Elastomer resin composition, laminated film, and molded article

Abstract

The present disclosure provides an elastomer resin composition that is suitable as a pressure-sensitive adhesive layer for a decorative film and can suppress the occurrence of a drawdown phenomenon and a shock line during a decoration process.　An elastomer resin composition disclosed herein comprises a thermoplastic elastomer selected from the group consisting of: a block copolymer having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit; and a hydrogenated product thereof, wherein when the peak temperature of tanδ of the elastomer resin composition is Tge [°C], Tge +50 °C is T1, and Tge+120 °C is T2, and the storage elastic modulus of the elastomer resin composition at T1 and T2 are G'1 [Pa] and G'2 [Pa], respectively, ΔG'2-1 [% / °C] (=[100×{Log(G'2)-Log(G'1)} / (T2-T1)] / Log (G'1)) is -0.18 to 0.00 % / °C.

Description

Elastomer resin composition, laminated film, and molded article

[0001] The present disclosure relates to an elastomer resin composition, a laminated film, and a molded article.

[0002] In applications such as interior and exterior components for automobiles and other vehicles, a decorated molded article may be used in which a decorative film is laminated onto an adherend (also referred to as a decorated member or decorated body) for purposes such as surface protection and decoration. In this specification, the term "decorating process" refers to the process of laminating a decorative film onto an adherend. Patent Documents 1 to 3 disclose elastomer resin compositions containing a thermoplastic elastomer, which is a block copolymer or a hydrogenated product thereof, having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit, and a polypropylene-based polymer (see claim 1 of Patent Document 1, claim 1 of Patent Document 2, and claim 1 of Patent Document 3). A decorative film containing an adhesive layer made of the elastomer resin composition can adhere well to an adherend. In this specification, "adhesive" is a general term for pressure-sensitive adhesive and adhesive.

[0003] International Publication No. WO 2013 / 105392 International Publication No. WO 2016 / 031550 International Publication No. WO 2020 / 179923 JP 2018-196945 A International Publication No. WO 2020 / 256118

[0004] Examples of methods for manufacturing decorative molded bodies include forming a decorative film onto a three-dimensionally formed adherend by a molding method such as vacuum forming, pressure forming, or vacuum pressure forming, according to the surface shape of the adherend. Among these, vacuum pressure forming is preferred, and the TOM (Three Dimension Overlay Method) method is particularly preferred. In this manufacturing method, a flat decorative film is placed above the adherend placed on a stage, and the decorative film, softened by preheating, is then tightly adhered to the adherend according to the surface shape.

[0005] In the above manufacturing method, the decorative film must be horizontal during the preheating stage. However, during the preheating stage, a drawdown phenomenon may occur, in which the decorative film bends downward under its own weight. In this case, the decorative film laminated on the adherend may develop poor appearance, such as wrinkles. Furthermore, in the above manufacturing method, when the decorative film softened by heating adheres to the surface shape of the adherend, the timing of contact with the adherend may vary depending on the location within the surface of the decorative film due to the influence of the three-dimensional shape of the adherend. In this case, uneven elongation may occur in the decorative film at the boundary between the part that is in contact with the adherend (contact part) and the part that is not in contact with the adherend (non-contact part), which may result in a line-shaped appearance defect known as a shock line.

[0006] Patent Document 4 discloses a method for manufacturing a decorative molded article, in which, for the purpose of suppressing the drawdown phenomenon, only the outer periphery of a decorative film is heated to attach it to a base abutted against a substrate, and then the inner periphery of the decorative film is heated and softened to attach it to the surface of the substrate (Claim 1). The decorative film preferably includes a hot-melt adhesive layer containing a thermoplastic resin and a tackifier, and exhibiting adhesive properties when heated to a temperature higher than room temperature (Claim 2, paragraph 0032). However, the technique described in Patent Document 4 requires that the decorative film be heated and softened in two stages, one for the outer periphery and the other for the inner periphery, which increases the number of steps in the decoration process, which is undesirable.

[0007] Patent Document 5 discloses a pressure-sensitive adhesive sheet for vacuum and pressure-sensitive adhesive forming, which aims to suppress the occurrence of shock lines and has a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive composition and a thin film layer thinner than the pressure-sensitive adhesive layer, the thin film layer having a melting point, softening point, or glass transition temperature (Tg) of 70°C or higher (claim 1). The pressure-sensitive adhesive composition is preferably an acrylic pressure-sensitive adhesive composition (claim 2). The thin film layer preferably contains at least one resin selected from the group consisting of polyolefin resins, rosin ester resins, polyester resins, and (meth)acrylic resins (claim 5). The thin film layer may be a surface layer of the pressure-sensitive adhesive layer (claim 1). However, the technology described in Patent Document 5 requires a thin film layer having a melting point, softening point, or glass transition temperature (Tg) of 70°C or higher, either separately from the pressure-sensitive adhesive layer or on the surface layer of the pressure-sensitive adhesive layer.

[0008] Patent Documents 4 and 5 do not relate to elastomer resin compositions, and these patent documents do not describe the dynamic viscoelastic properties of the adhesive layer or how to optimize them.

[0009] The present disclosure has been made in consideration of the above circumstances, and aims to provide an elastomer resin composition that is suitable as an adhesive layer of a decorative film, that can suppress the drawdown phenomenon and the occurrence of shock lines during the decoration process, and that can produce a decorated molded body with good appearance.

[0010] The present disclosure provides an elastomer resin composition, a laminated film, and a molded article according to the following items [1] to

[15] . [1] An elastomer resin composition comprising one or more thermoplastic elastomers (E) selected from the group consisting of block copolymers having a polymer block (a) containing an aromatic vinyl compound unit and a polymer block (b) containing a conjugated diene compound unit, and hydrogenated products of the block copolymers, wherein the peak temperature of the loss tangent (tan δ) of the elastomer resin composition is Tge [°C], and Tge + 50°C is T １ [°C], Tge + 120°C is T ２ [°C], T １ The storage modulus of the elastomer resin composition at [°C] is G' １ [Pa], T ２The storage modulus of the elastomer resin composition at [°C] is G' ２ [Pa], ΔG′ defined by the following formula (1) ２－１ The elastomer resin composition has a ΔG' of -0.18 to 0.00% / °C. ２－１ [% / ℃]=[100×{Log(G' ２ ) -Log(G' １ ) / (T ２ -T １ ) )] / Log(G' １ ) ... (1)

[0011] [2] The elastomer resin composition according to [1], wherein the conjugated diene compound units contained in the polymer block (b) are one or more units selected from the group consisting of isoprene units and butadiene units.

[0012] [3] The elastomer resin composition according to [1] or [2], wherein the thermoplastic elastomer (E) comprises one or more thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing a styrene unit and a polymer block (yb) containing a conjugated diene compound unit in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, and hydrogenated products of the block copolymers.

[0013] [4] The elastomer resin composition of [3], wherein the thermoplastic elastomer (E) comprises: one or more first thermoplastic elastomers (EX) selected from the group consisting of block copolymers having a polymer block (xa) containing a styrene unit and a polymer block (xb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is less than 40 mol%, and hydrogenated products of the block copolymers; and one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing a styrene unit and a polymer block (yb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, and hydrogenated products of the block copolymers.

[0014] [5] The elastomer resin composition according to [4], wherein the content of the first thermoplastic elastomer (EX) is 22 to 78 parts by mass and the content of the second thermoplastic elastomer (EY) is 12 to 77 parts by mass, relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E).

[0015] [6] The thermoplastic elastomer (E) comprises: one or more first thermoplastic elastomers (EX) selected from the group consisting of block copolymers having a polymer block (xa) containing a styrene unit and a polymer block (xb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is less than 40 mol%, and hydrogenated products of the block copolymers; and one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing a styrene unit and a polymer block (yb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, and hydrogenated products of the block copolymers. The elastomer resin composition according to [4], comprising one or more third thermoplastic elastomers (EZ) selected from the group consisting of block copolymers having a polymer block (za) containing an α-methylstyrene unit and a polymer block (zb) containing a conjugated diene compound unit in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, and hydrogenated products of the block copolymers.

[0016] [7] The elastomer resin composition according to [6], wherein the content of the first thermoplastic elastomer (EX) is 22 to 78 parts by mass, the content of the second thermoplastic elastomer (EY) is 12 to 77 parts by mass, and the content of the third thermoplastic elastomer (EZ) is 1 to 60 parts by mass, relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E).

[0017] [8] The elastomer resin composition of any of [1] to [7], further comprising one or more polypropylene-based polymers (P). [9] The elastomer resin composition of [8], wherein the total amount of the polypropylene-based polymers (P) is 1 to 35 parts by mass per 100 parts by mass of the total amount of the thermoplastic elastomers (E).

[10] The elastomer resin composition of [8] or [9], wherein the polypropylene-based polymer (P) comprises one or more first polypropylene-based polymers (PX) having no polar group and one or more second polypropylene-based polymers (PY) having a polar group.

[0018]

[11] A laminated film comprising an elastomer resin composition layer made of the elastomer resin composition according to any one of [1] to

[10] , and a support layer supporting the elastomer resin composition layer.

[12] The peak temperature of the loss tangent (tan δ) of the support layer is defined as Tgs [°C], and Tgs + 25°C is defined as T ３ [℃] 、 T ３ The storage modulus of the elastomer resin composition at [°C] is G' ３ [Pa], ΔG′ defined by the following formula (2) ３－１ The laminated film according to

[11] , wherein ΔG' is -0.18 to 0.00% / °C. ３－１ [% / ℃]=[100×{Log(G' ３ ) -Log(G' １ ) / (T ３ -T １ ) )] / Log(G' １ )...(2)

[13] G' ３ is 1.8 x 10 ５ ~50.0 x 10 ５

[14] The laminate film of any one of

[11] to

[13] , wherein the support layer is a (meth)acrylic resin-containing layer.

[0019]

[15] A molded article having the laminate film according to any one of

[11] to

[14] laminated on at least a part of the surface of an adherend.

[0020] According to the present disclosure, it is possible to provide an elastomer resin composition that is suitable as an adhesive layer of a decorative film, that can suppress the occurrence of drawdown and shock lines during the decoration process, and that can produce a decorated molded body with good appearance.

[0021] 1 is a schematic cross-sectional view showing a film of one embodiment according to the present invention. 2 is a schematic cross-sectional view showing a decorative film of one embodiment according to the present invention. 3 is a schematic cross-sectional view showing a decorated molded body of one embodiment according to the present invention. 4 is a graph showing the measurement results of the dynamic viscoelastic properties of the elastomer resin composition (ER1) obtained in Example E1.

[0022] Generally, the terms "film," "sheet," or "plate" are used for thin film molded bodies depending on their thickness, but there is no clear definition and no clear distinction between them. In this specification, "film" includes "sheet." In this specification, (meth)acrylic is a general term for acrylic and methacrylic, and the same applies to (meth)acrylonitrile, etc.

[0023] Unless otherwise specified, the weight average molecular weight (Mw) of a (meth)acrylic resin is a weight average molecular weight (Mw) calculated as a standard polymethyl methacrylate (PMMA) by gel permeation chromatography (GPC). The same applies to the number average molecular weight (Mn). Unless otherwise specified, the weight average molecular weight (Mw) of a resin other than a (meth)acrylic resin (such as a thermoplastic elastomer (E)) is a weight average molecular weight (Mw) calculated as a standard polystyrene by gel permeation chromatography (GPC). The same applies to the number average molecular weight (Mn).

[0024] [Elastomer Resin Composition] The elastomer resin composition of the present disclosure contains one or more thermoplastic elastomers (E) selected from the group consisting of block copolymers having 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 copolymers. The elastomer resin composition of the present disclosure may further contain one or more polypropylene-based polymers (P). The content of the thermoplastic elastomer (E) in the elastomer resin composition of the present disclosure (the total amount when multiple types are used) is preferably 50 to 100% by mass. The lower limit is more preferably 60% 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.

[0025] The elastomer resin composition of the present disclosure is suitable as a pressure-sensitive adhesive layer for a decorative film. Examples of methods for producing a decorative molded body include forming a decorative film onto a three-dimensionally formed adherend by a molding method such as vacuum forming, pressure forming, or vacuum pressure forming, so as to conform to the surface shape of the adherend. Among these, vacuum pressure forming is preferred, and the TOM (Three Dimension Overlay Method) method is particularly preferred. In this manufacturing method, a flat decorative film is placed above the adherend placed on a stage, and the decorative film, softened by preheating, is then tightly adhered to the adherend's surface shape.

[0026] As explained in the section "Problems to be Solved by the Invention," the above-mentioned manufacturing method requires that the decorative film be horizontal during the preheating stage. However, a drawdown phenomenon, in which the decorative film bends downward under its own weight, can occur during the preheating stage. This can result in wrinkles and other defects in appearance in the decorative film laminated on the substrate. Furthermore, in the above-mentioned manufacturing method, when the decorative film softened by heating adheres to the surface shape of the substrate, the timing of contact with the substrate can vary depending on the location within the surface of the decorative film due to the influence of the three-dimensional shape of the substrate. In this case, uneven elongation can occur in the decorative film at the boundary between the portion in contact with the substrate (contact portion) and the portion not in contact with the substrate (non-contact portion), potentially resulting in line-shaped defects in appearance known as shock lines.

[0027] To solve the above problems, the elastomer resin composition of the present disclosure has specific dynamic viscoelastic properties. The dynamic viscoelastic properties of the elastomer resin composition of the present disclosure can be measured using a rotational rheometer after preparing a 1 mm thick molded sheet made of the elastomer resin composition of the present disclosure. By measuring the dynamic viscoelasticity, temperature dependence data of the loss tangent (tan δ), storage modulus (G'), and loss modulus (G'') of the elastomer resin composition of the present disclosure can be obtained. For specific measurement methods, see the Examples section below.

[0028] The glass transition temperature (Tge) of the elastomer resin composition of the present disclosure is determined by determining the peak temperature of the loss tangent (tan δ) in the temperature dependency data of the loss tangent (tan δ). In the temperature dependency data of the loss tangent (tan δ), a region in which the loss tangent (tan δ) fluctuates between 0 and ±1% in a temperature range of 0°C or higher under measurement conditions in 0.5°C increments, for example, can be identified as the rubbery plateau region of the elastomer resin composition of the present disclosure. Research by the present inventors has revealed that the rubbery plateau region of the elastomer resin composition is generally in the range of Tge + 50°C to Tge + 120°C (see Figure 4). Therefore, in the present disclosure, "Tge + 50°C" is used as the representative temperature on the low-temperature side of the rubbery plateau region, and "Tge + 120°C" is used as the representative temperature on the high-temperature side of the rubbery plateau region. Tge + 50°C is used as T１ [°C], Tge + 120°C is T ２ [℃]. １ The storage modulus of the elastomer resin composition of the present disclosure at [°C] is G' １ [Pa], T ２ The storage modulus of the elastomer resin composition of the present disclosure at [°C] is G' ２ Let it be [Pa].

