Deodor-proof decorative film and decorative molded body

Abstract

The present invention provides a decorative film with odor-resistant properties that offers excellent weather resistance, suppressing deterioration of both the decorative film itself and the substrate even when used for extended periods in ultraviolet irradiation environments. [Solution] The deodorizing decorative film (1) of the present disclosure has a surface layer (11) made of an acrylic resin composition (AR) containing a methacrylic resin (M), a back layer (13) containing a vinyl alcohol resin (V), and an adhesive layer (12) provided between them, under a black panel temperature of 83°C, relative humidity of 50%, and irradiation energy of 100 mW / cm². 2 Under these conditions, when a weather resistance test was conducted on the odor-proof decorative film (1) by irradiating it with ultraviolet light from the surface layer (11) side for 200 hours, the difference in the haze value of the odor-proof decorative film (1) before and after the weather resistance test was 0-30%, and the ultraviolet transmittance of the odor-proof decorative film (1) at a wavelength of 315 nm after the weather resistance test was 0-5%.

Description

[Technical Field]

[0001] This disclosure relates to an odor-proof decorative film and a decorative molded article. [Background technology]

[0002] Traditionally, vehicles have been coated with paint by spray coating or other methods to form a protective film on the surface of exterior components for purposes such as surface protection and decoration. From the perspective of reducing environmental impact, paints containing solvents are being replaced by decorative films having a base film made of thermoplastic resin and a decorative layer. Against this backdrop, decorative molded bodies, in which a decorative film is laminated on at least a portion of the surface of the adherend, are becoming the mainstream for vehicle exterior components. Furthermore, in recent years, efforts toward a sustainable society have been progressing, and the recycling of the above-mentioned decorative molded bodies is being considered. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2024-45969 [Patent Document 2] Japanese Patent Publication No. 2007-210199 [Patent Document 3] Japanese Patent Publication No. 2012-144714 [Overview of the project] [Problems that the invention aims to solve]

[0004] Unlike virgin resins, which are synthesized and used for the first time in the manufacture of a product, recycled resins are materials that have been molded and processed in the past and used for a certain period of time under various environmental conditions (e.g., high temperature and UV irradiation). Therefore, recycled resins tend to degrade more than virgin resins due to heat and oxidation. Recycled resins may also contain various additives.

[0005] Adhesion materials containing recycled resin, which is in a degraded state compared to virgin resin, are susceptible to the effects of heat and / or light (ultraviolet rays, etc.) (Patent Document 1, paragraph 0005). Therefore, when recycled resin is molded and processed to remanufacture as an adherend, heat can cause decomposition of the degraded resin and / or various additives, and the resulting adherend may emit an odor derived from the decomposition products. Furthermore, the resulting adherend tends to degrade easily due to ultraviolet rays contained in sunlight, etc., under actual usage conditions.

[0006] Patent Document 2 discloses a method for deodorizing recycled plastics, in which 1 to 5% by weight of a hydroxide of a Group II metal of the periodic table (preferably calcium hydroxide) is added to waste plastics and the waste plastics are melted to produce recycled plastics (Claim 1, 2). However, adding additives to recycled resin for deodorization is undesirable because it increases the cost of the substrate containing the recycled resin. Furthermore, in cases of strong odors, sufficient deodorization may not be achieved. This document also does not disclose any means of preventing degradation caused by ultraviolet irradiation.

[0007] Patent Document 3 discloses a decorative film made of an acrylic resin composition containing a rubber-containing polymer (claims 1, 3, 6, etc.). Acrylic resins are resins that have relatively high weather resistance among resins. Furthermore, ultraviolet absorbers can be added to improve weather resistance (paragraph 0153). However, our research has shown that conventional decorative films made from commonly used acrylic resin compositions cannot suppress the release of odors from a substrate when laminated onto a substrate with a strong odor.

[0008] This disclosure is made in view of the above circumstances, and aims to provide a decorative film with deodorizing properties that has excellent weather resistance, suppresses deterioration of the decorative film itself and the substrate even when used for a long period of time in an ultraviolet irradiation environment, and suppresses the release of odors from the substrate containing recycled resin to the outside. [Means for solving the problem]

[0009] This disclosure provides the following deodorizing decorative films and decorative molded articles. [1] A surface layer made of an acrylic resin composition (AR) containing a methacrylic resin (M), A backing layer containing vinyl alcohol resin (V), It has an adhesive layer provided between the surface layer and the back layer, Black panel temperature 83°C, relative humidity 50%, irradiation energy 100mW / cm² 2 When a weather resistance test was conducted on a decorative film with deodorizing properties under the conditions of irradiating it with ultraviolet light from the surface side for 200 hours, The difference in haze values ​​of the odor-resistant decorative film before and after the weather resistance test was 0-30%. A decorative film with odor-resistant properties, exhibiting an ultraviolet transmittance of 0-5% at a wavelength of 315nm after weather resistance testing.

[0010] [2] The acrylic resin composition (AR) further comprises one or more ultraviolet absorbers (UVA) as the deodorizing decorative film of [1]. [3] An acrylic resin composition (AR) comprising 1 to 99% by mass of one or more rubber-like elastic materials (R) selected from the group consisting of crosslinked rubber particles (RP) and block copolymers (RB), the deodorizing decorative film of [1] or [2].

[0011] [4] Vinyl alcohol resin (V) is an ethylene vinyl alcohol copolymer having an ethylene unit content of 20 to 50 mol%, and is a deodorizing decorative film of any of [1] to [3].

[0012] [5] The adhesive layer comprises one or more thermoplastic elastomers (E) selected from the group consisting of a block copolymer comprising a polymer block (a) containing aromatic vinyl compound units and a polymer block (b) containing conjugated diene compound units, and hydrogenated versions of the block copolymer, as an odor-proof decorative film according to any of [1] to [4].

[0013] [6] The thermoplastic elastomer (E) is a block copolymer having a polymer block (ya) containing styrene units and a polymer block (yb) containing conjugated diene compound units with the total amount of 1,2-bonds and 3,4-bonds being 40 mol% or more, and one or more second thermoplastic elastomers (EY) selected from the group consisting of hydrogenated products of the block copolymer, or a modified film with an odor-proof function according to [5], comprising one or more third thermoplastic elastomers (EZ) selected from the group consisting of a block copolymer having a polymer block (za) containing α-methylstyrene units and a polymer block (zb) containing conjugated diene compound units with the total amount of 1,2-bonds and 3,4-bonds being 40 mol% or more, and hydrogenated products of the block copolymer.

[0014] [7] The thermoplastic elastomer (E) is one or more first thermoplastic elastomers (EX) selected from the group consisting of a block copolymer having a polymer block (xa) containing styrene units and a polymer block (xb) containing conjugated diene compound units with the total amount of 1,2-bonds and 3,4-bonds being less than 40 mol%, and hydrogenated products of the block copolymer, one or more second thermoplastic elastomers (EY) selected from the group consisting of a block copolymer having a polymer block (ya) containing styrene units and a polymer block (yb) containing conjugated diene compound units with the total amount of 1,2-bonds and 3,4-bonds being 40 mol% or more, and hydrogenated products of the block copolymer, and a modified film with an odor-proof function according to [6], comprising one or more third thermoplastic elastomers (EZ) selected from the group consisting of a block copolymer having a polymer block (za) containing α-methylstyrene units and a polymer block (zb) containing conjugated diene compound units with the total amount of 1,2-bonds and 3,4-bonds being 40 mol% or more, and hydrogenated products of the block copolymer.

[0015] [8] The adhesive layer further includes a decorative film with an odor-proof function according to any one of [5] to [7], which contains one or more polypropylene-based polymers (P).

[0016] [9] The polypropylene-based polymer (P) includes one or more first polypropylene-based polymers (PX) having no polar group and one or more second polypropylene-based polymers (PY) having a polar group, and is a decorative film with an odor-proof function according to [8].

[0017]

[10] The decorative film with an odor-proof function according to any one of [1] to [9], wherein when the decorative film with an odor-proof function is stretched 2 times in one direction at a temperature of 140°C, the surface layer does not break.

[11] The decorative film with an odor-proof function according to any one of [1] to

[10] , wherein when the decorative film with an odor-proof function is stretched 2 times in one direction at a temperature of 140°C, the back layer does not break.

[0018]

[12] The decorative film with an odor-proof function according to any one of [1] to

[11] , wherein the surface layer is a decorative layer containing a colorant or a matting agent.

[13] The decorative film with an odor-proof function according to any one of [1] to

[12] , further having a decorative layer laminated on the back surface of the back layer.

[0019]

[14] A decorative molded body in which a decorative film with an odor-proof function according to any one of [1] to

[13] is laminated on at least a part of the surface of an adherend containing a recycled resin through an adhesive layer, The decorative molded body, wherein the adhesive force of the decorative film with an odor-proof function to the adherend is 10 to 100 N / 25 mm.

[0020]

[15] The decorative molded body according to

[14] , wherein the recycled resin contains one or more thermoplastic resins selected from the group consisting of an olefin-based resin (O), a styrene-based resin (S), a polycarbonate-based resin (PC), and a (meth)acrylic-based resin (A).

Advantages of the Invention

[0021] According to this disclosure, it is possible to provide a decorative film with deodorizing properties that has excellent weather resistance, suppresses deterioration of the decorative film itself and the substrate even when used for a long period of time in an ultraviolet irradiation environment, and suppresses the release of odors from the substrate containing recycled resin to the outside. [Brief explanation of the drawing]

[0022] [Figure 1] These are schematic cross-sectional views of the deodorizing decorative film according to the first and second embodiments of the present invention. [Figure 2] This is a schematic cross-sectional view showing a decorated molded article according to the first and second embodiments of the present invention. [Modes for carrying out the invention]

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

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

[0025] In this specification, unless otherwise specified, the weight-average molecular weight (Mw) of (meth)acrylic resins is the weight-average molecular weight (Mw) converted to standard polymethyl methacrylate (PMMA) as determined by gel permeation chromatography (GPC). The same applies to the number-average molecular weight (Mn). In this specification, unless otherwise specified, the weight-average molecular weight (Mw) of resins other than (meth)acrylic resins (such as thermoplastic elastomers (E)) is the weight-average molecular weight (Mw) on a standard polystyrene basis, determined by gel permeation chromatography (GPC) measurement. The same applies to the number-average molecular weight (Mn).

[0026] Generally, thin film molded articles are referred to as "film," "sheet," or "plate" depending on their thickness, but there is no clear definition, and no clear distinction between them. In this specification, "film" includes "sheet."

[0027] [Decorative film with odor-resistant function] The odor-proof decorative film disclosed herein is A surface layer made of an acrylic resin composition (AR) containing one or more methacrylic resins (M), A backing layer made of a vinyl alcohol resin composition (VR) containing one or more types of vinyl alcohol resin (V), It has an adhesive layer provided between the surface layer and the back layer.

[0028] The deodorizing decorative film of this disclosure may include one or more decorative layers. In the deodorizing decorative film of this disclosure, one or more layers among the surface layer, adhesive layer, and back layer can also serve as a decorative layer. For example, the surface layer may contain a coloring agent (C) and / or a matting agent (F) and function as a decorative layer. The deodorizing decorative film of this disclosure may have a decorative layer in addition to the surface layer, adhesive layer, and back layer. For example, the deodorizing decorative film of this disclosure may have a decorative layer laminated on the back surface (the surface not facing the adhesive layer) of the back layer. Examples of decorative layers include printed layers, metal layers, fabrics, and combinations thereof. A decorative layer containing a metal layer can impart a metallic appearance and luster to the film. Examples of metals include Al, Si, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Pd, Ag, In, Sn, Hf, Ta, W, Pt, Au, alloys thereof (such as stainless steel), and combinations thereof.

[0029] Figure 1 is a schematic cross-sectional view of the deodorizing decorative film according to the first and second embodiments of the present invention. In the figure, reference numerals 1 and 2 indicate the deodorizing decorative film, reference numeral 11 indicates the surface layer, reference numeral 12 indicates the adhesive layer, reference numeral 13 indicates the back layer, and reference numeral 14 indicates the decorative layer laminated on the back surface (the side not facing the adhesive layer) 13S of the back layer. The deodorizing decorative film of this disclosure may have other resin layers and / or functional layers as necessary.

[0030] (Surface layer (weather-resistant resin layer)) The surface layer consists of an acrylic resin composition (AR) containing one or more methacrylic resins (M). (Meth)acrylic resins are resins that have relatively high weather resistance among resins. Therefore, a surface layer made of an acrylic resin composition (AR) has excellent weather resistance and can function as a weather-resistant resin layer. To improve weather resistance, the acrylic resin composition (AR) may contain one or more ultraviolet absorbers (UVA).

[0031] The acrylic resin composition (AR) preferably comprises one or more methacrylic resins (M) and one or more rubber-like elastic materials (R). From the viewpoint of transparency, impact resistance, and dispersibility, crosslinked rubber particles (RP) and / or block copolymers (RB) are preferred as the rubber-like elastic materials (R). The surface layer containing one or more rubber-like elastic materials (R) can exhibit excellent stretchability, flex resistance, impact resistance, and handling properties.

[0032] <Methacrylic resin (M)> The methacrylic resin (M) is a homopolymer or copolymer containing methyl methacrylate (MMA) units and one or more other monomer units. The content of MMA units in the methacrylic resin (M) is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass. The content of other monomer units (total amount if there are multiple types) is preferably 0 to 20% by mass. The upper limit is more preferably 10% by mass.

[0033] Other monomers besides MMA include methyl acrylate (MA), ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, pentadecyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and glycyethyl (meth)acrylate. Examples include (meth)acrylic acid esters such as sidyl, allyl (meth)acrylate, cyclohexyl (meth)acrylate, norborneyl (meth)acrylate, and isovonyl (meth)acrylate; unsaturated carboxylic acids such as (meth)acrylic acid, maleic anhydride, maleic acid, and itaconic acid; olefins such as ethylene, propylene, 1-butene, isobutylene, and 1-octene; conjugated dienes such as butadiene, isoprene, and myrcene; aromatic vinyl compounds such as styrene (St), α-methylstyrene (αMSt), and o-, m-, or p-methylstyrene; (meth)acrylamide, (meth)acrylonitrile; vinyl acetate, vinylpyridine, vinyl ketone, vinyl chloride, vinylidene chloride, and vinylidene fluoride.

