0059] As the base material, a film that has been pre-formed into a film shape by extrusion or stretching may be used. Such a film can be laminated onto the adhesive layer.

[0060] The base material composition can typically be produced by mixing the first copolymer, the second copolymer, the crosslinking agent, and optionally any other components as described above.

[0061] In some embodiments, when a pigment is incorporated into the base composition, it is preferable to prepare a pigment mixture by mixing (1) at least one selected from the group consisting of a second copolymer and a fifth copolymer containing structural units derived from an amide group monomer with the pigment, and then to produce the base composition by mixing the pigment mixture with a mixture containing the first copolymer and a crosslinking agent; or (2) prepare a pigment mixture by mixing at least one selected from the group consisting of a second copolymer and a fifth copolymer containing structural units derived from an amide group monomer with a crosslinking agent and the pigment, and then to produce the base composition by mixing the pigment mixture with the first copolymer. By producing in this way, a base composition with excellent pigment dispersibility can be obtained.

[0062] A fifth copolymer containing structural units 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 monoethylene unsaturated monomers, (meth)acrylate monomers containing carbon atoms of biological origin, and carboxyl group-containing unsaturated monomers. From the viewpoint of pigment dispersibility and the like, vinyl acetate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred as monoethylene unsaturated monomers, and (meth)acrylic acid is preferred as the carboxyl group-containing unsaturated monomer. From the viewpoint of improving performance such as compatibility with the first copolymer and the second copolymer described above, it is preferable that the fifth copolymer contains the same or the same type of structural units as those derived from the monoethylene unsaturated monomer constituting the first copolymer and / or the second copolymer.

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

[0064] The proportion of constituent units derived from amide group-containing monomers can be approximately 0.01% by mass or more, approximately 0.05% by mass or more, or approximately 0.1% by mass or more, approximately 5% by mass or less, approximately 1% by mass or less, or approximately 0.5% by mass or less, relative to the fifth copolymer.

[0065] In some embodiments, if the fifth copolymer does not contain bio-derived constituent units, the proportion of constituent units derived from the monoethylene unsaturated monomers other than bio-derived constituent units can be, for example, about 85% by mass or more, about 90% by mass or more, or about 92% by mass or more, about 99.5% by mass or less, about 99% by mass or less, or about 98% by mass or less, relative to the fifth copolymer. If the fifth copolymer contains biologically derived constituent units, the proportion of such constituent units can be, for example, about 40% by mass or more, about 50% by mass or more, about 55% by mass or more, or about 60% by mass or more, about 95% by mass or less, about 90% by mass or less, about 80% by mass or less, about 75% by mass or less, about 70% by mass or less, or about 65% by mass or less, relative to the fifth copolymer. If present, the proportion of constituent units derived from the above-mentioned monoethylene unsaturated monomers other than the biologically derived constituent units can be, for example, about 10% by mass or more, about 15% by mass or more, about 20% by mass or more, about 25% by mass or more, or about 30% by mass or more, about 50% by mass or less, about 45% by mass or less, about 40% by mass or less, or about 35% by mass or less, relative to the fifth copolymer.

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

[0067] When a substrate composition and a substrate formed from said composition contain a fifth copolymer containing structural units derived from an amide group-containing monomer, in one embodiment, the 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, 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, per 100 parts by mass of the second copolymer. Substrates containing the fifth copolymer in such proportions can improve performance such as pigment dispersibility.

[0068] There are no particular restrictions on the pigments that can be incorporated into the base material; conventionally known inorganic or organic pigments can be used. The pigments may be surface-treated with silicon dioxide or aluminum oxide, etc. The pigments can be used individually or in combination of two or more types.

[0069] Examples of inorganic pigments 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, Prussian blue, cobalt blue, titanium yellow, turquoise, and molybdate orange; and carbon blacks such as furnace black, channel black, thermal black, and acetylene black.

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

[0071] The amount of pigment added can be, for example, about 0.1% by mass or more, about 1% by mass or more, or about 5% by mass or more, about 55% by mass or less, about 50% by mass or less, about 20% by mass or less, or about 10% by mass or less, relative to the base composition (solid content) or the entire base material.

[0072] In some embodiments, the solids content of the substrate composition of this disclosure is about 45% or more. The solids 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. Using a substrate composition with a high solids content can, for example, reduce the energy required to dry the substrate, and as a result, make a favorable contribution to environmental issues.

[0073] The substrate may be entirely or partially translucent or opaque. However, if the laminate includes, for example, a decorative layer or a colored layer, it is preferable that the substrate be transparent from the viewpoint of the visibility of such layers. The substrate may be colored as long as it satisfies the above-described definitions of "transparent" or "translucent".

[0074] The thickness of the substrate may vary, for example, it 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 it 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 this disclosure includes an adhesive layer. As the adhesive layer, for example, commonly used solvent-type, emulsion-type, pressure-sensitive, heat-sensitive, thermosetting, or UV-curing adhesives such as (meth)acrylic, polyolefin-based, polyurethane-based, polyester-based, and rubber-based adhesives can be used. The adhesive layer can be applied by known coating methods or the like.