[0029] The elastomer resin composition of the present disclosure has a ΔG′ defined by the following formula (1): ２－１ is -0.18 to 0.00% / °C. The lower limit is more preferably -0.17% / °C, particularly preferably -0.16% / °C, and most preferably -0.15% / °C. The upper limit is more preferably -0.01% / °C, even more preferably -0.03% / °C, still more preferably -0.05% / °C, particularly preferably -0.08% / °C, and most preferably -0.10% / °C. ΔG' ２－１ [% / ℃]=[100×{Log(G' ２ ) -Log(G' １ ) / (T ２ -T １ ) )] / Log(G' １ ) ... (1)

[0030] ΔG' ２－１ In the temperature dependence data of the storage modulus (G') of the elastomer resin composition of the present disclosure, ΔG' roughly corresponds to the slope of the storage modulus (G') within the rubber-like plateau region. ２－１ means that there is no or almost no slope of the storage modulus (G') in the rubbery plateau region. ２－１ It has been found that the elastomer resin composition of the present disclosure, in which the value of (Zero or close to it) is within the above range, is suitable as an adhesive layer of a decorative film, and by using a decorative film containing this, it is possible to suppress the occurrence of drawdown and shock lines in the decoration process, and to obtain a decorated molded article with a good appearance.

[0031] The mechanism is not entirely clear, but is presumed to be as follows. In methods for forming a decorative molded body using a molding method such as vacuum forming, pressure forming, or vacuum-pressure forming, the decorative film is preheated and then softened by the preheating and adhered to the surface of the adherend. The decorative film is rapidly cooled and solidified upon contact with the adherend, which has a lower temperature than the decorative film, and is no longer stretchable. When the contact state between the decorative film and the adherend is examined microscopically, the decorative film is characterized by the presence of adjacent portions in the vicinity of the boundary between the contact portion with the adherend and the non-contact portion, where the contact portion is in contact with the adherend and has been cooled and solidified, making it unstretchable, and the non-contact portion is stretchable. Generally, it is presumed that this portion, where a significant stretch difference occurs, is prone to uneven elongation and shock lines. It is believed that the smaller the change in storage modulus of the elastomer resin composition contained in the decorative film in the temperature range from the preheating temperature to the cooling temperature, the smaller the stretch difference tends to be. ΔG', which corresponds to the slope of the storage modulus (G') in the rubbery plateau region ２－１ It is presumed that when the difference in elongation is zero or in a range close to zero, the difference in elongation is small, and the occurrence of shock lines can be effectively suppressed.

[0032] ΔG′ of the elastomer resin composition of the present disclosure ２－１ [% / °C] can be adjusted by the type and blending composition of one or more thermoplastic elastomers (E). According to the research of the present inventors, the following has been found: When the one or more thermoplastic elastomers (E) are only the first thermoplastic elastomer (EX) described below, the slope of the storage modulus (G') in the rubber-like plateau region of the elastomer resin composition of the present disclosure becomes large, and ΔG' ２－１ (See Comparative Examples EC1, EC2, and EC5 below.) When the one or more thermoplastic elastomers (E) contain an appropriate amount of the second thermoplastic elastomer (EY) described below, which has a relatively high rigidity, the slope of the storage modulus (G') in the rubber-like plateau region of the elastomer resin composition of the present disclosure can be reduced, and ΔG' ２－１When the one or more thermoplastic elastomers (E) preferably comprise a combination of an appropriate amount of a first thermoplastic elastomer (EX) described below and an appropriate amount of a second thermoplastic elastomer (EY) described below, more preferably a combination of an appropriate amount of a first thermoplastic elastomer (EX) described below, an appropriate amount of a second thermoplastic elastomer (EY) described below and an appropriate amount of a third thermoplastic elastomer (EZ) described below, the slope of the storage modulus (G') within the rubber-like plateau region of the elastomer resin composition of the present disclosure can be made small, and ΔG' ２－１ is easily adjusted within the above range.

[0033] G' １ is not particularly limited, and is preferably 1.8 × 10 ５ ~100.0 x 10 ５ The lower limit is more preferably 2.0 × 10 ５ Pa, particularly preferably 5.0 × 10 ５ Pa, most preferably 8.0 x 10 ５ The upper limit is more preferably 90.0 × 10 ５ Pa, more preferably 80.0 x 10 ５ Pa, more preferably 70.0 x 10 ５ Pa, more preferably 50.0 x 10 ５ Pa, more preferably 40.0 x 10 ５ Pa, most preferably 30.0 x 10 ５ It is Pa.

[0034] G' ２ is not particularly limited, and is preferably 1.8 × 10 ５ ~50.0 x 10 ５ The lower limit is more preferably 2.0 × 10 ５ Pa, particularly preferably 2.5 × 10 ５ Pa, most preferably 3.0 x 10 ５ The upper limit is more preferably 40.0 × 10 ５ Pa, more preferably 30.0 x 10 ５ Pa, more preferably 25.0 x 10 ５ Pa, more preferably 20.0 x 10 ５ Pa, particularly preferably 10.0 x 10 ５Pa, most preferably 5.0 x 10 ５ It is Pa.

[0035] (Thermoplastic Elastomer (E)) The elastomer resin composition of the present disclosure contains one or more thermoplastic elastomers (E) selected from the group consisting of block copolymers having 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 copolymers. The thermoplastic elastomer (E) is a matrix component of the elastomer resin composition and can impart excellent flexibility, impact resistance, etc. to the elastomer resin composition.

[0036] The thermoplastic elastomer (E) contains one or more polymer blocks (a) 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 the aromatic vinyl compound units. Examples of other monomers other than the aromatic vinyl compound include 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether.

[0037] The content of one or more aromatic vinyl compound units in polymer block (a) (total amount when multiple types are present) is not particularly limited and is preferably 80 to 100 mass%. The lower limit is more preferably 90 mass%, and particularly preferably 95 mass%. The content of other monomer units than aromatic vinyl compound units in polymer block (a) (total amount when multiple types are present) is not particularly limited and is 20 to 0 mass%. The upper limit is more preferably 10 mass%, and particularly preferably 5 mass%.

[0038] The thermoplastic elastomer (E) contains one or more polymer blocks (b) containing one or more conjugated diene compound units. Examples of conjugated diene compounds include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. The polymer block (b) preferably contains butadiene units and / or isoprene units as conjugated diene compound units, and is preferably composed of butadiene units and / or isoprene units. The polymer block (b) may contain one or more other monomer units other than the conjugated diene compound units. Examples of other monomers other than the conjugated diene compounds include styrene (St) and 4-methylstyrene.

[0039] The content of conjugated diene compound units in polymer block (b) (total amount when multiple types are present) is not particularly limited and is preferably 80 to 100 mass%. The lower limit is more preferably 90 mass%, and particularly preferably 95 mass%. The content of monomer units other than conjugated diene compound units in polymer block (b) (total amount when multiple types are present) is not particularly limited and is 20 to 0 mass%. The upper limit is more preferably 10 mass%, and particularly preferably 5 mass%.

[0040] The bonding form between the polymer block (a) and the polymer block (b) is not particularly limited, and examples thereof include linear, branched, radial, and combinations thereof, with linear being preferred. Examples of linear bonding forms include diblock copolymers represented by a-b, triblock copolymers represented by a-b-a or b-a-b, tetrablock copolymers represented by a-b-a-b, pentablock copolymers represented by a-b-a-b-a or b-a-b-a-b, and (a-b) ｎ Examples include X-type copolymers (X represents a coupling residue, and n represents an integer of 2 or more), and combinations thereof. Among these, triblock copolymers are preferred, and triblock copolymers represented by a-b-a are more preferred.

[0041] The content of polymer block (a) in 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 thermoplastic elastomer (E). The lower limit is more preferably 10% by mass. The upper limit is more preferably 70% by mass, even more preferably 65% ​​by mass, even more preferably 60% by mass, even more preferably 55% by mass, even more preferably 50% by mass, particularly preferably 45% by mass, and most preferably 40% by mass. The content of polymer block (b) in thermoplastic elastomer (E) is not particularly limited, but is preferably 95 to 25% by mass from the viewpoint of the flexibility and mechanical properties of thermoplastic elastomer (E). The upper limit is more preferably 90% by mass. The lower limit is more preferably 30% by mass, even more preferably 35% by mass, even more preferably 40% by mass, even more preferably 45% by mass, even more preferably 50% by mass, particularly preferably 55% by mass, and most preferably 60% by mass. The total content of the polymer block (a) and the polymer block (b) in the thermoplastic elastomer (E) is not particularly limited, but is preferably 95 to 100% by mass, with the lower limit being more preferably 97% by mass, particularly preferably 98% by mass, and most preferably 99% by mass.

[0042] 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 product thereof. The method for producing the unhydrogenated block copolymer is not particularly limited, and examples thereof include anionic polymerization. Examples include: (i) a method in which an alkyllithium compound is used as an initiator to sequentially polymerize one or more aromatic vinyl compounds, followed by sequentially polymerizing one or more conjugated diene compounds, and, if necessary, further sequentially polymerizing one or more aromatic vinyl compounds; (ii) a method in which an alkyllithium compound is used as an initiator to sequentially polymerize one or more aromatic vinyl compounds, followed by sequentially polymerizing one or more conjugated diene compounds, and then coupling the resulting mixture by adding a coupling agent; and (iii) a method in which a dilithium compound is used as an initiator to sequentially polymerize one or more conjugated diene compounds, followed by sequentially polymerizing one or more aromatic vinyl compounds, and, if necessary, further sequentially polymerizing one or more conjugated diene compounds.

[0043] 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 has been hydrogenated (also referred to as "hydrogenation"). The hydrogenation rate (hydrogenation rate) of the polymer block (b) is not particularly limited and is preferably 80 to 100%. The lower limit is more preferably 85%, and particularly preferably 90%. In this specification, the hydrogenation rate (hydrogenation rate) of the 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 in which an unhydrogenated block copolymer is dissolved in a solvent inert to the hydrogenation reaction and the hydrogenation catalyst, or a reaction liquid containing the unhydrogenated block copolymer obtained after the polymerization reaction, and then reacting the unhydrogenated block copolymer with hydrogen in the presence of a hydrogenation catalyst. Commercially available thermoplastic elastomers (E) may also be used.

[0044] The thermoplastic elastomer (E) may contain one or more functional groups such as a carboxy group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group in the molecular chain and / or at the molecular chain terminal, as necessary.

[0045] The thermoplastic elastomer (E) can include one or more first thermoplastic elastomers (EX) selected from the group consisting of block copolymers having a polymer block (xa) containing styrene (St) units and a polymer block (xb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is less than 40 mol%, and hydrogenated products of the block copolymers.

[0046] The thermoplastic elastomer (E) can comprise, alternatively or in addition to the first thermoplastic elastomer (EX), one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing styrene (St) units and a polymer block (yb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, and hydrogenated products of the block copolymers.

[0047] The thermoplastic elastomer (E) may comprise, alternatively or in addition to the first thermoplastic elastomer (EX) and / or the second thermoplastic elastomer (EY), one or more third thermoplastic elastomers (EZ) selected from the group consisting of block copolymers having a polymer block (za) containing α-methylstyrene (αMSt) units and a polymer block (zb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, and hydrogenated products of the block copolymers.

[0048] The thermoplastic elastomer (E) may comprise one or more of the thermoplastic elastomers (EX) to (EZ). The thermoplastic elastomer (E) preferably comprises one or more second thermoplastic elastomers (EY). The thermoplastic elastomer (E) more preferably comprises one or more first thermoplastic elastomers (EX) and one or more second thermoplastic elastomers (EY). The thermoplastic elastomer (E) particularly preferably comprises one or more first thermoplastic elastomers (EX), one or more second thermoplastic elastomers (EY), and one or more third thermoplastic elastomers (EZ).

[0049] The content of the first thermoplastic elastomer (EX) (total amount when multiple types are used) is preferably 22 to 78 parts by mass relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E). The lower limit is more preferably 25 parts by mass, particularly preferably 28 parts by mass, and most preferably 30 parts by mass. The upper limit is more preferably 75 parts by mass, even more preferably 70 parts by mass, even more preferably 60 parts by mass, particularly preferably 50 parts by mass, and most preferably 40 parts by mass.

[0050] The content of the second thermoplastic elastomer (EY) (total amount when multiple types are used) is preferably 12 to 77 parts by mass relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E). The lower limit is more preferably 15 parts by mass, 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.

[0051] The content of the third thermoplastic elastomer (EZ) (total amount when multiple types are used) is preferably 0 to 60 parts by mass relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E). The lower limit is more preferably 1 part by mass, even more preferably 3 parts by mass, even more preferably 5 parts by mass, even more preferably 10 parts by mass, particularly preferably 15 parts by mass, and most preferably 20 parts by mass. The upper limit is more preferably 55 parts by mass, particularly preferably 50 parts by mass.

[0052] <First Thermoplastic Elastomer (EX)> The elastomer resin composition of the present disclosure may contain one or more first thermoplastic elastomers (EX) selected from the group consisting of block copolymers having a polymer block (xa) containing styrene (St) units and a polymer block (xb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is less than 40 mol%, and hydrogenated products of such block copolymers. The first thermoplastic elastomer (EX) is one of the matrix components of the elastomer resin composition and can impart excellent flexibility and impact resistance to the elastomer resin composition. The first thermoplastic elastomer (EX) contains the polymer block (xb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is less than 40 mol%, thereby imparting excellent chipping resistance to the elastomer resin composition. In this specification, "chipping resistance" refers to resistance to damage and / or chipping caused by the impact of small particles such as pebbles and snow-melting salts.

[0053] <Polymer Block (xa)> The first thermoplastic elastomer (EX) contains one or more polymer blocks (xa) containing styrene (St) units. The polymer block (xa) may contain one or more aromatic vinyl compound units other than styrene (St) units. Examples of aromatic vinyl compounds other than styrene (St) include α-methylstyrene (αMSt), 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, and 2-vinylnaphthalene. The polymer block (xa) may contain one or more other monomer units other than aromatic vinyl compound units. Examples of other monomers other than aromatic vinyl compounds include 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether.

[0054] The content of styrene (St) units in the polymer block (xa) 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 one or more aromatic vinyl compound units containing styrene (St) units in the polymer block (xa) (the total amount if multiple types are present) is not particularly limited, but is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content of other monomer units than aromatic vinyl compound units in the polymer block (xa) (the total amount if multiple types are present) is not particularly limited, but is 20 to 0% by mass. The upper limit is more preferably 10% by mass, and particularly preferably 5% by mass.

[0055] <Polymer Block (xb)> The first thermoplastic elastomer (EX) contains one or more polymer blocks (xb) containing one or more types of conjugated diene compound units. The one or more types of conjugated diene compound units contained in the first thermoplastic elastomer (EX) have a total amount of 1,2-bonds and 3,4-bonds of less than 40 mol%. When the first thermoplastic elastomer (EX) contains multiple polymer blocks (xb), the total amount of 1,2-bonds and 3,4-bonds of the one or more types of conjugated diene compound units contained in all of the polymer blocks (xb) is less than 40 mol%.

[0056] Examples of the conjugated diene compound include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene. The polymer block (xb) preferably contains butadiene units and / or isoprene units as conjugated diene compound units, and is preferably composed of butadiene units and / or isoprene units. The polymer block (xb) may contain one or more other monomer units other than the conjugated diene compound units. Examples of the other monomers other than the conjugated diene compound include styrene (St) and 4-methylstyrene.

[0057] The content of conjugated diene compound units in polymer block (xb) (total amount when multiple types are present) is not particularly limited and is preferably 80 to 100 mass%. The lower limit is more preferably 90 mass%, and particularly preferably 95 mass%. The content of monomer units other than conjugated diene compound units in polymer block (xb) (total amount when multiple types are present) is not particularly limited and is 20 to 0 mass%. The upper limit is more preferably 10 mass%, and particularly preferably 5 mass%.

