Thermoplastic resin film

Abstract

To provide a thermoplastic resin film suppressed in coloration or discoloration at the time of melt molding and excellent in initial weatherability and long-term weatherability.SOLUTION: The thermoplastic resin film of the present disclosure includes an acrylic resin composition layer formed of an acrylic resin composition (AR) including a (meth) acrylic resin (A) and an ultraviolet absorber (UVA), and the ultraviolet absorber (UVA) includes a first triazine-based ultraviolet absorber (TAX) in which one monophenyl group which may have a substituent and two biphenyl groups which may have a substituent are bonded to one triazine ring, and a second triazine-based ultraviolet absorber (TAY) in which three monophenyl groups which may have a substituent are bonded to one triazine ring.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to thermoplastic resin films. [Background technology]

[0002] Films for agricultural greenhouses require transparency and weather resistance. Conventionally, ethylene-tetrafluoroethylene copolymer (ETFE) films have been widely used as films for agricultural greenhouses. However, because ETFE films are fluorine-based resin films, they are expensive in terms of materials and are undesirable from an environmental perspective. Therefore, there is a demand for alternative materials that do not contain fluorine-based resins, are low-cost, and have a low environmental impact.

[0003] (Meth)acrylic resins are excellent in transparency, weather resistance, appearance, etc., and are used in a variety of applications. Among resins, (meth)acrylic resins have relatively high weather resistance. However, ultraviolet rays contained in sunlight cause resin degradation, so higher weather resistance is required for applications such as automotive exterior components, building materials, and agricultural materials. UV absorbers are examples of additives that improve weather resistance.

[0004] In Patent Document 1, the present applicant has described the following as a thermoplastic resin film that is excellent in transparency, weather resistance, antifouling properties, etc. and is suitable for use in agricultural greenhouses, etc.: a surface layer made of an acrylic resin composition containing a methacrylic resin, a rubber-like elastomer, and an ultraviolet absorber; a backing layer that is an antifouling resin layer containing a vinyl alcohol resin; The present invention discloses a thermoplastic resin film having an adhesive layer disposed between the front layer and the back layer, the adhesive layer containing a thermoplastic elastomer that is a block copolymer containing a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit, or a hydrogenated product thereof (claims 1 and 2). The ultraviolet absorber is preferably a benzotriazole-based ultraviolet absorber and / or a triazine-based ultraviolet absorber (claim 2). The rubber-like elastic material is preferably crosslinked rubber particles and / or an acrylic block copolymer (claim 3). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2022 / 019310 [Patent Document 2] Japanese Patent Publication No. 2020-179568 [Patent Document 3] Japanese Patent Publication No. 2022-61324 [Patent Document 4] International Publication No. 2018 / 062299 Summary of the Invention [Problem to be solved by the invention]

[0006] Acrylic resin compositions used in applications such as agricultural greenhouse films preferably have long-term weather resistance that allows them to maintain their ultraviolet blocking effect for a long period of time (for example, 5 years or more or 10 years or more). As a result of the inventors' investigations, it was found that with the thermoplastic resin film disclosed in Patent Document 1, the UV blocking effect of the surface layer may decrease after long-term use, and the adhesive layer and / or back layer may deteriorate. Increasing the amount of ultraviolet absorber added can improve the initial weather resistance and / or long-term weather resistance, but there is a risk of discoloration occurring during melt molding, in which a transparent resin is colored or a resin that has been colored to a desired color using a colorant changes color.

[0007] As techniques related to the present disclosure, Patent Documents 2 to 4 can be cited. Patent Document 2 discloses a decorative sheet using a curable composition containing, as a material for the surface protective layer, a methacrylic monomer, a hydroxyphenyltriazine ultraviolet absorber in which three phenyl groups, including a hydroxyphenyl group, are bonded to one triazine ring, and a curing agent (Claim 1, Example 1). Patent Document 3 discloses a methacrylic resin composition containing a methacrylic resin, a triazine ultraviolet absorber in which three monophenyl groups are bonded to one triazine ring, and a benzotriazole ultraviolet absorber (claims 1 and 3, paragraph 0045).

[0008] Patent Document 4 discloses a decorative sheet using a curable composition as a primer layer material, which contains a mixture of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol resin, an ultraviolet absorber in which one monophenyl group and two biphenyl groups are bonded to a triazine ring, an ultraviolet absorber in which three monophenyl groups are bonded to one triazine ring, and a curing agent (Claim 11, Example 1).

[0009] In Patent Document 3, a triazine-based ultraviolet absorber and a benzotriazole-based ultraviolet absorber are used in combination, but the benzotriazole-based ultraviolet absorber is easily consumed by ultraviolet absorption and does not have good long-term weather resistance. Patent Documents 2 and 3 do not disclose an ultraviolet absorber in which one monophenyl group and two biphenyl groups are bonded to a triazine ring, and do not disclose that a combination of a first triazine-based ultraviolet absorber in which one monophenyl group and two biphenyl groups are bonded to a triazine ring and a second triazine-based ultraviolet absorber in which three monophenyl groups are bonded to a triazine ring is preferable. In Patent Documents 2 and 4, a surface protection layer or a primer layer is formed by coating and curing a curable composition. In these documents, the surface protection layer or primer layer containing a triazine-based UV absorber is not a thermoplastic resin layer. Furthermore, it is difficult to increase the thickness of a surface protection layer or primer layer made of a cured product of a curable composition obtained by the methods described in these documents. If the amount of UV absorber is increased to improve initial weather resistance and / or long-term weather resistance, discoloration may occur during melt molding, in which a transparent resin is colored or a resin colored to a desired color using a colorant changes color.

[0010] The present disclosure has been made in view of the above circumstances, and aims to provide a thermoplastic resin film that is inhibited from coloring or discoloring during melt molding and has excellent initial weather resistance and long-term weather resistance. [Means for solving the problem]

[0011] The present disclosure provides the following thermoplastic resin films [1] to

[16] . [1] A thermoplastic resin film comprising an acrylic resin composition layer made of an acrylic resin composition (AR) containing a (meth)acrylic resin (A) and an ultraviolet absorber (UVA), A thermoplastic resin film, wherein the ultraviolet absorber (UVA) comprises a first triazine-based ultraviolet absorber (TAX) in which one monophenyl group, which may have a substituent, and two biphenyl groups, which may have a substituent, are bonded to one triazine ring, and a second triazine-based ultraviolet absorber (TAY) in which three monophenyl groups, which may have a substituent, are bonded to one triazine ring.

[0012] [2] The thermoplastic resin film of [1], wherein the total amount of the first triazine-based ultraviolet absorber (TAX) and the second triazine-based ultraviolet absorber (TAY) is 0.8 to 5.0 parts by mass per 100 parts by mass of the (meth)acrylic resin (A). [3] The thermoplastic resin film of [2], wherein the total amount of the first triazine-based ultraviolet absorber (TAX) is 0.4 to 2.5 parts by mass and the total amount of the second triazine-based ultraviolet absorber (TAY) is 0.4 to 2.5 parts by mass, relative to 100 parts by mass of the (meth)acrylic resin (A).

[0013] [4] The thermoplastic resin film according to any one of [1] to [3], which has a light transmittance of 0 to 0.3% at 314 nm. [5] The thermoplastic resin film according to any one of [1] to [4], which has a light transmittance of 0 to 0.3% at 275 nm. [6] The thermoplastic resin film according to any one of [1] to [5], which has a light transmittance of 0 to 0.3% at 350 nm.

[0014] [7] A thermoplastic resin film according to any one of [1] to [6], wherein the (meth)acrylic resin (A) comprises one or more methacrylic resins (M) and one or more rubber-like elastomers (R) selected from the group consisting of acrylic rubber particles (RP) and acrylic block copolymers (RB).

[0015] [8] A surface layer made of the acrylic resin composition layer; The thermoplastic resin film according to any one of [1] to [7], which has a backing layer different from the acrylic resin composition layer. [9] The thermoplastic resin film of [8], further comprising an intermediate layer between the surface layer and the back layer.

[10] The thermoplastic resin film according to [9], wherein the intermediate layer contains one or more thermoplastic elastomers (E) selected from the group consisting of block copolymers containing a polymer block (a) containing an aromatic vinyl compound unit and a polymer block (b) containing a conjugated diene compound unit, and hydrogenated products of the block copolymers.

[0016]

[11] The thermoplastic elastomer (E) is one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing a styrene unit and a polymer block (yb) containing a conjugated diene compound unit in which the total amount of 1,2-bonds and 3,4-bonds is 40% by mole or more, and hydrogenated products of the block copolymers; or The thermoplastic resin film according to

[10] , comprising one or more third thermoplastic elastomers (EZ) selected from the group consisting of block copolymers having a polymer block (za) containing an α-methylstyrene unit and a polymer block (zb) containing a conjugated diene compound unit in which the total amount of 1,2-bonds and 3,4-bonds is 40% by molar mass or more, and hydrogenated products of the block copolymers.

[0017]

[12] The thermoplastic elastomer (E) is one or more first thermoplastic elastomers (EX) selected from the group consisting of block copolymers having a polymer block (xa) containing a styrene unit and a polymer block (xb) containing a conjugated diene compound unit in which the total amount of 1,2-bonds and 3,4-bonds is less than 40% by mole, and hydrogenated products of the block copolymers; one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing a styrene unit and a polymer block (yb) containing a conjugated diene compound unit in which the total amount of 1,2-bonds and 3,4-bonds is 40% by mole or more, and hydrogenated products of the block copolymers; and The thermoplastic resin film according to

[11] , comprising one or more third thermoplastic elastomers (EZ) selected from the group consisting of block copolymers having a polymer block (za) containing an α-methylstyrene unit and a polymer block (zb) containing a conjugated diene compound unit in which the total amount of 1,2-bonds and 3,4-bonds is 40% by molar mass or more, and hydrogenated products of the block copolymers.

[0018]

[13] The thermoplastic resin film according to any one of

[10] to

[12] , wherein the intermediate layer further contains one or more polypropylene polymers (P).

[14] The thermoplastic resin film according to

[13] , wherein the polypropylene polymer (P) comprises one or more first polypropylene polymers (PX) having no polar group and one or more second polypropylene polymers (PY) having a polar group.

[0019]

[15] The thermoplastic resin film according to any one of [8] to

[14] , wherein the backing layer contains one or more vinyl alcohol resins (V) including an ethylene-vinyl alcohol copolymer having an ethylene unit content of 20 to 50 mol%.

[0020]

[16] The thermoplastic resin film according to any one of [8] to

[15] , having a total thickness of 20 to 500 μm, wherein the ratio of the thickness of the surface layer to the total thickness is 1 / 20 to 2 / 3, and the ratio of the thickness of the back layer to the total thickness is 1 / 20 to 2 / 3. [Effects of the Invention]

[0021] According to the present disclosure, it is possible to provide a thermoplastic resin film that is inhibited from coloring or discoloring during melt molding and that has excellent initial weather resistance and long-term weather resistance. [Brief explanation of the drawings]

[0022] [Figure 1] 1 is a schematic cross-sectional view of a thermoplastic resin film according to one embodiment of the present invention. [Figure 2] 1 shows the absorption spectra of ultraviolet absorbers (TAX1), (TAY1), and (BT1). DETAILED DESCRIPTION OF THE INVENTION

[0023] In this specification, unless otherwise specified, ultraviolet light (UV) is light in the wavelength range of 250 to 380 nm, infrared light (IR) is light in the wavelength range of 780 to 2500 nm, and visible light is light in the wavelength range of 380 to 780 nm. In this specification, unless otherwise specified, an "alkyl group having 3 or more carbon atoms" may be either linear or branched. In this specification, unless otherwise specified, compounds that have isomers include all isomers.

[0024] In this specification, unless otherwise specified, a "unit" contained in a polymer is a repeating unit contained in the polymer, and is a monomer unit derived from a raw material monomer or a derived unit derived from one or more types of monomer units. In this specification, (meth)acrylic is a general term for acrylic and methacrylic, and the same applies to (meth)acrylonitrile and the like.

[0025] In this specification, unless otherwise specified, the weight average molecular weight (Mw) of a (meth)acrylic resin is the weight average molecular weight (Mw) calculated as standard polymethyl methacrylate (PMMA) determined by gel permeation chromatography (GPC). The same applies to the number average molecular weight (Mn). In this specification, unless otherwise specified, the weight average molecular weight (Mw) of a resin other than a (meth)acrylic resin (such as a thermoplastic elastomer (E)) is a weight average molecular weight (Mw) calculated in terms of standard polystyrene as determined by gel permeation chromatography (GPC). The same applies to the number average molecular weight (Mn).

[0026] Generally, the terms "film," "sheet," or "plate" are used for thin film molded bodies depending on their thickness, but there is no clear definition and no clear distinction between them. In this specification, "film" includes "sheet."

[0027] [Thermoplastic resin film] The thermoplastic resin film of the present disclosure is The film includes an acrylic resin composition layer made of an acrylic resin composition (AR) containing one or more kinds of (meth)acrylic resins (A) and multiple kinds of ultraviolet absorbers (UVA).

[0028] The thermoplastic resin film of the first embodiment according to the present invention is a thermoplastic resin film having a single layer structure composed of the above acrylic resin composition layer.

[0029] The thermoplastic resin film of the second embodiment according to the present invention is a surface layer formed of the acrylic resin composition layer; The thermoplastic resin film has a laminated structure having the acrylic resin composition layer and a backing layer different from the acrylic resin composition layer. The backing layer can be made of various resin compositions, and is preferably made of a vinyl alcohol resin composition (VR) containing one or more vinyl alcohol resins (V).

[0030] The thermoplastic resin film of the third embodiment of the present invention has the configuration of the thermoplastic resin film of the second embodiment described above, and is a laminated thermoplastic resin film further having an intermediate layer between the front layer and the back layer. The intermediate layer can be made of various resin compositions, and is preferably made of an elastomer resin composition (ER) containing one or more thermoplastic elastomers (E) selected from the group consisting of block copolymers containing a polymer block (a) containing an aromatic vinyl compound unit and a polymer block (b) containing a conjugated diene compound unit, and hydrogenated products of the block copolymers.

[0031] The terms "front and back" in the thermoplastic resin film of the present disclosure are names used for convenience in distinguishing between the two sides of the thermoplastic resin film, and do not necessarily correspond to the "front and back" in actual use. The "front layer" can also be referred to as one front layer, and the "back layer" can also be referred to as the other front layer, and in actual use, the "front layer" can be used as the back side and the "back layer" can be used as the front side.

[0032] The thermoplastic resin film having a laminated structure according to the third embodiment will be described in detail below. Fig. 1 is a schematic cross-sectional view of the thermoplastic resin film having a laminated structure according to the third embodiment. In the drawing, reference numeral 1 denotes a thermoplastic resin film, reference numeral 11 denotes a surface layer, reference numeral 12 denotes a back layer, and reference numeral 13 denotes an intermediate layer. If necessary, one or more resin layers other than the intermediate layer 13 made of an elastomer resin composition (ER) may be provided between the surface layer 11 and the back layer 12.

[0033] (surface) The surface layer is made of an acrylic resin composition (AR) containing one or more (meth)acrylic resins (A) and multiple ultraviolet absorbers (UVA). The one or more (meth)acrylic resins (A) may contain one or more methacrylic resins (M) and one or more rubber-like elastomers (R) selected from the group consisting of acrylic rubber particles (RP) and acrylic block copolymers (RB). The acrylic resin composition (AR) can have a phase structure in which one or more types of rubber-like elastomer (R) are dispersed in a matrix resin containing one or more types of methacrylic resin (M). In general, the (meth)acrylic resin (A) has relatively high weather resistance among resins, and therefore, a surface layer made of an acrylic resin composition (AR) containing one or more (meth)acrylic resins (A) and multiple ultraviolet absorbers (UVA) has excellent weather resistance and can function as a weather-resistant resin layer. The surface layer containing one or more kinds of rubber-like elastomers (R) can have excellent flex resistance, impact resistance, and handling properties.

[0034] <Methacrylic resin (M)> The methacrylic resin (M) is a homopolymer or copolymer containing methyl methacrylate (MMA) units and may contain one or more other monomer units. The content of MMA units in the methacrylic resin (M) is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass. The content of other monomer units (total amount when multiple types are present) is preferably 0 to 20% by mass. The upper limit is more preferably 10% by mass.

[0035] Other monomers besides MMA include ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, methacrylic acid esters other than MMA, such as 2-hydroxyethyl acrylate, 2-ethoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate, cyclohexyl methacrylate, norbornenyl methacrylate, and isobornyl methacrylate; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, amyl acrylate, isoa acrylate, acrylic acid esters such as myrcene, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-ethoxyethyl acrylate, glycidyl acrylate, allyl acrylate, cyclohexyl acrylate, norbornenyl acrylate, and isobornyl acrylate; unsaturated carboxylic acids such as (meth)acrylic acid, maleic anhydride, maleic acid, and itaconic acid; olefins such as ethylene, propylene, 1-butene, isobutylene, and 1-octene; conjugated dienes such as butadiene, isoprene, and myrcene; aromatic vinyl compounds such as styrene (St), α-methylstyrene (αMSt), p-methylstyrene, and m-methylstyrene; (meth)acrylamide, (meth)acrylonitrile, vinyl acetate, vinylpyridine, vinyl ketone, vinyl chloride, vinylidene chloride, and vinylidene fluoride.

[0036] The stereoregularity of the methacrylic resin (M) is not particularly limited, and methacrylic resins having stereoregularity such as isotactic, heterotactic, and syndiotactic may be used. As the methacrylic resin (M), a modified methacrylic resin that has been modified by introducing a ring structure into the main chain may be used in place of a general methacrylic resin (also called an unmodified methacrylic resin) that does not have a ring structural unit in the main chain. A methacrylic resin having no ring structural unit in the main chain can be produced by (co)polymerizing a monomer (mixture) containing methyl methacrylate (MMA) and, if necessary, one or more other monomers, by a known method. Methods for producing a methacrylic resin having a ring structural unit in the main chain include a method of copolymerizing, by a known method, multiple types of monomers including methyl methacrylate (MMA), a monomer having a ring structure, and, if necessary, other monomers; and a method of (co)polymerizing, by a known method, a methacrylic resin containing an MMA unit but no ring structural unit, and then introducing a ring structure into the main chain to form a ring structural unit. Examples of polymerization methods for methacrylic resins include radical polymerization methods such as suspension polymerization, (continuous) bulk polymerization, solution polymerization, and emulsion polymerization; and anionic polymerization.

