JP2023080776A - Coating alternative film - Google Patents

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

The present disclosure relates to paint replacement films.

BACKGROUND ART It is known to attach decorative films to automobile bodies, parts, etc., instead of painting them, to decorate their appearance.

Patent Document 1 (Japanese Patent Application Laid-Open No. 2013-039724) describes "a vehicle coating 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 dispersed in the acrylic polyol, which is a combination of an organic pigment and an inorganic pigment, a combination of an organic pigment and an aluminum glitter material, a combination of an organic pigment and a mica glitter material, or a combination of an inorganic pigment and an aluminum glitter material. a colorant premix comprising a colorant selected from the group consisting of a combination, a combination of an inorganic pigment and a mica glitter, a combination of an aluminum glitter and a mica glitter, and a combination thereof; and (ii) an adhesive polymer. and a solid content mass ratio represented by adhesive polymer / (adhesive polymer + acrylic polyol) is 25% or more.

Patent Document 2 (Japanese Unexamined Patent Application Publication No. 2007-297569) describes "a decorative layer-forming film having a top coat layer made of a polyurethane resin and a carrier film provided on the surface side of the top coat layer, wherein the polyurethane The resin consists of (1) a polyisocyanate containing 0.5 equivalents or more of an isocyanurate or adduct of isophorone diisocyanate, or both of them, relative to the total polyisocyanate, and (2) a caprolactone diol, a polycarbonate diol, or a mixture thereof. and a polyol containing 0.4 equivalents or more of a polyester polyol having an average molecular weight of 1000 or less with respect to all polyols, and the equivalent ratio of the polyisocyanate to the polyol is 0.7 to 2.0. "Decorative layer forming film characterized by consisting of a product".

Patent Document 3 (International Publication No. 2013/114964) discloses that "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. Further, in the decorative molding film having a laminated structure, the elongation at break at 120° C. of the base film and the protective layer is 200% or more, and the colored layer is composed of at least a binder resin and an average major axis of 5 to 12 μm. A film for decorative molding, which contains a certain glittering material, and the colored layer has a stress of 4 MPa or less at 100% elongation at 120°C.".

JP 2013-039724 A JP 2007-297569 A WO2013/114964

The coating substitute film is attached to an article having a curved surface using, for example, a dual vacuum thermoforming (DVT) method, a vacuum thermoforming (VT) method, a hydraulic transfer method, or the like. For the purpose of reducing investment in painting equipment, reducing environmental impact due to scattering of volatile organic compounds (VOC), _CO2 emission, wastewater discharge, etc., reducing energy consumption, takt time and cost of manufacturing process, etc. Opportunities to use paint substitute films are increasing. In particular, the DVT method can be applied without defects even to articles having curved surfaces with a small radius of curvature, so it can be used for decoration of automobile parts such as automobile outer panels, instrument panels, door trims, and home appliances. preferably used.

The painting substitute film used in the DVT method is stretched by an area ratio of 200% or more when the area before stretching is 100%, and is used for PC-ABS, electrodeposition coated plates used for automobile outer panels, etc. It is required to be able to adhere to a wide variety of substrates, and to maintain the appearance of the paint color and adhesion state even after being placed in a high temperature environment for a long time after stretching and adhesion.

The present disclosure provides stretchable, adhesive, decorative and durable paint replacement films suitable for use in DVT processes.

According to one embodiment of the present disclosure, a thermoplastic top layer, a thermoplastic resin containing a carboxy group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer, a colored layer containing a colorant, and A painting substitute film comprising in this order a heat-sensitive adhesive layer containing a polyurethane-based heat-sensitive adhesive, wherein the painting substitute film is heated to 165 ° C. ± 5 ° C., and the area of the painting substitute film before stretching is set to 100%. Then, it was stretched by 200% in terms of area ratio using a vacuum and pressure forming machine, laminated to a PC-ABS plate, cut into a grid shape with a width of 40 mm, and left at 95 ° C. for 144 hours. A paint replacement film is provided that is 1.0 mm or less.

ADVANTAGE OF THE INVENTION According to this disclosure, it is possible to provide a coating substitute film having stretchability, adhesiveness, decorativeness and durability suitable for use in the DVT method.

The above description should not be considered to disclose all embodiments of the invention or all advantages associated with the invention.

1 is a schematic cross-sectional view of a paint substitute film of one embodiment; FIG. FIG. 4 is an exemplary illustration of a method of applying a paint substitute film to a substrate to form an article using the DVT method. 1 is a schematic cross-sectional view of a vacuum pressure forming machine before stretching in evaluation of DVT formability in Examples. FIG. FIG. 4 is a top view showing the arrangement position of a substrate in DVT moldability evaluation of an example. It is a schematic cross-sectional view of a vacuum pressure forming machine after stretching in DVT formability evaluation of Examples. 1 is a photograph showing grid-like cuts made in a test piece in a heat shrinkage test of an example.

Hereinafter, for the purpose of illustrating representative embodiments of the present invention, the present invention will be described in more detail with reference to the drawings as necessary, but the present invention is not limited to these embodiments.

In the present disclosure, "(meth)acrylic" means acrylic or methacrylic, and "(meth)acrylate" means acrylate or methacrylate.

In the present disclosure, “curing” also includes the concept generally called “crosslinking”.

In the present disclosure, "film" also includes an article called "sheet".

In the present disclosure, for example, "on" in "the thermoplastic top layer is disposed on the colored layer" means that the thermoplastic top layer is disposed in direct contact with the colored layer, or that the thermoplastic top layer is arranged above the colored layer via another layer.

In the present disclosure, “transparent” means that the average transmittance in the visible light region (wavelength 400 nm to 700 nm) measured in accordance with JIS K 7375:2008 is about 80% or more, preferably about 85 % or more, or about 90% or more. Although the upper limit of the average transmittance is not particularly limited, it can be, for example, less than about 100%, about 99% or less, or about 98% or less.

In the present disclosure, “translucent” means that the average transmittance in the visible light region (wavelength 400 nm to 700 nm) measured in accordance with JIS K 7375:2008 is about 40% or more and less than about 80%. No, preferably less than or equal to about 75%.

A paint replacement film of one embodiment comprises, in order, a thermoplastic top layer, a colored layer comprising a thermoplastic resin and a colorant, and a thermal adhesive layer comprising a polyurethane-based thermal adhesive. The thermoplastic resin of the colored layer contains a carboxy group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer. In the paint substitute film of this embodiment, when the paint substitute film is heated to 165 ° C. ± 5 ° C. and the area of the paint substitute film before stretching is 100%, the area ratio is 200% using a vacuum pressure forming machine. It is stretched and attached to a PC-ABS plate, cut into grids with a width of 40 mm, and left at 95° C. for 144 hours.

In the paint substitute film of the present 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. While not wishing to be bound by any theory, it is believed that the materials of these layers and their properties (thermoplastic or thermoadhesive) cooperate to provide high stretchability (e.g., area ratio of 200% or more) suitable for DVT processes. Stretching) and adhesiveness are imparted to the paint substitute film, and durability such as heat shrinkage resistance is also imparted to the paint substitute film. In addition, since the colored layer disposed between the thermoplastic top layer and the heat-sensitive adhesive layer contains a combination of specific thermoplastic resins, it has high elongation properties and strength, and is a paint substitute film after stretching. can retain its decorativeness.

FIG. 1 shows a schematic cross-sectional view of a paint substitute film 10 of one embodiment. The paint substitute film 10 includes a thermoplastic top layer 12, a color layer 14, and a heat sensitive adhesive layer 16, in that order. Colored layer 14 includes thermoplastic resin 142 and colorant 144 . The paint replacement film may further include, as optional elements, an intermediate film layer 22 and/or a bonding layer 24 that bonds the layers described above, and may further include a liner 20 . In FIG. 1, an intermediate film layer 22 is positioned between the thermoplastic top layer 12 and the color layer 14, and a bonding layer 24 is positioned to bond the thermoplastic top layer 12 and the intermediate film layer 22 together. In one embodiment, the paint replacement film consists of a thermoplastic top layer, a pigmented layer, a heat sensitive adhesive layer, an intermediate film layer, and a tie layer. In another embodiment, the paint replacement film consists of a thermoplastic top layer, a color layer, and a heat sensitive adhesive layer.

Examples of thermoplastic top layers include acrylic resins such as polymethyl methacrylate (PMMA), polyurethane, ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), and methyl methacrylate-vinylidene fluoride copolymer. (PMMA-PVDF), fluororesins such as tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV), polyvinyl chloride (PVC), polycarbonate (PC), polyethylene (PE), polypropylene (PP), etc. polyolefins, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and ethylene-acrylic acid copolymers (EAA) and their ionomers, ethylene-ethyl acrylate copolymers, ethylene-vinyl acetate copolymers A copolymer such as can be used. The thermoplastic top layer preferably contains acrylic resin, polyurethane, fluororesin, polyvinyl chloride, or a mixture thereof because of its excellent weather resistance, and acrylic resin, It is more preferable to contain a fluororesin or a mixture thereof, and it is even more preferable to contain a fluororesin because of its excellent chemical resistance.

