Thermoplastic elastomer composition

Abstract

The present invention discloses a thermoplastic elastomer composition, which comprises the following components (A), (B), (C) and (D), wherein the weight ratio of component (C) to component (D) is 0.1 or more and less than 2. Component (A): An ethylene random copolymer containing 50% by weight or more and 90% by weight or less of monomer units derived from ethylene and monomer units derived from at least one monomer selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms, wherein the total amount of the ethylene random copolymer is 100% by weight; Component (B): A polymer containing more than 50% by weight and 100% by weight or less of monomer units derived from propylene, wherein the total amount of the polymer is 100% by weight; Component (C): A copolymer containing an ethylene polymerization block and an ethylene-α-olefin copolymerization block; Component (D): An ethylene polymer containing more than 90% by weight and 100% by weight or less of monomer units derived from ethylene, wherein the total amount of the ethylene polymer is 100% by weight.

Description

[0001] This application claims the priority of Japanese Patent Application No. 2017-099569 filed in Japan on May 19, 2017, the disclosure of which is incorporated herein by reference. TECHNICAL FIELD

[0002] The present invention relates to a thermoplastic elastomer composition. BACKGROUND ART

[0003] Thermoplastic elastomer compositions obtained by melt-kneading a composition containing an ethylene random copolymer rubber and a propylene polymer are used in various fields of automotive parts, various industrial parts, and various building materials due to their advantage of flexibility. For example, Patent Document 1 describes a thermoplastic elastomer composition obtained by dynamically heat-treating an ethylene-α-olefin copolymer rubber and a propylene polymer in the presence of a crosslinking agent.

[0004] [Prior Art Documents]

[0005] [Patent Documents]

[0006] [Patent Document 1] JP-A No. 2000-281845 SUMMARY OF THE INVENTION

[0007] In recent years, due to the diversification of automotive designs, there has been an increasing demand for composite molded bodies in which molded bodies containing a thermoplastic elastomer composition are welded to each other and for composite molded bodies in which a molded body containing a thermoplastic elastomer composition and a molded body containing an ethylene polymer are welded to each other. Although the adhesiveness between molded bodies containing a conventional thermoplastic elastomer composition is good, the adhesiveness of a molded body containing a conventional thermoplastic elastomer composition to a molded body containing an ethylene polymer is insufficient.

[0008] In view of such actual situations, the problem to be solved by the present invention is to provide a thermoplastic elastomer composition, and a molded body containing the thermoplastic elastomer composition, which exhibit excellent adhesiveness to both a thermoplastic elastomer molded body and a molded body containing an ethylene polymer.

[0009] The present invention includes the inventions described in [1] to

[10] .

[0010] [1] A thermoplastic elastomer composition comprising

[0011] the following components (A), (B), (C), and (D),

[0012] wherein the weight ratio of component (C) to component (D) is 0.1 or more and less than 2,

[0013] Component (A): An ethylene random copolymer containing monomer units derived from ethylene in an amount of 50% by weight or more and 90% by weight or less, and monomer units derived from at least one monomer selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms, wherein the total amount of the ethylene random copolymer is 100% by weight,

[0014] Component (B): A polymer containing monomer units derived from propylene in an amount of more than 50% by weight and 100% by weight or less, wherein the total amount of the polymer is 100% by weight,

[0015] Component (C): A copolymer containing an ethylene polymerization block and an ethylene-α-olefin copolymerization block,

[0016] Component (D): An ethylene polymer containing monomer units derived from ethylene in an amount of more than 90% by weight and 100% by weight or less, wherein the total amount of the ethylene polymer is 100% by weight.

[0017] [2] The thermoplastic elastomer composition according to [1], wherein the gel fraction of the component (A) exceeds 10% by weight.

[0018] [3] A thermoplastic elastomer composition prepared by melt-kneading the following components (A-2), (B), (C), (D) and (E),

[0019] wherein the weight ratio of the component (C) to the component (D) is 0.1 or more and less than 2,

[0020] Component (A-2): An ethylene random copolymer containing monomer units derived from ethylene in an amount of 50% by weight or more and 90% by weight or less, and monomer units derived from at least one monomer selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms, wherein the total amount of the ethylene random copolymer is 100% by weight, and

[0021] wherein the gel fraction of the ethylene random copolymer is 10% by weight or less,

[0022] Component (B): A polymer containing monomer units derived from propylene in an amount of more than 50% by weight and 100% by weight or less, wherein the total amount of the polymer is 100% by weight,

[0023] Component (C): An olefin block copolymer containing an ethylene polymerization block and an ethylene-α-olefin copolymerization block,

[0024] Component (D): A polymer containing monomer units derived from ethylene in an amount of more than 90% by weight and 100% by weight or less, wherein the total amount of the polymer is 100% by weight,

[0025] Component (E): A crosslinking agent.

[0026] [4] The thermoplastic elastomer composition according to [3], wherein the weight ratio of component (E) before melt-kneading to component (A-2) before melt-kneading is 0.001 or more and 0.3 or less.

[0027] [5] A thermoplastic elastomer composition which is prepared by melt-kneading the following components (A-2), (B) and (E) to obtain a composition, and then melt-kneading the obtained composition and the following components (C) and (D).

[0028] Component (A-2): An ethylene random copolymer containing 50% by weight or more and 90% by weight or less of monomer units derived from ethylene (where the total amount of the ethylene random copolymer is 100% by weight) and monomer units derived from at least one monomer selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms, wherein the gel fraction of the ethylene random copolymer is 10% by weight or less.

[0029] Component (B): A polymer containing more than 50% by weight and 100% by weight or less of monomer units derived from propylene, where the total amount of the polymer is 100% by weight.

[0030] Component (E): A crosslinking agent.

[0031] Component (C): An olefin block copolymer containing an ethylene polymerization block and an ethylene-α-olefin copolymerization block.

[0032] Component (D): A polymer containing more than 90% by weight and 100% by weight or less of monomer units derived from ethylene, where the total amount of the polymer is 100% by weight.

[0033] [6] The thermoplastic elastomer composition according to any one of [1] to [5], wherein the weight of the gel thermoplastic elastomer is 5% or more.

[0034] [7] A method for preparing a thermoplastic elastomer composition, the method comprising the step of melt-kneading the following components (A-2), (B), (C), (D) and (E).

[0035] Component (A-2): An ethylene random copolymer containing 50% by weight or more and 90% by weight or less of monomer units derived from ethylene (where the total amount of the ethylene random copolymer is 100% by weight) and monomer units derived from at least one monomer selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms, wherein the gel fraction of the ethylene random copolymer is 10% by weight or less.

[0036] Component (B): A polymer having monomer units derived from propylene in an amount of more than 50% by weight and 100% by weight or less (wherein the total amount of the polymer is 100% by weight),

[0037] Component (C): An olefin block copolymer containing an ethylene polymer block and an ethylene-α-olefin copolymer block,

[0038] Component (D): A polymer containing monomer units derived from ethylene in an amount of more than 90% by weight and 100% by weight or less, wherein the total amount of the polymer is 100% by weight,

[0039] Component (E): A crosslinking agent.

[0040] [8] A method for preparing a thermoplastic elastomer composition, the method comprising the following steps (1) and (2),

[0041] Step (1): A step of melt-kneading the following components (A-2), (B) and (E) to obtain a composition,

[0042] Step (2): A step of melt-kneading the composition prepared in step (1) and the following components (C) and (D).

[0043] Component (A-2): An ethylene random copolymer containing 50% by weight or more and 90% by weight or less of monomer units derived from ethylene (wherein the total amount of the ethylene random copolymer is 100% by weight) and monomer units derived from at least one monomer selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms, wherein the gel fraction of the ethylene random copolymer is 10% by weight or less,

[0044] Component (B): A polymer containing monomer units derived from propylene in an amount of more than 50% by weight and 100% by weight or less, wherein the total amount of the polymer is 100% by weight,

[0045] Component (E): A crosslinking agent,

[0046] Component (C): An olefin block copolymer containing an ethylene polymer block and an ethylene-α-olefin copolymer block,

[0047] Component (D): A polymer containing monomer units derived from ethylene in an amount of more than 90% by weight and 100% by weight or less, wherein the total amount of the polymer is 100% by weight,

[0048] [9] A molded article, the molded article comprising the thermoplastic elastomer composition according to any one of [1] to [6].

[0049]

[10] An automotive component, the automotive component comprising the molded article according to [9].

[0050] [Advantages of the Invention]

[0051] According to the present invention, a thermoplastic elastomer composition and a molded article containing the thermoplastic elastomer composition can be provided. The thermoplastic elastomer composition exhibits excellent adhesion to both a thermoplastic elastomer molded article and a molded article containing an ethylene polymer. Detailed Description of the Invention

[0052] [Definitions]

[0053] In the present specification, "α-olefin" means an olefin in which the carbon-carbon double bond is in the α-position.

[0054] In the present specification, "propylene polymer" means a polymer in which the content of monomer units derived from propylene exceeds 50% by weight, where the total weight of the polymer is 100% by weight.

[0055] In the present specification, "ethylene polymer" means a polymer in which the content of monomer units derived from ethylene is 50% by weight or more, where the total weight of the polymer is 100% by weight.

[0056] In the present specification, the term "ethylene polymerization block" means a part that constitutes a copolymer and is composed of two or more consecutive monomer units derived from ethylene.

[0057] In the present specification, "ethylene-α-olefin copolymer block" means a part that constitutes a copolymer and is composed of at least one monomer unit derived from ethylene and at least one monomer unit derived from an α-olefin having 3 or more carbon atoms.

[0058] In the present specification, "thermoplastic elastomer composition" means a composition that is a blend containing an amount of a thermoplastic resin sufficient to impart thermoplasticity and an amount of a rubber sufficient to impart rubber elasticity, where the thermoplastic resin, which consists of at least a continuous phase (matrix phase) and at least a rubber, exists as a discontinuous phase (domain phase).

[0059] [Component (A)]

[0060] Component (A) is an ethylene random copolymer having 50% by weight or more and 90% by weight or less of monomer units derived from ethylene and monomer units of at least one monomer selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms, where the total amount of the ethylene random copolymer is 100% by weight. Component (A) may also have monomer units derived from monomers other than ethylene and α-olefins having 3 or more and 10 or less carbon atoms.

[0061] α-olefins having 3 or more and 10 or less carbon atoms include propylene, 1-butene, 2-methylpropene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. The monomer unit derived from at least one selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms is more preferably a monomer unit derived from propylene, a monomer unit derived from 1-butene, or a monomer unit derived from 1-octene.

