Lamination film, and decorative article decorated with the lamination film

Abstract

[Problem] To provide a lamination film having excellent pencil hardness, acid resistance, water resistance, and car wash scratch resistance, as well as a decorative article decorated with the lamination film. [Means for Solving the Problems] A lamination film in which a cured coating layer is laminated directly or indirectly onto a thermoplastic polyurethane (TPU) substrate, using a two-component clear coating composition (CC), characterized in that said two-component clear coating composition (CC) comprises a hydroxy group-containing (meth)acrylic resin (A) with a theoretical glass transition temperature (Tg) of - 50°C to 10°C and an isocyanate curing agent (B), said cured clear coating layer (T) is a layer formed by heating at 80°C or lower, and the molecular weight between crosslinking points (Mc) is 200-800 g / mol.

Description

[Document Name] SPECIFICATION[Title of the Invention] Lamination film, and decorative article decorated with the lamination film [Technical Field]

[0001] The present invention pertains to lamination films, and to decorative articles decorated with the lamination films.[Background Art]

[0002] In recent years, attention has focused on alternative technologies to painting that are highly sophisticated in design, with a view to curtailing volatile organic compounds (VOCs), and providing workability and functionality. Among representative examples of decorative technologies substituting for conventional techniques are application of decorative films to automotive exteriors and parts, and color plastic molding through use of molded-in color, and some practical implementations of these are underway.

[0003] An injection molding machine is ordinarily used in methods for applying a decorative film to a plastic part for an automobile, etc. Specifically, a decorative film comprising a substrate and a decorative layer is set in a mold in advance, and thereafter a molded article is obtained by feeding molten resin into the mold, using the injection molding machine. The method for obtaining in this way a plastic part (i.e., a decorative article) on which both the substrate and decorative layer of a decorative film are left is referred to as inmold forming (IMF). Meanwhile, a method in which the decorative film is set in the mold as described above, but the molten resin is fed into the mold after the substrate has been peeled from the decorative layer, so that only the decorative layer is left on the decorative article, is referred to as in-mold release (IMR). There is also a three-dimension overlay method (TOM) of molding in which a film is laminated onto an already finished article, not limited to plastics, by vacuum forming, and a decorative film can also be applied to an automobile exterior, etc. by this method.

[0004] When a decorative article is obtained, the decorative film must be processable to enable deformation in accordance with the surface shape of the decorative article. The performance of a decorative film must be the same as or better than that of coatings obtained by conventional painting technologies, and requires, for example, pencil hardness, acid resistance, weather resistance, water resistance, and car wash scratch resistance.

[0005] As an example of decorative film prior art, Patent Document 1 discloses a surface protective film comprising a polyurethane resin having a tensile elongation at break of 120% or greater at 80° C and / or a gloss retention ratio of 80% or greater after two years of outdoor weathering.

[0006] Moreover, Patent Document 2 discloses a molding film, comprising a hard coating agent for decorative molding, that is used when forming a coating film, said hard coating agent for decorative molding being characterized in containing a (meth)acrylic polymer that has an imide ring.[Prior Art Documents][Patent Documents]

[0007] [Patent Document 1] JP 2010-260942 A[Patent Document 2] JP 2016-180082 A[Summary of the Invention][Problems to be Solved by the Invention]

[0008] However, the surface protective film disclosed in Patent Document 1, despite having excellentprocessability and weather resistance, lacked sufficient acid resistance, water resistance, and car wash scratch resistance in some cases.

[0009] The molding film disclosed in Patent Document 2 also, despite having excellent processability and durability against steel wool scratching and sunscreen agents, lacked sufficient acid resistance, water resistance, and car wash scratch resistance in some cases.

[0010] In view of the current state of the conventional art described above, the purpose of the present invention is to provide a lamination film, with performance not inferior to that of decorative films obtained by conventional technologies, and having excellent pencil hardness, acid resistance, water resistance, and car wash scratch resistance, as well as a decorative article decorated with the lamination film.[Means for Solving the Problems]

[0011] As a result of intensive research in an effort to resolve the problems, the inventors found that:The problems above were solved by a lamination film obtained by forming a cured clear coating layer (T) directly or indirectly on a thermoplastic polyurethane (TPU) substrate, using a two-component clear coating composition (CC), characterized in that the two-component clear coating composition (CC) comprises a hydroxy group-containing (meth)acrylic resin (A) with a theoretical glass transition temperature (Tg) of -50° C to 10° C and an isocyanate curing agent (B), the cured clear coating layer (T) is a layer formed by heating and drying at 80° C or lower, and the molecular weight between crosslinking points (Me) is 200-800 g / mol, and thus eventually perfected the present invention.

[0012] Moreover, the abovementioned lamination film is preferably characterized in that an adhesive layer is additionally formed on an outermost layer on the surface of the thermoplastic polyurethane (TPU) substrate on the opposite side to the surface on which the cured clear coating layer (T) is formed.

[0013] The abovementioned lamination film is also preferably characterized in that a color coating layer is formed on one surface of the thermoplastic polyurethane (TPU) substrate, and the cured clear coating layer (T) is formed on the color coating layer.

[0014] In addition, the abovementioned lamination film is preferably characterized in that a color coating layer is additionally formed on the surface of the thermoplastic polyurethane (TPU) substrate on the opposite side to the cured clear coating layer (T).

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

[0016] Additionally, the thickness of the thermoplastic polyurethane (TPU) substrate in the abovementioned lamination film is preferably 50-1000 pm.

[0017] The abovementioned lamination film is also preferably characterized in that the two-component clear coating composition (CC) comprises a matting agent. The abovementioned lamination film is preferably characterized in that a color coating layer is formed on one surface of the thermoplastic polyurethane (TPU) substrate, the cured clear coating layer (T) is formed on the color coating layer, and the color coating layer contains 10-200 parts by mass of a color pigment and / or 30 parts by mass or less of a luster pigment, based on 100 parts by mass of resin solids of the color coating layer.

[0018] The abovementioned lamination film is preferably characterized in that a color coating layer isadditionally formed on the surface of the thermoplastic polyurethane (TPU) substrate on the opposite side to the cured clear coating layer (T), and the color coating layer contains 10-200 parts by mass of a color pigment and / or 30 parts by mass or less of a luster pigment, based on 100 parts by mass of resin solids of the color coating layer.

[0019] Moreover, the abovementioned problems of the present invention are solved through use of a decorative article decorated with the abovementioned lamination film.

[0020] Preferably, in the abovementioned lamination film, a color coating layer is formed on one surface of the thermoplastic polyurethane (TPU) substrate, a cured clear coating layer (T) is formed on the color coating layer, the thickness of the color coating layer is 50 pm or less, and the thickness of the cured clear coating layer (T) is 60 pm or less.

[0021] Preferably, in the abovementioned lamination film, a color coating layer is formed on the surface of the thermoplastic polyurethane (TPU) substrate on the opposite side to the cured clear coating layer (T) that is on one side, the thickness of the color coating layer is 50 pm or less, and the thickness of the cured clear coating layer (T) is 60 pm or less.[Effects of the Invention]

[0022] The present invention makes it possible to obtain a lamination film that can be used as a decorative film, with performance not inferior to that of decorative films obtained by conventional technologies, and having excellent pencil hardness, acid resistance, water resistance, and car wash scratch resistance, as well as a decorative article that is decorated with the laminated film.[Brief Description of the Drawings]

[0023] [Figure 1] Figure 1 is a schematic cross-sectional view showing an embodiment (First Embodiment, H-l) of the lamination film of the present invention.[Figure 2] Figure 2 is a schematic cross-sectional view showing an embodiment (Second Embodiment, H- 2) of the lamination film of the present invention.[Figure 3] Figure 3 is a schematic cross-sectional view showing an embodiment (Third Embodiment, H-3) of the lamination film of the present invention.[Embodiments of the Invention]

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

[0025] Note that in the present invention, a prescribed layer (for example, a cured clear coating layer) being formed “directly” on the surface of another layer (for example, the surface of a substrate) means that the prescribed layer is provided in contact with, and especially in close contact with, that other layer. Meanwhile, a prescribed layer (for example, a cured clear coating layer) being formed “indirectly” on the surface of another layer (for example, the surface of a substrate) means that one or more other layers (for example, a color coating layer discussed below) are provided on the prescribed surface, and the prescribed layer is formed with the other layer or layers interposed.

[0026] [Substrate]A thermoplastic polyurethane (TPU) is used as a substrate in the lamination film of the present invention. Since the thermoplastic polyurethane (TPU) has excellent adhesion to the layer formed thereon, alamination film with excellent processability can be obtained without forming a primer layer between the substrate and the layer formed thereon.

[0027] The thermoplastic polyurethane (TPU) is generally a polymer having an intramolecular urethane bond, which is obtained by inducing a polyaddition reaction between a polymeric polyol, a polyisocyanate such as a diisocyanate, and a chain extender, using a catalyst such as dibutyltin dilaurate as required, the thermoplastic polyurethane (TPU) softening and becoming fluid through heating. The chain extender reacts with the polyisocyanate to form hard segments, while the polymeric polyol reacts with the polyisocyanate to form soft segments.

