Decorative film

Abstract

Provided is a decorative film excellent in performance such as solvent resistance, elongation, and followability without using a fluororesin for a surface layer. The decorative film includes a cover layer and a colored layer. The cover layer contains a cured product of a (meth)acrylic polyol and hexamethylene diisocyanate. The colored layer contains a (meth)acrylic polymer having a glass transition temperature of lower than about 0°C, a (meth)acrylic polymer having a glass transition temperature of about 0°C or higher, and a colorant.

Description

PA101509W002DescriptionTitle of the Invention: DECORATIVE FILMTechnical Field

[0001] The present disclosure relates to a decorative film.Background Art

[0002] In recent years, various decorative films for the purpose of imparting designability and protecting a surface have been developed.

[0003] Patent Document 1 (JP 2021-035724 A) describes a decorative film including at least a substrate film layer containing a plasticizer and a top layer containing a fluorine -containing polymer, the top layer being disposed on one surface, in which the fluorine-containing polymer includes a unit based on a fluoroolefin and a unit based on a vinyl ester, and a content of the unit based on a vinyl ester is from 5 to 70 mol% with respect to the total units included in the fluorine-containing polymer.

[0004] Patent Document 2 (JP 2019-177662 A) describes a decorative sheet used for three- dimensional molding, the decorative sheet including at least a substrate sheet and a surface protective layer, in which the surface protective layer is a cured product of a resin composition containing a fluororesin and a curing agent, and has a Martens hardness of 130 N / mm2or less and a gel fraction to methyl ethyl ketone of 80% or more and 100% or less.Citation ListPatent Documents

[0005] Patent Document 1 : JP 2021-035724 APatent Document 2: JP 2019-177662 ASummary of Invention Technical Problem

[0006] As described in Patent Documents 1 and 2, a fluororesin has been used for a surface layer of the decorative film in order to impart performance such as solvent resistance.

[0007] The present disclosure provides a decorative film excellent in performance such as solvent resistance, elongation, and followability without using a fluororesin for a surface layer.Solution to Problem

[0008] According to an embodiment of the present disclosure, there is provided a decorative film including a cover layer and a colored layer, wherein the cover layer contains a cured product of a (meth)acrylic polyol and hexamethylene diisocyanate, and the colored layercontains a (meth)acrylic polymer having a glass transition temperature of lower than about 0°C, a (meth)acrylic polymer having a glass transition temperature of about 0°C or higher, and a colorant.

[0009] According to another embodiment of the present disclosure, there is provided an article including the decorative film and an adherend, wherein the decorative film includes an adhesive layer and is disposed on the adherend via the adhesive layer.Advantageous Effects of Invention

[0010] According to the present disclosure, it is possible to provide a decorative film excellent in performance such as solvent resistance, elongation, and followability without using a fluororesin for a surface layer.

[0011] The above description is not to be construed as having disclosed all the embodiments of the present invention nor all the advantages related to the present invention.Brief Description of Drawings

[0012] FIG. 1 is a schematic cross-sectional view of a decorative film according to an embodiment of the present disclosure.FIG. 2 is a schematic cross-sectional view of an article according to an embodiment of the present disclosureDescription of Embodiments

[0013] The present invention will be described in further detail hereinafter, referring to figures as necessary, with the purpose of illustrating representative embodiments of the present invention, but the present invention is not limited to these embodiments.

[0014] In the present disclosure, the term “on” used, for example, in the phrase “an adhesive layer disposed on a release liner” means that the adhesive layer is disposed directly on the upper side of the release liner, or, that the adhesive layer is indirectly disposed on the upper side of the release liner via another layer.

[0015] In the present disclosure, the term “under”, for example, in “adhesive layer disposed under a colored layer” means that the adhesive layer is disposed directly below the colored layer, or that the adhesive layer is indirectly disposed below the colored layer via another layer.

[0016] In the present disclosure, "transparent" refers to an average transmittance in a visible light region (wavelength of 400 nm to 700 nm) measured in accordance with JIS K 7375 of approximately 80% or more, and the average transmittance may be desirably approximately 85% or more, or approximately 90% or more. The upper limit of the average transmittance is not particularly limited, and can be, for example, approximately less than 100%, approximately 99% or less, or approximately 98% or less.

[0017] In the present disclosure, the term “translucent” refers to an average transmittance in a visible light region (wavelength of 400 nm to 700 nm) measured in accordance with JIS K 7375 of approximately less than 80%, and the average transmittance may be desirably approximately 75% or less, and “translucent” is intended to mean that an underlying layer or the like is not completely hidden.

[0018] In the present disclosure, the term “film” encompasses articles referred to as “sheets”.

[0019] In the present disclosure, “(meth)acrylic” means acrylic or methacrylic, “(meth)acrylate” means acrylate or methacrylate, and “(meth)acryloyl” means acryloyl or methacryloyl.

[0020] FIG. l shows a schematic cross-sectional view of a decorative film according to an embodiment of the present disclosure. The decorative film 100 in FIG. l includes a cover layer 110, a colored layer 120, an adhesive layer 130 and a release liner 140. Here, the adhesive layer or the release liner shown in FIG. l is an optional layer, and the decorative film of the present disclosure may not include an adhesive layer or a release liner. In addition, the decorative film of the present disclosure may include any layer described below (for example, a decorative layer).

[0021] In some embodiments, the decorative film of the present disclosure can exhibit a B evaluation or an A evaluation in a solvent resistance test described later.

[0022] In some embodiments, the decorative film of the present disclosure exhibits elongation properties. Such elongation properties can be evaluated by an elongation test and a tensile strength test described later. In some embodiments, the decorative film of the present disclosure can exhibit an elongation of about 20% or more, about 40% or more, about 60% or more, about 80% or more, or about 100% or more, about 500% or less, about 400% or less, about 300% or less, about 200% or less, or about 160% or less, and can exhibit a 2% tensile strength of about 1 N / 25 mm or more, about 2 N / 25 mm or more, about 3 N / 25 mm or more, about 4 N / 25 mm or more, or about 5 N / 25 mm or more, about 30 N / 25 mm or less, about 20 N / 25 mm or less, or about 10 N / 25 mm or less.

[0023] In some embodiments, the decorative film of the present disclosure exhibits followability, and can reduce or suppress lifting and peeling from a substrate over time when the film is attached to an uneven surface of an uneven substrate. Such performance can be evaluated by a gloss retention by a gloss retention evaluation test described later. In some embodiments, the decorative film of the present disclosure may exhibit a gloss retention of less than about 400%, about 300% or less, about 200% or less, or about 150% or less. When lifting and peeling occur in the film applied to the uneven surface in such a test, smoothness of the film surface is enhanced, so that a gloss value of the film surface is increased, and the gloss retention is increased. Therefore, in such a test, unlike a general gloss retention after curing in a film applied to a smooth surface of a smooth substrate, an upper limit of the glossretention is adopted as an index of an effect of reducing or suppressing lifting and peeling of the decorative film.

[0024] In some embodiments, the decorative film of the present disclosure exhibits heat resistance. Such heat resistance can be evaluated by a heat shrinkage test described later. In some embodiments, the decorative film of the present disclosure can achieve about 0.50 mm or less, about 0.40 mm or less, about 0.30 mm or less, or about 0.25 mm or less with respect to a maximum width of opening (mouth opening) of a cut after the heat shrinkage test. The lower limit of such width is not particularly limited, and can be, for example, about 0 mm or more or more than about 0 mm.

[0025] In some embodiments, the decorative film of the present disclosure exhibits concealing properties. The concealing properties can be evaluated by a color difference in a test of the concealing properties described later. In some embodiments, the decorative film of the present disclosure exhibits a color difference of less than about 20, about 15 or less, about 10 or less, less than about 8.0, about 6.0 or less, about 4.0 or less, or about 2.0 or less. The lower limit of such color difference is not particularly limited, and may be, for example, about 0 or more or more than about 0.

[0026] The decorative film of the present disclosure includes a cover layer containing a cured product of (meth)acrylic polyol and hexamethylene diisocyanate (HDI). Since the decorative film of the present disclosure includes a specific cover layer, the performance such as solvent resistance, elongation, and followability of the decorative film can be improved. In some embodiments, since the cover layer of the present disclosure also has elongation properties, the decorative film including such a cover layer can exhibit an irregularity followability applicable also to a rough surface such as a wall. In the present disclosure, the “cover layer” means a layer that is located at least on the colored layer and covers the colored layer. In the present disclosure, the “cured product” is not limited to a reactant in a state in which such a reactive site that can be crosslinked or polymerized is completely reacted, and may include a reactant in a state in which a part of the reactive site remains without being reacted.

[0027] The (meth)acrylic polyol can react with hexamethylene diisocyanate to form a polyurethane resin. Such a reaction is preferably a thermosetting reaction from the viewpoint of solvent resistance, elongation, followability, and the like. Here, in the present disclosure, the term “polyol” refers to a compound having two or more hydroxyl groups. The number of hydroxyl groups per molecule of the (meth)acrylic polyol may be 2 or more, and may be 5 or less or 3 or less. From the viewpoint of solvent resistance, elongation, followability, and the like, the number of hydroxyl groups per molecule of the (meth)acrylic polyol is preferably 2, that is, a (meth)acrylic diol is preferable. The (meth)acrylic polyol can be used alone, or in combination of two or more types thereof.