In one embodiment, the thermoplastic top layer comprises at least one selected from the group consisting of polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), and methyl methacrylate-vinylidene fluoride copolymer (PMMA-PVDF). Contains resin. In this embodiment, the thermoplastic top layer comprises at least one selected from the group consisting of polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), and methyl methacrylate-vinylidene fluoride copolymer (PMMA-PVDF). The total resin may comprise about 50% or more, about 60% or more, or about 70% or more, 100% or less, about 95% or less, or about 90% or less by weight. The resin component of the thermoplastic top layer is at least one resin selected from the group consisting of polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), and methyl methacrylate-vinylidene fluoride copolymer (PMMA-PVDF). It can be anything.

The thermoplastic top layer may be preformed into a film by extrusion, stretching, or the like. Such a film can be laminated to a colored layer or other layer via a bonding layer. Alternatively, if the colored layer has adhesiveness to such a film, the film can be laminated directly to the colored layer without a bonding layer. By using a film with high flatness, it is possible to provide a coating appearance with high 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 multilayer melt extrusion with other layers.

The thermoplastic top layer can also be formed by applying a solution containing a resin for the thermoplastic top layer onto the colored layer or other layers, and heating and drying if necessary. Alternatively, the solution may be applied onto another liner, heated and dried as necessary to form a thermoplastic top layer film, and the film may be laminated onto the colored layer via a bonding layer. can also When the colored layer has adhesiveness to the thermoplastic top layer film formed on the liner, the film can be directly transfer-laminated to the colored layer without the bonding layer. For the thermoplastic top layer, for example, a solution containing a thermoplastic top layer resin is applied to the colored layer or liner by knife coating, bar coating, blade coating, doctor coating, roll coating, cast coating, etc., and if necessary It can be formed by heating and drying.

The thermoplastic top layer may optionally include benzotriazole, UV absorbers such as Tinuvin® 99-2, Tinuvin® 1130 (BASF Japan Ltd., Chuo-ku, Tokyo, Japan), Tinuvin ( Additives such as hindered amine light stabilizers (HALS) such as ®292 (BASF Japan Ltd., Chuo-ku, Tokyo, Japan) may also be included. By using an ultraviolet absorber or a hindered amine light stabilizer, it is possible to effectively prevent discoloration, fading, deterioration, etc., of the colorant contained in the colored layer, particularly of the organic pigment, which is relatively highly sensitive to light such as ultraviolet light. be able to. The thermoplastic top layer may include hardcoat materials, brighteners, etc., and may have additional hardcoat layers. The thermoplastic top layer may be transparent or translucent to provide the desired appearance. Advantageously, the thermoplastic top layer is transparent.

The thickness of the thermoplastic top layer may vary, but is generally no less than about 5 microns, no less than about 10 microns, or no less than about 15 microns, no more than about 200 microns, no more than about 150 microns, or no more than about 100 microns. When the coating substitute film is applied to an article having a complicated shape, a thinner thermoplastic top layer is advantageous from the viewpoint of conformability, and for example, about 100 μm or less, or about 80 μm or less is desirable. On the other hand, when imparting high light or weather resistance to the article, it is advantageous for the thermoplastic top layer to be thick, eg, about 15 μm or greater, or about 20 μm or greater.

The colored layer is a thermoplastic resin (hereinafter referred to as a Also referred to as “acrylic blend thermoplastic resin”) and a colorant.

The acrylic blend thermoplastic resin includes a polymer blend of a carboxy group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer. The non-covalent interaction between the carboxy group-containing (meth)acrylic polymer and the amino group-containing (meth)acrylic polymer imparts stretchability and strength to the colored layer. As a result, the coating substitute film has a high stretchability suitable for the DVT method, for example, a stretchability that enables stretching by an area ratio of 200% or more when the area of the coating substitute film before stretching is 100%. In addition, the coating substitute film can maintain the adhesive state without breaking or peeling even after being placed in a high-temperature environment for a long time after being stretched and adhered, and can maintain the appearance of the paint color. A carboxy group-containing (meth)acrylic polymer can be obtained by copolymerizing a monoethylenically unsaturated monomer and a carboxy group-containing unsaturated monomer. An amino group-containing (meth)acrylic polymer can be obtained by copolymerizing a monoethylenically unsaturated monomer and an amino group-containing unsaturated monomer.

A monoethylenically unsaturated monomer is a main component of a (meth)acrylic polymer and generally has the formula CH ₂ =CR ¹ COOR ² (wherein R ¹ is hydrogen or a methyl group, R ² is a linear, branched, or cyclic alkyl group, phenyl group, alkoxyalkyl group, phenoxyalkyl group, hydroxyalkyl group, or cyclic ether group), styrene, α-methylstyrene , aromatic vinyl monomers such as vinyl toluene, vinyl esters such as vinyl acetate, and unsaturated nitriles such as acrylonitrile and methacrylonitrile. Monoethylenically unsaturated monomers represented by the formula CH ₂ ═CR ¹ COOR ² include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate, Linear alkyl (meth)acrylates such as n-decyl (meth)acrylate and n-dodecyl (meth)acrylate; isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate branched alkyl (meth)acrylates such as; alicyclic (meth)acrylates such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; phenyl (meth)acrylate; ) alkoxyalkyl (meth)acrylates such as acrylate; phenoxyalkyl (meth)acrylates such as phenoxyethyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; ) hydroxyalkyl (meth)acrylates such as acrylates; and cyclic ether-containing (meth)acrylates such as glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate. As monoethylenically unsaturated monomers, one or more monoethylenically unsaturated monomers can be used for the purpose of obtaining desired glass transition temperature, tensile strength, elongation properties, and the like.

Carboxy group-containing unsaturated monomers include, for example, 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 succinate, and 2-(meth)acryloyloxyethyl hexahydrophthalate. As the carboxy group-containing unsaturated monomer, one or more carboxy group-containing unsaturated monomers can be used as necessary.

The carboxy group-containing (meth)acrylic polymer contains, for example, about 85 parts by mass or more, about 90 parts by mass or more, or about 92 parts by mass or more and about 99.5 parts by mass or less, about 99 parts by mass of a monoethylenically unsaturated monomer. and about 0.5 parts by weight or more, about 1 part by weight or more, or about 2 parts by weight or more and about 15 parts by weight or less, about 10 parts by weight or less of a carboxy group-containing monoethylenically unsaturated monomer. It can be obtained by copolymerization using an amount of not more than about 8 parts by mass.

Examples of amino group-containing unsaturated monomers include dialkylaminoalkyl (meth)acrylates such as N,N-dimethylaminoethyl acrylate (DMAEA) and N,N-dimethylaminoethyl methacrylate (DMAEMA); N,N-dimethylamino Dialkylaminoalkyl (meth)acrylamides such as propylacrylamide (DMAPAA), N,N-dimethylaminopropyl methacrylamide; dialkylaminoalkyl vinyl ethers such as N,N-dimethylaminoethyl vinyl ether, N,N-diethylaminoethyl vinyl ether; and vinyl A monomer having a tertiary amino group such as a vinyl monomer having a nitrogen-containing heterocycle such as imidazole can be mentioned. As the amino group-containing unsaturated monomer, one or more amino group-containing unsaturated monomers can be used as necessary.

The amino group-containing (meth)acrylic polymer contains, for example, about 80 parts by mass or more, about 85 parts by mass or more, or about 90 parts by mass or more and about 99.5 parts by mass or less, about 99 parts by mass of a monoethylenically unsaturated monomer. parts by weight or less, or about 97 parts by weight or less, and an amino group-containing unsaturated monomer of about 0.5 parts by weight or more, about 1 part by weight or more, or about 3 parts by weight or more, about 20 parts by weight or less, and about 15 parts by weight or less. , or by copolymerization in a proportion of about 10 parts by mass or less.

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. Examples of initiators include organic peroxides such as benzoyl peroxide, lauroyl peroxide, bis(4-tert-butylcyclohexyl)peroxydicarbonate, and 2,2′-azobisisobutyronitrile, 2, 2'-azobis (2-methylbutyronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis ( Azo polymerization initiators such as 2,4-dimethylvaleronitrile) (AVN) can be used. The amount of the initiator used is generally about 0.01 parts by weight or more, or about 0.05 parts by weight or more, about 5 parts by weight or less, or about 3 parts by weight or less based on 100 parts by weight of the monomer mixture.

