Vehicle paint replacement film

Abstract

To provide a vehicle coating alternative film which has high elongation property (for example, 140% elongation), is not peeled off even under high temperature environment, hardly allows wrinkles, peeling and deviation to occur in the film even when force is applied in a direction perpendicular to a vertical direction with respect to an adherend surface in a state that load is applied to the adherend surface from the vertical direction, and can be stuck with a hand.SOLUTION: A vehicle coating alternative film includes in the following order: a 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 and a coloring agent; a thermoplastic base film layer; and a heat-sensitive adhesive layer. Therein, elastic modulus at 23°C of the heat-sensitive adhesive layer is 0.35-10 MPa.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This disclosure relates to a vehicle 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. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2013-039724 [Patent Document 2] Japanese Patent Publication No. 2007-297569 [Overview of the project] [Problems that the invention aims to solve]

[0006] The application of paint substitute films to curved articles is generally carried out using methods such as dual vacuum thermoforming (DVT), vacuum forming (VT), and water transfer printing. Depending on the size, shape, and application location of the article, it may be desirable to apply the paint substitute film by hand. From the perspectives of reducing investment in manufacturing equipment, mitigating environmental impact such as the dispersion of volatile organic compounds (VOCs), and accommodating small-lot production, there is a market demand for paint substitute films that can be applied by hand. Because there is a limit to the stretchability of paint substitute films, if the film is stretched excessively during application, the film may peel or crack when the article to which the film is applied is placed in a high-temperature environment.

[0007] For example, when a paint substitute film is used in areas involving movable parts, the film may constantly be subjected to force from a direction perpendicular to the surface it is adhered to, such as by a rubber seal. When the movable part moves in this state, in addition to the load from the vertical direction, force is also applied to the film in a direction perpendicular to that vertical direction. As a result, wrinkles, peeling, or displacement may occur in the film, damaging the appearance of the decorative surface or even causing the film to break.

[0008] The present disclosure provides a vehicle painting alternative film that can be applied by hand, has high extensibility (e.g., 140% elongation), does not peel even in a high-temperature environment, and is less likely to wrinkle, peel, or shift when a force is applied in a direction orthogonal to the vertical direction while a load is applied from the vertical direction to the adherent surface.

Means for Solving the Problems

[0009] According to an embodiment of the present disclosure, there is provided a vehicle painting alternative film including a colored layer containing a top layer, a thermoplastic resin including a carboxy group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer, and a colorant, a thermoplastic base film layer, and a pressure-sensitive adhesive layer in this order, wherein the elastic modulus of the pressure-sensitive adhesive layer at 23°C is 0.35 MPa to 10 MPa.

Advantages of the Invention

[0010] According to the present disclosure, it is possible to provide a vehicle painting alternative film that can be applied by hand, has high extensibility (e.g., 140% elongation), does not peel even in a high-temperature environment, and is less likely to wrinkle, peel, or shift when a force is applied in a direction orthogonal to the vertical direction while a load is applied from the vertical direction to the adherent surface.

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

Brief Description of the Drawings

[0012] [Figure 1] It is a schematic cross-sectional view of a vehicle painting alternative film according to an embodiment. [Figure 2A] It is a top view (upper side) and a side view (lower side) of a measurement sample for the cockling test. [Figure 2B] It is a side view showing the state of a measurement sample during the cockling test. [Figure 3] It is a schematic top view of a measurement sample for each score in the cockling test. [Modes for carrying out the invention]

[0013] 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.

[0014] In this disclosure, "(meth)acrylic" means acrylic or methacrylic, and "(meth)acrylate" means acrylate or methacrylate.

[0015] In this disclosure, the term "hardening" also encompasses the concept commonly known as "crosslinking."

[0016] In this disclosure, the term "film" also includes articles referred to as "sheets."

[0017] In this disclosure, for example, "on top of" in "the colored layer is placed on top of the thermoplastic base film layer" means that the colored layer is placed in direct contact with the thermoplastic base film layer, or that the colored layer is placed above the thermoplastic base film layer via another layer.

[0018] 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.

[0019] In this disclosure, "translucent" means that the average transmittance in the visible light region (wavelength 400nm to 700nm), measured in accordance with JIS K 7375, is approximately 40% or more and less than approximately 80%, preferably approximately 75% or less.

[0020] One embodiment of the vehicle paint substitute film (hereinafter also simply referred to as "paint substitute film") comprises, in this order, a top layer, a colored layer containing a thermoplastic resin and a colorant, a thermoplastic base film layer, and a pressure-sensitive adhesive layer. The thermoplastic resin in the colored layer includes a carboxyl group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer. The elastic modulus of the pressure-sensitive adhesive layer at 23°C is 0.35 MPa to 10 MPa.

