Paint replacement film

Abstract

To provide a coating alternative film which is suitable for use in a vacuum air pressure molding (DVT, Dual Vacuum Thermoforming) method, and has stretch-ability, adhesion, decorativeness and durability.SOLUTION: A coating alternative film includes in the following order: a thermoplastic top layer; a coloring layer containing a thermoplastic resin containing a carboxy group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer; a coloring layer; and a heat-sensitive adhesive layer containing a polyurethane-based heat-sensitive adhesive. Therein, the coating alternative film is heated to 165°C ± 5°C, and upon assuming an area of the coating alternative film before stretching to be 100%, the coating alternative film is stretched by 200% in an area ratio using a vacuum air pressure molding machine, and stuck to a PC-ABS plate, cut in a lattice shape with a width of 40 mm, and left at 95°C for 144 hours, thereafter, an opening of a cut is to be 1.0 mm or less.SELECTED DRAWING: Figure 1

Description

[Technical Field] 【0001】 This disclosure relates to a paint alternative film. [Background technology] 【0002】 It is known that decorative films are applied to the body and parts of automobiles as an alternative to paint to enhance their appearance. 【0003】 Patent Document 1 (Japanese Patent Publication No. 2013-039724) describes a vehicle paint substitute film comprising a transparent material layer and a colored adhesive layer, wherein the colored adhesive layer comprises (i) (a) an acrylic polyol, (b) a colorant premix comprising a colorant dispersed in the acrylic polyol, selected from the group consisting of a combination of organic pigment and inorganic pigment, a combination of organic pigment and aluminum gloss material, a combination of organic pigment and mica gloss material, a combination of inorganic pigment and aluminum gloss material, a combination of inorganic pigment and mica gloss material, and a combination of aluminum gloss material and mica gloss material, and a combination of these combinations, and (ii) an adhesive polymer, wherein the solid content mass ratio expressed as adhesive polymer / (adhesive polymer + acrylic polyol) is 25% or more, and is a vehicle paint substitute film. 【0004】 Patent Document 2 (Japanese Unexamined Patent Publication No. 2007-297569) describes a decorative layer-forming film having a top coat layer made of polyurethane resin and a carrier film provided on the surface side of the top coat layer, wherein the polyurethane resin is a polyurethane resin composition characterized by containing (1) a polyisocyanate containing 0.5 equivalents or more of an isocyanurate or adduct of isophorone diisocyanate or both thereof with respect to the total polyisocyanate, and (2) a polyol containing 0.4 equivalents or more of a polyester polyol made of caprolactone diol, polycarbonate diol or a mixture thereof, and having an average molecular weight of 1000 or less, with an equivalent ratio of the polyisocyanate to the polyol being 0.7 to 2.0. 【0005】 Patent Document 3 (International Publication No. 2013 / 114964) describes a decorative molding film having a laminated structure in which a colored layer, a protective layer, and a base film are arranged in this order, or a base film is arranged between the colored layer and the protective layer, wherein the elongation at break of the base film and the protective layer at 120°C is 200% or more, the colored layer contains at least a binder resin and a brightening material having an average major axis of 5 to 12 μm, and the stress at 100% elongation of the colored layer at 120°C is 4 MPa or less. 【Prior Art Documents】 【Patent Documents】 【0006】 【Patent Document 1】 Japanese Unexamined Patent Application Publication No. 2013-039724 【Patent Document 2】 Japanese Unexamined Patent Application Publication No. 2007-297569 【Patent Document 3】 International Publication No. 2013 / 114964 【Summary of the Invention】 【Problems to be Solved by the Invention】 【0007】 The attachment of a coating replacement film to an article having a curved surface is performed using, for example, a vacuum pressure air forming (DVT, Dual Vacuum Thermoforming) method, a vacuum forming (VT, Vacuum Thermoforming) method, a hydrostatic transfer method, or the like. The opportunity to use a coating replacement film is increasing for the purpose of reducing investment in coating equipment, reducing environmental load due to the scattering of volatile organic compounds (VOCs), CO2 emissions, wastewater emissions, etc., reducing energy consumption, and reducing the tact time and cost of the manufacturing process. In particular, the DVT method can apply a coating replacement film to an article having a curved surface with a small radius of curvature without defects, and thus is preferably used for the decoration of automotive parts such as automotive outer panels, instrument panels, and door trims, and household appliances. 【0008】 The paint substitute films used in the DVT method are required to be able to be stretched by 200% or more in area ratio compared to the area before stretching (with the area before stretching being 100%), and to adhere to a variety of substrates such as PC-ABS and electrodeposited coating boards used for automobile exteriors, and to maintain the appearance and adhesion of the paint color even after being left in a high-temperature environment for a long time after stretching and adhesion. 【0009】 This disclosure provides a paint alternative film having stretchability, adhesiveness, decorative properties, and durability suitable for use in the DVT method. [Means for solving the problem] 【0010】 According to one embodiment of the present disclosure, a paint substitute film is provided, comprising, in this order, a thermoplastic top layer, a coloring layer comprising a thermoplastic resin containing a carboxyl group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer, a coloring agent, and a heat-sensitive adhesive layer comprising a polyurethane-based heat-sensitive adhesive, wherein the paint substitute film is heated to 165°C ± 5°C, and when the area of ​​the paint substitute film before stretching is set to 100%, it is stretched to 200% by area ratio using a vacuum pressure forming machine, bonded to a PC-ABS board, cut into a grid with a width of 40 mm, and the gap between the cuts after being left at 95°C for 144 hours is 1.0 mm or less. [Effects of the Invention] 【0011】 According to this disclosure, it is possible to provide a paint alternative film that has stretchability, adhesiveness, decorative properties, and durability suitable for use in the DVT method. 【0012】 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] 【0013】 [Figure 1] This is a schematic cross-sectional view of a paint substitute film according to one embodiment. [Figure 2]This figure illustrates a method for forming an article by applying a paint substitute film to a substrate using the DVT method. [Figure 3A] This is a schematic cross-sectional view of the vacuum pressure forming machine before stretching in the DVT moldability evaluation of the example. [Figure 3B] This is a top view showing the placement of the substrate in the DVT moldability evaluation of the example. [Figure 3C] This is a schematic cross-sectional view of the vacuum pressure forming machine after stretching in the DVT moldability evaluation of the example. [Figure 4] This is a photograph showing the grid-like cuts made in the test specimen during the heat shrinkage test of the example. [Modes for carrying out the invention] 【0014】 The present invention will be described in more detail below, with reference to the drawings as needed, to illustrate typical embodiments of the present invention, but the present invention is not limited to these embodiments. 【0015】 In this disclosure, "(meth)acrylic" means acrylic or methacrylic, and "(meth)acrylate" means acrylate or methacrylate. 【0016】 In this disclosure, the term "hardening" also encompasses the concept commonly known as "crosslinking." 【0017】 In this disclosure, the term "film" also includes articles referred to as "sheets." 【0018】 In this disclosure, for example, in "a thermoplastic top layer is placed on top of the colored layer," "on top" means that the thermoplastic top layer is placed in direct contact with the colored layer, or that the thermoplastic top layer is placed above the colored layer via another layer. 【0019】 In this disclosure, "transparent" means that the average transmittance in the visible light region (wavelength 400nm to 700nm), measured in accordance with JIS K 7375:2008, 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. 【0020】 In this disclosure, "translucent" means that the average transmittance in the visible light region (wavelength 400nm to 700nm), measured in accordance with JIS K 7375:2008, is approximately 40% or more and less than approximately 80%, preferably approximately 75% or less. 【0021】 One embodiment of the paint substitute film comprises, in this order, a thermoplastic top layer, a colored layer containing a thermoplastic resin and a colorant, and a heat-sensitive adhesive layer containing a polyurethane-based heat-sensitive adhesive. The thermoplastic resin in the colored layer includes a carboxyl group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer. In this embodiment of the paint substitute film, the paint substitute film is heated to 165°C ± 5°C, and when the area of ​​the paint substitute film before stretching is set to 100%, it is stretched to 200% by area ratio using a vacuum pressure forming machine, bonded to a PC-ABS board, cut into a grid with a width of 40 mm, and after being left at 95°C for 144 hours, the gap between the cuts is approximately 1.0 mm or less. 【0022】 In the paint-alternative film of this disclosure, a thermoplastic top layer, a colored layer containing a specific thermoplastic resin, and a heat-sensitive adhesive layer containing a polyurethane-based heat-sensitive adhesive are arranged in this order. Although not bound by any theory, the materials and properties (thermoplasticity or heat-sensitive adhesion) of these layers work together to impart high stretchability (e.g., stretching of 200% or more by area ratio) and adhesion to the paint-alternative film suitable for the DVT method, and also impart durability such as heat shrinkage resistance to the paint-alternative film. Furthermore, the colored layer placed between the thermoplastic top layer and the heat-sensitive adhesive layer contains a specific combination of thermoplastic resins, and therefore has high elongation properties and strength, and can maintain the decorative properties of the paint-alternative film after stretching. 