Decorative film

Abstract

A decorative film having performance equal to or higher than that of a known decorative film using polyvinyl chloride, and also having excellent performance such as workability. The decorative film includes a transparent surface layer containing a polyurethane resin or a cured product thereof and a colored adhesive layer. The decorative film has a portion to which the transparent surface layer and the colored adhesive layer are directly applied, and has a yield point.

Description

Description Title of Invention: DECORATIVE FILMTechnical Field

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

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

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

[0004] Patent Document 2 (JP 2023-174286 A) describes a decorative fdm including a transparent surface layer containing a non-yellowing thermoplastic polyurethane elastomer, a colored polyurethane layer, and an adhesive layer, in which the colored polyurethane layer contains an aqueous polyether- based polyurethane and a pigment, and the transparent surface layer and the colored polyurethane layer are arranged adjacent to each other.Citation List Patent Documents

[0005] Patent Document 1: JP 2018-034488 APatent Document 2: JP 2023-174286 ASummary of Invention Technical Problem

[0006] As described in Patent Document 1, as the decorative fdm, a decorative fdm including a polyvinyl chloride (PVC) fdm having excellent properties such as strength, shape followability, weather resistance, and dimensional stability is generally known. The decorative fdm described in Patent Document 2 is a decorative fdm using a polyurethane fdm instead of a PVC fdm. In such a decorative fdm, a colored polyurethane layer is used as a colored layer. In the case of coloring the polyurethane layer, it is difficult to select a material of a colorant such as a pigment and to blend the colorant at a high concentration, and as a result, it is difficult to keep performance constant as compared with a transparent polyurethane layer. In the decorative fdm described in Patent Document 2, the thermoplastic polyurethane elastomer is used for the transparent surface layer. Thus, such a decorative fdm is easy to stretch like rubber and may be difficult to handle, and therefore improvement of workability has been desired.

[0007] The present disclosure provides a decorative film having performance equal to or higher than that of a known decorative film using polyvinyl chloride, and also having excellent performance such as workability.Solution to Problem

[0008] According to an embodiment of the present disclosure, there is provided a decorative fdm including a transparent surface layer and a colored adhesive layer, wherein the transparent surface layer contains a polyurethane resin or a cured product thereof, and the decorative fdm has a portion to which the transparent surface layer and the colored adhesive layer are directly applied, and has a yield point.

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

[0010] According to the present disclosure, it is possible to provide a decorative fdm having performance equal to or higher than that of a known decorative fdm using polyvinyl chloride, and also having excellent performance such as workability.

[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 graph relating to elongation and tensile strength under a 20°C atmosphere in a decorative fdm according to an embodiment of the present disclosure.FIG. 2 is a graph relating to elongation and tensile strength under a 20°C atmosphere in a decorative fdm containing a polyurethane elastomer.FIG. 3 is a schematic cross-sectional view of a decorative fdm according to an embodiment of the present disclosure.FIG. 4 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 “a colored adhesive layer disposed on a release liner” means that the colored adhesive layer is disposed directly on the upper side of the release liner, or, that the colored 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 “colored adhesive layer disposed under a transparent surface layer” means that the colored adhesive layer is disposed directly below the transparent surface layer, or that the colored adhesive layer is indirectly disposed below the transparent surface 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.3 shows a schematic cross-sectional view of a decorative film according to an embodiment of the present disclosure. The decorative film 100 in FIG.3 includes a transparent surface layer 110, a colored adhesive layer 120, and a release liner 130. Here, the release liner shown in FIG.3 is an optional layer, and the decorative film of the present disclosure may not include a release liner. In addition, the decorative film of the present disclosure may include any layer (for example, a decorative layer) described below.

[0021] The decorative film of the present disclosure has a yield point. The presence or absence of the yield point can be confirmed, for example, from a graph of the elongation and tensile strength of the decorative film under a 20°C atmosphere as shown in FIG. 1. For example, since a decorative film containing a polyurethane elastomer exhibits stretchable performance like rubber, the yield point cannot be confirmed as shown in FIG. 2. In the decorative film of the present disclosure, the transparent surface layer and the colored adhesive layer are designed so as to have the yield point, and stretchable performance like rubber is not exhibited, so that workability can be improved.

[0022] In some embodiments, in the decorative film of the present disclosure, when a graph of the elongation and the tensile strength under the 20°C atmosphere is created, the yield point can be confirmed at a position of about 5 N / 25 mm or more, about 7 N / 25 mm or more, about 10 N / 25 mm or more, about 13 N / 25 mm or more, or about 15 N / 25 mm or more, about 100 N / 25 mm or less, about 80 N / 25 mm or less, about 70 N / 25 mm or less, about 60 N / 25 mm or less, or about 50 N / 25 mm or less in the tensile strength.

