Laminate film, and decorative article decorated by the laminate film

Abstract

To provide a laminate film having excellent pencil hardness, acid resistance, water resistance and car-wash scratch resistance, and a decorative article decorated by the laminate film.SOLUTION: Provided is a laminate film in which a cured coating layer by a two-component clear coating composition (CC) is directly or indirectly laminated on a thermoplastic polyurethane (TPU) substrate, where the two-component clear coating composition (CC) contains a hydroxy group-containing (meth)acrylic resin (A) having a calculated glass transition temperature (Tg) of -50°C or more and 10°C or less, and an isocyanate curing agent (B), the cured clear coating layer (T) is a layer formed by heating at 80°C or less, and the molecular weight between crosslinking points (Mc) is 200 g / mol or more and 800 g / mol or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a laminated film and a decorated article decorated with this laminated film. [Background technology]

[0002] In recent years, attention has been focused on alternative painting technologies that offer sophisticated designs, taking into account the reduction of VOCs (Volatile Organic Compounds), workability, and functionality.Typical examples of decorative technologies that can replace conventional methods include the application of decorative films to automotive exteriors and parts, and colored plastic molding using mold-in color, some of which have already begun to be put to practical use.

[0003] The most common method for applying decorative film to plastic parts, such as automobiles, is to use an injection molding machine. Specifically, the decorative film, consisting of a substrate and a decorative layer, is set in a mold beforehand, and then molten resin is poured into the mold using an injection molding machine to obtain a molded product. This method, in which both the substrate and decorative layer of the decorative film remain on the plastic part to be decorated (the decorated product), is called in-mold forming (IMF). On the other hand, a method similar to the above, in which the decorative film is set in a mold, but after peeling the substrate from the decorative layer, molten resin is poured into the mold, leaving only the decorative layer on the decorated product, is called in-mold release (IMR). In addition to plastics, there is also the TOM (Three Dimension Overlay Method) molding method, in which a film is laminated onto an already completed product using vacuum forming. This method allows decorative films to be applied to the exteriors of automobiles and other vehicles.

[0004] When producing a decorated article, the decorative film must be processable so that it can be deformed to fit the surface shape of the decorated article. Furthermore, the decorative film must also have properties equivalent to or better than those of coating films obtained by conventional coating techniques, such as pencil hardness, acid resistance, weather resistance, water resistance, and car wash scratch resistance.

[0005] As a conventional decorative film, for example, Patent Document 1 discloses a surface protection film made of a polyurethane resin having a tensile breaking elongation of 120% or more at 80°C and / or a gloss retention rate of 80% or more after two years of outdoor exposure.

[0006] Furthermore, Patent Document 2 discloses a molding film made from a hard coating agent for decorative molding, which is used when forming a coating film and is characterized by containing a (meth)acrylic polymer having an imide ring. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-260942 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-180082 Summary of the Invention [Problem to be solved by the invention]

[0008] However, although the surface protection film of Patent Document 1 has excellent processability and weather resistance, it may not have sufficient acid resistance, water resistance, and resistance to scratches caused by car washes.

[0009] Furthermore, although the molding film of Patent Document 2 has excellent processability and durability against steel wool scratches and sunscreen agents, it may not have sufficient performance in terms of acid resistance, water resistance, and car wash scratch resistance.

[0010] In view of the above-described state of the art, the present invention aims to provide a laminated film that has performance comparable to that of decorative films made by conventional techniques, and also has excellent pencil hardness, acid resistance, water resistance, and car wash scratch resistance, and a decorated part that is decorated with this laminated film. [Means for solving the problem]

[0011] As a result of extensive research to solve the above problems, the present inventors have discovered the following: The present inventors have found that the above-mentioned problems can be solved by a laminate film comprising a thermoplastic polyurethane (TPU) substrate and a cured clear coating layer (T) made from a two-component clear coating composition (CC) formed directly or indirectly on the substrate, wherein the two-component clear coating composition (CC) contains a hydroxyl group-containing (meth)acrylic resin (A) having a calculated glass transition temperature (Tg) of -50°C or higher and 10°C or lower, and an isocyanate curing agent (B), and the cured clear coating layer (T) is a layer formed by heating and drying at 80°C or lower, and the cured clear coating layer (T) has a molecular weight between crosslinks (Mc) of 200 g / mol or higher and 800 g / mol or lower, and have completed the present invention.

[0012] Furthermore, the laminated film is preferably a laminated film characterized in that an adhesive layer is further formed on the outermost layer of the surface of the thermoplastic polyurethane (TPU) substrate opposite to the surface on which the cured clear coating film layer (T) is formed.

[0013] Furthermore, the laminated film is preferably a laminated film characterized in that a colored coating layer is formed on one side of a thermoplastic polyurethane (TPU) substrate, and the cured clear coating layer (T) is formed on this colored coating layer.

[0014] Furthermore, the laminated film is preferably a laminated film characterized in that a colored coating layer is further formed on the surface of the thermoplastic polyurethane (TPU) substrate opposite to the cured clear coating layer (T).

[0015] The laminated film is preferably a laminated film characterized in that the thermoplastic polyurethane (TPU) substrate contains a color pigment and / or a luster pigment.

[0016] The thickness of the thermoplastic polyurethane (TPU) substrate of the laminated film is preferably 50 to 1000 μm.

[0017] The laminate film is preferably a laminate film in which the two-component clear coating composition (CC) contains a matting agent. The laminate film is preferably a laminate film in which a colored coating layer is formed on one side of a thermoplastic polyurethane (TPU) substrate and a cured clear coating layer (T) is formed on the colored coating layer, and the colored coating layer contains 10 to 200 parts by mass of a color pigment and / or 30 parts by mass or less of a luster pigment per 100 parts by mass of the solids content of the resin that forms the colored coating layer.

[0018] Furthermore, the laminate film is preferably a laminate film in which a colored coating layer is further formed on the surface of the thermoplastic polyurethane (TPU) substrate opposite the cured clear coating layer (T), and the colored coating layer contains 10 to 200 parts by mass of a color pigment and / or 30 parts by mass or less of a luster pigment per 100 parts by mass of the resin solid content forming the colored coating layer.

[0019] Furthermore, the above-mentioned object of the present invention is achieved by a decorated article decorated with the above-mentioned laminated film.

[0020] The laminated film is formed by forming a colored coating layer on one side of a thermoplastic polyurethane (TPU) substrate and then forming a cured clear coating layer (T) on the colored coating layer, and it is preferable that the thickness of the colored coating layer is 50 μm or less and the thickness of the cured clear coating layer (T) is 60 μm or less.

[0021] Furthermore, it is preferable that the laminated film further comprises a colored coating layer formed on one side of the thermoplastic polyurethane (TPU) substrate opposite to the cured clear coating layer (T), and that the colored coating layer has a thickness of 50 μm or less and the cured clear coating layer (T) has a thickness of 60 μm or less. [Effects of the Invention]

[0022] According to the present invention, it is possible to obtain a laminated film that can be used as a decorative film, which has performance comparable to that of decorative films made using conventional technology, and which has excellent pencil hardness, acid resistance, water resistance, and car wash scratch resistance, as well as a decorated article decorated with this laminated film. [Brief explanation of the drawings]

[0023] [Figure 1] FIG. 1 is a schematic cross-sectional view showing one embodiment (first embodiment, H-1) of the laminated film of the present invention. [Figure 2] FIG. 2 is a schematic cross-sectional view showing one embodiment (second embodiment, H-2) of the laminated film of the present invention. [Figure 3] FIG. 3 is a schematic cross-sectional view showing one embodiment (third embodiment, H-3) of the laminated film of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0024] The laminated film of the present invention is constructed by forming a cured clear coating layer (T) of a two-component clear coating composition (CC) directly or indirectly on one side of a thermoplastic polyurethane (TPU) substrate.

[0025] In the present invention, the expression "directly" forming a predetermined layer (e.g., a cured clear coating layer) on the surface of another layer (e.g., the surface of a substrate) means that the predetermined layer is provided in contact with the other layer, particularly in close contact with the other layer. On the other hand, the expression "indirectly" forming a predetermined layer (e.g., a cured clear coating layer) on the surface of another layer (e.g., the surface of a substrate) means that one or more other layers (e.g., a colored coating layer described below) are provided on the predetermined surface, and the predetermined layer is formed via the other layers.

[0026] [Base material] In the laminated film of the present invention, a thermoplastic polyurethane (TPU) is used as the substrate. Thermoplastic polyurethane (TPU) has excellent adhesion to the layer formed thereon, so a laminated film with excellent processability can be obtained without forming a primer layer between the substrate and the layer formed thereon.

[0027] Thermoplastic polyurethane (TPU) is a polymer with urethane bonds in its molecules, generally obtained by polyaddition reaction of a polymer polyol, a polyisocyanate such as a diisocyanate, and a chain extender, optionally using a catalyst such as dibutyltin dilaurate. It softens and becomes fluid when heated. The chain extender reacts with the polyisocyanate to form hard segments, while the polymer polyol reacts with the polyisocyanate to form soft segments.

[0028] Examples of polymer polyols include polyester polyols, polyether polyols, polycarbonate polyols, and combinations thereof, which have two or more hydroxyl groups in one molecule and have a number average molecular weight of 400 or more. Since excessive crosslinking structures introduced into polyurethane can impair thermoplasticity, the polymer polyol is preferably a diol having two hydroxyl groups in one molecule.