【0023】 Figure 1 shows a schematic cross-sectional view of a paint-alternative film 10 according to one embodiment. The paint-alternative film 10 includes a thermoplastic top layer 12, a colored layer 14, and a heat-sensitive adhesive layer 16 in that order. The colored layer 14 includes a thermoplastic resin 142 and a colorant 144. The paint-alternative film may further include an intermediate film layer 22 and / or a bonding layer 24 for bonding the above layers together, and may further include a liner 20. In Figure 1, the intermediate film layer 22 is positioned between the thermoplastic top layer 12 and the colored layer 14, and the bonding layer 24 is positioned to bond the thermoplastic top layer 12 and the intermediate film layer 22. In one embodiment, the paint-alternative film consists of a thermoplastic top layer, a colored layer, a heat-sensitive adhesive layer, an intermediate film layer, and a bonding layer. In another embodiment, the paint-alternative film consists of a thermoplastic top layer, a colored layer, and a heat-sensitive adhesive layer. 【0024】 As the thermoplastic top layer, for example, acrylic resins such as polymethyl methacrylate (PMMA), polyurethane, fluororesins such as ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), methyl methacrylate-vinylidene fluoride copolymer (PMMA-PVDF), and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV), polyolefins such as polyvinyl chloride (PVC), polycarbonate (PC), polyethylene (PE), and polypropylene (PP), polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and copolymers such as ethylene-acrylic acid copolymer (EAA) and its ionomers, ethylene-ethyl acrylate copolymer, and ethylene-vinyl acetate copolymer can be used. Due to its excellent weather resistance, the thermoplastic top layer preferably contains acrylic resin, polyurethane, fluororesin, or polyvinyl chloride, or mixtures thereof. Due to its excellent transparency, it is more preferable to contain acrylic resin, fluororesin, or mixtures thereof, and due to its excellent chemical resistance, it is even more preferable to contain fluororesin. 【0025】 In one embodiment, the thermoplastic top layer contains at least one resin selected from the group consisting of polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), and methyl methacrylate-vinylidene fluoride copolymer (PMMA-PVDF). In this embodiment, the thermoplastic top layer may contain at least one resin selected from the group consisting of polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), and methyl methacrylate-vinylidene fluoride copolymer (PMMA-PVDF) in a total amount of about 50% by mass or more, about 60% by mass or more, or about 70% by mass or more, 100% by mass or less, about 95% by mass or less, or about 90% by mass or less. The resin component of the thermoplastic top layer may consist of at least one resin selected from the group consisting of polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), and methyl methacrylate-vinylidene fluoride copolymer (PMMA-PVDF). 【0026】 As a thermoplastic top layer, a film pre-formed by extrusion, stretching, or other means can be used. Such a film can be laminated to a colored layer or other layers via a bonding layer. Alternatively, if the colored layer is adhesive to such a film, the film can be laminated directly to the colored layer without a bonding layer. Using a film with high flatness can provide a painted appearance with higher surface flatness. The thermoplastic top layer can also be formed by melt-extruding the resin component of the thermoplastic top layer onto other layers, or by multi-layer melt-extrusion with other layers. 【0027】 The thermoplastic top layer can also be formed by applying a solution containing the resin of the thermoplastic top layer onto a colored layer or other layer, and heating and drying as necessary. Alternatively, the solution can be applied onto another liner, and a thermoplastic top layer film can be formed by heating and drying as necessary, and this film can be laminated onto the colored layer via a bonding layer. If the colored layer is adhesive to the thermoplastic top layer film formed on the liner, the film can also be directly transferred and laminated onto the colored layer without a bonding layer. The thermoplastic top layer can be formed, for example, by applying a solution containing the resin of the thermoplastic top layer to the colored layer or liner using a knife coat, bar coat, blade coat, doctor coat, roll coat, cast coat, etc., and heating and drying as necessary. 【0028】 The thermoplastic top layer may optionally contain additives such as UV absorbers like benzotriazole, Tinuvin® 99-2, and Tinuvin® 1130 (BASF Japan Ltd., Chuo-ku, Tokyo, Japan), and hindered amine light stabilizers (HALS) like Tinuvin® 292 (BASF Japan Ltd., Chuo-ku, Tokyo, Japan). By using UV absorbers or hindered amine light stabilizers, discoloration, fading, and degradation of colorants in the colored layer, especially organic pigments that are relatively sensitive to light such as ultraviolet light, can be effectively prevented. The thermoplastic top layer may contain hard coat materials, gloss enhancers, etc., and may have an additional hard coat layer. The thermoplastic top layer may be transparent or translucent in order to provide the desired appearance. It is advantageous for the thermoplastic top layer to be transparent. 【0029】 The thickness of the thermoplastic top layer can vary, but is generally about 5 μm or more, about 10 μm or more, or about 15 μm or more, about 200 μm or less, about 150 μm or less, or about 100 μm or less. When applying a paint substitute film to articles with complex shapes, a thinner thermoplastic top layer is advantageous from the viewpoint of shape conformability, and for example, it is desirable to have a thickness of about 100 μm or less, or about 80 μm or less. On the other hand, when imparting high light resistance or weather resistance to an article, a thicker thermoplastic top layer is advantageous, and for example, it is desirable to have a thickness of about 15 μm or more, or about 20 μm or more. 【0030】 The colored layer contains a thermoplastic resin (hereinafter also referred to as "acrylic blend thermoplastic resin") containing carboxyl group-containing (meth)acrylic polymers and amino group-containing (meth)acrylic polymers (hereinafter collectively referred to simply as "(meth)acrylic polymers"), and a coloring agent. 【0031】 Acrylic blend thermoplastic resins include polymer blends of carboxyl group-containing (meth)acrylic polymers and amino group-containing (meth)acrylic polymers. The non-covalent interaction between the carboxyl group-containing (meth)acrylic polymers and the amino group-containing (meth)acrylic polymers imparts elongation properties and strength to the colored layer. As a result, the paint substitute film has high stretchability suitable for the DVT method, for example, enabling stretching of more than 200% in area ratio when the area of ​​the paint substitute film before stretching is taken as 100%. Furthermore, the paint substitute film can maintain its adhesive state without breaking or peeling, and maintain the appearance of the paint color, even after being left in a high-temperature environment for a long time after stretching and bonding. Carboxyl group-containing (meth)acrylic polymers can be obtained by copolymerizing a monoethylene unsaturated monomer with a carboxyl group-containing unsaturated monomer. Amino group-containing (meth)acrylic polymers can be obtained by copolymerizing a monoethylene unsaturated monomer with an amino group-containing unsaturated monomer. 【0032】 Monoethylene unsaturated monomers are the main components of (meth)acrylic polymers, and are generally represented by the formula CH2=CR 1COOR 2 (In the formula, R 1 R is a hydrogen or methyl group, 2 In addition to 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 2 Examples 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. As monoethylene unsaturated monomers, one or more monoethylene unsaturated monomers can be used, for example, to obtain a desired glass transition temperature, tensile strength, elongation properties, etc. 【0033】 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. If necessary, one or more carboxyl group-containing unsaturated monomers can be used. 【0034】 Carboxylic group-containing (meth)acrylic polymers can be obtained, for example, by copolymerizing monoethylene unsaturated monomers in amounts of approximately 85 parts by mass or more, approximately 90 parts by mass or more, or approximately 92 parts by mass or more, approximately 99.5 parts by mass or less, approximately 99 parts by mass or less, or approximately 98 parts by mass or less, with carboxylic group-containing monoethylene unsaturated monomers in amounts of approximately 0.5 parts by mass or more, approximately 1 part by mass or more, or approximately 2 parts by mass or more, approximately 15 parts by mass or less, approximately 10 parts by mass or less, or approximately 8 parts by mass or less. 【0035】 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. If necessary, one or more amino group-containing unsaturated monomers can be used as the amino group-containing unsaturated monomer. 【0036】 Amino group-containing (meth)acrylic polymers can be obtained, for example, by copolymerizing monoethylene unsaturated monomers in proportions of about 80 parts by mass or more, about 85 parts by mass or more, or about 90 parts by mass or more, about 99.5 parts by mass or less, about 99 parts by mass or less, or about 97 parts by mass or less, with amino group-containing unsaturated monomers in proportions of about 0.5 parts by mass or more, about 1 part by mass or more, or about 3 parts by mass or more, about 20 parts by mass or less, about 15 parts by mass or less, or about 10 parts by mass or less. 【0037】 Copolymerization is preferably carried out by radical polymerization, and known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization can be used. As initiators, for example, organic peroxides such as benzoyl peroxide, lauroyl peroxide, and bis(4-tert-butylcyclohexyl) peroxydicarbonate, and azo polymerization initiators such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile) (AVN) can be used. The amount of initiator used is generally 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. 