[0076] In some embodiments, the adhesive layer of the present disclosure comprises a third copolymer containing structural units derived from a carboxyl group-containing monomer, a fourth copolymer containing structural units derived from an amino group-containing monomer, and a cured product of a crosslinking agent, wherein the third copolymer has a weight-average molecular weight of about 800,000 or less and a glass transition temperature of less 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 more. The third copolymer can be the same copolymer as the first copolymer constituting the substrate described above, and the fourth copolymer can be the same copolymer as the second copolymer constituting the substrate described above. Using such an adhesive layer, a laminate with superior performance such as weather resistance and conformability can be obtained. Such adhesive layers can also be adjusted to be pressure-sensitive adhesive layers (for example, layers that exhibit tackiness at room temperature (e.g., about 20°C) and can adhere to various substrate surfaces with relatively light pressure), or heat-sensitive adhesive layers (for example, layers that do not exhibit tackiness at room temperature (e.g., about 20°C) but exhibit tackiness at high temperatures (e.g., 50°C)). Using the same copolymer for both the substrate and the adhesive layer can favorably contribute to cost and the adhesion between the two layers. Desired performance as a substrate and adhesive layer can also be imparted by adjusting the blending ratio of the copolymer used in the substrate and adhesive layer, and / or other conditions.

[0077] The glass transition temperatures and weight-average molecular weights of the third and fourth copolymers can be appropriately adjusted from the ranges described above for the first and second copolymers to obtain the desired adhesive performance. The molecular weight distributions of the third and fourth copolymers can also be appropriately adjusted from the ranges described above for the first and second copolymers. The use of the third and / or fourth copolymers with narrow molecular weight distributions can reduce the proportion of low molecular weight copolymers that cause a decrease in adhesive strength, thereby improving performance such as adhesive strength compared to adhesive layers prepared using copolymers with broad molecular weight distributions.

[0078] In some embodiments, the adhesive layer of the present disclosure includes at least one of the third copolymer and the fourth copolymer as a constituent unit derived from a bio-derived (meth)acrylate monomer containing carbon atoms. Such (meth)acrylate monomers can be the same monomers used in the substrates described above. Such adhesive layers can contribute more to reducing the use of petroleum resources.

[0079] By changing the blending ratio of a third copolymer containing structural units derived from carboxyl group-containing monomers and a fourth copolymer containing structural units derived from amino group-containing monomers, desired properties (e.g., pressure-sensitive, heat-sensitive, adhesive strength, heat shrinkage resistance, reworkability, conformability) 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, about 1 part by mass or more, about 2 parts by mass or more, or about 3 parts by mass or more, per 100 parts by mass of the third copolymer. An adhesive layer containing the fourth copolymer in such proportions can improve properties such as adhesive strength, heat shrinkage resistance, reworkability, and conformability. The third copolymer, with a weight-average molecular weight of about 800,000 or less, has a lower molecular weight and is more easily wettable than conventionally used copolymers, making it difficult to obtain significant performance in terms of reworkability. In this context, the inventors discovered that simply adding a small amount of the fourth copolymer alters the wettability, unexpectedly improving reworkability.

[0080] In some embodiments, the adhesive layer of the present disclosure can also be formed using an adhesive layer-forming composition comprising a third copolymer, a fourth copolymer, and a crosslinking agent, similar to the substrates described above. By using a composition comprising a crosslinking agent, the adhesive layer comprising cured products 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 that is directly applied may be the entire surface of the adhesive layer or the substrate, or a portion thereof. If the adhesive layer contains the same components as the substrate, the presence of such a portion that is directly applied can further improve the adhesion between the two layers.

[0082] In the adhesive layer, crosslinking agents, pigments, a fifth copolymer, and other optional components may also be used. The components and their proportions can be the same as those used for the substrate described above. For example, the type of adhesive layer can be adjusted to pressure-sensitive or heat-sensitive depending on the type or proportion of the crosslinking agent.

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

[0084] The adhesive layer of this disclosure can be obtained, for example, by applying an adhesive layer-forming composition containing a third copolymer, a fourth copolymer, a crosslinking agent, and optionally an optional component (e.g., a fifth copolymer, a pigment) to a release liner or the like, as described later, followed by heat treatment and / or radiation (e.g., ultraviolet) irradiation. Here, the heat treatment and / or radiation (e.g., ultraviolet) irradiation can be similar to the treatments performed on the substrate described above. When a pigment is incorporated into the adhesive composition, it can be prepared in the same manner as the substrate composition described above.

