Ethylenic copolymer composition, and hose product

Abstract

SOLUTION: An ethylenic copolymer composition includes: an ethylene α-olefin nonconjugated polyene copolymer (A) having a structural unit derived from ethylene (a1), a structural unit derived from a 3-20C α-olefin (a2), and a structural unit derived from a nonconjugated polyene (a3) including a total of two or more of a partial structure selected from the group consisting of the following general formulas (I) and (II) in a molecule where the structural unit derived from the nonconjugated polyene (a3) includes a structural unit derived from 5-vinyl-2-norbornene; and 1-300 pts. mass of siliceous earth (B) to 100 pts. mass of the ethylene α-olefin nonconjugated polyene copolymer (A).EFFECT: The present invention can provide a composition excellent in a balance of thermal aging resistance, compression set, resistance to coolant, and modulus. A hose product having high performance can be produced by using the composition of the present invention.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an ethylene-based copolymer composition and a hose product comprising an ethylene-based copolymer and a particular siliceous earth. [Background technology]

[0002] Ethylene-based copolymers such as ethylene-α-olefin copolymers, for example ethylene-α-olefin-non-conjugated polyene copolymers, have no unsaturated bonds in the main chain and therefore have superior weather resistance, heat resistance, and ozone resistance compared to diene-based rubbers, and are widely used in rubber products such as automotive industrial parts, industrial rubber products, electrical insulating materials, civil engineering and building materials, and rubber-coated fabrics.

[0003] For example, in vehicles such as automobiles, radiator hoses are used to connect the engine and the radiator. A resin composition mainly composed of ethylene-propylene-diene monomer (EPDM) has traditionally been used as the material for radiator hoses.

[0004] In recent years, as noise regulations have become stricter in Europe and other countries, there are cases where noise is suppressed by covering the engine and parts around the engine with soundproofing materials. This has led to increased demand for radiator hoses with heat aging resistance. Furthermore, there is a demand for improved compression set (CS) to prevent leakage of long-life coolant (LLC), improved strength after immersion in coolant, and increased modulus to allow for thinner walls for weight reduction.

[0005] Patent Document 1 discloses that by polymerizing an ethylene-propylene-5-vinyl-2-norbornene copolymer with a specific metallocene catalyst, long chain branching is reduced, and as a result, unreacted dienes after crosslinking are reduced, improving heat aging resistance.

[0006] Patent Document 2 discloses that heat aging resistance can be improved by blending a specific amount of magnesium hydroxide having a specific aspect ratio with an ethylene-propylene-5-vinyl-2-norbornene copolymer.

[0007] However, these resins were insufficient in terms of heat aging resistance, compression set, coolant resistance, and modulus, and there was room for improvement. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] International Publication No. 2015 / 122495 [Patent Document 2] JP 2020-84137 A Summary of the Invention [Problem to be solved by the invention]

[0009] An object of the present invention is to provide a composition having an excellent balance of heat aging resistance, compression set, coolant resistance, and modulus. [Means for solving the problem]

[0010] As a result of extensive research into solving the above problems, the inventors discovered that by blending a specific type of siliceous earth with an ethylene-α-olefin-non-conjugated polyene copolymer, the heat aging resistance, compression set, coolant resistance, and modulus are improved, leading to the completion of the present invention.

[0011] That is, the present invention relates to, for example, the following items [1] to [9]. [1] A polymer having a structural unit derived from ethylene (a1), a structural unit derived from an α-olefin (a2) having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene (a3) ​​containing, in one molecule, two or more partial structures selected from the group consisting of the following general formulae (I) and (II): an ethylene-α-olefin-non-conjugated polyene copolymer (A), in which the structural units derived from the non-conjugated polyene (a3) ​​include structural units derived from 5-vinyl-2-norbornene; and 1 to 300 parts by mass of siliceous earth (B) relative to 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A), An ethylene-based copolymer composition.

[0012] [ka] [2] The ethylene copolymer composition according to [1], wherein the copolymer (A) satisfies the following requirements (i) to (vi): (i) the molar ratio of structural units derived from ethylene (a1) to structural units derived from an α-olefin (a2) [(a1) / (a2)] is 40 / 60 to 99.9 / 0.1; (ii) the weight fraction of the structural units derived from the non-conjugated polyene (a3) ​​is 0.07% by mass to 10% by mass in 100% by mass of the copolymer (A); (iii) the weight average molecular weight (Mw) of the copolymer (A), the weight fraction of the structural unit derived from the non-conjugated polyene (a3) ​​(weight fraction (mass%) of (a3)), and the molecular weight of the non-conjugated polyene (a3) ​​(molecular weight of (a3)) satisfy the following formula (1); 4.5≦Mw×weight fraction of (a3) / 100 / molecular weight of (a3)≦40 … (1) (iv) Complex viscosity η at frequency ω = 0.1 rad / s obtained by linear viscoelastic measurement (190 °C) using a rheometer * (ω=0.1) (Pa sec) and the complex viscosity η at frequency ω = 100 rad / s * (ω=100) (Pa sec) P〔η * (ω=0.1) / η * (ω=100) ], the intrinsic viscosity [η] of the copolymer (A), and the weight fraction of (a3) ​​satisfy the following formula (2); P / ([η] 2.9 ) ≦ (a3) ​​weight fraction × 6 … (2) (v) the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (molecular weight distribution; Mw / Mn) measured by gel permeation chromatography (GPC) is in the range of 8 to 30; (vi) The number average molecular weight (Mn) is 30,000 or less. [3] The ethylene copolymer composition according to [1] or [2], wherein the siliceous earth (B) is Neuburg siliceous earth. [4] The ethylene copolymer composition according to [3], wherein the Neuburg siliceous earth is surface-treated with a silane coupling agent. [5] The ethylene-based copolymer composition according to [4], wherein the silane coupling agent is at least one selected from the group consisting of vinyl silane, amino silane, mercapto silane, tetrasulfane silane, and alkyl silane. [6] The ethylene copolymer composition according to any one of [1] to [5], wherein the α-olefin (a2) is propylene. [7] The ethylene copolymer composition according to any one of [1] to [6], which is for a hose. [8] A crosslinked product of the ethylene copolymer composition according to any one of [1] to [6]. [9] A hose product comprising the cross-linked body according to [8]. Effect of the Invention

[0013] The present invention can provide a composition having an excellent balance of heat aging resistance, compression set, coolant resistance, and modulus. Furthermore, by using the composition of the present invention, a high-performance hose product can be produced. [Brief description of the drawings]

[0014] [Figure 1] FIG. 1 is a schematic diagram of a continuous polymerization apparatus used in the examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] <Ethylene-α-olefin-non-conjugated polyene copolymer (A)> The copolymer (A) used in the present invention has a structural unit derived from ethylene (a1), a structural unit derived from an α-olefin (a2) having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene (a3).

[0016] [α-Olefin (a2)] Examples of the α-olefin (a2) include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-eicosene. Among these, α-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene, and 1-octene are preferred, and propylene is particularly preferred. Such α-olefins are preferred because the raw material cost is relatively low, the resulting copolymer (A) exhibits excellent mechanical properties, and a molded product having rubber elasticity can be obtained.

[0017] The α-olefin (a2) may be used alone or in combination of two or more kinds. That is, the copolymer (A) contains structural units derived from at least one α-olefin (a2) having 3 to 20 carbon atoms, and may contain structural units derived from two or more α-olefins (a2) having 3 to 20 carbon atoms.

[0018] [Non-conjugated polyene (a3)] The non-conjugated polyene (a3) ​​is not particularly limited as long as it is a compound that contains a total of two or more partial structures selected from the group consisting of the following general formulas (I) and (II) in the molecule and contains a structural unit derived from 5-vinyl-2-norbornene (VNB).

[0019] [ka]

[0020] By including a structural unit derived from VNB in ​​the non-conjugated polyene (a3), the reactivity with peroxide during the crosslinking reaction after polymerization is good, and the heat resistance of the polymer composition is likely to be improved. The non-conjugated polyene (a3) ​​may include one or more structural units derived from norbornadiene, 1,4-hexadiene, dicyclopentadiene, etc., in addition to VNB.

[0021] [Non-conjugated polyene (a4)] The copolymer (A) may have, in addition to the structural units derived from the above (a1), (a2), and (a3), a structural unit derived from a non-conjugated polyene (a4) containing in the molecule only one partial structure selected from the group consisting of the above general formulas (I) and (II).

[0022] Examples of the non-conjugated polyene (a4) include 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(3-butenyl)-2-norbornene, 5-(1-methyl-2-propenyl)-2-norbornene, 5-(4-pentenyl)-2-norbornene, 5-(1-methyl-3-butenyl)-2-norbornene, 5-(5-hexenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-(2,3-dimethyl-3-butenyl)-2-norbornene, 5-(2-ethyl-3-butenyl)-2-norbornene, Examples of such compounds include 5-(1,2-dimethyl-5-hexenyl)-2-norbornene, 5-(6-heptenyl)-2-norbornene, 5-(3-methyl-5-hexenyl)-2-norbornene, 5-(3,4-dimethyl-4-pentenyl)-2-norbornene, 5-(3-ethyl-4-pentenyl)-2-norbornene, 5-(7-octenyl)-2-norbornene, 5-(2-methyl-6-heptenyl)-2-norbornene, 5-(1,2-dimethyl-5-hexenyl)-2-norbornene, 5-(5-ethyl-5-hexenyl)-2-norbornene, and 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene. Among these, ENB is preferred because it is easily available, has high reactivity with sulfur and vulcanization accelerators during the crosslinking reaction after polymerization, is easy to control the crosslinking rate, and is easy to obtain good mechanical properties. The non-conjugated polyene (a4) may be used alone or in combination of two or more kinds.

[0023] When the copolymer (A) contains a structural unit derived from the non-conjugated polyene (a4), the proportion thereof is not particularly limited as long as the object of the present invention is not impaired. Generally, the weight fraction thereof is about 0 to 20 mass%, preferably 0 to 8 mass%, and more preferably 0.01 to 8 mass% (wherein the total weight fractions of (a1), (a2), (a3), and (a4) is taken as 100 mass%).

[0024] Each of the copolymers (A) may contain at least one biomass-derived monomer (ethylene (a1), an α-olefin having 3 to 20 carbon atoms (a2), a non-conjugated polyene (a3), and a non-conjugated polyene (a4)).

[0025] [Requirements] The copolymer (A) preferably satisfies the following requirements (i) to (vi) (hereinafter also referred to as requirements (i) to (vi), respectively). (i) The molar ratio of the structural units derived from ethylene (a1) to the structural units derived from an α-olefin (a2) [(a1) / (a2)] is 40 / 60 to 99.9 / 0.1. (ii) The weight fraction of the structural units derived from the non-conjugated polyene (a3) ​​is 0.07% by mass to 10% by mass in 100% by mass of the copolymer (A). (iii) The weight average molecular weight (Mw) of the copolymer (A), the weight fraction of the structural unit derived from the non-conjugated polyene (a3) ​​(weight fraction (mass%) of (a3)), and the molecular weight of the non-conjugated polyene (a3) ​​(molecular weight of (a3)) satisfy the following formula (1). 4.5≦Mw×weight fraction of (a3) / 100 / molecular weight of (a3)≦40 … (1) (iv) Complex viscosity η at frequency ω = 0.1 rad / s obtained by linear viscoelastic measurement (190 °C) using a rheometer * (ω=0.1) (Pa sec) and the complex viscosity η at frequency ω = 100 rad / s * (ω=100) (Pa sec) P〔η * (ω=0.1) / η * (ω=100) ], the intrinsic viscosity [η] of the copolymer (A), and the weight fraction of [a3] satisfy the following formula (2). P / ([η] 2.9 ) ≦ [a3] weight fraction × 6 … (2) (v) The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (molecular weight distribution; Mw / Mn) measured by gel permeation chromatography (GPC) is in the range of 8 to 30. (vi) The number average molecular weight (Mn) is 30,000 or less.