[0029] The polyester polyol can be obtained, for example, by a condensation reaction or transesterification reaction between a short-chain polyol having two or more hydroxyl groups in one molecule and a number average molecular weight of less than 400 and a polybasic acid or its alkyl ester, acid anhydride, or acid halide.

[0030] As the short-chain polyol, it is desirable to use a short-chain dihydric alcohol, since excessive crosslinking of polyurethane may impair thermoplasticity. Examples of the short-chain dihydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 2,6-dimethyl-1-octene-3,8-diol, C7 to C22 alkanediol, cyclohexanediol, cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,4-dihydro Examples of the short-chain polyol include 2-butene, bishydroxyethoxybenzene, xylene glycol, bishydroxyethylene terephthalate, diethylene glycol, trioxyethylene glycol, tetraoxyethylene glycol, pentaoxyethylene glycol, hexaoxyethylene glycol, dipropylene glycol, trioxypropylene glycol, tetraoxypropylene glycol, pentaoxypropylene glycol, and hexaoxypropylene glycol, and preferred examples include 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. The short-chain polyols can be used alone or in combination of two or more.

[0031] Examples of polybasic acids include saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethylglutaric acid, azelaic acid, and sebacic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; aromatic dicarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as hexahydrophthalic acid; and other polycarboxylic acids such as dimer acid, hydrogenated dimer acid, and HET acid.

[0032] Examples of alkyl esters, acid anhydrides, and acid halides of polybasic acids include methyl esters, ethyl esters, etc. of the above polybasic acids, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-C12 to C18 alkylsuccinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, etc., oxalic acid dichloride, adipic acid dichloride, sebacoyl dichloride, etc. The polybasic acids or their alkyl esters, acid anhydrides, or acid halides can be used alone or in combination of two or more.

[0033] If an excessive crosslinking structure is introduced into the polyurethane, the thermoplasticity may be impaired, so it is desirable to use a dicarboxylic acid, or an alkyl ester, acid anhydride or acid halide thereof.

[0034] In addition, as the polyester polyol, vegetable oil-based polyester polyols obtained by a condensation reaction of hydroxycarboxylic acids such as hydroxyl group-containing vegetable oil fatty acids, polycaprolactone polyols, polyvalerolactone polyols, polylactic acid polyols, and the like obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone, and lactides such as L-lactide and D-lactide, can also be used.

[0035] The polyester polyols can be used alone or in combination of two or more.

[0036] Examples of polyether polyols include polyoxyalkylene polyols obtained by ring-opening polymerization of alkylene oxides such as ethylene oxide, propylene oxide, etc. The polyether polyols can be used alone or in combination of two or more.

[0037] Examples of polycarbonate polyols include ring-opening polymerization products of ethylene carbonate in the presence of a short-chain polyol; polycarbonates obtained by reacting the above-mentioned short-chain dihydric alcohols such as 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol with phosgene or diphenyl carbonate; and amorphous polycarbonate polyols obtained by copolymerizing the above-mentioned short-chain dihydric alcohols with the above-mentioned ring-opening polymerization products.

[0038] The polycarbonate polyols can be used alone or in combination of two or more.

[0039] Examples of polyisocyanates include linear aliphatic polyisocyanates, cyclic aliphatic polyisocyanates, aromatic polyisocyanates, araliphatic polyisocyanates, and polymers (dimers, trimers, etc.) of these polyisocyanates, as well as uretdione-modified products, biuret-modified products, allophanate-modified products, isocyanurate-modified products, polyol-modified products, oxadiazinetrione-modified products, and carbodiimide-modified products. Polyisocyanates can be used alone or in combination of two or more. Since excessive crosslinking structures introduced into polyurethane can impair thermoplasticity, it is desirable to use a diisocyanate as the polyisocyanate.

[0040] Examples of the chain aliphatic polyisocyanate include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), octamethylene diisocyanate, and nonamethylene diisocyanate.

[0041] Examples of cycloaliphatic polyisocyanates include isophorone diisocyanate (IPDI), 1,3-bis(isocyanatomethyl)cyclohexane, trans,trans-, trans,cis-, and cis,cis-dicyclohexylmethane-4,4'-diisocyanate, and mixtures thereof (hydrogenated MDI).

[0042] Examples of aromatic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and isomer mixtures of these tolylene diisocyanates (TDI), 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 2,2'-diphenylmethane diisocyanate, and isomer mixtures of these diphenylmethane diisocyanates (MDI), toluidine diisocyanate (TODI), and naphthalene diisocyanate (NDI).

[0043] Examples of the araliphatic polyisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), and the like.

[0044] Examples of the chain extender include the same short-chain dihydric alcohols as those mentioned above. The chain extenders may be used alone or in combination of two or more.

[0045] The thermoplastic polyurethane (TPU) that is the base material of the laminated film of the present invention is formed into a sheet by a method such as calendar molding, inflation molding, T-die extrusion molding, blow molding, and lamination.

[0046] The thickness of the thermoplastic polyurethane (TPU) that is the substrate of the laminated film of the present invention is preferably 50 to 1000 μm, more preferably 100 to 1000 μm. By setting the thickness of the substrate to 50 to 1000 μm, it is possible to obtain practically satisfactory handling properties of the laminated film.

[0047] The tensile elongation of the thermoplastic polyurethane (TPU) that is the base material of the laminated film of the present invention is preferably 200 to 800%, more preferably 300 to 700%. By setting the tensile elongation to 200 to 800%, excellent processability can be obtained. The tensile elongation is a value measured in accordance with JIS K 7311:1995.

[0048] Since the laminated film of the present invention may be subjected to heat during molding, it is preferable that the thermoplastic polyurethane (TPU) substrate has heat resistance. In the present invention, heat resistance is sufficient if no or substantially no deformation is observed when the thermoplastic polyurethane (TPU) substrate is placed in an oven at 120°C for 5 seconds.

[0049] Furthermore, the thermoplastic polyurethane (TPU) substrate of the laminate film of the present invention may be previously surface-treated by corona surface treatment, flame treatment, plasma treatment, or the like. However, it is not necessary to provide a primer layer of chlorinated polyolefin, polyester, polyurethane, or the like. By selecting thermoplastic polyurethane (TPU) as the substrate, sufficient adhesion can be obtained between the substrate and adjacent layers even without a primer layer. This eliminates the need for a primer layer formation step in the laminate film manufacturing process, thereby improving the manufacturing efficiency of the laminate film.

[0050] Furthermore, the thermoplastic polyurethane (TPU) substrate of the laminated film of the present invention may be transparent, but may also contain a coloring pigment. Examples of the coloring pigment contained in the substrate of the present invention include inorganic pigments such as titanium oxide, iron oxide, and composite oxide pigments such as titanium yellow; organic pigments such as azo pigments, quinacridone pigments, diketopyrrolopyrrole pigments, perylene pigments, perinone pigments, benzimidazolone pigments, isoindoline pigments, isoindolinone pigments, metal chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, dioxazine pigments, threne pigments, and indigo pigments; and carbon black. These coloring pigments can be used alone or in combination.

[0051] The total content of the color pigment contained in the thermoplastic polyurethane (TPU) that is the base material of the laminated film of the present invention is not particularly limited, but is preferably 10 to 200 parts by mass, more preferably 30 to 180 parts by mass, and particularly preferably 50 to 160 parts by mass, per 100 parts by mass of the total amount of the base resin.

[0052] Furthermore, the thermoplastic polyurethane (TPU) that is the substrate of the laminate film of the present invention may contain a luster pigment. Examples of luster pigments include uncolored or colored aluminum pigments, vapor-deposited metal flake pigments, and optical interference pigments in which a transparent or translucent substrate is coated with a metal oxide. The luster pigments can be used alone or in combination of two or more. The total content of the luster pigments contained in the thermoplastic polyurethane (TPU) that is the substrate of the laminate film of the present invention is not particularly limited, but is preferably 0 to 30 parts by mass, more preferably 0 to 25 parts by mass, and particularly preferably 0.1 to 20 parts by mass, per 100 parts by mass of the total amount of the substrate resin.

[0053] [Two-component clear coating composition (CC)] In the present invention, the two-component clear coating composition (CC) essentially comprises a hydroxyl group-containing (meth)acrylic resin (A) having a calculated glass transition temperature (Tg) of −50° C. or higher and 10° C. or lower, and an isocyanate curing agent (B).

[0054] In the present invention, the hydroxyl group-containing (meth)acrylic resin (A) may be a homopolymer of a monomer (a) having a hydroxyl group, or a copolymer of the monomer (a) having a hydroxyl group and another monomer (c). However, a copolymer of the monomer (a) having a hydroxyl group, the monomer (b) having a carboxyl group, and another monomer (c) is preferred.

[0055] The hydroxyl group-containing monomer (a) used in the hydroxyl group-containing (meth)acrylic resin (A) can be a monomer having a hydroxyl group and a radically polymerizable unsaturated bond. This hydroxyl group mainly acts as a functional group that reacts with the isocyanate group of the isocyanate curing agent (B).

[0056] Examples of the hydroxyl group-containing monomer (a) include 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylate (HPA), 2-hydroxypropyl methacrylate (HPMA), 4-hydroxybutyl acrylate (4HBA), glycerin monomethacrylate (Blemmer GLM, Blemmer GLM-R, trade names, manufactured by NOF Corporation), etc. These hydroxyl group-containing monomers (a) can be used alone or in combination of two or more.