[0023] In some embodiments, the decorative film of the present disclosure exhibits elongation properties while having the yield point. 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 presentdisclosure can exhibit an elongation of about 50% or more, about 80% or more, about 100% or more, about 110% or more, or about 120% or more, about 200% or less, about 190% or less, about 180% or less, about 170% or less, or about 160% or less, and can exhibit a 2% tensile strength of about 5 N / 25 mm or more, about 6 N / 25 mm or more, about 7 N / 25 mm or more, or about 8 N / 25 mm or more, about 20 N / 25 mm or less, about 18 N / 25 mm or less, about 16 N / 25 mm or less, about 15 N / 25 mm or less, about 12 N / 25 mm or less, or about 10 N / 25 mm or less.

[0024] In some embodiments, the decorative fdm of the present disclosure can exhibit a breaking strength of about 10 N / 25 mm or more, about 15 N / 25 mm or more, about 20 N / 25 mm or more, about 25 N / 25 mm or more, or about 30 N / 25 mm or more, about 100 N / 25 mm or less, about 80 N / 25 mm or less, about 70 N / 25 mm or less, about 65 N / 25 mm or less, or about 60 N / 25 mm or less. Such breaking strength can be determined by a breaking strength test described below.

[0025] In some embodiments, the decorative fdm 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 fdm 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.

[0026] 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 12, about 10 or less, about 8.0 or less, less than about 6.0, about 4.0 or less, about 2.0 or less, or about 1.0 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.

[0027] In some embodiments, the decorative film of the present disclosure exhibits weather resistance. The weather resistance can be evaluated by a color difference based on a weather resistance test described below. 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 10, about 9.0 or less, or about 8.0 or less after exposure for 2500 hours or 5000 hours in accordance with JIS K 5600-7- 7: 2008. The lower limit of such a color difference is not particularly limited, and can be, for example, about 0 or more, more than about 0, about 1.0 or more, about 3.0 or more, or about 5.0 or more.

[0028] The coloring performance of the decorative film of the present disclosure is exhibited not by the polyurethane layer but by the adhesive layer. Thus, unlike the decorative film described in Patent Document 2, it is not necessary to color a polyurethane layer in which it is difficult to select a material of a colorant such as a pigment and to blend the colorant at a high concentration, so that deterioration in performance of the entire decorative film can be reduced or suppressed without requiring the skill of an operator. Since the decorative film of the present disclosure does not need to separately use a colored polyurethane layer, the cost can be reduced as compared with the decorative film described in Patent Document 2, and since the decorative film has a portion to which the transparent surface layer and the colored adhesive layer are directly applied, defects such as delamination that may occur with long-termuse and the like can be further reduced or prevented. In the portion to which the transparent surface layer and the colored adhesive layer are directly applied, for example, the colored adhesive layer may be directly applied to the entire surface of one side of the transparent surface layer, or the colored adhesive layer may be directly applied to a part of the transparent surface layer. When the colored adhesive layer is directly applied to a portion of the transparent surface layer, the colored adhesive layer may be applied to the entire surface of one side of the transparent surface layer in a proportion of about 10% or more, about 20% or more, about 40% or more, about 50% or more, about 70% or more, about 80% or more, or about 90% or more, less than about 100%, about 95% or less, about 90% or less, about 80% or less, or about 70% or less.

[0029] The decorative fdm of the present disclosure includes a transparent surface layer containing a polyurethane resin or a cured product thereof. The polyurethane resin or the cured product thereof is not particularly limited as long as the decorative fdm has the yield point. Although a polyurethane elastomer may be contained as the polyurethane resin, from the viewpoint of exhibiting the yield point in the decorative fdm, an amount of the polyurethane elastomer used is preferably about 10 mass% or less, about 5 mass% or less, or about 1 mass% or less with respect to a total amount of the polyurethane resin, and it is more preferable not to use the polyurethane elastomer.

[0030] From the viewpoint of durability such as weather resistance, elongation properties, expression of the yield point, and the like, the transparent surface layer preferably contains a polyurethane resin having a weight average molecular weight of about 50000 to about 350000 and an acid value of about 20.0 to about 30.0 mg-KOH / g, and more preferably contains a cured product of the polyurethane resin and a crosslinking agent.

[0031] The weight average molecular weight of polyurethane can be about 50000 or more, about 80000 or more, about 100000 or more, about 150000 or more, about 200000 or more, or about 250000 or more, about 350000 or less, about 320000 or less, about 300000 or less, or about 280000 or less. Here, the weight average molecular weight of the polyurethane refers to a weight average molecular weight measured after curing a polyurethane dispersion at 60°C for 3 hours. Such a molecular weight can be adjusted, for example, by setting a ratio between a diol and an isocyanate. Since the diol and the isocyanate are alternately connected to each other to increase the molecular weight, a high molecular weight product is obtained in a region where the isocyanate is excessively blended from the vicinity of an approximate equivalence in the molecule actually contributing to the reaction in terms of equivalent weight. By further finely adjusting the blending to increase a ratio at which both terminals of a prepolymer produced by reacting both of them remain as isocyanate groups, the increase in molecular weight with a chain extender proceeds, and as a result, a prepolymer having a more relatively high molecular weight can be obtained. In addition, for example, temperature control during water dispersion may also be involved. For example, by keeping the temperature low, a reaction between isocyanate and water can be prevented, and the increase in molecular weight with the chain extender can be secured. Typically, the prepolymer and a diamine chain extender are alternately connected to each other to increase the molecular weight. A polyurethane having a high molecular weight can beobtained by blending both the prepolymer and the diamine chain extender in a proper proportion so that either the prepolymer or the diamine chain extender is not excessive.

