Decorative film

Abstract

To provide a decorative film that has performance equal to or better than conventional decorative films using polyvinyl chloride, and also has superior performance in terms of workability and other properties. [Solution] A decorative film according to one embodiment of the present disclosure comprises a transparent surface layer containing a polyurethane resin or a cured product thereof, and a colored adhesive layer, having portions to which the transparent surface layer and the colored adhesive layer are directly applied, and having a yield point.

Description

[Technical Field]

[0001] This disclosure relates to decorative films. [Background technology]

[0002] In recent years, various decorative films have been developed for purposes such as adding aesthetic appeal and protecting surfaces.

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

[0004] Patent Document 2 (Japanese Patent Publication No. 2023-174286) describes a decorative film comprising a transparent surface layer containing a non-yellowing modified thermoplastic polyurethane elastomer, a colored polyurethane layer, and an adhesive layer, wherein the colored polyurethane layer comprises a water-based polyether-based polyurethane and a pigment, and the transparent surface layer and the colored polyurethane layer are arranged adjacent to each other. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2018-034488 [Patent Document 2] Japanese Patent Publication No. 2023-174286 [Overview of the project] [Problems that the invention aims to solve]

[0006] As described in Patent Document 1, decorative films generally include polyvinyl chloride (PVC) films that have excellent properties such as strength, shape conformability, weather resistance, and dimensional stability. The decorative film described in Patent Document 2 is a decorative film that uses a polyurethane film instead of a PVC film. In such a decorative film, a colored polyurethane layer is used as the coloring layer. When coloring the polyurethane layer, it is difficult to select the material of the coloring agent such as a pigment and to blend the coloring agent at a high concentration, and as a result, it has been difficult to maintain consistent performance compared to a transparent polyurethane layer. Furthermore, the decorative film described in Patent Document 2 uses a thermoplastic polyurethane elastomer for the transparent surface layer. Therefore, such a decorative film was sometimes difficult to handle because it stretched easily like rubber, and there was a desire for improvement in workability.

[0007] This disclosure provides a decorative film that has performance equivalent to or better than conventional decorative films using polyvinyl chloride, and also has superior performance in terms of workability and other properties. [Means for solving the problem]

[0008] According to one embodiment of the present disclosure, a decorative film is provided, comprising a transparent surface layer and a colored adhesive layer, wherein the transparent surface layer comprises a polyurethane resin or a cured product thereof, and the decorative film has portions 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, an article is provided in which the decorative film described above is disposed on a substrate via a colored adhesive layer. [Effects of the Invention]

[0010] According to this disclosure, it is possible to provide a decorative film that has performance equivalent to or better than conventional decorative films using polyvinyl chloride, and also has superior performance in terms of workability and other properties.

[0011] The above description should not be regarded as disclosing all embodiments of the present invention and all advantages related to the present invention.

Brief Description of the Drawings

[0012] [Figure 1] FIG. 1 is a graph regarding elongation and tensile strength in a decorative film according to an embodiment of the present disclosure under a 20°C atmosphere. [Figure 2] FIG. 2 is a graph regarding elongation and tensile strength in a decorative film containing a polyurethane elastomer under a 20°C atmosphere. [Figure 3] It is a schematic cross-sectional view of a decorative film according to an embodiment of the present disclosure. [Figure 4] It is a schematic cross-sectional view of an article according to an embodiment of the present disclosure.

Modes for Carrying Out the Invention

[0013] Hereinafter, for the purpose of exemplifying representative embodiments of the present invention, a more detailed description will be given with reference to the drawings as necessary, but the present invention is not limited to these embodiments.

[0014] In the present disclosure, for example, "above" in "a colored adhesive layer disposed above a release liner" means that the colored adhesive layer is directly disposed above the release liner, or the colored adhesive layer is indirectly disposed above the release liner through another layer.

[0015] In the present disclosure, for example, "below" in "a colored adhesive layer disposed below a transparent surface layer" means that the colored adhesive layer is directly disposed below the transparent surface layer, or the colored adhesive layer is indirectly disposed below the transparent surface layer through another layer.

[0016] In this disclosure, "transparent" means that the average transmittance in the visible light region (wavelength 400 nm to 700 nm), measured in accordance with JIS K 7375, is approximately 80% or higher, preferably approximately 85% or higher, or approximately 90% or higher. There are no particular restrictions on the upper limit of the average transmittance, but for example, it may be less than approximately 100%, approximately 99% or lower, or approximately 98% or lower.

[0017] In this disclosure, "translucent" means that the average transmittance in the visible light region (wavelength 400nm to 700nm), measured in accordance with JIS K 7375, is less than approximately 80%, preferably less than approximately 75%, and is intended not to completely conceal the substrate, etc.

[0018] In this disclosure, the term "film" also includes a component called a "sheet."

[0019] In this disclosure, "(meth)acrylic" means acrylic or methacrylic, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyl" means acryloyl or methacryloyl.

[0020] Figure 3 shows a schematic cross-sectional view of a decorative film according to one embodiment of the present disclosure. The decorative film 100 in Figure 3 includes a transparent surface layer 110, a colored adhesive layer 120, and a release liner 130. Here, the release liner shown in Figure 3 is an arbitrary layer, and the decorative film of the present disclosure does not have to include a release liner. In addition, the decorative film of the present disclosure may include an arbitrary layer (for example, a decorative layer) as described later.

[0021] The decorative film disclosed herein has a yield point. The presence or absence of a yield point can be confirmed, for example, from the graph of elongation and tensile strength of the decorative film in a 20°C atmosphere, as shown in Figure 1. For example, a decorative film containing polyurethane elastomer exhibits rubber-like stretchability, and therefore, as shown in Figure 2, the yield point cannot be confirmed. The decorative film disclosed herein is designed with a transparent surface layer and a colored adhesive layer to have a yield point and does not exhibit rubber-like stretchability, thus improving workability.

[0022] In some embodiments, when graphs of elongation and tensile strength are created for the decorative film of the present disclosure in a 20°C atmosphere, the yield point can be identified at positions of approximately 5 N / 25 mm or more, approximately 7 N / 25 mm or more, approximately 10 N / 25 mm or more, approximately 13 N / 25 mm or more, or approximately 15 N / 25 mm or more, approximately 100 N / 25 mm or less, approximately 80 N / 25 mm or less, approximately 70 N / 25 mm or less, approximately 60 N / 25 mm or less, or approximately 50 N / 25 mm or less in terms of tensile strength.

[0023] In some embodiments, the decorative films of the present disclosure exhibit elongation properties while having a yield point. Such elongation properties can be evaluated by elongation tests and tensile strength tests as described later. In some embodiments, the decorative films of the present disclosure can exhibit elongation rates 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 2% tensile strengths of about 5N / 25mm or more, about 6N / 25mm or more, about 7N / 25mm or more, or about 8N / 25mm or more, about 20N / 25mm or less, about 18N / 25mm or less, about 16N / 25mm or less, about 15N / 25mm or less, about 12N / 25mm or less, or about 10N / 25mm or less.

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

[0025] In some embodiments, the decorative films of the present disclosure exhibit heat resistance. Such heat resistance can be evaluated by a heat shrinkage test described later. In some embodiments, the decorative films of the present disclosure can achieve a maximum opening width of approximately 0.50 mm or less, approximately 0.40 mm or less, approximately 0.30 mm or less, or approximately 0.25 mm or less after a heat shrinkage test. There is no particular limit to the lower limit of such width, and it can be, for example, approximately 0 mm or more or approximately greater than 0 mm.