[0058] With regard to the bonding form of the conjugated diene compound units in the polymer block (xb), the butadiene units can have 1,2-bonds or 1,4-bonds, and the isoprene units can have 1,2-bonds, 3,4-bonds, or 1,4-bonds. The same applies to the polymer blocks (yb) and (zb). From the viewpoint of chipping resistance, the total amount of 1,2-bonds and 3,4-bonds in the polymer block (xb) is less than 40 mol%, preferably 39 mol% or less. The upper limit is more preferably 35 mol%, even more preferably 30 mol%, even more preferably 25 mol%, even more preferably 20 mol%, particularly preferably 15 mol%, and most preferably 10 mol%. The lower limit is 0 mol%.

[0059] The total amount of 1,2-bonds and 3,4-bonds in the conjugated diene compound units in the polymer block containing the conjugated diene compound units is １ Specifically, it can be calculated from the ratio of the integral value of the first peak at 4.2 to 5.0 ppm, which is derived from 1,2-bonded and 3,4-bonded conjugated diene compound units, to the integral value of the second peak at 5.0 to 5.45 ppm, which is derived from 1,4-bonded conjugated diene compound units.

[0060] The bonding form between the polymer block (xa) and the polymer block (xb) is not particularly limited, and examples thereof include linear, branched, radial, and combinations thereof, with linear being preferred. Examples of linear bonding forms include diblock copolymers represented by xa-xb, triblock copolymers represented by xa-xb-xa or xb-xa-xb, tetrablock copolymers represented by xa-xb-xa-xb, pentablock copolymers represented by xa-xb-xa-xb-xa or xb-xa-xb-xa-xb, and (xa-xb) ｎ Examples include X-type copolymers (X represents a coupling residue, and n represents an integer of 2 or more), and combinations thereof. Among these, triblock copolymers are preferred, and triblock copolymers represented by xa-xb-xa are more preferred.

[0061] The content of the polymer block (xa) in the first thermoplastic elastomer (EX) is not particularly limited, and from the viewpoint of the flexibility and mechanical properties of the first thermoplastic elastomer (EX), it is preferably 5 to 75 mass%. The lower limit is more preferably 10 mass%. The upper limit is more preferably 70 mass%, even more preferably 65 mass%, even more preferably 60 mass%, even more preferably 55 mass%, even more preferably 50 mass%, particularly preferably 45 mass%, and most preferably 40 mass%. The content of the polymer block (xb) in the first thermoplastic elastomer (EX) is not particularly limited, and from the viewpoint of the flexibility and mechanical properties of the first thermoplastic elastomer (EX), it is preferably 95 to 25 mass%. The upper limit is more preferably 90 mass%. The lower limit is more preferably 30 mass%, even more preferably 35 mass%, even more preferably 40 mass%, even more preferably 45 mass%, even more preferably 50 mass%, particularly preferably 55 mass%, and most preferably 60 mass%. The total content of the polymer block (xa) and the polymer block (xb) in the first thermoplastic elastomer (EX) 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.

[0062] The first thermoplastic elastomer (EX) may be an unhydrogenated block copolymer having one or more polymer blocks (xa) and one or more polymer blocks (xb), or a hydrogenated product thereof. The method for producing the unhydrogenated block copolymer is not particularly limited, and examples thereof include an anionic polymerization method. Examples of the method include: (i) a method in which an alkyllithium compound is used as an initiator to sequentially polymerize one or more aromatic vinyl compounds containing styrene (St), followed by sequential polymerization of one or more conjugated diene compounds, and, if necessary, further sequential polymerization of one or more aromatic vinyl compounds containing styrene (St); (ii) a method in which an alkyllithium compound is used as an initiator to sequentially polymerize one or more aromatic vinyl compounds containing styrene (St), followed by sequential polymerization of one or more conjugated diene compounds, and then coupling by adding a coupling agent; and (iii) a method in which a dilithium compound is used as an initiator to sequentially polymerize one or more conjugated diene compounds, followed by sequential polymerization of one or more aromatic vinyl compounds containing styrene (St), and, if necessary, further sequential polymerization of one or more conjugated diene compounds.

[0063] From the viewpoint of improving heat resistance and weather resistance, the first thermoplastic elastomer (EX) is preferably a hydrogenated product of a block copolymer in which at least a portion of the polymer block (xb) containing a conjugated diene compound unit is hydrogenated (also referred to as hydrogenation). The hydrogenation rate (hydrogenation rate) of the polymer block (xb) is not particularly limited and is preferably 80 to 100%. The lower limit is more preferably 85%, particularly preferably 90%. A commercially available product may be used as the first thermoplastic elastomer (EX).

[0064] The first thermoplastic elastomer (EX) may contain one or more functional groups such as a carboxy group, a hydroxyl group, an acid anhydride group, an amino group, and an epoxy group in the molecular chain and / or at the molecular chain terminal, as necessary.

[0065] The weight average molecular weight (Mw) (standard polystyrene equivalent) of the first thermoplastic elastomer (EX) is not particularly limited, and from the viewpoint of the mechanical properties and moldability of the first thermoplastic elastomer (EX), it is preferably 30,000 to 500,000. The lower limit is more preferably 50,000, even more preferably 60,000, particularly preferably 70,000, and most preferably 80,000. The upper limit is more preferably 400,000, even more preferably 300,000, even more preferably 200,000, particularly preferably 190,000, and most preferably 180,000.

[0066] <Second Thermoplastic Elastomer (EY)> The elastomer resin composition of the present disclosure may contain one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing styrene (St) units and a polymer block (yb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, and hydrogenated products of such block copolymers. The second thermoplastic elastomer (EY) is one of the matrix components of the elastomer resin composition. By including the 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, the second thermoplastic elastomer (EY) can impart excellent adhesion to non-polar resins to the elastomer resin composition.

[0067] <Polymer block (ya)> The second thermoplastic elastomer (EY) contains one or more polymer blocks (ya) containing styrene (St) units. The polymer block (ya) may contain one or more aromatic vinyl compound units other than styrene (St) units. The polymer block (ya) may contain one or more other monomer units other than aromatic vinyl compound units. Examples of aromatic vinyl compounds other than styrene (St) and other monomers other than aromatic vinyl compounds are the same as those for the polymer block (xa).

[0068] The content of styrene (St) units in the polymer block (ya) 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 one or more aromatic vinyl compound units containing styrene (St) units in the polymer block (ya) (the total amount if multiple types are present) is not particularly limited, but is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content of other monomer units than aromatic vinyl compound units in the polymer block (ya) (the total amount if multiple types are present) is not particularly limited, but is 20 to 0% by mass. The upper limit is more preferably 10% by mass, and particularly preferably 5% by mass.

[0069] <Polymer Block (yb)> The second thermoplastic elastomer (EY) contains one or more polymer blocks (yb) containing one or more types of conjugated diene compound units. The one or more types of conjugated diene compound units contained in the second thermoplastic elastomer (EY) have a total content of 1,2-bonds and 3,4-bonds of 40 mol% or more. When the second thermoplastic elastomer (EY) contains multiple polymer blocks (yb), the total content of 1,2-bonds and 3,4-bonds of the one or more types of conjugated diene compound units contained in all of the polymer blocks (yb) is 40 mol% or more. The polymer block (yb) may contain one or more types of other monomer units other than the conjugated diene compound units. Examples of conjugated diene compound units, preferred embodiments, and examples of other monomers are the same as those for the polymer block (xb). The content of the conjugated diene compound units in the polymer block (yb) (the total amount when multiple types are contained) is not particularly limited, and is preferably 80 to 100 mass%. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content (total amount when multiple types of monomer units are present) of other monomer units than the conjugated diene compound units in the polymer block (yb) is not particularly limited and is 20 to 0% by mass. The upper limit is more preferably 10% by mass, and particularly preferably 5% by mass.

[0070] The total amount of 1,2-bonds and 3,4-bonds in the polymer block (xb) is 40 mol% or more from the viewpoint of excellent adhesion to non-polar resins. The lower limit is more preferably 45 mol%, particularly preferably 50 mol%, and most preferably 55 mol%. The upper limit is preferably 90 mol%, more preferably 85 mol%, and particularly preferably 80 mol%.

[0071] The 1,2-bonds and 3,4-bonds of the conjugated diene compound units can be increased by adding one or more organic Lewis bases to the reaction solution during anionic polymerization. Furthermore, the total amount of 1,2-bonds and 3,4-bonds can be easily controlled by adjusting the amount of organic Lewis base added. Examples of organic Lewis bases include esters such as ethyl acetate; amines such as triethylamine, N,N,N',N'-tetramethylethylenediamine (TMEDA), and N-methylmorpholine; nitrogen-containing heterocyclic aromatic compounds such as pyridine; amides such as dimethylacetamide; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran (THF), and dioxane; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; sulfoxides such as dimethyl sulfoxide; and ketones such as acetone and methyl ethyl ketone.

[0072] The bonding form between the polymer block (ya) and the polymer block (yb) is not particularly limited, and examples thereof include linear, branched, radial, and combinations thereof, with linear being preferred. Examples of linear bonding forms include diblock copolymers represented by ya-yb, triblock copolymers represented by ya-yb-ya or yb-ya-yb, tetrablock copolymers represented by ya-yb-ya-yb, pentablock copolymers represented by ya-yb-ya-yb-ya or yb-ya-yb-ya-yb, and (ya-yb) ｎ Examples include X-type copolymers (X represents a coupling residue, and n represents an integer of 2 or more), and combinations thereof. Among these, triblock copolymers are preferred, and triblock copolymers represented by ya-yb-ya are more preferred.

[0073] The content of the polymer block (ya) in the second thermoplastic elastomer (EY) is not particularly limited, and from the viewpoint of the flexibility and mechanical properties of the second thermoplastic elastomer (EY), it is preferably 5 to 75 mass%. The lower limit is more preferably 10 mass%. The upper limit is more preferably 70 mass%, even more preferably 65 mass%, even more preferably 60 mass%, even more preferably 55 mass%, even more preferably 50 mass%, particularly preferably 45 mass%, and most preferably 40 mass%. The content of the polymer block (yb) in the second thermoplastic elastomer (EY) is not particularly limited, and from the viewpoint of the flexibility and mechanical properties of the second thermoplastic elastomer (EY), it is preferably 95 to 25 mass%. The upper limit is more preferably 90 mass%. The lower limit is more preferably 30 mass%, even more preferably 35 mass%, even more preferably 40 mass%, even more preferably 45 mass%, even more preferably 50 mass%, particularly preferably 55 mass%, and most preferably 60 mass%. The total content of the polymer block (ya) and the polymer block (yb) in the second thermoplastic elastomer (EY) is not particularly limited, but is preferably 95 to 100% by mass, with the lower limit being more preferably 97% by mass, particularly preferably 98% by mass, and most preferably 99% by mass.

[0074] The second thermoplastic elastomer (EY) may be an unhydrogenated block copolymer having one or more polymer blocks (ya) and one or more polymer blocks (yb), or a hydrogenated product thereof. From the viewpoint of improving heat resistance and weather resistance, the second thermoplastic elastomer (EY) is preferably a hydrogenated product of a block copolymer in which at least a portion of the polymer block (yb) containing a conjugated diene compound unit is hydrogenated. The hydrogenation rate (hydrogenation rate) of the polymer block (yb) is not particularly limited, but is preferably 80 to 100%. The lower limit is more preferably 85%, particularly preferably 90%.

[0075] The method for producing the second thermoplastic elastomer (EY) is the same as the method for producing the first thermoplastic elastomer (EX). A commercially available product may be used as the second thermoplastic elastomer (EY). The second thermoplastic elastomer (EY) may contain one or more functional groups, such as a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, or an epoxy group, in the molecular chain and / or at the molecular chain terminal, as necessary. The weight-average molecular weight (Mw) (standard polystyrene equivalent) of the second thermoplastic elastomer (EY) is not particularly limited, and from the viewpoints of the mechanical properties and moldability of the second thermoplastic elastomer (EY), the preferred range is the same as that of the first thermoplastic elastomer (EX).

[0076] <Third Thermoplastic Elastomer (EZ)> The elastomer resin composition of the present disclosure may contain one or more third thermoplastic elastomers (EZ) selected from the group consisting of block copolymers having a polymer block (za) containing α-methylstyrene (αMSt) units and a polymer block (zb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol % or more, and hydrogenated products of such block copolymers. The third thermoplastic elastomer (EZ) is one of the matrix components of the elastomer resin composition. By including the polymer block (za) containing α-methylstyrene (αMSt) units, the third thermoplastic elastomer (EZ) can impart rigidity and excellent adhesion to polar resins to the elastomer resin composition. The third thermoplastic elastomer (EZ) contains a polymer block (zb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, and thus can impart excellent adhesion to non-polar resins to the elastomer resin composition.

[0077] <Polymer Block (za)> The third thermoplastic elastomer (EZ) contains one or more polymer blocks (za) containing α-methylstyrene (αMSt) units. The polymer block (za) may contain one or more aromatic vinyl compound units other than α-methylstyrene (αMSt) units. Examples of aromatic vinyl compounds other than α-methylstyrene (αMSt) include styrene (St), 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, and 2-vinylnaphthalene. The polymer block (za) may contain one or more other monomer units other than aromatic vinyl compound units. Examples of other monomers other than aromatic vinyl compounds are the same as those for the polymer block (xa).

[0078] The content of α-methylstyrene (αMSt) units in the polymer block (za) is not particularly limited, but is preferably 80 to 100% by mass from the viewpoints of the rigidity of the elastomer resin composition and excellent adhesion to polar resins. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content of one or more aromatic vinyl compound units containing α-methylstyrene (αMSt) units in the polymer block (za) (the total amount if multiple types are present) is not particularly limited, but is preferably 80 to 100% by mass. The lower limit is more preferably 90% by mass, and particularly preferably 95% by mass. The content of other monomer units than aromatic vinyl compound units in the polymer block (za) (the total amount if multiple types are present) is not particularly limited, but is 20 to 0% by mass. The upper limit is more preferably 10% by mass, and particularly preferably 5% by mass.

[0079] <Polymer Block (zb)> The third thermoplastic elastomer (EZ) contains one or more polymer blocks (zb) containing one or more types of conjugated diene compound units. The one or more types of conjugated diene compound units contained in the third thermoplastic elastomer (EZ) have a total amount of 1,2-bonds and 3,4-bonds of 40 mol% or more. When the third thermoplastic elastomer (EZ) contains multiple polymer blocks (zb), the total amount of 1,2-bonds and 3,4-bonds of the one or more types of conjugated diene compound units contained in all of the polymer blocks (zb) is 40 mol% or more. The polymer block (zb) may contain one or more types of other monomer units other than the conjugated diene compound units. Examples of conjugated diene compounds, preferred embodiments, and examples of other monomers are the same as those for the polymer block (xb).

[0080] The content of conjugated diene compound units in polymer block (zb) (total amount when multiple types are present) is not particularly limited and is preferably 80 to 100 mass%. The lower limit is more preferably 90 mass%, and particularly preferably 95 mass%. The content of other monomer units than conjugated diene compound units in polymer block (zb) (total amount when multiple types are present) is not particularly limited and is 20 to 0 mass%. The upper limit is more preferably 10 mass%, and particularly preferably 5 mass%.