[0026] [Requirement (i)] The requirement (i) specifies that the molar ratio of ethylene (a1) / α-olefin (a2) in the copolymer (A) satisfies 40 / 60 to 99.9 / 0.1, and this molar ratio is preferably 50 / 50 to 90 / 10, more preferably 55 / 45 to 80 / 20, even more preferably 55 / 45 to 70 / 30, and particularly preferably 60 / 40 to 65 / 35.

[0027] By using the copolymer (A) that satisfies the requirement (i), an ethylene copolymer composition having excellent rubber elasticity, mechanical strength, and flexibility can be obtained. The amount of ethylene (content of structural units derived from ethylene (a1)) and the amount of α-olefin (content of structural units derived from α-olefin (a2)) in the copolymer (A), and the molar ratio of ethylene (a1) / α-olefin (a2) are as follows: 13 It can be determined by measurements using C-NMR.

[0028] [Requirement (ii)] Requirement (ii) specifies that the weight fraction of the structural unit derived from the non-conjugated polyene (a3) ​​is in the range of 0.07% by mass to 10% by mass in 100% by mass of the copolymer (A) (i.e., in the total weight fraction of all structural units, 100% by mass). The weight fraction of the structural unit derived from the non-conjugated polyene (a3) ​​is preferably 0.1% by mass to 8.0% by mass, more preferably 0.5% by mass to 5.0% by mass, even more preferably 0.5% by mass to 3.0% by mass, and particularly preferably 0.5% by mass to 2.0% by mass.

[0029] The copolymer (A) satisfying the requirement (ii) has sufficient hardness and excellent mechanical properties, and when crosslinked using a peroxide, it exhibits a fast crosslinking rate. The amount of non-conjugated polyene (a3) ​​in the copolymer (A) (the content of the constitutional unit derived from the non-conjugated polyene (a3)) is: 13 It can be determined by C-NMR.

[0030] [Requirement (iii)] Requirement (iii) specifies that, in the copolymer (A), the weight average molecular weight (Mw) of the copolymer (A), the weight fraction of the structural unit derived from the non-conjugated polyene (a3) ​​in the copolymer (A) (weight fraction of (a3): mass %), and the molecular weight of the non-conjugated polyene (a3) ​​(molecular weight of (a3)) satisfy the above formula (1). The above formula (1) in requirement (iii) is preferably the following formula (1'): 4.5≦Mw×weight fraction of (a3) / 100 / molecular weight of (a3)≦35 …(1')

[0031] When the copolymer (A) satisfies the requirement (iii), the content of the structural unit derived from the non-conjugated polyene (a3) ​​is appropriate, and an ethylene copolymer composition that exhibits sufficient crosslinking performance, excellent crosslinking rate, and excellent mechanical properties can be produced. The weight average molecular weight (Mw) of the copolymer (A) can be determined as a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0032] In the above copolymer (A), when "weight fraction of Mw × (a3) / 100 / molecular weight of (a3)" satisfies the above formula (1) or (1'), the degree of crosslinking becomes appropriate, and an ethylene-based copolymer composition having a good balance of mechanical properties and heat aging resistance can be produced. If the value of "weight fraction of Mw × (a3) / 100 / molecular weight of (a3)" is too low, the crosslinking may be insufficient, resulting in a slow crosslinking rate, and if the value is too high, excessive crosslinking may occur, resulting in deterioration of mechanical properties.

[0033] [Requirement (iv)] The requirement (iv) is that the complex viscosity η of the copolymer (A) at a frequency ω=0.1 rad / s obtained by linear viscoelasticity measurement (190° C.) using a rheometer * ( ω =0.1) (Pa sec) and the complex viscosity η at frequency ω = 100 rad / s * ( ω =100) (Pa sec) *( ω =0.1) / η * ( ω =100) ), the intrinsic viscosity [η], and the weight fraction of the structural unit derived from the non-conjugated polyene (a3) ​​(weight fraction of (a3): mass %) satisfy the above formula (2). The above formula (2) in requirement (iv) is preferably the following formula (2'). P / ([η] 2.9 ) ≦ (a3) ​​weight fraction × 5.7 … (2')

[0034] Here, the complex viscosity η at frequency ω=0.1rad / s * ( ω =0.1) and the complex viscosity η at frequency ω=100rad / s * ( ω =100) Relative to P(η * ( ω =0.1) / η * ( ω =100) ) represents the frequency dependence of viscosity and is the left side of equation (2), P / ([η] 2.9 ) tends to show a high value when there are many long chain branches, although it is influenced by short chain branches, molecular weight, etc. In general, in an ethylene-α-olefin-non-conjugated polyene copolymer, the more constitutional units derived from non-conjugated polyenes it contains, the more long chain branches it tends to contain. However, it is considered that the copolymer (A) of the present invention can satisfy the above formula (2) because it has fewer long chain branches than the conventionally known ethylene-α-olefin-non-conjugated polyene copolymers.

[0035] In the present invention, the P value is determined by performing measurements using a viscoelasticity measuring device Ares (manufactured by Rheometric Scientific) at 190° C., strain 1.0%, and various frequencies, and is calculated as the ratio (η * The intrinsic viscosity [η] is the value measured in decalin at 135°C.

[0036] [Requirement (v)] Requirement (v) specifies that the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (molecular weight distribution; Mw / Mn) of the copolymer (A) measured by gel permeation chromatography (GPC) is in the range of 8 to 30. This molecular weight distribution (Mw / Mn) is preferably in the range of 10 to 30, more preferably 15 to 28, further preferably 20 to 28, and particularly preferably 22 to 26.

[0037] When the copolymer (A) satisfies the requirement (v), it contains an appropriate amount of low molecular weight components, and therefore has good processability. The weight average molecular weight (Mw) and number average molecular weight of the copolymer (A) can be determined as polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC).

[0038] [Requirement (vi)] Requirement (vi) specifies that the number average molecular weight (Mn) of the copolymer (A) is not more than 30,000. The number average molecular weight (Mn) is preferably in the range of 3,000 to 26,000, more preferably 6,000 to 23,000, further preferably 7,000 to 18,000, and particularly preferably 8,000 to 12,000. When the copolymer (A) satisfies the requirement (vi), it contains an appropriate amount of low molecular weight components, and therefore has good processability.

[0039] The copolymer (A) preferably satisfies the requirements (i) to (vi) as well as the requirements (vii) to (ix).

[0040] [Requirement (vii)] The copolymer (A) was determined by 3D-GPC using the long chain branching (LCB) per 1000 carbon atoms. 1000C ) and the natural logarithm of the weight average molecular weight (Mw) [Ln(Mw)] preferably satisfy the following formula (3), and more preferably satisfy the following formula (3'). LCB 1000C≦1-0.07×Ln(Mw) …(3) LCB 1000C ≦1-0.071×Ln(Mw) …(3') The upper limit of the long chain branch content per unit carbon number of the copolymer (A) is specified by the above formula (3) or (3').

[0041] Such a copolymer (A) has a low proportion of long chain branches and is excellent in curing properties when crosslinked using a peroxide, and can give an ethylene copolymer composition having excellent heat aging resistance.

[0042] Here, Mw and the number of long chain branches (LCB) per 1000 carbon atoms 1000C ) can be determined by a structural analysis method using 3D-GPC. In this specification, it was specifically determined as follows.

[0043] The absolute molecular weight distribution was measured using a 3D-high temperature GPC device PL-GPC220 (Polymer Laboratories), and the intrinsic viscosity was measured using a viscometer. The main measurement conditions were as follows:

[0044] Detector: Differential refractometer / GPC device built-in 2-angle light scattering photometer PD2040 type (manufactured by Precison Detectors) Bridge type viscometer PL-BV400 (Polymer Laboratories) Column: TSKgel GMH HR -H(S)HT x 2 + TSKgel GMH HR -M(S) x 1 (each with inner diameter 7.8mmφ x length 300mm) Temperature: 140℃ Mobile phase: 1,2,4-trichlorobenzene (containing 0.025% BHT) Injection volume: 0.5mL Sample concentration: ca 1.5mg / mL Sample filtration: Filtration through a sintered filter with a pore size of 1.0 μm

[0045] In the above, the dn / dc value required to determine the absolute molecular weight was determined for each sample from the dn / dc value of standard polystyrene (molecular weight 190,000) of 0.053 and the response intensity of the differential refractometer per unit injected mass.

[0046] From the relationship between the intrinsic viscosity obtained from the viscometer and the absolute molecular weight obtained from the light scattering photometer, the long chain branching parameter g'i for each eluted component was calculated from the following formula (v-1). In formula (v-1), [η] = KM v , v = 0.725 was applied. This equation is called the Mark-Houwink-Sakurada equation, where K is the solvent constant and M is the average molecular weight.

[0047]

number

[0048] Further, the average values ​​of g' were calculated from the following formulas (v-2), (v-3), and (v-4). Note that a trendline assuming the presence of only short chain branches was determined for each sample.

[0049]

number

[0050] Furthermore, using g'w, the number of branching points per molecular chain, BrNo, and the number of long chain branches per 1000 carbon atoms, LCB, 1000C The branching degree λ per unit molecular weight was calculated. BrNo was calculated using the following Zimm-Stockmayer formula (v-5). 1000C The following formulas (v-6) and (v-7) were used to calculate and λ. g is the long chain branching parameter calculated from the radius of gyration Rg, and the following simple correlation is made between g' calculated from the intrinsic viscosity. Various values ​​have been proposed for ε in the formula depending on the shape of the molecule. Here, calculations were performed assuming ε=1 (i.e. g'=g).

[0051]

number

[0052] λ=BrNo / M …(V-6) LCB 1000C = λ × 14000 … (V-7) In formula (V-7), "14000" represents a molecular weight of 1000 methylene (CH2) units.

[0053] The intrinsic viscosity [η] of the copolymer (A) is preferably 0.1 to 5 dL / g, more preferably 0.5 to 5.0 dL / g, even more preferably 0.9 to 4.0 dL / g, particularly preferably 1.5 to 3.0 dL / g, and even more preferably 2.2 to 2.6 dL / g.

[0054] The weight average molecular weight (Mw) of the copolymer (A) is preferably 10,000 to 600,000, more preferably 30,000 to 500,000, still more preferably 50,000 to 400,000, particularly preferably 100,000 to 300,000, and even more preferably 200,000 to 250,000.

[0055] It is preferable that the copolymer (A) satisfies both of the above-mentioned intrinsic viscosity [η] and weight average molecular weight (Mw).

