Agricultural film

Abstract

The present invention provides a laminate having excellent transparency, weather resistance, antifouling property, chemical resistance, anti-fog property, and handleability. The laminate (1) has: an obverse layer (1A) that is a weather-resistant resin layer made of an acrylic resin composition (A) containing an elastic body (R) and an UV absorber; a reverse layer (1B) that is an antifouling resin layer containing a vinyl alcohol resin (B); and an adhesive layer (1C) that is provided between the obverse layer and the reverse layer and that contains a thermoplastic elastomer (C). The thermoplastic elastomer (C) is a block copolymer including a polymer block (c1) that includes aromatic vinyl compound units and a polymer block (c2) that includes conjugated diene compound units, or a hydrogenated product of said block copolymer.

Description

Technical Field

[0001] The present invention relates to a laminate having different functions on both sides. More specifically, the present invention relates to a laminate excellent in transparency, weather resistance, antifouling property, chemical resistance, anti-fogging property, and handleability, and suitable for automotive exterior applications, building material applications, agricultural applications, and the like.

Background Art

[0002] Methacrylic resin is excellent in transparency, weather resistance, appearance, etc., and is used in applications such as automotive interior and exterior and building materials. Although its development for agricultural applications and the like is expected due to its weather resistance, the methacrylic resin alone has problems in antifouling property and handleability.

[0003] Patent Document 1 discloses a hard coat film in which a hard coat layer made of a cured product of an active energy ray-curable composition excellent in antifouling property is laminated on an acrylic resin film as an antifouling film (Claim 1, 8). Patent Document 2 discloses a laminated sheet of a weather-resistant resin layer containing an acrylic resin, an acrylic rubber, and an ultraviolet absorber and a antifouling resin layer containing an ethylene vinyl alcohol copolymer resin (Claim 1). In one embodiment of Patent Document 2, the weather-resistant resin layer and the antifouling resin layer are directly laminated (Figure 1). Patent Document 3 discloses a multilayer structure in which an ethylene vinyl alcohol copolymer resin and another resin layer are laminated via an adhesive layer (Claim 1, 3).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

[0005] In the film described in Patent Document 1, which has a hard coat layer laminated on an acrylic resin film, the stretchability and bending resistance are poor, and there is a risk of cracking or other damage occurring in the hard coat layer when pulled or bent at room temperature, leaving some issues with handling. In the laminated sheet described in Patent Document 2, in which a weather-resistant resin layer and an antifouling resin layer are directly laminated, the adhesion between the weather-resistant resin layer containing methacrylic resin (an amorphous resin) and the antifouling resin layer containing ethylene vinyl alcohol copolymer resin (a crystalline resin) is insufficient, and there is a risk of delamination during handling. Patent Document 3 does not describe lamination of acrylic resin and ethylene vinyl alcohol copolymer resin via an adhesive layer, and does not disclose a technique for good adhesion between amorphous resin, acrylic resin, and crystalline resin, ethylene vinyl alcohol copolymer resin.

[0006] This invention has been made in view of the above circumstances, and aims to provide a laminate that is excellent in transparency, weather resistance, stain resistance, chemical resistance, anti-fogging properties, and handling. [Means for solving the problem]

[0007] The present invention provides the following laminates [1] to [6]. [1] A laminate with different functions on both sides, A surface layer which is a weather-resistant resin layer made of an acrylic resin composition (A) containing an elastic body (R) and an ultraviolet absorber, The back layer is a stain-resistant resin layer containing vinyl alcohol resin (B), The adhesive layer is provided between the surface layer and the back layer and comprises a block copolymer containing a polymer block (c1) containing aromatic vinyl compound units and a polymer block (c2) containing conjugated diene compound units, or a thermoplastic elastomer (C) which is a hydrogenated version of the block copolymer. Vinyl alcohol resin (B) is an ethylene vinyl alcohol copolymer having an ethylene unit content of 20-50 mol%, The adhesive layer is made of a thermoplastic polymer composition (X) comprising 100 parts by mass of a thermoplastic elastomer (C) and 10 to 100 parts by mass of one or more adhesion-improving components (D) selected from the group consisting of polyvinyl acetal resin (DV) and polar group-containing polypropylene resin (DP). A laminate in which the polymer block (c2) contains butadiene units and / or isoprene units, and the ratio of the sum of the amounts of 1,2-bonds and 3,4-bonds to the sum of the amounts of 1,2-bonds, 3,4-bonds and 1,4-bonds is 40 mol% or more.

[0008] [2] Acrylic resin composition (A) is A methacrylic resin (M) containing 80% by mass or more of methyl methacrylate units, an elastic body (R), and the ultraviolet absorber are included. The UV absorber is a benzotriazole-based UV absorber and / or a triazine-based UV absorber. An acrylic resin composition in which, per 100 parts by mass of the total of methacrylic resin (M) and elastic body (R), the content of methacrylic resin (M) is 10 to 99 parts by mass, and the content of elastic body (R) is 90 to 1 part by mass. The laminate of [1] wherein the transmittance of the laminate at a wavelength of 300 nm is 5% or less.

[0009] [3] The elastic body (R) is a laminate of [1] or [2], comprising a block copolymer of crosslinked rubber particles and / or methacrylic ester polymer blocks (g1) containing methacrylic ester units and acrylic ester polymer blocks (g2) containing acrylic ester units.

[0010] [4] A laminate of any of [1] to [3], wherein the total thickness is a laminated film of 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. [5] A stretched film, a laminate of any of [1] to [4]. [6] The laminate according to any one of [1] to [5], further having a functional layer having a function different from that of the surface layer, the back layer, and the adhesive layer between the surface layer and the back layer.

Effect of the Invention

[0011] According to the present invention, it is possible to provide a laminate excellent in transparency, weather resistance, antifouling property, chemical resistance, antifogging property, and handling property.

Brief Description of the Drawings

[0012] [Figure 1] FIG. 1 is a schematic cross-sectional view of a laminate according to an embodiment of the present invention. [Figure 2] FIG. 2 is a schematic view of a manufacturing apparatus for a laminated film according to an embodiment of the present invention.

Mode for Carrying Out the Invention

[0013] [Laminate with Different Functions on Both Sides] The laminate of the present invention includes a surface layer which is a weather-resistant resin layer made of an acrylic resin composition (A) containing an elastomer (R) and an ultraviolet absorber, and a back layer which is an antifouling resin layer containing a vinyl alcohol resin (B), and is a laminate having different functions on both sides. The laminate of the present invention has an adhesive layer containing a thermoplastic elastomer (C) between the surface layer and the back layer in order to improve the adhesiveness of these layers. Note that "front and back" in the laminate of the present invention is a convenient term for distinguishing both sides of the laminate, and does not necessarily coincide with "front and back" in actual use. The "surface layer" can also be referred to as one surface layer, and the "back layer" can be referred to as the other surface layer. In actual use, the "surface layer" may be used on the back side and the "back layer" may be used on the front side.

[0014] FIG. 1 is a schematic cross-sectional view of a laminate according to an embodiment of the present invention. In the figure, reference numeral 1 denotes a laminate, reference numeral 1A denotes a surface layer which is a weather-resistant resin layer, reference numeral 1B denotes a back layer which is an antifouling resin layer, and reference numeral 1C denotes an adhesive layer, respectively. Between the surface layer 1A which is a weather-resistant resin layer and the back layer 1B which is an antifouling resin layer, other resin layers other than the adhesive layer 1C may be provided as necessary.

[0015] (Surface layer (weather-resistant resin layer)) The surface layer which is a weather-resistant resin layer is made of an acrylic resin composition (A) containing an elastomer (R) and an ultraviolet absorber. Since the surface layer contains an ultraviolet absorber, it has a low ultraviolet transmittance (UV transmittance) and excellent weather resistance. The transmittance at a wavelength of 300 nm of the surface layer is preferably 5% or less. Since the surface layer contains an elastomer (R), it is excellent in stretchability and flex resistance. Since the acrylic resin composition (A) contains an elastomer (R) having impact resistance, it is also referred to as an impact-resistant acrylic resin. The laminate of the present invention including a surface layer made of an acrylic resin composition (A) containing an elastomer (R) and an ultraviolet absorber is excellent in weather resistance, stretchability, flex resistance, and handling properties.

[0016] From the viewpoint of the surface hardness of the surface layer and the like, the acrylic resin composition (A) preferably contains 1 to 99 parts by mass of a methacrylic resin (M) and 99 to 1 part by mass of an elastomer (R) as resin components, more preferably 10 to 90 parts by mass of a methacrylic resin (M) and 90 to 10 parts by mass of an elastomer (R).

[0017] <Methacrylic resin (M)> The methacrylic resin (M) is a homopolymer of methyl methacrylate (MMA) or a copolymer of MMA and one or more other monomers. In the methacrylic resin (M), the content of MMA units is preferably 80% by mass or more, more preferably 90% by mass or more, and the content of other monomer units is​​​Other monomers besides MMA include acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, 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, norborneyl acrylate, and isovonyl acrylate; ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate Methacrylic acid esters other than MMA, such as methyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate, cyclohexyl methacrylate, norborneyl methacrylate, and isovonyl methacrylate; (meth)acrylic acid, maleic anhydride, ma Examples include unsaturated carboxylic acids such as leic 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, α-methylstyrene, p-methylstyrene, and m-methylstyrene; and (meth)acrylamide, (meth)acrylonitrile, vinyl acetate, vinylpyridine, vinyl ketones, vinyl chloride, vinylidene chloride, and vinylidene fluoride.

[0019] In this specification, (meth)acrylic is a general term for acrylic and methacrylic, (meth)acrylonitrile is a general term for acrylonitrile and methacrylonitrile, and (meth)acryloyl is AcrylicRoyle and Meta This is a general term for kryloyl compounds. The stereoregularity of the methacrylic resin (M) is not particularly limited. Methacrylic resins (M) having stereoregularity such as isotactic, heterotactic, and syndiotactic may be used.