[0021] In the paint-alternative film of this disclosure, a colored layer containing a specific thermoplastic resin, a thermoplastic base film layer, and a pressure-sensitive adhesive layer having a specific modulus of elasticity are arranged in this order. Although not bound by any theory, the materials and properties of these layers impart high elongation (e.g., 140% elongation) to the paint-alternative film. In addition, it is believed that the cooperation of these layers imparts the strength necessary to exhibit high adhesion in high-temperature environments to the paint-alternative film, and suppresses the occurrence of wrinkles, peeling, and slippage under conditions where a load is applied perpendicular to the surface to be bonded, and a force is applied in a direction perpendicular to that perpendicular direction. These properties of the paint-alternative film offer several excellent advantages, such as enabling manual application of the film while stretching it to curved surfaces, suppressing peeling or wrinkles caused by interference between the film and other parts, and making it less likely for the film to peel or crack even if it is damaged by flying stones or the like while stretched and applied.

[0022] Figure 1 shows a schematic cross-sectional view of a vehicle paint substitute film 10 according to one embodiment. The vehicle paint substitute film 10 includes a top layer 12, a colored layer 14, a thermoplastic base film layer 16, and a pressure-sensitive adhesive layer 18 in that order. The colored layer 14 includes a thermoplastic resin 142 and a colorant 144. The paint substitute film may further include, as optional elements, a bonding layer that joins the above layers together, and a liner 20. In one embodiment, the paint substitute film consists of a top layer, a colored layer, a thermoplastic base film layer, and a pressure-sensitive adhesive layer.

[0023] For the 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), 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 their excellent weather resistance, acrylic resins, polyurethanes, fluororesins, and polyvinyl chloride are preferred, and acrylic resins and polyurethanes are more preferred because they have excellent scratch resistance and have a low environmental impact when incinerated or landfilled as waste.

[0024] The top layer can be formed by applying a top layer composition onto the colored layer. Alternatively, a top layer film can be formed by applying a top layer composition onto another liner, and this film can be laminated onto the colored layer via a bonding layer. If the colored layer is adhesive to the top layer film formed on the liner, the top layer film can also be directly transferred and laminated onto the colored layer without a bonding layer. The top layer can be formed, for example, by applying a top layer composition such as a reactive polyurethane composition to the colored layer or liner using a knife coat, bar coat, blade coat, doctor coat, roll coat, cast coat, etc., and then heat-curing it as needed.

[0025] Reactive polyurethane compositions generally contain a polyol and a crosslinking agent. Examples of polyols include polyester polyols such as acrylic polyols and polycaprolactone diol; polycarbonate polyols such as cyclohexanedimethanol carbonate and 1,6-hexanediol carbonate; and polyether polyols such as polyethylene glycol and polypropylene glycol. Examples of crosslinking agents include polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, methylenebis(4-phenylisocyanate), 4,4'-methylenebiscyclohexyl diisocyanate (also known as hydrogenated MDI, H12MDI, etc.), and their burette, isocyanurate, or adduct forms. Reactive polyurethane compositions may be aqueous or organic solvent-based. In the case of aqueous compositions, further crosslinking with polycarbodiimide, aziridine, oxazoline, etc., is possible. Water-based reactive polyurethane compositions preferably contain a combination of polycarbonate polyol, polycarbodiimide, 4,4'-methylenebiscyclohexyl diisocyanate, and / or aziridine. Organic solvent-based reactive polyurethane compositions preferably contain a combination of polycaprolactone diol and polycarbonate diol with isophorone diisocyanate trimer (isocyanurate).

[0026] As the top layer, a film pre-formed by extrusion, stretching, etc., may be used. Such a film can be laminated to the colored layer 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 top layer can also be formed by multi-layer extrusion with other layers. Examples of such films include thermoplastic polyurethane film, acrylic film, fluorine-based film, PVC film, and polyolefin film. Examples of acrylic films include polymethyl methacrylate (PMMA) resin, polybutyl acrylate resin, ethylene / acrylic copolymer resin, and ethylene vinyl acetate / acrylic copolymer resin. Acrylic films have excellent transparency, are resistant to heat and light, and are less prone to fading and gloss changes even when used outdoors. Acrylic films have excellent stain resistance even without the use of plasticizers and have good moldability. As fluorine-based films, polyvinylidene fluoride (PVdF), vinylidene fluoride-methyl methacrylate copolymer, ethylene-tetrafluoroethylene copolymer (ETFE), and tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV) can be used.

[0027] The top layer preferably contains cross-linked polyurethane. Cross-linked polyurethane can impart both moderate elongation and strength to the top layer. While not bound by any particular theory, a top layer with both moderate elongation and strength is thought to work in cooperation with other layers to more effectively suppress the occurrence of wrinkles, peeling, and shearing under conditions where a load is applied perpendicular to the bonded surface and a force is applied in a direction perpendicular to that perpendicular direction.

[0028] The top layer may optionally contain additives such as benzotriazole, UV absorbers such as Tinuvin® 99-2 (BASF Japan Ltd., Chuo-ku, Tokyo, Japan), and Tinuvin® 1130 (BASF Japan Ltd.), and hindered amine light stabilizers (HALS) such as Tinuvin® 292 (BASF Japan Ltd.). 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 top layer may contain hard coat materials, gloss enhancers, etc., and may have an additional hard coat layer. The top layer may be transparent or translucent in order to provide the desired appearance. It is advantageous for the top layer to be transparent.