[0037] The weight average molecular weight (Mw) of the methacrylic resin (M) is not particularly limited, and from the viewpoints of impact resistance, toughness, melt fluidity, and moldability, it is preferably 30,000 to 180,000, more preferably 40,000 to 150,000, and particularly preferably 50,000 to 130,000.

[0038] In the present disclosure, one or more types of rubber-like elastomers (R) may include one or more types of acrylic rubber particles (RP). Acrylic rubber particles (RP) in the material stage before being melt-kneaded with one or more other components (also referred to as raw acrylic rubber particles (RP)) have an outermost layer consisting of one or more thermoplastic resin component layers (II), and can have one or more crosslinked rubber component layers (I) inside. In the acrylic rubber particles (RP) with such a core-shell structure, at least a portion of the outermost layer consisting of one or more thermoplastic resin component layers (II) can be dissolved in the matrix resin of the acrylic resin composition (AR) and become a component of the matrix resin. At least a portion of the outermost layer consisting of one or more thermoplastic resin component layers (II) of the acrylic rubber particles (RP) that is dissolved in the matrix resin can contain a methacrylic resin. In this case, this methacrylic resin is included in the methacrylic resin (M) referred to in this specification.

[0039] To prevent deterioration in handling due to adhesion between acrylic rubber particles (RP) and deterioration in impact resistance due to poor dispersion during melt-kneading, the acrylic rubber particles (RP) can be used in the form of a latex or powder containing the acrylic rubber particles (RP) and a dispersant (D). As the dispersant (D), for example, methacrylic resin particles with a particle size smaller than that of the acrylic rubber particles (RP) can be used. The acrylic resin composition (AR) may also contain a polymer processing aid (PA) as an additive to improve molding processability. Polymer particles having a particle size of 0.05 to 0.5 μm, produced by emulsion polymerization, are preferably used as the polymer processing aid (PA). The polymer processing aid (PA) may be methacrylic resin particles. When the acrylic resin composition (AR) contains, as additives, a dispersant (D) made of a methacrylic resin and / or a polymer processing aid (PA) made of a methacrylic resin, these additives made of a methacrylic resin are included in the methacrylic resin (M) referred to in this specification.

[0040] The methacrylic resin (M) contained in the acrylic resin composition (AR) is It is composed of one or more thermoplastic resin component layers (II) of acrylic rubber particles (RP) that are compatible with a matrix resin, and at least a part of the outermost layer contains a methacrylic resin, a dispersing agent (D) made of a methacrylic resin, a polymer processing aid (PA) made of a methacrylic resin, or a combination thereof, It consists of one or more thermoplastic resin component layers of acrylic rubber particles (RP) that are compatible with the matrix resin, and can consist of at least a portion of the outermost layer containing a methacrylic resin, a dispersant (D) made of a methacrylic resin, a polymer processing aid (PA) made of a methacrylic resin, or a combination thereof.

[0041] The total amount of the matrix resin including the methacrylic resin (M) in 100% by mass of the acrylic resin composition (AR) is preferably 30 to 54% by mass. The lower limit is preferably 35% by mass. The upper limit is preferably 45% by mass. The content of the methacrylic resin (M) in 100% by mass of the matrix resin is preferably 50 to 100% by mass, and the lower limit is more preferably 60% by mass, even more preferably 70% by mass, particularly preferably 70% by mass, and most preferably 90% by mass.

[0042] <Acrylic rubber particles (RP)> In the present disclosure, one or more types of rubber-like elastomer (R) may contain one or more types of acrylic rubber particles (RP). The acrylic rubber particles (RP) in the material stage before being melt-kneaded with one or more other components (material acrylic rubber particles (RP)) may be multi-layered polymer particles with a core-shell structure having an outermost layer made of one or more thermoplastic resin component layers (II) and one or more cross-linked rubber component layers (I) inside. In the acrylic rubber particles (RP) with a core-shell structure, the center core at the center is considered to be a "layer." The number of layers of the acrylic rubber particles (RP) is preferably 2 to 4. Examples of the layer structure include, from the center, a two-layer structure of layer (I)-layer (II); a three-layer structure of layer (I)-layer (I)-layer (II), layer (I)-layer (II)-layer (II), or layer (II)-layer (I)-layer (II); and a four-layer structure such as layer (I)-layer (II)-layer (I)-layer (II). Among these, a two-layer structure of layer (I)-layer (II) and a three-layer structure of layer (I)-layer (I)-layer (II) or layer (II)-layer (I)-layer (II) are preferred.

[0043] For example, in the case of acrylic rubber particles (RP) having a three-layer structure of Layer (I)-Layer (I)-Layer (II) or Layer (II)-Layer (I)-Layer (II), typically, in the acrylic resin composition (AR), a portion of the outermost layer (the third layer from the center, Layer (II)) is compatible with the matrix resin and becomes a component of the matrix resin, while a portion of the innermost layer remains connected to the second layer from the center (Layer (I)). When a methacrylic resin is included in the outermost layer of the acrylic rubber particles (RP) that is compatible with the matrix resin, this methacrylic resin is included in the methacrylic resin (M) referred to in this specification.

[0044] The mass ratio (layer (I) / layer (II)) of the total amount of the crosslinked rubber component layers (I) to the total amount of the thermoplastic resin component layers (II) is preferably 30 / 70 to 90 / 10. If the proportion of layer (I) is less than the above range, the flexibility of the acrylic resin composition (AR) may be insufficient. If the proportion of layer (I) is more than the above range, it may be difficult to form a particle structure, and the melt fluidity of the acrylic rubber particles (RP) may decrease, making it difficult to melt-knead with other components and to mold the acrylic resin composition (AR). The mass ratio (layer (I) / layer (II)) is more preferably 50 / 50 to 90 / 10, and particularly preferably 60 / 40 to 80 / 20.

[0045] From the viewpoints of the rubber elasticity of the acrylic rubber particles (RP) and the ease of forming a layer structure of the acrylic rubber particles (RP), layer (I) preferably comprises a copolymer consisting of 50 to 99.99 mass% of acrylic acid ester monomer units, 49.99 to 0 mass% of other monofunctional monomer units, and 0.15 to 10 mass% of polyfunctional monomer units. The content of the acrylic acid ester monomer units is preferably 55 to 99.9 mass%, the content of the other monofunctional monomer units is preferably 44.9 to 0 mass%, and the content of the polyfunctional monomer units is preferably 0.16 to 2 mass%. This copolymer preferably contains 1 mass% or more of the other monomer units.

[0046] The raw material monomers for the layer (I) will be explained below. As the acrylic acid ester, one or more known acrylic acid esters can be used. A polyfunctional monomer is a monomer having two or more carbon-carbon double bonds in the molecule. Examples of polyfunctional monomers include esters of unsaturated monocarboxylic acids, such as (meth)acrylic acid and cinnamic acid, with unsaturated alcohols, such as (meth)allyl alcohol; diesters of unsaturated monocarboxylic acids with glycols, such as ethylene glycol, butanediol, and hexanediol; and esters of dicarboxylic acids, such as phthalic acid, terephthalic acid, isophthalic acid, and maleic acid, with unsaturated alcohols. Specific examples include allyl acrylate, methallyl acrylate, allyl methacrylate (ALMA), methallyl methacrylate, (meth)allyl cinnamate, diallyl maleate, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, divinylbenzene, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, and hexanediol di(meth)acrylate. Among these, allyl methacrylate (ALMA) is preferred. Other monofunctional monomers include methacrylic acid esters, aromatic vinyl monomers, and vinyl cyanide monomers.

[0047] From the viewpoint of compatibility between the acrylic rubber particles (RP) and other components, the layer (II) preferably comprises a (co)polymer consisting of 40 to 100% by mass of methacrylate ester units and 60 to 0% by mass of other monomer units. This (co)polymer preferably contains other monomer units. The content of the methacrylate ester units is preferably 60 to 99% by mass, more preferably 80 to 99% by mass, and the content of the other monomer units is preferably 40 to 1% by mass, more preferably 20 to 1% by mass.

[0048] The raw material monomers for the layer (II) will be explained below. As the methacrylic acid ester, one or more known methacrylic acid esters can be used, and methyl methacrylate (MMA) and the like are preferred. Examples of other monomers include acrylic esters, aromatic vinyl monomers, vinyl cyanide monomers, maleimide monomers such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-(p-bromophenyl)maleimide, and N-(chlorophenyl)maleimide, and the polyfunctional monomers exemplified for layer (I). Among the acrylic esters, aromatic vinyl monomers, and vinyl cyanide monomers, alkyl acrylate esters such as methyl acrylate (MA), ethyl acrylate, and n-butyl acrylate (BA) are preferred.

[0049] From the viewpoints of physical properties and ease of production, the acrylic rubber particles (RP) are preferably acrylic rubber particles (RP) having a three-layer structure consisting of, from the center, a crosslinked rubber component layer (Ia) which is the first crosslinked rubber component layer (I), a crosslinked rubber component layer (Ib) which is the second crosslinked rubber component layer (I), and a thermoplastic resin component layer (II). The mass ratio ((Ia) / (Ib)) of the crosslinked rubber component layer (Ia) to the crosslinked rubber component layer (Ib) is preferably 5 / 95 to 95 / 5, more preferably 20 / 80 to 80 / 20.

[0050] The method for producing the acrylic rubber particles (RP) can include a polymerization reaction step (S1) for forming a crosslinked rubber component layer (I) and a polymerization reaction step (S2) for forming a thermoplastic resin component layer (II). In the polymerization reaction step (S1), a monomer mixture (i) corresponding to the copolymer composition of the crosslinked rubber component layer (I) is copolymerized by a known method. Similarly, in the polymerization reaction step (S2), a monomer (mixture) (ii) corresponding to the (co)polymer composition of the thermoplastic resin component layer (II) is (co)polymerized by a known method. In the polymerization reaction step (S2), a molecular weight modifier can be used in an amount of 0.4 to 10% by mass, more preferably 0.4 to 5% by mass, and particularly preferably 0.6 to 2% by mass, relative to the monomer (mixture) (ii). Examples of molecular weight modifiers include mercaptans such as n-octyl mercaptan (n-OM), t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and mercaptoethanol; terpene mixtures consisting of terpinolene, dipentene, t-terpinene, and small amounts of other cyclic terpenes; and halogenated hydrocarbons such as chloroform and carbon tetrachloride. Among these, alkyl mercaptans such as n-octyl mercaptan (n-OM) are preferred.

[0051] The polymerization method for the acrylic rubber particles (RP) is not particularly limited, and examples thereof include emulsion polymerization, suspension emulsion polymerization, solution polymerization, and combinations thereof. As an example, suitable polymerization conditions for the acrylic rubber particles (RP) by emulsion polymerization will be described below. The polymerization temperature is generally 0 to 100°C. Examples of emulsifiers include alkali metal salts of fatty acids such as sodium oleate, sodium laurate, and sodium stearate; sulfate salts of fatty alcohols such as sodium lauryl sulfate; rosinate salts such as potassium rosinate; and alkylarylsulfonic acids such as dodecylbenzenesulfonic acid. The polymerization initiator is generally a radical polymerization initiator. As the radical polymerization initiator, peroxides such as persulfates, azobisisobutyronitrile, and benzoyl peroxide can be used alone. Redox initiators that combine organic hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, and paramenthane hydroperoxide with a reducing agent such as a transition metal salt can also be used. The average particle size of the acrylic rubber particles (RP) can be controlled within a preferred range by adjusting the polymerization conditions such as the amount of emulsifier added. After the polymerization is completed, the acrylic rubber particles (RP) can be separated from the reaction system by known methods such as acid precipitation, salting out, spray drying, and freeze-coagulation.

[0052] As described above, in the acrylic rubber particles (RP) having a core-shell structure, at least a portion of the outermost layer, which is made up of one or more thermoplastic resin component layers (II), is compatible with the matrix resin in the acrylic resin composition (AR) and can become one component of the matrix resin. Therefore, unless otherwise specified, in this disclosure, the average particle size of the acrylic rubber particles (RP) is taken as the average particle size data of the layer from the center to the outermost crosslinked rubber component layer (I) that is not compatible with the matrix resin. For example, in a two-layer structure of layer (I)-layer (II) from the center, and a three-layer structure of layer (I)-layer (II)-layer (II) from the center, the "outermost cross-linked rubber component layer (I)" is the first layer (first layer) from the center. In a three-layer structure of layer (I)-layer (I)-layer (II) and layer (II)-layer (I)-layer (II) from the center, the "outermost cross-linked rubber component layer (I)" is the second layer (second layer) from the center. In a four-layer structure of layer (I)-layer (II)-layer (I)-layer (II) from the center, the "outermost cross-linked rubber component layer (I)" is the third layer (third layer) from the center.

[0053] The crosslinked rubber component layer (I) contained in the acrylic rubber particles (RP) can be selectively electron-stained using phosphotungstic acid, ruthenium tetroxide, or the like. By electron-staining the crosslinked rubber component layer (I) of the acrylic rubber particles (RP) contained in the thermoplastic resin film of the present disclosure and observing an electron microscope image (preferably a transmission electron microscope image (TEM)), it is possible to identify the portion from the center of any one acrylic rubber particle (RP) to the outermost crosslinked rubber component layer (I). The diameter of this portion is determined as the particle size. Note that when the particle shape is non-circular, the particle size is the average of the major axis diameter and minor axis diameter of the portion from the center of the acrylic rubber particle (RP) to the outermost crosslinked rubber component layer (I). In this specification, unless otherwise specified, the "average particle size from the center to the outermost crosslinked rubber component layer (I)" refers to the average particle size (number average particle size) from the center to the outermost crosslinked rubber component layer (I) of 30 randomly selected acrylic rubber particles (RP). The volume average particle size (D50, median size) of the acrylic rubber particles (RP) in the latex can be measured by dynamic light scattering using a laser diffraction / scattering particle size distribution measuring device or the like.

[0054] In the acrylic resin composition (AR), the one or more acrylic rubber particles (RP) may comprise one or more first acrylic rubber particles (RP-S) which contain one or more crosslinked rubber component layers (I) and have an average particle diameter from the center to the outermost crosslinked rubber component layer of 50 nm or more and less than 160 nm, and / or one or more second acrylic rubber particles (RP-L) which contain one or more crosslinked rubber component layers (I) and have an average particle diameter from the center to the outermost crosslinked rubber component layer of 160 nm or more and 300 nm or less.

[0055] The lower limit of the average particle diameter from the center of the first acrylic rubber particle (RP-S) to the outermost crosslinked rubber component layer is more preferably 60 nm, even more preferably 70 nm, particularly preferably 80 nm, and most preferably 90 nm, and the upper limit is more preferably 155 nm, even more preferably 150 nm, even more preferably 140 nm, particularly preferably 130 nm, and most preferably 120 nm. The lower limit of the average particle diameter from the center of the second acrylic rubber particle (RP-L) to the outermost crosslinked rubber component layer is more preferably 170 nm, even more preferably 180 nm, particularly preferably 190 nm, and most preferably 200 nm.The upper limit is more preferably 290 nm, even more preferably 280 nm, even more preferably 270 nm, particularly preferably 260 nm, and most preferably 250 nm.

[0056] <Acrylic block copolymer (RB)> The one or more rubber-like elastomers (R) may include one or more acrylic block copolymers (RB) containing a methacrylic polymer block (mb) and an acrylic polymer block (ab).

[0057] The methacrylic polymer block (mb) is a polymer block that mainly contains methacrylic acid ester units and optionally contains other monomer units. The content of the methacrylic acid ester units in the methacrylic polymer block (mb) is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, particularly preferably 95% by mass, and most preferably 98% by mass. As the methacrylic acid ester, one or more known methacrylic acid esters can be used. From the viewpoints of transparency and heat resistance, methacrylic acid alkyl esters such as MMA, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate are preferred, and MMA is more preferred.

[0058] The content of other monomer units than the methacrylic acid ester units, which are optionally contained in the methacrylic polymer block (mb), is preferably 0 to 20% by mass, with the upper limit being more preferably 10% by mass, particularly preferably 5% by mass, and most preferably 2% by mass. Examples of the monomer other than the methacrylic acid ester include an acrylic acid ester, an unsaturated carboxylic acid, an aromatic vinyl monomer, an olefin, a conjugated diene, (meth)acrylonitrile, (meth)acrylamide, vinyl acetate, vinylpyridine, vinyl ketone, vinyl chloride, vinylidene chloride, and vinylidene fluoride.

[0059] The weight average molecular weight (Mw) of the methacrylic polymer block (mb) is not particularly limited, and is preferably 5,000 to 150,000, more preferably 8,000 to 120,000, and particularly preferably 12,000 to 100,000. When the acrylic block copolymer (RB) contains a plurality of methacrylic polymer blocks (mb), the monomer compositions and molecular weights of these blocks may be the same or different.

[0060] The acrylic polymer block (ab) is a polymer block that mainly contains acrylic ester units and optionally contains other monomer units. The content of the acrylic ester units in the acrylic polymer block (ab) is preferably 45 to 100% by mass. The lower limit is more preferably 50% by mass, particularly preferably 60% by mass, and most preferably 90% by mass.

[0061] One or more known acrylic esters can be used, and it is preferable that the acrylic ester contains an alkyl acrylate unit and an aromatic (meth)acrylate unit. Examples of alkyl acrylate esters include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and dodecyl acrylate. Of these, n-butyl acrylate and 2-ethylhexyl acrylate are preferred. The aromatic (meth)acrylate ester is an ester of an aromatic acrylate or aromatic methacrylate with a compound containing an aromatic ring. Examples include phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and styryl (meth)acrylate. Of these, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and benzyl acrylate are preferred. In the acrylic polymer block (ab), the content of the acrylic acid alkyl ester unit is preferably 50 to 90 mass %, more preferably 60 to 80 mass %, and the content of the (meth)acrylic acid aromatic ester unit is preferably 50 to 10 mass %, more preferably 40 to 20 mass %.

