Thermoplastic resin film

Abstract

To provide a thermoplastic resin film excellent in tear strength.SOLUTION: The thermoplastic resin film of the present disclosure has a surface layer including an acrylic resin composition containing a methacrylic resin, first acrylic rubber particles having an average particle size of 50 nm or more and less than 160 nm up to an outermost crosslinked rubber component layer, second acrylic rubber particles having an average particle size of 160 nm or more and 300 nm or less up to the outermost crosslinked rubber component layer, an acrylic block copolymer, a back layer containing a vinyl alcohol resin, and an intermediate layer containing a thermoplastic elastomer. In the acrylic resin composition, the total amount of the portion up to the outermost crosslinked rubber component layer of the first acrylic rubber particles is 22 to 60% by mass, the total amount of the portion up to the outermost crosslinked rubber component layer of the second acrylic rubber particles is 2 to 10% by mass, the total amount of the acrylic block copolymer is 5 to 30% by mass, and the acetone insoluble fraction is 46 to 70% by mass.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] 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]

[0004] [Patent Document 1] International Publication No. 2022 / 019310 [Patent Document 2] International Publication No. 2021 / 132557 Summary of the Invention [Problem to be solved by the invention]

[0005] It is preferable that the film for agricultural greenhouses does not break when stretched. The inventors have conducted research and found that the thermoplastic resin film disclosed in Patent Document 1 may break when stretched (see Comparative Example EC5 in the Examples section of this specification).

[0006] Patent Document 2 is an example of a technique related to the present disclosure. Patent Document 2 discloses a methacrylic resin composition that contains a methacrylic resin and a rubber-like elastomer, the rubber-like elastomer containing multilayer structure polymer particles with a relatively small particle size, multilayer structure polymer particles with a relatively large particle size, and a block copolymer, and that has good flexibility, bending resistance, cracking resistance, etc. (Claim 1). However, the inventors have found through their investigations that even if the methacrylic resin composition disclosed in Patent Document 2 is directly applied to the surface layer of the thermoplastic resin film disclosed in Patent Document 1, it is not possible to effectively prevent the film from breaking when stretched (see Comparative Example EC4 in the [Examples] section of this specification).

[0007] The present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide a thermoplastic resin film that is excellent in transparency and tear strength. [Means for solving the problem]

[0008] The present disclosure provides the following thermoplastic resin films [1] to

[13] . [1] A surface layer made of an acrylic resin composition (AR) containing a methacrylic resin (M) and a rubber-like elastomer (R), a backing layer containing a vinyl alcohol resin (V); a thermoplastic resin film having an intermediate layer provided between the front layer and the back layer, the intermediate layer comprising one or more thermoplastic elastomers (E) selected from the group consisting of block copolymers comprising 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; The rubber-like elastomer (R) comprises: first acrylic rubber particles (RP-S) each including one or more crosslinked rubber component layers, the average particle diameter from the center to the outermost crosslinked rubber component layer being 50 nm or more and less than 160 nm; second acrylic rubber particles (RP-L) each including one or more crosslinked rubber component layers, the average particle diameter from the center to the outermost crosslinked rubber component layer being 160 nm or more and 300 nm or less; and an acrylic block copolymer (RB) comprising a methacrylic polymer block (mb) and an acrylic polymer block (ab); The acrylic resin composition (AR) is a thermoplastic resin film in which, relative to 100% by mass of the acrylic resin composition (AR), the total amount of the portion from the center of the first acrylic rubber particle (RP-S) to the outermost cross-linked rubber component layer is 22 to 60% by mass, the total amount of the portion from the center of the second acrylic rubber particle (RP-L) to the outermost cross-linked rubber component layer is 2 to 10% by mass, the total amount of the acrylic block copolymer (RB) is 5 to 30% by mass, and the acetone insoluble content is 46 to 70% by mass.

[0009] [2] The thermoplastic resin film of [1], wherein the acrylic resin composition (AR) further contains one or more ultraviolet absorbers (UVA). [3] The thermoplastic resin film according to [2], wherein the ultraviolet absorber (UVA) comprises one or more ultraviolet absorbers selected from the group consisting of triazine-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers. [4] The thermoplastic resin film according to any one of [1] to [3], wherein the conjugated diene compound units contained in the polymer block (b) are one or more units selected from the group consisting of isoprene units and butadiene units.

[0010] [5] 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 any one of [1] to [4], 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.

