Thermoplastic elastomer composition and method for producing same

Abstract

[Problem] To provide a thermoplastic elastomer composition from which a molded article having excellent rubber elasticity, a small viscosity / swell ratio (a small viscosity and a large swell), and excellent appearance can be obtained. [Solution] A thermoplastic elastomer composition comprising: an ethylene-(α-olefin)-(non-conjugated polyene) copolymer (A) which has a structural unit derived from ethylene [A1], a structural unit derived from an α-olefin [A2] having 4-20 carbon atoms, and a structural unit derived from a non-conjugated polyene [A3] and satisfies the requirements (1) and (2) mentioned below; and a crystalline olefin-based polymer (B).　Requirement (1): The molar ratio ([A1] / [A2]) of the structural unit derived from ethylene [A1] to the structural unit derived from the α-olefin [A2] having 4-20 carbon atoms is 40 / 60 to 90 / 10.　Requirement (2): The intrinsic viscosity [η] as measured in decalin at 135°C is 4.0-7.0 dl / g.

Description

Thermoplastic elastomer composition and method for producing the same

[0001] The present invention relates to an olefin-based thermoplastic elastomer composition, and more particularly to a thermoplastic elastomer composition exhibiting good rubber elasticity and molded appearance.

[0002] Olefin-based thermoplastic elastomers (hereinafter sometimes referred to as thermoplastic elastomers) are lightweight and easily recyclable, making them energy-saving and resource-saving thermoplastic elastomers. In particular, they are used as a substitute for vulcanized rubber, exhibiting excellent heat aging resistance, weather resistance, and ozone resistance, and are widely used in applications such as automotive parts, electrical wire materials, electrical and electronic components, construction and civil engineering materials, and industrial parts. Thermoplastic elastomers are easy to mold and are expected to be used in a wide range of applications, and there is a demand for molded articles with even better appearance.

[0003] Patent Document 1 describes a thermoplastic elastomer composition in which a high molecular weight ethylene-α-olefin-non-conjugated polyene copolymer is used to enhance rubber elasticity and improve the balance with mechanical strength. However, due to the high molecular weight of the ethylene-α-olefin-non-conjugated polyene copolymer disclosed in Patent Document 1, the melt viscosity is high, and the appearance of the molded article is not necessarily good. On the other hand, reducing the melt viscosity and improving melt fluidity generally results in a smaller swell, poor transferability to the mold, and a tendency not to improve the appearance of the molded article. For these reasons, there has been a need for a thermoplastic elastomer composition that improves melt fluidity while also increasing swell.

[0004] International Publication No. 2019 / 199486 Pamphlet

[0005] When a thermoplastic elastomer is blow-molded, for example, to prevent surface roughness of the molded article, lowering the melt viscosity and increasing melt fluidity generally reduces the swell, which tends to worsen the transferability to the mold. Furthermore, conventional thermoplastic elastomers enhance their rubber elasticity by using relatively high molecular weight types of ethylene-α-olefin-non-conjugated polyene copolymers. Such thermoplastic elastomers have high melt viscosity, and the molded articles obtained from them do not necessarily have a good appearance. Therefore, the present invention aims to provide a thermoplastic elastomer composition that has excellent rubber elasticity, a small viscosity / swell ratio (low viscosity and large swell), and can produce a molded article with a superior appearance.

[0006] The inventors investigated various compositions and preparation methods to control the desired physical properties of thermoplastic elastomers and found that a thermoplastic elastomer composition containing a crystalline olefin polymer and a specific ethylene-α-olefin-non-conjugated polyene copolymer can solve the above problems, thus completing the present invention.

[0007] The present invention has the following embodiments [1] to

[11] . [1] A thermoplastic elastomer composition comprising an ethylene-α-olefin-non-conjugated polyene copolymer (A) having structural units derived from ethylene [A1], structural units derived from at least one type of α-olefin [A2] having 4 to 20 carbon atoms, and structural units derived from at least one type of non-conjugated polyene [A3], and satisfying the following requirements (1) and (2), and a crystalline olefin polymer (B). Requirement (1) The molar ratio [[A1] / [A2]] of structural units derived from ethylene [A1] to structural units derived from α-olefin [A2] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10. Requirement (2) The intrinsic viscosity [η] measured in decalin at 135°C is 4.0 to 7.0 dl / g. [2] The thermoplastic elastomer composition according to [1] above, characterized in that the α-olefin [A2] having 4 to 20 carbon atoms is 1-butene. [3] The thermoplastic elastomer composition according to [1] or [2] above, characterized in that the ethylene-α-olefin-non-conjugated polyene copolymer (A) further satisfies the following requirement (3). Requirement (3) The content of structural units derived from non-conjugated polyene [A3] is 0.1 to 6.0 mol%. (However, the total of the structural units of [A1], [A2] and [A3] shall be 100 mol%.) [4] The thermoplastic elastomer composition according to any one of [1] to [3] above, characterized in that the ethylene-α-olefin-non-conjugated polyene copolymer (A) further satisfies the following requirement (4). Requirement (4) The B value represented by the following formula (i) is 1.20 or more. B value = ([EX] + 2[Y]) / [2 × [E] × ([X] + [Y])] ... (i) Here, [E], [X] and [Y] are the mole fractions of ethylene [A1], α-olefin [A2] having 4 to 20 carbon atoms, and non-conjugated polyene [A3], respectively, and [EX] is the ethylene [A1] - α-olefin [A2] having 4 to 20 carbon atoms dyad chain fraction. [5] The thermoplastic elastomer composition according to any one of [1] to [4] above, further characterized by containing a crosslinking agent (C).[6] The thermoplastic elastomer composition according to [5] above, characterized in that it is prepared by dynamic crosslinking. [7] The thermoplastic elastomer composition according to any one of [1] to [6] above, containing the ethylene-α-olefin-non-conjugated polyene copolymer (A) and a crystalline olefin polymer (B) in a mass ratio of (A) / (B) = 90 / 10 to 10 / 90. [8] The thermoplastic elastomer composition according to any one of [1] to [7] above, wherein the content of the softener (D) is 50 to 300 parts by mass per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A). [9] The thermoplastic elastomer composition according to any one of [1] to [8] above, wherein the non-conjugated polyene [A3] is 5-ethylidene-2-norbornene (ENB).

[10] The thermoplastic elastomer composition according to [5] above, wherein the crosslinking agent (C) is at least one selected from the group consisting of phenolic resin crosslinking agents and peroxide crosslinking agents.

[11] The thermoplastic elastomer composition according to any one of [1] to

[10] above, characterized in that the viscosity / swell ratio of the thermoplastic elastomer composition is 300 to 446.

[0008] The thermoplastic elastomer composition of the present invention provides a molded article that maintains excellent moldability while having an excellent appearance.

[0009] The present invention relates to a thermoplastic elastomer composition comprising a specific ethylene-α-olefin-non-conjugated polyene copolymer (A) and a crystalline olefin polymer (B). Furthermore, the thermoplastic elastomer composition of the present invention preferably contains a crosslinking agent (C) to further improve its rubber elasticity, and it is even more preferable to prepare the composition by dynamic crosslinking. The following describes each component of the thermoplastic elastomer composition of the present invention, as well as embodiments containing the crosslinking agent (C) and embodiments prepared by dynamic crosslinking.

[0010] <<Ethylene-α-olefin-non-conjugated polyene copolymer (A)>> The ethylene-α-olefin-non-conjugated polyene copolymer (A) used in the present invention is a copolymer having structural units derived from ethylene [A1], structural units derived from at least one type of α-olefin [A2] having 4 to 20 carbon atoms, and structural units derived from at least one type of non-conjugated polyene [A3], and satisfying the following requirements (1) and (2). Requirement (1) The molar ratio [[A1] / [A2]] of structural units derived from ethylene [A1] to structural units derived from α-olefin [A2] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10. Requirement (2) The intrinsic viscosity [η] measured in decalin at 135°C is 4.0 to 7.0 dl / g.

[0011] The ethylene-α-olefin-non-conjugated polyene copolymer (A) is preferably further satisfied with the following requirement (3): Requirement (3) The content of structural units derived from non-conjugated polyene [A3] is 0.1 to 6.0 mol% (provided that the total of structural units of [A1], [A2], and [A3] is 100 mol%).

[0012] The ethylene-α-olefin-non-conjugated polyene copolymer (A) is further preferably satisfied with the following requirement (4). Requirement (4) The B value, expressed by the following formula (i), is 1.20 or greater. B value = ([EX] + 2[Y]) / [2 × [E] × ([X] + [Y])] ... (i) Here, [E], [X], and [Y] are the mole fractions of ethylene [A1], α-olefin [A2] having 4 to 20 carbon atoms, and non-conjugated polyene [A3], respectively, and [EX] is the ethylene [A1] - α-olefin [A2] having 4 to 20 carbon atoms dyad chain fraction.

[0013] Furthermore, α-olefins [A2] and non-conjugated polyenes [A3] having 4 to 20 carbon atoms may be used individually or in combination of two or more types.