It is preferable that one of the carboxy group-containing (meth)acrylic polymer and the amino group-containing (meth)acrylic polymer has a glass transition temperature of 0° C. or higher and the other has a glass transition temperature of 0° C. or lower. In other words, when the Tg of the carboxy 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 the Tg of the former is 0°C or lower. When the Tg of the latter is 0° C. or higher. Without wishing to be bound by any theory, it is believed that a (meth)acrylic polymer with a high Tg imparts high tensile strength to the colored layer, and a (meth)acrylic polymer with a low Tg gives the colored layer. It is believed to improve elongation properties. In some embodiments, the high Tg (meth)acrylic polymer has a Tg of about 5° C. or higher, about 20° C. or higher, or about 40° C. or higher, and the low Tg (meth)acrylic polymer has a Tg of is about -5°C or less, about -20°C or less, or about -40°C or less.

For example, homopolymers such as methyl methacrylate (MMA) and n-butyl methacrylate (BMA) are copolymerized as a main component with a (meth)acrylic monomer having a Tg of 0 ° C. or higher, so that Tg is 0. °C or higher (meth)acrylic polymer can be obtained.

For example, a homopolymer polymerized by itself, such as ethyl acrylate (EA), n-butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), is copolymerized mainly with a component having a Tg of 0° C. or less, A (meth)acrylic polymer having a Tg of 0° C. or less can be obtained.

を用いて計算ガラス転移温度として求めることができる。式中、Ｔｇ_ｉは成分ｉのホモポリマーのガラス転移温度（℃）、Ｘ_ｉは重合の際に添加した成分ｉのモノマーの質量分率をそれぞれ示し、ｉは１～ｎの自然数であり、

である。 The glass transition temperature (Tg) of a carboxy group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer is determined by the following FOX formula (Fox , TG, Bull. Am. Phys. Soc., 1 (1956), p. 123)

can be obtained as a calculated glass transition temperature using In the formula, Tg _i is the glass transition temperature (° C.) of the homopolymer of component i, X _i is the mass fraction of the monomer of component i added during polymerization, i is a natural number from 1 to n,

is.

When the carboxy group-containing (meth)acrylic polymer or the amino group-containing (meth)acrylic polymer is a blend of two or more (meth)acrylic polymers having different weight average molecular weights, the Tg of the blend is dynamic viscoelasticity. can be determined by measurement. Specifically, a solution of a (meth)acrylic polymer blend was applied to a release paper and dried to obtain a film (thickness of about 50 μm) as a test piece. Instruments Co., model number: RSA III), temperature range -20 ~ 160 ° C., Temp ramp mode, frequency 10 Hz conditions, loss tangent (tan δ) is measured, Tg of the polymer blend from the measured value of the loss tangent can be asked for.

The weight-average molecular weights of the carboxy group-containing (meth)acrylic polymer and the amino group-containing (meth)acrylic polymer are not particularly limited. It can be less than or equal to about 2,000,000, less than or equal to about 1,500,000, or less than or equal to about 1,000,000. The number-average molecular weight and weight-average molecular weight in the present disclosure mean values converted with standard polystyrene by GPC method.

In one embodiment, the (meth)acrylic polymer having a glass transition temperature of 0° C. or lower (low Tg (meth)acrylic polymer) has a weight average molecular weight of about 100,000 or more, about 150,000 or more, or about 200. ,000 or more, about 2,000,000 or less, about 1,500,000 or less, or about 1,000,000 or less.

In one embodiment, the (meth)acrylic polymer having a glass transition temperature of 0° C. or higher (high Tg (meth)acrylic polymer) has a weight average molecular weight of about 1,000 or more, about 5,000 or more, or about 10 ,000 or more, about 200,000 or less, about 180,000 or less, or about 150,000 or less.

By changing the compounding ratio of the carboxy group-containing (meth)acrylic polymer and the amino group-containing (meth)acrylic polymer, desired tensile strength and elongation properties can be imparted to the paint substitute film. In one embodiment, among the carboxy group-containing (meth)acrylic polymer and the amino group-containing (meth)acrylic polymer, the blending ratio of the high Tg (meth)acrylic polymer and the low Tg (meth)acrylic polymer is When the (meth) acrylic polymer is 100 parts by mass, the low Tg (meth) acrylic polymer is about 10 parts by mass or more, about 20 parts by mass or more, about 50 parts by mass or more, or about 80 parts by mass or more, about 900 parts by weight or less, about 500 parts by weight or less, about 200 parts by weight or less, or about 150 parts by weight or less.

The total content of the carboxy group-containing (meth)acrylic polymer and the amino group-containing (meth)acrylic polymer 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. Above, it is 100 mass % or less, about 90 mass % or less, or about 80 mass % or less.

Colorants include, for example, organic pigments, inorganic pigments, aluminum glitters, mica glitters, and blends of two or more of these. Colorants include combinations of organic pigments and inorganic pigments, combinations of organic pigments and aluminum luster materials, combinations of organic pigments and mica luster materials, combinations of inorganic pigments and aluminum luster materials, combinations of inorganic pigments and mica luster materials, and aluminum It is preferably selected from the group consisting of a combination of glitter and mica glitter, and combinations thereof. By using the above combinations of colorants, it is possible to obtain paint replacement films with various kinds of color tones, thereby meeting high design requirements.

Examples of organic pigments include phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, azo lake pigments, indigo pigments, perinone pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, and quinacridone pigments such as quinacridone red. is mentioned. Inorganic pigments include, for example, titanium dioxide, yellow lead, yellow iron oxide, red iron oxide, red iron oxide, and carbon black. Aluminum glitter materials include, for example, aluminum flakes, vapor-deposited aluminum flakes, metal oxide-coated aluminum flakes, and colored aluminum flakes. Examples of mica glittering materials include flaky mica coated with metal oxides such as titanium dioxide and iron oxide, and synthetic mica.

The content of the colorant in the colored layer is about 2.5 parts by mass or more, about 5 parts by mass or more, or about 10 parts by mass or more and about 400 parts by mass or less, or about 300 parts by mass with respect to 100 parts by mass of the acrylic blend thermoplastic resin. parts by weight or less, or about 200 parts by weight or less.

It is preferable to crosslink carboxy group-containing (meth)acrylic polymers with each other, or between carboxy group-containing (meth)acrylic polymers and amino group-containing (meth)acrylic polymers. These crosslinks form a network structure, further improving the strength and elongation properties of the coating substitute film. Examples of cross-linking agents for carboxy group-containing (meth)acrylic polymers include epoxy cross-linking agents, bisamide cross-linking agents, aziridine cross-linking agents, and carbodiimide cross-linking agents. As a cross-linking agent, one or two or more cross-linking agents can be used as necessary.

Examples of epoxy cross-linking agents include N,N,N',N'-tetraglycidyl-1,3-benzenedi(methanamine) (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(ethylene iminocarbonylamino)diphenylmethane, 1,8-bis(ethyleneiminocarbonylamino)octane and the like. Aziridine crosslinkers include, for example, Chemitite PZ33 (Nippon Shokubai Co., Ltd., Osaka City, Osaka, Japan), and NeoCryl CX-100 (DSM Coating Resins, LLC., Zwolle, Overijssel, The Netherlands). Carbodiimide crosslinkers include, for example, Carbodilite V-03, V-05, and V-07 (Nisshinbo Chemical Co., Ltd., Chuo-ku, Tokyo, Japan).

The amount of the cross-linking agent added is about 0.01 parts by mass or more, about 0.05 parts by mass or more, or about 0.1 parts by mass or more, or about 5 parts by mass with respect to 100 parts by mass of the carboxy group-containing (meth)acrylic polymer. parts or less, about 3 parts by weight or less, or about 2 parts by weight or less.

For the colored layer, for example, a colored layer composition containing a carboxy group-containing (meth)acrylic polymer, an amino group-containing (meth)acrylic polymer, a colorant, and optionally a solvent and/or a cross-linking agent is used. can be formed by Specifically, a colored layer can be formed on the liner by applying the colored layer composition to a liner such as a release-treated PET film, followed by drying, solidifying, or curing. Usual coaters such as bar coaters, knife coaters, roll coaters, and die coaters can be used as coating devices. Drying, solidification or curing can be carried out by drying a colored layer composition containing a volatile solvent, cooling a melted resin component, or the like. The colored layer can also be formed by melt extrusion.

The colored layer composition contains additives such as UV absorbers such as benzotriazole, light stabilizers such as hindered amines, antioxidants such as phenolic antioxidants, leveling agents such as silicone, waxes, and organic bentonite. Viscosity control agents, thickeners such as cellulose acetate butyrate, precipitated barium sulfate, clay, silica, talc, kaolin, bentonite and other extender pigments, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethylene Organic solvents such as glycol, propylene glycol, ethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate may be further included.