[0011] [6] 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 of [5], 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.

[0012] [7] The thermoplastic resin film according to [6], wherein the content of the first thermoplastic elastomer (EX) is 15 to 55 parts by mass, the content of the second thermoplastic elastomer (EY) is 25 to 65 parts by mass, and the content of the third thermoplastic elastomer (EZ) is 15 to 35 parts by mass, relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E).

[0013] [8] The thermoplastic resin film according to any one of [1] to [7], wherein the intermediate layer further contains one or more polypropylene polymers (P). [9] The thermoplastic resin film according to [8], 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.

[10] The thermoplastic resin film according to [9], wherein the content of the first polypropylene polymer (PX) is 3 to 15 parts by mass and the content of the second polypropylene polymer (PY) is 7.5 to 20 parts by mass, relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E).

[0014]

[11] The thermoplastic resin film of any one of [1] to

[10] , wherein the vinyl alcohol resin (V) contains an ethylene-vinyl alcohol copolymer having an ethylene unit content of 20 to 50 mol %.

[0015]

[12] The thermoplastic resin film according to any one of [1] to

[11] , 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.

[13] A thermoplastic resin film according to any one of [1] to

[12] , having a maximum tear strength of 40 to 200 N / mm as measured in accordance with the trouser tear method of JIS K7128. [Effects of the Invention]

[0016] According to the present disclosure, a thermoplastic resin film having excellent transparency and tear strength can be provided. [Brief explanation of the drawings]

[0017] [Figure 1] 1 is a schematic cross-sectional view of a thermoplastic resin film according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0018] 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.

[0019] 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.

[0020] 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).

[0021] 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."

[0022] [Thermoplastic resin film] The thermoplastic resin film of the present disclosure is a surface layer (acrylic resin composition layer) made of an acrylic resin composition (AR) containing multiple types of (meth)acrylic resins (A); a backing layer (vinyl alcohol resin composition layer) made of a vinyl alcohol resin composition (VR) containing one or more vinyl alcohol resins (V); The intermediate layer (elastomer resin composition layer) is disposed between the front layer and the back layer and is 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.

[0023] 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.

[0024] FIG. 1 is a schematic cross-sectional view of a thermoplastic resin film according to one embodiment of the present invention. 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.

[0025] (surface) The surface layer is made of an acrylic resin composition (AR) containing multiple types of (meth)acrylic resins (A). In the present disclosure, the multiple types of (meth)acrylic resins (A) include one or more types of methacrylic resins (M) and multiple types of rubber-like elastomers (R). The multiple types of rubber-like elastomers (R) include one or more types of first acrylic rubber particles (RP-S) having a relatively small particle size, one or more types of second acrylic rubber particles (RP-L) having a relatively large particle size, and one or more types of acrylic block copolymers (RB).

[0026] The acrylic resin composition (AR) can have a phase structure in which a plurality of types of rubber-like elastomers (R) are dispersed in a matrix resin containing one or more types of methacrylic resins (M). Generally, the (meth)acrylic resin (A) is a resin having relatively high weather resistance among resins. Therefore, the surface layer made of the acrylic resin composition (AR) has excellent weather resistance and can function as a weather-resistant resin layer. To improve weather resistance, the acrylic resin composition (AR) can contain one or more ultraviolet absorbers (UVA). The surface layer contains a plurality of types of rubber-like elastic material (R), and therefore can have excellent flex resistance, impact resistance, and ease of handling.

[0027] <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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] In the present disclosure, the multiple types of rubber-like elastomers (R) contain multiple 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.

[0032] 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.

[0033] 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.

[0034] 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 80% by mass, and most preferably 90% by mass.

[0035] <Acrylic rubber particles (RP)> In the present disclosure, the multiple types of rubber-like elastomers (R) include multiple 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)) can be multilayered polymer particles with a core-shell structure having an outermost layer consisting of one or more thermoplastic resin component layers (II) and one or more crosslinked 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.

[0036] 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. The total amount of the acrylic rubber particles (RP) present in particulate form in the acrylic resin composition (AR) (excluding the outermost part of the outermost layer that is compatible with the matrix resin) can correspond to the acetone-insoluble matter described below.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] In the acrylic resin composition (AR), the multiple types of acrylic rubber particles (RP) include one or more types of 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 one or more types of 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.

[0048] 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.