[0020] The weight-average molecular weight (Mw) of the methacrylic resin (M) is not particularly limited, but is preferably 30,000 to 180,000, more preferably 40,000 to 150,000, and particularly preferably 50,000 to 130,000. When Mw is less than 30,000, the impact resistance and toughness of the surface layer tend to decrease, and when Mw is greater than 180,000, the fluidity of the methacrylic resin (M) tends to decrease, and the moldability tends to decrease. In this specification, weight-average molecular weight (Mw) is the weight-average molecular weight on a polystyrene basis, determined by gel permeation chromatography (GPC) measurement.

[0021] Methacrylic resin (M) can be produced by (co)polymerizing a monomer (mixture) containing 80% by mass or more of methyl methacrylate (MMA) and optionally 20% by mass or less of one or more other monomers, using a known method. Commercially available methacrylic resin (M) may be used. Examples of commercially available products include "Parapet H1000B" (MFR: 22g / 10min), "Parapet GF" (MFR: 15g / 10min), "Parapet EH" (MFR: 1.3g / 10min), "Parapet HRL" (MFR: 2.0g / 10min), "Parapet HRS" (MFR: 2.4g / 10min), and "Parapet G" (MFR: 8.0g / 10min) [all manufactured by Kuraray Co., Ltd.]. In this specification, the MFR of methacrylic resin is the melt flow rate measured under conditions of 230°C and a load of 37.3N, in accordance with JIS K 7210-1.

[0022] <Elastic material (R)> As the elastic body (R), crosslinked rubber particles and / or block copolymers are preferred from the viewpoint of transparency, impact resistance, and dispersibility.

[0023] As the crosslinked rubber particles, multilayer structure particles (E) are preferred. The multilayer particle (E) is a particle in which at least two layers, an inner layer (e2) and an outer layer (e1), are stacked from the center. The multilayer particle (E) may further have a crosslinkable resin layer (e3) inside the inner layer (e2).

[0024] The inner layer (e2) is a layer containing a crosslinked elastic body obtained by copolymerizing one or more alkyl acrylates, one or more crosslinkable monomers, and optionally one or more other monofunctional monomers.

[0025] As the alkyl acrylate, alkyl acrylates having 2 to 8 carbon atoms in the alkyl group are preferred, for example, butyl acrylate and 2-ethylhexyl acrylate are preferred. The amount of alkyl acrylate relative to the total amount of raw material monomers in the inner layer (e2) is preferably 70 to 99.8% by mass, more preferably 80 to 90% by mass, from the viewpoint of impact resistance.

[0026] Crosslinkable monomers are monomers having at least two polymerizable carbon-carbon double bonds in one molecule. Examples include unsaturated carboxylic acid diesters of glycols such as ethylene glycol dimethacrylate and butanediol dimethacrylate; alkenyl esters of unsaturated carboxylic acids such as allyl (meth)acrylate and allyl cinnamate; polyalkenyl esters of polybasic acids such as diallyl phthalate, diallyl maleate, triallyl cyanurate, and triallyl isocyanurate; unsaturated carboxylic acid esters of polyhydric alcohols such as trimethylolpropane triacrylate; and divinylbenzene. Among these, alkenyl esters of unsaturated carboxylic acids and polyalkenyl esters of polybasic acids are preferred. The amount of crosslinkable monomers relative to the total amount of raw material monomers in the inner layer (e2) is preferably 0.2 to 30% by mass, more preferably 0.2 to 10% by mass, from the viewpoint of improving the impact resistance, heat resistance, and surface hardness of the surface layer.

[0027] Other monofunctional monomers that may be used as needed include, for example, alkyl methacrylates such as methyl methacrylate (MMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, myristyl methacrylate, palmityl methacrylate, stearyl methacrylate, and behenyl methacrylate; and phenyl methacrylate. Examples include methacrylic acid esters such as esters of acrylic acid with phenols and esters of methacrylic acid with aromatic alcohols such as benzyl methacrylate; aromatic vinyl monomers such as styrene, α-methylstyrene, 1-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, and halogenated styrenes; vinyl cyanide monomers such as (meth)acrylonitrile; and conjugated diene monomers such as butadiene and isoprene. The amount of other monofunctional monomers relative to the total amount of raw material monomers in the inner layer (e2) is preferably 24.5% by mass or less, more preferably 20% by mass or less, from the viewpoint of improving the impact resistance of the surface layer.

[0028] The outer layer (e1) is a layer made of a rigid thermoplastic resin obtained by (co)polymerizing a monomer (mixture) containing 80% by mass or more, preferably 90% by mass or more, methyl methacrylate (MMA), and optionally 20% by mass or less, preferably 10% by mass or less, of one or more other monofunctional monomers, from the viewpoint of heat resistance of the surface layer. Other monofunctional monomers that may be used as needed include, for example, alkyl acrylates such as methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate; and (meth)acrylic acid.

[0029] The content of the inner layer (e2) and outer layer (e1) in the multilayer particle (E) is not particularly limited. From the viewpoint of impact resistance, heat resistance, surface hardness, handling, and ease of melt-mixing with methacrylic resin (M) of the surface layer, it is preferable that the content of the inner layer (e2) is 40 to 80% by mass and the content of the outer layer (e1) is 60 to 20% by mass relative to the mass of the multilayer particle (E).

[0030] As the crosslinkable resin layer (e3) that may be included in the multilayer particle (E) as needed, a resin layer obtained by copolymerizing a monofunctional monomer that can be used in the outer layer (e1) and a crosslinkable monomer that can be used in the inner layer (e2) is preferred.

[0031] The method for producing the multilayer particles (E) is not particularly limited, but emulsion polymerization is preferred from the viewpoint of controlling the layer structure of the multilayer particles (E).

[0032] The block copolymer (G) is preferably a copolymer comprising one or more methacrylate ester polymer blocks (g1) and one or more acrylic acid ester polymer blocks (g2).

[0033] The methacrylic acid ester polymer block (g1) is a polymer block mainly containing methacrylic acid ester units, and optionally containing other monomer units. The content of methacrylic acid ester units in the methacrylic acid ester polymer block (g1) is preferably 80% by mass or more, more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 98% by mass or more, from the viewpoint of stretchability, flexural resistance, and surface hardness.

[0034] Examples of methacrylate esters include methyl methacrylate (MMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, and pentadecimal methacrylate. RuExamples include dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, glycidyl methacrylate, and allyl methacrylate. These can be used individually or in combination of two or more. Among these, alkyl methacrylates such as MMA, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate are preferred from the viewpoint of transparency and heat resistance, with MMA being more preferred.

[0035] The content of monomer units other than methacrylate units, as needed in the methacrylate ester polymer block (g1), is related to stretchability, flexural resistance, and From the viewpoint of surface hardness, it is preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably 5% by mass or less, and most preferably 2% by mass or less.

[0036] Other monomers besides methacrylic acid esters include, for example, acrylic acid esters, unsaturated carboxylic acids, aromatic vinyl compounds, olefins, conjugated dienes, (meth)acrylonitrile, (meth)acrylamide, vinyl acetate, vinylpyridine, vinyl ketones, vinyl chloride, vinylidene chloride, and vinylidene fluoride. These can be used individually or in combination of two or more.

[0037] The weight-average molecular weight (Mw) of the methacrylate ester polymer block (g1) is not particularly limited, but is preferably 5,000. 0 The elastic modulus (Mw) is ~150,000, more preferably 8,000~120,000, and particularly preferably 12,000~100,000. If Mw is less than 5,000, the elastic modulus is low and there is a risk of wrinkles forming when stretch molding at high temperatures, and if it is greater than 150,000, there is a risk of the laminate breaking during stretch molding and three-dimensional coating molding. If the block copolymer (G) contains multiple methacrylate ester polymer blocks (g1), the monomer composition and molecular weight of these blocks may be the same or different.

[0038] The acrylic acid ester polymer block (g2) is a polymer block mainly containing acrylic acid ester units, and optionally containing other monomer units. The proportion of acrylic acid ester units in the acrylic acid ester polymer block (g2) is preferably 45% by mass or more, more preferably 50% by mass or more, particularly preferably 60% by mass or more, and most preferably 90% by mass or more, from the viewpoint of stretchability, flexibility, and three-dimensional coating moldability.

[0039] Examples of acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, glycidyl acrylate, and allyl acrylate. These can be used individually or in combination of two or more.

[0040] The acrylic ester polymer block (g2) preferably contains alkyl acrylate units and (meth)acrylic aromatic ester units from the viewpoint of stretchability, flexibility, and transparency. Examples of alkyl acrylates include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and dodecyl acrylate. Among these, n-butyl acrylate and 2-ethylhexyl acrylate are preferred.

[0041] (Meth)acrylic acid aromatic esters are esters of acrylic acid aromatic esters or methacrylic acid aromatic esters with compounds containing an aromatic ring. Examples include phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and styryl (meth)acrylate. Among these, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and benzyl acrylate are preferred from the viewpoint of transparency.

[0042] From the viewpoint of transparency, the content of alkyl acrylate units in the acrylic acid ester polymer block (g2) is preferably 50 to 90% by mass, more preferably 60 to 80% by mass, and the content of (meth)acrylic acid aromatic ester units is preferably 50 to 10% by mass, more preferably 40 to 20% by mass.

[0043] The content of monomer units other than acrylic acid esters, which may be included in the acrylic acid ester polymer block (g2) as needed, is preferably 55% by mass or less, more preferably 50% by mass or less, particularly preferably 40% by mass or less, and most preferably 10% by mass or less.

