Elastomer resin composition, film, laminate, and molded body

Abstract

The present disclosure provides an elastomer resin composition having good process passability, film forming properties, adhesiveness to various materials, and chipping resistance. The elastomer resin composition of the present disclosure comprises thermoplastic elastomers (EX)-(EZ) and polypropylene-based polymers (PX) and (PY). Thermoplastic elastomer (EX) has a St unit-containing block and a conjugated diene compound unit-containing block in which the total amount of 1,2-linkage and 3,4-linkage is less than 40 mol%. Thermoplastic elastomer (EY) has a St unit-containing block and a conjugated diene compound unit-containing block in which the total amount of 1,2-linkage and 3,4-linkage is 40 mol% or more. Thermoplastic elastomer (EZ) has an αMSt unit-containing block and a conjugated diene compound unit-containing block in which the total amount of 1,2-linkage and 3,4-linkage is 40 mol% or more. Polypropylene-based polymer (PX) has no polar group and has a melt tension of 2.5 × 10-2 N or more. Polypropylene-based polymer (PY) has a polar group and has a melting point of 130°C or less.

Description

Elastomer resin composition, film, laminate, and molded article

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

[0002] For purposes such as surface protection and decoration, a coating may be formed by applying paint to the surface of a vehicle exterior member by a spray coating method or the like and drying the paint. In coatings for such applications, partial damage and / or defects may occur due to the impact of small particles such as pebbles and snow-melting salt, which may partially expose the underlying surface and prevent the desired function from being achieved. In this specification, such damage and defects are collectively referred to as "chipping," and the resistance to such damage and defects is referred to as "chipping resistance."

[0003] Among vehicle exterior components, bumpers are particularly prone to chipping, and their coatings require higher chipping resistance. Conventionally, polypropylene-based polymers have been widely used as materials for vehicle bumpers due to their properties such as impact resistance, low specific gravity, and low material costs. However, polypropylene-based polymers are generally nonpolar, and they tend to repel paint, making it difficult to form a coating with good adhesion thereon. A decrease in the adhesion of the coating leads to a decrease in chipping resistance, which is undesirable. Furthermore, methods using paints require long and large drying ovens and large amounts of energy, resulting in high costs.

[0004] Decorative films have been proposed as an alternative material to paints that solves the above-mentioned problems. Patent Documents 1 to 3 are examples of related art to the present disclosure. Patent Documents 1 and 2 disclose elastomer resin compositions that contain a thermoplastic elastomer, which is a block copolymer having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit, or a hydrogenated product thereof, and a polar group-containing polypropylene polymer (claim 1 of Patent Document 1, claim 1 of Patent Document 2).

[0005] Patent Document 3 discloses an elastomer resin composition containing a thermoplastic elastomer that is a block copolymer having a polymer block containing an aromatic vinyl compound unit and a polymer block containing a conjugated diene compound unit, or a hydrogenated product thereof, and a polypropylene-based polymer having specific uniaxial extensional viscosity characteristics, and more preferably a polar group-containing polypropylene-based polymer (claims 1, 4, 5, paragraph 0033).

[0006] International Publication No. WO 2013 / 105392 International Publication No. WO 2016 / 031550 International Publication No. WO 2020 / 179923

[0007] The elastomer resin compositions disclosed in Patent Documents 1 and 2 have good adhesion to various materials such as metals and resins, as well as good flexibility. The elastomer resin composition disclosed in Patent Document 1 also has good insert moldability. However, when extruded into a film, the elastomer resin compositions disclosed in these documents may suffer from necking, where the film width is narrower than the die width of a T-die, due to insufficient melt tension. The elastomer resin composition disclosed in Patent Document 3 can suppress necking during extrusion molding without sacrificing adhesion by adding a polypropylene-based polymer with specific uniaxial elongational viscosity characteristics (e.g., a polypropylene-based polymer with a long-chain branched structure) (paragraph 0010). However, research by the present inventors has revealed that the elastomer resin compositions disclosed in Patent Documents 1 to 3 have a relatively high tackiness, making them difficult to separate from cooling rolls or conveying rolls during the film-forming process, resulting in poor processability. Patent Documents 1 to 3 also do not describe chipping resistance or disclose compositions suitable for decorative film materials.

[0008] The present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide an elastomer resin composition that has good processability, film-forming ability, adhesion to various materials such as metals and resins, and chipping resistance.

[0009] The present disclosure provides the following films, laminates, and molded articles [1] to

[16] . [1] An elastomer resin composition comprising a thermoplastic elastomer (E) and a polypropylene-based polymer (P) and satisfying the following conditions 1 to 3: (Condition 1) 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; 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; and 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. (Condition 2) The polypropylene-based polymer (P) has no polar group and has a melt tension of 2.5 × 10 measured under conditions of 230°C and a take-up speed of 4.0 m / min. －２ and a second polypropylene polymer (PY) having a polar group and a melting point of 130° C. or lower. (Condition 3) With respect to 100 parts by mass of the total amount of the thermoplastic elastomer (E), the content of the first thermoplastic elastomer (EX) is 15 to 55 parts by mass, the content of the second thermoplastic elastomer (EY) is 25 to 65 parts by mass, the content of the third thermoplastic elastomer (EZ) is 15 to 35 parts by mass, the content of the first polypropylene polymer (PX) is 3 to 15 parts by mass, and the content of the second polypropylene polymer (PY) is 7.5 to 20 parts by mass.

[0010] [2] The first polypropylene polymer (PX) has a melt tension of 50×10 measured at 230° C. and a take-up speed of 4.0 m / min.－２ [3] The elastomer resin composition of [1] or [2], wherein the second polypropylene-based polymer (PY) has a melting point of 100°C or higher. [4] The elastomer resin composition of any of [1] to [3], further comprising multiple antioxidants (AO) including a phenol-based antioxidant (AO-F) and a phosphorus-based antioxidant (AO-P), wherein the content of the phenol-based antioxidant (AO-F) is 0.10 to 5.00 parts by mass and the content of the phosphorus-based antioxidant (AO-P) is 0.01 to 5.00 parts by mass per 100 parts by mass of the total of the thermoplastic elastomer (E) and the polypropylene-based polymer (P).

[0011] [5] A film comprising a layer made of the elastomer resin composition of any one of [1] to [4]. [6] The film of [5] further comprising a (meth)acrylic resin-containing layer. [7] The film of [6], wherein the (meth)acrylic resin-containing layer contains a (meth)acrylic resin and one or more rubber components selected from the group consisting of acrylic rubber particles and acrylic block copolymers. [8] The film of any one of [5] to [7] further comprising a metal layer. [9] The film of any one of [5] to [7] further comprising a decorative layer.

[0012]

[10] A laminate comprising a layer made of the elastomer resin composition of any one of [1] to [4].

[11] A molded article comprising a layer or member made of the elastomer resin composition of any one of [1] to [4].

[12] The molded article of

[11] , having, on at least a portion of the surface of an adherend, a layer made of the elastomer resin composition and a metal layer, in that order.

[13] The molded article of

[12] , further having, on the metal layer, a (meth)acrylic resin-containing layer.

[14] The molded article of

[11] , having, on at least a portion of the surface of an adherend, a layer made of the elastomer resin composition and a decorative layer, in that order.

[15] The molded article of

[14] , further having, on the decorative layer, a (meth)acrylic resin-containing layer.

[16] The molded article of

[13] or

[15] , wherein the (meth)acrylic resin-containing layer contains a (meth)acrylic resin and one or more rubber components selected from the group consisting of acrylic rubber particles and acrylic block copolymers.

[0013] According to the present disclosure, it is possible to provide an elastomer resin composition that has good processability, film-forming property, adhesion to various materials such as metals and resins, and chipping resistance.

[0014] It is a schematic cross-sectional view showing a film of one embodiment according to the present invention. It is a schematic cross-sectional view showing an example of a metal layer-containing film. It is a schematic cross-sectional view showing a decorative film of one embodiment according to the present invention. It is a schematic cross-sectional view showing a decorated molded body of one embodiment according to the present invention.

[0015] 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. In this specification, "adhesive" is a general term for pressure-sensitive adhesive and adhesive.

[0016] 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).

[0017] [Elastomer Resin Composition] The elastomer resin composition of the present disclosure contains a thermoplastic elastomer (E) and a polypropylene-based polymer (P), and satisfies the following conditions 1 to 3.