[0026] In some embodiments, the decorative films of the present disclosure exhibit opacity. Opacity can be evaluated by the color difference in the opacity test described later. In some embodiments, the decorative films of the present disclosure exhibit a color difference of less than about 12, less than or equal to about 10, less than or equal to about 8.0, less than or equal to about 6.0, less than or equal to about 4.0, less than or equal to about 2.0, or less than or equal to about 1.0. There is no particular limit to the lower limit of such color difference, and it can be, for example, about 0 or greater or greater than about 0.

[0027] In some embodiments, the decorative films of the present disclosure exhibit weather resistance. Weather resistance can be evaluated by color difference based on weather resistance tests described later. In some embodiments, the decorative films of the present disclosure exhibit 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 2,500 hours or 5,000 hours according to JIS K 5600-7-7:2008. There is no particular limit to the lower limit of such color difference, and it can be, for example, about 0 or more, greater 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 disclosed herein is achieved in the adhesive layer, not the polyurethane layer. Therefore, unlike the decorative film described in Patent Document 2, there is no need to color the polyurethane layer, which is difficult to color and to incorporate colorants at high concentrations, thus reducing the skill level of the worker and suppressing or preventing performance degradation of the decorative film as a whole. Because the decorative film disclosed herein does not require the separate use of a colored polyurethane layer, it can reduce costs compared to the decorative film described in Patent Document 2, and because it has portions where the transparent surface layer and the colored adhesive layer are directly applied, it can further reduce or prevent problems such as delamination that may occur with long-term use. The portions where the transparent surface layer and the colored adhesive layer are directly applied may, for example, have the colored adhesive layer 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 portion of the transparent surface layer. When a 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 on one side of the transparent surface layer in proportions of approximately 10% or more, approximately 20% or more, approximately 40% or more, approximately 50% or more, approximately 70% or more, approximately 80% or more, or approximately 90% or more, less than approximately 100%, approximately 95% or less, approximately 90% or less, approximately 80% or less, or approximately 70% or less.

[0029] The decorative film disclosed herein comprises a transparent surface layer containing a polyurethane resin or a cured product thereof. There are no particular restrictions on the polyurethane resin or cured product thereof, as long as the decorative film has a yield point. The polyurethane resin may contain a polyurethane elastomer, but from the viewpoint of enabling the decorative film to exhibit a yield point, the amount of polyurethane elastomer used is preferably about 10% by mass or less, about 5% by mass or less, or about 1% by mass or less, relative to the total amount of polyurethane resin, and it is more preferable not to use a polyurethane elastomer.

[0030] From the viewpoint of durability such as weather resistance, elongation characteristics, and yield strength, the transparent surface layer preferably contains a polyurethane resin having a weight-average molecular weight of about 50,000 to about 350,000 and an acid value of about 20.0 to about 30.0 mg·KOH / g, and more preferably contains a cured product of such polyurethane resin and a crosslinking agent.

[0031] The weight-average molecular weight of polyurethane can be approximately 50,000 or more, approximately 80,000 or more, approximately 100,000 or more, approximately 150,000 or more, approximately 200,000 or more, or approximately 250,000 or more, approximately 350,000 or less, approximately 320,000 or less, approximately 300,000 or less, or approximately 280,000 or less. Here, the weight-average molecular weight of polyurethane refers to the weight-average molecular weight measured after curing the polyurethane dispersion at 60°C for 3 hours. Such molecular weight can be adjusted, for example, by setting the ratio of diol to isocyanate. Since diol and isocyanate are linked alternately, increasing the molecular weight, high molecular weights can be obtained from around the range where the molecules actually contributing to the reaction in equivalent amounts are roughly equal, to the range where an excess of isocyanate is added. By further fine-tuning the formulation to increase the proportion of isocyanate groups remaining at both ends of the reacted prepolymer, the molecular weight increase by the chain extender is enhanced, resulting in a relatively higher molecular weight prepolymer. Other factors, such as temperature control during water dispersion, can also play a role. For example, keeping the temperature low prevents the reaction between isocyanate and water, ensuring high molecular weight increase by the chain extender. Typically, the prepolymer and diamine chain extender are linked alternately, leading to increased molecular weight. By blending the prepolymer and diamine chain extender in appropriate proportions so that neither is in excess, a high molecular weight polyurethane can be obtained.

[0032] The "weight-average molecular weight" in this disclosure can be measured by GPC (gel permeation chromatography). For example, the following conditions can be used as measurement conditions: Equipment: HP-1090 Series II (manufactured by Hewlett-Packard) Solvent: tetrahydrofuran Column: Plgel MIXED-Bx2 (300mm, outer diameter 7.5mm, inner diameter 5mm) Flow rate: 1.0 mL / min Detection means: refractive index Sample concentration: 0.1 wt% Calibration standard: Polystyrene

[0033] The acid value of polyurethane can be approximately 20.0 mg·KOH / g or higher, approximately 22.0 mg·KOH / g or higher, approximately 24.0 mg·KOH / g or higher, or approximately 25.0 mg·KOH / g or higher, approximately 30.0 mg·KOH / g or lower, approximately 29.0 mg·KOH / g or lower, approximately 28.5 mg·KOH / g or lower, approximately 28.0 mg·KOH / g or lower, or approximately 27.5 mg·KOH / g or lower. Here, "acid value" refers to the concentration of carbonyl groups obtained by titrating a polyurethane dispersion diluted in an organic solvent with a KOH-EtOH standard solution. The acid value can be controlled by the blending ratio of carbonyl group-containing diols in the diol. That is, a higher proportion of carbonyl group-containing diols can be obtained, resulting in a higher acid value.

[0034] In some embodiments, from the viewpoint of durability such as weather resistance, elongation properties, and yield strength, it is preferable to use a reaction product of a polyurethane prepolymer obtained by reacting a polycarbonate diol having an alicyclic structure, an aliphatic diol containing a carboxyl group, and an isocyanate containing 4,4'-cyclohexylmethane diisocyanate with a diamine chain extender as the polyurethane resin. Here, "polycarbonate diol" refers to a polymer chain linked via a carbonate bond that has one hydroxyl group at each end, and "polycarbonate diol having an alicyclic structure" refers to a polycarbonate diol that has one or more alicyclic structures within the molecule.

[0035] Examples of polycarbonate diols having an alicyclic structure include polycarbonate diols synthesized from 1,4-cyclohexanedimethanol and 1,6-hexanediol, specifically ETERNACOLL® UM90 manufactured by UBE Corporation (Minato-ku, Tokyo, Japan). Such polycarbonate diols can be used alone or in combination of two or more types.

[0036] Examples of aliphatic diols containing a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 3,3-dimethylolpropionic acid. Such aliphatic diols can be used individually or in combination of two or more.

[0037] In this disclosure, "isocyanate containing 4,4'-cyclohexylmethane diisocyanate" means an isocyanate containing 4,4'-cyclohexylmethane diisocyanate as an isocyanate component. There are no particular restrictions on the content of 4,4'-cyclohexylmethane diisocyanate contained in the isocyanate; for example, it may be about 30% by mass or more, about 40% by mass or more, or about 50% by mass or more, about 100% by mass or less, about 90% by mass or less, or about 80% by mass or less, relative to the total amount of the isocyanate.