[0057] The carboxyl group-containing monomer (b) used in the hydroxyl group-containing (meth)acrylic resin (A) can be, for example, a monomer having a carboxyl group and a radically polymerizable unsaturated bond. Examples of the carboxyl group-containing monomer (b) include acrylic acid, methacrylic acid, and 2-(methacryloyloxy)ethyl succinic acid. These carboxyl group-containing monomers (b) can be used alone or in combination of two or more.

[0058] The other monomer (c) used in the hydroxyl group-containing (meth)acrylic resin (A) is not particularly limited as long as it is a monomer having a radically polymerizable unsaturated bond, and is appropriately selected depending on its affinity with the other components in the two-component clear coating composition (CC). As the other monomer (c), a monomer having good copolymerizability with the hydroxyl group-containing monomer (a) and the carboxyl group-containing monomer (b) is more preferably used.

[0059] Specific examples of the other monomers (c) are listed below in (1) to (8).

[0060] (1) Monoesters of acrylic acid or methacrylic acid with monohydric alcohols having 1 to 20 carbon atoms: for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, etc.

[0061] (2) Aromatic vinyl monomers: for example, styrene, α-methylstyrene, vinyltoluene, etc.

[0062] (3) Glycidyl group-containing vinyl monomer: a compound having a glycidyl group and a radically polymerizable unsaturated bond in one molecule, specifically, glycidyl (meth)acrylate, etc.

[0063] (4) Nitrogen-containing alkyl (alkyl group having 1 to 20 carbon atoms) (meth)acrylates: for example, dimethylaminoethyl (meth)acrylate.

[0064] (5) Radically polymerizable unsaturated bond-containing amide monomers: for example, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methylol(meth)acrylamide, diacetone acrylamide, etc.

[0065] (6) Aliphatic vinyl compounds: for example, vinyl acetate, vinyl propionate, vinyl chloride, etc.

[0066] (7) Radically polymerizable unsaturated bond-containing nitrile compounds: for example, (meth)acrylonitrile, etc.

[0067] (8) Diene compounds: for example, butadiene, isoprene, etc.

[0068] The other monomers (c) may be used alone or in combination of two or more.

[0069] In the present invention, the calculated glass transition temperature (Tg) of the hydroxyl group-containing (meth)acrylic resin (A) is preferably −50° C. or higher and 10° C. or lower, more preferably −45° C. or higher and 5° C. or lower, particularly preferably −40° C. or higher and 5° C. or lower, and even more preferably −30° C. or higher and 5° C. or lower. By adjusting the calculated glass transition temperature (Tg) to −50° C. or higher and 10° C. or lower, it is possible to achieve both good pencil hardness and good processability of the cured clear coating film layer (T).

[0070] Here, the calculated glass transition temperature (Tg) of the hydroxyl group-containing (meth)acrylic resin (A) is a value calculated from the following (Equation 1).

[0071] 1 / Tg = Σ(Wi / Tgi) (Equation 1) Tg: Glass transition temperature (absolute temperature) of hydroxyl group-containing (meth)acrylic resin (A) Wi: Mass fraction of monomer i component Tgi: Glass transition temperature (absolute temperature) of the homopolymer of monomer i

[0072] The monomer i component refers to one of the monomers constituting the hydroxyl group-containing (meth)acrylic resin (A). That is, (Equation 1) indicates that the sum of the (Wi / Tgi) values ​​calculated for each of the monomers constituting the hydroxyl group-containing (meth)acrylic resin (A) is equal to the reciprocal (1 / Tg) of the glass transition temperature of the hydroxyl group-containing (meth)acrylic resin (A).

[0073] Therefore, the calculated glass transition temperature (Tg) of the hydroxyl group-containing (meth)acrylic resin (A) can be adjusted by changing the type and amount of the monomers constituting the hydroxyl group-containing (meth)acrylic resin (A).

[0074] In the present invention, the method for producing the hydroxyl group-containing (meth)acrylic resin (A) is not particularly limited, and it can be obtained, for example, by polymerizing the above-mentioned monomers by a known radical polymerization reaction. The reaction may be carried out in the absence of a solvent, but it is preferable to use an organic solvent from the viewpoints of synthesis stability and handling.

[0075] From the viewpoint of molecular weight control, it is preferable to use a radical polymerization initiator (hereinafter sometimes abbreviated as "polymerization initiator"). In addition, known additives such as a chain transfer agent may be used.

[0076] In the present invention, examples of the organic solvent used in producing the hydroxyl group-containing (meth)acrylic resin (A) include aromatic hydrocarbons such as toluene, xylene, and aromatic naphtha; ketones such as acetone, methyl ethyl ketone (MEK), and methyl amyl ketone; esters such as ethyl acetate, butyl acetate, 2-butoxyethyl acetate, pentyl acetate, and ethyl 3-ethoxypropionate (EEP); ethers; and aliphatic hydrocarbons including chlorinated hydrocarbons, or mixtures thereof.

[0077] The use of alcohol is not preferred because it inhibits the progress of the curing reaction of the two-component clear coating composition (CC).

[0078] These solvents can be used alone or in combination of two or more. In this case, the solids concentration of the hydroxyl group-containing (meth)acrylic resin (A) solution can be selected arbitrarily within a range that does not impair synthesis stability, but is usually preferably 10 to 70 mass %.

[0079] In the present invention, examples of the polymerization initiator used in the production of the hydroxyl group-containing (meth)acrylic resin (A) include organic peroxides such as benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyneodecanoate, tert-butylperoxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, and diacetyl peroxide; Examples of the azo compounds include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. These polymerization initiators can be used alone or in combination of two or more. The amount of the polymerization initiator added is preferably 0.1 to 20 parts by mass, particularly 1 to 10 parts by mass, per 100 parts by mass of the total of the hydroxyl group-containing monomer (a), the carboxyl group-containing monomer (b), and the other monomer (c).

[0080] In the production of the hydroxyl group-containing (meth)acrylic resin (A), a chain transfer agent may be used to adjust the molecular weight. Examples of the chain transfer agent include thioglycerol, alkyl mercaptans such as octyl mercaptan, nonyl mercaptan, decyl mercaptan, and dodecyl mercaptan, thioglycolic acid esters such as octyl thioglycolate, nonyl thioglycolate, and 2-ethylhexyl thioglycolate, 2,4-diphenyl-4-methyl-1-pentene, 1-methyl-4-isopropylidene-1-cyclohexene, α-pinene, and β-pinene.

[0081] In producing the hydroxyl group-containing (meth)acrylic resin (A), the method of adding the solvent and polymerization initiator is arbitrary, but for the purpose of controlling the heat of polymerization and the heat of reaction, a method is preferred in which an organic solvent is charged into a reaction tank and, while stirring, a radical polymerizable monomer mixture or an organic solvent solution thereof is dropped from a dropping tank.

[0082] The polymerization temperature for the above polymerization reaction varies depending on the type of polymerization initiator and whether or not a chain transfer agent is used in combination, but is preferably 50 to 200°C, and more preferably 80 to 160°C. Since the 10-hour half-life temperature of many polymerization initiators is 50°C or higher, setting the polymerization temperature to 50°C or higher can achieve the desired radical decomposition induction efficiency. On the other hand, setting the polymerization temperature to 200°C or lower can suppress side reactions such as depolymerization.

[0083] In the present invention, the mass average molecular weight (Mw) of the hydroxyl group-containing (meth)acrylic resin (A) is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, and particularly preferably 3,000 to 30,000. By adjusting the mass average molecular weight (Mw) to 1,000 to 50,000, sufficient compatibility with the isocyanate curing agent (B) can be achieved, resulting in a cured clear coating layer (T) with excellent acid resistance, water resistance, and car wash scratch resistance. Here, the mass average molecular weight (Mw) of the hydroxyl group-containing (meth)acrylic resin (A) can be adjusted by changing the polymerization temperature during production of the hydroxyl group-containing (meth)acrylic resin (A), the type and amount of polymerization initiator, etc.

[0084] In the present invention, the mass average molecular weight (Mw) was measured using gel permeation chromatography (GPC) HLC-8220 (trade name, manufactured by Tosoh Corporation). A calibration curve was prepared using a standard polystyrene sample. Tetrahydrofuran was used as the eluent, and a combination of TSKgel G2000HXL, G3000HXL, G4000HXL, and G5000HXL (trade names, manufactured by Tosoh Corporation) columns was used. Measurements were performed under conditions of a flow rate of 1.0 mL / min, an injection volume of 10 μL, and a column temperature of 40°C.

[0085] In the present invention, the hydroxyl value (OHV) of the hydroxyl-containing (meth)acrylic resin (A) is preferably 80 to 220 mgKOH / g, more preferably 100 to 210 mgKOH / g, and particularly preferably 120 to 200 mgKOH / g. By adjusting the hydroxyl value (OHV) to 80 to 220 mgKOH / g, it is possible to obtain a cured clear coating layer (T) having excellent acid resistance, water resistance, and car wash scratch resistance.

[0086] The hydroxyl value (OHV) of the hydroxyl-containing (meth)acrylic resin (A) can be adjusted by changing the amount of the hydroxyl-containing monomer (a). The hydroxyl value (OHV) is a value measured in accordance with JIS K 1557-1:2007.

[0087] In the present invention, the acid value of the hydroxyl group-containing (meth)acrylic resin (A) is preferably 0 to 60 mgKOH / g, more preferably 0 to 50 mgKOH / g, and particularly preferably 0.1 to 40 mgKOH / g. By adjusting the acid value to 0 to 60 mgKOH / g, it is possible to obtain a two-component clear coating composition (CC) that has an excellent balance between pot life (usable time) and curability.