[0018] (Condition 1) 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 (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 versions of the block copolymers; one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing styrene (St) units and a polymer block (yb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol% or more, and hydrogenated versions of the block copolymers; The thermoplastic elastomer comprises 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.

[0019] (Condition 2) The polypropylene polymer (P) has no polar group and has a melt tension of 2.5×10 or less when measured at 230° C. and a take-up speed of 4.0 m / min. －２ The polymer comprises a first polypropylene polymer (PX) having a molecular weight of N or more, and a second polypropylene polymer (PY) having a polar group and a melting point of 130° C. or less.

[0020] (Condition 3) With respect to 100 parts by mass of the total amount of the thermoplastic elastomer (E), the content of the first thermoplastic elastomer (EX) is 15 to 55 parts by mass, the content of the second thermoplastic elastomer (EY) is 25 to 65 parts by mass, the content of the third thermoplastic elastomer (EZ) is 15 to 35 parts by mass, the content of the first polypropylene-based polymer (PX) is 3 to 15 parts by mass, and the content of the second polypropylene-based polymer (PY) is 7.5 to 20 parts by mass.

[0021] (First Thermoplastic Elastomer (EX)) The elastomer resin composition of the present disclosure comprises one or more first thermoplastic elastomers (EX) selected from the group consisting of block copolymers having a polymer block (xa) containing styrene (St) units and a polymer block (xb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is less than 40 mol%, and hydrogenated products of the block copolymers. The first thermoplastic elastomer (EX) is one of the matrix components of the elastomer resin composition and can impart excellent flexibility and impact resistance to the elastomer resin composition. By including 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%, the first thermoplastic elastomer (EX) can impart excellent chipping resistance to the elastomer resin composition.

[0022] <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.

[0023] 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.

[0024] <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%.

[0025] 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.

[0026] 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%.

[0027] 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%.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] From the viewpoint of improving heat resistance and weather resistance, the first thermoplastic elastomer (EX) is preferably a hydrogenated block copolymer in which at least a portion of the polymer block (xb) containing conjugated diene compound units has been 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%, 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 products may be used as the first thermoplastic elastomer (EX).

[0033] 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.

[0034] 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.

[0035] Since the effects of the first thermoplastic elastomer (EX) (such as providing chipping resistance) are effectively exhibited, the content of the first thermoplastic elastomer (EX) is 15 to 55 parts by mass per 100 parts by mass of the total amount of the thermoplastic elastomer (E). The lower limit is more preferably 20 parts by mass, and particularly preferably 35 parts by mass. The upper limit is more preferably 50 parts by mass, and particularly preferably 45 parts by mass.

[0036] (Second Thermoplastic Elastomer (EY)) The elastomer resin composition of the present disclosure comprises one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing styrene (St) units and a polymer block (yb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol % or more, and hydrogenated products of the block copolymers. The second thermoplastic elastomer (EY) 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.

[0037] <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).

[0038] 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.

[0039] <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.

[0040] 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%.

[0041] 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.

[0042] 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.

[0043] 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. The lower limit is more preferably 97% by mass, particularly preferably 98% by mass, and most preferably 99% by mass.

[0044] 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%.

[0045] 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 viewpoint 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). The content of the second thermoplastic elastomer (EY) is 25 to 65 parts by mass per 100 parts by mass of the total amount of the thermoplastic elastomer (E), so that the functional effects of the second thermoplastic elastomer (EY) (such as imparting excellent adhesion to non-polar resins) can be effectively exhibited. The lower limit is more preferably 30 parts by mass, particularly preferably 35 parts by mass, and the upper limit is more preferably 60 parts by mass, particularly preferably 55 parts by mass, and most preferably 50 parts by mass.

[0046] (Third Thermoplastic Elastomer (EZ)) The elastomer resin composition of the present disclosure comprises one or more third thermoplastic elastomers (EZ) selected from the group consisting of block copolymers having a polymer block (za) containing α-methylstyrene (αMSt) units and a polymer block (zb) containing conjugated diene compound units in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol % or more, and hydrogenated products of the block copolymers. The third thermoplastic elastomer (EZ) 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.

[0047] <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).

[0048] 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.

[0049] <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).

[0050] 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%.

[0051] 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%.

[0052] 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.

[0053] 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.

[0054] 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%.

[0055] 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).

[0056] Since the effects of the third thermoplastic elastomer (EZ) (imparting rigidity, excellent adhesion to polar resins, excellent adhesion to non-polar resins, etc.) are effectively exhibited, the content of the third thermoplastic elastomer (EZ) is 15 to 35 parts by mass per 100 parts by mass of the total amount of the thermoplastic elastomer (E). The lower limit is more preferably 17 parts by mass, particularly preferably 18 parts by mass, and most preferably 19 parts by mass. The upper limit is more preferably 30 parts by mass, particularly preferably 27 parts by mass, and most preferably 25 parts by mass.

[0057] (First Polypropylene Polymer (PX)) The elastomer resin composition of the present disclosure contains one or more first polypropylene polymers (PX) (non-polar polypropylene polymers) that do not have a polar group. The first polypropylene polymer (PX) tends to have a higher melt tension as the melt flow rate (MFR) decreases. The first polypropylene polymer (PX) has a melt tension of 2.5 × 10 measured under conditions of 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 preferably 50×10 －２ N, more preferably 40×10 －２ N, particularly preferably 30 × 10 －２ It's N.

[0058] The elastomer resin composition of the present disclosure also contains a first polypropylene-based polymer (PX) having a melt tension equal to or greater than the above-mentioned lower limit, thereby providing an appropriate tackiness and good slipperiness on metal. Therefore, the elastomer resin composition of the present disclosure can be smoothly separated from the cooling roll and the conveying roll during the film-forming process, resulting in good processability. The elastomer resin composition of the present disclosure contains a first polypropylene-based polymer (PX) having a melt tension equal to or greater than the above-mentioned lower limit, thereby providing good film-forming properties in extrusion molding and the like, and good film thickness stability and other properties of the film obtained by extrusion molding and the like.

[0059] 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.

[0060] The first polypropylene-based polymer (PX) is a homopolymer or copolymer containing propylene units and, if necessary, one or more other monomer units not having a polar group. Examples of such 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. The proportion of propylene units relative to all structural units of the first polypropylene-based polymer (PX) is not particularly limited, but is preferably 55 to 100 mol%. The lower limit is more preferably 65 mol%, even more preferably 75 mol%, particularly preferably 85 mol%, and most preferably 95 mol%. The proportion of other monomer units other than propylene units relative to all structural units of the first polypropylene-based 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%.

[0061] 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.

[0062] 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.

[0063] 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 3 to 15 parts by mass per 100 parts by mass of the thermoplastic elastomer (E). The lower limit is preferably 5 parts by mass, more preferably 6 parts by mass, and particularly preferably 7 parts by mass. The upper limit is preferably 12 parts by mass, more preferably 10 parts by mass, and particularly 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.

[0064] (Second Polypropylene Polymer (PY)) The elastomer resin composition of the present disclosure contains one or more second polypropylene polymers (PY) having a polar group (polar group-containing polypropylene polymer). The second polypropylene polymer (PY) can impart excellent adhesion to metals to the elastomer resin composition.

[0065] Examples of polar groups include polar atoms such as oxygen, nitrogen, and sulfur atoms; (meth)acryloyloxy groups; hydroxyl groups; amide groups; carboxyl groups; acid anhydride groups; and halogen atoms such as chlorine atoms. A first method for producing a polar-group-containing polypropylene-based 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-based polymer includes graft copolymerizing a polar-group-containing monomer onto a polypropylene-based polymer (non-polar polypropylene-based polymer) that contains propylene units and, if necessary, one or more other monomer units but does not have polar groups. Among the above methods, graft copolymerization is preferred. The polar-group-containing polypropylene-based polymer produced by the first or second production method includes propylene units and polar-group-containing monomer units, and may further include, if necessary, one or more other monomer units.

[0066] 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.

[0067] 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%.

[0068] 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, polypropylene polymers obtained by graft copolymerizing a polypropylene polymer having no polar group (non-polar polypropylene polymer) with a carboxylic acid (anhydride) to modify the polypropylene polymer (also referred to as a (carboxylic acid anhydride)-modified polypropylene polymer) are preferred. Among them, maleic acid (anhydride)-modified polypropylene polymers are more preferred.

[0069] 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.

[0070] 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 (non-polar polypropylene-based polymer) is oxidized or halogenated (e.g., chlorinated) by a known method.

[0071] 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.