[0034] The stereoregularity of the methacrylic resin (M) is not particularly limited. Methacrylic resins having stereoregularity such as isotactic, heterotactic, and syndiotactic may be used. As the methacrylic resin (M), a modified methacrylic resin may be used, which is obtained by introducing a ring structure into the main chain, instead of a general methacrylic resin that does not have ring structural units in the main chain (also called an unmodified methacrylic resin). Methacrylic resins that do not have ring structural units in their main chain can be produced by (co)polymerizing a monomer (mixture) containing methyl methacrylate (MMA) and, if necessary, one or more other monomers, using a known method. Methods for producing methacrylic resins having ring structural units in the main chain include copolymerizing multiple types of monomers, including methyl methacrylate (MMA), a monomer having a ring structure, and other monomers as needed, by known methods; and a method in which a methacrylic resin containing MMA units but lacking ring structural units is (co)polymerized by known methods, and then a ring structure is introduced into the main chain to form ring structural units. Polymerization methods for methacrylic resins include radical polymerization methods such as suspension polymerization, (continuous) bulk polymerization, solution polymerization, and emulsion polymerization; and anionic polymerization.

[0035] Commercially available methacrylic resins (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 a 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.

[0036] The weight-average molecular weight (Mw) (converted to standard PMMA) 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, from the viewpoint of impact resistance, toughness, melt flowability, and moldability.

[0037] To suppress the decrease in handling properties due to adhesion between cross-linked rubber particles (RP) and the decrease in impact resistance due to poor dispersion during melt-mixing, the cross-linked rubber particles (RP) of the material can be used in the form of latex or powder containing cross-linked rubber particles (RP) and a dispersant (D). As the dispersant (D), for example, methacrylic resin particles with a particle size smaller than the cross-linked rubber particles (RP) can be used. The acrylic resin composition (AR) may also contain a polymer processing aid (PA) as an additive to improve moldability. Preferably, the polymer processing aid (PA) is a polymer particle having a particle size of 0.05 to 0.5 μm, produced by emulsion polymerization. The polymer processing aid (PA) may be a methacrylic resin particle. If an acrylic resin composition (AR) contains, as an additive, a dispersant (D) made of a methacrylic resin and / or a polymer processing aid (PA) made of a methacrylic resin, these additives made of methacrylic resins may be included in the methacrylic resin (M) as defined herein.

[0038] <Cross-linked rubber particles (RP)> The acrylic resin composition (AR) may contain one or more crosslinked rubber particles (RP). The crosslinked rubber particles (RP) may be multilayer polymer particles with a core-shell structure, having an outermost layer consisting of one or more thermoplastic resin component layers (II) and one or more crosslinked rubber component layers (I) inside. In the crosslinked rubber particles (RP) with a core-shell structure, the center core in the middle is considered a "layer". The number of layers of the crosslinked rubber particles (RP) is preferably 2 to 4. Examples of layer structures include a two-layer structure of layer(I)-layer(II) from the center; a three-layer structure of layer(I)-layer(I)-layer(II), layer(I)-layer(II)-layer(II), or layer(II)-layer(I)-layer(II); and a four-layer structure such as layer(I)-layer(II)-layer(I)-layer(II). Among these, the two-layer structure of layer(I)-layer(II) and the three-layer structure of layer(I)-layer(I)-layer(II) or layer(II)-layer(I)-layer(II) are preferred.

[0039] The mass ratio (layer(I) / layer(II)) of the total amount of crosslinked rubber component layer (I) to the total amount of thermoplastic resin component layer (II) is preferably 30 / 70 to 90 / 10. If the proportion of layer(I) is less than the above range, the flexibility of the acrylic resin composition (AR) may be insufficient. If the proportion of layer(I) is greater than the above range, it may become difficult to form the particle structure, and the melt fluidity of the crosslinked rubber particles (RP) may decrease, making melt mixing with other components and molding of the acrylic resin composition (AR) difficult. The mass ratio (layer(I) / layer(II)) is more preferably 50 / 50 to 90 / 10, and particularly preferably 60 / 40 to 80 / 20.

[0040] From the viewpoint of the rubber elasticity of the crosslinked rubber particles (RP) and the ease of forming the layer structure of the crosslinked rubber particles (RP), layer (I) is preferably composed of a copolymer consisting of 50 to 99.99% by mass of acrylic acid ester monomer units, 49.99 to 0% by mass of other monofunctional monomer units, and 0.15 to 10% by mass of polyfunctional monomer units. The content of acrylic acid ester monomer units is preferably 55 to 99.9% by mass, the content of other monofunctional monomer units is preferably 44.9 to 0% by mass, and the content of polyfunctional monomer units is preferably 0.16 to 2% by mass. This copolymer preferably contains 1% or more by mass of other monomer units.

[0041] The raw material monomers for layer (I) will be described below. One or more known acrylic acid esters can be used. A polyfunctional monomer is a monomer having two or more carbon-carbon double bonds in its molecule. Examples of polyfunctional monomers include esters of unsaturated monocarboxylic acids such as (meth)acrylic acid and cinnamic acid with unsaturated alcohols such as (meth)allyl alcohol; diesters of unsaturated monocarboxylic acids with glycols such as ethylene glycol, butanediol, and hexanediol; and esters of dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and maleic acid with unsaturated alcohols. Specifically, examples include allyl acrylate, metharyl acrylate, allyl methacrylate (ALMA), metharyl methacrylate, (meth)allyl cinnamate, diallyl maleate, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, divinylbenzene, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, and hexanediol di(meth)acrylate. Among these, allyl methacrylate (ALMA) is preferred. Other monofunctional monomers include methacrylic acid esters, aromatic vinyl monomers, and vinyl cyanide monomers.

[0042] From the viewpoint of compatibility between the cross-linked rubber particles (RP) and other components, layer (II) is preferably composed of a (co)polymer consisting of 40 to 100% by mass of methacrylic acid ester units and 60 to 0% by mass of other monomer units. This (co)polymer preferably contains other monomer units. The content of methacrylic acid ester units is preferably 60 to 99% by mass, more preferably 80 to 99% by mass, and the content of other monomer units is preferably 40 to 1% by mass, more preferably 20 to 1% by mass.

[0043] The raw material monomers for layer (II) will be explained below. One or more known methacrylate esters can be used, with methyl methacrylate (MMA) being preferred. Other monomers include acrylic acid esters; aromatic vinyl monomers; vinyl cyanide monomers; maleimide monomers such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-(p-bromophenyl)maleimide, and N-(chlorophenyl)maleimide; and polyfunctional monomers as exemplified in layer (I). Among acrylic acid esters, aromatic vinyl monomers, and vinyl cyanide monomers, alkyl acrylates such as methyl acrylate (MA), ethyl acrylate, and n-butyl acrylate (BA) are preferred.

[0044] As for the cross-linked rubber particles (RP), from the viewpoint of physical properties and ease of manufacture, a three-layer structure consisting of a first cross-linked rubber component layer (Ia), which is a cross-linked rubber component layer (Ia), a second cross-linked rubber component layer (Ib), which is a cross-linked rubber component layer (II), and a thermoplastic resin component layer (II) is preferred. The mass ratio ((Ia) / (Ib)) of the cross-linked rubber component layer (Ia) to the cross-linked rubber component layer (Ib) is preferably 5 / 95 to 95 / 5, and more preferably 20 / 80 to 80 / 20.

[0045] A method for producing crosslinked rubber particles (RP) may include a polymerization reaction step (S1) for forming a crosslinked rubber component layer (I) and a polymerization reaction step (S2) for forming a thermoplastic resin component layer (II). In polymerization reaction step (S1), a monomer mixture (i) corresponding to the copolymer composition of the crosslinked rubber component layer (I) is copolymerized by a known method. Similarly, in polymerization reaction step (S2), a monomer mixture (ii) corresponding to the (co)polymer composition of the thermoplastic resin component layer (II) is (co)polymerized by a known method. In the polymerization reaction step (S2), a molecular weight modifier can be used in a proportion of 0.4 to 10% by mass, more preferably 0.4 to 5% by mass, and particularly preferably 0.6 to 2% by mass, relative to the monomer (mixture) (ii). Examples of molecular weight modifiers include mercaptans such as n-octyl mercaptan (n-OM), t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and mercaptoethanol; terpene mixtures consisting of terpinolene, dipentene, t-terpinene, and small amounts of other cyclic terpenes; and halogenated hydrocarbons such as chloroform and carbon tetrachloride. Among these, alkyl mercaptans such as n-octyl mercaptan (n-OM) are preferred.

[0046] The polymerization method for cross-linked rubber particles (RP) is not particularly limited and includes emulsion polymerization, suspension emulsion polymerization, solution polymerization, and combinations thereof. Below, as an example, we will describe suitable polymerization conditions for cross-linked rubber particles (RP) produced by emulsion polymerization. The polymerization temperature is generally between 0 and 100°C. Examples of emulsifiers include alkali metal salts of fatty acids such as sodium oleate, sodium laurate, and sodium stearate; sulfate esters of fatty alcohols such as sodium lauryl sulfate; rosinates such as potassium rosinate; and alkylaryl sulfonic acids such as dodecylbenzenesulfonic acid. Radical polymerization initiators are commonly used as polymerization initiators. Peroxides such as persulfates, azobisisobutyronitrile, and benzoyl peroxide can be used alone as radical polymerization initiators. Redox initiators can also be used, which are combinations of organic hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, and paramenthane hydroperoxide with reducing agents such as transition metal salts. The average particle size of cross-linked rubber particles (RP) can be controlled within a desirable range by adjusting polymerization conditions such as the amount of emulsifier added. The cross-linked rubber particles (RP) after polymerization can be separated from the reaction system by known methods such as acid precipitation, salting out, spray drying, and freeze-coagulation.

[0047] The volume-average particle size (D50, median diameter) of cross-linked rubber particles (RP) in latex can be measured by dynamic light scattering using a laser diffraction / scattering particle size distribution analyzer or similar device.

[0048] In a core-shell structure, cross-linked rubber particles (RP) in an acrylic resin composition (AR) can have at least a portion of their outermost layer, consisting of one or more thermoplastic resin component layers (II), miscible with the matrix resin and become a component of the matrix resin. Therefore, the average particle diameter of the cross-linked rubber particles (RP) can be determined by using data representing the average particle diameter from the center to the outermost cross-linked rubber component layer (I) that is not miscible with the matrix resin.

[0049] The crosslinked rubber component layer (I) contained in the crosslinked rubber particles (RP) can be selectively electron-stained using phosphotungstic acid and ruthenium tetroxide, etc. By electron-staining the crosslinked rubber component layer (I) of the crosslinked rubber particles (RP) contained in the deodorizing decorative film of this disclosure and observing the electron microscope image (preferably a transmission electron microscope image (TEM)), the portion from the center of any one crosslinked rubber particle (RP) to the outermost crosslinked rubber component layer (I) can be identified. The diameter of this portion can be determined as the particle diameter. If the particle shape is not perfectly circular, the average value of the major axis diameter and minor axis diameter of the portion from the center of the crosslinked rubber particle (RP) to the outermost crosslinked rubber component layer (I) can be used as the particle diameter. The "average particle diameter from the center to the outermost cross-linked rubber component layer (I)" can be the average value (number-average particle diameter) of the particle diameters from the center to the outermost cross-linked rubber component layer (I) of 30 randomly selected cross-linked rubber particles (RP).

[0050] One or more cross-linked rubber particles (RP) may include one or more first cross-linked rubber particles (RP-S) (relatively small particles) having a volume-average particle diameter (D50) of 50 nm or more and less than 160 nm, and / or one or more second cross-linked rubber particles (RP-L) (relatively large particles) having a volume-average particle diameter (D50) of 160 nm or more and 300 nm or less.

[0051] The lower limit of the volume-average particle diameter (D50) of the first cross-linked rubber particles (RP-S) is more preferably 60 nm, even more preferably 70 nm, particularly preferably 80 nm, and most preferably 90 nm. The upper limit is more preferably 155 nm, even more preferably 150 nm, even more preferably 140 nm, particularly preferably 130 nm, and most preferably 120 nm. The lower limit of the volume-average particle diameter (D50) of the second cross-linked rubber particles (RP-L) is more preferably 170 nm, even more preferably 180 nm, particularly preferably 190 nm, and most preferably 200 nm. The upper limit is more preferably 290 nm, even more preferably 280 nm, even more preferably 270 nm, particularly preferably 260 nm, and most preferably 250 nm.

[0052] <Block Copolymer (RB)> One or more rubber-like elastic materials (R) may include one or more block copolymers (RB) comprising a methacrylic polymer block (mb) and an acrylic polymer block (ab).

[0053] A methacrylic polymer block (mb) is a polymer block that mainly contains methacrylic acid ester units and optionally other monomer units. One or more known methacrylic acid esters can be used, and MMA is preferred from the viewpoint of transparency and heat resistance. The weight-average molecular weight (Mw) of the methacrylic polymer block (mb) is not particularly limited, but is preferably 500 to 150,000, more preferably 8,000 to 120,000, and most preferably 12,000 to 100,000. When a block copolymer (RB) contains multiple methacrylic polymer blocks (mb), the monomer composition and molecular weight of these blocks may be the same or different.

[0054] The acrylic polymer block (ab) is a polymer block mainly comprising acrylic acid ester units, and optionally containing other monomer units. One or more known acrylic acid esters can be used, and it is preferable that the block contains alkyl acrylate units and (meth)acrylic acid aromatic ester units. Preferred alkyl acrylates include n-butyl acrylate and 2-ethylhexyl acrylate. The weight-average molecular weight (Mw) of the acrylic polymer block (ab) 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. When a block copolymer (RB) contains multiple acrylic polymer blocks (ab), the monomer composition and molecular weight of these blocks may be the same or different.

[0055] <Content of methacrylic resin (M) and rubbery elastic material (R)> The content of methacrylic resin (M) in 100% by mass of acrylic resin composition (AR) (total amount in the case of multiple types) is preferably 1 to 100% by mass. The lower limit is more preferably 5% by mass, even more preferably 8% by mass, even more preferably 10% by mass, even more preferably 12% by mass, particularly preferably 15% by mass, and most preferably 18% by mass.

[0056] The content of rubbery elastic material (R) in 100% by mass of the acrylic resin composition (AR) (total amount in the case of multiple types) is preferably 99 to 0% by mass. The lower limit is more preferably 1% by mass, even more preferably 2% by mass, even more preferably 5% by mass, even more preferably 8% by mass, even more preferably 10% by mass, even more preferably 12% by mass, even more preferably 15% by mass, even more preferably 18% by mass, even more preferably 20% by mass, even more preferably 22% by mass, even more preferably 25% by mass, even more preferably 28% by mass, even more preferably 30% by mass, particularly preferably 32% by mass, and most preferably 35% by mass. The upper limit is more preferably 95% by mass, even more preferably 90% by mass, particularly preferably 85% by mass, and most preferably 80% by mass. In this specification, unless otherwise specified, the content of cross-linked rubber particles (RP) refers to the amount added, and includes the amount of RP that is compatible with the matrix resin and becomes a component of the matrix resin.

