Thermoplastic elastomer molded article, composite molded article, and production method

Abstract

To provide a thermoplastic elastomer molded article that can effectively suppress peeling sound generated when an article is separated from glass and has an excellent bonding property to other members.SOLUTION: A molded article comprises: an ethylene-based copolymer (A): at least one component (B) selected from the group consisting of copolymers having structural units derived from aromatic vinyl compounds and structural units derived from conjugated diene compounds; a propylene-based polymer (C); and a lubricant (D). The molded article is configured in that: a flexural modulus of the article measured at room temperature according to JIS K7171 is 20 MPa or more and 300 MPa or less; and a shear strength is 40 N / cm2 or less when directly contacting a 110 mm×110 mm surface of a float glass plate measuring 110 mm-long×110 mm-wide×3 mm-thickness conforming to JIS R3202 and allowing the test piece to stand still at 80°C for 50 hours, an interlayer between the two test pieces and the float glass plate is pulled at 200 mm / min in a shear direction and length direction of the test piece.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a thermoplastic elastomer molded article. [Background technology]

[0002] Thermoplastic elastomer molded bodies are highly recyclable, suitable for injection molding, and have excellent product performance such as strength and flexibility, and are therefore widely used as materials for glass run channels and other automotive parts (see, for example, Patent Document 1). As the applications of thermoplastic elastomer molded articles expand, further improvements are being demanded in terms of various performances, such as suppression of peeling noise from glass and bondability to other members. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2021 / 193554 A1 Brochure Summary of the Invention [Problem to be solved by the invention]

[0004] Under these circumstances, the problem that the present invention aims to solve is to provide a thermoplastic elastomer molded article that can effectively suppress the peeling sound from glass and has excellent bondability to other members. [Means for solving the problem]

[0005] The present inventors have conducted intensive research in light of the above background and have completed the present invention. That is, the present invention provides: [1] A molded article comprising: (A) at least one component selected from the group consisting of an ethylene-based copolymer and (B) a copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound; (C) a propylene-based polymer; and (D) a lubricant, The flexural modulus at room temperature measured in accordance with JIS K7171 is 20 MPa or more and 300 MPa or less, Two test pieces measuring 50 mm in length, 6 mm in width, and 2 mm in thickness were cut out from the molded body and placed on a flat plate so that the distance between the opposing 50 mm x 2 mm faces was 60 mm. The two test pieces were fixed on the flat plate at the 50 mm x 6 mm faces, and the other 50 mm x 6 mm faces of the two test pieces were brought into direct contact with a 110 mm x 110 mm face of a float glass plate conforming to JIS R 3202, measuring 110 mm in length, 110 mm in width, and 3 mm in thickness. After leaving the plate at rest at 80°C for 50 hours, the shear strength between the two test pieces and the float glass plate was 40 N / cm when the layer between the two test pieces and the float glass was pulled in the shear direction and in the length direction of the test pieces at 200 mm / min. 2 The above molded body, which is Regarding.

[0006] Below, [2] to

[14] are each preferred aspects or embodiments of the present invention. [2] The molded article according to [1], comprising an ethylene-based copolymer (A). [3] The molded article according to [2], further comprising (E) a mineral oil. [4] The molded article according to [3], wherein the ethylene copolymer (A) is extended with a mineral oil (E). [5] (B) The molded article according to [1], which contains a copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound. [6] The molded article according to [5], further comprising (E) a mineral oil. [7] The molded article according to any one of [1] to [6], wherein the lubricant (D) contains at least a mono fatty acid amide (D1) and a bis fatty acid amide (D2), and the mass ratio of the mono fatty acid amide (D1) / bis fatty acid amide (D2) is within the range of 0.2 to 5. [8] The molded body according to [7], wherein the mass ratio of (D1) mono fatty acid amide / (D2) bis fatty acid amide is within the range of 0.2 to 1. [9] (D1) The molded body according to [7] or [8], wherein the mono fatty acid amide is erucic acid amide.

[10] (D2) The molded body according to any one of [7] to [9], wherein the bisfatty acid amide is ethylene bisstearic acid amide.

[11] A method for producing the molded article according to any one of [1] to

[10] , comprising a step of melt-kneading a mixture containing at least one component selected from the group consisting of (A) an ethylene-based copolymer and (B) a copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound, (C) a propylene-based polymer, and (D) a lubricant, in the presence of (F) a crosslinking agent.

[12] The molded article according to any one of [1] to

[10] , which is an injection molded article.

[13] A composite molded article obtained by bonding the injection molded article according to

[12] to an extrusion molded article containing a thermoplastic elastomer composition or a vulcanized rubber composition.

[14] The composite molding according to

[13] , which is a glass run channel. Effect of the Invention

[0007] According to the present invention, it is possible to provide a molded article that can effectively suppress the peeling sound from glass and has excellent bondability to other members. [Brief description of the drawings]

[0008] [Figure 1]FIG. 2 is a schematic diagram showing a method for measuring shear strength with glass in one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The present invention relates to A molded article comprising: (A) at least one component selected from the group consisting of an ethylene-based copolymer and (B) a copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound; (C) a propylene-based polymer; and (D) a lubricant, The flexural modulus at room temperature measured in accordance with JIS K7171 is 20 MPa or more and 300 MPa or less, Two test pieces measuring 50 mm in length, 6 mm in width, and 2 mm in thickness were cut out from the molded body and placed on a flat plate so that the distance between the opposing 50 mm x 2 mm faces was 60 mm. The two test pieces were fixed on the flat plate at the 50 mm x 6 mm faces, and the other 50 mm x 6 mm faces of the two test pieces were brought into direct contact with a 110 mm x 110 mm face of a float glass plate conforming to JIS R 3202, measuring 110 mm in length, 110 mm in width, and 3 mm in thickness. After leaving the plate at rest at 80°C for 50 hours, the shear strength between the two test pieces and the float glass plate was 40 N / cm when the layer between the two test pieces and the float glass was pulled in the shear direction and in the length direction of the test pieces at 200 mm / min. 2 The above-mentioned molded body is as follows. That is, the molded article of the present invention is a molded article that contains at least one component selected from the group consisting of the above-mentioned components (A) and (B), the component (C), and the component (D), and has a flexural modulus within a specific numerical range and a shear strength with glass measured under specific conditions within a specific numerical range. The molded article of the present invention contains at least one component selected from the group consisting of the above-mentioned components (A) and (B), the component (C), and the component (D), and thus can contain a thermoplastic elastomer composition, and as a result, can be endowed with rubber elasticity after molding, moldability derived from thermoplasticity, and the like.

[0010] (A) Ethylene-based copolymer The ethylene copolymer (A) constituting the molded article of the present invention is an ethylene copolymer having 50% by mass or more and 99% by mass or less of constitutional units derived from ethylene and constitutional units derived from at least one monomer selected from the group consisting of α-olefins having from 3 to 10 carbon atoms (wherein the total amount of the ethylene copolymer is taken as 100% by mass). Since it contains 50% by mass or more of constitutional units derived from ethylene, it is a crosslinkable polymer, and is suitable for forming island phases in the sea-island structure of a thermoplastic elastomer composition by dynamic crosslinking. The (A) ethylene-based copolymer is preferably a random copolymer. The (A) ethylene-based copolymer may have structural units derived from at least one monomer other than ethylene and α-olefins having 3 to 10 carbon atoms.

[0011] Examples of the α-olefin having 3 to 10 carbon atoms include propylene, 1-butene, 2-methylpropene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. In preparing the (A) ethylene-based copolymer, the α-olefin having 3 to 10 carbon atoms may be used alone or in combination of two or more. More preferred examples of the structural unit derived from at least one selected from the group consisting of α-olefins having 3 to 10 carbon atoms include a structural unit derived from propylene, a structural unit derived from 1-butene, and a structural unit derived from 1-octene.

[0012] The proportion of structural units derived from ethylene in the (A) ethylene-based copolymer is from 50% by mass to 99% by mass, preferably from 55% by mass to 90% by mass, and more preferably from 60% by mass to 85% by mass (where the total amount of the (A) ethylene-based copolymer is taken as 100% by mass). The proportion of structural units derived from at least one selected from the group consisting of α-olefins having from 3 to 10 carbon atoms in the (A) ethylene-based copolymer is from 1% by mass to 50% by mass, preferably from 10% by mass to 45% by mass, and more preferably from 15% by mass to 40% by mass (where the total amount of the (A) ethylene-based copolymer is taken as 100% by mass).

[0013] The proportion of the constitutional units derived from ethylene in the ethylene copolymer (A) and the proportion of the constitutional units derived from at least one monomer selected from the group consisting of α-olefins having 3 to 10 carbon atoms can be determined by infrared spectroscopy. Specifically, the infrared absorption spectrum of the ethylene copolymer (A) can be measured using an infrared spectrophotometer, and the proportion of the constitutional units derived from ethylene and the proportion of the constitutional units derived from at least one monomer selected from the group consisting of α-olefins having 3 to 10 carbon atoms can be calculated according to the method described in "Characterization of Polyethylene by Infrared Absorption Spectroscopy (Takayama, Usami, et al.)" or "Die Makromolekulare Chemie, 177, 461 (1976) (McRae, MA, Madam S, WF, et al.)". The proportion of the constitutional units derived from ethylene in the components (A-1) and (A-2) described below and the proportion of the constitutional units derived from at least one monomer selected from the group consisting of α-olefins having 3 to 10 carbon atoms can also be determined in the same manner.

[0014] The (A) ethylene-based copolymer may have a constituent unit derived from at least one monomer selected from the group consisting of ethylene and α-olefins having from 3 to 10 carbon atoms. Examples of the other monomer include conjugated dienes having from 4 to 8 carbon atoms, such as 1,3-butadiene, 2-methyl-1,3-butadiene, 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene; non-conjugated dienes having from 5 to 15 carbon atoms, such as dicyclopentadiene, 5-ethylidene-2-norbornene, 1,4-hexadiene, 1,5-dicyclooctadiene, 7-methyl-1,6-octadiene, and 5-vinyl-2-norbornene; vinyl carboxylate esters, such as vinyl acetate; unsaturated carboxylate esters, such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate; and unsaturated carboxylic acids, such as acrylic acid and methacrylic acid. The other monomer is preferably a non-conjugated diene having 5 to 15 carbon atoms, more preferably 5-ethylidene-2-norbornene or dicyclopentadiene. The (A) ethylene copolymer may contain two or more types of constitutional units derived from the other monomer.