【0038】 It is preferable that the glass transition temperature of one of the carboxyl group-containing (meth)acrylic polymer and the amino group-containing (meth)acrylic polymer is 0°C or higher, and the glass transition temperature of the other is 0°C or lower. In other words, if the Tg of the carboxyl group-containing (meth)acrylic polymer is 0°C or higher, the Tg of the amino group-containing (meth)acrylic polymer is 0°C or lower, and if the Tg of the former is 0°C or lower, the Tg of the latter is 0°C or higher. While we do not wish to be bound by any theory, it is believed that (meth)acrylic polymers with high Tg impart high tensile strength to the colored layer, and (meth)acrylic polymers with low Tg improve the elongation properties of the colored layer. In some embodiments, the Tg of the (meth)acrylic polymer with high Tg is about 5°C or higher, about 20°C or higher, or about 40°C or higher, and the Tg of the (meth)acrylic polymer with low Tg is about -5°C or lower, about -20°C or lower, or about -40°C or lower. 【0039】 For example, by copolymerizing homopolymers polymerized individually, such as methyl methacrylate (MMA) and n-butyl methacrylate (BMA), with (meth)acrylic monomers having a Tg of 0°C or higher as the main component, (meth)acrylic polymers with a Tg of 0°C or higher can be obtained. 【0040】 For example, by copolymerizing a homopolymer of a single component, such as ethyl acrylate (EA), n-butyl acrylate (BA), or 2-ethylhexyl acrylate (2EHA), which has a Tg of 0°C or less, a (meth)acrylic polymer with a Tg of 0°C or less can be obtained. 【0041】 The glass transition temperature (Tg) of carboxyl group-containing (meth)acrylic polymers and amino group-containing (meth)acrylic polymers is given by 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】 The glass transition temperature can be calculated using the following formula. In the formula, Tg i X is the glass transition temperature (°C) of the homopolymer of component i. i The terms and respectively represent the mass fraction of the monomer of component i added during polymerization, where i is a natural number from 1 to n. 【number】 That is the case. 【0042】 When a carboxyl group-containing (meth)acrylic polymer or an amino group-containing (meth)acrylic polymer is a blend of two or more (meth)acrylic polymers with different weight-average molecular weights, the Tg of the blend can be determined by dynamic viscoelasticity measurement. Specifically, a solution of the (meth)acrylic polymer blend is applied to release paper, and the resulting film (approximately 50 μm thick) is used as a test specimen. The loss tangent (tanδ) is measured using a dynamic viscoelasticity spectrometer (TA Instruments, model number: RSAIII) under the conditions of a temperature range of -20 to 160°C, Temp ramp mode, and frequency of 10 Hz. The Tg of the polymer blend can then be determined from this loss tangent measurement. 【0043】 The weight-average molecular weight of the carboxyl group-containing (meth)acrylic polymer and the amino group-containing (meth)acrylic polymer is not particularly limited, but can be, for example, about 1,000 or more, about 5,000 or more, or about 10,000 or more, about 2,000,000 or less, about 1,500,000 or less, or about 1,000,000 or less. The number-average molecular weight and weight-average molecular weight in this disclosure refer to values ​​converted using standard polystyrene by the GPC method. 【0044】 In one embodiment, the weight-average molecular weight of a (meth)acrylic polymer (low Tg (meth)acrylic polymer) having a glass transition temperature of 0°C or less is approximately 100,000 or more, approximately 150,000 or more, or approximately 200,000 or more, approximately 2,000,000 or less, approximately 1,500,000 or less, or approximately 1,000,000 or less. 【0045】 In one embodiment, the weight-average molecular weight of a (meth)acrylic polymer (high Tg (meth)acrylic polymer) having a glass transition temperature of 0°C or higher is approximately 1,000 or more, approximately 5,000 or more, or approximately 10,000 or more, approximately 200,000 or less, approximately 180,000 or less, or approximately 150,000 or less. 【0046】 By changing the blending ratio of carboxyl group-containing (meth)acrylic polymer and amino group-containing (meth)acrylic polymer, desired tensile strength and elongation properties can be imparted to the coating substitute film. In one embodiment, the blending ratio of high-Tg (meth)acrylic polymer and low-Tg (meth)acrylic polymer among the carboxyl group-containing (meth)acrylic polymer and amino group-containing (meth)acrylic polymer is such that, when the high-Tg (meth)acrylic polymer is 100 parts by mass, the low-Tg (meth)acrylic polymer is approximately 10 parts by mass or more, approximately 20 parts by mass or more, approximately 50 parts by mass or more, or approximately 80 parts by mass or more, approximately 900 parts by mass or less, approximately 500 parts by mass or less, approximately 200 parts by mass or less, or approximately 150 parts by mass or less. 【0047】 The total content of carboxyl group-containing (meth)acrylic polymers and amino group-containing (meth)acrylic polymers in the acrylic blend thermoplastic resin is generally about 25% by mass or more, about 35% by mass or more, or about 45% by mass or more, 100% by mass or less, about 90% by mass or less, or about 80% by mass or less. 【0048】 Examples of colorants include organic pigments, inorganic pigments, aluminum glossing agents, and mica glossing agents, as well as blends of two or more of these. It is preferable to select the colorant from the group consisting of combinations of organic and inorganic pigments, combinations of organic and aluminum glossing agents, combinations of organic and mica glossing agents, combinations of inorganic and aluminum glossing agents, combinations of inorganic and mica glossing agents, and combinations of aluminum and mica glossing agents, as well as combinations thereof. By using the above combinations of colorants, paint-alternative films with various shades can be obtained, thereby meeting sophisticated design requirements. 【0049】 Examples of organic pigments include phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, azolake pigments, indigo pigments, perinone pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, and quinacridone pigments such as quinacridone red. Examples of inorganic pigments include titanium dioxide, lead yellow, yellow iron oxide, red iron oxide, red iron oxide, and carbon black. Examples of aluminum luminous materials include aluminum flakes, vapor-deposited aluminum flakes, metal oxide-coated aluminum flakes, and colored aluminum flakes. Examples of mica luminous materials include flaked mica coated with metal oxides such as titanium dioxide and iron oxide, and synthetic mica. 【0050】 The coloring agent content in the colored layer can be approximately 2.5 parts by mass or more, approximately 5 parts by mass or more, or approximately 10 parts by mass or more, approximately 400 parts by mass or less, approximately 300 parts by mass or less, or approximately 200 parts by mass or less, per 100 parts by mass of the acrylic blend thermoplastic resin. 【0051】 It is preferable to crosslink carboxyl group-containing (meth)acrylic polymers with each other, or with an amino group-containing (meth)acrylic polymer. These crosslinks form a network structure, further improving the strength and elongation properties of the coating substitute film. Examples of crosslinking agents for carboxyl group-containing (meth)acrylic polymers include epoxy crosslinking agents, bisamide crosslinking agents, aziridine crosslinking agents, and carbodiimide crosslinking agents. One or more crosslinking agents can be used as needed. 【0052】 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). 【0053】 The amount of crosslinking agent added can be approximately 0.01 parts by mass or more, approximately 0.05 parts by mass or more, or approximately 0.1 parts by mass or more, approximately 5 parts by mass or less, approximately 3 parts by mass or less, or approximately 2 parts by mass or less, per 100 parts by mass of carboxyl group-containing (meth)acrylic polymer. 【0054】 The colored layer can be formed using a colored layer composition comprising, for example, a carboxyl group-containing (meth)acrylic polymer, an amino group-containing (meth)acrylic polymer, a colorant, and optionally a solvent and / or a crosslinking agent. Specifically, the colored layer composition can be applied to a liner such as a release-treated PET film, and then dried, solidified, or cured to form the colored layer on the liner. As the coating apparatus, a conventional coater, such as a bar coater, knife coater, roll coater, or die coater, can be used. Drying, solidification, or curing can be carried out by drying the colored layer composition containing a volatile solvent, or by cooling the molten resin components. The colored layer can also be formed by melt extrusion. 【0055】 The colored layer composition may further contain, as additives, for example, UV absorbers such as benzotriazole, light stabilizers such as hindered amines, antioxidants such as phenolic antioxidants, leveling agents such as silicones, viscosity regulators such as waxes and organic bentonite, thickeners such as cellulose acetate butyrate, extender pigments such as precipitated barium sulfate, clay, silica, talc, kaolin, and bentonite, and organic solvents such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethylene glycol, propylene glycol, ethylene glycol dimethyl ether, and propylene glycol monomethyl ether acetate. 【0056】 In one embodiment, the colored layer is formed using a colored layer composition obtained by mixing a colorant premix, a carboxyl group-containing (meth)acrylic polymer, an amino group-containing (meth)acrylic polymer, and, if necessary, a solvent and / or a crosslinking agent. The colorant premix contains an acrylic polyol and a colorant, the colorant being dispersed in the acrylic polyol. 【0057】 As the acrylic polyol included in the colorant premix, for example, acrylic copolymers containing hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate can be used. Monoethylene unsaturated monomers can be used as monomers that can be copolymerized with hydroxyl group-containing (meth)acrylates. Examples of monoethylene unsaturated monomers 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; monoethylene unsaturated monomers having an acidic group such as (meth)acrylic acid, itaconic acid, maleic acid, and styrenesulfonic acid; nitrogen-containing monoethylene unsaturated monomers such as N-vinylpyrrolidone, N-vinylcaprolactam, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and (meth)acrylonitrile; and aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluene. Acrylic polyols can be obtained by polymerizing hydroxyl group-containing (meth)acrylates and monoethylenically unsaturated monomers using an azo polymerization initiator such as 2,2'-azobisisobutyronitrile, or an organic peroxide such as benzoyl peroxide. During polymerization, hydroxyl group-containing chain transfer agents such as 2-mercaptoethanol, 1-mercapto-2-propanol, 3-mercapto-1-propanol, and p-mercaptophenol may also be used. 