Decorative film

Abstract

To provide a decorative film that offers excellent performance in solvent resistance, elongation, and conformability without using fluororesin in the surface layer. [Solution] A decorative film according to one embodiment of the present disclosure comprises a cover layer and a coloring layer, the cover layer comprising a cured product of (meth)acrylic polyol and hexamethylene diisocyanate, and the coloring layer comprising a (meth)acrylic polymer having a glass transition temperature of less than about 0°C, a (meth)acrylic polymer having a glass transition temperature of about 0°C or higher, and a colorant.

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. 2021-035724) describes a decorative film having at least a base film layer containing a plasticizer and a top layer containing a fluorine-containing polymer, wherein the top layer is disposed on one surface, and the fluorine-containing polymer contains units based on fluoroolefins and units based on vinyl esters, and the content of units based on vinyl esters is 5 to 70 mol% of the total units contained in the fluorine-containing polymer.

[0004] Patent Document 2 (Japanese Patent Publication No. 2019-177662) describes a decorative sheet used in three-dimensional molding, comprising at least a base sheet and a surface protective layer, wherein the surface protective layer is a cured product of a resin composition containing a fluororesin and a curing agent, and has a Martens hardness of 130 N / mm². 2 A decorative sheet is described below, wherein the gel fraction relative to methyl ethyl ketone is 80% or more and 100% or less. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2021-035724 [Patent Document 2] Japanese Patent Publication No. 2019-177662 [Overview of the project] [Problems that the invention aims to solve]

[0006] As described in Patent Documents 1 and 2, fluororesin was used in the surface layer of decorative films to impart properties such as solvent resistance.

[0007] This disclosure provides a decorative film that exhibits excellent properties such as solvent resistance, elongation, and conformability without using fluororesin in the surface layer. [Means for solving the problem]

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

[0009] According to another embodiment of the present disclosure, an article is provided in which the decorative film includes an adhesive layer and is disposed on a substrate via the adhesive layer. [Effects of the Invention]

[0010] According to this disclosure, a decorative film with excellent properties such as solvent resistance, elongation, and conformability can be provided without using fluororesin in the surface layer.

[0011] The foregoing description shall not be deemed to disclose all embodiments of the present invention and all advantages relating to the present invention. [Brief explanation of the drawing]

[0012] [Figure 1] This is a schematic cross-sectional view of a decorative film according to one embodiment of the present disclosure. [Figure 2] This is a schematic cross-sectional view of an article according to one 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, the "above" in "the adhesive layer disposed above the release liner" means that the adhesive layer is directly disposed above the release liner, or the adhesive layer is indirectly disposed above the release liner through another layer.

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

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

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

[0018] In the present disclosure, "film" includes a member called "sheet".

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

[0020] Figure 1 shows a schematic cross-sectional view of a decorative film according to one embodiment of the present disclosure. The decorative film 100 in Figure 1 includes a cover layer 110, a coloring layer 120, an adhesive layer 130, and a release liner 140. Here, the adhesive layer and release liner shown in Figure 1 are arbitrary layers, and the decorative film of the present disclosure may not include the adhesive layer and the release liner. In addition, the decorative film of the present disclosure may include any other layer (for example, a decorative layer) as described later.

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

[0022] In some embodiments, the decorative films of the present disclosure exhibit elongation properties. 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 20% or more, about 40% or more, about 60% or more, about 80% or more, or about 100% or more, about 500% or less, about 400% or less, about 300% or less, about 200% or less, or about 160% or less, and can exhibit 2% tensile strengths of about 1 N / 25 mm or more, about 2 N / 25 mm or more, about 3 N / 25 mm or more, about 4 N / 25 mm or more, or about 5 N / 25 mm or more, about 30 N / 25 mm or less, about 20 N / 25 mm or less, or about 10 N / 25 mm or less.

[0023] In some embodiments, the decorative films of the present disclosure exhibit conformability and can reduce or suppress lifting and peeling from the substrate over time when the film is applied to the uneven surface of an uneven substrate. This performance can be evaluated by the gloss retention rate in the gloss retention evaluation test described later. In some embodiments, the decorative films of the present disclosure may exhibit gloss retention rates of less than about 400%, less than or equal to 300%, less than or equal to 200%, or less than or equal to 150%. In such tests, if lifting and peeling occur in the film applied to an uneven surface, the smoothness of the film surface increases, and as a result, the gloss value of the film surface increases, resulting in a higher gloss retention rate. Therefore, in such tests, unlike the general gloss retention rate after curing for a film applied to the smooth surface of a smooth substrate, the upper limit of the gloss retention rate is adopted as an indicator of the effect of reducing or suppressing lifting and peeling of the decorative film.

[0024] 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.

[0025] 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 20, less than or equal to about 15, 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, or less than or equal to about 2.0. There is no particular limit to the lower limit of such color difference, and it can be, for example, about 0 or more or greater than about 0.

[0026] The decorative films of this disclosure include a cover layer comprising a cured (meth)acrylic polyol and hexamethylene diisocyanate (HDI). Because the decorative films of this disclosure include a specific cover layer, the properties of the decorative film, such as solvent resistance, elongation, and conformability, can be improved. In some embodiments, the cover layer of this disclosure also has elongation properties, so a decorative film having such a cover layer can exhibit surface conformability that is applicable even to rough surfaces such as walls. In this disclosure, "cover layer" means a layer that is located on and covers at least a colored layer. 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.