[0028] As the (meth)acrylic polyol, for example, a (meth)acrylic copolymer containing a hydroxyl group-containing (meth)acrylate such as hydroxyethyl (meth)acrylate,hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate can be used. As the monomer that can be copolymerized with the hydroxyl group-containing (meth) acrylate, a monomer having an ethylenically unsaturated group can be used, and examples thereof include alkyl (meth)acrylates such as ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate; (meth)acrylic acid, itaconic acid, maleic acid, styrene sulfonic acid, N-vinylpyrrolidone, N-vinylcaprolactam, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, (meth)acrylonitrile, and styrene. The (meth)acrylic polyol can be obtained, for example, by polymerizing a hydroxyl group- containing (meth)acrylate and the monomer having an ethylenically unsaturated group using, as a polymerization initiator, an azo-based initiator such as 2,2-azobisisobutyronitrile or a peroxide-based initiator such as benzoyl peroxide. During the polymerization, a chain transfer agent having a hydroxyl group such as 2-mercaptoethanol, l-mercapto-2-propanol, 3- mercapto-1 -propanol, and p-mercaptophenol may be used.

[0029] The weight average molecular weight of the (meth)acrylic polyol is preferably about 10000 or more, about 20000 or more, about 30000 or more, about 40000 or more, or about 50000 or more, and about 200000 or less, about 150000 or less, about 100000 or less, or about 80000 or less from the viewpoint of solvent resistance, elongation, followability, and the like. The “weight average molecular weight” of the present disclosure can be measured by a GPC method (gel permeation chromatography). For example, the following conditions can be adopted as the measurement conditions:Apparatus: HP- 1090 Series II (available from Hewlett-Packard Company) Solvent: tetrahydrofuranColumn: Plgel MIXED-Bx2 (300 mm, outer diameter: 7.5 mm, inner diameter: 5 mm) Flow rate: l .O mL / minDetecting means: refractive index Sample concentration: 0.1 wt.% Calibration standard: polystyrene

[0030] The glass transition temperature of the (meth)acrylic polyol is preferably about 0°C or higher, about 10°C or higher, about 20°C or higher, or about 30°C or higher, and about 100°C or lower, about 80°C or lower, about 60°C or lower, or about 50°C or lower from the viewpoint of solvent resistance, elongation, followability, and the like. The “glass transition temperature (Tg)” of the present disclosure can be determined as a calculated glass transition temperature by using the following Fox formula (Fox, T. G., Bull. Am. Phys. Soc., 1 (1956), p. 123) when the polymer is formed by copolymerization of n types of monomers:Math. 11 > / >Tg + 273.15 = 273.15In the formula, Tgi represents the glass transition temperature (°C) of a homopolymer of a component i, Xi represents the mass fraction of the monomer of the component i added during polymerization, and i is a natural number of 1 to n, and Math. 2

[0031] The cover layer can be prepared using a composition for forming a cover layer containing (meth)acrylic polyol and hexamethylene diisocyanate. A proportion of the (meth)acrylic polyol or a site derived from the (meth)acrylic polyol in the composition for forming a cover layer (solid content) or the cover layer can be about 30 mass% or more, about 40 mass% or more, about 45 mass% or more, about 50 mass% or more, or about 55 mass% or more, and about 70 mass% or less, about 65 mass% or less, or about 60 mass% or less.

[0032] In hexamethylene diisocyanate, for example, the hardness of the cover layer tends to be higher than that in the case of using isophorone diisocyanate. Since the decorative film of the present disclosure includes a specific colored layer in spite of the use of such a hard cover layer, the irregularity followability to a rough surface and the like can be improved. Since hexamethylene diisocyanate is typically a non-yellowing type aliphatic isocyanate, durability such as weather resistance in the cover layer can also be improved.

[0033] The hexamethylene diisocyanate may be any of a biuret form, an isocyanurate form, and an adduct form. From the viewpoint of elongation properties, irregularity followability to a rough surface, and the like, the adduct form is preferable.

[0034] A proportion of the hexamethylene diisocyanate or a site derived from the hexamethylene diisocyanate in the composition for forming a cover layer (solid content) or the cover layer can be about 15 mass% or more, about 20 mass% or more, about 25 mass% or more, about 30 mass% or more, or about 35 mass% or more, and about 50 mass% or less, about 45 mass% or less, or about 40 mass% or less.

[0035] The thickness of the cover layer may be appropriately set in consideration of required performance (for example, protection performance) and the like. Such a thickness can be, for example, about 1 micrometer or more, about 2 micrometers or more, or about 3 micrometersor more, and can be about 20 micrometers or less, about 15 micrometers or less, or about 10 micrometers or less.

[0036] In some embodiments, the cover layer of the present disclosure exhibits a 60-degree surface glossiness of about 5.0 or less, about 4.5 or less, or about 4.0 or less in a 60-degree surface glossiness test after aluminum plate application or rough surface application described later. The lower limit of such glossiness is not particularly limited, and may be 0 or more or more than 0. The cover layer having a glossiness of about 20 also generally exhibits low gloss (matte tone). However, when a decorative film including such a cover layer is applied to a rough surface, the gloss of the decorative film is locally increased, and there is a possibility that an appearance defect occurs. The present inventor has found that when the glossiness of the cover layer is set to about 5.0 or less (that is, in a super matte tone), the occurrence of such an appearance defect can be reduced or prevented even when the decorative film is applied to a rough surface.

[0037] The cover layer exhibiting such glossiness can be formed by, for example, matte processing. For example, by applying a material containing a filler at a high concentration to a release liner, forming a rough surface based on the filler on the liner, and then applying a composition for forming a cover layer to the rough surface, an uneven surface (matted surface) can be formed on the surface of the cover layer. Unlike the cover layer in which the filler is blended to impart the uneven surface, the cover layer prepared by such a method does not contain the filler or has a small blending amount of the filler, so that the performance of the cover layer is not reduced, and defects due to falling off of the filler and the like can be reduced or prevented. The content of the filler in the cover layer prepared by such a method can be about 10 mass% or less, about 5 mass% or less, about 1 mass% or less, or about 0.1 mass% or less, or no filler may be blended in the cover layer.

[0038] The composition for forming a cover layer may optionally contain other components alone or in combination of two or more as long as the effects of the present disclosure are not adversely affected. Examples of such optional components can include conductive agents, thermal conductivity imparting agents, antioxidants, UV absorbing agents, light stabilizers, heat stabilizers, dispersants, lubricants, surfactants, leveling agents, silane coupling agents, catalysts, pigments, dyes, and solvents.

[0039] The cover layer of the present disclosure can be obtained, for example, by applying a composition for forming a cover layer containing a (meth)acrylic polyol and hexamethylene diisocyanate to a colored layer or a release liner which will be described below, followed by a heat treatment and / or a radiation (for example, ultraviolet ray) irradiation treatment. From the viewpoint of solvent resistance, elongation, followability, and the like, the reaction of the (meth)acrylic polyol and hexamethylene diisocyanate is preferably a thermal curing reaction, and therefore it is preferable to use a heat treatment. As the component used in thecomposition for forming a cover layer, a component that can be used in the cover layer described above can be similarly employed.

[0040] The heat treatment can be performed using, for example, a heater such as an infrared heater, hot air, an oven, or the like. The heat treatment can be performed batchwise or continuously using a belt conveyor or the like, but is preferably performed continuously from the viewpoint of productivity or the like. A heating temperature (set temperature) can be, for example, about 70°C or higher, about 80°C or higher, about 90°C or higher, or about 100°C or higher. An upper limit of the heating temperature is not particularly limited, and can be, for example, about 165°C or lower, about 160°C or lower, or about 155°C or lower.

[0041] The decorative film of the present disclosure includes a colored layer containing a (meth)acrylic polymer having a glass transition temperature of lower than about 0°C, a (meth)acrylic polymer having a glass transition temperature of about 0°C or higher, and a colorant. Since the colored layer of the present disclosure uses such two types of (meth)acrylic polymers, the flexibility of the colored layer can be adjusted without using a plasticizer as in a vinyl chloride resin. Here, the “colored layer containing a (meth)acrylic polymer having a glass transition temperature of lower than about 0°C, a (meth)acrylic polymer having a glass transition temperature of about 0°C or higher, and a colorant” in the present disclosure can include a colored layer containing a cured product of a (meth)acrylic polymer having a glass transition temperature of lower than about 0°C, a (meth)acrylic polymer having a glass transition temperature of about 0°C or higher, and a crosslinking agent, and a colorant. Since the colored layer containing such a cured product is formed using the crosslinking agent, the colored layer can interact with hexamethylene diisocyanate or another crosslinking agent in the cover layer and / or the adhesive layer described later, and as a result, interlayer adhesion of the decorative film can be improved. The colored layer of the present disclosure may have a function as a substrate that supports the cover layer and the like. When the decorative film of the present disclosure includes a cover layer and an adhesive layer, the colored layer may have a function as an intermediate layer (for example, an intermediate film layer). As described later, when the adhesive layer contains a (meth)acrylic polymer having a glass transition temperature of lower than about 0°C, a (meth)acrylic polymer having a glass transition temperature of about 0°C or higher, and a colorant, such a colored adhesive layer can also be regarded as a colored layer. The colored layer of the present disclosure may be a single layer, or may be a layered configuration of two or more layers.