[0038] Polyurethane prepolymers can be obtained by reacting polycarbonate diols having an alicyclic structure, aliphatic diols containing carboxyl groups, and isocyanates including 4,4'-cyclohexylmethane diisocyanate using known methods.

[0039] From the viewpoint of durability such as weather resistance, elongation characteristics, and yield strength, preferred combinations of diols and isocyanates constituting the polyurethane prepolymer include, for example, polycarbonate diols synthesized by transesterification of 1,4-cyclohexanedimethanol and 1,6-hexanediol with ethylene carbonate, 2,2-dimethylolpropionic acid as the diol, and 4,4'-cyclohexylmethanediisocyanate as the isocyanate.

[0040] Polyurethane resin can be obtained by reacting a polyurethane prepolymer with a diamine chain extender. The polyurethane resin may be linear or branched, but a linear configuration is preferred from the viewpoint of durability such as weather resistance, elongation properties, and yield point development. As the diamine chain extender, known diamine compounds such as ethylenediamine, propylenediamine, or putrescine can be used. The diamine chain extender can be used alone or in combination of two or more. There are no particular restrictions on the amount of diamine chain extender used, and it can be appropriately selected considering the desired performance (durability such as weather resistance, elongation properties, workability, etc.).

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

[0042] The transparent surface layer forming composition for forming a transparent surface layer may optionally contain other components, either alone or in combination of two or more, as long as they do not adversely affect the effects of the present disclosure. Examples of such optional components include conductive agents, thermal conductivity imparters, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dispersants, crosslinking agents, lubricants, pH adjusters, surfactants, leveling agents, silane coupling agents, catalysts, colorants, and solvents.

[0043] In some embodiments, the transparent surface layer of the present disclosure may contain colorants as described below, insofar as it exhibits transparency and does not adversely affect the effects of the present disclosure. A transparent surface layer exhibiting colorability can be formed, for example, by blending a colorant in an amount of about 5 parts by mass or less, about 3 parts by mass or less, or about 1 part by mass or less per 100 parts by mass of a resin component (polyurethane resin or its cured product). If the colorant content in the surface layer is in such proportions, such a surface layer can be formed without requiring a high level of skill from the worker.

[0044] In some embodiments, the transparent surface layer includes a cured product of the polyurethane resin and crosslinking agent described above. Since the transparent surface layer containing such a cured product is formed using a crosslinking agent, for example, if the colored adhesive layer described later is also prepared using a crosslinking agent, the crosslinking agents in both layers interact with each other, thereby improving the interlayer adhesion of the decorative film. Herein, in this disclosure, "cured product" is not limited to a reactant in which the reactive sites that can be crosslinked or polymerized have completely reacted, but may also include a reactant in which some of the reactive sites remain unreacted.

[0045] There are no particular restrictions on the crosslinking agent that can be used with the polyurethane resin. For example, conventionally known crosslinking agents that can react with the carboxyl group of an aliphatic diol containing a carboxyl group can be used. Specific examples include polycarbondiimide, aziridine, or oxazoline. The crosslinking agent can be used alone or in combination of two or more. There are no particular restrictions on the amount of crosslinking agent used, and it can be appropriately selected considering the desired performance (durability such as weather resistance, elongation characteristics, workability, etc.). For example, the amount of crosslinking agent (solid content) used can be approximately 0.1 parts by mass or more, approximately 0.5 parts by mass or more, approximately 1 part by mass or more, or approximately 5 parts by mass or more, approximately 20 parts by mass or less, approximately 15 parts by mass or less, or approximately 10 parts by mass or less per 100 parts by mass of polyurethane resin.

[0046] The transparent surface layer of this disclosure can be obtained, for example, by applying a transparent surface layer forming composition containing a polyurethane resin or the like to a release liner or the like (described later), followed by heat treatment and / or radiation (e.g., ultraviolet light) irradiation treatment. From the viewpoint of durability such as weather resistance, elongation characteristics, and yield point development, heat treatment is preferable. The components used in the transparent surface layer forming composition can be the same as the components that can be used in the transparent surface layer described above.

[0047] Heat treatment can be carried out using, for example, heating heaters such as infrared heaters, hot air, or ovens. Heat treatment can be carried out in batches or continuously using a belt conveyor, but from the viewpoint of productivity, it is preferable to carry it out continuously. The heating temperature (set temperature) can be, for example, approximately 70°C or higher, approximately 80°C or higher, or approximately 90°C or higher. There is no particular upper limit to the heating temperature, and it can be, for example, approximately 150°C or lower, approximately 130°C or lower, or approximately 100°C or lower.

[0048] The thickness of the transparent surface layer can be set appropriately considering the required performance (e.g., protective performance). For example, such a thickness can be approximately 1 micrometer or more, approximately 2 micrometers or more, or approximately 3 micrometers or more, and can be approximately 100 micrometers or less, approximately 70 micrometers or less, approximately 50 micrometers or less, approximately 40 micrometers or less, approximately 30 micrometers or less, approximately 20 micrometers or less, approximately 15 micrometers or less, or approximately 10 micrometers or less.

[0049] The decorative film disclosed herein comprises a colored adhesive layer (sometimes simply referred to as the "adhesive layer"). Such an adhesive layer may be a solvent-type, emulsion-type, pressure-sensitive, heat-sensitive, thermosetting, or UV-curing adhesive, such as those commonly used (meth)acrylic, polyolefin, polyurethane, or polyester adhesives. The adhesive layer can be applied by known coating methods or the like.

[0050] In some embodiments, the colored adhesive layer of the present disclosure comprises a carboxyl group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer as polymer components. Herein, "containing a carboxyl group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer" may include cured products of the carboxyl group-containing (meth)acrylic polymer, the amino group-containing (meth)acrylic polymer, and a crosslinking agent. Since the adhesive layer containing such cured products is formed using a crosslinking agent, it can interact with other crosslinking agents that may be used in the transparent surface layer, thereby improving the interlayer adhesion of the decorative film.

[0051] Carboxylate group-containing (meth)acrylic polymers can be obtained by copolymerizing a monoethylene unsaturated monomer with a carboxylate group-containing unsaturated monomer. Carboxylate group-containing (meth)acrylic polymers can also be referred to as "(meth)acrylic polymers containing constituent units derived from carboxylate group-containing monomers."

[0052] Monoethylenically unsaturated monomers are generally represented by the formula CH2=CR 1 COOR 2 (R in the formula 1 R is a hydrogen or methyl group, 2 In addition to (meth)acrylates represented by the formula CH2=CR (where CH2 is a linear, branched, or cyclic alkyl group, phenyl group, alkoxyalkyl group, phenoxyalkyl group, hydroxyalkyl group, or cyclic ether group), the formula also includes aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluene, vinyl esters such as vinyl acetate, and unsaturated nitriles such as acrylonitrile and methacrylonitrile. 1 COOR 2Examples of monoethylene unsaturated monomers represented by include linear alkyl(meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate, n-hexyl(meth)acrylate, n-decyl(meth)acrylate, and n-dodecyl(meth)acrylate; branched alkyl(meth)acrylates such as isoamyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, isooctyl(meth)acrylate, and isononyl(meth)acrylate; and alicyclic(meth)acrylates such as cyclohexyl(meth)acrylate and isobornyl(meth)acrylate. Examples include phenyl (meth)acrylate; alkoxyalkyl (meth)acrylates such as methoxypropyl (meth)acrylate and 2-methoxybutyl (meth)acrylate; phenoxyalkyl (meth)acrylates such as phenoxyethyl (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and cyclic ether-containing (meth)acrylates such as glycidyl (meth)acrylate and tetrahydrofurfuryl (meth)acrylate. Among these, n-butyl (meth)acrylate is preferred from the viewpoint of compatibility and conformability with the amino group-containing (meth)acrylic polymer and, if present, the third polymer, as described later. Monoethylene unsaturated monomers can be used alone or in combination of two or more. From the viewpoint of improving performance such as compatibility with the amino group-containing (meth)acrylic polymer and, if present, the third polymer, as described later, it is preferable that the carboxyl group-containing (meth)acrylic polymer contains the same or similar structural units as structural units derived from monoethylene unsaturated monomers constituting the amino group-containing (meth)acrylic polymer and / or the third polymer. In this disclosure, "same structural units" may refer to structural units composed of monomers having the same main skeleton, such as n-butyl acrylate and n-butyl methacrylate.