[0027] (Meth)acrylic polyols can react with hexamethylene diisocyanate to form polyurethane resins. Such reactions are preferably thermosetting reactions from the viewpoint of solvent resistance, elongation, and conformability. Here, "polyol" in this disclosure refers to a compound having two or more hydroxyl groups. The number of hydroxyl groups per molecule of (meth)acrylic polyol can be two or more, and can be five or fewer, or three or fewer. From the viewpoint of solvent resistance, elongation, and conformability, it is preferable that the number of hydroxyl groups per molecule of (meth)acrylic polyol is two, that is, that it is a (meth)acrylic diol. (Meth)acrylic polyols can be used alone or in combination of two or more types.

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

[0029] The weight-average molecular weight of the (meth)acrylic polyol is preferably about 10,000 or more, about 20,000 or more, about 30,000 or more, about 40,000 or more, or about 50,000 or more, about 200,000 or less, about 150,000 or less, about 100,000 or less, or about 80,000 or less, from the viewpoint of solvent resistance, elongation, conformability, etc. The "weight-average molecular weight" in this disclosure can be measured by the GPC method (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

[0030] The glass transition temperature of (meth)acrylic polyols is preferably about 0°C or higher, about 10°C or higher, about 20°C or higher, or about 30°C or higher, about 100°C or lower, about 80°C or lower, about 60°C or lower, or about 50°C or lower, from the viewpoint of solvent resistance, elongation, conformability, etc. 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

[0031] The cover layer can be prepared using a cover layer forming composition containing (meth)acrylic polyol and hexamethylene diisocyanate. The proportion of (meth)acrylic polyol or (meth)acrylic polyol-derived parts in the cover layer forming composition (solids) or the cover 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, or about 55% by mass or more, about 70% by mass or less, about 65% by mass or less, or about 60% by mass or less.

[0032] Hexamethylene diisocyanate tends to result in a harder cover layer compared to, for example, isophorone diisocyanate. Despite using such a hard cover layer, the decorative film disclosed herein can improve conformability to rough surfaces and other unevenness due to the presence of a specific colored layer. Since hexamethylene diisocyanate is typically a non-yellowing aliphatic isocyanate, it can also improve the durability of the cover layer, such as weather resistance.

[0033] Hexamethylene diisocyanate may be in the form of biuret, isocyanurate, or adduct. From the viewpoint of elongation properties and conformability to uneven surfaces, the adduct form is preferred.

[0034] The proportion of hexamethylene diisocyanate or hexamethylene diisocyanate-derived parts in the cover layer-forming composition (solid content) or the cover layer can be approximately 15% by mass or more, approximately 20% by mass or more, approximately 25% by mass or more, approximately 30% by mass or more, or approximately 35% by mass or more, approximately 50% by mass or less, approximately 45% by mass or less, or approximately 40% by mass or less.

[0035] The thickness of the cover layer should be set appropriately considering the required performance (e.g., protective performance). For example, the thickness can be approximately 1 micrometer or more, approximately 2 micrometers or more, or approximately 3 micrometers or more, and approximately 20 micrometers or less, approximately 15 micrometers or less, or approximately 10 micrometers or less.

[0036] In some embodiments, the cover layer of this disclosure exhibits a 60-degree surface gloss of approximately 5.0 or less, approximately 4.5 or less, or approximately 4.0 or less in a 60-degree surface gloss test after application to an aluminum plate or rough surface, as described later. There is no particular limit to the lower limit of such gloss, and it can be 0 or greater or greater than 0. Cover layers with a gloss of about 20 generally exhibit low gloss (matte finish). However, when a decorative film equipped with such a cover layer is applied to a rough surface, the gloss of the decorative film may increase locally, potentially causing an appearance defect. The inventors have found that by setting the gloss of the cover layer to approximately 5.0 or less (i.e., making it super matte), the occurrence of such appearance defects can be reduced or prevented even when the decorative film is applied to a rough surface.

[0037] A cover layer exhibiting such gloss can be formed, for example, by a matte finish treatment. For instance, by applying a material containing a high concentration of filler to a release liner to form a rough surface based on the filler on the liner, and then applying a cover layer forming composition to this rough surface, an uneven surface (matte finish) can be formed on the surface of the cover layer. Unlike a cover layer with an uneven surface created by incorporating filler, a cover layer prepared by this method does not contain filler or contains only a small amount of filler, thus not reducing the performance of the cover layer, and also reducing or preventing problems such as filler shedding. The filler content in a cover layer prepared by this method can be about 10% by mass or less, about 5% by mass or less, about 1% by mass or less, or about 0.1% by mass or less, or the cover layer may not contain any filler at all.

[0038] The cover layer-forming composition for forming the cover 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, lubricants, surfactants, leveling agents, silane coupling agents, catalysts, pigments, dyes, and solvents.

[0039] The cover layer of this disclosure can be obtained, for example, by applying a cover layer-forming composition containing (meth)acrylic polyol and hexamethylene diisocyanate to a colored layer or release liner described later, followed by heat treatment and / or radiation (e.g., ultraviolet light) irradiation. From the viewpoint of solvent resistance, elongation, conformability, etc., the reaction between (meth)acrylic polyol and hexamethylene diisocyanate is preferably a thermosetting reaction, and therefore heat treatment is preferred. The components used in the cover layer-forming composition can be the same as the components that can be used in the cover layer described above.

[0040] 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, approximately 90°C or higher, or approximately 100°C or higher. There is no particular upper limit to the heating temperature, and it can be, for example, approximately 165°C or lower, approximately 160°C or lower, or approximately 155°C or lower.