【0058】 The hydroxyl value of acrylic polyols is generally about 10 mg / g or more, about 20 mg / g or more, or about 40 mg / g or more, and about 1000 mg / g or less, about 500 mg / g or less, or about 200 mg / g or less. The acid value of acrylic polyols is generally about 0.1 mg / g or more, about 0.5 mg / g or more, or about 2 mg / g or more. By setting the hydroxyl value and / or acid value of acrylic polyols to the above values, the colorant can be well dispersed in the acrylic polyol, and the miscibility with (meth)acrylic polymers can be improved. The weight-average molecular weight of acrylic polyols is generally about 2,000 or more, about 5,000 or more, or about 10,000 or more, and about 300,000 or less, about 200,000 or less, or about 100,000 or less. By keeping the weight-average molecular weight of the acrylic polyol within the above range, the colorant can be well dispersed in the acrylic polyol, and the miscibility with (meth)acrylic polymers can be improved. 【0059】 The colorant premix may further contain, as additives, for example, UV absorbers such as benzotriazole, antioxidants such as phenolic antioxidants, leveling agents such as silicones, viscosity regulators such as waxes and organic bentonite, thickeners such as cellulose acetate butyrate, extender pigments such as precipitated barium sulfate, clay, silica, talc, kaolin, and bentonite, and organic solvents such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethylene glycol, propylene glycol, ethylene glycol dimethyl ether, and propylene glycol monomethyl ether acetate. 【0060】 The colorant content in the colorant premix can be approximately 20% by mass or more, or approximately 30% by mass or more, approximately 80% by mass or less, or approximately 70% by mass or less, based on the total mass of the acrylic polyol and the colorant. The entire amount of acrylic polyol may be used to disperse the colorant, or a portion of the acrylic polyol may be used to disperse the colorant and the remainder added to the dispersion. By keeping the amount of colorant in the colorant premix within the above range, the desired color can be provided while incorporating the required amount of (meth)acrylic polymer into the colored layer. 【0061】 The solid content mass ratio expressed as acrylic blend thermoplastic resin / (acrylic blend thermoplastic resin + acrylic polyol) is approximately 25% or more, preferably approximately 50% or more, and more preferably approximately 75% or more. The solid content mass ratio refers to the dry mass of the acrylic blend thermoplastic resin and acrylic polyol, and does not include the mass of the added crosslinking agent. By setting the solid content mass ratio expressed as acrylic blend thermoplastic resin / (acrylic blend thermoplastic resin + acrylic polyol) within the above range, the elongation characteristics of the colored layer are improved, and as a result, the DVT moldability of the paint substitute film can be improved. By setting the solid content mass ratio within the above range, even when the paint substitute film is stretched by the DVT method and attached to an article, it is possible to maintain an excellent appearance (e.g., gloss, opacity, etc.). 【0062】 The colored layer may have adhesive properties. An adhesive colored layer can be laminated onto a thermoplastic top layer or a heat-sensitive adhesive layer without requiring a bonding layer. 【0063】 The thickness of the colored layer can vary, but is generally about 10 μm or more, about 20 μm or more, or about 30 μm or more, about 120 μm or less, about 100 μm or less, or about 80 μm or less. By setting the thickness of the colored layer to about 10 μm or more, a desired decorative appearance can be provided. By setting the thickness of the colored layer to about 120 μm or less, the paint substitute film can be given stretchability suitable for the DVT method. 【0064】 The heat-sensitive adhesive layer includes a polyurethane-based heat-sensitive adhesive. In this disclosure, "heat-sensitive adhesive" refers to a material that does not exhibit tackiness at room temperature but becomes tacky and adheres to an adherend at high temperatures, and includes heat-activated adhesives and hot-melt adhesives. Heat-activated adhesives, also called delayed-tack heat-sensitive adhesives, are activated by heating to produce tackiness, and the tackiness persists for a period of time even after the heat source is removed. Hot-melt adhesives melt or soften by heating to produce tackiness, and rapidly solidify and lose tackiness when the heat source is removed. Generally, heat-sensitive adhesives have a glass transition temperature Tg or melting point Tm that is higher than room temperature. When the temperature is higher than Tg or Tm, the storage modulus of the heat-sensitive adhesive decreases, and the heat-sensitive adhesive exhibits tackiness. The Tg and Tm of the heat-sensitive adhesive are measured using differential scanning calorimetry (DSC). 【0065】 Polyurethane-based heat-sensitive adhesives contain polyurethane, which is a reaction product of a polyol and a polyisocyanate. Examples of polyols include high molecular weight polyols such as polyester polyols, polyether polyols, and polycarbonate polyols, and low molecular weight polyols with 2 to 20 carbon atoms such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, glycerin, diethylene glycol, trimethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexanedimethanol, methylpentanediol adipate, trimethylolpropane, and pentaerythritol. Examples of polyisocyanates include aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate, trans and / or cis-1,4-cyclohexane diisocyanate, norbornene diisocyanate, and hydrogenated diphenylmethane diisocyanate; aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 2,2'-diphenylmethane diisocyanate; and their biuret-modified, isocyanurate-modified, carbodiimide-modified, or adduct-modified forms. One or more polyols or polyisocyanates can be used as the polyol or polyisocyanate. 【0066】 Polyurethane-based heat-sensitive adhesives preferably contain linear polyurethane. The polyurethane may have hydroxyl groups. Polyurethane having hydroxyl groups can be obtained by reacting a polyol and a polyisocyanate such that the NCO / OH ratio (number of moles of isocyanate groups in the polyisocyanate / number of moles of hydroxyl groups in the polyol) is less than 1, i.e., there is an excess of hydroxyl groups. 【0067】 From the viewpoint of suppressing thermal shrinkage of the paint substitute film, it is preferable that the polyurethane-based heat-sensitive adhesive is crosslinked. A crosslinked polyurethane-based heat-sensitive adhesive can be formed by reacting a polyurethane having hydroxyl groups with the above-mentioned polyisocyanate as a crosslinking agent. Excess isocyanate groups of the above-mentioned polyisocyanate also react with moisture contained in the air and elsewhere to contribute to crosslinking. The NCO / OH ratio (moles of isocyanate groups of the polyisocyanate / moles of hydroxyl groups of the polyurethane having hydroxyl groups) of the polyurethane having hydroxyl groups and the crosslinking agent polyisocyanate can be, for example, about 0.5 or more, about 1 or more, or about 2 or more, about 10 or less, about 8 or less, or about 6 or less. 【0068】 The melting point Tm of the polyurethane-based heat-sensitive adhesive before crosslinking can be approximately 30°C or higher, approximately 35°C or higher, or approximately 40°C or higher, approximately 80°C or lower, approximately 65°C or lower, or approximately 50°C or lower. The melting point Tm of the polyurethane-based heat-sensitive adhesive is a value measured using a differential scanning calorimeter. 【0069】 The heat-sensitive adhesive layer may further contain a tackifier. Examples of tackifiers include rosin derivatives, terpene resins, petroleum resins, phenolic resins, and xylene resins. 【0070】 The heat-activated heat-sensitive adhesive layer may further contain a solid plasticizer. The solid plasticizer is solid at room temperature and melts when heated above its melting point, causing the polyurethane and / or tackifier to swell or dissolve. This enhances the tack of the heat-sensitive adhesive layer at high temperatures. On the other hand, once the solid plasticizer melts, crystallization proceeds slowly even when the temperature drops below its melting point, so the tack generated by heat activation can be maintained for a long time. Examples of solid plasticizers include diphenyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, dihydroabiethyl phthalate, dimethyl isophthalate, sucrose benzoate, ethylene glycol dibenzoate, trimethylolethane tribenzoate, glyceride tribenzoate, sucrose octaacetate, tricyclohexyl citrate, and N-cyclohexyl-p-toluenesulfonamide. 【0071】 The heat-sensitive adhesive layer may contain, as additives, for example, UV absorbers such as benzotriazole, light stabilizers such as hindered amines, antioxidants such as phenolic antioxidants, silane coupling agents, and fillers. 【0072】 The heat-sensitive adhesive layer can be formed using a heat-sensitive adhesive composition comprising polyurethane and a solvent, and optionally a crosslinking agent, tackifier, solid plasticizer, etc. Specifically, the heat-sensitive adhesive layer can be formed by applying the heat-sensitive adhesive composition onto the colored layer and drying, solidifying, or curing it. Alternatively, the heat-sensitive adhesive layer can be formed by applying the heat-sensitive adhesive composition onto another liner and drying, solidifying, or curing it, and then heat-laminating the heat-sensitive adhesive layer onto the colored layer. For example, the heat-sensitive adhesive layer can be formed by applying the heat-sensitive adhesive composition to the colored layer or liner using a knife coat, bar coat, blade coat, doctor coat, roll coat, cast coat, etc., and heating, drying, solidifying, or curing it as needed. The liner may have a surface that has been peeled off with silicone or the like. 