[0029] The thickness of the top layer can vary, but generally it is approximately 1 μm or more, approximately 5 μm or more, or approximately 10 μm or more, approximately 100 μm or less, approximately 80 μm or less, or approximately 60 μm or less. When applying a paint substitute film to articles with complex shapes, a thinner top layer is advantageous from the viewpoint of shape conformability, and for example, it is desirable to have a thickness of approximately 80 μm or less, or approximately 60 μm or less. On the other hand, when imparting high light resistance or weather resistance to an article, a thicker top layer is advantageous, and for example, it is desirable to have a thickness of approximately 5 μm or more, or approximately 10 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 elongation and can maintain its adhesive state without breaking or peeling even in high-temperature environments. Carboxyl group-containing (meth)acrylic polymers can be obtained by copolymerizing monoethylene unsaturated monomers with carboxyl group-containing unsaturated monomers. Amino group-containing (meth)acrylic polymers can be obtained by copolymerizing monoethylene unsaturated monomers with amino group-containing unsaturated monomers.

[0032] Monoethylene unsaturated monomers are the main components of (meth)acrylic polymers, and are generally represented by the formula CH2=CR 1 COOR 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 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. 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

number

[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. In this disclosure, the weight-average molecular weight refers to the molecular weight converted using the GPC method for standard polystyrene.

[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 100,000 or less, or approximately 80,000 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 can be formed by applying the colored layer composition to a thermoplastic base film layer and drying, solidifying, or curing it. As the coating apparatus, a conventional coater, such as a bar coater, knife coater, roll coater, or die coater, can be used. Drying, solidifying, or curing can be carried out by drying the colored layer composition containing a volatile solvent, or by cooling the molten resin component. 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, antioxidants such as phenolic antioxidants, leveling agents such as silicone, viscosity control agents such as wax 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 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 setting the 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 elongation characteristics 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 applied to an article in an elongated state, it is possible to maintain an excellent appearance (e.g., clarity, gloss retention rate, etc.).

[0062] The colored layer may have adhesive properties. An adhesive colored layer can be laminated onto the top layer or thermoplastic resin base film 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 100 μm or less, about 80 μm or less, or about 60 μm or less. By making the thickness of the colored layer about 10 μm or more, the base color can be concealed and the desired decorative appearance can be provided. When high shape conformability is required, a thinner colored layer is advantageous, and for example, a thickness of about 80 μm or less, or about 60 μm or less is desirable.

[0064] The thermoplastic base film layer, acting as an intermediate layer between the colored layer and the pressure-sensitive adhesive layer, imparts toughness to the paint-alternative film. Working in cooperation with the pressure-sensitive adhesive layer, which has a specific modulus of elasticity, it suppresses wrinkles, peeling, or displacement of the paint-alternative film when a load is applied perpendicular to the surface and a force is applied in a direction perpendicular to that perpendicular direction. Because the thermoplastic base film layer is thermoplastic, it can also impart sufficient flexibility to the paint-alternative film to maintain its adhesive state even in high-temperature environments.

[0065] As the thermoplastic base film layer, for example, a thermoplastic resin film made of polyurethane, polyvinyl chloride, polyethylene, polyolefin such as polypropylene, polyester such as polyethylene terephthalate and polybutylene terephthalate, acrylic polymer, or fluoropolymer can be used. Preferably, the thermoplastic base film layer contains at least one thermoplastic resin selected from the group consisting of polyurethane, polyvinyl chloride, polyolefin, and polyester.

[0066] The thickness of the thermoplastic base film layer is preferably about 10 μm or more and about 500 μm or less, more preferably about 30 μm or more and about 300 μm or less, and even more preferably about 80 μm or more and about 200 μm or less. When the paint substitute film is used on the lower side or front of an automobile, considering the resistance to flying stones, the thickness of the thermoplastic base film layer is preferably about 80 μm or more. Except when the paint substitute film is temporarily applied to the surface of the adherend as a protective tape, the thickness of the thermoplastic base film layer is preferably about 30 μm or more, as it is less likely to wrinkle when applied to a curved surface. If the paint substitute film is too thick, its ability to conform to curved surfaces tends to be impaired, and from an economic standpoint, it is advantageous for the thickness of the thermoplastic base film layer to be about 300 μm or less.

[0067] The pressure-sensitive adhesive layer generally contains an adhesive polymer as an adhesive component. The adhesive polymer may be an acrylic resin, polyurethane, polyolefin, polyester, rubber resin, silicone resin, vinyl acetate resin, or other adhesive polymer. The adhesive polymer may be crosslinked. The pressure-sensitive adhesive layer may further contain a tackifier.

[0068] From the viewpoint of weather resistance and adhesive strength, the pressure-sensitive adhesive layer preferably contains an acrylic adhesive polymer, and more preferably contains a crosslinked acrylic adhesive polymer.