[0041] The decorative film disclosed herein comprises a colored layer containing a (meth)acrylic polymer having a glass transition temperature of less than approximately 0°C, a (meth)acrylic polymer having a glass transition temperature of approximately 0°C or higher, and a coloring agent. Because the colored layer of this disclosure uses these two types of (meth)acrylic polymers, the flexibility of the colored layer can be adjusted without using a plasticizer, as is the case with polyvinyl chloride resin. Here, the "colored layer containing a (meth)acrylic polymer having a glass transition temperature of less than approximately 0°C, a (meth)acrylic polymer having a glass transition temperature of approximately 0°C or higher, and a coloring agent" of this disclosure may include a colored layer containing a cured product of a (meth)acrylic polymer having a glass transition temperature of less than approximately 0°C, a (meth)acrylic polymer having a glass transition temperature of approximately 0°C or higher, and a crosslinking agent, and a coloring agent. Since such a colored layer containing a cured product is formed using a crosslinking agent, it can interact with hexamethylene diisocyanate or other crosslinking agents in the cover layer and / or the adhesive layer described later, thereby improving the interlayer adhesion of the decorative film. The colored layer of this disclosure may also function as a substrate for supporting the cover layer and the like. If the decorative film of the present disclosure comprises a cover layer and an adhesive layer, the colored layer may function as an intermediate layer (e.g., an intermediate film layer). As described later, if the adhesive layer contains a (meth)acrylic polymer with a glass transition temperature of less than approximately 0°C, a (meth)acrylic polymer with a glass transition temperature of approximately 0°C or higher, and a coloring agent, such a colored adhesive layer can also be considered as a colored layer. The colored layer of the present disclosure may be a single layer or a laminated structure of two or more layers.

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

[0043] The weight-average molecular weight of the low-Tg polymer can be about 200,000 or more, about 300,000 or more, about 400,000 or more, about 500,000 or more, about 600,000 or more, or about 700,000 or more, and can be about 1,500,000 or less, about 1,000,000 or less, about 900,000 or less, about 800,000 or less, about 700,000 or less, or about 600,000 or less.

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

[0045] The monoethylenically unsaturated monomer generally has the formula CH2=CR 1 COOR 2 (where R 1 is hydrogen or a methyl group, and R 2 is a linear, branched, or cyclic alkyl group, a phenyl group, an alkoxyalkyl group, a phenoxyalkyl group, a hydroxyalkyl group, or a cyclic ether group), in addition to (meth)acrylates represented by the formula, aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, vinyl esters such as vinyl acetate, and unsaturated nitriles such as acrylonitrile and methacrylonitrile are also included. The formula CH2=CR 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 (meth)acrylic polymers with a glass transition temperature of about 0°C or higher, and, if present, with a third polymer, as described later. Monoethylene unsaturated monomers can be used alone or in combination of two or more. From the viewpoint of improving compatibility and other properties with (meth)acrylic polymers having a glass transition temperature of approximately 0°C or higher, and, if present, with a third polymer, it is preferable that the low-Tg polymer contains the same or similar structural units as those derived from monoethylene unsaturated monomers constituting the (meth)acrylic polymers having a glass transition temperature of approximately 0°C or higher 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.

[0046] The proportion of constituent units derived from monoethylene unsaturated monomers in a low-Tg 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 low-Tg polymer.

[0047] 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.

[0048] 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 low Tg polymer.

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

[0050] The weight-average molecular weight of high-Tg polymers can be approximately 30,000 or more, approximately 35,000 or more, approximately 40,000 or more, approximately 45,000 or more, approximately 50,000 or more, approximately 55,000 or more, or approximately 60,000 or more, and can be approximately 100,000 or less, approximately 90,000 or less, approximately 85,000 or less, approximately 80,000 or less, or approximately 75,000 or less.

[0051] In some embodiments, the (meth)acrylic polymers of the present disclosure having a glass transition temperature of about 0°C or higher can be obtained by copolymerizing a monoethylene unsaturated monomer with an amino group-containing unsaturated monomer. Such polymers may be referred to as "amino group-containing (meth)acrylic polymers" or "(meth)acrylic polymers containing constituent units derived from amino group-containing monomers."

[0052] Monoethylene unsaturated monomers can be used in the same way as those used in the low-Tg polymer described above. Among these, methyl (meth)acrylate, ethyl (meth)acrylate, and n-butyl (meth)acrylate are preferred from the viewpoint of compatibility, conformability, and strength with the low-Tg 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 low-Tg polymer described above and, if present, a third polymer described later, it is preferable that the high-Tg polymer contains the same or the same type of constituent units as those derived from the monoethylene unsaturated monomers constituting the low-Tg polymer and / or the third polymer.

[0053] The proportion of constituent units derived from monoethylene unsaturated monomers in the high-Tg 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 high-Tg polymer.

[0054] 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.

[0055] 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 high Tg polymer.

[0056] Low-Tg polymers and high-Tg 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.

[0057] In some embodiments, the colored layer of the present disclosure can be prepared using a colored layer-forming composition comprising a low-Tg polymer, a high-Tg polymer, a crosslinking agent, and a colorant. By using a composition containing a crosslinking agent, the colored layer comprising a cured product of the low-Tg polymer, the high-Tg 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.

[0058] 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).

[0059] 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 low Tg polymer (for example, low Tg polymer containing structural units derived from carboxyl group monomers).

[0060] By changing the blending ratio of low-Tg polymers and high-Tg polymers, desired properties (e.g., flexibility, conformability) can be imparted to the decorative film. In one embodiment, the content of low-Tg polymers can be about 25 parts by mass or more, about 50 parts by mass or more, about 80 parts by mass or more, about 100 parts by mass or more, or more than about 100 parts by mass, and about 400 parts by mass or less, about 300 parts by mass or less, about 200 parts by mass or less, or about 150 parts by mass or less, per 100 parts by mass of high-Tg polymer.