[0044] Other monomers besides acrylic acid esters include, for example, methacrylic acid esters, unsaturated carboxylic acids, aromatic vinyl compounds, olefins, conjugated dienes, (meth)acrylonitrile, (meth)acrylamide, vinyl acetate, vinylpyridine, vinyl ketones, vinyl chloride, vinylidene chloride, and vinylidene fluoride. These can be used individually or in combination of two or more.

[0045] The weight-average molecular weight (Mw) of the acrylic ester polymer block (g2) is not particularly limited, but is preferably 5,000 to 120,000, more preferably 15,000 to 110,000, and most preferably 30,000 to 100,000, from the viewpoint of stretchability, flexibility, and three-dimensional coating moldability. When the block copolymer (G) contains multiple acrylic acid ester polymer blocks (g2), the monomer composition and molecular weight of these blocks may be the same or different.

[0046] <UV absorber> The acrylic resin composition (A) contains one or more ultraviolet absorbers. UV absorbers are compounds that have the ability to absorb ultraviolet light, and examples include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalate anilides, malonic acid esters, and formamidines. Among these, benzotriazoles and triazines are preferred from the viewpoint of suppressing bleed-out, and benzotriazoles are more preferred from the viewpoint of suppressing resin degradation due to ultraviolet light.

[0047] Examples of benzotriazoles include 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-yl)phenol] (e.g., "Adekastab LA-31" manufactured by Asahi Denka Kogyo Co., Ltd.), 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (e.g., "TINUVIN329" manufactured by Ciba Specialty Chemicals), and 2-(2H-benzotriazole-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (e.g., "TINUVIN234" manufactured by Ciba Specialty Chemicals).

[0048] Examples of triazines include 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine (such as "LA-F70" manufactured by ADEKA) and its analogues, such as hydroxyphenyltriazine-based UV absorbers (such as "TINUVIN477-D", "TINUVIN460", "TINUVIN479", and "TINUVIN1600" manufactured by BASF).

[0049] The amount of ultraviolet absorber added to the acrylic resin composition (A) can be designed according to its ultraviolet absorption performance, and it is preferable to adjust the type and amount of ultraviolet absorber so that the transmittance of the surface layer at a wavelength of 300 nm is 5% or less.

[0050] <Other additives> The acrylic resin composition (A) may contain, as needed, antioxidants, heat stabilizers, lubricants, processing aids, antistatic agents, Coloring agents It may also contain other additives such as impact-absorbing agents.

[0051] (Backing layer (stain-resistant resin layer)) The laminate of the present invention includes a backing layer which is a stain-resistant resin layer containing vinyl alcohol resin (B). The stain-resistant resin layer containing vinyl alcohol resin (B) has excellent stain resistance, chemical resistance, and anti-fogging properties. Known vinyl alcohol resins can be used as vinyl alcohol resin (B), and from the viewpoint of stain resistance, ethylene-vinyl alcohol copolymer is preferred. The laminate of the present invention includes a back layer which is a stain-resistant resin layer containing vinyl alcohol resin (B), and therefore the back side has excellent stain resistance, chemical resistance, and anti-fogging properties. Accordingly, the laminate of the present invention can be used by arranging the laminate so that the back side is located on the side where these properties are required.

[0052] <Ethylene-vinyl alcohol copolymer> Ethylene-vinyl alcohol copolymer is a copolymer of ethylene and vinyl ester that has been saponified. Hereafter, this copolymer may be abbreviated as "EVOH". The copolymerization of ethylene and vinyl esters can be carried out by known polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization. These copolymerizations may be carried out in either a continuous or batch manner.

[0053] In EVOH, the lower limit of the ethylene unit content (also simply called "ethylene content") is preferably 10 mol%, more preferably 20 mol%, and particularly preferably 25 mol%. The upper limit of the ethylene content is preferably 60 mol%, more preferably 55 mol%, particularly preferably 50 mol%, and most preferably 40 mol%. If the ethylene content is below the lower limit, the thermal stability during melt extrusion will decrease, causing the copolymer to gel and potentially resulting in defects such as streaks and fisheyes. In particular, prolonged operation under conditions higher than typical melt extrusion molding temperatures or speeds increases the likelihood of gelation. If the ethylene content exceeds the upper limit, gas barrier properties and other characteristics may decrease, potentially preventing EVOH from fully exhibiting its advantageous properties. The ethylene unit content is preferably 20 to 50 mol%.

[0054] As a vinyl ester, vinyl acetate is preferred from the viewpoint of industrial availability and other factors. Vinyl acetate usually contains a small amount of acetaldehyde as an unavoidable impurity. The acetaldehyde content in vinyl acetate is preferably less than 100 ppm, more preferably 60 ppm or less, particularly preferably 25 ppm or less, and most preferably 15 ppm or less.

[0055] EVOH may contain units derived from monomers other than ethylene and vinyl esters. Examples of other monomers include vinylsilane compounds. The content of other monomer units in EVOH is preferably 0.2 mol% or less.

[0056] The degree of saponification of vinyl ester units is typically 85 mol% or higher, preferably 90 mol% or higher, more preferably 98 mol% or higher, and particularly preferably 98.9 mol% or higher. If the degree of saponification is below the above lower limit, the thermal stability may be insufficient.

[0057] The lower limit of the melt flow rate (MFR) of EVOH is preferably 0.5 g / 10 min, more preferably 1.0 g / 10 min, and most preferably 1.4 g / 10 min. The upper limit of the MFR is preferably 30 g / 10 min, more preferably 25 g / 10 min, even more preferably 20 g / 10 min, even more preferably 15 g / 10 min, most preferably 10 g / 10 min, and most preferably 1.6 g / 10 min. If the MFR of EVOH is below the lower limit or above the upper limit, moldability and appearance may deteriorate.

[0058] 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 2,160g.

[0059] <Optional ingredients> The backing layer, which is an antifouling resin layer, may contain optional components such as other resins and various additives other than vinyl alcohol resin (B), as needed.

[0060] (adhesive layer) The laminate of the present invention has an adhesive layer containing a thermoplastic elastomer (C) between the surface layer, which is a weather-resistant resin layer, and the back layer, which is an antifouling resin layer, in order to improve the adhesion between these layers. Although the adhesion between a weather-resistant resin layer containing methacrylic resin (an amorphous resin) and an antifouling resin layer containing ethylene vinyl alcohol copolymer resin is poor, interlayer adhesion can be improved by providing an adhesive layer containing thermoplastic elastomer (C) between these layers. The adhesive layer containing thermoplastic elastomer (C) also exhibits excellent stretchability and flexural resistance. The laminate of the present invention, having the above-mentioned adhesive layer between the surface layer and the back layer, exhibits excellent stretchability, flexibility, and interlayer adhesion, as well as excellent handling properties. The adhesive layer preferably consists of a thermoplastic polymer composition (X) containing a thermoplastic elastomer (C) and an adhesion-enhancing component (D).

[0061] <Thermoplastic elastomer (C)> The thermoplastic elastomer (C) is a block copolymer or a hydrogenated version thereof, comprising a polymer block (c1) containing aromatic vinyl compound units and a polymer block (c2) containing conjugated diene compound units.

[0062] Examples of aromatic vinyl compounds used as raw materials for polymer block (c1) include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, and 2-vinylnaphthalene. One or more of these can be used. Among these, styrene, α-methylstyrene, and 4-methylstyrene are preferred from the viewpoint of fluidity.

[0063] The content of aromatic vinyl compound units in the polymer block (c1) is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. The polymer block (c1) may have other copolymerizable monomer units along with aromatic vinyl compound units. Examples of other copolymerizable monomers include 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether. The content of other copolymerizable monomer units in the polymer block (c1) is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

[0064] Examples of conjugated diene compounds used as raw materials for polymer block (c2) include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. One or more of these can be used. Among these, butadiene and / or isoprene are preferred, and butadiene and isoprene are more preferred.

[0065] The bonding configuration of conjugated diene compounds is not particularly limited. For example, butadiene can have 1,2- and 1,4-bonds, while isoprene can have 1,2-, 3,4-, and 1,4-bonds. In polymer block (c2), the ratio of the sum of the amounts of 1,2-bonds and 3,4-bonds to the sum of the amounts of 1,2-bonds, 3,4-bonds, and 1,4-bonds is preferably 1 to 99 mol%, more preferably 35 to 98 mol%, particularly preferably 40 to 90 mol%, and most preferably 50 to 80 mol%. In polymer block (c2), the ratio of the sum of the amounts of 1,2-bonds and 3,4-bonds to the sum of the amounts of 1,2-bonds, 3,4-bonds, and 1,4-bonds is preferably 40 mol% or more. Furthermore, the ratio of the amounts of 1,2-bonds, 3,4-bonds, and 1,4-bonds is: 1 It can be calculated from the ratio of the integral values ​​of the peaks in the 4.2-5.0 ppm range originating from 1,2-bonds and 3,4-bonds in the 1H-NMR spectrum, and the integral values ​​of the peaks in the 5.0-5.45 ppm range originating from 1,4-bonds.

[0066] The content of conjugated diene compound units in the polymer block (c2) is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more (all values ​​are calculated based on the amount of raw materials used). The polymer block (c2) may have other copolymerizable monomer units along with the conjugated diene compound unit. Examples of other copolymerizable monomers include styrene, α-methylstyrene, and 4-methylstyrene. The proportion of other copolymerizable monomer units is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less, relative to the total amount of the conjugated diene compound unit and other copolymerizable monomer units.

[0067] From the viewpoint of heat resistance and weather resistance, it is preferable that part or all of the polymer block (c2) of the thermoplastic elastomer (C) is hydrogenated (also simply called "hydrogenated"). The hydrogenation rate of the polymer block (c2) is preferably 80% or more, more preferably 90% or more. In this specification, the hydrogenation rate is a value obtained by measuring the iodine value of the block copolymer before and after the hydrogenation reaction.