[0062] The content of the monomer unit derived from ethylene in component (A) is 50% by weight or more and 90% by weight or less, preferably 55% by weight or more and 85% by weight or less, more preferably 60% by weight or more and 75% by weight or less, where the total amount of the ethylene random copolymer is 100% by weight. The content of the monomer unit derived from at least one selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms in component (A) is 10% by weight or more and 50% by weight or less, preferably 15% by weight or more and 45% by weight or less, more preferably 25% by weight or more and 40% by weight or less, where the total amount of the ethylene random copolymer is 100% by weight.

[0063] The content of the monomer unit derived from ethylene and the content of the monomer unit derived from at least one monomer selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms in component (A) can be determined by infrared spectroscopy. Specifically, using an infrared spectrophotometer, the infrared absorption spectrum of component (A) is measured, and the content of the monomer unit derived from ethylene and the content of the monomer unit derived from at least one monomer selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms are calculated according to the method described in "Die Makromolekulare Chemie (Macromolecular Chemistry), 177, 461 (1976)" written by McRae, M.A., Madams, W.F., etc.

[0064] Component (A) may also have monomer units derived from at least one monomer other than those selected from the group consisting of ethylene and α-olefins having 3 or more and 10 or less carbon atoms. Other monomers include: conjugated dienes having 4 or more and 8 or less 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 5 or more and 15 or less 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 carboxylates, such as vinyl acetate; unsaturated carboxylic acid esters, such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate; unsaturated carboxylic acids, such as acrylic acid and methacrylic acid; and the like. Other monomers are preferably non-conjugated dienes having 5 or more and 15 or less carbon atoms, more preferably 5-ethylidene-2-norbornene or dicyclopentadiene. Component (A) may contain two or more monomer units derived from other monomers.

[0065] The content of the monomer units derived from other monomers is preferably 30% by weight or less, more preferably 20% by weight or less, based on the total amount of component (A) being 100% by weight. The content of the monomer units derived from other monomers can be determined by infrared spectroscopy. Specifically, using an infrared spectrophotometer, the peak intensity of the peaks of other monomers derived from component (A) is measured, and the content of the monomer units derived from other monomers in component (A) is calculated from the peak intensity. The content of the monomer units derived from other monomers in component (A-1) and component (A-2) can also be determined in the same manner.

[0066] Component (A) includes ethylene-propylene copolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-1-octene copolymers, ethylene-propylene-1-butene copolymers, ethylene-propylene-1-hexene copolymers, ethylene-propylene-1-octene copolymers, 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. One or more ethylene random copolymers can be used as component (A). Component (A) is preferably an ethylene-propylene copolymer or an ethylene-propylene-5-ethylidene-2-norbornene copolymer.

[0067] Component (A-1) is component (A) whose gel fraction exceeds 10% by weight. Component (A-2) is component (A) whose gel fraction is 10% by weight or less.

[0068] The higher the content of the component (A) having a crosslinked structure, the larger the gel fraction. The gel fraction of the component (A-1) is preferably 20% by weight or more, more preferably 40% by weight or more.

[0069] The component (A-1) can be obtained by crosslinking the component (A-2).

[0070] The gel fraction of the component (A-1) can be determined by the following method.

[0071] The raw material of the thermoplastic elastomer containing the component (A-2) is melt-kneaded to obtain a thermoplastic elastomer. The gel fraction is measured using a Soxhlet extractor, in which the extraction tube is connected to the lower part of the reflux condenser and the flask is connected to the lower part of the extraction tube. Weigh approximately 1 g of the thermoplastic elastomer composition and a wire basket (X) made of a wire mesh with a mesh size of 400 mesh, respectively. Introduce the wire basket containing the thermoplastic elastomer composition into the extraction tube. Introduce 300 ml of o-xylene into the flask. Heat the flask and reflux the o-xylene for 24 hours for extraction. After extraction, take out the wire basket from the extraction tube, dry it in a vacuum dryer at 100 °C under reduced pressure, and weigh the dried wire basket (Y). The gel fraction (% by weight) is calculated according to the following formula.

[0072] Gel fraction = (((weight of (Y)) - (weight of (X))) / weight of (A-2) per 1 g of thermoplastic elastomer) × 100

[0073] The process for crosslinking the component (A-2) includes the process for melt-kneading the composition containing the component (A-2) and the component (E) described below. Crosslinking can be carried out simultaneously during the melt-kneading of the thermoplastic elastomer. In this case, the composition containing the component (A-1) and the component (B) can be prepared by melt-kneading the composition containing the component (A-2), the component (B) described later, and the crosslinking agent (E), and the details are described below.

[0074] The gel fraction of the component (A-2) is preferably 5% by weight or less, more preferably 0% by weight.

[0075] Preferably, the component (A-2) has substantially no crosslinkable structure.

[0076] The Mooney viscosity (ML 1+4 100 °C) of the component (A-2) measured at 100 °C is preferably 5 or more and 300 or less, more preferably 10 or more and 200 or less. The Mooney viscosity (ML 1+4 100 °C) is measured according to JIS K6300, and "ML 1+4 100 °C" has the following meaning.

[0077] M: Mooney viscosity

[0078] L: Using large rotor

[0079] 100 °C: Measurement temperature

[0080] 1 + 4: Value measured when the rotor rotates at 2 rpm for 4 minutes after heating the sample for 1 minute

[0081] The intrinsic viscosity of component (A-2) measured in tetralin at 135 °C is preferably 0.5 dl / g or more and 8 dl / g or less, more preferably 1 dl / g or more and 6 dl / g or less.

[0082] The reduced viscosity is measured in tetralin at 135 °C using an Ubbelohde viscometer, and the intrinsic viscosity is determined by extrapolation according to the calculation method described on page 491 of "Polymer Solution, Polymer Experiment (Kobunshi Jikkengaku, 11)", published by Kyoritsu Shuppan Co., Ltd., in 1982.

[0083] Preferably, component (A-2) has no crystal melting peak in the temperature range of 110 °C or more and 125 °C or less. Preferably, for component (A-2), the crystal melting heat in the temperature range of 110 °C or more and 125 °C or less is 10 J / g or less.

[0084] The process for preparing component (A-2) includes a process for copolymerizing ethylene and at least one monomer selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms in the presence of a known complex type catalyst (such as Ziegler-Natta type catalyst, metallocene type complex, and non-metallocene type complex). The polymerization methods include slurry polymerization method, solution polymerization method, bulk polymerization method, and gas phase polymerization method.

[0085] <Component (B)>

[0086] Component (B) may also have monomer units derived from monomers different from propylene.

[0087] Monomers different from propylene include ethylene and α-olefins having 4 or more carbon atoms, and preferably ethylene and α-olefins having 4 or more and 20 or less carbon atoms.

[0088] α-olefins having 4 or more and 20 or less 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.

[0089] In component (B), the content of monomer units derived from propylene, the content of monomer units derived from ethylene, and the content of monomer units derived from at least one monomer selected from the group consisting of α-olefins having 4 or more carbon atoms can be determined by the same method as that for the content of each monomer unit in component (A).

[0090] Component (B) includes a propylene homopolymer, a propylene random copolymer, and a heterophasic propylene polymer material. The thermoplastic elastomer composition may contain only one component (B) or two or more thereof.

[0091] The propylene random copolymer includes

[0092] (1) A propylene-ethylene random copolymer in which the content of monomer units derived from propylene is 90% by weight or more and 99.5% by weight or less, and the content of monomer units derived from ethylene is 0.5% by weight or more and 10% by weight or less, and the total amount of monomer units derived from propylene and monomer units derived from ethylene is 100% by weight;

[0093] (2) A propylene-ethylene-α-olefin random copolymer in which the content of monomer units derived from propylene is 81% by weight or more and 99% by weight or less, the content of monomer units derived from ethylene is 0.5% by weight or more and 9.5% by weight or less, and the content of monomer units derived from an α-olefin having 4 or more and 10 or less carbon atoms is 0.5% by weight or more and 9.5% by weight or less, and the total amount of monomer units derived from propylene, monomer units derived from ethylene, and monomer units derived from an α-olefin having 4 or more and 10 or less carbon atoms is 100% by weight; and

[0094] (3) A propylene-α-olefin random copolymer in which the content of monomer units derived from propylene is 90% by weight or more and 99.5% by weight or less, and the content of monomer units derived from an α-olefin having 4 or more and 10 or less carbon atoms is 0.5% by weight or more and 10% by weight or less, and the total amount of monomer units derived from propylene and monomer units derived from an α-olefin having 4 or more and 10 or less carbon atoms is 100% by weight.

[0095] The α-olefins having 4 or more and 10 or less carbon atoms in (1) and (2) include linear α-olefins such as 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-decene; and branched α-olefins such as 3-methyl-1-butene and 3-methyl-1-pentene. In the preparation of (1) and (2), one or more α-olefins having 4 or more and 10 or less carbon atoms can be used.

[0096] The processes for preparing propylene homopolymers and propylene random copolymers include the processes for polymerizing propylene in the presence of complex-type catalysts such as Ziegler-Natta catalysts, metallocene complexes, and non-metallocene complexes. The polymerization methods include slurry polymerization, solution polymerization, bulk polymerization, and gas-phase polymerization.

[0097] The heterophasic propylene polymer materials include the following copolymers (I) and (II). The heterophasic propylene polymer material is a mixture having a structure in which the copolymer (II) is dispersed in the matrix of the polymer (I), and contains 50% by weight or more of monomer units derived from propylene, where the total amount of the heterophasic propylene polymer material is 100% by weight. The copolymer (II) is a copolymer containing 20% by weight or more and 90% by weight or less of monomer units derived from ethylene and monomer units derived from at least one monomer selected from the group consisting of α-olefins having 3 or more carbon atoms, where the total weight of the copolymer is 100% by weight. The polymer (I) is a polymer containing more than 80% by weight and 100% by weight or less of monomer units derived from propylene, where the total weight of the polymer is 100% by weight.

[0098] The content of the polymer (I) contained in the heterophasic propylene polymer material is preferably 70% by weight or more and 90% by weight or less, more preferably 75% by weight or more and 90% by weight or less, where the total amount of the heterophasic propylene polymer material is 100% by weight. The content of the copolymer (II) contained in the heterophasic propylene polymer material is preferably 10% by weight or more and 30% by weight or less, more preferably 10% by weight or more and 25% by weight or less, where the total amount of the heterophasic propylene polymer material is 100% by weight.