[0053] The proportion of constituent units derived from monoethylene unsaturated monomers in a carboxyl group-containing (meth)acrylic polymer can be, for example, about 85% by mass or more, about 90% by mass or more, or about 92% by mass or more, about 99.5% by mass or less, about 99% by mass or less, or about 98% by mass or less, relative to the carboxyl group-containing (meth)acrylic polymer.

[0054] Examples of carboxyl group-containing unsaturated monomers include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; unsaturated dicarboxylic acids such as itaconic acid, fumaric acid, citraconic acid, and maleic acid; ω-carboxypolycaprolactone monoacrylate, monohydroxyethyl (meth)acrylate phthalate, β-carboxyethyl acrylate, 2-(meth)acryloyloxyethyl succinic acid, and 2-(meth)acryloyloxyethyl hexahydrophthalic acid. Carboxyl group-containing unsaturated monomers can be used alone or in combination of two or more.

[0055] The proportion of constituent units derived from carboxyl group-containing unsaturated monomers can be approximately 0.5% by mass or more, approximately 1% by mass or more, or approximately 2% by mass or more, approximately 15% by mass or less, approximately 10% by mass or less, or approximately 8% by mass or less, relative to the carboxyl group-containing (meth)acrylic polymer.

[0056] The glass transition temperature of a carboxyl group-containing (meth)acrylic polymer can be less than approximately 0°C, less than or equal to approximately -5°C, less than or equal to approximately -10°C, less than or equal to approximately -20°C, less than or equal to approximately -30°C, less than or equal to approximately -40°C, or less than or equal to approximately -45°C, and can be above approximately -100°C, above approximately -80°C, above approximately -70°C, above approximately -65°C, above approximately -60°C, above approximately -55°C, or above approximately -50°C.

[0057] The weight-average molecular weight of the carboxyl group-containing (meth)acrylic polymer can be approximately 200,000 or more, approximately 300,000 or more, approximately 400,000 or more, approximately 500,000 or more, approximately 600,000 or more, or approximately 700,000 or more, and can be approximately 1,500,000 or less, approximately 1,000,000 or less, approximately 900,000 or less, approximately 800,000 or less, approximately 700,000 or less, or approximately 600,000 or less. The "glass transition temperature (Tg)" in this disclosure can be determined as the glass transition temperature calculated using the following FOX formula (Fox, TG, Bull. Am. Phys. Soc., 1 (1956), p. 123), assuming that each polymer is copolymerized from n types of monomers:

number

number

[0058] The weight-average molecular weight of the carboxyl group-containing (meth)acrylic polymer can be approximately 200,000 or more, approximately 300,000 or more, approximately 400,000 or more, approximately 500,000 or more, approximately 600,000 or more, or approximately 700,000 or more, and can be approximately 1,500,000 or less, approximately 1,000,000 or less, approximately 900,000 or less, approximately 800,000 or less, approximately 700,000 or less, or approximately 600,000 or less.

[0059] Amino group-containing (meth)acrylic polymers can be obtained by copolymerizing a monoethylene unsaturated monomer with an amino group-containing unsaturated monomer. Amino group-containing (meth)acrylic polymers can be referred to as "(meth)acrylic polymers containing constituent units derived from amino group-containing monomers."

[0060] Monoethylene unsaturated monomers can be used in the same way as the monoethylene unsaturated monomers in the carboxyl group-containing (meth)acrylic polymer described above. Among these, methyl (meth)acrylate and n-butyl (meth)acrylate are preferred from the viewpoint of compatibility and conformability with the carboxyl group-containing (meth)acrylic polymer described above. Monoethylene unsaturated monomers can be used alone or in combination of two or more. From the viewpoint of improving performance such as compatibility with the carboxyl group-containing (meth)acrylic polymer described above and, if present, a third polymer described later, it is preferable that the amino group-containing (meth)acrylic polymer contains the same or the same type of constituent units as those derived from the monoethylene unsaturated monomers constituting the carboxyl group-containing (meth)acrylic polymer and / or the third polymer.

[0061] The proportion of constituent units derived from monoethylene unsaturated monomers in the amino group-containing (meth)acrylic polymer can be, for example, about 85% by mass or more, about 90% by mass or more, or about 92% by mass or more, about 99.5% by mass or less, about 99% by mass or less, or about 98% by mass or less, relative to the amino group-containing (meth)acrylic polymer.

[0062] Examples of amino group-containing unsaturated monomers include dialkylaminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl acrylate (DMAEA) and N,N-dimethylaminoethyl methacrylate (DMAEMA); dialkylaminoalkyl (meth)acrylamides such as N,N-dimethylaminopropyl acrylamide (DMAPAA) and N,N-dimethylaminopropyl methacrylamide; dialkylaminoalkyl vinyl ethers such as N,N-dimethylaminoethyl vinyl ether and N,N-diethylaminoethyl vinyl ether; and monomers having tertiary amino groups, such as vinyl monomers having nitrogen-containing heterocycles, such as vinylimidazole. Amino group-containing unsaturated monomers can be used alone or in combination of two or more.

[0063] The proportion of constituent units derived from amino group-containing monomers can be approximately 0.5% by mass or more, approximately 1% by mass or more, or approximately 2% by mass or more, approximately 15% by mass or less, approximately 10% by mass or less, or approximately 8% by mass or less, relative to the amino group-containing (meth)acrylic polymer.

[0064] Carboxylate group-containing (meth)acrylic polymers and amino group-containing (meth)acrylic polymers can be prepared, for example, using radical polymerization, and can also be prepared using known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization. As initiators, for example, organic peroxides such as benzoyl peroxide, lauroyl peroxide, and bis(4-tert-butylcyclohexyl) peroxydicarbonate, and azo polymerization initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile) (AVN) can be used. The amount of initiator (solids) used can be, for example, about 0.01 parts by mass or more, or about 0.05 parts by mass or more, about 5 parts by mass or less, or about 3 parts by mass or less, per 100 parts by mass of the monomer mixture.

[0065] The colored adhesive layer of this disclosure typically contains a colorant. The colorant is not particularly limited; for example, conventionally known inorganic or organic pigments can be used. Such pigments may be surface-treated with silicon dioxide or aluminum oxide, etc. The colorants can be used alone or in combination of two or more.