[0057] In 100% by mass of the acrylic resin composition (AR), the total amount of methacrylic resin (M) and rubbery elastic material (R) is preferably 50 to 100% by mass. The lower limit is more preferably 55% by mass, even more preferably 60% by mass, even more preferably 65% ​​by mass, even more preferably 70% by mass, even more preferably 75% by mass, even more preferably 80% by mass, particularly preferably 85% by mass, and most preferably 90% by mass.

[0058] <UV absorber (UVA)> To improve weather resistance, the acrylic resin composition (AR) may contain one or more ultraviolet absorbers (UVA). Examples of ultraviolet absorbers (UVA) include triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, benzodithiol-based ultraviolet absorbers, azomethine-based ultraviolet absorbers, indole-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, oxalate anilide-based ultraviolet absorbers, malonic acid ester-based ultraviolet absorbers, and formamidine-based ultraviolet absorbers. Among these, triazine-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers are preferred from the viewpoint of ultraviolet absorption performance and bleed-out suppression, and triazine-based ultraviolet absorbers are particularly preferred.

[0059] Examples of triazine-based UV absorbers include 2-[4,6-bis(1,1'-biphenyl-4-yl)-1,3,5-triazine-2-yl]-5-[(2-ethylhexyl)oxy]phenol (e.g., BASF's "Tinuvin 1600"), 2-[4-[4,6-bis(1,1'-biphenyl-4-yl)-1,3,5-triazine-2-yl]-3-hydroxyphenoxy]isooctyl propanoate (e.g., BASF's "Tinuvin 479"), and 2-[4,6-diphenyl-1,3,5-triazine-2-yl]-5-(hexyloxy)phenol (e.g., BASF's "Tinuvin 1577ED"), 2,4-bis(2,4-dibenzotriazole)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine (e.g., Sun Chemical's "CYASORB UV-1164"), 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (e.g., ADEKA's "ADEKA Stab LA-46"), a mixture of the reaction product of 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-hydroxyphenyl and oxirane[(C10-C16 alkyloxy)methyl]oxirane (85%) and 1-methoxy-2-propanol (15%) (e.g., BASF's "Tinuvin") Examples include reaction products of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid esters (e.g., BASF's "Tinuvin 405"), 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-triazine (e.g., BASF's "Tinuvin 460"), and other triazine-based UV absorbers (e.g., BASF's "Tinuvin 477").

[0060] Examples of benzotriazole-based UV absorbers include 2-(2H-benzotriazole-2-yl)-4-t-butylphenol (e.g., Everlight Chemical's "Eversorb 70"), 2-(3'-t-butyl-2'-hydroxy-5'-benzotriazole)-5-chlorobenzotriazole (e.g., Everlight Chemical's "Eversorb 73"), 2-(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole (e.g., Everlight Chemical's "Eversorb 74"), 2-[2'-hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole (e.g., Everlight Chemical's "Eversorb 76"), and 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (e.g., ADEKA's "ADEKA Stab"). LA-29), 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] (e.g., ADEKA's "ADEKA Stab LA-31"), 2-(2H-benzotriazol-2-yl)-p-cresol (e.g., ADEKA's "ADEKA Stab LA-32"), 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chloro-benzotriazole (e.g., Everlight Chemical's "Eversorb 75"), mixtures of octyl-3-[3-t-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl)phenyl]propionate and 2-ethylhexyl-3-[3-t-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl)phenyl]propionate (e.g., Everlight Chemical's "Eversorb 109"), other benzotriazole-based UV absorbers (e.g., Everlight Chemical's "Eversorb 77", "Eversorb 79", "Eversorb 88", "Eversorb 89", BASF's "Tinuvin 326", "Tinuvin 571", Yamato Kasei's "DAINSORB T-7", "DAINSORB T-0", "DAINSORB Examples include the "T-52," "DAINSORB T-53," and the "SEESORB701" manufactured by Cipro Chemical Co., Ltd.

[0061] The amount of ultraviolet absorbers (UVA) in an acrylic resin composition (AR) (or the total amount if there are multiple types) can be designed according to the ultraviolet absorption performance of the ultraviolet absorbers (UVA) and the thickness of the surface layer. From the viewpoint of initial weather resistance, long-term weather resistance, and suppression of coloring or discoloration during melt molding, it is preferable to design the content of ultraviolet absorber (UVA) per 100 parts by mass of the total of methacrylic resin (M) and rubbery elastic body (R) as follows. When using only one or more triazine-based ultraviolet absorbers as the ultraviolet absorber (UVA), the content of the triazine-based ultraviolet absorbers (total amount if multiple types are used) is preferably 0.5 parts by mass or more. The lower limit is more preferably 0.8 parts by mass, and particularly preferably 1.0 part by mass. When using only one or more benzotriazole-based ultraviolet absorbers as ultraviolet absorbers (UVA), the content of benzotriazole-based ultraviolet absorbers (total amount in the case of multiple types) is preferably 2.0 parts by mass or more. When using one or more triazine-based ultraviolet absorbers and one or more benzotriazole-based ultraviolet absorbers in combination as ultraviolet absorbers (UVA), the content of triazine-based ultraviolet absorbers (total amount in the case of multiple types) is preferably 0.5 parts by mass or more, and the content of benzotriazole-based ultraviolet absorbers (total amount in the case of multiple types) is preferably 1.0 part by mass or more. From the viewpoint of suppressing the bleed-out of ultraviolet absorbers (UVA), regardless of the type of ultraviolet absorber (UVA), the upper limit of the amount of ultraviolet absorber (UVA) (total amount in the case of multiple types) is preferably 5 parts by mass.

[0062] <Light stabilizer (LS)> The acrylic resin composition (AR) may optionally contain one or more light stabilizers (LS). The light stabilizers (LS) can capture and neutralize radicals (specifically alkyl radicals and peroxide radicals, etc.) generated by heat and / or ultraviolet light. As the light stabilizer (LS), a hindered amine light stabilizer (HALS) is preferred. Examples of hindered amine light stabilizers (HALS) include the NH type having an imino group (>NH), the NR type having a group (>NR) in which the H of the imino group (>NH) is substituted with an organic group such as an alkyl group (e.g., a methyl group), and the NOR type having a group (>N-OR) in which the H of the imino group (>NH) is substituted with an organic group such as an alkoxy group. Here, R represents a substituted or unsubstituted saturated or unsaturated hydrocarbon group. Examples of R include alkyl groups, aralkyl groups, and aryl groups. The alkyl group may be linear, branched, or cyclic.

[0063] <Antioxidant (AO)> The acrylic resin composition (AR) may optionally contain one or more antioxidants (AO). Examples of antioxidants (AO) include phenolic, phosphorus-based, lactone-based, and hydroxyl-based antioxidants. Among these, phenolic antioxidants, phosphorus-based antioxidants, and combinations thereof are preferred.

[0064] Examples of phenolic antioxidants include pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-(1,6-hexanediyl)bis[3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanamide], 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid Examples include tearyl, 4,4'-butylidenebis(6-t-butyl-m-cresol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, bis[3-[3-(t-butyl)-4-hydroxy-5-methylphenyl]propanoic acid]2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl), and 1,3,5-trimethyl-2,4,6-tris(3',5'-di-t-butyl4'-hydroxybenzyl).

[0065] Examples of phosphorus-based antioxidants include 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-t-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,4,8,10-tetra-t-butyl-6-[(2-ethylhexane-1-yl)oxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphosine, tris(2,4-di-t-butylphenyl)phosphite, trisnonylphenylphosphite, diphenylisodecylphosphite, and triphenylphosphitebiphenyl-4,4'-diylbis[bis(2,4-di-t-butylphenoxy)phosphine].

[0066] <Coloring agent (C)> The acrylic resin composition (AR) may optionally contain one or more colorants (C). The surface layer containing the colorants (C) can function as a decorative layer. Examples of colorants (C) include pigments, dyes, and combinations thereof. Examples of dyes include anthraquinones, azos, anthrapyridones, perylenes, anthracenes, perinones, indanthrons, quinacridones, xanthenes, thioxanthenes, oxazines, oxazolines, indigoids, thioindigoids, quinophthalones, naphthalimides, cyanines, methines, pyrazolones, lactones, coumarins, bis-benzoxazolylthiophenes, naphthalenetetracarboxylic acids, phthalocyanines, triarylmethanes, aminoketones, bis(styryl)biphenyls, azines, rhodamines, derivatives thereof, and combinations thereof. From the viewpoint of high heat resistance and weather resistance, perinones, perylenes, azos, methines, and quinolines are preferred, and anthraquinones are more preferred.

[0067] The pigment can be either an organic or inorganic pigment. Examples of organic pigments include azo, azomethine, polyazo, phthalocyanine, quinacridone, anthraquinone, indigo, thioindigo, quinophthalone, benzimidazolone, isoindoline, isoindolinone, and diacetacetallide. Examples of inorganic pigments include carbon black (CB), titanium dioxide, zinc oxide, zinc oxide, lithopone, iron oxide, aluminum oxide, silicon dioxide, kaolinite, montmorillonite, talc, barium sulfate, calcium carbonate, silica, alumina, cadmium red, red iron oxide, molybdenum red, chrome vermilion, molybdate orange, lead yellow, chrome yellow, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, pyridian, cobalt green, titanium cobalt green, cobalt chrome green, ultramarine blue, dark blue, cobalt blue, cerulean blue, manganese violet, cobalt violet, and mica.

[0068] <Matte agent (F)> The acrylic resin composition (AR) may optionally contain one or more matting agents (F) (also called light diffusing agents). The matting agents (F) can impart a matte appearance to the deodorizing decorative film of this disclosure through their light diffusing effect and / or surface irregularity-imparting effect. The surface layer containing the matting agent (F) can function as a decorative layer. Furthermore, at the time of film formation, at least one surface of the deodorizing decorative film of this disclosure may be a smooth surface without surface irregularities. In this case, after film formation, the deodorizing decorative film of this disclosure may be heated at an appropriate temperature to soften it, causing the matting agent (F) to protrude from the film surface, thereby changing the smooth surface without surface irregularities into an uneven surface.

[0069] The matting agent (F) may be inorganic particles, organic particles, organic-inorganic composite particles, or a combination thereof. Examples of inorganic particles include calcium carbonate, magnesium carbonate, barium sulfate, titanium dioxide, magnesium oxide, zinc oxide, zirconium oxide, aluminum oxide, aluminum hydroxide, silica (silicon dioxide), calcined calcium silicate, calcined kaolin, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, glass, talc, clay, mica, carbon black, and white carbon. Examples of organic particles include resin particles such as cross-linked styrene resin particles, high molecular weight styrene resin particles, and cross-linked siloxane resin particles. The matting agent (F) may also be particles that have been surface-treated with fatty acids or the like, based on the examples above.

[0070] As the matting agent (F), inorganic particles are preferred, and one or more inorganic particles selected from the group consisting of mica and talc are preferred, with mica being more preferred. The mica may be either synthetic mica or natural mica. Mica is a type of ore called "mica," and has a structure in which multiple crystal faces that have grown in the planar direction are stacked on top of each other, and has a large aspect ratio.

[0071] The aspect ratio (major axis / thickness) of the matting agent (F) having a layered structure such as mica is preferably 10 to 100 from the viewpoint of moldability and mechanical properties of the deodorizing decorative film of this disclosure. The lower limit is more preferably 20, and particularly preferably 30. The upper limit is more preferably 90, even more preferably 80, even more preferably 70, particularly preferably 60, and most preferably 50.

[0072] Furthermore, the cross-linked rubber particles (RP) have a small refractive index difference with the methacrylic resin (M) and do not act as a matting agent; therefore, they are not included in the matting agent (F).

[0073] The content of the matting agent (F) in the acrylic resin composition (AR) (total amount in the case of multiple types) is not particularly limited and can be 0.1 to 30 parts by mass per 100 parts by mass of the total of the methacrylic resin (M) and the rubbery elastic body (R). The lower limit is preferably 0.2 parts by mass, more preferably 0.5 parts by mass, even more preferably 1 part by mass, even more preferably 2 parts by mass, even more preferably 3 parts by mass, particularly preferably 4 parts by mass, and most preferably 5 parts by mass. The upper limit is preferably 25 parts by mass, more preferably 22 parts by mass, and even more preferably 20 parts by mass. If the content of the matting agent (F) is equal to or greater than the lower limit mentioned above, the light diffusion effect and / or surface irregularity-forming effect of the matting agent (F), and the resulting matting effect, can be effectively obtained. If the content of the matting agent (F) is excessive, the flexibility of the odor-proof decorative film of this disclosure may decrease, potentially leading to a decline in mechanical properties such as bending resistance. If the content of the matting agent (F) is below the above upper limit, the odor-proof decorative film of this disclosure can have good flexibility and good mechanical properties such as bending resistance.

[0074] <Other thermoplastic resins> The acrylic resin composition (AR) may optionally contain one or more other thermoplastic resins other than those mentioned above. Other thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene ionomers; polystyrene, syndiotactic polystyrene resins, styrene-maleic anhydride copolymers, ABS resins (acrylonitrile-butadiene-styrene copolymers), AS resins (acrylonitrile-styrene copolymers), BAAS resins (butadiene-acrylonitrile-acrylic rubber-styrene copolymers), MBS resins (methyl methacrylate-butadiene-styrene copolymers), AAS resins (acrylonitrile-acrylic rubber-styrene copolymers), and SAS resins (silicone-A Examples include styrene resins such as crironitrile-styrene copolymers; polycarbonate resins and polycarbonate-ABS resin alloys; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyamides such as nylon 6, nylon 66, and polyamide elastomers; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride; polyurethane, phenoxy resin, modified polyphenylene ether, polyphenylene sulfide; styrene-based thermoplastic elastomers such as SEPS, SEBS, and SIS; olefin rubbers such as IR, EPR, and EPDM; and biodegradable resins.

[0075] <Other additives> The acrylic resin composition (AR) may optionally contain one or more other additives not listed above. Examples of other additives include compatibilizers, heat stabilizers, plasticizers, mold release agents, antistatic agents, flame retardants, flame retardant enhancers, lubricants, thickeners, defoaming agents, rust inhibitors, antimicrobial and antifungal agents, and antifouling agents.