[0056] In the copolymer (A), as described above, the non-conjugated polyene (a3) ​​preferably contains VNB, and more preferably is VNB. That is, in the above formula (1), formula (2), and formula (4) described later, the "weight fraction of (a3)" is preferably the "weight fraction of VNB" (mass%).

[0057] As described above, the copolymer (A) preferably contains, in addition to the structural units derived from the above (a1), (a2) and (a3), a structural unit derived from the non-conjugated polyene (a4) in a weight fraction of 0% to 20% by mass (where the total weight fractions of (a1), (a2), (a3) ​​and (a4) are taken as 100% by mass). In this case, it is preferable that the following requirement (viii) is satisfied.

[0058] [Requirement (viii)] The weight average molecular weight (Mw) of the copolymer (A), the weight fraction of the structural unit derived from the non-conjugated polyene (a3) ​​(weight fraction (mass%) of (a3)), the weight fraction of the structural unit derived from the non-conjugated polyene (a4) (weight fraction (mass%) of (a4)), the molecular weight of the non-conjugated polyene (a3) ​​(molecular weight of (a3)), and the molecular weight of the non-conjugated polyene (a4) (molecular weight of (a4)) satisfy the following formula (4). 4.5≦Mw×{(weight fraction of (a3) / 100 / molecular weight of (a3))+(weight fraction of (a4) / 100 / molecular weight of (a4))}≦45 …(4) Formula (4) specifies the content of non-conjugated diene (the sum of (a3) ​​and (a4)) in one copolymer molecule.

[0059] When the copolymer (A) containing the structural unit derived from the above (a4) satisfies the formula (4), an ethylene-based copolymer composition excellent in mechanical properties and heat aging resistance can be obtained.

[0060] If the requirement (viii) is not satisfied, and the value of "Mw × {(weight fraction of (a3) / 100 / molecular weight of (a3)) + (weight fraction of (a4) / 100 / molecular weight of (a4))}" in formula (4) is too low, that is, if the content of non-conjugated diene is too low, sufficient crosslinking may not be achieved and appropriate mechanical properties may not be obtained. Conversely, if the value is too high, that is, if the content of non-conjugated diene is too high, excessive crosslinking may occur, resulting in deterioration of mechanical properties and further deterioration of heat aging resistance.

[0061] [Requirement (ix)] The copolymer (A) is not particularly limited, but has a complex viscosity η at a frequency ω=0.01 rad / s obtained by linear viscoelasticity measurement (190° C.) using a rheometer. * ( ω =0.01) (Pa sec) and the complex viscosity η at frequency ω=10rad / s * ( ω =10)It is preferable that the apparent iodine value (Pa·sec) and the apparent iodine value derived from the non-conjugated polyene (a3) ​​satisfy the following formula (5). Log{η * ( ω =0.01)} / Log{η * ( ω =10)}≦0.0753×{apparent iodine value derived from non-conjugated polyene (a3)}+1.42 … (5)

[0062] Here, the complex viscosity η * ( ω =0.01) and the complex viscosity η * ( ω =10) is the complex viscosity η in requirement (iv) * ( ω =0.1) and the complex viscosity η * ( ω =100) The apparent iodine value derived from the non-conjugated polyene (a3) ​​can be calculated in the same manner as above, except for the measurement frequency. Apparent iodine value derived from (a3) ​​= weight fraction of (a3) ​​× 253.81 / molecular weight of (a3)

[0063] In the above formula (5), the left side represents the shear rate dependency which is an index of the amount of long chain branches, and the right side represents an index of the content of non-conjugated polyene (a3) ​​that is not consumed as long chain branches during polymerization. If the above copolymer (A) satisfies the above formula (5), the degree of long chain branches is not too high, which is preferable. On the other hand, if the above formula (5) is not satisfied, it is found that a large proportion of the copolymerized non-conjugated polyene (a3) ​​is consumed to form long chain branches.

[0064] Furthermore, the copolymer (A) preferably contains a sufficient amount of structural units derived from the non-conjugated polyene (a3), and it is more preferable that the weight fraction of the structural units derived from the non-conjugated polyene (a3) ​​in the copolymer (weight fraction (mass%) of (a3)) and the weight average molecular weight (Mw) of the copolymer satisfy the following formula (6). 6-0.45×Ln(Mw)≦(a3) weight fraction≦10 …(6)

[0065] In addition, the copolymer (A) has a number (n a3 ) is preferably 6 or more, more preferably 6 or more and 40 or less, further preferably 7 or more and 39 or less, and particularly preferably 10 or more and 38 or less.

[0066] Such a copolymer (A) contains a sufficient amount of structural units derived from a non-conjugated polyene (a3) ​​such as VNB, has a low content of long chain branches, is excellent in curing characteristics when crosslinked using a peroxide, has good moldability, and is excellent in balance of physical properties such as mechanical properties, and is particularly excellent in heat aging resistance.

[0067] In addition, the copolymer (A) has a number (n a4 ) is preferably 29 or less, more preferably 10 or less, and even more preferably less than 1.

[0068] In such a copolymer (A), the content of structural units derived from a non-conjugated polyene (a4) such as ENB is controlled within a range that does not impair the object of the present invention, and it is less likely to undergo post-crosslinking and has sufficient heat aging resistance.

[0069] Here, the number of constitutional units derived from the non-conjugated polyene (a3) ​​per weight average molecular weight (Mw) of the copolymer (A) (n a3 ) or the number of constitutional units derived from the non-conjugated polyene (a4) (n a4 ) can be calculated from the molecular weight of the non-conjugated polyene (a3) ​​or (a4), the weight fraction of the structural units derived from the non-conjugated polyene (a3) ​​or (a4) in the copolymer (weight fraction (mass%) of (a3) ​​or (a4)), and the weight average molecular weight (Mw) of the copolymer (A) according to the following formula. (n a3 )=(Mw)×{weight fraction of (a3) / 100} / molecular weight of non-conjugated polyene (a3) (n a4 )=(Mw)×{weight fraction of (a4) / 100} / molecular weight of non-conjugated polyene (a4)

[0070] In the copolymer (A), the number of structural units derived from the non-conjugated polyenes (a3) ​​and (a4) per weight average molecular weight (Mw) (n a3 ) and (n a4 ) satisfy the above ranges, the copolymer (A) has a low content of long chain branches, is excellent in curing characteristics when crosslinking is performed using a peroxide, has good moldability, and is excellent in balance of physical properties such as mechanical properties, and is less likely to cause post-crosslinking, and is particularly excellent in heat aging resistance, which is preferable.

[0071] <Production of Copolymer (A)> The copolymer (A) is a copolymer obtained by copolymerizing monomers consisting of ethylene (a1), an α-olefin (a2), a non-conjugated polyene (a3), and, if necessary, a non-conjugated polyene (a4).

[0072] The copolymer (A) may be produced by any method as long as it satisfies the above requirements (i) to (vi), but is preferably produced by copolymerizing a monomer in the presence of a metallocene compound, more preferably produced by copolymerizing a monomer in the presence of a catalyst system containing a metallocene compound, and even more preferably produced by a method including step (1) of copolymerizing in the presence of a polymerization catalyst containing a specific metallocene compound, and step (2) of deactivating the polymerization catalyst by adding an alcohol as a catalyst deactivator. Specific production methods and conditions will be described later.

[0073] [Metallocene compounds] The copolymer (A) is preferably one obtained by copolymerizing monomers in the presence of a polymerization catalyst system containing at least one metallocene compound selected from the compounds represented by the following general formula [A1]. When the copolymerization of monomers is carried out using a polymerization catalyst system containing such a metallocene compound, the long chain branching contained in the obtained copolymer is suppressed, and the copolymer (A) satisfying the above requirements can be easily produced.

[0074] [ka]

[0075] In formula [A1], R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 and R 12 each independently represents a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a heteroatom-containing group other than a silicon-containing group; R 1 ~R 4 Among these, adjacent two groups may be bonded to each other to form a ring.

[0076] The hydrocarbon group is preferably a hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof include an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group or a substituted aryl group having 6 to 20 carbon atoms, etc. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an allyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an amyl group, an n-pentyl group, a neopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decanyl group, a 3-methylpentyl group, a 1,1-diethylpropyl group, a 1,1-dimethylbutyl group, a 1-methyl-1-propylbutyl group, a 1,1-propylbutyl group, a 1,1-dimethyl-2-methylpropyl group, a 1-methyl-1-isopropyl-2-methylpropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. Examples of the hydrocarbon group include oxygen-containing groups such as a methoxy group, an ethoxy group, and a phenoxy group; nitrogen-containing groups such as a nitro group, a cyano group, an N-methylamino group, an N,N-dimethylamino group, and an N-phenylamino group; boron-containing groups such as a boranetriyl group and a diboranyl group; and sulfur-containing groups such as a sulfonyl group and a sulfenyl group.

[0077] The above-mentioned hydrocarbon group may have a hydrogen atom substituted with a halogen atom, and examples thereof include a trifluoromethyl group, a trifluoromethylphenyl group, a pentafluorophenyl group, and a chlorophenyl group.

[0078] Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, etc. Examples of the silicon-containing group include a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group, a dimethylphenylsilyl group, a dimethyl-t-butylsilyl group, and a dimethyl(pentafluorophenyl)silyl group.

[0079] R 6 and R 11 are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than a silicon-containing group, and R 7 and R 10 are the same atom or the same group selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than a silicon-containing group, and R 6 and R 7 may be bonded to each other to form a ring, R 10 and R 11 may be bonded to each other to form a ring. 6 , R 7 , R 10 and R 11 are not all hydrogen atoms.

[0080] R 13 and R 14 each independently represents an aryl group. M 1 indicates a zirconium atom. Y 1 represents a carbon atom or a silicon atom.

[0081] Q represents a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene having 4 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, j represents an integer of 1 to 4, and when j is an integer of 2 or greater, multiple Qs may be the same or different.

[0082] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a chlorine atom. The hydrocarbon group is preferably a hydrocarbon group having 1 to 10 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a 2-methylpropyl group, a 1,1-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1,1-diethylpropyl group, a 1-ethyl-1-methylpropyl group, a 1,1,2,2-tetramethylpropyl group, a sec-butyl group, a t-butyl group, a 1,1-dimethylbutyl group, a 1,1,3-trimethylbutyl group, a neopentyl group, a cyclohexylmethyl group, a cyclohexyl group, a 1-methyl-1-cyclohexyl group, and a benzyl group. Of these, a methyl group, an ethyl group, and a benzyl group are preferred.

[0083] As the neutral conjugated or non-conjugated diene having 4 to 20 carbon atoms, a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms is preferable. Specific examples of the neutral conjugated or non-conjugated diene include s-cis- or s-trans-η 4 -1,3-butadiene, s-cis- or s-trans-η 4 -1,4-diphenyl-1,3-butadiene, s-cis- or s-trans-η 4 -3-Methyl-1,3-pentadiene, s-cis- or s-trans-η 4 -1,4-Dibenzyl-1,3-butadiene, s-cis- or s-trans-η 4 -2,4-Hexadiene, s-cis- or s-trans-η 4 -1,3-Pentadiene, s-cis- or s-trans-η 4 -1,4-Ditolyl-1,3-butadiene, s-cis- or s-trans-η 4 -1,4-bis(trimethylsilyl)-1,3-butadiene and the like.