[0068] The content of polymer blocks (c1) in the thermoplastic elastomer (C) is preferably 5 to 75% by mass, more preferably 5 to 60% by mass, and particularly preferably 10 to 40% by mass, from the viewpoint of flexibility, stretchability, bending resistance, and adhesion. The weight-average molecular weight (Mw) of the thermoplastic elastomer (C) is not particularly limited, but is preferably 30,000 to 500,000, more preferably 60,000 to 200,000, and particularly preferably 80,000 to 180,000, from the viewpoint of stretchability, flex resistance, adhesion, and moldability. Thermoplastic elastomer (C) can be of one type or two or more types. In particular, a combination of a medium molecular weight product with Mw of 50,000 to 150,000 and a high molecular weight product with Mw of 150,000 to 300,000 is preferable because it is easier to balance stretchability, flex resistance, adhesion, and moldability. The mass ratio of the medium molecular weight product to the high molecular weight product is preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 75 / 25, and particularly preferably 20 / 80 to 55 / 45.

[0069] To enhance adhesion between the surface layer and the back layer, the adhesive layer may consist of a thermoplastic polymer composition (X) containing a thermoplastic elastomer (C) and an adhesion-enhancing component (D). As the adhesion-imparting component (D), polyvinyl acetal resin (DV) and / or polar group-containing polypropylene resin (DP) are preferred.

[0070] The content of the adhesion-enhancing component (D) is preferably 10 parts by mass, more preferably 12 parts by mass, and particularly preferably 15 parts by mass per 100 parts by mass of thermoplastic elastomer (C), with an upper limit of preferably 100 parts by mass, more preferably 70 parts by mass, and particularly preferably 50 parts by mass. The content of the adhesion-enhancing component (D) is preferably 10 to 100 parts by mass, more preferably 10 to 70 parts by mass, even more preferably 12 to 70 parts by mass, even more preferably 15 to 70 parts by mass, particularly preferably 15 to 50 parts by mass, and most preferably 15 to 45 parts by mass per 100 parts by mass of thermoplastic elastomer (C). If the content of the adhesion-enhancing component (D) is less than 10 parts by mass, the effect of improving adhesion due to the addition of the adhesion-enhancing component (D) may not be effectively obtained, and if it exceeds 100 parts by mass, the flexibility and adhesion of the adhesive layer may decrease.

[0071] Polyvinyl acetal resin (DV) is a resin obtained by acetalizing two adjacent hydroxyl groups of polyvinyl alcohol with one or more alkylaldehydes such as acetaldehyde and n-butyraldehyde. The one or more alkylaldehydes used for acetalization preferably include n-butyraldehyde. The proportion (molar ratio) of butyral units among the acetal units present in the polyvinyl acetal resin (DV) is preferably 0.8 or higher, more preferably 0.9 or higher, and particularly preferably 0.95 or higher.

[0072] The degree of acetalization (mole fraction of acetalized vinyl alcohol units) of polyvinyl acetal resin (DV) is preferably 55-88 mol%, more preferably 60-88 mol%, particularly preferably 70-88 mol%, and most preferably 75-85 mol%. Polyvinyl acetal resin (DV) with a degree of acetalization of 55 mol% or more has low manufacturing costs, is readily available, and has good melt processability. Polyvinyl acetal resin (DV) with a degree of acetalization of 88 mol% or less is easy to manufacture and economical because the acetalization reaction does not require a long time. Polyvinyl acetal resin (DV) with a degree of acetalization of 88 mol% or less has excellent adhesion. Polyvinyl acetal resin (DV) with a degree of acetalization of 55 mol% or more has good affinity and compatibility with thermoplastic elastomer (C), and the stretchability, flexural resistance, and adhesive strength of the thermoplastic polymer composition (X) containing it are high. The degree of acetalization of polyvinyl acetal resin (DV) can be determined in accordance with JIS K 6728.

[0073] From the viewpoint of affinity with thermoplastic elastomer (C), the content of vinyl alcohol units in the polyvinyl acetal resin (DV) is preferably 12 to 45 mol%, more preferably 12 to 40 mol%, and the content of vinyl acetate units is preferably 0 to 5 mol%, more preferably 0 to 3 mol%.

[0074] In polyvinyl acetal resin (DV), the arrangement order of each unit is not particularly limited; they may be arranged randomly, in blocks, or in a tapered manner.

[0075] Examples of polar groups found in polypropylene resins containing polar groups (DP) include (meth)acryloyloxy groups, hydroxyl groups, amide groups, halogen atoms such as chlorine atoms, carboxyl groups, and acid anhydride groups. From the viewpoint of adhesion, polypropylene resins containing carboxyl groups as polar groups, i.e., carboxylic acid-modified polypropylene resins, are preferred as polar group-containing polypropylene resins (DP). Among these, maleic acid-modified polypropylene resins and maleic anhydride-modified polypropylene resins are more preferred.

[0076] The polar group-containing polypropylene resin (DP) may be obtained by copolymerizing propylene with an α-olefin other than propylene with a polar group-containing copolymerizable monomer. Examples of α-olefins other than propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and cyclohexene. The α-olefin can be copolymerized with the polar group-containing copolymerizable monomer by known methods, such as random copolymerization, block copolymerization, and graft copolymerization. From the viewpoint of affinity with the thermoplastic elastomer (C), the proportion of α-olefin units other than propylene in the polar group-containing polypropylene resin (DP) is preferably 0 to 45 mol%, more preferably 0 to 35 mol%, and particularly preferably 0 to 25 mol%.

[0077] The polar groups in the polar group-containing polypropylene resin (DP) may be post-treated after polymerization. For example, the (meth)acrylic acid group or carboxyl group may be neutralized with a metal ion to form an ionomer, or the (meth)acrylic acid group or carboxyl group may be esterified with methanol and ethanol, etc. Hydrolysis of vinyl acetate may also be performed.

[0078] The thermoplastic polymer composition (X) may further contain a polar group-containing polyolefin copolymer (O) other than the polar group-containing polypropylene resin (DP) from the viewpoint of moldability, stretchability, flexibility, and adhesion.

[0079] The amount of polar group-containing polyolefin copolymer (O) added per 100 parts by mass of thermoplastic elastomer (C) is preferably 5 to 100 parts by mass, more preferably 20 to 70 parts by mass, and particularly preferably 35 to 60 parts by mass. When the amount of polar group-containing polyolefin copolymer (O) added is 5 parts by mass or more, the adhesive layer tends to have excellent adhesion at 190°C or below, and when it is 100 parts by mass or less, the adhesive layer tends to have excellent flexibility, stretchability, and flexural resistance.

[0080] As the polar group-containing polyolefin copolymer (O), a polyolefin copolymer consisting of an olefin copolymerizable monomer and a polar group-containing copolymerizable monomer is preferred. Examples of olefin copolymerizable monomers include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and cyclohexene. These can be used individually or in combination of two or more. Among these, ethylene is preferred from the viewpoint of adhesion. Examples of polar groups in a polar group-containing polyolefin copolymer (O) include ester groups, hydroxyl groups, amide groups, halogen atoms such as chlorine atoms, carboxyl groups, and acid anhydride groups. Examples of copolymerizable monomers containing polar groups include (meth)acrylic acid esters, (meth)acrylic acid, vinyl acetate, vinyl chloride, ethylene oxide, propylene oxide, and acrylamide. These can be used individually or in combination of two or more. Among these, (meth)acrylic acid esters are preferred from the viewpoint of adhesion.

[0081] Suitable (meth)acrylic acid esters as polar group-containing copolymerizable monomers include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, isohexyl acrylate, n-octyl acrylate, isooctyl acrylate, and 2-ethylhexyl acrylate; and alkyl methacrylates such as methyl methacrylate (MMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, isohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, and 2-ethylhexyl methacrylate. These can be used individually or in combination of two or more. Among these, alkyl acrylates are preferred because they provide high adhesion even when heated at temperatures below 190°C, methyl acrylate and ethyl acrylate are more preferred, and methyl acrylate is particularly preferred.

[0082] The thermoplastic polymer composition (X) may contain other thermoplastic polymers such as olefin polymers, styrene polymers, polyphenylene ether resins, polyethylene glycol, and various tackifying resins. Examples of olefin polymers include block copolymers and random copolymers of polyethylene, polypropylene, polybutene; propylene, and other α-olefins such as ethylene and 1-butene. The amount of other thermoplastic polymer added is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and particularly preferably 2 parts by mass or less, per 100 parts by mass of thermoplastic elastomer (C).

[0083] The thermoplastic polymer composition (X) may contain inorganic fillers from the viewpoint of heat resistance, weather resistance, and hardness adjustment. Examples of inorganic fillers include calcium carbonate, talc, magnesium hydroxide, aluminum hydroxide, mica, clay, natural silicic acid, synthetic silicic acid, titanium dioxide, carbon black, barium sulfate, glass balloons, and glass fibers. One or more of these can be used. When inorganic fillers are included, the amount added is preferably within a range that does not impair the flexibility of the thermoplastic polymer composition (X), and is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 2 parts by mass or less, per 100 parts by mass of thermoplastic elastomer (C).

[0084] The thermoplastic polymer composition (X) may contain additives such as softeners, antioxidants, lubricants, light stabilizers, processing aids, colorants such as pigments and dyes, flame retardants, antistatic agents, matting agents, silicone oils, antiblocking agents, UV absorbers, mold release agents, foaming agents, antibacterial agents, antifungal agents, and fragrances. Examples of antioxidants include hindered phenol-based, phosphorus-based, lactone-based, and hydroxyl-based antioxidants. Among these, hindered phenol-based antioxidants are preferred. The amount of antioxidant added is preferably within a range that does not cause discoloration when the thermoplastic polymer composition (X) is melt-kneaded, and is preferably 0.1 to 5 parts by mass per 100 parts by mass of thermoplastic elastomer (C).