[0076] An acrylic resin composition (AR) can be produced by melt-kneading one or more materials containing one or more methacrylic resins (M), more preferably one or more rubbery elastic materials (R), and more preferably one or more ultraviolet absorbers (UVA), using a known method. The multiple materials may be kneaded together or in stages, and the compounding procedure is not particularly limited. Melt-kneading can be carried out using known mixing or kneading equipment such as an extruder, kneader-ruder, mixing roll, and Banbury mixer. Extruders such as single-screw extruders, twin-screw extruders, and multi-screw extruders are preferred, with twin-screw extruders being more preferred.

[0077] (adhesive layer) The deodorizing decorative film of this disclosure has an adhesive layer between the surface layer and the back layer. The adhesive layer preferably comprises an elastomer resin composition (ER) containing one or more thermoplastic elastomers (E) selected from the group consisting of a block copolymer having a polymer block (a) containing aromatic vinyl compound units and a polymer block (b) containing conjugated diene compound units, and hydrogenated versions of the block copolymer. Generally, the adhesion between a surface layer containing methacrylic resin (M) and a back layer containing vinyl alcohol resin (V) is poor. However, by providing an adhesive layer containing thermoplastic elastomer (E) between these layers, the interlayer adhesion can be improved. The adhesive layer containing thermoplastic elastomer (E) also exhibits excellent bending resistance, flexibility, and impact resistance.

[0078] The thermoplastic elastomer (E) contains one or more polymer blocks (a) each containing one or more aromatic vinyl compound units. Examples of aromatic vinyl compounds include styrene (St), α-methylstyrene (αMSt), 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, and 2-vinylnaphthalene. The polymer block (a) may contain one or more other monomer units other than aromatic vinyl compound units. Examples of other monomers other than aromatic vinyl compounds include 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether.

[0079] The content of one or more aromatic vinyl compound units in polymer block (a) (total amount if there are multiple types) is not particularly limited, but is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content of monomer units other than aromatic vinyl compound units in polymer block (a) (total amount in the case of multiple types) is not particularly limited and is between 20% and 0% by mass. The upper limit is more preferably 10% by mass, and particularly preferably 5% by mass.

[0080] The thermoplastic elastomer (E) comprises one or more polymer blocks (b) containing one or more conjugated diene compound units. Examples of conjugated diene compounds include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. The polymer block (b) preferably contains butadiene units and / or isoprene units as conjugated diene compound units, and preferably consists of butadiene units and / or isoprene units. The polymer block (b) may contain one or more other monomer units other than the conjugated diene compound unit. Examples of other monomers other than the conjugated diene compound include styrene (St) and 4-methylstyrene.

[0081] The content of conjugated diene compound units in polymer block (b) (total amount in the case of multiple types) is not particularly limited, but is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content of monomer units other than conjugated diene compound units in polymer block (b) (total amount in the case of multiple types) is not particularly limited and is between 20% and 0% by mass. The upper limit is more preferably 10% by mass, and particularly preferably 5% by mass.

[0082] The bonding configuration between polymer block (a) and polymer block (b) is not particularly limited and can be linear, branched, radial, or a combination thereof, with linear being preferred. Examples of linear bonding configurations include diblock copolymers represented by ab, triblock copolymers represented by aba or b-a-b, tetrablock copolymers represented by abab, pentablock copolymers represented by a-b-a-b-a or b-a-b-a-b, (a-b) n Examples include X-type copolymers (where X represents a coupling residue and n represents an integer of 2 or more), and combinations thereof. Among these, triblock copolymers are preferred, and triblock copolymers represented as a-b-a are more preferred.

[0083] The content of polymer blocks (a) in the thermoplastic elastomer (E) is not particularly limited, but is preferably 5 to 75% by mass from the viewpoint of the flexibility and mechanical properties of the thermoplastic elastomer (E). The lower limit is more preferably 10% by mass. The upper limit is more preferably 70% by mass, even more preferably 65% ​​by mass, even more preferably 60% by mass, even more preferably 55% by mass, even more preferably 50% by mass, particularly preferably 45% by mass, and most preferably 40% by mass. The content of polymer blocks (b) in the thermoplastic elastomer (E) is not particularly limited, but is preferably 95 to 25% by mass from the viewpoint of the flexibility and mechanical properties of the thermoplastic elastomer (E). The upper limit is more preferably 90% by mass. The lower limit is more preferably 30% by mass, even more preferably 35% by mass, even more preferably 40% by mass, even more preferably 45% by mass, even more preferably 50% by mass, particularly preferably 55% by mass, and most preferably 60% by mass. The total content of polymer blocks (a) and polymer blocks (b) in the thermoplastic elastomer (E) is not particularly limited, but is preferably 95 to 100% by mass. The lower limit is more preferably 97% by mass, particularly preferably 98% by mass, and most preferably 99% by mass.

[0084] The thermoplastic elastomer (E) may be an unhydrogenated block copolymer having one or more polymer blocks (a) and one or more polymer blocks (b), or a hydrogenated version thereof. There are no particular limitations on the method for producing unhydrogenated block copolymers, and examples include anionic polymerization. For example, (i) a method in which an alkyllithium compound is used as an initiator to sequentially polymerize one or more aromatic vinyl compounds, then one or more conjugated diene compounds, and if necessary, one or more aromatic vinyl compounds are sequentially polymerized; (ii) a method in which an alkyllithium compound is used as an initiator to sequentially polymerize one or more aromatic vinyl compounds, then one or more conjugated diene compounds are sequentially polymerized, and then a coupling agent is added for coupling; (iii) a method in which a dilithium compound is used as an initiator to sequentially polymerize one or more conjugated diene compounds, then one or more aromatic vinyl compounds are sequentially polymerized, and if necessary, one or more conjugated diene compounds are sequentially polymerized.

[0085] From the viewpoint of improving heat resistance and weather resistance, the thermoplastic elastomer (E) is preferably a hydrogenated block copolymer in which at least a portion of the polymer block (b) containing conjugated diene compound units is hydrogenated. The hydrogenation rate of the polymer block (b) is not particularly limited, but is preferably 80-100%. The lower limit is more preferably 85%, and particularly preferably 90%. In this specification, the hydrogenation rate of a polymer block containing conjugated diene compound units can be determined by measuring the iodine value of the block copolymer before and after the hydrogenation reaction. Examples of hydrogenation reactions include a solution prepared by dissolving an unhydrogenated block copolymer in a solvent inert to the hydrogenation reaction and the hydrogenation catalyst, or a reaction solution containing the unhydrogenated block copolymer obtained after the polymerization reaction, in which the unhydrogenated block copolymer is reacted with hydrogen in the presence of a hydrogenation catalyst. A commercially available thermoplastic elastomer (E) may be used.

[0086] The thermoplastic elastomer (E) may optionally contain one or more functional groups, such as a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group, in and / or at the ends of the molecular chain.

[0087] The thermoplastic elastomer (E) may include one or more first thermoplastic elastomers (EX) selected from the group consisting of block copolymers having polymer blocks (xa) containing styrene (St) units and polymer blocks (xb) containing conjugated diene compound units in which the total amount of 1,2- and 3,4-bonds is less than 40 mol%, and hydrogenated versions of said block copolymers.

[0088] The thermoplastic elastomer (E) may, in addition or alternative to the first thermoplastic elastomer (EX), include one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing styrene (St) units and a polymer block (yb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, and hydrogenated versions of said block copolymers.

[0089] The thermoplastic elastomer (E) may, in addition or alternative to the first thermoplastic elastomer (EX) and / or the second thermoplastic elastomer (EY), include one or more third thermoplastic elastomers (EZ) selected from the group consisting of block copolymers having polymer blocks (za) containing α-methylstyrene (αMSt) units and polymer blocks (zb) containing conjugated diene compound units in a total amount of 1,2-bonds and 3,4-bonds of 40 mol% or more, and hydrogenated versions of said block copolymers.

[0090] Thermoplastic elastomer (E) may contain one or more thermoplastic elastomers (EX) to (EZ). The thermoplastic elastomer (E) preferably comprises one or more second thermoplastic elastomers (EY) and / or one or more third thermoplastic elastomers (EZ). The thermoplastic elastomer (E) more preferably comprises one or more first thermoplastic elastomers (EX), one or more second thermoplastic elastomers (EY), and one or more third thermoplastic elastomers (EZ).

[0091] The content of the first thermoplastic elastomer (EX) (total amount in the case of multiple types) per 100 parts by mass of the total amount of thermoplastic elastomer (E) is preferably 22 to 78 parts by mass. The lower limit is more preferably 25 parts by mass, particularly preferably 28 parts by mass, and most preferably 30 parts by mass. The upper limit is more preferably 75 parts by mass, even more preferably 70 parts by mass, even more preferably 60 parts by mass, particularly preferably 50 parts by mass, and most preferably 40 parts by mass.

[0092] The content of the second thermoplastic elastomer (EY) (total amount in the case of multiple types) is preferably 12 to 78 parts by mass per 100 parts by mass of the total amount of thermoplastic elastomer (E). The lower limit is more preferably 15 parts by mass, and particularly preferably 20 parts by mass. The upper limit is more preferably 75 parts by mass, even more preferably 70 parts by mass, even more preferably 60 parts by mass, particularly preferably 50 parts by mass, and most preferably 40 parts by mass.

[0093] The content of the third thermoplastic elastomer (EZ) (total amount in the case of multiple types) is preferably 0 to 60 parts by mass per 100 parts by mass of the total amount of thermoplastic elastomer (E). The lower limit is more preferably 1 part by mass, even more preferably 3 parts by mass, even more preferably 5 parts by mass, even more preferably 10 parts by mass, particularly preferably 15 parts by mass, and most preferably 20 parts by mass. The upper limit is more preferably 55 parts by mass, and particularly preferably 50 parts by mass.

[0094] <Polypropylene polymer (P)> The elastomer resin composition (ER) may contain one or more polypropylene polymers (P). The propylene polymer (P) is a homopolymer or copolymer comprising propylene units and, optionally, one or more other monomer units. The content of polypropylene polymer (P) (total amount if there are multiple types) is preferably 1 to 35 parts by mass per 100 parts by mass of thermoplastic elastomer (E). From the viewpoint of adhesion to various materials (polar resins or non-polar resins), the polypropylene polymer (P) preferably includes a combination of one or more first polypropylene polymers (PX) that do not have polar groups (also called polar group-free polypropylene polymers) and one or more second polypropylene polymers (PY) that have polar groups (also called polar group-containing polypropylene polymers).

[0095] <First polypropylene polymer (PX) (Polar group-free polypropylene polymer)> The first polypropylene polymer (PX) is a homopolymer or copolymer comprising propylene units and, optionally, one or more other monomer units that do not have polar groups. Examples of other monomers include α-olefins other than propylene, specifically including ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and cyclohexene.

[0096] The ratio of propylene units to the total structural units of the first polypropylene polymer (PX) is not particularly limited, but is preferably 55 to 100 mol%. The lower limit is more preferably 65 mol%, even more preferably 75 mol%, particularly preferably 85 mol%, and most preferably 95 mol%. The proportion of monomer units other than propylene units to the total structural units of the first polypropylene polymer (PX) is not particularly limited, but is preferably 45 to 0 mol%. The upper limit is more preferably 35 mol%, even more preferably 25 mol%, particularly preferably 15 mol%, and most preferably 5 mol%.

[0097] The first polypropylene-based polymer (PX) tends to have a greater melt tension as its melt flow rate (MFR) is smaller. From the perspective of film-forming properties in extrusion molding and the like, the melt tension of the first polypropylene-based polymer (PX) measured under the conditions of 230°C and a take-up speed of 4.0 m / min is preferably 2.5×10 -2 N or more. The lower limit is more preferably 3.0×10 -2 N, even more preferably 3.5×10 -2 N, particularly preferably 4×4×10 -2 N, most preferably 4.5×10 -2 N. The upper limit is not particularly limited, and for example, it is 50×10 -2 N, 40×10 -2 N, or 30×10 -2 N.

[0098] The MFR of the first polypropylene-based polymer (PX) is not particularly limited and is preferably 0.1 to 20 g / 10 min. The lower limit is preferably 0.5 g / 10 min, more preferably 1.0 g / 10 min. The upper limit is preferably 15 g / 10 min, more preferably 10 g / 10 min. In this specification, unless otherwise specified, the MFR of the polypropylene-based polymer is a value measured using a melt indexer under the conditions of a temperature of 230°C and a load of 21.18 N in accordance with JIS K7210.

[0099] Polypropylene polymers (PX) having the melt tension specified above include polypropylene polymers having a crosslinked structure, a long-chain branched structure, a high molecular weight component, or a combination thereof. Among these, polypropylene polymers having a long-chain branched structure are preferred from the viewpoint of maintaining the flexibility of the film. Methods for producing polypropylene polymers having a long-chain branched structure include a method of graft copolymerizing a radically polymerizable monomer into polypropylene (Macromolecules 26 (1993) 3467), a method of copolymerizing propylene and polyene (Japanese Patent Publication No. 5-194778), a macromer copolymerization method using a metallocene catalyst (Japanese Patent Publication No. 2009-057542), and a method of melt-mixing polypropylene, a conjugated diene compound, and a radical polymerization initiator (Japanese Patent Publication No. 2015-098542). Among these, macromer copolymerization methods using a metallocene type catalyst are preferred from the viewpoint of suppressing gel formation.

[0100] The melting point (Tm) of the first polypropylene polymer (PX) is not particularly limited, but is preferably 100°C or higher from the viewpoint of heat resistance. The lower limit is more preferably 110°C. The upper limit is preferably 170°C, more preferably 160°C, and most preferably 150°C.

[0101] From the viewpoint of achieving both film-forming properties and adhesive properties of the elastomer resin composition (ER), the content of the first polypropylene polymer (PX) is preferably 3 to 15 parts by mass per 100 parts by mass of the total amount of thermoplastic elastomer (E). The lower limit is more preferably 5 parts by mass, particularly preferably 6 parts by mass, and most preferably 7 parts by mass. The upper limit is more preferably 12 parts by mass, particularly preferably 10 parts by mass, and most preferably 8 parts by mass.