[0014] α-olefins [A2] Examples of α-olefins [A2] having 4 to 20 carbon atoms in the ethylene-α-olefin-non-conjugated polyene copolymer (A) include linear α-olefins without side chains such as 1-butene (4 carbon atoms), 1-nonene (9 carbon atoms), 1-decene (10 carbon atoms), 1-nonadecene (19 carbon atoms), and 1-eicosene (20 carbon atoms); and α-olefins with side chains such as 4-methyl-1-pentene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. These α-olefins may be used individually or in combination of two or more. Among these, α-olefins having 4 to 10 carbon atoms are preferred, with 1-butene, 1-hexene, and 1-octene being more preferred. 1-butene is particularly preferred because it exhibits excellent mechanical properties such as low-temperature impact resistance, tensile strength, and tensile elongation, and can improve impact resistance and elongation at break at low temperatures. In the case of α-olefins having 4 to 20 carbon atoms [A2], the rubber elasticity at low temperatures is higher than that of ethylene-propylene-unconjugated polyene copolymers where the α-olefin is propylene, and the range of applications is also broader.

[0015] Non-conjugated polyenes [A3] Specific examples of non-conjugated polyenes [A3] in the ethylene-α-olefin-non-conjugated polyene copolymer (A) include the linear non-conjugated dienes 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, and the cyclic non-conjugated dienes cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene (ENB), 5 Examples include methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, and trienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, 1,3,7-octatriene, 1,4,9-decatriene, 4,8-dimethyl-1,4,8-decatriene, and 4-ethylidene-8-methyl-1,7-nonadien.

[0016] These non-conjugated polyenes [A3] can be used alone or in combination of two or more. Among these, linear non-conjugated dienes such as 1,4-hexadiene and cyclic non-conjugated dienes such as 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are preferred, with cyclic non-conjugated dienes being more preferred, and 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene being even more preferred.

[0017] Examples of ethylene-α-olefin-non-conjugated polyene copolymers (A) used in the present invention include: ethylene-1-butene-1,4-hexadiene copolymer, ethylene-1-butene-1-octene-1,4-hexadiene copolymer, ethylene-1-butene-5-ethylidene-2-norbornene copolymer, ethylene-1-butene-1-octene-5-ethylidene-2-norbornene copolymer, ethylene-1-butene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, and ethylene-1-butene-1-octene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer.

[0018] When using ethylene-α-olefin-non-conjugated polyene copolymer (A) by oil spreading, the amount of oil spread is preferably 50 to 150 parts by mass, more preferably 60 to 140 parts by mass, and even more preferably 70 to 130 parts by mass, per 100 parts by mass of ethylene-α-olefin-non-conjugated polyene copolymer (A). The amount of oil used for this oil spreading is included in the content of the softener (D) in the thermoplastic elastomer composition of the present invention as described below. It is preferable that the amount of oil spread is within the above range because the resulting thermoplastic elastomer composition tends to be highly fluid and low hardness. The softener (D) used for oil spreading is one of the following, and among them, petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, and polypropylene wax are preferred.

[0019] Each of the above-mentioned ethylene-α-olefin-non-conjugated polyene copolymers (A) may contain structural units derived from one or more biomass-derived monomers (biomass-derived ethylene [A1], α-olefins having 3 to 20 carbon atoms [A2], and non-conjugated polyenes [A3]). Furthermore, each of the above-mentioned copolymers (A) may contain structural units derived from one or more chemically recycled monomers (chemically recycled ethylene [A1], α-olefins having 3 to 20 carbon atoms [A2], and non-conjugated polyenes [A3]).

[0020] The requirements (1) and (2) that ethylene-α-olefin-non-conjugated polyene copolymer (A) must satisfy, and the requirements (3) and (4) that are desirable to satisfy, are explained below.

[0021] Regarding requirement (1), requirement (1) specifies that the molar ratio [[A1] / [A2]] of structural units derived from ethylene [A1] to structural units derived from α-olefins [A2] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10. The lower limit of this molar ratio ([A1] / [A2]) is preferably 45 / 55, more preferably 50 / 50, even more preferably 55 / 45, and particularly preferably 60 / 40. The upper limit of this molar ratio ([A1] / [A2]) is preferably 90 / 10, more preferably 85 / 15, even more preferably 80 / 20, and particularly preferably 75 / 25.

[0022] When the molar ratio ([A1] / [A2]) of structural units derived from ethylene [A1] to structural units derived from α-olefin [A2] is within the above range, an ethylene-based copolymer is obtained that has an excellent balance between rubber elasticity at low temperatures and tensile strength at room temperature, and a low viscosity / swell ratio (large swell at the same viscosity), due to the bulkiness of the side chains derived from α-olefin [A2].

[0023] Regarding requirement (2), requirement (2) specifies that the intrinsic viscosity [η] measured in decalin at 135°C is 4.0 to 7.0 dl / g. The intrinsic viscosity [η] of the ethylene-α-olefin-non-conjugated polyene copolymer (A) used in the present invention is in the range of 4.0 to 7.0 dl / g, which improves cold resistance and roll processability while maintaining its high strength and high rubber elasticity. This intrinsic viscosity [η] range of 4.0 to 7.0 dl / g is preferably 4.2 to 6.5 dl / g, more preferably 4.4 to 6.3 dl / g, and particularly preferably 4.6 to 6.0 dl / g.

[0024] Regarding requirement (3), requirement (3) specifies that the content of structural units derived from non-conjugated polyene [A3] is 0.1 to 6.0 mol%, with the total of structural units of [A1], [A2], and [A3] being 100 mol%. The ethylene-α-olefin-non-conjugated polyene copolymer (A) used in the present invention has a content of structural units derived from non-conjugated polyene [A3] in the range of 0.1 to 6.0 mol%, with the total of structural units of [A1], [A2], and [A3] being 100 mol%, thereby obtaining an ethylene-based copolymer with an excellent balance of strength, rubber elasticity, and cold resistance. The content of structural units derived from non-conjugated polyene [A3] is more preferably 0.3 to 4.0 mol%, even more preferably 0.5 to 3.0 mol%, particularly preferably 0.7 to 2.0 mol%, and most preferably 1.0 to 1.5 mol%.

[0025] Regarding requirement (4), requirement (4) stipulates that the B value, expressed by the following formula (i), must be 1.20 or greater. B value = ([EX] + 2[Y]) / [2 × [E] × ([X] + [Y])] ... (i) Here, [E], [X], and [Y] represent the mole fractions of ethylene [A1], α-olefins with 4 to 20 carbon atoms [A2], and unconjugated polyenes [A3], respectively, and [EX] represents the ethylene [A1] - α-olefins with 4 to 20 carbon atoms [A2] dyad chain fraction.

[0026] The B value represented by the above formula (i) of the ethylene-α-olefin-non-conjugated polyene copolymer (A) used in the present invention is preferably 1.20 or higher. More preferably, it is in the range of 1.20 to 1.80, and even more preferably, 1.22 to 1.40.

[0027] The B value of the ethylene-α-olefin-non-conjugated polyene copolymer (A) used in this invention is 1.20 or higher, which prevents excessive compression set at low temperatures and results in an excellent balance between rubber elasticity at low temperatures and tensile strength at room temperature.

[0028] Furthermore, when the B value falls within the above range, the alternation of monomer units constituting the ethylene-α-olefin-non-conjugated polyene copolymer (A) is high and the crystallinity is low, thus improving its processability and the sound insulation performance of the resulting molded article. The B value specified in this requirement (4) is an indicator of the randomness of the chain distribution of copolymer monomers in the ethylene-α-olefin-non-conjugated polyene copolymer (A), and in the above formula (i), [E], [X], [Y], and [EX] are, １３ The 13C-NMR spectrum can be measured and determined based on reports such as J. C. Randall Macromolecules, 15, 353 (1982) and J. Ray Macromolecules, 10, 773 (1977). Furthermore, the molar amounts of structural units derived from ethylene [B], α-olefin [A2], and non-conjugated polyene [A3] in the above requirement (1) are: １ It can be determined by measuring the intensity of the 1H-NMR spectrum.

[0029] <Mechanism> The mechanism by which the thermoplastic elastomer composition of the present invention exhibits excellent rubber elasticity and moldability is presumed to be due to the ethylene-α-olefin-non-conjugated polyene copolymer (A), which exhibits excellent rubber elasticity at low temperatures due to the bulkiness of the side chains derived from α-olefin [A2], resulting in a small viscosity / swell ratio (large swell at the same viscosity), and exhibiting high rubber elasticity because the intrinsic viscosity [η] is in the range of 4.0 to 7.0 dl / g.

[0030] Process for Producing Ethylene-α-Olefin-Nonconjugated Polyene Copolymer (A) As a process for producing the ethylene-α-olefin-nonconjugated polyene copolymer (A) used in the present invention, specifically, a crosslinked metallocene compound (t) represented by the following general formula (1), and an organometallic compound (u-1), an organoaluminum oxy compound (u-2), and at least one compound (u) selected from the group consisting of a compound (u-3) that reacts with the above crosslinked metallocene compound (t) to form an ion pair are contained. A process for producing an ethylene-α-olefin-nonconjugated polyene copolymer (A) in which ethylene, 1-butene (or, together with 1-butene, further an α-olefin having 5 to 20 carbon atoms), and a nonconjugated polyene are copolymerized is suitable.