[0061] The total content of low-Tg polymers, high-Tg polymers, and, if present, a third polymer described later, in the colored layer or colored 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.

[0062] There are no particular restrictions on the colorants that can be incorporated into the colored layer; 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.

[0063] 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.

[0064] 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.

[0065] 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 coloring layer-forming composition (solid content) or the entire coloring layer.

[0066] The colored layer-forming composition for forming a colored 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 besides the low-Tg polymer and high-Tg polymer described above (e.g., thermoplastic resins, a third polymer described later), fillers, conductive agents, thermal conductivity imparters, antioxidants, ultraviolet absorbers, crosslinking agents, light stabilizers, heat stabilizers, dispersants, lubricants, surfactants, leveling agents, silane coupling agents, catalysts, and solvents.

[0067] A colored layer-forming composition can typically be produced by mixing the low-Tg polymer, high-Tg polymer, colorant, and optionally other components (e.g., a crosslinking agent, a third polymer) as described above.

[0068] In some embodiments, it is preferable to produce a colored layer-forming composition by (1) mixing a colorant mixture with at least one polymer selected from the group consisting of a high Tg polymer and a third polymer containing structural units derived from an amide group monomer, and a colorant, and then mixing the colorant mixture with a mixture containing a low Tg polymer and a crosslinking agent; or (2) mixing a colorant mixture with at least one polymer selected from the group consisting of a high Tg polymer and a third polymer containing structural units derived from an amide group, and a crosslinking agent and a colorant, and then mixing the colorant mixture with a low Tg polymer. By producing the composition in this way, a colored layer-forming composition with excellent dispersibility of the colorant can be obtained.

[0069] 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 low-Tg polymer and high-Tg 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 low-Tg polymer and / or high-Tg polymer.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] When the colored layer-forming composition and the colored 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 low-Tg polymer. A colored layer containing the third polymer in such proportions has excellent dispersibility of the colorant and can improve performance such as opacity.

[0075] The colored layer of this disclosure can be obtained, for example, by applying a colored layer-forming composition, which includes a low-Tg polymer, a high-Tg 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 colored layer-forming composition can be the same as the components that can be used in the colored layer described above.

[0076] 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 160°C or lower, approximately 140°C or lower, or approximately 120°C or lower.

[0077] Ultraviolet irradiation, a type of radiation irradiation, can be carried out using light sources such as low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, electrodeless lamps, or UV-LEDs. Ultraviolet irradiation can be performed in batches or continuously using a conveyor belt, but from the viewpoint of productivity, continuous irradiation is preferable. The irradiation dose of ultraviolet light (UV-C) is, for example, about 1 mJ / cm². 2 Above, about 50mJ / cm 2 Above, or approximately 100 mJ / cm² 2 The above is acceptable. There are no particular restrictions on the upper limit of ultraviolet radiation exposure, but for example, approximately 500 mJ / cm² is acceptable. 2 The following or approximately 450 mJ / cm² 2 The following is possible:

[0078] The thickness of the colored layer in this disclosure may be set appropriately considering the required performance (e.g., colorability, opacity, rigidity). For example, such a thickness may be approximately 1 micrometer or more, approximately 5 micrometers or more, approximately 10 micrometers or more, approximately 30 micrometers or more, or approximately 50 micrometers or more, or approximately 200 micrometers or less, approximately 150 micrometers or less, approximately 100 micrometers or less, or approximately 90 micrometers or less.

[0079] In some embodiments, the colored layer of the present disclosure and the cover layer described above have portions that are directly applied. The directly applied portion may be the entire surface of the colored layer or the cover layer, or a portion thereof. When the colored layer contains a cured product of the crosslinking agent described above, the presence of such a directly applied portion can further improve the adhesion between the two layers.

[0080] In some embodiments, the decorative film of the present disclosure optionally includes additional layers. Such additional layers may include, for example, at least one selected from the group consisting of decorative layers (e.g., color layers, pattern layers, relief layers), glossy layers, bonding layers, intermediate film layers, adhesive layers, and release liners. The additional layers may be applied to the entire surface or to a portion of the decorative film.

[0081] The decorative layers may include, but are not limited to, the following: a color layer exhibiting paint color, such as light colors like white and yellow, or dark colors like red, brown, green, blue, gray, and black; a pattern layer that imparts patterns such as wood grain, stone pattern, geometric patterns, or leather patterns to an article; a relief layer with an uneven surface; and combinations thereof. The decorative layers may be single-layer or multi-layer, and may be transparent, translucent, or opaque.

[0082] The decorative layer is not limited to the following, but can be applied directly or via a bonding layer, etc., to all or part of the layers constituting the decorative film, such as the coloring layer and / or adhesive layer. Here, the coloring layer, etc., in the additional layer is typically intended to be a layer that does not use the two specific types of (meth)acrylic polymers used in the coloring layer of the Disclosure, and is intended to be a layer different from the coloring layer of the Disclosure.

[0083] The material for the color layer is not limited to the following, but can be a material in which pigments such as inorganic pigments such as carbon black, lead yellow, yellow iron oxide, red iron oxide, etc., phthalocyanine pigments such as phthalocyanine blue, phthalocyanine green, etc., organic pigments such as azolake pigments, indigo pigments, perinone pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments such as quinacridone red, etc. are dispersed in a binder resin such as a (meth)acrylic resin or a resin having urethane bonds. Here, in this disclosure, "resin having urethane bonds" can include not only urethane resins but also resins prepared using, for example, at least one selected from urethane (meth)acrylate and urethane (meth)acrylate oligomers, and urethane resins can also include (meth)acrylic urethane resins.