[0049] <Acrylic block copolymer (RB)> The multiple types of rubber-like elastomers (R) include one or more types of acrylic block copolymers (RB) containing a methacrylic polymer block (mb) and an acrylic polymer block (ab).

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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 %.

[0055] 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.

[0056] 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.

[0057] The acrylic resin composition (AR) contains one or more types of first acrylic rubber particles (RP-S) having a relatively small particle size, one or more types of second acrylic rubber particles (RP-L) having a relatively large particle size, and one or more types of acrylic block copolymers (RB). The acrylic resin composition (AR) has, relative to 100% by mass of the acrylic resin composition (AR), a total amount of the portion from the center of the first acrylic rubber particle (RP-S) to the outermost cross-linked rubber component layer of 22 to 60% by mass, a total amount of the portion from the center of the second acrylic rubber particle (RP-L) to the outermost cross-linked rubber component layer of 2 to 10% by mass, a total amount of the acrylic block copolymer (RB) of 5 to 30% by mass, and an acetone insoluble content of 46 to 70% by mass.

[0058] The lower limit of the total amount of the portion from the center of the first acrylic rubber particle (RP-S) to the outermost crosslinked rubber component layer is preferably 25 mass%, more preferably 30 mass%, and particularly preferably 35 mass%, and the upper limit is preferably 55 mass%, more preferably 50 mass%, and particularly preferably 45 mass%. The lower limit of the total amount of the portion from the center of the second acrylic rubber particle (RP-L) to the outermost crosslinked rubber component layer is preferably 5% by mass, more preferably 7% by mass, and the upper limit is preferably 9% by mass, more preferably 8% by mass. The lower limit of the total amount of the acrylic block copolymer (RB) is more preferably 6% by mass, even more preferably 7% by mass, particularly preferably 8% by mass, and most preferably 9% by mass, and the upper limit is preferably 25% by mass, more preferably 20% by mass, particularly preferably 15% by mass, and most preferably 10% by mass. The lower limit of the acetone insoluble matter is preferably 48 mass%, more preferably 50 mass%, particularly preferably 52 mass%, and most preferably 55 mass%, and the upper limit is preferably 68 mass%, more preferably 65 mass%.

[0059] In the technology of the present disclosure, in the acrylic resin composition (AR), one or more types of first acrylic rubber particles (RP-S), one or more types of second acrylic rubber particles (RP-L), and one or more types of acrylic block copolymers (RB) are used in combination as the rubber-like elastomer (R), and the amounts of these are relatively high. According to the research of the present inventors, it has been found that a thermoplastic resin film including a surface layer made of the acrylic resin composition (AR) having the above-mentioned configuration can effectively improve tear strength. When a tearing force (F) is applied to the thermoplastic resin film, the multiple types of rubber-like elastomers (R) dispersed in the surface layer prevent the force (F) from propagating, effectively suppressing the force (F) from propagating in a single direction, thereby improving tear strength. However, according to the research of the present inventors, no improvement in tear strength was observed in a single-layer thermoplastic resin film consisting only of a surface layer made of an acrylic resin composition (AR) (see Comparative Example EC1 described below). The thermoplastic resin film of the present disclosure includes an intermediate layer containing a thermoplastic elastomer (E) as an underlying layer for a surface layer made of the acrylic resin composition (AR) having the above-described configuration. In the thermoplastic resin film of the present disclosure having such a laminated structure, a deviation occurs in the propagation direction of the force (F) between the surface layer and the underlying layer, and elongation modes are mixed in a tear test due to the influence of interfacial adhesion, requiring more energy for the propagation of the force (F), which is thought to more effectively improve tear strength.

[0060] <Ultraviolet absorber (UVA)> To improve weather resistance, the acrylic resin composition (AR) may contain one or more ultraviolet absorbers (UVA). Examples of ultraviolet absorbers (UVA) include 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, anilide oxalate-based ultraviolet absorbers, malonic acid ester-based ultraviolet absorbers, and formamidine-based ultraviolet absorbers. Among these, triazine-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers are preferred, with triazine-based ultraviolet absorbers being particularly preferred, from the viewpoints of ultraviolet absorption performance and bleed-out suppression.

[0061] 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).

[0062] 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.

[0063] The content of the ultraviolet absorber (UVA) in the acrylic resin composition (AR) (the total amount if multiple types are used) can be designed depending on the ultraviolet absorbing performance of the ultraviolet absorber (UVA) and the thickness of the surface layer. The light transmittance at 300 nm of the thermoplastic resin film of the present disclosure is not particularly limited, and is preferably 0 to 5%.