[0031]

[0032] Crosslinked metallocene compound (t) The crosslinked metallocene compound (t) is a compound represented by the above general formula (1).

[0033] R in general formula (1) １ to R １４ In the above general formula (1), R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ and R １４ are each independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and among the substituents from R １ to R ４ , any two substituents may be bonded to each other to form a ring, and among the substituents from R ５ to R １２ , any two substituents may be bonded to each other to form a ring, and R １３ and R １４ may be bonded to each other to form a ring.

[0034] R１ From R １４ Examples of hydrocarbon groups include linear hydrocarbon groups, branched hydrocarbon groups, cyclic saturated hydrocarbon groups, cyclic unsaturated hydrocarbon groups, and groups obtained by substituting one or more hydrogen atoms of a saturated hydrocarbon group with cyclic unsaturated hydrocarbon groups. The number of carbon atoms in the hydrocarbon group is usually 1 to 20, preferably 1 to 15, and more preferably 1 to 10.

[0035] Examples of linear hydrocarbon groups include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decanyl groups; and linear alkenyl groups such as allyl groups.

[0036] Examples of branched hydrocarbon groups include branched alkyl groups such as isopropyl group, tert-butyl group, tert-amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, and 1-methyl-1-isopropyl-2-methylpropyl group.

[0037] Examples of cyclic saturated hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and methylcyclohexyl groups; and polycyclic groups such as norbornyl, adamantyl, and methyladamantyl groups.

[0038] Examples of cyclic unsaturated hydrocarbon groups include aryl groups such as phenyl, tolyl, naphthyl, biphenyl, phenanthryl, and anthracenyl groups; cycloalkenyl groups such as cyclohexenyl groups; and polycyclic unsaturated alicyclic groups such as 5-bicyclo[2.2.1]hepta-2-enyl groups.

[0039] Examples of groups formed by substituting one or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group include groups formed by substituting one or more hydrogen atoms of an alkyl group such as a benzyl group, cumyl group, 1,1-diphenylethyl group, or triphenylmethyl group with an aryl group.

[0040] R １ From R １４ Examples of heteroatom-containing hydrocarbon groups include alkoxy groups such as methoxy and ethoxy groups, aryloxy groups such as phenoxy groups, oxygen atom-containing hydrocarbon groups such as furyl groups; amino groups such as N-methylamino groups, N,N-dimethylamino groups, and N-phenylamino groups, nitrogen atom-containing hydrocarbon groups such as pyryl groups; and sulfur atom-containing hydrocarbon groups such as thienyl groups. The number of carbon atoms in the heteroatom-containing hydrocarbon groups is usually 1 to 20, preferably 2 to 18, and more preferably 2 to 15. However, silicon-containing groups are excluded from the heteroatom-containing hydrocarbon groups.

[0041] R １ From R １４ Examples of silicon-containing groups in this context include trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, etc., of the formula -Si(-R １５ ) (-R １６ ) (-R １７ ) (In the formula, R １５ , R １６ , R １７ Each of these is independently an alkyl group or phenyl group having 1 to 15 carbon atoms. Examples of groups represented by ( ) include:

[0042] R １ From R １４ Of the substituents up to R, any two substituents, for example, two adjacent substituents (for example, R １ and R ２ , R ２ and R ３ , R ３ and R ４ , R ５ and R ６ , R ６ and R ７ , R ７ and R ８ , R ９ and R １０ , R １０ and R １１ , R １１ and R １２ , R １３ and R １４These elements may be bonded to each other to form a ring. The ring formation may occur at two or more locations within the molecule.

[0043] In this specification, examples of rings formed by the bonding of two substituents (additional rings) include alicyclic rings, aromatic rings, and heterocyclic rings. Specifically, examples include cyclohexane rings, benzene rings, hydrogenated benzene rings, cyclopentene rings, furan rings, thiophene rings, and other heterocyclic rings and their corresponding hydrogenated heterocyclic rings, with cyclohexane rings, benzene rings, and hydrogenated benzene rings being preferred. Furthermore, such ring structures may have substituents such as alkyl groups on the ring.

[0044] R ５ , R ８ , R ９ and R １２ R is preferably a hydrogen atom. ６ , R ７ , R １０ and R １１ R is preferably a hydrogen atom, a hydrocarbon group, an oxygen atom-containing hydrocarbon group, or a nitrogen atom-containing hydrocarbon group, and more preferably a hydrocarbon group. ６ and R ７ They bond to each other to form a ring, and R １０ and R １１ These may be bonded to each other to form a ring. An example of such a fluorenyl group structure is represented by the following structural formula.

[0045]

[0046] R １３ and R １４ Preferably, this is a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group, and more preferably an aryl group or a substituted aryl group (an aryl group having a heteroatom-containing hydrocarbon group or a silicon-containing group).

[0047] Regarding Y in general formula (1), in general formula (1), Y is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and is preferably a carbon atom.

[0048] Regarding M, Q, and j in general formula (1), in general formula (1), M is a group 4 transition metal, preferably Ti, Zr, or Hf, more preferably Zr or Hf, and even more preferably Hf. Q is a halogen atom, hydrocarbon group, anionic ligand, or a neutral ligand that can coordinate with a lone pair of electrons, and when j is an integer of 2 or more, Q is selected in the same or different combinations.

[0049] Examples of halogen atoms in Q include fluorine, chlorine, bromine, and iodine. Examples of hydrocarbon groups in Q include R. １ From R １４ Examples of groups similar to hydrocarbon groups in the above include alkyl groups, preferably linear alkyl groups, branched alkyl groups, and the like.

[0050] Examples of anionic ligands in Q include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate; and amide groups such as dimethylamide, diisopropylamide, methylanilide, and diphenylamide.

[0051] Examples of neutral ligands that can coordinate with the lone pair of electrons in Q include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; and ethers such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane.

[0052] Q is preferably at least one halogen atom or alkyl group. j is an integer from 1 to 4, preferably 2. When j is an integer of 2 or more, Q may be selected in the same or different combinations.

[0053] Crosslinked metallocene compound (t) represented by general formula (2) In the method for producing the ethylene-α-olefin-non-conjugated polyene copolymer (A) used in the present invention, it is preferable to use the crosslinked metallocene compound (t) represented by the following general formula (2).

[0054]

[0055] In the general formula (2) above, R １３ , R １４ M, Q, and j are the same as in the general formula (1) above. Furthermore, M is preferably a hafnium atom. Additionally, Q is preferably a methyl group and j is preferably an integer of 2. Also, R １３ and R １４ However, it is preferable that both are 4-methoxyphenyl groups. Specific examples of crosslinked metallocene compounds (t) include the compounds listed on pages 29-43 of International Publication No. 2004 / 87775, the compounds listed on pages 9-37 of International Publication No. 2006 / 25540, the compounds listed in

[0117] of International Publication No. 2015 / 122414, and the compounds listed in

[0143] of International Publication No. 2015 / 122415.

[0056] Next, we will describe each of the compounds (u) selected from the group consisting of organometallic compounds (u-1), organoaluminum oxy compounds (u-2), and compounds (u-3) that react with crosslinked metallocene compounds (t) to form ion pairs.

[0057] Organometallic compounds (u-1) Specifically, organometallic compounds from groups 1 and 2 and 12 and 13 of the periodic table, such as (u-1a), (u-1b), and (u-1c) shown in the general formulas (3) to (5) below, are used as organometallic compounds (u-1).

[0058] (u-1a) R １８ ｍ Al(OR) １９ ) ｎ H ｐ X ｑ ...General formula (3) (In general formula (3), R １８ and R １９ An organoaluminum compound represented by (where ) may be the same or different from each other, representing a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X representing a halogen atom, m being a number where 0 < m ≤ 3, n being 0 ≤ n < 3, p being 0 ≤ p < 3, and q being a number where 0 ≤ q < 3, and m + n + p + q = 3.

[0059] Examples of such compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methylaluminum dichloride, dimethylaluminum chloride, and diisobutylaluminum hydride.

[0060] (u-1b) M ２ AlR ２０ ４ ...... General formula (4) (In general formula (4), M ２ represents Li, Na or K, and R ２０ is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.) A complex alkyl compound of a Group 1 metal of the periodic table and aluminum represented by.

[0061] Examples of such compounds include LiAl(C ２ H ５ ) ４ , LiAl(C ７ H １５ ) ４ and the like.

[0062] (u-1c) R ２１ R ２２ M ３ ...... General formula (5) (In general formula (5), R ２１ and R ２２ may be the same or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ３ is Mg, Zn or Cd.) A dialkyl compound having a Group 2 or Group 12 metal of the periodic table.

[0063] Among the above organometallic compounds (u-1), organoaluminum compounds such as triethylaluminum, triisobutylaluminum, and tri-n-octylaluminum are preferred. Further, such an organometallic compound (u-1) may be used alone or in combination of two or more.

[0064] The organoaluminum oxy compound (u-2) may be a conventionally known aluminoxane, or it may be a benzene-insoluble organoaluminum oxy compound as exemplified in Japanese Patent Application Publication No. 2-78687.