[0062] The content of other monomer units than acrylic acid esters, which may be optionally contained in the acrylic polymer block (ab), is preferably 0 to 55% by mass, with the upper limit being more preferably 50% by mass, particularly preferably 40% by mass, and most preferably 10% by mass. Examples of other monomers besides acrylic acid esters include methacrylic acid esters, unsaturated carboxylic acids, aromatic vinyl monomers, olefins, conjugated dienes, (meth)acrylonitrile, (meth)acrylamide, vinyl acetate, vinylpyridine, vinyl ketone, vinyl chloride, vinylidene chloride, and vinylidene fluoride.

[0063] The weight average molecular weight (Mw) of the acrylic polymer block (ab) is not particularly limited, and is preferably 5,000 to 120,000, more preferably 15,000 to 110,000, and particularly preferably 30,000 to 100,000. When the acrylic block copolymer (RB) contains a plurality of acrylic polymer blocks (ab), the monomer compositions and molecular weights of these blocks may be the same or different.

[0064] <Ultraviolet absorber (UVA)> The acrylic resin composition (AR) contains multiple types of ultraviolet absorbers (UVA), such as triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, benzodithiol-based ultraviolet absorbers, azomethine-based ultraviolet absorbers, indole-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, oxalic acid anilide-based ultraviolet absorbers, malonic acid ester-based ultraviolet absorbers, and formamidine-based ultraviolet absorbers.

[0065] Examples of triazine-based ultraviolet absorbers include 2-[4,6-bis(1,1'-biphenyl-4-yl)-1,3,5-triazin-2-yl]-5-[(2-ethylhexyl)oxy]phenol (e.g., "Tinuvin 1600" manufactured by BASF), isooctyl 2-[4-[4,6-bis(1,1'-biphenyl-4-yl)-1,3,5-triazin-2-yl]-3-hydroxyphenoxy]propanoate (e.g., "Tinuvin 479" manufactured by BASF), and 2-[4,6-diphenyl-1,3,5-triazin-2-yl]-5-(hexyloxy)phenol (e.g., "Tinuvin 1600" manufactured by BASF). 1577ED"), 2,4-bis(2,4-dibenzotriazole)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine (e.g., "CYASORB UV-1164" manufactured by Sun Chemical), 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (e.g., "ADEKA STAB LA-46" manufactured by ADEKA), a mixture of a reaction product of 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hydroxyphenyl with oxirane [(C10-C16 alkyloxy)methyl]oxirane (85%) and 1-methoxy-2-propanol (15%) (e.g., "Tinuvin" manufactured by BASF), 400"), a reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester (for example, "Tinuvin 405" manufactured by BASF), 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-triazine (for example, "Tinuvin 460" manufactured by BASF), and other triazine-based ultraviolet absorbers (for example, "Tinuvin 477" manufactured by BASF).

[0066] Examples of the benzotriazole-based ultraviolet absorber include 2-(2H-benzotriazol-2-yl)-4-t-butylphenol (e.g., "Eversorb 70" manufactured by Everlight Chemical Co.), 2-(3'-t-butyl-2'-hydroxy-5'-benzotriazole)-5-chlorobenzotriazole (e.g., "Eversorb 73" manufactured by Everlight Chemical Co.), 2-(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole (e.g., "Eversorb 74" manufactured by Everlight Chemical Co.), 2-[2'-hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole (e.g., "Eversorb 76" manufactured by Everlight Chemical Co.), and 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (e.g., "ADEKA STAB" manufactured by ADEKA Corporation). LA-29), 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (e.g., ADEKA "ADK STAB LA-31"), 2-(2H-benzotriazol-2-yl)-p-cresol (e.g., ADEKA "ADK STAB LA-32"), 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chloro-benzotriazole (e.g., "Eversorb 75" manufactured by Everlight Chemical Co.), a mixture of octyl-3-[3-t-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethylhexyl-3-[3-t-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate (e.g., "Eversorb 109" manufactured by Everlight Chemical Co.), other benzotriazole-based UV absorbers (e.g., "Eversorb 77," "Eversorb 79," "Eversorb 88," and "Eversorb 89" manufactured by Everlight Chemical Co., Ltd., "Tinuvin 326," and "Tinuvin 571" manufactured by BASF, "DAINSORB T-7," "DAINSORB T-0," and "DAINSORB T-10" manufactured by Daiwa Kasei Co., Ltd.), Examples include "DAINSORB T-52", "DAINSORB T-53", and "SEESORB 701" manufactured by Shipro Kasei Co., Ltd.

[0067] In the present disclosure, the multiple types of ultraviolet absorbers (UVA) include a first triazine-based ultraviolet absorber (TAX) in which one monophenyl group, which may have a substituent, and two biphenyl groups, which may have a substituent, are bonded to one triazine ring, and a second triazine-based ultraviolet absorber (TAY) in which three monophenyl groups, which may have a substituent, are bonded to one triazine ring. The monophenyl group contained in the first triazine-based ultraviolet absorber (TAX) can be a phenol group. At least one of the three monophenyl groups contained in the second triazine-based ultraviolet absorber (TAY) can be a phenol group.

[0068] In the first triazine-based ultraviolet absorber (TAX) and the second triazine-based ultraviolet absorber (TAY), examples of the substituent that the monophenyl group or biphenyl group may have include alkyl groups (e.g., methyl, ethyl, propyl, butyl, hexyl, and octyl groups), groups of the general formula -OR (where R is any organic group, e.g., alkyl groups, carbonyl groups, carboxylic acid ester groups, sulfonic acid ester groups, and phosphate ester groups), amide groups, amino groups, sulfide groups, hydroxyl groups, and halogen atoms. The alkyl groups may be linear, branched, or cyclic.

[0069] The first triazine-based ultraviolet absorber (TAX) includes a triazine-based ultraviolet absorber (TAXR) represented by the following formula: [ka] (TAXR)

[0070] In the triazine-based ultraviolet absorber (TAXR), R is any organic group, such as an alkyl group, a carbonyl group, a carboxylic acid ester group, a sulfonic acid ester group, and a phosphate ester group. Alkyl groups and carboxylic acid ester groups are preferred.

[0071] Specific examples of the first triazine-based ultraviolet absorber (TAX) include: (TAX1) 2-[4,6-bis(1,1'-biphenyl-4-yl)-1,3,5-triazin-2-yl]-5-[(2-ethylhexyl)oxy]phenol (e.g., "Tinuvin 1600" manufactured by BASF), (TAX2) isooctyl 2-[4-[4,6-bis(1,1'-biphenyl-4-yl)-1,3,5-triazin-2-yl]-3-hydroxyphenoxy]propanoate (for example, "Tinuvin 479" manufactured by BASF) and the like. Their chemical structures are shown below.

[0072] [ka] (TAX1)

[0073] [ka] (TAX2)

[0074] The second triazine-based ultraviolet absorber (TAY) includes a triazine-based ultraviolet absorber (TAYR) represented by the following formula: [ka] (TAYR)

[0075] In the triazine-based ultraviolet absorber (TAYR), R is any organic group, such as an alkyl group, a carbonyl group, a carboxylic acid ester group, a sulfonic acid ester group, and a phosphate ester group. Alkyl groups and carboxylic acid ester groups are preferred.

[0076] It should be noted that R contained in the triazine-based ultraviolet absorber (TAXR) and R contained in the triazine-based ultraviolet absorber (TAYR) can be selected independently.

[0077] Specific examples of the second triazine-based ultraviolet absorber (TAY) include: (TAY1) 2-[4,6-diphenyl-1,3,5-triazin-2-yl]-5-(hexyloxy)phenol (e.g., "Tinuvin 1577ED" manufactured by BASF), (TAY2) 2-[4,6-diphenyl-1,3,5-triazin-2-yl]-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (for example, "LA-46" manufactured by ADEKA Corporation) and the like. Their chemical structures are shown below.

[0078] [ka] (TAY1)

[0079] [ka] (TAY2)

[0080] The first triazine-based ultraviolet absorber (TAX) has a large absorption peak in the wavelength region of 250 to 400 nm, and has high absorbance in a wide range of about 290 to about 350 nm (for example, absorbance of 0.50 or more or 0.6 or more), and the absorption peak wavelength (the wavelength at which the absorbance is maximum) can be 300 to 340 nm (see the absorption spectrum of the ultraviolet absorber (TAX1) in Figure 2). The second triazine-based ultraviolet absorber (TAY) has a large absorption peak in the wavelength region of 250 to 330 nm, and has high absorbance in the range of about 250 to about 300 nm (for example, absorbance of 0.50 or more or 0.6 or more), and the absorption peak wavelength (the wavelength at which the absorbance is maximum) can be 250 to 300 nm (see the absorption spectrum of the ultraviolet absorber (TAY1) in Figure 2).

[0081] The first triazine-based ultraviolet absorber (TAX) and the second triazine-based ultraviolet absorber (TAY) have different absorption peak wavelengths and can be complementary to each other. When the first triazine-based ultraviolet absorber (TAX) and the second triazine-based ultraviolet absorber (TAY) are used in combination, the second triazine-based ultraviolet absorber (TAY) can absorb light in the low wavelength range where the absorbance of the first triazine-based ultraviolet absorber (TAX) alone is low, and high absorbance (for example, absorbance of 0.50 or more or 0.60 or more) can be achieved in a wide range from 250 to 350 nm.

[0082] Generally, if the amount of ultraviolet absorber in a resin composition is increased in order to improve the initial weather resistance and / or long-term weather resistance, there is a risk of discoloration occurring during melt molding, in which a transparent resin is colored or a resin colored to a desired color using a colorant changes color. The thermoplastic resin film of the present disclosure, having a single-layer structure or a laminate structure, including an acrylic resin composition layer made of an acrylic resin composition (AR) containing a first triazine-based ultraviolet absorber (TAX) and a second triazine-based ultraviolet absorber (TAY), can improve initial weather resistance and long-term weather resistance without increasing the total amount of ultraviolet absorber (UVA) in the acrylic resin composition (AR). Since the total amount of ultraviolet absorber (UVA) in the acrylic resin composition (AR) does not need to be increased, coloring or discoloration during melt molding can be suppressed.

[0083] From the viewpoints of initial weather resistance, long-term weather resistance, and prevention of coloring or discoloration during melt molding, the total amount of the first triazine ultraviolet absorber (TAX) and the second triazine ultraviolet absorber (TAY) is preferably 0.8 to 5.0 parts by mass per 100 parts by mass of the total amount of (meth)acrylic resin (A) (for example, 100 parts by mass of the total amount of methacrylic resin (M) and rubber-like elastomer (R)). The lower limit is more preferably 0.9 parts by mass, and particularly preferably 1.0 part by mass. The upper limit is more preferably 4.5 parts by mass, and particularly preferably 4.2 parts by mass.

[0084] The total amount of the first triazine ultraviolet absorber (TAX) is preferably 0.4 to 2.5 parts by mass relative to 100 parts by mass of the (meth)acrylic resin (A). The lower limit is more preferably 0.45 parts by mass, and particularly preferably 0.5 parts by mass. The upper limit is more preferably 2.25 parts by mass, and particularly preferably 2.1 parts by mass. The total amount of the second triazine ultraviolet absorber (TAY) is preferably 0.4 to 2.5 parts by mass relative to 100 parts by mass of the (meth)acrylic resin (A), with the upper limit being more preferably 2.25 parts by mass, and particularly preferably 2.1 parts by mass.

[0085] The ratio (mass ratio) of the total amount of the first triazine-based ultraviolet absorber (TAX) to the total amount of the second triazine-based ultraviolet absorber (TAY) is preferably 0.16 to 6.25. The lower limit is more preferably 0.2, even more preferably 0.5, and particularly preferably 0.8. The upper limit is more preferably 6.0, even more preferably 5.0, even more preferably 4.0, even more preferably 3.0, even more preferably 2.0, even more preferably 1.5, and particularly preferably 1.2. The ratio (mass ratio) of the total amount of the first triazine-based ultraviolet absorber (TAX) to the total amount of the second triazine-based ultraviolet absorber (TAY) is most preferably 1.

[0086] The thermoplastic resin film of the present disclosure, which has a single-layer structure or a laminate structure and includes an acrylic resin composition layer made of an acrylic resin composition (AR) containing a first triazine-based ultraviolet absorber (TAX) and a second triazine-based ultraviolet absorber (TAY), can have excellent initial weather resistance and long-term weather resistance. The long-term weather resistance can be evaluated by conducting an accelerated weather resistance test using an accelerated weather resistance test device such as a weather meter, and comparing the optical properties before and after the accelerated weather resistance test.

[0087] The initial weather resistance can be measured using the transmittance (also called UV transmittance) of ultraviolet light (light in the wavelength range of 300 to 380 nm) of the thermoplastic resin film at an initial stage (before the accelerated weather resistance test). Long-term weather resistance can be evaluated by the UV transmittance of the thermoplastic resin film after an accelerated weather resistance test and / or the rate of change in the UV transmittance of the thermoplastic resin film after an accelerated weather resistance test relative to the initial value (before the accelerated weather resistance test). The accelerated weathering test, measurement of UV transmittance before and after the accelerated weathering test, and calculation of the rate of change in UV transmittance after the accelerated weathering test relative to the initial value (before the accelerated weathering test) can be performed by the method described in the section [Examples] below.

[0088] The rate of change in UV transmittance after the accelerated weathering test relative to the initial value (before the accelerated weathering test) can be determined when the UV transmittance after the accelerated weathering test is 0.001% or more. If the UV transmittance of the thermoplastic resin film after the accelerated weathering test is less than 0.001%, the UV transmittance after the accelerated weathering test is very small, and it can be determined that the long-term weathering resistance is good regardless of the rate of change in UV transmittance after the accelerated weathering test.

[0089] The thermoplastic resin film of the present disclosure in its initial state (before the accelerated weathering test) has a light transmittance (T 314 ) is preferably 0 to 0.3%. The upper limit is more preferably 0.25%, even more preferably 0.2%, even more preferably 0.15%, even more preferably 0.1%, even more preferably 0.08%, particularly preferably 0.07%, and most preferably 0.06%. After the accelerated weathering test, the thermoplastic resin film of the present disclosure exhibited a light transmittance (T 314 ) is preferably 0 to 0.3%. The upper limit is more preferably 0.25%, even more preferably 0.2%, even more preferably 0.15%, even more preferably 0.1%, even more preferably 0.08%, particularly preferably 0.07%, and most preferably 0.06%.

[0090] The light transmittance (T) of the thermoplastic resin film of the present disclosure at a wavelength of 314 nm after an accelerated weathering test 314 ) is 0.001% or more, the rate of change in UV transmittance at a wavelength of 314 nm defined by the following formula (ΔT 314 ) can be obtained. [Change rate of UV transmittance (ΔT 314 )(%)]=100×[(UV transmittance after accelerated weathering test (T 314 ))-(Initial UV transmittance (T 314 ))] / [UV transmittance after accelerated weathering test (T 314 )]

[0091] ΔT 314 The larger the value, the greater the increase in UV transmittance at 314 nm after the accelerated weathering test compared to the initial value (before the accelerated weathering test). For example, a ΔT of 90% or more 314indicates that the UV transmittance after the accelerated weathering test increased by 10 times or more compared to the initial value (before the accelerated weathering test) (in other words, the UV blocking performance after the accelerated weathering test decreased by 10 times or more compared to the initial value (before the accelerated weathering test)). T of the thermoplastic resin film of the present disclosure after accelerated weathering test 314 ΔT when is 0.001% or more 314 is preferably 0 to 95%. The upper limit is more preferably 90%, further preferably 85%, further preferably 80%, particularly preferably 75%, and most preferably 70%.

[0092] The thermoplastic resin film of the present disclosure at the initial stage (before the accelerated weathering test) exhibits a light transmittance (T 275 ) is preferably 0 to 0.3%. The upper limit is more preferably 0.25%, even more preferably 0.2%, even more preferably 0.15%, even more preferably 0.1%, even more preferably 0.08%, particularly preferably 0.07%, and most preferably 0.06%. The thermoplastic resin film of the present disclosure in its initial state (before accelerated weathering test) has a light transmittance at 350 nm (T 350 ) is preferably 0 to 0.3%. The upper limit is more preferably 0.25%, even more preferably 0.2%, even more preferably 0.15%, even more preferably 0.1%, even more preferably 0.08%, particularly preferably 0.07%, and most preferably 0.06%. The initial (before accelerated weather resistance test) thermoplastic resin film of the present disclosure preferably has a light transmittance of 0 to 0.3% at each wavelength (250+N (nm) (N is an integer from 0 to 100) within a wavelength range of 250 to 350 nm. The upper limit is more preferably 0.25%, even more preferably 0.2%, even more preferably 0.15%, even more preferably 0.1%, still more preferably 0.08%, particularly preferably 0.07%, and most preferably 0.06%.

[0093] <Light stabilizer (LS)> The acrylic resin composition (AR) may contain one or more light stabilizers (LS) as needed. The light stabilizers (LS) can capture and detoxify radicals (specifically, alkyl radicals, peroxide radicals, etc.) generated by heat and / or ultraviolet light. The light stabilizer (LS) is preferably a hindered amine light stabilizer (HALS). Examples of hindered amine light stabilizers (HALS) include NH-type HALS having an imino group (>NH), NR-type HALS having an imino group (>NH) with an organic group (>NR) substituted with an alkyl group (e.g., a methyl group) or the like, and NOR-type HALS having an imino group (>NH) with an organic group (>N-OR) substituted with an alkoxy group or the like. Here, R represents a substituted or unsubstituted saturated or unsaturated hydrocarbon group. Examples of R include alkyl groups, aralkyl groups, and aryl groups. The alkyl group may be linear, branched, or cyclic. It should be noted that R, a group that can be contained in the light stabilizer (LS), is unrelated to R, a group that can be contained in the triazine-based ultraviolet absorber (TAX) or (TAY).