[0032] 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

[0033] The acid value of the polyurethane can be about 20.0 mg-KOH / g or more, about 22.0 mg-KOH / g or more, about 24.0 mg-KOH / g or more, or about 25.0 mg-KOH / g or more, about 30.0 mg-KOH / g or less, about 29.0 mg-KOH / g or less, about 28.5 mg-KOH / g or less, about 28.0 mg-KOH / g or less, or about 27.5 mg-KOH / g or less. Here, the “acid value” refers to a concentration of a carbonyl group obtained by titrating a polyurethane dispersion diluted with an organic solvent with a KOH-EtOH standard solution. The acid value can be controlled by a blending ratio of a carbonyl group-containing diol in a diol. That is, when the proportion of the carbonyl group-containing diol is high, a high acid value can be obtained.

[0034] In some embodiments, from the viewpoint of durability such as weather resistance, elongation properties, expression of the yield point, and the like, it is preferable to use, as the polyurethane resin, a reaction product between a diamine chain extender and a polyurethane prepolymer produced by reacting a polycarbonate diol having an alicyclic structure, an aliphatic diol containing a carboxyl group, and an isocyanate containing 4,4 ’-cyclohexylmethane diisocyanate. Here, the “polycarbonate diol” refers to those having one hydroxyl group at each of both terminals of a polymer chain linked via a carbonate bond, and the “polycarbonate diol having an alicyclic structure” refers to those having one or more alicyclic structures in the molecule of the polycarbonate diol.

[0035] Examples of the polycarbonate diol having an alicyclic structure include a polycarbonate diol synthesized from 1,4-cyclohexanedimethanol and 1,6-hexanediol, and specifically, ETERNACOLL (trademark) UM90 available from UBE Corporation (Minato-ku, Tokyo, Japan). The polycarbonate diol can be used alone, or in combination of two or more types thereof.

[0036] Examples of the aliphatic diol containing a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 3, 3 -dimethylolpropionic acid. The aliphatic diol can be used alone, or in combination of two or more types thereof.

[0037] In the present disclosure, the “isocyanate containing 4,4’ -cyclohexylmethane diisocyanate” refers to an isocyanate containing 4,4 ’-cyclohexylmethane diisocyanate as the isocyanate component. The content of 4,4 ’-cyclohexylmethane diisocyanate contained in the isocyanate is not particularly limited, and can be, for example, about 30 mass% or more, about 40 mass% or more, or about 50mass% or more, and about 100 mass% or less, about 90 mass% or less, or about 80 mass% or less with respect to the total amount of the isocyanate.

[0038] The polyurethane prepolymer can be obtained by reacting an isocyanate containing a polycarbonate diol having an alicyclic structure, an aliphatic diol containing a carboxyl group, and 4,4'- cyclohexylmethane diisocyanate by a known method.

[0039] From the viewpoint of durability such as weather resistance, elongation properties, expression of the yield point, and the like, examples of a preferable combination of a diol and an isocyanate included in the polyurethane prepolymer include polycarbonate diol synthesized by transesterification of 1,4-cyclohexanedimethanol and 1,6-hexanediol with ethylene carbonate as the diol, 2,2-dimethylolpropionic acid, and 4,4'-cyclohexylmethane diisocyanate as the isocyanate.

[0040] The polyurethane resin can be obtained by reacting a polyurethane prepolymer with a diamine chain extender. The polyurethane resin may be linear or branched, and is preferably linear from the viewpoint of durability such as weather resistance, elongation properties, expression of the yield point, and the like. As the diamine chain extender, for example, a known diamine-based compound such as ethylenediamine, propylenediamine, or putrescine can be used. The diamine chain extender can be used alone, or in combination of two or more types thereof. An amount of the diamine chain extender used is not particularly limited, and can be appropriately employed in consideration of desired performance (durability such as weather resistance, elongation properties, workability, and the like).

[0041] The transparent surface layer can be prepared using a transparent surface layer forming composition containing a polyurethane resin and the like. A proportion of the polyurethane resin or a cured product of the polyurethane resin in the transparent surface layer forming composition (solid content) or the transparent surface layer can be about 30 mass% or more, about 40 mass% or more, about 45 mass% or more, about 50 mass% or more, about 55 mass% or more, or about 60 mass% or more, about 100 mass% or less, less than about 100 mass%, about 95 mass% or less, about 90 mass% or less, about 80 mass% or less, about 70 mass% or less, about 65 mass% or less, or about 60 mass% or less.