[0015] When the (A) ethylene-based copolymer has a constituent unit derived from at least one monomer other than ethylene and α-olefins having 3 to 10 carbon atoms, the proportion of the constituent units derived from the other monomer is preferably 30% by mass or less, more preferably 20% by mass or less (where the total amount of the (A) ethylene-based copolymer is taken as 100% by mass). The proportion of the constituent units derived from the other monomer can be determined by infrared spectroscopy. Specifically, an infrared spectrophotometer is used to measure the peak intensity of the peak derived from the other monomer in the (A) ethylene-based copolymer, and the proportion of the constituent units derived from the other monomer in the (A) ethylene-based copolymer is calculated from the peak intensity. The proportion of the constituent units derived from the other monomer in the components (A-1) and (A-2) described below can also be determined in the same manner.

[0016] Examples of the ethylene copolymer (A) include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-propylene-1-butene copolymer, ethylene-propylene-1-hexene copolymer, ethylene-propylene-1-octene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-1,4-hexadiene copolymer, and ethylene-propylene-5-vinyl-2-norbornene copolymer. The ethylene copolymer may be an olefin block copolymer containing a polymerization block of ethylene and an ethylene-α-olefin copolymerization block. The ethylene copolymer as component (A) may be used alone or in combination of two or more. As component (A), preferably, an ethylene-propylene copolymer or an ethylene-propylene-5-ethylidene-2-norbornene copolymer can be used.

[0017] Preferred examples of the ethylene copolymer (A) include the following ethylene random copolymer (A-1) and the following ethylene random copolymer (A-2).

[0018] The ethylene random copolymer (A-1) (hereinafter, sometimes referred to as component (A-1)) is an ethylene random copolymer having 50% to 90% by mass of structural units derived from ethylene and structural units derived from at least one monomer selected from the group consisting of α-olefins having 3 to 10 carbon atoms, and having a gel fraction of more than 10% by mass (where the total amount of the ethylene random copolymer is taken as 100% by mass). Component (A-1) may have structural units derived from at least one monomer other than ethylene and selected from the group consisting of α-olefins having 3 to 10 carbon atoms. Specific examples of the α-olefin having 3 to 10 carbon atoms in component (A-1), the preferred range of the proportion of structural units derived from ethylene in component (A-1), the preferred range of the proportion of structural units derived from at least one selected from the group consisting of α-olefins having 3 to 10 carbon atoms, specific examples of structural units derived from monomers other than ethylene and at least one selected from the group consisting of α-olefins having 3 to 10 carbon atoms, the preferred range of the proportion of the other monomers, and specific examples of ethylene random copolymers are the same as those for the (A) ethylene copolymer.

[0019] The more crosslinked structures the ethylene random copolymer has, the larger the gel fraction becomes. Component (A-1) can be obtained by crosslinking component (A-2) described later. The gel fraction of component (A-1) can be calculated by the following method from the gel mass of a molded product containing component (A-1) and the mass of component (A-2) contained in the raw material of the molded product. The gel fraction of component (A-1) is determined by the following method using a Soxhlet extractor with an extraction tube connected to the bottom of a reflux condenser and a flask connected to the bottom of the extraction tube. Approximately 1 g of the molded product and an empty wire basket made of wire mesh (mesh size: 400 mesh) are weighed. The wire basket containing the molded product is introduced into the extraction tube. 300 ml of o-xylene is introduced into the flask. The flask is heated and o-xylene is refluxed for 24 hours to perform extraction. After extraction, the wire basket containing the extraction residue is removed from the test tube and dried under reduced pressure at 100°C in a vacuum dryer, and the wire basket containing the extraction residue after drying is weighed. The gel mass of the molded product is calculated from the mass difference between the wire basket containing the extraction residue after drying and the empty wire basket. The gel fraction (mass%) of component (A-1) is calculated based on the following formula. Gel fraction of component (A-1) = (gel mass of molded body / mass of component (A-2)) x 100 The gel fraction of the component (A-1) is preferably 20% by mass or more, and more preferably 40% by mass or more. The more crosslinked structures the ethylene random copolymer has, the greater the gel fraction of the molded article becomes. The gel fraction of the molded article can be calculated from the gel mass of the molded article obtained by the same method as above, according to the following formula. Gel fraction of molded body=(gel mass of molded body / mass of molded body)×100 The gel fraction of the molded article is preferably 10% by mass or more and 90% by mass or less, more preferably 15% by mass or more and 60% by mass or less, and further preferably 18% by mass or more and 40% by mass or less.

[0020] Component (A-1) can be obtained by crosslinking component (A-2) described later. As a method of crosslinking, a method of melt-kneading a composition containing component (A-2) and a crosslinking agent (C) described later can be mentioned. Crosslinking may be carried out simultaneously with the production of the molded article of the present invention. In this case, a composition containing component (A-1) and a propylene-based polymer (B) can be produced by melt-kneading a composition containing component (A-2), a propylene-based polymer (B) described later, and a crosslinking agent (F), as described in detail later.

[0021] The ethylene random copolymer (A-2) (hereinafter, sometimes referred to as component (A-2)) is an ethylene random copolymer having 50% to 90% by mass of constitutional units derived from ethylene and constitutional units derived from at least one monomer selected from the group consisting of α-olefins having 3 to 10 carbon atoms, and having a gel fraction of 10% by mass or less (where the total amount of the ethylene random copolymer is taken as 100% by mass). Component (A-2) may have constitutional units derived from at least one monomer other than ethylene and selected from the group consisting of α-olefins having 3 to 10 carbon atoms. Specific examples of the α-olefin having 3 to 10 carbon atoms in component (A-2), the preferred range of the proportion of structural units derived from ethylene in component (A-2), the preferred range of the proportion of structural units derived from at least one selected from the group consisting of α-olefins having 3 to 10 carbon atoms, specific examples of structural units derived from monomers other than ethylene and at least one selected from the group consisting of α-olefins having 3 to 10 carbon atoms, the preferred range of the proportion of the other monomers, and specific examples of ethylene random copolymers are the same as those in the case of (A) ethylene-based copolymer.

[0022] The gel fraction of the component (A-2) is preferably 5 mass % or less, and more preferably 0 mass part.It is preferable that the component (A-2) does not substantially have a crosslinked structure.

[0023] The Mooney viscosity (ML) of component (A-2) measured at 125°C 1+4 125°C) is preferably 5 or more and 350 or less, more preferably 10 or more and 300 or less, and further preferably 40 or more and 250 or less. 1+4 125℃) is measured according to JIS K6300 and is 1+4 "125°C" has the following meaning: M: Mooney viscosity L: Uses a large rotor 125℃: Measurement temperature 1+4: The measured value when the sample was heated for 1 minute and then rotated at 2 rpm for 4 minutes.

[0024] The method for producing component (A-2) includes a method of copolymerizing ethylene with at least one monomer selected from the group consisting of α-olefins having 3 to 10 carbon atoms in the presence of a known complex catalyst such as a Ziegler-Natta catalyst, a metallocene complex, or a nonmetallocene complex. Examples of the polymerization method include a slurry polymerization method, a solution polymerization method, a bulk polymerization method, and a gas phase polymerization method.

[0025] (A1) Ethylene-α-olefin-non-conjugated diene copolymer In the (A1) ethylene-α-olefin-non-conjugated diene copolymer preferably used as the (A) ethylene-based copolymer, the proportion of non-conjugated diene units is preferably 4 wt% to 15 wt%, more preferably 6 wt% to 15 wt%. The (A1) ethylene-α-olefin-non-conjugated diene copolymer in this embodiment is an ethylene-α-olefin-non-conjugated diene copolymer rubber having a JIS K6253 A hardness of 85 or less.

[0026] The α-olefin is preferably an α-olefin having 3 to 20 carbon atoms, and examples thereof include propylene, 1-butene, 2-methylpropylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene, as well as combinations of two or more of these. Among these, from the viewpoint of availability, propylene or 1-butene is preferred, and propylene is more preferred.

[0027] The non-conjugated dienes include linear non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6-octadiene; and cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, and the like. Examples of such non-conjugated cyclic dienes include bornene, 5-isopropylidene-2-norbornene, and 6-chloromethyl-5-isopropenyl-2-norbornene; and trienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, and 4-ethylidene-8-methyl-1,7-nanodiene. Among these, 5-ethylidene-2-norbornene or dicyclopentadiene is preferred.

[0028] When the total of the ethylene units, α-olefin units having 3 to 20 carbon atoms, and non-conjugated diene units contained in the (A1) ethylene-α-olefin-non-conjugated diene copolymer is taken as 100% by mass, the amount of the ethylene units contained in the (A1) ethylene-α-olefin-non-conjugated diene copolymer is usually 30% by mass to 80% by mass, preferably 40% by mass to 80% by mass, the amount of the α-olefin units having 3 to 20 carbon atoms is usually 5% by mass to 50% by mass, preferably 15% by mass to 45% by mass, and the amount of the non-conjugated diene units contained in the (A1) ethylene-α-olefin-non-conjugated diene copolymer is 4% by mass to 15% by mass, preferably 6% by mass to 15% by mass (the total of these three types of structural units is taken as 100% by mass). Specific examples of preferred (A1) ethylene-α-olefin-non-conjugated diene copolymers include ethylene-propylene-5-ethylidene-2-norbornene copolymers, ethylene-propylene-dicyclopentadiene copolymers, ethylene-propylene-1,4-hexadiene copolymers, and ethylene-propylene-5-vinyl-2-norbornene copolymers; as well as combinations of two or more of these. Among these, ethylene-propylene-5-ethylidene-2-norbornene copolymers having an ethylene unit ratio of 40% to 80% by mass, a propylene unit ratio of 15% to 45% by mass, and a 5-ethylidene-2-norbornene unit ratio of 4% to 15% by mass are preferred.