[0081] The total amount of 1,2-bonds and 3,4-bonds in the polymer block (zb) is 40 mol% or more from the viewpoint of excellent adhesion to non-polar resins. The lower limit is more preferably 45 mol%, particularly preferably 50 mol%, and most preferably 55 mol%. The upper limit is preferably 90 mol%, more preferably 85 mol%, and particularly preferably 80 mol%.

[0082] The bonding form between the polymer block (za) and the polymer block (zb) is not particularly limited, and examples thereof include linear, branched, radial, and combinations thereof, with linear being preferred. Examples of linear bonding forms include diblock copolymers represented by za-zb, triblock copolymers represented by za-zb-za or zb-za-zb, tetrablock copolymers represented by za-zb-za-zb, pentablock copolymers represented by za-zb-za-zb-za or zb-za-zb-za-zb, and (za-zb) ｎ Examples include X-type copolymers (X represents a coupling residue, and n represents an integer of 2 or more), and combinations thereof. Among these, triblock copolymers are preferred, and triblock copolymers represented by za-zb-za are more preferred.

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

[0084] The third thermoplastic elastomer (EZ) may be an unhydrogenated block copolymer having one or more polymer blocks (za) and one or more polymer blocks (zb), or a hydrogenated product thereof. From the viewpoint of improving heat resistance and weather resistance, the third thermoplastic elastomer (EZ) is preferably a hydrogenated product of a block copolymer in which at least a portion of the polymer block (zb) containing a conjugated diene compound unit is hydrogenated. The hydrogenation rate (hydrogenation rate) of the polymer block (zb) is not particularly limited, but is preferably 80 to 100%. The lower limit is more preferably 85%, particularly preferably 90%.

[0085] The method for producing the third thermoplastic elastomer (EZ) is the same as the method for producing the second thermoplastic elastomer (EY). A commercially available product may be used as the third thermoplastic elastomer (EZ). The third thermoplastic elastomer (EZ) may contain one or more functional groups, such as a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, or an epoxy group, in the molecular chain and / or at the molecular chain terminal, as necessary. The weight-average molecular weight (Mw) (standard polystyrene equivalent) of the third thermoplastic elastomer (EZ) is not particularly limited, and from the viewpoint of the mechanical properties and moldability of the third thermoplastic elastomer (EZ), the preferred range is the same as that of the first thermoplastic elastomer (EX).

[0086] (Polypropylene-Based Polymer (P)) The elastomer resin composition of the present disclosure can contain one or more polypropylene-based polymers (P). The propylene-based polymer (P) is a homopolymer or copolymer containing propylene units and, as necessary, one or more other monomer units. The content of the polypropylene-based polymer (P) (total amount in the case of multiple types) is preferably 1 to 35 parts by mass per 100 parts by mass of the total amount of the thermoplastic elastomer (E). From the viewpoint of adhesion to various materials (polar resins, non-polar resins, or metals), the polypropylene-based polymer (P) preferably contains a combination of one or more first polypropylene-based polymers (PX) that do not have a polar group (also referred to as polar-group-free polypropylene-based polymers) and one or more second polypropylene-based polymers (PY) that have a polar group (also referred to as polar-group-containing polypropylene-based polymers).

[0087] <First Polypropylene Polymer (PX) (Polar Group-Free Polypropylene Polymer)> The first polypropylene polymer (PX) is a homopolymer or copolymer containing propylene units and, as necessary, one or more other monomer units not containing a polar group. Examples of the other monomers include α-olefins other than propylene, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and cyclohexene.

[0088] The ratio of propylene units to all structural units of the first polypropylene polymer (PX) is not particularly limited, but is preferably 55 to 100 mol%. The lower limit is more preferably 65 mol%, even more preferably 75 mol%, particularly preferably 85 mol%, and most preferably 95 mol%. The ratio of monomer units other than propylene units to all structural units of the first polypropylene polymer (PX) is not particularly limited, 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%.

[0089] The first polypropylene polymer (PX) tends to have a higher melt tension as the melt flow rate (MFR) decreases. The first polypropylene polymer (PX) preferably has a melt tension of 2.5×10 or less as measured at 230° C. and a take-up speed of 4.0 m / min. －２ The lower limit is more preferably 3.0 × 10 －２ N, more preferably 3.5 × 10 －２ N, particularly preferably 4.0 × 10 －２ N, most preferably 4.5 x 10 －２ N. The upper limit is not particularly limited, and is, for example, 50×10 －２ N, 40 x 10 －２ N, or 30 x 10 －２ It's N.

[0090] The elastomer resin composition of the present disclosure, which contains a first polypropylene-based polymer (PX) having a melt tension equal to or greater than the above lower limit, has good film-formability in extrusion molding, etc., and can provide good properties such as film thickness stability of the film obtained by extrusion molding, etc. The elastomer resin composition of the present disclosure, which contains a first polypropylene-based polymer (PX) having a melt tension equal to or greater than the above lower limit, has good tackiness, good slip properties on metal, and can be smoothly separated from a cooling roll and a transport roll in a film-forming process, thereby providing good processability.

[0091] The MFR of the first polypropylene polymer (PX) is not particularly limited, and is preferably 0.1 to 20 g / 10 min. The lower limit is preferably 0.5 g / 10 min, more preferably 1.0 g / 10 min. The upper limit is preferably 15 g / 10 min, more preferably 10 g / 10 min. Unless otherwise specified, the MFR of the polypropylene polymer in this specification is a value measured in accordance with JIS K7210 using a melt indexer at a temperature of 230°C and a load of 21.18 N.

[0092] Examples of polypropylene-based polymers (PX) having the above-specified melt tension include polypropylene-based polymers having a crosslinked structure, a long-chain branched structure, a high-molecular-weight component, or a combination thereof. Among these, polypropylene-based polymers having a long-chain branched structure are preferred from the viewpoint of maintaining the flexibility of the film. Examples of methods for producing polypropylene-based polymers having a long-chain branched structure include a method of graft copolymerizing a radically polymerizable monomer onto polypropylene (Macromolecules 26 (1993) 3467), a method of copolymerizing propylene and a polyene (JP-A-5-194778), a macromer copolymerization method using a metallocene catalyst (JP-A-2009-057542), and a method of melt-mixing polypropylene, a conjugated diene compound, and a radical polymerization initiator (JP-A-2015-098542). Among these, a macromer copolymerization method using a metallocene catalyst is preferred from the viewpoint of suppressing gel formation.

[0093] The melting point (Tm) of the first polypropylene polymer (PX) is not particularly limited, and is preferably 100°C or higher from the viewpoint of the heat resistance of the elastomer resin composition. The lower limit is more preferably 110°C. The upper limit is preferably 170°C, more preferably 160°C, and most preferably 150°C.

[0094] From the viewpoint of achieving both excellent processability and film-formability (such as film thickness stability) of the elastomer resin composition and adhesiveness to various materials, the content of the first polypropylene-based polymer (PX) is preferably 3 to 15 parts by mass per 100 parts by mass of the total amount of the thermoplastic elastomer (E). The lower limit is more preferably 5 parts by mass, particularly preferably 6 parts by mass, and most preferably 7 parts by mass. The upper limit is more preferably 12 parts by mass, particularly preferably 10 parts by mass, and most preferably 8 parts by mass. If the content of the first polypropylene-based polymer (PX) is less than the above-mentioned lower limit, the processability and film-formability (such as film thickness stability) of the elastomer resin composition may be reduced, whereas if the content exceeds the above-mentioned upper limit, the adhesiveness of the elastomer resin composition to polar resins, non-polar resins, or metals may be reduced.

[0095] <Second Polypropylene Polymer (PY) (Polar Group-Containing Polypropylene Polymer)> The second polypropylene polymer (PY) can impart excellent adhesion to metals to the elastomer resin composition. Examples of polar groups include polar atoms such as oxygen atoms, nitrogen atoms, 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 includes 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 examples include random copolymerization and block copolymerization. A second method for producing a polar group-containing polypropylene polymer includes graft copolymerizing a polar group-containing monomer onto a polypropylene polymer containing propylene units and, if necessary, one or more other monomer units, but not having polar groups (polar group-free polypropylene polymer). Among these methods, graft copolymerization is preferred. The polar group-containing polypropylene polymer produced by the first or second production method contains propylene units and polar group-containing monomer units, and can further contain one or more other monomer units as required.

[0096] 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, maleic acid (anhydride), fumaric acid (anhydride), itaconic acid (anhydride), and himic acid (anhydride). Among these, carboxylic acid (anhydrides) such as maleic acid (anhydride) are more preferred. In this specification, carboxylic acid (anhydride) is a general term for carboxylic acids and carboxylic acid anhydrides.

[0097] Examples of other monomers include α-olefins other than propylene, and specific examples thereof include ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, and cyclohexene. The total proportion of propylene units and polar group-containing monomer units relative to all structural units of the polar group-containing polypropylene-based 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 relative to all structural units of the polar group-containing polypropylene-based 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%.

[0098] As the polar group-containing polypropylene polymer, polypropylene having a carboxy group or a carboxylic acid anhydride group as the polar group is preferred from the viewpoint of adhesiveness to various materials. Among them, a polypropylene polymer (also called a (carboxylic acid anhydride)-modified polypropylene polymer) obtained by graft copolymerizing a polypropylene polymer having no polar group (polar group-free polypropylene polymer) with a carboxylic acid (anhydride) is preferred. Among them, a maleic acid (anhydride)-modified polypropylene polymer is more preferred.

[0099] The polar groups contained in the polar-group-containing polypropylene polymer produced by the first or second production method may be post-treated after the polymerization reaction. Polar groups such as (meth)acrylic acid groups and carboxyl groups may be neutralized with metal ions to form ionomers, or may be esterified with alcohols such as methanol and ethanol. Polar groups such as vinyl acetate groups may also be hydrolyzed.

[0100] A third method for producing a polar group-containing polypropylene-based polymer includes a method in which a polypropylene-based polymer containing propylene units and, if necessary, one or more other monomer units but not having a polar group (polar group-free polypropylene-based polymer) is oxidized or halogenated (e.g., chlorinated) by a known method.

[0101] The melting point (Tm) of the second polypropylene polymer (PY) is 130°C or lower from the viewpoint of excellent adhesion to metal of the elastomer resin composition. The lower limit is not particularly limited, and from the viewpoint of heat resistance of the elastomer resin composition, it is preferably 100°C, more preferably 105°C, and particularly preferably 110°C. The upper limit is more preferably 125°C.

[0102] From the viewpoint of achieving both excellent adhesion to metals 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 the thermoplastic elastomer (E). The lower limit is more preferably 8 parts by mass, particularly preferably 9 parts by mass, and most preferably 10 parts by mass. The upper limit is more preferably 17.5 parts by mass, particularly preferably 15 parts by mass. When the content of the second polypropylene polymer (PY) is equal to or greater than the lower limit, the elastomer resin composition has good adhesion to metals, and when the content is equal to or less than the upper limit, the elastomer resin composition has good heat resistance.

[0103] (Optional Components) The elastomer resin composition of the present disclosure may contain one or more other polymers other than those described above. Other polymers include polyolefin resins other than polypropylene polymers (P), such as polyethylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; (meth)acrylic resins; styrene resins such as polystyrene, high impact polystyrene, methyl methacrylate-styrene copolymer (MS resin), styrene-maleic anhydride copolymer (SMA resin), styrene-maleic anhydride-methyl methacrylate copolymer (SMM resin), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-ethylene-propylene-diene-styrene (AES) resin, acrylic-acrylonitrile-styrene (AAS) resin, acrylonitrile-chlorinated ethylene-styrene (ACS) resin, and methacrylic butadiene styrene (MBS) resin; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 66, and polyamide. polyamide-based resins such as olefin elastomers; polycarbonate-based resins; other thermoplastic resins such as polyphenylene sulfide, polyether ether ketone, polysulfone, polyphenylene oxide, polyimide, polyetherimide, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, ethylene-vinyl acetate copolymer, phenoxy resin, and ethylene-based ionomer; thermosetting resins such as epoxy-based resin, phenol-based resin, melamine-based resin, and silicone-based resin; polyurethane and chlorinated polyurethane resin; modified polyphenylene ether; silicone-modified resin; acrylic rubber, silicone rubber; acrylic thermoplastic elastomers such as diblock copolymers and triblock copolymers of methyl methacrylate polymer block-n-butyl acrylate polymer block; and olefin-based rubbers such as IR, EPR, and EPDM.

[0104] The elastomer resin composition of the present disclosure may contain one or more additives as needed, such as tackifier resins, softeners, antioxidants, lubricants, heat stabilizers, heat degradation inhibitors, light stabilizers, polymer processing aids, colorants such as pigments and dyes, flame retardants, antistatic agents, matting agents, silicone oils, antiblocking agents, UV absorbers, release agents, foaming agents, antifoaming agents, antibacterial agents, antifungal agents, and fragrances.

[0105] 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.

[0106] As the softener, a general softener 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; ethylene and α-olefin oligomers; paraffin wax; liquid paraffin; polybutene; low-molecular-weight polybutadiene; and low-molecular-weight polyisoprene. Examples of antioxidants include hindered phenol, phosphorus, lactone, and hydroxyl antioxidants. Among these, a combination of a hindered phenol antioxidant and a phosphorus-based antioxidant is preferred. The timing of addition of other polymers and additives that may be contained in the elastomer resin composition of the present disclosure is optional, such as during or after the production of the thermoplastic elastomer (E), during or after the production of the polypropylene polymer (P), or during the production of the elastomer resin composition.

[0107] As described above, according to the present disclosure, it is possible to provide an elastomer resin composition that is suitable as an adhesive layer of a decorative film, that can suppress the occurrence of drawdown and shock lines during the decoration process, and that can produce a decorated molded body with good appearance.

[0108] [Method of Manufacturing Elastomer Resin Composition] The method of manufacturing the elastomer resin composition of the present disclosure is not particularly limited, and a method of melt-kneading one or more thermoplastic elastomers (E), optionally one or more polypropylene-based polymers (P), and optionally one or more optional components is preferred. Melt-kneading can be performed using known mixing or kneading devices such as an extruder, kneader-ruder, mixing roll, or Banbury mixer. From the viewpoints of kneadability and compatibility, extruders such as single-screw extruders, twin-screw extruders, and multi-screw extruders are preferred. The melt-kneading temperature should be equal to or higher than the melting temperature of the one or more thermoplastic elastomers (E) and the one or more polypropylene-based polymers (P) added as needed, and is preferably 150 to 300°C, more preferably 200 to 300°C. The form of the elastomer resin composition of the present disclosure is not particularly limited, and examples include pellets and powder.

[0109] [Film] The film of the present disclosure is a monolayer film or a laminate film including one or more elastomer resin composition layers made of the elastomer resin composition of the present disclosure. In the laminate film, at least one elastomer resin composition layer is preferably disposed as the outermost layer. In the film of the present disclosure, the elastomer resin composition layer can function as a pressure-sensitive adhesive layer, an impact-absorbing layer, or the like. Therefore, the film of the present disclosure is suitable as a pressure-sensitive adhesive film, an impact-absorbing film, or the like. Examples of methods for producing the film of the present disclosure include solution casting, extrusion molding, compression molding (press molding), inflation molding, blow molding, calendar molding, and melt casting, with extrusion molding and compression molding (press molding) being preferred. Among these, extrusion molding is preferred, and the T-die method is more preferred.