In one embodiment, the colored layer is formed by mixing a colorant premix, a carboxy group-containing (meth)acrylic polymer, an amino group-containing (meth)acrylic polymer, and optionally a solvent and/or a cross-linking agent. It is formed using the colored layer composition obtained by The colorant premix contains an acrylic polyol and a colorant, with the colorant dispersed in the acrylic polyol.

Examples of acrylic polyols contained in the colorant premix include acrylics containing hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. system copolymers can be used. Monoethylenically unsaturated monomers can be used as monomers that can be copolymerized with hydroxyl-containing (meth)acrylates. Monoethylenically unsaturated monomers include, for example, 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, isobornyl (meth)acrylate; (meth)acrylic acid, Monoethylenically unsaturated monomers having acidic groups such as itaconic acid, maleic acid, styrenesulfonic acid; N-vinylpyrrolidone, N-vinylcaprolactam, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth) Nitrogen-containing monoethylenically unsaturated monomers such as acrylamide, (meth)acrylonitrile; and aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene. Acrylic polyol is a polymerization initiator, using an azo polymerization initiator such as 2,2'-azobisisobutyronitrile, or an organic peroxide such as benzoyl peroxide, a hydroxyl group-containing (meth) acrylate and mono It can be obtained by polymerizing an ethylenically unsaturated monomer. A chain transfer agent having a hydroxyl group such as 2-mercaptoethanol, 1-mercapto-2-propanol, 3-mercapto-1-propanol and p-mercaptophenol may be used during the polymerization.

The hydroxyl value of the acrylic polyol 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. . Acrylic polyols generally have an acid value of about 0.1 mg/g or greater, about 0.5 mg/g or greater, or about 2 mg/g or greater. By setting the hydroxyl value and/or acid value of the acrylic polyol to the above values, the colorant can be well dispersed in the acrylic polyol, and the miscibility with the (meth)acrylic polymer can be enhanced. The acrylic polyol generally has a weight average molecular weight of 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. be. By setting 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 the (meth)acrylic polymer can be enhanced.

The colorant premix contains additives such as ultraviolet absorbers such as benzotriazole, antioxidants such as phenolic antioxidants, leveling agents such as silicone, waxes, viscosity control agents such as organic bentonite, and cellulose acetate butyrate. Thickeners such as latex, extender pigments such as precipitated barium sulfate, clay, silica, talc, kaolin, bentonite, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethylene glycol, propylene glycol, ethylene glycol Organic solvents such as dimethyl ether and propylene glycol monomethyl ether acetate may be further included.

The content of the colorant in the colorant premix is about 20 wt% or more, or about 30 wt% or more, about 80 wt% or less, or about 70 wt% or less, based on the total weight of the acrylic polyol and the colorant. can be The entire 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 setting the amount of the colorant in the colorant premix within the above range, the required amount of (meth)acrylic polymer can be blended in the colored layer while providing the desired color.

The solid content mass ratio expressed as acrylic blend thermoplastic resin/(acrylic blend thermoplastic resin + acrylic polyol) is about 25% or more, preferably about 50% or more, and more preferably about 75% or more. The solids weight ratio refers to the dry weight of the acrylic blend thermoplastic resin and the acrylic polyol and does not include the weight of any added crosslinker. By setting the solid content mass ratio represented by acrylic blend thermoplastic resin / (acrylic blend thermoplastic resin + acrylic polyol) within the above range, the elongation property of the colored layer is enhanced, and as a result, DVT molding of the paint substitute film can enhance sexuality. By setting the solid content mass ratio within the above range, even when the coating substitute film is stretched by the DVT method and attached to an article, it is possible to maintain excellent appearance (eg, glossiness, concealability, etc.).

The colored layer may have adhesive properties. The adhesive colored layer can be laminated to the thermoplastic top layer or the heat sensitive adhesive layer without the need for a tie layer.

The thickness of the colored layer may vary, but is generally no less than about 10 μm, no less than about 20 μm, or no less than about 30 μm, no more than about 120 μm, no more than about 100 μm, or no more than about 80 μm. A desired decorative appearance can be provided by setting the thickness of the colored layer to about 10 μm or more. By setting the thickness of the colored layer to about 120 μm or less, it is possible to impart stretchability suitable for the DVT method to the coating substitute film.

The heat-sensitive adhesive layer contains a polyurethane heat-sensitive adhesive. In the present disclosure, the term “heat-sensitive adhesive” refers to a material that does not exhibit tackiness at room temperature but has tackiness at high temperatures and becomes capable of adhering to an adherend. Includes adhesive. A heat activated adhesive, also called a delayed tack heat sensitive adhesive, is activated by heat to produce tack, and the tack persists for some time even after the heat source is removed. Hot-melt adhesives melt or soften when heated to develop tack, and when the heat source is removed, they rapidly solidify and lose tack. In general, thermal adhesives have a glass transition temperature Tg or melting point Tm above room temperature. When the temperature is higher than Tg or Tm, the storage modulus of the thermal adhesive decreases and the thermal adhesive exhibits tack. The Tg and Tm of thermal adhesives are measured using Differential Scanning Calorimetry (DSC).

Polyurethane-based heat-sensitive adhesives contain polyurethanes that are reactants of polyols and polyisocyanates. Polyols include, for example, polyester polyols, polyether polyols, high molecular weight polyols such as polycarbonate polyols, 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 - carbon such as hexanediol, neopentyl glycol, glycerin, diethylene glycol, trimethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexanedimethanol, methylpentanediol adipate, trimethylolpropane, pentaerythritol, etc. Examples include low-molecular-weight polyols having 2 to 20 atoms. 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; and/or cycloaliphatic polyisocyanates such as cis-1,4-cyclohexane diisocyanate, norbornene diisocyanate, hydrogenated diphenylmethane diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate , 2,4′-diphenylmethane diisocyanate and 2,2′-diphenylmethane diisocyanate; and burette modified products, isocyanurate modified products, carbodiimide modified products and adduct modified products thereof. As polyols or polyisocyanates, one or more polyols or polyisocyanates can be used.

The polyurethane heat-sensitive adhesive preferably contains linear polyurethane. Polyurethane may have a hydroxyl group. Polyurethanes having hydroxyl groups are mixed with polyols and polyisocyanates so that the NCO/OH ratio (number of moles of isocyanate groups in polyisocyanate/number of moles of hydroxyl groups in polyol) is less than 1, i.e., hydroxyl groups are in excess. It can be obtained by reacting.

From the viewpoint of suppressing heat shrinkage of the coating substitute film, the polyurethane-based heat-sensitive adhesive is preferably crosslinked. The crosslinked polyurethane heat-sensitive adhesive can be formed by reacting a polyurethane having a hydroxyl group with the polyisocyanate as a crosslinking agent. Excess isocyanato groups of the above polyisocyanate also react with moisture contained in air and other sources to contribute to cross-linking. The NCO/OH ratio (the number of moles of isocyanato groups in the polyisocyanate/the number of moles of hydroxyl groups in the polyurethane with hydroxyl groups) between the polyurethane having hydroxyl groups and the polyisocyanate as a cross-linking agent is, 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.

The melting point Tm of the polyurethane-based heat-sensitive adhesive before crosslinking can be about 30° C. or higher, about 35° C. or higher, or about 40° C. or higher and about 80° C. or lower, about 65° C. or lower, or about 50° C. or lower. The melting point Tm of the polyurethane heat-sensitive adhesive is a value measured using a differential scanning calorimeter.

The thermal adhesive layer may further comprise a tackifier. Examples of tackifiers include rosin derivatives, terpene resin-based, petroleum resin-based, phenolic resin-based, and xylene resin-based tackifiers.

The heat-activatable thermal adhesive layer may further comprise a solid plasticizer. A 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 tackiness of the heat-sensitive adhesive layer at high temperatures. On the other hand, once the solid plasticizer is melted, the crystallization progresses slowly even if the temperature drops below the melting point, so the tack produced 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, and tribenzoic acid. Glycerides, sucrose octaacetate, tricyclohexyl citrate, and N-cyclohexyl-p-toluenesulfonamide.

The heat-sensitive adhesive layer may contain additives such as UV absorbers such as benzotriazole, light stabilizers such as hindered amines, antioxidants such as phenolic antioxidants, silane coupling agents, and fillers. .