[0099] The α-olefins 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, and 2,2,4-trimethyl-1-pentene. The α-olefins having 3 or more carbon atoms are preferably α-olefins having 3 or more and 20 or less carbon atoms, more preferably α-olefins having 3 or more and 10 or less carbon atoms, still more preferably propylene, 1-butene, 1-hexene, or 1-octene. In the copolymer (II), one or more α-olefins having 3 or more carbon atoms can be used.

[0100] The content of the monomer unit derived from ethylene in the copolymer (II) is preferably 22% by weight or more and 80% by weight or less, more preferably 25% by weight or more and 70% by weight or less, still more preferably 27% by weight or more and 60% by weight or less, where the total amount of the monomer unit derived from at least one selected from the group consisting of α-olefins having 3 or more carbon atoms and the monomer unit derived from ethylene is 100% by weight. The content of the monomer unit derived from at least one monomer selected from the group consisting of α-olefins having 3 or more carbon atoms in the copolymer (II) is preferably 20% by weight or more and 78% by weight or less, more preferably 30% by weight or more and 75% by weight or less, still more preferably 40% by weight or more and 73% by weight or less, where the total amount of the monomer unit derived from at least one monomer selected from the group consisting of α-olefins having 3 or more carbon atoms and the monomer unit derived from ethylene is 100% by weight.

[0101] The copolymer (II) includes 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, and propylene-ethylene-1-octene copolymer, and preferably propylene-ethylene copolymer or propylene-ethylene-1-butene copolymer. The copolymer (II) is usually a random copolymer.

[0102] The process for preparing the heterophasic propylene polymer material includes a process for multi-stage polymerization of monomers including propylene and ethylene in the presence of a polymerization catalyst, and

[0103] The process includes a first step of polymerizing monomers including propylene in the presence of a polymerization catalyst to obtain a polymer (I), and a second step of copolymerizing ethylene and at least one monomer selected from the group consisting of α-olefins having 3 or more carbon atoms in the presence of the obtained polymer (I) to prepare a copolymer (II). The polymerization catalysts for preparing the heterogeneous propylene polymer materials include Ziegler catalysts or Ziegler-Natta catalysts, catalysts comprising an alkylaluminoxane and a compound of a transition metal belonging to Group 4 of the periodic table having a cyclopentadienyl ring, and catalysts comprising a compound of a transition metal belonging to Group 4 of the periodic table having a cyclopentadienyl group, a compound that reacts with the transition metal compound to form an ionic complex, and an organoaluminum compound. A prepolymerization catalyst can be used in the presence of the polymerization catalyst. The prepolymerization catalysts include the catalysts described in JP-A No. Sho-61-218606, JP-A No. Sho-61-287904, JP-A No. Hei-5-194685, JP-A No. Hei-7-216017, JP-A No. Hei-9-316147, JP-A No. Hei-10-212319, and JP-A No. 2004-182981.

[0104] The polymerization methods for preparing the heterogeneous propylene polymer materials include bulk polymerization, solution polymerization, slurry polymerization, and gas-phase polymerization. The inert hydrocarbon solvents used in solution polymerization and slurry polymerization include propane, butane, isobutane, pentane, hexane, heptane, and octane. Two or more of these polymerization methods can be combined, and the polymerization method can be either batch or continuous. The polymerization method for preparing the heterogeneous propylene polymer materials is preferably continuous gas-phase polymerization and bulk-gas-phase polymerization, in which bulk polymerization and gas-phase polymerization are carried out continuously.

[0105] From the standpoint of the adhesion to both the thermoplastic elastomer molded body and the molded body containing an ethylene polymer, the melt flow rate (hereinafter referred to as "MFR") of component (B) measured under the conditions of a temperature of 230 °C and a load of 21.18 N according to JIS K7210 is preferably 0.1 g / 10 min or more and 150 g / 10 min or less, more preferably 0.1 g / 10 min or more and 50 g / 10 min or less, still more preferably 0.2 g / 10 min or more and 15 g / 10 min or less.

[0106] Component (B) is preferably a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-ethylene-1-butene random copolymer, or a heterogeneous propylene polymer material, more preferably a propylene homopolymer, an ethylene-propylene random copolymer, or a heterogeneous propylene polymer material.

[0107] <Component (C)>

[0108] In component (C), the ethylene polymerization block and the ethylene-α-olefin copolymerization block are bonded by a covalent bond.

[0109] The thermoplastic elastomer composition may contain a single kind or two or more kinds of component (C).

[0110] Component (C) has a crystal melting peak in the temperature range of above 110°C and below 125°C, and the heat of crystal melting of the crystal melting peak is preferably 20 J / g or more and 60 J / g or less, more preferably 30 J / g or more and 50 J / g or less. The crystal melting peak in the temperature range of above 110°C and below 125°C in component (C) originates from the ethylene polymerization block of component (C).

[0111] The ethylene polymerization block in component (C) may have monomer units derived from other monomers different from ethylene. Other monomers include propylene, 1-butene, 2-methylpropene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Other monomers are preferably α-olefins having 3 or more and 10 or less carbon atoms, such as propylene, 1-butene, 1-hexene, and 1-octene. The ethylene polymerization block of component (C) may contain a single kind or two or more kinds of monomer units derived from monomers different from ethylene.

[0112] The content of the monomer unit derived from ethylene in the ethylene polymerization block is preferably 95% by weight or more, more preferably 98% by weight or more, where the total amount of the ethylene polymerization block is 100% by weight.

[0113] The ethylene-α-olefin copolymerization block is a copolymerization block having a monomer unit derived from ethylene and a monomer unit derived from an α-olefin having 3 or more carbon atoms. In the ethylene-α-olefin copolymerization block, the α-olefin having 3 or more carbon atoms includes propylene, 1-butene, 2-methylpropene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene, and preferably an α-olefin having 3 or more and 10 or less carbon atoms, such as propylene, 1-butene, 1-hexene, and 1-octene. The ethylene-α-olefin copolymerization block may contain only a single kind or two or more kinds of monomer units derived from an α-olefin having 3 or more carbon atoms.

[0114] The ethylene-α-olefin copolymerization block includes an ethylene-1-butene copolymerization block, an ethylene-1-hexene copolymerization block, an ethylene-1-octene copolymerization block, an ethylene-propylene-1-butene copolymerization block, an ethylene-propylene-1-hexene copolymerization block, and an ethylene-propylene-1-octene copolymerization block. The ethylene-α-olefin copolymerization block is preferably an ethylene-1-octene copolymerization block.

[0115] Component (C) may contain a single type or two or more ethylene-α-olefin copolymer blocks.

[0116] The content of monomer units derived from ethylene in the ethylene-α-olefin copolymer block is preferably less than 95% by weight, more preferably 90% by weight or less, still more preferably 60% by weight or less, where the total amount of the ethylene-α-olefin copolymer block is 100% by weight.

[0117] The ethylene-α-olefin copolymer block may also have monomer units derived from other monomers different from ethylene and α-olefins having 3 or more carbon atoms. Other monomers include non-conjugated dienes. 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; cyclic non-conjugated dienes such as cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene and 6-chloromethyl-5-isopropenyl-2-norbornene. Preferred are 5-ethylidene-2-norbornene and dicyclopentadiene.

[0118] When component (C) has monomer units derived from other monomers different from ethylene and α-olefins having 3 or more carbon atoms, the content is usually 10% by weight or less, preferably 5% by weight or less, where the total amount of component (C) is 100% by weight. The content of each monomer unit of component (C) can be determined by infrared spectroscopy.

[0119] The content of monomer units derived from ethylene in component (C) is 50% by weight or more and 90% by weight or less, preferably 55% by weight or more and 85% by weight or less, still more preferably 60% by weight or more and 75% by weight or less, where the total amount of monomer units derived from ethylene and at least one monomer unit selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms in component (C) is 100% by weight. The content of monomer units derived from at least one monomer selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms in component (C) is 10% by weight or more and 50% by weight or less, preferably 15% by weight or more and 45% by weight or less, still more preferably 25% by weight or more and 40% by weight or less, where the total amount of monomer units derived from ethylene and at least one monomer unit selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms in component (C) is 100% by weight.

[0120] The content of the monomer unit derived from ethylene in component (C) and the content of the monomer unit derived from at least one selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms can be determined by infrared spectroscopy.

[0121] Component (C) is preferably an olefin block copolymer containing an ethylene homopolymer block and an ethylene-1-octene copolymer block.

[0122] The glass transition temperature of component (C) is preferably -80°C or higher and -50°C or lower, more preferably -75°C or higher and -60°C or lower. The glass transition temperature of component (C) is derived from the ethylene-α-olefin copolymer block. The glass transition temperature is determined by the DSC method.

[0123] The MFR of component (C) measured under the conditions of a temperature of 190°C and a load of 21.18 N according to JIS K7210 is not particularly limited, and it is 0.01 g / 10 min or more and 10 g / 10 min or less, preferably 0.05 g / 10 min or more and 8 g / 10 min or less, more preferably 0.10 g / 10 min or more and 5 g / 10 min or less.

[0124] Component (C) can be synthesized according to the methods disclosed in Translated International Publication No. 2007-529617, Translated International Publication No. 2008-537563, and Translated International Publication No. 2008-543978. For example, a composition containing a mixture or reaction product obtained by combining the following is prepared: a first olefin polymerization catalyst, a second olefin polymerization catalyst capable of preparing a polymer having different chemical or physical properties from the polymer prepared under the same polymerization conditions using the first olefin polymerization catalyst, and a chain shuttling agent, and component (C) can be prepared by a step of bringing an α-olefin and ethylene into contact with the composition under addition polymerization conditions.

[0125] For the polymerization of component (C), a continuous solution polymerization method is preferably applied. In the continuous solution polymerization method, the catalyst component, the chain shuttling agent, the monomer, and, if necessary, the solvent, the auxiliary agent, the scavenger, and the polymerization auxiliary agent are continuously fed into the reaction zone, and the polymer product is continuously taken out of the system. The length of the block can be changed by controlling the ratio and type of the catalyst, the ratio and type of the chain shuttling agent, and the polymerization temperature.

[0126] Other conditions for the synthesis method of component (C) are disclosed in translated International Publication No. 2007-529617, translated International Publication No. 2008-537563, and translated International Publication No. 2008-543978. Commercially available corresponding products include, for example, the Engage (registered trademark)-XLT series and INFUSE (registered trademark) series manufactured by The Dow Chemical Company.

[0127] <Component (D)>

[0128] Component (D) may also have monomer units derived from monomers other than ethylene.