[0064] <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.

[0065] <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.

[0066] 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).

[0067] 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].

[0068] <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.

[0069] <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.

[0070] The acrylic resin composition (AR) can be produced by melt-kneading multiple materials including one or more methacrylic resins (M) and multiple rubber-like elastomers (R) 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 a single-screw extruder, twin-screw extruder, or multi-screw extruder are preferred, with a twin-screw extruder being more preferred.

[0071] (middle class) The thermoplastic resin film of the present disclosure has an intermediate layer between the front layer and the back layer, which is made of an elastomer resin composition (ER) containing one or more thermoplastic elastomers (E). 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.

[0072] 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.

[0073] 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 %.

[0074] 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.

[0075] 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 %.

[0076] 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.

[0077] 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.

[0078] 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;

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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).

[0085] 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.

[0086] 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.

[0087] 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.

[0088] <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.

[0089] <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.

[0090] 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 %.

[0091] <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%.

[0092] 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.

[0093] 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 %.

[0094] 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%.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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%.

[0099] 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.

[0100] 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.

[0101] <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).

[0102] <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).

[0103] 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 %.

[0104] <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 %.

[0105] 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%.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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%.

[0110] 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).

[0111] <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).

[0112] <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).

[0113] 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 %.

[0114] <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).

[0115] 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 %.

[0116] 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%.

[0117] 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.

[0118] 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.

[0119] 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%.

[0120] 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).

[0121] <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).

[0122] <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.

[0123] 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%.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] <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.

[0130] 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.

[0131] 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%.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] The melting point (Tm) of the second polypropylene polymer (PY) is preferably 130° C. or lower. 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.

[0136] 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.

[0137] <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.

[0138] <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.

[0139] <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.).

[0140] 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.

[0141] 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.

[0142] 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.

[0143] (Back layer) The thermoplastic resin film of the present disclosure includes 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.

[0144] <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.

[0145] 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.

[0146] 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.

[0147] 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%.

[0148] 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 %.

[0149] 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.

[0150] <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.

[0151] (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.

[0152] [Thickness of thermoplastic resin film and each layer] In the thermoplastic resin film of the present disclosure, 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. In the thermoplastic resin film of the present disclosure, the thickness of the backing 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. 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 the thermoplastic resin film of the present disclosure, from the viewpoint of ensuring 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 of the present disclosure can be designed depending on the application, etc., and is preferably 20 to 500 μm, more preferably 50 to 300 μm.

[0153] [Physical Properties] The thermoplastic resin film of the present disclosure can have good transparency. The total light transmittance (TT) of the thermoplastic resin film of the present disclosure is preferably 85 to 100%, with the lower limit being more preferably 88%, and particularly preferably 90%. The haze of the thermoplastic resin film of the present disclosure is preferably 15% or less, and more preferably 10% or less.

[0154] The thermoplastic resin film of the present disclosure can have good tear strength. The thermoplastic resin film of the present disclosure may have a maximum tear strength of 40 to 200 N / mm as measured in accordance with the trouser tearing method of JIS K7128. The lower limit is more preferably 45 N / mm, even more preferably 50 N / mm, still more preferably 55 N / mm, particularly preferably 60 N / mm, and most preferably 65 N / mm. The upper limit may be 180 N / mm, 150 N / mm, 120 N / mm, or 100 N / mm. The total light transmittance, haze, and tear strength can be measured by the methods described in the section [Examples] below.

[0155] [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 thermoplastic resin film of the present disclosure include known multilayer molding methods such as coextrusion molding, multilayer blow molding, multilayer injection molding, heat pressing, and heat lamination. Among these, coextrusion molding is preferred, in which multiple resin compositions melt-kneaded using different extruders are coextruded from a common extrusion die (such as a T-die). 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.

[0156] As described above, according to the present disclosure, it is possible to provide a thermoplastic resin film having excellent transparency and tear strength. The present disclosure also makes it possible to provide a thermoplastic resin film that is excellent in transparency and tear strength, as well as in weather resistance, stain resistance, chemical resistance, anti-fogging properties, bending resistance, interlayer adhesion, heat retention, and handleability.

[0157] [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]

[0158] 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.

[0159] (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.

[0160] (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).