[0072] From the viewpoint of achieving both excellent adhesion to metals and heat resistance, the content of the second polypropylene polymer (PY) is 7.5 to 20 parts by mass per 100 parts by mass of the thermoplastic elastomer (E). The lower limit is preferably 8 parts by mass, more preferably 9 parts by mass, and particularly preferably 10 parts by mass. The upper limit is preferably 17.5 parts by mass, and more 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.

[0073] (Optional Component) <Antioxidant (AO)> The elastomer resin composition of the present disclosure may contain one or more antioxidants (AO). Examples of antioxidants (AO) include phenolic antioxidants, phosphorus-based antioxidants, lactone-based antioxidants, and hydroxyl-based antioxidants. The elastomer resin composition of the present disclosure preferably contains multiple antioxidants (AO) including a phenolic antioxidant (AO-F) and a phosphorus-based antioxidant (AO-P). Generally, thermoplastic elastomers and polypropylene-based polymers containing aromatic vinyl compound units and conjugated diene compound units have poor thermal stability, and prolonged heat-melting times can lead to oxidative degradation and even decomposition and / or crosslinking. Therefore, prolonged residence times in a heat-molten state during production, molding, or other processes of elastomer resin compositions containing these resins can lead to thermal decomposition of the thermoplastic elastomer and / or polypropylene-based polymer, resulting in an increase in the amount of residual monomer in the resin composition and a decrease in heat resistance. Furthermore, foreign matter such as oxidized and deteriorated products of the thermoplastic elastomer and / or polypropylene polymer may be generated, which may result in poor appearance.

[0074] Generally, in the mechanism of oxidative degradation of a resin composition, first, one C-H bond in the carbon chain is decomposed by heat to generate a radical, which immediately reacts with oxygen to become a peroxy radical (ROO.). This peroxy radical abstracts an H from a nearby carbon chain, generating a new radical and a peroxide. Oxidation by this radical chain reaction is also called primary oxidation. Furthermore, new radicals are generated by the self-cleavage of the peroxide produced in the above reaction, and the radical chain reaction progresses. Oxidation by this radical chain reaction is also called secondary oxidation.

[0075] The inventors' research has revealed the following: Phenol-based antioxidants (AO-F), acting as primary antioxidants (also called primary oxidation inhibitors), capture peroxy radicals, converting them into peroxides, which themselves become phenoxy radicals and can then capture other peroxy radicals. However, unstable peroxides can re-convert into peroxy radicals when exposed to heat, potentially causing a radical chain reaction in the presence of oxygen. Phosphorus-based antioxidants (AO-P), acting as secondary antioxidants (also called secondary oxidation inhibitors), can decompose unstable peroxides into stable alcohols.

[0076] The combined use of an appropriate amount of a phenolic antioxidant (AO-F) as a primary antioxidant and an appropriate amount of a phosphorus-based antioxidant (AO-P) as a secondary antioxidant can effectively improve the thermal stability of the thermoplastic elastomer (E) and the polypropylene-based polymer (P) and effectively suppress oxidative degradation and decomposition during prolonged heat-melting. Therefore, the technology of the present disclosure, which uses these antioxidants (AO) in combination, can effectively improve the thermal stability and thermal decomposition resistance of the elastomer resin composition. Furthermore, the technology of the present disclosure, which uses these antioxidants (AO) in combination, can suppress the generation of foreign matter, such as oxidative degradation products, of the thermoplastic elastomer and / or the polypropylene-based polymer during prolonged heat-melting, thereby suppressing the occurrence of poor appearance.

[0077] As the phenolic antioxidant (AO-F), one or more known antioxidants can be used. For example, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, pentaerythritol tetroxide, and the like can be used. Examples of suitable phenolic antioxidants include rachis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[3-[3-(tert-butyl)-4-hydroxy-5-methylphenyl]propanoic acid]2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl), and 1,3,5-trimethyl-2,4,6-tris(3',5'-di-t-butyl-4'-hydroxybenzyl). One or more commercially available products can be used as the phenolic antioxidant (AO-F). The phenolic antioxidant (AO-F) preferably contains a hindered phenolic antioxidant. The phenolic antioxidant (AO-F) preferably contains a phenolic antioxidant having a quaternary carbon and a molecular weight of 250 to 1500. The molecular weight is more preferably 700 to 1200. The phenol-based antioxidant (AO-F) preferably contains a hindered phenol-based antioxidant having a quaternary carbon and a molecular weight of 250 to 1,500.

[0078] In the elastomer resin composition of the present disclosure, the content of the phenolic antioxidant (AO-F) (total amount if multiple types are used, unless otherwise specified) is preferably 0.10 to 5.00 parts by mass relative to 100 parts by mass of the total of the thermoplastic elastomer (E) and the polypropylene polymer (P). The lower limit is more preferably 0.15 parts by mass, and particularly preferably 0.20 parts by mass. The upper limit is more preferably 4.00 parts by mass, even more preferably 3.00 parts by mass, particularly preferably 2.00 parts by mass, and most preferably 1.50 parts by mass.

[0079] As the phosphorus-based antioxidant (AO-P), one or more known antioxidants can be used. For example, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,4,8,10-tetra-tert-butyl-6-[(2-ethylhexan-1-yl)oxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphocin, tris(2,4-di-tert-butylphenyl)phosphite, trisnonylphenylphosphite, diphenylisodecylphosphite, and triphenylphosphite biphenyl-4,4′-diylbis[bis(2,4-di-tert-butylphenoxy)phosphine], and the like. One or more commercially available products can be used as the phosphorus-based antioxidant (AO-P). A commercially available multi-component phosphorus-based antioxidant containing multiple types of phosphorus-based antioxidants may also be used as the phosphorus-based antioxidant (AO-P). The phosphorus-based antioxidant (AO-P) preferably contains a phosphorus-based antioxidant having a spiro structure or a biphenyl structure and a molecular weight of 500 to 1,500. The molecular weight is more preferably 500 to 1,200.

[0080] In the elastomer resin composition of the present disclosure, the content of the phosphorus-based antioxidant (AO-P) (total amount when multiple types are used unless otherwise specified) is preferably 0.01 to 5.00 parts by mass relative to 100 parts by mass of the total of the thermoplastic elastomer (E) and the polypropylene-based polymer (P). The lower limit is more preferably 0.05 parts by mass, particularly preferably 0.10 parts by mass, and most preferably 0.15 parts by mass. The upper limit is more preferably 4.00 parts by mass, even more preferably 3.00 parts by mass, particularly preferably 2.00 parts by mass, and most preferably 1.50 parts by mass.

[0081] The elastomer resin composition of the present disclosure, which contains a phenolic antioxidant (AO-F) and a phosphorus-based antioxidant (AO-P), can have excellent thermal decomposition resistance. Thermal decomposition resistance can be measured, for example, by the time it takes for a weight loss rate to reach 5% (also referred to as the 5% weight loss time) when the composition is heated to 240°C in an air atmosphere and maintained at that temperature, based on the time and weight at which the composition reaches 240°C. The 5% weight loss time can be measured using a thermogravimetric analyzer. The 5% weight loss time of the elastomer resin composition of the present disclosure, which contains a phenolic antioxidant (AO-F) and a phosphorus-based antioxidant (AO-P), can be 10 minutes or more, 15 minutes or more, 20 minutes or more, or 25 minutes or more.

[0082] <Other Polymers> The elastomer resin composition of the present disclosure may contain one or more other polymers other than those described above. Other polymers include polyethylene, polypropylene polymers (PX), polypropylene polymers other than (PY), polyolefin resins such as 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 Examples of the thermoplastic resin include polyamide resins such as 66 and polyamide elastomers; polycarbonate 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 ionomer; thermosetting resins such as epoxy resin, phenol resin, melamine resin, and silicone 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 rubbers such as IR, EPR, and EPDM.

[0083] <Other Additives> The elastomer resin composition of the present disclosure may contain one or more additives other than the antioxidant (AO), as necessary. Examples of the additives include a tackifying resin, a softener, a lubricant, a heat stabilizer, a heat degradation inhibitor, a light stabilizer, a polymer processing aid, a colorant such as a pigment or a coloring matter, a flame retardant, an antistatic agent, a matting agent, a silicone oil, an antiblocking agent, an ultraviolet absorber, a release agent, a foaming agent, an antifoaming agent, an antibacterial agent, an antifungal agent, and a fragrance.

[0084] 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.