[0129] Monomers other than ethylene include: conjugated dienes having 4 or more and 8 or less carbon atoms, such as α-olefins having 3 or more and 10 or less carbon atoms, 1,3-butadiene, 2-methyl-1,3-butadiene, 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene; non-conjugated dienes having 5 or more and 15 or less 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 carboxylates, such as vinyl acetate; unsaturated carboxylic acid esters, such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate; unsaturated carboxylic acids, such as acrylic acid and methacrylic acid.

[0130] Component (D) includes ethylene homopolymers and ethylene copolymers having monomer units derived from ethylene and monomer units derived from monomers other than ethylene. The ethylene copolymer as component (D) may have only one monomer unit derived from a monomer other than ethylene, or may have two or more monomer units derived from monomers other than ethylene. Component (D) is preferably an ethylene homopolymer, an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-pentene copolymer, an ethylene-4-methyl-1-pentene copolymer, an ethylene-1-hexene copolymer, etc., and more preferably high-density polyethylene.

[0131] The MFR of component (D) measured under the conditions of a temperature of 190 °C and a load of 21.18 N according to JIS K7210 is not particularly limited, and it is generally 0.01 g / 10 min or more and 200 g / 10 min or less, preferably 1.0 g / 10 min or more and 100 g / 10 min or less, and more preferably 5 g / 10 min or more and 30 g / 10 min or less.

[0132] The density of component (D) measured according to JIS K7112 is preferably 0.91 g / cm 3Above and 0.97 g / cm 3 Below, more preferably 0.94 g / cm 3 Above and 0.97 g / cm 3 Below.

[0133] Component (D) can be prepared by polymerizing ethylene in the presence of a polymerization catalyst such as a Ziegler-Natta catalyst and a metallocene catalyst. The polymerization methods include solution polymerization, bulk polymerization, slurry polymerization and gas phase polymerization, and two or more of these methods can be combined.

[0134] <Component (E)>

[0135] Component (E) includes organic peroxides, sulfur compounds and alkylphenol resins, and organic peroxides are preferred.

[0136] Organic peroxides include ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates, diperoxycarbonates and peroxy esters. 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-butyl cumyl peroxide, di-tert-butyl peroxide, 2,2,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzohydroperoxide, cumene hydroperoxide, tert-butyl peroxide, 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide and p-chlorobenzoyl peroxide.

[0137] One or more organic peroxides can be used.

[0138] Component (E) can also be combined with a crosslinking aid for increasing the crosslinking degree of component (A-1). Preferred crosslinking aids are compounds having two or more double bonds. Crosslinking aids include: peroxide crosslinking aids such as N,N'-m-phenylenebismaleimide, tolylene bismaleimide, p-benzoquinone dioxime, nitrobenzene, diphenyl guanidine and trimethylolpropane; and divinyl benzene, triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and allyl methacrylate, and trimethylolpropane trimethacrylate is preferred.

[0139] <Component (F)>

[0140] Component (F) is a mineral oil. The thermoplastic elastomer composition may contain Component (F). Component (F) includes high-boiling fractions of petroleum having an average molecular weight of more than 300 and less than 1500 and a pour point of 0 °C or lower, such as aromatic mineral oil, naphthenic mineral oil, and paraffinic mineral oil. Paraffinic mineral oil is preferably used as Component (F).

[0141] Component (F) can be blended as an extender oil for Component (A-2). The process for blending Component (F) into Component (A-2) includes a process of mechanically kneading Component (A-2) and Component (F) using a kneading device (such as a roll and a Banbury mixer), a process of adding a specified amount of Component (F) to a solution of Component (A-2) to obtain a mixed liquid, and then removing the solvent from the obtained mixed liquid by a method such as spray drying, steam stripping, and supercritical drying using carbon dioxide, and a process of directly adding the oil to the rubber in the form of latex and stripping the mixture, and then coagulating the rubber.

[0142] When Component (F) is blended as an extender oil for Component (A-2), the Mooney viscosity (ML 1+4 100 °C) of the composition containing Component (F) and Component (A-2) is preferably 5 or more and 300 or less, more preferably 10 or more and 200 or less. The Mooney viscosity (ML 1+4 100 °C) is measured according to JIS K6300.

[0143] (Thermoplastic elastomer composition)

[0144] The thermoplastic elastomer composition contains Components (A), (B), (C), and (D), where the weight ratio of Component (C) to Component (D) (weight of Component (C) / weight of Component (D)) is 0.1 or more and less than 2.

[0145] The gel fraction of Component (A) contained in the thermoplastic elastomer composition may exceed 10% by weight.

[0146] From the viewpoint of the adhesion to both the thermoplastic elastomer molded body and the molded body containing an ethylene polymer, the content of Component (A) in the thermoplastic elastomer composition is preferably 10 parts by weight or more and 80 parts by weight or less, more preferably 30 parts by weight or more and 70 parts by weight or less, still more preferably 40 parts by weight or more and 60 parts by weight or less, based on the total amount of 100 parts by weight of Components (A), (B), (C), and (D).

[0147] From the viewpoint of the adhesiveness to both the thermoplastic elastomer molded body and the molded body containing an ethylene polymer, the content of component (B) in the thermoplastic elastomer composition is preferably 5 parts by weight or more and 50 parts by weight or less, more preferably 10 parts by weight or more and 40 parts by weight or less, still more preferably 15 parts by weight or more and 30 parts by weight or less, based on the total amount of 100 parts by weight of components (A), (B), (C) and (D).

[0148] From the viewpoint of the adhesiveness to both the thermoplastic elastomer molded body and the molded body containing an ethylene polymer, the content of component (C) in the thermoplastic elastomer composition is preferably 0.1 part by weight or more and 40 parts by weight or less, more preferably 3 parts by weight or more and 25 parts by weight or less, still more preferably 5 parts by weight or more and 20 parts by weight or less, based on the total amount of 100 parts by weight of components (A), (B), (C) and (D).

[0149] From the viewpoint of the adhesiveness to both the thermoplastic elastomer molded body and the molded body containing an ethylene polymer, the content of component (D) in the thermoplastic elastomer composition is preferably 0.1 part by weight or more and 50 parts by weight or less, more preferably 10 parts by weight or more and 40 parts by weight or less, still more preferably 20 parts by weight or more and 30 parts by weight or less, based on the total amount of 100 parts by weight of components (A), (B), (C) and (D).

[0150] From the viewpoint of the adhesiveness to both the thermoplastic elastomer molded body and the molded body containing an ethylene polymer, the weight ratio of component (C) to component (D) is preferably 0.2 or more and less than 1.5, more preferably 0.2 or more and 1 or less, and still more preferably 0.25 or more and less than 1.0.

[0151] Preferably, the total amount of components (A), (B), (C) and (D) is 60% by weight or more, with the total amount of the thermoplastic elastomer composition being 100% by weight.

[0152] A thermoplastic elastomer composition prepared by melt-kneading components (A-2), (B), (C), (D) and (E), wherein the weight ratio of component (C) to component (D) is 0.1 or more and less than 2.

[0153] From the viewpoint of the adhesiveness to both the thermoplastic elastomer molded body and the molded body containing an ethylene polymer, the weight of component (A-2) before melt-kneading is preferably 10 parts by weight or more and 80 parts by weight or less, more preferably 30 parts by weight or more and 70 parts by weight or less, still more preferably 40 parts by weight or more and 60 parts by weight or less, based on the total amount of 100 parts by weight of components (A-2), (B), (C) and (D) before melt-kneading.

[0154] From the viewpoint of the adhesiveness to both the thermoplastic elastomer molded article and the molded article containing an ethylene polymer, the content of component (B) in the thermoplastic elastomer composition is preferably 5 parts by weight or more and 50 parts by weight or less, more preferably 10 parts by weight or more and 40 parts by weight or less, still more preferably 15 parts by weight or more and 30 parts by weight or less, based on the total amount of 100 parts by weight of components (A-2), (B), (C) and (D) before melt-kneading.

[0155] From the viewpoint of the adhesiveness to both the thermoplastic elastomer molded article and the molded article containing an ethylene polymer, the content of component (C) in the thermoplastic elastomer composition is preferably 0.1 part by weight or more and 40 parts by weight or less, more preferably 3 parts by weight or more and 25 parts by weight or less, still more preferably 5 parts by weight or more and 20 parts by weight or less, based on the total amount of 100 parts by weight of components (A-2), (B), (C) and (D) before melt-kneading.

[0156] From the viewpoint of the adhesiveness to both the thermoplastic elastomer molded article and the molded article containing an ethylene polymer, the content of component (D) in the thermoplastic elastomer composition is preferably 0.1 part by weight or more and 50 parts by weight or less, more preferably 10 parts by weight or more and 40 parts by weight or less, still more preferably 20 parts by weight or more and 30 parts by weight or less, based on the total amount of 100 parts by weight of components (A-2), (B), (C) and (D) before melt-kneading.

[0157] From the viewpoint of the adhesiveness to both the thermoplastic elastomer molded article and the molded article containing an ethylene polymer, the weight ratio of component (C) to component (D) is preferably 0.2 or more and less than 1.5, still more preferably 0.25 or more and less than 1.0.

[0158] From the viewpoint of the adhesiveness to both the thermoplastic elastomer molded article and the molded article containing an ethylene polymer, the weight of component (E) before melt-kneading is preferably 0.001 part by weight or more and 3 parts by weight or less, more preferably 0.1 part by weight or more and 2.5 parts by weight or less, still more preferably 0.2 part by weight or more and 2 parts by weight or less, based on the total amount of 100 parts by weight of components (A-2), (B), (C) and (D) before melt-kneading.

[0159] When a crosslinking aid is used together with component (E), the weight of the crosslinking aid before melt-kneading is preferably 0.01 part by weight or more and 10 parts by weight or less, more preferably 0.05 part by weight or more and 2 parts by weight or less, based on the total amount of 100 parts by weight of components (A-2), (B), (C) and (D).

[0160] From the viewpoint of the adhesiveness to both the thermoplastic elastomer molded body and the molded body containing an ethylene polymer, the weight ratio of the component (E) before melt-kneading to the component (A-2) before melt-kneading (weight of component (E) / weight of component (A-2)) is preferably 0.001 or more and 0.3 or less, more preferably 0.002 or more and 0.2 or less, still more preferably 0.003 or more and 0.01 or less.

[0161] Preferably, the total amount of the component (A-2), the component (B), the component (C) and the component (D) before melt-kneading is 60% by weight or more, where the total amount of the thermoplastic elastomer composition is 100% by weight.