[0085] The thickness of the adhesive layer in this disclosure can be set appropriately considering the required adhesive strength, etc. For example, such a thickness can be 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 laminates of the present disclosure optionally include additional layers. Such additional layers may include, for example, at least one selected from the group consisting of a cover layer, a decorative layer (e.g., a color layer, a pattern layer, a relief layer), a glossy layer, a bonding layer, an intermediate film layer, and a release liner. The additional layers may be applied to the entire surface or to a portion of the laminate. The additional layers may have a three-dimensional shape, such as an embossed pattern, on their surface. Laminates including a layer that can exhibit decorative properties (e.g., a decorative layer) may also be referred to as "decorative laminates." If they provide protective properties, such as the ability to prevent chipping by pebbles, they may also be referred to as "protective laminates."

[0087] There are no particular restrictions on the material of the cover layer. For example, (meth)acrylic resins containing polymethyl methacrylate (PMMA) and (meth)acrylic copolymers, resins having urethane bonds (e.g., polyurethane), silicone resins, polyolefins such as polycarbonate (PC), polyethylene (PE), and polypropylene (PP), polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyamides such as nylon, ethylene / acrylic acid copolymers (EAA) and their ionomers, copolymers such as ethylene-ethyl acrylate copolymers, ethylene-vinyl acetate copolymers, and ethylene-vinyl alcohol copolymers (EVOH) can be used individually or in blends of two or more. The cover layer may have a multilayer structure. For example, the cover layer may be a laminate of films formed from the above resins, or a multilayer coating of the above resins. The cover layer may have a three-dimensional uneven shape, such as an embossed pattern, on all or part of its surface. Herein, in this disclosure, "resin having a urethane bond" can include not only urethane resins but also resins prepared using, for example, at least one selected from urethane (meth)acrylate and urethane (meth)acrylate oligomer, and urethane resins can also include (meth)acrylic urethane resins.

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

[0089] As the cover layer, a film that has been pre-formed into a film shape by extrusion, stretching, etc., may be used. Such a film can be laminated to the substrate via a bonding layer. By using a film with high flatness as the cover layer, an appearance with higher surface flatness can be given to the article (structure). The cover layer can also be formed by multilayer extrusion with other layers. As the other layers, for example, a (meth)acrylic film can be used. As the (meth)acrylic film, for example, a resin containing polymethyl methacrylate (PMMA), butyl polyacrylate, (meth)acrylic copolymer, ethylene / acrylic copolymer, ethylene vinyl acetate / acrylic copolymer, etc., can be used in film form.

[0090] The cover layer of this disclosure may contain, to the extent that it does not impair the performance (e.g., protective performance) of the application, optional components such as fillers, antioxidants, UV absorbers, light stabilizers, heat stabilizers, hard coat materials, gloss enhancers, dispersants, plasticizers, flow enhancers, surfactants, leveling agents, silane coupling agents, catalysts, pigments, dyes, etc.

[0091] The cover layer may be entirely or partially translucent or opaque. However, if the laminate includes, for example, a decorative layer, it is preferable that the cover layer be transparent from the viewpoint of the visibility of such layer. The cover layer may be colored as long as it satisfies the above-described definitions of "transparent" or "translucent".

[0092] The thickness of the cover layer may vary, for example, it may be about 1 micrometer or more, about 5 micrometers or more, or about 10 micrometers or more, or it may be about 200 micrometers or less, about 100 micrometers or less, or about 80 micrometers or less.

[0093] Decorative layers include, but are not limited to, the following: color layers exhibiting paint colors, such as light colors like white and yellow, and dark colors like red, brown, green, blue, gray, and black; pattern layers that impart patterns such as wood grain, stone patterns, geometric patterns, and leather patterns to an object; relief layers with raised or recessed shapes on the surface; and combinations thereof.

[0094] The decorative layer is not limited to the following, but can be applied directly or via a bonding layer to all or part of the layers constituting the laminate, such as the substrate and / or adhesive layer.

[0095] The material for the color layer is not limited to the following, but for example, materials can be used in which pigments such as inorganic pigments such as carbon black, lead yellow, yellow iron oxide, red iron oxide, etc., phthalocyanine pigments such as phthalocyanine blue, phthalocyanine green, etc., organic pigments such as azolake pigments, indigo pigments, perinone pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments such as quinacridone red, etc. are dispersed in a binder resin such as (meth)acrylic resin or a resin having urethane bonds.

[0096] The color layer can be formed using such materials by coating methods such as gravure coating, roll coating, die coating, bar coating, and knife coating.

[0097] The pattern layer is not limited to the following, but may be a pattern such as a design, logo, or illustration applied directly to the substrate and / or adhesive layer using a printing method such as gravure direct printing, gravure offset printing, inkjet printing, laser printing, or screen printing. Alternatively, a film or sheet having a design, logo, or illustration formed by a coating such as gravure coating, roll coating, die coating, bar coating, or knife coating, or by die-cutting or etching may be used. As for the material of the pattern layer, for example, the same material used for the color layer may be used.

[0098] As the relief layer, a thermoplastic resin film having an uneven surface shape achieved by conventionally known methods, such as embossing, scratching, laser processing, dry etching, or hot pressing, can be used. Alternatively, a thermosetting or radiation-curable resin, such as a curable (meth)acrylic resin, can be applied to a release liner having an uneven surface shape, cured by heating or radiation, and then the release liner can be removed to form the relief layer.