[0084] The color layer can be formed using such materials by coating methods such as gravure coating, roll coating, die coating, bar coating, and knife coating.

[0085] The pattern layer is not limited to the following, but for example, patterns such as designs, logos, and illustrations may be applied directly to the color layer and / or adhesive layer using printing methods such as gravure direct printing, gravure offset printing, inkjet printing, laser printing, and screen printing. Alternatively, films, sheets, etc., having designs, logos, and illustrations formed by coatings such as gravure coat, roll coat, die coat, bar coat, and knife coat, as well as by die-cutting, etching, etc., may be used. As for the material of the pattern layer, for example, the same material used for the color layer may be used.

[0086] As the relief layer, a thermoplastic resin film having an uneven surface shape achieved by conventionally known methods, such as embossing, scratching, laser processing, dry etching, or hot pressing, can be used. Alternatively, a thermosetting or radiation-curable resin, such as a curable (meth)acrylic resin, can be applied to a release liner having an uneven surface shape, cured by heating or radiation, and then the release liner can be removed to form the relief layer.

[0087] The thermoplastic resin, thermosetting resin, and radiation-curable resin used in the relief layer are not particularly limited, but examples include polyester resins such as PET and PEN, polyolefin resins such as (meth)acrylic resins, polyethylene and polypropylene, thermoplastic elastomers, polycarbonate, polyamide, ABS resin, acrylonitrile-styrene resin, polystyrene, vinyl chloride, and resins having urethane bonds. The relief layer may also contain at least one of the pigments used in the color layer.

[0088] 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, catalysts, and the like.

[0089] 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.

[0090] The lustrous layer is not limited to the following, but may be a layer containing a metal selected from aluminum, nickel, gold, silver, copper, platinum, chromium, iron, tin, indium, titanium, lead, zinc, germanium, or an alloy or compound thereof, formed on all or part of the colored layer and / or adhesive layer constituting the decorative film by vacuum deposition, sputtering, ion plating, plating, etc. The thickness of the lustrous layer can be appropriately set according to the required decorative effect.

[0091] 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, polyester, and rubber-based solvent-type, emulsion-type, pressure-sensitive, heat-sensitive, thermosetting, or UV-curing adhesives can be used as the bonding layer. The bonding layer can be applied by known coating methods or the like.

[0092] The decorative film disclosed herein may include an intermediate film layer. As the intermediate film layer, for example, a resin film of a resin having urethane bonds, polyolefin such as polyvinyl chloride, polyethylene, or polypropylene, polyester such as polyethylene terephthalate or polybutylene terephthalate, or a (meth)acrylic polymer can be used.

[0093] The thickness of the intermediate film layer can be approximately 5 micrometers or more, approximately 10 micrometers or more, or approximately 15 micrometers or more, approximately 200 micrometers or less, approximately 100 micrometers or less, or approximately 50 micrometers or less.

[0094] The decorative film disclosed herein may include an adhesive layer. As the adhesive layer, for example, commonly used solvent-type, emulsion-type, pressure-sensitive, heat-sensitive, thermosetting, or UV-curing adhesives such as (meth)acrylic, polyolefin-based, polyurethane-based, polyester-based, and rubber-based adhesives can be used. The adhesive layer can be applied by known coating methods or the like.

[0095] In some embodiments, the adhesive layer of the present disclosure is formed using a (meth)acrylic polymer with a glass transition temperature of less than approximately 0°C (low Tg polymer) and a (meth)acrylic polymer with a glass transition temperature of approximately 0°C or higher (high Tg polymer), as used in the colored layer described above. In the adhesive layer, as with the colored layer, the crosslinking agent, colorant, and other optional components described above may also be used. The adhesive layer can typically be formed by adjusting the blending ratio of the low Tg polymer and the high Tg polymer. In one embodiment, the blending ratio of the high Tg polymer is less than approximately 20 parts by mass, approximately 15 parts by mass or less, approximately 10 parts by mass or less, or approximately 7 parts by mass or less, approximately 1 part by mass or more, approximately 2 parts by mass or more, or approximately 3 parts by mass or more, per 100 parts by mass of the low Tg polymer. An adhesive layer containing the high Tg polymer in such proportions can improve performance such as adhesive strength, heat shrinkage resistance, reworkability, and conformability.

[0096] The glass transition temperatures and weight-average molecular weights of the low-Tg polymer and high-Tg polymer can be appropriately adjusted from the above-mentioned ranges to obtain the desired adhesive performance.

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

[0098] In some embodiments, the adhesive layer and the colored layer described above have portions that are directly applied. The directly applied portion may be the entire surface of the adhesive layer or the colored layer, or a portion thereof. When the adhesive layer and the colored layer contain cured products of the crosslinking agent described above, the presence of such directly applied portions can further improve the adhesion between the two layers.

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

[0100] 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 the third polymer described above, fillers, conductive agents, thermal conductivity imparters, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, dispersants, lubricants, surfactants, leveling agents, silane coupling agents, catalysts, colorants (e.g., pigments and dyes), and solvents.

[0101] The adhesive layer of this disclosure can be obtained, for example, by applying an adhesive layer-forming composition containing a low-Tg polymer, a high-Tg polymer, and optionally an optional component (e.g., a crosslinking agent, a third polymer, a colorant) to a release liner, etc., as described later, followed by heat treatment and / or radiation (e.g., ultraviolet) irradiation treatment. Here, the heat treatment and / or radiation (e.g., ultraviolet) irradiation treatment can be similar to the treatment for the colored layer described above. If the adhesive layer contains a low-Tg polymer, a high-Tg polymer, and a colorant, and as a result is colored, the colored adhesive layer can be considered as the colored layer of this disclosure. In this case, the colored layer described above does not have to be included in the decorative film, may be included as a transparent layer instead of a colored layer, or may be used in combination with the colored layer described above. When a colored layer is used in combination, the colored layer described above may be referred to as the first colored layer, and the colored adhesive layer as the second colored layer.