[0028] Examples of polymeric polyols include polyester polyols, polyether polyols, and polycarbonate polyols with two or more hydroxy groups in each molecule and a number average molecular weight of 400 or greater, as well as combinations thereof. A diol with two hydroxy groups in each molecule is preferable as the polymeric polyol, since there are cases in which thermoplasticity is lost upon introduction of an excessively crosslinked structure into a polyurethane.

[0029] A polyester polyol could, for example, be obtained by a condensation reaction or a transesterification reaction between a short-chain polyol, having two or more hydroxy groups in each molecule and a number average molecular weight of less than 400, and a polybasic acid or an alkyl ester, acid anhydride, or acid halide thereof.

[0030] Use of a short-chain dihydric alcohol as the short-chain polyol is preferable, since there are cases in which thermoplasticity is lost upon introduction of an excessively crosslinked structure into a polyurethane. Examples of short-chain dihydric alcohols which may be cited 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-l,5-pentanediol, 2,4-diethyl-l,5-pentanediol, 1,6-hexanediol, 2,6-dimethyl-l-octene-3,8-diol, C7-C22 alkanediol, cyclohexanediol, cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, l,4-dihydroxy-2-butene, bis-hydroxy ethoxy benzene, xylene glycol, bishydroxy ethylene terephthalate, diethylene glycol, trioxyethylene glycol, tetraoxyethylene glycol, pentaoxyethylene glycol, hexaoxyethylene glycol, dipropylene glycol, trioxypropylene glycol, tetraoxypropylene glycol, pentaoxypropylene glycol, and hexaoxypropylene glycol; and 1,4-butanediol, 1,5-pentanediol, 3-methyl-l,5-pentanediol, and 1,6-hexanediol are preferable. The short-chain polyol can be used singly or as a combination of two or more types thereof.

[0031] Examples of polybasic acids which may be cited include saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, l,l-dimethyl-l,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, toluene dicarboxylic acid, and naphthalene dicarboxylic acid; alicyclic dicarboxylic acids such as hexahydrophthalic acid; and other polycarboxylic acids such as dimer acids, hydrogenated dimer acids, and HET acid.

[0032] Examples of alkyl esters, acid anhydrides, and acid halides of the abovementioned polybasic acids which may be cited include methyl esters and ethyl esters; oxalic anhydrides, succinic anhydrides, maleic anhydrides, phthalic anhydrides, 2-alkyl (C12-C18) succinic anhydrides, tetrahydrophthalic anhydrides, hexahydrophthalic anhydrides, and trimellitic anhydrides; and oxalic acid dichlorides, adipic acid dichlorides, and sebacic acid dichlorides of the polybasic acids. The polybasic acid or alkyl ester, acid anhydride, or acid halide thereof can be used singly or as a combination of two or more types.

[0033] Use of a dicarboxylic acid or alkyl ester, acid anhydride, or acid halide thereof is preferable, since there are cases in which thermoplasticity is lost upon introduction of an excessively crosslinked structure into a polyurethane.

[0034] A vegetable oil-based polyester polyol obtained by a condensation reaction of a hydroxycarboxylic acid such as a hydroxy group-containing vegetable oil fatty acid, or a polycaprolactone polyol, polyvalerolactone polyol, polylactic acid polyol, or the like, obtained by ring-opening polymerization of a lactone such as E -caprolactone or y -valerolactone, or of a lactide such as L-lactide or D-lactide, can be used as the polyester polyol.

[0035] The polyester polyol can be used singly or as a combination of two or more types thereof.

[0036] Examples of polyether polyols include polyoxyalkylene polyols obtained by ring-opening polymerization of an alkylene oxide such as ethylene oxide or propylene oxide. The polyether polyol can be used singly or as a combination of two or more types thereof.

[0037] Examples of polycarbonate polyols which may be cited include polycarbonates obtained by reacting a ring-opening polymer of ethylene carbonate in the presence of a short-chain polyol, the abovementioned short-chain dihydric alcohol such as 1 ,4-butanediol, 1,5-pentanediol, 3-methyl-l,5-pentanediol, or 1,6- hexanediol, and phosgene or diphenyl carbonate; and amorphous polycarbonate polyols obtained by copolymerizing the short-chain dihydric alcohol with the ring-opening polymer.

[0038] The polycarbonate polyol can be used singly or as a combination of two or more types thereof.

[0039] Examples of polyisocyanates which may be cited include linear aliphatic polyisocyanates, cycloaliphatic polyisocyanates, aromatic polyisocyanates, and aromatic / aliphatic polyisocyanates, as well as oligomers (i.e. dimers, trimers, etc.), and uretdione-modified, biuref-modified, allophanate-modified, isocyanurate- modified, polyol-modified, oxadiazinetrione-modified, and carbodiimide-modified polyisocyanates. The polyisocyanate can be used singly or as a combination of two or more types thereof. Use of a diisocyanate as the polyisocyanate is preferable, since there are cases in which thermoplasticity is lost upon introduction of an excessively crosslinked structure into a polyurethane.

[0040] Examples of linear aliphatic polyisocyanates which may be cited include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (EDI), hexamethylene diisocyanate (HDI), octamethylene diisocyanate, and nonamethylene diisocyanate.

[0041] Examples of cycloaliphatic polyisocyanates which may be cited include isophorone diisocyanate (IPDI) and l,3-bis(isocyanatomethyl)cyclohexane, as well as trans, trans-, trans, cis-, and cis,cis- dicyclohexylmethane-4,4’-diisocyanate, and mixtures thereof (hydrogenated MDI).

[0042] Examples of aromatic polyisocyanates which may be cited include 2,4-folylene diisocyanate and 2,6- tolylene diisocyanate, as well as isomeric mixtures of the tolylene diisocyanates (TDIs); 4, d’diphenylmethane diisocyanate, 2, 4’ -diphenylmethane diisocyanate, and 2, 2 ’-diphenylmethane diisocyanate, as well as isomeric mixtures of the diphenylmethane diisocyanates (MDIs); tolidine diisocyanates (TODIs); and naphthalene diisocyanates (NDIs).

[0043] Examples of aromatic / aliphatic polyisocyanates which may be cited include 1,3- and 1,4-xylylenediisocyanates (XDIs) and mixtures thereof, and 1,3- and 1,4-fetramethyl xylylene diisocyanates (TMXDIs).

[0044] The same examples may be cited for the chain extender as for the abovementioned short-chain dihydric alcohol. The chain extender can be used singly or as a combination of two or more types thereof.

[0045] The thermoplastic polyurethane (TPU) serving as the substrate of the lamination film in the present invention is formed into a sheet. Calendering, inflation molding, T-die extrusion molding, blow molding, lamination, etc. are cited as molding methods.

[0046] The thickness of the thermoplastic polyurethane (TPU) serving as the substrate of the lamination film in the present invention is preferably 50-1000 pm, and more preferably 100-1000 pm. Problem-free handling can be achieved in practice by adoption of a substrate thickness of 50-1000 pm.

[0047] The thermoplastic polyurethane (TPU) serving as the substrate of the lamination film in the present invention preferably has a tensile elongation of 200-800%, and more preferably 300-700%. Excellent processability is obtained by adoption of a tensile elongation of 200-800%. Note that the tensile elongation is the value as measured in compliance with JIS K 7311:1995.

[0048] Since heat is applied to the lamination film in the present invention during molding, the thermoplastic polyurethane (TPU) serving as the substrate thereof is preferably heat resistant. The heat resistance of the present invention should be such that when the thermoplastic polyurethane (TPU) serving as the substrate is placed in an oven at 120° C for 5 seconds, no deformation at all is found, or substantially no deformation is found.

[0049] The thermoplastic polyurethane (TPU) serving as the substrate of the lamination film in the present invention may also undergo a surface treatment such as a corona surface treatment, flame treatment, or plasma treatment in advance. However, it is not always necessary to provide a primer layer of e.g. chlorinated polyolefin, polyester, or polyurethane. Selection of the thermoplastic polyurethane (TPU) for the substrate enables attainment of sufficient adhesion to the layer adjacent to the substrate without a primer layer. As a result, there is no need to include a primer layer forming step in the lamination film manufacturing process, and thus production efficiency can be increased.

[0050] The thermoplastic polyurethane (TPU) serving as the substrate of the lamination film in the present invention may be transparent, but may also contain a color pigment. Examples of color pigments included in the substrate of the present invention which may be cited include inorganic pigments such as titanium oxide, iron oxide, and complex oxides 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 color pigments can be used singly or as a combination of two or more types thereof.

[0051] While there are no specific limitations as to the total color pigment content included in the thermoplastic polyurethane (TPU) serving as the substrate of the lamination film in the present invention, 10-200 parts by mass thereof, based on 100 parts by mass of total resin in the substrate is preferable, 30-180 parts by mass thereof is more preferable, and 50-160 parts by mass thereof is especially preferable.

[0052] The thermoplastic polyurethane (TPU) serving as the substrate of the lamination film in the presentinvention may also contain a luster pigment. Examples of luster pigments which may be cited include colorless or color aluminum pigments, vapor-deposited metal flake pigments, and optical interference pigments that coat a transparent or translucent substrate with a metal oxide. The luster pigment can be used singly or as a combination of two or more types thereof. While there are no specific limitations as to the total luster pigment content included in the thermoplastic polyurethane (TPU) serving as the substrate of the lamination film in the present invention, 0-30 parts by mass thereof, based on 100 parts by mass of total resin in the substrate is preferable, 0-25 parts by mass thereof is more preferable, and 0.1-20 parts by mass thereof is especially preferable.