[0069] The pressure-sensitive adhesive layer may contain achromatic pigments such as white pigment, black pigment, or mixtures thereof, chromatic pigments such as yellow pigment, red pigment, green pigment, blue pigment, orange pigment, or combinations thereof. These pigments may be dispersed directly in the adhesive polymer, or they may be dispersed in the pressure-sensitive adhesive layer using a polymer binder such as acrylic resin as a dispersant. The pressure-sensitive adhesive layer containing a white pigment also functions as an opacity layer that conceals the surface (substrate) of the adherend. Titanium dioxide is preferably used as the white pigment due to its high whiteness.

[0070] The pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition containing an adhesive polymer. Specifically, the pressure-sensitive adhesive layer can be formed by applying the pressure-sensitive adhesive composition onto a thermoplastic base film layer. Alternatively, the pressure-sensitive adhesive layer can be formed by applying the pressure-sensitive adhesive composition onto another liner, and then the pressure-sensitive adhesive layer can be transferred and laminated onto the thermoplastic base film layer. For example, the pressure-sensitive adhesive layer can be formed by applying the pressure-sensitive adhesive composition to a thermoplastic base film layer or liner using a knife coat, bar coat, blade coat, doctor coat, roll coat, cast coat, etc., and then heat-curing it as needed. The liner may have a surface that has been peeled off with silicone or the like.

[0071] The elastic modulus of the pressure-sensitive adhesive layer at 23°C is about 0.35 MPa or more and about 10 MPa or less. When a load is applied to the pressure-sensitive adhesive layer from a direction perpendicular to the adherent surface, the pressure-sensitive adhesive layer having an elastic modulus within the above range has sufficient cohesive force to suppress the occurrence of wrinkles, peeling, and displacement of the coating replacement film when a force is applied in a direction orthogonal to the vertical direction. The elastic modulus of the pressure-sensitive adhesive layer at 23°C is preferably about 0.4 MPa or more and about 5 MPa or less, and more preferably about 0.45 MPa or more and about 1 MPa or less.

[0072] In the present disclosure, the elastic modulus of the pressure-sensitive adhesive layer is determined using an atomic force microscope (AFM). Specifically, using an atomic force microscope (Cypher AFM, Oxford Instruments Co., Ltd.), at room temperature (23°C), in a region of 10×10 square micrometers (μm 2 ), the surface morphology of the pressure-sensitive adhesive layer is observed. Then, in a 2×2 square micrometer or 1×1 square micrometer region that is substantially flat within that region, force curve measurement is performed under the following measurement conditions to determine the elastic modulus of the pressure-sensitive adhesive layer. (A) Probe OMCL-AC240TS (spring constant (k) = 2 N / m, tip radius: 7 nm, vibration frequency: 58 - 65 kHz, Olympus Corporation), Calibration of spring constant: Thermal noise method (B) Image Target amplitude: 2 V Set point: 1.6 V Integration gain: 78 Drive amplitude: 100 - 300 mV (C) Force curve Force distance: 1 micrometer Trigger point: 0.2 V Tip speed: 1.98 micrometers / second

[0073] The thickness of the pressure-sensitive adhesive layer can vary, but is generally about 5 μm or more, about 10 μm or more, or about 20 μm or more, about 100 μm or less, about 80 μm or less, or about 50 μm or less. To obtain high adhesive strength that allows the pressure-sensitive adhesive layer to follow the irregularities of the adherend surface and prevents peeling, it is preferable that the thickness of the pressure-sensitive adhesive layer be about 20 μm or more. To reduce the phenomenon of the pressure-sensitive adhesive oozing out at the edges of the paint substitute film when the film shrinks in a high-temperature environment after being stretched and applied, it is preferable that the thickness of the pressure-sensitive adhesive layer be about 50 μm or less.

[0074] The paint substitute film may have a liner that protects the pressure-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 peeled off with silicone or the like. 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 pressure-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 pressure-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 pressure-sensitive adhesive composition is applied to the release surface of this liner and heated as necessary to form a pressure-sensitive adhesive layer. This transfers the uneven structure (negative structure) of the liner to the surface of the pressure-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 pressure-sensitive adhesive layer may be arranged in a regular pattern on the adhesive surface by arranging grooves of a certain shape along a regular pattern, as long as they prevent air bubbles from remaining when the paint substitute film is attached to the article, or irregular grooves may be arranged to form an irregular pattern. 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 base 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 perpendicular to the adhesive surface.

[0078] A paint-alternative film can be manufactured, for example, by the following procedure: A thermoplastic resin film having a first carrier liner on one side is prepared as a thermoplastic base film layer. A colored layer composition is prepared and applied to the exposed surface of the base film layer, and heated and dried as necessary to form a colored layer. A top layer composition is prepared and applied on top of the colored layer, and heated and dried as necessary to form a top layer. A second carrier liner is laminated on top of the top layer, and the first carrier liner on top of the thermoplastic resin film is removed. A pressure-sensitive adhesive composition is prepared and applied on top of another release liner, and heated and dried as necessary to form a pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer is laminated on top of the thermoplastic resin film so that the pressure-sensitive adhesive layer and the exposed surface of the thermoplastic resin film are in contact. By removing the second carrier liner from the top layer, a paint-alternative film having a release liner can be obtained.