[0085] The method for preparing the thermoplastic polymer composition (X) can be any method that allows for the uniform mixing of multiple components, and is usually performed by a melt-kneading method. Melt-kneading can be performed using a melt-kneading apparatus such as a single-screw extruder, twin-screw extruder, kneader, batch mixer, roller, and Banbury mixer. The melt-kneading temperature is preferably 170 to 270°C.

[0086] The thermoplastic polymer composition (X) has a hardness, measured according to the JIS-A method of JIS K 6253, preferably 90 or less, more preferably 30 to 90, and particularly preferably 35 to 85. When the hardness exceeds 90, flexibility and elastic modulus tend to decrease.

[0087] (Other resin layers) The laminate of the present invention may optionally have other resin layers besides the adhesive layer between the surface layer, which is a weather-resistant resin layer, and the back layer, which is a stain-resistant resin layer. The laminate of the present invention may optionally have a functional layer other than the weather-resistant resin layer, the stain-resistant resin layer, and the adhesive layer between the surface layer, which is a weather-resistant resin layer, and the back layer, which is a stain-resistant resin layer.

[0088] (film) One embodiment of the laminate of the present invention is a laminated film (also called a "multilayer film"). The laminated film may be an unstretched film or a stretched film. In this specification, unless otherwise specified, "film" refers to an unstretched film, and "stretched film" refers to a film obtained by stretching an unstretched film using a known method. Generally, thin film molded articles are referred to as "films" or "sheets" depending on their thickness, but there is no clear distinction between them. In this specification, "film" includes both "films" and "sheets."

[0089] The unstretched laminated film of the present invention, which includes a weather-resistant resin surface layer, a stain-resistant resin back layer, and an adhesive layer provided between them, exhibits excellent stretchability, thus suppressing breakage even when stretch-molded. According to the present invention, it is possible to provide a stretched film that is excellent in transparency, weather resistance, stain resistance, chemical resistance, and anti-fogging properties, as well as excellent in flexibility and interlayer adhesion, making it easy to handle.

[0090] The laminated film of the present invention may be used in three-dimensional coating molding. Because the laminated film of the present invention has excellent stretchability and flexibility, breakage is suppressed even when used in three-dimensional coating molding. A three-dimensional coated molded body can be manufactured by known three-dimensional coating molding, consisting of a molded body of any three-dimensional shape and the laminated film of the present invention that coats it. Examples of methods for manufacturing a three-dimensional coated molded body include: an integral molding method in which the laminated film of the present invention is superimposed on a pre-molded three-dimensional body to be adhered to, and these are then pressed together; a method in which the laminated film of the present invention is three-dimensionally molded by vacuum forming, and the body to be adhered to is injection molded in the presence of the three-dimensionally molded laminated film by film insert molding; and a method in which the laminated film of the present invention is tightly bonded to a pre-molded three-dimensional body to conform to its three-dimensional shape by vacuum forming. According to the present invention, it is possible to provide a three-dimensional coated molded article that is excellent in transparency, weather resistance, stain resistance, chemical resistance, and anti-fogging properties.

[0091] (Laminate and thickness of each layer) In the laminate of the present invention, the thickness of the surface layer is preferably 1 / 20 to 2 / 3, more preferably 1 / 10 to 2 / 3, of the total thickness of the laminate. In the laminate of the present invention, the thickness of the backing layer is preferably 1 / 20 to 2 / 3, more preferably 1 / 10 to 2 / 3, of the total thickness of the laminate. When the thickness of the surface and back layers is 1 / 20 or more of the total thickness of the laminate, the functions of the surface and back layers, which are functional layers, are sufficiently obtained. When it is 2 / 3 or less, sufficient thickness of the adhesive layer is ensured, and the flexibility-enhancing effect of the adhesive layer is preferably exhibited. In the laminate of the present invention, from the viewpoint of ensuring good functionality of the surface layer and the back layer while also providing good adhesion between these layers, the thickness of the adhesive layer is preferably 1 / 5 to 9 / 10, more preferably 1 / 5 to 8 / 10, of the total thickness of the laminate. The total thickness of the laminate of the present invention can be designed according to the application and other factors. When the laminate of the present invention is a laminated film, the total thickness is preferably 20 to 500 μm, more preferably 50 to 300 μm.

[0092] (Manufacturing method) The laminate of the present invention can be manufactured by known molding methods such as extrusion molding, inflation molding, and calendering, with co-extrusion molding being preferred. A laminated film, which is one embodiment of the laminate of the present invention, can be manufactured by known techniques such as co-extrusion molding, hot pressing, and thermal lamination, with co-extrusion molding being preferred.

[0093] The following describes the method for manufacturing laminated films using co-extrusion molding. Figure 2 shows a schematic diagram of an extrusion molding apparatus, as one embodiment, which includes a T-die 11, first to third cooling rolls 12 to 14, and a pair of take-up rolls 15. Each constituent resin of each layer is melt-kneaded using an extruder and co-extruded in the desired laminated structure as a film from a T-die 11 having a wide discharge port. Lamination methods include a feed block method where the material is laminated before it enters the T-die, and a multi-manifold method where the material is laminated inside the T-die. From the viewpoint of improving inter-layer interface smoothness, the multi-manifold method is preferred. The molten thermoplastic resin laminate co-extruded from the T-die 11 is pressurized and cooled using a plurality of cooling rolls 12-14. The laminated film 16 obtained after pressurization and cooling is taken up by a pair of take-up rolls 15. The number of cooling rolls can be designed as appropriate. The configuration of the manufacturing apparatus can be modified as appropriate without departing from the spirit of the present invention.

[0094] The laminate of the present invention includes a surface layer which is a weather-resistant resin layer made of an acrylic resin composition (A) containing an elastic body (R) and an ultraviolet absorber, and therefore has low ultraviolet transmittance (UV transmittance) and excellent weather resistance. The transmittance of the laminate of the present invention at a wavelength of 300 nm is preferably 5% or less.

[0095] The laminate of the present invention includes a back layer which is an antifouling resin layer containing vinyl alcohol resin (B), preferably ethylene vinyl alcohol copolymer resin (EVOH), and therefore exhibits excellent antifouling, chemical resistance, and antifogging properties on the back side.

[0096] The laminate of the present invention has an adhesive layer between the surface layer and the back layer, which contains a thermoplastic elastomer (C), and more preferably, one or more adhesion-imparting components (D) selected from the group consisting of polyvinyl acetal resin (DV) and / or polar group-containing polypropylene resin (DP). Originally, the adhesion between the surface layer containing acrylic resin, which is an amorphous resin, and the back layer containing ethylene vinyl alcohol copolymer resin (EVOH), which is a crystalline resin, is low. However, by providing the above-mentioned adhesive layer between these layers, the adhesion between the surface layer and the back layer can be improved, and the interlayer adhesion can be enhanced.

[0097] In the case of a laminate of the present invention that does not include a hard coat layer, the surface layer contains a flexible elastic material (R) and the adhesive layer contains a flexible thermoplastic elastomer (C), thus exhibiting excellent stretchability and bending resistance. The laminate of the present invention exhibits excellent stretchability, flexibility, and interlayer adhesion, thus suppressing cracking or delamination even when stretched or bent at room temperature, resulting in excellent handling properties. The laminate of the present invention has excellent stretchability, flexibility, and interlayer adhesion, making it suitable for use in stretch molding and three-dimensional coating molding, etc.

[0098] The laminate of the present invention can have good transparency. The haze of the laminate of the present invention is preferably 15% or less, more preferably 10% or less. "Haze" can be measured by the method described in the [Examples] section below.

[0099] As described above, the present invention provides a laminate that is excellent in transparency, weather resistance, stain resistance, chemical resistance, and anti-fogging properties, as well as excellent in stretchability, flexibility, and interlayer adhesion, thus offering superior handling.

[0100] [Application] The laminate of the present invention exhibits excellent transparency, weather resistance, stain resistance, chemical resistance, anti-fogging properties, and ease of handling, making it suitable for automotive exterior applications, building material applications, agricultural applications, and the like. [Examples]

[0101] Examples and comparative examples of the present invention will be described below. [Evaluation items and evaluation methods] The evaluation items and methods are as follows: (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). A Tosoh Corporation HLC-8320 (model number) equipped with a differential refractive index detector (RI detector) was used as the GPC instrument. Tetrahydrofuran was used as the eluent, and two Tosoh Corporation "TSKgel SuperMultipore HZM-M" columns and one "SuperHZ4000" column connected in series were used as the column. 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, and the chromatogram was measured. GPC measurements were performed using 10 standard polystyrene samples with molecular weights in the range of 400 to 5,000,000, and a calibration curve showing the relationship between retention time and molecular weight was created. Based on this calibration curve, the Mw and Mw / Mn of the resin were determined.

[0102] (weather resistance) A multilayer film was cut to obtain a 50mm x 50mm test specimen. Using a Super UV tester (Iwasaki Electric Co., Ltd. "SUV-W161"), the test specimen was subjected to irradiation at a black panel temperature of 83°C, relative humidity of 50%, and irradiation energy of 100mW / cm². 2Under these conditions, the specimens were irradiated with ultraviolet light for 200 hours. Afterwards, the test specimens were removed from the testing machine, and a transmission spectrum in the wavelength range of 200 to 800 nm was obtained using a spectrophotometer (Shimadzu Corporation "UV3600"), and the transmittance at a wavelength of 300 nm was determined. This transmittance is called the "UV transmittance after weathering test." A lower UV transmittance after weathering test indicates better weather resistance.