[0053] [Two-component clear coating composition (CC)]The two-component clear coating composition (CC) in the present invention has a hydroxy group- containing (meth)acrylic resin (A) with a theoretical glass transition temperature (Tg) of -50° C to 10° C and an isocyanate curing agent (B) as essential components.

[0054] The hydroxy group-containing (meth)acrylic resin (A) in the present invention may be a homopolymer of a hydroxy group-containing monomer (a), or may be a copolymer of the hydroxy group-containing monomer (a) and another monomer (c), but a copolymer of the hydroxy group-containing monomer (a), a carboxyl group-containing monomer (b), and another monomer (c) is preferable.

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

[0056] Examples of the hydroxy group-containing monomer (a) which may be cited include 2-hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylate (HPA), 2-hydroxypropyl methacrylate (HPMA), 4-hydroxybutyl acrylate (4HBA), and glycerol monomethacrylate (under the trade names BLEMMER GEM and BLEMMER GLM-R, produced by NOE Corporation). The hydroxy group- containing monomer (a) can be used singly or as a combination of two or more types thereof.

[0057] A monomer having a carboxyl group and a radical polymerizable unsaturated bond, for example, can be adopted as the carboxyl group-containing monomer (b) used for the hydroxy group-containing (meth)acrylic resin (A). Acrylic acid, methacrylic acid, 2-methacryloyloxy ethyl succinic acid, etc. may be cited as the carboxyl group-containing monomer (b). The carboxyl group-containing monomer (b) can be used singly or as a combination of two or more types thereof.

[0058] Provided that the monomer has a radical polymerizable unsaturated bond, there are no specific limitations as to the other monomer (c) used in the hydroxy group-containing (meth)acrylic resin (A), and the other monomer (c) is selected as appropriate, depending on the affinity thereof with other components in the two-component clear coating composition (CC). A monomer having good copolymerizability with the hydroxy group-containing monomer (a) and the carboxyl group-containing monomer (b) is more preferably used as the other monomer (c).

[0059] Specific examples of the other monomer (c) are listed as (l)-(8) below.

[0060] (1) Monoesters of acrylic acid or methacrylic acid and a C1-C20 monohydric alcohol: Examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, and lauryl (meth)acrylate, etc.

[0061] (2) Aromatic vinyl monomers: Examples include styrene, a -methylstyrene, and vinyltoluene, etc.

[0062] (3) Glycidyl group-containing vinyl monomers: Compounds that have a glycidyl group and a radical polymerizable unsaturated bond in each molecule; specifically glycidyl (meth)acrylate, etc.

[0063] (4) Nitrogen-containing alkyl (a C1-C20 alkyl group) (meth)acrylates: Examples include dimethylaminoethyl (meth)acrylate, etc.

[0064] (5) Radical polymerizable unsaturated bond-containing amide monomers: Examples include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methylol (meth)acrylamide, and diacetone acrylamide, etc.

[0065] (6) Aliphatic vinyl compounds: Examples include vinyl acetate, vinyl propionate, and vinyl chloride, etc.

[0066] (7) Radical polymerizable unsaturated bond-containing nitrile compounds: Examples include (meth)acrylonitrile, etc.

[0067] (8) Diene compounds: Examples include butadiene and isoprene, etc.

[0068] The other monomer (c) can be used singly or as a combination of two or more types thereof.

[0069] The theoretical glass transition temperature (Tg) of the hydroxy group-containing (meth)acrylic resin (A) in the present invention is preferably -50° C to 10° C, -45° C to 5° C is more preferable, -40° C to 5° C is especially preferable, and furthermore -30° C to 5° C is most preferable. Both pencil hardness and processability are obtained in the cured clear coating layer (T) by adopting a theoretical glass transition temperature (Tg) of -50° C to 10° C.

[0070] The theoretical glass transition temperature (Tg) in this context is a numeric value calculated using Equation 1 below.

[0071] Equation 1: 1 / Tg = S (Wi / Tgi)T g : (absolute) glass transition temperature (Tg) of the hydroxy group-containing (meth)acrylic resin (A)W i : mass fraction of a monomer i componentT g i : (absolute) glass transition temperature of a homopolymer of the monomer i component

[0072] It should be noted that the monomer i component represents one monomer constituting the hydroxy group-containing (meth)acrylic resin (A). That is, Equation 1 indicates that the total of all of the values of (Wi / Tgi) obtained for the respective monomers constituting the hydroxy group-containing (meth)acrylic resin (A) is equal to the reciprocal of the glass transition temperature (1 / Tg) of the hydroxy group- containing (meth)acrylic resin (A).

[0073] Thus, the theoretical glass transition temperature (Tg) of the hydroxy group-containing (meth)acrylic resin (A) can be adjusted by changing the types and / or amounts of the monomers constituting the hydroxy group-containing (meth)acrylic resin (A).

[0074] There are no specific limitations as to the method of manufacturing the hydroxy group-containing(meth)acrylic resin (A) of the present invention, which can be obtained by polymerizing the abovementioned monomers using, for example, a well-known radical polymerization reaction. The reaction may be performed without a solvent, but use of an organic solvent is preferable in terms of synthesis stability and handling.

[0075] Use of a radical polymerization initiator (shortened below to “polymerization initiator”) is preferred in terms of molecular weight control. Other well-known additives, such as a chain transfer agent, may also be used.

[0076] Examples of the organic solvent used in manufacturing the hydroxy group-containing (meth)acrylic resin (A) of the present invention which may be cited 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); as well as ethers, aliphatic hydrocarbons including chlorohydrocarbons, etc., and mixtures thereof.

[0077] Use of an alcohol would impede the progress of the curing reaction of the two-component clear coating composition (CC), and is therefore not recommended.

[0078] These solvents can be used singly or as a combination of two or more types thereof. Any given solid content concentration can be selected for the hydroxy group-containing (meth)acrylic resin (A) solution at this time, within a range in which there will be no loss of synthesis stability, but 10-70 mass% is ordinarily preferable.

[0079] Examples of the polymerization initiator used in manufacturing the hydroxy group-containing (meth)acrylic resin (A) of the present invention which may be cited include organic peroxides such as benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di- n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy neodecanoate, tert-butyl peroxy pivalate, (3,5,5-frimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide, as well as azo compounds such as 2,2’-azobisisobutyronitrile (AIBN), 2,2’-azobis(2-methylbutyronitrile), l,l’-azobis(cyclohexane-l-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 singly or as a combination of two or more types thereof. The amount of polymerization initiator added is preferably 0.1-20 parts by mass, based on 100 parts by mass of total of the hydroxy group-containing monomer (a), the carboxyl group-containing monomer (b), and the other monomer (c), 1-10 parts by mass thereof is especially preferable.

[0080] A chain transfer agent may also be used for the purpose of adjusting molecular weight in the course of manufacturing the hydroxy group-containing (meth)acrylic resin (A). Examples of the chain transfer agent which may be cited include thioglycerol and 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; as well as 2,4-diphenyl-4-methyl-f-pentene, l-methyl-4- isopropylidene-f-cyclohexene, a -pinene, and -pinene.

[0081] The methods of adding the solvent and the polymerization initiator during manufacture of the hydroxy group-containing (meth)acrylic resin (A) are discretionary, but a method in which the organic solvent is fed into a reaction tank, and a radical polymerizable monomer mixture or organic solvent solution thereofis dripped from a drip tank while being stirred, is preferable for the purpose of controlling the heat of polymerization and the heat of reaction.

[0082] The polymerization temperature for the abovementioned polymerization reaction depends on the type of polymerization initiator and whether or not the latter is used in combination with a chain extender, but a temperature of 50-200° C is preferable, and a temperature of 80-160° C is more preferable. Decomposition of the desired radicals can be induced efficiently at a polymerization temperature of 50° C or greater, since the 10-hour half-life temperature of many polymerization initiators is 50° C or greater. Meanwhile, adopting a polymerization temperature of 200° C or lower enables suppression of side reactions such as depolymerization.

[0083] A hydroxy group-containing (meth)acrylic resin (A) having mass average molecular weight (Mw) of 1,000- 50,000 is preferable in the present invention, but 2,000-40,000 is more preferable, and 3,000-30,000 is especially preferable. The compatibility thereof with the isocyanate curing agent (B) is sufficient as a result of adopting a mass average molecular weight (Mw) of 1,000-50,000, and thus a cured clear coating layer (T) with excellent acid resistance, water resistance, and car wash scratch resistance can be obtained. The mass average molecular weight (Mw) of the hydroxy group-containing (meth)acrylic resin (A) herein can be adjusted e.g. by changing the polymerization temperature and the types and / or amounts, etc. of polymerization initiator when manufacturing the hydroxy group-containing (meth)acrylic resin (A).

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

[0085] A hydroxy group-containing (meth)acrylic resin (A) having hydroxyl value (OHV) of 80-220 mgKOH / g is preferable in the present invention, 100-210 mgKOH / g is more preferable, and 120-200 mgKOH / g is especially preferable. As a result of adopting a hydroxyl value (OHV) of 80-220 mgKOH / g, a cured clear coating layer (T) with excellent acid resistance, water resistance, and car wash scratch resistance can be obtained.