[0085] The softening agent may be any softening agent commonly used for rubber or plastics, such as paraffinic, naphthenic, and aromatic process oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oil; mineral oil; ethylene and α-olefin oligomers; paraffin wax; liquid paraffin; polybutene; low-molecular-weight polybutadiene; and low-molecular-weight polyisoprene.

[0086] The timing of addition of other polymers and additives that can be contained in the elastomer resin composition of the present disclosure may be during or after the production of one or more resins among the thermoplastic elastomers (EX) to (EZ) and the polypropylene-based polymers (PX) and (PY), or may be during the production of the elastomer resin composition.

[0087] As described above, according to the present disclosure, it is possible to provide an elastomer resin composition that has good processability, film-forming property, adhesion to various materials such as metals and resins, and chipping resistance.

[0088] [Method for Producing Elastomer Resin Composition] The method for producing the elastomer resin composition of the present disclosure is not particularly limited. From the viewpoints of dispersibility and compatibility of each component, a method of melt-kneading the thermoplastic elastomers (EX) to (EZ), the polypropylene-based polymers (PX) and (PY), and, if necessary, one or more optional components is preferred. Melt-kneading can be performed using known mixing or kneading devices such as an extruder, a kneader-ruder, a mixing roll, or a Banbury mixer. From the viewpoints of kneadability and compatibility, extruders such as single-screw extruders, twin-screw extruders, and multi-screw extruders are preferred, with twin-screw extruders being more preferred. The melt-kneading temperature should be equal to or higher than the melting temperature of the thermoplastic elastomers (EX) to (EZ) and the polypropylene-based polymers (PX) and (PY), 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.

[0089] [Molded Article] The molded article of the present disclosure includes a layer or member made of the elastomer resin composition of the present disclosure, and may be a layer or member made entirely of the elastomer resin composition of the present disclosure. Examples of molding methods include solution casting, extrusion molding, compression molding (also known as press molding), injection molding, inflation molding, blow molding, calendar molding, solution casting, vacuum molding, and pressure molding. Examples of molded articles include single-layer or multilayer planar objects such as films, sheets, and plates; fibers, pipes, tubes, rods; particles; and any three-dimensional structures. The molded article may also be a laminate or composite containing a layer or member made of the elastomer resin composition of the present disclosure and a layer or member made of other resins or various materials other than resins. The molded article obtained by a known molding method may, as needed, be subjected to surface treatments such as printing, painting, plating, vapor deposition, and sputtering; or shaping processes such as curving, bending, and cutting (also known as secondary molding).

[0090] [Film] The film of the present disclosure includes a layer (also referred to as an elastomer resin composition layer) made of the elastomer resin composition of the present disclosure, and may be a layer (elastomer resin composition layer) made entirely of the elastomer resin composition of the present disclosure. The film of the present disclosure is a single-layer film or a laminate film including one or more layers made of the elastomer resin composition of the present disclosure. Unless otherwise specified, in this specification, an "elastomer resin composition layer" refers to a resin layer made of the elastomer resin composition of the present disclosure. The layer (elastomer resin composition layer) made of the elastomer resin composition of the present disclosure can function as an adhesive layer, an impact absorbing layer, etc. In a laminate film, at least one elastomer resin composition layer is preferably disposed as the outermost layer. The film of the present disclosure having the single-layer structure or laminate structure described above can be used as an adhesive film, an impact absorbing film, etc.

[0091] Examples of methods for producing the film of the present disclosure include solution casting, extrusion, compression molding (press molding), inflation molding, blow molding, calendar molding, and melt casting, with extrusion and compression molding (press molding) being preferred. Among these, extrusion is preferred, with the T-die method being more preferred.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] The film of the present disclosure may be a coextruded film containing two or more layers made of the elastomer resin composition of the present disclosure, or a coextruded film containing a layer made of the elastomer resin composition of the present disclosure and another resin layer. In coextrusion, the constituent resins (compositions) of each layer are melt-kneaded using an extruder and coextruded in the desired laminate 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.

[0096] 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.

[0097] In the film of the present disclosure, a layer (elastomer resin composition layer) made of the elastomer resin composition of the present disclosure can function as a pressure-sensitive adhesive layer, and the film of the present disclosure can be a pressure-sensitive adhesive film. The film of the present disclosure can be sandwiched between a pair of release films, as needed, during or after film formation. Examples of release films include substrates made of thermoplastic resins, paper, metal foil, and combinations thereof, with at least one surface thereof subjected 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; poly4-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.

[0098] [Composite Film, Decorative Film] In one aspect, the film of the present disclosure can be a composite film having one or more layers (elastomer resin composition layers) made of the elastomer resin composition of the present disclosure and one or more metal layers. The metal layers can function as decorative layers. In another aspect, the film of the present disclosure can be a decorative film having one or more layers (elastomer resin composition layers) made of the elastomer resin composition of the present disclosure and one or more decorative layers. Examples of decorative layers include metal layers, colored layers, printed layers, nonwoven fabrics, 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 thickness of the decorative layer is not particularly limited, but from the standpoints of moldability, economy, etc., it is preferably thinner than the layer (elastomer resin composition layer) made of the elastomer resin composition of the present disclosure.

[0099] As described above, a layer made of the elastomer resin composition of the present disclosure (elastomer resin composition layer) can function as an adhesive layer, an impact absorbing layer, etc. In the composite film and decorative film of the present disclosure, at least one elastomer resin composition layer is preferably disposed as the outermost layer.

[0100] Because a layer made of the elastomer resin composition of the present disclosure (elastomer resin composition layer) has good adhesion to metals, the composite film and decorative film of the present disclosure can include a metal layer with good adhesive strength. Examples of metals include Al, Si, Ti, Cr, Ni, Zn, Ga, Y, Zr, Nb, In, Sn, Hf, Ta, W, alloys thereof, and combinations thereof. Because a layer made of the elastomer resin composition of the present disclosure (elastomer resin composition layer) has good adhesion to various materials, the decorative film of the present disclosure can include a decorative layer made of any material.

[0101] The film of the present disclosure may include one or more resin layers other than the layer made of the elastomer resin composition of the present disclosure (elastomer resin composition layer), such as a substrate layer, a decorative layer, a protective layer for a metal layer, or a protective layer for a decorative layer.

[0102] Examples of the constituent resin of the other resin 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 copolymer (AS resin) and acrylonitrile-butadiene-styrene (ABS) resin; polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate; polyamide resins such as nylon 6, nylon 66, and polyamide elastomer; polycarbonate resins; thermoplastic resins such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer; polyacetal; polyurethane; and combinations thereof.

[0103] 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 other resin 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.

[0104] The other resin 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.

[0105] The composite film of the present disclosure may have another resin layer, such as a (meth)acrylic resin-containing layer, on the metal layer as a substrate layer and / or protective layer for the metal layer. The decorative film of the present disclosure may have another resin layer, such as a (meth)acrylic resin-containing layer, on the decorative layer as a substrate layer and / or protective layer for the decorative layer.

[0106] The other resin layer may be a colored or uncolored layer. Examples of coloring methods for resin films made of other resin layer materials include a method in which pigments and / or dyes are incorporated into the resin before film formation; and a dyeing method in which the resin film is immersed in a dye dispersion to color it. The resin film made of the other resin layer material may have a printed layer on at least one surface, which may include a pattern such as a picture, letter, or graphic, a color, or a combination thereof. The resin film made of the other resin layer material may have a metal layer on at least one surface. The metal layer may be made of metal foil. The metal layer may also be formed on the resin film by a gas-phase method such as vacuum deposition, sputtering, ion plating (IP), laser ablation, thermal chemical vapor deposition, chemical vapor deposition (CVD), or plasma-enhanced chemical vapor deposition (plasma CVD). From the perspective of suppressing stress whitening during molding, it is preferable that the resin film does not whiten when bent 180 degrees.

[0107] The composite film and decorative film of the present disclosure can be produced by a known method, such as laminating a monolayer film or laminate film containing a layer made of the elastomer resin composition of the present disclosure (elastomer resin composition layer) and a metal layer or decorative layer-containing film having a metal layer or decorative layer on at least one surface of a resin film by compression bonding (preferably thermocompression bonding) or the like.