[0094] <Antioxidants (AO)> The acrylic resin composition (AR) may contain one or more antioxidants (AO) as needed. Examples of the antioxidants (AO) include phenol-based, phosphorus-based, lactone-based, and hydroxy-based antioxidants. Among these, phenol-based antioxidants, phosphorus-based antioxidants, and combinations thereof are preferred.

[0095] Phenolic antioxidants include pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-(1,6-hexanediyl)bis[3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanamide], 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid sucrose. Examples include tearyl, 4,4'-butylidenebis(6-t-butyl-m-cresol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, bis[3-[3-(t-butyl)-4-hydroxy-5-methylphenyl]propanoic acid]2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl), and 1,3,5-trimethyl-2,4,6-tris(3',5'-di-t-butyl-4'-hydroxybenzyl).

[0096] Examples of phosphorus-based antioxidants include 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-t-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,4,8,10-tetra-t-butyl-6-[(2-ethylhexan-1-yl)oxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, tris(2,4-di-t-butylphenyl)phosphite, trisnonylphenylphosphite, diphenylisodecylphosphite, and triphenylphosphite biphenyl-4,4'-diylbis[bis(2,4-di-t-butylphenoxy)phosphine].

[0097] <Other thermoplastic resins> The acrylic resin composition (AR) may contain one or more other thermoplastic resins other than the (meth)acrylic resin (A) as required. Examples of other thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene-based ionomers; polystyrene, syndiotactic polystyrene-based resins, styrene-maleic anhydride copolymers, ABS-based resins (acrylonitrile-butadiene-styrene copolymers), AS-based resins (acrylonitrile-styrene copolymers), BAAS-based resins (butadiene-acrylonitrile-acrylonitrile rubber-styrene copolymers), MBS-based resins (methyl methacrylate-butadiene-styrene copolymers), AAS-based resins (acrylonitrile-acrylonitrile rubber-styrene copolymers), and SAS-based resins (silicone copolymers). Examples of suitable materials include styrene-based resins such as styrene-based copolymers (styrene-acrylonitrile-styrene copolymers); polycarbonate resins and polycarbonate-ABS resin alloys; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyamides such as nylon 6, nylon 66, and polyamide elastomers; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, and polyvinylidene fluoride; polyurethanes, phenoxy resins, modified polyphenylene ethers, and polyphenylene sulfides; styrene-based thermoplastic elastomers such as SEPS, SEBS, and SIS; olefin-based rubbers such as IR, EPR, and EPDM; and biodegradable resins.

[0098] <Other additives> The acrylic resin composition (AR) may contain one or more additives other than those mentioned above, as needed, such as a compatibilizer, a heat stabilizer, a plasticizer, a release agent, an antistatic agent, a flame retardant, a flame retardant aid, a lubricant, a thickener, a filler, an antifoaming agent, a rust inhibitor, an antibacterial / antifungal agent, an antifouling agent, and a colorant.

[0099] The acrylic resin composition (AR) can be produced by melt-kneading multiple materials, including one or more (meth)acrylic resins (A) and multiple triazine-based UV absorbers, using a known method. The multiple materials may be kneaded all at once or in portions, and the blending procedure is not particularly limited. Melt-kneading can be carried out using known mixing or kneading devices such as an extruder, kneader-ruder, mixing roll, or Banbury mixer. Extruders such as single-screw extruders, twin-screw extruders, and multi-screw extruders are preferred, with twin-screw extruders being more preferred.

[0100] (middle class) The constituent resin of the intermediate layer that can be contained in the thermoplastic resin film of the present disclosure is not particularly limited, and examples thereof include thermoplastic elastomers, polyvinyl acetal resins, polar group-containing polyolefin resins, polyurethane resins, and combinations thereof. The intermediate layer is preferably made of an elastomer resin composition (ER) containing one or more thermoplastic elastomers (E).

[0101] The elastomer resin composition (ER) contains one or more thermoplastic elastomers (E) selected from the group consisting of block copolymers having a polymer block (a) containing an aromatic vinyl compound unit and a polymer block (b) containing a conjugated diene compound unit, and hydrogenated products of the block copolymers. Generally, the adhesion between a surface layer containing a (meth)acrylic resin (A) and a backing layer containing a vinyl alcohol resin (V) is poor, but by providing an intermediate layer containing a thermoplastic elastomer (E) between these layers, the interlayer adhesion can be improved. The intermediate layer containing a thermoplastic elastomer (E) can function as an adhesive layer and is also excellent in flex resistance, flexibility, impact resistance, etc.

[0102] The thermoplastic elastomer (E) contains one or more polymer blocks (a) containing one or more aromatic vinyl compound units, such as styrene (St), α-methylstyrene (αMSt), 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, and 2-vinylnaphthalene. The polymer block (a) may contain one or more other monomer units other than the aromatic vinyl compound units. Examples of the other monomers other than the aromatic vinyl compound units include 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether.

[0103] The content of one or more aromatic vinyl compound units in the polymer block (a) (the total amount when multiple types are present) is not particularly limited, but is preferably 80 to 100% by mass, with the lower limit being more preferably 90% by mass, and particularly preferably 95% by mass. The content of other monomer units than aromatic vinyl compound units in polymer block (a) (total amount when multiple types are present) is not particularly limited and is 20 to 0 mass %, with the upper limit being more preferably 10 mass %, particularly preferably 5 mass %.

[0104] The thermoplastic elastomer (E) contains one or more polymer blocks (b) containing one or more conjugated diene compound units. Examples of conjugated diene compounds include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. The polymer block (b) preferably contains butadiene units and / or isoprene units as conjugated diene compound units, and is preferably composed of butadiene units and / or isoprene units. The polymer block (b) may contain one or more other monomer units other than the conjugated diene compound units. Examples of the other monomers other than the conjugated diene compound units include styrene (St) and 4-methylstyrene.

[0105] The content of conjugated diene compound units in polymer block (b) (total amount when multiple types are used) is not particularly limited and is preferably 80 to 100% by mass, with the lower limit being more preferably 90% by mass, and particularly preferably 95% by mass. The content of other monomer units than the conjugated diene compound units in the polymer block (b) (total amount when multiple types are present) is not particularly limited and is 20 to 0 mass %, with the upper limit being more preferably 10 mass %, particularly preferably 5 mass %.

[0106] The bonding form between the polymer block (a) and the polymer block (b) is not particularly limited, and examples thereof include linear, branched, radial, and combinations thereof, with linear being preferred. Examples of linear bonding forms include diblock copolymers represented by ab, triblock copolymers represented by aba or b-a-b, tetrablock copolymers represented by abab, pentablock copolymers represented by a-b-a-b-a or b-a-b-a-b, (a-b) n Examples include X-type copolymers (X represents a coupling residue, and n represents an integer of 2 or more), and combinations thereof. Among these, triblock copolymers are preferred, and triblock copolymers represented by a-b-a are more preferred.

[0107] The content of the polymer block (a) in the thermoplastic elastomer (E) is not particularly limited, and is preferably 5 to 75% by mass from the viewpoint of the flexibility and mechanical properties of the thermoplastic elastomer (E). The lower limit is more preferably 10% by mass. The upper limit is more preferably 70% by mass, even more preferably 65% ​​by mass, even more preferably 60% by mass, even more preferably 55% by mass, even more preferably 50% by mass, particularly preferably 45% by mass, and most preferably 40% by mass. The content of polymer block (b) in thermoplastic elastomer (E) is not particularly limited, and is preferably 95 to 25% by mass from the viewpoint of the flexibility and mechanical properties of thermoplastic elastomer (E). The upper limit is more preferably 90% by mass. The lower limit is more preferably 30% by mass, even more preferably 35% by mass, even more preferably 40% by mass, even more preferably 45% by mass, even more preferably 50% by mass, particularly preferably 55% by mass, and most preferably 60% by mass. The total content of the polymer block (a) and the polymer block (b) in the thermoplastic elastomer (E) is not particularly limited and is preferably 95 to 100% by mass, with the lower limit being more preferably 97% by mass, particularly preferably 98% by mass, and most preferably 99% by mass.

[0108] The thermoplastic elastomer (E) may be an unhydrogenated block copolymer having one or more polymer blocks (a) and one or more polymer blocks (b), or may be a hydrogenated product thereof. The method for producing the unhydrogenated block copolymer is not particularly limited, and examples thereof include anionic polymerization methods. For example, (i) a method in which an alkyllithium compound is used as an initiator to sequentially polymerize one or more aromatic vinyl compounds, then one or more conjugated diene compounds, and if necessary, one or more aromatic vinyl compounds are sequentially polymerized; (ii) a method in which an alkyllithium compound is used as an initiator to sequentially polymerize one or more aromatic vinyl compounds, then one or more conjugated diene compounds, and then a coupling agent is added to couple; (iii) a method in which a dilithium compound is used as an initiator to sequentially polymerize one or more conjugated diene compounds, then one or more aromatic vinyl compounds, and if necessary, one or more conjugated diene compounds are sequentially polymerized;

[0109] From the viewpoint of improving heat resistance and weather resistance, the thermoplastic elastomer (E) is preferably a hydrogenated block copolymer in which at least a portion of the polymer block (b) containing a conjugated diene compound unit is hydrogenated (also referred to as hydrogenation). The hydrogenation rate (hydrogenation rate) of the polymer block (b) is not particularly limited, but is preferably 80 to 100%. The lower limit is more preferably 85%, particularly preferably 90%. In this specification, the hydrogenation rate (hydrogenation ratio) of a polymer block containing a conjugated diene compound unit can be determined by measuring the iodine value of the block copolymer before and after the hydrogenation reaction. Examples of the hydrogenation reaction include a method in which a solution of an unhydrogenated block copolymer is dissolved in a solvent inert to the hydrogenation reaction and the hydrogenation catalyst, or a reaction liquid containing the unhydrogenated block copolymer obtained after the polymerization reaction is prepared, and the unhydrogenated block copolymer is reacted with hydrogen in the presence of a hydrogenation catalyst. The thermoplastic elastomer (E) may be a commercially available product.

[0110] The thermoplastic elastomer (E) may contain one or more functional groups such as a carboxy group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group in the molecular chain and / or at the molecular chain terminal, as required.

[0111] The thermoplastic elastomer (E) can include one or more first thermoplastic elastomers (EX) selected from the group consisting of block copolymers having a polymer block (xa) containing styrene (St) units and a polymer block (xb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is less than 40 mol %, and hydrogenated products of the block copolymers.

[0112] The thermoplastic elastomer (E) may comprise, alternatively or in addition to the first thermoplastic elastomer (EX), one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing styrene (St) units and a polymer block (yb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, and hydrogenated products of the block copolymers.

[0113] The thermoplastic elastomer (E) may comprise, alternatively or in addition to the first thermoplastic elastomer (EX) and / or the second thermoplastic elastomer (EY), one or more third thermoplastic elastomers (EZ) selected from the group consisting of block copolymers having a polymer block (za) containing α-methylstyrene (αMSt) units and a polymer block (zb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, and hydrogenated products of the block copolymers.

[0114] The thermoplastic elastomer (E) can include one or more of the thermoplastic elastomers (EX) to (EZ). The thermoplastic elastomer (E) preferably comprises one or more second thermoplastic elastomers (EY) and / or one or more third thermoplastic elastomers (EZ). The thermoplastic elastomer (E) more preferably comprises one or more first thermoplastic elastomers (EX), one or more second thermoplastic elastomers (EY), and one or more third thermoplastic elastomers (EZ).

[0115] The content of the first thermoplastic elastomer (EX) (total amount when multiple types are used) is preferably 22 to 78 parts by mass relative to 100 parts by mass of the total amount of thermoplastic elastomer (E). The lower limit is more preferably 25 parts by mass, particularly preferably 28 parts by mass, and most preferably 30 parts by mass. The upper limit is more preferably 75 parts by mass, even more preferably 70 parts by mass, even more preferably 60 parts by mass, particularly preferably 50 parts by mass, and most preferably 40 parts by mass.

[0116] The content of the second thermoplastic elastomer (EY) (total amount when multiple types are used) is preferably 12 to 78 parts by mass relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E). The lower limit is more preferably 15 parts by mass, and particularly preferably 20 parts by mass. The upper limit is more preferably 75 parts by mass, even more preferably 70 parts by mass, even more preferably 60 parts by mass, particularly preferably 50 parts by mass, and most preferably 40 parts by mass.

[0117] The content of the third thermoplastic elastomer (EZ) (total amount when multiple types are used) is preferably 0 to 60 parts by mass relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E). The lower limit is more preferably 1 part by mass, even more preferably 3 parts by mass, even more preferably 5 parts by mass, even more preferably 10 parts by mass, particularly preferably 15 parts by mass, and most preferably 20 parts by mass. The upper limit is more preferably 55 parts by mass, especially preferably 50 parts by mass.

[0118] <First thermoplastic elastomer (EX)> The elastomer resin composition (ER) can contain one or more first thermoplastic elastomers (EX) selected from the group consisting of block copolymers having a polymer block (xa) containing styrene (St) units and a polymer block (xb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is less than 40 mol %, and hydrogenated products of the block copolymers. The first thermoplastic elastomer (EX) can impart excellent flexibility and impact resistance to the elastomer resin composition (ER). The first thermoplastic elastomer (EX) contains a polymer block (xb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is less than 40 mol %, thereby imparting excellent chipping resistance to the elastomer resin composition (ER). In this specification, "chipping resistance" refers to resistance to damage and / or chipping caused by the impact of small particles such as pebbles and snow-melting salts.

[0119] <Polymer block (xa)> The first thermoplastic elastomer (EX) contains one or more polymer blocks (xa) containing styrene (St) units. The polymer block (xa) may contain one or more aromatic vinyl compound units other than styrene (St) units. Examples of aromatic vinyl compounds other than styrene (St) include α-methylstyrene (αMSt), 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, and 2-vinylnaphthalene. The polymer block (xa) may contain one or more other monomer units other than the aromatic vinyl compound units. Examples of the other monomers other than the aromatic vinyl compound units include 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether.

[0120] The content of styrene (St) units in the polymer block (xa) is not particularly limited, but is preferably 80 to 100% by mass, with the lower limit being more preferably 90% by mass, and particularly preferably 95% by mass. The content of one or more aromatic vinyl compound units containing styrene (St) units in the polymer block (xa) (the total amount when multiple types are present) is not particularly limited, but is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content of other monomer units than aromatic vinyl compound units in the polymer block (xa) (total amount when multiple types are present) is not particularly limited and is 20 to 0 mass %, with the upper limit being more preferably 10 mass %, particularly preferably 5 mass %.

[0121] <Polymer block (xb)> The first thermoplastic elastomer (EX) contains one or more polymer blocks (xb) containing one or more types of conjugated diene compound units. The one or more types of conjugated diene compound units contained in the first thermoplastic elastomer (EX) have a total amount of 1,2-bonds and 3,4-bonds of less than 40 mol%. When the first thermoplastic elastomer (EX) contains multiple polymer blocks (xb), the total amount of 1,2-bonds and 3,4-bonds of the one or more types of conjugated diene compound units contained in all of the polymer blocks (xb) is less than 40 mol%.

[0122] Examples of the conjugated diene compound include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. The polymer block (xb) preferably contains butadiene units and / or isoprene units as conjugated diene compound units, and is preferably composed of butadiene units and / or isoprene units. The polymer block (xb) may contain one or more other monomer units other than the conjugated diene compound units. Examples of the other monomers other than the conjugated diene compound units include styrene (St) and 4-methylstyrene.

[0123] The content of conjugated diene compound units in the polymer block (xb) (total amount when multiple types are used) is not particularly limited, but is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content of other monomer units than the conjugated diene compound units in the polymer block (xb) (total amount when multiple types are present) is not particularly limited and is 20 to 0 mass %, with the upper limit being more preferably 10 mass %, particularly preferably 5 mass %.

[0124] Regarding the bonding form of the conjugated diene compound units in the polymer block (xb), the butadiene units can have 1,2-bonds or 1,4-bonds, and the isoprene units can have 1,2-bonds, 3,4-bonds, or 1,4-bonds. The same applies to the polymer blocks (yb) and (zb). From the viewpoint of chipping resistance, the total amount of 1,2-bonds and 3,4-bonds in the polymer block (xb) is less than 40 mol%, preferably 39 mol% or less. The upper limit is more preferably 35 mol%, even more preferably 30 mol%, even more preferably 25 mol%, even more preferably 20 mol%, particularly preferably 15 mol%, and most preferably 10 mol%. The lower limit is 0 mol%.

[0125] The total amount of 1,2-bonds and 3,4-bonds in the conjugated diene compound units in the polymer block containing the conjugated diene compound units is 1 It can be calculated by H-NMR measurement, specifically, from the ratio of the integral value of the first peak at 4.2 to 5.0 ppm derived from 1,2-bonded and 3,4-bonded conjugated diene compound units to the integral value of the second peak at 5.0 to 5.45 ppm derived from 1,4-bonded conjugated diene compound units.

[0126] The bonding form between the polymer block (xa) and the polymer block (xb) is not particularly limited, and examples thereof include linear, branched, radial, and combinations thereof, with linear being preferred. Examples of linear bonding forms include diblock copolymers represented by xa-xb, triblock copolymers represented by xa-xb-xa or xb-xa-xb, tetrablock copolymers represented by xa-xb-xa-xb, pentablock copolymers represented by xa-xb-xa-xb-xa or xb-xa-xb-xa-xb, and (xa-xb) n Examples include X-type copolymers (X represents a coupling residue, and n represents an integer of 2 or more), and combinations thereof. Among these, triblock copolymers are preferred, and triblock copolymers represented by xa-xb-xa are more preferred.