[0103] (Stain-resistant) A multilayer film was cut to obtain a 50mm x 50mm test piece. The back side of the multilayer film (the side with the third layer as shown in Table 3) was used as the test surface, and this test surface was rubbed back and forth 30 times with a thoroughly dried flannel cloth. Next, this test surface was brought into contact with polyester fiber dust for 10 minutes. After that, the presence or absence of dust adhering to the test surface was visually observed and evaluated. The evaluation criteria are as follows. A (Good): No dust adhering to the test surface. C (Defective): Dust is present on the test surface.

[0104] (Chemical resistance) A 50mm x 50mm test specimen was obtained by cutting a multilayer film. The back side of the multilayer film (the side with the third layer as shown in Table 3) was used as the test surface. 0.2 ml of oleic acid (manufactured by Neutrogena) was dropped onto this test surface using a dropper at room temperature (20-25°C), and then the specimen was held at 80°C for 24 hours. After that, the chemical on the test surface was wiped off with gauze, and the surface was visually inspected for any abnormalities and evaluated. The evaluation criteria are as follows. A (Good): There were no visible abnormalities on the entire test surface. B (Acceptable): Dissolution was observed in a portion of the test surface, but there was no overall whitening of the test surface. C (Poor): Dissolution and whitening were observed throughout the test surface.

[0105] (Anti-fog properties) A 50mm x 50mm test piece was obtained by cutting a multilayer film. The back surface of the multilayer film (the side with the third layer, as shown in Table 3) was used as the test surface. A water bath was placed inside a rectangular plastic case with an open top, and the temperature and humidity inside the case were adjusted to 27°C and 85% relative humidity. A test specimen was placed on the top surface of this plastic case. At this time, the test surface of the test specimen was positioned so that it faced the inside of the case. After holding it in this state for 10 minutes, the size of the largest water droplet that condensed on the test surface was measured. The evaluation criteria are as follows. A (Good): The largest condensed water droplet was less than 3 mm in size. C (Defective): The largest condensed water droplet was 3 mm or larger.

[0106] (transparency) A multilayer film was cut to obtain a 50mm x 50mm test specimen. In accordance with JIS K 7361-1, haze was measured at 23°C using a haze meter (HM-150, manufactured by Murakami Color Research Institute).

[0107] (Stretchability) A multilayer film was cut to obtain 50mm x 50mm test specimens. To evaluate the stretchability, a Shimadzu Autograph AG-5000B was used to measure the tensile elongation at break of the test specimens in accordance with JIS-K 7127.

[0108] (Interlayer adhesion) A multilayer film was cut to obtain 50mm x 50mm test specimens. Using a desktop precision universal testing machine (Shimadzu Corporation "AGS-X"), the T-type peel strength between the backing layer and the adhesive layer was measured in accordance with JIS K 6854-2, under conditions of a tensile speed of 300mm / min and an ambient temperature of 23°C.

[0109] (Bending resistance) A 50 x 50 mm test specimen was cut from the center of the multilayer film. In accordance with ISO 5626 (JIS P 8115:2001), the test specimen was repeatedly folded and unfolded perpendicular to the film's extrusion direction, and the number of back-and-forth folds until the test specimen broke was measured.

[0110] [Synthesis Example 1] (Synthesis of thermoplastic elastomer (C-1)) In a dry, pressure-resistant vessel with the interior purged with nitrogen, 64 L of cyclohexane was charged as the solvent, 0.20 L of sec-butyllithium (10% by mass solution of cyclohexane) as the initiator, and 0.3 L of tetrahydrofuran as the organic Lewis base. After raising the temperature to 50°C, 2.3 L of styrene was added and polymerization was carried out for 3 hours, followed by 23 L of isoprene and polymerization for 4 hours, and then another 2.3 L of styrene was added and polymerization was carried out for 3 hours. The resulting reaction solution was poured into 80 L of methanol, the precipitated solid was filtered off, and the mixture was dried at 50°C for 20 hours to obtain a triblock copolymer consisting of polystyrene-polyisoprene-polystyrene. Next, 10 kg of the above triblock copolymer was dissolved in 200 L of cyclohexane, and 5% by mass of palladium carbon (palladium loading: 5% by mass) was added to the copolymer as a hydrogenation catalyst. The reaction was carried out for 10 hours under conditions of hydrogen pressure of 2 MPa and temperature of 150°C. After cooling and release of pressure, the palladium carbon was removed by filtration, the obtained filtrate was concentrated, and this was vacuum-dried to obtain a hydrogenated product of the triblock copolymer consisting of polystyrene-polyisoprene-polystyrene. Hereinafter, this copolymer will be referred to as "thermoplastic elastomer (C-1)". The obtained thermoplastic elastomer (C-1) had a weight-average molecular weight (Mw) of 107,000, a styrene unit content of 21% by mass, a hydrogenation rate of 85%, and a molecular weight distribution (Mw / Mn) of 1.04. In the polyisoprene block contained in thermoplastic elastomer (C-1), the total amount of 1,2-bonds and 3,4-bonds relative to the sum of the amounts of 1,2-bonds, 3,4-bonds, and 1,4-bonds was 60 mol%.

[0111] [Synthesis Example 2] (Synthesis of thermoplastic elastomer (C-2)) In a dry, pressure-resistant vessel with its interior purged with nitrogen, 80 L of cyclohexane was charged as the solvent, 0.46 L of sec-butyllithium (10% by mass solution of cyclohexane) as the initiator, and 0.25 L of tetrahydrofuran (equivalent to 5.4 times the lithium atoms in the initiator in stoichiometric ratio) was charged as the organic Lewis base. After raising the temperature to 50°C, 3.5 L of styrene was added and polymerization was carried out for 3 hours, followed by the addition of 34 L of butadiene and polymerization was carried out for 4 hours. The resulting reaction mixture was poured into 80 L of methanol, the precipitated solid was filtered off, and the mixture was dried at 50°C for 20 hours to obtain a diblock copolymer consisting of polystyrene and polybutadiene. Next, 10 kg of the above diblock copolymer was dissolved in 200 L of cyclohexane, and 5% by mass of palladium carbon (palladium loading: 5% by mass) was added to the copolymer as a hydrogenation catalyst. The reaction was carried out for 10 hours under conditions of hydrogen pressure of 2 MPa and temperature of 50°C. After cooling and release of pressure, the palladium carbon was removed by filtration, the filtrate was concentrated, and this was vacuum-dried to obtain a hydrogenated product of the diblock copolymer consisting of polystyrene-polybutadiene. Hereinafter, this copolymer will be referred to as "thermoplastic elastomer (C-2)". The obtained thermoplastic elastomer (C-2) had a weight-average molecular weight (Mw) of 70,500, a styrene content of 13% by mass, a hydrogenation rate of 98%, and a molecular weight distribution of 1.05. In the polybutadiene block contained in thermoplastic elastomer (C-2), the total amount of 1,2-bonds and 3,4-bonds relative to the sum of the amounts of 1,2-bonds, 3,4-bonds, and 1,4-bonds was 40 mol%.

[0112] [Synthesis Example 3] (Synthesis of thermoplastic elastomer (C-3)) In the same manner as in Synthesis Example 1, a thermoplastic elastomer (C-3) was obtained in which the total amount of 1,2-bonds and 3,4-bonds relative to the sum of the amounts of 1,2-bonds, 3,4-bonds, and 1,4-bonds in a polyisoprene block was 30 mol%.

[0113] [Synthesis Example 4] (Synthesis of polyvinyl acetal resin (DV-1)) 100 kg of polyvinyl alcohol resin with an average degree of polymerization of 500 and a degree of saponification of 99 mol% was dissolved in an aqueous solution. 75 kg of n-butyraldehyde and 110 kg of 35-37% hydrochloric acid were added to this solution and stirred to acetalize the resin, causing it to precipitate. The obtained resin was washed by a known method until the pH became 7, and then dried until the volatile matter content was 0.3%. In this manner, polyvinyl acetal resin (DV-1) with a degree of acetalization of 80 mol% was obtained.

[0114] [Synthesis Example 5] (Synthesis of polar group-containing polypropylene resin (DP-1)) 42 kg of polypropylene (Prime PolyPro F327, manufactured by Prime Polymer Co., Ltd.), 160 g of maleic anhydride, and 42 g of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane were melt-kneaded in a batch mixer at 180°C and a screw rotation speed of 40 rpm to obtain a polar group-containing polypropylene resin (DP-1). The polar group-containing polypropylene resin (DP-1) had an MFR of 6 g / 10 min at 230°C and a load of 2.16 kg (21.18 N), a maleic anhydride concentration of 0.3%, and a melting point of 138°C. The maleic anhydride concentration was obtained by titration using a methanol solution of potassium hydroxide. The melting point was determined from the endothermic peak of the differential scanning calorimetry curve when the temperature was increased at 10°C / min.

[0115] [Synthesis Example 6] (Synthesis of multilayer structured particles (E-1)) A reactor equipped with a stirrer, thermometer, nitrogen gas inlet tube, monomer inlet tube, and reflux condenser was charged with 1050 parts by mass of deionized water, 1 part by mass of sodium dodecylbenzenesulfonate, and 0.05 parts by mass of sodium carbonate. The reactor was thoroughly purged with nitrogen gas to create a substantially oxygen-free environment, and the temperature inside the reactor was raised to 80°C. 0.1 parts by mass of a 3% aqueous potassium persulfate solution was added to the reactor and stirred for 5 minutes. Subsequently, 26.2 parts by mass of mixture (i), consisting of 49.9% by mass of methyl methacrylate (MMA), 49.9% by mass of butyl acrylate (BA), and 0.2% by mass of allyl methacrylate (ALMA), were continuously added over 20 minutes. After the addition was complete, the polymerization reaction was further carried out for at least 30 minutes to achieve a polymerization rate of 98% or higher.

[0116] Next, 0.05 parts by mass of a 3% by mass aqueous solution of potassium persulfate was added to the reactor and stirred for 5 minutes. Then, 157.4 parts by mass of mixture (ii), consisting of 5% by mass of MMA, 93.5% by mass of BA, and 1.5% by mass of ALMA, was continuously added over 40 minutes. After the addition was complete, the polymerization reaction was carried out for at least 30 minutes until the polymerization rate reached 98% or higher.