The thermal adhesive layer can be formed using a thermal adhesive composition containing polyurethane and solvent, and optionally a cross-linking agent, tackifier, solid plasticizer, and the like. Specifically, a heat-sensitive adhesive layer can be formed by applying a heat-sensitive adhesive composition onto a colored layer and drying, solidifying, or curing the composition. Alternatively, the heat-sensitive adhesive composition can be coated on another liner, dried, solidified or cured to form a heat-sensitive adhesive layer, and the heat-sensitive adhesive layer can be thermally laminated on the colored layer. For example, a heat-sensitive adhesive layer is formed by applying a heat-sensitive adhesive composition to a colored layer or a liner by knife coating, bar coating, blade coating, doctor coating, roll coating, cast coating, etc., followed by heating and drying as necessary. , solidifying or curing. The liner may have a release treated surface such as with silicone.

The thickness of the thermal adhesive layer can vary, but is generally no less than about 5 microns, no less than about 10 microns, or no less than about 15 microns, no more than about 100 microns, no more than about 80 microns, or no more than about 50 microns.

The paint replacement film may have a liner to protect the heat sensitive adhesive layer. Liners can include, for example, paper, plastic materials such as polyethylene, polypropylene, polyester, cellulose acetate, paper coated with such plastic materials, and the like. These liners may have a release treated surface such as with silicone. The thickness of the liner is generally greater than or equal to about 5 μm, greater than or equal to about 15 μm, or greater than or equal to about 25 μm, less than or equal to about 300 μm, less than or equal to about 200 μm, or less than or equal to about 150 μm.

The heat-sensitive adhesive layer generally forms a flat adhesive surface, but may form an uneven adhesive surface. In the uneven adhesive surface, a convex portion containing an adhesive and a concave portion surrounding the convex portion are formed on the adhesive surface of the heat-sensitive adhesive layer. It includes an adhesive surface in which a communication path communicating with the outside defined by a recess is formed between the surface and the adhesive surface. An example of a method for forming the uneven adhesive surface will be described below.

A liner having a release surface with a predetermined uneven structure is prepared. A heat-sensitive adhesive composition is applied to the release surface of the liner and heated as necessary to form a heat-sensitive adhesive layer. As a result, the concave-convex structure (negative structure) of the liner is transferred to the surface of the heat-sensitive adhesive layer in contact with the liner (this becomes the adhesive surface of the coating substitute film), and the adhesive surface has a predetermined structure (positive structure). Form an uneven adhesive surface. As described above, the unevenness of the bonding surface is designed in advance so as to include grooves that can form communication paths when the projections are bonded to the adherend.

The grooves of the heat-sensitive adhesive layer are arranged in a regular pattern on the adhesive surface as long as air bubbles can be prevented when the coating substitute film is attached to the article by the DVT method. may be formed, or irregular grooves may be arranged to form irregular pattern grooves. When a plurality of grooves are formed so as to be arranged substantially parallel to each other, the arrangement interval of the grooves is preferably 10 to 2000 μm. The depth of the groove (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 groove is also not particularly limited as long as it does not impair the effects of the present invention. For example, the shape of the groove can be substantially rectangular (including trapezoidal), substantially semicircular, or substantially semielliptical in cross section of the groove in the direction perpendicular to the bonding surface.

The paint replacement film may optionally include an intermediate film layer interposed between the thermoplastic top layer and the pigmented layer or between the pigmented layer and the heat sensitive adhesive layer. The intermediate film layer can increase the strength of the paint replacement film.

As the intermediate film layer, for example, resin films of polyolefins such as polyurethane, polyvinyl chloride, polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, acrylic polymers, and fluoropolymers can be used. Preferably, the intermediate film layer is thermoplastic. In one embodiment, the intermediate film layer comprises a waterborne polyurethane resin.

The thickness of the intermediate film layer can be greater than or equal to about 5 μm, greater than or equal to about 10 μm, or greater than or equal to about 15 μm, less than or equal to about 200 μm, less than or equal to about 100 μm, or less than or equal to about 50 μm.

The paint replacement film may optionally include a tie layer between the two layers that make up the paint replacement film. In one embodiment, the paint replacement film has a tie layer between the thermoplastic top layer and the optional intermediate film layer.

The bonding layer includes, for example, urethane resin, acrylic resin, epoxy resin, or phenoxy resin, or a blend of two or more of these resins. In one embodiment, the tie layer comprises a resin blend of urethane resin and phenoxy resin.

The thickness of the bonding layer can be greater than or equal to about 0.1 μm, greater than or equal to about 0.2 μm, or greater than or equal to about 0.5 μm, less than or equal to about 10 μm, less than or equal to about 5 μm, or less than or equal to about 2 μm.

The paint substitute film can be produced, for example, by the following procedure. A colored layer composition is prepared, applied onto a release liner, and optionally dried by heating to form a colored layer. An intermediate film layer composition is prepared, applied to the exposed surface of the colored layer, and optionally dried by heating to form an intermediate film layer. A bonding layer composition is prepared, applied onto a carrier film, and optionally dried by heating to form a bonding layer. The exposed surface of the bonding layer and the exposed surface of the intermediate film layer are brought into contact with each other for thermal lamination, and the carrier film is removed. As a thermoplastic top layer, a thermoplastic resin film is thermally laminated in contact with the exposed surface of the bonding layer. After preparing a heat-sensitive adhesive layer composition and removing the release liner to expose the colored layer, the heat-sensitive adhesive layer composition is applied on the colored layer, and if necessary, dried by heating to form a heat-sensitive adhesive. form a layer. Thus, a coating substitute film can be obtained. A release liner may be laminated over the thermal adhesive layer of the paint replacement film to protect the thermal adhesive layer.

In the production of the paint substitute film, after forming the colored layer, a thermoplastic resin film is heat-laminated as a thermoplastic top layer in contact with the exposed surface of the colored layer without forming an intermediate film layer and a bonding layer. Alternatively, the resin component of the thermoplastic top layer may be melt extruded onto the exposed surface of the colored layer. In the production of the paint substitute film, the heat-sensitive adhesive layer is formed not on the colored layer but on the release liner, and the exposed surface of the colored layer and the exposed surface of the heat-sensitive adhesive layer are brought into contact with each other to laminate at room temperature or heat. May be laminated.

The total thickness of the paint replacement film, excluding the thickness of the release liner, is generally greater than or equal to about 30 μm, greater than or equal to about 80 μm, or greater than or equal to about 120 μm, less than or equal to about 600 μm, less than or equal to about 400 μm, or less than or equal to about 350 μm.

When the paint substitute film is heated to 165°C ± 5°C and the area of the paint substitute film before stretching is set to 100%, it is stretched by 200% in terms of area ratio using a vacuum pressure forming machine and attached to a PC-ABS plate. Together, it is cut into a grid shape with a width of 40 mm, and the opening of the cut after being placed at 95° C. for 144 hours is about 1.0 mm or less. The cut opening is preferably about 0.8 mm or less, more preferably about 0.5 mm or less. The opening of the gap indicates the heat resistance of the paint substitute film, specifically the behavior of the heat shrinkage of the paint substitute film. Adhesion to the substrate and appearance of the coating substitute film can be maintained at a higher level. Specific measurement conditions for the opening of the cut are as described in "4. Heat shrinkage" in Examples.

In one embodiment, the coating substitute film is heated to 165 ° C. ± 5 ° C., and when the area of the coating substitute film before stretching is 100%, the area ratio is stretched by 200% using a vacuum pressure forming machine to PC. - The adhesive strength is about 6.4 N/10 mm or more when it is pasted on an ABS plate, cut into strips with a width of 10 mm, and peeled 180 degrees at 23° C. and a peel speed of 200 mm/min. Adhesion is preferably about 6.8 N/10 mm or greater, more preferably about 7.2 N/10 mm or greater. The adhesive strength is less than the force required for cohesive failure of the adherend or paint substitute film, generally about 20 N/10 mm or less, or about 15 N/10 mm or less. Specific measurement conditions for adhesive strength are as described in "2. Adhesive strength" in Examples.

In one embodiment, the coating substitute film is heated to 165 ° C. ± 5 ° C., and when the area of the coating substitute film before stretching is 100%, the area ratio is stretched by 200% using a vacuum pressure forming machine to PC. -After bonding to the ABS plate, the stretched paint substitute film conforms to JIS K 5600-7-7: 2008, and the integrated energy of light with a wavelength of 300 nm to 400 nm at a black panel thermometer display temperature of 63 ° C. The 60 degree gloss retention of the paint replacement film is about 80% or more after the accelerated weathering test with an amount of 750 MJ/m ² . The 60 degree glossiness retention rate is preferably about 85% or more, more preferably about 90% or more. Specific measurement conditions for the 60-degree glossiness retention rate are as described in "5. Glossiness" and "7. Weather resistance" in Examples.