[0088] The acid value of the hydroxyl group-containing (meth)acrylic resin (A) can be adjusted by changing the amount of the carboxyl group-containing monomer (b). The acid value is a value measured in accordance with JIS K 5601-2-1:1999.

[0089] From the viewpoint of acid resistance, the isocyanate curing agent (B) of the two-component clear coating composition (CC) used in the present invention is preferably an aliphatic polyisocyanate compound, and is preferably one or more compounds selected from the group consisting of biuret, isocyanurate, adduct, uretdione, and allophanate compounds of compounds having two or more isocyanate groups in one molecule.

[0090] Examples of commercially available isocyanate curing agents (B) mainly containing biuret compounds include Desmodur N-75 (trade name, manufactured by Sumika Covestro Urethane Co., Ltd.), Duranate 24A-100, 22A-75P (trade name, manufactured by Asahi Kasei Corporation), and the like.

[0091] Examples of commercially available isocyanate curing agents (B) mainly containing an isocyanurate include Desmodur N-3600 and N-3300 (trade names, manufactured by Sumika Covestro Urethane Co., Ltd.), Duranate TPA-100 and TKA-100 (trade names, manufactured by Asahi Kasei Corporation), and the like.

[0092] Examples of commercially available isocyanate curing agents (B) mainly containing adducts include Duranate E402-80B and E405-70B (trade names, manufactured by Asahi Kasei Corporation).

[0093] Examples of commercially available isocyanate curing agents (B) containing uretdione compounds include Desmodur N-3400 (trade name, manufactured by Sumika Covestro Urethane Co., Ltd.), Duranate TLA-100, and TUL-100 (trade name, manufactured by Asahi Kasei Corporation).

[0094] Examples of commercially available isocyanate curing agents (B) mainly containing allophanate compounds include Duranate A201H, D101, and D201 (trade names, manufactured by Asahi Kasei Corporation), and Coronate 2793 and 2770 (trade names, manufactured by Tosoh Corporation).

[0095] These isocyanate curing agents (B) can be used alone or in combination of two or more.

[0096] In the two-component clear coating composition (CC) used in the present invention, the molar ratio (NCO / OH) of the isocyanate groups in the isocyanate curing agent (B) to the hydroxyl groups in the hydroxyl group-containing (meth)acrylic resin (A) is preferably 0.5 to 1.7, and particularly preferably 0.8 to 1.3. By adjusting the NCO / OH molar ratio to 0.5 to 1.7, it is possible to obtain a cured clear coating film layer (T) having excellent acid resistance, water resistance, and car wash scratch resistance.

[0097] The two-component clear coating composition (CC) used in the present invention may contain a catalyst that promotes the crosslinking reaction between the hydroxyl group-containing (meth)acrylic resin (A) and the isocyanate curing agent (B). Examples of the catalyst include known metal catalysts and amine catalysts. Metal catalysts include dibutyltin dilaurate, tin octoate, dibutyltin di(2-ethylhexanoate), lead 2-ethylhexylate, 2-ethylhexyl titanate, titanium diisopropoxybis(ethylacetoacetate), iron 2-ethylhexylate, cobalt 2-ethylhexylate, zinc naphthenate, cobalt naphthenate, and tetra-n-butyltin. Amine catalysts include tertiary amines such as tetramethylbutanediamine. These catalysts can be used alone or in combination. The amount of these catalysts is preferably 0.001 to 1 part by mass per 100 parts by mass of the two-component clear coating composition (CC).

[0098] The two-component clear coating composition (CC) used in the present invention may contain a polyester resin (C) for the purpose of further improving processability. The content of the polyester resin (C) is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, and particularly preferably 5 to 30 parts by mass, per 100 parts by mass of the resin solids content of the two-component clear coating composition (CC). By setting the content of the polyester resin (C) to 1 to 50 parts by mass, processability can be improved without reducing the acid resistance and water resistance of the cured clear coating film layer (T).

[0099] In the present invention, the polyester resin (C) used in the two-component clear coating composition (CC) is preferably a polyester polyol containing hydroxyl groups. Examples of the polyester polyol include the same polyester polyols as those used in the thermoplastic polyurethane (TPU).

[0100] In the present invention, examples of commercially available polyester resins (C) used in the two-component clear coating composition (CC) include D620, D623, D643, and D645 (trade names, manufactured by Mitsubishi Chemical Corporation), Adeka CycloAid PNB series (trade names, manufactured by ADEKA CORPORATION), K-FLEX148, 188, 171-90, A307, A308, UD-320-100, XM-332, XM-337, and XM-359 (trade names, manufactured by KING INDUSTRIES), and Desmophen C1200 and 3601 (trade names, manufactured by COVESTRO).

[0101] In the present invention, the hydroxyl value (OHV) of the polyester resin (C) used in the two-component clear coating composition (CC) is preferably 10 to 300 mg KOH / g, more preferably 10 to 250 mg KOH / g. The mass average molecular weight (Mw) of the polyester resin (C) is preferably 500 to 30,000, more preferably 1,000 to 20,000. These polyesters can be used alone or in combination of two or more.

[0102] The two-component clear coating composition (CC) used in the present invention may contain an ultraviolet absorber (F). The ultraviolet absorber (F) is preferably a triazine-based ultraviolet absorber. Examples of commercially available triazine-based ultraviolet absorbers include Eversorb 40, Eversorb 41 FD, and Eversorb 45 (trade names, manufactured by Everlight Chemical Co.), Tinuvin 1600, and Tinuvin 1577ED (trade names, manufactured by BASF). These ultraviolet absorbers (F) may be used alone or in combination of two or more.

[0103] The content of the ultraviolet absorber (F) in the two-component clear coating composition (CC) used in the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 25 parts by mass, and even more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the two-component clear coating composition (CC). By adjusting the content of the ultraviolet absorber (F) to 0.1 to 30 parts by mass, a cured clear coating film layer (T) with excellent weather resistance can be obtained.

[0104] The two-component clear coating composition (CC) used in the present invention may contain a light stabilizer (E). The light stabilizer (E) is preferably a NOR-type hindered amine light stabilizer. Examples of commercially available NOR-type hindered amine light stabilizers include Eversorb 93, Eversorb 90, and Eversorb 95 (trade names, manufactured by Everlight Chemical Co.), Tinuvin 123, Tinuvin 144, Tinuvin 765, and Tinuvin 770 (trade names, manufactured by BASF). These light stabilizers (E) may be used alone or in combination of two or more.

[0105] The content of the light stabilizer (E) in the two-component clear coating composition (CC) used in the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 25 parts by mass, and even more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the two-component clear coating composition (CC). By adjusting the content of the light stabilizer (E) to 0.1 to 30 parts by mass, a cured clear coating film layer (T) with excellent weather resistance can be obtained.

[0106] The two-component clear coating composition (CC) used in the present invention may contain a coloring pigment to the extent that transparency is not impaired. Examples of the coloring pigment include the same examples of the coloring pigment used in the thermoplastic polyurethane (TPU). The coloring pigments can be used alone or in combination of two or more. The total content of the coloring pigments in the two-component clear coating composition (CC) used in the present invention is not particularly limited, but is preferably 10 parts by mass or less, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the resin solids content of the two-component clear coating composition (CC).

[0107] The two-pack clear coating composition (CC) used in the present invention may contain a matting agent, such as finely divided silica or resin beads.

[0108] Representative examples of commercially available finely powdered silica include the Nipsil series (trade name, manufactured by Tosoh Silica Corporation), the Sylysia series (trade name, manufactured by Fuji Silysia Chemical Ltd.), the Mizukasil series (trade name, manufactured by Mizusawa Industrial Chemicals Ltd.), and the ACEMATT series (trade name, manufactured by Evonik).

[0109] The resin beads are not particularly limited in terms of resin composition or synthesis route, and beads of polyamide (nylon) resin, polyolefin resin, (meth)acrylic resin, polystyrene resin, epoxy resin, polyester resin, urethane resin, melamine resin, etc. Representative commercially available resin beads include the Bestsint series (trade name, manufactured by Daicel-Evonik Ltd.), Orgasol series (trade name, manufactured by Arkema Co., Ltd.), Mipelon series (trade name, manufactured by Mitsui Chemicals, Inc.), Chemisnow series (trade name, manufactured by Soken Chemical & Engineering Co., Ltd.), Techpolymer series (trade name, manufactured by Sekisui Plastics Co., Ltd.), and Tuftic series (trade name, manufactured by Nippon Exlan Kogyo Co., Ltd.).

[0110] These matting agents can be used alone or in combination of two or more. The total content of matting agents in the two-component clear coating composition (CC) used in the present invention is not particularly limited, but is preferably 0 to 50 parts by mass, and more preferably 0.1 to 30 parts by mass, per 100 parts by mass of the resin solids content of the two-component clear coating composition (CC). By adjusting the content of the matting agents to 0 to 50 parts by mass, the 20° gloss value of the cured clear coating film layer (T) can be adjusted within the range of 1 to 100.

[0111] The two-component clear coating composition (CC) used in the present invention can be used as is, or, if necessary, with the addition of one or more of various additives, such as antioxidants, surfactants, surface conditioners, antistatic agents, fragrances, dehydrating agents, and rheology adjusters such as polyethylene wax, polyamide wax, and internally crosslinked resin microparticles.