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

[0087] A hydroxy group-containing (meth)acrylic resin (A) acid value of 0-60 mgKOH / g is preferable in the present invention, 0-50 mgKOH / g is more preferable, and 0.1-40 mgKOH / g is especially preferable. As a result of adopting an acid value of 0-60 mgKOH / g, a two-component clear coating composition (CO) with excellent balance between pot life (i.e., usable time) and curability can be obtained.

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

[0089] The isocyanate curing agent (B) in the two-component clear coating composition (CC) used in the present invention is preferably an aliphatic polyisocyanate compound, in terms of acid resistance, and ispreferably one or more selected from the group consisting of biurets, isocyanurates, adducts, uretdiones, and allophanates of compounds that each contain two or more isocyanate groups in each molecule.

[0090] Examples of commercially available isocyanate curing agents (B) that mainly contain biurets which may be cited include Desmodur N-75 (trade name; manufactured by Sumika Covestro Urethane Co., Ltd.) and Duranate 24A-100 and 22A-75P (trade names; manufactured by Asahi Kasei Corporation).

[0091] Examples of commercially available isocyanate curing agents (B) that mainly contain isocyanurates which may be cited include Desmodur N-3600 and N-3300 (trade names; manufactured by Sumika Covestro Urethane Co., Ltd.) and Duranate TPA-100 and TKA-100 (trade names; manufactured by Asahi Kasei Corporation).

[0092] Examples of commercially available isocyanate curing agents (B) that mainly contain adducts which may be cited include Duranate E402-80B and E405-70B (trade names; manufactured by Asahi Kasei Corporation).

[0093] Examples of commercially available isocyanate curing agents (B) that contain uretdiones which may be cited include Desmodur N-3400 (trade name; manufactured by Sumika Covestro Urethane Co., Ltd.) and Duranate TEA-100 and TUL-100 (trade names; manufactured by Asahi Kasei Corporation).

[0094] Examples of commercially available isocyanate curing agents (B) that mainly contain allophanates which may be cited 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 singly or as a combination of two or more types thereof.

[0096] The ratio (NCO / OH) of the isocyanate groups of the isocyanate curing agent (B) to the hydroxy groups of the hydroxy group-containing (meth)acrylic resin (A) in the two-component clear coating composition (CC) used in the present invention, expressed as a molar ratio, is preferably 0.5-1.7, 0.8-1.3 is especially preferable. As a result of adopting a molar ratio NCO / OH of 0.5-1.7, a cured clear coating layer (T) with excellent acid resistance, water resistance, and car wash scratch resistance can be obtained.

[0097] The two-component clear coating composition (CC) used in the present invention may contain a catalyst for promoting a crosslinking reaction between the hydroxy group-containing (meth)acrylic resin (A) and the isocyanate curing agent (B). A well-known metal catalyst, amine catalyst, etc. can be used as the catalyst. Metal catalysts which may be cited 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 singly or as a combination of two or more types thereof. The amount of the catalysts admixed is preferably within the range of 0.001-1 part by mass, based on 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 include a polyester resin (C) for the purpose of further improvement of processability. The polyester resin (C) content is preferably 1-50 parts by mass, based on 100 parts by mass of resin solids in the two-component clear coating composition (CC), 3-40 parts by mass thereof is more preferable, and 5-30 parts by mass is especially preferable. The processability of the cured clear coating layer (T) can be improved withoutreducing acid resistance or water resistance by adopting a polyester resin (C) content of 1-50 parts by mass.

[0099] The polyester resin (C) used in the two-component clear coating composition (CC) of the present invention is preferably a polyester polyol that contains a hydroxy group. The same examples are cited for the polyester polyol as for the polyester polyol used in the abovementioned thermoplastic polyurethane (TPU).

[0100] Examples of commercially available polyester resins (C) for use in the two-component clear coating composition (CC) of the present invention which may be cited include D620, D623, D643, and D645 (trade names; manufactured by Mitsubishi Chemical Corporation); the Adeka Cycloaid PNB series (trade name; 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, Inc.); and Desmophen C 1200 and 3601 (trade names; manufactured by Covestro AG).

[0101] A hydroxyl value (OHV) of 10-300 mgKOH / g is preferable, 10-250 mgKOH / g is more preferable, for the polyester resin (C) used in the two-component clear coating composition (CC) of the present invention. A polyester resin (C) mass average molecular weight (Mw) of 500-30,000 is also preferable, 1,000-20,000 is more preferable. These polyesters can be used singly or as a combination of two or more types thereof.

[0102] The two-component clear coating composition (CC) used in the present invention may contain a UV absorber (F). A triazine UV absorber is preferred as the UV absorber (F). Examples of commercially available triazine UV absorbers which may be cited include Eversorb 40, Eversorb 41 FD, and Eversorb 45 (trade names; manufactured by Everlight Chemical Industrial Corp.), and Tinuvin 1600 and Tinuvin 1577ED (trade names; manufactured by BASF). These UV absorbers (F) can be used singly or as a combination of two or more types thereof.

[0103] The UV absorber (F) content in the two-component clear coating composition (CC) used in the present invention is preferably 0.1-30 parts by mass, based on 100 parts by mass of the two-component clear coating composition (CC), 0.1-25 parts by mass thereof is more preferable, and 0.1-20 parts by mass is especially preferable. As a result of adopting a UV absorber (F) content of 0.1-30 parts by mass, a cured clear coating 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). An NOR hindered amine light stabilizer is preferable as the light stabilizer (E). Examples of commercially available NOR hindered amine light stabilizers include Eversorb 93, Eversorb 90, and Eversorb 95 (trade names; manufactured by Everlight Chemical Industrial Corp.), as well as Tinuvin 123, Tinuvin 144, Tinuvin 765, and Tinuvin 770 (trade names; manufactured by BASF). These light stabilizers (E) can be used singly or as a combination of two or more types thereof.

[0105] The light stabilizer (E) content in the two-component clear coating composition (CC) used in the present invention is preferably 0.1-30 parts by mass, based on 100 parts by mass of the two-component clear coating composition (CC), 0.1-25 parts by mass thereof is more preferable, and 0.1-20 parts by mass is especially preferable. As a result of adopting a light stabilizer (E) content of 0.1-30 parts by mass, a cured clear coating 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 color pigment, to the extent that there is no loss of transparency. The same examples are cited for the colorpigment as for the color pigment used in the abovementioned thermoplastic polyurethane (TPU). The color pigment can be used singly or as a combination of two or more types thereof. While there are no specific limitations as to the total color pigment content in the two-component clear coating composition (CC) used in the present invention, 10 parts by mass thereof, based on 100 parts by mass of resin solids in the two-component clear coating composition (CC) is preferable, and 0.1-5 parts by mass thereof is more preferable.

[0107] The two-component clear coating composition (CC) used in the present invention may contain a matting agent. Examples of the matting agent include fine silica and resin beads.

[0108] Typical examples of commercially available fine silica which may be cited include Nipseal series (trade name; manufactured by Tosoh Silica Corporation), Sylysia series (trade name; manufactured by Fuji Silysia Chemical Ltd.), Mizukasil series (trade name; manufactured by Mizusawa Industrial Chemicals, Ltd.), and Acematt series (trade name; manufactured by Evonik Industries AG).

[0109] There are no specific limitations as to the resin composition and synthesis route of the resin beads, and e.g. polyamide (nylon) resin, polyolefin resin, (meth)acrylic resin, polystyrene resin, epoxy resin, polyester resin, urethane resin, or melamine resin beads can be used. Typical examples of commercially available resin beads which may be cited include Vestosint series (trade name; manufactured by Daicel-Evonik Ltd.), Orgasol series (trade name; manufactured by Arkema S.A.), Mipelon series (trade name; manufactured by Mitsui Chemicals, Inc.), Chemisnow series (trade name; manufactured by Soken Chemical Co., Ltd.), Techpolymer series (trade name; manufactured by Sekisui Kasei Co., Ltd.), and Taftic series (trade name; manufactured by Japan Exlan Co., Ltd.).

[0110] These matting agents can be used singly or as a combination of two or more types thereof. While there are no specific limitations as to the total matting agent content in the two-component clear coating composition (CC) used in the present invention, 0-50 parts by mass thereof, based on 100 parts by mass of resin solids in the two-component clear coating composition (CC) is preferable, and 0.1-30 parts by mass thereof is more preferable. As a result of adopting a matting agent content of 0-50 parts by mass, the 20-degree gloss value of the cured clear coating layer (T) can be controlled within a range of 1-100.

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

[0112] The viscosity of the two-component clear coating composition (CC) used in the present invention depends on the method of coating formation, but the viscosity thereof is preferably adjusted, using an organic solvent, to 50-5,000 mPa-s at 23° C, and more preferably adjusted to 300-3,000 mPa-s. Problem- free coating workability can be achieved in practice by adoption of a two-component clear coating composition (CC) viscosity of 50-5,000 mPa-s.

[0113] The same examples are cited for the organic solvent used in the two-component clear coating composition (CC) as for the organic solvent used in the abovementioned hydroxy group-containing (meth)acrylic resin (A). The organic solvent can be used singly or as a combination of two or more types thereof. As indicated above, use of an alcohol would impede the progress of the curing reaction of the two- component clear coating composition (CC), and is therefore not recommended.The organic solvent content in the two-component clear coating composition (CC) used in the present invention is preferably 10-90 parts by mass, based on 100 parts by mass of the two-component clear coating composition (CC). Problem-free coating workability can be achieved in practice by adoption of an organic solvent content of 10-90 parts by mass.