[0099] The thermoplastic resin, thermosetting resin, and radiation-curable resin used in the relief layer are not particularly limited, but examples include polyester resins such as PET and PEN, polyolefin resins such as (meth)acrylic resins, polyethylene and polypropylene, thermoplastic elastomers, polycarbonate, polyamide, ABS resin, acrylonitrile-styrene resin, polystyrene, vinyl chloride, and resins having urethane bonds. The relief layer may also contain at least one of the pigments used in the color layer.

[0100] The decorative layer of the present disclosure may include, to the extent that it does not adversely affect the effects of the present disclosure, optional components such as fillers, reinforcing agents, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dispersants, plasticizers, flow enhancers, surfactants, leveling agents, silane coupling agents, catalysts, and the like.

[0101] The thickness of the decorative layer is not particularly limited and can be adjusted as appropriate according to the required level of decoration. For example, such a thickness can be approximately 1 micrometer or more, approximately 3 micrometers or more, or approximately 5 micrometers or more, and approximately 50 micrometers or less, approximately 40 micrometers or less, or approximately 30 micrometers or less.

[0102] The glossy layer is not limited to the following, but may be a layer containing a metal selected from aluminum, nickel, gold, silver, copper, platinum, chromium, iron, tin, indium, titanium, lead, zinc, germanium, or an alloy or compound thereof, formed on all or part of the substrate and / or adhesive layer of the laminate by vacuum deposition, sputtering, ion plating, plating, etc. The thickness of the glossy layer can be set appropriately according to the required decorative effect.

[0103] The laminates of this disclosure may use a bonding layer (sometimes called a "primer layer," etc.) to bond additional layers in the laminate. As the bonding layer, commonly used solvent-type, emulsion-type, pressure-sensitive, heat-sensitive, thermosetting, or UV-curing adhesives such as (meth)acrylic, polyolefin-based, polyurethane-based, polyester-based, and rubber-based adhesives can be used. The bonding layer can be applied by known coating methods, etc.

[0104] The laminate of this disclosure may include an intermediate film layer. As the intermediate film layer, for example, a resin film of a resin having urethane bonds, a polyolefin such as polyethylene or polypropylene, a polyester such as polyethylene terephthalate or polybutylene terephthalate, or a (meth)acrylic polymer can be used.

[0105] The thickness of the intermediate film layer can be approximately 5 micrometers or more, approximately 10 micrometers or more, or approximately 15 micrometers or more, approximately 200 micrometers or less, approximately 100 micrometers or less, or approximately 50 micrometers or less.

[0106] The laminates of this disclosure typically have a release liner applied to the adhesive layer. Examples of release liners include paper; plastic materials such as polyethylene, polypropylene, polyester (e.g., PET), and cellulose acetate; and paper coated with such plastic materials. These liners may have a surface that has been released with a release agent such as silicone.

[0107] The thickness of the release liner can generally 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 this disclosure may be, for example, a single sheet, a roll wound into a roll, or a three-dimensional object.

[0109] The following manufacturing method is described as an example, but the manufacturing method of the laminate described herein is not limited thereto.

[0110] For example, in the case of a laminate comprising a cover layer, a substrate, an adhesive layer, and a release liner in that order, the cover layer composition is coated onto the first release liner, and drying and curing steps are applied as necessary to form the cover layer. Subsequently, the substrate composition is coated onto the cover layer, and drying and curing steps are applied as necessary to form the substrate. The adhesive composition is coated onto the second release liner, and drying and curing steps are applied as necessary to form the adhesive layer. The substrate and the adhesive layer are bonded together, and the first release liner is removed to form the laminate.

[0111] In some embodiments, the laminates of the present disclosure described above are arranged on a substrate via an adhesive layer to provide an article comprising the laminate.

[0112] There are no particular restrictions on the material of the substrate to which the laminate can be applied. Examples of such materials include resin materials (e.g., polyolefin resins, polyester resins, (meth)acrylic resins, polycarbonate resins, resins having urethane bonds, acrylonitrile-butadiene-styrene copolymers), inorganic materials (e.g., glass, ceramics, concrete, gypsum, calcium silicate, natural stone, asphalt), rubber materials, fabric materials (e.g., woven fabrics, knitted fabrics, nonwoven fabrics), metal or metal alloy materials (e.g., iron, aluminum, stainless steel), and wood-based materials including paper.

[0113] There are no particular restrictions on the shape or structure of the adherend; for example, it may be planar (e.g., film shape, plate shape), curved shape, irregular shape, or three-dimensional shape, and it may be a single-layer structure, a laminated structure, or a composite structure in which multiple members of different shapes or materials are combined.