In one embodiment, the tensile strength of the coating substitute film at 200% elongation at a temperature of 120° C. is about 0.6 MPa or more, about 0.8 MPa or more, or about 1.0 MPa or more, 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 in which the film is stretched to a length of 200% (twice) when the length of the film before stretching is 100%. For the tensile strength at 200% elongation, prepare a measurement sample with a length of about 100 mm and a width of 25 mm, use a tensile tester described in ISO7500-1:2015, temperature 120 ° C., tensile speed 150 mm / min, chuck It is the tensile strength when the measurement sample is stretched to 200% elongation at intervals of 50 mm.

The paint replacement film of the present disclosure can be applied to a vehicle body (including roof, doors, bonnet, etc.) or portions thereof, or vehicle components (e.g., bumpers, roof moldings, side guard moldings, pillars, etc.). can. 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 ships such as motorboats. The paint replacement film of the present disclosure is particularly suitable for applications where the DVT method is used to apply to the surface of an article having a curved surface.

A method for forming an article by applying a coating substitute film to a substrate using the DVT method will now be exemplified with reference to FIG.

As shown in FIG. 2(A), an exemplary vacuum pressure forming machine 30 has a first vacuum chamber 31 and a second vacuum chamber 32 on the top and bottom, respectively, and a coating material is deposited between the top and bottom vacuum chambers. A jig is provided for setting the coating substitute film 10 to be attached to the base material 40 which is the body. In the first vacuum chamber 31 on the lower side, a partition plate 34 and a pedestal 33 are installed on a lift table 35 (not shown in FIG. 2A) that can be lifted up and down, so that a three-dimensional object or the like can be placed. The base material 40 is set on this pedestal 33 . As such a vacuum and pressure forming machine, a commercially available one such as a double-sided vacuum forming machine (Fuse Vacuum Co., Ltd.) can be used.

As shown in FIG. 2(A), first, with the first vacuum chamber 31 and the second vacuum chamber 32 of the vacuum pressure forming machine 30 released to the atmospheric pressure, the coating substitute film 10 is placed between the upper and lower vacuum chambers. to set. A substrate 40 is set on the pedestal 33 in the first vacuum chamber 31 .

Next, as shown in FIG. 2B, the first vacuum chamber 31 and the second vacuum chamber 32 are closed, the pressure is reduced, and the inside of each chamber is evacuated (when the atmospheric pressure is 1 atm, for example, about 0 atm). ). The film is then heated, or simultaneously with the vacuum.

Next, as shown in FIG. 2(C), the 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) built 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 degree of vacuum of the reduced pressure atmosphere can be about 0.10 atm or less, about 0.05 atm or less, or about 0.01 atm or less, where atmospheric pressure is 1 atm.

The heated coating substitute film 10 is pressed against the surface of the substrate 40 and stretched. After that or simultaneously with the stretching, as shown in FIG. 2(D), the inside of the second vacuum chamber 32 is pressurized to a suitable pressure (for example, about 3 atm to about 1 atm). Due to the pressure difference, the coating substitute film 10 adheres to the exposed surface of the substrate 40 and is stretched following the three-dimensional shape of the exposed surface to form a coating that adheres to the substrate surface. At least a part of the paint substitute film 10 has an area ratio of about 4 times or more, about 4.5 times or more, or about 5 times or more when stretched following the three-dimensional shape of the substrate 40, for example. It may be stretched. After depressurizing and heating in the state of FIG. 2B, the inside of the second vacuum chamber 32 can be pressurized to cover the exposed surface of the substrate 40 with the coating substitute film 10 .

After that, the upper and lower first vacuum chambers 31 and second vacuum chambers 32 are opened to the atmospheric pressure again, and the substrate 40 coated with the coating substitute film 10 is taken out. As shown in FIG. 2(E), the DVT process is completed by trimming the edge of the painting substitute film 10 that adheres to the surface of the substrate 40 . In this way, it is possible to obtain an article 42 with good wrap-around coating, in which the coating substitute film 10 wraps around the edge of the base material 40 to its back surface 41 to cleanly cover the exposed surface.

The following examples illustrate specific embodiments of the present disclosure, but the invention is not limited thereto. All parts and percentages are by weight unless otherwise specified. Numerical values inherently contain errors resulting from measurement principles and measurement equipment. Numbers are shown to significant digits with normal rounding applied.

Synthesis of carboxy group-containing (meth)acrylic polymer (polymer A) 94 parts by weight of n-butyl acrylate (BA) and 6 parts by weight of acrylic acid (AA), mixed solvent of 100 parts by weight of toluene and 100 parts by weight of ethyl acetate 2,2′-azobis(2,4-dimethylvaleronitrile) (trade name V-65, Fujifilm Wako Pure Chemical Industries, Ltd. (Osaka City, Osaka Prefecture, Japan)) as a polymerization initiator 0.2 After adding parts by mass, the mixture was allowed to react at 50° C. for 24 hours in a nitrogen atmosphere to obtain a toluene/ethyl acetate mixed solution of polymer A (solid content: 33% by mass). Polymer A had a weight average molecular weight of 760,000 and a glass transition temperature (Tg) of -48°C calculated from the FOX formula.

Synthesis of amino group-containing (meth)acrylic polymer (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 mixed with ethyl acetate. Dissolved in 150 parts by mass, dimethyl-2,2'-azobis(2-methylpropionate) (trade name V-601, Fujifilm Wako Pure Chemical Industries, Ltd. (Osaka City, Osaka Prefecture, Japan) as a polymerization initiator. ) was added, and the mixture was reacted at 65° C. for 24 hours in a nitrogen atmosphere to obtain an ethyl acetate solution of polymer B (solid content: 39% by mass). Polymer B had a weight average molecular weight of 68,000 and a glass transition temperature (Tg) of 63° C. calculated from the FOX formula.

Synthesis of Polyurethane (PUR1) 157.5 parts by weight of Polylite® OD-X-2640, 0.9 parts by weight of 1,4-butanediol, 1.2 parts by weight of 1,6-hexanediol, and 430.1 parts by mass of ethyl acetate was mixed to prepare a homogeneous solution. 25.0 parts by mass of 4,4′-diphenylmethane diisocyanate and 0.01 part of dibutyltin dilaurate were added to the resulting solution and reacted at 80° C. for 24 hours to obtain an ethyl acetate solution of PUR1 (solid content: 30 mass %) was obtained. PUR1 had a number average molecular weight of 84,000, a weight average molecular weight of 200,000, and a glass transition temperature (Tg) of -10°C.

Table 1 shows the materials, reagents, etc. used in Examples and Comparative Examples.

Table 2 shows the compositions of paints A to D.

<Example 1>
A painting substitute film having a five-layer structure was produced by the following procedure. The colored layer composition E1 in Table 3 was coated on a release-treated PET film (Film Biner (registered trademark) NSD, 50 μm thick, Fujimori Industry Co., Ltd. (Bunkyo-ku, Tokyo, Japan)) using a bar coater, C. for 3 minutes and then in a 120.degree. C. hot air oven for 3 minutes to form a 60 .mu.m thick colored layer.

The intermediate film layer composition (aqueous polyurethane solution) in Table 5 was applied onto the colored layer using a bar coater, placed in a hot air oven at 80°C for 3 minutes, and then placed in a hot air oven at 120°C for 3 minutes to form a 20 μm thick film. An intermediate film layer was formed.

A bonding layer composition (phenoxy resin solution) in Table 6 was applied onto a PET film using a bar coater and placed in a hot air oven at 80° C. for 1 minute to form a bonding layer having a thickness of about 1 μm. A bonding layer was laminated on the intermediate film layer using a heat laminator heated to 120° C., and the PET film used for forming the bonding layer was removed.

As a thermoplastic top layer, a 75 μm thick acrylic film (Technolloy (registered trademark) S014G, Sumika Acrylic Sales Co., Ltd. (Chuo-ku, Tokyo, Japan)) was laminated on the bonding layer side using a heat laminator heated to 120 ° C. bottom.

Adhesive layer composition E1 in Table 4 was applied using a bar coater to the surface from which the release-treated PET film used for forming the colored layer was peeled off from the above laminate, and placed in a hot air oven at 80°C for 5 minutes, followed by 100°C. C. for 3 minutes to form a 20 .mu.m thick heat-sensitive adhesive layer.

A 60 μm-thick biaxially stretched PP film (PY-002, Oji F-Tex Co., Ltd. (Chuo-ku, Tokyo, Japan)) was laminated on the heat-sensitive adhesive layer as a release liner to obtain the paint substitute film of Example 1. rice field.

<Example 2, Comparative Example 1, and Comparative Example 2>
Example 2, Comparative Example 1, and Comparative Example 2 were carried out in the same manner as in Example 1 except that the colored layer composition was E2, C1 or C2 in Table 3 and the thickness of the colored layer was as shown in Table 8. of coating substitute film was obtained.