[0108] FIG. 1 is a schematic cross-sectional view of a film according to one embodiment of the present invention. The film 1 of this embodiment has a three-layer structure in which layers 11A and 11B made of the elastomer resin composition of the present disclosure (elastomer resin composition layers) are laminated on both sides of another resin layer 12 (preferably a (meth)acrylic resin-containing layer). The compositions and thicknesses of the elastomer resin composition layer 11A and the elastomer resin composition layer 11B may be the same or different. The configuration of the film according to the present disclosure can be appropriately modified, such as a single-layer film made of only the layer 11A or 11B made of the elastomer resin composition of the present disclosure (elastomer resin composition layer), or a two-layer film in which the layer 11A or 11B made of the elastomer resin composition of the present disclosure (elastomer resin composition layer) is laminated on one side of the other resin layer 12.

[0109] 2 is a schematic cross-sectional view showing an example of a metal layer-containing film. In the figure, reference numeral 2 denotes the metal layer-containing film, reference numeral 21 denotes a substrate layer, and reference numeral 22 denotes a metal layer. The metal layer-containing film 2 has a substrate layer 21 made of a resin layer such as a methacrylic resin-containing layer, and a metal layer 22 formed on one surface of the substrate layer 21 by a vapor deposition method or the like. The metal layer 22 can function as a decorative layer.

[0110] Fig. 3 is a schematic cross-sectional view showing a decorative film according to one embodiment of the present invention. The decorative film 3 is obtained by laminating the metal layer-containing film 2 shown in Fig. 2 on one elastomer resin composition layer 11B of the film 1 shown in Fig. 1. The decorative film 3 shown in Fig. 3 can be produced by laminating the film 1 shown in Fig. 1 and the metal layer-containing film 2 shown in Fig. 2 by a method such as compression bonding (preferably thermocompression bonding). By laminating the films so that the surface of the metal layer 22 is covered by the base layer 21, the base layer 21 can function as a protective layer for the metal layer 22.

[0111] [Composite Molded Article, Decorated Molded Article] In one embodiment, the molded article of the present disclosure can be a composite molded article having, on at least a portion of the surface of an adherend, a layer made of the elastomer resin composition of the present disclosure and a metal layer, in that order. In one embodiment, the molded article of the present disclosure can be a decorated molded article having, on at least a portion of the surface of an adherend, a layer made of the elastomer resin composition of the present disclosure and a decorative layer, in that order. The layer made of the elastomer resin composition of the present disclosure (elastomer resin composition layer) can provide good adhesion between the adherend and the metal layer or the decorative layer.

[0112] 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.

[0113] The composite molded body and decorated molded body of the present disclosure can be manufactured by known methods using the composite film or decorative film of the present disclosure described above. Examples of manufacturing methods include methods such as vacuum forming, pressure forming, vacuum-pressure forming, and compression molding, in which the composite film or decorative film of the present disclosure is laminated to at least a portion of the surface of a previously prepared adherend, and secondary molding of the composite film or decorative film of the present disclosure is simultaneously performed; for example, a simultaneous injection molding and lamination method is used in which the composite film or decorative film of the present disclosure, which has been secondary molded (also referred to as pre-molded) by vacuum forming, 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.

[0114] 4 is a schematic cross-sectional view showing a decorative molded body according to one embodiment of the present invention. The decorative molded body 4 is formed by laminating the decorative film 3 shown in FIG. 3 on at least a portion of the surface of an adherend 30.

[0115] [Applications] The elastomer resin composition of the present disclosure, and films, laminates, or molded articles containing the same, can be used in any application. The elastomer resin composition of the present disclosure has good film-forming properties, processability, adhesion to various materials, and chipping resistance, and is suitable for applications such as decorative films and decorative molded articles. The decorative films and decorative molded articles of the present disclosure can be preferably used in various applications requiring design.

[0116] Suitable uses include sign parts or marking films such as billboards, stand signs, side signs, transom signs, and rooftop signs; display parts such as showcases, partitions, and store displays; lighting parts such as fluorescent light covers, mood lighting covers, lampshades, lighted ceilings, lighted walls, and chandeliers; interior parts such as furniture, wallpaper, pendant lights, and mirrors; architectural parts such as doors, sashes, domes, safety window glass, partitions, staircase wainscoting, balcony wainscoting, and roofs of leisure buildings; aircraft windshields, pilot visors, motorcycle windshields, motorboat windshields, bus sunshades, automobile side visors, rear visors, head wings, headlight covers, automobile interior parts, and bumpers. transportation-related parts such as automobile exterior components; electronic device parts for mobile phones and personal computers; various home appliance parts such as television protective masks; solar cell parts such as solar cell back films and flexible solar cell front films; audiovisual nameplates, stereo covers; vending machines; medical device parts such as incubators and X-ray parts; equipment-related parts such as clock panels, machine covers, instrument covers, laboratory equipment, dial faces, and observation windows; transportation-related parts such as road signs, information boards, convex mirrors, and soundproof walls; bathroom parts such as bathtubs, sanitary parts; greenhouses, large aquariums, box aquariums; stationery such as rulers and desk mats; game parts, toys, musical instruments; decorative and protective films provided on the surface of face protection masks used during welding, etc.

[0117] 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.

[0118] (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.

[0119] (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.

[0120] (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.

[0121] (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).

[0122] (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).

[0123] (Sliding Property) A 100 mm x 200 mm test piece was cut out from a monolayer film (E-Ex) (150 μm thick) made of an elastomer resin composition. The test piece was pressed by hand onto one surface of a stainless steel plate (SUS plate) that was placed horizontally on the ground, had a smooth surface, and was larger than the monolayer film (E-Ex), and a metal plate weighing 100 g was placed on top of the test piece. In this state, the monolayer film (E-Ex) was pulled by hand and evaluated according to the following criteria. Good (◯): The monolayer film was able to slide smoothly without getting caught. Poor (×): The monolayer film was able to slide but there was some snagging.

[0124] (Film Thickness Stability) A 120 mm x 200 mm test piece was cut out from a monolayer film (E-Ex) (150 μm thick) made of an elastomer resin composition. The long axis direction of the test piece was the extrusion direction (direction of resin flow) during molding. The thickness was measured with a micrometer at five points (50 mm intervals) located at 0 mm, 50 mm, 100 mm, 150 mm, and 200 mm from the center point of one short side along the central axis parallel to the long axis direction. The difference between the maximum and minimum values ​​(also referred to as maximum film thickness difference) was determined and evaluated according to the following criteria: Good (◯): Maximum film thickness difference is 25 μm or less; Poor (×): Maximum film thickness difference is more than 25 μm.

[0125] (Adhesion Strength of Elastomer Resin Composition to Polypropylene (PP)) A 25 mm long x 150 mm wide test piece having a laminated structure of elastomer resin composition layer / polyimide layer / polypropylene layer, including the direct bonded portion between the elastomer resin composition layer and the polypropylene layer, was cut out from the laminated film (E-PP). A peel test was conducted in accordance with JIS K6854-2 using an autograph (Shimadzu Corporation's "AGS-X") at a peel angle of 180°, a tensile speed of 300 mm / min, and an ambient temperature of 23°C. Peeling of the elastomer resin composition layer was initiated from the location where the polyimide film was placed as a non-adhesive spacer, and the peel strength of the elastomer resin composition layer from the polypropylene layer at the direct bonded portion between the elastomer resin composition layer and the polypropylene layer was measured. This peel strength was used as data on the adhesive strength of the elastomer resin composition to polypropylene (PP) and was evaluated according to the following criteria. Good (◯): Adhesion strength is 20N / 25mm or more, Poor (×): Adhesion strength is less than 20N / 25mm.

[0126] Since the elastomer resin composition layer and the polypropylene layer were not directly bonded at the location where the polyimide layer was disposed, the peel test could be easily performed by starting the peeling from the location where the polyimide layer was disposed. The same applies to the evaluation items of the adhesive strength of the elastomer resin composition to the methacrylic resin and the adhesive strength of the elastomer resin composition to indium, which will be described later. The polyimide layer is a layer that facilitates the start of the peel test and is not an essential layer in actual decorative films and decorated molded articles.

[0127] (Adhesion Strength of Elastomer Resin Composition to Methacrylic Resin) A test piece measuring 25 mm long x 150 mm wide was cut from the laminate film (E-M). The test piece had a laminate structure of elastomer resin composition layer / polyimide layer / methacrylic resin composition layer and included a direct bonded portion between the elastomer resin composition layer and the methacrylic resin composition layer. A peel test was performed using the same method as in the "Adhesion Strength of Elastomer Resin Composition to Polypropylene (PP)" above. Peeling of the elastomer resin composition layer was initiated from the location where the polyimide film was placed as a non-adhesive spacer, and the peel strength of the elastomer resin composition layer from the methacrylic resin composition layer at the direct bonded portion between the elastomer resin composition layer and the methacrylic resin composition layer was measured. This peel strength was used as data on the adhesion strength of the elastomer resin composition to the methacrylic resin and was evaluated according to the following criteria: Good (◯): Adhesion strength of 50 N / 25 mm or more; Poor (×): Adhesion strength of less than 50 N / 25 mm.