【0073】 The thickness of the heat-sensitive adhesive layer may vary, but generally it is approximately 5 μm or more, approximately 10 μm or more, or approximately 15 μm or more, approximately 100 μm or less, approximately 80 μm or less, or approximately 50 μm or less. 【0074】 The paint substitute film may have a liner that protects the heat-sensitive adhesive layer. Examples of the liner include paper, polyethylene, polypropylene, polyester, plastic materials such as 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. The thickness of the liner is generally about 5 μm or more, about 15 μm or more, or about 25 μm or more, about 300 μm or less, about 200 μm or less, or about 150 μm or less. 【0075】 The heat-sensitive adhesive layer generally forms a flat adhesive surface, but it may also form an uneven adhesive surface. This uneven adhesive surface includes an adhesive surface in which protrusions containing adhesive and recesses surrounding the protrusions are formed on the adhesive surface of the heat-sensitive adhesive layer, and when adhered to an object, a communication passage is formed between the surface of the object and the adhesive surface, which is defined by the recesses and communicates with the outside. An example of a method for forming an uneven adhesive surface is described below. 【0076】 A liner is prepared that has a release surface with a predetermined uneven structure. A heat-sensitive adhesive composition is applied to the release surface of this liner and heated as necessary to form a heat-sensitive adhesive layer. This transfers the uneven structure (negative structure) of the liner to the surface of the heat-sensitive adhesive layer that comes into contact with the liner (this becomes the adhesive surface in the paint substitute film), forming an uneven adhesive surface with a predetermined structure (positive structure) on the adhesive surface. As described above, the unevenness of the adhesive surface is designed in advance to include grooves that can form communication channels when the protrusions are adhered to the adherend. 【0077】 The grooves in the heat-sensitive adhesive layer may be arranged in a regular pattern on the adhesive surface by placing grooves of a certain shape along a regular pattern, or irregular grooves may be arranged to form an irregular pattern, as long as it prevents air bubbles from remaining when the paint substitute film is attached to the article by the DVT method. When multiple grooves are formed so as to be substantially parallel to each other, the spacing between the grooves is preferably 10 to 2000 μm. The depth of the grooves (the distance from the adhesive surface to the bottom of the groove measured in the direction of the thermoplastic intermediate film layer) is usually about 10 μm or more and about 100 μm or less. The shape of the grooves is also not particularly limited as long as it does not impair the effects of the present invention. For example, the shape of the grooves can be substantially rectangular (including trapezoidal), substantially semicircular, or substantially semielliptical in the cross-section of the groove in the direction perpendicular to the adhesive surface. 【0078】 The paint-alternative film may optionally include an intermediate film layer interposed between the thermoplastic top layer and the colored layer, or between the colored layer and the heat-sensitive adhesive layer. The intermediate film layer can increase the strength of the paint-alternative film. 【0079】 As the intermediate film layer, for example, a resin film of polyurethane, polyvinyl chloride, polyolefin such as polyethylene and polypropylene, polyester such as polyethylene terephthalate and polybutylene terephthalate, acrylic polymer, or fluoropolymer can be used. The intermediate film layer is preferably thermoplastic. In one embodiment, the intermediate film layer contains a water-based polyurethane resin. 【0080】 The thickness of the intermediate film layer can be approximately 5 μm or more, approximately 10 μm or more, or approximately 15 μm or more, approximately 200 μm or less, approximately 100 μm or less, or approximately 50 μm or less. 【0081】 The paint substitute film may optionally include a bonding layer between the two layers constituting the paint substitute film. In one embodiment, the paint substitute film has a bonding layer between a thermoplastic top layer and an optional intermediate film layer. 【0082】 The bonding layer includes, for example, a urethane resin, an acrylic resin, an epoxy resin, or a phenoxy resin, or a blend of two or more of these resins. In one embodiment, the bonding layer includes a resin blend of a urethane resin and a phenoxy resin. 【0083】 The thickness of the bonding layer can be approximately 0.1 μm or more, approximately 0.2 μm or more, or approximately 0.5 μm or more, approximately 10 μm or less, approximately 5 μm or less, or approximately 2 μm or less. 【0084】 A paint-alternative film can be manufactured, for example, by the following procedure: Prepare a colored layer composition and apply it to a release liner, and heat-dry it as needed to form a colored layer. Prepare an intermediate film layer composition and apply it to the exposed surface of the colored layer, and heat-dry it as needed to form an intermediate film layer. Prepare a bonding layer composition and apply it to a carrier film, and heat-dry it as needed to form a bonding layer. Heat-laminate the exposed surface of the bonding layer and the exposed surface of the intermediate film layer, and then remove the carrier film. As a thermoplastic top layer, heat-laminate a thermoplastic resin film to the exposed surface of the bonding layer. Prepare a heat-sensitive adhesive layer composition, remove the release liner to expose the colored layer, and then apply the heat-sensitive adhesive layer composition to the colored layer, and heat-dry it as needed to form a heat-sensitive adhesive layer. In this way, a paint-alternative film can be obtained. A release liner may be laminated onto the heat-sensitive adhesive layer of the paint-alternative film to protect the heat-sensitive adhesive layer. 【0085】 In the manufacture of the above-mentioned paint-alternative film, after forming the colored layer, instead of forming an intermediate film layer and a bonding layer, a thermoplastic resin film may be brought into contact with the exposed surface of the colored layer and heat-laminated as a thermoplastic top layer, or the resin component of the thermoplastic top layer may be melt-extruded onto the exposed surface of the colored layer. In the manufacture of the above-mentioned paint-alternative film, a heat-sensitive adhesive layer may be formed on a release liner instead of on the colored layer, and the exposed surface of the colored layer and the exposed surface of the heat-sensitive adhesive layer may be brought into contact and laminated at room temperature or heat-laminated. 【0086】 Excluding the thickness of the release liner, the total thickness of the paint substitute film is generally about 30 μm or more, about 80 μm or more, or about 120 μm or more, about 600 μm or less, about 400 μm or less, or about 350 μm or less. 【0087】 The paint substitute film is heated to 165°C ± 5°C, and when the area of ​​the paint substitute film before stretching is set to 100%, it is stretched to 200% by area ratio using a vacuum pressure forming machine and bonded to a PC-ABS board. After cutting it into a grid with a width of 40 mm and leaving it at 95°C for 144 hours, the opening of the cuts is approximately 1.0 mm or less. Preferably, the opening of the cuts is approximately 0.8 mm or less, and more preferably approximately 0.5 mm or less. The opening of the cuts represents the heat resistance of the paint substitute film, specifically the behavior of the heat shrinkage of the paint substitute film. The smaller the value of the opening of the cuts, the less the paint substitute film shrinks even in high-temperature environments, and the better the adhesion to the substrate and the appearance of the paint substitute film can be maintained. The specific measurement conditions for the opening of the cuts are as described in "4. Heat Shrinkage" of the Examples. 【0088】 In one embodiment, the paint substitute film is heated to 165°C ± 5°C, and when the area of ​​the paint substitute film before stretching is set to 100%, it is stretched to 200% by area ratio using a vacuum pressure forming machine and bonded to a PC-ABS board. When cut into strips with a width of 10 mm and peeled at 23°C and a peeling speed of 200 mm / min at 180 degrees, the adhesive strength is approximately 6.4 N / 10 mm or more. The adhesive strength is preferably approximately 6.8 N / 10 mm or more, and more preferably approximately 7.2 N / 10 mm or more. The adhesive strength is less than the force required to cause cohesive failure of the adherend or the paint substitute film, and is generally about 20 N / 10 mm or less, or about 15 N / 10 mm or less. The specific measurement conditions for the adhesive strength are as described in "2. Adhesion Strength" of the Examples. 【0089】 In one embodiment, the coating substitute film is heated to 165°C ± 5°C. When the area of the coating substitute film before stretching is taken as 100%, after stretching it by 200% in terms of area ratio using a vacuum pressure forming machine and laminating it to a PC-ABS board, the integrated energy amount of light with wavelengths from 300 nm to 400 nm is 750 MJ / m 2 at a display temperature of 63°C of a black panel thermometer in accordance with JIS K 5600-7-7:2008. After conducting an accelerated weather resistance test to achieve this, the 60-degree gloss retention rate of the coating substitute film is about 80% or more. The 60-degree gloss retention rate is preferably about 85% or more, more preferably about 90% or more. The specific measurement conditions for the 60-degree gloss retention rate are as described in "5. Glossiness" and "7. Weather resistance" of the examples. 【0090】 In one embodiment, the tensile strength at 200% elongation at a temperature of 120°C of the coating substitute film is about 0.6 MPa or more, about 0.8 MPa or more, or about 1.0 MPa or more, and about 20 MPa or less, about 10 MPa or less, or about 5.0 MPa or less. In the present disclosure, 200% elongation means a state where the film is stretched until its length becomes 200% (twice) of the length before stretching when the length before stretching is taken as 100%. The tensile strength at 200% elongation is the tensile strength at the time when a measurement sample with a length of about 100 mm and a width of 25 mm is prepared and stretched to 200% elongation using a tensile testing machine described in ISO7500-1:2015 at a temperature of 120°C, a tensile speed of 150 mm / min, and a chuck interval of 50 mm. 