[0102] The thickness of the adhesive layer in this disclosure can be set appropriately considering the required adhesive strength, etc. For example, such a thickness can be about 10 micrometers or more, about 20 micrometers or more, or about 30 micrometers or more, and can be about 300 micrometers or less, about 200 micrometers or less, or about 100 micrometers or less.

[0103] 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.

[0104] 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.

[0105] The decorative film disclosed herein may be, for example, a sheet, a roll wound into a roll, or a three-dimensional object.

[0106] The following manufacturing method is described as an example, but the manufacturing method of the decorative film disclosed herein is not limited thereto.

[0107] For example, in the case of a decorative film comprising a release liner, an adhesive layer, a colored layer, and a cover layer in that order, a cover layer-forming composition is coated onto the release liner, and a drying and curing process is applied as necessary to form the cover layer. Subsequently, a colored layer-forming composition is coated onto the cover layer, and a drying and curing process is applied as necessary to form the colored layer. Subsequently, an adhesive layer-forming composition is coated onto the release liner, and a drying and curing process is applied as necessary to form the adhesive layer. By applying this adhesive layer to the colored layer and removing the release liner on the cover layer side as necessary, a decorative film can be formed.

[0108] In some embodiments, the decorative film of the present disclosure described above is disposed on a substrate via an 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 2. Article 201 in Figure 2 is configured such that a decorative film 200 comprising a cover layer 210, a coloring layer 220, and an adhesive layer 230 is applied to a substrate 250 via the adhesive layer 230.

[0109] 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, resin having a urethane bond, 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.

[0110] 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.

[0111] The decorative film disclosed herein can be used in a variety of applications. Such applications include, for example, signs (e.g., internally illuminated signs and externally illuminated signs); signs (e.g., internally illuminated signs and externally illuminated signs); various interior or exterior parts, such as interior or exterior parts for vehicles such as automobiles, trains, aircraft, and ships (e.g., roof members, pillar members, door trim members, instrument panel members, front members such as 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. The decorative film disclosed herein has a specific cover layer and coloring layer and is excellent in durability such as solvent resistance and weather resistance, so it can be 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.). The decorative film disclosed herein comprises a specific cover layer and a coloring layer, and also exhibits excellent performance in terms of flexibility, conformability, etc., making it suitable for use on rough surfaces. For example, the decorative film disclosed herein is suitable for use on rough surfaces having irregularities where the maximum height from the protrusion to the bottom is approximately 1 mm or more, approximately 1.5 mm or more, 1 cm or less, 7 mm or less, 5 mm or less, 3 mm or less, 2.5 mm or less, or 2 mm or less. In particular, when the coloring layer and / or adhesive layer described above contain a cured product of a low-Tg polymer, a high-Tg polymer, and a crosslinking agent, the interlayer adhesion of the entire decorative film is improved, so that interlayer delamination can be further reduced or suppressed when the film is applied to, for example, a rough surface.

[0112] There are no particular limitations 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 manual application, 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). [Examples]

[0113] 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.

[0114] Table 1 shows the various materials used. In the table, "Mw" and "Tg" refer to "weight-average molecular weight" and "glass transition temperature," respectively. For polymers AP1-3 and ADH1-2, polymer-containing solutions were prepared by mixing each monomer component, chain transfer agent (such as isooctyl thioglycolate), polymerization initiator (such as 2,2'-azobis(2,4-dimethylvaleronitrile)), and solvent (such as ethyl acetate) 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 obtained by polymerizing these compositions using conventional polymerization methods.

[0115] [Table 1]

[0116] Table 2 shows the colorant mixtures used when preparing the colored intermediate layer forming composition and the colored adhesive layer forming composition, which contain colorants. Table 3 shows the amount (parts by mass) and solid content (%) of each component in the colored intermediate layer forming composition and the colored adhesive layer forming composition prepared using these colorant mixtures. Here, the amount of each component in Table 3 is based on the non-volatile content. The layers formed using the colored intermediate layer forming composition and the colored adhesive layer forming composition both correspond to colored layers.

[0117] [Table 2]

[0118] [Table 3]

[0119] <Example Test 1> In Test Example 1, solvent resistance, elongation, and conformability were evaluated with and without a specific cover layer.

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

[0121] To the colored intermediate layer forming composition CA1, CL1 was added so that the solid weight ratio of CL1 to both AP2 and AP3 was 0.2:100. The CA1 containing the crosslinking agent was coated onto the cover layer using a knife coater. The coated layer was dried at 95°C for 5 minutes to obtain a colored intermediate layer with a thickness of 45 micrometers, corresponding to the colored layer.

[0122] To CA2, a composition for forming a colored adhesive layer, CL1 was added so that the solid weight ratio of CL1 to ADH1 was 0.05:100. The CA2 containing the crosslinking agent was coated onto a silicone-coated polyethylene laminate paper liner using a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain a colored adhesive layer with a thickness of 40 micrometers, corresponding to the colored layer. After laminating this adhesive layer onto a colored intermediate layer, the polyester liner on the cover layer side was peeled off to obtain the decorative film of Example 1.