[0042] The glass transition temperature of the (meth)acrylic polymer having a glass transition temperature of lower than about 0°C (hereinafter, sometimes referred to as “low Tg polymer” or “first polymer”) can be about -5 °C or lower, about -10°C or lower, about -20°C or lower, about -30°C or lower, about -40°C or lower, or about -45°C or lower, and can be about-100°C or higher, about -80°C or higher, about -70°C or higher, about -65°C or higher, about -60°C or higher, about -55°C or higher, or about -50°C or higher.

[0043] The weight average molecular weight of the low Tg polymer can be about 200000 or more, about 300000 or more, about 400000 or more, about 500000 or more, about 600000 or more, or about 700000 or more, and can be about 1500000 or less, about 1000000 or less, about 900000 or less, about 800000 or less, about 700000 or less, or about 600000 or less.

[0044] In some embodiments, the (meth)acrylic polymer of the present disclosure having a glass transition temperature of lower than about 0°C can be obtained by copolymerization of a monoethylenically unsaturated monomer and a carboxy group-containing unsaturated monomer. Such a polymer can be referred to as a “carboxy group-containing (meth)acrylic polymer” or a “(meth)acrylic polymer including a constituent unit derived from a carboxyl group-containing monomer”.

[0045] The monoethylenically unsaturated monomer typically includes (meth)acylates represented by the formula CH2=CR1COOR2(in the formula, R1is hydrogen or a methyl group, and R2is a linear, branched, or cyclic alkyl group, a phenyl group, an alkoxyalkyl group, a phenoxyalkyl group, a hydroxyalkyl group, or a cyclic ether group), and additionally, aromatic vinyl monomers such as styrene, a-methyl styrene, and vinyl toluene, vinyl esters such as vinyl acetate, and unsaturated nitriles such as acrylonitrile and methacrylonitrile. Examples of the monoethylenically unsaturated monomer represented by CH2=CR1COOR2can include linear alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-decyl (meth)acrylate, and n-dodecyl (meth)acrylate; branched alkyl (meth)acrylates such as isoamyl (meth) acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, and isononyl (meth)acrylate; alicyclic (meth)acrylates such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; phenyl (meth)acrylates; alkoxyalkyl (meth)acrylates such as methoxypropyl (meth)acrylate and 2- methoxybutyl (meth)acrylate; phenoxyalkyl (meth)acrylates such as phenoxyethyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth) acrylate, 2- hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and cyclic ether- containing (meth)acrylates such as glycidyl (meth)acrylate and tetrahydrofurfuryl (meth)acrylate. Among them, n-butyl (meth) acrylate is preferable from the viewpoint of compatibility, followability, and the like with a (meth)acrylic polymer having a glass transition temperature of about 0°C or higher, which will be described later, and, if present, the third polymer. The monoethylenically unsaturated monomers can be used alone, or two or more types thereof can be used in combination. From the viewpoint of improving the performance such as compatibility with the (meth)acrylic polymer having a glass transition temperature of about 0°C or higher and, if present, the third polymer, which will be described later, the low Tg polymer preferably includes the same or the same kind of constituent unit as the constituent unit derived from the (meth)acrylic polymer having a glass transitiontemperature of about 0°C or higher and / or the monoethylenically unsaturated monomer included in the third polymer. In the present disclosure, the “same kind of constituent unit” can mean a constituent unit containing monomers having the same main skeleton, such as n- butyl acrylate and n-butyl methacrylate.

[0046] A proportion of the constituent unit derived from the monoethylenically unsaturated monomer in the low Tg polymer can be, for example, about 85 mass% or more, about 90 mass% or more, or about 92 mass% or more, and about 99.5 mass% or less, about 99 mass% or less, or about 98 mass% or less with respect to the low Tg polymer.

[0047] Examples of the carboxy group-containing unsaturated monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; unsaturated dicarboxylic acids such as itaconic acid, fumaric acid, citraconic acid, and maleic acid; co- carboxy polycaprolactone monoacrylate, phthalic acid monohydroxyethyl (meth)acrylate, [3- carboxyethyl acrylate, 2-(meth)acryloyl oxyethyl succinate, and 2-(meth)acryloyl oxyethyl hexahydrophthalate. The carboxy group-containing unsaturated monomers can be used alone, or two or more types thereof can be used in combination.

[0048] A proportion of the constituent unit derived from the carboxy group-containing unsaturated monomer can be about 0.5 mass% or more, about 1 mass% or more, or about 2 mass% or more, and about 15 mass% or less, about 10 mass% or less, or about 8 mass% or less with respect to the low Tg polymer.

[0049] The glass transition temperature of the (meth)acrylic polymer having a glass transition temperature of about 0°C or higher (hereinafter, sometimes referred to as “high Tg polymer” or “second polymer”) can be about 10°C or higher, about 20°C or higher, about 30°C or higher, about 40°C or higher, about 45°C or higher, about 50°C or higher, or about 55°C or higher, and can be about 100°C or lower, about 90°C or lower, about 80°C or lower, about 75°C or lower, about 70°C or lower, or about 65°C or lower.

[0050] The weight average molecular weight of the high Tg polymer can be about 30000 or more, about 35000 or more, about 40000 or more, about 45000 or more, about 50000 or more, about 55000 or more, or about 60000 or more, and can be about 100000 or less, about 90000 or less, about 85000 or less, about 80000 or less, or about 75000 or less.

[0051] In some embodiments, the (meth)acrylic polymer of the present disclosure having a glass transition temperature of about 0°C or higher can be obtained by copolymerization of a monoethylenically unsaturated monomer and an amino group-containing unsaturated monomer. Such a polymer can be referred to as an “amino group-containing (meth)acrylic polymer” or a “(meth)acrylic polymer including a constituent unit derived from an amino group-containing monomer”.

[0052] As the monoethylenically unsaturated monomer, the monoethylenically unsaturated monomer in the low Tg polymer described above can be similarly used. Among them, methyl (meth)acrylate, ethyl (meth)acrylate, and n-butyl (meth)acrylate are preferable from theviewpoint of compatibility, followability, strength, and the like of the above-described low Tg polymer. The monoethylenically unsaturated monomers can be used alone, or two or more types thereof can be used in combination. From the viewpoint of improving the performance such as compatibility with the low Tg polymer described above and, if present, the third polymer described later, the high Tg polymer preferably includes the same or the same kind of constituent unit as the constituent unit derived from the monoethylenically unsaturated monomer included in the low Tg polymer and / or the third polymer.

[0053] A proportion of the constituent unit derived from the monoethylenically unsaturated monomer in the high Tg polymer can be, for example, about 85 mass% or more, about 90 mass% or more, or about 92 mass% or more, and about 99.5 mass% or less, about 99 mass% or less, or about 98 mass% or less with respect to the high Tg polymer.

[0054] Examples of the amino group-containing unsaturated monomer include dialkylaminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl acrylate (DMAEA) and N,N-dimethylaminoethyl methacrylate (DMAEMA); dialkylaminoalkyl (meth)acrylamides such as N,N-dimethylaminopropyl acrylamide (DMAPAA) and N,N-dimethylaminopropyl methacrylamide; dialkylaminoalkyl vinyl ethers such as N,N-dimethylaminoethyl vinyl ether and N,N-diethylaminoethyl vinyl ether; and monomers having a tertiary amino group, e.g., vinyl monomers having a nitrogen-containing heterocycle such as vinylimidazole. The amino group-containing unsaturated monomers can be used alone, or two or more types thereof can be used in combination.

[0055] A proportion of the constituent unit derived from the amino group-containing monomer can be about 0.5 mass% or more, about 1 mass% or more, or about 2 mass% or more, and about 15 mass% or less, about 10 mass% or less, or about 8 mass% or less with respect to the high Tg polymer.

[0056] The low Tg polymer and the high Tg polymer can be prepared using, for example, radical polymerization, and can be prepared by known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization. Examples of the initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide, and bis(4-tert-butylcyclohexyl) peroxydicarbonate, and azo-based polymerization initiators such as 2,2'-azobisisobutyronitile, 2,2'-azobis(2- methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile) (AVN). An amount of the initiator (solid content) used can be, for example, about 0.01 parts by mass or more or about 0.05 parts by mass or more, and about 5 parts by mass or less or about 3 parts by mass or less, with respect to 100 parts by mass of the monomer mixture.