[0114] The laminates of this disclosure can be used in a variety of applications. Such applications include, for example, signs (e.g., internally illuminated signs and externally illuminated signs); signs (e.g., internally illuminated signs and externally illuminated signs); various interior or exterior parts, such as interior or exterior parts for vehicles such as automobiles, trains, aircraft, and ships (e.g., roof members, pillar members, door trim members, instrument panel members, front members such as bonnets, bumper members, fender members, side sill members, and interior panel members); and interior or exterior parts for buildings (e.g., window glass, doors, sashes, roof members such as tiles, exterior wall members, wallpaper, etc.); electrical appliances such as personal computers, smartphones, mobile phones, refrigerators, and air conditioners; stationery; furniture; desks; and various containers such as cans. Because the laminates of this disclosure have excellent weather resistance, they can be suitably used for exterior applications, more specifically for the exterior of vehicles (e.g., automobiles) and the exterior of buildings (e.g., exterior wall members, etc.). In some embodiments, the laminates of this disclosure also have excellent conformability, and can therefore be suitably used for rough surfaces. For example, the laminate of this disclosure can be suitably used on rough surfaces (e.g., wall surfaces) having irregularities such as a maximum height from the protrusion to the bottom being approximately 1 mm or more, approximately 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] There are no particular limitations on the method of applying the laminate of this disclosure to the adherend (support member) constituting the article, and known methods can be used as appropriate. Examples of such methods include manual bonding, insert injection molding, in-mold molding, over-mold molding, two-color injection molding, core-back injection molding, sandwich injection molding, and other injection molding methods, lamination methods, and three-dimensional heat stretch molding (TOM). [Examples]

[0116] The following examples illustrate specific embodiments of the present disclosure, but the present invention is not limited thereto. All parts and percentages are by mass unless otherwise specified. Numerical values ​​include errors inherent to the measurement principle and measuring device. Numerical values ​​are shown with significant figures after normal rounding.

[0117] Table 1 shows the various materials used. In the table, "Mw" and "Tg" refer to "weight-average molecular weight" and "glass transition temperature," respectively. For polymers AP1-9 and ADH1-3, polymerizable compositions were prepared by mixing each monomer component, a chain transfer agent (such as isooctyl thioglycolate), a polymerization initiator (such as 2,2'-azobis(2,4-dimethylvaleronitrile)), and a solvent (such as ethyl acetate) so that the mass ratio of constituent units derived from the monomers listed in the table (e.g., NOAA (n-octyl acrylate), BA (n-butyl acrylate), AA (acrylic acid)) was such that polymerizable compositions were prepared by polymerizing these compositions using conventional polymerization methods. Here, NOAA (n-octyl acrylate) and 2OA (2-octyl acrylate) correspond to (meth)acrylate monomers containing carbon atoms of biological origin.

[0118] [Table 1]

[0119] Table 2 shows the pigment mixtures used when preparing colored substrate compositions and colored adhesive layer compositions containing colorants. Table 3 shows the amount (parts by mass) and solid content (%) of each component in the colored adhesive layer compositions prepared using the pigment mixtures (AD1, AD2, and AD5-7) and the transparent adhesive layer compositions prepared without the pigment mixtures (AD3 and 4). Table 4 shows the amount (parts by mass) and solid content (%) of each component in the colored substrate composition prepared using the pigment mixtures. Here, the amounts of each component in Tables 3 and 4 are based on non-volatile content.

[0120] [Table 2]

[0121] [Table 3]

[0122] [Table 4]

[0123] Example 1 A 50-micrometer thick polyester backing liner coated with a release layer was coated with a cover layer forming solution TC1 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 a second copolymer (AP1) containing constituent units derived from an amino group-containing monomer, a first copolymer (AP2) containing constituent units derived from a carboxyl group-containing monomer, and a crosslinking agent (CL1) in a mass ratio of 100:110:0.2 based on non-volatile content. This composition was coated onto a cover layer using a knife coater. The resulting coating layer was dried at 95°C for 5 minutes to obtain a substrate (FL1) with a thickness of 53 micrometers.

[0125] A polyethylene laminate paper liner having a silicone release layer on one side was coated with a white adhesive layer composition (AD1) using a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain an adhesive layer 40 micrometers thick. After laminating this adhesive layer onto a substrate, the polyester backing liner on the cover layer side was peeled off to obtain the laminate of Example 1. Here, AP1 in the adhesive layer composition (AD1) corresponds to a fourth copolymer containing constituent units derived from an amino group-containing monomer, and ADH1 corresponds to a third copolymer containing constituent units derived from a carboxyl group-containing monomer.

[0126] Example 2 A cover layer was obtained in the same manner as in Example 1. Next, AP1, AP2, and CL1 were mixed in a mass ratio of 100:75:1 based on non-volatile content to prepare a substrate composition with a solid content of 43%. This composition was coated onto the cover layer using a knife coater. The resulting coating layer was dried at 95°C for 5 minutes to obtain a substrate (FL2) with a thickness of 58 micrometers.

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

[0128] Example 3 A cover layer, substrate, and adhesive layer were obtained in the same manner as in Example 2. Next, Latex gen3 magenta ink was printed onto the substrate using an HP Latex 365 printer (manufactured by HP Japan Inc., Minato-ku, Tokyo, Japan). The printed sample and the adhesive layer were laminated, and the polyester backing liner on the cover layer side was peeled off to obtain the laminate of Example 3.