[0084] Specific examples of the anionic ligand include alkoxy groups such as methoxy, t-butoxy, and phenoxy; carboxylate groups such as acetate and benzoate; and sulfonate groups such as mesylate and tosylate.

[0085] Specific examples of neutral ligands capable of coordinating with lone electron pairs include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, and ethers such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane.

[0086] The substituent R in the above formula [A1] 1 ~R 4 Cyclopentadienyl groups having the formula R 1 ~R 4 unsubstituted cyclopentadienyl group in which the first position is a hydrogen atom; 3-substituted cyclopentadienyl groups such as 3-t-butylcyclopentadienyl group, 3-methylcyclopentadienyl group, 3-trimethylsilylcyclopentadienyl group, 3-phenylcyclopentadienyl group, 3-adamantylcyclopentadienyl group, 3-amylcyclopentadienyl group, and 3-cyclohexylcyclopentadienyl group; Examples of 3,5-disubstituted cyclopentadienyl groups include, but are not limited to, 3-,5-disubstituted cyclopentadienyl groups such as 3-t-butyl-5-ethylcyclopentadienyl group, 3-phenyl-5-methylcyclopentadienyl group, 3,5-di-t-butylcyclopentadienyl group, 3,5-dimethylcyclopentadienyl group, 3-phenyl-5-methylcyclopentadienyl group, and 3-trimethylsilyl-5-methylcyclopentadienyl group. From the viewpoints of ease of synthesis of the metallocene compound, production costs, and copolymerization ability of the non-conjugated polyene, unsubstituted (R 1 ~R 4 A cyclopentadienyl group in which R is a hydrogen atom is preferred.

[0087] Substituent R in formula [A1] 5 ~R 12 As the fluorenyl group having the formula R 5 ~R 12is a hydrogen atom; 2-position mono-substituted fluorenyl groups such as 2-methylfluorenyl group, 2-t-butylfluorenyl group, and 2-phenylfluorenyl group; 4-position mono-substituted fluorenyl groups such as 4-methylfluorenyl group, 4-t-butylfluorenyl group, and 4-phenylfluorenyl group; 2-position di-substituted fluorenyl groups such as 2,7-di-t-butylfluorenyl group and 3,6-di-t-butylfluorenyl group; 2-position tetra-substituted fluorenyl groups such as 2,7-dimethyl-3,6-di-t-butylfluorenyl group and 2,7-diphenyl-3,6-di-t-butylfluorenyl group; and R 6 and R 7 are bonded to each other to form a ring, and R 10 and R 11 are bonded to each other to form a ring, and the like.

[0088] [ka]

[0089] [ka]

[0090] In formulas [VI] and [V-II], R 5 , R 8 , R 9 , R 12 is the same as defined in the above general formula [A1], R a , R b , R c , R d , R e , R f , R g and R hare each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may be bonded to adjacent substituents to form a ring. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an amyl group, and an n-pentyl group. In formula [VI], R x and R y are each independently a hydrocarbon group having 1 to 3 carbon atoms which may have an unsaturated bond, and R x R a or R c may form a double bond together with the carbon to which R is bonded; y R e or R g may form a double bond together with the carbon to which R is bonded; x and R y and each are preferably a saturated or unsaturated hydrocarbon group having 1 or 2 carbon atoms.

[0091] Specific examples of the compound represented by the above general formula [VI] or [V-II] include an octamethyloctahydrodibenzofluorenyl group represented by formula [V-III], a tetramethyldodecahydrodibenzofluorenyl group represented by formula [V-IV], an octamethyltetrahydrodicyclopentafluorenyl group represented by formula [VV], a hexamethyldihydrodicyclopentafluorenyl group represented by formula [V-VI], and a b,h-dibenzofluorenyl group represented by formula [V-VII].

[0092] [ka]

[0093] [ka]

[0094] [ka]

[0095] [ka]

[0096] [ka]

[0097] All of these metallocene compounds containing a fluorenyl group and represented by the above general formula [A1] have excellent copolymerization ability with non-conjugated polyenes. 1 When Y is a silicon atom, a transition metal compound having a 2-substituted fluorenyl group at the 2,7-position, a 2-substituted fluorenyl group at the 3,6-position, a 4-substituted fluorenyl group at the 2,3,6,7-position, or a 4-substituted fluorenyl group at the 2,3,6,7-position represented by the above general formula [VI] is particularly preferable. 5 From R 12 Particularly preferred are metallocene compounds having an unsubstituted fluorenyl group in which R is a hydrogen atom, a 3- and 6-disubstituted fluorenyl group, a 2-, 3-, 6- and 7-tetrasubstituted fluorenyl group, and a 2-, 3-, 6- and 7-tetrasubstituted fluorenyl group represented by the above general formula [VI].

[0098] In the present invention, in the metallocene compound represented by the above general formula [A1], Y 1 is a silicon atom, and R 5 From R 12 If all are hydrogen atoms, R 13 and R 14 is selected from groups other than a methyl group, a butyl group, a phenyl group, a silicon-substituted phenyl group, a cyclohexyl group, and a benzyl group; Y 1 is a silicon atom, and R 6 and R 11 and R are both t-butyl groups. 5 , R 7 , R 8 , R 9 , R 10 , R 12 If is not a t-butyl group, R 13 and R 14 is selected from groups other than a benzyl group and a silicon-substituted phenyl group; Y 1 is a carbon atom, and R 5 From R 12 If all are hydrogen atoms, R 13 , R 14 is selected from groups other than a methyl group, an isopropyl group, a t-butyl group, an isobutyl group, a phenyl group, a pt-butylphenyl group, a pn-butylphenyl group, a silicon-substituted phenyl group, a 4-biphenyl group, a p-tolyl group, a naphthyl group, a benzyl group, a cyclopentyl group, a cyclohexyl group, and a xylyl group; Y 1 is a carbon atom, and R 6 and R 11 is a common group selected from a t-butyl group, a methyl group, or a phenyl group, and R 5 , R 7 , R 8 , R 9 , R 10 and R 12 If it is a group or atom different from R 13 , R 14 is selected from groups other than a methyl group, a phenyl group, a pt-butylphenyl group, a pn-butylphenyl group, a silicon-substituted phenyl group, and a benzyl group; Y 1 is a carbon atom, and R 6 is a dimethylamino group, a methoxy group, or a methyl group, and R 5 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 But R 6 If it is a group or atom different from R 13 , R 14 is selected from groups other than a methyl group and a phenyl group; Y 1 is a carbon atom, and R is a fluorenyl group. 5 ~R 12 When the moiety is b,h-dibenzofluorenyl or a,i-dibenzofluorenyl, R 13 , R 14 is preferably selected from groups other than a methyl group and a phenyl group.

[0099] Specific examples of the metallocene compound represented by the above general formula [A1] are shown below, but the scope of the present invention is not particularly limited thereto. Specific examples of the metallocene compound represented by the above general formula [A1] include: When Y is a silicon atom, diphenylsilylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(octamethyltetrahydrodibenzofluorenyl)zirconium dichloride dicyclopentafluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(fluorenyl)zirconium dichloride di(p-tolyl)silylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride pentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(p-tolyl)silylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(3,6-di-t -butylfluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride di(m-tolyl)silylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(m-tolyl)silylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, etc.

[0100] When Y is a carbon atom, diphenylmethylene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di-t-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di-t-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, Diphenylmethylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadiene) di(p-tolyl)methylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(phenyl) di(p-tolyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(p-tolyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)( cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride di(m-tolyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(m-tolyl)methylene(cyclopentadienyl)(b,h- dibenzofluorenyl)zirconium dichloride, di(pt-butylphenyl)methylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(pt-butylphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(pt-butylphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(pt-butylphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(pt-butylphenyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(pt-butylphenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(pt-butylphenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(pt-butylphenyl)methylene(cyclopentadienyl) cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(pt-butylphenyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)( 2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(4-biphenyl)methylene( cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(4-biphenyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-bu di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl) Zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(p-chlorophenyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(3,7-di-t-butylfluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(3,7-di-t-butylfluorenyl)zirconium dichloride, ,6-di-t-butylfluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di (m-trifluoromethylphenyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, di(2-naphthyl)methylene di(2-naphthyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentafluorenyl)zirconium dichloride, di(2-naphthyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl), zirconium dichloride and the like.

[0101] As examples of the structural formulas of these metallocene compounds, the structural formulas of di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride ((A) below) and di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride ((B) below) are shown below.

[0102] [ka]

[0103] The above metallocene compounds may be used alone or in combination of two or more.

[0104] The metallocene compound represented by the formula [A1], which can be suitably used for the production of the copolymer (A), can be produced by any method without any particular limitation.For example, it can be produced according to the methods described in J.Organomet.Chem.,63,509(1996), WO2005 / 100410, WO2006 / 123759, WO01 / 27124, JP-A-2004-168744, JP-A-2004-175759, JP-A-2000-212194, etc.

[0105] [Catalysts containing metallocene compounds] The polymerization catalyst that can be suitably used in the production of the copolymer (A) includes those that contain the above-mentioned metallocene compound [A1] and are capable of copolymerizing monomers.

[0106] A preferable polymerization catalyst is one which is composed of (a) a metallocene compound represented by the general formula [A1], (b) at least one compound selected from (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) a compound which reacts with the metallocene compound (a) to form an ion pair (hereinafter also referred to as an "ionizing ionic compound"), and, if necessary, (c) a particulate carrier. Each component will be specifically described below.

[0107] [Compound (b)] The compound (b) is at least one compound selected from (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) an ionizing ionic compound, and preferably contains at least the organometallic compound (b-1).

[0108] (b-1) Organometallic compound As the organometallic compound (b-1), for example, organometallic compounds of Groups 1, 2, 12 and 13 of the periodic table, such as those represented by the following general formulas [VII] to [IX], are used.

[0109] (b-1a) General formula: Ra m Al(OR b ) n H p X q …[VII] (In formula [VII], R a and R b may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. X represents a halogen atom, m is a number where 0 < m ≦ 3, n is a number where 0 ≦ n < 3, p is a number where 0 ≦ p < 3, q is a number where 0 ≦ q < 3, and m + n + p + q = 3.) An organoaluminum compound represented by.

[0110] Examples of such compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methylaluminum dichloride, dimethylaluminum chloride, and diisobutylaluminum hydride.

[0111] (b-1b) General formula: M 2 AlR a 4…[VIII] (In formula [VIII], M 2 represents Li, Na or K, and R a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.) A complex alkylide of a Group 1 metal of the periodic table and aluminum represented by.

[0112] Examples of such compounds include LiAl(C2H5)4, LiAl(C7H 15 )4, etc.

[0113] (b-1c) General formula: R a R b M 3 …[IX] (In formula [IX], R a and R bmay be the same or different and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; M 3 is Mg, Zn or Cd. Dialkyl compounds having a metal of Group 2 or 12 of the periodic table represented by the formula:

[0114] Among the above organometallic compounds (b-1), organoaluminum compounds such as triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, etc. are preferred. Moreover, such organometallic compounds (b-1) may be used alone or in combination of two or more.

[0115] (b-2) Organoaluminum oxy compounds The organoaluminum oxy compound (b-2) may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound such as those exemplified in JP-A-2-78687.