[0057] In some embodiments, the colored layer of the present disclosure can be prepared using a composition for forming a colored layer including a low Tg polymer, a high Tg polymer, a crosslinking agent, and a colorant. By using a composition containing acrosslinking agent, the colored layer containing a cured product of the low Tg polymer, the high Tg polymer, and the crosslinking agent can have a crosslinked structure. As the crosslinking agent, for example, a thermal crosslinking agent and a radiation crosslinking agent (for example, an ultraviolet crosslinking agent) can be used, and specifically, an epoxy crosslinking agent, a bisamide crosslinking agent, an aziridine crosslinking agent, a carbodiimide crosslinking agent, and the like can be used. The crosslinking agents can be used alone, or two or more types thereof can be used in combination.

[0058] Examples of the epoxy crosslinking agents include N,N,N',N'-tetraglycidyl-l,3- benzenedi(methanamine) (product name: TETRAD-X (Mitsubishi Gas Chemical Company Inc., Chiyoda-ku, Tokyo, Japan), E-AX, E-5XM (Soken Chemical & Engineering Co., Ltd., Toshima-ku, Tokyo, Japan)); and N,N'-(cyclohexane-l,3- diylbismethylene)bis(diglycidylamine) (product name: TETRAD-C (Mitsubishi Gas Chemical Company Inc., Chiyoda-ku, Tokyo, Japan), E-5C (Soken Chemical & Engineering Co., Ltd., Toshima-ku, Tokyo, Japan)). Examples of the bisamide crosslinking agent include 1 , 1 '-(1 ,3- phenylenedicarbonyl)bis(2-methylaziridine), l,4-bis(ethyleneiminocarbonylamino)benzene, 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane, and 1,8- bis(ethyleneiminocarbonylamino)octane. Examples of the aziridine crosslinking agents include CHEMITITE PZ33 (Nippon Shokubai Co., Ltd., Osaka-shi, Osaka, Japan), and NeoCryl CX-100 (DSM Coating Resins, LLC., Zwolle, Provincie Overijssel, Netherlands). Examples of carbodiimide crosslinking agents include Carbodilite V-03, V-05, and V-07 (Nisshinbo Chemical Inc., Chuo-ku, Tokyo, Japan).

[0059] An amount of the crosslinking agent (solid content) used can be about 0.01 parts by mass or more, about 0.05 parts by mass or more, or about 0.1 parts by mass or more, and about 5 parts by mass or less, about 3 parts by mass or less, or about 2 parts by mass or less, with respect to 100 parts by mass of the low Tg polymer (for example, low Tg polymer including a constituent unit derived from a carboxyl group-containing monomer.

[0060] By changing a blending ratio of the low Tg polymer and the high Tg polymer, desired performance (for example, flexibility and followability) can be imparted to the decorative film. In an embodiment, the content of the low Tg polymer can be about 25 parts by mass or more, about 50 parts by mass or more, about 80 parts by mass or more, about 100 parts by mass or more, or more than about 100 parts by mass, and can be about 400 parts by mass or less, about 300 parts by mass or less, about 200 parts by mass or less, or about 150 parts by mass or less with respect to 100 parts by mass of the high Tg polymer.

[0061] A total content of the low Tg polymer, the high Tg polymer, and, if present, the third polymer, which will be described later, in the colored layer or the composition for forming a colored layer (solid content) can be, for example, about 25 mass% or more, about 30 mass% or more, about 35 mass% or more, about 40 mass% or more, about 45 mass% or more, about 50 mass% or more, about 55 mass% or more, about 60 mass% or more, about 80 mass% ormore, or about 90 mass% or more, 99.9 mass% or less, about 99 mass% or less, about 95 mass% or less, about 90 mass% or less, about 80 mass% or less, about 70 mass% or less, about 60 mass% or less, about 55 mass% or less, or about 50 mass% or less.

[0062] The colorant that can be blended in the colored layer is not particularly limited, and, for example, an inorganic pigment or an organic pigment that has been known as a pigment can be used. Such a pigment may be surface-treated with silicon oxide, aluminum oxide, or the like. The colorant may be used alone or in combination of two or more types.

[0063] Examples of the inorganic pigment include white pigments such as zinc carbonate, zinc oxide, zinc sulfide, and titanium dioxide (titanium oxide); colored pigments such as black iron oxide, yellow iron oxide, red iron oxide, ultramarine blue, Prussian blue, cobalt blue, titanium yellow, turquoise, and molybdenum orange; and carbon blacks such as furnace black, channel black, thermal black, and acetylene black.

[0064] Examples of the organic pigment include C.I. Pigment White 6, C.I. Pigment Black 7, C.I. Pigment Red 122, 202, 254, and 255, C.I. Pigment Orange 43, C.I. Pigment Violet 19 and 23, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, and 15: 4, and C.I. Pigment Brown 23 and 25, C.I. Pigment Yellow 74, 109, 110, and 128, and C.I. Pigment Green 7 and 36.

[0065] A blending amount of the colorant can be, for example, about 0.1 mass% or more, about 1 mass% or more, or about 5 mass% or more, and about 55 mass% or less, about 50 mass% or less, about 20 mass% or less, or about 10 mass% or less with respect to the entire composition for forming a colored layer (solid content) or colored layer.

[0066] The composition for forming a colored layer may optionally contain other components alone or in combination of two or more as long as the effects of the present disclosure are not adversely affected. Examples of such optional components can include other resins (for example, thermoplastic resins and the third polymer described later) other than the abovedescribed low Tg polymer and high Tg polymer, fillers, conductive agents, thermal conductivity imparting agents, antioxidants, UV absorbing agents, crosslinking agents, light stabilizers, heat stabilizers, dispersants, lubricants, surfactants, leveling agents, silane coupling agents, catalysts, and solvents.

[0067] The composition for forming a colored layer can be typically produced by mixing the above-described low Tg polymer, high Tg polymer, colorant, and optional components (for example, the crosslinking agent, the third polymer) as necessary.

[0068] In some embodiments, in the composition for forming a colored layer, it is preferable that (1) at least one selected from the group consisting of the high Tg polymer and the third polymer including a constituent unit derived from an amide group -containing monomer is mixed with a colorant to prepare a colorant mixture, and the colorant mixture is mixed with a mixture containing the low Tg polymer and a crosslinking agent to produce the composition for forming a colored layer, or it is preferable that (2) at least one selected from the group consisting of the high Tg polymer and the third polymer including a constituent unit derivedfrom an amide group-containing monomer, a crosslinking agent, and a colorant are mixed to prepare a colorant mixture, and the colorant mixture is mixed with the low Tg polymer to produce the composition for forming a colored layer. By producing the composition for forming a colored layer in this manner, a composition for forming a colored layer, which has excellent colorant dispersibility, can be obtained.

[0069] In some embodiments, as the third polymer, a polymer including a constituent unit derived from an amide group-containing monomer may be used. The third polymer including a constituent unit derived from an amide group-containing monomer can be obtained by copolymerizing an amide group-containing monomer with at least one selected from the group consisting of the above-described monoethylenically unsaturated monomer and a carboxy group-containing unsaturated monomer. From the viewpoint of the dispersibility and the like of the colorant, vinyl acetate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferable as the monoethylenically unsaturated monomer, and (meth)acrylic acid is preferable as the carboxy group-containing unsaturated monomer. From the viewpoint of improving the performance such as compatibility with the above-described low Tg polymer and high Tg polymer, the third polymer preferably includes the same or the same kind of constituent unit as the constituent unit derived from the monoethylenically unsaturated monomer included in the low Tg polymer and / or the high Tg polymer.

[0070] Examples of the amide group-containing monomer include N-vinylcaprolactam, N- vinylpyrrolidone, (meth)acrylamide, N-methyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, and N-octyl (meth)acrylamide. Among them, (meth)acrylamide is preferable from the viewpoint of the dispersibility and the like of the colorant. The amide group-containing monomers can be used alone, or two or more types thereof can be used in combination.

[0071] A proportion of the constituent unit derived from the amide group-containing monomer can be about 0.01 mass% or more, about 0.05 mass% or more, or about 0.1 mass% or more, and about 5 mass% or less, about 1 mass% or less, or about 0.5 mass% or less with respect to the third polymer.

[0072] In some embodiments, a proportion of the constituent unit derived from the monoethylenically unsaturated monomer in the third polymer can be, for example, about 85 mass% or more, about 90 mass% or more, or about 92 mass% or more, and about 99.5 mass% or less, about 99 mass% or less, or about 98 mass% or less with respect to the third polymer.

[0073] In some embodiments, a proportion of the constituent unit derived from the carboxy group-containing unsaturated monomer in the third polymer can be about 0.5 mass% or more, about 1 mass% or more, or about 2 mass% or more, and about 15 mass% or less, about 10 mass% or less, or about 8 mass% or less with respect to the third polymer.