[0065] Conventionally known aluminoxanes can be produced by, for example, the following methods, and are usually obtained as solutions in a hydrocarbon solvent: (a) Adding an organoaluminum compound such as trialkylaluminum to a suspension of a hydrocarbon medium containing a compound or salt containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerium chloride hydrate, and reacting the adsorbed water or crystal water with the organoaluminum compound. (b) Directly reacting an organoaluminum compound such as trialkylaluminum with water, ice, or water vapor in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran. (c) Reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0066] Specific examples of organoaluminum compounds used in preparing aluminoxanes include those similar to those exemplified as organoaluminum compounds belonging to (u-1a) above.

[0067] Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and among them, trimethylaluminum and triisobutylaluminum are particularly preferred.

[0068] The organoaluminum compounds described above can be used individually or in combination of two or more types.

[0069] Examples of organoaluminum oxy compounds (u-2) include organoaluminum oxy compounds containing boron, represented by the following general formula (6).

[0070] (R ２４-) (R ２５ -)Al-O-B(-R ２３ )-O-Al(-R ２６ ) (-R ２７ )...General formula (6) (In general formula (6), R ２３ R represents a hydrocarbon group having 1 to 10 carbon atoms. ２４ ~R ２７ These may be identical or different from each other, and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

[0071] As the organoaluminum oxy compound (u-2), methylaluminoxane, which is readily available as a commercially available product, and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferred. Of these, MMAO with improved solubility in various solvents and storage stability is particularly preferred.

[0072] Compounds (u-3) that react with crosslinked metallocene compounds (t) to form ion pairs (hereinafter referred to as "ionized ionic compounds") include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Publication No. 3-179005, Japanese Patent Publication No. 3-179006, Japanese Patent Publication No. 3-207703, Japanese Patent Publication No. 3-207704, USP-5321106, etc. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned. Such ionized ionic compounds can be used individually or in combination of two or more.

[0073] Specifically, as a Lewis acid, BR ２８ ３ (R ２８Compounds represented by a phenyl group or fluorine (which may have substituents such as fluorine, a methyl group, or a trifluoromethyl group) include, for example, trifluoroborone, triphenylborone, tris(4-fluorophenyl)borone, tris(3,5-difluorophenyl)borone, tris(4-fluoromethylphenyl)borone, tris(pentafluorophenyl)borone, tris(p-tolyl)borone, tris(o-tolyl)borone, and tris(3,5-dimethylphenyl)borone.

[0074] Among ionized ionic compounds, the above-mentioned ionic compounds are preferred, and among them, triphenylcarbenium tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate are more preferred.

[0075] Ionized ionic compounds are used individually or in combination of two or more types.

[0076] When the crosslinked metallocene compound (t) represented by the above general formula (1) is used as a catalyst, when an organometallic compound such as triisobutylaluminum (u-1), an organoaluminum oxy compound such as methylaluminoxane (u-2), or an ionized ionic compound such as triphenylcarbenium tetrakis (pentafluorophenyl) borate (u-3) is used in combination, it exhibits very high polymerization activity in the production of ethylene-α-olefin-non-conjugated polyene copolymer (A).

[0077] Production of Ethylene-α-olefin-non-conjugated polyene copolymer (A) The ethylene-α-olefin-non-conjugated polyene copolymer (A) used in the present invention is produced by copolymerizing ethylene, 1-butene (or 1-butene together with an α-olefin having 5 to 20 carbon atoms), and a non-conjugated polyene in the presence of an olefin polymerization catalyst containing the above-mentioned crosslinked metallocene compound (t) and at least one compound (u) selected from the group consisting of the above-mentioned organometallic compound (u-1), organoaluminum oxy compound (u-2), and a compound (u-3) that reacts with the above-mentioned crosslinked metallocene compound (t) to form an ion pair.

[0078] When copolymerizing ethylene, α-olefins, and non-conjugated polyenes, the method of use and the order of addition of each component constituting the olefin polymerization catalyst can be arbitrarily selected, and either liquid-phase polymerization methods such as solution polymerization or suspension polymerization, or gas-phase polymerization methods can be employed.

[0079] Examples of inert hydrocarbon media used in liquid-phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These can be used individually or in combination of two or more. Olefins themselves can also be used as solvents.

[0080] When using the olefin polymerization catalyst described above, the amount of crosslinked metallocene compound (t) is usually 10 per liter of reaction volume. ―１２ ~10 ―２ moles, preferably 10 ―１０ ~10 ―８ It is used in quantities that equal moles.

[0081] The ratios used for the cross-linked metallocene compound (t), organometallic compound (u-1), organoaluminum oxy compound (u-2), and compound (u-3) that reacts with the cross-linked metallocene compound (t) to form an ion pair are as follows: Compound (u-1) is used in an amount such that the molar ratio [(u-1) / M] of compound (u-1) to the total transition metal atoms (M) in the cross-linked metallocene compound (t) is usually 0.01 to 50,000, preferably 0.05 to 10,000. Compound (u-2) is used in an amount such that the molar ratio [(u-2) / M] of aluminum atoms in compound (u-2) to the total transition metals (M) in the cross-linked metallocene compound (t) is usually 10 to 50,000, preferably 20 to 10,000. Compound (u-3) is used in an amount such that the molar ratio [(u-3) / M] of compound (u-3) to the transition metal atom (M) in the cross-linked metallocene compound (t) is usually 1 to 20, preferably 1 to 15.

[0082] Furthermore, the polymerization temperature using such copolymer catalysts is typically in the range of -50 to +200°C, preferably 0 to 200°C, and more preferably 70 to 200°C.

[0083] The polymerization pressure is typically atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in batch, semi-continuous, or continuous manner. Furthermore, polymerization can be carried out in two or more stages with different reaction conditions.

[0084] The molecular weight of the resulting ethylene-α-olefin-non-conjugated polyene copolymer (A) can be adjusted by introducing hydrogen into the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of the above-mentioned compound (u) used. Specifically, examples include triisobutylaluminum, methylaluminoxane, and diethylzinc. When hydrogen is added, the appropriate amount is about 0.001 to 100 NL per kg of olefin.

[0085] <<Crystalline Olefin Polymer (B)>> Crystalline olefin polymer (B) (hereinafter also simply referred to as "polymer (B)") plays a role in improving the fluidity and heat resistance of thermoplastic elastomer compositions obtained by dynamic crosslinking. Crystallinity means that the melting point (Tm) can be measured by differential scanning calorimetry (DSC). Specifically, the melting point (Tm) is determined by the differential scanning calorimetry (DSC) measurement method described below.

[0086] Polymer (B) is not particularly limited as long as it is a crystalline polymer obtained from an olefin, but it is preferably a polymer consisting of a crystalline high molecular weight solid product obtained by polymerizing one or more monoolefins by either a high-pressure method or a low-pressure method. Examples of such polymers include isotactic monoolefin polymers and syndiotactic monoolefin polymers.

[0087] Polymer (B) may be synthesized by conventionally known methods, or a commercially available product may be used. Polymer (B) may be used alone or in combination of two or more types. Examples of monoolefins that can be used as raw materials for polymer (B) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 5-methyl-1-hexene. The above olefins may be used alone or in combination of two or more types.

[0088] From the viewpoint of excellent heat resistance, oil resistance, and moldability, the crystalline olefin polymer (B) is preferably at least one of a propylene homopolymer and a copolymer of propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene) (propylene copolymer), and more preferably a propylene homopolymer. In the case of a propylene copolymer, the content of structural units derived from propylene is preferably 80 mol% or more, more preferably 90 mol% or more, and the monoolefin that becomes the monomer structural unit derived from the α-olefin having 2 to 20 carbon atoms (excluding propylene) is preferably the above monoolefin other than propylene, more preferably ethylene and 1-butene.

[0089] The polymerization mode of polymer (B) may be random or block-type; any polymerization mode is acceptable as long as a crystalline resinous material is obtained. Preferred examples include propylene homopolymers and propylene-ethylene block copolymers.

[0090] The polymer (B) has a melt flow rate (MFR) (ASTMD1238-65T, 230°C, 2.16 kg load) of typically 0.01 to 100 g / 10 min, preferably 0.05 to 50 g / 10 min.

[0091] Polymer (B) typically has a melting point (Tm) of 100°C or higher, preferably 105°C or higher, obtained by differential scanning calorimetry (DSC). Differential scanning calorimetry (DSC) is performed, for example, as follows: Approximately 5 mg of the sample is placed in a dedicated aluminum pan, and using a DSCPyris1 or DSC7 manufactured by PerkinElmer, the temperature is increased from 30°C to 200°C at a rate of 320°C / min, held at 200°C for 5 minutes, then cooled from 200°C to 30°C at a rate of 10°C / min, held at 30°C for another 5 minutes, and the melting point is determined from the endothermic curve when the temperature is increased at a rate of 10°C / min. If multiple peaks are detected during DSC measurement, the peak temperature detected on the highest temperature side is defined as the melting point (Tm).

[0092] Crosslinking agent (C) In a preferred embodiment of the thermoplastic elastomer composition of the present invention, the crosslinking agent (C) used is not particularly limited and various crosslinking agents can be used. Among these, phenolic resin-based crosslinking agents and peroxide-based crosslinking agents are preferred.