[0127] The content of the polymer block (xa) in the first thermoplastic elastomer (EX) is not particularly limited, and is preferably 5 to 75% by mass from the viewpoint of the flexibility and mechanical properties of the first thermoplastic elastomer (EX). The lower limit is more preferably 10% by mass. The upper limit is more preferably 70% by mass, even more preferably 65% ​​by mass, even more preferably 60% by mass, even more preferably 55% by mass, even more preferably 50% by mass, particularly preferably 45% by mass, and most preferably 40% by mass. The content of the polymer block (xb) in the first thermoplastic elastomer (EX) is not particularly limited, and is preferably 95 to 25% by mass from the viewpoint of the flexibility and mechanical properties of the first thermoplastic elastomer (EX). The upper limit is more preferably 90% by mass. The lower limit is more preferably 30% by mass, even more preferably 35% by mass, even more preferably 40% by mass, even more preferably 45% by mass, even more preferably 50% by mass, particularly preferably 55% by mass, and most preferably 60% by mass. The total content of the polymer block (xa) and the polymer block (xb) in the first thermoplastic elastomer (EX) is not particularly limited and is preferably 95 to 100% by mass, with the lower limit being more preferably 97% by mass, particularly preferably 98% by mass, and most preferably 99% by mass.

[0128] The first thermoplastic elastomer (EX) may be an unhydrogenated block copolymer having one or more polymer blocks (xa) and one or more polymer blocks (xb), or may be a hydrogenated product thereof. From the viewpoint of improving heat resistance and weather resistance, the first thermoplastic elastomer (EX) is preferably a hydrogenated block copolymer in which at least a portion of the polymer block (xb) containing a conjugated diene compound unit is hydrogenated. The hydrogenation rate (hydrogenation rate) of the polymer block (xb) is not particularly limited, but is preferably 80 to 100%. The lower limit is more preferably 85%, particularly preferably 90%.

[0129] The first thermoplastic elastomer (EX) may contain one or more functional groups such as a carboxy group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group in the molecular chain and / or at the molecular chain terminal, as necessary.

[0130] The weight-average molecular weight (Mw) (standard polystyrene equivalent) of the first thermoplastic elastomer (EX) is not particularly limited, and from the viewpoint of the mechanical properties and moldability of the first thermoplastic elastomer (EX), it is preferably 30,000 to 500,000. The lower limit is more preferably 50,000, even more preferably 60,000, particularly preferably 70,000, and most preferably 80,000. The upper limit is more preferably 400,000, even more preferably 300,000, even more preferably 200,000, particularly preferably 190,000, and most preferably 180,000.

[0131] <Second Thermoplastic Elastomer (EY)> The elastomer resin composition (ER) can contain one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing styrene (St) units and a polymer block (yb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, and hydrogenated products of the block copolymers. The second thermoplastic elastomer (EY) contains a polymer block (yb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, and thus can impart excellent adhesion to non-polar resins to the elastomer resin composition (ER).

[0132] <Polymer block (ya)> The second thermoplastic elastomer (EY) contains one or more polymer blocks (ya) containing styrene (St) units. The polymer block (ya) may contain one or more aromatic vinyl compound units other than styrene (St) units. The polymer block (ya) may contain one or more other monomer units other than aromatic vinyl compound units. Examples of aromatic vinyl compounds other than styrene (St) and other monomers other than aromatic vinyl compounds are the same as those for the polymer block (xa).

[0133] The content of styrene (St) units in the polymer block (ya) is not particularly limited and is preferably 80 to 100% by mass, with the lower limit being more preferably 90% by mass, and particularly preferably 95% by mass. The content of one or more aromatic vinyl compound units containing styrene (St) units in the polymer block (ya) (the total amount when multiple types are present) is not particularly limited, but is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content (total amount when multiple types of monomer units are present) of other monomer units than aromatic vinyl compound units in the polymer block (ya) is not particularly limited and is 20 to 0 mass %, with the upper limit being more preferably 10 mass %, particularly preferably 5 mass %.

[0134] <Polymer block (yb)> The second thermoplastic elastomer (EY) contains one or more polymer blocks (yb) containing one or more types of conjugated diene compound units. The one or more types of conjugated diene compound units contained in the second thermoplastic elastomer (EY) have a total amount of 1,2-bonds and 3,4-bonds of 40 mol% or more. When the second thermoplastic elastomer (EY) contains multiple polymer blocks (yb), the total amount of 1,2-bonds and 3,4-bonds of the one or more types of conjugated diene compound units contained in all of the polymer blocks (yb) is 40 mol% or more. The polymer block (yb) may contain one or more other monomer units other than the conjugated diene compound units. Examples and preferred embodiments of the conjugated diene compound and examples of other monomers are the same as those for the polymer block (xb). The content of conjugated diene compound units in the polymer block (yb) (total amount when multiple types are used) is not particularly limited, but is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content (total amount when multiple types of monomer units are present) of other monomer units than the conjugated diene compound units in the polymer block (yb) is not particularly limited and is 20 to 0 mass %, with the upper limit being more preferably 10 mass %, particularly preferably 5 mass %.

[0135] The total amount of 1,2-bonds and 3,4-bonds in the polymer block (xb) is 40 mol% or more from the viewpoint of excellent adhesion to non-polar resins. The lower limit is more preferably 45 mol%, particularly preferably 50 mol%, and most preferably 55 mol%. The upper limit is preferably 90 mol%, more preferably 85 mol%, and particularly preferably 80 mol%.

[0136] The 1,2-bonds and 3,4-bonds of the conjugated diene compound units can be increased by adding one or more organic Lewis bases to the reaction solution during anionic polymerization. The total amount of 1,2-bonds and 3,4-bonds can be easily controlled by the amount of organic Lewis base added. Examples of the organic Lewis base include esters such as ethyl acetate; amines such as triethylamine, N,N,N',N'-tetramethylethylenediamine (TMEDA), and N-methylmorpholine; nitrogen-containing heterocyclic aromatic compounds such as pyridine; amides such as dimethylacetamide; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran (THF), and dioxane; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; sulfoxides such as dimethyl sulfoxide; and ketones such as acetone and methyl ethyl ketone.

[0137] The bonding form between the polymer block (ya) and the polymer block (yb) is not particularly limited, and examples thereof include linear, branched, radial, and combinations thereof, with linear being preferred. Examples of linear bonding forms include diblock copolymers represented by ya-yb, triblock copolymers represented by ya-yb-ya or yb-ya-yb, tetrablock copolymers represented by ya-yb-ya-yb, pentablock copolymers represented by ya-yb-ya-yb-ya or yb-ya-yb-ya-yb, and (ya-yb) n Examples include X-type copolymers (X represents a coupling residue, and n represents an integer of 2 or more), and combinations thereof. Among these, triblock copolymers are preferred, and triblock copolymers represented by ya-yb-ya are more preferred.

[0138] The content of the polymer block (ya) in the second thermoplastic elastomer (EY) is not particularly limited, and is preferably 5 to 75% by mass from the viewpoint of the flexibility and mechanical properties of the second thermoplastic elastomer (EY). The lower limit is more preferably 10% by mass. The upper limit is more preferably 70% by mass, even more preferably 65% ​​by mass, even more preferably 60% by mass, even more preferably 55% by mass, even more preferably 50% by mass, particularly preferably 45% by mass, and most preferably 40% by mass. The content of the polymer block (yb) in the second thermoplastic elastomer (EY) is not particularly limited, and is preferably 95 to 25% by mass from the viewpoint of the flexibility and mechanical properties of the second thermoplastic elastomer (EY). The upper limit is more preferably 90% by mass. The lower limit is more preferably 30% by mass, even more preferably 35% by mass, even more preferably 40% by mass, even more preferably 45% by mass, even more preferably 50% by mass, particularly preferably 55% by mass, and most preferably 60% by mass. The total content of the polymer block (ya) and the polymer block (yb) in the second thermoplastic elastomer (EY) is not particularly limited and is preferably 95 to 100% by mass, with the lower limit being more preferably 97% by mass, particularly preferably 98% by mass, and most preferably 99% by mass.

[0139] The second thermoplastic elastomer (EY) may be an unhydrogenated block copolymer having one or more polymer blocks (ya) and one or more polymer blocks (yb), or may be a hydrogenated product thereof. From the viewpoint of improving heat resistance and weather resistance, the second thermoplastic elastomer (EY) is preferably a hydrogenated block copolymer in which at least a portion of the polymer block (yb) containing a conjugated diene compound unit is hydrogenated. The hydrogenation rate (hydrogenation rate) of the polymer block (yb) is not particularly limited, but is preferably 80 to 100%. The lower limit is more preferably 85%, particularly preferably 90%.

[0140] The second thermoplastic elastomer (EY) may contain one or more functional groups such as a carboxy group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group in the molecular chain and / or at the molecular chain terminal, as necessary. The weight average molecular weight (Mw) (standard polystyrene equivalent) of the second thermoplastic elastomer (EY) is not particularly limited, and from the viewpoints of the mechanical properties and molding processability of the second thermoplastic elastomer (EY), the preferred range is the same as that of the first thermoplastic elastomer (EX).

[0141] <The third thermoplastic elastomer (EZ)> The elastomer resin composition (ER) can contain one or more third thermoplastic elastomers (EZ) selected from the group consisting of block copolymers having a polymer block (za) containing α-methylstyrene (αMSt) units and a polymer block (zb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, and hydrogenated products of the block copolymers. The third thermoplastic elastomer (EZ) contains a polymer block (za) containing α-methylstyrene (αMSt) units, which can impart rigidity and excellent adhesion to polar resins to the elastomer resin composition (ER). The third thermoplastic elastomer (EZ) contains a polymer block (zb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol % or more, which can impart excellent adhesion to non-polar resins to the elastomer resin composition (ER).

[0142] <Polymer block (za)> The third thermoplastic elastomer (EZ) comprises one or more polymer blocks (za) comprising α-methylstyrene (αMSt) units. The polymer block (za) may contain one or more aromatic vinyl compound units other than α-methylstyrene (αMSt) units. Examples of aromatic vinyl compounds other than α-methylstyrene (αMSt) include styrene (St), 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, and 2-vinylnaphthalene. The polymer block (za) may contain one or more other monomer units other than the aromatic vinyl compound units. Examples of the other monomers other than the aromatic vinyl compound are the same as those for the polymer block (xa).

[0143] The content of α-methylstyrene (αMSt) units in the polymer block (za) is not particularly limited, and is preferably 80 to 100% by mass from the viewpoints of the rigidity of the elastomer resin composition (ER) and excellent adhesion to polar resins. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content of one or more aromatic vinyl compound units containing α-methylstyrene (αMSt) units in the polymer block (za) (the total amount when multiple types are present) is not particularly limited, but is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content (total amount when multiple types of monomer units are present) of other monomer units than aromatic vinyl compound units in the polymer block (za) is not particularly limited and is 20 to 0 mass %, with the upper limit being more preferably 10 mass %, particularly preferably 5 mass %.

[0144] <Polymer block (zb)> The third thermoplastic elastomer (EZ) contains one or more polymer blocks (zb) containing one or more types of conjugated diene compound units. The one or more types of conjugated diene compound units contained in the third thermoplastic elastomer (EZ) have a total amount of 1,2-bonds and 3,4-bonds of 40 mol% or more. When the third thermoplastic elastomer (EZ) contains multiple polymer blocks (zb), the total amount of 1,2-bonds and 3,4-bonds of the one or more types of conjugated diene compound units contained in all of the polymer blocks (zb) is 40 mol% or more. The polymer block (zb) may contain one or more other monomer units other than the conjugated diene compound units. Examples and preferred embodiments of the conjugated diene compound and examples of other monomers are the same as those for the polymer block (xb).

[0145] The content of conjugated diene compound units in the polymer block (zb) (total amount when multiple types are used) is not particularly limited and is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content (total amount when multiple types of monomer units are present) of other monomer units than the conjugated diene compound units in the polymer block (zb) is not particularly limited and is 20 to 0 mass %, with the upper limit being more preferably 10 mass %, particularly preferably 5 mass %.

[0146] The total amount of 1,2-bonds and 3,4-bonds in the polymer block (zb) is 40 mol% or more from the viewpoint of excellent adhesion to non-polar resins. The lower limit is more preferably 45 mol%, particularly preferably 50 mol%, and most preferably 55 mol%. The upper limit is preferably 90 mol%, more preferably 85 mol%, and particularly preferably 80 mol%.

[0147] The bonding form between the polymer block (za) and the polymer block (zb) is not particularly limited, and examples thereof include linear, branched, radial, and combinations thereof, with linear being preferred. Examples of linear bonding forms include diblock copolymers represented by za-zb, triblock copolymers represented by za-zb-za or zb-za-zb, tetrablock copolymers represented by za-zb-za-zb, pentablock copolymers represented by za-zb-za-zb-za or zb-za-zb-za-zb, and (za-zb) n Examples include X-type copolymers (X represents a coupling residue, and n represents an integer of 2 or more), and combinations thereof. Among these, triblock copolymers are preferred, and triblock copolymers represented by za-zb-za are more preferred.

[0148] The content of the polymer block (za) in the third thermoplastic elastomer (EZ) is not particularly limited, and is preferably 5 to 75% by mass from the viewpoint of the flexibility and mechanical properties of the third thermoplastic elastomer (EZ). The lower limit is more preferably 10% by mass. The upper limit is more preferably 70% by mass, even more preferably 65% ​​by mass, even more preferably 60% by mass, even more preferably 55% by mass, even more preferably 50% by mass, particularly preferably 45% by mass, and most preferably 40% by mass. The content of the polymer block (zb) in the third thermoplastic elastomer (EZ) is not particularly limited, and is preferably 95 to 25% by mass from the viewpoint of the flexibility and mechanical properties of the third thermoplastic elastomer (EZ). The upper limit is more preferably 90% by mass. The lower limit is more preferably 30% by mass, even more preferably 35% by mass, even more preferably 40% by mass, even more preferably 45% by mass, even more preferably 50% by mass, particularly preferably 55% by mass, and most preferably 60% by mass. The total content of the polymer block (za) and the polymer block (zb) in the third thermoplastic elastomer (EZ) is not particularly limited and is preferably 95 to 100% by mass, with the lower limit being more preferably 97% by mass, particularly preferably 98% by mass, and most preferably 99% by mass.

[0149] The third thermoplastic elastomer (EZ) may be an unhydrogenated block copolymer having one or more polymer blocks (za) and one or more polymer blocks (zb), or may be a hydrogenated product thereof. From the viewpoint of improving heat resistance and weather resistance, the third thermoplastic elastomer (EZ) is preferably a hydrogenated block copolymer in which at least a portion of the polymer block (zb) containing a conjugated diene compound unit is hydrogenated. The hydrogenation rate (hydrogenation rate) of the polymer block (zb) is not particularly limited, but is preferably 80 to 100%. The lower limit is more preferably 85%, particularly preferably 90%.

[0150] The third thermoplastic elastomer (EZ) may contain one or more functional groups such as a carboxy group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group in the molecular chain and / or at the molecular chain terminal, as necessary. The weight average molecular weight (Mw) (standard polystyrene equivalent) of the third thermoplastic elastomer (EZ) is not particularly limited, and from the viewpoint of the mechanical properties and molding processability of the third thermoplastic elastomer (EZ), the preferred range is the same as that of the first thermoplastic elastomer (EX).

[0151] <Polypropylene polymer (P)> The elastomer resin composition (ER) can contain one or more polypropylene polymers (P). The propylene polymers (P) are homopolymers or copolymers containing propylene units and, if necessary, one or more other monomer units. The content of the polypropylene polymer (P) (total amount when multiple types are used) is preferably 1 to 35 parts by mass relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E). From the viewpoint of adhesiveness to various materials (polar resins or non-polar resins), the polypropylene polymer (P) preferably comprises a combination of one or more first polypropylene polymers (PX) that do not have polar groups (also referred to as polar group-free polypropylene polymers) and one or more second polypropylene polymers (PY) that have polar groups (also referred to as polar group-containing polypropylene polymers).

[0152] <First Polypropylene Polymer (PX) (Polar Group-Free Polypropylene Polymer)> The first polypropylene polymer (PX) is a homopolymer or copolymer containing propylene units and, if necessary, one or more other monomer units not having a polar group. Examples of the other monomers include α-olefins other than propylene, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and cyclohexene.

[0153] The ratio of propylene units to all structural units of the first polypropylene polymer (PX) is not particularly limited, but is preferably 55 to 100 mol %. The lower limit is more preferably 65 mol %, even more preferably 75 mol %, particularly preferably 85 mol %, and most preferably 95 mol %. The ratio of monomer units other than propylene units to all structural units of the first polypropylene polymer (PX) is not particularly limited and is preferably 45 to 0 mol%, with the upper limit being more preferably 35 mol%, even more preferably 25 mol%, particularly preferably 15 mol%, and most preferably 5 mol%.

[0154] The first polypropylene polymer (PX) tends to have a higher melt tension as the melt flow rate (MFR) is smaller. From the viewpoint of film formability in extrusion molding, the first polypropylene polymer (PX) preferably has a melt tension of 2.5×10 or less measured at 230° C. and a take-up speed of 4.0 m / min. -2 The lower limit is more preferably 3.0 × 10 -2 N, more preferably 3.5 × 10 -2 N, particularly preferably 4.0 × 10 -2 N, most preferably 4.5 × 10 -2 N. The upper limit is not particularly limited, and is, for example, 50×10 -2 N, 40 × 10 -2 N, or 30 x 10 -2 It's N.

[0155] The MFR of the first polypropylene polymer (PX) is not particularly limited and is preferably 0.1 to 20 g / 10 min. The lower limit is preferably 0.5 g / 10 min, more preferably 1.0 g / 10 min. The upper limit is preferably 15 g / 10 min, more preferably 10 g / 10 min. Unless otherwise specified in this specification, the MFR of a polypropylene polymer is a value measured in accordance with JIS K7210 using a melt indexer at a temperature of 230°C and a load of 21.18N.