[0074] When the composition for forming a colored layer and the colored layer formed from the composition contain the third polymer, in an embodiment, a blending ratio of the thirdpolymer can be about 1 part by mass or more, about 5 parts by mass or more, about 10 parts by mass or more, about 15 parts by mass or more, or about 20 parts by mass or more, and about 35 parts by mass or less, about 30 parts by mass or less, about 25 parts by mass or less, or about 20 parts by mass or less with respect to 100 parts by mass of the low Tg polymer. The colored layer containing the third polymer in such a ratio is excellent in colorant dispersibility and can improve the performance such as concealing properties.

[0075] The colored layer of the present disclosure can be obtained, for example, by applying the composition for forming a colored layer containing a low Tg polymer, a high Tg polymer, a colorant, and optional components (for example, the crosslinking agent, the third polymer) as necessary to a release liner described later or the like, and then subjecting the composition to a heat treatment and / or a radiation (for example, ultraviolet rays) irradiation treatment. Here, as the component used in the composition for forming a colored layer, a component that can be used in the colored layer described above can be similarly employed.

[0076] The heat treatment can be performed using, for example, a heater such as an infrared heater, hot air, an oven, or the like. The heat treatment can be performed batchwise or continuously using a belt conveyor or the like, but is preferably performed continuously from the viewpoint of productivity or the like. A heating temperature (set temperature) can be, for example, about 70°C or higher, about 80°C or higher, or about 90°C or higher. An upper limit of the heating temperature is not particularly limited, and can be, for example, about 160°C or lower, about 140°C or lower, or about 120°C or lower.

[0077] The ultraviolet irradiation, which is a type of radiation irradiation, can be performed using, for example, a low-pressure mercury lamp, moderate-pressure mercury lamp, high- pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, metal halide lamp, electrode-free lamp, UV-LED, or the like as a light source. The ultraviolet irradiation can be performed batchwise or continuously using a belt conveyor or the like, but is preferably performed continuously from the viewpoint of productivity or the like. An irradiation dose of ultraviolet rays (UV-C) can be, for example, about 1 mJ / cm2or more, about 50 mJ / cm2or more, or about 100 mJ / cm2or more. An upper limit of the irradiation dose of ultraviolet rays is not particularly limited, and can be, for example, about 500 mJ / cm2or less or about 450 mJ / cm2or less.

[0078] The thickness of the colored layer of the present disclosure may be appropriately set in consideration of required performance (for example, colorability, concealing properties, and rigidity) and the like. Such a thickness may be, for example, for example, about 1 micrometer or more, about 5 micrometers or more, about 10 micrometers or more, about 30 micrometers or more, or about 50 micrometers or more, and may be about 200 micrometers or less, about 150 micrometers or less, about 100 micrometers or less, or about 90 micrometers or less.

[0079] In some embodiments, the colored layer of the present disclosure and the cover layer described above have a portion that is directly applied. The portion directly applied may be the entire surface of the colored layer or the cover layer, or may be a part thereof. When the colored layer contains a cured product by the crosslinking agent described above, the adhesion between both layers can be further improved if such a portion directly applied is present.

[0080] In some embodiments, the decorative film of the present disclosure optionally includes an additional layer. Examples of such an additional layer can include at least one selected from the group consisting of decorative layers (e.g., color layers, pattern layers, and relief layers), brightening layers, bonding layers, middle film layers, adhesive layers, and release liners. The additional layer can be applied to the entire surface or a portion of the decorative film.

[0081] Examples of the decorative layer include, but are not limited to, a color layer that exhibits a paint color, for example, a light color, such as white and yellow, and a strong color, such as red, brown, green, blue, gray, and black; a pattern layer that imparts a design pattern (such as a wood grain, a stone grain, a geometric pattern, or a leather pattern), a logo, a picture pattern, or the like to an article; a relief (embossed pattern) layer in which an uneven shape is provided on the surface; and combinations of these layers. The decorative layer may have a single layer structure or a multilayer structure, and may be transparent, translucent, or opaque.

[0082] The decorative layer can be applied to, but not limited to, the entirety or part of the surface of a layer included in the decorative film, such as the colored layer and / or the adhesive layer, directly or via a bonding layer and the like. Here, the color layer or the like in the additional layer is typically intended for a layer that does not use two specific types of (meth)acrylic polymers used in the colored layer of the present disclosure, and is intended for a layer different from the colored layer of the present disclosure.

[0083] The material for the color layer is not limited to the following, but for example, a material obtained by dispersing a pigment in a binder resin, such as a (meth)acrylic resin or a resin having a urethane bond, can be used. Examples of the pigment include inorganic pigments, such as carbon black, chrome yellow, yellow iron oxide, colcothar, or red iron oxide; or organic pigments, such as a phthalocyanine pigment such as phthalocyanine blue or phthalocyanine green, an azo lake pigment, an indigo pigment, a perinone pigment, a perylene pigment, a quinophthalone pigment, a dioxazine pigment, and a quinacridone pigment such as quinacridone red. Here, in the present disclosure, the term “resins having urethane bonds” may include, for example, a resin prepared using at least one selected from urethane (meth)acrylate and urethane (meth)acrylate oligomer besides a urethane resin, and the urethane resin can also include a (meth)acrylic urethane resin, and the like.

[0084] The color layer can be formed using such a material, for example, by a coating method, such as gravure coating, roll coating, die coating, bar coating, or knife coating.

[0085] As a pattern layer, although not limited to the following, pattern layers obtained by printing a pattern such as a pattern, logo, or design directly on the colored layer and / or the adhesive layer using a printing method such as gravure direct printing, gravure offset printing, inkjet printing, laser printing, or screen printing may be employed, or a film, sheet, or the like having a pattern, logo, design, or the like formed by coating such as gravure coating, roll coating, die coating, bar coating, or knife coating, punching, etching, or the like also can be used. For example, a material similar to those used in the color layer can be used for the pattern layer.

[0086] For the relief layer, a thermoplastic resin film having an uneven shape on the surface may be used, the uneven shape being obtained by a well-known method in the art, such as, for example, emboss finishing, scratch processing, laser processing, dry etching processing, or hot press processing. The relief layer may be also formed by applying a thermosetting or radiation-curable resin, such as a curable (meth)acrylic resin, on a release liner having an uneven shape, curing the resin by heat or radiation, and removing the release liner.

[0087] The thermoplastic resin, thermosetting resin, and radiation-curable resin used in the relief layer are not particularly limited but, for example, a polyester resin such as PET or PEN, a (meth)acrylic resin, a polyolefin resin such as polyethylene or polypropylene, a thermoplastic elastomer, polycarbonate, polyamide, an ABS resin, an acrylonitrile-styrene resin, polystyrene, vinyl chloride, or a resin having a urethane bond can be used. The relief layer may contain at least one of the pigments used in the color layer.

[0088] The decorative layer of the present disclosure can contain, for example, fillers, reinforcing agents, antioxidants, UV absorbing agents, light stabilizers, heat stabilizers, dispersants, flow improvers, surfactants, leveling agents, silane coupling agents, and catalysts as optional components in a range that does not negatively affect the effect of the present disclosure.

[0089] A thickness of the decorative layer may be appropriately adjusted according to the required decorativeness or the like and is not particularly limited. Such a thickness can be, for example, about 1 micrometer or more, about 3 micrometers or more, or about 5 micrometers or more, and can be about 50 micrometers or less, about 40 micrometers or less, or about 30 micrometers or less.

[0090] Examples of the brightening layer may include, but are not limited to, layers included in the decorative film, for example, layers containing a metal selected from aluminum, nickel, gold, silver, copper, platinum, chromium, iron, tin, indium, titanium, lead, zinc, and germanium, or an alloy or compound thereof, formed by vacuum deposition, sputtering, ion plating, plating, or the like on the entire surface or a part of the colored layer and / or theadhesive layer. The thickness of the brightening layer may be appropriately set in accordance with the required decorativeness and the like.

[0091] In the decorative film of the present disclosure, a bonding layer (sometimes referred to as “primer layer”, for example) can be used to bond an additional layer in the decorative film. As the bonding layer, a generally used adhesive agent such as a solvent -type, emulsiontype, pressure-sensitive type, heat-sensitive type, and heat-curable or ultraviolet-curable type adhesive agent, including (meth)acrylics, polyolefins, polyurethanes, polyesters, rubbers, and the like can be used. The bonding layer may be applied by a well-known coating method or the like.

[0092] The decorative film of the present disclosure may include a middle film layer. As the middle film layer, for example, resin films of resins having a urethane bond, polyvinyl chlorides, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, or (meth)acrylic polymers can be used.

[0093] A thickness of the middle film layer can be, for example, about 5 micrometers or more, about 10 micrometers or more, or about 15 micrometers or more, and about 200 micrometers or less, about 100 micrometers or less, or about 50 micrometers or less.

[0094] The decorative film of the present disclosure may include an adhesive layer. For the adhesive layer, for example, a typically used adhesive can be used, such as a solvent, emulsion, pressure-sensitive, heat-sensitive, thermosetting, or ultraviolet-curable adhesive of (meth)acrylic, polyolefin, polyurethane, polyester, or rubber. The adhesive layer may be applied by a well-known coating method or the like.