[0102] <Second polypropylene polymer (PY) (Polar group-containing polypropylene polymer)> The polar groups included in the second polypropylene polymer (PY) include polar atoms such as oxygen, nitrogen, and sulfur atoms; (meth)acryloyloxy groups; hydroxyl groups; amide groups; carboxyl groups; acid anhydride groups; and halogen atoms such as chlorine atoms. A first method for producing a polar group-containing polypropylene polymer involves copolymerizing propylene, a polar group-containing monomer, and, if necessary, one or more other monomers using a known method. The copolymerization form is not particularly limited and includes random copolymerization and block copolymerization. A second method for producing a polar group-containing polypropylene polymer involves graft copolymerizing a polar group-containing monomer onto a polypropylene polymer that contains propylene units and, optionally, one or more other monomer units, but does not have polar groups (a polar group-free polypropylene polymer). Among the above methods, graft copolymerization is preferred. The polar group-containing polypropylene polymer produced by the first or second manufacturing method described above comprises propylene units and polar group-containing monomer units, and may further contain one or more other monomer units as needed.

[0103] Examples of polar group-containing monomers include vinyl acetate, vinyl chloride; ethylene oxide, propylene oxide; unsaturated carboxylic acids or their esters or anhydrides; and (meth)acrylamide. Among these, unsaturated carboxylic acids or their esters or anhydrides are preferred, including (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylic acid anhydride, (meth)acrylic acid anhydride, (meth)acrylic acid anhydride, (meth)acrylic acid anhydride, (meth)acrylic acid anhydride, and (meth)acrylic acid anhydride. Among these, (meth)acrylic acid anhydrides such as (meth)acrylic acid anhydride are more preferred. In this specification, (anhydrous)carboxylic acid is a general term for carboxylic acids and carboxylic anhydrous carboxylic acids.

[0104] Other monomers include α-olefins other than propylene, specifically including ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and cyclohexene. The total ratio of propylene units and polar group-containing monomer units to the total structural units of the polar group-containing polypropylene polymer is not particularly limited, but is preferably 55 to 100 mol%. The lower limit is more preferably 65 mol%, even more preferably 75 mol%, particularly preferably 85 mol%, and most preferably 95 mol%. The proportion of α-olefin units other than propylene units to the total structural units of the polar group-containing polypropylene polymer is not particularly limited, but is preferably 45 to 0 mol%. The upper limit is more preferably 35 mol%, even more preferably 25 mol%, particularly preferably 15 mol%, and most preferably 5 mol%.

[0105] As a polypropylene polymer containing polar groups, polypropylene having a carboxyl group or a carboxylic acid anhydride group as the polar group is preferred from the viewpoint of adhesion to various materials. Among these, polypropylene polymers modified by graft copolymerization of (carboxylic acid anhydride) with a polypropylene polymer that does not contain polar groups (polypropylene polymer without polar groups) are preferred. Among these, (maleic anhydride) modified polypropylene polymers are more preferred.

[0106] The polar groups contained in the polar group-containing polypropylene polymer produced by the first or second manufacturing method described above may be post-treated after the polymerization reaction. Polar groups such as (meth)acrylic acid groups and carboxyl groups may be neutralized with metal ions to form ionomers, or esterified with alcohols such as methanol and ethanol. Polar groups such as vinyl acetate groups may also be hydrolyzed.

[0107] A third method for producing a polar group-containing polypropylene polymer involves oxidizing or halogenating (e.g., chlorinating) a polypropylene polymer (a polar group-free polypropylene polymer) containing propylene units and, optionally, one or more other monomer units, but without polar groups, using a known method.

[0108] The melting point (Tm) of the second polypropylene polymer (PY) is preferably 130°C or lower. The lower limit is not particularly limited, but from the viewpoint of the heat resistance of the elastomer resin composition (ER), it is preferably 100°C, more preferably 105°C, and particularly preferably 110°C. The upper limit is more preferably 125°C.

[0109] From the viewpoint of achieving both adhesion and heat resistance, the content of the second polypropylene polymer (PY) is preferably 7.5 to 20 parts by mass per 100 parts by mass of the total amount of thermoplastic elastomer (E). The lower limit is more preferably 8 parts by mass, particularly preferably 9 parts by mass, and most preferably 10 parts by mass. The upper limit is more preferably 17.5 parts by mass, and particularly preferably 15 parts by mass.

[0110] <UV absorber (UVA), light stabilizer (LS), antioxidant (AO)> The elastomer resin composition (ER), like the acrylic resin composition (AR), may optionally contain one or more ultraviolet absorbers (UVA), one or more light stabilizers (LS), one or more antioxidants (AO), or a combination thereof.

[0111] <Other thermoplastic resins> The elastomer resin composition (ER) may contain one or more other thermoplastic resins other than those mentioned above. Examples of other thermoplastic resins include (meth)acrylic resins; polyolefin resins other than polypropylene polymers; ethylene ionomers; styrene resins; polycarbonate resins, polycarbonate-ABS resin alloys; polyester resins; polyamides; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymers, polyacetals, polyvinylidene fluoride; polyurethanes, phenoxy resins, modified polyphenylene ethers, polyphenylene sulfides; olefin rubbers such as IR, EPR, and EPDM; and biodegradable resins.

[0112] <Other additives> The elastomer resin composition (ER) may optionally contain one or more additives other than those listed above. Other additives include tackifying resins, softeners, heat stabilizers, heat degradation inhibitors, plasticizers, mold release agents, antistatic agents, flame retardants, flame retardant aids, lubricants, thickeners, polymer processing aids, silicone oils, antiblocking agents, fillers, defoamers, rust inhibitors, antibacterial and antifungal agents, antifouling agents, and colorants (pigments and dyes, etc.). An adhesive layer containing a coloring agent can function as a decorative layer.

[0113] Examples of tackifying resins include aliphatic unsaturated hydrocarbon resins, aliphatic saturated hydrocarbon resins, alicyclic unsaturated hydrocarbon resins, alicyclic saturated hydrocarbon resins, aromatic hydrocarbon resins, hydrogenated aromatic hydrocarbon resins, rosin ester resins, hydrogenated rosin ester resins, terpene phenol resins, hydrogenated terpene phenol resins, terpene resins, hydrogenated terpene resins, aromatic hydrocarbon-modified terpene resins, coumarone-indene resins, phenol resins, and xylene resins.

[0114] As a softening agent, general softening agents for rubber or plastics can be used. Examples include paraffinic, naphthenic, and aromatic process oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oil; mineral oil; oligomers of ethylene and α-olefins; paraffinic wax; liquid paraffin; polybutene; low molecular weight polybutadiene; and low molecular weight polyisoprene.

[0115] An elastomer resin composition (ER) can be produced by melt-kneading one or more materials, including a thermoplastic elastomer (E), using a known method. If the elastomer resin composition (ER) contains multiple materials, it may be kneaded all at once or in stages, and the compounding procedure is not particularly limited.

[0116] (Underlayer) The deodorizing decorative film of this disclosure includes a backing layer made of a vinyl alcohol resin composition (VR) containing one or more vinyl alcohol resins (V). Vinyl alcohol resin (V) has excellent stain resistance, chemical resistance, anti-fogging properties, and heat retention properties. Furthermore, our research has shown that the backing layer containing vinyl alcohol resin (V) exhibits excellent gas barrier properties and can function as an odor barrier layer. The odor-proof decorative film of this disclosure, which includes a backing layer containing vinyl alcohol resin (V), can effectively suppress the release of odors from an odorous substrate to the outside, even if the substrate has a strong odor, when laminated on top of an odorous substrate.

[0117] <Ethylene-vinyl alcohol copolymer> As the vinyl alcohol resin (V), any known resin can be used, but from the viewpoint of odor barrier properties and moldability, an ethylene-vinyl alcohol copolymer is preferred. 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.

[0118] The ethylene unit content (also simply called "ethylene content") in EVOH is preferably 10 to 60 mol%. The lower limit is more preferably 20 mol%, and particularly preferably 25 mol%. The upper limit is more preferably 55 mol%, particularly preferably 50 mol%, and most preferably 40 mol%. If the ethylene content is 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, the gas barrier properties may decrease.

[0119] As a vinyl ester, vinyl acetate is preferred from the viewpoint of 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 0 to 100 ppm. The upper limit is more preferably 60 ppm, particularly preferably 25 ppm, and most preferably 15 ppm.

[0120] 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 to 0.2 mol%.

[0121] From the viewpoint of thermal stability, the degree of saponification of vinyl ester units is usually 85 to 100 mol%. The lower limit is preferably 90 mol%, more preferably 98 mol%, and particularly preferably 98.9 mol%.

[0122] From the viewpoint of moldability, the melt flow rate (MFR) of EVOH is preferably 0.5 to 30 g / 10 min. The lower limit is more preferably 1.0 g / 10 min, and particularly preferably 1.4 g / 10 min. The upper limit is more preferably 25 g / 10 min, even more preferably 20 g / 10 min, even more preferably 15 g / 10 min, particularly preferably 10 g / 10 min, and most preferably 1.6 g / 10 min. In this specification, the MFR of EVOH is the melt flow rate measured in accordance with JIS K 7210-1 under conditions of a temperature of 190°C and a load of 2,160g.

[0123] <UV absorber (UVA), light stabilizer (LS), antioxidant (AO)> The vinyl alcohol resin composition (VR), like the acrylic resin composition (AR), may optionally contain one or more other thermoplastic resins, one or more ultraviolet absorbers (UVA), one or more light stabilizers (LS), one or more antioxidants (AO), one or more other additives, or a combination thereof. A vinyl alcohol resin composition (VR) can be produced by melt-kneading one or more materials containing a vinyl alcohol resin (V) using a known method. If the vinyl alcohol resin (V) contains multiple materials, the materials may be kneaded together or in stages, and the compounding procedure is not particularly limited.

[0124] (Total thickness and thickness of each layer) The total thickness of the deodorizing decorative film of this disclosure is not particularly limited, but is preferably 20 to 500 μm. The lower limit is more preferably 30 μm, even more preferably 60 μm, particularly preferably 90 μm, and most preferably 120 μm. The upper limit is more preferably 400 μm, particularly preferably 300 μm, and most preferably 200 μm. The thickness of the surface layer is preferably 1 / 20 to 2 / 3, more preferably 1 / 10 to 2 / 3, of the total thickness. The thickness of the backing layer is preferably 1 / 20 to 2 / 3, more preferably 1 / 10 to 2 / 3, of the total thickness. When the thickness of the surface and back layers is 1 / 20 or more of the total thickness, the functions of the surface and back layers, which are functional layers, are sufficiently obtained. When the thickness 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 deodorizing decorative film of this disclosure, from the viewpoint of ensuring good functionality of the surface layer and the back layer while also ensuring 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.

[0125] (Physical properties) The odor-proof decorative film of this disclosure can be used in a decorative molded article in which the odor-proof decorative film of this disclosure is laminated on at least a portion of the surface of an adherend. In recent years, efforts toward a sustainable society have been progressing, and the adherend may contain one or more types of recycled resin. Adhesion materials containing recycled resin, which is in a degraded state compared to virgin resin, are susceptible to the effects of heat and / or light (ultraviolet rays, etc.). Therefore, when recycled resin is molded and processed to create a new product as an adherend, heat can cause decomposition of the degraded resin and / or various additives, which may result in the production of an odor derived from the decomposition products.

[0126] The backing layer containing vinyl alcohol resin (V) included in the odor-proof decorative film of this disclosure can function as an odor barrier layer. The odor-proof decorative film of this disclosure, which includes a backing layer containing vinyl alcohol resin (V), contains recycled resin and, when laminated on an odorous substrate, can effectively suppress the release of odor from the substrate to the outside, even if the substrate has a strong odor. From the viewpoint of odor prevention, it is preferable to laminate the odor-preventive decorative film of this disclosure so as to cover the entire substrate.

[0127] A decorative molded article in which the deodorizing decorative film of this disclosure is laminated on at least a portion of the surface of a substrate is expected to be used for a long period of time in ultraviolet irradiation environments such as sunlight irradiation environments. Adhes containing recycled resin, which is in a degraded state compared to virgin resin, tend to degrade more easily in actual usage environments due to ultraviolet rays contained in sunlight, etc. It is preferable that the deterioration of the decorative film itself and the substrate due to ultraviolet rays is effectively suppressed even when used for a long period of time under the above-mentioned conditions.

[0128] (Meth)acrylic resins are resins that have relatively high weather resistance among resins. Therefore, a surface layer made of an acrylic resin composition (AR) has excellent weather resistance and can function as a weather-resistant resin layer. To improve weather resistance, the acrylic resin composition (AR) may contain one or more ultraviolet absorbers (UVA). Black panel temperature 83°C, relative humidity 50%, irradiation energy 100mW / cm² 2Under these conditions, a weather resistance test can be performed on the odor-proof decorative film of this disclosure by irradiating it with ultraviolet light from the surface side for 200 hours. The initial (before weather resistance test) and post-weather resistance test light transmittance (also called UV transmittance) at 315 nm of the deodorizing decorative film disclosed herein is 0-5%. The upper limit is more preferably 4%, particularly preferably 3%, and most preferably 2%. In this case, even if a decorative molded body in which the deodorizing decorative film of this disclosure is laminated on at least a portion of the surface of the adherend is used for a long period of time under ultraviolet irradiation conditions (e.g., sunlight irradiation conditions), the deterioration of the decorative film itself and the adherend due to ultraviolet light is effectively suppressed. Weather resistance testing and UV transmittance measurement can be performed using the method described in the [Examples] section below.

[0129] The odor-proof decorative film of this disclosure may be a colorless transparent film without a colored layer, a colored film with a colored layer, or a matte film. Therefore, the initial haze value of the odor-proof decorative film of this disclosure is not particularly limited. However, it is preferable that the haze value does not change significantly after the weathering test. The odor-proof decorative film of this disclosure has a haze value difference of 0 to 30% between the haze value of the odor-proof decorative film before the weathering test and after the weathering test. The upper limit is preferably 25%, more preferably 20%, even more preferably 18%, even more preferably 15%, even more preferably 12%, even more preferably 10%, particularly preferably 7%, and most preferably 5%. In this case, even if a decorative molded body on which the odor-proof decorative film of the present disclosure is laminated on at least a portion of the surface of the adherend is used for a long period of time under ultraviolet irradiation conditions (e.g., sunlight irradiation conditions), the odor-proof decorative film of the present disclosure can maintain a good appearance. The haze value can be measured by the method described in the [Examples] section below.

[0130] The odor-proof decorative film of this disclosure may have an adhesive layer comprising a flexible thermoplastic elastomer (E) and not comprising a hard coat layer. The surface layer may preferably include a flexible rubber-like elastic material (R). The odor-proof decorative film of this disclosure having such a configuration may have excellent stretchability and flexural resistance. The deodorizing decorative film of this disclosure has an adhesive layer between the surface layer and the back layer that enhances the adhesion between these layers, and therefore can exhibit excellent interlayer adhesion. The odor-resistant decorative film disclosed herein has excellent stretchability, flexibility, and interlayer adhesion, so cracking or delamination is suppressed even when stretched or bent at room temperature, and it is easy to handle. The deodorizing decorative film disclosed herein has excellent stretchability, flexibility, and interlayer adhesion, making it suitable for use in stretch molding and three-dimensional coating molding.