[0112] The viscosity of the two-component clear coating composition (CC) used in the present invention depends on the coating film formation method, but is preferably adjusted with an organic solvent to 50 to 5,000 mPa·s, and more preferably 300 to 3,000 mPa·s, at 23° C. By adjusting the viscosity of the two-component clear coating composition (CC) to 50 to 5,000 mPa·s, practically acceptable coating workability can be achieved.

[0113] Examples of organic solvents used in the two-component clear coating composition (CC) include the same organic solvents as those used in the production of the hydroxyl group-containing (meth)acrylic resin (A). These organic solvents can be used alone or in combination of two or more. As mentioned above, alcohols are not preferred because they inhibit the progress of the curing reaction of the two-component clear coating composition (CC).

[0114] The content of the organic solvent in the two-component clear coating composition (CC) used in the present invention is preferably 10 parts by mass or more and 90 parts by mass or less per 100 parts by mass of the two-component clear coating composition (CC). By setting the content of the organic solvent to 10 parts by mass or more and 90 parts by mass or less, coating workability that does not cause any practical problems can be obtained.

[0115] The two-component clear coating composition (CC) used in the present invention can be produced by known methods. Specifically, to achieve the desired coating properties, the hydroxyl group-containing (meth)acrylic resin (A) and the other components except the isocyanate curing agent (B) are first mixed and thoroughly stirred to prepare a base material. Then, just before use, the isocyanate curing agent (B) is added and the mixture is stirred again to obtain the two-component clear coating composition (CC). If necessary, a step of removing coarse particles using a filter or the like can be included during any part of the production process.

[0116] In the present invention, the cured clear coating layer (T) is produced by applying a two-component clear coating composition (CC) directly or via at least one colored coating layer to a thermoplastic polyurethane (TPU) substrate. The method for applying the two-component clear coating composition (CC) to a thermoplastic polyurethane (TPU) substrate is not particularly limited, and examples thereof include conventionally known methods such as bar coating, knife coating, roll coating, blade coating, die coating, gravure coating, curtain coating, and spraying. The cured clear coating layer (T) can then be obtained by evaporating the organic solvent by heating and promoting a crosslinking reaction. The heating temperature is preferably 80°C or lower. The heating time is preferably 15 minutes to 10 days.

[0117] In the present invention, the cured clear coating layer (T) preferably has an inter-crosslinking molecular weight (Mc) of 200 g / mol or more and 800 g / mol or less. By adjusting the inter-crosslinking molecular weight (Mc) to 200 g / mol or more and 800 g / mol or less, the cured clear coating layer (T) exhibits excellent acid resistance, water resistance, and car wash scratch resistance.

[0118] In the present invention, the molecular weight between crosslinks (Mc) of the cured clear coating layer (T) was determined by preparing a test piece having a width of 5 mm, a length of 10 mm, and a film thickness of 30 μm, and measuring dynamic viscoelasticity (storage modulus (E'), loss modulus (E''), and loss tangent (tanδ)) under the following conditions, and then calculating it using the following (Equation 2). A smaller molecular weight between crosslinks (Mc) indicates a denser crosslinked structure.

[0119] Apparatus: Dynamic viscoelasticity measuring device RSA3 (TA Instruments) Measurement mode: Non-resonant forced vibration method Heating rate: 3.0℃ / min Measurement interval: 12 times / min Frequency: 1.0Hz Temperature range: 30~180℃

[0120] Molecular weight between crosslinking points (Mc)=3ρRT / E'min (Formula 2)

[0121] Here, the units of the values ​​represented by each symbol are as follows:

[0122] Molecular weight between crosslinking points (Mc): g / mol E'min:Pa ρ (density): g / m 3 R (gas constant): J / mol K T (absolute temperature of E'min): K

[0123] In the present invention, the cured clear coating layer (T) preferably has a pencil hardness of 6B or more, particularly preferably 4B or more, measured according to ISO 15184:2020. By adjusting the pencil hardness to 6B or more, the cured clear coating layer (T) exhibits excellent acid resistance and water resistance. The pencil hardness of the cured clear coating layer (T) can be adjusted to the above range by appropriately adjusting the calculated glass transition temperature (Tg), mass average molecular weight (Mw), and hydroxyl value (OHV) of the hydroxyl group-containing (meth)acrylic resin (A), or the NCO / OH molar ratio, which is the mixing ratio of the hydroxyl group-containing (meth)acrylic resin (A) and the isocyanate curing agent (B).

[0124] [Adhesive layer] The laminate film of the present invention may have an adhesive layer formed on the outermost layer of the surface opposite the cured clear coating layer (T) on a thermoplastic polyurethane (TPU) substrate, either directly or via at least one colored coating layer. The resin component used in the adhesive layer is not particularly limited as long as it can adhere the laminate film to the article to be decorated, and examples thereof include (meth)acrylic resins, polyurethane resins, polyester resins, polyvinyl acetate resins, and epoxy resins. These resin components can be used alone or in combination of two or more.

[0125] [Colored coating layer] The laminate film of the present invention may have a colored coating layer formed thereon. The colored coating layer may be formed on one side of the thermoplastic polyurethane (TPU) substrate, between the cured clear coating layer (T) and the thermoplastic polyurethane (TPU) substrate, or on the side opposite the cured clear coating layer (T). In another embodiment, the colored coating layer may be formed on both sides of the thermoplastic polyurethane (TPU) substrate. The colored coating layer may be a single layer or multiple layers. Furthermore, the colored coating layer is preferably formed directly on the thermoplastic polyurethane (TPU) substrate. The colored coating layer is formed from a colored coating composition containing a film-forming resin and a color pigment and / or a luster pigment.

[0126] The film-forming resin of the colored coating composition of the present invention may be a thermosetting resin composition that forms a coating film by heating to cause a crosslinking reaction after application, or a thermoplastic resin composition that forms a coating film by volatilizing the solvent. The film-forming resin can be used by dissolving or dispersing it in a solvent such as an organic solvent.

[0127] The thermosetting resin composition in the colored coating composition of the present invention may be, for example, a thermosetting resin composition comprising a base resin and a curing agent. The content of the curing agent in this resin composition (base resin + curing agent) is not particularly limited, but is preferably 0.1 to 50 parts by mass, more preferably 5 to 45 parts by mass, and particularly preferably 10 to 40 parts by mass, per 100 parts by mass of the film-forming resin solids. When the colored coating composition of the present invention is a thermosetting resin composition, it may be a one-component coating composition in which the base resin and curing agent are mixed in advance, or a two-component coating composition in which the base resin and curing agent are mixed immediately before application.

[0128] Examples of the base resin of the thermosetting resin composition in the colored coating composition of the present invention include (meth)acrylic resin, polyester resin, polyurethane resin, polyurea resin, (meth)acrylic urethane resin, polyurethane polyurea resin, polyolefin resin (including chlorinated and / or modified ones), epoxy resin, etc. The base resin preferably has a hydroxyl group as a functional group. These base resins can be used alone or in combination of two or more.

[0129] Examples of the curing agent for the thermosetting resin composition in the colored coating composition of the present invention include amino resins, polyisocyanate compounds, and blocked polyisocyanate compounds. Among these, polyisocyanate compounds and blocked polyisocyanate compounds are particularly preferred. These curing agents can be used alone or in combination of two or more.

[0130] The amino resin is a general term for resins obtained by adding and condensing formaldehyde to a compound containing an amino group. Examples of the amino resin include melamine resin, urea resin, and guanamine resin, and among these, melamine resin is particularly preferred.

[0131] Examples of melamine resins include partially or fully methylolated melamine resins obtained by reacting melamine with formaldehyde, partially or fully alkyl ether melamine resins obtained by partially or completely etherifying the methylol groups of methylolated melamine resins with an alcohol component, imino group-containing melamine resins, and mixed melamine resins obtained by mixing two or more of these melamine resins.Furthermore, examples of alkyl ether melamine resins include methylated melamine resins, butylated melamine resins, and methyl / butyl mixed alkyl ether melamine resins.

[0132] Examples of the polyisocyanate compound include the same compounds as the examples of the isocyanate curing agent (B) in the two-component clear coating composition (CC).

[0133] Examples of blocked polyisocyanate compounds include those in which the isocyanate groups of the above-mentioned polyisocyanate compounds are blocked with, for example, alcohols such as butanol, oximes such as methyl ethyl ketoxime, lactams such as ε-caprolactams, active methylenes such as malonic acid diesters and acetoacetic esters, pyrazoles such as 3,5-dimethylpyrazole, imidazoles such as imidazole and 2-ethylimidazole, phenols such as m-cresol, and the like. Among these, those blocked with active methylenes are particularly preferred.

[0134] Examples of the thermoplastic resin composition in the colored coating composition of the present invention include thermoplastic resin compositions containing a base resin such as a (meth)acrylic resin, a polyester resin, a polyurethane resin, a polyurea resin, a (meth)acrylic urethane resin, a polyurethane polyurea resin, a polyolefin resin (including chlorinated and / or modified resins), or an epoxy resin, all of which have a mass average molecular weight (Mw) of 30,000 or more.

[0135] Examples of the color pigments in the colored coating composition of the present invention include the same examples of the color pigments used in the thermoplastic polyurethane (TPU). The color pigments can be used alone or in combination of two or more. The total content of the color pigments contained in the colored coating composition used in the present invention is not particularly limited, but is preferably 10 to 200 parts by mass, more preferably 30 to 180 parts by mass, and particularly preferably 50 to 160 parts by mass, per 100 parts by mass of the film-forming resin solids of the colored coating composition.