[0110] A method for producing a monolayer film using a T-die method will be described below. The elastomer resin composition of the present disclosure is melt-kneaded using an extruder and extruded in a molten state from a T-die with a wide discharge port. Examples of extruders include single-screw extruders, twin-screw extruders, multi-screw extruders, and combinations thereof. The melting temperature is higher than the glass transition temperature (Tg) of the elastomer resin composition, preferably 150 to 300°C, more preferably 200 to 300°C. From the viewpoint of suppressing discoloration, it is preferable to perform the melt-kneading under reduced pressure using a vent or under a nitrogen gas flow.

[0111] To remove foreign matter, the molten resin is preferably melt-filtered using a filter before extrusion. By forming a film using the melt-filtered molten resin, a film with fewer defects caused by foreign matter and gels can be obtained. The filter material is appropriately selected based on the operating temperature, viscosity, filtration accuracy, etc. Examples include nonwoven fabrics made of glass fiber, etc.; sheets made of phenolic resin-impregnated cellulose; sintered metal fiber nonwoven sheets; sintered metal powder sheets; wire mesh; and combinations thereof. Among these, from the viewpoint of heat resistance and durability, a filter formed by stacking multiple sintered metal fiber nonwoven sheets is preferred. The filtration accuracy of the filter is not particularly limited, but is preferably 200 μm or less, more preferably 100 μm or less, and particularly preferably 50 μm or less. To improve the thickness accuracy of the film, a gear pump may be installed in the extrusion molding line to perform film formation.

[0112] The molten resin extruded into a film form from a T-die is cooled using multiple cooling rolls. Examples of cooling rolls include rigid metal rolls and elastic metal rolls. Rigid metal rolls are inelastic rolls made of metal such as stainless steel, and include drilled rolls and spiral rolls. The surface of the rigid metal roll is preferably a mirror finish, as this allows for the production of a film with high surface smoothness. Elastic metal rolls are rolls equipped with an elastic outer cylinder made of a thin metal film on their outer periphery. The elastic metal roll, for example, comprises a metal shaft roll made of stainless steel or the like, a thin metal film (elastic outer cylinder) made of stainless steel or the like covering the outer surface of the shaft roll, and a fluid sealed between the shaft roll and the thin metal film (elastic outer cylinder), and exhibits elasticity in the presence of the fluid. Examples of fluids include water and oil. The thickness of the thin metal film of the elastic metal roll is not particularly limited, but is preferably approximately 2 to 8 mm. The thin metal film preferably has flexibility and bendability, and preferably has a seamless structure without welded joints. Such a metal elastic roll equipped with a metal thin film has excellent durability, and if the metal thin film is mirror-finished, it can be handled in the same way as a normal mirror-finished roll, and a film with high surface smoothness can be produced. After cooling, the obtained monolayer film is taken up by a take-up roll. The above steps of extrusion, cooling, and take-up are carried out continuously.

[0113] The film of the present disclosure may be a coextruded film containing two or more elastomer resin composition layers, or a coextruded film containing an elastomer resin composition layer and another resin layer. In coextrusion, the constituent resins (compositions) of each layer are melt-kneaded using an extruder and coextruded in the desired laminated structure into a film form from a T-die with a wide discharge opening. Examples of lamination methods include a feedblock method in which lamination is performed before entering the T-die, and a multi-manifold method in which lamination is performed inside the T-die. The multi-manifold method is preferred from the viewpoint of improving interfacial smoothness between layers. The molten thermoplastic resin laminate coextruded from the T-die is pressurized and cooled using multiple cooling rolls. The laminated film obtained after cooling is taken up by a pair of take-up rolls. The above extrusion, cooling, and take-up processes are carried out continuously. In this specification, a heated and molten material is mainly referred to as a "thermoplastic resin laminate" and a solidified material is mainly referred to as a "thermoplastic resin laminate film," but there is no clear boundary between the two.

[0114] The thickness of the film of the present disclosure can be designed depending on the application, etc., and is preferably 10 to 700 μm. The lower limit is more preferably 30 μm, particularly preferably 50 μm. The upper limit is more preferably 500 μm, even more preferably 400 μm, even more preferably 300 μm, particularly preferably 200 μm, and most preferably 150 μm. When the thickness is equal to or greater than the above lower limit, the film is easy to form and can be excellent in impact resistance and reduced warping during heating. When the thickness is equal to or less than the above upper limit, the film has good film-forming properties or film-forming stability.

[0115] The film of the present disclosure may preferably be a laminate film including one or more elastomer resin composition layers and a support layer (also referred to as a substrate layer) that supports the elastomer resin composition layers. Examples of materials constituting the support layer include (meth)acrylic resins; polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; styrene resins such as acrylonitrile-styrene copolymers (AS resins) and acrylonitrile-butadiene-styrene (ABS) resins; polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate; polyamide resins such as nylon 6, nylon 66, and polyamide elastomers; polycarbonate resins; thermoplastic resins such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl alcohol, ethylene-vinyl alcohol copolymers; polyacetal; polyurethane; and combinations thereof.

[0116] From the viewpoints of transparency, weather resistance, surface gloss, and scratch resistance, etc., a (meth)acrylic resin-containing layer or the like is preferred as the support layer. From the viewpoints of moldability and impact resistance, etc., the (meth)acrylic resin-containing layer preferably contains one or more (meth)acrylic resins and one or more rubber components selected from the group consisting of acrylic rubber particles (preferably 2-3 layer acrylic multilayer structure polymer particles) and acrylic block copolymers. The (meth)acrylic resin is a homopolymer or copolymer containing one or more (meth)acrylic acid ester units, and known ones can be used. Among these, methacrylic resins that are homopolymers or copolymers containing one or more methacrylic acid ester units including methyl methacrylate (MMA) units are preferred. Known ones can be used as the acrylic rubber particles (preferably 2-3 layer acrylic multilayer structure polymer particles) and acrylic block copolymers.

[0117] The support layer may contain one or more additives as needed. Examples of additives are the same as those in the elastomer resin composition of the present disclosure.

[0118] As with the elastomer resin composition of the present disclosure, a 1 mm thick molded sheet can be prepared for the support layer, and dynamic viscoelasticity measurements can be performed using a rotational rheometer. Temperature dependency data of the loss tangent (tan δ) of the support layer can be obtained by dynamic viscoelasticity measurements. The peak temperature of the loss tangent (tan δ) in the temperature dependency data of the loss tangent (tan δ) is determined as the glass transition temperature (Tgs) of the support layer. Tgs + 25°C is used as the T ３ [℃] 、 T ３ The storage modulus of the elastomer resin composition of the present disclosure at [°C] is G' ３ Let it be [Pa].

[0119] The elastomer resin composition of the present disclosure has a ΔG′ defined by the following formula (2): ３－１ is preferably -0.18 to 0.00% / °C. The lower limit is more preferably -0.17% / °C, particularly preferably -0.16% / °C, and most preferably -0.15% / °C. The upper limit is more preferably -0.01% / °C, even more preferably -0.03% / °C, still more preferably -0.05% / °C, particularly preferably -0.08% / °C, and most preferably -0.10% / °C. ΔG' ３－１ [% / ℃]=[100×{Log(G' ３ ) -Log(G' １ ) / (T ３ -T １ ) )] / Log(G' １ ) ... (2)

[0120] According to the research of the present inventors, ΔG′ ３－１ It has been found that by using the laminate film of the present disclosure, which includes an elastomer resin composition layer and a support layer that satisfy the condition that is within the above range, the drawdown phenomenon and the occurrence of shock lines can be suppressed during the decoration process, and a decorated molded article with a good appearance can be obtained.

[0121] The mechanism is not entirely clear, but is presumed to be as follows: In methods for forming a decorative molded body using a molding method such as vacuum forming, pressure forming, or vacuum pressure forming, the decorative film needs to be horizontal during the preheating stage. However, if the rigidity of the decorative film is significantly reduced when it softens, drawdown occurs, causing a discrepancy in the timing of contact with the adherend, which is presumed to lead to the occurrence of shock lines. ΔG' ３－１ It is presumed that if the value of is zero or within a range close to zero, the warping and drawdown of the decorative film during preheating can be suppressed, and the occurrence of shock lines can be effectively suppressed.

[0122] The thermoplastic elastomer (EY) preferably contained in the elastomer resin composition of the present disclosure has a peak temperature of tan δ (Tge) near room temperature (20 to 30°C) and high rigidity in the rubber-like plateau region due to the presence of conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more in the polymer block (yb). When the elastomer resin composition of the present disclosure contains the thermoplastic elastomer (EY), the peak temperature of tan δ (Tg) of the support layer + 25°C (T ３ The temperature range of the rubber-like plateau region is expanded as the content of the polymer block (b) containing the conjugated diene compound unit increases, and the temperature range of the rubber-like plateau region is expanded as the temperature range of the tan δ peak temperature (Tgs) of the support layer + 25°C (T ３ By adjusting the composition of the elastomer resin composition in this way, the T ３ The storage modulus G' of the elastomer resin composition ３ The decrease in ΔG′ defined by the formula (2) can be suppressed. ３－１ can approach 0.00% / °C.

[0123] G' ３ is not particularly limited, and ΔG′ ３－１ is easily adjusted to fall within the above range, and is therefore preferably 1.8 × 10 ５ ~50.0 x 10 ５ The lower limit is more preferably 2.0 × 10 ５Pa, particularly preferably 2.2 × 10 ５ Pa, most preferably 2.4 x 10 ５ The upper limit is more preferably 40.0 × 10 ５ Pa, more preferably 30.0 x 10 ５ Pa, more preferably 20.0 x 10 ５ Pa, more preferably 10.0 x 10 ５ Pa, particularly preferably 5.0 × 10 ５ Pa, most preferably 3.0 x 10 ５ It is Pa.

[0124] The film of the present disclosure can be sandwiched between a pair of release films, if necessary, during or after film formation. Examples of release films include those obtained by subjecting at least one surface of a substrate made of a thermoplastic resin, paper, metal foil, or a combination thereof to a release treatment. Examples of thermoplastic resins include polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate; saponified ethylene-vinyl acetate copolymers; polyvinyl chloride, polyvinylidene chloride; polyethylene; polypropylene; poly-4-methyl-1-pentene; polycarbonate-based resins; and polyamide resins such as polyamide 6, polyamide 66, and polyamide 12. Examples of metal foils include aluminum foil and iron foil. The thickness of the release film is not particularly limited and is typically about 5 to 100 μm.

[0125] [Composite Film, Decorative Film] In one embodiment, the film of the present disclosure can be a laminate film (also referred to as a composite film or decorative film) having one or more elastomer resin composition layers and one or more metal layers or decorative layers. The thickness of the metal layer or decorative layer is not particularly limited, and from the viewpoints of moldability, economy, etc., it is preferable that it be thinner than the elastomer resin composition layer. In the above embodiment, the film of the present disclosure can preferably be a laminate film (also referred to as a composite film or decorative film) having one or more elastomer resin composition layers, a support layer supporting the elastomer resin composition layers, and one or more metal layers or decorative layers. As described above, the elastomer resin composition layer can function as an adhesive layer, an impact absorbing layer, etc. In the above embodiment, it is preferable that at least one elastomer resin composition layer is disposed as the outermost layer.

[0126] The metal layer can function as a decorative layer. Examples of metals include Al, Si, Ti, Cr, Ni, Zn, Ga, Y, Zr, Nb, In, Sn, Hf, Ta, W, alloys thereof, and combinations thereof. The metal layer can be made of a metal foil. The metal layer can also be formed by a gas phase method such as vacuum deposition, sputtering, ion plating (IP), laser ablation, thermal chemical vapor deposition, chemical vapor deposition (CVD), and plasma enhanced chemical vapor deposition (plasma CVD).

[0127] Examples of the decorative layer include a metal layer, a colored layer, a printed layer, a nonwoven fabric, artificial leather, natural leather, and combinations thereof. A decorative layer including a metal layer can impart a metallic tone and gloss to the film. The printed layer can have a pattern such as a picture, letter, or figure, a color, or a combination thereof. The colored layer can be made of a colored resin film. Methods for coloring a resin film include a method in which a pigment and / or dye is added to a resin before film formation to color it; and a dyeing method in which a resin film is immersed in a dye dispersion to color it.

[0128] The composite film or decorative film of the present disclosure may have another resin layer, such as a (meth)acrylic resin-containing layer, on the metal layer or decorative layer as a base layer and / or protective layer for the metal layer or decorative layer.

[0129] Examples of methods for producing the composite film or decorative film of the present disclosure include a method of laminating, by compression bonding (preferably thermocompression bonding), a monolayer film or laminate film containing one or more elastomer resin composition layers and, if necessary, a support layer supporting the layers, and a metal layer or decorative layer-containing film having a metal layer or decorative layer on at least one surface of a base resin film.

[0130] FIG. 1 is a schematic cross-sectional view of a film according to one embodiment of the present invention. Film 1 of this embodiment is a three-layer laminate film in which elastomer resin composition layers 11A and 11B are laminated on both sides of support layer 12 (preferably a (meth)acrylic resin-containing layer). The elastomer resin composition layer 11A and the elastomer resin composition layer 11B may be identical or different in composition and thickness. The film configuration of the present disclosure can be appropriately modified, such as a single-layer film consisting of only elastomer resin composition layer 11A or 11B, or a two-layer laminate film in which elastomer resin composition layer 11A or 11B is laminated on one side of support layer 12.

[0131] FIG. 2 is a schematic cross-sectional view showing one embodiment of a decorative film according to the present invention. In the figure, reference numeral 2 denotes a metal layer or decorative layer-containing film, reference numeral 21 denotes a substrate layer, and reference numeral 22 denotes a metal layer or decorative layer. The metal layer or decorative layer-containing film 2 includes a substrate layer 21 made of a resin layer such as a (meth)acrylic resin-containing layer, and a metal layer or decorative layer 22 on one surface of the substrate layer 21. The decorative film 3 is formed by laminating the metal layer or decorative layer-containing film 2 on one elastomer resin composition layer 11B of the film 1 shown in FIG. 1. The decorative film 3 can be produced by laminating the film 1 shown in FIG. 1 and the metal layer or decorative layer-containing film 2 by a method such as compression bonding (preferably thermocompression bonding). By laminating the film 1 so that the surface of the metal layer or decorative layer 22 is covered by the substrate layer 21, the substrate layer 21 can function as a protective layer for the metal layer or decorative layer 22.

[0132] [Molded body] The molded body of the present disclosure is a laminated body of the present disclosure, comprising one or more elastomer resin composition layers and a support layer (substrate layer) supporting the layers, on at least a portion of the surface of an adherend. Examples of the molded body of the present disclosure include a composite molded body or a decorated molded body in which a composite film or a decorative film of the present disclosure, comprising one or more elastomer resin composition layers and a support layer (substrate layer) supporting the layers, and a metal layer or a decorative layer, is laminated on at least a portion of the surface of an adherend. In the composite molded body or decorated molded body of the present disclosure, the elastomer resin composition layer can provide good adhesion between the adherend and the metal layer or the decorative layer.

[0133] Examples of materials for the adherend include thermoplastic or thermosetting resins, organic materials such as processed wood or non-wood plants (e.g., kenaf), inorganic materials such as metals, metal compounds, ceramics, carbon, and stone (e.g., marble), and combinations thereof. Examples of thermoplastic resins are the same as the examples of the constituent resins of the other resin layers that can be included in the composite film and decorative film of the present disclosure, with polypropylene-based resins and ABS resins being preferred. Examples of thermosetting resins include epoxy-based resins, phenol-based resins, and melamine-based resins. 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 (e.g., stainless steel), and combinations thereof.