[0115] The two-component clear coating composition (CC) used in the present invention can be manufactured by well-known methods. As a specific example, in order to produce the desired coating properties, a main agent is first of all prepared by mixing and thoroughly stirring the hydroxy group-containing (meth)acrylic resin (A) with the components other than the isocyanate curing agent (B). The two-component clear coating composition (CC) can then be obtained by adding and once more stirring in the isocyanate curing agent (B) immediately before use. In addition, a step for e.g. removing coarse particles through use of a filter, etc. can be introduced at any point in the manufacturing process, as necessary.

[0116] The cured clear coating layer (T) in the present invention is manufactured by coating the thermoplastic polyurethane (TPU) substrate with the two-component clear coating composition (CC), either directly or with one or more color coating layers interposed therebetween. There are no specific limitations as to methods for coating the thermoplastic polyurethane (TPU) substrate with the two-component clear coating composition (CC), and examples include conventionally well-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 through heating, thus promoting a crosslinking reaction. Note that a heating temperature of 80° C or lower is preferable. Moreover, a heating time of from 15 minutes to 10 days is preferable.

[0117] The cured clear coating layer (T) in the present invention preferably has a molecular weight between crosslinking points (Me) of 200-800 g / mol. As a result of adopting a molecular weight between crosslinking points (Me) of 200-800 g / mol, the cured clear coating layer (T) displays excellent acid resistance, water resistance, and car wash scratch resistance.

[0118] The molecular weight between crosslinking points (Me) of the cured clear coating layer (T) in the present invention was calculated, using Equation 2 below, by preparing a test piece with a width of 5 mm, a length of 10 mm, and a film thickness of 30 pm, and measuring dynamic viscoelasticity (i.e. the storage elastic modulus (E’), loss elastic modulus (E’ ’ ), and loss tangent (tan 3 )) under the following conditions. A lower the molecular weight between crosslinking points (Me) indicates a denser crosslinked structure.

[0119] ■ Device: Dynamic viscoelasticity measurement device, RSA3 (manufactured by TA Instruments).■ Measurement mode: Non-resonant forced vibration mode■ Temperature increase rate: 3.0° C / min■ Measurement interval: 12 times / minute■ Frequency: 1.0 Hz■ Temperature range: 30-180°C

[0120] Equation 2: Molecular weight between crosslinking points (Me) = 3 p RT / E’ min

[0121] The units of the values shown by symbols are as follows.

[0122] Molecular weight between crosslinking points (Me): g / molE’ min: Pap (density) : g / m3R (gas constant): J / mol-KT (absolute temperature at E ’ m i n ) : K

[0123] The pencil hardness of the cured clear coating layer (T) in the present invention as measured in accordance with ISO 15184:2020 is preferably 6B or harder, 4B or harder is especially preferable. As a result of adopting a pencil hardness of 6B or harder, the cured clear coating layer (T) displays excellent acid resistance and water resistance. The abovementioned range of pencil hardness can be obtained in the cured clear coating layer (T) by adjusting the theoretical glass transition temperature (Tg), mass average molecular weight (Mw), or hydroxyl value (OHV) of the hydroxy group-containing (meth)acrylic resin (A), or the molar ratio NCO / OH, i.e. the blending ratio between the hydroxy group-containing (meth)acrylic resin (A) and the isocyanate curing agent (B), as appropriate.

[0124] [Adhesive layer]An adhesive layer may be formed on the outermost layer on the surface of the thermoplastic polyurethane (TPU) substrate of the lamination film in the present invention, on the opposite side to the cured clear coating layer (T), either directly or with one or more color coating layers interposed therebetween. There are no specific limitations as to the resin component used in the adhesive layer, provided that the lamination film is capable of adhering to a decorated article, and e.g. a (meth)acrylic resin, polyurethane resin, polyester resin, polyvinyl acetate resin, and / or epoxy resin, etc. can be used. These resin components can be used singly or as a combination of two or more types thereof.

[0125] [Color coating layer]A color coating layer may be formed in the lamination film in the present invention. The location in which the color coating layer is formed is on one surface of the thermoplastic polyurethane (TPU) substrate, and may be between the cured clear coating layer (T) and the thermoplastic polyurethane (TPU) substrate or on the opposite side to the cured clear coating layer (T). Moreover, color coating layers may be formed on both surfaces of the thermoplastic polyurethane (TPU) substrate in other embodiments. There may also be one or a plurality of color coating layers. The color coating layer is preferably formed directly on the thermoplastic polyurethane (TPU) substrate. The color coating layer is formed from a color coating composition containing a film-forming resin and a color pigment and / or luster pigment.

[0126] The film-forming resin in the color coating composition of the present invention may be a thermosetting resin composition that forms a coating through a crosslinking reaction promoted by heating after coating, or a thermoplastic resin composition that forms a coating film through evaporation of a solvent. The filmforming resin can be dissolved or dispersed in a solvent such as an organic solvent for use.

[0127] A thermosetting resin composition that contains the main resin and a curing agent, for example, can be used as the thermosetting resin composition for the color coating composition of the present invention. While there are no specific limitations as to the curing agent content in the resin composition (main resin+curing agent), 0.1-50 parts by mass, based on 100 parts by mass of the film forming resin solids is preferable, 5-45 parts by mass thereof is more preferable, and 10-40 parts by mass is especially preferable. The color coating composition of the present invention, when it is a thermosetting resin composition, may be a one-component coating composition in which the main resin is mixed in advance with the curing agent, or may be a two -component coating composition in which the main resin is mixed with the curing agent immediately before coating.

[0128] Examples of main resins for the thermosetting resin composition in the color coating composition of thepresent invention which may be cited include (meth)acrylic resins, polyester resins, polyurethane resins, polyurea resins, (meth)acrylic urethane resins, polyurethane polyurea resins, polyolefin resins (including chlorinated and / or modified forms thereof), and epoxy resins. The main resin also preferably has hydroxy groups as functional groups. These main resins can be used singly or as a combination of two or more types thereof.

[0129] Examples of curing agents for the thermosetting resin composition in the color coating composition of the present invention include amino resins, polyisocyanate compounds, and blocked polyisocyanate compounds. Among these, polyisocyanate compounds and blocked polyisocyanate compounds are especially preferable. These curing agents can be used singly or as a combination of two or more types thereof.

[0130] Amino resin is a general term for resins obtained by condensing an amino group-containing compound through addition of formaldehyde thereto. Examples of amino resins which may be cited include melamine resins, urea resins, and guanamine resins, and among these, a melamine resin is preferable.

[0131] Examples of melamine resins which may be cited include partially or fully methylolated melamine resins obtained by reacting melamine with formaldehyde, partially or fully alkyl-etherified melamine resins obtained by partially or fully etherifying the methylol groups in a methylolated melamine resin with an alcohol component, imino group-containing melamine resins, and mixtures of two or more said melamine resins. In addition, examples of alkyl-etherified melamine resins which may be cited include methylated melamine resin, butylated melamine resin, and methyl / butyl mixed alkyl-etherified melamine resins.

[0132] The same examples are cited for the polyisocyanate compounds as for the isocyanate curing agent (B) in the abovementioned two-component clear coating composition (CC).

[0133] Examples of blocked polyisocyanate compounds which may be cited include polyisocyanate compounds in which the isocyanate groups in the abovementioned polyisocyanate compounds are blocked by alcohols such as butanol, oximes such as methyl ethyl ketoxime, lactams such as E -caprolactam, active methylenes such as malonic diesters and acetoacetic esters, pyrazoles such as 3,5-dimethylpyrazole, imidazoles such as imidazole and 2-ethylimidazole, and phenols such as m-cresol, among which, those in which the isocyanate groups are blocked by an active methylene are especially preferable.

[0134] Examples of thermoplastic resin compositions in the color coating composition of the present invention include (meth)acrylic resins, polyester resins, polyurethane resins, polyurea resins, (meth)acrylic urethane resins, polyurethane polyurea resins, polyolefin resins (including chlorinated and / or modified forms thereof), and epoxy resins with mass average molecular weights (Mw) of 30,000 or greater.

[0135] The same examples may be cited for the color pigment in the color coating composition of the present invention as for the color pigment used in the abovementioned thermoplastic polyurethane (TPU). The color pigment can be used singly or as a combination of two or more types thereof. While there are no specific limitations as to the total color pigment content in the color coating composition used in the present invention, 10-200 parts by mass thereof, based on 100 parts by mass of the film-forming resin solids in the color coating composition is preferable, 30-180 parts by mass thereof is more preferable, and 50-160 parts by mass thereof is especially preferable.

[0136] The same examples may be cited for the luster pigment in the color coating composition of the present invention as for the luster pigment used in the abovementioned thermoplastic polyurethane (TPU). Theluster pigment can be used singly or as a combination of two or more types thereof. While there are no specific limitations as to the total luster pigment content in the color coating composition used in the present invention, 0-30 parts by mass thereof, based on 100 parts by mass of the film-forming resin solids in the color coating composition is preferable, 0-25 parts by mass thereof is more preferable, and 0.1-20 parts by mass thereof is especially preferable.