[0129] Examples 4-6 Laminates 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 7 AP1, AP2, and CL1 were mixed in a mass ratio of 100:110:0.2 based on non-volatile content to prepare a substrate composition with a solid content of 43%. This composition was coated onto a 50-micrometer thick polyester backing liner coated with a release layer using a knife coater. The resulting 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 8 The laminate of Example 8 was obtained in the same manner as in Example 7, except that AP2 was changed to AP4 and the substrate thickness was changed to 41 micrometers. In Table 5, the substrate of this laminate is denoted as FL4.

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

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

[0135] After laminating the adhesive layer prepared in the same manner as in Example 1 onto the substrate, the polyester backing liner was peeled off to obtain the laminate of Example 10.

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

[0137] Similar to Example 1, an adhesive layer prepared using the adhesive layer composition (AD1) was laminated onto the substrate, and then the polyester backing liner was peeled off to obtain the laminate of Example 11.

[0138] Example 12 The laminate of Example 12 was obtained in the same manner as in Example 10, except that AD1 was changed to AD3.

[0139] Example 13 The laminate of Example 13 was obtained in the same manner as in Example 11, except that AD1 was changed to AD3.

[0140] Example 14 AP1, AP2, and CL1 were mixed in a mass ratio of 100:90:1 based on non-volatile content to prepare a substrate composition with a solid content of 43%. This composition was coated onto a 50-micrometer thick polyester backing liner coated with a release layer using a knife coater. The resulting coating layer was dried at 95°C for 5 minutes to obtain a 25-micrometer thick substrate (FL8).

[0141] Similar to Example 2, an adhesive layer prepared using the adhesive layer composition (AD2) was laminated onto the substrate, and then the polyester backing liner was peeled off to obtain the laminate of Example 14.

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

[0143] Example 16 After preparing the substrate, the laminate of Example 16 was obtained in the same manner as in Example 14, except that SS21 black ink was printed onto the substrate using a Mimaki JV330 printer (manufactured by Mimaki Engineering Co., Ltd. (Tomi City, Nagano Prefecture, Japan)).

[0144] Example 17 After preparing the substrate, the laminate of Example 17 was obtained in the same manner as in Example 15, except that SS21 black ink was printed onto the substrate using a Mimaki JV330 printer (manufactured by Mimaki Engineering Co., Ltd. (Tomi City, Nagano Prefecture, Japan)).

[0145] Example 18 AP1, AP6, and CL1 were mixed in a mass ratio of 100:50:1 based on non-volatile content to prepare a substrate composition with a solid content of 39%. This composition was coated onto a 50-micrometer thick polyester backing liner coated with a release layer using a knife coater. The resulting coating layer was dried at 95°C for 5 minutes to obtain a 51-micrometer thick substrate (FL9).

[0146] A polyethylene laminate paper liner having a silicone release layer on one side was coated with an adhesive layer composition (AD5) using a knife coater. The coated layer was dried at 95°C for 5 minutes to obtain an adhesive layer with a thickness of 33 micrometers. After laminating this adhesive layer onto a substrate, the polyester backing liner was peeled off to obtain the laminate of Example 18.

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

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

[0149] The substrate (FL10) was obtained in the same manner as in Example 7, except that AP2 was changed to AP7 and the substrate thickness was changed to 38 micrometers.

[0150] After laminating the adhesive layer onto the substrate, the polyester backing liner was peeled off to obtain the laminate of Example 20.

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

[0152] In the following examples 1-6, the laminated test samples were prepared using conventional petroleum-derived materials.

[0153] Reference example 1 A 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] AP1, AP3, and CL1 were mixed in a mass ratio of 100:110:0.2 based on non-volatile content to prepare a substrate composition. This composition was coated onto a cover layer using a knife coater. The resulting coating layer was dried at 95°C for 5 minutes to obtain a substrate (FL12) with a thickness of 43 micrometers.

[0155] A polyethylene laminate paper liner having a silicone release layer on one side was coated with a white adhesive layer composition (AD1) using a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain an adhesive layer 40 micrometers thick. After laminating this adhesive layer to a substrate, the polyester backing liner on the cover layer side was peeled off to obtain the laminate of Reference Example 1. Here, AP3 used in the substrate composition is a copolymer prepared using conventional petroleum-derived materials, and is not a copolymer prepared using (meth)acrylate monomers containing bio-derived carbon atoms (e.g., n-octyl acrylate or 2-octyl acrylate).

[0156] Reference example 2 A cover layer was obtained in the same manner as in Example 1. Next, AP1, AP3, and CL1 were mixed in a mass ratio of 100:75:1 based on non-volatile content to prepare a substrate composition with a solid content of 29%. This composition was coated onto the cover layer using a knife coater. The resulting coating layer was dried at 95°C for 5 minutes to obtain a substrate (FL13) with a thickness of 52 micrometers.