[0042] The transparent surface layer forming composition for forming a transparent surface 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, crosslinking agents, lubricants, pH adjusters, surfactants, leveling agents, silane coupling agents, catalysts, colorants, and solvents.

[0043] In some embodiments, as long as the transparent surface layer of the present disclosure exhibits transparency, the transparent surface layer may contain a colorant as described below to the extent that the effects of the present disclosure are not adversely affected. The transparent surface layer exhibiting colorability can be formed, for example, by blending about 5 parts by mass or less, about 3 parts by mass or less, or about 1 part by mass or less of a colorant with respect to 100 parts by mass of a resin component (polyurethane resin or cured product thereof). When the content of the colorant in thesurface layer is such a proportion, the surface layer can be formed without requiring the skill of an operator.

[0044] In some embodiments, the transparent surface layer contains the cured product of the polyurethane resin and the crosslinking agent as described above. Since the transparent surface layer containing such a cured product is formed using a crosslinking agent, for example, when the colored adhesive layer described below is also prepared using a crosslinking agent, the crosslinking agents in both layers interact with each other, and as a result, interlayer adhesion of the decorative fdm can be improved. Here, in the present disclosure, the “cured product” is not limited to a reaction product in a state in which such a reactive site that can be crosslinked or polymerized is completely reacted, and may include a reaction product in a state in which a part of the reactive site remains without being reacted.

[0045] The crosslinking agent that can be used together with the polyurethane resin is not particularly limited, and for example, a known crosslinking agent capable of reacting with a carboxyl group of an aliphatic diol containing the carboxyl group and the like can be used. Specific examples thereof include polycarbodiimide, aziridine, and oxazoline. The crosslinking agents can be used alone, or two or more types thereof can be used in combination. An amount of the crosslinking agent used is not particularly limited, and can be appropriately employed in consideration of desired performance (durability such as weather resistance, elongation properties, workability, and the like). For example, the amount of the crosslinking agent (solid content) used can be about 0.1 parts by mass or more, about 0.5 parts by mass or more, about 1 part by mass or more, or about 5 parts by mass or more, and about 20 parts by mass or less, about 15 parts by mass or less, or about 10 parts by mass or less with respect to 100 parts by mass of the polyurethane resin.

[0046] The transparent surface layer of the present disclosure can be obtained, for example, by applying the transparent surface layer forming composition containing a polyurethane resin and the like to a release liner and the like which will be described below, followed by a heat treatment and / or a radiation (for example, ultraviolet ray) irradiation treatment. It is preferable to use a heat treatment from the viewpoint of durability such as weather resistance, elongation properties, expression of the yield point, and the like. As the component used in the transparent surface layer forming composition, a component that can be used in the transparent surface layer described above can be similarly employed.

[0047] 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 150°C or lower, about 130°C or lower, or about 100°C or lower.

[0048] The thickness of the transparent surface layer may be appropriately set in consideration of required performance (for example, protection performance) and the like. The thickness can be, for example, about 1 micrometer or more, about 2 micrometers or more, or about 3 micrometers or more, and can be about 100 micrometers or less, about 70 micrometers or less, about 50 micrometers or less,about 40 micrometers or less, about 30 micrometers or less, about 20 micrometers or less, about 15 micrometers or less, or about 10 micrometers or less.

[0049] The decorative film of the present disclosure includes a colored adhesive layer (which may be simply referred to as an “adhesive layer”). For such an 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, or polyester. The adhesive layer may be applied by a well-known coating method or the like.

[0050] In some embodiments, the colored adhesive layer of the present disclosure contains, as polymer components, a carboxy group-containing (meth)acrylic polymer and an amino group- containing (meth)acrylic polymer. Here, the phrase “includes a carboxy group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer” in the present disclosure can include a cured product of a carboxy group-containing (meth)acrylic polymer, an amino group-containing (meth)acrylic polymer, and a crosslinking agent. Since the adhesive layer containing such a cured product is formed using the crosslinking agent, the adhesive layer can interact with another crosslinking agent and the like that can be used in the transparent surface layer, and as a result, the interlayer adhesion of the decorative fdm can be improved.

[0051] The carboxy group-containing (meth)acrylic polymer can be formed by copolymerization of a monoethylenically unsaturated monomer and a carboxy group-containing unsaturated monomer. The carboxy group-containing (meth)acrylic polymer can also be referred to as a “(meth)acrylic polymer including a constituent unit derived from a carboxyl group-containing monomer”.