[0079] 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 150 μm or more, about 600 μm or less, about 400 μm or less, or about 350 μm or less.

[0080] In one embodiment, the tensile strength of the vehicle paint replacement film at 140% elongation is approximately 2.0 MPa or more, approximately 2.5 MPa or more, or approximately 3.0 MPa or more, approximately 20 MPa or less, approximately 10 MPa or less, or approximately 5.0 MPa or less at a temperature of 95°C. In this disclosure, 140% elongation means the state in which the film is stretched to 140% of its original length, with the length of the film before stretching being set to 100%. The tensile strength at 140% elongation is the tensile strength at the point when a measurement sample of approximately 100 mm in length and 25 mm in width is stretched to 140% elongation using a tensile testing machine described in ISO7500-1:2015 at a temperature of 95°C, a tensile speed of 150 mm / min, and a chuck spacing of 50 mm.

[0081] In one embodiment, the elongation at break of the vehicle paint substitute film is approximately 40% or more, approximately 70% or more, or approximately 100% or more, approximately 700% or less, approximately 500% or less, or approximately 300% or less at a temperature of 23°C. The elongation at break is calculated by preparing a measurement sample of approximately 100 mm in length and 25 mm in width, and using a tensile testing machine at a temperature of 23°C, a tensile speed of 150 mm / min, and a chuck spacing of 50 mm, at the point when the measurement sample is stretched until it breaks along its entire width, using the formula: [Chuck spacing at break (mm) - Chuck spacing before stretching (mm) (=50 mm)] / Chuck spacing before stretching (mm) (=50 mm) × 100 (%).

[0082] The paint substitute film of this disclosure can be applied to the body of a vehicle (including the roof, doors, hood, etc.) or a part thereof, or to components of a vehicle (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, pleasure boats, yachts, and motorboats. The paint substitute film of this disclosure is particularly suitable for application by hand to the surface of curved articles. [Examples]

[0083] 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.

[0084] 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.

[0085] 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.

[0086] Table 1 shows the materials, reagents, etc., used in the examples and comparative examples.

[0087] [Table 1]

[0088] Table 2 shows the composition of paint A (white color sol). [Table 2]

[0089] The composition of paint B (blue color sol) is shown in Table 3. [Table 3]

[0090] Example 1 The vehicle paint replacement film for Example 1 was manufactured using the following procedure.

[0091] 1. Colored layer and base film layer A white layer composition with a solid content of 43.0% by mass was prepared using the composition described in Table 4. A 150 μm thick corona-treated thermoplastic polyurethane (TPU) film (Huntsman Corporation, Port Neches, Texas, USA) was prepared as the base film layer. An 80 μm thick OP liner (Seedam Co., Ltd., Osaka, Japan) was laminated to one side of the TPU film. The white layer composition was applied onto the TPU film using a knife coater. The TPU film coated with the white layer composition was placed on corrugated cardboard and dried in an 80°C hot air oven for 10 minutes to form a white colored layer approximately 40 μm thick.

[0092] [Table 4]

[0093] 2. Top Tier A top layer composition with a solid content of 76.3% by mass was prepared using the composition described in Table 5. The top layer composition was applied to the colored layer using a knife coater. The TPU film with the top layer composition applied to the colored layer was placed on corrugated cardboard and dried in an 80°C hot air oven for 4 minutes to form a top layer approximately 25 μm thick. The top layer was not completely cured and the surface was sticky. A high-gloss 50 μm thick polyethylene terephthalate (PET) film T60 (Toray Industries, Inc., Chuo-ku, Tokyo, Japan) was laminated onto the top layer using a laminator and left at room temperature for one week to completely cure the top layer. After that, the OP liner was removed.

[0094] [Table 5]

[0095] 3. Pressure-sensitive adhesive layer A pressure-sensitive adhesive composition with a solid content of 34.0% by mass was prepared using the composition described in Table 6. The pressure-sensitive adhesive composition was applied to an embossed PE / PET / PE / silicone release liner using a knife coater. The release liner coated with the pressure-sensitive adhesive composition was placed on corrugated cardboard and dried in an 80°C hot air oven for 10 minutes to form a pressure-sensitive adhesive layer approximately 35 μm thick.

[0096] [Table 6]

[0097] 4. Lamination By laminating a pressure-sensitive adhesive layer onto the TPU film side of the laminate from step 2 above and removing T60, the vehicle paint replacement film of Example 1 was produced.

[0098] Example 2 and Comparative Example 1 Vehicle paint substitute films were prepared using the same procedure as in Example 1, except that the pressure-sensitive adhesive composition was changed to one of the formulations listed in Table 7. The solid content of the pressure-sensitive adhesive composition in Example 2 was 36.9% by mass, and the solid content of the pressure-sensitive adhesive composition in Comparative Example 1 was 33.3% by mass.