[0156] Examples of polypropylene-based polymers (PX) having the above-specified melt tension include polypropylene-based polymers having a crosslinked structure, a long-chain branched structure, a high-molecular-weight component, or a combination thereof. Among these, polypropylene-based polymers having a long-chain branched structure are preferred from the viewpoint of maintaining the flexibility of the film. Examples of methods for producing polypropylene-based polymers having a long-chain branched structure include a method of graft copolymerizing a radically polymerizable monomer onto polypropylene (Macromolecules 26 (1993) 3467), a method of copolymerizing propylene and a polyene (JP-A-5-194778), a macromer copolymerization method using a metallocene catalyst (JP-A-2009-057542), and a method of melt-mixing polypropylene, a conjugated diene compound, and a radical polymerization initiator (JP-A-2015-098542). Among these, a macromer copolymerization method using a metallocene catalyst is preferred from the viewpoint of suppressing gel formation.

[0157] The melting point (Tm) of the first polypropylene polymer (PX) is not particularly limited, and from the viewpoint of heat resistance, it is preferably 100°C or higher. The lower limit is more preferably 110°C. The upper limit is preferably 170°C, more preferably 160°C, and most preferably 150°C.

[0158] From the viewpoint of achieving both film-forming properties and adhesive properties of the elastomer resin composition (ER), the content of the first polypropylene polymer (PX) is preferably 3 to 15 parts by mass relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E). The lower limit is more preferably 5 parts by mass, particularly preferably 6 parts by mass, and most preferably 7 parts by mass. The upper limit is more preferably 12 parts by mass, particularly preferably 10 parts by mass, and most preferably 8 parts by mass.

[0159] <Second Polypropylene Polymer (PY) (Polar Group-Containing Polypropylene Polymer)> Examples of the polar group contained in the second polypropylene polymer (PY) include polar atoms such as oxygen atoms, nitrogen atoms, and sulfur atoms; (meth)acryloyloxy groups; hydroxyl groups; amide groups; carboxy groups; acid anhydride groups; and halogen atoms such as chlorine atoms. A first method for producing a polar group-containing polypropylene polymer includes copolymerizing propylene, a polar group-containing monomer, and, if necessary, one or more other monomers by a known method. The copolymerization form is not particularly limited, and examples thereof include random copolymerization and block copolymerization. A second method for producing a polar group-containing polypropylene polymer includes graft copolymerizing a polar group-containing monomer onto a polypropylene polymer that contains propylene units and, if necessary, one or more other monomer units and does not have a polar group (polar group-free polypropylene polymer). Among the above, the graft copolymerization method is preferred. The polar group-containing polypropylene polymer produced by the first or second production method contains propylene units and polar group-containing monomer units, and can further contain one or more other monomer units as required.

[0160] Examples of polar group-containing monomers include vinyl acetate, vinyl chloride, ethylene oxide, propylene oxide, unsaturated carboxylic acids or their esters or anhydrides, and (meth)acrylamide. Of these, unsaturated carboxylic acids or their esters or anhydrides are preferred, including (meth)acrylic acid, (meth)acrylic acid esters, maleic acid (anhydride), fumaric acid (anhydride), itaconic acid (anhydride), and himic acid (anhydride). Of these, carboxylic acid (anhydrides) such as maleic acid (anhydride) are more preferred. In this specification, carboxylic acid (anhydride) is a general term for carboxylic acids and carboxylic acid anhydrides.

[0161] The other monomers include α-olefins other than propylene, and specific examples thereof include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and cyclohexene. The total proportion of propylene units and polar group-containing monomer units to all structural units of the polar group-containing polypropylene polymer is not particularly limited, but is preferably 55 to 100 mol %. The lower limit is more preferably 65 mol %, even more preferably 75 mol %, particularly preferably 85 mol %, and most preferably 95 mol %. The proportion of α-olefin units other than propylene units to all structural units of the polar group-containing polypropylene polymer is not particularly limited, but is preferably 45 to 0 mol%, with the upper limit being more preferably 35 mol%, even more preferably 25 mol%, particularly preferably 15 mol%, and most preferably 5 mol%.

[0162] As the polar group-containing polypropylene polymer, polypropylene having a carboxy group or a carboxylic anhydride group as the polar group is preferred from the viewpoint of adhesiveness to various materials. Among these, polypropylene polymers (also referred to as (carboxylic acid anhydride) modified polypropylene polymers) obtained by graft copolymerizing a polypropylene polymer not having a polar group (polar group-free polypropylene polymer) with a carboxylic acid (anhydride) are preferred. Among these, maleic acid (anhydride) modified polypropylene polymers are more preferred.

[0163] The polar groups contained in the polar group-containing polypropylene polymer produced by the first or second production method may be post-treated after the polymerization reaction. Polar groups such as (meth)acrylic acid groups and carboxyl groups may be neutralized with metal ions to form ionomers, or may be esterified with alcohols such as methanol and ethanol. Polar groups such as vinyl acetate groups may also be hydrolyzed.

[0164] A third method for producing a polar group-containing polypropylene polymer includes oxidizing or halogenating (e.g., chlorinating) a polypropylene polymer that contains propylene units and, if necessary, one or more other monomer units but does not have a polar group (polar group-free polypropylene polymer) by a known method.

[0165] The melting point (Tm) of the second polypropylene polymer (PY) is preferably 130°C or lower from the viewpoint of the adhesiveness of the elastomer resin composition (ER). The lower limit is not particularly limited, and from the viewpoint of the heat resistance of the elastomer resin composition (ER), it is preferably 100°C, more preferably 105°C, and particularly preferably 110°C. The upper limit is more preferably 125°C.

[0166] From the viewpoint of achieving both adhesiveness and heat resistance, the content of the second polypropylene polymer (PY) is preferably 7.5 to 20 parts by mass relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E). The lower limit is more preferably 8 parts by mass, particularly preferably 9 parts by mass, and most preferably 10 parts by mass. The upper limit is more preferably 17.5 parts by mass, particularly preferably 15 parts by mass.

[0167] <Ultraviolet absorber (UVA), light stabilizer (LS), antioxidant (AO)> The elastomer resin composition (ER), like the acrylic resin composition (AR), may contain, if necessary, one or more ultraviolet absorbers (UVA), one or more light stabilizers (LS), one or more antioxidants (AO), or a combination thereof.

[0168] <Other thermoplastic resins> The elastomer resin composition (ER) may contain one or more other thermoplastic resins in addition to those mentioned above. Examples of other thermoplastic resins include (meth)acrylic resins, polyolefin resins other than polypropylene polymers, ethylene ionomers, styrene resins, polycarbonate resins, polycarbonate-ABS resin alloys, polyester resins, polyamides, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymers, polyacetal, polyvinylidene fluoride, polyurethanes, phenoxy resins, modified polyphenylene ethers, polyphenylene sulfides, olefin rubbers such as IR, EPR, and EPDM, and biodegradable resins.

[0169] <Other additives> The elastomer resin composition (ER) may contain one or more additives other than those mentioned above, as needed. Examples of other additives include tackifying resins, softeners, heat stabilizers, heat degradation inhibitors, plasticizers, release agents, antistatic agents, flame retardants, flame retardant assistants, lubricants, thickeners, polymer processing aids, silicone oils, antiblocking agents, fillers, defoamers, rust inhibitors, antibacterial and antifungal agents, antifouling agents, and colorants (pigments, dyes, etc.).

[0170] Examples of tackifying resins include aliphatic unsaturated hydrocarbon resins, aliphatic saturated hydrocarbon resins, alicyclic unsaturated hydrocarbon resins, alicyclic saturated hydrocarbon resins, aromatic hydrocarbon resins, hydrogenated aromatic hydrocarbon resins, rosin ester resins, hydrogenated rosin ester resins, terpene phenolic resins, hydrogenated terpene phenolic resins, terpene resins, hydrogenated terpene resins, aromatic hydrocarbon-modified terpene resins, coumarone-indene resins, phenolic resins, and xylene resins.

[0171] The softening agent may be any softening agent commonly used for rubber or plastics, such as paraffinic, naphthenic, and aromatic process oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oil; mineral oil; ethylene and α-olefin oligomers; paraffin wax; liquid paraffin; polybutene; low-molecular-weight polybutadiene; and low-molecular-weight polyisoprene.

[0172] The elastomer resin composition (ER) can be produced by melt-kneading one or more materials including the thermoplastic elastomer (E) by a known method. When the elastomer resin composition (ER) contains multiple materials, they may be kneaded all at once or separately, and the compounding procedure is not particularly limited.

[0173] (Back layer) The thermoplastic resin film of the present disclosure preferably comprises a backing layer made of a vinyl alcohol resin composition (VR) containing one or more vinyl alcohol resins (V). The vinyl alcohol resin (V) is excellent in antifouling properties, chemical resistance, antifogging properties, heat retention, etc. A backing layer containing this resin can function as an antifouling resin layer, etc. Known vinyl alcohol resins can be used as the vinyl alcohol resin (V), and from the viewpoints of antifouling properties and moldability, an ethylene-vinyl alcohol copolymer is preferred.

[0174] <Ethylene-vinyl alcohol copolymer> Ethylene-vinyl alcohol copolymer is a saponified copolymer of ethylene and vinyl ester. Hereinafter, this copolymer may be abbreviated as "EVOH." The copolymerization of ethylene and vinyl ester can be carried out by known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization, etc. The copolymerization may be carried out either continuously or batchwise.

[0175] The content of ethylene units in EVOH (also simply referred to as "ethylene content") is preferably 10 to 60 mol%. The lower limit is more preferably 20 mol%, particularly preferably 25 mol%. The upper limit is more preferably 55 mol%, particularly preferably 50 mol%, and most preferably 40 mol%. If the ethylene content is less than the lower limit, the thermal stability during melt extrusion may decrease, causing gelation of the copolymer and the occurrence of defects such as streaks and fish eyes. The possibility of gelation increases particularly when the extrusion is performed for a long period of time under conditions of higher temperature or higher speed than those used in general melt extrusion molding. If the ethylene content exceeds the upper limit, the gas barrier properties may decrease, and the advantageous properties of EVOH may not be fully exhibited.

[0176] As the vinyl ester, vinyl acetate is preferred from the viewpoint of availability, etc. Vinyl acetate usually contains a small amount of acetaldehyde as an unavoidable impurity. The acetaldehyde content in vinyl acetate is preferably 0 to 100 ppm. The upper limit is more preferably 60 ppm, particularly preferably 25 ppm, and most preferably 15 ppm.

[0177] EVOH may contain units derived from other monomers besides ethylene and vinyl ester. Examples of such other monomers include vinylsilane compounds. The content of such other monomer units in EVOH is preferably 0 to 0.2 mol%.

[0178] From the viewpoint of thermal stability, the degree of saponification of the vinyl ester unit is usually 85 to 100 mol %, with the lower limit being preferably 90 mol %, more preferably 98 mol %, and particularly preferably 98.9 mol %.

[0179] From the viewpoint of moldability, the melt flow rate (MFR) of EVOH is preferably 0.5 to 30 g / 10 min. The lower limit is more preferably 1.0 g / 10 min, particularly preferably 1.4 g / 10 min. The upper limit is more preferably 25 g / 10 min, even more preferably 20 g / 10 min, still more preferably 15 g / 10 min, particularly preferably 10 g / 10 min, and most preferably 1.6 g / 10 min. In this specification, the MFR of EVOH is the melt flow rate measured in accordance with JIS K 7210-1 under conditions of a temperature of 190°C and a load of 2,160 g.

[0180] <Ultraviolet absorber (UVA), light stabilizer (LS), antioxidant (AO)> The vinyl alcohol resin composition (VR), like the acrylic resin composition (AR), may contain, if necessary, one or more other thermoplastic resins, one or more ultraviolet absorbers (UVA), one or more light stabilizers (LS), one or more antioxidants (AO), one or more other additives, or a combination thereof. The vinyl alcohol resin composition (VR) can be produced by melt-kneading one or more materials including the vinyl alcohol resin (V) by a known method. When the vinyl alcohol resin (V) contains multiple materials, they may be kneaded all at once or in portions, and the blending procedure is not particularly limited.

[0181] (Other resin layers) The thermoplastic resin film of the present disclosure may have other resin layers and / or functional layers in addition to those described above, as necessary.

[0182] [Thickness of thermoplastic resin film and each layer] The thickness of the thermoplastic resin film of the present disclosure having a single layer structure composed of the acrylic resin composition layer can be designed depending on the application, etc., and is preferably 1 to 500 μm. The lower limit is more preferably 2 μm, even more preferably 5 μm, particularly preferably 8 μm, and most preferably 10 μm. The upper limit is more preferably 400 μm, even more preferably 300 μm, even more preferably 200 μm, even more preferably 100 μm, particularly preferably 80 μm, and most preferably 60 μm.

[0183] In the thermoplastic resin film of the present disclosure having a laminated structure including a surface layer made of the acrylic resin composition layer, a back layer different from the acrylic resin composition layer, and preferably an intermediate layer therebetween, it is preferable that the thickness of each layer and the total thickness satisfy the following conditions: The thickness of the surface layer is preferably 1 / 20 to 2 / 3, and more preferably 1 / 10 to 2 / 3, of the total thickness of the thermoplastic resin film. The thickness of the backing layer is preferably 1 / 20 to 2 / 3, more preferably 1 / 10 to 2 / 3, of the total thickness of the thermoplastic resin film. When the thickness of the surface layer and the back layer is 1 / 20 or more of the total thickness of the thermoplastic resin film, the functions of the surface layer and the back layer, which are functional layers, are sufficiently obtained, and when it is 2 / 3 or less, the thickness of the intermediate layer is sufficiently ensured, and the flexibility-improving effect of the intermediate layer is preferably exerted. In order to ensure good adhesion between the front and back layers while ensuring good functionality of these layers, the thickness of the intermediate layer is preferably 1 / 5 to 9 / 10, and more preferably 1 / 5 to 8 / 10, of the total thickness of the thermoplastic resin film. The total thickness of the thermoplastic resin film having a laminated structure can be designed depending on the application, etc., and is preferably 20 to 500 μm, more preferably 50 to 300 μm.

[0184] [Method of manufacturing thermoplastic resin film] The thermoplastic resin film of the present disclosure can be produced by known methods. Examples of methods for producing the single-layer thermoplastic resin film of the present disclosure include melt molding methods such as extrusion molding, injection molding, inflation molding, blow molding, and calendar molding; compression molding (also called press molding); and solution casting.

[0185] Examples of methods for producing the thermoplastic resin film of the present disclosure having a laminated structure include known multilayer molding methods such as coextrusion molding (also called multilayer extrusion molding), multilayer blow molding, multilayer injection molding, heat press, and heat lamination. Among these, coextrusion molding, in which multiple resin compositions melt-kneaded using different extruders are coextruded from a common extrusion die (such as a T-die), is preferred. Coextrusion die types include a multi-manifold die type and a field block type. In the feed block type, multiple resin compositions in a molten state are laminated in a feed block, then introduced into a T-die or the like, formed into a sheet, and coextruded. In the multi-manifold die type, multiple resin compositions in a molten state are introduced into a T-die or the like, formed into a sheet, then laminated and coextruded. Of these, the multi-manifold die type is preferred. In either type, the thermoplastic resin laminate extruded from the T-die or the like is cooled by passing through a gap between at least a pair of cooling pressure rolls, and then taken up by a take-up roll. The above coextrusion, cooling, and take-up steps are carried out continuously.

[0186] As described above, according to the present disclosure, it is possible to provide a thermoplastic resin film of a single layer structure or a laminate structure that is inhibited from coloring or discoloring during melt molding and has excellent initial weather resistance and long-term weather resistance. The present disclosure also makes it possible to provide a thermoplastic resin film with a laminated structure that is inhibited from coloring or discoloring during melt molding, has excellent initial weather resistance and long-term weather resistance, and is also excellent in transparency, antifouling properties, chemical resistance, antifogging properties, bending resistance, interlayer adhesion, heat retention, and handleability.

[0187] [Application] The thermoplastic resin film of the present disclosure is suitable for automobile exterior applications, building material applications, agricultural applications, and the like, and is particularly suitable for agricultural applications such as films for agricultural greenhouses. [Example]

[0188] Examples and comparative examples according to the present disclosure will be described. [Evaluation items and evaluation methods] The evaluation items and evaluation methods are as follows. (polymerization conversion rate) The polymerization conversion rate was determined by gas chromatography analysis. A Shimadzu Gas Chromatograph GC-14A was connected to a GL Sciences InertCap1 column (film thickness 0.4 μm, inner diameter 0.25 mmφ, length 60 m). Analysis was performed under the following conditions, and the polymerization conversion rate was calculated from the obtained data. Injection temperature: 250℃, Detector temperature: 250℃, Temperature profile: Hold at 60°C for 5 minutes → Heat to 250°C at a rate of 10°C / min → Hold at 250°C for 10 minutes.

[0189] (Weight average molecular weight (Mw), molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) The weight average molecular weight (Mw) and molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin were determined by gel permeation chromatography (GPC). The GPC apparatus used was a Tosoh HLC-8320 (product number) equipped with a differential refractive index detector (RI detector). Tetrahydrofuran was used as the eluent, and TSKgel SuperMultipore Column (manufactured by Tosoh) was used as the column. Two "HZM-M" columns and a "SuperHZ4000" column connected in series were used. A sample solution was prepared by dissolving 4 mg of resin in 5 mL of tetrahydrofuran. The column oven temperature was set to 40°C, and 20 μL of the sample solution was injected at an eluent flow rate of 0.35 mL / min to measure the chromatogram. GPC measurements were performed using 10 standard polystyrene or polymethyl methacrylate (PMMA) samples with molecular weights ranging from 400 to 5,000,000, and a calibration curve showing the relationship between retention time and molecular weight was prepared. Based on this calibration curve, the Mw, Mn, and Mw / Mn of the resin, converted into standard polystyrene or standard PMMA, were determined.