[0066] Examples of inorganic pigments include white pigments such as zinc carbonate, zinc oxide, zinc sulfide, and titanium dioxide (titanium oxide); colored pigments such as black iron oxide, yellow iron oxide, red iron oxide, ultramarine, Prussian blue, cobalt blue, titanium yellow, turquoise, and molybdate orange; and carbon blacks such as furnace black, channel black, thermal black, and acetylene black.

[0067] Examples of organic pigments include CIPigment White 6, CIPigment Black 7, CIPigment Red 122, 202, 254, 255, CIPigment Orange 43, CIPigment Violet 19, 23, CIPigment Blue 15, 15:1, 15:2, 15:3, 15:4, CIPigment Brown 23, 25, CIPigment Yellow 74, 109, 110, 128, CIPigment Green 7, and 36.

[0068] The amount of coloring agent can be, for example, about 0.1% by mass or more, about 1% by mass or more, or about 5% by mass or more, about 55% by mass or less, about 50% by mass or less, about 20% by mass or less, or about 10% by mass or less, relative to the entire composition for forming the colored adhesive layer (solid content) or the colored adhesive layer.

[0069] In some embodiments, the colored adhesive layer of the present disclosure can be prepared using a colored adhesive layer-forming composition comprising a carboxyl 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 comprising a cured product of the carboxyl group-containing (meth)acrylic polymer, the amino group-containing (meth)acrylic polymer, and the crosslinking agent can have a crosslinked structure. Examples of crosslinking agents include thermal crosslinking agents and radiation crosslinking agents (e.g., ultraviolet crosslinking agents), and specifically, epoxy crosslinking agents, bisamide crosslinking agents, aziridine crosslinking agents, and carbodiimide crosslinking agents can be used. The crosslinking agents can be used alone or in combination of two or more.

[0070] Examples of epoxy crosslinking agents include N,N,N',N'-tetraglycidyl-1,3-benzenedi(methaneamine) (product name TETRAD-X (Mitsubishi Gas Chemical Co., Ltd., Chiyoda-ku, Tokyo, Japan), E-AX, E-5XM (Soken Chemical Co., Ltd., Toshima-ku, Tokyo, Japan)); and N,N'-(cyclohexane-1,3-diylbismethylene)bis(diglycidylamine) (product name TETRAD-C (Mitsubishi Gas Chemical Co., Ltd., Chiyoda-ku, Tokyo, Japan), E-5C (Soken Chemical Co., Ltd., Toshima-ku, Tokyo, Japan)). Examples of bisamide crosslinking agents include 1,1'-(1,3-phenylenedicarbonyl)bis(2-methylaziridine), 1,4-bis(ethyleneiminocarbonylamino)benzene, 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane, and 1,8-bis(ethyleneiminocarbonylamino)octane. Examples of aziridine crosslinking agents include Chemitite PZ33 (Nippon Shokubai Co., Ltd., Osaka, Japan) and NeoCryl CX-100 (DSM Coating Resins, LLC., Zwolle, Overijssel, Netherlands). Examples of carbodiimide crosslinking agents include Carbodilite V-03, V-05, and V-07 (Nisshinbo Chemical Co., Ltd., Chuo-ku, Tokyo, Japan).

[0071] The amount of crosslinking agent (solids) used may be about 0.01 parts by mass or more, about 0.05 parts by mass or more, or about 0.1 parts by mass or more, about 5 parts by mass or less, about 3 parts by mass or less, or about 2 parts by mass or less, per 100 parts by mass of carboxyl group-containing (meth)acrylic polymer (for example, a carboxyl group-containing (meth)acrylic polymer containing structural units derived from carboxyl group-containing monomers).

[0072] The adhesive layer can typically be formed by adjusting the blending ratio of carboxyl group-containing (meth)acrylic polymer and amino group-containing (meth)acrylic polymer. In one embodiment, the 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, about 1 part by mass or more, about 2 parts by mass or more, or about 3 parts by mass or more, per 100 parts by mass of the carboxyl group-containing (meth)acrylic polymer. An adhesive layer containing the amino group-containing (meth)acrylic polymer in such proportions can improve performance such as adhesive strength, heat shrinkage resistance, reworkability, and conformability.

[0073] The total content of carboxyl group-containing (meth)acrylic polymers, amino group-containing (meth)acrylic polymers, and, if present, a third polymer described later, in the adhesive layer or adhesive layer-forming composition (solid content) can be, for example, about 25% by mass or more, about 30% by mass or more, about 35% by mass or more, about 40% by mass or more, about 45% by mass or more, about 50% by mass or more, about 55% by mass or more, about 60% by mass or more, about 80% by mass or more, or about 90% by mass or more, 99.9% by mass or less, about 99% by mass or less, about 95% by mass or less, about 90% by mass or less, about 80% by mass or less, about 70% by mass or less, about 60% by mass or less, about 55% by mass or less, or about 50% by mass or less.

[0074] The adhesive layer-forming composition for forming an adhesive layer may optionally contain other components, either alone or in combination of two or more, as long as they do not adversely affect the effects of the present disclosure. Examples of such optional components include other resins other than the carboxyl group-containing (meth)acrylic polymer and amino group-containing (meth)acrylic polymer described above (e.g., thermoplastic resins, a third polymer described later), fillers, conductive agents, thermal conductivity imparters, crosslinking agents, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dispersants, lubricants, surfactants, leveling agents, silane coupling agents, catalysts, and solvents.

[0075] A composition for forming a colored adhesive layer can typically be produced by mixing the above-mentioned carboxyl group-containing (meth)acrylic polymer, amino group-containing (meth)acrylic polymer, colorant, and optionally other components (e.g., a crosslinking agent, a third polymer).

[0076] In some embodiments, it is preferable to produce a colored adhesive layer-forming composition by (1) mixing a colorant mixture with at least one polymer selected from the group consisting of amino group-containing (meth)acrylic polymers and a third polymer containing structural units derived from amide group-containing monomers, and mixing the colorant mixture with a mixture containing a carboxyl group-containing (meth)acrylic polymer and a crosslinking agent; or (2) mixing a colorant mixture with at least one polymer selected from the group consisting of amino group-containing (meth)acrylic polymers and a third polymer containing structural units derived from amide group-containing monomers, and mixing the colorant mixture with a carboxyl group-containing (meth)acrylic polymer. By producing the composition in this way, a colored adhesive layer-forming composition with excellent dispersibility of the colorant can be obtained.

[0077] In some embodiments, a polymer containing structural units derived from an amide group-containing monomer may be used as the third polymer. This third polymer containing structural units derived from an amide group-containing monomer can be obtained by copolymerizing an amide group-containing monomer with at least one selected from the group consisting of monoethylene unsaturated monomers and carboxyl group-containing unsaturated monomers as described above. From the viewpoint of dispersibility of colorants, vinyl acetate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred as monoethylene unsaturated monomers, and (meth)acrylic acid is preferred as the carboxyl group-containing unsaturated monomer. From the viewpoint of improving performance such as compatibility with the carboxyl group-containing (meth)acrylic polymer and amino group-containing (meth)acrylic polymer described above, it is preferable that the third polymer contains the same or the same type of structural units as those derived from the monoethylene unsaturated monomer constituting such carboxyl group-containing (meth)acrylic polymer and / or amino group-containing (meth)acrylic polymer.