[0095] In some embodiments, the adhesive layer of the present disclosure is formed using the (meth)acrylic polymer having a glass transition temperature of lower than about 0°C (low Tg polymer) and the (meth)acrylic polymer having a glass transition temperature of about 0°C or higher (high Tg polymer) used in the colored layer described above. Also in the adhesive layer, similarly to the colored layer, the above-described crosslinking agent, colorant, other optional components other than these, and the like can be used. The adhesive layer can typically be formed by adjusting a blending ratio of the low Tg polymer and the high Tg polymer. In an embodiment, the blending ratio of the high Tg polymer is less than about 20 parts by mass, about 15 parts by mass or less, about 10 parts by mass or less, or about 7 parts by mass or less, and is about 1 part by mass or more, about 2 parts by mass or more, or about 3 parts by mass or more with respect to 100 parts by mass of the low Tg polymer. The adhesive layer containing the high Tg polymer in such a ratio can improve performance such as adhesive force, heat shrinkage resistance, reworkability, and followability.

[0096] The glass transition temperature and the weight average molecular weight of the low Tg polymer and the high Tg polymer can be appropriately adjusted from the above-described ranges such that desired adhesion performance is obtained.

[0097] In some embodiments, the adhesive layer of the present disclosure can also be formed using a composition for forming an adhesive layer containing a low Tg polymer, a high Tg polymer, and a crosslinking agent, similarly to the colored layer described above. By using a composition containing a crosslinking agent, the adhesive layer containing a cured product of the low Tg polymer, the high Tg polymer, and the crosslinking agent can have a crosslinked structure .

[0098] In some embodiments, the adhesive layer of the present disclosure and the colored layer described above have a portion that is directly applied. The portion directly applied may be the entire surface of the adhesive layer or the colored layer, or may be a part thereof. When the adhesive layer and the colored layer contain a cured product by the crosslinking agent described above, the adhesion between both layers can be further improved if such a portion directly applied is present.

[0099] The total content of the low Tg polymer, the high Tg polymer, and, if present, the above-described third polymer in the adhesive layer or the composition for forming an adhesive layer (solid content) can be, for example, about 25 mass% or more, about 30 mass% or more, about 35 mass% or more, about 40 mass% or more, about 45 mass% or more, about 50 mass% or more, about 55 mass% or more, about 60 mass% or more, about 80 mass% or more, or about 90 mass% or more, 100 mass% or less, 99.9 mass% or less, about 99 mass% or less, about 95 mass% or less, about 90 mass% or less, about 80 mass% or less, about 70 mass% or less, about 60 mass% or less, about 55 mass% or less, or about 50 mass% or less.

[0100] The composition for forming an adhesive layer may optionally contain other components alone or in combination of two or more as long as the effects of the present disclosure are not adversely affected. Examples of such optional components can include the third polymer described above, fillers, conductive agents, thermal conductivity imparting agents, antioxidants, UV absorbing agents, light stabilizers, heat stabilizers, dispersants, lubricants, surfactants, leveling agents, silane coupling agents, catalysts, colorants (for example, pigments and dyes), and solvents.

[0101] The adhesive layer of the present disclosure can be obtained, for example, by applying the composition for forming an adhesive layer containing a low Tg polymer, a high Tg polymer, and optional components (for example, the crosslinking agent, the third polymer, colorant) as necessary to a release liner described later or the like, and then subjecting the composition to a heat treatment and / or a radiation (for example, ultraviolet rays) irradiation treatment. Here, for the heat treatment and / or the radiation (for example, ultraviolet rays) irradiation treatment, the treatment in the colored layer described above can be similarly adopted. When the adhesive layer includes a low Tg polymer, a high Tg polymer and a colorant and, as a result, is colored, the colored adhesive layer can be regarded as the colored layer of the present disclosure. In this case, the colored layer described above may not be included in the decorative film, may be included as a transparent layer instead of the coloredlayer, or may be used in combination with the colored layer described above. When the colored layer is used in combination, the colored layer described above may be referred to as a first colored layer, and the colored adhesive layer may be referred to as a second colored layer.

[0102] A thickness of the adhesive layer of the present disclosure may be appropriately set in consideration of the required adhesive force and the like. Such a thickness can be, for example, about 10 micrometers or more, about 20 micrometers or more, or about 30 micrometers or more, and can be about 300 micrometers or less, about 200 micrometers or less, or about 100 micrometers or less.

[0103] In the decorative film of the present disclosure, a release liner can be typically applied to the adhesive layer. Examples of the release liner include paper; a plastic material such as polyethylene, polypropylene, polyester (e.g., PET), and cellulose acetate; and paper coated with such a plastic material. These liners may have a surface that has been subjected to release treatment with a release agent such as silicone.

[0104] A thickness of the release liner, generally, can be about 5 micrometers or more, about 15 micrometers or more, or about 25 micrometers or more, and can be about 500 micrometers or less, about 300 micrometers or less, about 100 micrometers or less, or about 50 micrometers or less.

[0105] The decorative film of the present disclosure may be, for example, a sheet-like article, a rolled body wound in a roll shape, or an article with a three-dimensional shape.

[0106] The following production method will be described as an example, but a method for producing the decorative film of the present disclosure is not limited thereto.

[0107] For example, in the case of a decorative film having a structure in which a release liner, an adhesive layer, a colored layer, and a cover layer are provided in this order, the composition for forming a cover layer is coated on the release liner, and a drying step and a curing step are applied as necessary to form a cover layer. Subsequently, the composition for forming a colored layer is coated on the cover layer, and the drying step and the curing step are applied as necessary to form a colored layer. Subsequently, the composition for forming an adhesive layer is coated on the release liner, and the drying step and the curing step are applied as necessary to form an adhesive layer. The decorative film can be formed by applying the adhesive layer to the colored layer and removing the release liner on the cover layer side as necessary.

[0108] In some embodiments, the above-described decorative film of the present disclosure is disposed on an adherend via the adhesive layer, and an article including the decorative film is provided. FIG. 2 shows a schematic cross-sectional view of an article according to one embodiment of the present disclosure. The article 201 in FIG. 2 comprises a decorative film 200, which includes a cover layer 210, a colored layer 220 and an adhesive layer 230, applied to an adherend 250 via the adhesive layer 230.

[0109] A material for the adherend to which the decorative film can be applied is not particularly limited. Examples of such a material include resin materials (e.g., polyolefin resins, polyester resins, (meth)acrylic resins, polycarbonate resins, resins having a urethane bond, and acrylonitrile-butadiene-styrene copolymers), inorganic materials (e.g., glass, ceramic, concrete, gypsum, calcium silicate, natural stone, and asphalt), rubber materials, cloth materials (e.g., woven fabrics, knitted fabrics, and nonwoven fabrics), metal or metal alloy materials (e.g., iron, aluminum, and stainless steel), and woody materials including paper and the like.

[0110] A shape or structure of the adherend is not particularly limited. The shape may be, for example, a plane shape (e.g., film shape or plate shape), curved surface shape, deformed shape, or three-dimensional shape, and the structure may be a single-layer structure, a laminated structure, or a composite structure in which a plurality of members having different shapes or materials are combined.

[0111] The decorative film of the present disclosure can be used in a variety of applications. Examples of such purposes include signboards (e.g., internally illuminated signboards and externally illuminated signboards); signs (e.g., internally illuminated signs and externally illuminated signs); various interior or exterior articles such as interior or exterior articles for vehicles, such as automobiles, railways, aircrafts, and ships (e.g., roof members; pillar members; door trim members; instrument panel members; front members, such as hoods; bumper members; fender members; side sill members; and interior panel members); and interior or exterior articles of buildings (e.g., window glass, doors, sashes, roof members such as tiling, outer wall members, and wall papers); electrical appliances, such as personal computers, smartphones, cellular phones, refrigerators, and air conditioners; stationery; furniture; desks; and various containers such as cans. The decorative film of the present disclosure includes a specific cover layer and a specific colored layer, is excellent in durability such as solvent resistance and weather resistance, and thus can be suitably used for exterior applications, more specifically, for exterior applications of vehicles (for example, automobiles) and for exterior applications (for example, exterior wall members) of buildings. The decorative film of the present disclosure includes a specific cover layer and a specific colored layer, is excellent in performance such as flexibility and followability, and thus can be suitably used for a rough surface. For example, the decorative film of the present disclosure can be suitably used for a rough surface having irregularities with a maximum height from a protrusion to a bottom of about 1 mm or more or about 1.5 mm or more, 1 cm or less, 7 mm or less, 5 mm or less, 3 mm or less, 2.5 mm or less, or 2 mm or less. In particular, when the colored layer and / or the adhesive layer described above contains a cured product of a low Tg polymer, a high Tg polymer, and a crosslinking agent, the interlayer adhesion of the entire decorative film is improved, so that delamination when the film is applied to, for example, a rough surface can be further reduced or suppressed.