[0117] Next, 0.5 parts by mass of a 3% aqueous potassium persulfate solution was added to the reactor and stirred for 5 minutes. Then, 341.1 parts by mass of mixture (iii), consisting of 87.2% by mass of MMA, 12.5% ​​by mass of BA, and 0.3% by mass of n-octyl mercaptan (n-OM), were continuously added over 100 minutes. After the addition was complete, the polymerization reaction was further carried out for at least 60 minutes to achieve a polymerization rate of 98% or more. In this manner, an emulsion containing acrylic multilayer structure particles (E-1) with a number average particle size of 100 nm was obtained.

[0118] Next, the emulsion containing acrylic multilayer particles (E-1) was frozen at -30°C for 4 hours. The frozen emulsion was dissolved in twice the volume of 80°C hot water, and then held at 80°C for 20 minutes to obtain a slurry. The slurry was then dehydrated and dried at 70°C to obtain a powder of acrylic multilayer particles (E-1). This powder was pelletized using a known method.

[0119] [Synthesis Example 7] (Synthesis of block copolymer (G-1)) A triblock copolymer (G-1) was synthesized using a known method, consisting of [methyl methacrylate (MMA) polymer block (g1)]-[n-butyl acrylate (BA) polymer block (g2)]-[methyl methacrylate (MMA) polymer block (g1)], with a weight-average molecular weight (Mw) of 70,000, a mass ratio of polymer blocks (g1):(g2):(g1) = 14.3:50.0:35.7, and a mass ratio of each monomer (MMA:BA) = (50:50).

[0120] [Synthesis Example 8] (Synthesis of vinyl alcohol resin (B-1)) (Polymerization of ethylene-vinyl acetate copolymer) In a 250L pressurized reactor equipped with a jacket, stirrer, nitrogen inlet, ethylene inlet, and initiator addition port, 83 kg of vinyl acetate and 14.9 kg of methanol were charged. After raising the temperature to 60°C, nitrogen gas was bubbled into the reaction mixture for 30 minutes to purge the reactor with nitrogen. Next, ethylene was introduced so that the pressure (ethylene pressure) in the reactor reached 4.0 MPa. After adjusting the temperature in the reactor to 60°C, a solution of 12.3 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd. "V-65") dissolved in methanol was added as an initiator, and polymerization was started. During polymerization, the ethylene pressure was maintained at 4.0 MPa and the polymerization temperature at 60°C. After 5 hours, when the polymerization rate of vinyl acetate reached 40%, the reactor was cooled and polymerization was stopped. Ethylene was evacuated from the reactor, and nitrogen gas was further bubbled into the reaction mixture to completely remove the ethylene. Next, unreacted vinyl acetate was removed under reduced pressure to obtain an ethylene-vinyl acetate copolymer (hereinafter referred to as "EVAc").

[0121] (Saponification) Methanol was added to the obtained EVAc solution to obtain a 15% by mass EVAc solution. To 253.4 kg of this methanol solution of EVAc (38 kg of EVAc in the solution), 76.6 L of methanol solution containing 10% by mass sodium hydroxide (molar ratio of 0.4 to vinyl acetate units in EVAc) was added, and the mixture was stirred at 60°C for 4 hours to saponify the EVAc. Six hours after the start of the reaction, 9.2 kg of acetic acid and 60 L of water were added to neutralize the reaction mixture and stop the reaction.

[0122] (Washing) The neutralized reaction solution was transferred from the reactor to a drum and left at room temperature (20-25°C) for 16 hours to cool and solidify into a cake-like consistency. Subsequently, the cake-like resin was dehydrated using a centrifuge (H-130, manufactured by Kokusan Centrifuge Co., Ltd., rotation speed 1200 rpm). Next, the resin was washed by continuously supplying deionized water from above to the center of the centrifuge for 10 hours. The conductivity of the washing solution 10 hours after the start of washing was 30 μS / cm (measured with a CM-30ET, manufactured by Toa Denpa Kogyo Co., Ltd.).

[0123] (granulation) The washed resin was dried in a dryer at 60°C for 48 hours to obtain powdered ethylene vinyl alcohol resin (EVOH). 20 kg of the dried powdered EVOH was dissolved in 43 L of a water / methanol mixture (mass ratio: water / methanol = 4 / 6) and stirred at 80°C for 12 hours. Next, stirring was stopped, the temperature of the dissolution tank was lowered to 65°C, and the mixture was left to stand for 5 hours to degas the EVOH water / methanol solution. Then, this was extruded through a metal plate with a circular opening of 3.5 mm in diameter into a water / methanol mixture at 5°C (mass ratio: water / methanol = 9 / 1) to precipitate in strands, which were then cut to obtain water-containing EVOH pellets with a diameter of approximately 4 mm and a length of approximately 5 mm.

[0124] (purification) The obtained water-containing EVOH pellets were subjected to centrifugation to remove liquid, and then washed by repeatedly adding a large amount of water and removing liquid again to obtain ethylene vinyl alcohol resin (EVOH) pellets. The degree of saponification of the obtained EVOH was 99 mol%, and the ethylene unit content was 44 mol. These EVOH pellets were designated as vinyl alcohol resin (B-1).

[0125] [Synthesis Example 9] (Synthesis of vinyl alcohol resin (B-2)) In the same manner as in Synthesis Example 8, ethylene vinyl alcohol resin (EVOH) pellets with an ethylene unit content of 38 mol% were obtained. These EVOH pellets were designated as vinyl alcohol resin (B-2).

[0126] [Synthesis Example 10] (Synthesis of vinyl alcohol resin (B-3)) In the same manner as in Synthesis Example 8, ethylene vinyl alcohol resin (EVOH) pellets with an ethylene unit content of 27 mol% were obtained. These EVOH pellets were designated as vinyl alcohol resin (B-3).

[0127] [Synthesis Example 11] (Synthesis of vinyl alcohol resin (B-4)) In the same manner as in Synthesis Example 8, ethylene vinyl alcohol resin (EVOH) pellets with an ethylene unit content of 5 mol% were obtained. These EVOH pellets were designated as vinyl alcohol resin (B-4).

[0128] [Manufacturing Example 1] (Manufacturing of thermoplastic polymer composition (X-1)) 56 parts by mass of thermoplastic elastomer (C-1), 19 parts by mass of polyvinyl acetal resin (DV-1), and 25 parts by mass of polar group-containing polypropylene resin (DP-1) were melt-kneaded at 230°C using a twin-screw extruder, then extruded into strands and cut to produce pellets of thermoplastic polymer composition (X-1). The compound composition is shown in Table 1. In manufacturing examples 1 to 7, a Toshiba Machine Co., Ltd. "TEM-28" twin-screw extruder was used.

[0129] [Manufacturing Example 2] (Manufacturing of thermoplastic polymer composition (X-2)) 81 parts by mass of thermoplastic elastomer (C-1) and 19 parts by mass of polyvinyl acetal resin (DV-1) were melt-kneaded at 230°C using a twin-screw extruder, then extruded into strands and cut to produce pellets of thermoplastic polymer composition (X-2). The composition is shown in Table 1.

[0130] [Manufacturing Example 3] (Manufacturing of thermoplastic polymer composition (X-3)) 85 parts by mass of thermoplastic elastomer (C-2) and 15 parts by mass of polar group-containing polypropylene resin (DP-1) were melt-kneaded at 230°C using a twin-screw extruder, then extruded into strands and cut to produce pellets of thermoplastic polymer composition (X-3). The compound composition is shown in Table 1.

[0131] [Manufacturing Example 4] (Manufacturing of thermoplastic polymer composition (X-4)) 98 parts by mass of thermoplastic elastomer (C-1) and 2 parts by mass of polar group-containing polypropylene resin (DP-1) were melt-kneaded at 230°C using a twin-screw extruder, then extruded into strands and cut to produce pellets of thermoplastic polymer composition (X-4). The compound composition is shown in Table 1.

[0132] [Manufacturing Example 5] (Manufacturing of thermoplastic polymer composition (X-5)) 85 parts by mass of thermoplastic elastomer (C-3) and 15 parts by mass of polar group-containing polypropylene resin (DP-1) were melt-kneaded at 230°C using a twin-screw extruder, then extruded into strands and cut to produce pellets of thermoplastic polymer composition (X-5). The compound composition is shown in Table 1.

[0133] [Table 1]

[0134] [Manufacturing Example 6] (Manufacturing of acrylic resin composition (A-1)) As the methacrylic resin (M-1), a commercially available homopolymer of methyl methacrylate (MMA) (weight-average molecular weight (Mw): 80,000) was prepared. 20 parts by mass of methacrylic resin (M-1), 80 parts by mass of pellets of acrylic multilayer structured particles (E-1), UV absorber One part by mass of 2-[4,6-bis(1,1'-biphenyl-4-yl)-1,3,5-triazine-2-yl]-5-[(2-ethylhexyl)oxy]phenol (BASF "Tinuvin 1600") was kneaded using a twin-screw extruder and pelletized using a pelletizer to obtain acrylic resin composition (A-1). The composition is shown in Table 2.

[0135] [Manufacturing Example 7] (Manufacturing of acrylic resin composition (A-2)) As the methacrylic resin (M-2), a methyl methacrylate (MMA) / methyl acrylate (MA) copolymer (MMA unit content: 95% by mass, MA unit content: 5% by mass, weight-average molecular weight (Mw): 80,000) was prepared. Acrylic resin composition (A-2) was obtained in the same manner as in Production Example 6, except that the raw material resin composition was changed to 70 parts by mass of methacrylic resin (M-2) and 30 parts by mass of block copolymer (G-1). The compound composition is shown in Table 2.