[0162] From the viewpoint of the adhesiveness to both the thermoplastic elastomer molded body and the molded body containing an ethylene polymer, the weight ratio of the component (C) to the component (B) (weight of component (C) / weight of component (B)) is preferably 0.1 or more and less than 2, more preferably 0.2 or more and less than 1.5, still more preferably 0.25 or more and less than 1.0.

[0163] The thermoplastic elastomer composition may contain the component (F), or may not contain the component (F). When the thermoplastic elastomer composition contains the component (F), the content of the component (F) in the thermoplastic elastomer composition is preferably 1 part by weight or more and 100 parts by weight or less, more preferably 10 parts by weight or more and 80 parts by weight or less, still more preferably 20 parts by weight or more and 60 parts by weight or less, based on the total amount of 100 parts by weight of the components (A), (B), (C) and (D).

[0164] When the thermoplastic elastomer composition contains the component (F), preferably, the total amount of the components (A), (B), (C), (D) and (F) is 80% by weight or more, where the total amount of the thermoplastic elastomer composition is 100% by weight.

[0165] When the thermoplastic elastomer composition contains the component (F), the content of the component (F) in the thermoplastic elastomer composition is 1 part by weight or more and 100 parts by weight or less, more preferably 10 parts by weight or more and 80 parts by weight or less, still more preferably 20 parts by weight or more and 60 parts by weight or less, based on the total amount of 100 parts by weight of the components (A-2), (B), (C) and (D) before melt-kneading.

[0166] When the thermoplastic elastomer composition contains the component (F), preferably, the total amount of the components (A-2), (B), (C), (D) and (F) before melt-kneading is 80% by weight or more, where the total amount of the thermoplastic elastomer composition is 100% by weight.

[0167] The content of the gel contained in the thermoplastic elastomer composition is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 20% by weight or more.

[0168] The content (%) of the gel is measured by the following method.

[0169] Weigh approximately 1 g of the thermoplastic elastomer composition and a wire basket (X) made of a wire mesh with a mesh size of 400 mesh respectively. Introduce the wire basket containing the thermoplastic elastomer composition into the extraction tube. Introduce 300 ml of o-xylene into the flask. Heat the flask and reflux the o-xylene for 24 hours for extraction. After extraction, take the wire basket out of the extraction tube and dry it in a vacuum dryer at 100 °C under reduced pressure, and then weigh the dried wire basket (Y). The weight of the gel contained in the thermoplastic elastomer composition is calculated by the following formula.

[0170] The weight of the gel contained in the thermoplastic elastomer composition = ((weight of (Y)) - ((weight of (X)))

[0171] The weight of the ash of the residue taken out from the wire basket (Y) after extraction is measured by the following ash determination method.

[0172] The content of the gel contained in the thermoplastic elastomer = ((weight of the gel contained in the thermoplastic elastomer) - (weight of the ash)) / (weight of the thermoplastic elastomer) * 100

[0173] (Ash determination method)

[0174] Heat all the obtained residues from 23 °C to 850 °C at a rate of 20 °C / min, then place them in a thermogravimetric analyzer, i.e., the TGA Q500 type manufactured by TA instruments Co., Ltd., at 850 °C for 10 minutes, and then weigh the obtained residue. The weight of the thermoplastic elastomer composition is the weight of the ash.

[0175] By the following method, the Shore A hardness of the test piece made of the thermoplastic elastomer composition measured according to JIS K6253 is preferably 30 or more, more preferably 50 or more, still more preferably 60 or more, and particularly preferably 70 or more. The Shore A hardness is preferably 99 or less, more preferably 95 or less, still more preferably 90 or less.

[0176] (Method for manufacturing a test piece for measuring Shore A hardness)

[0177] Using an injection molding machine, the thermoplastic elastomer composition is injection molded under the conditions of a molding temperature of 220 °C, a mold temperature of 50 °C, an injection time of 10 seconds, and a cooling time of 30 seconds to produce a test piece having a length of 150 mm, a width of 90 mm, and a thickness of 2.0 mm.

[0178] The method for adjusting the Shore A hardness of the thermoplastic elastomer composition to 30 or more and 99 or less includes: a method in which the total content of component (A) and component (F) is adjusted to 50% by weight or more and 90% by weight or less relative to the total amount of 100% by weight of the thermoplastic elastomer composition. When the thermoplastic elastomer composition does not contain component (F), the method for adjusting the Shore A hardness of the thermoplastic elastomer composition to 30 or more and 99 or less includes: a method in which the content of component (A) is adjusted to 50% by weight or more and 90% by weight or less relative to the total amount of 100% by weight of the thermoplastic elastomer composition. The greater the total content of component (A) and component (F) contained in the thermoplastic composition, the lower the Shore A hardness of the thermoplastic elastomer composition.

[0179] The thermoplastic elastomer composition may contain other additives and other thermoplastic resins. Other additives include inorganic fillers, organic fillers, fatty acid derivatives, antioxidants, weathering stabilizers, ultraviolet absorbers, heat stabilizers, light stabilizers, antistatic agents, nucleating agents, pigments, adsorbents, metal chlorides, flame retardants, silicone compounds, antifriction agents, antibacterial agents, and antifungal agents.

[0180] Inorganic fillers include calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, calcium sulfate, barium sulfate, magnesium sulfate, calcium phosphate, zinc oxide, iron oxide, calcium oxide, magnesium oxide, aluminum oxide, titanium oxide, barium oxide, magnesium hydroxide, calcium silicate, pyrophyllite clay, calcined clay, kaolin, talc, pyrogenic silica, fumed silica, precipitated silica, microsilica, fused silica, diatomaceous earth, mica powder, asbestos, glass fiber, glass ball, shirasu balloon, graphite, tungsten sulfide, molybdenum sulfide, alumina, mica, zeolite, clay silicate, cement, and carbon black. Among them, calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, calcium sulfate, barium sulfate, magnesium sulfate, zinc oxide, iron oxide, calcium oxide, magnesium oxide, aluminum oxide, titanium oxide, barium oxide, calcium silicate, pyrophyllite clay, calcined clay, kaolin, talc, and carbon black are preferred. One or more than two inorganic fillers can be used. The shape of the inorganic filler can be various shapes, such as powder, spherical, and flaky. The surface of the inorganic filler can be coated with at least one fatty acid derivative selected from fatty acids, fatty acid esters, and fatty acid metal salts.

[0181] Organic fillers include fibers, wood powder, and cellulose powder.

[0182] Fatty acid derivatives include fatty acids, fatty acid esters, fatty acid amides, and fatty acid metal salts. Two or more fatty acid derivatives may be included. Fatty acids include: straight-chain saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, and melissic acid; unsaturated fatty acids such as cetoleic acid and sorbic acid; aromatic carboxylic acids such as benzoic acid and phenylacetic acid. As the fatty acid ester, esters of higher fatty acids having 8 or more carbon atoms are preferred, and examples thereof include stearyl stearate, lauryl stearate, stearyl palmitate, lauryl palmitate, tristearin, and tripalmitin. Fatty acid amides include: amides of saturated fatty acids such as lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, and behenic acid amide; and amides of unsaturated fatty acids such as oleic acid amide, linoleic acid amide, linolenic acid amide, erucic acid amide, arachidonic acid amide, eicosapentaenoic acid amide, and docosahexaenoic acid amide. As the fatty acid amide, unsaturated fatty acid amides are preferred, and among them, monounsaturated fatty acid amides such as erucic acid amide and oleic acid amide are more preferred. Fatty acid metal salts preferably include sodium salts, potassium salts, calcium salts, aluminum salts, and zinc salts of fatty acids having 10 to 25 carbon atoms.

[0183] Antioxidants include phenolic antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, lactone-type antioxidants, and vitamin-based antioxidants.

[0184] Ultraviolet absorbers include benzotriazole-type ultraviolet absorbers, triazine-type ultraviolet absorbers, aniline-type ultraviolet absorbers, and benzophenone-type ultraviolet absorbers.

[0185] Light stabilizers include hindered amine-type light stabilizers and benzoate-type light stabilizers.

[0186] Metal chlorides include ferric chloride and calcium chloride.

[0187] Anti-friction agents include fluoropolymers such as polytetrafluoroethylene, perfluoroalkoxy polymer resins, fluorinated ethylene-propylene copolymers (copolymers of hexafluoropropylene and tetrafluoroethylene), polytetrafluoroethylene-polyethylene, polyvinyl fluoride, polyvinyl chlorotrifluoroethylene, polyvinylidene fluoride, polychlorotrifluoroethylene, perfluoroelastomers, and fluoroelastomers.

[0188] With respect to the total amount of 100 parts by weight of components (A), (B), (C), and (D), the content of other additives and other thermoplastic resins in the thermoplastic elastomer composition is preferably 200 parts by weight or less.

[0189] (Process for preparing the thermoplastic elastomer composition)

[0190] The process for preparing the thermoplastic elastomer composition includes the following methods (A), (B), and (C).

[0191] Method (A): A method including step (1a) of melt-kneading components (A-2), (B), (C) and (D).

[0192] Method (B): A method including step (1b) of melt-kneading components (A-2), (B), (C), (D) and (E).

[0193] Method (C): A method including step (1c) of melt-kneading components (A-2), (B) and (E) to obtain a composition and step (2c) of melt-kneading the obtained composition, component (C) and component (D).

[0194] In method (A), component (E), component (F), other additives and other thermoplastic resins may be pre-blended into component (A-2), (B), (C) or (D), may be added thereto during step (1a), or may be added after step (1a) and melt-kneaded.

[0195] In method (B), component (F), other additives and other thermoplastic resins may be pre-blended into component (A-2), (B), (C), (D) or (E), may be added thereto during step (1b), or may be added to the composition containing component (E) after step (1b) and melt-kneaded.

[0196] In method (C), component (F), other additives and other thermoplastic resins may be pre-blended into component (A-2), (B) or (E), may be added thereto and melt-kneaded during step (1c) or step (2c), or may be added after step (2c) and melt-kneaded.

[0197] From the viewpoint of the adhesion to both a thermoplastic elastomer molded body and a molded body containing an ethylene polymer, method (C) is preferred.

[0198] The melt-kneading equipment includes a mixing roll as an open-type equipment and a Banbury mixer, an extruder, a kneader and a continuous mixer as closed-type equipments, and the closed-type equipment is preferred. All components to be kneaded may be melt-kneaded together, or some components may be kneaded first, and then the remaining components may be added and melt-kneaded, or the melt-kneading may be carried out one or more times. The temperature in the melt-kneading is preferably 150 °C or higher and 250 °C or lower, and the melt-kneading time is preferably 30 seconds or longer and 30 minutes or shorter.