[0116] Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in a hydrocarbon solvent. (1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerous chloride hydrate, to react the adsorbed water or the water of crystallization with the organoaluminum compound. (2) A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0117] The aluminoxane may contain a small amount of an organometallic component. After the solvent or unreacted organoaluminum compound is removed by distillation from the recovered aluminoxane solution, the aluminoxane may be redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

[0118] As the organoaluminum compound used in preparing the aluminoxane, there can be mentioned the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above (b-1a).

[0119] Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and among these, trimethylaluminum and triisobutylaluminum are particularly preferred.

[0120] The above organoaluminum compounds may be used singly or in combination of two or more.

[0121] The benzene-insoluble organoaluminum oxy-compound, which is one embodiment of the organoaluminum oxy-compound (b-2) used in the present invention, is preferably one in which the Al component soluble in benzene at 60°C is usually 10% by mass or less, preferably 5% by mass or less, and particularly preferably 2% by mass or less, calculated as Al atoms, relative to 100% by mass of benzene, i.e., one which is insoluble or poorly soluble in benzene.

[0122] The organoaluminum oxy compound (b-2) used in the present invention may also include boron-containing organoaluminum oxy compounds represented by the following general formula [X].

[0123] [ka]

[0124] In formula [X], R 1 represents a hydrocarbon group having 1 to 10 carbon atoms, R 2 ~R 5may be the same or different and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

[0125] The boron-containing organoaluminum oxy compound represented by the general formula [X] is represented by the general formula: R 1 It can be produced by reacting an alkylboronic acid represented by -B(OH)2...[XI] (in formula [XI], R1 represents the same group as R1 in the general formula [X]) with an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of -80°C to room temperature for 1 minute to 24 hours.

[0126] Examples of the alkylboronic acid represented by the general formula [XI] include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, and 3,5-bis(trifluoromethyl)phenylboronic acid.

[0127] Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred, and these may be used alone or in combination of two or more.

[0128] Examples of the organoaluminum compound to be reacted with such an alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above (b-1a). Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferred.

[0129] The above organoaluminum oxy compounds (b-2) may be used singly or in combination of two or more.

[0130] (b-3) Ionized ionic compounds Examples of the ionized ionic compound (b-3) include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and USP 5321106.Furthermore, examples include heteropoly compounds and isopoly compounds.Such ionized ionic compounds (b-3) can be used alone or in combination of two or more.

[0131] Specifically, Lewis acids include compounds represented by BR3 (R is fluorine or a phenyl group which may have a substituent such as fluorine, a methyl group, or a trifluoromethyl group), such as trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron, and tris(3,5-dimethylphenyl)boron.

[0132] The ionic compound may, for example, be a compound represented by the following general formula [XII].

[0133] [ka]

[0134] In formula [XII], R 1+ As for H + , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, etc. 2 ~R 5 may be the same or different and are organic groups, preferably aryl groups or substituted aryl groups.

[0135] Specific examples of the carbonium cation include tri-substituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0136] Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri(n-butyl)ammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N,2,4,6-pentamethylanilinium cation; Examples of the cation include dialkylammonium cations such as di(isopropyl)ammonium cation and dicyclohexylammonium cation.

[0137] Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

[0138] R 1+ As the cation, a carbonium cation, an ammonium cation, etc. are preferred, and in particular, a triphenylcarbonium cation, an N,N-dimethylanilinium cation, and an N,N-diethylanilinium cation are preferred.

[0139] Further, examples of the ionic compound include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

[0140] Specific examples of trialkyl-substituted ammonium salts include triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tri(n-butyl)ammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(N,N-dimethylphenyl)boron, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)boron, and tri(n-butyl)ammonium tetra(o-tolyl)boron.

[0141] Specific examples of N,N-dialkylanilinium salts include N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, and N,N,2,4,6-pentamethylanilinium tetra(phenyl)boron.

[0142] Specific examples of dialkylammonium salts include di(1-propyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron, and the like.

[0143] Further examples of the ionic compound include triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and boron compounds represented by the following formula [XIII] or [XIV]. In the following formula, Et represents an ethyl group.

[0144] [ka]

[0145] [ka]

[0146] Specific examples of the borane compound include decaborane; salts of anions such as bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis[tri(n-butyl)ammonium]dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate, and bis[tri(n-butyl)ammonium]dodecachlorododecaborate; and salts of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydridedodecaborate)cobaltate(III) and bis[tri(n-butyl)ammonium]bis(dodecahydridedodecaborate)nickelate(III).

[0147] Specific examples of the carborane compound include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, and undecahydride-7,8-dimethyl-7,8- Dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborane, tri(n-butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium-1-carbaundecaborate, tri(n-butyl)ammonium-1-carbadodecaborate, tri(n-butyl)ammonium-1-trimethylsilyl-1-carbadecaborate, tri(n-butyl)ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium Ammonium-6-carbadecaborate, tri(n-butyl)ammonium-7-carbaundecaborate, tri(n-butyl)ammonium-7,8-dicaundecaborate, tri(n-butyl)ammonium-2,9-dicaundecaborate, tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicaundecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dicaundecaborate , tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarboxaundecaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarboxaundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarboxaundecaborate, tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbaundecaborate, and other anionic salts; Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)ferrate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)nickelate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)cuprate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbandecaborate)aurate(III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbandecaborate)ferrate salt (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarboxaborate)chromate (III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarboxaborate)cobaltate (III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)chromate (III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)manganate (IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)cobaltate (III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbowndecaborate)nickelate (IV), and the like.

[0148] The heteropoly compound is composed of an atom selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, usable are phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanomolybdic acid, germanomolybdic acid, arsenic molybdic acid, tinmolybdic acid, phosphotungstic acid, germanotungstic acid, tintungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid, phosphomolybdoniobic acid, and salts of these acids, for example, salts with metals of Group 1 or 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, etc., and organic salts such as triphenylethyl salts. However, the present invention is not limited to these.

[0149] Among the ionizing ionic compounds (b-3), the above-mentioned ionic compounds are preferred, and among them, triphenylcarbenium tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate are more preferred.

[0150] In the present invention, when a metallocene catalyst containing a metallocene compound (a) represented by the above general formula [A1], an organometallic compound (b-1) such as triisobutylaluminum, an organoaluminum oxy compound (b-2) such as methylaluminoxane, and an ionizing ionic compound (b-3) such as triphenylcarbenium tetrakis(pentafluorophenyl)borate is used as a polymerization catalyst, extremely high polymerization activity can be exhibited in the production of the copolymer (A).

[0151] (c) Particulate carrier In the present invention, the particulate carrier (c) used as necessary is an inorganic or organic compound, and is a granular or fine particle solid. The inorganic compound is preferably a porous oxide, an inorganic halide, a clay, a clay mineral, or an ion-exchangeable layered compound, specific examples of which are described in WO2015 / 122495.

[0152] The above clays, clay minerals, and ion-exchangeable layered compounds may be used as they are, or after treatment such as ball milling or sieving. They may also be used after adding and adsorbing new water or after heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more kinds.

[0153] Of these, clay or clay minerals are preferred, and montmorillonite, vermiculite, hectorite, taeniolite and synthetic mica are particularly preferred. The organic compound may be a granular or particulate solid having a particle size in the range of 10 to 300 μm.Specific examples include (co)polymers mainly made of α-olefins having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, or (co)polymers mainly made of vinylcyclohexane and styrene, and their modifications.

[0154] The metallocene catalyst used in the present invention comprises a metallocene compound (a), at least one compound (b) selected from an organometallic compound (b-1), an organoaluminum oxy compound (b-2) and an ionizing ionic compound (b-3), and a carrier (c) used as needed, and may further contain a specific organic compound component (d) as needed.

[0155] (d) Organic compound component In the present invention, the organic compound component (d) is used as necessary for the purpose of improving the polymerization performance and the physical properties of the resulting polymer. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.

[0156] [Manufacturing method and conditions] The copolymer (A) can be produced by copolymerizing monomers consisting of ethylene (a1), an α-olefin (a2) having 3 to 20 carbon atoms, a non-conjugated polyene (a3), and, if necessary, a non-conjugated polyene (a4).

[0157] When copolymerizing such monomers, the method of use and the order of addition of each component constituting the above-mentioned polymerization catalyst may be selected arbitrarily, and examples thereof include the following methods (1) to (5). (1) A method in which the metallocene compound (a) is added alone to a polymerization reactor. (2) A method in which the metallocene compound (a) and the compound (b) are added to a polymerization reactor in any order. (3) A method in which a catalyst component in which a metallocene compound (a) is supported on a carrier (c) and a compound (b) are added to a polymerization reactor in any order. (4) A method in which a catalyst component in which the compound (b) is supported on a carrier (c) and a metallocene compound (a) are added to a polymerization reactor in any order. (5) A catalyst component comprising a metallocene compound (a) and a compound (b) supported on a carrier (c) is added to a polymerization reactor.

[0158] In each of the above methods (2) to (5), at least two of the metallocene compound (a), the compound (b) and the support (c) may be contacted in advance. In the above methods (4) and (5) in which the compound (b) is supported, the unsupported compound (b) may be added in any order, if necessary. In this case, the compound (b) may be the same as or different from the compound (b) supported on the support (c).

[0159] In addition, the solid catalyst component in which the metallocene compound (a) is supported on the support (c) and the solid catalyst component in which the metallocene compound (a) and the compound (b) are supported on the support (c) may be prepolymerized with an olefin, or a catalyst component may be further supported on the prepolymerized solid catalyst component.

[0160] The copolymer (A) can be suitably obtained by copolymerizing monomers in the presence of the above-mentioned polymerization catalyst. When olefin polymerization is carried out using the above-mentioned polymerization catalyst, the metallocene compound (a) is usually used in an amount of 10 -12 ~10 -2 Molar, preferably 10 -10 ~10 -8 It is used in molar amounts.

[0161] The compound (b-1) is used in an amount such that the molar ratio [(b-1) / M] of the compound (b-1) to the total transition metal atoms (M) in the metallocene compound (a) is usually 0.01-50000, preferably 0.05-10000. The compound (b-2) is used in an amount such that the molar ratio [(b-2) / M] of the aluminum atoms in the compound (b-2) to the total transition metals (M) in the metallocene compound (a) is usually 10-50000, preferably 20-10000. The compound (b-3) is used in an amount such that the molar ratio [(b-3) / M] of the compound (b-3) to the transition metal atoms (M) in the metallocene compound (a) is usually 1-20, preferably 1-15.

[0162] In the present invention, the method for producing the copolymer (A) can be carried out by any of liquid phase polymerization methods such as solution (dissolution) polymerization and suspension polymerization, or gas phase polymerization methods, and is not particularly limited. However, it is preferable that the method includes a step of obtaining the following polymerization reaction liquid.

[0163] The step of obtaining a polymerization reaction liquid is a step of carrying out a polymerization reaction using an aliphatic hydrocarbon as a polymerization solvent, 1 R bonded to 13 , R 14 is a phenyl group or a phenyl group substituted with an alkyl group or a halogen group, and R 7 , R 10The process comprises copolymerizing monomers consisting of ethylene (a1), an α-olefin (a2) having 3 to 20 carbon atoms, a non-conjugated polyene (a3) ​​and, if necessary, a non-conjugated polyene (a4) in the presence of a polymerization catalyst containing a transition metal compound having an alkyl substituent, to obtain a polymerization reaction liquid of copolymer (A).