[0190] (Average particle size) Using an ultramicrotome (Leica EM UC7rt, manufactured by JEOL Ltd.), cross-sectional sections (50 nm thick) parallel to the extrusion direction were cut from the thermoplastic resin film. The obtained sections were electro-stained using a 10% by mass aqueous solution of phosphotungstic acid. This method selectively stains only the cross-linked rubber component layer contained in the acrylic rubber particles. Transmission electron microscope (TEM) images of the above sections were observed using a scanning electron microscope (SEM) (JEOL Ltd., "JSM-7600F") and its optional transmission electron detector (SM-74240RTED). For 30 randomly selected first acrylic rubber particles (RP-S) whose diameter from the center to the outermost cross-linked rubber component layer was 50 nm or more and less than 160 nm, the diameter from the center to the outermost cross-linked rubber component layer was measured as the particle diameter. If the particle shape was non-circular, the average of the major axis diameter and minor axis diameter from the center to the outermost cross-linked rubber component layer of the acrylic rubber particle (RP-S) was used as the particle diameter. The average particle diameter of the 30 particles was used as the data for "average particle diameter of first acrylic rubber particles (RP-S)." Similarly, for 30 randomly selected second acrylic rubber particles (RP-L) whose entire particle was visible and whose diameter from the center to the outermost cross-linked rubber component layer was 160 nm or more and 300 nm or less, the diameter from the center to the outermost cross-linked rubber component layer (if the particle shape was non-circular, the average of the major axis diameter and minor axis diameter) was measured as the particle diameter, and these average values ​​were used as the data for the "average particle diameter of the second acrylic rubber particles (RP-L)." In addition, in all of the acrylic rubber particles (RP) used in the section [Examples], the outermost crosslinked rubber component layer is the second layer from the center (second layer).

[0191] (hydrogenation rate) The hydrogenation rate of the polymer block containing conjugated diene compound units was determined by measuring the iodine value of the block copolymer before and after the hydrogenation reaction.

[0192] (Total amount of 1,2-bonds and 3,4-bonds) Thermoplastic elastomers containing polymer blocks containing conjugated diene compound units 1 H-NMR measurement was performed. The total amount of 1,2-bonds and 3,4-bonds was calculated from the ratio of the integral value of the first peak at 4.2 to 5.0 ppm, which is derived from 1,2-bonded and 3,4-bonded conjugated diene compound units, to the integral value of the second peak at 5.0 to 5.45 ppm, which is derived from 1,4-bonded conjugated diene compound units.

[0193] (Melting Point) The melting point of the polypropylene polymer was measured using a differential scanning calorimeter (Shimadzu Corporation, "DSC-50 (product number)"). Approximately 5 mg of a polypropylene film sample was placed in an aluminum pan and set in the apparatus. After nitrogen replacement for 30 minutes or more, the sample was heated from room temperature (20-25°C) to 200°C at a rate of 10°C / min in a 10 ml / min nitrogen stream, held for 5 minutes, and then cooled to 40°C at a rate of 10°C / min (first scan). The sample was then heated to 200°C at a rate of 10°C / min (second scan), and a fusion calorimeter curve was obtained. The melting point (Tm) was determined as the maximum peak temperature of melting (°C).

[0194] (melt tension) The melt tension of the polypropylene polymer was measured using a capillary rheometer ("Capilograph 1D" manufactured by Toyo Seiki Seisakusho Co., Ltd.) equipped with a pulley-type tension measurement unit. The polypropylene polymer was placed in a 9.55 mm diameter cylinder heated to 230°C. The molten polypropylene polymer was extruded through a 2.0 mm diameter, 40 mm long orifice at an extrusion rate of 20 mm / min and taken up by a pair of take-up rolls at a take-up rate of 4.0 m / min. The tension applied to the pulley-type tension measurement jig was measured as the melt tension (N).

[0195] (Total thickness and thickness of each layer) The total thickness of the thermoplastic resin film was measured using a micrometer. The thickness of each layer included in the laminated thermoplastic resin film was determined by cutting the thermoplastic resin film in the thickness direction with a razor and observing the resulting cross section under a microscope, and the ratio of the thickness of each layer to the total thickness was determined.

[0196] (Transmittance before and after accelerated weathering test) <Initial transmittance (before weather resistance test)> A 50 mm x 50 mm test piece was cut out from the thermoplastic resin film. A spectrophotometer (Shimadzu Corporation, "UV3600") was used to obtain a transmission spectrum in the wavelength range of 250 to 600 nm, and the light transmittance (initial transmittance (before weather resistance test)) (TW ) was obtained. T W represents the light transmittance at wavelength W nm (W is an integer between 250 and 600). The initial UV transmittance (T 275 ), (T 314 ), (T 350 ) was identified.

[0197] <Accelerated weather resistance test> The accelerated weathering test equipment used was an Iwasaki Electric Metal Halide Lamp Weather Meter SUV-W161. A 1,000-hour accelerated weathering test was conducted under conditions of a black panel temperature of 63°C, UV irradiation, and rainfall. For laminated thermoplastic resin films, the thermoplastic resin film was positioned so that light was shining on the surface side. The rainfall consisted of a cycle of 12 minutes of rain followed by 48 minutes of rest. This accelerated weathering test is considered equivalent to a 20-year weathering test under actual usage conditions.

[0198] <Transmittance after accelerated weathering test> The transmission spectrum of the thermoplastic resin film in the wavelength range of 250 to 600 nm after the accelerated weathering test was obtained in the same manner as before the accelerated weathering test, and the light transmittance (transmittance after the weathering test) (T W The UV transmittance (T 275 ), (T 314 ), (T 350 ) was identified. In Examples E1 to E8, the UV transmittance (T 275 ), (T 350 ) is (T 314 Therefore, in Table 4, the UV transmittance data after the accelerated weathering test is shown as T 314 Only the above is listed.

[0199] The rate of change in UV transmittance (ΔT 314 ) was sought. [Change rate of UV transmittance (ΔT 314)(%)]=100×[(UV transmittance after accelerated weathering test (T 314 ))-(Initial UV transmittance (T 314 ))] / [UV transmittance after accelerated weathering test (T 314 )] ΔT 314 The larger the value, the greater the increase in UV transmittance at 314 nm after the accelerated weathering test compared to the initial value (before the accelerated weathering test). For example, a ΔT of 90% or more 314 indicates that the UV transmittance after the accelerated weathering test increased by 10 times or more compared to the initial value (before the accelerated weathering test) (in other words, the UV blocking performance after the accelerated weathering test decreased by 10 times or more compared to the initial value (before the accelerated weathering test)).

[0200] (heating test) A 50 mm x 50 mm test piece was cut out from a transparent thermoplastic resin film. This test piece was placed in an oven set to 250°C and heated for 2 hours. After heating, the appearance of the test piece was visually observed and evaluated according to the following criteria. A (good): No coloring was observed. C (poor): Brownish coloring was observed. [material] <Methacrylic resin (M)> The following methacrylic resins (M) were prepared. (M1) Polymethyl methacrylate (PMMA), Mw (standard PMMA equivalent): 80,000), (M2) Methyl methacrylate (MMA) / methyl acrylate (MA) copolymer (MMA unit content: 95% by mass, MA unit content: 5% by mass, Mw (standard PMMA equivalent): 80,000).

[0201] <Acrylic rubber particles (RP), dispersant (D), powder containing acrylic rubber particles> The following acrylic rubber particles (RP) and acrylic rubber particle-containing powders were produced. The average particle size of the two-layer or three-layer acrylic rubber particles (RP) is the volume average particle size (D50) of the polymer particles contained in the latex obtained after polymerization of the second or third layer, measured using a laser diffraction / scattering particle size distribution analyzer. The average particle size of the methacrylic copolymer particles is the volume average particle size (D50) of the copolymer particles contained in the latex, measured using a laser diffraction / scattering particle size distribution analyzer.

[0202] (RP-S1) According to the method described in Synthesis Example 6 (Synthesis of multilayer structure particles (E-1)) in the section [Examples] of WO 2022 / 019310, powdery three-layer structure acrylic rubber particles (RP-S1) were obtained. The composition of each layer, the mass ratio of each layer, and the average particle diameter are as follows. First layer: methyl methacrylate (MMA) unit / butyl acrylate (BA) unit / allyl methacrylate (ALMA) unit (mass ratio) = 49.9 / 49.9 / 0.2, Second layer: MMA unit / BA unit / ALMA unit (mass ratio) = 5 / 93.5 / 1.5, Third layer: MMA unit / BA unit (mass ratio) = 87.2 / 12.5 1st layer / 2nd layer / 3rd layer (mass ratio) = 26.2 / 157.4 / 341.1, Average particle size of the three layers: 0.10 μm.

[0203] (RP-L1) A reactor equipped with a stirrer, thermometer, nitrogen gas inlet tube, monomer inlet tube, and reflux condenser was charged with 1050 parts by weight of ion-exchanged water, 0.3 parts by weight of sodium polyoxyethylene tridecyl ether acetate, and 0.7 parts by weight of sodium carbonate, and the atmosphere inside the reactor was thoroughly purged with nitrogen gas. The internal temperature was then raised to 80°C. 0.25 parts by weight of potassium persulfate was added and stirred for 5 minutes. 245 parts by weight of a monomer mixture consisting of 95.4% by weight of MMA, 4.4% by weight of MA, and 0.2% by weight of ALMA was continuously added dropwise over 60 minutes. After the dropwise addition was completed, the polymerization reaction was continued for an additional 30 minutes to achieve a polymerization conversion rate of 98% or higher. Next, 0.32 parts by mass of potassium persulfate was added to the reactor and stirred for 5 minutes. Then, 315 parts by mass of a monomer mixture consisting of 80.5% by mass of BA, 17.5% by mass of St, and 2% by mass of ALMA was continuously added dropwise over 60 minutes. After the dropwise addition was completed, the polymerization reaction was continued for an additional 30 minutes until the polymerization conversion rate reached 98% or higher. Next, 0.14 parts by mass of potassium persulfate was added to the reactor and stirred for 5 minutes. Then, 140 parts by mass of a monomer mixture consisting of 95.2% by mass of MMA, 4.4% by mass of MA, and 0.4% by mass of n-octyl mercaptan was continuously added dropwise over 30 minutes. After the addition was completed, the polymerization reaction was continued for an additional 60 minutes to achieve a polymerization conversion rate of 98% or higher, yielding a latex (RP-L1-L) containing acrylic rubber particles (RP-L1). The composition of each layer, the mass ratio of each layer, and the average particle size were as follows: Layer 1: MMA units / MA units / ALMA units (mass ratio) = 95.4 / 4.4 / 0.2 Layer 2: BA units / St units / ALMA units (mass ratio) = 80.5 / 17.5 / 2 Third layer: MMA unit / MA unit (mass ratio) = 95.2 / 4.4 1st layer / 2nd layer / 3rd layer (mass ratio) = 35 / 45 / 20, Average particle size of the three layers: 0.23 μm.

[0204] (D1) A latex (D1-L) containing methacrylic copolymer particles (dispersant (D1)) was obtained by a known emulsion polymerization method. The composition and physical properties of the copolymer particles are as follows: MMA unit / methyl acrylate unit (mass ratio) = 94 / 6, Number average molecular weight (Mn): 80,000, Glass transition temperature (Tg): 100℃.

[0205] (RP-L1-D) A latex (RP-L1-L) containing acrylic rubber particles (RP-L1) with a three-layer structure was mixed with a latex (D1-L) containing methacrylic copolymer particles (dispersant (D1)). The resulting dispersion was freeze-coagulated, washed with water, and dried to obtain a mixed powder of acrylic rubber particles (RP-L1) and methacrylic copolymer particles (dispersant (D1)) (acrylic rubber particle-containing powder (RP-L1-D)). The mass ratio of each particle in the mixed powder and the average particle size of each particle are as follows: Acrylic rubber particles (RP-L1) / methacrylic copolymer particles (dispersant (D1)) (mass ratio) = 67 / 33, Average particle size of acrylic rubber particles (RP-L1): 0.23 μm; Average particle size of methacrylic copolymer particles (dispersant (D1)): 0.13 μm.

[0206] <Block copolymer (RB)> The following block copolymers (RB) were prepared: (RB1) A triblock copolymer (RB1) consisting of [methyl methacrylate (MMA) polymer block (mb)]-[n-butyl acrylate (BA) polymer block (ab)]-[methyl methacrylate (MMA) polymer block (mb)], with Mw (standard PMMA equivalent) of 70,000, a polymer block mass ratio of (mb):(ab):(mb) = 14.3:50.0:35.7, and an MMA unit / BA unit (mass ratio) = 50 / 50, was obtained by a known method.

[0207] <Thermoplastic elastomer (E)> The following thermoplastic elastomers (EX), (EY), and (EZ) were produced. (First Thermoplastic Elastomer (EX-1)) A pressure vessel, the interior of which had been purged with nitrogen and dried, was charged with 50.0 kg of cyclohexane as a solvent and 61.1 g of a 10.5 wt% cyclohexane solution of sec-butyllithium (6.42 g of sec-butyllithium) as an anionic polymerization initiator, and mixed. The solution was heated to 50°C, and 0.81 kg of styrene (St) was added and polymerized for 1 hour. 10.87 kg of isoprene was then added and polymerized for 2 hours. 0.81 kg of styrene (St) was then added and polymerized for 1 hour. In this way, a reaction solution containing a polystyrene-polyisoprene-polystyrene triblock copolymer was obtained. Palladium carbon (palladium loading: 5 wt%) was added as a hydrogenation catalyst at 5 wt% relative to the block copolymer, and the reaction was carried out for 10 hours at a hydrogen pressure of 2 MPa and 150°C. After cooling and depressurization, the palladium carbon was removed by filtration, and the filtrate was concentrated and vacuum dried to obtain thermoplastic elastomer (EX-a) (a hydrogenated product of polystyrene-polyisoprene-polystyrene triblock copolymer). The total proportion of 1,2-bonds and 3,4-bonds in the polyisoprene blocks in the thermoplastic elastomer (EX-a) was 7 mol%.

[0208] Separately, a pressure vessel whose interior had been purged with nitrogen and dried was charged with 50.0 kg of cyclohexane as a solvent and 420.0 g of a 10.5% by mass cyclohexane solution of sec-butyllithium (44.1 g of sec-butyllithium) as an anionic polymerization initiator, and mixed. After heating this solution to 50°C, 2.83 kg of styrene (St) was added and polymerized for 1 hour, followed by 19.81 kg of isoprene and polymerized for 2 hours. This yielded a reaction solution containing a polystyrene-polyisoprene diblock copolymer. Next, hydrogenation, filtration to remove the palladium carbon, and vacuum drying were carried out in the same manner as above to obtain thermoplastic elastomer (EX-b) (a hydrogenated product of polystyrene-polyisoprene diblock copolymer). The total proportion of 1,2-bonds and 3,4-bonds in the polyisoprene blocks in thermoplastic elastomer (EX-b) was 7 mol%.

[0209] The obtained thermoplastic elastomers (EX-a) and (EX-b) were melt-kneaded using a twin-screw extruder (Coperion's "ZSK26 MegaCompounder" (ratio of effective screw length (L) to screw diameter (D) (L / D) = 54) at a screw rotation speed of 300 rpm and a melt-kneading temperature of 200°C, thereby obtaining a first thermoplastic elastomer (EX-1). The total proportion of 1,2-bonds and 3,4-bonds in the polyisoprene blocks in the first thermoplastic elastomer (EX-1) was 7 mol%.

[0210] (Second Thermoplastic Elastomer (EY-1)) A pressure vessel, the interior of which had been purged with nitrogen and dried, was charged with 50.0 kg of cyclohexane as a solvent, 94.1 g of a 10.5% by mass cyclohexane solution of sec-butyllithium (9.9 g of sec-butyllithium) as an anionic polymerization initiator, and 300 g of tetrahydrofuran as a Lewis base, and mixed. After heating the solution to 50°C, 1.25 kg of styrene (St) was added and polymerized for 1 hour. Subsequently, 10.00 kg of isoprene was added and polymerized for 2 hours. Subsequently, 1.25 kg of styrene (St) was added and polymerized for 1 hour. In this way, a reaction solution containing a polystyrene-polyisoprene-polystyrene triblock copolymer was obtained. Next, hydrogenation, filtration removal of palladium carbon, and vacuum drying were carried out in the same manner as in Production Example 1, yielding a second thermoplastic elastomer (EY-1) (a hydrogenated product of a polystyrene-polyisoprene-polystyrene triblock copolymer). The total proportion of 1,2-bonds and 3,4-bonds in the polyisoprene blocks in the second thermoplastic elastomer (EY-1) was 55 mol %.

[0211] (Third Thermoplastic Elastomer (EZ-1)) A pressure vessel, the interior of which had been purged with nitrogen and dried, was charged with 4.29 kg of α-methylstyrene (αMSt), 6.25 kg of cyclohexane, 1.18 kg of methylcyclohexane, and 0.15 kg of tetrahydrofuran, and mixed. 0.42 L of a 1.3 M cyclohexane solution of sec-butyllithium was added to this solution, and polymerization was carried out at -10°C for 5 hours. Three hours after the start of polymerization, the weight-average molecular weight (Mw, calculated as standard polystyrene) of poly(α-methylstyrene) (block S) was 6600, and the polymerization conversion of α-methylstyrene was 90%. Next, 0.88 kg of butadiene was added to this reaction solution, and polymerization was carried out at -10°C for 30 minutes. After this process, 41.8 kg of cyclohexane was added. The polymerization conversion of butadiene at this point was 90%. After this process, a poly(α-methylstyrene) block (S)-polybutadiene block (t1) copolymer was obtained. The polybutadiene block (t1) had a weight average molecular weight (Mw, calculated as standard polystyrene) of 3700 and a 1,2-bond content of 81 mol %.

[0212] An additional 7.71 kg of butadiene was added to the reaction mixture, and polymerization was carried out at 50°C for 2 hours to obtain a poly(α-methylstyrene) block (S)-polybutadiene block (t1)-polybutadiene block (t2) copolymer. The weight-average molecular weight (Mw, calculated as standard polystyrene) of the polybutadiene block (t2) was 29,800, and the 1,2-bond content was 40 mol%.