[0131] The odor-proof decorative film of this disclosure can be laminated along any surface shape of an adherend. In this process, the odor-proof decorative film of this disclosure is often stretched or pulled while heated. In this case as well, it is preferable that the odor-proof decorative film of this disclosure does not break.

[0132] The deodorizing decorative film of the present disclosure preferably has processability (stretchability) such that the surface layer does not break when the deodorizing decorative film of the present disclosure is stretched twice in one direction at a temperature of 140°C. For this purpose, it is preferable that the surface layer softens sufficiently at 140°C, and that the glass transition temperature (Tg) of the methacrylic resin (M) and the acrylic resin composition (AR) containing it be 140°C or lower. The upper limit is more preferably 135°C, and particularly preferably 130°C. From the viewpoint of heat resistance, the lower limit is preferably 80°C, particularly preferably 85°C, and most preferably 90°C.

[0133] The deodorizing decorative film of the present disclosure preferably has processability (stretchability) such that the backing layer does not break when the deodorizing decorative film of the present disclosure is stretched twice in one direction at a temperature of 140°C. For this purpose, it is preferable that the backing layer softens sufficiently at 140°C, and that the glass transition temperature (Tg) of the vinyl alcohol resin (V) and the backing layer containing it be 140°C or lower. The upper limit is more preferably 130°C, even more preferably 120°C, even more preferably 110°C, even more preferably 100°C, particularly preferably 90°C, and most preferably 80°C. From the viewpoint of heat resistance, the lower limit is preferably 40°C, particularly preferably 45°C, and most preferably 50°C.

[0134] (Method for manufacturing decorative film with deodorizing function) The deodorizing decorative film disclosed herein can be manufactured by known methods. Examples of methods for manufacturing the odor-proof decorative film of this disclosure include known multilayer molding methods such as co-extrusion molding, multilayer blow molding, multilayer injection molding, hot pressing, and hot lamination. Among these, co-extrusion molding, in which multiple resin compositions melt-kneaded using different extruders are co-extruded from a common extrusion die (such as a T-die), is preferred. Examples of co-extrusion die systems include the multi-manifold die system and the field block system. In the field block system, multiple types of molten resin compositions are laminated within the feed block, then guided to a T-die or the like to form a sheet and co-extruded. In the multi-manifold die system, multiple types of molten resin compositions are guided to a T-die or the like to form a sheet, then laminated and co-extruded. Among these, the multi-manifold die system is preferred. In either system, the thermoplastic resin laminate extruded from the T-die or the like is cooled by passing through the gap between at least one pair of cooling pressure rolls, and then taken up by a take-up roll. The above processes of co-extrusion, cooling, and take-up are carried out continuously.

[0135] As described above, this disclosure provides a decorative film with deodorizing properties that exhibits excellent weather resistance, suppresses deterioration of the decorative film itself and the substrate even when used for a long period of time in an ultraviolet irradiation environment, and suppresses the release of odors from the substrate containing recycled resin to the outside.

[0136] [Decorated molded product] The decorative molded article of the present disclosure has the above-mentioned deodorizing decorative film of the present disclosure laminated on at least a portion of the surface of a substrate via an adhesive layer (preferably an adhesive film). From the viewpoint of odor prevention, it is preferable to laminate the odor-preventive decorative film of this disclosure so as to cover the entire substrate. Figure 2 is a schematic cross-sectional view of the decorative molded articles of the first and second embodiments of the present invention. In the figure, reference numerals 3 and 4 indicate the decorative molded articles, reference numeral 21 indicates the adherend, and reference numeral 22 indicates the adhesive layer. The same reference numerals are used for the same components as in Figure 1, and their descriptions are omitted.

[0137] The adherend may contain one or more types of recycled resin (also known as rework material). In this specification, "virgin material" refers to a resin material that has never been subjected to molding in the past, and "recycled resin (rework material)" refers to a resin material that has been molded at least once in the past as a molded product. The recycled resin may include one or more thermoplastic resins selected from the group consisting of olefin resins (O), styrene resins (S), polycarbonate resins (PC), and (meth)acrylic resins (A).

[0138] Olefin resin (O) is a homopolymer or copolymer containing one or more α-olefin units. Examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, and cyclohexene. Examples of olefin resins (O) include ethylene resins, propylene resins, polybutene, and poly-4-methylpentene-1. Examples of olefin copolymers include copolymers containing ethylene units and / or α-olefin units having 3 or more carbon atoms (preferably 3 to 20 carbon atoms), such as propylene-ethylene block copolymers and propylene-ethylene-butene-1 block copolymers.

[0139] The styrene-based resin (S) is a homopolymer or copolymer containing one or more styrene-based monomer units and, if necessary, one or more other monomer units. Examples of styrene monomer units include styrene (St), α-methylstyrene (αMSt), o-, m-, or p-methylstyrene, and combinations thereof, with styrene (St) being preferred. Examples of styrene-based resins (S) include methyl methacrylate-styrene copolymer (MS resin), acrylonitrile-styrene copolymer (AS resin), styrene-maleic anhydride copolymer (SMA resin), styrene-maleic anhydride-methyl methacrylate copolymer (SMM resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), butadiene-acrylonitrile-acrylic rubber-styrene copolymer (BAAS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), and silicon-acrylonitrile-styrene copolymer (SAS resin), as well as high-impact polystyrene (HIPS resin) obtained by graft copolymerization of butadiene. The styrene-based resin (S) may also be a styrene-based block copolymer. Examples of styrene-based block copolymers include XY-type diblock copolymers or XYX-type triblock copolymers consisting of a styrene polymer block (X) and a butadiene polymer block or isoprene polymer block (Y), and hydrogenated versions thereof.

[0140] Polycarbonate resins (PC) are preferably obtained by copolymerizing one or more divalent phenols with one or more carbonate precursors. Methods for production include interfacial polymerization, in which an aqueous solution of a divalent phenol reacts with an organic solvent solution of a carbonate precursor at the interface, and transesterification, in which a divalent phenol and a carbonate precursor react under high temperature, reduced pressure, and solvent-free conditions.

[0141] Examples of divalent phenols include 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfide, and bis(4-hydroxyphenyl)sulfone, with bisphenol A being preferred among them. Examples of carbonate precursors include carbonyl halides such as phosgene; carbonate esters such as diphenyl carbonate; and haloformates such as dihaloformates of divalent phenols.

[0142] (Meth)acrylic resin (A) is a homopolymer or copolymer containing one or more (meth)acrylic acid ester units.

[0143] The adhesive layer (preferably the adhesive film) disposed between the adherend and the deodorizing decorative film of this disclosure is not particularly limited and may contain one or more thermoplastic elastomers (E), and may further optionally contain one or more (meth)acrylic resins (A) and / or one or more olefin resins (O). The adhesive layer may further optionally contain one or more optional components. The adhesive layer may have a single-layer structure or a laminated structure. The adhesive layer may include a thermoplastic elastomer-containing layer comprising one or more thermoplastic elastomers (E), and optionally one or more olefin resins (O), such as polypropylene resins; or lamination of this thermoplastic elastomer-containing layer with one or more other resin layers (for example, a (meth)acrylic resin-containing layer).

[0144] Before laminating the odor-proof decorative film of this disclosure onto a substrate, an adhesive layer may be formed in advance on the back surface of the odor-proof decorative film of this disclosure. A decorative film with an adhesive layer formed in advance on the back surface of the odor-proof decorative film of this disclosure is also called an adhesive-layered decorative film.

[0145] Decorative molded articles can be manufactured by known methods. One manufacturing method involves simultaneously laminating an adhesive-coated decorative film onto at least a portion of the surface of a pre-prepared substrate and performing secondary molding of the adhesive-coated decorative film using molding methods such as vacuum forming, pressure forming, vacuum pressure forming, and compression molding. Another method involves inserting an adhesive-coated decorative film, which has been secondarily molded (also called pre-molded) by vacuum forming and pressure forming as needed, into an injection molding die, and then injecting a thermoplastic resin into the die to simultaneously mold the substrate and laminate the adhesive-coated decorative film onto at least a portion of its surface. In the latter method, pre-molding of the adhesive-coated decorative film may be performed using an injection molding machine for substrate molding. Instead of using a decorative film with an adhesive layer, lamination may be performed by sequentially or simultaneously layering an adhesive film that will serve as the adhesive layer and the deodorizing decorative film of this disclosure onto the substrate.

[0146] Methods for forming the adherend include solution casting, extrusion molding, compression molding (also called press molding), injection molding, inflation molding, blow molding, calendering, solution casting, vacuum forming, pressure forming, and vacuum pressure forming. Examples of adherends include single-layer or laminated planar objects such as films, sheets, and plates; pipes, tubes, rods; and any three-dimensional structures. The adherend may also be a laminate or a composite.

[0147] In the decorative molded articles of this disclosure, the adhesive strength of the deodorizing decorative film of this disclosure to the adherend is not particularly limited and can be 10 to 100 N / 25 mm. The lower limit is more preferably 20 N / 25 mm, particularly preferably 30 N / 25 mm, and most preferably 40 N / 25 mm. The upper limit can be 90 N / 25 mm or 80 N / 25 mm. The adhesive strength of the deodorizing decorative film of this disclosure to the adherend can be measured by the method described in the [Examples] section below.

[0148] [Application] The deodorizing decorative film and decorative molded articles containing the same as disclosed herein can be used for any purpose and are preferably used for various applications where aesthetic appeal is required. Suitable applications include automotive interior components, as well as transportation equipment parts such as side visors, rear visors, head wings, headlight covers, and bumpers. [Examples]

[0149] Examples and comparative examples relating to this disclosure will be described below. [Evaluation items and evaluation methods] The evaluation items and methods are as follows: (Weight average molecular weight (Mw)) The weight-average molecular weight (Mw) of methacrylic resins was determined by gel permeation chromatography (GPC). A Tosoh 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 "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 polymethyl methacrylate (PMMA) samples with molecular weights ranging from 400 to 5,000,000, and a calibration curve showing the relationship between retention time and molecular weight was created. Based on this calibration curve, the Mw of the resins in terms of standard PMMA was determined.

[0150] (Glass transition temperature (Tg)) The glass transition temperature (Tg) of the target resin was measured in accordance with JIS K7121 using a differential scanning calorimetry device (Shimadzu Corporation "DSC-50"). 10 mg of the target resin was placed in an aluminum pan and set in the device. After purging with nitrogen for more than 30 minutes, the temperature was increased from room temperature (20-25°C) to 250°C at a rate of 20°C / min in a nitrogen stream of 10 ml / min, held for 5 minutes, and then cooled to room temperature (primary scan). Next, the temperature was increased to 200°C at a rate of 10°C / min (secondary scan), and the DSC curve was measured. The midpoint glass transition temperature obtained from the DSC curve obtained in the secondary scan was defined as the glass transition temperature (Tg).

[0151] (Average particle size) The average particle size of the three layers of cross-linked rubber particles (RP) was measured using a laser diffraction / scattering particle size distribution analyzer. The volume-average particle size (D50) of the polymer particles contained in the latex obtained after polymerization of the third layer was used as the average particle size.

[0152] (Hydrogenation rate) The hydrogenation rate of polymer blocks containing conjugated diene compound units was determined by measuring the iodine value of the block copolymer before and after the hydrogenation reaction.

[0153] (Total amount of 1,2-bonded and 3,4-bonded materials) Thermoplastic elastomer containing polymer blocks containing conjugated diene compound units 1 ¹H-NMR measurements were performed. The total amount of 1,2-bonds and 3,4-bonds was calculated from the ratio of the integral value of the first peak located at 4.2–5.0 ppm, which originates from 1,2-bond and 3,4-bond conjugated diene compound units, to the integral value of the second peak located at 5.0–5.45 ppm, which originates from 1,4-bond conjugated diene compound units.

[0154] (Melting point) The melting point of polypropylene polymers was measured using a differential scanning calorimetry system (Shimadzu Corporation, "DSC-50"). Approximately 5 mg of a polypropylene film sample was placed in an aluminum pan and set in the system. After purging with nitrogen for more than 30 minutes, the sample was heated from room temperature (20-25°C) to 200°C at a rate of 10°C / min in a 10 ml / min nitrogen stream, held for 5 minutes, and then cooled to 40°C at a rate of 10°C / min (first scan). Subsequently, the sample was heated again at a rate of 10°C / min to 200°C (second scan) to obtain the heat of fusion curve. The melting point (Tm) was determined by finding the maximum melting peak temperature (°C).

[0155] (Melting tension) The melt tension of the polypropylene polymer was measured using a capillary rheometer (Toyo Seiki Seisakusho Co., Ltd. "Capillograph 1D") equipped with a pulley-type tension measuring unit. The polypropylene polymer was placed in a 9.55 mm diameter cylinder heated to 230°C. The molten polypropylene polymer was extruded through a 2.0 mm diameter, 40 mm long orifice at an extrusion speed of 20 mm / min and taken up by a pair of take-up rolls at a take-up speed of 4.0 m / min. The melt tension (N) was measured by the tension applied to the pulley-type tension measuring jig.

[0156] (Total thickness and thickness of each layer) The total thickness of the single-layer or laminated resin film obtained in each example was measured using a micrometer. The thickness of each layer in the laminated resin film was determined by cutting the resin film in the thickness direction using a razor blade and observing the resulting cross-section under a microscope. The ratio of the thickness of each layer to the total thickness was then calculated.

[0157] (Weather resistance test) From the single-layer or laminated resin films obtained in each example, 50mm x 50mm test specimens were cut out. A super UV tester (Iwasaki Electric Co., Ltd. "SUV-W161") was used as the accelerated weathering test apparatus, and the test specimens were subjected to irradiation at a black panel temperature of 83°C, relative humidity of 50%, and irradiation energy of 100mW / cm². 2Under these conditions, ultraviolet light was irradiated from the surface side for 200 hours. After that, the test specimen was removed from the testing machine.

[0158] (UV transmittance after weathering test) Using a spectrophotometer (Shimadzu Corporation "UV3600"), the transmission spectrum in the wavelength range of 200-800 nm was obtained from the test specimens after the weathering test, and the transmittance at a wavelength of 315 nm was determined. This transmittance is called the "UV transmittance after the weathering test." A lower UV transmittance after the weathering test indicates better weather resistance.