[0164] Examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Specific examples 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 alone or in combination of two or more. Olefin itself can also be used as the solvent. Among these, hexane is preferred from the viewpoint of separation and purification from the resulting copolymer (A).

[0165] The polymerization temperature is usually in the range of -50 to +200°C, preferably in the range of 0 to +150°C, and more preferably in the range of +70 to +110°C. Although it depends on the attained molecular weight and polymerization activity of the metallocene catalyst system used, a higher temperature (+70°C or higher) is desirable from the viewpoints of catalytic activity, copolymerizability, and productivity.

[0166] The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably 1.1 to 5 MPa gauge pressure, more preferably 1.2 to 2.0 MPa gauge pressure, and the polymerization reaction can be carried out by any of batch, semi-continuous, and continuous methods. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions. Among these, in the present invention, it is preferable to adopt a method in which the monomers are continuously fed into a reactor to carry out copolymerization.

[0167] The reaction time (average residence time when copolymerization is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours, and more preferably 10 minutes to 2 hours.

[0168] The molecular weight of the resulting copolymer (A) can be adjusted by making hydrogen exist in the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of compound (b) used. Specific examples include triisobutylaluminum, methylaluminoxane, and diethylzinc. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of olefin.

[0169] The molar ratio of ethylene (a1) to the α-olefin (a2) (ethylene (a1) / α-olefin (a2)) is preferably 40 / 60 to 99.9 / 0.1, more preferably 50 / 50 to 90 / 10, further preferably 55 / 45 to 85 / 15, and most preferably 55 / 45 to 78 / 22.

[0170] The amount of the non-conjugated polyene (a3) ​​charged is usually 0.07 to 10 mass%, preferably 0.1 to 8.0 mass%, and more preferably 0.5 to 5.0 mass%, relative to 100 mass% of the total of ethylene (a1), α-olefin (a2), and non-conjugated polyene (a3) ​​(total monomer charging amount).

[0171] In the present invention, it is preferable to include a step (2) of deactivating the polymerization catalyst by adding a catalyst deactivator after the step (1) of carrying out copolymerization in the presence of the polymerization catalyst. As the catalyst deactivator, alcohols can be used, with methanol or ethanol being preferred, and ethanol being particularly preferred.

[0172] In the above step (2), the catalyst deactivator is preferably added in an amount of 0.05 to 3.0 mol times, more preferably 0.06 to 2.5 mol times, and even more preferably 0.08 to 2.0 mol times, relative to the organometallic compound (b-1), so that a small amount of catalyst degraded by the catalyst deactivator such as ethanol is generated and the low molecular weight component is moderately polymerized, resulting in a copolymer (A) with a moderately wide molecular weight distribution. On the other hand, if the amount of catalyst deactivator added is too large, almost no modified catalyst is generated and almost no polymerization of low molecular weight components is performed, so the molecular weight distribution of the obtained copolymer (A) tends to be narrow. In addition, if the catalyst deactivator is not added or the amount added is too small, a large amount of modified catalyst is generated and a large amount of low molecular weight components are polymerized, so the content of low molecular weight components in the obtained copolymer (A) tends to be too high.

[0173] [Other polymers (C)] The ethylene copolymer composition of the present invention may contain a polymer (C) other than the ethylene-α-olefin-non-conjugated polyene copolymer (A).

[0174] Examples of the other polymer (C) include ethylene-α-olefin-non-conjugated polyene copolymers other than the ethylene-α-olefin-non-conjugated polyene copolymer (A) and ethylene-α-olefin copolymers.

[0175] The α-olefin in the other polymer (C) is usually an α-olefin having 3 to 20 carbon atoms, and among these, α-olefins having 3 to 10 carbon atoms such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene are preferred, with propylene and 1-butene being particularly preferred.

[0176] Examples of the non-conjugated polyene in the other polymer (C) include the compounds exemplified in the above section "Non-conjugated polyene (a4)".

[0177] Examples of the other polymer (C) include ethylene-propylene-5-ethylidene-2-norbornene (ENB) copolymer (hereinafter also referred to as "ENB-EPT"), ethylene-propylene copolymer, and ethylene-1-butene copolymer. Among these, the other polymer (C) is preferably ENB-EPT.

[0178] When the ethylene copolymer composition of the present invention contains another polymer (C), the content ratio of the polymer (C) is preferably 5 to 100 parts by mass, more preferably 10 to 70 parts by mass, further preferably 20 to 50 parts by mass, and particularly preferably 30 to 40 parts by mass, per 100 parts by mass of the total of the copolymer (A) and the other polymer (C).

[0179] The other polymers (C) can be produced by known methods. For example, ENB-EPT can be produced in the same manner as in the above "Production method and conditions for copolymer (A)".

[0180] <siliceous soil (B)> The ethylene copolymer composition of the present invention contains siliceous earth (B). As the siliceous earth (B), Neuburg siliceous earth (also called Neuburg siliceous earth) is preferable. Neuburg siliceous earth is a siliceous earth produced in the Neuburg region in southern Germany, and is a natural mineral consisting of spherical silica and plate-like kaolinite.

[0181] The Neuburg siliceous earth (B) preferably contains 75 to 95 mass % SiO2 and 5 to 15 mass % Al2O3 (however, the total content of SiO2 and Al2O3 does not exceed 100 mass %).

[0182] The Neuburg siliceous earth may be surface-treated with a silane coupling agent, which is preferably at least one selected from the group consisting of vinyl silane, amino silane, mercapto silane, tetrasulfane silane, and alkyl silane.

[0183] As the Neuburg siliceous earth, for example, commercially available products such as Sillitin (registered trademark), Sillikolloid (registered trademark), and surface-treated aktiSil (registered trademark), manufactured by HOFFMANN MINERAL, can be used.

[0184] Examples of silitin include silitin V85, silitin V88, silitin N75, silitin N82, silitin N85, silitin N86, silitin Z86, and silitin Z89, and examples of silicolloid include silicolloid P87 (all manufactured by HOFFMANN MINERAL).

[0185] Examples of Actisil include Actisil AM, which is cylitin Z86 surface-treated with aminosilane, Actisil MAM, which is cylitin V88 surface-treated with methacrylsilane, Actisil MAM-R, which is cylitin V85 surface-treated with methacrylsilane, Actisil MM, which is cylitin Z86 surface-treated with mercaptosilane, Actisil PF216, which is cylitin Z86 surface-treated with tetrasulfanesilane, Actisil PF777, which is cylitin Z86 surface-treated with alkylsilane, Actisil VM56, which is cylitin Z86 surface-treated with vinylsilane, and Actisil VM56 / 89, which is cylitin Z89 surface-treated with vinylsilane (all manufactured by HOFFMANN MINERAL).

[0186] The above Neuburg siliceous earths may be used alone or in combination of two or more kinds.

[0187] <Ethylene-Based Copolymer Composition> The ethylene-based copolymer composition of the present invention contains the ethylene-α-olefin-non-conjugated polyene copolymer (A) and 1 to 300 parts by mass, preferably 50 to 200 parts by mass, more preferably 80 to 150 parts by mass, and even more preferably 100 to 130 parts by mass of siliceous earth (B), per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A).

[0188] The ethylene-based copolymer composition of the present invention contains the ethylene-α-olefin-non-conjugated polyene copolymer (A) and the siliceous earth (B) in the above-mentioned ranges, and thus has an excellent balance of heat aging resistance, compression set, coolant resistance, and modulus.

[0189] The ethylene copolymer composition of the present invention may further contain, in addition to the ethylene-α-olefin-non-conjugated polyene copolymer (A) and siliceous earth (B), as well as any other polymer (C) that may be optionally contained, a softener, a filler, a crosslinking agent, and other additives, such as a processing aid, an activator, a moisture absorbent, a heat stabilizer, a weather stabilizer, an antistatic agent, a colorant, a lubricant, and a thickener.

[0190] When the ethylene copolymer composition of the present invention contains another polymer (C), the proportion of the ethylene-α-olefin-non-conjugated polyene copolymer (A) in the copolymer composition is generally 5 mass% or more, preferably 5 to 50 mass%, more preferably 10 to 30 mass%, and even more preferably 15 to 25 mass%.

[0191] The ethylene-based copolymer composition of the present invention can be prepared by kneading the ethylene-α-olefin-non-conjugated polyene copolymer (A) and the siliceous earth (B) with other components that are blended as necessary at a desired temperature using a kneading machine such as a mixer, kneader, roll, etc. As described above, the ethylene-based copolymer composition of the present invention is excellent in the balance of heat aging resistance, compression set, coolant resistance, and modulus, and therefore the ethylene-based copolymer composition can be well prepared.

[0192] [Crosslinking agent] Examples of the crosslinking agent include crosslinking agents generally used for crosslinking rubber, such as organic peroxides, phenolic resins, hydrosilicone compounds, amino resins, quinones or derivatives thereof, amine compounds, azo compounds, epoxy compounds, isocyanate compounds, etc. Of these, organic peroxides are preferred.

[0193] Examples of organic peroxides include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-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-butyl peroxybenzoate, ert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

[0194] Among these, bifunctional organic peroxides such as 2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, and n-butyl-4,4-bis(tert-butylperoxy)valerate are preferred, and among these, 2,5-di-(tert-butylperoxy)hexane and 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane are most preferred.

[0195] When an organic peroxide is used as a crosslinking agent, the blending amount is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A) and the other polymer (C) blended as necessary. When the blending amount of the organic peroxide is within the above range, the ethylene copolymer composition exhibits excellent crosslinking properties, which is preferable.

[0196] In addition, when an organic peroxide is used as a crosslinking agent, it is preferable to use a crosslinking assistant in combination. Examples of the crosslinking assistant include sulfur; quinone dioxime crosslinking assistants such as p-quinone dioxime; acrylic crosslinking assistants such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; allyl crosslinking assistants such as diallyl phthalate and triallyl isocyanurate; maleimide crosslinking assistants; divinylbenzene; and metal oxides such as zinc oxide (e.g., ZnO#1 / zinc oxide type 2 (JIS standard (K-1410)), manufactured by Hakusui Tech Co., Ltd.), magnesium oxide, and zinc oxide (e.g., zinc oxide such as "Meta Z 102" (trade name: manufactured by Inoue Seki Kogyo Co., Ltd.)). The amount of the crosslinking assistant is usually 0.5 to 10 mol, preferably 0.5 to 7 mol, and more preferably 1 to 5 mol, per mol of the organic peroxide.

[0197] [Softener] Specific examples of softeners include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and Vaseline; coal tar-based softeners such as coal tar; fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; waxes such as beeswax and carnauba wax; fatty acids or salts thereof such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, and calcium stearate; naphthenic acid, pine oil, rosin, and derivatives thereof; synthetic polymeric substances such as terpene resins, petroleum resins, and coumarone-indene resins; ester-based softeners such as dioctyl phthalate and dioctyl adipate; and other microcrystalline waxes, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oils, tall oil, and sub(factice). Petroleum-based softeners are preferred, and process oils are particularly preferred.