<Example 3, Example 4, Comparative Example 3, and Comparative Example 4>
Coating substitute films of Examples 3, 4, Comparative Examples 3 and 4 were obtained in the same manner as in Example 1 except that the adhesive layer composition was E3, E4, C3 or C4 in Table 4.

<Examples 5 to 7, Comparative Example 5, and Comparative Example 6>
Coating substitute films of Examples 5 to 7, Comparative Examples 5, and 6 were prepared in the same manner as in Example 2, except that the adhesive layer composition was E3, E4, E5, C3, or C4 in Table 4. Obtained.

<Examples 8 to 10, Comparative Example 7, and Comparative Example 8>
The films of Example 5, Example 2, Example 6, Comparative Example 5, and Comparative Example 6 were used as the films of Examples 8-10, Comparative Example 7, and Comparative Example 8, respectively.

<Example 11>
An example was prepared in the same manner as in Example 1, except that a 75 μm thick PMMA-PVDF copolymer film (Acryprene (registered trademark) FBA015, Mitsubishi Chemical Co., Ltd. (Chiyoda-ku, Tokyo, Japan)) was used as the thermoplastic top layer. 11 paint replacement films were obtained.

<Example 12>
Coating of Example 12 was carried out in the same manner as in Example 1, except that a 75 μm thick polycarbonate film (Technoloy® C000, Sumika Acrylic Co., Ltd. (Chuo-ku, Tokyo, Japan)) was used as the thermoplastic top layer. Got a replacement film.

<Comparative Example 9>
Instead of laminating an acrylic film (Technolloy (registered trademark) S014G), the top layer composition (transparent two-part curable polyurethane composition) in Table 7 was applied onto the bonding layer using a bar coater, and heated at 80°C. A paint substitute film of Comparative Example 9 was obtained in the same manner as in Example 1, except that the film was placed in a hot air oven for 1 hour to form a 50 μm thick top layer.

Table 8 shows the composition of the painting substitute films of Examples 1 to 12 and Comparative Examples 1 to 9.

The coating substitute film was evaluated for the following items.

1. DVT formability

The following were used as substrates.

A. PC-ABS plate 3mm thick, 150mm x 150mm square PC-ABS plate test panel with a mirror-finished surface (product name: “flat plate test piece”, black PC-ABS resin CK43 made by Techno Polymer, MC Yamasan Polymers Co., Ltd. (Chuo-ku, Tokyo, Japan) was cut into a rectangle of 75 mm x 50 mm to obtain the substrate. The 20° gloss of the mirror-finished surface of the PC-ABS plate measured according to JIS Z8741:1997 was 85-90.

B. Electrodeposition coated steel plate A cationic electrodeposition coated steel plate (JIS, G, 3141 (SPCC, SD), Testpiece Co., Ltd. (Sagamihara City, Kanagawa Prefecture, Japan)) having a thickness of 0.8 mm and 150 mm × 65 mm was cut into a 75 mm × 50 mm rectangle. The base material was obtained by cutting into two pieces.

Using the DVT method, the coating substitute film was stretched by 200% in terms of area ratio and attached to the substrate in the following procedure.

A double-sided vacuum forming machine NGF0709 (Fuse Vacuum Co., Ltd. (Habikino City, Osaka Prefecture, Japan)) was used as a vacuum pressure forming machine. FIG. 3A shows a schematic cross-sectional view of a vacuum pressure forming machine before stretching. The first vacuum chamber 31 and the second vacuum chamber 32 of the vacuum pressure forming machine 30 are sandwiched between the lower hook 311, the lower hook frame 312, the upper hook 321, the upper hook frame 322, and the lower hook frame 312 and the upper hook frame 322. separated from each other by a paint substitute film 10 which An IR lamp heater 323 for heating was attached to the inner wall of the upper pot 321 on the ceiling of the second vacuum chamber 32 . The opening of the lower hook frame 312 was a square of 260 mm×260 mm.

On a lower hook table 313 arranged at the bottom of the lower hook 311, a well-shaped extending jig 314 having the same size as the opening of the lower hook frame 312 and having an open top and bottom is arranged. The height of the stretching well-shaped jig 314 was 60 mm, which was confirmed in advance so that the paint substitute film 10 was attached to the substrate 40 in a state of being stretched 200% in terms of area ratio.

A 75 mm×50 mm rectangular base material 40 is stretched by 200% in area ratio on the lower pot table 313 and inside the stretching well-shaped jig 314, and the coating substitute film 10 is attached to the base material 40. It was installed in a position where it was confirmed in advance. FIG. 3B shows the placement position of the substrate in a top view. As shown in FIG. 3B, the base material 40 was placed at four locations 90 mm apart from the center of the stretching well-shaped jig 314 so that the center thereof was located. The circle indicated by the dashed-dotted line in FIG. 3B represents the position where the paint substitute film 10 is attached to the substrate 40 in a state of being stretched 200% in area ratio.

The coating substitute film 10 was cut into a square of 300 mm×300 mm and placed on the lower hook frame 312 . The lower hook frame 312 had a thickness of 20 mm. Therefore, the distance between the coating substitute film 10 and the base material 40 was 80 mm in total, which is the thickness of the lower hook frame 312 (20 mm) and the height of the stretching well-shaped jig 314 (60 mm).

After setting the base material 40 and the coating substitute film 10, the upper hook 321 and the upper hook frame 322 are lowered, and the coating replacement film 10 placed on the lower hook frame 312 is sandwiched between the upper hook frame 322 and the lower hook frame 312. . After that, while reducing the pressure inside the first vacuum chamber 31 and the second vacuum chamber 32, the IR lamp heater 323 heated the coating substitute film 10 to a forming temperature of 165°C ± 5°C. At this time, the vacuum state (2 to 4 kPa) was reached before reaching the molding temperature. The molding temperature is a value obtained based on the set temperature of the vacuum/compressed air forming machine 30 and the correspondence relation between the set temperature of the vacuum/compressed air forming machine 30 and the actual temperature of the coating substitute film 10, which is prepared in advance by the procedure described later. rice field.

DVT molding was started when the molding temperature was reached. The lower hook table 313 was raised until the drawing well-shaped jig 314 came into contact with the lower hook frame 312 . By setting the internal pressure of the second vacuum chamber 32 to 200 to 205 kPa while maintaining the vacuum state inside the first vacuum chamber 31, the pressure difference between the first vacuum chamber 31 and the second vacuum chamber 32 is reduced. By this, the coating substitute film 10 was attached to the substrate 40 while being stretched. FIG. 3C shows a schematic cross-sectional view of the vacuum pressure forming machine after stretching. In the central part of the base material 40, the painting substitute film 10 was stretched by 200% in area ratio and attached.

After returning the insides of the first vacuum chamber 31 and the second vacuum chamber 32 to the atmospheric pressure, the substrate 40 to which the stretched coating substitute film 10 was attached was taken out. A cutter knife was used to trim the surplus coating substitute film 10 along the edge of the substrate 40 to obtain a DVT formability evaluation sample.

It is known that there is generally 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 relationship between the set temperature of the vacuum pressure forming machine and the actual temperature of the coating substitute film is determined in advance, and the actual temperature of the coating substitute film during DVT molding is determined by the set temperature of the vacuum pressure forming machine and the actual temperature of the coating substitute film. It was regarded as a value obtained based on the above correspondence.

Measurement of the actual temperature of the coating substitute film during DVT molding is performed by using a temperature/voltage measurement unit NR-TH08 and a multi-input data logger NR-500 (both Keyence Corporation (Osaka City, Osaka Prefecture, Japan)) and a thermocouple ( Symbol 0.1×1P K-2-H-J2 (KH), wire: K type, Ninomiya Electric Wire Industry Co., Ltd. (Sagamihara City, Kanagawa Prefecture, Japan)).

A thermocouple was attached to the surface of the paint substitute film 10 with a heat-resistant tape so that the metal part, which is the measurement site of the thermocouple, does not come into contact with the paint substitute film 10 . The coating substitute film 10 was placed on the lower pot frame 312 with the surface to which the thermocouple was attached facing upward.

The upper hook 321 and the upper hook frame 322 are lowered, and the coating substitute film 10 placed on the lower hook frame 312 is sandwiched between the upper hook frame 322 and the lower hook frame 312 . After that, the coating substitute film 10 was heated with the IR lamp heater 323 . When the measured value of the thermocouple was 165±5°C, the set temperature of the vacuum pressure molding machine was 136°C. Based on this correspondence, it was assumed that the coating substitute film 10 was heated to 165±5° C. by setting the temperature of the vacuum pressure forming machine to 136° C. during DVT molding.