[0134] Examples of methods for producing the composite molded body and decorated molded body of the present disclosure include methods in which a composite film or decorative film of the present disclosure is laminated to at least a portion of the surface of a previously prepared adherend by a molding method such as vacuum forming, pressure forming, vacuum-pressure forming, or compression molding, and the like, and the composite film or decorative film of the present disclosure is simultaneously secondary-molded: an injection molding and simultaneous lamination method is used in which a composite film or decorative film of the present disclosure, which has been secondary-molded (also called pre-molded) as necessary by a vacuum forming method, pressure forming, or the like, is inserted into an injection molding mold, and a thermoplastic resin is then injected into the mold to simultaneously mold the adherend and laminate the composite film or decorative film of the present disclosure to at least a portion of the surface of the adherend. In the latter method, the composite film or decorative film of the present disclosure may be pre-molded using an injection molding machine for molding the adherend.

[0135] Among the above, vacuum pressure forming is preferred, and the TOM (Three Dimension Overlay Method) method is particularly preferred. One embodiment of a method for manufacturing a decorative molded body using the TOM method will be described. A vacuum pressure forming machine for the TOM method includes a space (molding space) that can be evacuated, a stage provided therein, and a fixing frame to which a decorative film can be fixed. First, an adherend is set on the stage of the forming machine, and a decorative film (flat at this point) is set in the fixing frame. The decorative film fixed to the fixing frame divides one space within the forming machine into two spaces. At this time, the adherend is set in one of the two spaces, and the other is empty. In this state, a vacuum is drawn within the two spaces, and the decorative film is preheated using an infrared heater or the like. Once the decorative film has softened due to heating, air is introduced only into the empty space, allowing the decorative film to be tightly adhered to the adherend in a vacuum atmosphere, conforming to its surface shape. Thereafter, the decorative film is removed from the fixing frame, and unnecessary portions of the decorative film are trimmed as necessary.

[0136] The elastomer resin composition layer made of the elastomer resin composition of the present disclosure is suitable as an adhesive layer of a decorative film, and by using a decorative film of the present disclosure containing this, it is possible to suppress the drawdown phenomenon and the occurrence of shock lines during the decoration process, and to obtain a decorated molded body with a good appearance. Figure 3 is a schematic cross-sectional view showing a decorated molded body of one embodiment of the present invention. The decorated molded body 4 is formed by laminating the decorative film 3 shown in Figure 2 on at least a portion of the surface of an adherend 30.

[0137] [Applications] The elastomer resin composition of the present disclosure can be used for any application, and is suitable for applications such as decorative films and decorative molded articles. The decorative films and decorative molded articles can be preferably used for various applications requiring design. Suitable applications include automobile interior components, and transportation-related parts such as automobile exterior components such as side visors, rear visors, head wings, headlight covers, and bumpers.

[0138] Examples and comparative examples according to the present invention will be described. [Evaluation Items and Evaluation Methods] The evaluation items and evaluation methods are as follows. (Polymerization Conversion Rate) The polymerization conversion rate was determined by gas chromatography analysis. A gas chromatograph GC-14A manufactured by Shimadzu Corporation was connected to an INERTCAP1 column manufactured by GL Sciences Inc. (film thickness 0.4 μm, inner diameter 0.25 mmφ, length 60 m). Analysis was carried out under the following conditions, and the polymerization conversion rate was calculated from the obtained data. Injection temperature: 250°C, Detector temperature: 250°C, Temperature profile: Hold at 60°C for 5 minutes → Heat to 250°C at a heating rate of 10°C / min → Hold at 250°C for 10 minutes.

[0139] (Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)) The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the resin were determined by gel permeation chromatography (GPC) analysis. The measurement device used was a GPC device "HLC-8320" manufactured by Tosoh Corporation. The separation column used was a series connection of "TSKguardcolumnSuperHZ-H", "TSKgelHZM-M", and "TSKgelSuperHZ4000" manufactured by Tosoh Corporation. A differential refractive index detector (RI detector) was used as the detector. A sample solution was prepared by dissolving 4 mg of the resin to be measured in 5 ml of tetrahydrofuran. The column oven temperature was set to 40°C. Tetrahydrofuran was used as the eluent, and the eluent flow rate was set to 0.35 ml / min. 20 μl of sample solution was injected into the instrument and a chromatogram was measured. Ten standard polystyrene or standard polymethyl methacrylate (PMMA) samples with molecular weights ranging from 400 to 5,000,000 were subjected to GPC measurement, and a calibration curve showing the relationship between retention time and molecular weight was created. Based on this calibration curve, the Mw, Mn, and Mw / Mn of the resin to be measured, converted to standard polystyrene or standard PMMA, were determined.

[0140] (Hydrogenation Rate) The hydrogenation rate of the polymer block containing conjugated diene compound units was determined by measuring the iodine value of the block copolymer before and after the hydrogenation reaction.

[0141] (Total amount of 1,2-bonds and 3,4-bonds) of a thermoplastic elastomer containing a polymer block containing a conjugated diene compound unit １ H-NMR measurement was performed. The total amount of 1,2-bonds and 3,4-bonds was calculated from the ratio of the integral value of the first peak at 4.2 to 5.0 ppm, which is derived from 1,2-bonded and 3,4-bonded conjugated diene compound units, to the integral value of the second peak at 5.0 to 5.45 ppm, which is derived from 1,4-bonded conjugated diene compound units.

[0142] (Melting Point) The melting point of the polypropylene polymer was measured using a differential scanning calorimeter (Shimadzu Corporation, "DSC-50 (product number)"). Approximately 5 mg of a polypropylene film sample was placed in an aluminum pan and set in the above-mentioned apparatus. After nitrogen substitution for 30 minutes or more, the sample was heated from room temperature (20-25°C) to 200°C at a rate of 10°C / min in a nitrogen stream of 10 ml / min, held for 5 minutes, and then cooled to 40°C at a rate of 10°C / min (primary scan). Next, the sample was heated to 200°C at a rate of 10°C / min (secondary scan) to obtain a calorimetry curve of fusion. The maximum peak temperature of fusion (°C) was determined as the melting point (Tm).

[0143] (Melt Tension) The melt tension of the polypropylene-based polymer was measured using a capillary rheometer ("Capillograph 1D" manufactured by Toyo Seiki Seisakusho, Ltd.) equipped with a pulley-type tension measurement unit. The polypropylene-based polymer was placed in a cylinder with a diameter of 9.55 mmφ heated to a temperature of 230°C. The molten polypropylene-based polymer was extruded through an orifice with a diameter of 2.0 mmφ and a length of 40 mm 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 tension applied to the pulley-type tension measurement jig was measured as the melt tension (N).

[0144] (Dynamic Viscoelasticity) Elastomer resin composition pellets (ER) or (ERC) were press-molded at 200°C to obtain a 1 mm thick sheet, from which circular test specimens with a diameter of 25 mm were cut. Using a rotational rheometer (Rheometric Scientific, Inc., "ARES"), the test specimen was sandwiched between a pair of parallel circular plates with a diameter of 25 mm. Dynamic viscoelasticity measurements were performed under the following conditions: strain of 5%, heating rate of 3°C / min, frequency of 1 Hz, temperature range of -50 to 250°C, in 1.0°C increments. Data on the temperature dependence of the loss tangent (tan δ), storage modulus (G'), and loss modulus (G'') were obtained. The peak temperature of the loss tangent (tan δ) in the temperature dependence data of the loss tangent (tan δ) was determined as the glass transition temperature (Tge) of the elastomer resin composition.

[0145] In the temperature dependency data of the loss tangent (tan δ), the region in which the loss tangent (tan δ) fluctuates between 0 and ±1% under measurement conditions in 0.5°C increments in the temperature range of 0°C or higher was identified as the rubbery plateau region of the elastomer resin composition. The rubbery plateau region of the elastomer resin composition was generally in the range of Tge + 50°C to Tge + 120°C. Representative measurement results of the dynamic viscoelastic properties of the elastomer resin composition (ER1) obtained in Example E1 are shown in Figure 4.

[0146] Tge + 50 ° C (T １ The storage modulus (G') of the elastomer resin composition at 100°C ( １ ) [Pa] and Tge + 120 ° C (T ２ The storage modulus (G') of the elastomer resin composition at 100°C ( ２ ) [Pa] and ΔG′ defined by the following formula (1) ２－１ The temperature change [% / °C] was calculated. ２－１ [% / ℃]=[100×{Log(G' ２ ) -Log(G' １ ) / (T ２ -T １ ) )] / Log(G' １ ) ... (1)

[0147] A 1 mm thick sheet of the methacrylic resin composition (MR2) prepared as a material for the support layer supporting the elastomer resin composition layer was also obtained in the same manner as above, and dynamic viscoelasticity measurements were performed. The glass transition temperature (Tgs) of the methacrylic resin composition (MR2) was determined as the peak temperature of the loss tangent (tan δ) in the temperature dependency data of the loss tangent (tan δ). Tgs + 25°C (T ３ The storage modulus (G') of the elastomer resin composition at 100°C ( ３ ) [Pa] was calculated, and ΔG′ defined by the following formula (2) ３－１ The temperature change [% / °C] was calculated. ３－１ [% / ℃]=[100×{Log(G' ３ ) -Log(G' １ ) / (T ３ -T １ ) )] / Log(G' １ ) ... (2)

[0148] (Presence or absence of drawdown) A vacuum and compressed air forming machine ("NGF-0406-T" manufactured by Fuse Vacuum Co., Ltd.) equipped with a fixed frame (210 mm x 297 mm, A4 size) capable of fixing the decorative film and an infrared heater capable of heating the decorative film was prepared. The decorative film (DF) (flat at this point) was set in the fixed frame. One space inside the forming machine was divided into two spaces by the decorative film (DF) fixed to the fixed frame. In this state, a vacuum was drawn inside the two spaces, and the decorative film was preheated using the infrared heater. The degree of vacuum was set to 0.5 kPa. The heating temperature of the decorative film (DF) was set to 160°C. The temperature of the decorative film (DF) was measured with a radiation thermometer, and the measured temperature was displayed on the temperature display. When the measured temperature displayed on the temperature display reached 160°C, the deflection state of the decorative film (DF) was confirmed using images from the video camera attached to the device, and evaluated according to the following criteria. Good (◯): No deflection was observed (maximum deflection amount was 0 mm). Fair (Δ): Maximum deflection amount was 5 to 15 mm. Poor (×): Maximum deflection amount was more than 15 mm.

[0149] (Presence or absence of shock lines and shock line height) The surface of the decorated molded body (DM) was visually observed under a lit white light-emitting diode (white LED) light to confirm the presence or absence of shock lines. If shock lines were confirmed, the height of the shock lines was measured using a stylus-type surface profiler ("Dektak 150" manufactured by ULVAC, Inc.) equipped with a stylus with a tip radius of 12.5 μm. With the tip of the stylus in contact with the surface of the decorated molded body (DM), the stylus was scanned across the shock lines in a direction approximately perpendicular to the line direction of the shock lines in a planar view to obtain data on the surface irregularities. The height of the shock lines was determined as the height of the apex of the convex portion relative to the flat portion (the portion where no shock lines were formed).

[0150] [Materials] <Thermoplastic elastomer (E)> The following thermoplastic elastomer (E) was produced. (Production Example 1-1) (Production of First Thermoplastic Elastomer (EX-1)) A pressure-resistant vessel whose interior had been replaced with nitrogen and dried was charged with 50.0 kg of cyclohexane as a solvent and 61.1 g of a 10.5 mass % cyclohexane solution of sec-butyllithium (6.42 g of sec-butyllithium) as an anionic polymerization initiator, and mixed. The solution was heated to 50°C, and 0.81 kg of styrene (St) was added and polymerized for 1 hour. Subsequently, 10.87 kg of isoprene was added and polymerized for 2 hours. Subsequently, 0.81 kg of styrene (St) was added and polymerized for 1 hour. In this manner, a reaction liquid containing a polystyrene-polyisoprene-polystyrene triblock copolymer was obtained. Palladium carbon (palladium loading: 5% by mass) was added as a hydrogenation catalyst to this reaction solution in an amount of 5% by mass relative to the block copolymer, and the reaction was carried out for 10 hours under conditions of a hydrogen pressure of 2 MPa and 150°C. After cooling and pressure release, the palladium carbon was removed by filtration, and the filtrate was concentrated and vacuum dried to obtain thermoplastic elastomer (EX-a1) (a hydrogenated product of polystyrene-polyisoprene-polystyrene triblock copolymer). The total proportion of 1,2-bonds and 3,4-bonds in the polyisoprene blocks in thermoplastic elastomer (EX-a1) was 7 mol%.

[0151] Separately, a pressure vessel whose interior had been purged with nitrogen and dried was charged with 50.0 kg of cyclohexane as a solvent and 420.0 g of a 10.5 mass % cyclohexane solution of sec-butyllithium (44.1 g of sec-butyllithium) as an anionic polymerization initiator, and mixed. After heating this solution to 50°C, 2.83 kg of styrene (St) was added and polymerized for 1 hour, followed by the addition of 19.81 kg of isoprene and polymerization for 2 hours. In this manner, a reaction solution containing a polystyrene-polyisoprene diblock copolymer was obtained. Next, hydrogenation, filtration removal of palladium carbon, and vacuum drying were carried out in the same manner as above to obtain thermoplastic elastomer (EX-b1) (a hydrogenated product of polystyrene-polyisoprene diblock copolymer). The total proportion of 1,2-bonds and 3,4-bonds in the polyisoprene blocks of thermoplastic elastomer (EX-1b) was 7 mol%.

[0152] The obtained thermoplastic elastomers (EX-a1) and (EX-b1) were melt-kneaded using a twin-screw extruder ("ZSK26 MegaCompounder" manufactured by Coperion) (ratio of effective screw length (L) to screw diameter (D) (L / D) = 54) at a screw rotation speed of 300 rpm and a melt-kneading temperature of 200°C, to obtain a first thermoplastic elastomer (EX-1). The total proportion of 1,2-bonds and 3,4-bonds in the polyisoprene blocks in the first thermoplastic elastomer (EX-1) was 7 mol%.

[0153] (Production Example 1-2) (Production of First Thermoplastic Elastomer (EX-2)) 50.0 kg of cyclohexane as a solvent and 170.6 g of a 10.5 mass % cyclohexane solution of sec-butyllithium (17.91 g of sec-butyllithium) as an anionic polymerization initiator were charged into a pressure-resistant vessel whose interior had been replaced with nitrogen and dried, and then mixed. The solution was heated to 50°C, and 1.87 kg of styrene (St) was added and polymerized for 1 hour. Subsequently, 8.75 kg of butadiene was added and polymerized for 2 hours, and subsequently 1.87 kg of styrene (St) was added and polymerized for 1 hour. In this way, a reaction liquid containing a polystyrene-polybutadiene-polystyrene triblock copolymer was obtained. Next, hydrogenation, filtration removal of palladium carbon, and vacuum drying were carried out in the same manner as for the thermoplastic elastomer (EX-a1) of Production Example 1-1, to obtain a thermoplastic elastomer (EX-a2) (a hydrogenated product of a polystyrene-polybutadiene-polystyrene triblock copolymer). The total proportion of 1,2-bonds and 3,4-bonds in the polybutadiene block in the thermoplastic elastomer (EX-a2) was 6 mol %.