[0198] The amount of the softener in the ethylene-based copolymer composition is generally 2 to 100 parts by mass, preferably 10 to 100 parts by mass, more preferably 15 to 50 parts by mass, and even more preferably 20 to 40 parts by mass, per 100 parts by mass in total of the ethylene-α-olefin-non-conjugated polyene copolymer (A) and the other polymer (C) that is blended as necessary.

[0199] [Inorganic filler] Specific examples of inorganic fillers that can be used include one or more of light calcium carbonate, heavy calcium carbonate, talc, clay, etc., and of these, heavy calcium carbonate such as "Whiten SB" (product name: Shiraishi Calcium Co., Ltd.) is preferred.

[0200] When the ethylene-based copolymer composition contains an inorganic filler, the blending amount of the inorganic filler is usually 2 to 50 parts by mass, preferably 5 to 50 parts by mass, per 100 parts by mass in total of the ethylene-α-olefin-non-conjugated polyene copolymer (A) and the other polymer (C) blended as necessary. When the blending amount is within the above range, the kneading processability of the ethylene-based copolymer composition is excellent, and an office automation equipment roll having excellent mechanical properties can be obtained.

[0201] [Reinforcing agent] Specific examples of the reinforcing agent include carbon black, carbon black surface-treated with a silane coupling agent, silica, calcium carbonate, activated calcium carbonate, fine powder of talc, fine powder of silicic acid, etc. Among these, carbon black is preferred. When a reinforcing material is added, the amount is generally 30 to 200 parts by mass, preferably 40 to 150 parts by mass, more preferably 50 to 100 parts by mass, and even more preferably 60 to 90 parts by mass, per 100 parts by mass of the total of the ethylene-α-olefin-non-conjugated polyene copolymer (A) and the other polymer (C) added as necessary.

[0202] [Anti-aging agent (stabilizer)] By blending an antioxidant (stabilizer) with the ethylene copolymer composition of the present invention, the life of a molded article formed therefrom can be extended. Examples of such antioxidants include conventionally known antioxidants, such as amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

[0203] Further examples of the antiaging agent include aromatic secondary amine-based antiaging agents such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine; phenol-based antiaging agents such as dibutylhydroxytoluene and tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane; thioether-based antiaging agents such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide; dithiocarbamate-based antiaging agents such as nickel dibutyldithiocarbamate; and sulfur-based antiaging agents such as 2-mercaptobenzoylimidazole, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dilaurylthiodipropionate, and distearylthiodipropionate.

[0204] These antioxidants can be used alone or in combination of two or more, and the blending amount thereof is usually 0.3 to 15 parts by mass, preferably 1.0 to 12 parts by mass, more preferably 3.0 to 11 parts by mass, and even more preferably 5.0 to 10 parts by mass, based on 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A) and the other polymer (C) blended as necessary. By adjusting the blending amount within such a range, no bloom occurs on the surface of a molded article obtained from the resulting ethylene copolymer composition, and furthermore, the occurrence of vulcanization inhibition can be suppressed.

[0205] [Processing aids] As the processing aid according to the present invention, a wide variety of processing aids that are generally compounded with rubber can be used.

[0206] Specific examples of processing aids include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, esters, etc. Of these, stearic acid is preferred.

[0207] The amount of the processing aid is usually 10 parts by mass or less, preferably 8.0 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 2.0 parts by mass or less, based on 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A) and other polymers (C) added as necessary contained in the ethylene-based copolymer composition.

[0208] [Activator] Specific examples of the surfactant include amines such as di-n-butylamine, dicyclohexylamine, and monoethanolamine; surfactants such as diethylene glycol, polyethylene glycol, lecithin, triaryl ether mellate, and zinc compounds of aliphatic or aromatic carboxylic acids; zinc peroxide preparations; octadecyltrimethylammonium bromide, synthetic hydrotalcite, and special quaternary ammonium compounds.

[0209] The amount of the activator is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass, per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A) and its polymer (C) which is added as required.

[0210] [Moisture absorbent] Specific examples of the moisture absorbent include calcium oxide, silica gel, sodium sulfate, molecular sieve, zeolite, and white carbon.

[0211] The amount of the moisture absorbent is usually 0.5 to 15 parts by mass, preferably 1.0 to 12 parts by mass, per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A) and other polymers (C) that are added as necessary.

[0212] The ethylene copolymer composition according to the present invention has a Mooney viscosity ML(1+4)125°C at 125°C in the range of preferably 5 to 150, more preferably 10 to 100, further preferably 30 to 80, and particularly preferably 50 to 60. When the Mooney viscosity at 125°C is in the above range, the ethylene copolymer (L) has excellent roll processability even in a high hardness oil-less compound, and also exhibits good post-treatment quality (ribbon handleability) and has excellent rubber physical properties.

[0213] <Crosslinked product of ethylene copolymer composition> The crosslinked product of the present invention is obtained by crosslinking the ethylene-based copolymer composition. To produce a crosslinked product from the ethylene copolymer composition, an unvulcanized rubber composition is prepared by the above-mentioned method, as in the case of vulcanizing general rubber, and then the rubber composition is molded into an intended shape and then vulcanized.

[0214] The unvulcanized rubber composition prepared as described above can be molded and vulcanized by various molding methods, but its properties can be best exhibited when it is molded and vulcanized by mold molding such as compression molding, injection molding, and casting.

[0215] In the case of compression molding, for example, a pre-weighed amount of unvulcanized rubber composition is placed in a mold, and after closing the mold, the composition is heated at a temperature of 120 to 270° C. for 30 seconds to 120 minutes to obtain the desired crosslinked product.

[0216] In the case of injection molding, for example, a ribbon-shaped or pellet-shaped rubber composition is fed into a pot in a preset amount by a screw. Then, the preheated rubber composition is fed into a mold by a plunger in 1 to 20 seconds. After the rubber composition is injected, it is heated at a temperature of 120 to 270°C for 30 seconds to 120 minutes to obtain the desired crosslinked product.

[0217] In the case of injection molding, for example, a pre-weighed amount of the rubber composition is placed in a pot and injected into a mold by a piston in 1 to 20 seconds. After the rubber composition is injected, it is heated at a temperature of 120 to 270°C for 30 seconds to 120 minutes to obtain the desired crosslinked product.

[0218] <Uses of ethylene copolymer composition> A crosslinked body obtained from the ethylene copolymer composition can be molded into a desired shape to obtain various products.

[0219] As described above, the ethylene-based copolymer composition of the present invention has an excellent balance of heat aging resistance, compression set, coolant resistance and modulus. Therefore, the ethylene-based copolymer composition of the present invention can be suitably used for hoses, and a hose product having excellent performance can be obtained from the ethylene-based copolymer composition of the present invention. EXAMPLES

[0220] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The physical properties in the following examples and comparative examples were evaluated as follows.

[0221] <Composition of ethylene-α-olefin-non-conjugated polyene copolymer> The weight fraction (mass%) of each structural unit of the ethylene-α-olefin-non-conjugated polyene copolymer and the molar ratio of ethylene (a1) / α-olefin (a2) are: 13 The measured values ​​were obtained by C-NMR. The measured values ​​were obtained by using an ECX400P nuclear magnetic resonance apparatus (manufactured by JEOL Ltd.) at a measurement temperature of 120°C, a measurement solvent of orthodichlorobenzene / deuterated benzene = 4 / 1, and an accumulation number of 8000 times. 13 The C-NMR spectrum was obtained.

[0222] <Iodine value> The iodine value of ethylene-α-olefin-non-conjugated polyene copolymer rubber was determined by titration. Specifically, it was measured by the following method.

[0223] 0.5g of ethylene-α-olefin-non-conjugated polyene copolymer rubber was dissolved in 60ml of carbon tetrachloride, a small amount of Wiss's reagent and 20% potassium iodide solution were added, and the solution was titrated with 0.1mol / L sodium thiosulfate solution. Near the end point, starch indicator was added, and the solution was titrated while stirring well until the light purple color disappeared. The amount of halogen consumed per 100g of sample was calculated as the number of grams of iodine.

[0224] <Intrinsic viscosity> The intrinsic viscosity [η] was measured using a fully automatic intrinsic viscometer manufactured by Rigo Co., Ltd. at a temperature of 135° C. and in decalin as a measurement solvent.

[0225] <Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn)> The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) are values ​​calculated in terms of polystyrene measured by gel permeation chromatography (GPC). The measuring device and conditions are as follows. The molecular weight was calculated based on a calibration curve prepared using commercially available monodisperse polystyrene and a conversion method. Apparatus: Gel permeation chromatograph Alliance GP2000 type (Waters),

[0226] Analysis equipment: Empower2 (Waters), Column: TSKgel GMH6-HT x 2 + TSKgel GMH6-HTL x 2 (7.5 mm I.D. x 30 cm, Tosoh Corporation), Column temperature: 140°C, Mobile phase: o-dichlorobenzene (containing 0.025% BHT), Detector: differential refractometer (RI), flow rate: 1.0 mL / min, Injection volume: 400μL, Sampling time interval: 1s, Column calibration: monodisperse polystyrene (Tosoh Corporation), Molecular weight conversion: Old EPR conversion / calibration method that takes viscosity into account.

[0227] <Complex viscosity η * > The rheometer used was the Ares viscoelasticity measuring device (manufactured by Rheometric Scientific), and the complex viscosity η at a frequency of ω = 0.01 rad / s was measured under the conditions of 190°C and 1.0% strain. * ( ω =0.01) , complex viscosity η at frequency ω=0.1rad / s * ( ω =0.1) , complex viscosity η at frequency ω=10rad / s * ( ω =10) and the complex viscosity η at frequency ω = 100 rad / s * ( ω =100) (All units are Pa sec) were measured. * ( ω =0.1) and η * ( ω =100) The ratio of complex viscosity to * The P-value (η * ( ω =0.1) / η * ( ω =100) ) was calculated.

[0228] < Number of long chain branches (LCB) per 1000 carbon atoms 1000c )> Long Chain Branching (LCB 1000c ) was measured by the method described above.

[0229] <Extrusion property> First, the extruder feed ribbons prepared using the blends obtained in the first stage of the Examples and Comparative Examples were fed into an extruder, and a hollow tube was extruded at a speed of 6 m / min. After that, the extrudability was evaluated based on the surface condition of the extruded tube. The extrudability was evaluated according to the following ratings 1 to 5. Rating 1: The surface is wavy, there is significant burrs, and there is no gloss. Rating 2: The surface is not wavy, there is significant burrs, and there is no gloss. Rating 3: The surface is not wavy, there is not significant burrs, and there is no gloss. Rating 4: The surface is not wavy, there is almost no burrs, and there is a little gloss. Rating 5: The surface is not wavy, there is no burrs at all, and there is a clear gloss.

[0230] <Evaluation of unvulcanized rubber properties> (1) Coach Mooney The minimum viscosity (Vm) and scorch time (t5) at 145°C were measured in accordance with JIS K6300 using a Mooney viscometer (SMV202 model, manufactured by Shimadzu Corporation) at 145°C.

[0231] (2) Mooney viscosity The Mooney viscosity ML(1+4) 125° C. of the compound was measured using a Mooney viscometer (SMV-301 model, manufactured by Shimadzu Corporation) in accordance with JIS K 6300 (1994).