[0099] [Table 7]

[0100] Examples 4, 5, 6, Comparative Example 5, and Comparative Example 6 A vehicle paint substitute film was prepared using the same procedure as in Example 1, except that the blue layer composition described in Table 8 was used instead of the white layer composition. [Table 8]

[0101] Example 3 A vehicle paint substitute film was prepared using the same procedure as in Example 5, except that SP P-40 (Tatsuta Chemical Co., Ltd. (Chuo-ku, Tokyo, Japan)), which consists of a 150 μm thick PVC film laminated with a peelable 38 μm PET film, was used instead of the base film layer in Example 5, a blue layer composition was applied on top of the PVC film, and the PET film was removed instead of the OP liner after the top layer lamination process.

[0102] Comparative Example 2 A vehicle paint substitute film was prepared using the same procedure as in Example 5, except that the base film layer of Example 5 was not used, and the blue layer composition was applied onto a 60 μm thick OP film PY-002 (Oji F-Tex Co., Ltd. (Chuo-ku, Tokyo, Japan)), and the OP film was removed after the top layer lamination process.

[0103] Comparative Example 3 A vehicle paint substitute film was prepared using the same procedure as in Comparative Example 2, except that the application of the blue layer composition of Comparative Example 2 was repeated four times to achieve a colored layer thickness of 160 μm.

[0104] Comparative Example 4 A vehicle paint substitute film was prepared using the same procedure as in Comparative Example 2, except that a base film layer composition with a solid content of 83.8% having the composition described in Table 9 was applied to the OP film of Comparative Example 2, and the process of laminating a 75 μm thick base film layer by drying and curing at 80°C for 30 minutes was repeated twice to form a 150 μm thick base film layer, on which the blue layer composition was applied.

[0105] [Table 9]

[0106] Table 10 shows the composition and structure of the colored layer, base film layer, and pressure-sensitive adhesive layer of the vehicle paint substitute films for Examples 1-6 and Comparative Examples 1-6.

[0107] [Table 10]

[0108] The paint substitute film was evaluated based on the following criteria.

[0109] 1.Adhesive strength Test specimens were prepared by cutting the paint substitute film to a length of 80 mm and a width of 10 mm. The test specimens were then attached to a black PC-ABS flat panel (product number Techno Polymer Co.Ltd. CK43, thickness 3 mm, MC Yamasan Polymers Co., Ltd. (Chuo-ku, Tokyo, Japan)) or a KINO painted steel sheet (product number KINO1210TW-202, thickness 1 mm, Eguchi Iwao Shoten Co., Ltd. (Nagoya, Aichi Prefecture, Japan)) using a 2 kg pressure roller at 20°C in accordance with JIS Z 0237:2009 to prepare measurement samples. After leaving the test specimens at 20°C for 24 hours, 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 20°C and a peeling speed of 200 mm / min, followed by a 180-degree peel.

[0110] 2. Springback test The springback test simulates the durability of paint substitute films under actual usage conditions. The test results reflect the elongation of the paint substitute film during and after application, damage from pebbles during use, and long-term heat resistance. Two lines were marked along the width direction of a 65mm long, 20mm wide piece of paint substitute film, spaced 25mm apart along the length. The paint substitute film was stretched along its length so that the distance between the two lines became 35mm (140% elongation), and then wrapped around and attached to a 35mm wide PC-ABS flat panel (product number Techno Polymer Co.Ltd. CK43, thickness 3mm, MC Yamasan Polymers Co., Ltd. (Chuo-ku, Tokyo, Japan)) or a KINO painted steel sheet (product number KINO1210TW-202, thickness 1mm, Eguchi Iwao Shoten Co., Ltd. (Nagoya, Aichi Prefecture, Japan)) in the width direction. Measurement samples were prepared by fixing the two short sides of the paint substitute film to a PC-ABS flat panel or KINO coated steel sheet using 3M® heat-resistant polyimide tape 5413 (3M Japan Limited (Shinagawa-ku, Tokyo, Japan)). Three measurement samples were prepared for both the PC-ABS flat panel and the KINO coated steel sheet. At this point, paint substitute films without cracks were evaluated as A, and those with cracks were evaluated as C. The test was terminated for paint substitute films with a score of C.

[0111] After leaving the sample at 95°C for 5 hours, the presence or absence of cracks and delamination was visually observed. The evaluation criteria were as follows: A and B were judged as pass, and C, D1 and D2 were judged as fail. A: No cracks or peeling. B: Only thin cracks, no peeling. C: Cracks or peeling present D1: Film shrinkage D2: Full-thickness delamination

[0112] Afterward, the center of the paint substitute film was pierced with a pin, and the sample was again left at 95°C for 5 hours before being observed for cracks and peeling. The evaluation criteria were as follows: A1, A2, and B were judged as passable, and C, D1, and D2 were judged as failing. A1: No cracks or peeling. A2: Only thin cracks, no peeling. B: No cracks, but delamination in an area narrower than the film width. C: Cracks or delamination across the entire width of the film. D1: Film shrinkage D2: Full-thickness delamination