[0029] The amounts of ethylene units, α-olefin units having 3 to 20 carbon atoms, and non-conjugated diene units contained in the (A1) ethylene-α-olefin-non-conjugated diene copolymer can be determined by infrared spectroscopy (IR method). Specifically, the (A1) ethylene-α-olefin-non-conjugated diene copolymer is formed into a film having a thickness of about 0.5 mm, and then, using an infrared spectrophotometer, the peak (1688 cm) derived from 5-ethylidene-2-norbornene of the film is measured. -1The amount of 5-ethylidene-2-norbornene units in the copolymer is calculated by measuring the absorption peak of the ethylene unit and the propylene unit. The copolymer is then molded into a film having a thickness of about 0.1 mm, and the infrared absorption spectrum of the film is measured using an infrared spectrophotometer. The ratio of ethylene units to propylene units is calculated according to the method described in the literature (Characterization of Polyethylene by Infrared Absorption Spectroscopy, Takayama, Usami, et al., or Die Makromolekulare Chemie, 177, 461 (1976) by McRae, MA, Madam S, WF, et al.), and the amounts of ethylene units and propylene units can be calculated from the ratio and the amount of 5-ethylidene-2-norbornene units.

[0030] (A1) Ethylene-α-olefin-non-conjugated diene copolymer can be obtained by polymerization by a known method, for example, a method of polymerization in an inert solvent such as hexane, heptane, toluene, or xylene using a polymerization catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst.

[0031] (A1) Mooney viscosity (ML 1+4 The Mooney viscosity (ML 125°C) is preferably 5 or more and 350 or less, more preferably 10 or more and 300 or less, and even more preferably 50 or more and 250 or less. An olefin-based thermoplastic elastomer composition obtained by using the ethylene-α-olefin-non-conjugated diene copolymer (A1) having a Mooney viscosity within the above range can give molded articles having excellent mechanical strength and extremely good appearance when molded. The Mooney viscosity (ML 1+4 125°C) is measured in accordance with JIS K6300. In addition, when component (A1) and mineral oil (hereinafter sometimes referred to as component (E)) are mixed in advance, the Mooney viscosity (ML 1+4 125℃) can be calculated using the following formula (1). log(ML1 / ML2)=0.0066(△PHR) (1) ML1: Mooney viscosity of component (A1) ML2: Mooney viscosity of the mixture of component (A1) and component (E) △PHR: Ratio of component (E) to 100 parts by weight of component (A1)

[0032] (B) A copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound (B) Examples of the copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound include an aromatic vinyl compound-conjugated diene compound polymer, an aromatic vinyl compound-conjugated diene compound-aromatic vinyl compound polymer, and hydrogenated products thereof. Among these, a hydrogenated product of an aromatic vinyl compound-conjugated diene compound-aromatic vinyl compound polymer is preferred.

[0033] Examples of the aromatic vinyl compound in component (B) include styrene, α-methylstyrene, o-, m-, or p-methylstyrene, 1,3-dimethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, ethylstyrene, and vinylnaphthalene, with styrene being preferred.

[0034] Examples of the conjugated diene compound in component (B) include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene, and 2-cyano-1,3-butadiene, with butadiene or isoprene being preferred.

[0035] The ratio of the structural unit derived from the aromatic vinyl compound is preferably 10% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 45% by mass or less, and even more preferably 20% by mass or more and 40% by mass or less, in order to prevent the mold from being soiled during molding of the molded product and to improve the tensile properties and appearance of the molded product. However, the total amount of the copolymer having the structural unit derived from the aromatic vinyl compound and the structural unit derived from the conjugated diene compound is 100% by mass. The ratio of the structural unit derived from the aromatic vinyl compound can be determined by 1H-NMR measurement.

[0036] The ratio of the structural units derived from the conjugated diene compound is preferably 50% by mass or more and 90% by mass or less, more preferably 55% by mass or more and 85% by mass or less, and even more preferably 60% by mass or more and 80% by mass or less. However, the total amount of the copolymer having structural units derived from the aromatic vinyl compound and structural units derived from the conjugated diene compound is taken as 100% by mass. The ratio of the structural units derived from the conjugated diene compound can be determined by 1H-NMR measurement.

[0037] The component (B) may be a hydrogenated product, and in that case, the hydrogenation rate is preferably 80% or more, and more preferably 90% or more, where the hydrogenation rate is expressed as a molar ratio with the amount of double bonds in the structural units derived from the conjugated diene compound in the copolymer before hydrogenation being taken as 100%.

[0038] Examples of the method for producing the component (B) include the method described in JP-B-40-23798. Examples of the method for hydrogenating a copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound include the methods described in JP-B-42-8704, JP-B-43-6636, JP-A-59-133203, and JP-A-60-79005. Examples of the copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound include commercially available products such as "KRATON-G" manufactured by Kraton Polymers, "Septon" manufactured by Kuraray Co., Ltd., "Tuftec" manufactured by Asahi Kasei Corporation, and "TAIPOL" manufactured by TSRC.

[0039] (C) Propylene-based polymer The molded article of the present invention contains (C) a propylene-based polymer. The propylene-based polymer (C) (hereinafter sometimes referred to as component (C)) contained in the molded article according to the present invention is a propylene (co)polymer having more than 50% by mass and not more than 100% by mass of structural units derived from propylene. Component (C) may have structural units derived from monomers other than propylene. Since it contains 50% by mass or more of structural units derived from propylene, it is a non-crosslinkable or decomposable polymer compared to components (A), (B), etc., and is suitable for forming the sea phase of the islands-in-sea structure of a thermoplastic elastomer composition which is suitable as a material for forming the molded article of the present invention.

[0040] Examples of the monomer other than propylene include ethylene and α-olefins having 4 or more carbon atoms, and ethylene and α-olefins having 4 or more and 20 or less carbon atoms are preferred. Examples of the α-olefins having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, and 2,2,4-trimethyl-1-pentene. The proportion of structural units derived from propylene, the proportion of structural units derived from ethylene, and the proportion of structural units derived from at least one monomer selected from the group consisting of α-olefins having 4 or more carbon atoms in the (C) propylene-based polymer can be determined in the same manner as the proportion of each structural unit in the (A) ethylene-based copolymer.

[0041] Examples of the propylene polymer (C) include a propylene homopolymer (C1), a propylene random copolymer, a heterophasic propylene polymer material (C2), etc. The molded article according to the present invention may contain only one type of the propylene polymer (C), or may contain two or more types.

[0042] Preferred propylene random copolymers include, for example, (1) A propylene-ethylene random copolymer having a proportion of structural units derived from propylene of 90% by mass or more and 99.5% by mass or less and a proportion of structural units derived from ethylene of 0.5% by mass or more and 10% by mass or less (the total amount of structural units derived from propylene and structural units derived from ethylene is taken as 100% by mass); (2) A propylene-ethylene-α-olefin random copolymer having a proportion of propylene units of 81% by mass or more and 99% by mass or less, a proportion of structural units derived from ethylene of 0.5% by mass or more and 9.5% by mass or less, and a proportion of structural units derived from α-olefins having 4 to 10 carbon atoms of 0.5% by mass or more and 9.5% by mass or less (the total amount of structural units derived from propylene, structural units derived from ethylene, and structural units derived from α-olefins having 4 to 10 carbon atoms is taken as 100% by mass); (3) Propylene-α-olefin random copolymers having a proportion of structural units derived from propylene of 90% by mass or more and 99.5% by mass or less and a proportion of structural units derived from α-olefins having 4 to 10 carbon atoms of 0.5% by mass or more and 10% by mass or less (wherein the total amount of structural units derived from propylene and structural units derived from α-olefins having 4 to 10 carbon atoms is taken as 100% by mass). In the above (1) and (2), the α-olefin having 4 to 10 carbon atoms includes linear α-olefins such as 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, etc.; and branched α-olefins such as 3-methyl-1-butene, 3-methyl-1-pentene, etc. In the preparation of the above (1) and (2), the α-olefin having 4 to 10 carbon atoms may be used alone or in combination of two or more kinds.

[0043] (C1) The method for producing propylene homopolymer and propylene random copolymer includes a method for polymerizing propylene (and other monomers as necessary) in the presence of a Ziegler-Natta catalyst or a complex catalyst such as a metallocene complex or a nonmetallocene complex. Examples of the polymerization method include a slurry polymerization method, a solution polymerization method, a bulk polymerization method, and a gas phase polymerization method.

[0044] In this specification, the term "heterophagic propylene polymerization material" refers to a polymer (I) having structural units derived from more than 80 mass% and not more than 100% propylene (wherein the total mass of the polymer is taken as 100 mass%) (hereinafter, may be simply referred to as "polymer (I)"). The term "copolymer (II)" refers to a mixture having a structure in which copolymer (II) (wherein the total mass of the copolymer is 100 mass%) having 20 mass% or more and 90 mass% or less of structural units derived from ethylene and structural units derived from at least one monomer selected from the group consisting of α-olefins having 3 or more carbon atoms is dispersed in a matrix of (II) (wherein the total mass of the copolymer is 100 mass%) (hereinafter, sometimes simply referred to as "copolymer (II)"). The heterophasic propylene polymerization material (C2) as component (C) contains propylene-derived constitutional units in an amount of 50 mass% or more, with the total amount of the heterophasic propylene polymerization material being 100 mass%. The amount of polymer (I) contained in the (C2) heterophasic propylene polymerization material is preferably 70% by mass or more and 90% by mass or less, more preferably 75% by mass or more and 90% by mass or less (wherein the total amount of the (C2) heterophasic propylene polymerization material is taken as 100% by mass). The amount of copolymer (II) contained in the (C2) heterophasic propylene polymerization material is preferably 10% by mass or more and 30% by mass or less, more preferably 10% by mass or more and 25% by mass or less (wherein the total amount of the (C2) heterophasic propylene polymerization material is taken as 100% by mass).

[0045] Examples of the α-olefin having 3 or more carbon atoms in the copolymer (II) include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, 2,2,4-trimethyl-1-pentene, etc. The α-olefin having 3 or more carbon atoms is preferably an α-olefin having 3 to 20 carbon atoms, more preferably an α-olefin having 3 to 10 carbon atoms, and even more preferably propylene, 1-butene, 1-hexene, or 1-octene. In the copolymer (II), the α-olefins having 3 or more carbon atoms may be used alone or in combination of two or more kinds.