[0112] A method of applying the decorative film of the present disclosure to the adherend (support member) constituting the article is not particularly limited, and a known method can be appropriately used. Examples of such a method can include hand application, injection molding methods such as an insert injection molding method, an in-molding method, an overmolding method, a two-color injection molding method, a core back injection molding method, and a sandwich injection molding method, a lamination method, and a three- dimensional heat stretch blow molding method (TOM).Examples

[0113] In the following examples, specific embodiments of the present disclosure are illustrated, but the present invention is not limited to these embodiments. All 'part' and 'percent' are based on mass unless otherwise specified. A numerical value essentially includes an error resulting from a measurement principle and a measuring device. The numerical value is generally indicated by a significant digit that is rounded.

[0114] Table 1 shows various materials used. In the table, the “Mw” and “Tg” mean “weight average molecular weight” and “glass transition temperature”, respectively. Regarding the polymers of API to AP3 and ADH1 to ADH2, polymer-containing solutions were each prepared by polymerizing a polymerizable composition, obtained by mixing each monomer component, a chain transfer agent (such as isooctylthioglycolate), a polymerization initiator (such as 2,2'-azobis (2,4-dimethylvaleronitrile)), and a solvent (such as ethyl acetate), by a known polymerization method so as to have a mass ratio of a constituent unit derived from the monomer (for example, MMA (methyl methacrylate), BA (n-butyl acrylate), and AA(acrylic acid)) described in the table.

[0115] Table 1BA: n-butyl acrylate, AN: acrylonitrile, AA: acrylic acid, 2EHA: 2-ethylhexyl acrylate, MMA: methyl methacrylateBMA: n-butyl methacrylate, DMAEMA: 2-(dimethylamino) ethyl methacrylate, Vac: vinyl acetate, ACM: acrylamide

[0116] Table 2 shows a colorant mixture containing a colorant and used in preparing a composition for forming a colored intermediate layer and the composition for forming a colored adhesive layer, and Table 3 shows an amount (parts by mass) of each component and the solid content (%) of the composition for forming a colored intermediate layer and the composition for forming a colored adhesive layer prepared using the colorant mixture. Here, each component amount in Table 3 is a value based on the nonvolatile content. Each layer formed using the composition for forming a colored intermediate layer and the composition for forming a colored adhesive layer corresponds to a colored layer.

[0117] Table 20118] Table 3

[0119] Test Example 1In Test Example 1, evaluation of solvent resistance, elongation, followability, and the like according to the presence or absence of a specific cover layer was performed.

[0120] Example 1A composition for forming a cover layer was prepared by mixing PO1, ISO1, UVA1, and HALS1 so that a solid content weight ratio of these components was 45:27:2.5:2.5. A 50 micrometer-thick polyester liner coated with a release layer was coated with the composition for forming a cover layer using a knife coater. The coating layer was dried at 155°C for 15 seconds to obtain a 3 micrometer-thick cover layer.

[0121] CL1 was blended such that the solid content weight ratio of the crosslinking agent (CL1) to both AP2 and AP3 was 0.2: 100 with respect to CAI of the composition for forming a colored intermediate layer. The cover layer was coated with CAI blended with thecrosslinking agent using a knife coater. The coating layer was dried at 95 °C for 5 minutes to obtain a 45 micrometer-thick colored intermediate layer corresponding to the colored layer.

[0122] CL1 was blended such that the solid content weight ratio of the crosslinking agent (CL1) and ADH1 was 0.05: 100 with respect to CA2 of the composition for forming a colored adhesive layer. CA2 blended with a crosslinking agent was coated on a liner of silicone- coated polyethylene laminate paper with a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain a 40 micrometer-thick colored adhesive layer corresponding to the colored layer. After the adhesive layer was laminated on the colored intermediate layer, the polyester liner on the cover layer side was peeled off to obtain a decorative film of Example 1.

[0123] Example 2A cover layer was produced in the same manner as in Example 1. API and AP2 were mixed so that the solid content weight ratio of API and AP2 was 100: 110 to prepare a composition for forming a transparent intermediate layer (FL1). 0.2 parts by mass of the crosslinking agent (CL1) was blended with 100 parts by mass of the composition for forming a transparent intermediate layer. The cover layer was coated with the composition for forming a transparent intermediate layer blended with the crosslinking agent using a knife coater. The coating layer was dried at 95 °C for 5 minutes to obtain a 37 micrometer-thick transparent intermediate layer.

[0124] CL2 was blended such that the solid content weight ratio of the crosslinking agent (CL2) and ADH2 was 0.05: 100 with respect to CA3 of the composition for forming a colored adhesive layer. CA3 blended with a crosslinking agent was coated on a liner of silicone- coated polyethylene laminate paper with a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain a 39 micrometer-thick colored adhesive layer corresponding to the colored layer. After the adhesive layer was laminated on the transparent intermediate layer, the polyester liner on the cover layer side was peeled off to obtain a decorative film of Example 2.

[0125] Example 3A decorative film of Example 3 was obtained in the same manner as in Example 2 except that the composition for forming a colored adhesive layer was changed to CA4.

[0126] Example 4A cover layer was produced in the same manner as in Example 1. CL1 was blended such that the solid content weight ratio of the crosslinking agent (CL1) to AP2 was 0.2: 100 with respect to CA5 of the composition for forming a colored intermediate layer. The cover layer was coated with CA5 blended with the crosslinking agent using a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain a 48 micrometer-thick colored intermediate layer corresponding to the colored layer.

[0127] CL2 was blended such that the solid content weight ratio of the crosslinking agent (CL2) and ADH2 was 0.05: 100 with respect to CA6 of the composition for forming a colored adhesive layer. CA6 blended with a crosslinking agent was coated on a liner of silicone- coated polyethylene laminate paper with a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain a 39 micrometer-thick colored adhesive layer corresponding to the colored layer. After the adhesive layer was laminated on the colored intermediate layer, the polyester liner on the cover layer side was peeled off to obtain a decorative film of Example 4.

[0128] Comparative Example 1A decorative film of Comparative Example 1 was obtained in the same manner as in Example1 except for forming no cover layer.

[0129] Comparative Example 2A decorative film of Comparative Example 2 was obtained in the same manner as in Example2 except for forming no cover layer.

[0130] Comparative Example 3A decorative film of Comparative Example 3 was obtained in the same manner as in Example3 except for forming no cover layer.

[0131] Comparative Example 4A decorative film of Comparative Example 4 was obtained in the same manner as in Example4 except for forming no cover layer.

[0132] Evaluation test 1Each of the obtained test samples was evaluated according to the following test method. The results are indicated in Table 4. Here, the “colored layer” and the “transparent layer” in Table 4 correspond to the “colored intermediate layer” and the “transparent intermediate layer”, respectively.

[0133] Solvent resistance testA test piece was prepared by cutting a test sample into a width of 50 mm and a length of 100 mm. The test piece was placed on an aluminum plate and left at 23°C for 24 hours. About 0.2 ml of isopropyl alcohol (IPA) was added dropwise to the test piece using a syringe. After drying IPA, the solvent resistance on a dropping surface was determined as follows. A case where no trace of IPA was observed was evaluated as “A”, a case where a slight trace of IPA was observed and tackiness of the surface was not observed was evaluated as “B”, and a case where the tackiness of the surface was observed was evaluated as “C”. Here, the “A” and “B” evaluations were defined as acceptable levels.

[0134] Concealing property testA test sample was cut into a 100 mm x 50 mm square to prepare a test piece. The test piece was attached to a “concealing power chart sheet” (zebra pattern). L*, a*, and b* values in a white region and a black region were measured using a spectrophotometer (CM-3700d,available from Konica Minolta, Inc. (Chiyoda-ku, Tokyo, Japan)). The values in the white region were set to L , a , and bi*, and the values in the black region were set to L2*, a2*, and b2*. A color difference (AE) was calculated from the following Formula 1 :Here, a sample having a color difference of less than 6 in the black region and the white region was evaluated as “A”, a sample having a color difference of 6 or more and less than 12 was evaluated as “B”, and a sample having a color difference of 12 or more was evaluated as “C”. The “A” and “B” evaluations were defined as acceptable levels.

[0135] Adhesive force test: Adhesive force to coated plateA test piece was prepared by cutting a test sample into a width of 25 mm and a length of 150 mm. The test piece was applied to a melamine-coated plate (available from PALTEK CORPORATION (Hiratsuka-shi, Kanagawa, Japan)) under an atmosphere of 20°C according to JIS Z 0237 8.2.3. The test piece was left standing at 20°C for 48 hours, and then a 180- degree peel strength of the test piece was measured using a Tensilon universal material testing machine (available from A&D Company, Limited (Toshima-ku, Tokyo, Japan)). A speed of an air jaw was 300 mm per minute.

[0136] 60-degree surface glossiness test after aluminum plate applicationA test piece was prepared by cutting a test sample into a width of 100 mm and a length of 50 mm. The test piece was placed on a smooth aluminum plate. The surface glossiness of each test sample was measured at a measurement angle of 60° using a portable glossmeter GMX- 202 (Murakami Color Research Laboratory Co., Ltd., Chuo-ku, Tokyo, Japan). Measurements were made at three different locations, and the average value was recorded.