[0232] <Properties of vulcanized rubber> (1) Hardness test (Duro-A hardness) The flat portions of the 2 mm thick vulcanized rubber sheets produced in the Examples and Comparative Examples were stacked to form a 12 mm thick sheet, and the hardness (JIS-A) was measured in accordance with JIS K6253.

[0233] (2) Tensile test The vulcanized rubber sheets produced in the Examples and Comparative Examples were punched out to produce No. 3 dumbbell test pieces described in JIS K6251 (1993). Using these test pieces, tensile tests were carried out according to the method specified in JIS K6251, section 3, at a measurement temperature of 25°C and a tensile speed of 500 mm / min, and the tensile stress (25% modulus (M25) to 300% modulus (M300)), tensile stress at break (TB), and tensile elongation at break (EB) were measured.

[0234] (3) Tear strength (trouser type) A test piece measuring 150 mm x 50 mm was cut out from a vulcanized rubber sheet having a thickness of 2 mm produced in the examples. Next, a slit having a length of 75 mm was made in the center of the longitudinal direction of the test piece, and the trouser tear strength was measured using a tensile tester (tensile speed: 200 mm / min, measurement environment temperature: 23°C). The tear strength was calculated by dividing the tear strength (N) by the sheet thickness (mm). The test was performed three times, and the average value was used.

[0235] <Heat aging test> The 2 mm thick vulcanized rubber sheets produced in the examples were subjected to a heat aging test at 150°C for 504 hours in accordance with JIS K 6257. The hardness, tensile stress at break, and tensile elongation at break of the sheets after the heat aging test were measured in the same manner as in the above [Hardness test] and [Tensile test] items.

[0236] AH (shore-A) was calculated from the difference in hardness before and after the heat aging test, and the rate of change after the test from the values ​​before the heat aging test to the values ​​before the test was calculated as Ac(TB) and Ac(EB), respectively, from the tensile stress at break (TB) and tensile elongation at break (EB) before and after the heat aging test.

[0237] <Compression set test> The compounds prepared in the examples were vulcanized at 180°C for 15 minutes using a press molding machine equipped with a cylindrical mold to prepare a right cylindrical test piece with a thickness of 12.7 mm and a diameter of 29 mm, and a test piece (vulcanizate) for compression set test was obtained. The compression set of the test piece for compression set measurement was measured after treatment at 150°C for 24 hours according to JIS K 6262 (1997).

[0238] <Coolant resistance> As an index of hot water resistance, an evaluation was conducted using the coolant used in automobile radiators. Following the method defined in JIS D2602, the volume change rate, tensile strength change rate, and elongation change rate were measured after immersion in a 50% ethylene glycol aqueous solution at 100°C ± 1°C for 168 hours.

[0239] [Production Example 1] Using the continuous polymerization apparatus shown in Figure 1, ethylene-propylene-VNB copolymer (A-1) (hereinafter also referred to as "VNB-EPT") was produced as follows.

[0240] A dehydrated and purified hexane solvent was continuously fed from tube 6 at 58.3 L / hr, triisobutylaluminum (TiBA) at 4.5 mmol / hr, (C6H5)3CB(C6F5)4 at 0.150 mmol / hr, and di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride at 0.030 mmol / hr from tube 7 into a 300-liter polymerization reactor C. At the same time, ethylene was continuously fed from tubes 2, 3, 4, and 5 at 6.6 kg / hr, propylene at 9.3 kg / hr, hydrogen at 18 L / hr, and VNB at 340 g / hr, respectively, into the polymerization reactor C, and copolymerization was carried out under the conditions of a polymerization temperature of 87°C, a total pressure of 1.6 MPaG, and a residence time of 1.0 hour.

[0241] The ethylene-propylene-VNB copolymer solution produced in the polymerization reactor C was continuously discharged through the pipe 8 at a flow rate of 88.0 L / hr, heated to 170°C (pressure increased to 4.1 MPaG), and supplied to the phase separator D. At this time, ethanol, a polymerization inhibitor, was continuously introduced into the pipe 8 in an amount of 0.1 mol times the amount of TiBA in the liquid component extracted from the polymerization reactor C.

[0242] In phase separator D, the ethylene-propylene-vinyl alcohol copolymer solution was separated into a dense phase (lower phase) containing most of the ethylene-propylene-vinyl alcohol copolymer and a dilute phase (upper phase) containing a small amount of the polymer.

[0243] The separated thick phase was led to heat exchanger K via pipe 11 at a rate of 85.4 L / hr, and then led to hopper E, where the solvent was evaporated and separated, yielding ethylene-propylene-VNB copolymer at a rate of 7.8 kg / hr.

[0244] The physical properties of the resulting ethylene-propylene-VNB copolymer (A-1) were evaluated as described above, and the results are shown in Table 1.

[0245] [Table 1]

[0246] [Example 1] In the first step, 60 parts by mass of the ethylene-propylene-VNB copolymer (A-1) obtained in Production Example 1 and ENB-EPT (manufactured by Mitsui Chemicals, Inc., trade name Mitsui EPT 0045) were mixed in a BB-4 type Banbury mixer (manufactured by Kobe Steel, Ltd.). Mooney Viscosity (ML (1+4)100°C):40, ethylene content:51% (40 parts by weight) was masticated for 1 minute, and then 80 parts by weight of SILLITIN Z86 (Hoffmann Mineral), 5 parts by weight of vulcanization accelerator (Meta Z102, Inoue Lime Industry Co., Ltd.), 62 parts by weight of carbon black (Asahi #60UG, Asahi Carbon Co., Ltd.), 31 parts by weight of paraffinic process oil (Diana Process Oil PW-380, Idemitsu Kosan Co., Ltd.), 3 parts by weight of primary anti-aging agent (Irganox 1010, BASF), 6 parts by weight of secondary anti-aging agent (Sandant MB, Sanshin Chemical Industry Co., Ltd.), and 1 part by weight of stearic acid (Beads Stearic Acid Camellia, NOF Chemical Co., Ltd.) were added thereto, and the mixture was kneaded at 140°C for 2 minutes. Thereafter, the ram was raised and cleaned, and kneading was further carried out for 1 minute, and the kneaded product was discharged at about 150° C. to obtain a first-stage compound.

[0247] Next, in the second step, the mixture obtained in the first step was wound around a 6-inch roll (manufactured by Nippon Roll Co., Ltd., front roll surface temperature 50°C, rear roll surface temperature 50°C, front roll rotation speed 16 rpm, rear roll rotation speed 18 rpm), to which 8.5 parts by mass of Perhexa 25B-40 (manufactured by NOF Chemical Co., Ltd.: 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane) was added and kneaded for 10 minutes to obtain an uncrosslinked rubber mixture (compound). Using this compound, the unvulcanized rubber properties and compression set were evaluated by the above-mentioned methods.

[0248] The uncrosslinked compound was cut into a sheet and pressed at 160°C for 20 minutes using a 100-ton press molding machine to prepare a vulcanized rubber sheet with a thickness of 2 mm. The vulcanized rubber properties and coolant resistance were evaluated using the above-mentioned methods. The results are shown in Table 2.

[0249] [Examples 2 to 6] The rubber compositions and crosslinked bodies of Examples 2 to 6 were produced in the same manner as in Example 1, except that Neuburg siliceous earth (B) SILLITIN Z86 was replaced with AKTISIL VM56 (manufactured by Hoffmann Mineral: Example 2), AKTISIL AM (manufactured by Hoffmann Mineral: Example 3), AKTISIL MM (manufactured by Hoffmann Mineral: Example 4), AKTISIL PF216 (manufactured by Hoffmann Mineral: Example 5), and AKTISIL PF777 (manufactured by Hoffmann Mineral: Example 6), all of which are also Neuburg siliceous earth (B). The results are shown in Tables 2 to 3.

[0250] [Comparative Example 1] The rubber composition and crosslinked body of Comparative Example 1 were produced in the same manner as in Example 1, except that Mistron Vapor Talc (manufactured by Nippon Mistron Co., Ltd.) was used instead of SILLITIN Z86, which is Neuburg siliceous earth (B), and the same evaluations were carried out as in Example 1. The results are shown in Table 3.

[0251] [Table 2]

[0252] [Table 3] [Explanation of symbols]

[0253] C Polymerization reactor D phase separator E Hopper F Pump G Heat exchanger H heat exchanger

Claims

1. The copolymer has a structural unit derived from ethylene (a1), a structural unit derived from an α-olefin (a2) having 3 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene (a3) ​​containing, in one molecule, two or more partial structures selected from the group consisting of the following general formulae (I) and (II): an ethylene / α-olefin / non-conjugated polyene copolymer (A), in which the structural unit derived from the non-conjugated polyene (a3) ​​contains a structural unit derived from 5-vinyl-2-norbornene; and 1 to 300 parts by mass of siliceous earth (B) per 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer (A), An ethylene-based copolymer composition. 【Chemistry 1】

2. The ethylene copolymer composition according to claim 1, wherein the copolymer (A) satisfies the following requirements (i) to (vi): (i) the molar ratio of the structural units derived from ethylene (a1) to the structural units derived from the α-olefin (a2) [(a1) / (a2)] is 40 / 60 to 99.9 / 0.1; (ii) the weight fraction of the structural unit derived from the non-conjugated polyene (a3) ​​is 0.07% by mass to 10% by mass in 100% by mass of the copolymer (A); (iii) the weight average molecular weight (Mw) of the copolymer (A), the weight fraction of the structural unit derived from the non-conjugated polyene (a3) ​​(weight fraction (mass%) of (a3)), and the molecular weight of the non-conjugated polyene (a3) ​​(molecular weight of (a3)) satisfy the following formula (1); 4.5≦Mw×weight fraction of (a3) / 100 / molecular weight of (a3)≦40 (1) (iv) Complex viscosity η at frequency ω = 0.1 rad / s obtained by linear viscoelastic measurement (190°C) using a rheometer ＊ （ω＝０．１） (Pa sec) and the complex viscosity η at a frequency ω = 100 rad / s ＊ （ω＝１００） (Pa sec) P [η ＊ （ω＝０．１） / ＊ （ω＝１００） ], the intrinsic viscosity [η] of the copolymer (A), and the weight fraction of (a3) ​​satisfy the following formula (2); P / ([η] ２．９ ) ≦ weight fraction of (a3) ​​× 6 ... (2) (v) the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (molecular weight distribution; Mw / Mn) measured by gel permeation chromatography (GPC) is in the range of 8 to 30; (vi) The number average molecular weight (Mn) is 30,000 or less.

3. 2. The ethylene copolymer composition according to claim 1, wherein the siliceous earth (B) is Neuburg siliceous earth.

4. 4. The ethylene copolymer composition according to claim 3, wherein the Neuburg siliceous earth is surface-treated with a silane coupling agent.

5. 5. The ethylene copolymer composition according to claim 4, wherein the silane coupling agent is at least one selected from the group consisting of vinyl silane, amino silane, mercapto silane, tetrasulfane silane, and alkyl silane.

6. The ethylene copolymer composition according to claim 1, wherein the α-olefin (a2) is propylene.

7. The ethylene copolymer composition according to any one of claims 1 to 6, which is for use in a hose.

8. A crosslinked product of the ethylene copolymer composition according to any one of claims 1 to 6.

9. A hose product comprising the crosslinked body according to claim 8.

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