[0123] Example 2 A cover layer was prepared in the same manner as in Example 1. AP1 and AP2 were mixed to prepare a transparent intermediate layer forming composition (FL1) with a solid content weight ratio of 100:110. 0.2 parts by mass of a crosslinking agent (CL1) was added to 100 parts by mass of the transparent intermediate layer forming composition. The transparent intermediate layer forming composition containing the crosslinking agent was coated onto the cover layer using a knife coater. The coated layer was dried at 95°C for 5 minutes to obtain a transparent intermediate layer with a thickness of 37 micrometers.

[0124] To CA3, a composition for forming a colored adhesive layer, CL2 was added so that the solid weight ratio of CL2 to ADH2 was 0.05:100. The CA3 containing the crosslinking agent was coated onto a silicone-coated polyethylene laminate paper liner using a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain a colored adhesive layer with a thickness of 39 micrometers, corresponding to the colored layer. After laminating this adhesive layer onto a transparent intermediate layer, the polyester liner on the cover layer side was peeled off to obtain the decorative film of Example 2.

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

[0126] Example 4 A cover layer was prepared in the same manner as in Example 1. CL1 was added to CA5, the composition for forming the colored intermediate layer, so that the solid weight ratio of CL1 to AP2 was 0.2:100. The CA5 containing the crosslinking agent was coated onto the cover layer using a knife coater. The coated layer was dried at 95°C for 5 minutes to obtain a colored intermediate layer with a thickness of 48 micrometers, corresponding to the colored layer.

[0127] To the CA6 composition for forming a colored adhesive layer, CL2 was added so that the solid weight ratio of CL2 to ADH2 was 0.05:100. The CA6 containing the crosslinking agent was coated onto a silicone-coated polyethylene laminate paper liner using a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain a colored adhesive layer with a thickness of 39 micrometers, corresponding to the colored layer. After laminating this adhesive layer onto the colored intermediate layer, the polyester liner on the cover layer side was peeled off to obtain the decorative film of Example 4.

[0128] Comparative Example 1 A decorative film for Comparative Example 1 was obtained in the same manner as in Example 1, except that a cover layer was not formed.

[0129] Comparative Example 2 A decorative film for Comparative Example 2 was obtained in the same manner as in Example 2, except that a cover layer was not formed.

[0130] Comparative Example 3 A decorative film for Comparative Example 3 was obtained in the same manner as in Example 3, except that a cover layer was not formed.

[0131] Comparative Example 4 A decorative film for Comparative Example 4 was obtained in the same manner as in Example 4, except that a cover layer was not formed.

[0132] Evaluation Test 1 Each test sample obtained was evaluated according to the following test method. The results are shown in Table 4. Here, "colored layer" and "transparent layer" in Table 4 correspond to "colored intermediate layer" and "transparent intermediate layer."

[0133] Solvent resistance test Test specimens were prepared by cutting the test sample into pieces 50 mm wide and 100 mm long. These specimens were placed on an aluminum plate and left at 23°C for 24 hours. Approximately 0.2 ml of isopropyl alcohol (IPA) was dropped onto the specimen using a syringe. After the IPA dried, the solvent resistance of the dropped surface was determined as follows: If no trace of IPA was observed, it was evaluated as "A"; if slight traces of IPA were observed but no surface tackiness was observed, it was evaluated as "B"; and if surface tackiness was observed, it was evaluated as "C". Here, evaluations of "A" and "B" were considered passing levels.

[0134] 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

[0135] Adhesion strength test: Adhesion strength to painted boards 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.

[0136] 60-degree surface gloss test after application of aluminum plate Test specimens were prepared by cutting the test sample into pieces 100 mm wide and 50 mm long. These specimens were placed on a smooth aluminum plate. The surface gloss of each test specimen was measured at a 60° angle using a portable gloss meter GMX-202 (Murakami Color Technology Laboratory Co., Ltd., Chuo-ku, Tokyo, Japan). Measurements were taken at three different locations, and the average value was recorded.

[0137] 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).

[0138] 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.

[0139] 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.

[0140] Followability test Test specimens were prepared by cutting the test sample to a width of 70 mm and a length of 75 mm. In an atmosphere of 25°C, the test specimens equipped with pre-masks were attached to a stucco-coated substrate (manufactured by Test Materials Co., Ltd., Kawaguchi City, Saitama Prefecture, Japan). The pre-masks were removed, and the test specimens were pressed without heating using a rivet brush "PFA-1" (manufactured by 3M Japan Limited, Shinagawa Ward, Tokyo, Japan). The press was performed three times back and forth on the test specimen. The maximum roughness between the top and bottom of the substrate surface was approximately 1.5 mm. After attaching the test specimens, the conformability to the rough substrate surface was visually judged. Specimens with good conformability to the rough substrate surface were evaluated as "good," and those with insufficient conformability to the rough substrate surface were evaluated as "poor."

[0141] Gloss retention evaluation test Test specimens were prepared in the same manner as in the conformability test. The specimens were left in a 65°C oven for 48 hours. Using a portable gloss meter (GMX-202, manufactured by Murakami Color Research Institute Co., Ltd. (Chuo-ku, Tokyo, Japan)), the initial gloss value and the gloss value after aging at 65°C were measured, and the gloss retention rate was calculated using the following formula 2: Gloss retention rate (%) = Gloss value after aging at 65°C / Initial gloss value × 100 ... Equation 2 Here, the test was repeated three times, and the average value was recorded as the representative value. Products with a gloss retention rate of less than 200% were evaluated as "good," and those with a gloss retention rate of 200% or more were evaluated as "poor."

[0142] [Table 4]

[0143] <Example Test 2> In Test Example 2, the effect of the matte finish treatment of the cover layer on the rough surface was evaluated.