[0052] The monoethylenically unsaturated monomer typically includes (meth)acylates represented by the formula CH2=CR1COOR2(in the formula, R1is hydrogen or a methyl group, and R2is a linear, branched, or cyclic alkyl group, a phenyl group, an alkoxyalkyl group, a phenoxyalkyl group, a hydroxyalkyl group, or a cyclic ether group), and additionally, aromatic vinyl monomers such as styrene, a-methylstyrene, and vinyl toluene, vinyl esters such as vinyl acetate, and unsaturated nitriles such as acrylonitrile and methacrylonitrile. Examples of the monoethylenically unsaturated monomer represented by CH2=CR1COOR2can include linear alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate, n-decyl (meth)acrylate, and n-dodecyl (meth)acrylate; branched alkyl (meth)acrylates such as isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, and isononyl (meth)acrylate; alicyclic (meth)acrylates such as cyclohexyl (meth)acrylate and isobomyl (meth)acrylate; phenyl (meth)acrylates; alkoxyalkyl (meth)acrylates such as methoxypropyl (meth)acrylate and 2- methoxybutyl (meth)acrylate; phenoxyalkyl (meth)acrylates such as phenoxyethyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and cyclic ether-containing (meth)acrylates such as glycidyl (meth)acrylate and tetrahydrofurfuryl (meth)acrylate. Among them, n-butyl (meth)acrylate is preferable from the viewpoint of compatibility, followability, and the like with an amino group-containing (meth)acrylic polymer described below, and, if present, a 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 amino group- containing (meth)acrylic polymer and, if present, the third polymer, which will be described below, the carboxy group-containing (meth)acrylic 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 amino group-containing (meth)acrylic polymer and / or 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.

[0053] A proportion of the constituent unit derived from the monoethylenically unsaturated monomer in the carboxy group-containing (meth)acrylic 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 carboxy group-containing (meth)acrylic polymer.

[0054] 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.

[0055] 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 carboxy group-containing (meth)acrylic polymer.

[0056] The glass transition temperature of the carboxy group-containing (meth)acrylic polymer can be less than about 0°C, 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.

[0057] The weight average molecular weight of the carboxy group-containing (meth)acrylic 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. The “glass transition temperature (Tg)” of the present disclosure can be determined as a calculated glass transition temperature by using the following Fox formula (Fox, T. G., Bull. Am. Phys. Soc., 1 (1956), p. 123) when the polymer is formed by copolymerization of n types of monomers:Math. 1- 1 - = V _ 5 _ 'ITg + 273.15 Zu \.Tgt+ 273.15 / In the equation, Tgi represents the glass transition temperature (°C) of a homopolymer of a component i, Xi represents the mass fraction of the monomer of the component i added during polymerization, and i is a natural number of 1 to n, and Math. 2

[0058] The weight average molecular weight of the carboxy group-containing (meth)acrylic 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.

[0059] The amino group-containing (meth)acrylic polymer can be formed by copolymerization of a monoethylenically unsaturated monomer and an amino group-containing unsaturated monomer. The amino group-containing (meth)acrylic polymer can be referred to as a “(meth)acrylic polymer including a constituent unit derived from an amino group-containing monomer”.

[0060] As the monoethylenically unsaturated monomer, the monoethylenically unsaturated monomer in the carboxy group-containing (meth)acrylic polymer described above can be similarly used. Among them, methyl (meth)acrylate and n-butyl (meth)acrylate are preferable from the viewpoint of compatibility, followability, and the like of the carboxy group-containing (meth)acrylic polymer described above. 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 carboxy group-containing (meth)acrylic polymer described above and, if present, the third polymer described below, the amino group-containing (meth)acrylic 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 carboxy group-containing (meth)acrylic polymer and / or the third polymer.

[0061] A proportion of the constituent unit derived from the monoethylenically unsaturated monomer of the amino group-containing (meth)acrylic 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 99mass% or less, or about 98 mass% or less with respect to the amino group-containing (meth)acrylic polymer.

[0062] 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.

[0063] 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 amino group-containing (meth)acrylic polymer.

[0064] The carboxy group-containing (meth)acrylic polymer and the amino group-containing (meth)acrylic 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) peroxy dicarbonate, and azo-based polymerization initiators such as 2,2'-azobisisobutyronitile, 2,2'-azobis(2- methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile) (AVN). An amount of the initiator (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.

[0065] The colored adhesive layer of the present disclosure typically contains a colorant. The colorant 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.

[0066] 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.

[0067] 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.

[0068] 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 adhesive layer (solid content) or colored adhesive layer.

[0069] In some embodiments, the colored adhesive layer of the present disclosure can be prepared using a composition for forming a colored adhesive layer including a carboxy group-containing (meth)acrylic polymer, an amino group-containing (meth)acrylic polymer, a crosslinking agent, and a colorant. By using a composition containing a crosslinking agent, the colored adhesive layer containing a cured product of the carboxy group-containing (meth)acrylic polymer, the amino group-containing (meth)acrylic 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.

[0070] 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 l,r-(l,3-phenylenedicarbonyl)bis(2-methylaziridine), 1,4- bis(ethyleneiminocarbonylamino)benzene, 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane, and l,8-bis(ethyleneiminocarbonylamino)octane. Examples of the aziridine crosslinking agents include CHEMITITE PZ33 (Nippon Shokubai Co., Ltd., Osaka-shi, Osaka, Japan), and NeoCryl CX-100 (DSM Coating Resins, LLC., Zwolle, Provincie Overijssel, Netherlands). Examples of carbodiimide crosslinking agents include Carbodilite V-03, V-05, and V-07 (Nisshinbo Chemical Inc., Chuo-ku, Tokyo, Japan).