[0128] (Adhesion Strength of Elastomer Resin Composition to Indium) A test piece measuring 25 mm long x 100 mm wide was cut from the decorative film (DF2). The test piece had a laminated structure of methacrylic resin composition layer / indium layer / polyimide layer / second elastomer resin composition layer / methacrylic resin composition layer / first elastomer resin composition layer, and included a direct bond between the indium layer and the second elastomer resin composition layer. A peel test was performed using the same method as in the "Adhesion Strength of Elastomer Resin Composition to Polypropylene (PP)" above. Peeling of the second elastomer resin composition layer was initiated from the location where the polyimide film was placed as a non-adhesive spacer, and the peel strength of the indium layer from the second elastomer resin composition layer at the direct bond between the indium layer and the second elastomer resin composition layer was measured. This peel strength was used as data on the adhesive strength of the elastomer resin composition to indium and was evaluated according to the following criteria. Good (◯): Adhesive strength is 10N / 25mm or more, Poor (×): Adhesive strength is less than 10N / 25mm.

[0129] (Chipping resistance) Using a Gravello tester (manufactured by Suga Test Instruments Co., Ltd.), 50 g of No. 7 crushed stone was collided with the surface of the indium layer (decorative layer) side of a plate-shaped decorated molded body (DM) from a distance of 350 mm under the following conditions: test piece temperature: -20 ° C, test piece mounting angle: 90 ° relative to the shot material spraying axis, air pressure: 0.4 MPa. The surface of the decorated molded body after the test was visually observed and evaluated according to the following criteria. Good (◯): No chipping (damage and / or chipping) was observed. Poor (×): Chipping (damage and / or chipping) was observed in one or more places.

[0130] (5% Weight Loss Time) Using a thermogravimetric analyzer (Shimadzu Corporation, "TGA-50"), 5 mg of the resin to be measured was heated from room temperature (20 to 25°C) to 240°C at a heating rate of 10°C / min in an air atmosphere, and the temperature was maintained for 45 minutes to obtain a TG curve. The time when 240°C was reached was designated as the reference time (0 minutes), and the weight at this time was designated as the reference weight (100%), and the time at which the weight loss rate reached 5% (5% weight loss time) was determined.

[0131] [Production or Preparation of Resin (Composition)] The resin (composition) produced or prepared is as follows.

[0132] (Production Example 1) (Production of First Thermoplastic Elastomer (EX-1)) 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 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 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 way, a reaction solution containing a polystyrene-polyisoprene-polystyrene triblock copolymer was obtained. Palladium carbon (palladium loading: 5 mass%) was added as a hydrogenation catalyst to this reaction solution in an amount of 5 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 depressurization, the palladium carbon was removed by filtration, and the filtrate was concentrated and vacuum dried to obtain a thermoplastic elastomer (EX-a) (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 thermoplastic elastomer (EX-a) was 7 mol%.

[0133] Separately, a pressure-resistant 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 polymerization was allowed 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-b) (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-b) was 7 mol%.

[0134] The obtained thermoplastic elastomers (EX-a) and (EX-b) 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%.

[0135] (Production Example 2) (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, 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 %.

[0136] (Production Example 3) (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 %.

[0137] 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%.

[0138] 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%.

[0139] 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 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 total proportion of 1,2-bonds and 3,4-bonds in the polybutadiene block was 45 mol%.

[0140] (First Polypropylene Polymer (PX) or (PXC)) (PX-1) "Waymax (registered trademark) MFX8" manufactured by Japan Polypropylene Corporation, MFR at 230°C and 21.18 N: 1.1 g / 10 min, melt tension: 24.5 × 10 －２ N, (PX-2) "Waymax (registered trademark) MFX3" manufactured by Japan Polypropylene Corporation, MFR at 230°C and 21.18N: 9.0 g / 10 min, melt tension: 4.9 × 10 －２ N, (PXC-3) (for comparison) "Wintec (registered trademark) WSX03" manufactured by Japan Polypropylene Corporation, MFR at 230°C and 21.18N: 7.0 g / 10 min, melt tension: 0.4 x 10 －２ N.

[0141] (Second Polypropylene Polymer (PY) or (PYC)) (PY-1) Maleic anhydride modified polypropylene, Sanyo Chemical Industries, Ltd. "UMEX (registered trademark) 5200", melting point 124°C, (PY-2) Maleic anhydride modified polypropylene, Sanyo Chemical Industries, Ltd. "UMEX (registered trademark) 5500", melting point 123°C, (PY-3) Maleic anhydride modified polypropylene, Sanyo Chemical Industries, Ltd. "UMEX (registered trademark) 5202W", melting point 115°C, (PYC-4) Maleic anhydride modified polypropylene, Sanyo Chemical Industries, Ltd. "UMEX (registered trademark) 1001", melting point 142°C, (PYC-5) Maleic anhydride modified polypropylene, Sanyo Chemical Industries, Ltd. "UMEX (registered trademark) 1010", melting point 135°C, (PYC-6) Maleic anhydride modified polypropylene, "Admer (registered trademark) QF551" manufactured by Mitsui Chemicals, Inc., melting point 147°C.

[0142] (Polypropylene Film) (PP-F) Non-polar polypropylene film, "Novatec (registered trademark) MA3" manufactured by Japan Polypropylene Corporation.

[0143] (Adherend) As the adherend (PP-M), a plate-shaped polypropylene molded product having a length of 100 mm, a width of 40 mm, and a thickness of 3 mm was prepared by injection molding non-polar polypropylene (Prime Polymer Co., Ltd.'s "J708UG") at 230°C using an injection molding machine (Sumitomo Heavy Industries, Ltd.'s "SG-100").

[0144] (Production Example 4) (Production of Methacrylic Resin (M)) The following methacrylic resins (M1) and (M2) 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).

[0145] (Production Example 5) (Production of Multilayer Structure Polymer Particles (R1)) A reactor equipped with a stirrer, a thermometer, a nitrogen gas inlet, a monomer inlet tube, and a 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 maintained for 40 minutes so that the polymerization rate reached 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 of the multilayer structure 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 (R1).

[0146] (Production Example 6) (Production of Multilayered Structure Polymer Particles (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. After that, 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 continuously added dropwise 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 carried out. The volume average particle diameter at this point was 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 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 maintained for 60 minutes so that the polymerization rate reached 98% or higher, and seed emulsion polymerization was carried out. Next, 0.07 parts by mass of potassium persulfate was added to the obtained latex and stirred for 5 minutes, and then 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 completion of the addition, the mixture was maintained for 60 minutes so that the polymerization rate reached 98% or higher, and seed emulsion polymerization was carried out. The finally obtained latex was placed in a vessel equipped with a stirrer, and an aqueous magnesium sulfate solution was added to the stirred latex, and salting-out coagulation was carried out. The obtained coagulum was washed with water, dehydrated and dried to obtain acrylic multilayer structure polymer particles (R2).

[0147] (Production Example 7) (Production of multilayer structure polymer particles (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 so that the polymerization rate was 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) was 0.10 μm. 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 (R3).

[0148] (Production Example 8) (Production of Block Copolymer (B-1)) The following block copolymer (B-1) was produced by a conventional method. (B-1) 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.

[0149] (Production Example 9) (Production of methacrylic resin composition (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 (B-1) 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).

[0150] (Production Example 10) (Production of methacrylic resin composition (MR2)) 10 parts by mass of methacrylic resin (M2) and 90 parts by mass of 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 methacrylic resin composition (MR2).

[0151] (Phenol-based antioxidants (AO-F)) (AO-F1) Hindered phenol-based antioxidant, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], "Irganox 1010" manufactured by BASF Japan Ltd., molecular weight: 1178, (AO-F2) Hindered phenol-based antioxidant, bis[3-[3-(tert-butyl)-4-hydroxy-5-methylphenyl]propanoic acid]2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl), "ADEKA STAB AO-80" manufactured by ADEKA Corporation, molecular weight: 741.

[0152] (Phosphorus-based antioxidant (AO-P)) (AO-P1) A multi-component phosphorus-based antioxidant containing the following five compounds, "HOSTANOX P-EPQ" manufactured by Clariant Japan, molecular weight: 595 to 1035.