2. Adhesive strength A test piece bonded under the same conditions as DVT moldability is cut into strips with a width of 10 mm, and a tensile tester (Tensilon (registered trademark) universal testing machine, model number: RTC-1210A, A&D Co., Ltd. (Toshima Ward, Tokyo, Japan)) was used to measure the adhesive strength when peeled 180 degrees at a temperature of 23° C. and a peel speed of 200 mm/min. It is required that the adhesive strength is 6.4 N/10 mm or more for use as a paint substitute for the exterior of automobiles.

3. Opacity (concealability)
The opacity test is a test to evaluate the concealability (the ability to hide the base color) of the paint substitute film. The coating substitute film used in the DVT method is required to maintain sufficient opacity even after stretching because the colored layer becomes thin and its opacity decreases after stretching. Using the DVT method, the coating substitute film was heated to 165 ° C. ± 5 ° C., and the area of the coating substitute film before stretching was set to 100% on the mirror-finished surface of the black PC-ABS plate used for DVT moldability. Sometimes, it was stretched and pasted so that the area ratio was 100% (non-stretched) or the area ratio was 200% to prepare a measurement sample. The values of L ^* , a ^* , and b ^* of the measurement sample were measured using a spectrophotometer (CM-3700d, Konica Minolta Japan Co., Ltd. (Minato-ku, Tokyo, Japan)). As a reference, the values of the black PC-ABS flat panel to which the non-stretched paint substitute film is attached are L ₁ ^* , a ₁ ^* , b ₁ ^* , and the black PC to which the paint substitute film is attached at an area ratio of 200%. - When the values of the ABS flat panel are L ₂ ^* , a ₂ ^* , and b ₂ ^* , the color difference ΔE ^* is calculated by the following formula:
ΔE ^* = [(L ₂ ^* - L ₁ ^* ) ² + (a ₂ ^* - a ₁ ^* ) ² + (b ₂ ^* - b ₁ ^* ) ² ] ^1/2
was calculated by Automotive exterior paint replacement applications require ΔE ^* to be less than 1.

4. Heat Shrinkage A 40 mm-wide grid-like slit was made in the center of a test piece adhered under the same conditions as for DVT moldability, and left at 95° C. for 144 hours (6 days) as shown in FIG. The opening of the cut was measured at four locations, and the average of the measured values at the four locations was used as an index of thermal shrinkage. A cut opening of 1.0 mm or less was accepted, and a cut opening of more than 1.0 mm was rejected.

5. Glossiness The 60-degree glossiness of the surface of the test piece adhered under the same conditions as the DVT formability was measured using a portable glossmeter GMX-202 (Murakami Color Research Institute, Inc. (Chuo-ku, Tokyo, Japan)). . For the paint substitute application for automobile exterior, the 60-degree glossiness is desirably 85 or more, and if it is less than 85 and 75 or more, it can be used.

6. Chemical resistance On the surface of the test piece adhered under the same conditions as the DVT moldability, (A) 1% by mass HCl aqueous solution, (B) 1% by mass NaOH aqueous solution, or (C) 30% by mass _H3PO4 aqueous solution was applied to the _surface . .2 mL was added dropwise, left at 85° C. for 30 minutes, and then rinsed with detergent and water. The presence or absence of traces of droplets on the surface after washing was visually observed. Automotive exterior paint replacement applications require no trace of droplets.

7. Weather resistance A test piece adhered under the same conditions as DVT moldability, in accordance with JIS K 5600-7-7: 2008, the integrated energy of light with a wavelength of 300 nm to 400 nm at a black panel thermometer display temperature of 63 ° C. An accelerated weathering test was performed with a loading of 750 MJ/m ² . An accumulated energy amount of 750 MJ/m ² corresponds to three years of outdoor exposure. The 60 degree glossiness and L ^* , a ^* , b ^* of the test piece before and after the accelerated weather resistance test were measured. Gloss retention rate (%) = _G2 / _G1 was calculated, where _G1 was the 60-degree gloss before the accelerated weather resistance test and _G2 was the 60-degree gloss after the accelerated weather resistance test. Further, when the values before the accelerated weather resistance test are L ₁ ^* , a ₁ ^* , b ₁ ^* and the values after the accelerated weather resistance test are L ₂ ^* , a ₂ ^* , b ₂ ^* , the color difference ΔE ^* to the following formula:
ΔE ^* = [(L ₂ ^* - L ₁ ^* ) ² + (a ₂ ^* - a ₁ ^* ) ² + (b ₂ ^* - b ₁ ^* ) ² ] ^1/2
was calculated by For automotive exterior paint substitute applications, gloss retention of 80% or more and ΔE ^* of less than 3 are required.

8. Tensile strength at 200% elongation 3M (registered trademark) heat-resistant polyimide tape 5413 (3M Japan stock (Shinagawa-ku, Tokyo, Japan)) was attached to both sides of the paint substitute film to prepare a measurement sample in which the two short sides of the paint substitute film were sandwiched between 3M (registered trademark) heat-resistant polyimide tape 5413. Tensilon (registered trademark) universal testing machine, model number: RTC-1210A, A&D Co., Ltd. (Toshima-ku, Tokyo, Japan). The measurement sample was fixed so that the heat-resistant polyimide tape 5413 was in contact with it. A constant temperature bath was placed so as to cover the entire chuck part, and when the temperature display inside the constant temperature bath reached 120 ° C., measurement was started, and the temperature was 120 ° C. and the tensile speed was 150 mm / min. Tensile strength was measured when stretched to twice its original length). Measurements were taken twice and averaged. For use as a paint substitute for automobile exteriors, the tensile strength at 200% elongation is required to be 0.6 MPa or more at a temperature of 120°C.

Tables 9 to 11 show the evaluation results of the painting substitute films.

It will be apparent to those skilled in the art that various modifications may be made to the above-described embodiments and examples without departing from the underlying principles of the invention. In addition, it will be apparent to those skilled in the art that various modifications and alterations of this invention can be made without departing from its spirit and scope.

REFERENCE SIGNS LIST 10 painting substitute film 12 thermoplastic top layer 14 colored layer 142 thermoplastic resin 144 coloring agent 16 heat-sensitive adhesive layer 20 liner 22 intermediate film layer 24 joining layer 30 vacuum pressure forming machine 31 first vacuum chamber 311 lower pot 312 lower pot frame 313 lower pot Table 314 Well-shaped jig for stretching 32 Second vacuum chamber 321 Upper pot 322 Upper pot frame 323 IR lamp heater 33 Pedestal 34 Partition plate 35 Elevating table 40 Base material 41 Back part 42 Article

Claims (6)

a thermoplastic top layer,
A colored layer containing a thermoplastic resin containing a carboxy group-containing (meth)acrylic polymer and an amino group-containing (meth)acrylic polymer, a coloring layer containing a coloring agent, and a heat-sensitive adhesive layer containing a polyurethane-based heat-sensitive adhesive, in this order. A paint substitute film containing, when the paint substitute film is heated to 165 ° C. ± 5 ° C. and the area of the paint substitute film before stretching is 100%, the area ratio is 200 using a vacuum pressure forming machine % stretched, attached to a PC-ABS plate, cut into a grid shape with a width of 40 mm, left at 95° C. for 144 hours, and the gap between cuts is 1.0 mm or less. When the paint substitute film is heated to 165 ° C. ± 5 ° C. and the area of the paint substitute film before stretching is 100%, the area ratio is stretched by 200% using a vacuum pressure forming machine to form a PC-ABS plate. 2. The paint substitute film according to claim 1, wherein the adhesive force is 6.4 N / 10 mm or more when the film is cut into strips with a width of 10 mm and peeled 180 degrees at 23 ° C. and a peeling speed of 200 mm / min. . 2. The glass transition temperature of one of the carboxy 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 coating substitute film according to any one of 2. When the paint substitute film is heated to 165 ° C. ± 5 ° C. and the area of the paint substitute film before stretching is 100%, the area ratio is stretched by 200% using a vacuum pressure forming machine to form a PC-ABS plate. After bonding, the stretched paint substitute film conforms to JIS K 5600-7-7: 2008, and the integrated energy amount of light with a wavelength of 300 nm to 400 nm at a black panel thermometer display temperature of 63 ° C. The coating according to any one of claims 1 to 3, wherein the coating substitute film has a 60 degree glossiness retention rate of 80% or more after an accelerated weather resistance test is performed so as to be 750 MJ/m ² . alternative film. 5. The thermoplastic top layer 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. Paint replacement film as described. The paint substitute film according to any one of claims 1 to 5, wherein the paint substitute film has a tensile strength of 0.6 MPa to 20 MPa at 200% elongation at a temperature of 120°C.

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