[0213] To the reaction mixture, 0.54 L of a 0.5 M toluene solution of dichlorodimethylsilane was added, and the coupling reaction was carried out at 50°C for 1 hour. After this reaction, a poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) triblock copolymer (poly(α-methylstyrene) block (S)-polybutadiene block (t1)-polybutadiene block (t2)-X-polybutadiene block (t2)-polybutadiene block (t1)-poly(α-methylstyrene) block (S) copolymer) was produced as the coupling product. Here, X is a coupling residue. The obtained poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) triblock copolymer had a poly(α-methylstyrene) block content of 31 mass % and a 1,4-bond content of 55 mol % in the total polybutadiene blocks (t1 + t2). The coupling product and the uncoupling-reacted block copolymer (poly(α-methylstyrene) block (S)-polybutadiene block (t1)-polybutadiene block (t2) copolymer) were subjected to GPC analysis, and the coupling efficiency was calculated from the ratio of the UV absorption peak integral values, which was 94%.

[0214] A Ziegler hydrogenation catalyst consisting of nickel octylate and triethylaluminum was added to the reaction solution under a hydrogen atmosphere, and a hydrogenation reaction was carried out for 5 hours at a hydrogen pressure of 0.8 MPa and 80°C to obtain a third thermoplastic elastomer (EZ-1). The main component of the third thermoplastic elastomer (EZ-1) was a hydrogenated product of poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) triblock copolymer (a hydrogenated product of the above-mentioned coupling product), and its content was 94 mass%. The third thermoplastic elastomer (EZ-1) had a weight average molecular weight (Mw, converted into standard polystyrene) of 79,500, a number average molecular weight (Mn, converted into standard polystyrene) of 78,700, Mw / Mn of 1.01, a hydrogenation rate of 97.5% in the entire polybutadiene block (t1+t2), and a total proportion of 1,2-bonds and 3,4-bonds in the polybutadiene block of 45 mol%.

[0215] <Polypropylene polymer (P)> The following polypropylene polymers (PX) and (PY) were prepared. (PX-1) "Waymax (registered trademark) MFX3" manufactured by Japan Polypropylene Corporation, MFR at 230°C and 21.18 N: 9.0 g / 10 min, melt tension: 4.9 × 10 -2 N, (PY-1) Maleic anhydride modified polypropylene, "UMEX (registered trademark) 5200" manufactured by Sanyo Chemical Industries, Ltd., melting point 124°C.

[0216] <Vinyl alcohol resin (V)> The following vinyl alcohol resins (V) were prepared: (V1) According to the method described in Synthesis Example 8 (Synthesis of vinyl alcohol resin (B-1)) in the section [Examples] of WO 2022 / 019310, pellets of vinyl alcohol resin (V1) (saponification degree: 99 mol%, ethylene unit content: 44 mol%) were obtained.

[0217] <Triazine-based UV absorbers> (TAX1) 2-[4,6-bis(1,1′-biphenyl-4-yl)-1,3,5-triazin-2-yl]-5-[(2-ethylhexyl)oxy]phenol, “Tinuvin® 1600” manufactured by BASF. (TAY1) 2-[4,6-diphenyl-1,3,5-triazin-2-yl]-5-(hexyloxy)phenol, "Tinuvin® 1577ED" manufactured by BASF.

[0218] <Benzotriazole-based UV absorbers> (BT1) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol ("Tinuvin (registered trademark) 234" manufactured by BASF), (BT2) 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], manufactured by ADEKA Corporation ("ADEKA STAB LA-31RG").

[0219] <Light stabilizer> (LS1) Hindered amine light stabilizer, 1,2,3,4-butanetetracarboxylic acid tetrakis(2,2,6,6-tetramethyl-4-piperidinyl), ADEKA Corporation "ADEKA STAB LA-57", (LS2) Hindered amine light stabilizer, "Tinuvin (registered trademark) NOR 371FF" manufactured by BASF.

[0220] <Antioxidants> (AO1) Hindered phenolic antioxidant, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], "Irganox 1010" manufactured by BASF Japan Ltd. (AO2) Hindered phenolic antioxidant, N,N'-(1,6-hexanediyl)bis[3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanamide] (BASF "Irganox 1098").

[0221] <Polymer processing aid> (PA1) High molecular weight methacrylic polymer, "Metablen P-530A" manufactured by Mitsubishi Chemical Corporation.

[0222] <Acrylic Resin Compositions (AR1) to (AR5), (ARC1) to (ARC4)> A mixture of one or more methacrylic resins (M), one or more acrylic rubber particles (RP), one or more acrylic rubber particle-containing powders, one or more block copolymers (RB), one or more polymer processing aids (PA), one or more ultraviolet absorbers (UVA), one or more light stabilizers (LS), and one or more antioxidants (AO) was melt-mixed using a twin-screw extruder and extruded into strands. The strands were cut using a pelletizer to obtain pellets of acrylic resin compositions (AR1) to (AR5) and (ARC1) to (ARC4).

[0223] The blending composition (charged composition) of the acrylic resin composition (AR) or (ARC) is shown in Table 1. The blending amount is expressed in parts by mass. The total amount of the (meth)acrylic resin (A) (specifically, the total amount of one or more methacrylic resins (M), one or more acrylic rubber particles (RP), one or more dispersants (D), one or more block copolymers (RB), and one or more polymer processing aids (PA)) is 100 parts by mass. Furthermore, the dispersant (D) and polymer processing aid (PA) used in the section [Examples] are both included in the methacrylic resin (M).

[0224] [Table 1]

[0225] <Elastomer resin composition (ER)> The following elastomer resin compositions (ER) were prepared. (ER1) 40 parts by weight of the first thermoplastic elastomer (EX-1), 40 parts by weight of the second thermoplastic elastomer (EY-1), 20 parts by weight of the third thermoplastic elastomer (EZ-1), 7.5 parts by weight of the first polypropylene polymer (PX-1), 10 parts by weight of the second polypropylene polymer (PY-1), 0.3 parts by weight of a benzotriazole-based UV absorber (BT2), 0.3 parts by weight of a hindered amine-based light stabilizer (LS1), and 0.1 parts by weight of a hindered phenol-based antioxidant (AO1) were melt-kneaded using a twin-screw extruder and extruded into strands. The strands were cut using a pelletizer to obtain pellets of the elastomer resin composition (ER1). The formulation is shown in Table 2.

[0226] [Table 2]

[0227] <Vinyl alcohol resin composition (VR)> The following vinyl alcohol resin compositions (VR) were prepared. (VR1) 100 parts by mass of vinyl alcohol resin (V1), 0.4 parts by mass of hindered amine light stabilizer (LS2), and 0.3 parts by mass of hindered phenol antioxidant (AO2) were melt-kneaded using a twin-screw extruder and extruded into strands. The strands were cut using a pelletizer to obtain pellets of vinyl alcohol resin composition (VR1). The formulation is shown in Table 3.

[0228] [Table 3]

[0229] [Examples E1 to E6, Comparative Examples EC1 to EC4] Pellets of the acrylic resin composition (AR) (any of (AR1) to (AR5) and (ARC1) to (AR4)) were placed in the hopper of a single-screw extruder and melt-kneaded. The molten resin composition was extruded using a T-die, pressed and cooled using multiple cooling rolls, and taken up by a pair of take-up rolls. In this manner, single-layer thermoplastic resin films with thicknesses of 10 μm, 15 μm, 30 μm, or 50 μm were obtained. The structures and evaluation results of the obtained thermoplastic resin films are shown in Table 4.

[0230] [Examples E7 and E8] Pellets of an acrylic resin composition (AR1) or (AR2) were prepared as the surface layer (first layer), pellets of an elastomer resin composition (ER1) were prepared as the middle layer (second layer), and pellets of a vinyl alcohol resin composition (VR1) were prepared as the back layer (third layer). These resin compositions were each placed in the hoppers of separate single-screw extruders and melt-kneaded. These molten resin compositions were co-extruded using a multi-manifold die, pressed and cooled using multiple cooling rolls, and taken up by a pair of take-up rolls. In this manner, a three-layer thermoplastic resin film (width 30 cm, total thickness 150 μm) was obtained, consisting of a surface layer (first layer, acrylic resin composition layer, 50 μm thick), an intermediate layer (second layer, elastomer resin composition layer, 50 μm thick), and a back layer (third layer, vinyl alcohol resin composition layer, 50 μm thick). The total thickness was 150 μm, with the surface layer accounting for 1 / 3 of the total thickness, and the back layer accounting for 1 / 3 of the total thickness. The thickness of each layer was controlled by the extrusion flow rate. The structure and evaluation results of the obtained thermoplastic resin film are shown in Table 4.

[0231] [Table 4]

[0232] [Summary of results] The absorption spectra of the ultraviolet absorbers (TAX1), (TAY1), and (BT1) used as the surface layer materials in the section [Examples] were measured. A chloroform solution (concentration: 10 mg / L) of UV absorber (TAX1), (TAY1), or (BT1) was prepared. The resulting sample was placed in a quartz cell, and its absorption spectrum was measured using a spectrophotometer (Shimadzu Corporation, "UV3600") at a measurement temperature of 23°C and a measurement wavelength range of 250 to 600 nm. The absorption spectra of UV absorbers (TAX1), (TAY1), and (BT1) are shown in Figure 2.

[0233] The first triazine-based ultraviolet absorber (TAX1) had a large absorption peak in the wavelength range of 250 to 400 nm, and an absorbance of 0.60 or more over a wide range of 288 to 352 nm (approximately 290 to approximately 352 nm), with an absorption peak wavelength (the wavelength at which the absorbance is maximum) of 319 nm. The second triazine-based ultraviolet absorber (TAY1) had a large absorption peak in the wavelength range of 250 to 325 nm, an absorbance of 0.60 or more in the range of 250 to 300 nm, and an absorption peak wavelength (the wavelength at which the absorbance is maximum) of 275 nm. It was found that the first triazine-based UV absorber (TAX1) and the second triazine-based UV absorber (TAY1) have different absorption peak wavelengths and are complementary to each other. When the first triazine-based UV absorber (TAX1) and the second triazine-based UV absorber (TAY1) are used in combination, the second triazine-based UV absorber (TAY1) can absorb light in the wavelength range of 250 to 288 nm, where the absorbance of the first triazine-based UV absorber (TAX1) alone is low, and it was found that an absorbance of 0.60 or more can be achieved over a wide range from 250 to 350 nm.

[0234] The benzotriazole-based compound (BT1) tended to have lower absorbance across the entire wavelength range of 250 to 400 nm compared to the two triazine-based UV absorbers (TAX1) and (TAY1). The benzotriazole-based compound (BT1) had two small absorbance peaks in the wavelength range of 250 to 400 nm, with the absorbance peak wavelengths (wavelengths at which absorbance was greatest) at 303 nm and 346 nm. The absorbance at the 303 nm peak was 0.43 (less than 0.50), and the absorbance at the 346 nm peak was 0.43 (less than 0.50).

[0235] In Examples E1 to E8, a thermoplastic resin film was obtained that included an acrylic resin composition layer made of an acrylic resin composition (AR) containing one or more (meth)acrylic resins (A), one or more first triazine ultraviolet absorbers (TAX) in which one monophenyl group, which may have a substituent, and two biphenyl groups, which may have a substituent, are bonded to one triazine ring, and one or more second triazine ultraviolet absorbers (TAY) in which three monophenyl groups, which may have a substituent, are bonded to one triazine ring. All of the thermoplastic resin films obtained in these examples had an initial UV transmittance (T 275 ), (T 314 ), (T 350 ) is 0.3% or less, and the UV transmittance (T 275 ), (T 314 ), (T 350 ) was 0.3% or less, and the initial weather resistance and long-term weather resistance were excellent. In all of the thermoplastic resin films obtained in these Examples, the amount of ultraviolet absorber in the acrylic resin composition layer was appropriate, and no coloring was observed during melt molding, resulting in thermoplastic resin films with good appearance.

[0236] In Comparative Example EC1, a thermoplastic resin film was obtained comprising an acrylic resin composition layer made of a comparative acrylic resin composition (ARC) containing only a second triazine-based ultraviolet absorber (TAY) as the ultraviolet absorber (UVA). The thermoplastic resin film obtained in this comparative example had a UV transmittance (T 314 ) exceeded 0.3%, and the long-term weather resistance was poor.

[0237] In Comparative Examples EC2 and EC3, a thermoplastic resin film was obtained comprising an acrylic resin composition layer made of a comparative acrylic resin composition (ARC) in which a second triazine-based ultraviolet absorber (TAY) and a benzotriazole-based ultraviolet absorber (BT) were used in combination as ultraviolet absorbers (UVA). The thermoplastic resin film obtained in Comparative Example EC2 had a UV transmittance (T 314 ) is more than 0.3%, and the rate of change in UV transmittance after accelerated weathering test (ΔT 314 ) was 99% or more, and the long-term weather resistance was poor. The thermoplastic resin film obtained in Comparative Example EC3 exhibited a change in UV transmittance (ΔT 314 ) was 99% or more, and the long-term weather resistance was poor. In addition, the thermoplastic resin film obtained in Comparative Example EC3 had a large amount of ultraviolet absorber in the acrylic resin composition layer, and coloring was observed during melt molding, and a thermoplastic resin film with good appearance was not obtained.

[0238] In Comparative Example EC4, a thermoplastic resin film was obtained comprising an acrylic resin composition layer made of a comparative acrylic resin composition (ARC) containing only a first triazine-based ultraviolet absorber (TAX) as the ultraviolet absorber (UVA). The thermoplastic resin film obtained in this comparative example had an initial UV transmittance (T 275 ) was more than 0.3%, and the initial weather resistance was poor.

[0239] The present invention is not limited to the above-described embodiments and examples, and appropriate design changes are possible without departing from the spirit of the present invention. [Explanation of symbols]

[0240] 1. Thermoplastic resin film 11 Surface layer 12 Lining 13 Middle class

Claims

1. A thermoplastic resin film including an acrylic resin composition layer made of an acrylic resin composition (AR) containing a (meth)acrylic resin (A) and an ultraviolet absorber (UVA), A thermoplastic resin film, comprising an ultraviolet absorber (UVA) comprising a first triazine-based ultraviolet absorber (TAX) in which one monophenyl group, which may have a substituent, and two biphenyl groups, which may have a substituent, are bonded to one triazine ring, and a second triazine-based ultraviolet absorber (TAY) in which three monophenyl groups, which may have a substituent, are bonded to one triazine ring.

2. 2. The thermoplastic resin film according to claim 1, wherein the total amount of the first triazine-based ultraviolet absorber (TAX) and the second triazine-based ultraviolet absorber (TAY) is 0.8 to 5.0 parts by mass relative to 100 parts by mass of the total amount of the (meth)acrylic resin (A).

3. 3. The thermoplastic resin film according to claim 2, wherein the total amount of the first triazine-based ultraviolet absorber (TAX) is 0.4 to 2.5 parts by mass and the total amount of the second triazine-based ultraviolet absorber (TAY) is 0.4 to 2.5 parts by mass, relative to 100 parts by mass of the total amount of the (meth)acrylic resin (A).

4. The thermoplastic resin film according to claim 1, having a light transmittance at 314 nm of 0 to 0.3%.

5. The thermoplastic resin film according to claim 1, having a light transmittance at 275 nm of 0 to 0.3%.

6. The thermoplastic resin film according to claim 1, having a light transmittance at 350 nm of 0 to 0.3%.

7. 2. The thermoplastic resin film according to claim 1, wherein the (meth)acrylic resin (A) comprises one or more methacrylic resins (M) and one or more rubber-like elastomers (R) selected from the group consisting of acrylic rubber particles (RP) and acrylic block copolymers (RB).

8. a surface layer formed of the acrylic resin composition layer; The thermoplastic resin film according to any one of claims 1 to 7, which has a backing layer different from the acrylic resin composition layer.

9. The thermoplastic resin film according to claim 8 , further comprising an intermediate layer between the front layer and the back layer.

10. 10. The thermoplastic resin film according to claim 9, wherein the intermediate layer comprises one or more thermoplastic elastomers (E) selected from the group consisting of block copolymers containing a polymer block (a) containing an aromatic vinyl compound unit and a polymer block (b) containing a conjugated diene compound unit, and hydrogenated products of the block copolymers.

11. The thermoplastic elastomer (E) is one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing a styrene unit and a polymer block (yb) containing a conjugated diene compound unit in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol mass% or more, and hydrogenated products of the block copolymers; or The thermoplastic resin film according to claim 10, comprising one or more third thermoplastic elastomers (EZ) selected from the group consisting of block copolymers having a polymer block (za) containing an α-methylstyrene unit and a polymer block (zb) containing a conjugated diene compound unit in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol mass% or more, and hydrogenated products of the block copolymers.

12. The thermoplastic elastomer (E) is one or more first thermoplastic elastomers (EX) selected from the group consisting of block copolymers having a polymer block (xa) containing a styrene unit and a polymer block (xb) containing a conjugated diene compound unit in which the total amount of 1,2-bonds and 3,4-bonds is less than 40 mol mass%, and hydrogenated products of the block copolymers; one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing a styrene unit and a polymer block (yb) containing a conjugated diene compound unit in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol mass% or more, and hydrogenated products of the block copolymers; and The thermoplastic resin film according to claim 11, comprising one or more third thermoplastic elastomers (EZ) selected from the group consisting of block copolymers having a polymer block (za) containing an α-methylstyrene unit and a polymer block (zb) containing a conjugated diene compound unit in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol mass% or more, and hydrogenated products of the block copolymers.

13. The thermoplastic resin film according to claim 10 , wherein the intermediate layer further comprises one or more polypropylene-based polymers (P).

14. The thermoplastic resin film according to claim 13, wherein the polypropylene-based polymer (P) comprises one or more first polypropylene-based polymers (PX) having no polar group and one or more second polypropylene-based polymers (PY) having a polar group.

15. The thermoplastic resin film according to claim 8, wherein the backing layer comprises one or more vinyl alcohol resins (V) including an ethylene-vinyl alcohol copolymer having an ethylene unit content of 20 to 50 mol%.

16. The thermoplastic resin film according to claim 8, wherein the total thickness is 20 to 500 μm, the ratio of the thickness of the surface layer to the total thickness is 1 / 20 to 2 / 3, and the ratio of the thickness of the back layer to the total thickness is 1 / 20 to 2 / 3.

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