[0154] Separately, a pressure-resistant vessel whose interior had been replaced with nitrogen and dried was charged with 50.0 kg of cyclohexane as a solvent and 313.1 g of a 10.5 mass % cyclohexane solution of sec-butyllithium (32.9 g of sec-butyllithium) as an anionic polymerization initiator, and mixed. After heating this solution to 50°C, 3.75 kg of styrene (St) was added and polymerization was allowed for 1 hour, followed by the addition of 8.75 kg of butadiene and polymerization for 2 hours. In this manner, a reaction solution containing a polystyrene-polybutadiene diblock copolymer was obtained. Next, hydrogenation, filtration removal of the palladium carbon, and vacuum drying were carried out in the same manner as above to obtain thermoplastic elastomer (EX-b2) (a hydrogenated product of polystyrene-polybutadiene diblock copolymer). The total proportion of 1,2-bonds and 3,4-bonds in the polyisoprene blocks in thermoplastic elastomer (EX-b2) was 6 mol%.

[0155] The resulting thermoplastic elastomers (EX-a2) and (EX-b2) were melt-kneaded in the same manner as in Production Example 1-1 to obtain a first thermoplastic elastomer (EX-2). The total proportion of 1,2-bonds and 3,4-bonds in the polybutadiene block in the first thermoplastic elastomer (EX-2) was 6 mol %.

[0156] (Production Example 1-3) (Production of First Thermoplastic Elastomer (EX-3)) In a pressure vessel whose interior had been replaced with nitrogen and dried, 50.0 kg of cyclohexane as a solvent and 880 g of a 10.5 mass % cyclohexane solution of sec-butyllithium (17.91 g of sec-butyllithium) as an anionic polymerization initiator were charged and mixed. The solution was heated to 50°C, and 0.79 kg of styrene (St) was added and polymerized for 1 hour. Subsequently, 7.24 kg of isoprene was added and polymerized for 2 hours. Subsequently, 0.79 kg of styrene (St) was added and polymerized for 1 hour. In this way, a reaction liquid containing a polystyrene-polyisoprene-polystyrene triblock copolymer was obtained. Next, hydrogenation, filtration removal of palladium carbon, and vacuum drying were carried out in the same manner as for the thermoplastic elastomer (EX-a1) of Production Example 1-1, to obtain thermoplastic elastomer (EX-3) (a hydrogenated product of polystyrene-polyisoprene-polystyrene triblock copolymer). The total proportion of 1,2-bonds and 3,4-bonds in the polyisoprene blocks in the thermoplastic elastomer (EX-3) was 4.9 mol %.

[0157] (Production Example 2-1) (Production of Second Thermoplastic Elastomer (EY-1)) In a pressure vessel whose interior had been replaced with nitrogen and dried, 50.0 kg of cyclohexane as a solvent, 94.1 g of a 10.5 mass % cyclohexane solution of sec-butyllithium (9.9 g of sec-butyllithium) as an anionic polymerization initiator, and 300 g of tetrahydrofuran as a Lewis base were charged and mixed. After heating this solution to 50°C, 1.25 kg of styrene (St) was added and polymerized 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 liquid containing a polystyrene-polyisoprene-polystyrene triblock copolymer was obtained. Next, hydrogenation, filtration removal of palladium carbon, and vacuum drying were carried out in the same manner as in Production Example 1-1, to obtain a second thermoplastic elastomer (EY-1) (a hydrogenated product of a polystyrene-polyisoprene-polystyrene triblock copolymer). The total proportion of 1,2-bonds and 3,4-bonds in the polyisoprene blocks in the second thermoplastic elastomer (EY-1) was 55 mol %.

[0158] (Production Example 3-1) (Production of Third Thermoplastic Elastomer (EZ-1)) 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 into a pressure vessel whose interior had been replaced with nitrogen and dried, and then mixed. 0.42 L of a 1.3 M cyclohexane solution of sec-butyllithium was added to this solution, and polymerization was carried out at −10°C for 5 hours. Three hours after the start of polymerization, the weight-average molecular weight (Mw, calculated as standard polystyrene) of poly(α-methylstyrene) (block S) was 6,600, and the polymerization conversion of α-methylstyrene was 90%. Next, 0.88 kg of butadiene was added to this reaction solution, and polymerization was carried out at −10°C for 30 minutes, after which 41.8 kg of cyclohexane was added. The polymerization conversion of butadiene at this point 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, calculated as standard polystyrene) of 3,700 and a 1,2-bond content of 81 mol %.

[0159] To the reaction mixture was further added 7.71 kg of butadiene, and polymerization was carried out at 50°C for 2 hours to obtain a poly(α-methylstyrene) block (S)-polybutadiene block (t1)-polybutadiene block (t2) copolymer. The weight-average molecular weight (Mw, calculated as standard polystyrene) of the polybutadiene block (t2) was 29,800, and the 1,2-bond content was 40 mol%.

[0160] To the reaction mixture, 0.54 L of a 0.5 M toluene solution of dichlorodimethylsilane was added, and a coupling reaction was carried out at 50°C for 1 hour. After this reaction, a poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) triblock copolymer (poly(α-methylstyrene) block (S)-polybutadiene block (t1)-polybutadiene block (t2)-X-polybutadiene block (t2)-polybutadiene block (t1)-poly(α-methylstyrene) block (S) copolymer) was produced as a coupling product. Here, X represents a coupling residue. The resulting poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) triblock copolymer had a poly(α-methylstyrene) block content of 31% by mass, and the 1,4-bond content in the total polybutadiene blocks (t1 + t2) was 55 mol%. The coupling product and the block copolymer (poly(α-methylstyrene) block (S)-polybutadiene block (t1)-polybutadiene block (t2) copolymer) that had not undergone the coupling reaction were subjected to GPC analysis, and the coupling efficiency was determined from the ratio of the UV absorption peak integral values ​​to be 94%.

[0161] A Ziegler hydrogenation catalyst consisting of nickel octylate and triethylaluminum was added to the reaction solution under a hydrogen atmosphere, and a hydrogenation reaction was carried out for 5 hours at a hydrogen pressure of 0.8 MPa and 80°C to obtain a third thermoplastic elastomer (EZ-1). The third thermoplastic elastomer (EZ-1) was mainly composed of a hydrogenated poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) triblock copolymer (a hydrogenated product of the above-mentioned coupling product), and its content was 94% by mass. The third thermoplastic elastomer (EZ-1) had a weight-average molecular weight (Mw, calculated as standard polystyrene) of 79,500, a number-average molecular weight (Mn, calculated as standard polystyrene) of 78,700, and Mw / Mn of 1.01. The hydrogenation rate of the entire polybutadiene block (t1 + t2) was 97.5%, and the combined proportion of 1,2-bonds and 3,4-bonds in the polybutadiene block was 45 mol%.

[0162] <Polypropylene-based polymer (P), other olefin-based resins (O)> The following polypropylene-based polymer (P) and other olefin-based resins for comparison were prepared. (PX1) Long-chain branched polypropylene, "Waymax (registered trademark) MFX3" manufactured by Japan Polypropylene Corporation, MFR at 230°C and 21.18 N: 9.0 g / 10 min, melt tension: 4.9 × 10 －２ N, (PY1) Maleic anhydride modified polypropylene, manufactured by Sanyo Chemical Industries, Ltd., "UMEX (registered trademark) 5200", melting point 124°C, (PY2) Maleic anhydride modified polypropylene, manufactured by Sanyo Chemical Industries, Ltd., "UMEX (registered trademark) 5500", melting point 123°C, (O1) α-olefin copolymer, manufactured by Mitsui Chemicals, Inc., "TAFMER (registered trademark) XM7090", melting point 98°C.

[0163] <Methacrylic Resin (M)> The following methacrylic resins (M) were produced by a conventional method: (M1) methyl methacrylate (MMA)-methyl acrylate (MA) copolymer (MMA unit content: 93.6% by mass, MA unit content: 6.4% by mass, Mw (standard PMMA equivalent) = 120,000, Mw / Mn = 2.1), (M2) methyl methacrylate (MMA)-methyl acrylate (MA) copolymer (MMA unit content: 99.3% by mass, MA unit content: 0.7% by mass, Mw (standard PMMA equivalent) = 84,000, Mw / Mn = 2.1).

[0164] <Multilayered Polymer Particles (R)> The following multilayered polymer particles (R) were produced. (R1) A reactor equipped with a stirrer, thermometer, nitrogen gas inlet, monomer inlet tube, and reflux condenser was charged with 100 parts by mass of deionized water, and 0.019 parts by mass of a surfactant (polyoxyethylene alkyl ether sodium acetate (NIKKOL-ECT-3NEX, manufactured by Nikko Chemicals Co., Ltd.)) and 0.10 parts by mass of sodium carbonate were added and dissolved. The atmosphere inside the reactor was purged with nitrogen gas to create a substantially oxygen-free state, and the aqueous solution was heated to 80°C. 0.04 parts by mass of potassium persulfate was added to the aqueous solution and stirred for 5 minutes, after which a mixture of 32.6 parts by mass of methyl methacrylate (MMA), 2.1 parts by mass of methyl acrylate (MA), and 0.07 parts by mass of allyl methacrylate was continuously added dropwise over 50 minutes. After completion of the addition, the mixture was held for 40 minutes to achieve a polymerization rate of 98% or higher, and emulsion polymerization was carried out. Next, 0.05 parts by mass of potassium persulfate was added to the obtained latex and stirred for 5 minutes, after which a mixture of 36.6 parts by mass of n-butyl acrylate (n-BA), 7.9 parts by mass of styrene (St), and 0.89 parts by mass of allyl methacrylate was continuously added dropwise over 60 minutes. After completion of the addition, the mixture was held for 90 minutes to achieve a polymerization rate of 98% or higher, and seed emulsion polymerization was carried out. At this point, the volume average particle size (D50) of the polymer particles in the latex was measured by dynamic light scattering using a laser diffraction / scattering particle size distribution analyzer and found to be 0.09 μm. Next, 0.02 parts by mass of potassium persulfate was added to the obtained latex and stirred for 5 minutes, after which a mixture of 18.6 parts by mass of methyl methacrylate (MMA), 1.2 parts by mass of methyl acrylate (MA), and 0.04 parts by mass of n-octyl mercaptan (n-OM) was continuously added dropwise over 30 minutes. After the addition was completed, the mixture was maintained for 60 minutes until the polymerization rate reached 98% or more, and seed emulsion polymerization was carried out. The final latex was placed in a vessel equipped with a stirrer, and an aqueous magnesium sulfate solution was added to the stirred latex to cause salting-out coagulation. The coagulated material obtained was washed with water, dehydrated, and dried to obtain acrylic multilayer structure polymer particles (acrylic rubber particles) (R1).

[0165] (R2) A reactor equipped with a stirrer, thermometer, nitrogen gas inlet, monomer inlet tube, and reflux condenser was charged with 100 parts by mass of deionized water, and 0.019 parts by mass of a surfactant ("Pelex SS-H" manufactured by Kao Corporation) and 0.5 parts by mass of sodium carbonate were added and dissolved. The atmosphere inside the reactor was purged with nitrogen gas to create a substantially oxygen-free state, and the aqueous solution was heated to 80°C. 0.02 parts by mass of potassium persulfate was added to the aqueous solution and stirred for 5 minutes. A mixture of 9.4 parts by mass of methyl methacrylate (MMA), 0.6 parts by mass of methyl acrylate (MA), and 0.02 parts by mass of allyl methacrylate was then added dropwise continuously over 20 minutes. After the addition was completed, the mixture was maintained for 30 minutes to achieve a polymerization rate of 98% or higher, and emulsion polymerization was then carried out. Next, 0.07 parts by mass of potassium persulfate was added to the obtained latex and stirred for 5 minutes, after which a mixture of 41.1 parts by mass of n-butyl acrylate (n-BA), 8.9 parts by mass of styrene (St), and 2.0 parts by mass of allyl methacrylate was continuously added dropwise over 80 minutes. After completion of the addition, the mixture was held for 60 minutes to achieve a polymerization rate of 98% or higher, and seed emulsion polymerization was carried out. At this point, the volume average particle size (D50) of the polymer particles in the latex was measured by dynamic light scattering using a laser diffraction / scattering particle size distribution analyzer and found to be 0.21 μm. Next, 0.07 parts by mass of potassium persulfate was added to the obtained latex and stirred for 5 minutes, after which a mixture of 37.6 parts by mass of methyl methacrylate (MMA), 2.4 parts by mass of methyl acrylate (MA), and 0.12 parts by mass of n-octyl mercaptan (n-OM) was continuously added dropwise over 60 minutes. After the addition was completed, the mixture was maintained for 60 minutes until the polymerization rate reached 98% or more, and seed emulsion polymerization was carried out. The final latex was placed in a vessel equipped with a stirrer, and an aqueous magnesium sulfate solution was added to the stirred latex to cause salting-out coagulation. The coagulated material obtained was washed with water, dehydrated, and dried to obtain acrylic multilayer structure polymer particles (acrylic rubber particles) (R2).

[0166] (R3) A reactor equipped with a stirrer, thermometer, nitrogen gas inlet, monomer inlet tube, and reflux condenser was charged with 200 parts by mass of deionized water, 1 part by mass of sodium dodecylbenzenesulfonate, and 0.05 parts by mass of sodium carbonate. The reactor was thoroughly purged with nitrogen gas to create a substantially oxygen-free state, and the aqueous solution was heated to 80 ° C. 0.01 parts by mass of potassium persulfate was added to the aqueous solution and stirred for 5 minutes, after which a mixture of 9.48 parts by mass of methyl methacrylate (MMA), 0.5 parts by mass of n-butyl acrylate (n-BA), and 0.02 parts by mass of allyl methacrylate was continuously added dropwise over 20 minutes. After completion of the addition, the mixture was maintained for 30 minutes to achieve a polymerization rate of 98% or higher, and emulsion polymerization was carried out. Next, 0.03 parts by mass of potassium persulfate was added to the obtained latex and stirred for 5 minutes, after which a mixture of 1.45 parts by mass of methyl methacrylate (MMA), 27.67 parts by mass of n-butyl acrylate (n-BA), and 0.88 parts by mass of allyl methacrylate was continuously added dropwise over 40 minutes. After completion of the addition, the mixture was held for 30 minutes so that the polymerization rate was 98% or higher, and seed emulsion polymerization was carried out. Next, 0.06 parts by mass of potassium persulfate was added to the obtained latex and stirred for 5 minutes, and then a mixture of 53.73 parts by mass of methyl methacrylate (MMA), 5.97 parts by mass of n-butyl acrylate (n-BA), and 0.3 parts by mass of n-octyl mercaptan (n-OM) was continuously added dropwise over 100 minutes. After completion of the addition, the mixture was held for 60 minutes so that the polymerization rate was 98% or higher, and seed emulsion polymerization was carried out to obtain a latex containing multilayer structure polymer particles (R3). The volume average particle diameter of the multilayer structure polymer particles (R3) in the latex was measured by dynamic light scattering using a laser diffraction / scattering particle size distribution analyzer and found to be 100 nm. Next, the latex containing the multilayer structure polymer particles (R3) was frozen at -30°C for 4 hours. The frozen latex was poured into twice the amount of hot water at 80°C and stirred to form a slurry, which was then maintained at 80°C for 20 minutes. Next, the slurry was dehydrated and dried at 70°C to obtain acrylic multilayer structure polymer particles (acrylic rubber particles) (R3).