[0113] 3. Opacity (Opacity) The opacity test is a test to evaluate the opacity (ability to hide the color of the substrate) of a paint substitute film. Test samples were prepared by attaching the paint substitute film to a white paint panel (product number KINO1210TW-040, thickness 1 mm, Eguchi Iwao Shoten Co., Ltd. (Nagoya City, Aichi Prefecture, Japan)) or a black paint panel (product number KINO1210TW-040, thickness 1 mm, Eguchi Iwao Shoten Co., Ltd. (Nagoya City, Aichi Prefecture, Japan)) in a state of 100% elongation (no elongation) and 140% elongation. L of the test 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 white paint panel with 100% elongation was used as L1. * a1 * , b1 * And the values ​​for the other three cases (140% stretch white paint panel, 100% stretch black paint panel, and 140% stretch black paint panel) are set to 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 The calculation was performed using the formula shown. Two measurements were taken and the average value was recorded. The opacity of the paint substitute film is ΔE * A score of 1.5 or less is good, a score greater than 1.5 but 3 or less is acceptable, and a score greater than 3 is unacceptable.

[0114] 4. Takure Test The delamination test evaluates whether wrinkles, peeling, or displacement occur in a paint substitute film when it is applied to an substrate, loaded perpendicular to the substrate, and then subjected to a force perpendicular to that perpendicular direction. For example, it simulates a situation where a paint substitute film is applied around a door window and is in contact with a rubber part. A KINO painted steel plate (product number KINO1210TW-202, thickness 1 mm, Eguchi Iwao Shoten Co., Ltd. (Nagoya City, Aichi Prefecture, Japan)) approximately 50 mm long and 25 mm wide was cleaned using Kimwipes and isopropanol and dried. The paint substitute film was applied to the painted surface of the KINO painted steel plate using a squeegee at a speed of 300 mm / min. The dimensions of the applied paint substitute film were 30 mm in the length direction (direction of squeegee movement) and 25 mm in the width direction. After application, the sample was left at room temperature (approximately 23°C) for 3 hours to prepare the measurement sample. Figure 2A shows a top view (upper side) and a side view (lower side) of the measurement sample. The paint substitute film 10 is attached to the painted surface 32 of the painted steel plate 30. The painted steel plate 30 has mounting holes 34 for attaching weights that apply a load in the horizontal direction.

[0115] Next, a square piece of EPDM rubber (20mm x 10mm x 5mm thick) was placed on top of the paint substitute film in an oven at 80°C. A 4kg weight was used to apply a vertical load, followed by a 500g weight to apply a horizontal load. Figure 2B shows a side view of the sample after vertical and horizontal loads were applied. In Figure 2B, 40 is the EPDM rubber. After 24 hours had elapsed since the horizontal load was applied, the sample was removed and the appearance of the paint substitute film was observed. The evaluation criteria for appearance were as follows, and Figure 3 schematically shows the top surface of the sample for each score. In Figure 3, 42 represents the indentation from the weight, 44 represents film lifting, 46 represents film wrinkles (folds), and 48 represents film displacement. S, A, and B were considered pass, and C and D were considered fail. S: No change in appearance. Indentations from the EPDM rubber remain, but no film misalignment or lifting is observed. A: Partial lifting of the film is observed at the edges of the EPDM rubber indentation, but the lifting is smaller than that of a grade B, and no wrinkles (folds) occur. B: Partial lifting of the film is observed at the edges of the EPDM rubber indentation, but no wrinkles (folds) are present. Alternatively, slight misalignment of the adhesive surface of the film is observed, but no wrinkles (folds) are present. C: Partial wrinkles (folds) occurred in the film at the edges of the indentations made by the EPDM rubber. D: At the edges of the indentation marks on the EPDM rubber, the film shifted, peeled, or wrinkled (crinkled).

[0116] 5. Elastic modulus of the pressure-sensitive adhesive layer Using an atomic force microscope (Cypher AFM, Oxford Instruments Ltd.), at room temperature (23°C), the image was taken at a size of 10 × 10 square micrometers (μm). 2 The surface morphology of the pressure-sensitive adhesive layer of the paint substitute film was observed in the region. Then, force curve measurements were performed in a substantially flat area of ​​2 × 2 square micrometers or 1 × 1 square micrometer within that region to determine the elastic modulus of the pressure-sensitive adhesive layer. The measurement conditions were as follows. (A) Probe OMCL-AC240TS (Spring constant (k) = 2N / m, Tip radius: 7nm, Frequency: 58~65kHz, Olympus Corporation) Calibration of spring constant: Thermal noise method (B) Image Target amplitude: 2V Set point: 1.6V Integral gain: 78 Drive amplitude: 100~300mV (C) Force Curve Force distance: 1 micrometer Trigger point: 0.2V Chip speed: 1.98 micrometers / second

[0117] 6. Tensile strength at 140% elongation and elongation at break 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 in the length direction. The sample was fixed to a tensile testing machine (Tensilon® universal tester, model number: RTC-1210A, A&D Company, Limited, Toshima-ku, Tokyo, Japan) with the chucks spaced 50 mm apart, so that the 3M® heat-resistant polyimide tape 5413 was in contact with the chucks. The tensile strength was measured at a temperature of 95°C (tensile strength at 140% elongation) or 23°C (elongation at break) and a tensile speed of 150 mm / min until all or part of the layers of the paint substitute film broke. If a portion of the layer ruptured, the measurement was terminated when the rupture reached the entire width of the replacement coating film. For measurements at 95°C, the constant temperature chamber was positioned to cover the entire chuck area, and the measurement began when the temperature display inside the chamber reached 95°C. Two measurements were taken, and the average value was calculated.