[0137] Organic solvents and additives such as, for example, surface conditioners, thickeners, rheology control agents, pigment dispersants, anti-settling agents, crosslinking reaction-promoting catalysts, antifoaming agents, antioxidants, UV absorbers, various coating additives such as light stabilizers, and extender pigments can also be blended into the color coating composition used in the present invention, as necessary and as appropriate.

[0138] The same examples may be cited for the organic solvent used in the color coating composition as for the organic solvent used in the abovementioned hydroxy group-containing (meth)acrylic resin (A). The organic solvent can be used singly or as a combination of two or more types thereof. Moreover, when the color coating composition is a thermosetting resin composition that contains a polyisocyanate compound and / or a blocked polyisocyanate compound as a curing agent, use of an alcohol would, as indicated above, impede the progress of the curing reaction of the two-component clear coating composition (CC), and is therefore not recommended. However, when the color coating composition is a thermosetting resin composition that does not contain a polyisocyanate compound and / or a blocked polyisocyanate compound as a curing agent, or when the color coating composition is a thermoplastic resin composition, use of an alcohol such as isopropanol, butanol, 2-butoxyethanol, and / or 2-ethylhexanol would not be problematic.

[0139] [Lamination film (H)]The lamination film (H) of the present invention is preferably selected from the three modes presented below. These will be described below with reference to the drawings.

[0140] [First Mode]In the lamination film (H-l) of the First Mode, as shown in Figure 1, a color coating layer 3 and a cured clear coating layer 1 are formed in that order on a transparent thermoplastic polyurethane (TPU) substrate 2, and an adhesive layer 4 is formed on the opposite side thereto (i.e., the back).

[0141] [Second Mode]In the lamination film (H-2) of the Second Mode, as shown in Figure 2, a cured clear coating layer 1 is formed on a transparent thermoplastic polyurethane (TPU) substrate 2, and a color coating layer 3 and adhesive layer 4 are formed in that order on the opposite side thereto (i.e., the back).

[0142] [Third Mode]In the lamination film (H-3) of the Third Mode, as shown in Figure 3, a cured clear coating layer 1 is formed on the surface of a color thermoplastic polyurethane (TPU) substrate 5, and an adhesive layer 4 is formed on the opposite side thereto (i.e., the back).

[0143] [Cured clear coating layer (T)]A cured clear coating layer (T) film thickness of 10-60 pm is preferable in the lamination film (H) of the present invention, 20-50 pm is more preferable, and 25-40 pm is especially preferable. Excellent acid resistance and weather resistance can be obtained through adoption of a cured clear coating layer (T) film thickness of 10 pm or greater, and 60 pm or less can ensure film processability.

[0144] [Color coating layer]The film thickness of the color coating layer formed as necessary in the lamination film (H) of the present invention is preferably 10-50 pm, 10-40 pm is more preferable, and 15-30 pm is especially preferable. Concealment of the substrate can be ensured through adoption of a color coating layer film thickness of 10 pm or greater, and 50 pm or less can ensure film processability.

[0145] [Release layer]A release layer may if necessary be formed on the adhesive layer for the purpose of temporarily protecting the adhesive layer, which has been formed as the outermost layer of the lamination film (H) of the present invention, until immediately before use. There are no specific limitations as to the release layer, and a well- known release film can be used. For example, a film of e.g. a polyester, polyvinyl chloride, polyvinylidene chloride, or polyethylene terephthalate, a paper such as a high quality paper or glassine, or a laminate film formed from a high quality paper or glassine, etc. and a polyolefin, having undergone release treatment by coating thereof with e.g. a silicone resin or a fluorine resin on the surface in contact with the adhesive layer, is used as the release layer. The release layer thickness is preferably 10-200 pm, and more preferably 25-100 pm.

[0146] The peel strength of the release layer from the adhesive layer is preferably 0.5-8.0 N / 25 mm, and more preferably 0. 1-5.0 N / 25 mm. The release layer peels off smoothly when removed, through adoption of a peel strength of 0.5-8.0 N / 25 mm. Note that the peel strength of the release layer from the adhesive layer can be measured in accordance with the test method for 180-degree peel strength of adhesives in JIS K 6854-2:1999.

[0147] [Decorative article]There are no specific limitations as to the decorative article of the present invention, and examples of articles decorated using the lamination film (H) of the present invention include vehicle parts such as automobile bodies, bumpers, emblems, and vehicle exteriors and interiors; building materials and components such as wall materials, window glass, window frames, and bathroom wall materials; articles of daily use such as tableware, toys, and musical instruments; parts for household appliances such as vacuum cleaner housings, television housings, and air conditioner housings; interior components such as doors; and ship components. Among these, the decorative article of the present invention can improve both the design and durability of automobile bodies, bumpers, interior and exterior vehicle parts, and can be advantageously used therein.

[0148] The lamination film (H) of the present invention may be stretched to decorate an article. When stretched, the layers on the decorative article are thinner than the lamination film thickness prior to decoration. While there are no specific limitations as to the film thicknesses of the layers on the decorative article, the film thickness of the color coating layer formed as necessary is preferably 5-50 pm, and the cured clear coating layer (T) film thickness is preferably 5-60 pm. A decorative article with excellent pencil hardness, acid resistance, weather resistance, water resistance, and car wash scratch resistance can be obtained through adoption of said film thicknesses.[Examples]

[0149] The present invention is more specifically described on the basis of the following examples, but the following examples do not in any way limit the scope of protection. Unless otherwise noted, “parts” in the examples means “parts by mass,” and “%” in blending amounts and contents means “mass%”. Mw means mass average molecular weight, Tg means glass transition temperature, OHV means hydroxyl value, AVmeans acid value, and Me means molecular weight between crosslinking points.

[0150] <Synthesis of hydroxy group-containing (meth)acrylic resin (A) solutionh[Synthesis Example 1]While nitrogen gas was introduced into a four-mouthed flask equipped with a reflux condenser, a dropping funnel, a gas feed tube, a stirrer, and a thermometer, 73.6 parts of the solvent MEK were fed thereinto, and heated to 75° C with 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 fed into the dropping funnel, with dripping continued for three hours while maintaining the internal temperature at 75° C, and stirring was continued for a further 5 hours. After it had been confirmed by solid content measurement that the conversion rate had exceeded 98%, 60 parts of ethyl 3-ethoxypropionate (EEP) solvent were added. Thereafter, a hydroxy group-containing (meth)acrylic resin (A-l) solution was obtained by evaporating the MEK with a vacuum pump until the solid content reached 60%.

[0151] [Synthesis Examples 2-7]Hydroxy group-containing (meth)acrylic resin (A-2 to A-7) solutions were obtained by manufacturing methods similar to that for the hydroxy group-containing (meth)acrylic resin (A-l) solution, except that the compositions and blending amounts were changed to those shown in table 1.

[0152] [Table 1]Table 1

[0153] The full forms of the abbreviations from Table 1 are shown below.

[0154] ST: Styrene4HBA: 4-hydroxybutyl acrylateHPMA: 2-hydroxypropyl methacrylateMMA: Methyl methacrylate2EHA: 2-ethylhexyl acrylateCHMA: Cyclohexyl methacrylateAA: Acrylic acidMEK: Methyl ethyl ketoneAIBN: 2,2’-azobisisobutyronitrile

[0155] [Preparation Example 1][Preparation of two-component clear coating composition (CC-1)]100 parts of the hydroxy group-containing (meth)acrylic resin (A-l) solution, 0.01 parts of a catalyst (D-l), 6 parts of a polyester resin (C-l), 1 part of a light stabilizer (E-l), 1 part of a UV absorber (F-l), and 55.63 parts of ethyl 3-ethoxypropionate (EEP) as an organic solvent were measured out and stirred in a paint shaker until sufficiently uniform. Thereafter, the main agent for a two-component clear coating composition (CC-1) was prepared by removing coarse particles through filtration with a membrane filter having an aperture size of 200 pm. Then, immediately before use, 36 parts of an isocyanate curing agent (B-l) were added to the main agent, and the materials were thoroughly stirred in a dispersion mixer, to be used as the two-component clear coating composition (CC-1). The solid content (also referred to “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 CC-19)]Two-component clear coating compositions (CC-2 to CC-19) were prepared by a method similar to that in Preparation Example 1, except that the blending ratios were changed to those shown in Table 2.

[0157] [Table 2]

[0158] Details of the abbreviations from Table 2 are shown below.