[0136] Examples of the luster pigment in the colored coating composition of the present invention include the same examples of the luster pigment used in the thermoplastic polyurethane (TPU). The luster pigment can be used alone or in combination of two or more. The total content of the luster pigment contained in the colored coating composition used in the present invention is not particularly limited, but is preferably 0 to 30 parts by mass, more preferably 0 to 25 parts by mass, and particularly preferably 0.1 to 20 parts by mass, per 100 parts by mass of the film-forming resin solids of the colored coating composition.

[0137] The colored coating composition used in the present invention may further contain, as necessary, an organic solvent and various additives such as a surface conditioner, a thickener, a rheology control agent, a pigment dispersant, an anti-settling agent, a catalyst for accelerating the crosslinking reaction, an antifoaming agent, an antioxidant, an ultraviolet absorber, a light stabilizer, and other paint additives, extender pigments, etc.

[0138] Examples of organic solvents used in the colored coating composition include the same organic solvents used in the production of the hydroxyl group-containing (meth)acrylic resin (A). These organic solvents can be used alone or in combination. Furthermore, when the colored coating composition is a thermosetting resin composition containing a polyisocyanate compound and / or a blocked polyisocyanate compound as a curing agent, the use of alcohols is not preferred, as they inhibit the progress of the curing reaction of the colored coating composition, as described above. However, when the colored coating composition is a thermosetting resin composition not containing a polyisocyanate compound and / or a blocked polyisocyanate compound as a curing agent, or when the colored coating composition is a thermosetting resin composition, alcohols such as isopropanol, butanol, 2-butoxyethanol, and 2-ethylhexanol can be used without any problems.

[0139] [Laminated Film (H)] The laminated film (H) of the present invention preferably takes, for example, the following three forms, which will be explained below with reference to the drawings.

[0140] [First form] As shown in FIG. 1, the laminate film (H-1) in the first embodiment of the present invention has a colored coating layer 3 and a cured clear coating layer 1 formed in this order on the surface of a transparent thermoplastic polyurethane (TPU) substrate 2, and an adhesive layer 4 formed on the opposite surface (back surface).

[0141] [Second Form] As shown in FIG. 2, the laminated film (H-2) in the second embodiment of the present invention has a cured clear coating layer 1 formed on the surface of a transparent thermoplastic polyurethane (TPU) substrate 2, and a colored coating layer 3 and an adhesive layer 4 formed in this order on the opposite surface (back surface).

[0142] [Third Form] As shown in FIG. 3, the laminated film (H-3) in the third embodiment of the present invention has a cured clear coating layer 1 formed on the surface of a colored thermoplastic polyurethane (TPU) substrate 5, and an adhesive layer 4 formed on the opposite surface (back surface).

[0143] [Cured clear coating layer (T)] In the laminate film (H) of the present invention, the thickness of the cured clear coating layer (T) is preferably 10 to 60 μm, more preferably 20 to 50 μm, and particularly preferably 25 to 40 μm. By making the thickness of the cured clear coating layer (T) 10 μm or more, excellent acid resistance and weather resistance can be obtained, and by making it 60 μm or less, the processability of the film can be ensured.

[0144] [Colored coating layer] In the laminate film (H) of the present invention, the thickness of the colored coating layer formed as needed is preferably 10 to 50 μm, more preferably 10 to 40 μm, and particularly preferably 15 to 30 μm. By making the thickness of the colored coating layer 10 μm or more, the hiding power of the substrate can be ensured, and by making it 50 μm or less, the processability of the film can be ensured.

[0145] [Peeling layer] In the laminated film (H) of the present invention, a release layer may be formed on the adhesive layer formed as the outermost layer, if necessary, for the purpose of temporarily protecting the adhesive layer until immediately before use. The release layer is not particularly limited, and known release films can be used. Examples of the release layer include films of polyester, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, etc., which have been subjected to a release treatment by applying a silicone resin, a fluororesin, etc. to the surface that comes into contact with the adhesive layer, papers such as fine paper and glassine paper, and laminate films of fine paper or glassine paper with polyolefin. The thickness of the release layer is preferably 10 to 200 μm, more preferably 25 to 100 μm.

[0146] The peel strength between the release layer and the adhesive layer is preferably 0.05 to 8.0 N / 25 mm, and more preferably 0.1 to 5.0 N / 25 mm. By setting the peel strength to 0.05 to 8.0 N / 25 mm, the release layer can be removed smoothly. The peel strength between the release layer and the adhesive layer can be measured according to JIS K 6854-2:1999, Test Method for 180° Peel Adhesion Strength of Adhesives.

[0147] [Decorative items] The decorative article of the present invention is not particularly limited, and examples thereof include articles in which the laminate film (H) of the present invention is used to decorate objects such as automobile bodies, bumpers, emblems, vehicle exteriors, vehicle interiors, and other vehicle parts, building materials and parts such as wall materials, window glass, window frames, and bathroom wall materials, daily necessities such as tableware, toys, and musical instruments, home appliance parts such as vacuum cleaner housings, television housings, and air conditioner housings, interior parts such as doors, and ship parts. Among these, the decorative article of the present invention can improve both the design and durability of automobile bodies, bumpers, and interior and exterior vehicle parts, and can be suitably used.

[0148] The laminated film (H) of the present invention may be stretched to decorate an article. When stretched, the thickness of each layer on the decorated article becomes thinner than the thickness of the laminated film before decoration. There are no particular restrictions on the thickness of each layer on the decorated article, but the thickness of the colored coating film layer formed as needed is preferably 5 μm or more and 50 μm or less, and the thickness of the cured clear coating film layer (T) is preferably 5 μm or more and 60 μm or less. By achieving these thicknesses, a decorated article with excellent pencil hardness, acid resistance, weather resistance, water resistance, and car wash scratch resistance can be obtained. [Example]

[0149] The present invention will be described in more detail with reference to the following examples, which are not intended to limit the scope of the invention. In the examples, unless otherwise specified, "parts" means "parts by mass," and "%" regarding blend amounts and contents means "% by mass." Furthermore, Mw means mass average molecular weight, Tg means glass transition temperature, OHV means hydroxyl value, AV means acid value, and Mc means molecular weight between crosslink points.

[0150] <Synthesis of Hydroxyl Group-Containing (Meth)acrylic Resin (A) Solution> [Synthesis Example 1] A four-necked French boiler equipped with a reflux condenser, dropping funnel, gas inlet, stirrer, and thermometer was charged with 73.6 parts of MEK solvent while introducing nitrogen gas and heating to 75°C under stirring. Next, a mixture of 10 parts of ST, 30 parts of 4HBA, 11 parts of HPMA, 1 part of AA, 9 parts of MMA, 10 parts of CHMA, and 29 parts of 2EHA as monomers and 6.4 parts of AIBN as a polymerization initiator was charged to the dropping funnel. The mixture was added dropwise for 3 hours while maintaining the internal temperature at 75°C, and stirring was continued for an additional 5 hours. After confirming that the conversion rate exceeded 98% by solids content measurement, 60 parts of ethyl 3-ethoxypropionate (EEP) solvent was added. The MEK was then volatilized using a vacuum pump until the solids content reached 60%, yielding a hydroxyl group-containing (meth)acrylic resin (A-1) solution.

[0151] [Synthesis Examples 2 to 7] Solutions of hydroxyl group-containing (meth)acrylic resins (A-2 to A-7) were obtained by the same production method as for the hydroxyl group-containing (meth)acrylic resin (A-1) solution, except that the compositions and blending amounts were changed to those in Table 1.

[0152] [Table 1]

[0153] The abbreviations in Table 1 are listed below.

[0154] ST: styrene 4HBA: 4-hydroxybutyl acrylate HPMA: 2-hydroxypropyl methacrylate MMA: Methyl methacrylate 2EHA: 2-ethylhexyl acrylate CHMA: Cyclohexyl methacrylate AA: acrylic acid MEK: Methyl ethyl ketone AIBN: 2,2'-azobisisobutyronitrile

[0155] [Preparation Example 1] [Preparation of two-component clear coating composition (CC-1)] 100 parts of hydroxyl group-containing (meth)acrylic resin (A-1) solution, 0.01 parts of catalyst (D-1), 6 parts of polyester resin (C-1), 1 part of light stabilizer (E-1), 1 part of ultraviolet absorber (F-1), and 55.63 parts of 3-ethoxypropionate ethyl EEP (EEP) as an organic solvent were weighed and stirred with a paint shaker until thoroughly homogenized. Then, the mixture was filtered through a 200 μm membrane filter to remove coarse particles, and the main component of a two-component clear coating composition (CC-1) was prepared. Then, just before use, 36 parts of isocyanate curing agent (B-1) was added to the main component, and the mixture was thoroughly stirred with a disperser, and used as a two-component clear coating composition (CC-1). The solids content (also referred to as "coating NV") of the two-component clear coating composition (CC-1) was 52.0%.

[0156] [Preparation Examples 2-17], [Comparative Preparation Examples 1-2] [Preparation of two-component clear coating compositions (CC-2 to 19)] Two-component clear coating compositions (CC-2 to 19) were prepared in the same manner as in Preparation Example 1, except that the compounding ratios were changed to those shown in Table 2.

[0157] [Table 2]

[0158] The details of the abbreviations in Table 2 are shown below.