[0046] The proportion of structural units derived from ethylene contained in the copolymer (II) is preferably 22% by mass or more and 80% by mass or less, more preferably 25% by mass or more and 70% by mass or less, and even more preferably 27% by mass or more and 60% by mass or less (wherein the total amount of structural units derived from at least one selected from the group consisting of α-olefins having 3 or more carbon atoms and structural units derived from ethylene is 100% by mass). The proportion of structural units derived from at least one monomer selected from the group consisting of α-olefins having 3 or more carbon atoms contained in the copolymer (II) is preferably 20% by mass or more and 78% by mass or less, more preferably 30% by mass or more and 75% by mass or less, and even more preferably 40% by mass or more and 73% by mass or less (wherein the total amount of structural units derived from at least one monomer selected from the group consisting of α-olefins having 3 or more carbon atoms and structural units derived from ethylene is 100% by mass).

[0047] Examples of the copolymer (II) include propylene-ethylene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene copolymer, etc., and propylene-ethylene copolymer or propylene-ethylene-1-butene copolymer is preferred. The copolymer (II) is usually a random copolymer.

[0048] A method for producing the (C2) heterophasic propylene polymerization material as component (C) includes a method of multi-stage polymerization of monomers including propylene and ethylene in the presence of a polymerization catalyst. For example, a method in which a monomer containing propylene is polymerized in the presence of a polymerization catalyst in a first polymerization step to produce a polymer (I), and in a second polymerization step, ethylene and at least one monomer selected from the group consisting of α-olefins having 3 or more carbon atoms are copolymerized in the presence of the polymer (I) obtained in the first polymerization step to produce a copolymer (II). Examples of the polymerization catalyst used for producing the (C2) heterophasic propylene polymerization material include a Ziegler catalyst, a Ziegler-Natta catalyst, a catalyst consisting of a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane, a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring, a compound that reacts with the transition metal compound to form an ionic complex, and a catalyst consisting of an organoaluminum compound. In addition, a prepolymerization catalyst may be used in the presence of the above-mentioned polymerization catalyst. Examples of the prepolymerization catalyst include those described in JP-A-61-218606, JP-A-61-287904, JP-A-5-194685, JP-A-7-216017, JP-A-9-316147, JP-A-10-212319, and JP-A-2004-182981.

[0049] Polymerization methods for producing the (C2) heterophasic propylene polymerization material as component (C) include bulk polymerization, solution polymerization, slurry polymerization, gas phase polymerization, etc. Inert hydrocarbon solvents used in solution polymerization and slurry polymerization include propane, butane, isobutane, pentane, hexane, heptane, octane, etc. Two or more of these polymerization methods may be combined, and may be either batch or continuous. Polymerization methods for producing the (C2) heterophasic propylene polymerization material are preferably continuous gas phase polymerization, or bulk-gas phase polymerization in which bulk polymerization and gas phase polymerization are performed continuously.

[0050] The melt flow rate (MFR) of the propylene polymer (C), measured in accordance with JIS K7210 at a temperature of 230° C. and a load of 21.18 N, is preferably 0.3 g / 10 min to 200 g / 10 min from the viewpoint of bondability with other members, more preferably 2.5 g / 10 min to 150 g / 10 min, and even more preferably 10 g / 10 min to 105 g / 10 min.

[0051] (C) The intrinsic viscosity (hereinafter, [η cxis ]) is preferably from 0.1 dl / g to 6.0 dl / g, more preferably from 0.3 dl / g to 5.0 dl / g, and even more preferably from 0.3 dl / g to 3.1 dl / g. The intrinsic viscosity can be determined according to the following procedure: Using an Ubbelohde viscometer, the reduced viscosity is measured in tetralin at 135° C., and the intrinsic viscosity is calculated from the reduced viscosity by extrapolation according to the calculation method described on page 491 of "Polymer Solutions, Polymer Experiments 11" (published by Kyoritsu Shuppan Co., Ltd. in 1982). Here, the CXS and CXIS fractions are obtained by the following method. (C) About 5 g of a propylene-based polymer is completely dissolved in 500 ml of boiling xylene. The resulting xylene solution is gradually cooled to 20°C, and the state is adjusted at 20°C for 4 hours or more, and the precipitate and the solution are separated by filtration. The precipitate is the CXIS fraction. The substance obtained by removing the solvent from the solution is the xylene soluble fraction at 20°C (CXS fraction).

[0052] The (C) propylene-based polymer is preferably a (C1) propylene homopolymer, a propylene-ethylene random copolymer, a propylene-ethylene-1-butene random copolymer, or a (C2) heterophasic propylene polymerization material, more preferably a (C1) propylene homopolymer or a (C2) heterophasic propylene polymerization material, and even more preferably a (C1) propylene homopolymer.

[0053] (D) Lubricant (D) The lubricant is not particularly limited, and various compounds that have been conventionally used as lubricants in the art can be used as appropriate.Specific examples include, but are not limited to, hydrocarbon-based lubricants, fatty acid-based lubricants, fatty acid amide-based lubricants, ester-based lubricants, alcohol-based lubricants, metal soap-based lubricants, silicone-based lubricants such as silicone oil and silicone gum, and inorganic lubricants. Among them, it is preferable to use a fatty acid amide-based lubricant, and it is particularly preferable to use a higher fatty acid amide.

[0054] There are no particular limitations on the fatty acid amide-based lubricant, and any of the conventionally known compounds can be used. The fatty acid constituting the fatty acid amide is preferably a higher fatty acid, and examples of the higher fatty acid include fatty acids having 6 or more carbon atoms, preferably 12 or more, and preferably 24 or less (however, the carbon number is the carbon number of the higher fatty acid, not the total carbon number of the fatty acid amide as component (D); for example, the carbon number of the bis fatty acid amide described below is about twice the above carbon number). The fatty acid amides may be used alone or in combination of two or more. Suitable fatty acid amides include, for example, (D1) mono fatty acid amides, (D2) bis fatty acid amides, and the like.

[0055] The amount of the fatty acid amide-based lubricant is not particularly limited, but is preferably 0.05 parts by mass to 5 parts by mass, more preferably 0.24 parts by mass or more, even more preferably 1.2 parts by mass or more, more preferably 3.0 parts by mass or less, and even more preferably 1.8 parts by mass or less, relative to 100 parts by mass in total of components (A) to (C). When the amount of the fatty acid amide-based lubricant is equal to or more than the lower limit, it is preferable in terms of the objective of suppressing peeling noise, etc. When the amount of the fatty acid amide-based lubricant is equal to or less than the upper limit, it is preferable in terms of suppressing poor appearance due to bleeding, etc.

[0056] (D1) Mono fatty acid amide The (D1) mono fatty acid amide is not particularly limited as long as it is an amide formed from one fatty acid and one amine. The (D1) mono fatty acid amide may be a saturated fatty acid amide or an unsaturated fatty acid amide. Here, the saturated fatty acid constituting the (D1) monofatty acid amide is preferably a saturated fatty acid having 6 to 25 carbon atoms, and examples thereof include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, heneicosylic acid, behenic acid, and lignoceric acid. The unsaturated fatty acid constituting the (D1) monofatty acid amide is preferably an unsaturated fatty acid having 6 to 25 carbon atoms, and examples thereof include erucic acid, oleic acid, myristoleic acid, palmitoleic acid, sapienic acid, vaccenic acid, gadoleic acid, eicosenoic acid, nervonic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, bosseopentaenoic acid, eicosapentaenoic acid, osbondo acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid, herring acid, brassidic acid, elaidic acid, and ricinoleic acid. Among the (D1) mono fatty acid amides formed from these, erucic acid amide and oleic acid amide are preferred, with erucic acid amide being particularly preferred.

[0057] The amount of (D1) mono fatty acid amide is not particularly limited, but is preferably 0.05 parts by mass to 3 parts by mass, more preferably 0.08 parts by mass or more, even more preferably 0.4 parts by mass or more, more preferably 1.8 parts by mass or less, and even more preferably 0.6 parts by mass or less, relative to 100 parts by mass of the total of components (A) to (C). The amount of (D1) mono fatty acid amide is preferably equal to or more than the lower limit, which is the objective of suppressing peeling noise, etc. The amount of (D1) mono fatty acid amide is preferably equal to or less than the upper limit, which is the objective of suppressing poor appearance due to bleeding, etc.

[0058] The molecular weight of the (D1) mono fatty acid amide is not particularly limited, but is preferably 101 to 499, more preferably 201 to 449, and even more preferably 251 to 399. If the molecular weight of the (D1) mono fatty acid amide is within this range, it is preferable in terms of suppressing the intended peeling noise and appearance defects due to bleeding.

[0059] (D2) Bis-fatty acid amide The (D2) bisfatty acid amide is not particularly limited as long as it is an amide formed from 2 fatty acids and 1 diamine. The (D2) bisfatty acid amide may be a bissaturated fatty acid amide or a bisunsaturated fatty acid amide. Preferred examples of (D2) bisfatty acid amide include methylene bissaturated fatty acid amide, methylene bisunsaturated fatty acid amide, ethylene bissaturated fatty acid amide, and ethylene bisunsaturated fatty acid amide. Here, specific examples of the saturated fatty acid and the unsaturated fatty acid constituting (D2) bisfatty acid amide are the same as those described above in relation to (D1) monofatty acid amide. The two fatty acids contained in (D2) bisfatty acid amide may be one type, that is, two fatty acids of the same type may be used, or two different fatty acids may be used in combination. Among these, ethylene bisstearic acid amide and ethylene bisoleic acid amide are preferred, and ethylene bisstearic acid amide is particularly preferred.

[0060] The amount of (D2) bisfatty acid amide is not particularly limited, but is preferably 0.05 parts by mass to 3 parts by mass, more preferably 0.16 parts by mass or more, even more preferably 0.8 parts by mass or more, more preferably 1.8 parts by mass or less, and even more preferably 1.2 parts by mass or less, relative to 100 parts by mass of the total of components (A) to (C). When the amount of (D2) bisfatty acid amide is equal to or more than the lower limit, it is preferable from the viewpoint of the objective of suppressing peeling noise, etc. When the amount of (D2) bisfatty acid amide is equal to or less than the upper limit, it is preferable from the viewpoint of suppressing poor appearance due to bleeding, etc.