[0153]

[0154] (AO-P2) Phosphorus-based antioxidant, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, “ADEKA STAB PEP-8” manufactured by ADEKA Corporation, molecular weight: 733.

[0155] [Examples E1 to E5, Comparative Examples EC1 to EC11] (Production of Elastomer Resin Compositions) In each of Examples E1 to E5 and Comparative Examples EC1 to EC11, one or more thermoplastic elastomers (E) and one or more polypropylene-based polymers (P) were melt-mixed at 230°C using a twin-screw extruder ("TEM-28" manufactured by Toshiba Machine Co., Ltd.) according to the blending compositions shown in Table 1 or Table 2, and extruded into strands. The strands were cut using a pelletizer to obtain pellets (EP) of the elastomer resin composition. In Tables 1 and 2, EP1 to EP5 and EPC1 to EPC11 represent elastomer resin compositions (elastomer resin compositions to which no antioxidant was added) composed of a mixture of one or more thermoplastic elastomers (E) and one or more polypropylene-based polymers (P), obtained in each Example and Comparative Example. The blend amounts in Tables 1 and 2 are expressed in parts by mass.

[0156] (Production of Monolayer Film (E-Ex) Made of Elastomer Resin Composition) In each of Examples E1 to E5 and Comparative Examples EC1 to EC11, pellets of the obtained elastomer resin composition (E-P) were melt-kneaded at 230°C using a 20 mmφ single-screw extruder (manufactured by OCS Corporation) and extruded through a 150 mm wide T-die. The resin composition 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 monolayer film (E-Ex) made of the elastomer resin composition having a width of 120 mm and a thickness of 150 μm was produced.

[0157] (Production of Laminated Film (E-PP) Comprising Elastomer Resin Composition Layer and Polypropylene Layer) In each of Examples E1 to E5 and Comparative Examples EC1 to EC11, the pellets (EP) of the obtained elastomer resin composition were compressed in a compression molding machine at 200°C and a load of 50 kgf / cm. ２ The film was compression molded for 2 minutes under the conditions of (1) to (3), to obtain a monolayer film (E-HP) made of an elastomer resin composition. A polyimide film ("Kapton (registered trademark) film" manufactured by DuPont-Toray Co., Ltd., 75 mm long x 150 mm wide x 0.05 mm thick) and a non-polar polypropylene film (PP-F) (150 mm long x 150 mm wide x 0.4 mm thick) were sequentially stacked on top of the monolayer film (E-HP) made of an elastomer resin composition (150 mm long x 150 mm wide x 0.5 mm thick). The central axes of each film were aligned. A metal frame with inner dimensions of 150 mm x 150 mm and a thickness of 0.8 mm was prepared as a spacer, and the resulting pre-laminated film was fitted into this metal frame. The film was then sandwiched between a pair of polytetrafluoroethylene (PTFE) films (release films) and further sandwiched between a pair of metal plates from the outside. The obtained temporary laminate was compressed at 200°C under a load of 50 kgf / cm using a compression molding machine. ２After heating and pressing for 2 minutes under the conditions of [0.5 mm thick], the pair of metal plates, the pair of PTFE films, and the metal frame were removed. In this way, a laminated film (E-PP) (150 mm long x 150 mm wide) having a laminated structure of an elastomer resin composition layer (0.5 mm thick) / a polyimide layer (0.05 mm thick) / a polypropylene (PP) layer (0.4 mm thick) was obtained.

[0158] (Production of Laminated Film (E-M) Comprising Elastomer Resin Composition Layer and Methacrylic Resin Composition Layer) Pellets of the methacrylic resin composition (MR1) were compression molded in the same manner as for the monolayer film (E-HP) composed of the elastomer resin composition to obtain a monolayer film (M-HP) composed of the methacrylic resin composition (MR1). In each of Examples E1 to E5 and Comparative Examples EC1 to EC11, a monolayer film (M-HP) (length 150 mm × width 150 mm × thickness 0.4 mm) composed of the methacrylic resin composition (MR1) was used instead of the non-polar polypropylene film (PP-F). A laminated film (E-M) (length 150 mm × width 150 mm) having a laminated structure of elastomer resin composition layer (0.5 mm thick) / polyimide layer (0.05 mm thick) / methacrylic resin composition layer (0.4 mm thick) was obtained in the same manner as for the laminated film (E-PP).

[0159] (Production of Decorative Layer-Containing Film (Metal Layer-Containing Film) (M-In)) In each of Examples E1 to E5 and Comparative Examples EC1 to EC11, 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 (M-Ex) consisting of the methacrylic resin composition (MR1) having a width of 500 mm and a thickness of 75 μm was produced.

[0160] 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 (M-Ex) 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 deposition was carried out at a pressure of 0.8 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 (see FIG. 2).

[0161] (Production of Decorative Film) In each of Examples E1 to E5 and Comparative Examples EC1 to EC11, pellets of the resulting elastomer resin composition (EP), pellets of the methacrylic resin composition (MR2), and pellets of the resulting elastomer resin composition (EP) 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, 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.

[0162] 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 (DF1) (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 / first elastomer resin composition layer (adhesive layer and impact absorbing layer) was obtained (see FIG. 3 ).

[0163] In addition, a polyimide film ("Kapton (registered trademark) film" manufactured by DuPont-Toray Co., Ltd., length 30 mm x width 40 mm x thickness 0.05 mm) was placed between the laminate film (E-M-E) (length 100 mm x width 40 mm x thickness 300 μm) and the decorative layer-containing film (metal layer-containing film) (M-In) (length 100 mm x width 40 mm x thickness approximately 75 μm) and thermocompression bonded in the same manner as above to obtain a decorative film (DF2) having a laminate structure of methacrylic resin composition layer (substrate layer and protective layer) / indium layer (decorative layer, metal layer) / polyimide layer / second elastomer resin composition layer (adhesive layer and impact absorbing layer) / methacrylic resin composition layer / first elastomer resin composition layer (adhesive layer and impact absorbing layer). The central axes of each film were aligned. This decorative film is a film for measuring adhesive strength.

[0164] (Production of Decorative Molded Body) Using a vacuum pressure molding machine ("NGF-0406-T" manufactured by Fuse Vacuum Co., Ltd.), three-dimensional surface decorative molding was performed by a known method to cover one surface of the adherend (PP-M) with a decorative film (DF1), thereby obtaining a decorated molded body (DM). The degree of vacuum was 0.5 kPa, and the heating temperature of the decorative film (DF1) was 130°C. Molding was performed so that the adherend (PP-M) and the first elastomer resin composition layer (adhesive layer and impact absorbing layer) contained in the decorative film (DF1) were in contact with each other. The temperature of the decorative film (DF1) was measured with a radiation thermometer. In this manner, a decorated molded body (DM) was obtained 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 / first elastomer resin composition layer (adhesive layer and impact absorbing layer) / adherend (see FIG. 4 ).

[0165] [Summary of Results] The evaluation results are shown in Tables 1 and 2.

[0166]

[0167] In Examples E1 to E5, elastomer resin compositions were produced which contained a first thermoplastic elastomer (EX), a second thermoplastic elastomer (EY), a third thermoplastic elastomer (EZ), a first polypropylene-based polymer (PX), and a second polypropylene-based polymer (PY), and in which the content of the first thermoplastic elastomer (EX) was 15 to 55 parts by mass, the content of the second thermoplastic elastomer (EY) was 25 to 65 parts by mass, the content of the third thermoplastic elastomer (EZ) was 15 to 35 parts by mass, the content of the first polypropylene-based polymer (PX) was 3 to 15 parts by mass, and the content of the second polypropylene-based polymer (PY) was 7.5 to 20 parts by mass, relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E).

[0168] All of the elastomer resin compositions obtained in these examples had a suitable tackiness, good slipperiness on metals, and good processability. All of the films obtained in these examples had good film thickness stability and good film-forming properties. All of the elastomer resin compositions obtained in these examples had good adhesion to various materials, and good adhesion to non-polar resins (non-polar polypropylene, etc.), polar resins (methacrylic resins, etc.), and metals (indium, etc.). The decorated molded articles including a resin layer and a decorative layer made of the elastomer resin composition obtained in these examples had good chipping resistance and were suitable for decorative applications such as vehicle exterior components.