[0118] Table 11 shows the results of the adhesive strength and springback tests.

[0119] [Table 11]

[0120] Table 12 shows the results for opacity.

[0121] [Table 12]

[0122] Table 13 shows the results of the sloshing test.

[0123] [Table 13]

[0124] Table 14 shows the breaking strength and elongation at 140% elongation.

[0125] [Table 14]

[0126] Table 15 shows the elastic modulus and their average values ​​at six arbitrary locations in the pressure-sensitive adhesive layer.

[0127] [Table 15]

[0128] 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] Top tier, A thermoplastic resin containing a carboxyl group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer, and a coloring agent, a colored layer, Thermoplastic base film layer, and Pressure-sensitive adhesive layer A vehicle paint substitute film comprising the elements in this order, wherein the elastic modulus of the pressure-sensitive adhesive layer at 23°C is 0.35 MPa to 10 MPa. [Aspect 2] The vehicle paint substitute film according to Embodiment 1, 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 3] The vehicle paint substitute film according to either embodiment 1 or 2, wherein the thermoplastic base film layer comprises at least one thermoplastic resin selected from the group consisting of polyurethane, polyvinyl chloride, polyolefin, and polyester. [Aspect 4] A vehicle paint substitute film according to any one of embodiments 1 to 3, wherein the thickness of the thermoplastic base film layer is 10 μm to 500 μm. [Aspect 5] A vehicle paint substitute film according to any one of embodiments 1 to 4, wherein the pressure-sensitive adhesive layer contains a cross-linked acrylic adhesive polymer. [Aspect 6] A vehicle paint substitute film according to any one of embodiments 1 to 5, wherein the top layer contains cross-linked polyurethane. [Aspect 7] The vehicle paint substitute film according to any one of embodiments 1 to 6, wherein the tensile strength of the vehicle paint substitute film at 140% elongation is 2.0 MPa to 20 MPa at a temperature of 95°C. [Aspect 8] The vehicle paint substitute film according to any one of embodiments 1 to 7, wherein the elongation at break of the vehicle paint substitute film is 40% to 700% at a temperature of 23°C. [Explanation of Symbols]

[0129] 10. Vehicle paint replacement film 12 Top Tier 14 Colored layer 142 Thermoplastic resin 144 Colorants 16 Thermoplastic base film layer 18 Pressure-sensitive adhesive layer 20 Liners 30 Painted steel plate 32 Painted surface 34 mounting holes 40 weight 42. Indentation of the weight 44. Film lifting 46. ​​Wrinkles in the film 48. Film misalignment

Claims

1. Top tier, A thermoplastic resin containing a carboxyl group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer, and a coloring agent, comprising a colored layer. Thermoplastic base film layer, and Pressure-sensitive adhesive layer A vehicle paint substitute film comprising the elements in this order, wherein the elastic modulus of the pressure-sensitive adhesive layer at 23°C is 0.35 MPa to 10 MPa.

2. The vehicle paint substitute film according to claim 1, 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.

3. The vehicle paint substitute film according to claim 1 or 2, wherein the thermoplastic base film layer comprises at least one thermoplastic resin selected from the group consisting of polyurethane, polyvinyl chloride, polyolefin, and polyester.

4. The vehicle paint substitute film according to any one of claims 1 to 3, wherein the thickness of the thermoplastic base film layer is 10 μm to 500 μm.

5. The vehicle paint substitute film according to any one of claims 1 to 4, wherein the pressure-sensitive adhesive layer comprises a cross-linked acrylic adhesive polymer.

6. The vehicle paint substitute film according to any one of claims 1 to 5, wherein the top layer comprises crosslinked polyurethane.

7. The vehicle paint substitute film according to any one of claims 1 to 6, wherein the tensile strength of the vehicle paint substitute film at 140% elongation is 2.0 MPa to 20 MPa at a temperature of 95°C, and the tensile strength at 140% 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 140% elongation using a tensile testing machine described in ISO 7500-1:2015 at a temperature of 95°C, a tensile speed of 150 mm / min, and a chuck spacing of 50 mm, and 140% elongation means the state in which the film is stretched to a length of 140% when the length of the film before stretching is taken as 100%.

8. The vehicle paint substitute film according to any one of claims 1 to 6, wherein the elongation at break of the vehicle paint substitute film is 40% to 700% at a temperature of 23°C.

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