[0159] (Haze value) For test specimens before and after the weathering resistance test, the haze value was measured at 23°C using a haze meter (HM-150, manufactured by Murakami Color Research Institute Co., Ltd.) in accordance with JIS K 7361-1. The difference in haze values ​​before and after the weathering test was calculated based on the following formula. [Difference in haze value before and after weathering test (%)] = [Haze value after weathering test (%)] - [Haze value before weathering test (%)]

[0160] (Workability (stretchability)) 50mm x 50mm test specimens were cut from the single-layer or laminated resin films obtained in each example. Tensile tests were performed on the test specimens using a Shimadzu Autograph AG-5000B in accordance with JIS-K 7127. The test specimens were stretched twice in one direction at a temperature of 140°C, and the presence or absence of cracks was checked by visual inspection of the surface layer and back layer (if present), and evaluated according to the following criteria. <Judgment criteria> Good (○): No cracks were observed. Acceptable (△): Minor cracks were observed. Defective (×): A crack of a size that was immediately noticeable was observed.

[0161] (odor resistance) A 2mm thick sheet was produced by hot-press molding a melt-mixed recycled polypropylene resin (RePP) ((RePP-1) or (RePP-2)), and 3cm x 3cm sheet pieces were cut out. On each side of this recycled PP resin sheet (3cm x 3cm), a (meth)acrylic resin film (Kuraray's "Parapure FB50", 5cm x 5cm) was sequentially laminated as an adhesive layer, along with the single-layer or laminated resin film (5cm x 5cm) obtained in each example. The obtained temporary laminate was hot-pressed at 200°C to obtain a laminate having a single-layer or laminated resin film / (meth)acrylic resin film (adhesive layer) / recycled PP resin sheet / (meth)acrylic resin film (adhesive layer) / single-layer or laminated resin film laminate structure. Lamination was performed so that the centers and diagonals of all sheets and films were aligned. Furthermore, the lamination was performed so that the surface layer contained in the single-layer or laminated resin film obtained in each example became the outermost layer. This laminate is intended to represent a decorative molded body obtained by laminating the single-layer or laminated resin film obtained in each example onto a substrate made of recycled PP resin, with the adhesive layer in between, so as to cover the substrate. The resulting laminate was placed in a 1L glass container, sealed, and heated in a furnace at 80°C for 2 hours. The glass container was removed from the furnace and allowed to stand at room temperature (20-25°C) for 1 hour. The glass container was opened, and a sensory evaluation of the odor was performed, evaluated according to the following criteria. <Judgment criteria> Good (○): Slight odor is noticeable. High odor-blocking properties. Acceptable (△): A moderate level of odor is noticeable. Moderate odor-blocking effect. Poor (×): Strong odor. Poor odor-blocking properties.

[0162] (Adhesion strength to the adherend) The adhesive strength of the resin film obtained in Example E1 was evaluated by changing the resin to which it was bonded. The following five commercially available resins were prepared as the resins to which it was bonded. Polypropylene resin (PP), Polycarbonate resin (PC), Acrylonitrile-butadiene-styrene copolymer (ABS), Polycarbonate-based resin-acrylonitrile-butadiene-styrene copolymer alloy (PC / ABS), Polyvinyl chloride (PVC).

[0163] A 2mm thick sheet of the resin to be bonded was produced by hot-press molding the molten and kneaded resin, and then sheet pieces measuring 3cm wide x 3cm long were cut out. On both sides of the resin sheet to be bonded (3cm x 3cm) (adherent), a (meth)acrylic resin film (Kuraray's "Parapure FB50", 2.5cm wide x 5cm long) was sequentially laminated as an adhesive layer, and the laminated resin film obtained in Example E1 (2.5cm wide x 5cm long) was sequentially laminated. The obtained temporary laminate was hot-pressed at 200°C to obtain a laminate of the laminated resin film obtained in Example E1 / (meth)acrylic resin film (adhesive layer) / resin sheet to be bonded / (meth)acrylic resin film (adhesive layer) / laminated resin film obtained in Example E1. Lamination was performed so that the centers, width, and length directions of all sheets and films were aligned. Furthermore, the lamination was performed so that the surface layer contained in the resin film obtained in Example E1 became the outermost layer.

[0164] The resulting laminate was fixed onto a flat plate (stainless steel panel) using double-sided adhesive tape and set in a small benchtop testing machine (Shimadzu Corporation "EZ-SX"). Two straight cuts parallel to the length of the resin film were made in the uppermost laminated structure at 25 mm intervals. One of the short sides (25 mm wide) of the portion sandwiched between the two straight cuts in the uppermost laminated structure resin film was peeled off from the resin sheet to be bonded at a 180° angle using a film chuck, under conditions of a tensile load of 100 N and a peeling speed of 300 mm / min. The tensile stress [N / 25 mm] at this time was measured at 0.1-second intervals. After every second, the average value of 10 data points obtained in that second (average value for 1 second) was calculated, and the relationship between time and stress was graphed. The average tensile stress between the point when the first 10 mm was peeled off and the point when another 15 mm was peeled off was defined as the adhesive force [N / 25 mm] to the adherend.

[0165] [material] <Methacrylic resin (M)> The following methacrylic resin (M) was prepared. (M-1) Polymethyl methacrylate (PMMA), Mw (equivalent to standard PMMA): 80,000) (M-2) Methyl methacrylate (MMA) / methyl acrylate (MA) copolymer (MMA unit content: 95% by mass, MA unit content: 5% by mass, Mw (standard PMMA equivalent): 80,000).

[0166] <Cross-linked rubber particles (RP)> The following cross-linked rubber particles (RP) were manufactured. (RP-1) Powdered three-layer acrylic crosslinked rubber particles (RP-1) were obtained in accordance with the method described in Synthesis Example 6 (Synthesis of multilayer structured particles (E-1)) in the [Examples] section of International Publication No. 2022 / 019310. The composition of each layer, the mass ratio of each layer, and the average particle size are as follows. Layer 1: Methyl methacrylate (MMA) units / Butyl acrylate (BA) units / Allyl methacrylate (ALMA) units (mass ratio) = 49.9 / 49.9 / 0.2 Layer 2: MMA units / BA units / ALMA units (mass ratio) = 5 / 93.5 / 1.5 Layer 3: MMA units / BA units (mass ratio) = 87.2 / 12.5 1st layer / 2nd layer / 3rd layer (mass ratio) = 5.0 / 30.0 / 65.0, Average particle size (D50) of the three layers: 100 nm.

[0167] (RP-2) Using the same method as for the multilayer structured particles (RP-1), powdered three-layered acrylic cross-linked rubber particles (RP-2) were obtained. The composition of each layer, the mass ratio of each layer, and the average particle size are as follows. Layer 1: MMA units / MA units / ALMA units (mass ratio) = 95.4 / 4.4 / 0.2 Layer 2: BA units / St units / ALMA units (mass ratio) = 80.5 / 17.5 / 2 Layer 3: MMA units / MA units (mass ratio) = 95.2 / 4.4 1st layer / 2nd layer / 3rd layer (mass ratio) = 35 / 45 / 20, Average particle size (D50) of the three layers: 230 nm.

[0168] <UV absorber (UVA)> (UVA-1) Triazine-based UV absorber, 2-[4,6-bis(1,1'-biphenyl-4-yl)-1,3,5-triazin-2-yl]-5-[(2-ethylhexyl)oxy]phenol, manufactured by BASF as "Tinuvin® 1600".

[0169] <Matte agent (F)> (F-1) Mica microparticles, "Micromica MK100" manufactured by Katakura Coop Agri Co., Ltd., average particle size: 5 μm (catalog value).

[0170] <Acrylic resin composition (AR)> Multiple materials, including one or more methacrylic resins (M), one or more cross-linked rubber particles (RP), one or more ultraviolet absorbers (UVA), and one or more matting agents (F), were melt-kneaded using a twin-screw extruder and extruded into strands. The strands were cut using a pelletizer to obtain pellets of acrylic resin compositions (AR1) to (AR3). Table 1 shows the compound composition (starting composition) and Tg of acrylic resin compositions (AR). The unit of compounding is parts by mass.

[0171] [Table 1]

[0172] <Thermoplastic elastomer (E)> The following thermoplastic elastomers (EX), (EY), and (EZ) were manufactured. (First thermoplastic elastomer (EX-1)) In a pressure vessel dried by purging the inside with nitrogen, 50.0 kg of cyclohexane was charged as a solvent, and 61.1 g of a 10.5 mass% cyclohexane solution of sec-butyllithium (6.42 g of sec-butyllithium) was charged as an anionic polymerization initiator and mixed. This solution was heated to 50°C, 0.81 kg of styrene (St) was added and polymerization was carried out for 1 hour, followed by 10.87 kg of isoprene and polymerization was carried out for 2 hours, followed by 0.81 kg of styrene (St) and polymerization was carried out for 1 hour. In this way, a reaction solution containing a polystyrene-polyisoprene-polystyrene triblock copolymer was obtained. To this reaction solution, 5 mass% of palladium carbon (palladium loading: 5 mass%) was added to the block copolymer as a hydrogenation catalyst, and the reaction was carried out for 10 hours under conditions of hydrogen pressure of 2 MPa and 150°C. After cooling and depressurization, palladium carbon was removed by filtration, the filtrate was concentrated, and vacuum-dried to obtain thermoplastic elastomer (EX-a) (hydrogenated polystyrene-polyisoprene-polystyrene triblock copolymer). The total amount of 1,2-bonds and 3,4-bonds in the polyisoprene block in thermoplastic elastomer (EX-a) was 7 mol%.

[0173] Separately, 50.0 kg of cyclohexane as a solvent and 420.0 g of a 10.5 mass% cyclohexane solution of sec-butyllithium (44.1 g of sec-butyllithium) as an anionic polymerization initiator were charged into a pressure vessel that had been dried by purging the inside with nitrogen, and mixed. After raising the temperature of this solution to 50°C, 2.83 kg of styrene (St) was added and polymerization was carried out for 1 hour, followed by the addition of 19.81 kg of isoprene and polymerization was carried out for 2 hours. In this way, a reaction solution containing polystyrene-polyisoprene block copolymer was obtained. Next, hydrogenation, palladium carbon removal by filtration, and vacuum drying were carried out in the same manner as above to obtain thermoplastic elastomer (EX-b) (hydrogenated polystyrene-polyisoprene block copolymer). The total amount of 1,2-bonds and 3,4-bonds in the polyisoprene block in thermoplastic elastomer (EX-b) was 7 mol%.

[0174] The obtained thermoplastic elastomers (EX-a) and (EX-b) were melt-kneaded using a twin-screw extruder (Coperion "ZSK26MegaCompounder" (ratio of effective screw length (L) to screw diameter (D) = 54)) at a screw rotation speed of 300 rpm and a melt-kneading temperature of 200°C to obtain the first thermoplastic elastomer (EX-1). The total amount of 1,2-bonds and 3,4-bonds in the polyisoprene block of the first thermoplastic elastomer (EX-1) was 7 mol%.

[0175] (Second thermoplastic elastomer (EY-1)) In a pressure vessel dried by purging the inside with nitrogen, 50.0 kg of cyclohexane was charged as a solvent, 94.1 g of a 10.5 mass% cyclohexane solution of sec-butyllithium (9.9 g of sec-butyllithium) was added as an anionic polymerization initiator, and 300 g of tetrahydrofuran was added as a Lewis base and mixed. After raising the temperature of this solution to 50°C, 1.25 kg of styrene (St) was added and polymerization was carried out for 1 hour, followed by the addition of 10.00 kg of isoprene and polymerization for 2 hours, followed by the addition of 1.25 kg of styrene (St) and polymerization for 1 hour. In this way, a reaction solution containing polystyrene-polyisoprene-polystyrene triblock copolymer was obtained. Next, hydrogenation, palladium carbon removal by filtration, and vacuum drying were carried out in the same manner as in Production Example 1 to obtain a second thermoplastic elastomer (EY-1) (hydrogenated polystyrene-polyisoprene-polystyrene triblock copolymer). The total amount of 1,2-bonds and 3,4-bonds in the polyisoprene block within the second thermoplastic elastomer (EY-1) was 55 mol%.

[0176] (Third thermoplastic elastomer (EZ-1)) In a pressure vessel dried by purging the inside with nitrogen, 4.29 kg of α-methylstyrene (αMSt), 6.25 kg of cyclohexane, 1.18 kg of methylcyclohexane, and 0.15 kg of tetrahydrofuran were charged and mixed. To this solution, 0.42 L of a 1.3 M cyclohexane solution of sec-butyllithium was added, and polymerization was carried out at -10°C for 5 hours. Three hours after the start of polymerization, the weight-average molecular weight (Mw, on a standard polystyrene basis) of poly(α-methylstyrene) (block S) was 6600, and the polymerization conversion rate of α-methylstyrene was 90%. Next, 0.88 kg of butadiene was added to this reaction mixture, and polymerization was carried out at -10°C for 30 minutes, after which 41.8 kg of cyclohexane was added. At this point, the polymerization conversion rate of butadiene was 90%. After this step, a poly(α-methylstyrene) block (S)-polybutadiene block (t1) copolymer was obtained. The polybutadiene block (t1) had a weight-average molecular weight (Mw, equivalent to standard polystyrene) of 3700 and a 1,2-bonding content of 81 mol%.

[0177] 7.71 kg of butadiene was added to the above reaction solution, and polymerization was carried out at 50°C for 2 hours to obtain a poly(α-methylstyrene) block (S)-polybutadiene block (t1)-polybutadiene block (t2) copolymer. The weight-average molecular weight (Mw, on a standard polystyrene basis) of polybutadiene block (t2) was 29800, and the 1,2-bonding amount was 40 mol%.

[0178] To the above reaction solution, 0.54 L of a 0.5 M toluene solution of dichlorodimethylsilane was added, and the coupling reaction was carried out at 50°C for 1 hour. After this reaction, the coupling product was poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) triblock copolymer (poly(α-methylstyrene) block (S)-polybutadiene block (t1)-polybutadiene block (t2)-X-polybutadiene block (t2)-polybutadiene block (t1)-poly(α-methylstyrene) block (S) copolymer). Here, X is the coupling residue. The obtained poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) triblock copolymer had a poly(α-methylstyrene) block content of 31% by mass, and the amount of 1,4-bonds in the entire polybutadiene block (t1+t2) was 55 mol%. Furthermore, GPC analysis was performed on the above coupling product and the unreacted block copolymer (poly(α-methylstyrene) block (S)-polybutadiene block (t1)-polybutadiene block (t2) copolymer), and the coupling efficiency was determined from the ratio of the peak integral values ​​of UV absorption to be 94%.