[0199] The components to be kneaded may be added in any order or may be added simultaneously.

[0200] The MFR of the thermoplastic elastomer composition measured according to JIS K7210 under the conditions of a temperature of 230 °C and a load of 49 N is preferably 1 g / 10 min or more, more preferably 5 g / 10 min or more, still more preferably 10 g / 10 min or more.

[0201] The density of the thermoplastic elastomer composition measured according to JIS K7112 without annealing is preferably 0.80 g / cm 3 or more and 1.5 g / cm 3 or less, more preferably 0.85 g / cm 3 or more and 1.2 g / cm 3 or less, still more preferably 0.88 g / cm 3 or more and 1.0 g / cm 3 or less.

[0202] According to JIS K6251, using a test piece of JIS No. 3, the elongation at break of the molded body containing the thermoplastic elastomer composition measured at a tensile rate of 200 mm / min is preferably 300% or more, more preferably 400% or more, still more preferably 500% or more.

[0203] The test piece of the thermoplastic is produced by the following method. The compression set measured according to JIS K6262 is preferably 70% or less, more preferably 60% or less, still more preferably 50% or less. In the method for measuring the compression set, specifically, the test piece is placed at 23 °C for 24 hours, then compressed with a compression device at a compression rate of 25%, and then immediately the test piece compressed with the compression device is placed in a constant temperature bath at 70 °C and left standing for 22 hours. After that, the test piece compressed with the compression device is removed from the constant temperature bath, and immediately the compression device is removed from the test piece compressed with the compression device. The obtained test piece is left standing at 23 °C in a constant temperature room for 30 minutes, then the thickness of the test piece is measured, and the compression set is calculated according to formula (1) of JIS K6262.

[0204] (Method for producing a test piece for measuring compression set)

[0205] Using an injection molding machine, the thermoplastic elastomer composition is injection molded under the conditions of a molding temperature of 220 °C, a mold temperature of 50 °C, an injection time of 10 seconds, and a cooling time of 30 seconds to produce a test piece having a length of 150 mm, a width of 90 mm, and a thickness of 2.0 mm.

[0206] By molding the thermoplastic elastomer composition, a molded body containing the thermoplastic elastomer composition can be obtained.

[0207] The process for preparing a molded article comprising a thermoplastic elastomer composition includes known molding methods using equipment commonly used for molding thermoplastic resins, such as extrusion molding, calendering molding, and injection molding.

[0208] The compression set of the molded article comprising the thermoplastic elastomer composition is preferably 70% or less, more preferably 60% or less, and still more preferably 50% or less. The compression set of the molded article comprising the thermoplastic elastomer composition is determined by measuring a test piece cut out from the molded article comprising the thermoplastic elastomer composition according to JIS K6262. Specifically, the test piece is placed at a temperature of 23°C for 24 hours, then compressed with a compression device at a compression rate of 25%, and then immediately the test piece compressed with the compression device is placed in a constant temperature bath at 70°C and left standing for 22 hours. Thereafter, the test piece compressed with the compression device is removed from the constant temperature bath, and immediately the compression device is removed from the test piece compressed with the compression device. The obtained test piece is left standing in a constant temperature room at 23°C for 30 minutes, then the thickness of the test piece is measured, and the compression set is calculated according to formula (1) of JIS K6262.

[0209] The molded article comprising the thermoplastic elastomer composition can be used as: materials for automotive parts, such as sealing strips, roof lining materials, interior trim panels, bumper trims, side trims, air spoilers, ventilation hoses, cup holders, side brake levers, shift knob covers, sheet adjustment knobs, flapper door seals, wire harness grommets, rack and pinion covers, suspension cover boots, glass guides, inner waistline seals, roof rail guides, trunk lid seals, molded quarter wind gaskets, corner moldings, glass encapsulations, food seals, glass run channels, secondary seals, and various packages; civil engineering and building material parts, such as waterproof materials, jointing materials, and building window frames; sports goods, such as golf club shafts and tennis racket handles; industrial parts, such as hoses and gaskets; household appliance parts, such as hoses and packages; medical device parts, wires, and various goods, and it is preferably used as a sealing strip.

[0210] Examples

[0211] The present invention will be described in more detail based on the examples below, but the present invention is not limited to these examples.

[0212] Physical property measurement methods

[0213] (1) Mooney viscosity (ML 1+4 100 °C)

[0214] The Mooney viscosity of component (A) is measured at a temperature of 100 °C according to JIS K6300.

[0215] (2) Melt flow rate (MFR, unit: g / 10 min)

[0216] The MFR of component (A), the MFR of component (C), and the MFR of component (D) are measured under the conditions of a temperature of 190 °C and a load of 21.18 N according to JIS K7210.

[0217] The MFR of component (B) is measured under the conditions of a temperature of 230 °C and a load of 21.18 N according to JIS K7210.

[0218] The MFR of the thermoplastic elastomer composition is measured under the conditions of a temperature of 230 °C and a load of 49 N according to JIS K7210.

[0219] (3) Contents of monomer units derived from ethylene, monomer units derived from propylene, and monomer units derived from 5-ethylidene-2-norbornene (unit: wt%)

[0220] The said contents are measured by infrared spectroscopy (IR method). Specifically, an ethylene-propylene-5-ethylidene-2-norbornene copolymer is formed into a film with a thickness of about 0.5 mm, and then, using an infrared spectrophotometer, the intensity of the peak (absorption peak at 1688 cm -1 −1) derived from 5-ethylidene-2-norbornene of the film is measured, and the content of the monomer units derived from 5-ethylidene-2-norbornene in the copolymer is calculated. Next, the ethylene-propylene-5-ethylidene-2-norbornene copolymer is formed into a film with a thickness of about 0.1 mm, and the infrared absorption spectrum of the film is measured using an infrared spectrophotometer, and the contents of the monomer units derived from ethylene and the monomer units derived from propylene are calculated according to the method described in the literature (Die Makromolekulare Chemie (Macromolecular Chemistry), 177, 461 (1976) written by McRae, M.A., MadamS, W.F., etc.).

[0221] (4) Injection molding

[0222] Using an injection molding machine IS100EN-3A type manufactured by Toshiba Machine Co., Ltd., the thermoplastic elastomer composition was injection molded under the conditions of a molding temperature of 220 °C, a mold temperature of 50 °C, an injection time of 10 seconds, and a cooling time of 30 seconds to obtain an injection molded body having a length of 150 mm, a width of 90 mm, and a thickness of 2.0 mm.

[0223] (5) Shore A hardness

[0224] The Shore A hardness of the injection molded body prepared in (4) above was measured according to JIS K6253.

[0225] (6) Compression set

[0226] The compression set of the injection molded body prepared in (4) above was measured according to JIS K6262. Specifically, the injection molded body was placed at 23 °C for 24 hours, and then compressed with a compression device at a compression rate of 25%. Immediately, the compression device with the injection molded body was placed in a constant temperature furnace and allowed to stand at 70 °C in the constant temperature furnace for 22 hours. Thereafter, the injection molded body compressed with the compression device was removed from the constant temperature furnace, and immediately the compression device was removed from the injection molded body compressed with the compression device. The obtained injection molded body was allowed to stand at 23 °C in a constant temperature room for 30 minutes, then the thickness of the injection molded body was measured, and the compression set was calculated according to Equation (1) of JIS K6262.

[0227] (7) Adhesion

[0228] [Adhesion to the thermoplastic elastomer molded body]

[0229] The thermoplastic elastomer molded body obtained in [Reference Example 1] (hereinafter, sometimes referred to as molded body (X) in some cases) was used as the adherend. The molded body (X) was adhered to the metal mold for injection molding with double-sided tape.

[0230] Using an injection molding machine IS100EN-3A type manufactured by Toshiba Machine Co., Ltd., each of the thermoplastic elastomer compositions prepared in the examples was injection molded under the conditions of a molding temperature of 250 °C and a mold temperature of 50 °C to obtain a molded body (Z1) in which the molded body (X) and the injection molded body containing the thermoplastic elastomer composition obtained in each example were welded. The injection direction of the molded body (X) was perpendicular to the welding plane.

[0231] The molded body (Z1) was punched with a JIS No. 3 dumbbell to produce a test piece containing the welding plane. The injection direction of the test piece was perpendicular to the welding plane. The welding plane was located in the middle of the test piece in the longer direction.

[0232] The test piece was subjected to a peeling test at a stretching rate of 200 mm / min, and the adhesion strength of the molded body (Z1) was measured simultaneously. The peeling surface of the molded body (X) of the peeled test piece was visually observed. When a part of the injection molded body containing the thermoplastic elastomer composition obtained in each example adhered to the peeling surface and the adhesion area was 50% or more with respect to the total area of the 100% peeling surface, the adhesion was evaluated as good (hereinafter, in some cases referred to as "G"). When a part of the injection molded body containing the thermoplastic elastomer composition obtained in each example adhered to the peeling surface and the adhesion area was less than 50% with respect to the total area of the 100% peeling surface, or when a part of the injection molded body containing the thermoplastic elastomer composition obtained in each example did not adhere to the peeling surface, the adhesion was evaluated as poor (hereinafter, in some cases referred to as "B").

[0233] The strength of the welding of the molded body (Z1) is preferably 3.0 MPa or more, more preferably 3.3 MPa or more.

[0234] [Adhesion to the molded body containing the ethylene polymer]

[0235] The molded body (hereinafter, in some cases referred to as molded body (Y)) containing the ethylene polymer obtained in [Reference Example 2] was used as the adherend. The molded body (Y) was adhered to the metal mold for injection molding with double-sided tape.

[0236] Using an injection molding machine IS100EN-3A type manufactured by Toshiba Machine Co., Ltd., each of the thermoplastic elastomer compositions prepared in the examples described below was injection molded under the conditions of a molding temperature of 250 °C and a mold temperature of 50 °C to obtain a molded body (Z2) in which the molded body (Y) and the injection molded body containing the thermoplastic elastomer composition obtained in each example were melt-bonded.