[0093] Examples of phenolic resin crosslinking agents include phenolic resins produced by the condensation of substituted or unsubstituted phenols with aldehydes, phenolic resins produced by the condensation of bifunctional phenol dialcohols, and halogenated phenolic resins. Substituted phenols are preferably alkyl-substituted with 1 to 10 carbon atoms. The aldehyde used in the condensation with substituted or unsubstituted phenols is preferably formaldehyde. Furthermore, dimethylolphenols or phenolic resins substituted with alkyl groups having 1 to 10 carbon atoms at the p-position are preferred. Among these phenolic resin crosslinking agents, resol resin crosslinking agents are preferred.

[0094] For phenolic resin-based crosslinking agents among the crosslinking agents (C), refer to the descriptions in U.S. Patents No. 3,287,440, No. 3,709,840 and No. 4,311,628.

[0095] As a phenolic resin crosslinking agent, commercially available phenolic resins can be appropriately selected and used. Examples of commercially available products that can be used as phenolic resin crosslinking agents include Tackirol 201 (alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.), Tackirol 250-I (brominated alkylphenol formaldehyde resin with a bromination rate of 4%, manufactured by Taoka Chemical Industry Co., Ltd.), Tackirol 250-III (brominated alkylphenol formaldehyde resin, manufactured by Taoka Chemical Industry Co., Ltd.), PR-4507 (manufactured by Gun-ei Chemical Industry Co., Ltd.), Vulkaresat 510E (manufactured by Hoechst), Vulkaresat 532E (manufactured by Hoechst), Vulkaresen E (manufactured by Hoechst), Vulkaresen 105E (manufactured by Hoechst), Vulkaresen 130E (manufactured by Hoechst), and Vulkaresol 315E (manufactured by Hoechst), Amberol ST 137X (manufactured by Rohm & Haas), Sumilight Resin PR-22193 (manufactured by Sumitomo Durez Co., Ltd.), Symphorm-C-100 (manufactured by Anchor Chem.), Symphorm-C-1001 (manufactured by Anchor Chem.), Tamanol 531 (manufactured by Arakawa Chemical Corporation), Schenectady SP1059 (manufactured by Schenectady Chem.), Schenectady SP1045 (manufactured by Schenectady Chem.), CRR-0803 (manufactured by U.C.C.), Schenectady SP-1055 (Schenectady Examples include Chem., Schenectady SP-1056 (Schenectady Chem.), CRM-0803 (Showa Union Synthetic Co., Ltd.), and Vulkadur A (Bayer). Among these, brominated alkylphenol formaldehyde resin is preferred in terms of the degree of crosslinking.

[0096] When a phenolic resin-based crosslinking agent is used in the thermoplastic elastomer composition of the present invention, the content of the phenolic resin-based crosslinking agent in the composition is preferably 1 to 20 parts by mass, more preferably 5 to 15 parts by mass, and even more preferably 7 to 12 parts by mass, per 100 parts by mass of copolymer (A). When the content of the phenolic resin-based crosslinking agent is within the above range, the resulting composition is preferable because it exhibits excellent oil resistance and rubber elasticity.

[0097] In addition, a peroxide-based crosslinking agent is used as the crosslinking agent (C) in a preferred embodiment of the present invention. Examples of peroxide-based crosslinking agents include inorganic peroxides and organic peroxides. Among these, organic peroxides are preferred from the viewpoint of rubber elasticity.

[0098] Examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyn-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

[0099] Of these organic peroxides, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyn-3, and 1,3-bis(tert-butylperoxyisopropyl)benzene are preferred in terms of odor and scorch stability, and 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane is more preferred.

[0100] In a preferred embodiment of the thermoplastic elastomer composition of the present invention, when a peroxide crosslinking agent is used, the amount of peroxide crosslinking agent in the composition is usually 0.02 to 3 parts by mass, preferably 0.05 to 1 part by mass, per 100 parts by mass of copolymer (A). When the content of the peroxide crosslinking agent is within the above range, the resulting composition exhibits excellent oil resistance and rubber elasticity, which is preferable.

[0101] Softener (D) The thermoplastic elastomer composition of the present invention preferably contains a softener (D) for the purpose of adjusting fluidity and hardness. Specific examples of softener (D) include petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt, and petrolatum; coal tar-based softeners such as coal tar and coal tar pitch; fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; tall oil; sub(factis); waxes such as beeswax, carnauba wax, and lanolin; ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, and lauan. Examples include fatty acids or fatty acid salts such as zinc phosphate; naphthenic acid; pine oil, rosin or its derivatives; synthetic polymer softeners such as terpene resins, petroleum resins, coumarone indene resins, and atactic polypropylene; ester-based softeners such as dioctyl phthalate, dioctyl adipate, and dioctyl sebacate; microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid polyisoprene, terminal-modified polyisoprene, hydrogenated terminal-modified polyisoprene, liquid thiocol, and hydrocarbon-based synthetic lubricants. Among these, process oils are preferred.

[0102] As mentioned above, the softening agent (D) may be used, for example, by pre-mixing (oil spreading) it with the copolymer (A), by using it when preparing the composition, or by adding it after mixing each component to be incorporated into the composition.

[0103] In the thermoplastic elastomer composition of the present invention, the content of the softener (D) is preferably 50 to 300 parts by mass, more preferably 80 to 200 parts by mass, more preferably 100 to 150 parts by mass, and even more preferably 120 to 140 parts by mass, per 100 parts by mass of copolymer (A). The content of the softener (D) in the composition is adjusted in this way. Here, "content of softener (D)" refers to the sum of the amount of softener used for oil spreading when copolymer (A) is oil spread, and the amount of softener added during the production of the thermoplastic elastomer composition of the present invention or other processes. A softener (D) content within the above range is preferable because it tends to result in a composition that is highly fluid and low hardness.

[0104] <<Other Polymers>> The thermoplastic elastomer composition of the present invention may also contain other thermoplastic resins such as polyolefin resins, elastomers, rubber (except copolymer (A) and crystalline olefin polymer (B)), and polymers other than ethylene-α-olefin-non-conjugated polyene copolymer (A), as long as it provides the effects of the present invention.

[0105] Other thermoplastic resins, such as polyolefin resins, include, for example, ethylene-α-olefin copolymer (E). Copolymer (E) is a polymer obtained by copolymerizing ethylene and α-olefin, and is a polymer that has rubber elasticity at room temperature. The inclusion of ethylene-α-olefin copolymer (E) in the thermoplastic elastomer composition of the present invention improves impact resistance and elongation at break at low temperatures.

[0106] Examples of α-olefins with three or more carbon atoms that can be used as raw materials for ethylene-α-olefin copolymers (E) include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 5-methyl-1-hexene. Among these α-olefins, α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 5-methyl-1-hexene, are preferred, and α-olefins having 3 to 8 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 5-methyl-1-hexene, are preferred.

[0107] Examples of ethylene-α-olefin copolymers (E) include ethylene-1-butene copolymer, ethylene-1-hexene copolymer, and ethylene-1-octene copolymer. Ethylene-1-butene copolymer and ethylene-1-octene copolymer are more preferred because they provide particularly excellent impact resistance and elongation at break at low temperatures.

[0108] The ethylene-α-olefin copolymer (E) may be used alone or in combination of two or more types. Examples of polymer elastomers and rubbers with added components include styrene-based thermoplastic elastomers, butyl rubber, polyisobutylene rubber, nitrile rubber (NBR), natural rubber (NR), and silicone rubber.

[0109] The content of other polymers is usually 1 to 60 parts by mass, preferably 3 to 58 parts by mass, and more preferably 5 to 55 parts by mass (provided that the total of ethylene-α-olefin-non-conjugated polyene copolymer (A) and crystalline olefin polymer (B) and copolymer (E) is 100 parts by mass).

[0110] <<Other Additives>> This composition may contain other additives, such as activators including crosslinking aids and crosslinking agents (C), and resin additives (e.g., slip agents, antioxidants, UV absorbers, light stabilizers, conductivity imparters, antistatic agents, dispersants, flame retardants, antibacterial agents, acid acceptors, reinforcing agents, fillers, colorants, thermally conductive fillers, etc.), as long as they do not impair the purpose of the present invention. Each of these other additives may be used individually or in combination of two or more.

[0111] If the above-mentioned other additives are included, the total amount of the above-mentioned other additives in this composition is usually 10% by mass or less, preferably 9% by mass or less, and more preferably 8% by mass or less, based on 100% by mass of the total of copolymer (A) and crystalline olefin polymer (B).

[0112] In a preferred embodiment of the thermoplastic elastomer composition of the present invention, which includes a crosslinking agent (C) consisting of a phenolic resin crosslinking agent, if the phenolic resin crosslinking agent is not halogenated, it is preferable to use the phenolic resin crosslinking agent together with the activator. As the activator, halogen donors such as stannous chloride, ferric chloride, chlorinated paraffin, chlorinated polyethylene, and chlorosulfonated polyethylene can be used. However, if the phenolic resin crosslinking agent is halogenated, the halogen donor does not need to be used.