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

[0158] Reference example 3 A cover layer, substrate, and adhesive layer were obtained in the same manner as in Reference Example 2. Next, Latex gen3 magenta ink was printed onto the substrate using an HP Latex 365 printer (manufactured by HP Japan Inc., Minato-ku, Tokyo, Japan). The printed sample and the adhesive layer were laminated, and the polyester backing liner on the cover layer side was peeled off to obtain the laminate of Reference Example 3.

[0159] Reference examples 4~6 Laminates 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 cyan ink, yellow ink, or black ink.

[0160] Evaluation Test Each test sample obtained was evaluated according to the following test method. The results are shown in Table 5.

[0161] Weather resistance test Test specimens were prepared by cutting the test sample into pieces 70 mm wide and 40 mm long, and these specimens were mounted on a 1.5 mm thick aluminum plate. After mounting, the specimens were exposed in an Atlas Xenon Ci5000 Weather-Ometer (trademark) in accordance with JIS K 5600-7-7:2008.

[0162] Using a spectrophotometer (CM-3700d, manufactured by Konica Minolta, Inc. (Chiyoda-ku, Tokyo, Japan)), L was measured initially (before exposure) and after 500 hours of exposure. * a * and b * The value of the initial test specimen was measured. * a1 * , b1 *The value of the test specimen after 500 hours of exposure was then measured as L2. * a2 * , b2 * The color difference (ΔE) was calculated using the following equation 1:

number

[0163] Yield point evaluation test Test specimens were prepared by cutting the test sample into pieces 25 mm wide and 150 mm long. The tensile force and elongation of the test specimens were measured using a Tensilon universal material testing machine (manufactured by A&D Company, Limited (Toshima-ku, Tokyo, Japan)) in an atmosphere of 20°C. The air jaw speed was set to 300 mm per minute, and the air jaw spacing was 100 mm. The yield point was determined from the graphs of elongation (x axis) and tensile force (y axis).

[0164] Breaking strength test Test specimens were prepared by cutting the test sample into pieces 25 mm wide and 150 mm long. The fracture strength of the test specimens was measured in an atmosphere of 20°C using a Tensilon universal material testing machine (manufactured by A&D Company, Limited (Toshima-ku, Tokyo, Japan)). The air jaw speed was set to 300 mm per minute, and the air jaw spacing was set to 100 mm.

[0165] Elongation test Test specimens were prepared by cutting the test sample into pieces 25 mm wide and 150 mm long. The elongation of the test specimens was measured using a Tensilon universal material testing machine (manufactured by A&D Company, Limited (Toshima-ku, Tokyo, Japan)) in an atmosphere of 20°C. The air jaw speed was set to 300 mm per minute, and the air jaw spacing was set to 100 mm.

[0166] Tensile strength test Test specimens were prepared by cutting the test sample into pieces 25 mm wide and 150 mm long. The tensile force and elongation of the test specimens were measured using a Tensilon universal material testing machine (manufactured by A&D Company, Limited (Toshima-ku, Tokyo, Japan)) in an atmosphere of 20°C. The air jaw speed was set to 300 mm per minute, and the air jaw spacing was set to 100 mm. The tensile force at 2% elongation was recorded as the tensile strength (2% tensile strength).

[0167] Tear strength test Test samples were prepared in accordance with JIS K-7128-3. The tear strength of the test specimens was measured using a Tensilon universal material tester (manufactured by A&D Company, Limited (Toshima-ku, Tokyo, Japan)) in an atmosphere of 20°C. The air jaw speed was set to 200 mm per minute. The values ​​in the table are the average values ​​obtained from five test specimens.

[0168] Adhesion strength test Test specimens were prepared by cutting the test sample into pieces 25 mm wide and 150 mm long. In accordance with JIS Z 0237 8.2.3, the test specimens were applied to a melamine-coated board (manufactured by Paltec Co., Ltd., Hiratsuka City, Kanagawa Prefecture, Japan) in an atmosphere of 20°C. After leaving the test specimens at 20°C for 48 hours, the 180-degree peel force of the test specimens was measured using a Tensilon universal material tester (manufactured by A&D Company, Limited, Toshima-ku, Tokyo, Japan). The air jaw speed was set to 300 mm per minute.

[0169] Heat shrinkage test Test specimens were prepared by cutting the test sample into pieces 50 mm wide and 100 mm long. These specimens were mounted on an aluminum plate and set at 23°C for 24 hours, after which the specimens were cut in a cross shape. These specimens were left at 65°C for 48 hours. After thermal aging, the maximum width of the cut opening (mouth opening) was measured under a microscope.