[0237] A test piece including a welding plane was produced using a JIS No.3 dumbbell stamping formed body (Z2). The injection direction of the test piece was perpendicular to the welding plane. A peel test was performed on the test piece at a tensile rate of 200 mm / min, and at the same time, the strength of the adhesion of the formed body (Z2) was measured. The peeled surface of the formed body (Y) of the test piece was visually observed. When a part of the injection molded body containing the thermoplastic elastomer composition obtained in each example adhered to the peeled surface and the adhesion area was 50% or more with respect to the total area of the 100% peeled surface, the adhesion was evaluated as good (hereinafter, sometimes referred to as "G" in some cases). When a part of the injection molded body containing the thermoplastic elastomer composition obtained in each example adhered to the peeled surface and the adhesion area was less than 50% with respect to the total area of the 100% peeled surface, or when a part of the injection molded body containing the thermoplastic elastomer composition obtained in each example did not adhere to the peeled surface, the adhesion was evaluated as poor (hereinafter, sometimes referred to as "B" in some cases).

[0238] The strength of the adhesion of the formed body (Z2) is preferably 3.0 MPa or more, more preferably 3.3 MPa or more.

[0239] [Reference Example 1]

[0240] (Preparation of the formed body (X))

[0241] By the method described in (4) above, "Santoprene 121-73W175" (a thermoplastic elastomer produced by ExxonMobil) was injection molded to obtain an injection molded body having a length of 150 mm, a width of 90 mm, and a thickness of 2.0 mm. Next, the injection molded body was cut with a cutting machine into a formed body (X) having a length of 30 mm, a width of 90 mm, and a thickness of 2.0 mm.

[0242] [Reference Example 2]

[0243] (Preparation of the formed body (Y))

[0244] By the method described in (4) above, "M6901" (an ethylene polymer produced by Keiyo Polyethylene Co., Ltd.) was injection molded to obtain an injection molded body having a length of 150 mm, a width of 90 mm, and a thickness of 2.0 mm. Next, the injection molded body was cut with a cutting machine into a formed body (Y) having a length of 30 mm, a width of 90 mm, and a thickness of 2.0 mm.

[0245] (8) Heat of crystal melting

[0246] The heat of crystal melting in the temperature range above 110 °C and below 125 °C is determined as such heat of melting: the heat of melting obtained by analyzing a part of the melting curve measured by differential scanning calorimetry in the temperature range above 110 °C and below 125 °C by the method according to JIS K7122-1987.

[0247] The crystal melting peak temperature in the temperature range above 110 °C and below 125 °C is determined as the top temperature of such melting peak: the top temperature of the melting peak obtained by analyzing a part of the melting curve measured by the following differential scanning calorimetry in the temperature range above 110 °C and below 125 °C by the method according to JIS K7121-1987.

[0248] The glass transition temperature is determined as such intermediate point glass transition temperature: the intermediate point glass transition temperature obtained by analyzing the melting curve measured by the following differential scanning calorimetry by the method according to JIS K7121-1987.

[0249] [Differential Scanning Calorimetry]

[0250] Using a differential scanning calorimeter, in a nitrogen atmosphere, an aluminum pan (1) with a sealed sample of about 5 mg was held at 150 °C for 5 minutes, then, (2) cooled from 150 °C to -50 °C at a rate of 5 °C / min, then, (3) held at -50 °C for 5 minutes, and then, (4) heated from -50 °C to 150 °C at a rate of 5 °C / min. The differential scanning calorimetry curve obtained by calorimetry in step (4) is the melting curve.

[0251] The materials used in the examples are described below.

[0252] A composition comprising component (A-2) and component (F)

[0253] ((A-2)1 + F1): A composition obtained by adding 100 parts by weight of a paraffinic mineral oil (F1) (produced by Idemitsu Kosan Co., Ltd., trade name "PW-380") to 100 parts by weight of an ethylene-propylene-5-ethylidene-2-norbornene copolymer ((A-2)1).

[0254] The Mooney viscosity of ((A-2)1 + F1) (ML 1+4100 °C) = 53, the content of monomer units derived from ethylene in ((A - 2)1) = 62.0 wt%, the content of monomer units derived from propylene in ((A - 2)1) = 28.1 wt%, the content of monomer units derived from 5 - ethylidene - 2 - norbornene in ((A - 2)1) = 9.9 wt%, the gel fraction of ((A - 2)1) = 0 wt%

[0255] Component (B)

[0256] (B1): Polypropylene homopolymer, produced by Sumitomo Chemical Co., Ltd., trade name "Norbrene Y501N"

[0257] MFR (230 °C, 21.18 N) = 13 g / 10 min

[0258] (B2): Heterogeneous propylene polymer material, produced by Sumitomo Chemical Co., Ltd., trade name "Norbrene AZ864"

[0259] MFR (230 °C, 21.18 N) = 30 g / 10 min

[0260] Component (C)

[0261] (C1): Trade name "Engage XLT8677", produced by The Dow Chemical Company

[0262] Crystal melting peak temperature: 119 °C, crystal melting heat in the temperature range above 110 °C and below 125 °C: 37 J / g, MFR (190 °C, 21.18 N): 0.5 g / 10 min, glass transition temperature (DSC method): -67 °C, density: 0.87 g / cm 3

[0263] (C2): Trade name "INFUSE D9007", manufactured by The Dow Chemical Company

[0264] Crystal melting peak temperature: 119 °C, crystal melting heat in the temperature range above 110 °C and below 125 °C: 37 J / g, MFR (190 °C, 21.18 N): 0.5 g / 10 min, glass transition temperature (DSC method): -67 °C, density: 0.87 g / cm 3

[0265] Component (D)

[0266] (D1): High-density polyethylene, produced by Keiyo Polyethylene Co., Ltd., trade name "M6901"

[0267] MFR (190°C, 21.18 N) = 13 g / 10 min, density 0.962 g / cm 3

[0268] The content of monomer units derived from ethylene in (D1) exceeds 90% by weight.

[0269] (D2): Low-density polyethylene, produced by Sumitomo Chemical Co., Ltd., trade name "Sumicacene-L GA801"

[0270] MFR (190°C, 21.18 N) = 20 g / 10 min, density 0.920 g / cm 3

[0271] The content of monomer units derived from ethylene in (D1) exceeds 90% by weight.

[0272] (D3): High-density polyethylene, produced by Keiyo Polyethylene Co., Ltd., trade name "M8500"

[0273] MFR (190°C, 21.18 N) = 5 g / 10 min, density 0.962 g / cm 3

[0274] The content of monomer units derived from ethylene in (D1) exceeds 90% by weight.

[0275] Component (E)

[0276] (E1 + F2): Trade name "APO-10DL", produced by Kayaku Akuzo Corporation

[0277] (A composition containing 10% by weight of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (E1) and 90% by weight of paraffinic mineral oil (F2), produced by Idemitsu Kosan Co., Ltd., trade name "PW-100"), where the total amount of (E1) and (F2) is 100% by weight)

[0278] Fatty acid amide: Produced by Nippon Fine Chemical Co., Ltd., trade name "Neutron-S" (erucic acid amide)

[0279] Crosslinking aid: Produced by Sumitomo Chemical Co., Ltd., trade name "Sumifine BM" (N, N'-m-phenylene bismaleimide)

[0280] Antioxidant: Produced by BASF Japan, trade name "Irganox 1010"

[0281] In the following Examples and Comparative Examples, a twin-screw kneading extruder (TEX-44HCT, manufactured by The Japan Steel Works, Ltd.) was used to melt-knead the materials within the range of 200°C ± 20°C for a time within the range of 40 seconds ± 20 seconds to prepare a thermoplastic elastomer composition.

[0282] [Example 1]

[0283] 100 parts by weight of ((A-2)1+F1), 25% by weight of (B1), 4.0 parts by weight of (E1+F2), 0.1 part by weight of Sumifine BM, 0.5 part by weight of Neutron-S, and 0.1 part by weight of Irganox 1010 were melt-kneaded to prepare a precursor of a thermoplastic elastomer composition. The obtained precursor of the thermoplastic elastomer composition, 12.5 parts by weight of (C1), and 12.5 parts by weight of (D1) were melt-kneaded to prepare a thermoplastic elastomer composition. The gel fraction of component (A) in the obtained thermoplastic elastomer composition was 84% by weight. The gel fraction of the obtained thermoplastic elastomer was 27%. The obtained thermoplastic elastomer composition was injection-molded by the method described in (4) above to obtain a molded article. The measurement results of the physical properties of the molded article are shown in Table 1. By the above molding method described in (7) above, the obtained thermoplastic elastomer composition was injection-molded to obtain molded articles (Z1) and (Z2). Using each of the molded articles (Z1) and (Z2), the adhesiveness described in (7) above was evaluated, and the evaluation results of the adhesiveness are shown in Table 1.

[0284] [Example 2]

[0285] The thermoplastic elastomer composition was prepared in the same manner as in Example 1, except that its components and / or contents were set as shown in Table 1. The gel fraction of component (A) in the obtained thermoplastic elastomer composition was 81% by weight. The gel content of the obtained thermoplastic elastomer was 27%. The obtained thermoplastic elastomer composition was injection-molded by the method described in (4) above to obtain a molded article. The measurement results of the physical properties of the molded article are shown in Table 1.

[0286] By the molding method described above (7), the obtained thermoplastic elastomer composition is injection molded to obtain a molded body (Z1) and a molded body (Z2). Using each of the molded body (Z1) and the molded body (Z2), the adhesiveness described above (7) is evaluated, and the evaluation results of the adhesiveness to the molded body (X) and the adhesiveness to the molded body (Y) are shown in Table 1.

[0287] [Example 3]

[0288] The thermoplastic elastomer composition was prepared in the same manner as in Example 1, except that its components and / or contents were set as shown in Table 1. The gel fraction of component (A) in the obtained thermoplastic elastomer composition was 86% by weight. The gel content of the obtained thermoplastic elastomer was 27%. By the method described above (4), the obtained thermoplastic elastomer composition was injection molded to obtain a molded body. The measurement results of the physical properties of the molded body are shown in Table 1.

[0289] By the molding method described above (7), the obtained thermoplastic elastomer composition is injection molded to obtain a molded body (Z1) and a molded body (Z2). Using each of the molded body (Z1) and the molded body (Z2), the adhesiveness described above (7) is evaluated, and the evaluation results of the adhesiveness to the molded body (X) and the adhesiveness to the molded body (Y) are shown in Table 1.