[0167] <Block Copolymer (B)> The following block copolymer (B) was produced by a conventional method. (B1) Acrylic triblock copolymer, methyl methacrylate (MMA) polymer block (b1))-(n-butyl acrylate (n-BA) polymer block (b2))-(methyl methacrylate (MMA) polymer block (b1), b1:b2:b1 (mass ratio) = 14.3:50.0:35.7, MMA unit:n-BA unit (mass ratio) = 50:50, weight average molecular weight (Mw, standard PMMA equivalent) = 70,000.

[0168] <Methacrylic Resin Composition (MR)> The following methacrylic resin composition (MR) was produced. (MR1) 55.7 parts by mass of pellets of methacrylic resin (M1), 33.6 parts by mass of pellets of multilayer structure polymer particles (R1), 6.7 parts by mass of pellets of multilayer structure polymer particles (R2), and 4 parts by mass of pellets of block copolymer (B1) were melt-kneaded using a twin-screw extruder and extruded into strands. The strands were cut using a pelletizer to obtain pellets of methacrylic resin composition (MR1).

[0169] (MR2) 10 parts by mass of the methacrylic resin (M2) and 90 parts by mass of the multilayer structure polymer particles (R3) were melt-kneaded at 230°C using a twin-screw extruder and extruded into strands. The strands were cut using a pelletizer to obtain pellets of the methacrylic resin composition (MR2).

[0170] [Examples E1 to E5, Comparative Examples EC1 to EC8] (Production of Decorative Layer-Containing Film (Metal Layer-Containing Film) (M-In)) In each of the Examples and Comparative Examples, pellets of the methacrylic resin composition (MR1) were melt-kneaded at 260°C using a 50 mmφ vented single-screw extruder and extruded from a 500 mm wide T-die. The resin extruded in a molten state was sandwiched between adjacent first and second cooling rolls, wrapped around the second cooling roll, sandwiched between the second and third cooling rolls, and cooled by being wrapped around the third cooling roll. The film obtained after cooling was taken up by a pair of take-up rolls. In this way, a single-layer film (MRF) consisting of the methacrylic resin composition (MR1) having a width of 500 mm and a thickness of 75 μm was produced.

[0171] Using a vacuum deposition apparatus ("VE-2030" manufactured by Vacuum Device Co., Ltd., resistance heating type) and indium particles with a purity of 99.99% and a particle size of 1 mm, a 50 nm thick indium layer was vacuum-deposited as a decorative layer (metal layer) on the entire surface of one surface of a single-layer film (MRF) made of a methacrylic resin composition (MR1). A basket heater (alumina 92%) was used for resistance heating. The deposition conditions were a vacuum of 7 x 10 －３ The coating was performed at a pressure of 0.05 Pa and a speed of 0.8 Å / sec for 10 minutes. In this manner, a decorative layer-containing film (metal layer-containing film) (M-In) having a laminate structure of a methacrylic resin composition layer (substrate layer and protective layer) (75 μm thick) and an indium layer (decorative layer, metal layer) (50 nm thick) was obtained.

[0172] (Production of Elastomer Resin Composition) In each Example and Comparative Example, two or more resins selected from one or more thermoplastic elastomers (E), one or more polypropylene-based polymers (P), and one or more other olefin-based resins (O) were melt-kneaded at 230°C using a twin-screw extruder ("TEM-28" manufactured by Toshiba Machine Co., Ltd.) in the blending compositions shown in Table 1, and extruded into strands. The strands were cut using a pelletizer to obtain pellets (ER) or (ERC) (ER1 to ER5, ERC1 to ERC8) of the elastomer resin composition. The blend amounts in Table 1 are expressed in parts by mass.

[0173]

[0174] (Production of Decorative Film) In each Example and Comparative Example, pellets of the obtained elastomer resin composition (ER) or (ERC), pellets of the methacrylic resin composition (MR2), and pellets of the obtained elastomer resin composition (ER) or (ERC) were melt-kneaded using a single-screw extruder (G.M. ENGINEERING, "VGM25-28EX"). These molten resins were layered in a multi-manifold die, and a three-layer thermoplastic resin laminate was co-extruded from a T-die at 240°C and a flow rate of 5 kg / h. This thermoplastic resin laminate was sandwiched between adjacent first and second cooling rolls, wrapped around the second cooling roll, sandwiched between the second and third cooling rolls, and cooled by being wrapped around the third cooling roll. After cooling, the resulting film was taken up by a pair of take-up rolls. In this manner, a laminate film (E-M-E) having a width of 300 mm and a total thickness of 300 μm was obtained, which had a laminate structure of a first elastomer resin composition layer (50 μm thick, adhesive layer and impact absorbing layer), a methacrylic resin composition layer (200 μm thick, support layer or substrate layer), and a second elastomer resin composition layer (50 μm thick, adhesive layer and impact absorbing layer) (see FIG. 1 ). The first elastomer resin composition layer and the second elastomer resin composition layer have the same composition and thickness and are not particularly distinguishable from each other, and both can function as an adhesive layer and an impact absorbing layer.

[0175] Next, using a thermal lamination device (manufactured by Taisei Laminator Co., Ltd., "VAII-700 type"), a pair of heated rolls set at 110 ° C. were used to thermocompress the laminate film (E-M-E) (100 mm long x 40 mm wide x 300 μm thick) and the decorative layer-containing film (metal layer-containing film) (M-In) (100 mm long x 40 mm wide x approximately 75 μm thick). Note that the second elastomer resin composition layer (adhesive layer and impact absorbing layer) contained in the laminate film (E-M-E) and the indium layer (decorative layer, metal layer) contained in the decorative layer-containing film (metal layer-containing film) (M-In) were thermocompression bonded to each other. In this manner, a decorative film (DF) (length 100 mm × width 40 mm) having a laminate structure of methacrylic resin composition layer (base layer and protective layer) / indium layer (decorative layer, metal layer) / second elastomer resin composition layer (adhesive layer and impact absorbing layer) / methacrylic resin composition layer (support layer or base layer) / first elastomer resin composition layer (adhesive layer and impact absorbing layer) was obtained (see FIG. 2 ).

[0176] (Adherend) The following adherend was prepared: (PP-M) An injection-molded plate measuring 100 mm in length, 40 mm in width, and 3 mm in thickness, obtained by injection molding a non-polar talc-reinforced polypropylene resin (PT6N1 manufactured by Daicel Polymers, talc content: 30% by mass) at 230°C using an injection molding machine (SG-100 manufactured by Sumitomo Heavy Industries, Ltd.).

[0177] (Production of Decorative Molded Body) A vacuum / compressed air molding machine ("NGF-0406-T" manufactured by Fuse Vacuum Co., Ltd.) equipped with a fixed frame (210 mm x 297 mm, A4 size) capable of fixing the decorative film and an infrared heater capable of heating the decorative film was prepared. Using this molding machine, three-dimensional surface decorative molding was performed to cover one surface of the adherend (PP-M) with a decorative film (DF), thereby obtaining a decorated molded body (DM). First, the adherend was set on the stage of the molding machine, and the decorative film (DF) (flat at this point) was set in the fixed frame. One space in the molding machine was divided into two spaces by the decorative film (DF) fixed to the fixed frame. In this state, the two spaces were evacuated, and the decorative film was preheated using an infrared heater. The degree of vacuum was 0.5 kPa, and the heating temperature of the decorative film (DF) was 130 ° C. The adherend (PP-M) and the first elastomer resin composition layer (adhesive layer and impact absorbing layer) included in the decorative film (DF) were molded so that they were in contact with each other. The temperature of the decorative film (DF) was measured with a radiation thermometer. In this manner, a decorated molded article (DM) was obtained having a laminate structure of methacrylic resin composition layer (substrate layer and protective layer) / indium layer (decorative layer, metal layer) / second elastomer resin composition layer (adhesive layer and impact absorbing layer) / methacrylic resin composition layer (support layer or substrate layer) / first elastomer resin composition layer (adhesive layer and impact absorbing layer) / adherend (see FIG. 3 ).

[0178] [Summary of Results] Table 2 shows the evaluation results.

[0179] The elastomer resin compositions obtained in Examples E1 to E5 contained a first thermoplastic elastomer (EX) and a second thermoplastic elastomer (EY), and optionally further contained a third thermoplastic elastomer (EZ). The content of the first thermoplastic elastomer (EX) was 22 to 78 parts by mass, the content of the second thermoplastic elastomer (EY) was 12 to 77 parts by mass, and the content of the third thermoplastic elastomer (EZ) was 0 to 60 parts by mass, relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E). All of the elastomer resin compositions obtained in these Examples had a ΔG' ２－１ is -0.18 to 0.00% / °C, and ΔG'３－１ In all of these Examples, it was possible to obtain an elastomer resin composition that is suitable as a pressure-sensitive adhesive layer for a decorative film, can suppress the occurrence of drawdown and shock lines in the decoration process, and can obtain a decorated molded article with good appearance.

[0180] The elastomer resin compositions obtained in Comparative Examples EC1, EC2, and EC5 contained a first thermoplastic elastomer (EX) but did not contain a second thermoplastic elastomer (EY) or a third thermoplastic elastomer (EZ), and the content of the first thermoplastic elastomer (EX) was 100 parts by mass per 100 parts by mass of the total amount of the thermoplastic elastomer (E). The elastomer resin compositions obtained in Comparative Examples EC3, EC4, and EC6 contained a first thermoplastic elastomer (EX) and a second thermoplastic elastomer (EY) but did not contain a third thermoplastic elastomer (EZ), and the content of the first thermoplastic elastomer (EX) was more than 78 parts by mass per 100 parts by mass of the total amount of the thermoplastic elastomer (E). The elastomer resin composition obtained in Comparative Example EC7 contained a first thermoplastic elastomer (EX), a second thermoplastic elastomer (EY), and a third thermoplastic elastomer (EZ), and the content of the second thermoplastic elastomer (EY) was less than 12 parts by mass per 100 parts by mass of the total amount of the thermoplastic elastomer (E). The elastomer resin composition obtained in Comparative Example EC8 contained a first thermoplastic elastomer (EX), a second thermoplastic elastomer (EY), and a third thermoplastic elastomer (EZ), and the content of the first thermoplastic elastomer (EX) was less than 22 parts by mass per 100 parts by mass of the total amount of the thermoplastic elastomer (E). All of the elastomer resin compositions obtained in these Comparative Examples had a ΔG' ２－１ is less than −0.18% / ° C., and ΔG′ ３－１ The value was less than −0.18% / ° C. In all of these comparative examples, the drawdown phenomenon and the occurrence of shock lines were observed during the decorating process.

[0181] The present invention is not limited to the above-described embodiments and examples, and appropriate design changes are possible without departing from the spirit of the present invention.

[0182] This application claims priority based on Japanese Patent Application No. 2024-114507, filed July 18, 2024, the disclosure of which is incorporated herein by reference in its entirety.

[0183] REFERENCE SIGNS LIST 1 Film 2 Metal layer or decorative layer-containing film 3 Decorative film 4 Decorated molded body 11A, 11B Elastomer resin composition layer 12 Support layer 21 Base film 22 Metal layer or decorative layer 30 Adherend

Claims

1. An elastomer resin composition comprising one or more thermoplastic elastomers (E) selected from the group consisting of block copolymers having a polymer block (a) containing an aromatic vinyl compound unit and a polymer block (b) containing a conjugated diene compound unit, and hydrogenated products of the block copolymers, wherein the peak temperature of the loss tangent (tanδ) of the elastomer resin composition is defined as Tge [°C], and Tge + 50°C is defined as T １ [°C], Tge + 120°C is T ２ [°C], T １ The storage modulus of the elastomer resin composition at [°C] is G' １ [Pa], T ２ The storage modulus of the elastomer resin composition at [°C] is G' ２ [Pa], ΔG′ defined by the following formula (1) ２－１ The elastomer resin composition has a ΔG' of -0.18 to 0.00% / °C. ２－１ [% / ℃]=[100×{Log(G' ２ ) -Log(G' １ ) / (T ２ -T １ ) )] / Log(G' １ ) ... (1) 2. The elastomer resin composition according to claim 1, wherein the conjugated diene compound units contained in polymer block (b) are one or more units selected from the group consisting of isoprene units and butadiene units.

3. The elastomer resin composition according to claim 1, wherein the thermoplastic elastomer (E) comprises one or more thermoplastic elastomers (EY) selected from the group consisting of block copolymers 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 mol % or more, and hydrogenated products of said block copolymers.

4. The elastomer resin composition according to claim 3, wherein the thermoplastic elastomer (E) comprises: one or more first thermoplastic elastomers (EX) selected from the group consisting of block copolymers 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%, and hydrogenated versions of said block copolymers; and one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers 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 mol% or more, and hydrogenated versions of said block copolymers.

5. The elastomer resin composition according to claim 4, wherein the content of the first thermoplastic elastomer (EX) is 22 to 78 parts by mass and the content of the second thermoplastic elastomer (EY) is 12 to 77 parts by mass, relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E).

6. The thermoplastic elastomer (E) comprises: one or more first thermoplastic elastomers (EX) selected from the group consisting of block copolymers having a polymer block (xa) containing a styrene unit and a polymer block (xb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is less than 40 mol%, and hydrogenated versions of the block copolymers; and one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing a styrene unit and a polymer block (yb) containing 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 the block copolymers.

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

7. The elastomer resin composition according to claim 6, wherein the content of the first thermoplastic elastomer (EX) is 22 to 78 parts by mass, the content of the second thermoplastic elastomer (EY) is 12 to 77 parts by mass, and the content of the third thermoplastic elastomer (EZ) is 1 to 60 parts by mass, relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E).

8. The elastomer resin composition according to claim 1, further comprising one or more polypropylene polymers (P).

9. The elastomer resin composition according to claim 8, wherein the total amount of the polypropylene polymer (P) is 1 to 35 parts by mass per 100 parts by mass of the thermoplastic elastomer (E).

10. The elastomer resin composition according to claim 8, wherein the polypropylene polymer (P) comprises one or more first polypropylene polymers (PX) having no polar group and one or more second polypropylene polymers (PY) having a polar group.

11. A laminated film comprising an elastomer resin composition layer made of the elastomer resin composition according to any one of claims 1 to 10, and a support layer supporting the elastomer resin composition layer.

12. The peak temperature of the loss tangent (tanδ) of the support layer is Tgs [°C], and Tgs + 25°C is T ３ [℃] 、 T ３ The storage modulus of the elastomer resin composition at [°C] is G' ３ [Pa], ΔG′ defined by the following formula (2) ３－１ The laminated film according to claim 11, wherein ΔG' is -0.18 to 0.00% / °C. ３－１ [% / ℃]=[100×{Log(G' ３ ) -Log(G' １ ) / (T ３ -T １ ) )] / Log(G' １ ) ... (2) 13. G' ３ is 1.8 x 10 ５ ~50.0 x 10 ５ The laminated film according to claim 12, wherein the viscosity is 100 MPa.

14. The laminated film according to claim 11, wherein the support layer is a layer containing a (meth)acrylic resin.

15. A molded article having the laminate film according to claim 11 laminated on at least a portion of the surface of an adherend.

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