[0159] Isocyanate curing agent (B-l): Duranate TPA-100 (trade name; manufactured by Asahi Kasei Corporation; mainly contains isocyanurate form)Isocyanate curing agent (B-2): Duranate TKA-100 (trade name; manufactured by Asahi Kasei Corporation; mainly contains isocyanurate form)Isocyanate curing agent (B-3): Duranate 24A-100 (trade name; manufactured by Asahi Kasei Corporation; mainly contains biuret form)Isocyanate curing agent (B-4): Duranate E402-80B (trade name; manufactured by Asahi Kasei Corporation; mainly contains adduct form)Polyester resin (C-l): K-FLEX 171-90 (trade name; manufactured by King Industries, Inc.)Polyester resin (C-2): K-FLEX A308 (trade name; manufactured by King Industries, Inc.)Catalyst (D-l): K-KAT XK-614 (trade name; manufactured by King Industries, Inc.)Catalyst (D-2): K-KAT 670 (trade name; manufactured by King Industries, Inc.)Light stabilizer (E-l): Eversorb 93 (trade name; manufactured by Everlight Chemical Industrial Corp.; hindered amine light stabilizer)UV absorber (F-l): Eversorb 40 (trade name; manufactured by Everlight Chemical Industrial Corp.; triazine UV absorber)Matting agent (G-l): Acematt TS-100 (trade name; manufactured by Evonik Industries AG; fine silica)

[0160] [Preparation of cured clear coating layer (T-l) as a free film]A release film GS (trade name; manufactured by Lintec Corporation) was coated with the two-component clear coating composition (CC-1) from Preparation Example 1, using an applicator, such that the dry film thickness was 30 pm. Next, the release film GS (trade name; manufactured by Lintec Corporation) was affixed to the upper surface of a coating film before drying so as to be closely bonded thereto. A cured clear coating layer (T-l) was obtained as a free film (i.e., a single-layer film) by heating and drying the film with a three-layer structure thus obtained, having a coating layer formed between release layers, for 4 days in an oven at 80° C, and thereafter removing the release layers.

[0161] [Preparation of cured clear coating layers (T-2 to T-l 9) as free films]Cured clear coating layers (T-2 to T-l 9) were prepared as free films by a method similar to that for the cured clear coating layer (T-l), using the two-component clear coating compositions (CC-2 to CC-19) from Preparation Examples 2-19.

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

[0163] [Example 1]Preparation of[Lamination Film (H-l-1)]A TPU film (TPU-1) was used as a substrate, and the surface of the substrate was coated with Primac No. 8650 Black (trade name; manufactured by BASF Japan Ltd.; one-component curable blocked isocyanate paint) as a color coating composition, on a horizontal table, using an applicator, such that the dry film thickness was 15 pm. After being left to stand for 5 minutes at room temperature, the color coating film thus obtained was coated with the two-component clear coating composition (CC-1), using an applicator, such that the dry film thickness was 30 pm, and heated and dried for 4 days in an oven at 80° C.

[0164] Next, the opposite side of the substrate was coated with SK Dyne 1310DT (trade name; manufactured by Soken Chemical Co., Ltd.), using an applicator, such that the dry film thickness was 100 pm, to form an adhesive layer. A lamination film (H-l-1) was obtained by laminating the release film GS (trade name; manufactured by Lintec Corporation) onto the adhesive layer thus obtained.

[0165] [Examples 2-5, 16-17] and[Comparative Examples 1-2]Preparation of[Lamination Films (H-l-2 to H-l-5, H-l-8 to H-l-9) and Comparative Lamination Films (H-l-6 to H-l-7)]The lamination films (H-l-2 to H-l-5 and H-l-8 to H-l-9), and comparative lamination films (H-l-6 to H-l-7) indicated in Table 3 were obtained by manufacturing methods similar to that for the lamination film (H-l-1), using two-component clear coating compositions (CC-2 to CC-5 and CC-16 to CC-19). The lamination films were used to perform the tests discussed below.

[0166] [Table 3]Table 3

[0167] Details of the abbreviations from Table 3 are shown below.

[0168] TPU film (TPU-1): DUS 601 (trade name; manufactured by Sheedom Co., Ltd., thickness 120 pm)TPU film (TPU-2): SHG 2393 (trade name; manufactured by Sheedom Co., Ltd., thickness 120 pm)TPU film (TPU-3): Black TPU film (manufactured by Zanchen New Materials Co., Ltd. in Guangzhou, China, thickness 125 pm)

[0169] [Example 6][Preparation of Lamination Film (H-2-1)]A TPU film (TPU-2) was used as a substrate, and the surface of the substrate was coated with a two- component clear coating composition (CC-6) on a horizontal table, using a laminator, such that the dry film thickness was 30 pm, and the back of the substrate was coated with Primac No. 8650 Black (trade name; manufactured by BASF Japan Ltd.; one-component curable blocked isocyanate paint) as a color coating composition such that the dry film thickness was 15 pm. Thereafter, drying was performed by heating in an oven for 4 days at 80° C. Next, an adhesive layer was formed by coating the color coating film thus obtained with SK Dyne 1310DT (trade name; manufactured by Soken Chemical Co., Ltd.), using an applicator, such that the dry film thickness was 100 pm. A laminated film (H-2-1) was obtained by laminating the release film GS (trade name; manufactured by Lintec Corporation) onto the adhesive layer thus obtained.

[0170] [Examples 7-10][Preparation of Lamination Films (H-2-2 to H-2-5)]The lamination films (H-2-2 to H-2-5) indicated in Table 3 were obtained by manufacturing methods similar to that for the lamination film (H-2-1), using two-component clear coating compositions (CC-7 to CC-10). The lamination films were used to perform the tests discussed below.

[0171] [Example 11][Preparation of Lamination Film (H-3-1)]A TPU film (TPU-3) was used as a substrate, and the surface of the substrate was coated with a two- component clear coating composition (CC-11) on a horizontal table, using an applicator, such that the dry film thickness was 30 pm. Thereafter, drying was performed by heating in an oven for 4 days at 80° C. Next, the opposite side of the substrate was coated with SK Dyne 1310DT (trade name; manufactured by Soken Chemical Co., Ltd.), using an applicator, such that the dry film thickness was 100 pm, to form an adhesive layer. A lamination film (H-3-1) was obtained by laminating the release film GS (trade name; manufactured by Lintec Corporation) onto the adhesive layer thus obtained.

[0172] [Examples 12-15][Preparation of Lamination Films (H-3-2 to H-2-5)]The lamination films (H-3-2 to H-3-5) indicated in Table 3 were obtained by manufacturing methods similar to that for the laminated film (H-3-1), using two-component clear coating compositions (CC-12 to CC-15). The lamination films were used to perform the tests discussed below.

[0173] [Comparative Example 3][Preparation of Comparative Lamination Film (H-4-1)]An unstretched polyvinyl chloride (PVC) film (PV-1), 200 pm in thickness, was used as the substrate. The surface of the substrate was coated with Primac No. 8650 Black (trade name; manufactured by BASF Japan Ltd.; one-component curable blocked isocyanate paint) as a color coating composition, on a horizontal table, using an applicator, such that the dry film thickness was 15 pm. After being left to stand for 5 minutes at room temperature, the color coating film thus obtained was coated with the two-component clear coating composition (CC-1), using an applicator, such that the dry film thickness was 30 pm, and heated and dried for 4 days in an oven at 80° C.

[0174] Next, the opposite side of the substrate was coated with SK Dyne 1310DT (trade name; manufactured by Soken Chemical Co., Ltd.), using an applicator, such that the dry film thickness was 100 pm, to form an adhesive layer. A comparative lamination film (H-4-1) was obtained by laminating a release film GS (trade name; manufactured by Lintec Corporation) onto the adhesive layer thus obtained.

[0175] [Comparative Example 4][Preparation of Comparative Lamination Film (H-5-1)]An unstretched polypropylene (PP) film (PP-1), 200 pm in thickness, was used as the substrate. The surface of the substrate was coated with Primac No. 8650 Black (trade name; manufactured by BASF Japan Ltd.; one-component curable blocked isocyanate paint) as a color coating composition, on a horizontal table, using an applicator, such that the dry film thickness was 15 pm. After being left to stand for 5 minutes at room temperature, the color coating film thus obtained was coated with the two-component clear coating composition (CC-1), using an applicator, such that the dry film thickness was 30 pm, and heated and dried for 4 days in an oven at 80° C.

[0176] Next, the opposite side of the substrate was coated with SK Dyne 1310DT (trade name; manufactured by Soken Chemical Co., Ltd.), using an applicator, such that the dry film thickness was 100 pm, to form an adhesive layer. A comparative lamination film (H-5-1) was obtained by laminating a release film GS (trade name; manufactured by Lintec Corporation) onto the adhesive layer thus obtained.

[0177] <Assessment>[Molecular weight between crosslinking points (Me)]Dynamic viscoelasticity (i.e. the storage elastic modulus (E’ ), loss elastic modulus (E’ ’), and loss tangent (tan 3 )) were measured under the abovementioned conditions, using the cured clear coating layers (T-l to T-19) obtained in Preparation Examples 1-17 and Comparative Preparation Examples 1-2, molecular weights between crosslinking points (Me) of the cured clear coating layer (T) were calculated using abovementioned Equation 2, and the results are summarized in Table 3 using the indicators listed below. The symbols O and A were defined as acceptable ranges.

[0178] O : 200<Mc<500A : 500<Mc<800X : M c < 2 0 0 or 8 0 0 <M c

[0179] [20-degree gloss value]The 20-degree gloss values on the cured clear coating layer sides of the lamination films (H-l-1 to H- 1-5 and H-l-8 to H-l-9), (H-2-1 to H-2-5), and (H-3-1 to H-3-5) in Examples 1-17 and the comparative lamination films (H-l-6 to H-l-7), (H-4-1), and (H-5-1) in Comparative Examples 1-4 were measured using a micro-TRI-gloss (trade name; manufactured by BYK-Gardner GmbH)

[0180] [Pencil hardness]The pencil hardnesses on the cured clear coating layer sides of the lamination films (H-l-1 to H-l-5 and H-l-8 to H-l-9), (H-2-1 to H-2-5), and (H-3-1 to H-3-5) in Examples 1-17 and the comparative lamination films (H-l-6 to H-l-7), (H-4-1), and (H-5-1) in Comparative Examples 1-4 were measured in accordance with ISO 15184:2020, and the results are summarized in Table 3 using the indicators listed below. The symbols ©, O, and A were defined as acceptable ranges.