[0161] (Acetone insoluble matter of acrylic resin composition (AR)) 2 g of the acrylic resin composition (AR) (this mass is referred to as the mass before centrifugation) was added to 50 mL of acetone and stirred at room temperature (20 to 25°C) for 24 hours. The entire liquid obtained was centrifuged using a centrifuge (Hitachi Koki Co., Ltd., "CR20GIII") at 20,000 rpm, 0°C, and for 180 minutes. The precipitate was collected and vacuum-dried at 50°C for 8 hours, after which its mass (this mass is referred to as the mass of the precipitate) was measured. The acetone-insoluble content was calculated based on the following formula: Acetone insoluble matter (mass%) = [(mass of precipitate) / (mass before centrifugation)] × 100

[0162] (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.

[0163] (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.

[0164] (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).

[0165] (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).

[0166] (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.

[0167] (Total light transmittance (TT), haze) A 50 mm × 50 mm test piece was cut out from the thermoplastic resin film. Total light transmittance (TT) and haze were measured at 23°C using a haze meter (Murakami Color Research Laboratory, "HM-150") in accordance with JIS K 7361-1.

[0168] (tear strength) A 50mm x 50mm test piece was cut out from the thermoplastic resin film. The tear strength was measured at 23°C using an Autograph AG-5000B manufactured by Shimadzu Corporation in accordance with the trouser tear method of JIS K7128, and the maximum value was used as the data.

[0169] [material] <Methacrylic resin (M)> The following methacrylic resins (M) were prepared. (M1) 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), (M2) Polymethyl methacrylate (PMMA), Mw (standard PMMA equivalent): 80,000).

[0170] <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.

[0171] (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.

[0172] (RP-S2) According to the method described in the section [Example] of Japanese Patent Laid-Open No. 2023-123955 (acrylic rubber particles (b-1)), powdery three-layer structure acrylic rubber particles (RP-S2) were obtained. The composition and average particle diameter of each layer are as follows. First layer: BA units / styrene (St) units / ALMA units (mass ratio) = 41.25 / 8.75 / 0.3 Layer 2: BA units / St units / MMA units / ALMA units (mass ratio) = 15.81 / 3.19 / 1.0 / 0.16 Third layer: MMA unit / methyl acrylate (MA) unit (mass ratio) = 28.5 / 1.5 1st layer / 2nd layer / 3rd layer (mass ratio) = 50 / 20 / 30, Average particle size of the three layers: 0.10 μm.

[0173] (RP-S3) Polymerization of the first to third layers was carried out in accordance with the method described in Production Example 1 (acrylic rubber particles (mb)) in the section [Examples] of WO 2021 / 132557 to obtain a latex (RP-S3-L) containing acrylic rubber particles (RP-S3) with a three-layer structure. The composition of each layer, the mass ratio of each layer, and the average particle diameter are as follows. Layer 1: MMA units / MA units / ALMA units (mass ratio) = 94 / 6 / 0.2 Layer 2: BA units / St units / ALMA units (mass ratio) = 82 / 18 / 2 Third layer: MMA unit / MA unit (mass ratio) = 95 / 5, 1st layer / 2nd layer / 3rd layer (mass ratio) = 10 / 50 / 40, Average particle size of the two layers: 0.09 μm, Average particle size of the three layers: 0.11 μm.

[0174] (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, Mn (standard PMMA equivalent): 80,000, Glass transition temperature (Tg): 100℃.

[0175] (RP-S3-D) A latex (RP-S3-L) containing three-layer acrylic rubber particles (RP-S3) was mixed with a latex (D1-L) containing methacrylic copolymer particles (dispersant (D1)). The resulting dispersion was frozen and solidified, washed with water, and dried to obtain a mixed powder (acrylic rubber particle-containing powder (RP-S3-D)) consisting of acrylic rubber particles (RP-S3) and methacrylic copolymer particles (dispersant (D1)). The mass ratio and average particle size of each particle in the mixed powder are as follows: Acrylic rubber particles (RP-S3) / methacrylic copolymer particles (dispersant (D1)) (mass ratio) = 3 / 2, Average particle size of acrylic rubber particles (RP-S3): 0.11 μm; Average particle size of methacrylic copolymer particles (dispersant (D1)): 0.13 μm.

[0176] (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.

[0177] (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.