[0159] Isocyanate curing agent (B-1): Duranate TPA-100 (trade name, manufactured by Asahi Kasei Corporation, mainly contains isocyanurate) Isocyanate curing agent (B-2): Duranate TKA-100 (trade name, manufactured by Asahi Kasei Corporation, mainly contains isocyanurate) Isocyanate curing agent (B-3): Duranate 24A-100 (trade name, manufactured by Asahi Kasei Corporation, mainly contains biuret) Isocyanate curing agent (B-4): Duranate E402-80B (trade name, manufactured by Asahi Kasei Corporation, mainly contains adduct) Polyester resin (C-1): K-FLEX171-90 (product name, manufactured by KING INDUSTERIES) Polyester resin (C-2): K-FLEX A308 (product name, manufactured by KING INDUSTERIES) Catalyst (D-1): K-KAT XK-614 (product name, manufactured by KING INDUSTERIES) Catalyst (D-2): K-KAT 670 (trade name, manufactured by KING INDUSTERIES) Light stabilizer (E-1): Eversorb 93 (trade name, manufactured by Everlight Chemical Co., Ltd., hindered amine light stabilizer) Ultraviolet absorber (F-1): Eversorb 40 (trade name, manufactured by Everlight Chemical Co., Ltd., triazine-based ultraviolet absorber) Matting agent (G-1): ACEMATT TS-100 (trade name, manufactured by Evonik, finely divided silica)

[0160] [Preparation of free film of cured clear coating layer (T-1)] The two-component clear coating composition (CC-1) of Preparation Example 1 was applied to a release film GS (trade name, manufactured by Lintec Corporation) with an applicator to a dry film thickness of 30 μm. Next, a release film GS (trade name, manufactured by Lintec Corporation) was adhered to the top surface of the coating film before drying. The resulting three-layer film with a coating layer formed between the release layers was heated and dried in an oven at 80°C for 4 days, after which the release layer was removed to obtain a free film (single layer) of the cured clear coating layer (T-1).

[0161] [Preparation of free film of cured clear coating layer (T-2 to 19)] Using the two-component clear coating compositions of Preparation Examples 2 to 19 (CC-2 to 19), free films of cured clear coating layers (T-2 to 19) were obtained in the same manner as for the cured clear coating layer (T-1).

[0162] These free films were used as samples for measuring the molecular weight between crosslink points (Mc) of the cured clear coating layer (T).

[0163] [Example 1] Preparation of [Laminated Film (H-1-1)] Using a TPU film (TPU-1) as the substrate, a colored coating composition, Primac No. 8650 Black (trade name, one-component blocked isocyanate curing coating, manufactured by BASF Japan Ltd.), was applied to the surface of the substrate on a horizontal table with an applicator to a dry film thickness of 15 μm. After leaving it at room temperature for 5 minutes, a two-component clear coating composition (CC-1) was applied to the resulting colored coating film with an applicator to a dry film thickness of 30 μm, and the coating was dried by heating in an oven at 80°C for 4 days.

[0164] Next, SK Dyne 1310DT (trade name, manufactured by Soken Chemical & Engineering Co., Ltd.) was applied to the opposite surface of the substrate with an applicator to a dry film thickness of 100 μm to form an adhesive layer. Further, a release film GS (trade name, manufactured by Lintec Corporation) was laminated on the obtained adhesive layer to obtain a laminated film (H-1-1).

[0165] [Examples 2 to 5, 16 to 17], [Comparative Examples 1 to 2] Preparation of [Laminated Films (H-1-2 to 5, 8 to 9) and Comparative Laminated Films (H-1-6 to 7)] Using the two-component clear coating compositions (CC-2 to 5, 16 to 19), laminate films (H-1-2 to 5, 8 to 9) and comparative laminate films (H-1-6 to 7) listed in Table 3 were obtained by the same manufacturing method as for laminate film (H-1-1). These laminate films were used to carry out the tests described below.

[0166] [Table 3]

[0167] The details of the abbreviations in Table 3 are shown below.

[0168] TPU film (TPU-1): DUS601 (product name, manufactured by Seedum Co., Ltd., film thickness 120 μm) TPU film (TPU-2): SHG2393 (product name, manufactured by Seedom Co., Ltd., film thickness 120 μm) TPU film (TPU-3): Black TPU film (manufactured by Guangzhou Zanchen New Materials Co., Ltd., China, film thickness 125 μm)

[0169] [Example 6] [Preparation of laminated film (H-2-1)] A TPU film (TPU-2) was used as the substrate. A two-component clear coating composition (CC-6) was applied to the front surface of the substrate on a horizontal table to a dry film thickness of 30 μm, and a colored coating composition, Primac No. 8650 Black (trade name, manufactured by BASF Japan Ltd., a one-component blocked isocyanate curing coating), was applied to the back surface of the substrate using a laminator to a dry film thickness of 15 μm. The coating was then heated and dried in an oven at 80°C for 4 days. Next, SK Dyne 1310DT (trade name, manufactured by Soken Chemical & Engineering Co., Ltd.) was applied to the resulting colored coating film using an applicator to a dry film thickness of 100 μm to form an adhesive layer. A release film GS (trade name, manufactured by Lintec Corporation) was then laminated on the resulting adhesive layer to obtain a laminated film (H-2-1).

[0170] [Examples 7 to 10] [Preparation of laminated films (H-2-2 to H-2-5)] The two-component clear coating compositions (CC-7 to 10) were used in the same manufacturing method as for the laminate film (H-2-1) to obtain the laminate films (H-2-2 to 5) listed in Table 3. These laminate films were used to carry out the tests described below.

[0171] [Example 11] [Preparation of laminated film (H-3-1)] A TPU film (TPU-3) was used as the substrate, and a two-component clear coating composition (CC-11) was applied to the surface of the substrate on a horizontal table using an applicator to a dry film thickness of 30 μm. The coating was then dried in an oven at 80°C for 4 days. Next, SK Dyne 1310DT (trade name, manufactured by Soken Chemical & Engineering Co., Ltd.) was applied to the opposite side of the substrate using an applicator to a dry film thickness of 100 μm to form an adhesive layer. A release film GS (trade name, manufactured by Lintec Corporation) was then laminated on the resulting adhesive layer to obtain a laminated film (H-3-1).

[0172] [Examples 12 to 15] [Preparation of laminated films (H-3-2 to H-3-5)] The two-component clear coating compositions (CC-12 to 15) were used in the same manufacturing method as for the laminate film (H-3-1) to obtain the laminate films (H-3-2 to 5) listed in Table 3. These laminate films were used to carry out the tests described below.

[0173] Comparative Example 3 [Preparation of Comparative Laminate Film (H-4-1)] A 200 μm thick unstretched polyvinyl chloride (PVC) film (PV-1) was used as the substrate. On a horizontal table, a colored coating composition, Primac No. 8650 Black (product name, manufactured by BASF Japan Ltd., a one-component blocked isocyanate curing coating), was applied to the surface of the substrate with an applicator to a dry film thickness of 15 μm. After leaving the coating at room temperature for 5 minutes, a two-component clear coating composition (CC-1) was applied to the resulting colored coating with an applicator to a dry film thickness of 30 μm, and the coating was dried in an oven at 80°C for 4 days.

[0174] Next, SK Dyne 1310DT (trade name, manufactured by Soken Chemical & Engineering Co., Ltd.) was applied to the opposite surface of the substrate with an applicator to a dry film thickness of 100 μm to form an adhesive layer. Furthermore, a release film GS (trade name, manufactured by Lintec Corporation) was laminated on the obtained adhesive layer to obtain a comparative laminate film (H-4-1).

[0175] Comparative Example 4 [Preparation of Comparative Laminate Film (H-5-1)] A 200 μm thick unstretched polypropylene (PP) film (PP-1) was used as the substrate. On a horizontal table, a colored coating composition, Primac No. 8650 Black (product name, manufactured by BASF Japan Ltd., one-component blocked isocyanate curing coating), was applied to the surface of the substrate with an applicator to a dry film thickness of 15 μm. After leaving the coating at room temperature for 5 minutes, a two-component clear coating composition (CC-1) was applied to the resulting colored coating with an applicator to a dry film thickness of 30 μm, and the coating was dried in an oven at 80°C for 4 days.

[0176] Next, SK Dyne 1310DT (trade name, manufactured by Soken Chemical & Engineering Co., Ltd.) was applied to the opposite surface of the substrate with an applicator to a dry film thickness of 100 μm to form an adhesive layer. Furthermore, a release film GS (trade name, manufactured by Lintec Corporation) was laminated on the obtained adhesive layer to obtain a comparative laminate film (H-5-1).

[0177] <Evaluation> [Molecular weight between crosslinking points (Mc)] Using free films of the cured clear coating layers (T-1 to 19) obtained in Preparation Examples 1 to 17 and Comparative Preparation Examples 1 and 2, dynamic viscoelasticity measurements (storage modulus (E'), loss modulus (E''), and loss tangent (tanδ)) were carried out under the conditions described above, and the molecular weight between crosslinking points (Mc) of the cured clear coating layer (T) was determined using the above-mentioned (Equation 2). The results are summarized in Table 3 using the following index. ◯ and △ were considered to be within the acceptable range.

[0178] ○:200≦Mc≦500 △:500 <Mc≦800 ×: Mc<200 or 800 <Mc

[0179] [20° Gloss Value] Using a Micro Trigloss gloss meter (trade name, manufactured by BYK-Gardner), the 20° gloss values ​​of the cured clear coating layer surface of the laminate films (H-1-1 to 5, 8 to 9), (H-2-1 to 5), (H-3-1 to 5) of Examples 1 to 17 and the comparative laminate films (H-1-6 to 7), (H-4-1), (H-5-1) of Comparative Examples 1 to 4 were measured.