[0181] © : 2B or harderO : 4B or harder, 3B or softerA : 6B or harder, 5B or softerX : Scratched with 6B

[0182] [Processability]The lamination films (H-l-1 to H-l-5 and H-l-8 to H-l-9), (H-2-1 to H-2-5), and (H-3-1 to H-3- 5) in Examples 1-17 and the comparative lamination films (H-l-6 to H-l-7), (H-4-1), and (H-5-1) in Comparative Examples 1-4 were cut to A4 size (210 mm long X 297 mm wide), and the release films were removed. Next, each lamination film was arranged with the cured clear coating layer side facing upward, so as to cover completely a rectangular mold 50 mm long X 50 mm wide by 10 mm high, and molded with a compressed air molding machine at a heating temperature of 60° C. The molded lamination film was then examined with a magnifying glass for cracks, and the results are summarized in Table 3 using the indicators listed below. The symbols ©, O, and A were defined as acceptable ranges.

[0183] © : No cracks at all were found.O : There were some cracks.A : There was moderate cracking.X : There were many cracks.

[0184] [Acid resistance]A 40% aqueous sulfuric acid solution was applied in 0.2 mL spots to the cured clear coating layer sides of the lamination films (H-l-1 to H-l-5 and H-l-8 to H-l-9), (H-2-1 to H-2-5), and (H-3-1 to H-3-5) in Examples 1-17 and the comparative lamination films (H-l-6 to H-l-7), (H-4-1), and (H-5-1) in Comparative Examples 1-4, and heated at 60° C for 15 minutes. Thereafter the lamination films were rinsed with water and visually examined as to degree of staining, and the results are summarized in Table 3 using the indicators listed below. The symbols ©, O, and A were defined as acceptable ranges.

[0185] © : Almost no change visibleO : Slight water staining visibleA : Usable despite visible stainingX : Conspicuous water staining visible, unusable

[0186] [Weather resistance]The cured clear coating layer sides of the lamination films (H-l-1 to H-l-5 and H-l-8 to H-l-9), (H- 2-1 to H-2-5), and (H-3-1 to H-3-5) in Examples 1-17 and the comparative lamination films (H-l-6 to H-l-7), (H-4-1), and (H-5-1) in Comparative Examples 1-4 were exposed to a sunshine carbon arc lamp accelerated weather resistance testing device (JIS B 7753:2007) for 3000 hours each. The lamination films were then visually examined in that state, and the results are summarized in Table 3 using the indicators listed below. The symbols ©, O, and A were defined as acceptable ranges.

[0187] © : Almost no change visibleO : Slight whitening or substrate peeling visibleA : Usable despite visible whitening or substrate peelingX : Conspicuous whitening or substrate peeling visible, unusable

[0188] [Water resistance]The lamination films (H-l-1 to H-l-5 and H-l-8 to H-l-9), (H-2-1 to H-2-5), and (H-3-1 to H-3- 5) in Examples 1-17 and the comparative lamination films (H-l-6 to H-l-7), (H-4-1), and (H-5-1) inComparative Examples 1-4 were immersed in warm water at 40° C for 240 hours. Thereafter the appearances (wrinkling, cracking, etc.) thereof were visually examined, and the results are summarized in Table 3 using the indicators listed below. The symbols ©, O, and A were defined as acceptable ranges.

[0189] © : Almost no change visibleO : Slight wrinkling and / or cracking visibleA : Usable despite visible wrinkling and / or crackingX : Conspicuous wrinkling and / or cracking visible, unusable

[0190] [Car wash scratch resistance]The lamination films (H-l-1 to H-l-5 and H-l-8 to H-l-9), (H-2-1 to H-2-5), and (H-3-1 to H-3- 5) in Examples 1-17 and the comparative lamination films (H-l-6 to H-l-7), (H-4-1), and (H-5-1) in Comparative Examples l-4were cut to 70 mm long X 150 mm wide. The cut lamination film test pieces were each arranged with the cured clear coating layer side facing upward, and after application of muddy water (mixed in a mass ratio of Test Powder Class 8 / water / neutral detergent = 10 / 99 / 1 per JIS Z 8901:2006) thereto with a brush, the test pieces were washed with a car wash brush in which 120 bundles of 30 nylon brushes, each 1 mm in thickness and 20 cm in length, per bundle were embedded uniformly into a cylindrical pipe with an outer diameter of 10 cm and a length of 15 cm, which was made rotate for 10 seconds at 150 rpm. In this test, each test piece was positioned 20 cm from the center of the cylindrical pipe. After cleaning by brush, the muddy water was completely rinsed off the test pieces under running water. Assessments were made after the abovementioned operation had been repeated 10 times.

[0191] The assessment was conducted by measuring the pre-test and post-test L values of the test pieces at an incidence angle of 0° and an acceptance angle of 10° to determine the difference in lightness ( A L). The results are summarized in Table 3 using the indicators listed below. The symbols ©, O, and A were defined as acceptable ranges.

[0192]

[0193] The invention as obtained by the present inventors is specifically described above on the basis of embodiments, but the embodiments do not in any way limit the invention, and needless to say, various changes could be made without departing from the gist thereof.[Industrial Applicability]

[0194] The lamination film in the invention of the present application has excellent pencil hardness, processability, acid resistance, weather resistance, water resistance, and car wash scratch resistance, and can therefore be used to decorate e.g. automobile bodies, bumpers, interior and exterior vehicle parts, building materials and components, articles of daily use, household appliances, interior components, and ship components, and among these, can be especially advantageously used to decorate automobile bodies, bumpers, and interior and exterior vehicle parts.[Key to Symbols]

[0195] 1 Cured clear coating layer (T)2 Transparent thermoplastic polyurethane (TPU) substrate3 Color coating layer4 Adhesive layerColor thermoplastic polyurethane (TPU) substrate

Claims

[Document Name] CLAIMS

1. A lamination film obtained by forming a cured clear coating layer (T) directly or indirectly on one surface of a thermoplastic polyurethane (TPU) substrate, using a two-component clear coating composition (CC), characterized in that the two-component clear coating composition (CC) comprises a hydroxy group- containing (meth)acrylic resin (A) with a theoretical glass transition temperature (Tg) of -50° C to 10° C 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 molecular weight between crosslinking points (Me) is 200-800 g / mol.

2. The lamination film as claimed in Claim 1, characterized in that an adhesive layer is additionally formed on an outermost layer on the surface of the thermoplastic polyurethane (TPU) substrate on the opposite side to the surface on which the cured clear coating layer (T) is formed.

3. The lamination film as claimed in Claim 1 or 2, characterized in that a color coating layer is formed on one surface of the thermoplastic polyurethane (TPU) substrate, and the cured clear coating layer (T) is formed on said color coating layer.

4. The lamination film as claimed in Claim 1 or 2, characterized in that a color coating layer is additionally formed on the surface of the thermoplastic polyurethane (TPU) substrate on the opposite side to the cured clear coating layer (T).

5. The lamination film as claimed in Claim 1 or 2, characterized in that the thermoplastic polyurethane (TPU) substrate contains a color pigment and / or luster pigment.

6. The lamination film as claimed in Claim 1 or 2, characterized in that the thickness of the thermoplastic polyurethane (TPU) substrate is 50-1000 pm.

7. The lamination film as claimed in Claim 1 or 2, characterized in that the two-component clear coating composition (CC) comprises a matting agent.

8. The lamination film as claimed in Claim 1 or 2, characterized in that a color coating layer is formed on one surface of the thermoplastic polyurethane (TPU) substrate, the cured clear coating layer (T) is formed on said color coating layer, and the color coating layer contains 10-200 parts by mass of a color pigment and / or 30 parts by mass or less of a luster pigment, based on 100 parts by mass of resin solids of the color coating layer.

9. The lamination film as claimed in Claim 1 or 2, characterized in that a color coating layer is additionally formed on the surface of the thermoplastic polyurethane (TPU) substrate on the opposite side to the cured clear coating layer (T), and the color coating layer contains 10-200 parts by mass of a color pigment and / or 30 parts by mass or less of a luster pigment, based on 100 parts by mass of resin solids of the color coating layer.

10. A decorative article decorated with the lamination film as claimed in Claim 1 or 2.

11. The decorative article as claimed in Claim 10, characterized in that a color coating layer is formed on one surface of the thermoplastic polyurethane (TPU) substrate, a cured clear coating layer (T) is formed on said color coating layer, the thickness of the color coating layer is 50 pm or less, and the thickness ofthe cured clear coating layer (T) is 60 pm or less.

12. The decorative article as claimed in Claim 10, characterized in that a color coating layer is additionally formed on the surface of the thermoplastic polyurethane (TPU) substrate on the opposite side to the cured clear coating layer (T), the thickness of the color coating layer is 50 pm or less, and the thickness of the cured clear coating layer (T) is 60 pm or less.

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