【0091】 The coating substitute film of the present disclosure can be applied to the body of a vehicle (including the roof, doors, bonnet, etc.) or a part thereof, or vehicle components (e.g., bumpers, roof moldings, side guard moldings, pillars, etc.). Examples of vehicles include automobiles such as trucks, buses, and passenger cars, two-wheeled vehicles such as motorcycles and scooters, bicycles, trains, sightseeing boats, ships such as yachts and motorboats. The coating substitute film of the present disclosure is particularly suitable for applications where it is attached to the surface of an article having a curved surface using the DVT method. 【0092】 The following describes, with reference to Figure 2, an exemplary method for forming an article by applying a paint substitute film to a substrate using the DVT method. 【0093】 As shown in Figure 2(A), the exemplary vacuum pressure forming machine 30 has a first vacuum chamber 31 and a second vacuum chamber 32, respectively, located above and below the first vacuum chamber. A jig for setting the paint substitute film 10, which is to be attached to the substrate 40, is provided between the upper and lower vacuum chambers. In the lower first vacuum chamber 31, a partition plate 34 and a base 33 are installed on a lifting platform 35 (not shown in Figure 2(A)) that can be raised and lowered, and the substrate 40, such as a three-dimensional object, is set on this base 33. Commercially available vacuum pressure forming machines, such as a double-sided vacuum forming machine (Fuse Vacuum Co., Ltd.), can be used as such a vacuum pressure forming machine. 【0094】 As shown in Figure 2(A), first, with the first vacuum chamber 31 and the second vacuum chamber 32 of the vacuum pressure forming machine 30 released to atmospheric pressure, the paint substitute film 10 is set between the upper and lower vacuum chambers. In the first vacuum chamber 31, the base material 40 is set on the base 33. 【0095】 Next, as shown in Figure 2(B), the first vacuum chamber 31 and the second vacuum chamber 32 are closed and the pressure is reduced in each chamber to create a vacuum inside each chamber (for example, approximately 0 atm, assuming atmospheric pressure is 1 atm). After that, or simultaneously with the reduction in pressure, the film is heated. 【0096】 Next, as shown in Figure 2(C), the lifting platform 35 is raised to push the substrate 40 up to the second vacuum chamber 32. Heating can be performed, for example, by an IR lamp heater (not shown) incorporated into the ceiling of the second vacuum chamber 32. The heating temperature can generally be about 50°C or higher and about 180°C or lower, preferably about 130°C or higher and about 160°C or lower. The vacuum level of the reduced pressure atmosphere can be about 0.10 atm or lower, about 0.05 atm or lower, or about 0.01 atm or lower, with atmospheric pressure being 1 atm. 【0097】 The heated coating substitute film 10 is pressed against the surface of the substrate 40 and stretched. Subsequently, or simultaneously with stretching, the second vacuum chamber 32 is pressurized to an appropriate pressure (e.g., about 3 atm to about 1 atm), as shown in Figure 2(D). Due to the pressure difference, the coating substitute film 10 adheres closely to the exposed surface of the substrate 40, stretches to conform to the three-dimensional shape of the exposed surface, and forms a coating that adheres closely to the substrate surface. At least a portion of the coating substitute film 10 may be stretched by, for example, about 4 times or more, about 4.5 times or more, or about 5 times or more in area ratio when stretched to conform to the three-dimensional shape of the substrate 40. Alternatively, after depressurizing and heating in the state shown in Figure 2(B), the second vacuum chamber 32 can be pressurized immediately to coat the exposed surface of the substrate 40 with the coating substitute film 10. 【0098】 Subsequently, the upper and lower first vacuum chambers 31 and second vacuum chambers 32 are opened to atmospheric pressure again, and the substrate 40 covered with the paint substitute film 10 is removed. As shown in Figure 2(E), the edges of the paint substitute film 10 that are in close contact with the surface of the substrate 40 are trimmed, and the DVT process is completed. In this way, an article 42 with good wrap-around coating is obtained, in which the paint substitute film 10 wraps around to the back surface 41 at the edges of the substrate 40 and neatly covers the exposed surface. [Examples] 【0099】 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. 【0100】 Synthesis of carboxyl group-containing (meth)acrylic polymers (polymer A) 94 parts by mass of n-butyl acrylate (BA) and 6 parts by mass of acrylic acid (AA) were dissolved in a mixed solvent of 100 parts by mass of toluene and 100 parts by mass of ethyl acetate. 0.2 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name V-65, Fujifilm Wako Pure Chemical Industries, Ltd. (Osaka, Osaka, Japan)) were added as a polymerization initiator. The mixture was then reacted at 50°C for 24 hours under a nitrogen atmosphere to obtain a toluene / ethyl acetate mixed solution of polymer A (solid content 33% by mass). The weight-average molecular weight of polymer A was 760,000, and the glass transition temperature (Tg) calculated from the FOX formula was -48°C. 【0101】 Synthesis of amino group-containing (meth)acrylic polymers (polymer B) 60 parts by mass of methyl methacrylate (MMA), 34 parts by mass of n-butyl methacrylate (BMA), and 6 parts by mass of dimethylaminoethyl methacrylate (DMAEMA) were dissolved in 150 parts by mass of ethyl acetate. 0.6 parts by mass of dimethyl-2,2'-azobis(2-methylpropionate) (trade name V-601, Fujifilm Wako Pure Chemical Industries, Ltd. (Osaka, Osaka, Japan)) was added as a polymerization initiator. The mixture was then reacted under a nitrogen atmosphere at 65°C for 24 hours to obtain an ethyl acetate solution of polymer B (solid content 39% by mass). The weight-average molecular weight of polymer B was 68,000, and the glass transition temperature (Tg) calculated from the FOX formula was 63°C. 【0102】 Polyurethane (PUR1) synthesis A homogeneous solution was prepared by mixing 157.5 parts by mass of Polylite® OD-X-2640, 0.9 parts by mass of 1,4-butanediol, 1.2 parts by mass of 1,6-hexanediol, and 430.1 parts by mass of ethyl acetate. To the resulting solution, 25.0 parts by mass of 4,4'-diphenylmethane diisocyanate and 0.01 parts of dibutyltin dilaurate were added and reacted at 80°C for 24 hours to obtain an ethyl acetate solution of PUR1 (solid content 30% by mass). The number-average molecular weight of PUR1 was 84,000, the weight-average molecular weight was 200,000, and the glass transition temperature (Tg) was -10°C. 【0103】 Table 1 shows the materials, reagents, etc., used in the examples and comparative examples. 【0104】 [Table 1-1] [Table 1-2] 【0105】 Table 2 shows the compositions of paints A through D. [Table 2] 【0106】 <Example 1> A five-layer coating substitute film was prepared using the following procedure. The colored layer composition E1 shown in Table 3 was applied to a release-treated PET film (Film Vina® NSD, 50 μm thick, Fujimori Kogyo Co., Ltd. (Bunkyo-ku, Tokyo, Japan)) using a bar coater, and then placed in an 80°C hot air oven for 3 minutes, followed by a 120°C hot air oven for 3 minutes to form a 60 μm thick colored layer. 【0107】 The intermediate film layer composition (aqueous polyurethane solution) shown in Table 5 was applied onto the colored layer using a bar coater, and then placed in an 80°C hot air oven for 3 minutes, followed by a 120°C hot air oven for 3 minutes to form a 20 μm thick intermediate film layer. 【0108】 The bonding layer composition (phenoxy resin solution) shown in Table 6 was applied onto a PET film using a bar coater, and then placed in an 80°C hot air oven for 1 minute to form a bonding layer approximately 1 μm thick. The bonding layer was laminated onto an intermediate film layer using a heat laminator heated to 120°C, and the PET film used to form the bonding layer was removed. 【0109】 As a thermoplastic top layer, a 75 μm thick acrylic film (Technoloy® S014G, Sumika Acrylic Sales Co., Ltd. (Chuo-ku, Tokyo, Japan)) was laminated to the bonding layer side using a heat laminator heated to 120°C. 【0110】 The adhesive layer composition E1 shown in Table 4 was applied to the surface from which the release-treated PET film used for colored layer formation had been peeled off the laminate using a bar coater, and the laminate was placed in an 80°C hot air oven for 5 minutes, followed by a 100°C hot air oven for 3 minutes to form a 20 μm thick heat-sensitive adhesive layer. 【0111】 A 60 μm thick biaxially oriented PP film (PY-002, Oji F-Tex Co., Ltd. (Chuo-ku, Tokyo, Japan)) was laminated onto the heat-sensitive adhesive layer as a release liner to obtain the coating substitute film of Example 1. 【0112】 <Example 2, Comparative Example 1, and Comparative Example 2> The coating substitute films for Example 2, Comparative Example 1, and Comparative Example 2 were obtained using the same procedure as in Example 1, except that the colored layer composition was E2, C1, or C2 from Table 3, and the thickness of the colored layer was as described in Table 8. 【0113】 <Examples 3, 4, Comparative Example 3, and Comparative Example 4> Except for using E3, E4, C3, or C4 of Table 4 as the adhesive layer composition, the coating substitute films for Examples 3, 4, Comparative Example 3, and Comparative Example 4 were obtained using the same procedure as in Example 1. 【0114】 <Examples 5-7, Comparative Example 5, and Comparative Example 6> Except for using E3, E4, E5, C3, or C4 of Table 4 as the adhesive layer composition, the coating substitute films of Examples 5 to 7, Comparative Example 5, and Comparative Example 6 were obtained using the same procedure as in Example 2. 【0115】 <Examples 8-10, Comparative Example 7, and Comparative Example 8> The films from Example 5, Example 2, Example 6, Comparative Example 5, and Comparative Example 6 were used as the films from Examples 8 to 10, Comparative Example 7, and Comparative Example 8, respectively. 【0116】 <Example 11> The coating substitute film of Example 11 was obtained using the same procedure as in Example 1, except that a 75 μm thick PMMA-PVDF copolymer film (Acryprene® FBA015, Mitsubishi Chemical Corporation (Chiyoda-ku, Tokyo, Japan)) was used as the thermoplastic top layer. 