[0137] Tensile strength testA test piece was prepared by cutting a test sample into a width of 25 mm and a length of 150 mm. Under an atmosphere of 20°C, the tensile force and elongation of the test piece were measured using a Tensilon universal material testing machine (available from A&D Company, Limited (Toshima-ku, Tokyo, Japan)). The speed of the air jaw was 300 mm per minute, and an air jaw interval was 100 mm. The tensile force at 2% elongation was recorded as the tensile strength (2% tensile strength).

[0138] Elongation testA test piece was prepared by cutting a test sample into a width of 25 mm and a length of 150 mm. Under an atmosphere of 20°C, the elongation of the test piece was measured using a Tensilon universal material testing machine (available from A&D Company, Limited (Toshima-ku, Tokyo, Japan)). The speed of the air jaw was 300 mm per minute, and an air jaw interval was 100 mm.

[0139] Heat shrinkage testA test piece was prepared by cutting a test sample into a width of 50 mm and a length of 100 mm. This test piece was attached to an aluminum plate and left at 23°C for 24 hours, and then the test piece was cut into a cross shape. The test piece was left at 65°C for 48 hours. After heat aging, the value of the maximum width of the opening (mouth opening) of the cut was measured with a microscope.

[0140] Followability testA test piece was prepared by cutting a test sample into a width of 70 mm and a length of 75 mm. Under an atmosphere of 25°C, a test piece provided with a pre-mask was attached to a “stucco” painted finishing substrate (available from Test Materials Co., Ltd. (Kawaguchi-shi, Saitama, Japan)). The pre-mask was peeled off, and the test piece was pressed without heating using a rivet brush "PFA-1" (available from 3M Japan Ltd. (Shinagawa-ku, Tokyo, Japan)). The pressing was performed three times back and forth on the test piece. Here, with respect to a rough surface of the substrate, maximum roughness between a top and a bottom was about 1.5 mm. After attachment of the test piece, followability to the roughened substrate was visually determined. A sample having good followability to the roughened substrate was evaluated as “Good”, and a sample having insufficient followability to the roughened substrate was evaluated as “Poor”.

[0141] Gloss retention evaluation testA test piece was prepared in the same manner as in the followability test. The test piece was left in an oven at 65°C for 48 hours. An initial gloss value and a gloss value after aging at 65 °C were measured using a portable gloss meter (GMX-202, available from MURAKAMI COLOR RESEARCH LABORATORY CO., LTD. (Chuo-ku, Tokyo, Japan)), and the gloss retention was calculated from the following Formula 2:Gloss retention (%) = gloss value after aging at 65 °C / initial gloss value x 100 ... Formula 2Here, the number of repetitions was three, and an average value was recorded as a representative value. The test piece having a gloss retention of less than 200% was evaluated as “good”, and the test piece having a gloss retention of 200% or more was evaluated as “poor”.

[0142] Table 4Table 4

[0143] Test Example 2In Test Example 2, an influence of matte processing of the cover layer on the rough surface was evaluated.

[0144] Example 5A pre-sized solution containing both an alkyd resin (Rl) and a formaldehyde-urea resin (R2) was prepared such that the solid content weight ratio of Rl to R2 was 100:35. Fl was mixed with the pre-sized solution so that the solid content weight ratio of all the resins (Rl and R2) and the silica particles (Fl) was 100: 18 in terms of the weight of the nonvolatile content. The pre-sized solution containing Fl was coated on a 50 micrometer-thick polyester liner using a knife coater. The coating layer was dried at 95°C for 3 minutes and at 155°C for 3 minutes and simultaneously crosslinked. After drying, a pre-sized liner having a release layer having a supermatte tone was obtained. The thickness of the pre-sized layer was about 5 micrometers.

[0145] A composition for forming a cover layer was prepared by mixing PO1, ISO1, UVA1, and HALS1 so that a solid content weight ratio of these components was 45:27:2.5:2.5. The release layer having a supermatte tone of the pre-sized liner was coated with the composition for forming a cover layer using a knife coater. The coating layer was dried at 155°C for 15 seconds to obtain a 3 micrometer-thick cover layer.

[0146] CL1 was blended such that the solid content weight ratio of the crosslinking agent (CL1) to AP2 was 0.2: 100 with respect to CA5 of the composition for forming a colored intermediate layer. The cover layer was coated with CA5 blended with the crosslinking agent using a knife coater. The coating layer was dried at 95 °C for 5 minutes to obtain a 45 micrometer-thick colored intermediate layer corresponding to the colored layer.

[0147] CL1 was blended such that the solid content weight ratio of the crosslinking agent (CL1) and ADH1 was 0.05: 100 with respect to CA6 of the composition for forming a colored adhesive layer. CA6 blended with a crosslinking agent was coated on a liner of silicone- coated polyethylene laminate paper with a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain a 40 micrometer-thick colored adhesive layer corresponding to the colored layer. After the adhesive layer was laminated on the colored intermediate layer, the polyester liner on the cover layer side was peeled off to obtain a decorative film of Example 5 to which a supermatte surface in the release layer was transferred.

[0148] Reference Example (Example 4)As a reference example, the decorative film of Example 4 described above was adopted. Here, the liner used at the time of forming the cover layer of such a film was the same liner as in Example 1, and was a liner having no release layer having a supermatte tone.

[0149] Evaluation test 2Each of the obtained test samples was evaluated according to the test method in Evaluation Test 1 described above and the following test method. The results are indicated in Table 5. Here, the “colored layer” in Table 5 corresponds to the “colored intermediate layer”.

[0150] 60-degree surface glossiness test after aluminum plate applicationA test piece was prepared by cutting a test sample into a width of 100 mm and a length of 50 mm. The test piece was placed on a smooth aluminum plate. The surface glossiness of each test sample was measured at a measurement angle of 60° using a portable glossmeter GMX- 202 (Murakami Color Research Laboratory Co., Ltd., Chuo-ku, Tokyo, Japan). Measurements were made at three different locations, and the average value was recorded.

[0151] 60-degree surface glossiness test after rough surface applicationA test piece was prepared by cutting a test sample into a width of 70 mm and a length of 75 mm. Under an atmosphere of 25°C, a test piece provided with a pre-mask was attached to a “stucco” painted finishing substrate (available from Test Materials Co., Ltd. (Kawaguchi-shi, Saitama, Japan)). The pre-mask was peeled off, and the test piece was pressed without heating using a rivet brush "PFA-1" (available from 3M Japan Ltd. (Shinagawa-ku, Tokyo, Japan)). The pressing was performed three times back and forth on the test piece. Here, with respect to a rough surface of the substrate, maximum roughness between a top and a bottom was about 1.5 mm.

[0152] The surface glossiness of each test sample was measured at a measurement angle of 60° using a portable glossmeter GMX-202 (Murakami Color Research Laboratory Co., Ltd., Chuo-ku, Tokyo, Japan). Measurements were made at three different locations, and the average value was recorded.

[0153] Surface reflection evaluation test after rough surface applicationA test piece was prepared in the same manner as in the 60-degree surface glossiness test after the rough surface application. In a room, surface reflection to a roughened substrate was visually determined. A case where the surface reflection of the test piece was not observed with respect to the roughened substrate was evaluated as “good”, and a case where the surface reflection of the test piece was observed with respect to the roughened substrate was evaluated as “poor”.

[0154] Table 5Table 5

[0155] It is apparent for a person skilled in the art that various variations of the embodiments and examples described above can be made without departing from the basic principles of the present invention. In addition, it is apparent for a person skilled in the art that various modifications and variations of the present invention can be made without departing from the spirit and scope of the present invention.

[0156] Reference Signs List100, 200 Decorative film110, 210 Cover layer120, 220 Colored layer130, 230 Adhesive layer140 Release liner201 Article250 Adherend

Claims

Claims

1. A decorative film comprising: a cover layer; and a colored layer, wherein the cover layer contains a cured product of a (meth)acrylic polyol and hexamethylene diisocyanate, and the colored layer contains a (meth)acrylic polymer having a glass transition temperature of lower than 0°C, a (meth)acrylic polymer having a glass transition temperature of 0°C or higher, and a colorant.

2. The decorative film according to claim 1, wherein the hexamethylene diisocyanate is an adduct form of hexamethylene diisocyanate.

3. The decorative film according to claim 1 or 2, wherein the cover layer has a 60- degree surface glossiness of 5.0 or less.

4. The decorative film according to claim 3, wherein the cover layer has a matted surface.

5. The decorative film according to claim 3, wherein a content of a filler in the cover layer is 10 mass% or less.

6. The decorative film according to claim 1 or 2, further comprising an adhesive layer.

7. The decorative film according to claim 1 or 2, wherein the decorative film is for an exterior.

8. The decorative film according to claim 3, wherein the decorative film is for a rough surface.

9. An article comprising the decorative film described in claim 1 or 2 and an adherend, wherein the decorative film includes an adhesive layer and is disposed on the adherend via the adhesive layer.

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