[0170] Ink Adhesion Test Test specimens were prepared by printing Latex gen3 ink or SS21 ink onto a test sample substrate using an HP Latex 365 printer or a Mimaki JV330 printer. 100 grid-like cuts were made in the ink layer of the test specimen. Cellophane tape (manufactured by Nichiban Co., Ltd., Bunkyo-ku, Tokyo, Japan) was then applied to the ink layer using a squeegee. The tape was then peeled off at high speed, and the number of remaining squares on the test specimen was counted. Ink adhesion was evaluated as "good" if there was no ink transfer to the tape surface and all 100 squares were firmly attached to the test specimen. Ink adhesion was evaluated as "acceptable" if 90 to 99 squares remained on the test specimen. Ink adhesion was evaluated as "poor" if fewer than 90 squares remained on the test specimen.

[0171] Ink quality testing The printed surface of the test specimens prepared for the ink adhesion test was visually inspected. Those that did not show banding, granularity, or uneven image quality were evaluated as "good," while those that showed banding, granularity, or uneven image quality were evaluated as "poor."

[0172] [Table 5]

[0173] It will be apparent to those skilled in the art that the above embodiments and examples can be modified in various ways without departing from the basic principles of the present invention. Furthermore, it will be apparent to those skilled in the art that various improvements and modifications of the present invention can be implemented without departing from the spirit and scope of the invention.

[0174] Some embodiments of this disclosure are described in the following sections [1]-

[10] . [Item 1] A substrate comprising a first copolymer containing structural units derived from carboxyl group-containing monomers, a second copolymer containing structural units derived from amino group-containing monomers, and a cured product of a crosslinking agent, and an adhesive layer, The first copolymer has a weight-average molecular weight of 800,000 or less and a glass transition temperature of less 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. At least one of the first copolymer and the second copolymer contains constituent units derived from a (meth)acrylate monomer containing bio-derived carbon atoms. Laminated structure. [Item 2] The adhesive layer comprises a third copolymer containing structural units derived from a carboxyl group-containing monomer, a fourth copolymer containing structural units 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 less 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. At least one of the third copolymer and the fourth copolymer contains constituent units derived from a (meth)acrylate monomer containing bio-derived carbon atoms. The laminate described in item 1. [Item 3] The laminate according to item 1 or 2, wherein the (meth)acrylate monomer has an alkyl group having 4 to 12 carbon atoms. [Item 4] The laminate according to any one of items 1 to 3, wherein the (meth)acrylate monomer comprises at least one selected from the group consisting of n-octyl (meth)acrylate and 2-octyl (meth)acrylate. [Item 5] A laminate according to any one of items 1 to 4, wherein the proportion of constituent units derived from (meth)acrylate monomers containing bio-derived carbon atoms is 40% by mass or more relative to the copolymer containing said constituent units. [Item 6] The substrate is a laminate according to any one of items 1 to 5, having a 2% tensile strength of 2N / 25mm or more. [Item 7] The laminate according to any one of items 1 to 6, wherein the content of the first copolymer is 25 parts by mass or more and 400 parts by mass or less per 100 parts by mass of the second copolymer. [Item 8] The laminate according to any one of items 2 to 7, wherein the content of the fourth copolymer is 1 part by mass or more and less than 20 parts by mass per 100 parts by mass of the third copolymer. [Item 9] A laminate according to any one of items 1 to 8, wherein at least one of the substrate and the adhesive layer further comprises a pigment. [Item 10] A laminate according to any one of items 1 to 9, further comprising a cover layer.

Claims

1. A substrate comprising a first copolymer containing structural units derived from a carboxyl group-containing monomer, a second copolymer containing structural units 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 800,000 or less and a glass transition temperature of less 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. At least one of the first copolymer and the second copolymer contains constituent units derived from a (meth)acrylate monomer containing bio-derived carbon atoms. Laminated structure.

2. The adhesive layer comprises a third copolymer containing structural units derived from a carboxyl group-containing monomer, a fourth copolymer containing structural units 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 less 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. At least one of the third copolymer and the fourth copolymer contains constituent units derived from a (meth)acrylate monomer containing bio-derived carbon atoms. The laminate according to claim 1.

3. The laminate according to claim 1 or 2, wherein the (meth)acrylate monomer has an alkyl group having 4 to 12 carbon atoms.

4. The laminate according to claim 1 or 2, wherein the (meth)acrylate monomer comprises at least one selected from the group consisting of n-octyl (meth)acrylate and 2-octyl (meth)acrylate.

5. The laminate according to claim 1 or 2, wherein the proportion of constituent units derived from (meth)acrylate monomers containing bio-derived carbon atoms is 40% by mass or more with respect to the copolymer containing said constituent units.

6. The laminate according to claim 1 or 2, wherein the substrate has a 2% tensile strength of 2.0 N / 25 mm or more.

7. The laminate according to claim 1 or 2, wherein the content of the first copolymer is 25 parts by mass or more and 400 parts by mass or less per 100 parts by mass of the second copolymer.

8. The laminate according to claim 2, wherein the content of the fourth copolymer is 1 part by mass or more and less than 20 parts by mass per 100 parts by mass of the third copolymer.

9. The laminate according to claim 1 or 2, wherein at least one of the substrate and the adhesive layer further comprises a pigment.

10. The laminate according to claim 1 or 2, further comprising a cover layer.

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