【0117】 <Example 12> The paint substitute film of Example 12 was obtained using the same procedure as in Example 1, except that a 75 μm thick polycarbonate film (Technoloy® C000, Sumika Acrylic Sales Co., Ltd. (Chuo-ku, Tokyo, Japan)) was used as the thermoplastic top layer. 【0118】 <Comparative Example 9> A coating alternative film for Comparative Example 9 was obtained using the same procedure as in Example 1, except that instead of laminating with an acrylic film (Technoloy® S014G), the top layer composition (transparent two-component curable polyurethane composition) shown in Table 7 was applied to the bonding layer using a bar coater, and then placed in an 80°C hot air oven for 1 hour to form a 50 μm thick top layer. 【0119】 [Table 3] 【0120】 [Table 4] 【0121】 [Table 5] 【0122】 [Table 6] 【0123】 [Table 7] 【0124】 Table 8 shows the composition of the paint substitute films for Examples 1 to 12 and Comparative Examples 1 to 9. [Table 8] 【0125】 The paint substitute film was evaluated based on the following criteria. 【0126】 1.DVT formability 【0127】 The following were used as the base material. 【0128】 A.PC-ABS board The base material was obtained by cutting a 3mm thick, 150mm x 150mm square PC-ABS plate test panel (product name "flat plate test piece", made of Technopolymer black PC-ABS resin CK43, MC Yamasan Polymers Co., Ltd. (Chuo-ku, Tokyo, Japan)) with a mirror-finished surface into a 75mm x 50mm rectangle. The 20° gloss of the mirror-finished surface of the PC-ABS plate, measured according to JIS Z8741:1997, was 85-90. 【0129】 B. Electrodeposited coated steel sheet The base material was obtained by cutting a 0.8mm thick, 150mm x 65mm cationic electrodeposition coated steel sheet (JIS G 3141 (SPCC SD), Testpiece Co., Ltd. (Sagamihara City, Kanagawa Prefecture, Japan)) into a 75mm x 50mm rectangle. 【0130】 Using the DVT method, the paint substitute film was stretched to 200% by area ratio and attached to the substrate using the following procedure. 【0131】 A double-sided vacuum forming machine NGF0709 (Fuse Vacuum Co., Ltd., Habikino City, Osaka Prefecture, Japan) was used as the vacuum pressure forming machine. Figure 3A shows a schematic cross-sectional view of the vacuum pressure forming machine before stretching. The first vacuum chamber 31 and the second vacuum chamber 32 of the vacuum pressure forming machine 30 were separated from each other by the lower boiler 311, the lower boiler frame 312, the upper boiler 321, the upper boiler frame 322, and the paint substitute film 10 sandwiched between the lower boiler frame 312 and the upper boiler frame 322. An IR lamp heater 323 for heating was attached to the inner wall of the upper boiler 321 at the ceiling of the second vacuum chamber 32. The opening of the lower boiler frame 312 was a 260 mm x 260 mm square. 【0132】 A rectangular, open-topped, rectangular stretching jig 314, with an inner dimension the same size as the opening of the lower boiler frame 312, was placed on the lower boiler table 313 located at the bottom of the lower boiler 311. The height of the stretching jig 314 was 60 mm, which had been confirmed in advance to allow the paint substitute film 10 to be attached to the base material 40 when stretched by 200% in area ratio. 【0133】 A rectangular base material 40 measuring 75 mm x 50 mm was placed on the lower boiler table 313 and inside the stretching well-shaped jig 314, in a position where it had been confirmed in advance that the paint substitute film 10 would be attached to the base material 40 when it was stretched by 200% in area ratio. Figure 3B shows the placement of the base material in a top view. As shown in Figure 3B, the base material 40 was placed at four locations 90 mm away from the center of the stretching well-shaped jig 314, with its center located therein. The circles shown by dashed lines in Figure 3B represent the positions where the paint substitute film 10 will be attached to the base material 40 when it is stretched by 200% in area ratio. 【0134】 The paint substitute film 10 was cut into a 300mm x 300mm square and placed on the lower boiler frame 312. The thickness of the lower boiler frame 312 was 20mm. Therefore, the distance between the paint substitute film 10 and the base material 40 was 80mm, which is the sum of the thickness of the lower boiler frame 312 (20mm) and the height of the stretching well-shaped jig 314 (60mm). 【0135】 After the substrate 40 and the paint substitute film 10 were placed, the upper kettle 321 and upper kettle frame 322 were lowered, and the paint substitute film 10, which was placed on the lower kettle frame 312, was sandwiched between the upper kettle frame 322 and the lower kettle frame 312. Then, while reducing the pressure inside the first vacuum chamber 31 and the second vacuum chamber 32, the paint substitute film 10 was heated with an IR lamp heater 323 until it reached the molding temperature of 165°C ± 5°C. At this time, a vacuum state (2-4 kPa) was reached before reaching the molding temperature. The molding temperature was a value obtained based on the set temperature of the vacuum pressure forming machine 30 and the correspondence between the set temperature of the vacuum pressure forming machine 30 and the actual temperature of the paint substitute film 10, which was created in advance using a procedure described later. 【0136】 DVT molding was started when the molding temperature was reached. The lower boiler table 313 was raised until the stretching well-shaped jig 314 contacted the lower boiler frame 312. While maintaining the vacuum state inside the first vacuum chamber 31, the internal pressure of the second vacuum chamber 32 was set to 200-205 kPa, creating a pressure difference between the first vacuum chamber 31 and the second vacuum chamber 32, thereby stretching the paint substitute film 10 and attaching it to the substrate 40. Figure 3C shows a schematic cross-sectional view of the vacuum pressure forming machine after stretching. In the central part of the substrate 40, the paint substitute film 10 was stretched by 200% in area ratio and attached. 【0137】 After returning the first vacuum chamber 31 and the second vacuum chamber 32 to atmospheric pressure, the substrate 40 to which the stretched paint substitute film 10 was attached was removed. By using a utility knife to trim the excess paint substitute film 10 along the edges of the substrate 40, an evaluation sample for DVT moldability was obtained. 【0138】 It is generally known that there is a difference between the set temperature of the vacuum pressure forming machine and the actual temperature of the paint substitute film heated inside the vacuum pressure forming machine. Therefore, in this embodiment, the correspondence between the set temperature of the vacuum pressure forming machine and the actual temperature of the paint substitute film was determined in advance, and the actual temperature of the paint substitute film during DVT forming was considered to be a value obtained based on the set temperature of the vacuum pressure forming machine and the above correspondence. 【0139】 The actual temperature of the paint substitute film during DVT molding was measured using a temperature / voltage measurement unit NR-TH08 and a multi-input data logger NR-500 (both manufactured by Keyence Corporation, Osaka, Japan) and a thermocouple (symbol 0.1×1P K-2-H-J2(KH), wire: K type, manufactured by Ninomiya Electric Wire Industry Co., Ltd., Sagamihara, Kanagawa, Japan). 【0140】 To prevent the metal part of the thermocouple, which is the measurement area, from coming into contact with the paint substitute film 10, the thermocouple was attached to the surface of the paint substitute film 10 with heat-resistant tape. The paint substitute film 10 was then placed on the lower boiler frame 312 with the side to which the thermocouple was attached facing upwards. 【0141】 The upper kettle 321 and upper kettle frame 322 were lowered, and the paint substitute film 10, which was placed on the lower kettle frame 312, was sandwiched between the upper kettle frame 322 and the lower kettle frame 312. Then, the paint substitute film 10 was heated with an IR lamp heater 323. The set temperature of the vacuum pressure forming machine was 136°C when the thermocouple reading reached 165±5°C. Based on this relationship, during DVT forming, setting the vacuum pressure forming machine temperature to 136°C was considered to have heated the paint substitute film 10 to 165±5°C. 【0142】 2.Adhesive strength Test specimens bonded under the same conditions as DVT moldability were cut into 10mm wide strips, and the adhesive strength was measured using a tensile testing machine (Tensilon® universal testing machine, model number: RTC-1210A, A&D Company, Limited (Toshima-ku, Tokyo, Japan)) at a temperature of 23°C and a peeling speed of 200mm / min, followed by a 180-degree peel. For automotive exterior paint replacement applications, an adhesive strength of 6.4 N / 10mm or higher is required. 【0143】 3. Opacity (Opacity) The opacity test evaluates the opacity (ability to hide the underlying color) of a paint substitute film. Paint substitute films used in the DVT method require sufficient opacity to be maintained even after stretching, as the colored layer thins and opacity decreases after stretching. Using the DVT method, the paint substitute film was heated to 165°C ± 5°C and stretched to 100% (unstretched) or 200% of the surface area of ​​the paint substitute film before stretching, and then attached to the mirror-finished surface of a black PC-ABS board used in the DVT moldability test. The measurement sample was then prepared. L of the measurement sample... * a * , b * The value was measured using a spectrophotometer (CM-3700d, Konica Minolta Japan, Inc. (Minato-ku, Tokyo, Japan)). As a reference, the value of a black PC-ABS flat panel with an unstretched paint substitute film attached was used as L1. * a1 * , b1 * The value of a black PC-ABS flat panel with a paint substitute film applied at an area ratio of 200% is L2 * a2 * , b2 * When this is done, the color difference ΔE * The following formula: ΔE * =[(L2 * -L1 * ) 2 +(a2 * -a1 * ) 2 +(b2 * -b1 * ) 2 ] 1 / 2 It was calculated using the following method. For use as a substitute for paint on the exterior of automobiles, ΔE * It is required that the value be less than 1. 