[0078] Examples of amide group-containing monomers include N-vinylcaprolactam, N-vinylpyrrolidone, (meth)acrylamide, N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N-octyl(meth)acrylamide. Among these, (meth)acrylamide is preferred from the viewpoint of dispersibility of the colorant. The amide group-containing monomers can be used alone or in combination of two or more.

[0079] The proportion of constituent units derived from amide group-containing monomers can be approximately 0.01% by mass or more, approximately 0.05% by mass or more, or approximately 0.1% by mass or more, approximately 5% by mass or less, approximately 1% by mass or less, or approximately 0.5% by mass or less, relative to the third polymer.

[0080] In some embodiments, the proportion of the constituent units of the third polymer derived from the above-mentioned monoethylene unsaturated monomer can be, for example, about 85% by mass or more, about 90% by mass or more, or about 92% by mass or more, about 99.5% by mass or less, about 99% by mass or less, or about 98% by mass or less, relative to the third polymer.

[0081] In some embodiments, the proportion of the constituent units of the third polymer derived from the carboxyl group-containing unsaturated monomer described above can be about 0.5% by mass or more, about 1% by mass or more, or about 2% by mass or more, about 15% by mass or less, about 10% by mass or less, or about 8% by mass or less, relative to the third polymer.

[0082] When the composition for forming a colored adhesive layer and the colored adhesive layer formed from the composition contain a third polymer, in one embodiment, the 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, 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, per 100 parts by mass of the carboxyl group-containing (meth)acrylic polymer. A colored adhesive layer containing the third polymer in such proportions has excellent dispersibility of the colorant and can improve performance such as opacity.

[0083] The colored adhesive layer of this disclosure can be obtained, for example, by applying a composition for forming a colored adhesive layer, which includes a carboxyl group-containing (meth)acrylic polymer, an amino group-containing (meth)acrylic polymer, a colorant, and optionally an optional component (e.g., a crosslinking agent, a third polymer), to a release liner or the like, as described later, followed by heat treatment and / or radiation (e.g., ultraviolet light) irradiation. Here, the components used in the composition for forming the colored adhesive layer can be the same as the components that can be used in the colored adhesive layer described above.

[0084] The heat treatment can be carried out using, for example, a heating heater such as an infrared heater, hot air, an oven, etc. The heat treatment can be carried out batchwise or continuously using a belt conveyor or the like, but from the viewpoint of productivity, etc., it is preferably carried out continuously. As the heating temperature (set temperature), for example, it can be set to about 70°C or higher, about 80°C or higher, or about 90°C or higher. There is no particular limitation on the upper limit value of the heating temperature, and for example, it can be set to about 160°C or lower, about 140°C or lower, or about 120°C or lower.

[0085] As ultraviolet irradiation, which is a kind of radiation irradiation, for example, it can be carried out using a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp, or a UV-LED, etc. as a light source. The ultraviolet irradiation can be carried out batchwise or continuously using a belt conveyor or the like, but from the viewpoint of productivity, etc., it is preferably carried out continuously. As the irradiation dose of ultraviolet rays (UV-C), for example, it can be set to about 1 mJ / cm 2 or more, about 50 mJ / cm 2 or more, or about 100 mJ / cm 2 [[ID=,10]]or more. There is no particular limitation on the upper limit value of the irradiation dose of ultraviolet rays, but for example, it can be set to about 500 mJ / cm 2 or less or about 450 mJ / cm 2 or less.

[0086] The thickness of the colored adhesive layer of the present disclosure may be appropriately set in consideration of required performances (adhesive strength, coloring property, hiding property), etc. Such 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 film of the present disclosure optionally includes additional layers. Examples of such additional layers include decorative layers, bonding layers, and release liners. The additional layers can be used alone or in combination of two or more. When an additional layer (e.g., a decorative layer) is applied between the transparent surface layer and the colored adhesive layer, such additional layer is applied to only a portion of the transparent surface layer or the colored adhesive layer, rather than covering the entire surface. Metal thin film layers, such as those formed by vapor deposition, are preferably not used as additional layers because they may conceal the coloring performance of the colored adhesive layer.

[0088] Examples of decorative layers include pattern layers that impart patterns such as wood grain, stone pattern, geometric patterns, or leather patterns, as well as logos and illustrations to the object. The decorative layer may have a single-layer or multi-layer structure, and may be transparent, translucent, or opaque.

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

[0090] The decorative layer is not limited to the following, but may be, for example, a pattern such as a design, logo, or illustration applied directly to the transparent surface layer and / or colored adhesive layer using a printing method such as gravure direct printing, gravure offset printing, inkjet printing, laser printing, or screen printing. Alternatively, films, sheets, etc., having designs, logos, or illustrations formed by coatings such as gravure coat, roll coat, die coat, bar coat, or knife coat, as well as by die-cutting, etching, etc., may be used.

[0091] The materials used for the decorative layer include, but are not limited to, inorganic pigments such as carbon black, lead yellow, yellow iron oxide, red iron oxide, etc., phthalocyanine pigments such as phthalocyanine blue, phthalocyanine green, etc., organic pigments such as azolake pigments, indigo pigments, perinone pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments such as quinacridone red, etc., in which pigments are dispersed in a binder resin such as (meth)acrylic resin.

[0092] The decorative layer of the present disclosure may include, to the extent that it does not adversely affect the effects of the present disclosure, optional components such as fillers, reinforcing agents, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dispersants, flow enhancers, surfactants, leveling agents, silane coupling agents, and catalysts.

[0093] The thickness of the decorative layer is not particularly limited and can be adjusted as appropriate according to the required level of decoration. For example, such a thickness can be approximately 1 micrometer or more, approximately 3 micrometers or more, or approximately 5 micrometers or more, and approximately 50 micrometers or less, approximately 40 micrometers or less, or approximately 30 micrometers or less.

[0094] The decorative film disclosed herein may utilize a bonding layer (sometimes referred to as a "primer layer") to bond additional layers within the decorative film. Commonly used adhesives such as (meth)acrylic, polyolefin, polyurethane, and polyester adhesives, including solvent-based, emulsion-based, pressure-sensitive, heat-sensitive, thermosetting, or UV-curing types, can be used as the bonding layer. The bonding layer can be applied by known coating methods or the like.

[0095] The decorative films of the present disclosure typically have a release liner applied to the adhesive layer. Examples of release liners include paper; plastic materials such as polyethylene, polypropylene, polyester (e.g., PET), and cellulose acetate; and paper coated with such plastic materials. These liners may have a surface that has been treated with a release agent such as silicone.

[0096] The thickness of the release liner can generally be about 5 micrometers or more, about 15 micrometers or more, or about 25 micrometers or more, and can be about 500 micrometers or less, about 300 micrometers or less, about 100 micrometers or less, or about 50 micrometers or less.

[0097] The decorative film disclosed herein may be, for example, a sheet, a roll wound into a roll, or a three-dimensional object.

[0098] The following manufacturing method is described as an example, but the manufacturing method of the decorative film disclosed herein is not limited thereto.

[0099] For example, in the case of a decorative film comprising a release liner, a colored adhesive layer, and a transparent surface layer in that order, a composition for forming the transparent surface layer is coated onto the release liner, and drying and curing processes are applied as necessary to form the transparent surface layer. Subsequently, a composition for forming the colored adhesive layer is coated onto the release liner, and drying and curing processes are applied as necessary to form the adhesive layer. This adhesive layer is applied to the transparent surface layer, and the release liner on the transparent surface layer side is removed as necessary to form the decorative film.