[0061] The molecular weight of the (D2) bisfatty acid amide is not particularly limited, but is preferably 200 to 999, more preferably 450 to 849, and even more preferably 500 to 799. If the molecular weight of the (D2) bisfatty acid amide is within this range, it is preferred in terms of suppressing peeling noise and appearance defects due to bleeding, which are the objectives.

[0062] As the (D) lubricant, it is preferable to use a combination of the (D1) mono fatty acid amide and the (D2) bis fatty acid amide, that is, it is preferable that the (D) lubricant contains at least the (D-1) mono fatty acid amide and the (D-2) bis fatty acid amide. By using (D1) mono fatty acid amide and (D2) bis fatty acid amide in combination, the molded article of the present embodiment can more effectively suppress the peeling sound from glass and can have better bondability to other components.

[0063] When (D1) mono fatty acid amide and (D2) bis fatty acid amide are used in combination, there is no particular restriction on the mass ratio of (D-1) mono fatty acid amide / (D-2) bis fatty acid amide, but it is preferably within the range of 0.2 to 5, more preferably within the range of 0.2 to 1, and even more preferably within the range of 0.4 to 0.6. By the mass ratio of (D-1) mono fatty acid amide / (D-2) bis fatty acid amide being within the range of 0.2 to 5, the molded body of this embodiment can more effectively suppress the peeling sound with glass and can have more excellent bondability with other components. In this embodiment, by using (D1) mono fatty acid amide in combination with (D2) bis fatty acid amide and setting the mass ratio of (D-1) mono fatty acid amide / (D-2) bis fatty acid amide within the range of 0.2 to 5, the peeling sound with glass can be more effectively suppressed and the bondability with other components can be more excellent. Although the mechanism is not necessarily clear, it is presumed that there is some relationship to the improved affinity between (D1) mono fatty acid amide and a glass surface having many polar groups via (D2) bis fatty acid amide having two amide groups.

[0064] (E) Mineral oil The molded article of the present invention may contain (E) a mineral oil. (E) Mineral oil may be mixed with (A) ethylene-based copolymer or (B) copolymer having structural units derived from an aromatic vinyl compound and structural units derived from a conjugated diene compound, i.e., (A) ethylene-based copolymer and / or (B) copolymer having structural units derived from an aromatic vinyl compound and structural units derived from a conjugated diene compound may be extended with (E) mineral oil. Examples of the mineral oil (E) preferably used as a softening agent in this embodiment include high-boiling fractions of petroleum (average molecular weight of 300 to 1500, pour point of 0° C. or lower) such as aromatic mineral oil, naphthenic mineral oil, and paraffinic mineral oil. Among these, paraffinic mineral oil is preferred.

[0065] It is desirable to add (E) mineral oil as an extender oil to (A) ethylene copolymer, particularly preferably (A1) ethylene-α-olefin-non-conjugated diene copolymer, or (B) copolymer having structural units derived from an aromatic vinyl compound and structural units derived from a conjugated diene compound. The method of addition may be a known method, for example, (1) a method of mechanically kneading the two using a kneading device such as a roll or a Banbury mixer, or (2) a method of adding component (E) to a solution of component (A) or (B) produced in a solution state, and then removing the solvent by a method such as steam stripping.

[0066] In the case where (E) mineral oil is blended as an extender oil for (A) an ethylene-based copolymer or (B) a copolymer having structural units derived from an aromatic vinyl compound and structural units derived from a conjugated diene compound, the Mooney viscosity (ML ) measured at 125°C of a composition (oil-extended polymer) consisting of (E) mineral oil and (A) an ethylene-based copolymer and / or (B) a copolymer having structural units derived from an aromatic vinyl compound and structural units derived from a conjugated diene compound is 1+4 125°C) is preferably 5 or more and 300 or less, more preferably 10 or more and 250 or less, and further preferably 40 or more and 200 or less. 1+4 125°C) is measured in accordance with JIS K6300. From the viewpoint of achieving the above-mentioned Mooney viscosity, the amount of (E) mineral oil added is preferably 20 to 80 parts by mass, more preferably 25 to 70 parts by mass, and even more preferably 30 to 60 parts by mass, relative to 100 parts by mass of the total amount of (A) ethylene-based copolymer and / or (B) copolymer having structural units derived from an aromatic vinyl compound and structural units derived from a conjugated diene compound, and (E) mineral oil.

[0067] (F) Crosslinking agent In producing the molded article of the present invention, it is preferable to form a thermoplastic elastomer composition having an islands-in-a-sea structure, and for that purpose, the molded article is preferably produced via a step of melt-kneading a mixture containing (A) an ethylene-based copolymer, and (B) at least one component selected from the group consisting of a copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound, (C) a propylene-based polymer, and (D) a lubricant, in the presence of (F) a crosslinking agent. As the (F) crosslinking agent preferably used in this embodiment, a crosslinking agent generally used for crosslinking rubber can be used, and examples thereof include organic peroxides, phenolic resins, sulfur, sulfur-containing compounds, p-quinone, p-quinone dioxime derivatives, bismaleimide compounds, epoxy compounds, silane compounds, and amino resins. Among these, organic peroxides and phenolic resins are preferred.

[0068] Examples of organic peroxides include ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates, peroxydicarbonates, and peroxyesters. Specific organic peroxides include dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne, 1,3-bis(tert-butylperoxyisopropyl)benzene, tert-butylcumyl peroxide, di-tert-butyl peroxide, 2,2,4-trimethylpentyl-2-hydroperoxide, diisopropyl benzohydroperoxide, and cumyl peroxide. Examples of peroxides include tert-butyl peroxide, 1,1-di(tert-butylperoxy)3,5,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide, and p-chlorobenzoyl peroxide. The organic peroxides may be used alone or in combination of two or more kinds.

[0069] The organic peroxide used in this embodiment may be in any form such as liquid, powder, pellet, etc. In addition, in order to improve dispersibility, it is more preferable to dilute the organic peroxide with a diluent such as an inorganic filler, mineral oil, or solvent that is inactive in the crosslinking reaction. In addition, it is more preferable to add it in a liquid state. Among them, paraffin-based oil is a preferred diluent in consideration of its handling property and its effect on the product.

[0070] In order to make the crosslinking reaction proceed uniformly and slowly, an organic peroxide may be used in combination with a crosslinking aid. As the crosslinking aid, a polyfunctional compound such as a sulfur-based, methacrylate-based, or maleimide-based compound may be blended. As the crosslinking aid, sulfur, p-quinone dioxime, p,p'-dibenzoylquinone dioxime, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, diallyl phthalate, tetraallyloxyethane, triallyl isocyanurate, N,N'-m-phenylene bismaleimide, maleic anhydride, divinylbenzene, zinc diacrylate, and zinc dimethacrylate may be exemplified. Among them, N,N'-m-phenylene bismaleimide, p,p'-dibenzoylquinone dioxime, divinylbenzene, trimethylolpropane trimethacrylate, or triallyl isocyanurate is preferred. N,N'-m-phenylenebismaleimide can also be used alone as a crosslinking agent.

[0071] (F) An example of the phenolic resin used as a crosslinking agent is a compound represented by the following formula, which is generally used as a crosslinking agent for rubber (see U.S. Pat. Nos. 3,287,440 and 3,709,840): [ka] In the formula, n is an integer of 0 to 10, X and Y are each independently a hydroxyl group, a halogenated alkyl group or a halogen atom, and R is a saturated hydrocarbon group having 1 to 15 carbon atoms. The compound can be produced by condensation polymerization of a substituted phenol and an aldehyde with an alkali catalyst.

[0072] Further examples of the phenol resin include alkylphenol formaldehyde and brominated alkylphenol formaldehyde. When using a phenolic resin as a crosslinking agent, it may be combined with a crosslinking accelerator to adjust the rate of the crosslinking reaction. Examples of the crosslinking accelerator include metal halides such as stannous chloride and ferric chloride, and organic halides such as chlorinated polypropylene, brominated butyl rubber, and chloroprene rubber. The phenolic resin is preferably used in combination with a metal oxide (eg, zinc oxide) and a dispersing agent such as stearic acid.

[0073] The amount of the crosslinking agent (F) to be added is not particularly limited, and a person skilled in the art can appropriately determine the amount of the crosslinking agent (F) to be added that is suitable for crosslinking the ethylene-based copolymer (A), the copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound (B), and the like, at a desired level. The (F) crosslinking agent may decompose during a process for crosslinking (A) the ethylene-based copolymer, (B) the copolymer having structural units derived from an aromatic vinyl compound and structural units derived from a conjugated diene compound, and the like, such as melt kneading. Therefore, a suitable amount of the (F) crosslinking agent is generally determined not by the amount of the (F) crosslinking agent remaining in the molded article of the present invention, but by the amount of the (F) crosslinking agent before the (A) ethylene-based copolymer, (B) the copolymer having structural units derived from an aromatic vinyl compound and structural units derived from a conjugated diene compound, and (C) the propylene-based polymer are melt kneaded in the presence of the (F) crosslinking agent. The amount of the (F) crosslinking agent before melt kneading is preferably 0.001 parts by mass or more and 3.0 parts by mass or less, more preferably 0.01 parts by mass or more and 2.0 parts by mass or less, and even more preferably 0.1 parts by mass or more and 1.0 parts by mass or less, relative to 100 parts by mass of the total amount of the (A) ethylene-based copolymer, the (B) copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound, and the (C) propylene-based polymer. When a crosslinking aid is used together with the (F) crosslinking agent, the amount of the crosslinking aid before melt-kneading is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.05 parts by mass or more and 1.0 part by mass or less, relative to 100 parts by mass of the total amount of the (A) ethylene-based copolymer, the (B) copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound, and the (C) propylene-based polymer.