【0144】 4. Heat shrinkage A grid-like pattern of cuts 40 mm wide was made in the center of a test specimen bonded under the same conditions as for DVT moldability, as shown in Figure 4, and it was left at 95°C for 144 hours (6 days). The opening of the cuts was measured at four locations, and the average of the four measurements was used as an indicator of thermal shrinkage. A cut opening of 1.0 mm or less was considered a pass, and an opening greater than 1.0 mm was considered a fail. 【0145】 5. Glossiness The 60-degree gloss of the surface of test pieces bonded under the same conditions as DVT moldability was measured using a portable gloss meter GMX-202 (Murakami Color Research Institute Co., Ltd., Chuo-ku, Tokyo, Japan). For use as a substitute for automotive exterior paint, a 60-degree gloss of 85 or higher is desirable, and a value between 75 and 85 is acceptable. 【0146】 6. Chemical resistance 0.2 mL of (A) 1% by mass HCl aqueous solution, (B) 1% by mass NaOH aqueous solution, or (C) 30% by mass H3PO4 aqueous solution was dropped onto the surface of a test specimen bonded under the same conditions as for DVT moldability. After being left at 85°C for 30 minutes, the specimen was washed with detergent and water. The presence or absence of droplet traces on the surface after washing was visually observed. For applications as a substitute for paint on automotive exteriors, the absence of droplet traces is required. 【0147】 7. Weather resistance Test specimens bonded under the same conditions as DVT moldability were subjected to a black panel thermometer reading of 63°C, in accordance with JIS K 5600-7-7:2008, and the integrated energy of light with wavelengths of 300nm to 400nm was 750MJ / m². 2 An accelerated weathering test was conducted to achieve the following result: Cumulative energy amount: 750 MJ / m³ 2 This corresponds to 3 years of outdoor exposure. The 60-degree gloss and L of the test specimens before and after the accelerated weathering test. * a * , b * The gloss was measured. The gloss retention rate (%) was calculated as G2 / G1, where G1 was the 60-degree gloss before the accelerated weathering test and G2 was the 60-degree gloss after the accelerated weathering test. The value before the accelerated weathering test was also measured as L1. * a1 * , b1 * The value after the accelerated weathering test is L2* a2 * , b2 * When this is done, the color difference ΔE * The following formula: ΔE * =[(L2 * -L1 * ) 2 +(a2 * -a1 * ) 2 +(b2 * -b1 * ) 2 ] 1 / 2 It was calculated using the following method. For use as a substitute for paint on automotive exteriors, the gloss retention rate must be 80% or higher, and ΔE * The value must be less than 3. 【0148】 8.200% tensile strength A sample was prepared in which two short sides of the paint substitute film were sandwiched between 3M® heat-resistant polyimide tape 5413 (3M Japan Ltd., Shinagawa-ku, Tokyo, Japan), with a width of 25 mm, attached to both sides of a paint substitute film cut to a length of approximately 100 mm and a width of 25 mm, with a 50 mm gap along the length of the film. The sample was fixed to a tensile testing machine (Tensilon® universal testing machine, model number: RTC-1210A, A&D Company, Limited, Toshima-ku, Tokyo, Japan) with the chucks spaced 55 mm apart, so that the 3M® heat-resistant polyimide tape 5413 was in contact with the chucks. A constant temperature chamber was positioned to completely cover the chuck area, and measurements were started when the temperature display inside the chamber reached 120°C. The tensile strength of the paint replacement film was measured when it was stretched to 200% elongation (twice its original length) at a temperature of 120°C and a tensile speed of 150 mm / min. Two measurements were taken and the average value was calculated. For paint replacement applications on automotive exteriors, a tensile strength of 0.6 MPa or higher at 200% elongation is required at a temperature of 120°C. 【0149】 The evaluation results of the paint substitute films are shown in Tables 9 to 11. 【0150】 [Table 9] 【0151】 [Table 10] 【0152】 [Table 11] 【0153】 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. Some embodiments of the present invention are described below. [Aspect 1] Thermoplastic top layer, A thermoplastic resin containing a carboxyl group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer, and a colored layer containing a colorant, and Thermal adhesive layer containing polyurethane-based thermal adhesive A paint substitute film comprising the following in this order, wherein the paint substitute film is heated to 165°C ± 5°C, and when the area of ​​the paint substitute film before stretching is set to 100%, it is stretched to 200% by area ratio using a vacuum pressure forming machine, bonded to a PC-ABS board, cut into a grid pattern with a width of 40 mm, and the gap between the cuts after being left at 95°C for 144 hours is 1.0 mm or less. [Aspect 2] The paint substitute film according to Embodiment 1, wherein the paint substitute film is heated to 165°C ± 5°C, and when the area of ​​the paint substitute film before stretching is set to 100%, it is stretched to 200% by area ratio using a vacuum pressure forming machine, bonded to a PC-ABS board, cut into strips with a width of 10 mm, and the adhesive strength when peeled at 180 degrees at 23°C and a peeling speed of 200 mm / min is 6.4 N / 10 mm or more. [Aspect 3] A coating substitute film according to either embodiment 1 or 2, wherein the glass transition temperature of one of the carboxyl group-containing (meth)acrylic polymer and the amino group-containing (meth)acrylic polymer is 0°C or higher, and the glass transition temperature of the other is 0°C or lower. [Aspect 4] The aforementioned paint substitute film is heated to 165°C ± 5°C, and when the area of ​​the paint substitute film before stretching is set to 100%, it is stretched to 200% by area ratio using a vacuum pressure forming machine and bonded to a PC-ABS board, and then the stretched paint substitute film is subjected to JIS K In accordance with 5600-7-7:2008, the integrated energy of light with wavelengths of 300nm to 400nm is 750MJ / m² at a black panel thermometer display temperature of 63°C. 2 A paint substitute film according to any one of embodiments 1 to 3, wherein, after undergoing accelerated weathering tests to achieve the above, the paint substitute film has a 60-degree gloss retention rate of 80% or more. [Aspect 5] The coating substitute film according to any one of embodiments 1 to 4, wherein the thermoplastic top layer comprises at least one resin selected from the group consisting of polymethyl methacrylate, polyvinylidene fluoride, and methyl methacrylate-vinylidene fluoride copolymer. [Aspect 6] The paint substitute film according to any one of embodiments 1 to 5, wherein the tensile strength of the paint substitute film at 200% elongation at a temperature of 120°C is 0.6 MPa to 20 MPa. [Explanation of symbols] 【0154】 10 Paint Replacement Film 12 Thermoplastic top layer 14 Colored layer 142 Thermoplastic resin 144 Colorants 16. Heat-sensitive adhesive layer 20 Liners 22 Intermediate film layer 24 Bonding layer 30 Vacuum pressure forming machine 31 1st vacuum chamber 311 Lower pot 312 Lower boiler frame 313 Lower boiler table 314 Well-shaped jig for extension 32 Second vacuum chamber 321 Upper pot 322 Upper boiler frame 323 IR Lamp Heater 33 Pedestal 34 partition plates 35 Elevating platform 40 Base material 41 Back part 42 Goods

Claims

[Claim 1] Thermoplastic top layer, A thermoplastic resin containing a carboxyl group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer, and a colored layer containing a colorant, and A heat-sensitive adhesive layer containing a cross-linked polyurethane-based heat-sensitive adhesive. A paint substitute film comprising the following in this order: The paint substitute film is heated to 165°C ± 5°C, and when the area of ​​the paint substitute film before stretching is set to 100%, it is stretched to 200% by area ratio using a vacuum pressure forming machine, bonded to a PC-ABS board, cut into a grid pattern with a width of 40 mm, and the gap between the cuts after being left at 95°C for 144 hours is 1.0 mm or less. [Claim 2] The paint substitute film according to claim 1, wherein the paint substitute film is heated to 165°C ± 5°C, and when the area of ​​the paint substitute film before stretching is set to 100%, it is stretched to 200% by area ratio using a vacuum pressure forming machine and bonded to a PC-ABS board, cut into strips with a width of 10 mm, and when peeled at 180 degrees at 23°C and a peeling speed of 200 mm / min, the adhesive strength is 6.4 N / 10 mm or more. [Claim 3] The coating substitute film according to claim 1 or 2, wherein the glass transition temperature of one of the carboxyl group-containing (meth)acrylic polymer and the amino group-containing (meth)acrylic polymer is 0°C or higher, and the glass transition temperature of the other is 0°C or lower. [Claim 4] The aforementioned paint substitute film is heated to 165°C ± 5°C, and with the area of ​​the paint substitute film before stretching set to 100%, it is stretched to 200% by area ratio using a vacuum pressure forming machine and bonded to a PC-ABS board. Then, in accordance with JIS K 5600-7-7:2008, the stretched paint substitute film is subjected to a black panel thermometer reading of 63°C, and the integrated energy of light with wavelengths of 300 nm to 400 nm is 750 MJ / m². ２ The paint substitute film according to any one of claims 1 to 3, wherein the paint substitute film has a 60-degree gloss retention rate of 80% or more after undergoing an accelerated weathering test to achieve the above. [Claim 5] The coating substitute film according to any one of claims 1 to 4, wherein the thermoplastic top layer comprises at least one resin selected from the group consisting of polymethyl methacrylate, polyvinylidene fluoride, and methyl methacrylate-vinylidene fluoride copolymer. [Claim 6] The coating substitute film according to any one of claims 1 to 5, wherein the tensile strength of the coating substitute film at 200% elongation at a temperature of 120°C is 0.6 MPa to 20 MPa, and the tensile strength at 200% elongation is measured by preparing a measurement sample with a length of 100 mm and a width of 25 mm, and stretching the measurement sample to 200% elongation using a tensile testing machine described in ISO 7500-1:2015 at a temperature of 120°C, a tensile speed of 150 mm / min, and a chuck spacing of 50 mm, and 200% elongation means the state in which the film is stretched to a length of 200% when the length of the film before stretching is considered to be 100%.

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