[0100] In some embodiments, the decorative film of the present disclosure described above is disposed on a substrate via a colored adhesive layer, providing an article comprising the decorative film. A schematic cross-sectional view of an article according to one embodiment of the present disclosure is shown in Figure 4. Article 201 in Figure 4 is configured such that a decorative film 200 comprising a transparent surface layer 210 and a colored adhesive layer 220 is applied to a substrate 240 via the colored adhesive layer 220.

[0101] There are no particular restrictions on the material of the substrate to which the decorative film can be applied. Examples of such materials include resin materials (e.g., polyolefin resin, polyester resin, (meth)acrylic resin, polycarbonate resin, polyurethane resin, acrylonitrile-butadiene-styrene copolymer), inorganic materials (e.g., glass, ceramic, concrete, gypsum, calcium silicate, natural stone, asphalt), rubber materials, fabric materials (e.g., woven fabrics, knitted fabrics, nonwoven fabrics), metal or metal alloy materials (e.g., iron, aluminum, stainless steel), and wood-based materials including paper.

[0102] There are no particular restrictions on the shape or structure of the adherend; for example, it may be planar (e.g., film shape, plate shape), curved shape, irregular shape, or three-dimensional shape, and it may be a single-layer structure, a laminated structure, or a composite structure in which multiple members of different shapes or materials are combined.

[0103] The decorative film disclosed herein can be used for a variety of applications. Such applications include, for example, signs (e.g., internally illuminated signs and externally illuminated signs); signs (e.g., internally illuminated signs and externally illuminated signs); various interior or exterior parts, such as interior or exterior parts for vehicles such as automobiles, trains, aircraft, and ships (e.g., roof members, pillar members, door trim members, instrument panel members, front members such as hoods, bumper members, fender members, side sill members, and interior panel members); and interior or exterior parts for buildings (e.g., window glass, doors, sashes, roof members such as tiles, exterior wall members, wallpaper, etc.); electrical appliances such as personal computers, smartphones, mobile phones, refrigerators, and air conditioners; stationery; furniture; desks; and various containers such as cans. Because the decorative film disclosed herein has excellent durability, such as weather resistance, it can be suitably used for vehicles or buildings, and in particular suitably used for exteriors, more specifically for the exteriors of vehicles (e.g., automobiles) and the exteriors of buildings (e.g., exterior wall members, etc.).

[0104] There are no particular restrictions on the method of applying the decorative film of this disclosure to the adherend (support member) constituting the article, and known methods can be used as appropriate. Examples of such methods include direct application by hand, injection molding methods such as insert injection molding, in-mold molding, over-mold molding, two-color injection molding, core-back injection molding, and sandwich injection molding, lamination, and three-dimensional heat stretch molding (TOM). For example, decorative films formed using polyurethane elastomers are stretchable like rubber and therefore unsuitable for direct application by hand. The decorative film of this disclosure is designed with a transparent surface layer and a colored adhesive layer to have a yield point and does not exhibit the stretchable properties of rubber, so it can be suitably used for direct application. [Examples]

[0105] The following examples illustrate specific embodiments of the present disclosure, but the present invention is not limited thereto. All parts and percentages are by mass unless otherwise specified. Numerical values ​​include errors inherent to the measurement principle and measuring device. Numerical values ​​are shown with significant figures after normal rounding.

[0106] Table 1 shows the various materials used. In the table, "Mw" and "Tg" refer to "weight-average molecular weight" and "glass transition temperature," respectively. For the polymers AP1 (amino group-containing (meth)acrylic polymer), AP2 (third polymer), and ADH1 (carboxyl group-containing (meth)acrylic polymer), polymerizable compositions were prepared by mixing each monomer component, chain transfer agent (isooctyl thioglycolate, etc.), polymerization initiator (2,2'-azobis(2,4-dimethylvaleronitrile), etc.), and solvent (ethyl acetate, etc.) so that the mass ratio of constituent units derived from the monomers listed in the table (e.g., MMA (methyl methacrylate), BA (n-butyl acrylate), AA (acrylic acid)) was such that polymerizable compositions were prepared by polymerizing these compositions using conventional polymerization methods.

[0107] [Table 1]

[0108] Table 2 shows the colorant mixtures used when preparing colored adhesive layer-forming compositions containing colorants, and Table 3 shows the amount (parts by mass) of each component in the colored adhesive layer-forming compositions prepared using such colorant mixtures. Here, the amounts of each component in Table 3 are based on the non-volatile content.

[0109] [Table 2]

[0110] [Table 3]

[0111] Example 1 A composition for forming a transparent surface layer was prepared by mixing PU1 and CL2 so that their solid content weight ratio was 100:16. The composition for forming a transparent surface layer was coated onto a 50-micrometer thick polyester backing film coated with a release layer using a knife coater. The coated layer was dried at 95°C for 5 minutes to obtain a 30-micrometer thick polyurethane resin transparent surface layer.

[0112] The CA1 colored adhesive layer-forming composition was coated onto a release liner (L1) using a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain a 25-micrometer thick colored adhesive layer. After laminating this adhesive layer onto a transparent surface layer, the backing film on the transparent surface layer side was peeled off to obtain the decorative film of Example 1.

[0113] Example 2 The decorative film of Example 2 was obtained in the same manner as in Example 1, except that CA1 in the colored adhesive layer forming composition was changed to CA2.

[0114] Example 3 The decorative film of Example 3 was obtained in the same manner as in Example 1, except that PU1 in the transparent surface layer forming composition was changed to PU2.

[0115] Example 4 The decorative film of Example 4 was obtained in the same manner as in Example 2, except that PU1 in the transparent surface layer forming composition was changed to PU2.

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

[0117] Comparative Example 2 A decorative film for 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 3 A decorative film for 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 4 A decorative film for 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 Test Each test sample obtained was evaluated according to the following test method. The results are shown in Table 4.

[0121] Yield point evaluation test Test specimens were prepared by cutting the test sample into pieces 25 mm wide and 150 mm long. The tensile strength and elongation of the test specimens were measured using a Tensilon universal material testing machine (manufactured by A&D Company, Limited (Toshima-ku, Tokyo, Japan)) in an atmosphere of 20°C. The air jaw speed was set to 300 mm per minute, and the air jaw spacing was 100 mm. The yield point was determined from the graphs of elongation (x axis) and tensile strength (y axis). Table 4 shows the tensile strength values ​​at the location where the yield point was confirmed, as shown in Figure 1.

[0122] Opacity test Test specimens were prepared by cutting the test sample into 100mm x 50mm squares. These specimens were attached to "Opacity Chart Paper" (zebra pattern). A spectrophotometer (CM-3700d, manufactured by Konica Minolta, Inc. (Chiyoda-ku, Tokyo, Japan)) was used to measure L in the white and black regions. * a * and b * The value of the white area was measured. * a1 * , b1 * The value of the black area is L2 * a2 * , b2 * The color difference (ΔE) was calculated using the following equation 1:

number

[0123] Adhesion strength test 1A: Adhesion strength to painted board Test specimens were prepared by cutting the test sample into pieces 25 mm wide and 150 mm long. In accordance with JIS Z 0237 8.2.3, the test specimens were applied to a melamine-coated board (manufactured by Paltec Co., Ltd., Hiratsuka City, Kanagawa Prefecture, Japan) in an atmosphere of 20°C. After leaving the test specimens at 20°C for 48 hours, the 180-degree peel force of the test specimens was measured using a Tensilon universal material tester (manufactured by A&D Company, Limited, Toshima-ku, Tokyo, Japan). The air jaw speed was set to 300 mm per minute.