[0113] When a halogen donor is added as an activator along with a phenol resin crosslinking agent, the amount of halogen donor is preferably such that the mass ratio of the phenol resin crosslinking agent to the halogen donor (phenol resin crosslinking agent / (halogen donor)) is 1 to 100, more preferably 2 to 50.

[0114] Acid Acceptor In embodiments of the thermoplastic elastomer composition of the present invention that include a phenolic resin-based crosslinking agent, the acid acceptor may be zinc oxide (ZnO), iron oxide, titanium oxide, magnesium oxide, silicon dioxide, zinc oxide, etc. When an acid acceptor is included, the amount of the acid acceptor added is preferably such that the mass ratio of the phenolic resin-based crosslinking agent to the acid acceptor (phenolic resin-based crosslinking agent / (acid acceptor)) is 1 to 100, more preferably 2 to 50.

[0115] Reinforcements and Fillers The thermoplastic elastomer composition of the present invention may contain reinforcements and fillers depending on its purpose and application. Specific examples of reinforcements and fillers include carbon black, carbon black surface-treated with a silane coupling agent, silica, calcium carbonate, activated calcium carbonate, fine talc, differential silicic acid, calcium silicate, clay, kaolin, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass spheres, shirasu balloons, basic magnesium sulfate whiskers, calcium titanate whiskers, aluminum borate whiskers, and the like.

[0116] Among these, carbon black, carbon black surface-treated with a silane coupling agent, light calcium carbonate, heavy calcium carbonate, fine talc, and differential silica are suitable as inorganic fillers, and among these, carbon black masterbatch (CB-MB) is particularly suitable.

[0117] If the thermoplastic elastomer composition of the present invention contains a reinforcing agent and a filler, their content is usually 2 to 50 parts by mass, preferably 3 to 30 parts by mass, per 100 parts by mass of copolymer (A). When the blending amount is within the above range, the composition of the present invention exhibits excellent kneadability and a molded article with excellent mechanical properties can be obtained.

[0118] Anti-aging agents (stabilizers) When the thermoplastic elastomer composition of the present invention contains an anti-aging agent, conventionally known anti-aging agents are used. Examples include amine-based anti-aging agents, phenol-based anti-aging agents, sulfur-based anti-aging agents, etc. By incorporating an anti-aging agent (stabilizer), the lifespan of the molded article formed therefrom can be extended.

[0119] These antioxidants can be used individually or in combination of two or more types, and the amount added is usually 0.1 to 10 parts by mass, preferably 0.3 to 7.0 parts by mass, per 100 parts by mass of copolymer (A). By keeping the amount within this range, blooming on the surface of the molded article obtained using copolymer (A) is eliminated, and the occurrence of vulcanization inhibition can be suppressed.

[0120] <Method for producing the thermoplastic elastomer composition of the present invention> The thermoplastic elastomer composition of the present invention comprises a copolymer (A), a crystalline olefin polymer (B), a crosslinking agent (C) as needed, a softening agent (D), an ethylene-α-olefin copolymer (E), and the aforementioned other additives, and is produced by mixing these or, preferably, by dynamic crosslinking.

[0121] According to a preferred embodiment of the thermoplastic elastomer composition of the present invention, it is obtained by mixing an ethylene-α-olefin-non-conjugated polyene copolymer (A), a crystalline olefin polymer (B), and optionally a crosslinking agent (C), a softener (D), the aforementioned other polymers, and other additives. In this case, the ratio of copolymer (A) to polymer (B), (A) / (B), is preferably 90 / 10 to 10 / 90 by mass, and more preferably 80 / 20 to 30 / 70. Within this range, a molded article with excellent mechanical properties and moldability can be obtained.

[0122] In the present invention, "dynamic crosslinking" refers to a process in which a crosslinked structure is formed in at least a portion of a copolymer (A) by melt-kneading a mixture containing necessary components such as copolymer (A) while applying shear force.

[0123] The heat treatment in dynamic crosslinking is preferably carried out in a closed-type apparatus and preferably in an inert gas atmosphere such as nitrogen or carbon dioxide. The heat treatment temperature is in the range of 300°C from the melting point of the crystalline olefin polymer (B), preferably 150 to 280°C, more preferably 170 to 270°C. The kneading time is usually 0.25 to 20 minutes, preferably 0.5 to 10 minutes, more preferably 1 to 10 minutes. The shear force applied is usually 10 to 100,000 sec at the maximum shear rate. －1 Preferably 100 to 50,000 seconds －1 , more preferably 1,000 to 10,000 seconds －1 More preferably 2,000 to 7,000 seconds －1 It is within the range.

[0124] During melt-mixing, it is preferable to use conventionally known mixing and kneading equipment such as a Banbury mixer, mixing rolls, Henschel mixer, kneader, or single-screw or twin-screw extruder. The order in which each component is added during mixing and kneading is not particularly limited, as long as the crosslinking agent (C) is added at the same time.

[0125] In this specification, "simultaneous addition" means the timing at which the crosslinking reaction by the crosslinking agent (C) has not substantially occurred on its own. The fact that the crosslinking reaction by the crosslinking agent (C) has not started can be confirmed by the fact that the melt viscosity of the mixture has not substantially increased.

[0126] Dynamic crosslinking can be used to obtain a composition containing a component in which at least a portion of the copolymer (A) is crosslinked. In this specification, "at least a portion is crosslinked" means that the gel content is in the range of 30 to 100% by mass, preferably 40 to 100% by mass.

[0127] As described above, the thermoplastic elastomer composition obtained by dynamic crosslinking is low in hardness and exhibits excellent fluidity, mechanical strength, and oil resistance.

[0128] The olefin-based thermoplastic elastomer composition of the present invention is excellent in terms of lightness, heat resistance, flexibility, rubber elasticity, moldability, weather resistance, and compatibility. In particular, despite having a relatively high molecular weight, it exhibits a relatively large swell, resulting in molded articles with excellent moldability and appearance.

[0129] The thermoplastic elastomer compositions of the present invention are characterized by having a relatively small viscosity / swell ratio compared to conventional thermoplastic elastomers of the same viscosity. Among these, thermoplastic elastomer compositions with a viscosity / swell ratio of 300 to 446, preferably 400 to 443, and more preferably 420 to 440, exhibit particularly excellent moldability and yield molded articles with excellent appearance.

[0130] Molded articles can be formed using various molding methods, including extrusion molding, injection molding, compression molding, calendering, vacuum forming, press molding, stamping, and blow molding. Blow molding methods include press blow molding, direct blow molding, and injection blow molding. Furthermore, waste and burrs generated by these molding methods can be collected and reused.

[0131] Molded products are widely used in applications such as automotive parts, wire materials, electrical and electronic components, construction and civil engineering materials, and industrial parts.

[0132] <<Examples>> The present invention will now be described in more detail with reference to examples, but the present invention is not limited thereto. In the following descriptions of examples, etc., unless otherwise specified, "parts" refers to "parts by mass". In the present invention, parts by weight and parts by mass are treated as synonymous.

[0133] The methods for evaluating the physical properties of the thermoplastic elastomer compositions in the examples and comparative examples are as follows.

[0134] [Melt Flow Rate (MFR)] Measured in accordance with ASTM D1238. The MFR of crystalline olefin polymer (B) was measured using ASTM D1238-65T, 230°C, and a load of 2.16 kg. The MFR of thermoplastic elastomer compositions was measured at a heating temperature of 230°C and a load of 5.0 kg.

[0135] [Shore D Hardness (HD)] Using a 100-ton electric automatic press (manufactured by Shoji Co., Ltd.), the obtained thermoplastic elastomer composition pellets were press-molded at 230°C for 10 minutes, and then cooled and pressed at room temperature for 5 minutes to produce a 2 mm thick press sheet. Using this sheet, the value was read 5 seconds after contact with the indenter using a D-type measuring instrument in accordance with JIS K6253.

[0136] [Tensile Properties] Using a 100-ton electric automatic press (manufactured by Shoji Co., Ltd.), the obtained thermoplastic elastomer composition pellets were press-molded at 230°C for 10 minutes, and then cooled and pressed at room temperature for 5 minutes to produce a 2 mm thick press sheet. A No. 3 dumbbell piece was punched out from the sheet and measured according to the method of JIS K6301. Measurement temperature: 23°C EB: Tensile elongation at break (%)

[0137] [Compression Set (CS)] Using a 100-ton electric automatic press (manufactured by Shoji Co., Ltd.), the obtained thermoplastic elastomer composition pellets were press-molded at 230°C for 10 minutes, and then cooled and pressed at room temperature for 5 minutes to produce a 2 mm thick press sheet. This sheet was laminated in accordance with JIS K6250, and a compression set test was performed in accordance with JIS K6262. The test conditions were as follows: a laminated sheet with a thickness of 12 mm (six layers of 2 mm thick pieces) was compressed at 25% compression, 70°C, and for 22 hours, and the thickness was measured 30 minutes after the strain (compression) was removed.

[0138] [Melting Viscosity and Swell] The melting viscosity (Pa·s) was measured using a capillary rheometer (Capillograph 1C, manufactured by Toyo Seiki Kogyo Co., Ltd.). The orifice used had a diameter D = 1 mm and an L / D ratio of 30. The melting viscosity was measured at 200°C in the range of shear rates from 121.6 (1 / s) to 2430 (1 / s).