[0071] The 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 carboxy group-containing (meth)acrylic polymer (for example, carboxy group-containing (meth)acrylic polymer including a constituent unit derived from a carboxyl group-containing monomer).

[0072] Typically, the adhesive layer can be formed by adjusting a blending ratio of a carboxy group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer. In an embodiment, a blending ratio of the amino group-containing (meth)acrylic 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 bymass or more with respect to 100 parts by mass of the carboxy group-containing (meth)acrylic polymer. The adhesive layer containing the amino group-containing (meth)acrylic polymer in such a proportion can improve performance such as adhesive force, heat shrinkage resistance, reworkability, and followability.

[0073] The total content of the carboxy group-containing (meth)acrylic polymer, the amino group- containing (meth)acrylic polymer, and, if present, the third polymer described below 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, 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.

[0074] 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 other resins (for example, thermoplastic resins and the third polymer described below) other than the above-described carboxy group-containing (meth)acrylic polymer and amino group-containing (meth)acrylic polymer, fdlers, conductive agents, thermal conductivity imparting agents, crosslinking agents, antioxidants, UV absorbing agents, light stabilizers, heat stabilizers, dispersants, lubricants, surfactants, leveling agents, silane coupling agents, catalysts, and solvents.

[0075] The composition for forming a colored adhesive layer can be typically produced by mixing the above-described carboxy group-containing (meth)acrylic polymer, amino group-containing (meth)acrylic polymer, a colorant, and optional components (for example, the crosslinking agent, the third polymer) as necessary.

[0076] In some embodiments, in the composition for forming a colored adhesive layer, it is preferable that (1) at least one selected from the group consisting of the amino group-containing (meth)acrylic 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 carboxy group-containing (meth)acrylic polymer and a crosslinking agent to produce the composition for forming a colored adhesive layer, or it is preferable that (2) at least one selected from the group consisting of the amino group-containing (meth)acrylic polymer and the third polymer including a constituent unit derived from 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 carboxy group-containing (meth)acrylic polymer to produce the composition for forming a colored adhesive layer. By producing the composition for forming a colored adhesive layer in this manner, a composition for forming a colored adhesive layer, which has excellent colorant dispersibility, can be obtained.

[0077] 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 unitderived 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 carboxy group-containing (meth)acrylic polymer and the amino group-containing (meth)acrylic polymer described above, 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 carboxy group-containing (meth)acrylic polymer and / or the amino group-containing (meth)acrylic polymer.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] When the composition for forming a colored adhesive layer and the colored adhesive layer formed from the composition contain the third polymer, in an embodiment, a blending ratio of the third polymer 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 carboxy group-containing (meth)acrylic polymer. The colored adhesive layer containing the third polymer in such a proportion is excellent in colorant dispersibility and can improve the performance such as concealing properties.

[0083] The colored adhesive layer of the present disclosure can be obtained, for example, by applying the composition for forming a colored adhesive layer containing a carboxy group-containing (meth)acrylic polymer, an amino group-containing (meth)acrylic polymer, a colorant, and optional components (for example, the crosslinking agent, the third polymer) as necessary to a release linerdescribed below 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 adhesive layer, a component that can be used in the colored adhesive layer described above can be similarly employed.

[0084] 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.

[0085] 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.

[0086] The thickness of the colored adhesive layer of the present disclosure may be appropriately set in consideration of required performance (adhesive force, colorability, and concealing properties) 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.

[0087] In some embodiments, the decorative fdm of the present disclosure optionally includes an additional layer. Examples of the additional layer include a decorative layer, a bonding layer, and a release liner. The additional layers can be used alone, or two or more types thereof can be used in combination. Here, when an additional layer (for example, a decorative layer) is applied between the transparent surface layer and the colored adhesive layer, the additional layer is applied to a part of the transparent surface layer or the colored adhesive layer rather than the entire surface on one side. A metal thin-fdm layer formed by vapor deposition and the like may conceal the coloring performance of the colored adhesive layer, and therefore is preferably not employed as an additional layer.

[0088] Examples of the decorative layer include a pattern layer that imparts patterns such as wood grain, stone grain, geometric patterns, and leather patterns, logos, picture patterns, and the like to an article. The decorative layer may have a single layer structure or a multilayer structure, and may be transparent, translucent, or opaque.

[0089] The decorative layer can be applied to a layer included in the decorative fdm, such as the transparent surface layer and / or the colored adhesive layer, directly or via a bonding layer and the like.

[0090] As the decorative layer, although not limited to the following, layers obtained by applying a pattern such as a pattern, logo, or a picture pattern directly to the transparent surface layer and / or the colored 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, a picture pattern, 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.

[0091] The material for the decorative 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, 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.

[0092] The decorative layer of the present disclosure can contain, for example, fdlers, 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.

[0093] 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.