[0074] Other Ingredients The molded article of the present invention may contain at least one component selected from the group consisting of (A) an ethylene-based copolymer and (B) a copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound, which are essential components, (C) a propylene-based polymer, and (D) a lubricant, as well as various additives other than the above-mentioned preferred components (E) mineral oil and (F) crosslinking agent. Examples of additives include polymers or oligomers other than the above components (A) to (C), (E) softeners other than mineral oils, inorganic fillers (talc, calcium carbonate, calcined kaolin, glass fibers, hollow glass spheres, silica, metal soap, titanium dioxide, mica, potassium titanate fibers, etc.), organic fillers (fibers, wood flour, cellulose powder, carbon fibers, carbon black, etc.), antioxidants (phenol-based, sulfur-based, phosphorus-based, lactone-based, vitamin-based, etc.), weathering stabilizers, ultraviolet absorbing agents (benzotriazole-based, triazine-based, anilide-based, benzophenone-based etc.), heat stabilizers, light stabilizers (hindered amines, benzoates, etc.), pigments (inorganic pigments, organic pigments, pigment dispersants, etc.), nucleating agents, foaming agents, foam nucleating agents, plasticizers, flame retardants, brightness enhancers, antibacterial agents, light diffusing agents, adsorbents (metal oxides (zinc oxide, magnesium oxide, etc.), wetting and dispersing agents, VOC / odor stripping agents, water storage agents (aqueous media containing amphiphilic polymers, etc.), scratch resistance improvers, metal chlorides (iron chloride, calcium chloride, etc.), hydrotalcite, aluminates, etc. These additives may be used alone or in combination of two or more.

[0075] Examples of resins other than components (A) to (C) include olefin-based resins (excluding those corresponding to components (A) and (C)), olefin-based elastomers (excluding those corresponding to components (A) and (C)), polyphenylene ether-based resins, polyamide-based resins, polyester-based resins, polyoxymethylene-based resins, polymethyl methacrylate-based resins, and the like.

[0076] The thermoplastic elastomer molded article of the present invention may contain carbon-14 (14C) as a constituent element, and may be one that has been material recycled (mechanically recycled).

[0077] The concentration of carbon-14 (14C) contained in a thermoplastic elastomer molded body is determined as pMC (percentage of moderate carbon: unit %) by the AMS (Accelerator mass spectrometry) method specified in ISO 16620-2:2019. Carbon-14 (14C) is contained in a certain proportion in carbon dioxide in the atmosphere, and it is therefore known that plants that grow by absorbing carbon dioxide from the atmosphere, such as corn and trees, contain 14C. It is also known that fossil resources such as petroleum, which are thought to have been stored underground for a long time, contain almost no carbon-14 (14C). Therefore, carbon-14 (14C) can be contained in the constituent elements of the thermoplastic elastomer by using a plant-derived substance as the raw material for the monomers of component (A) ethylene copolymer, component (B) copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound, component (C) propylene-based polymer, and / or component (E) mineral oil, which are used in the thermoplastic elastomer molded product.

[0078] In producing the component (A) ethylene copolymer, the component (B) copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound, the component (C) propylene-based polymer, and / or the component (E) mineral oil used in the thermoplastic elastomer molded article, monomers derived from fossil resources (ethylene, propylene, 1-butene, 1-hexene, etc.), plant-derived monomers (ethylene, propylene, 1-butene, 1-hexene, etc.), chemically recycled monomers (ethylene, propylene, 1-butene, 1-hexene, etc.), etc., can be used, and two or more of these may be used in combination. Specific monomer combinations include, for example, fossil resource-derived ethylene / plant-derived ethylene / chemically recycled ethylene, fossil resource-derived propylene / plant-derived propylene / chemically recycled propylene, and fossil resource-derived propylene / plant-derived propylene / chemically recycled propylene / fossil resource-derived ethylene / plant-derived ethylene / chemically recycled ethylene.

[0079] Fossil resource-derived monomers are derived from underground carbon resources such as petroleum, coal, and natural gas, and generally contain almost no carbon-14 (14C). Methods for producing fossil resource-derived monomers include known methods, such as cracking petroleum-derived naphtha and ethane, and dehydrogenating ethane and propane to produce olefins.

[0080] Plant-derived monomers are derived from carbon circulating on the earth's surface as plants and animals, and generally contain a certain percentage of carbon-14 (14C). Methods for producing plant-derived monomers include known methods, such as cracking bionaphtha, vegetable oil, animal oil, etc., dehydrogenation of biopropane, etc., methods of separating alcohol from fermented products such as sugar extracted from plant raw materials such as sugarcane and corn, and subjecting it to a dehydration reaction (JP Patent Publication No. 2010-511634, JP Patent Publication No. 2011-506628, JP Patent Publication No. 2013-503647, etc.), and methods of subjecting ethylene obtained from plant-derived ethanol to a metathesis reaction with n-butene (WO2007 / 055361, etc.).

[0081] Chemical recycling monomers are derived from carbon generated by the decomposition and combustion of waste, and the amount of carbon 14 (14C) contained therein varies depending on the waste. Methods for producing chemical recycling monomers include known methods, such as a method of thermally decomposing waste plastics (JP Patent Publication No. 2017-512246, etc.), a method of cracking waste vegetable oil, waste animal oil, etc. (JP Patent Publication No. 2018-522087, etc.), and a method of gasifying, converting to alcohol, and dehydrating waste such as food waste, biomass waste, food waste, waste oil, waste wood, waste paper, and waste plastics (JP Patent Publication No. 2019-167424, WO2021 / 006245, etc.).

[0082] When two or more of fossil resource-derived olefins, plant-derived olefins, and chemically recycled olefins are used, the olefins produced individually may be mixed and used in combinations such as fossil resource-derived olefins / plant-derived olefins, fossil resource-derived olefins / chemically recycled olefins, plant-derived olefins / chemically recycled olefins, and fossil resource-derived olefins / plant-derived olefins / chemically recycled olefins. In addition, a mixture of the above olefin combinations may be produced by using a mixture of combinations such as fossil resource-derived compounds / plant-derived compounds, fossil resource-derived compounds / chemically recycled compounds, plant-derived compounds / chemically recycled compounds, and fossil resource-derived compounds / plant-derived compounds / chemically recycled compounds as raw materials or intermediates in the olefin production process.

[0083] As the component (A) ethylene copolymer containing carbon 14 (14C), a commercially available ethylene copolymer or an ethylene polymer having monomer units derived from more than 90% by mass of ethylene can be used. Examples include the "I'M GREEN" (green polyethylene) series manufactured by Braskem, the "TRUCIRCLE" series manufactured by SABIC, and the "CirculenRenew" series manufactured by LyondellBasell.

[0084] As the propylene-based polymer containing carbon 14 (14C) as component (C), commercially available propylene-based polymers can be used, such as the "Bornewables" series manufactured by Borealis, the "TRUCIRCLE" series manufactured by SABIC, and the "CirculenRenew" series manufactured by LyondellBasell.

[0085] From the viewpoint of reducing the environmental load, the carbon-14 (14C) concentration of the thermoplastic elastomer molded product is preferably 0.2 pMC% or more, more preferably 0.5 pMC% or more, even more preferably 1 pMC% or more, still more preferably 5 pMC% or more, and particularly preferably 10 pMC% or more. From the viewpoint of cost, the carbon-14 (14C) concentration is preferably 99 pMC% or less, more preferably 95 pMC% or less, even more preferably 90 pMC% or less, still more preferably 70 pMC% or less, and particularly preferably 50 pMC% or less.

[0086] The carbon-14 (14C) concentration of the thermoplastic elastomer molded article can be adjusted by changing the ratio of fossil resource-derived olefins, plant-derived olefins, and chemically recycled olefins used in the production of the thermoplastic elastomer molded article.

[0087] Molded body The molded article of the present invention may contain at least one component selected from the group consisting of (A) an ethylene-based copolymer and (B) a copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound, (C) a propylene-based polymer, and (D) a lubricant. There are no particular limitations on the amount of each component blended, but it is preferable that the molded article contains a total of 40 to 85 parts by mass of (A) the ethylene-based copolymer and / or (B) the copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound, and 15 to 60 parts by mass of (C) the propylene-based polymer, relative to 100 parts by mass in total of components (A) to (C). The total amount of (A) the ethylene-based copolymer and / or (B) the copolymer having structural units derived from an aromatic vinyl compound and structural units derived from a conjugated diene compound is more preferably 50% by mass to 90% by mass, and particularly preferably 55% by mass to 85% by mass. The amount of the (C) propylene-based polymer is more preferably 10% by mass to 50% by mass, and particularly preferably 15% by mass to 45% by mass. By having the above-mentioned blending, the molded article of the present embodiment can further improve various performances such as suppression of peeling sound from glass and bondability to other members.

[0088] The molded article of the present invention has a flexural modulus at room temperature measured in accordance with JIS K7171 of 20 MPa or more and 300 MPa or less. When the flexural modulus is within the above range, the molded article of the present invention can achieve technical effects such as flexibility and shape retention in addition to satisfying the other requirements of the present invention.

[0089] More specifically, it is preferable that the flexural modulus of the molded article is 20 MPa or more from the viewpoint of shape retention and the like. From these viewpoints, the flexural modulus of the molded article of the present invention is preferably 40 MPa or more, and more preferably 50 MPa or more.

[0090] More specifically, it is preferable from the viewpoint of flexibility and the like that the flexural modulus of the molded article is 300 MPa or less. From these viewpoints, the flexural modulus of the molded article of the present invention is preferably 200 MPa or less, and more preferably 100 MPa or less.

[0091] The flexural modulus of the molded article can be measured in accordance with JIS K7171, and more specifically, for example, can be measured in accordance with the method described in the examples of the present application. The flexural modulus of the molded article can be appropriately adjusted by selecting and adjusting the components constituting the molded article, particularly the materials and / or blending amounts of components (A) to (C), adjusting the degree of crosslinking when crosslinking agent (F) is used, changing the melt-kneading conditions, etc.