[0139] [Swell Ratio] The swell ratio at 200°C was measured using a capillary rheometer (Capillograph 1C, manufactured by Toyo Seiki Kogyo Co., Ltd.). The orifice used had a diameter D = 1 mm and an L / D ratio of 30. The sample was extruded with the cylinder temperature set to 200°C and the piston descent speed set to 1 mm / min, 2 mm / min, 5 mm / min, 10 mm / min, 20 mm / min, 50 mm / min, 100 mm / min, and 200 mm / min. The strand diameter (Di) 17 mm below the nozzle exit at a piston descent speed of 10 mm / min was measured using a laser beam. The ratio of the strand diameter (Di) to the nozzle diameter (DO) measured in this way (swell ratio = Di / DO) was determined.

[0140] [Appearance of Molded Body] From the obtained thermoplastic elastomer composition pellets, a 150 mm × 120 mm × 2 mm molded body (square plate) was produced using a 140-ton injection molding machine under the temperature conditions of C1 / C2 / C3 / C4 / H = 170°C / 180°C / 190°C / 200°C / 200°C and mold temperature of 40°C. The appearance of the obtained molded body (square plate) was visually evaluated. ○: Good. Visual evaluation shows no noticeable weld marks or flow marks on the surface of the molded body. △: Poor. Visual evaluation shows noticeable weld marks and flow marks on the surface of the molded body.

[0141] <Production of Ethylene-1-Butene-5-Ethylene-2-Norbornene Copolymer (EBDM-1)> [Production Example 1] Using a polymerizer with a volume of 300 L equipped with stirring blades, the polymerization reaction of ethylene, 1-butene, and 5-ethylidene-2-norbornene (ENB) was carried out continuously at 85°C. Hexane (feed rate: 50.5 L / h) was used as the polymerization solvent and was continuously supplied to the polymerizer so that the ethylene feed rate was 4.2 kg / h, the 1-butene feed rate was 4.7 kg / h, the ENB feed rate was 432 g / h, and the hydrogen feed rate was 5.2 NL / h.

[0142] While maintaining a polymerization pressure of 1.7 MPaG and a polymerization temperature of 85°C, catalyst-a1 [bis(4-methoxyphenyl)methylene(η5-cyclopentadienyl)(η5-2,3,6,7-tetramethylfluorenyl)]hafniumdimethyl was continuously supplied to the polymerizer as the main catalyst at a feed rate of 0.0056 mmol / h. In addition, triphenylcarbeniumtetrakis(pentafluorophenyl)borate (CB-3) was continuously supplied to the polymerizer as a co-catalyst at a feed rate of 0.035 mmol / h, and triisobutylaluminum (TiBA) as an organoaluminum compound at a feed rate of 13 mmol / h.

[0143] In this manner, a solution containing 6.0% by mass of ethylene-1-butene-ENB copolymer formed from ethylene, 1-butene, and ENB was obtained. A small amount of methanol was added to the polymerization reaction solution withdrawn from the bottom of the polymerizer to stop the polymerization reaction. 100 parts by mass of paraffin oil was added to 100 parts by mass of ethylene-1-butene-ENB copolymer, and the ethylene-1-butene-ENB copolymer was separated from the solvent by steam stripping, and then dried under reduced pressure at 80°C for 24 hours. Through these operations, ethylene-1-butene-ENB copolymer (EBDM-1) formed from ethylene, 1-butene, and ENB was obtained at a rate of 2.5 kg per hour. Its intrinsic viscosity [η] was 6.2 dl / g.

[0144] <Production of Ethylene-1-Butene-5-Ethylene-2-Norbornene Copolymer (EBDM-2)> [Production Example 2] Using a 300 L polymerizer equipped with stirring blades, the polymerization reaction of ethylene, 1-butene, and 5-ethylidene-2-norbornene (ENB) was carried out continuously at 75°C. Hexane (feed rate: 46.5 L / h) was used as the polymerization solvent and was continuously supplied to the polymerizer at a rate of 4.2 kg / h for ethylene, 9.8 kg / h for 1-butene, 612 g / h for ENB, and 3.4 NL / h for hydrogen.

[0145] While maintaining a polymerization pressure of 1.7 MPaG and a polymerization temperature of 75°C, catalyst-a1 [bis(4-methoxyphenyl)methylene(η5-cyclopentadienyl)(η5-2,3,6,7-tetramethylfluorenyl)]hafniumdimethyl was continuously supplied to the polymerizer as the main catalyst at a feed rate of 0.006 mmol / h. In addition, triphenylcarbeniumtetrakis(pentafluorophenyl)borate (CB-3) was continuously supplied to the polymerizer as a co-catalyst at a feed rate of 0.038 mmol / h, and triisobutylaluminum (TiBA) as an organoaluminum compound at a feed rate of 13 mmol / h.

[0146] In this manner, a solution containing 5.7% by mass of ethylene-1-butene-ENB copolymer formed from ethylene, 1-butene, and ENB was obtained. A small amount of methanol was added to the polymerization reaction solution withdrawn from the bottom of the polymerizer to stop the polymerization reaction. 75 parts by mass of paraffin oil were added to 100 parts by mass of ethylene-1-butene-ENB copolymer, and the ethylene-1-butene-ENB copolymer was separated from the solvent by steam stripping, and then dried under reduced pressure at 80°C for 24 hours. Through these operations, ethylene-1-butene-ENB copolymer (EBDM-2) formed from ethylene, 1-butene, and ENB was obtained at a rate of 2.5 kg per hour. Its intrinsic viscosity [η] was 5.8 dl / g.

[0147] <Production of Ethylene-1-Butene-5-Ethylene-2-Norbornene Copolymer (EBDM-3)> [Production Example 3] Using a polymerizer with a volume of 300 L equipped with stirring blades, the polymerization reaction of ethylene, 1-butene, and 5-ethylidene-2-norbornene (ENB) was carried out continuously at 85°C. Hexane (feed rate: 38.9 L / h) was used as the polymerization solvent and was continuously supplied to the polymerizer so that the ethylene feed rate was 3.6 kg / h, the 1-butene feed rate was 4.0 kg / h, the ENB feed rate was 396 g / h, and the hydrogen feed rate was 5.6 NL / h.

[0148] While maintaining a polymerization pressure of 1.7 MPaG and a polymerization temperature of 85°C, catalyst-a1 [bis(4-methoxyphenyl)methylene(η5-cyclopentadienyl)(η5-2,3,6,7-tetramethylfluorenyl)]hafniumdimethyl was continuously supplied to the polymerizer as the main catalyst at a feed rate of 0.0047 mmol / h. In addition, triphenylcarbenium tetrakis(pentafluorophenyl) borate (CB-3) was continuously supplied to the polymerizer as a co-catalyst at a feed rate of 0.024 mmol / h, and triisobutylaluminum (TiBA) as an organoaluminum compound at a feed rate of 15 mmol / h.

[0149] In this manner, a solution containing 5.7% by mass of ethylene-1-butene-ENB copolymer formed from ethylene, 1-butene, and ENB was obtained. A small amount of methanol was added to the polymerization reaction solution withdrawn from the bottom of the polymerizer to stop the polymerization reaction. 75 parts by mass of paraffin oil were added to 100 parts by mass of ethylene-1-butene-ENB copolymer, and the ethylene-1-butene-ENB copolymer was separated from the solvent by steam stripping, and then dried under reduced pressure at 80°C for 24 hours. Through these operations, ethylene-1-butene-ENB copolymer (EBDM-3) formed from ethylene, 1-butene, and ENB was obtained at a rate of 2.4 kg per hour. Its intrinsic viscosity [η] was 4.8 dl / g.

[0150] <Production of Ethylene-1-Butene-5-Ethylene-2-Norbornene Copolymer (EBDM-4)> [Production Example 4] Using a polymerizer with a volume of 300 L equipped with stirring blades, the polymerization reaction of ethylene, 1-butene, and 5-ethylidene-2-norbornene (ENB) was carried out continuously at 95°C. Hexane (feed rate: 41 L / h) was used as the polymerization solvent and was continuously supplied to the polymerizer at a rate of ethylene feed of 4.2 kg / h, 1-butene feed of 10 kg / h, ENB feed of 580 g / h, and hydrogen feed of 1.8 NL / h.

[0151] While maintaining a polymerization pressure of 1.6 MPaG and a polymerization temperature of 95°C, catalyst-a1 [bis(4-methoxyphenyl)methylene(η5-cyclopentadienyl)(η5-2,3,6,7-tetramethylfluorenyl)]hafniumdimethyl was continuously supplied to the polymerizer as the main catalyst at a feed rate of 0.0025 mmol / h. In addition, triphenylcarbenium tetrakis(pentafluorophenyl)borate (CB-3) was continuously supplied to the polymerizer as a co-catalyst at a feed rate of 0.125 mmol / h, and triisobutylaluminum (TiBA) as an organoaluminum compound at a feed rate of 10 mmol / h.