[0094] In the decorative fdm 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 fdm. As the bonding layer, a generally used adhesive agent such as a solvent-type, emulsion-type, pressure-sensitive type, heat-sensitive type, and heat-curable or ultraviolet-curable type adhesive agent, including (meth)acrylics, polyolefins, polyurethanes, polyesters, and the like can be used. The bonding layer may be applied by a well-known coating method or the like.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] For example, in the case of a decorative film having a structure in which a release liner, a colored adhesive layer, and a transparent surface layer are provided in this order, the composition for forming a transparent surface layer is coated on the release liner, and a drying step and a curing step are applied as necessary to form a transparent surface layer. Subsequently, the composition for forming a colored 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 transparent surface layer and removing the release liner on the transparent surface layer side as necessary.

[0100] In some embodiments, the above-described decorative film of the present disclosure is disposed on an adherend via the colored adhesive layer, and an article including the decorative film is provided. FIG. 4 shows a schematic cross-sectional view of an article according to one embodiment of the present disclosure. The article 201 in FIG. 4 comprises a decorative film 200, which includes a transparent surface layer 210 and a colored adhesive layer 220, applied to an adherend 240 via the colored adhesive layer 220.

[0101] 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 (for example, polyolefin resins, polyester resins, (meth)acrylic resins, polycarbonate resins, polyurethane resins, and acrylonitrile-butadiene- styrene copolymers), inorganic materials (for example, glass, ceramic, concrete, gypsum, calcium silicate, natural stone, and asphalt), rubber materials, cloth materials (for example, woven fabrics, knitted fabrics, and nonwoven fabrics), metal or metal alloy materials (for example, iron, aluminum, and stainless steel), and woody materials including paper and the like.

[0102] 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.

[0103] 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 is excellent in durability such as weather resistance, and thus can be suitably used for vehicles or buildings, and among them, the decorative film can be suitably used for exterior applications, more specifically, for exterior applications of vehicles (for example, automobiles) and for exterior applications of buildings (for example, exterior wall members).

[0104] A method of applying the decorative fdm 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 direct attachment by hand or the like, injection molding methods such as an insert injection molding method, an in-molding method, an over-molding method, a two-color injection molding method, a core back injection molding method, and a sandwich injection molding method, a lamination method, and a three-dimensional heat stretch blow molding method (TOM). For example, a decorative film formed using a polyurethane elastomer is easy to stretch like rubber, and thus is not suitable for direct attachment by hand or the like. In the decorative film of the present disclosure, the transparent surface layer and the colored adhesive layer are designed so as to have the yield point, and stretchable performance like rubber is not exhibited, so that the decorative film can be suitably used for direct attachment.Example 1

[0105] 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.

[0106] 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 (amino group-containing (meth)acrylic polymer), AP2 (third polymer), and ADH1 (carboxy group-containing (meth)acrylic polymer), 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.

[0107] Table 1Table 1BA: n-butyl acrylate, AN: acrylonitrile, AA: acrylic acid, 2EHA: 2-ethylhexyl acrylate, MMA: methyl methacrylate BMA: n-butyl methacrylate, DMAEMA: 2-(dimethylamino) ethyl methacrylate, Vac: vinyl acetate, ACM: acrylamide

[0109] Table 2Table 2

[0110] Table 3Table 3

[0111] Example 1PU 1 and CL2 were mixed so that the solid content weight ratio of PU 1 and CL2 was 100: 16 to prepare a composition for forming a transparent surface layer. A 50 micrometer-thick polyester backing fdm coated with a release layer was coated with the composition for forming a transparent surface layer using a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain a 30 micrometer-thick polyurethane resin transparent surface layer.

[0112] CAI of the composition for forming a colored adhesive layer was coated on a release liner (LI) using a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain a 25 micrometerthick colored adhesive layer. After the adhesive layer was laminated on the transparent surface layer, the backing film on the transparent surface layer side was peeled off to obtain a decorative film of Example 1.

[0113] Example 2A decorative film of Example 2 was obtained in the same manner as in Example 1 except that CAI of the composition for forming a colored adhesive layer was changed to CA2.

[0114] Example 3A decorative film of Example 3 was obtained in the same manner as in Example 1 except that PU 1 of the composition for forming a transparent surface layer was changed to PU2.

[0115] Example 4A decorative film of Example 4 was obtained in the same manner as in Example 1 except that PU 1 of the composition for forming a transparent surface layer was changed to PU2.

[0116] Comparative Example 1A decorative film of Comparative Example 1 was obtained in the same manner as in Example 1 except that a non-yellowing thermoplastic polyurethane elastomer film (PU3) was used as the transparent surface layer.

[0117] Comparative Example 2A decorative film of Comparative Example 2 was obtained in the same manner as in Example 2 except that PU3 was used as the transparent surface layer.

[0118] Comparative Example 3A decorative film of Comparative Example 3 was obtained in the same manner as in Example 1 except that a transparent polyvinyl chloride cast film (PVC1) was used as the transparent surface layer.