[0124] Adhesion strength test 1B: Adhesion strength to painted board after aging at 65°C Test specimens were prepared by cutting the test sample into pieces 25 mm wide and 150 mm long. In accordance with JIS Z 0237 8.2.3, the test specimens were applied to a melamine-coated board (manufactured by Paltec Co., Ltd., Hiratsuka City, Kanagawa Prefecture, Japan) in an atmosphere of 20°C. After leaving the test specimens at 65°C for 7 days, the 180-degree peel force of the test specimens was measured using a Tensilon universal material testing machine (manufactured by A&D Company, Limited, Toshima-ku, Tokyo, Japan). The air jaw speed was set to 300 mm per minute.

[0125] Adhesion strength test 2A: Adhesion strength to aluminum plate Test specimens were prepared by cutting the test sample into pieces 25 mm wide and 150 mm long. The specimens were applied to an aluminum plate in an atmosphere of 20°C, according to JIS Z 0237 8.2.3. After leaving the specimens at 20°C for 48 hours, the 180-degree peel force of the specimens was measured using a Tensilon universal material testing machine (manufactured by A&D Company, Limited (Toshima-ku, Tokyo, Japan)). The air jaw speed was set to 300 mm per minute.

[0126] Adhesion strength test 2B: Adhesion strength to aluminum plate after aging at 65°C Test specimens were prepared by cutting the test sample into pieces 25 mm wide and 150 mm long. The specimens were applied to an aluminum plate in an atmosphere of 20°C, according to JIS Z 0237 8.2.3. After leaving the specimens at 65°C for 7 days, the 180-degree peel force of the specimens was measured using a Tensilon universal material testing machine (manufactured by A&D Company, Limited (Toshima-ku, Tokyo, Japan)). The air jaw speed was set to 300 mm per minute.

[0127] Heat shrinkage test Test specimens were prepared by cutting the test sample into pieces 50 mm wide and 100 mm long. These specimens were mounted on an aluminum plate and left at 23°C for 24 hours, after which the specimens were cut in a cross shape. These specimens were then left at 65°C for 48 hours. After thermal aging, the maximum width of the cut opening (mouth opening) was measured under a microscope.

[0128] Breaking strength test Test specimens were prepared by cutting the test sample into pieces 25 mm wide and 150 mm long. The fracture strength of the test specimens was measured in an atmosphere of 20°C using a Tensilon universal material testing machine (manufactured by A&D Company, Limited (Toshima-ku, Tokyo, Japan)). The air jaw speed was set to 300 mm per minute, and the air jaw spacing was set to 100 mm.

[0129] Elongation test Test specimens were prepared by cutting the test sample into pieces 25 mm wide and 150 mm long. The elongation of the test specimens was measured using a Tensilon universal material testing machine (manufactured by A&D Company, Limited (Toshima-ku, Tokyo, Japan)) in an atmosphere of 20°C. The air jaw speed was set to 300 mm per minute, and the air jaw spacing was set to 100 mm.

[0130] Tensile strength test Test specimens were prepared by cutting the test sample into pieces 25 mm wide and 150 mm long. The tensile force and elongation of the test specimens were measured using a Tensilon universal material testing machine (manufactured by A&D Company, Limited (Toshima-ku, Tokyo, Japan)) in an atmosphere of 20°C. The air jaw speed was set to 300 mm per minute, and the air jaw spacing was set to 100 mm. The tensile force at 2% elongation was recorded as the tensile strength (2% tensile strength).

[0131] Weather resistance test Test specimens were prepared by cutting the test sample into pieces 70 mm wide and 40 mm long, and these specimens were mounted on a 1.5 mm thick aluminum plate. After mounting, the specimens were exposed in an Atlas Xenon Ci5000 Weather-Ometer (trademark) in accordance with JIS K 5600-7-7:2008.

[0132] Using a spectrophotometer (CM-3700d, manufactured by Konica Minolta, Inc. (Chiyoda-ku, Tokyo, Japan)), L was measured initially (before exposure) and after 2,500 hours or 5,000 hours of exposure. * a * and b * The value of the initial test specimen was measured. * a1 * , b1 * The value of the test specimen after 2,500 hours or 5,000 hours of exposure is L2 * a2 * , b2 * The color difference (ΔE) was calculated using the following formula 1, similar to the opacity test described above:

number

[0133] [Table 4]

[0134] It will be apparent to those skilled in the art that the above embodiments and examples can be modified in various ways without departing from the basic principles of the present invention. Furthermore, it will be apparent to those skilled in the art that various improvements and modifications of the present invention can be implemented without departing from the spirit and scope of the invention. [Explanation of Symbols]

[0135] 100, 200 decorative film 110, 210 transparent surface layer 120, 220 colored adhesive layer 201 Goods 240 Adherent

[0136] Some embodiments of this disclosure are described in the following sections [1]-[8]. [Item 1] A decorative film comprising a transparent surface layer and a colored adhesive layer, The transparent surface layer comprises a polyurethane resin or a cured product thereof. The decorative film has portions to which the transparent surface layer and the colored adhesive layer are directly applied, and has a yield point. Decorative film. [Item 2] The decorative film according to item 1, wherein the transparent surface layer comprises a polyurethane resin having a weight-average molecular weight of 50,000 to 350,000 and an acid value of 20.0 to 30.0 mg·KOH / g, or a cured product thereof. [Item 3] The decorative film according to item 1 or 2, wherein the polyurethane resin is a reaction product of a polyurethane prepolymer obtained by reacting a polycarbonate diol having an alicyclic structure, an aliphatic diol containing a carboxyl group, and an isocyanate containing 4,4'-cyclohexylmethane diisocyanate with a diamine chain extender. [Item 4] The decorative film according to any one of items 1 to 3, wherein the colored adhesive layer comprises a carboxyl group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer. [Item 5] The decorative film described in any one of items 1 to 4, wherein the 2% tensile strength of the decorative film is 5 N / 25 mm or more. [Item 6] A decorative film intended for direct application, as described in one of items 1 through 5. [Item 7] A decorative film for architectural use, as described in any one of items 1 through 6. [Item 8] An article in which a decorative film described in any one of items 1 to 7 is placed on a substrate via the colored adhesive layer.

Claims

1. A decorative film comprising a transparent surface layer and a colored adhesive layer, The transparent surface layer comprises a polyurethane resin or a cured product thereof. The decorative film has portions to which the transparent surface layer and the colored adhesive layer are directly applied, and has a yield point. Decorative film.

2. The decorative film according to claim 1, wherein the transparent surface layer comprises a polyurethane resin having a weight-average molecular weight of 50,000 to 350,000 and an acid value of 20.0 to 30.0 mg・KOH / g, or a cured product thereof.

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

4. The decorative film according to any one of claims 1 to 3, wherein the colored adhesive layer comprises a carboxyl 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 2% tensile strength of the decorative film is 5 N / 25 mm or more.

6. A decorative film according to any one of claims 1 to 3, for direct application.

7. A decorative film for architectural use, according to any one of claims 1 to 3.

8. An article in which a decorative film according to any one of claims 1 to 3 is disposed on a substrate via the colored adhesive layer.

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