[0152] In this manner, a solution containing 12% by mass of ethylene-1-butene-ENB copolymer formed from ethylene, 1-butene, and ENB was obtained. A small amount of methanol was added to the polymerization reaction solution withdrawn from the bottom of the polymerizer to stop the polymerization reaction. 30 parts by mass of paraffin oil were added to 100 parts by mass of ethylene-1-butene-ENB copolymer, and the ethylene-1-butene-ENB copolymer was separated from the solvent by steam stripping, and then dried under reduced pressure at 80°C for 24 hours. Through these operations, ethylene-1-butene-ENB copolymer (EBDM-4) formed from ethylene, 1-butene, and ENB was obtained at a rate of 5 kg per hour. Its intrinsic viscosity [η] was 3.5 dl / g.

[0153] <Method for producing thermoplastic elastomer compositions and molded articles> The following components were used for the examples and comparative examples.

[0154] Copolymer (A) The copolymer (A) below is the product after oil spreading. The same process oil used for spreading was the same as that used for the softener (D). (A-1): Ethylene-1-butene-5-ethylidene-2-norbornene copolymer (EBDM-1) obtained in Production Example 1 (intrinsic viscosity [η]: 6.2 dl / g, ethylene content: 66 mass%, ENB content: 4.2 mass%, oil spread: 100 parts by mass) (A-2): Ethylene-1-butene-5-ethylidene-2-norbornene copolymer (EBDM-2) obtained in Production Example 2 (intrinsic viscosity [η]: 5.8 dl / g, ethylene content: 51 mass%, ENB content: 3.8 mass%, oil spread: 75 parts by mass) (A-3): Ethylene-1-butene-5-ethylidene-2-norbornene copolymer (EBDM-3) obtained in Production Example 3 (intrinsic viscosity [η]: 4.8 dl / g, ethylene content: 66 mass%, (A-4): Ethylene-1-butene-5-ethylidene-2-norbornene copolymer (EBDM-4) obtained in Production Example 4 (intrinsic viscosity [η]: 3.5 dl / g, ethylene content: 50% by mass, ENB content: 4.7% by mass, oil spreadability: 30 parts by mass) (A-5): Commercially available ethylene-propylene-5-ethylidene-2-norbornene copolymer, registered trademark Keltan 5469C from Arlanxeo (Mooney viscosity ML １＋４ (125°C): 52, Ethylene content: 58% by mass, ENB content: 4.5% by mass, Oil spread: 100 parts by mass) Note that the oil spread in (A-1) to (A-5) is the amount per 100 parts by mass of the copolymer used in each of the ethylene-1-butene-5-ethylidene-2-norbornene copolymers.

[0155] Crystalline olefin polymer (B) (B-1): A commercially available propylene homopolymer (PP) was used (MFR (conditions: 230°C, 2.16 kg load) = 0.5 g / 10 min).

[0156] The crosslinking agent (C) used was brominated alkylphenol formaldehyde resin (Ph resin) (product name: SP-1055F, manufactured by Schenectady).

[0157] Softener (D) Paraffin-based process oil (Product name: Diana Process Oil) ＴＭ PW-100 (manufactured by Idemitsu Kosan Co., Ltd.) was used.

[0158] As the acid acid, zinc oxide (ZnO) (product name: Zinc Oxide 2 types, manufactured by Hakusui Tech Co., Ltd.) was used.

[0159] As a filler, carbon black masterbatch (CB-MB) (product name: PEONY BLACK F3238MM, manufactured by DIC Corporation) was used.

[0160] [Example 1] 200 parts by mass of EBDM-1 (A-1) obtained in Production Example 1 (oil spread rate 100 parts by mass), 170 parts by mass of crystalline olefin polymer (B-1) (MFR (conditions: 230°C, 2.16 kg load) = 0.5 g / 10 min), and Diana Process Oil manufactured by Idemitsu Kosan Co., Ltd. as an olefin process oil. ＴＭ 35 parts by mass of PW-100, 10 parts by mass of brominated alkylphenol formaldehyde resin (SP-1055F manufactured by Schenectady) as a phenolic resin crosslinking agent, 1 part by mass of zinc oxide (two types of zinc oxide manufactured by Hakusui Tech) as an acid acceptor, and 10 parts by mass of carbon black masterbatch (PEONY BLACK F3287MM manufactured by DIC) as a filler were kneaded and dynamically crosslinked using an extruder (model number: KTX-30, manufactured by Kobe Steel, Ltd., cylinder temperature: C1: 50°C, C2: 90°C, C3: 100°C, C4: 120°C, C5: 180°C, C6-C14: 200°C, die temperature: 200°C, screw rotation speed: 500 rpm, extrusion rate: 40 kg / h) to obtain pellets of a thermoplastic elastomer composition.

[0161] [Example 2] In Example 1, the copolymer to be blended is changed to EBDM-2 obtained in Production Example 2, and the blended Idemitsu Kosan Diana Process Oil is changed. ＴＭ A pellet of thermoplastic elastomer composition was produced in the same manner as in Example 1, except that the amount of PW-100 was changed to 60 parts by mass.

[0162] [Example 3] In Example 1, the copolymer to be blended is changed to EBDM-3 obtained in Production Example 3, and the blended is Diana Process Oil manufactured by Idemitsu Kosan Co., Ltd. ＴＭ A pellet of thermoplastic elastomer composition was produced in the same manner as in Example 1, except that the amount of PW-100 was changed to 60 parts by mass.

[0163] [Reference Example 1] In Example 1, the copolymer to be blended is changed to EBDM-4 obtained in Production Example 4, and the blended Diana Process Oil manufactured by Idemitsu Kosan Co., Ltd. is changed. ＴＭ A pellet of thermoplastic elastomer composition was produced in the same manner as in Example 1, except that PW-100 was changed to 105 parts by mass.

[0164] [Comparative Example 1] In Example 1, the copolymer to be blended is ethylene propylene 5-ethylidene-2-norbornene copolymer (EPDM), which is Keltan® 5469C manufactured by ARLANXEO. Mooney viscosity ML １＋４ A pellet of thermoplastic elastomer composition was produced in the same manner as in Example 1, except that the following was changed: (125°C): 52, ethylene content: 58% by mass, ENB content: 4.5% by mass, oil spreadability: 100 parts by mass).

[0165]

Claims

1. A thermoplastic elastomer composition comprising an ethylene-α-olefin-non-conjugated polyene copolymer (A) and a crystalline olefin polymer (B), which is a copolymer having structural units derived from ethylene [A1], structural units derived from at least one type of α-olefin having 4 to 20 carbon atoms [A2], and structural units derived from at least one type of non-conjugated polyene [A3], and satisfying the following requirements (1) and (2). Requirement (1) The molar ratio [[A1] / [A2]] of structural units derived from ethylene [A1] to structural units derived from α-olefin having 4 to 20 carbon atoms is 40 / 60 to 90 / 10. Requirement (2) The intrinsic viscosity [η] measured in decalin at 135°C is 4.0 to 7.0 dl / g.

2. The thermoplastic elastomer composition according to claim 1, characterized in that the α-olefin [A2] having 4 to 20 carbon atoms is 1-butene.

3. The thermoplastic elastomer composition according to claim 1, characterized in that the ethylene-α-olefin-non-conjugated polyene copolymer (A) further satisfies the following requirement (3): Requirement (3) The content of structural units derived from non-conjugated polyene [A3] is 0.1 to 6.0 mol%. (However, the total of structural units of [A1], [A2], and [A3] is 100 mol%) 4. The thermoplastic elastomer composition according to claim 1, characterized in that the ethylene-α-olefin-non-conjugated polyene copolymer (A) further satisfies the following requirement (4). Requirement (4) The B value, represented by the following formula (i), is 1.20 or greater. B value = ([EX] + 2[Y]) / [2 × [E] × ([X] + [Y])] ... (i) Here, [E], [X], and [Y] represent the mole fractions of ethylene [A1], α-olefin [A2] having 4 to 20 carbon atoms, and non-conjugated polyene [A3], respectively, and [EX] represents the ethylene [A1]-α-olefin [A2] having 4 to 20 carbon atoms dyad chain fraction.

5. The thermoplastic elastomer composition according to claim 1, further characterized by containing a crosslinking agent (C).

6. The thermoplastic elastomer composition according to claim 5, characterized in that it is prepared by dynamic crosslinking.

7. The thermoplastic elastomer composition according to claim 1, comprising the ethylene-α-olefin-non-conjugated polyene copolymer (A) and a crystalline olefin polymer (B) in a mass ratio of (A) / (B) = 90 / 10 to 10 / 90.

8. The thermoplastic elastomer composition according to claim 1, wherein the content of the softener (D) is 50 to 300 parts by mass per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A).

9. The thermoplastic elastomer composition according to claim 1, wherein the non-conjugated polyene [A3] is 5-ethylidene-2-norbornene (ENB).

10. The thermoplastic elastomer composition according to claim 4, wherein the crosslinking agent (C) is at least one selected from the group consisting of phenolic resin-based crosslinking agents and peroxide-based crosslinking agents.

11. The thermoplastic elastomer composition according to claim 1, characterized in that the viscosity / swell ratio of the thermoplastic elastomer composition is 300 to 446.

Images