[0119] Comparative Example 4A decorative film of Comparative Example 4 was obtained in the same manner as in Example 2 except that PVC1 was used as the transparent surface layer.

[0120] Evaluation testEach of the obtained test samples was evaluated according to the following test method. The results are indicated in Table 4.

[0121] Yield point evaluation testA test piece was prepared by cutting a test sample into a width of 25 mm and a length of 150 mm. Under an atmosphere of 20°C, the tensile force (tensile strength) and elongation of the test piece were measured using a Tensilon universal material testing machine (available from A&D Company, Limited (Toshima-ku, Tokyo, Japan)). The speed of the air jaw was 300 mm per minute, and an air jaw interval was 100 mm. The yield point was determined from a graph of the elongation (x-axis) and the tensile strength (y-axis). In Table 4, as shown in FIG. 1, the values of the tensile strength at the position where the yield point was confirmed are described.

[0122] 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 Li*, af, 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 :• • • Formula 1Here, 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.

[0123] Adhesive force test 1A: 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.

[0124] Adhesive force test IB: adhesive force to coated plate after aging at 65°CA 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 65°C for 7 days, 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.

[0125] Adhesive force test 2A: Adhesive force to aluminum 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 an aluminum plate 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.

[0126] Adhesive force test 2B: adhesive force to aluminum plate after aging at 65°CA 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 an aluminum plate under an atmosphere of 20°C according to JIS Z 0237 8.2.3. The test piece was left standing at 65°C for 7 days, 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.

[0127] 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.

[0128] Breaking strength testA test piece was prepared by cutting a test sample into a width of 25 mm and a length of 150 mm. Under an atmosphere of 20°C, the breaking strength of the test piece was measured using a Tensilon universal material testing machine (available from A&D Company, Limited (Toshima-ku, Tokyo, Japan)). The speed of the air jaw was 300 mm per minute, and an air jaw interval was 100 mm.

[0129] 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.

[0130] 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).

[0131] Weather resistance testA test sample was cut to a width of 70 mm and a length of 40 mm to prepare a test piece, and the test piece was placed on an aluminum plate having a thickness of 1.5 mm. After the placement, the test piece was exposed in Xenon Ci5000 Weather-Ometer (trademark) available from ATLUS in accordance with JIS K 5600-7-7: 2008.

[0132] L*, a*, and b* values were measured at an initial stage (before exposure) and after exposure for 2500 hours or 5000 hours using a spectrophotometer (CM-3700d, available from Konica Minolta, Inc. (Chiyoda-ku, Tokyo, Japan)). The values of the test piece at the initial stage were Li*, ai*, and bi*, and the values of the test piece after exposure for 2500 hours or 5000 hours were L2*, a2*, and b2*. The color difference (AE) was calculated from the following Formula 1 in the same manner as in the concealing property test described above:• • « Formula 1Here, a case where the color difference at the initial stage (before exposure) and after exposure for 2500 hours or 5000 hours was less than 5 was evaluated as “A”, a case where the color difference was 5 or more and less than 10 was evaluated as “B”, a case where the color difference was 10 or more and less than 20 was evaluated as “C”, and a case where the color difference was 20 or more was evaluated as “D”. Here, “A” was determined as “excellent”, “B” was determined as “good”, “C” was determined as “acceptable”, and “D” is determined as “unacceptable”.

[0133] Table 4Table 4

[0134] 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.

[0135] Reference Signs List100, 200 Decorative film110, 210 Transparent surface layer120, 220 Colored adhesive layer201 Article240 Adherend

Claims

Claims

1. A decorative film comprising: a transparent surface layer; and a colored adhesive layer, wherein the transparent surface layer contains a polyurethane resin or a cured product of the polyurethane resin, and the decorative film has a portion to which the transparent surface layer and the colored adhesive layer are directly applied, and has a yield point.

2. The decorative film according to claim 1, wherein the transparent surface layer contains a polyurethane resin having a weight average molecular weight of 50000 to 350000 and an acid value of 20.0 to 30.0 mg-KOH / g, or a cured product of the polyurethane resin.

3. The decorative film according to claim 2, wherein the polyurethane resin is a reaction product between a diamine chain extender and a polyurethane prepolymer produced by reacting a polycarbonate diol having an alicyclic structure, an aliphatic diol containing a carboxyl group, and an isocyanate containing 4,4 ’-cyclohexylmethane diisocyanate.

4. The decorative film according to any one of claims 1 to 3, wherein the colored adhesive layer contains a carboxy group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer.

5. The decorative film according to any one of claims 1 to 3, wherein the decorative film has a 2% tensile strength of 5 N / 25 mm or more.

6. The decorative film according to any one of claims 1 to 3, wherein the decorative film is for direct attachment.

7. The decorative film according to any one of claims 1 to 3, wherein the decorative film is for construction.

8. An article comprising the decorative film described in any one of claims 1 to 3 and an adherend, wherein the decorative film is disposed on the adherend via the colored adhesive layer.

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