[0092] The molded product of the present invention has a shear strength between itself and a float plate glass measured under specific conditions. More specifically, two test pieces of 50 mm long x 6 mm wide x 2 mm thick cut out from the molded product of the present invention are placed on a flat plate so that the distance between the opposing 50 mm x 2 mm faces is 60 mm, the two test pieces are fixed on the flat plate at the 50 mm x 6 mm faces, and the other 50 mm x 6 mm face of the two test pieces is brought into direct contact with a 110 mm x 110 mm face of a float plate glass of 110 mm long x 110 mm wide x 3 mm thick conforming to JIS R 3202, and the two test pieces are allowed to stand at 80°C for 50 hours. When the layer between the two test pieces and the float plate glass is pulled in the shear direction and in the length (50 mm) direction of the test pieces at 200 mm / min, the shear strength is 40 N / cm. 2 The following is the result.

[0093] The shear strength between float glass and the glass measured under the above specific conditions is 40N / cm 2 By satisfying the following conditions, coupled with the other conditions of the present invention, the molded body of the present invention can effectively suppress the peeling sound from glass and has excellent bondability to other components, thereby achieving remarkable technical effects of great practical value. The shear strength between float glass and the glass measured under the above specific conditions is 40N / cm 2 The mechanism by which the above technical effects are achieved by satisfying the following criteria is not necessarily clear; however, it is presumed that there is some connection between the shear strength between glass and the molded body and the peeling sound between the glass and the molded body, which are properties that can be affected by the state of the glass / molded body interface, and the fact that the interface state that can effectively suppress the peeling sound can be indirectly evaluated by the shear strength.

[0094] The shear strength between float glass and the sheet glass measured under the above specific conditions is 30N / cm 2It is preferable that the resistance is less than 14N / cm 2 It is particularly preferable that the value is equal to or less than 9 N / cm 2 It is even more preferable that: There is no particular lower limit to the shear strength between float glass and the sheet glass measured under the above specific conditions, but from the viewpoint of adhesion to glass, etc., a lower limit of 0.1 N / cm 2 It is preferable that the resistance is 1N / cm or more. 2 More preferably, it is equal to or greater than this.

[0095] The shear strength between the float plate glass and the sheet glass can be measured by the method described above, and more specifically, by the method described in the examples of the present application. The shear strength between the molded product of the present invention and float plate glass measured under the above-mentioned specific conditions can be appropriately adjusted by selecting and adjusting each component constituting the molded product, particularly the material and blending amount of the (D) lubricant and other components. Particularly effective adjustment means include using (D-1) monofatty acid amide and (D-2) bisfatty acid amide as the (D) lubricant and adjusting the mass ratio of the two, or increasing the amount of the (C) propylene polymer.

[0096] The molded product of the present invention is subjected to a shear rate of 12 sec at a temperature of 220°C. -1 It is preferable that the melt viscosity measured by is 2500 Pa·sec or less. Since the melt viscosity is 2500 Pa sec or less, the molded body of the present embodiment has high fluidity when molded by injection molding or the like in the molding process, and is excellent in moldability. In addition, the molded body has good appearance such as surface smoothness, and also has excellent bondability to other members. The melt viscosity can be measured by melting the molded body at a predetermined temperature and measuring the melt viscosity at a predetermined shear rate according to a method known in the art.

[0097] The melt viscosity can be appropriately increased or decreased by adjusting the content and melt flow rate of the (C) propylene-based polymer used in the molded product, and the proportion and particle size of the island phases in the sea-island structure usually composed of the (A) ethylene-based copolymer and / or (B) copolymer having structural units derived from an aromatic vinyl compound and structural units derived from a conjugated diene compound, gel fraction, etc.

[0098] The method for producing the molded article of the present invention is not particularly limited, but the raw materials thereof (A) ethylene-based copolymer and (B) copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound, (C) propylene-based polymer, and (D) a mixture containing a lubricant, and various additives as desired, can be produced by kneading them in a conventional manner using a normal extruder, Banbury mixer, roll, Brabender Plastograph, Kneader Brabender, etc. It is preferable to produce the molded article by melt kneading using an extruder, particularly a twin-screw extruder. In addition, all the components to be kneaded may be melt kneaded at once, or after kneading a portion of the components, the remaining components may be added and melt kneaded, or the components may be melt kneaded once or twice or more. The temperature during melt kneading is preferably 150°C to 300°C, more preferably 180°C to 250°C. The time during melt kneading is preferably 20 seconds to 30 minutes, more preferably 30 seconds to 20 minutes. The components to be kneaded may be added in any order or may be added simultaneously.

[0099] In producing the molded article of the present invention, crosslinking may be performed or not. From the viewpoints of controlling the sea-island structure, melt viscosity, etc., crosslinking is preferably performed. In a preferred production method for crosslinking, a step of melt-kneading a mixture containing at least one component selected from the group consisting of (A) an ethylene-based copolymer and (B) a copolymer having a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound, (C) a propylene-based polymer, and (D) a lubricant, in the presence of (F) a crosslinking agent is preferably carried out. When an ethylene copolymer (A) is used, the Mooney viscosity (ML 1+4 125°C) is 40 or more, and the melt flow rate of the propylene polymer (C) measured under conditions of a temperature of 230°C and a load of 21.18 N is preferably 0.3 g / 10 min to 200 g / 10 min. When the ethylene copolymer (A) is oil-extended with the mineral oil (E), it is preferable to carry out a step of melt-kneading the oil-extended polymer consisting of the mineral oil (E) and the ethylene copolymer (A), the propylene polymer (C), and the lubricant (D) in the presence of the crosslinking agent (F). The Mooney viscosity (ML 1+4 125°C) is 40 or more, and the melt flow rate of the propylene polymer (C) measured under conditions of a temperature of 230°C and a load of 21.18 N is preferably 0.3 g / 10 min to 200 g / 10 min.

[0100] The molded article of the present invention is preferably used in various applications in which thermoplastic elastomers have conventionally been used, and is particularly preferably used to constitute a part or all of various members and products produced by injection molding or extrusion molding. Furthermore, by using the molded article of the present invention, it is possible to obtain an extrusion molded article or an injection molded article having good surface smoothness, and therefore the molded article can be preferably used in applications where a smooth appearance of the molded article is required. The surface smoothness can be evaluated, for example, by measuring the ten-point average roughness of the surface of the molded article.

[0101] Furthermore, the molded article of the present invention has excellent bonding properties with other members, particularly with members formed of a thermoplastic elastomer composition using a propylene-based polymer in the sea phase, and therefore can be particularly preferably used in producing a composite molded article with such members.

[0102] More specifically, preferred applications of the molded article of the present invention include various automobile interior and exterior parts such as glass run channels, weather strips, door grommets, instrument panels, glove boxes, trims, housings, pillars, bumpers, fenders, and back doors, as well as various parts for home appliances, various housing equipment parts, various industrial parts, and various building material parts, but are not limited to these.

[0103] The injection molded article, which is a preferred embodiment of the present invention, can be produced by using a thermoplastic elastomer composition having substantially the same composition as the molded article of the present invention, for example, by a normal injection molding method, or, if necessary, by various molding methods such as a gas injection molding method, an injection compression molding method, a short shot foam molding method, etc. There are no particular restrictions on the molding conditions in the above-mentioned injection molding, but it can be generally carried out at a molding temperature of 100°C to 300°C, preferably 180°C to 280°C, an injection pressure of 5 MPa to 100 MPa, preferably 10 MPa to 80 MPa, and a mold temperature of 20°C to 80°C, preferably 20°C to 60°C.

[0104] The injection molded article, which is a preferred embodiment of the present invention, may be bonded to another member to form a composite molded article by utilizing its excellent bonding property. In this case, the other member may be an extrusion molded article containing a thermoplastic elastomer composition or a vulcanized rubber composition. It is preferable to use a molded article containing a thermoplastic elastomer composition having the same blend as the molded article of the present invention, particularly a molded article containing a thermoplastic elastomer composition in which the sea phase of the sea-island structure is composed of a propylene-based polymer, and in this case, even more excellent bonding property can be realized. In this embodiment, the bonding strength with other members is preferably 3.0 MPa or more, more preferably 3.3 MPa or more, and particularly preferably 3.5 MPa or more. The higher the bonding strength with other components, the better, and there is no particular upper limit, but when producing a composite molded product at a practical cost, it is usually 6.0 MPa or less in most cases. In producing the composite molded product of this embodiment, it is preferable to place other members such as an extrusion molded product in a mold, and then inject a thermoplastic elastomer composition having the same composition as the molded product of the present invention into the mold to bond the other members to the molded product of the present invention to produce the composite molded product. For example, the main body (straight part) of a glass run channel is placed in a mold for injection molding as the extrusion molded product, and then the molded product of the present invention is formed by injection molding to form corner parts bonded to the main body part, thereby producing a glass run channel that is excellent in appearance, bonding strength between the main body part and the corner parts, etc. The molded article of the present invention can effectively suppress the sound of peeling off from glass, and when used in a glass run channel, it can effectively suppress the abnormal noise generated when a glass ascends or descends. EXAMPLES

[0105] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0106] The physical properties and characteristics in the examples and comparative examples were evaluated by the following methods. 1. Manufacturing method of injection molded products Using a Toshiba Machine Co., Ltd. IS100EN-3A injection molding machine, the thermoplastic elastomer compositions produced in the Examples and Comparative Examples were injection molded at a molding temperature of 220°C and a mold temperature of 50°C to obtain injection molded articles measuring 150 mm in length, 90 mm in width, and 2.0 mm in thickness.

[0107] 2. Rigidity (flexural modulus) According to JIS K7171, the flexural modulus of the injection molded article produced in the above item 1 was measured at a standard atmosphere of 23° C. / 50% RH and a test speed of 1 mm / min.