[0290] [Example 4]

[0291] 94 parts by weight of ((A-2)1+F1), 24% by weight of (B1), 6% by weight of (C1), 24% by weight of (D1), 3.8 parts by weight of (E1+F2), 0.1 part by weight of Sumifine BM, 0.5 part by weight of Neutron-S and 0.1 part by weight of Irganox 1010 were melt-kneaded to prepare a thermoplastic elastomer composition. By the method described above (4), the obtained thermoplastic elastomer composition was injection molded to obtain a molded body. The measurement results of the physical properties of the molded body are shown in Table 1. By the molding method described above (7), the obtained thermoplastic elastomer composition was injection molded to obtain a molded body (Z1) and a molded body (Z2). Using each of the molded body (Z1) and the molded body (Z2), the adhesiveness described above (7) is evaluated, and the evaluation results of the adhesiveness are shown in Table 1.

[0292] [Examples 5 to 9, and Comparative Examples 1, 2, 7 and 8]

[0293] The thermoplastic elastomer composition was prepared in the same manner as in Example 1, except that its components and / or contents were set as shown in Tables 1, 2, 3, and 4, respectively. By the method described in (4) above, each of the obtained thermoplastic elastomer compositions was injection molded to obtain a molded body. The measurement results of the physical properties of each molded body are shown in Tables 1, 2, 3, and 4. By the molding method described in (7) above, each of the obtained thermoplastic elastomer compositions was injection molded to obtain a molded body (Z1) and a molded body (Z2). Using each of the molded bodies (Z1) and (Z2), the adhesion described in (7) above was evaluated, and the evaluation results of the adhesion are shown in Tables 1, 2, 3, and 4.

[0294] [Comparative Example 3]

[0295] 114 parts by weight of ((A-2)1+F1), 29% by weight of (B1), 4.6 parts by weight of (E1+F2), 0.1 part by weight of Sumifine BM, 0.5 part by weight of Neutron-S, and 0.1 part by weight of Irganox 1010 were melt-kneaded to prepare a precursor of a thermoplastic elastomer composition. The obtained precursor of the thermoplastic elastomer composition and 14% by weight of (D1) were melt-kneaded to prepare a thermoplastic elastomer composition. By the method described in (4) above, the thermoplastic elastomer composition was injection molded to obtain a molded body. The measurement results of the physical properties of each molded body are shown in Table 3. By the molding method described in (7) above, the obtained thermoplastic elastomer composition was injection molded to obtain a molded body (Z1) and a molded body (Z2). Using each of the molded bodies (Z1) and (Z2), the adhesion described in (7) above was evaluated, and the evaluation results of the adhesion are shown in Table 3.

[0296] [Comparative Example 4]

[0297] 114 parts by weight of ((A-2)1+F1), 29% by weight of (B1), 4.6 parts by weight of (E1+F2), 0.1 part by weight of Sumifine BM, 0.5 part by weight of Neutron-S, and 0.1 part by weight of Irganox 1010 were melt-kneaded to prepare a precursor of a thermoplastic elastomer composition. The obtained precursor of the thermoplastic elastomer composition and 14% by weight of (C1) were melt-kneaded to prepare a thermoplastic elastomer composition. The obtained thermoplastic elastomer composition was injection-molded by the method described in (4) above to obtain a molded article. The measurement results of the physical properties of the molded article are shown in Table 3. The obtained thermoplastic elastomer composition was injection-molded by the molding method described in (7) above to obtain a molded article (Z1) and a molded article (Z2). Using each of the molded articles (Z1) and (Z2), the adhesiveness described in (7) above was evaluated, and the evaluation results of the adhesiveness are shown in Table 3.

[0298] [Comparative Example 5]

[0299] 134 parts by weight of ((A-2)1+F1), 33% by weight of (B1), 5.3 parts by weight of (E1+F2), 0.1 part by weight of Sumifine BM, 0.5 part by weight of Neutron-S, and 0.1 part by weight of Irganox 1010 were melt-kneaded to prepare a thermoplastic elastomer composition. The obtained thermoplastic elastomer composition was injection-molded by the method described in (4) above to obtain a molded article. The measurement results of the physical properties of the molded article are shown in Table 4. The obtained thermoplastic elastomer composition was injection-molded by the molding method described in (7) above to obtain a molded article (Z1) and a molded article (Z2). Using each of the molded articles (Z1) and (Z2), the adhesiveness described in (7) above was evaluated, and the evaluation results of the adhesiveness are shown in Table 4.

[0300] [Comparative Example 6]

[0301] 30% by weight of (B1), 30% by weight of (C1), 40% by weight of (D1), 0.5 part by weight of Neutron-S, and 0.1 part by weight of Irganox 1010 were melt-kneaded to prepare a thermoplastic elastomer composition. The obtained thermoplastic elastomer was injection-molded by the method described in (4) above. The measurement results of the physical properties of the molded article are shown in Table 4. The obtained thermoplastic elastomer composition was injection-molded by the molding method described in (7) above to obtain a molded article (Z1) and a molded article (Z2). Using each of the molded articles (Z1) and (Z2), the adhesiveness described in (7) above was evaluated, and the evaluation results of the adhesiveness are shown in Table 4.

[0302] [Table 1]

[0303]

[0304] [Table 2]

[0305]

[0306] [Table 3]

[0307]

[0308] [Table 4]

[0309]

Claims

1. A thermoplastic elastomer composition, the thermoplastic elastomer composition comprising the following components (A), (B), (C) and (D), wherein the weight ratio of component (C) to component (D) is 0.1 or more and less than 1.5, Component (A): An ethylene random copolymer comprising 50% by weight or more and 90% by weight or less of monomer units derived from ethylene and monomer units derived from at least one monomer selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms, wherein the total amount of the ethylene random copolymer is 100% by weight, Component (B): A polymer comprising more than 50% by weight and 100% by weight or less of monomer units derived from propylene, wherein the total amount of the polymer is 100% by weight, Component (C): A copolymer comprising an ethylene polymerization block and an ethylene-α-olefin copolymerization block, Component (D): An ethylene polymer comprising more than 90% by weight and 100% by weight or less of monomer units derived from ethylene, wherein the total amount of the ethylene polymer is 100% by weight.

2. The thermoplastic elastomer composition according to claim 1, wherein the gel fraction of component (A) exceeds 10% by weight.

3. A thermoplastic elastomer composition prepared by melt-kneading the following components (A-2), (B), (C), (D) and (E), wherein the weight ratio of component (C) to component (D) is 0.1 or more and less than 1.5, Component (A-2): An ethylene random copolymer comprising 50% by weight or more and 90% by weight or less of monomer units derived from ethylene and monomer units derived from at least one monomer selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms, wherein the total amount of the ethylene random copolymer is 100% by weight, and wherein the gel fraction of the ethylene random copolymer is 10% by weight or less, Component (B): A polymer comprising more than 50% by weight and 100% by weight or less of monomer units derived from propylene, wherein the total amount of the polymer is 100% by weight, Component (C): An olefin block copolymer comprising an ethylene polymerization block and an ethylene-α-olefin copolymerization block, Component (D): A polymer comprising more than 90% by weight and 100% by weight or less of monomer units derived from ethylene, wherein the total amount of the polymer is 100% by weight, Component (E): A crosslinking agent.

4. The thermoplastic elastomer composition according to claim 3, wherein the weight ratio of component (E) before melt-kneading to component (A-2) before melt-kneading is 0.001 or more and 0.3 or less.

5. A thermoplastic elastomer composition obtained by melt-kneading the following components (A-2), (B) and (E) to obtain a composition, and then melt-kneading the obtained composition and the following components (C) and (D), wherein the weight ratio of component (C) to component (D) is 0.1 or more and less than 1.5, Component (A-2): An ethylene random copolymer containing 50% by weight or more and 90% by weight or less of monomer units derived from ethylene and monomer units derived from at least one monomer selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms, wherein the total amount of the ethylene random copolymer is 100% by weight, and the gel fraction of the ethylene random copolymer is 10% by weight or less. Component (B): A polymer containing more than 50% by weight and 100% by weight or less of monomer units derived from propylene, wherein the total amount of the polymer is 100% by weight. Component (E): A crosslinking agent. Component (C): An olefin block copolymer containing an ethylene polymerization block and an ethylene-α-olefin copolymerization block. Component (D): A polymer containing more than 90% by weight and 100% by weight or less of monomer units derived from ethylene, wherein the total amount of the polymer is 100% by weight.

6. The thermoplastic elastomer composition according to any one of claims 1 to 5, wherein the weight of the gel thermoplastic elastomer is 5% or more.

7. A method for preparing a thermoplastic elastomer composition, the method comprising the step of melt-kneading the following components (A-2), (B), (C), (D) and (E), wherein the weight ratio of component (C) to component (D) is 0.1 or more and less than 1.

5. Component (A-2): An ethylene random copolymer containing 50% by weight or more and 90% by weight or less of monomer units derived from ethylene and monomer units derived from at least one monomer selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms, wherein the total amount of the ethylene random copolymer is 100% by weight, and the gel fraction of the ethylene random copolymer is 10% by weight or less. Component (B): a polymer having more than 50% by weight and not more than 100% by weight of monomer units derived from propylene (wherein, The total amount of the polymer is 100% by weight). Component (C): An olefin block copolymer containing an ethylene polymerization block and an ethylene-α-olefin copolymerization block. Component (D): A polymer containing more than 90% by weight and 100% by weight or less of monomer units derived from ethylene, wherein the total amount of the polymer is 100% by weight. Component (E): A crosslinking agent.

8. A method for preparing a thermoplastic elastomer composition, the method comprising the following steps (1) and (2). Step (1): A step of melt-kneading the following components (A-2), (B) and (E) to obtain a composition. Step (2): A step of melt-kneading the composition prepared in step (1) and the following components (C) and (D), wherein the weight ratio of component (C) to component (D) is 0.1 or more and less than 1.

5. Component (A-2): An ethylene random copolymer containing 50% by weight or more and 90% by weight or less of monomer units derived from ethylene and monomer units derived from at least one monomer selected from the group consisting of α-olefins having 3 or more and 10 or less carbon atoms, wherein the total amount of the ethylene random copolymer is 100% by weight, and the gel fraction of the ethylene random copolymer is 10% by weight or less. Component (B): A polymer containing more than 50% by weight and 100% by weight or less of monomer units derived from propylene, where the total amount of the polymer is 100% by weight, Component (E): A crosslinking agent, Component (C): An olefin block copolymer containing an ethylene polymerization block and an ethylene-α-olefin copolymerization block, Component (D): A polymer containing more than 90% by weight and 100% by weight or less of monomer units derived from ethylene, where the total amount of the polymer is 100% by weight, 9. A molded article, the molded article comprising the thermoplastic elastomer composition according to any one of claims 1 to 6.

10. An automotive component, the automotive component comprising the molded article according to claim 9.

Images