[0169] In Comparative Example EC1, the content of the third thermoplastic elastomer (EZ) was less than 15 parts by mass per 100 parts by mass of the total amount of the thermoplastic elastomer (E). The elastomer resin composition obtained in this comparative example had poor adhesion to polar resins (such as methacrylic resins). In Comparative Example EC2, the third thermoplastic elastomer (EZ) was not used. The elastomer resin composition obtained in this comparative example had a high tackiness, poor slipperiness on metal, and poor processability. In addition, the adhesion to polar resins (such as methacrylic resins) was poor.

[0170] In Comparative Example EC3, the first thermoplastic elastomer (EX) was not used, and the content of the third thermoplastic elastomer (EZ) was more than 35 parts by mass and the content of the first polypropylene-based polymer (PX) was more than 15 parts by mass relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E). The elastomer resin composition obtained in this Comparative Example had poor adhesion to metals (such as In) and poor chipping resistance.

[0171] In Comparative Example EC4, the first polypropylene-based polymer (PX) was not used. The elastomer resin composition obtained in this comparative example had a high tackiness, poor slipperiness to metals, and poor processability. Furthermore, the film thickness stability was poor, and film formability was poor. Furthermore, the adhesion to metals (e.g., In) was poor.

[0172] In Comparative Example EC5, instead of the first polypropylene-based polymer (PX), a polypropylene-based polymer having a melt tension of 2.5 × 10 measured under conditions of 230 ° C. and a take-up speed of 4.0 m / min was used. －２ A comparative polypropylene-based polymer (PXC) having a viscosity of less than N was used. The elastomer resin composition obtained in this comparative example had a high tackiness, poor slipperiness to metal, and poor processability. In addition, the film thickness stability was poor, and film formability was also poor.

[0173] In Comparative Example EC6, the content of the first polypropylene polymer (PX) was less than 3 parts by mass per 100 parts by mass of the total amount of the thermoplastic elastomer (E), and a comparative polypropylene polymer (PYC) having a melting point of over 130°C was used instead of the second polypropylene polymer (PY). The elastomer resin composition obtained in this Comparative Example had poor film thickness stability and poor film formability. Furthermore, the adhesiveness to metals (such as In) was poor.

[0174] In Comparative Example EC7, the content of the second polypropylene polymer (PY) was less than 7.5 parts by mass relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E). The elastomer resin composition obtained in this Comparative Example had poor adhesion to metals (such as In).

[0175] In Comparative Examples EC8 to EC11, a comparative polypropylene-based polymer (PYC) having a melting point of over 130°C was used instead of the second polypropylene-based polymer (PY). All of the elastomer resin compositions obtained in these Comparative Examples had poor adhesion to metals (such as In). The elastomer resin composition obtained in Comparative Example EC8 also had poor adhesion to non-polar resins (such as non-polar polypropylene). None of the elastomer resin compositions obtained in Comparative Examples EC1 to EC11 were suitable for decorative applications such as vehicle exterior members.

[0176] [Examples E3-1 to E3-10] In each of Examples E3-1 to E3-10, the antioxidant-free elastomer resin composition (EP3) obtained in Example E3 and one or more antioxidants (AO) were melt-kneaded at 230°C for 4 minutes using a laboratory kneader ("Labo Plastomill" manufactured by Toyo Seiki Seisaku-sho, Ltd.) to obtain an antioxidant-added elastomer resin composition. The blending composition and evaluation results of each example are shown in Table 3. ">45.0" in Table 3 means that the 5% weight loss time was longer than 45.0 minutes.

[0177]

[0178] [Summary of Results] In Examples E3-1 to E3-3, no phosphorus-based antioxidant (AO-P) was added to an antioxidant-free elastomer resin composition (EP3) comprising one or more thermoplastic elastomers (E), a first polypropylene-based polymer (PX), and a second polypropylene-based polymer (PY), but 0.10 to 5.00 parts by mass of one or more phenol-based antioxidants (AO-F) (the total amount when multiple antioxidants are used) were added. The elastomer resin compositions obtained in these examples had a 5% weight loss time of 8.8 to 9.7 minutes.

[0179] In Examples E3-4 to E3-10, 0.10 to 5.00 parts by mass (total amount if multiple types of antioxidants were used) of one or more phenolic antioxidants (AO-F) and 0.01 to 5.00 parts by mass (total amount if multiple types of antioxidants were used) of one or more phosphorus-based antioxidants (AO-P) were added to an antioxidant-free elastomer resin composition (EP3) consisting of one or more thermoplastic elastomers (E), a first polypropylene-based polymer (PX), and a second polypropylene-based polymer (PY). All of the elastomer resin compositions obtained in these Examples had a 5% weight loss time of 10 minutes or longer, indicating high resistance to thermal decomposition. In these Examples, it is believed that the synergistic effect of the appropriate amounts of the phenolic antioxidant (AO-F) and the phosphorus-based antioxidant (AO-P) effectively suppressed thermal degradation and thermal decomposition of the thermoplastic elastomer (E) and the polypropylene-based polymer (P) when maintained in a heated, molten state.

[0180] 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.

[0181] This application claims priority based on Japanese Patent Application No. 2023-120616 filed on July 25, 2023, and Japanese Patent Application No. 2024-018382 filed on February 9, 2024, the disclosures of which are incorporated herein in their entireties.

Claims

1. An elastomer resin composition comprising a thermoplastic elastomer (E) and a polypropylene-based polymer (P) and satisfying the following conditions 1 to 3. (Condition 1) 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 a conjugated diene compound unit 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, one or more second thermoplastic elastomers (EY) selected from the group consisting of block copolymers having a polymer block (ya) containing a styrene unit and a polymer block (yb) containing a conjugated diene compound unit in which the total amount of 1,2-bonds and 3,4-bonds is 40 mol % or more, and hydrogenated products of the block copolymers, and 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. (Condition 2) The polypropylene polymer (P) has no polar group, and has a melt tension of 2.5×10 or less measured under conditions of 230° C. and a take-up speed of 4.0 m / min. －２ and a second polypropylene-based polymer (PY) having a polar group and a melting point of 130° C. or lower. (Condition 3) The content of the first thermoplastic elastomer (EX) is 15 to 55 parts by mass, the content of the second thermoplastic elastomer (EY) is 25 to 65 parts by mass, the content of the third thermoplastic elastomer (EZ) is 15 to 35 parts by mass, the content of the first polypropylene-based polymer (PX) is 3 to 15 parts by mass, and the content of the second polypropylene-based polymer (PY) is 7.5 to 20 parts by mass, relative to 100 parts by mass of the total amount of the thermoplastic elastomer (E).

2. The first polypropylene polymer (PX) has a melt tension of 50×10 measured at 230° C. and a take-up speed of 4.0 m / min. －２ The elastomer resin composition according to claim 1, wherein the elastic modulus is N or less.

3. The elastomer resin composition according to claim 1, wherein the second polypropylene polymer (PY) has a melting point of 100°C or higher.

4. The elastomer resin composition according to claim 1, further comprising multiple types of antioxidants (AO) including a phenolic antioxidant (AO-F) and a phosphorus-based antioxidant (AO-P), wherein the content of the phenolic antioxidant (AO-F) is 0.10 to 5.00 parts by mass and the content of the phosphorus-based antioxidant (AO-P) is 0.01 to 5.00 parts by mass per 100 parts by mass of the total of the thermoplastic elastomer (E) and the polypropylene polymer (P).

5. A film comprising a layer made of the elastomer resin composition according to claim 1.

6. The film according to claim 5, further comprising a (meth)acrylic resin-containing layer.

7. The film according to claim 6, wherein the (meth)acrylic resin-containing layer contains a (meth)acrylic resin and one or more rubber components selected from the group consisting of acrylic rubber particles and acrylic block copolymers.

8. The film of claim 5 or 6, further comprising a metal layer.

9. The film according to claim 5 or 6, further comprising a decorative layer.

10. A laminate comprising a layer made of the elastomer resin composition according to claim 1.

11. A molded article comprising a layer or member made of the elastomer resin composition according to claim 1.

12. The molded article according to claim 11, which has a layer of said elastomer resin composition and a metal layer, successively formed on at least a portion of the surface of an adherend.

13. The molded article according to claim 12, further comprising a (meth)acrylic resin-containing layer on the metal layer.

14. The molded article according to claim 11, which has a layer made of the elastomer resin composition and a decorative layer, successively formed on at least a portion of the surface of an adherend.

15. The molded article according to claim 14, further comprising a (meth)acrylic resin-containing layer on the decorative layer.

Images