[0108] 3. Evaluation of adhesion to thermoplastic elastomer molded bodies The thermoplastic elastomer molded article (Y) obtained in [Reference Example 1] described later was used as the adherend. First, the thermoplastic elastomer molded article (Y) was placed in a mold for injection molding. The thermoplastic elastomer compositions produced in each Example / Comparative Example were injection molded using a Toshiba Machine Co., Ltd. IS100EN-3A injection molding machine at a molding temperature of 250°C and a mold temperature of 50°C to obtain a composite molded body (Z1) in which the above-mentioned thermoplastic elastomer molded body (Y) and the injection molded body portion made of the thermoplastic elastomer composition obtained in each Example / Comparative Example were melt-bonded. A test specimen was prepared by punching out the molded body (Z1) with a JIS K6251 No. 3 dumbbell so that the molten adhesive surface was perpendicular to the length direction of the test specimen. A tensile test was carried out on the test specimen at a tensile speed of 200 mm / min and a standard atmosphere of 23°C / 50% RH to evaluate the adhesive strength. [Reference example 1] (Preparation of Thermoplastic Elastomer Molded Body (Y)) Using an IS100EN-3A injection molding machine manufactured by Toshiba Machine Co., Ltd., thermoplastic elastomer "Santoprene 121-73W175" manufactured by ExxonMobil was injection molded under the conditions of molding temperature 220°C, mold temperature 50°C, injection time 10 seconds, and cooling time 30 seconds to obtain an injection molded body (length 150 mm, width 90 mm, thickness 2.0 mm). Next, the injection molded body was cut with a cutter to a length of 30 mm, width 90 mm, and thickness of 2.0 mm, and this was used as thermoplastic elastomer molded body (Y).

[0109] 4.Shear strength with glass Two test pieces, each 50 mm long and 6 mm wide, were punched out from a 2 mm thick press sheet obtained by press molding the thermoplastic elastomer compositions produced in the Examples and Comparative Examples described below under the following molding conditions, and the test pieces were placed parallel to each other on a 100 mm long, 100 mm wide, and 1.5 mm thick SUS plate so that the opposing 50 mm x 2 mm faces were spaced 60 mm apart, and the 50 mm x 6 mm faces were attached using double-sided tape. A float glass plate with a length of 110 mm, width of 110 mm, and thickness of 3.0 mm conforming to JIS R3202 was placed on the other 50 mm x 6 mm face of the test piece, and after 50 hours at 80 ° C. in an oven, it was air-cooled for 12 hours under a standard atmosphere at 23 ° C. / 50% RH. A tensile test was performed on the float glass plate in the length direction of the test piece at 200 mm / min and 23 ° C. / 50% RH to evaluate the shear strength ([Figure 1]). Molding conditions: The thermoplastic elastomer composition was sandwiched between polyester films and hot-press molded for 5 minutes at a temperature of 200°C and a maximum pressure of 10 MPa, and then cooled-press molded for 5 minutes at a temperature of 23°C and a maximum pressure of 10 MPa to produce a pressed sheet.

[0110] 5. Sound of glass peeling off In the test in 4 above, the presence or absence of sound when the examiner peeled the test piece from the float glass plate at a position about 30 cm away from the test piece was evaluated based on the average of two measurements on the following 5-point scale. The average difference between the two measurements was 0.4, indicating that the measurements were reliable. 1: The sound of peeling is very loud 2: The sound of peeling is loud 3: The sound of peeling is low 4: The sound of peeling is very quiet 5: No noise is heard when peeling

[0111] Details of the materials used in the examples and comparative examples are as follows.

[0112] <Component (A)> Ethylene-based copolymer (A1-i)+(E) Oil-extended ethylene-propylene-5-ethylidene-2-norbornene copolymer (mixture of 100 parts by mass of component (A2-i) and 100 parts by mass of component (E)) Mooney viscosity (ML 1+4 125℃)=47 The Mooney viscosity (ML 1+4 125℃)=215 Composition of (A1-i) Proportion of structural units derived from ethylene = 70.0% by mass Proportion of structural units derived from propylene=21.5% by mass Proportion of structural units derived from 5-ethylidene-2-norbornene = 8.5% by mass

[0113] <Component (B)> A copolymer having structural units derived from an aromatic vinyl compound and structural units derived from a conjugated diene compound. (Bi): Trade name "TAIPOL (registered trademark) 6151" manufactured by TSRC Co., Ltd. Proportion of monomer units derived from styrene = 32.5 mass%, weight average molecular weight in terms of polystyrene = 240,000

[0114] <Component (C)> Propylene polymer (C1-i): Propylene homopolymer, manufactured by Sumitomo Chemical Co., Ltd., product name "Sumitomo Noblen D101", MFR (230°C, 21.18N) = 0.5g / 10min (C1-ii): Propylene homopolymer manufactured by Sumitomo Chemical Co., Ltd. Product name "Sumitomo Noblen R101" (230°C, 21.18N) = 20g / 10min

[0115] <Component (D)> Lubricant (D1-i): Erucic acid amide, manufactured by Nippon Fine Chemical Co., Ltd., trade name "Neutron S", molecular weight = 338 (D2-i): Ethylenebisstearic acid amide, product name "Alflow H-50P" manufactured by NOF Corporation, molecular weight = 593

[0116] <Component (F)> Crosslinking agent (Fi)+(Ei): Trade name "APO-10DL" manufactured by Kayaku Akzo Co., Ltd. (a mixture of 10% by mass of component (Fi) and 90% by mass of component (Ei) (wherein the total amount of (Fi) and (Ei) is 100% by weight)) (Fi): 2,5-dimethyl-2,5-di(t-butylperoxy)hexane

[0117] <Component (E)> Mineral oil (Ei): Paraffinic mineral oil, manufactured by Idemitsu Kosan Co., Ltd., product name "PW-100", pour point = -12.5°C

[0118] Crosslinking agent: Sumitomo Chemical Co., Ltd., product name "Sumifine BM" (N,N'-m-phenylene bismaleimide)

[0119] Antioxidant: BASF Japan Ltd., product name "IRGANOX (registered trademark) 1010"

[0120] Black pigment masterbatch: Sumika Color Co., Ltd. Product name "PEM8080G"

[0121] <Example 1> 75.0 parts by mass of oil-extended ethylene random copolymer ((A2-i)+(F)), 20.0 parts by mass of propylene homopolymer (Ci), 0.125 parts by mass of fatty acid amide (Di), 0.2 parts by mass of fatty acid amide (D-ii), 3 parts by mass of crosslinking agent ((Ei)+(Fi)), 0.1 parts by mass of crosslinking coagent, 0.2 parts by mass of antioxidant, and 1.2 parts by mass of pigment were melt-kneaded at a cylinder temperature of 200°C±20°C in the upstream process of a twin-screw extruder (TEX34αIII) manufactured by Japan Steel Works, Ltd., and 5 parts by mass of propylene homopolymer (Ci) were melt-kneaded at a cylinder temperature of 200°C±20°C in the downstream process of the twin-screw extruder to obtain a thermoplastic elastomer composition. The obtained thermoplastic elastomer composition was injection molded by the above method (1) or (3), and press molded by the above method (4) to obtain a molded body. The results of measuring the physical properties of the molded product and the evaluation results of the adhesion to a thermoplastic elastomer molded product are shown in Table 1.

[0122] <Examples 2 to 5 and Comparative Examples 1 and 2> Thermoplastic elastomer molded articles were produced and evaluated in the same manner as in Example 1, except that the composition of the raw materials was changed as shown in Table 1. The results are shown in Table 1.

[0123] [Table 1] [Industrial Applicability]

[0124] The thermoplastic elastomer molded product of the present invention can effectively suppress the peeling sound from glass and has excellent bondability to other members, and is therefore suitable for use in a variety of automobile interior and exterior parts, such as glass run channels, weather strips, door grommets, instrument panels, glove boxes, trims, housings, pillars, bumpers, fenders, and back doors, as well as various parts for home appliances, various housing equipment parts, various industrial parts, and various building material parts, and has high applicability in various industrial fields, such as the transportation machinery industry, the electrical and electronics industry, and the building and construction industry.

Claims

1. A molded article comprising (A) an ethylene copolymer and (B) at least one component selected from the group consisting of copolymers having structural units derived from aromatic vinyl compounds and structural units derived from conjugated diene compounds, (C) a propylene polymer, and (D) a lubricant, The flexural modulus at room temperature, as measured in accordance with JIS K7171, is between 20 MPa and 300 MPa. Two test pieces, each measuring 50 mm in length, 6 mm in width, and 2 mm in thickness, cut from the molded body, are placed on a flat plate with a 60 mm gap between their opposing 50 mm x 2 mm surfaces. The two test pieces are fixed to the flat plate on one 50 mm x 6 mm surface, and the other 50 mm x 6 mm surface is placed in direct contact with a 110 mm x 110 mm surface of a float glass plate measuring 110 mm in length, 110 mm in width, and 3 mm in thickness, conforming to JIS R 3202. After standing at 80°C for 50 hours, the shear strength obtained when the interlayer between the two test pieces and the float glass plate is tensed at 200 mm / min in the shear direction and along the length of the test piece is 40 N / cm². ２ The above-mentioned molded body is as follows:

2. (A) The molded article according to claim 1, comprising an ethylene copolymer.

3. The molded article according to claim 2, further comprising (E) mineral oil.

4. The molded article according to claim 3, wherein (A) an ethylene copolymer is spread in (E) mineral oil.

5. (B) The molded article according to claim 1, comprising a copolymer having structural units derived from an aromatic vinyl compound and structural units derived from a conjugated diene compound.

6. The molded article according to claim 5, further comprising (E) mineral oil.

7. (D) The molded article according to claim 1, wherein the lubricant contains at least (D1) monofatty acid amide and (D2) bisfatty acid amide, and the mass ratio of (D1) monofatty acid amide to (D2) bisfatty acid amide is in the range of 0.2 to 5.

8. The molded article according to claim 7, wherein the mass ratio of (D1) monofatty acid amide / (D2) bisfatty acid amide is in the range of 0.2 to 1.

9. (D1) The molded article according to claim 7, wherein the monofatty acid amide is erucic acid amide.

10. (D2) The molded article according to claim 7(1), wherein the bis fatty acid amide is ethylene bisstearic acid amide.

11. A method for producing a molded article according to any one of claims 1 to 10, comprising the step of melt-kneading a mixture containing (A) an ethylene copolymer and (B) a copolymer having structural units derived from an aromatic vinyl compound and structural units derived from a conjugated diene compound, (C) a propylene polymer, and (D) a lubricant, in the presence of (F) a crosslinking agent.

12. The molded article according to any one of claims 1 to 10, which is an injection-molded article.

13. A composite molded article obtained by joining an injection-molded article according to claim 12 with an extruded article comprising a thermoplastic elastomer composition or a vulcanized rubber composition.

14. A composite molded article according to claim 13, wherein the glass run channel.

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