[0180] [Pencil hardness] The pencil hardness of the cured clear coating layer surface of the laminate films (H-1-1 to 5, 8 to 9), (H-2-1 to 5), (H-3-1 to 5) of Examples 1 to 17, and the comparative laminate films (H-1-6 to 7), (H-4-1), and (H-5-1) of Comparative Examples 1 to 4 was measured according to ISO 15184:2020, and the results are summarized in Table 3 using the following index. ◎, ◯, and △ were considered to be within the acceptable range.

[0181] ◎: 2B or more. 〇: 4B or more, 3B or less. △: 6B or more, 5B or less. ×: 6B with scratches.

[0182] [Workability] The laminate films (H-1-1 to 5, 8 to 9), (H-2-1 to 5), (H-3-1 to 5) of Examples 1 to 17 and the comparative laminate films (H-1-6 to 7), (H-4-1), and (H-5-1) of Comparative Examples 1 to 4 were cut to A4 size (210 mm long x 297 mm wide), and the release films were removed. Next, these laminate films were placed with the cured clear coating layer facing up on a rectangular mold measuring 50 mm long x 50 mm wide x 10 mm high, so that the entire surface was covered, and molded using a pressure molding machine at a heating temperature of 60°C. Thereafter, the molded laminate films were observed for cracks using a magnifying glass, and the results were evaluated using the following criteria are shown in Table 3. ◎, ◯, and △ were considered acceptable.

[0183] ⊚: No cracks were observed. ○: There were some cracks. △: There was moderate cracking. ×: Many cracks were found.

[0184] [Acid resistance] A 0.2 ml spot of 40% aqueous sulfuric acid solution was placed on the cured clear coating layer surface of the laminate films (H-1-1 to 5, 8 to 9), (H-2-1 to 5), and (H-3-1 to 5) of Examples 1 to 17, and the comparative laminate films (H-1-6 to 7), (H-4-1), and (H-5-1) of Comparative Examples 1 to 4, and heated at 60°C for 15 minutes. After rinsing with water, the degree of staining was visually observed, and the results were evaluated using the following criteria in Table 3. ◎, ◯, and △ were considered acceptable.

[0185] ◎: Almost no change is observed. ○: Slight water stains are visible. △: Water stains are visible, but still usable. ×: Significant water stains are visible and the product cannot be used.

[0186] [Weather resistance] Using a sunshine carbon arc lamp accelerated weathering tester (JIS B 7753:2007), the cured clear coating layer surfaces of the laminate films (H-1-1 to 5, 8 to 9), (H-2-1 to 5), and (H-3-1 to 5) of Examples 1 to 17 and the comparative laminate films (H-1-6 to 7), (H-4-1), and (H-5-1) of Comparative Examples 1 to 4 were each exposed for 3000 hours. The condition of these laminate films was then visually observed, and the results were evaluated using the following criteria, as shown in Table 3. ◎, ◯, and △ were considered acceptable.

[0187] ◎: Almost no change is observed. ◯: Slight whitening or peeling of the substrate is observed. △: Whitening or peeling of the substrate is observed, but usable. ×: Significant whitening or peeling of the substrate was observed, and the sample was unusable.

[0188] [water resistance] The laminate films of Examples 1 to 17 (H-1-1 to 5, 8 to 9), (H-2-1 to 5), (H-3-1 to 5), and the comparative laminate films of Comparative Examples 1 to 4 (H-1-6 to 7), (H-4-1), and (H-5-1) were immersed in warm water at 40°C for 240 hours. Thereafter, the appearance (wrinkles, cracks) was visually observed, and the results were evaluated using the following indexes, as shown in Table 3. ◎, ◯, and △ were considered to be within the acceptable range.

[0189] ◎: Almost no change is observed. ○: Slight wrinkles and cracks are observed. △: Wrinkles and cracks are visible, but still usable. ×: Significant wrinkles and cracks are observed and the product is unusable.

[0190] [Car wash machine scratch resistance] The laminate films (H-1-1 to 5, 8 to 9), (H-2-1 to 5), (H-3-1 to 5) of Examples 1 to 17 and the comparative laminate films (H-1-6 to 7), (H-4-1), and (H-5-1) of Comparative Examples 1 to 4 were cut into 70 mm x 150 mm pieces. The cured clear coating layer of each cut laminate film specimen was facing upwards, and 1 g of muddy water (JIS Z 8901:2006 test powder, water, and neutral detergent mixed in a 10 / 99 / 1 mass ratio) was applied with a brush. Then, 120 bundles of 30 nylon brushes, each 1 mm thick and 20 cm long, were evenly arranged in a cylindrical pipe with an outer diameter of 10 cm and a length of 15 cm. The car wash brush was rotated at 150 rpm for 10 seconds to clean the evaluation panel. In this test, the test specimen was positioned 20 cm from the center of the cylindrical pipe. After brush cleaning, the test piece was washed with running water to remove all the muddy water. This procedure was repeated 10 times before evaluation.

[0191] The evaluation was performed by measuring the L value of the test piece before and after the test at an incident angle of 0° and an acceptance angle of 10°, and calculating the difference in lightness (ΔL). The results are summarized in Table 3 using the following index. ◎, ◯, and △ were considered to be within the acceptable range.

[0192] ◎:ΔL≦1 ○:1<ΔL≦3 △:3<ΔL≦4 ×:4<ΔL

[0193] The invention made by the present inventors has been specifically described above based on an embodiment, but it goes without saying that the present invention is not limited to the above embodiment and can be modified in various ways without departing from the spirit of the invention. [Industrial Applicability]

[0194] The laminated film of the present invention has excellent pencil hardness, processability, acid resistance, weather resistance, water resistance, and resistance to scratches in car washes, and is therefore applicable to the decoration of, for example, automobile bodies, bumpers, interior and exterior vehicle parts, building materials, daily necessities, home appliance parts, interior components, marine components, etc., and is particularly suitable for use in the decoration of automobile bodies, bumpers, and interior and exterior vehicle parts. [Explanation of symbols]

[0195] 1 Cured clear coating layer (T) 2. Transparent thermoplastic polyurethane (TPU) substrate 3 Colored coating layer 4 Adhesive layer 5. Colored thermoplastic polyurethane (TPU) substrate

Claims

1. A laminated film comprising a thermoplastic polyurethane (TPU) substrate and a cured clear coating layer (T) made of a two-component clear coating composition (CC) formed directly or indirectly on one surface of the substrate, The two-component clear coating composition (CC) comprises a hydroxyl group-containing (meth)acrylic resin (A) having a calculated glass transition temperature (Tg) of −50° C. or higher and 10° C. or lower, and an isocyanate curing agent (B), The cured clear coating layer (T) is a layer formed by heating and drying at 80°C or less, and has a molecular weight between crosslinking points (Mc) of 200 g / mol or more and 800 g / mol or less.

2. 2. The laminated film according to claim 1, further comprising an adhesive layer formed on the outermost layer of the surface of the thermoplastic polyurethane (TPU) substrate opposite to the surface on which the cured clear coating layer (T) is formed.

3. 3. The laminated film according to claim 1 or 2, characterized in that a colored coating layer is formed on one surface of the thermoplastic polyurethane (TPU) substrate, and the cured clear coating layer (T) is formed on the colored coating layer.

4. 3. The laminated film according to claim 1, further comprising a colored coating layer formed on the surface of the thermoplastic polyurethane (TPU) substrate opposite to the cured clear coating layer (T).

5. 3. The laminated film according to claim 1, wherein the thermoplastic polyurethane (TPU) substrate contains a color pigment and / or a luster pigment.

6. 3. The laminated film according to claim 1, wherein the thickness of the thermoplastic polyurethane (TPU) substrate is 50 to 1000 μm.

7. 3. The laminated film according to claim 1, wherein the two-component clear coating composition (CC) contains a matting agent.

8. 3. The laminate film according to claim 1 or 2, wherein the laminate film comprises a colored coating layer formed on one surface of the thermoplastic polyurethane (TPU) substrate, and the cured clear coating layer (T) formed on the colored coating layer, and the colored coating layer contains 10 to 200 parts by mass of a color pigment and / or 30 parts by mass or less of a luster pigment per 100 parts by mass of the solid content of the resin forming the colored coating layer.

9. 3. The laminate film according to claim 1 or 2, wherein the laminate film further comprises a colored coating layer formed on a surface of the thermoplastic polyurethane (TPU) substrate opposite to the cured clear coating layer (T), and the colored coating layer contains 10 to 200 parts by mass of a color pigment and / or 30 parts by mass or less of a luster pigment per 100 parts by mass of a resin solid content forming the colored coating layer.

10. A decorated article decorated with the laminate film according to claim 1 or 2.

11. The decorated article according to claim 10, characterized in that the laminated film comprises a colored coating layer formed on one surface of the thermoplastic polyurethane (TPU) substrate and a cured clear coating layer (T) formed on the colored coating layer, the colored coating layer having a thickness of 50 μm or less and the cured clear coating layer (T) having a thickness of 60 μm or less.

12. The decorated article according to claim 10, characterized in that the laminated film further comprises a colored coating layer formed on one surface of the thermoplastic polyurethane (TPU) substrate opposite to the cured clear coating layer (T), the colored coating layer having a thickness of 50 μm or less, and the cured clear coating layer (T) having a thickness of 60 μm or less.

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