[0136] [Table 2]

[0137] [Example 1] Acrylic resin composition (A-1) pellets were prepared as the material for the surface layer (1st layer), thermoplastic polymer composition (X-1) pellets as the material for the intermediate layer (2nd layer), and vinyl alcohol resin (B-1) (EVOH pellets) as the material for the back layer (3rd layer). Each of these resins was put into the hopper of a separate single-screw extruder (GMENGINEERING "VGM25-28EX") and melted and kneaded. These molten resins 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. As described above, a multilayer film with a three-layer structure (width 30 cm, total thickness 100 μm) was obtained, consisting of a surface layer (first layer, impact-resistant acrylic resin layer, 30 μm thick), an intermediate layer (second layer, adhesive layer, 50 μm thick), and a backing layer (third layer, EVOH layer, 20 μm thick). The thickness of each layer was controlled by the extrusion flow rate. The laminated structure of the obtained multilayer film and the evaluation results are shown in Table 3.

[0138] [Examples 2-6] The materials of each layer Table 3 A multilayer film was obtained in the same manner as in Example 1, except for the modifications shown in the diagram. The laminated structure of the obtained multilayer film and the evaluation results are shown in Table 3.

[0139] [Table 3]

[0140] [Comparative Example 1] Pellets of acrylic resin composition (A-1) were placed in the hopper of a single-screw extruder (GMENGINEERING "VGM25-28EX") and melted and kneaded. The molten resin was extruded using a single-layer die, pressurized and cooled using multiple cooling rolls, and taken up by a pair of take-up rolls to obtain a single-layer film with a width of 30 cm and a thickness of 100 μm. On one side of the obtained single-layer film, a coating solution consisting of a mixture of 100 parts by mass of a hard coat agent (Daicel Cytec's "EBECRYL40") and 5 parts by mass of a fluorine-based additive (Shin-Etsu Chemical's "SUBELYN KY-1203") was applied using a wire bar (#40), and dried at 60°C for 1 minute. Then, under an air atmosphere, the film was irradiated using an ultraviolet irradiation device (I-Graphics' "MIDN-042-C1", UV lamp output: 120W) at an irradiation intensity of 0.5 J / cm². 2 Under these conditions, ultraviolet light was irradiated onto the coating film to form a 10 μm thick hard coat layer (also called a "cured film"). As described above, a multilayer film with a two-layer structure consisting of a surface layer (first layer, impact-resistant acrylic resin layer, 100 μm thick) and a back layer (third layer, fluorine-based hard coat layer, 10 μm thick) was obtained. The laminated structure of the obtained multilayer film and the evaluation results are shown in Table 4.

[0141] [Comparative Example 2] A multilayer film (width 30 cm, total thickness 100 μm) was obtained in the same manner as in Example 1, except that a two-layer multilayer film was obtained by directly laminating the surface layer (first layer, impact-resistant acrylic resin layer, 50 μm thick) and the back layer (third layer, EVOH layer, 50 μm thick) without an intermediate layer (second layer, adhesive layer). The laminated structure of the obtained multilayer film and the evaluation results are shown in Table 4.

[0142] [Comparative Example 3] A multilayer film was obtained in the same manner as in Example 1, except that the material of the backing layer (third layer) was changed to polypropylene resin (PP-1) (Prime PolyPro E222, manufactured by Prime Polymer Co., Ltd.). The laminated structure and evaluation results of the obtained multilayer film are shown in Table 4.

[0143] [Comparative Examples 4-6] A multilayer film was obtained in the same manner as in Example 1, except that the materials of each layer were changed as shown in Table 4. The laminated structure of the obtained multilayer film and the evaluation results are shown in Table 4.

[0144] [Table 4]

[0145] [Summary of results] In Examples 1 to 6, a multilayer film was produced comprising a surface layer which is a weather-resistant resin layer made of an acrylic resin composition (A) containing an elastic body (R) and an ultraviolet absorber, a back layer which is an antifouling resin layer containing a vinyl alcohol resin (B), and an adhesive layer provided between the surface layer and the back layer which contains a thermoplastic elastomer (C) and a polyvinyl acetal resin (DV) and / or a polar group-containing polypropylene resin (DP). All of the resulting multilayer films exhibited excellent weather resistance, as well as superior stain resistance, chemical resistance, and anti-fogging properties on the reverse side. Furthermore, all of the resulting multilayer films exhibited excellent transparency, stretchability, flexibility, and interlayer adhesion, resulting in superior handling.

[0146] In Comparative Example 1, a fluorine-based hard coat layer was formed on one surface of a single-layer film made of an acrylic resin composition (A) containing an elastic body (R) and an ultraviolet absorber to obtain a multilayer film. The resulting multilayer film had poor stretchability and flexibility, and was prone to cracking during handling.

[0147] In Comparative Example 2, a two-layer multilayer film was obtained by directly laminating the surface layer (first layer, impact-resistant acrylic resin layer) and the back layer (third layer, EVOH layer) without an intermediate layer (second layer, adhesive layer). The resulting multilayer film had low interlayer adhesion, and delamination occurred during the bending resistance test. The resulting multilayer film was prone to delamination during handling. In Comparative Example 3, polypropylene resin was used as the material for the backing layer (third layer). The resulting multilayer film had poor transparency and anti-fogging properties. It was unsuitable for applications requiring transparency and anti-fogging.

[0148] In Comparative Example 4, a thermoplastic polymer composition (X) containing a thermoplastic elastomer (C) and an adhesion-enhancing component (D), with an adhesion-enhancing component (D) content of 2% by mass, was used as the intermediate layer material. The resulting multilayer film exhibited low interlayer adhesion between the intermediate layer and the EVOH layer, and delamination occurred during the bending resistance test. The resulting multilayer film was prone to delamination during handling.

[0149] In Comparative Example 5, a thermoplastic elastomer (C) was used as the intermediate layer material, in which the polymer block (c2) contained butadiene units and / or isoprene units, and the ratio of the sum of the amounts of 1,2-bonds and 3,4-bonds to the sum of the amounts of 1,2-bonds, 3,4-bonds and 1,4-bonds was 30 mol%. The resulting multilayer film had low interlayer adhesion, and delamination occurred during the bending resistance test. The resulting multilayer film was prone to delamination during handling.

[0150] In Comparative Example 6, a vinyl alcohol resin (B) with an ethylene content of 5 mol% was used as the material for the backing layer (third layer). The resulting multilayer film had poor stain resistance. It could not be used for applications requiring stain resistance.

[0151] The present invention is not limited to the embodiments and examples described above, and design modifications can be made as appropriate without departing from the spirit of the invention.

[0152] This application claims priority based on Japanese Patent Application No. 2020-125189, filed on 22 July 2020, and incorporates all of its disclosures herein. [Explanation of symbols]

[0153] 1. Laminate 1A Surface layer (weather-resistant resin layer) 1B Backing layer (stain-resistant resin layer) 1C adhesive layer 16 Laminated film

Claims

1. An agricultural film consisting of a laminate with different functions on both sides, A surface layer which is a weather-resistant resin layer made of an acrylic resin composition (A) containing an elastic body (R) and an ultraviolet absorber, The back layer is a stain-resistant resin layer containing vinyl alcohol resin (B), Between the surface layer and the back layer, there is an adhesive layer provided in contact with the surface layer and the back layer, comprising a block copolymer comprising a polymer block (c1) comprising aromatic vinyl compound units and a polymer block (c2) comprising conjugated diene compound units, or a thermoplastic elastomer (C) which is a hydrogenated material of the block copolymer, Vinyl alcohol resin (B) is an ethylene vinyl alcohol copolymer having an ethylene unit content of 20 to 50 mol%, The adhesive layer is made of a thermoplastic polymer composition (X) comprising 100 parts by mass of a thermoplastic elastomer (C) and 10 to 100 parts by mass of one or more adhesion-imparting components (D) selected from the group consisting of polyvinyl acetal resin (DV) and polar group-containing polypropylene resin (DP). The polymer block (c2) is a polymer block containing butadiene units and / or isoprene units, wherein the ratio of the sum of the amounts of 1,2-bonds and 3,4-bonds to the sum of the amounts of 1,2-bonds, 3,4-bonds and 1,4-bonds is 40 mol% or more. An agricultural film in which the largest water droplet size that condenses on the back layer in the anti-fogging test described below is less than 3 mm. (Anti-fogging test) The laminate is cut to obtain a 50 mm x 50 mm test piece. The aforementioned back layer is used as the test surface. A water bath is placed inside a rectangular plastic case with an open top surface, and the temperature and humidity inside the case are adjusted to 27°C and 85% relative humidity. The test specimen is placed on the top surface of this plastic case. At this time, the test specimen is positioned so that the test surface is on the inside of the case. After holding it in this state for 10 minutes, the size of the largest water droplet that condenses on the test surface is measured.

2. Acrylic resin composition (A) is A methacrylic resin (M) containing 80% by mass or more of methyl methacrylate units, an elastic body (R), and the ultraviolet absorber are included. The UV absorber is a benzotriazole-based UV absorber and / or a triazine-based UV absorber. An acrylic resin composition wherein, with a total of 100 parts by mass of methacrylic resin (M) and elastic body (R), the content of methacrylic resin (M) is 10 to 99 parts by mass, and the content of elastic body (R) is 90 to 1 part by mass. The agricultural film according to claim 1, wherein the transmittance of the laminate at a wavelength of 300 nm is 5% or less.

3. The agricultural film according to claim 1 or 2, wherein the haze of the laminate is 15% or less.

4. An agricultural film according to any one of claims 1 to 3, wherein the laminated film has a total thickness of 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.

5. Furthermore, the agricultural film according to any one of claims 1 to 4, further comprising a functional layer having a function different from that of the surface layer, the back layer, and the adhesive layer.

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