[0178] <Block copolymer (RB)> The following block copolymers (RB) were prepared: (RB1) An acrylic triblock copolymer (RB1) was obtained by a known method. The copolymer consisted of [methyl methacrylate (MMA) polymer block (mb)]-[n-butyl acrylate (BA) polymer block (ab)]-[methyl methacrylate (MMA) polymer block (mb)], had a 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.

[0179] (RB2) In accordance with the method described in Production Example 1 (Production of Acrylic Triblock Copolymer (B-1)) in the section [Examples] of JP 2020-169295 A, an acrylic triblock copolymer (RB2) consisting of [methyl methacrylate (MMA) polymer block (mb)]-[copolymer block (ab) of methyl acrylate (MA) and n-butyl acrylate (BA)]-[methyl methacrylate (MMA) polymer block (mb)], having Mw (standard PMMA equivalent) of 147,000, and having a polymer block mass ratio (mb):(ab):(mb) = 21.8 / 246 / 25.2, MMA unit / MA unit / BA unit (mass ratio) = 47 / 123 / 123 was obtained.

[0180] <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%.

[0181] 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%.

[0182] 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%.

[0183] (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 %.

[0184] (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 %.

[0185] 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%.

[0186] 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%.

[0187] 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%.

[0188] <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.

[0189] <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.

[0190] <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 (registered trademark) 1600" manufactured by BASF. The chemical structure is shown below.

[0191] [ka]

[0192] (TAY1) 2-[4,6-diphenyl-1,3,5-triazin-2-yl]-5-(hexyloxy)phenol, "Tinuvin (registered trademark) 1577ED" manufactured by BASF. The chemical structure is shown below.

[0193] [ka]

[0194] <Benzotriazole-based UV absorbers> (BT1) 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], manufactured by ADEKA Corporation ("ADEKA STAB LA-31RG").

[0195] <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.

[0196] <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").

[0197] <Polymer processing aid> (PA1) High molecular weight methacrylic polymer, "Metablen P-530A" manufactured by Mitsubishi Chemical Corporation.

[0198] <Acrylic Resin Compositions (AR1) to (AR3), (ARC1), and (ARC2)> 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 (AR3), (ARC1), and (ARC2).

[0199] The blending composition (charged composition) of the acrylic resin composition (AR) or (ARC) is shown in Table 1-1, where 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).

[0200] In the acrylic resin composition (AR) or (ARC), the amount (parts by mass) of the portion from the center of each acrylic rubber particle (RP) to the outermost crosslinked rubber component layer (second layer) and the total amount (parts by mass) of the portion from the center of each first acrylic rubber particle (RP-S) to the outermost crosslinked rubber component layer (second layer) per 100 parts by mass of the total amount of (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)) are shown in Table 1-2. The acetone insoluble matter (mass %) and the amount of matrix resin (mass %) in the acrylic resin composition (AR) or (ARC) are shown in Table 1-2.

[0201] [Table 1-1]

[0202] [Table 1-2]

[0203] <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 (BT1), 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.

[0204] [Table 2]

[0205] <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.

[0206] [Table 3]

[0207] [Example E1] Pellets of an acrylic resin composition (AR1) 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, pressurized 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.

[0208] [Examples E2 and E3, Comparative Examples EC4 and EC5] A thermoplastic resin film was obtained in the same manner as in Example E1, except that the material of the surface layer (first layer) was changed to the acrylic resin composition (AR2), (AR3), (ARC1), or (ARC2). The structure and evaluation results of the obtained thermoplastic resin film are shown in Table 4.

[0209] [Comparative Example EC1] Pellets of the acrylic resin composition (AR1) 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, a 50 μm-thick single-layer thermoplastic resin film was obtained. The structure and evaluation results of the obtained thermoplastic resin film are shown in Table 4.

[0210] [Comparative examples EC2, EC3] A single-layer thermoplastic resin film was obtained in the same manner as in Comparative Example EC1, except that the acrylic resin composition (AR1) was replaced with the acrylic resin composition (ARC1) or (ARC2). The structure and evaluation results of the obtained thermoplastic resin film are shown in Table 4.