[0144] Example 5 A pre-size solution containing both alkyd resin (R1) and formaldehyde-urea resin (R2) was prepared so that the solids weight ratio of R1 to R2 was 100:35. F1 was mixed into the pre-size solution so that the solids weight ratio of the total resin (R1 and R2) to silica particles (F1) was 100:18 by weight of non-volatile matter. The pre-size solution containing F1 was coated onto a 50-micrometer thick polyester liner using a knife coater. The coating layer was dried at 95°C for 3 minutes and then at 155°C for 3 minutes, simultaneously causing crosslinking. After drying, a pre-size liner with a super-matte release layer was obtained. The thickness of the pre-size layer was approximately 5 micrometers.

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

[0146] To the CA5 composition for forming the colored intermediate layer, CL1 was added so that the solid weight ratio of CL1 to AP2 was 0.2:100. The CA5 containing the crosslinking agent was coated onto the cover layer using a knife coater. The coated layer was dried at 95°C for 5 minutes to obtain a colored intermediate layer with a thickness of 45 micrometers, corresponding to the colored layer.

[0147] To CA6, a composition for forming a colored adhesive layer, CL1 was added so that the solid weight ratio of CL1 to ADH1 was 0.05:100. The CA6 containing the crosslinking agent was coated onto a silicone-coated polyethylene laminate paper liner using a knife coater. The coating layer was dried at 95°C for 5 minutes to obtain a 40-micrometer thick colored adhesive layer corresponding to the colored layer. After laminating this adhesive layer onto a colored intermediate layer, the polyester liner on the cover layer side was peeled off to obtain the decorative film of Example 5, in which the super-matte surface of the release layer was transferred.

[0148] Reference example (Example 4) As a reference example, the decorative film of Example 4 described above was used. Here, the liner used when forming the cover layer of this film was the same liner as in Example 1, and was a liner without a super-matte release layer.

[0149] Evaluation Test 2 Each test sample obtained was evaluated according to the test method in Evaluation Test 1 described above, and the test method described below. The results are shown in Table 5. Here, "colored layer" in Table 5 corresponds to "colored intermediate layer".

[0150] 60-degree surface gloss test after application of aluminum plate Test specimens were prepared by cutting the test sample into pieces 100 mm wide and 50 mm long. These specimens were placed on a smooth aluminum plate. The surface gloss of each test specimen was measured at a 60° angle using a portable gloss meter GMX-202 (Murakami Color Technology Laboratory Co., Ltd., Chuo-ku, Tokyo, Japan). Measurements were taken at three different locations, and the average value was recorded.

[0151] 60-degree surface gloss test after roughening treatment Test specimens were prepared by cutting the test sample to a width of 70 mm and a length of 75 mm. Under a 25°C atmosphere, the test specimens, equipped with a pre-mask, were attached to a stucco-coated substrate (manufactured by Test Materials Co., Ltd., Kawaguchi City, Saitama Prefecture, Japan). The pre-mask was removed, and the test specimens were pressed without heating using a rivet brush "PFA-1" (manufactured by 3M Japan Limited, Shinagawa Ward, Tokyo, Japan). The press was performed three times back and forth on the test specimen. The maximum roughness between the top and bottom of the substrate surface was approximately 1.5 mm.

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

[0153] Surface reflection evaluation test after roughening treatment Test specimens were prepared in the same manner as in the 60-degree surface gloss test after roughening. Surface reflection against the roughened substrate was visually determined indoors. If no surface reflection of the test specimen was observed against the roughened substrate, it was evaluated as "good," and if surface reflection of the test specimen was observed against the roughened substrate, it was evaluated as "bad."

[0154] [Table 5]

[0155] 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]

[0156] 100, 200 decorative film 110, 210 Cover Layer 120, 220 colored layer 130, 230 adhesive layer 140 Release Liner 201 Goods 250 Adherent

[0157] Some embodiments of this disclosure are described in the following sections [1]-[9]. [Item 1] A decorative film comprising a cover layer and a colored layer, The cover layer comprises a cured product of (meth)acrylic diol and hexamethylene diisocyanate. The colored layer comprises a (meth)acrylic polymer having a glass transition temperature of approximately 0°C or higher, a (meth)acrylic polymer having a glass transition temperature of less than approximately 0°C, and a coloring agent. Decorative film. [Item 2] The decorative film described in item 1, wherein the hexamethylene diisocyanate is an adduct of hexamethylene diisocyanate. [Item 3] The decorative film according to item 1 or 2, wherein the cover layer has a 60-degree surface gloss of approximately 5.0 or less. [Item 4] The decorative film according to item 3, wherein the cover layer has a matte finish. [Item 5] The decorative film according to item 3 or 4, wherein the filler content in the cover layer is approximately 10% by mass or less. [Item 6] A decorative film as described in any of items 1-5, further comprising an adhesive layer. [Item 7] A decorative film for exterior use, as described in any of items 1-6. [Item 8] Decorative film for rough surfaces, as described in any of items 3-7. [Item 9] An article wherein a decorative film as described in any of items 1 to 8 includes an adhesive layer and is disposed on a substrate via the adhesive layer.

Claims

1. A decorative film comprising a cover layer and a colored layer, The cover layer comprises a cured product of (meth)acrylic polyol and hexamethylene diisocyanate. The colored layer comprises a (meth)acrylic polymer having a glass transition temperature of less than 0°C, a (meth)acrylic polymer having a glass transition temperature of 0°C or higher, and a coloring agent. Decorative film.

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

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

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

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

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

7. A decorative film according to claim 1 or 2, for exterior use.

8. The decorative film according to claim 3, which is for use on rough surfaces.

9. An article wherein the decorative film according to claim 1 or 2 includes an adhesive layer and is disposed on a substrate via the adhesive layer.

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