[0179] A Ziegler-type hydrogenation catalyst consisting of nickel octoate and triethylaluminum was added to the above reaction solution under a hydrogen atmosphere, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and 80°C for 5 hours to obtain a third thermoplastic elastomer (EZ-1). The main component of the third thermoplastic elastomer (EZ-1) was a hydrogenated poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) triblock copolymer (a hydrogenated product of the above coupling product), and its content was 94% by mass. The third thermoplastic elastomer (EZ-1) had a weight-average molecular weight (Mw, equivalent to standard polystyrene) of 79,500, a number-average molecular weight (Mn, equivalent to standard polystyrene) of 78,700, an Mw / Mn ratio of 1.01, a hydrogenation rate of 97.5% in the entire polybutadiene block (t1+t2), and a total proportion of 1,2- and 3,4-bonds in the polybutadiene block of 45 mol%.

[0180] <Polypropylene polymer (P)> The following polypropylene polymers (PX) and (PY) were prepared. (PX-1) "Waymax® MFX3" manufactured by Nippon Polypropylene Co., Ltd., MFR at 230℃, 21.18N: 9.0g / 10min, melt tension: 4.9×10 -2 N, (PY-1) Maleic anhydride-modified polypropylene, manufactured by Sanyo Chemical Industries, Ltd., "YUMEX® 5200", melting point 124℃.

[0181] <Elastomer resin composition (ER)> The following elastomer resin compositions (ERs) were manufactured. (ER-1) 40 parts by mass of the first thermoplastic elastomer (EX-1), 40 parts by mass of the second thermoplastic elastomer (EY-1), 20 parts by mass of the third thermoplastic elastomer (EZ-1), 7.5 parts by mass of the first polypropylene polymer (PX-1), and 10 parts by mass of the second polypropylene polymer (PY-1) were melt-kneaded using a twin-screw extruder and extruded into strands. The strands were cut using a pelletizer to obtain pellets of the elastomer resin composition (ER-1). The compound composition is shown in Table 2.

[0182] [Table 2]

[0183] <Vinyl alcohol resin (V)> The following vinyl alcohol resin (V) was prepared. (V-1) Ethylene-vinyl alcohol copolymer (Eval® Grade E, manufactured by Kuraray Co., Ltd.), ethylene unit content 20-50 mol%, Tg: 53℃, (V-2) Ethylene-vinyl alcohol copolymer (Kuraray Co., Ltd. "EVAL" (registered trademark) F grade), ethylene unit content 20-50 mol%, Tg: 60℃.

[0184] <Antioxidant> (AO-1) Hindered phenol antioxidant, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Japan as "Irganox 1010".

[0185] <Recycled polypropylene resin (RePP)> (RePP-1) 100 parts by mass of commercially available polypropylene resin (virgin material) were mixed with 0.2 parts by mass of antioxidant (AO-1) and 0.2 parts by mass of ultraviolet absorber (UVA-1), and melt-mixed at 240°C for 5 minutes. Ten minutes after the completion of the first melt-mix, a second melt-mix was performed under the same conditions as the first. This operation was repeated, resulting in a total of four melt-mixes. After a total of four melt-mixing cycles, 0.2 parts by mass of antioxidant (AO-1) and 0.2 parts by mass of ultraviolet absorber (UVA-1) were added to 100 parts by mass of the resin composition obtained, and melt-mixing was performed under the same conditions as the first time (fifth melt-mixing cycle). A resin composition that underwent a total of five melt-kneading processes was designated as recycled polypropylene resin (RePP-1) (rework material). This rework material corresponds to a rework material obtained by repeating melt-kneading and injection molding several times, and it had a strong odor on its own.

[0186] (RePP-2) 100 parts by mass of commercially available polypropylene resin (virgin material) was mixed with 0.2 parts by mass of antioxidant (AO-1) and 0.2 parts by mass of ultraviolet absorber (UVA-1), and melt-kneaded at 240°C for 5 minutes. The resulting resin composition was designated as recycled polypropylene resin (RePP-2) (rework material). This rework material is relatively new and had a slight odor when used alone.

[0187] [Example E1] Pellets of an acrylic resin composition (AR-1) were prepared as the material for the surface layer (1st layer), pellets of an elastomer resin composition (ER-1) were prepared as the material for the adhesive layer (2nd layer), and pellets of vinyl alcohol resin (V-1) were prepared as the material for the back layer (3rd layer). These resins (compositions) were each put into the hopper of a separate single-screw extruder and melted and kneaded. These molten resin compositions were co-extruded using a multi-manifold die, pressurized and cooled using multiple cooling rolls, and taken up by a pair of take-up rolls. As described above, a resin film with a three-layer structure was obtained, consisting of a surface layer (first layer, acrylic resin composition layer, 50 μm thick), an adhesive layer (second layer, elastomer resin composition layer, 50 μm thick), and a backing layer (third layer, vinyl alcohol resin layer, 50 μm thick). The total thickness was 150 μm, with the surface layer accounting for 1 / 3 of the total thickness and the backing layer accounting for 1 / 3. The thickness of each layer was controlled by the extrusion flow rate. The structure of the obtained resin film and the evaluation results are shown in Tables 3 and 4. In Table 3, conditions not listed in the table were considered common conditions. In the table, "<" indicates less than or equal to.

[0188] [Examples E2 to E4, Comparative Example EC2] A resin film having a three-layer structure was obtained in the same manner as in Example E1 except that the material of the surface layer (first layer) or the material of the back layer (third layer) was changed. The structure and evaluation results of the obtained resin film are shown in Table 3.

[0189] [Comparative Example EC1] Pellets of an acrylic resin composition (AR-1) were charged into the hopper of a single-screw extruder and melt-kneaded. The molten resin composition was extruded using a T-die, pressurized and cooled using a plurality of cooling rolls, and taken up by a pair of take-up rolls. In this way, a resin film having a single-layer structure with a thickness of 150 μm was obtained. The structure and evaluation results of the obtained resin film are shown in Table 3.

[0190]

Table 3

[0191]

Table 4

[0192] [Summary of Results] In Examples E1 to E4, a resin film having a laminated structure having a surface layer made of an acrylic resin composition (AR) containing a methacrylic resin (M), a back layer containing a vinyl alcohol resin (V) (ethylene vinyl alcohol copolymer having an ethylene unit content of 20 to 50 mol%), and an adhesive layer provided between these layers was obtained. All of the obtained resin films had a difference in haze value before and after the weather resistance test of 0 to 30%, an ultraviolet transmittance at a wavelength of 315 nm of the resin film after the weather resistance test of 0 to 5%, and had good weather resistance. All of the obtained resin films had good processability (stretchability) in that the surface layer and the back layer did not break when stretched two-fold in one direction at a temperature of 140°C. In these examples, an evaluation of odor prevention properties was carried out using a recycled PP resin sheet made of a recycled polypropylene-based resin (RePP-1) that has a strong odor by itself. On both sides of the recycled PP resin sheet, a resin film obtained was laminated via an adhesive layer so as to cover the recycled PP resin sheet, and a laminate (assuming a decorated molded body) was obtained. All of the resin films obtained in these examples had high odor prevention properties, and effectively suppressed the release of the strong odor of the recycled polypropylene-based resin (RePP-1) itself to the outside. Typically, for the resin film obtained in Example E1, the evaluation of the adhesive strength to an adherend was carried out by changing the resin to be adhered. The resin film obtained in Example E1 could have good adhesive strength to various resins to be adhered. It was confirmed that the obtained resin film had the adhesive strength required as a decorative film. All of the resin films obtained in Examples E1 to E4 were usable as decorative films with an odor prevention function. In other words, in Examples E1 to E4, decorative films with an odor prevention function could be obtained.

[0193] In Comparative Example EC1, a resin film having a single-layer structure composed only of a surface layer made of an acrylic resin composition (AR) containing a methacrylic resin (M) was obtained. In this comparative example, an evaluation of odor prevention properties was carried out using two types of recycled PP resin sheets having different odor levels (specifically, a recycled PP resin sheet made of a recycled polypropylene-based resin (RePP-1) that has a strong odor by itself, and a recycled PP resin sheet made of a recycled polypropylene-based resin (RePP-2) that has a slight odor by itself). On both sides of the recycled PP resin sheet, a resin film obtained was laminated via an adhesive layer so as to cover the recycled PP resin sheet, and a laminate (assuming a decorated molded body) was obtained. When a recycled PP resin sheet made of a recycled polypropylene-based resin (RePP-2) that has a slight odor by itself was used, the odor from the laminate (assuming a decorated molded body) was weak. However, when using recycled PP resin sheets made from recycled polypropylene resin (RePP-1), which has a strong odor on its own, the odor from the laminate (assuming a decorated molded product) was strong. The resin film obtained in this comparative example had poor odor-resistant properties and was unable to suppress the release of the strong odor of the recycled polypropylene resin (RePP-1) itself to the outside. In this comparative example, it was not possible to obtain a decorative film with odor-resistant properties.

[0194] In Comparative Example EC2, a resin film with a laminated structure was obtained, having a surface layer made of an acrylic resin composition (AR) containing a methacrylic resin (M), a back layer also made of an acrylic resin composition (AR) containing a methacrylic resin (M), and an adhesive layer provided between these layers. In this comparative example, the odor-resistant properties were evaluated using a recycled PP resin sheet made of recycled polypropylene resin (RePP-1), which has a strong odor on its own, as the rework material. A laminate (assuming a decorative molded body) was obtained by laminating the obtained resin film on both sides of the recycled PP resin sheet with an adhesive layer in between, so as to cover the recycled PP resin sheet. The resin film obtained in this comparative example had poor odor-resistant properties and was unable to suppress the release of the strong odor of the recycled polypropylene resin (RePP-1) itself to the outside. In this comparative example, it was not possible to obtain a decorative film with odor-resistant properties.

[0195] 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. [Explanation of symbols]

[0196] 1, 2 Decorative film with odor-resistant function 3, 4 Decorated molded body 11 Surface layer 12 Adhesive layer 13 Underlayer 21 Adherent 22 Adhesive layer

Claims

1. A surface layer made of an acrylic resin composition (AR) containing a methacrylic resin (M), A backing layer containing vinyl alcohol resin (V), It has an adhesive layer provided between the surface layer and the back layer, Black panel temperature 83°C, relative humidity 50%, irradiation energy 100 mW / cm² ２ When a weather resistance test was conducted on a decorative film with deodorizing properties by irradiating it with ultraviolet light from the surface side for 200 hours under the following conditions, The difference in haze values ​​of the odor-resistant decorative film before and after the weather resistance test was 0-30%. A decorative film with odor-resistant properties, exhibiting an ultraviolet transmittance of 0-5% at a wavelength of 315 nm after weather resistance testing.

2. The acrylic resin composition (AR) further comprises one or more ultraviolet absorbers (UVA), wherein the decorative film with deodorizing function is as described in claim 1.

3. The deodorizing decorative film according to claim 1, wherein the acrylic resin composition (AR) contains 1 to 99% by mass of one or more rubber-like elastic materials (R) selected from the group consisting of crosslinked rubber particles (RP) and block copolymers (RB).

4. The deodorizing decorative film according to claim 1, wherein the vinyl alcohol resin (V) comprises an ethylene vinyl alcohol copolymer having an ethylene unit content of 20 to 50 mol%.

5. The deodorizing decorative film according to claim 1, wherein the adhesive layer comprises one or more thermoplastic elastomers (E) selected from the group consisting of a block copolymer comprising a polymer block (a) containing aromatic vinyl compound units and a polymer block (b) containing conjugated diene compound units, and hydrogenated products of the block copolymer.

6. Thermoplastic elastomer (E) One or more second thermoplastic elastomers (EY) selected from the group consisting of a block copolymer having a polymer block (ya) containing styrene units and a polymer block (yb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 molar mass% or more, and hydrogenated versions of the block copolymer, or The deodorizing decorative film according to claim 5, comprising a block copolymer having a polymer block (za) containing α-methylstyrene units and a polymer block (zb) containing conjugated diene compound units in a total amount of 1,2-bonds and 3,4-bonds of 40 molar mass% or more, and one or more third thermoplastic elastomers (EZ) selected from the group consisting of hydrogenated block copolymers.

7. Thermoplastic elastomer (E) One or more first thermoplastic elastomers (EX) selected from the group consisting of a block copolymer having a polymer block (xa) containing styrene units and a polymer block (xb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is less than 40 mol by mass, and hydrogenated products of the block copolymer, One or more second thermoplastic elastomers (EY) selected from the group consisting of a block copolymer having a polymer block (ya) containing styrene units and a polymer block (yb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 molar mass% or more, and hydrogenated products of the block copolymer, A decorative film with deodorizing function according to claim 6, comprising a block copolymer having a polymer block (za) containing α-methylstyrene units and a polymer block (zb) containing conjugated diene compound units in a total amount of 1,2-bonds and 3,4-bonds of 40 mol by mass or more, and one or more third thermoplastic elastomers (EZ) selected from the group consisting of hydrogenated block copolymers.

8. The deodorizing decorative film according to claim 5, wherein the adhesive layer further comprises one or more polypropylene polymers (P).

9. The deodorizing decorative film according to claim 8, wherein the polypropylene polymer (P) comprises one or more first polypropylene polymers (PX) that do not have polar groups and one or more second polypropylene polymers (PY) that have polar groups.

10. The deodor-proof decorative film according to claim 1, wherein the surface layer does not break when the deodor-proof decorative film is stretched twice in one direction at a temperature of 140°C.

11. The deodor-proof decorative film according to claim 1, wherein the backing layer does not break when the deodor-proof decorative film is stretched twice in one direction at a temperature of 140°C.

12. The deodorizing decorative film according to claim 1, wherein the surface layer is a decorative layer containing a coloring agent or a matting agent.

13. Furthermore, the decorative film with deodorizing function according to claim 1, further comprising a decorative layer laminated on the back surface of the back layer.

14. A decorative molded body comprising a deodorizing decorative film according to claim 1 or 12 laminated on at least a portion of the surface of a substrate containing recycled resin via an adhesive layer, A decorative molded body wherein the adhesive strength of the deodorizing decorative film to the adherend is 10 to 100 N / 25 mm.

15. The decorated molded article according to claim 14, wherein the recycled resin comprises one or more thermoplastic resins selected from the group consisting of olefin resins (O), styrene resins (S), polycarbonate resins (PC), and (meth)acrylic resins (A).

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