[0211] [Table 4]

[0212] [Summary of results] In Examples E1 to E3, a thermoplastic resin film having a laminated structure was obtained, in which the total amount of the first acrylic rubber particles (RP-S) from the center to the outermost crosslinked rubber component layer was 22 to 60% by mass, the total amount of the second acrylic rubber particles (RP-L) from the center to the outermost crosslinked rubber component layer was 2 to 10% by mass, the total amount of the acrylic block copolymer (RB) was 5 to 30% by mass, and the acetone insoluble matter was 46 to 70% by mass. A thermoplastic resin film having a surface layer made of an acrylic resin composition (AR), an intermediate layer containing a thermoplastic elastomer (E), and a back layer containing a vinyl alcohol resin (V). In all of these Examples, a thermoplastic resin film having a high total light transmittance (TT), low haze, excellent transparency, and high tear strength was obtained.

[0213] All of the single-layer thermoplastic resin films obtained in Comparative Examples EC1 to EC3 had insufficient tear strength. In Comparative Examples EC4 and EC5, thermoplastic resin films were obtained having a laminated structure of a surface layer made of a comparative acrylic resin composition (ARC), an intermediate layer containing a thermoplastic elastomer (E), and a back layer containing a vinyl alcohol resin (V). All of the thermoplastic resin films obtained in these Comparative Examples had insufficient tear strength.

[0214] 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]

[0215] 1. Thermoplastic resin film 11 Surface layer 12 Lining 13 Middle class

Claims

1. a surface layer made of an acrylic resin composition (AR) containing a methacrylic resin (M) and a rubber-like elastomer (R); a backing layer containing a vinyl alcohol resin (V); a thermoplastic resin film having an intermediate layer provided between the front layer and the back layer, the intermediate layer comprising one or more thermoplastic elastomers (E) selected from the group consisting of block copolymers comprising 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, The rubber-like elastomer (R) comprises: first acrylic rubber particles (RP-S) each including one or more crosslinked rubber component layers, the average particle diameter from the center to the outermost crosslinked rubber component layer being 50 nm or more and less than 160 nm; second acrylic rubber particles (RP-L) each including one or more crosslinked rubber component layers, the average particle diameter from the center to the outermost crosslinked rubber component layer being 160 nm or more and 300 nm or less; and an acrylic block copolymer (RB) including a methacrylic polymer block (mb) and an acrylic polymer block (ab); The acrylic resin composition (AR) is a thermoplastic resin film in which, relative to 100% by mass of the acrylic resin composition (AR), the total amount of a portion from the center of a first acrylic rubber particle (RP-S) to the outermost cross-linked rubber component layer is 22 to 60% by mass, the total amount of a portion from the center of a second acrylic rubber particle (RP-L) to the outermost cross-linked rubber component layer is 2 to 10% by mass, the total amount of an acrylic block copolymer (RB) is 5 to 30% by mass, and an acetone-insoluble matter is 46 to 70% by mass.

2. The thermoplastic resin film according to claim 1 , wherein the acrylic resin composition (AR) further comprises one or more ultraviolet absorbers (UVA).

3. The thermoplastic resin film according to claim 2, wherein the ultraviolet absorber (UVA) comprises one or more ultraviolet absorbers selected from the group consisting of triazine-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers.

4. 2. The thermoplastic resin film according to claim 1, wherein the conjugated diene compound units contained in the polymer block (b) are at least one unit selected from the group consisting of isoprene units and butadiene units.

5. 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 2. The thermoplastic resin film according to claim 1, 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.

6. 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 5, 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.

7. 7. The thermoplastic resin film according to claim 6, wherein the content of the first thermoplastic elastomer (EX) is 15 to 55 parts by mass, the content of the second thermoplastic elastomer (EY) is 25 to 65 parts by mass, and the content of the third thermoplastic elastomer (EZ) is 15 to 35 parts by mass, relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E).

8. The thermoplastic resin film according to claim 1 , wherein the intermediate layer further comprises one or more polypropylene-based polymers (P).

9. 9. The thermoplastic resin film according to claim 8, 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.

10. The thermoplastic resin film according to claim 9, wherein the content of the first polypropylene-based polymer (PX) is 3 to 15 parts by mass and the content of the second polypropylene-based polymer (PY) is 7.5 to 20 parts by mass, relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E).

11. The thermoplastic resin film according to claim 1, wherein the vinyl alcohol resin (V) contains an ethylene-vinyl alcohol copolymer having an ethylene unit content of 20 to 50 mol%.

12. The thermoplastic resin film according to claim 1, 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.

13. 2. The thermoplastic resin film according to claim 1, wherein the maximum tear strength measured in accordance with the trouser tear method of JIS K7128 is 40 to 200 N / mm.

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