Ethylene-based copolymer composition and hose product

Abstract

To provide an ethylene-based copolymer composition that is suitable for automotive aqueous hose applications and is capable of yielding molded products having a superior balance of insulation performance, coolant resistance, and thermal aging resistance in comparison with traditional EPDM-based rubber compositions for automotive aqueous hoses, and also to provide a hose product having a superior balance of insulation performance, coolant resistance, and thermal aging resistance.SOLUTION: An ethylene-based copolymer composition comprises: an ethylene-α-olefin-non-conjugated polyene copolymer (A) comprising structural units derived from ethylene (a1), structural units derived from an α-olefin (a2) having 3 to 20 carbon atoms, and structural units derived from a non-conjugated polyene (a3) having two or more partial structures in one molecule selected from the group consisting of the following general formulas (I) and (II), where the structural units derived from the non-conjugated polyene (a3) include structural units derived from 5-vinyl-2-norbornene; and a modified polybutadiene (B).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an ethylene-based copolymer composition and its use, and more particularly to an ethylene-based copolymer composition suitable for hose applications, a crosslinked product using the same, and a hose product.

Background Art

[0002] Ethylene-based copolymers such as ethylene-α-olefin copolymers, for example ethylene-α-olefin-non-conjugated polyene copolymers, do not have unsaturated bonds in the main chain, and thus are superior in weather resistance, heat resistance, and ozone resistance compared to diene-based rubbers. They 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] When an ethylene-α-olefin copolymer is used for hose applications, generally, a rubber composition mainly composed of an ethylene-propylene copolymer and containing a reinforcing material such as carbon black is used.

[0004] Patent Document 1 discloses an ethylene-α-olefin-non-conjugated polyene copolymer having 3 to 20 carbon atoms in the α-olefin, a graft-modified ethylene-α-olefin copolymer grafted with an unsaturated carboxylic acid or its derivative, and a reinforcing material such as carbon black as a means for improving the volume resistivity without deteriorating the moldability and preventing the corrosion and deterioration of the hose due to the microcurrent flowing through the vehicle body in an automotive water-based hose rubber composition.

[0005] Furthermore, in recent years, the following requirements for automobiles have been increasing, and the rubber composition for automotive water-based hoses, which is a material in the engine room, requires further heat aging resistance. 1) Reduction of the engine room due to the expansion of the cabin area for improving the riding comfort 2) Covering of the engine and its surrounding parts with sound insulation materials due to the strengthening of noise regulations in Japan, Europe, etc.

Prior Art Documents

Patent Documents

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2018-119097 [Summary of the Invention] [Problems to be Solved by the Invention]

[0007] Under such circumstances, there was room for improvement in the heat aging resistance of automotive water hoses obtained from conventional EPDM-based rubber compositions for automotive water hoses. Also, in automotive water hoses used in coolant systems for cooling the batteries and motors of electric vehicles, it has been found that even better insulation and coolant resistance are desired from the perspective of safety. An object of the present invention is to provide an ethylene-based copolymer composition that is suitable for automotive water hose applications and can produce molded articles such as hoses with an excellent balance of insulation, coolant resistance, and heat aging resistance compared to conventional EPDM-based rubber compositions for automotive water hoses, and to provide hose products with an excellent balance of insulation, coolant resistance, and heat aging resistance. [Means for Solving the Problems]

[0008] As a result of intensive research to solve the above problems, the present inventors have found that by adding modified polybutadiene to a specific ethylene·α-olefin·non-conjugated polyene copolymer, a composition excellent in the balance of insulation, coolant resistance, and heat aging resistance can be obtained, and thus the present invention has been completed.

[0009] That is, the present invention relates to, for example, the following [1] to [9]. [1] A copolymer (A) of ethylene, an α-olefin, and a non-conjugated polyene, which has a structural unit derived from ethylene (a1), a structural unit derived from an α-olefin having 3 to 20 carbon atoms (a2), and two or more structural units selected from the group consisting of the following general formulas (I) and (II) in one molecule, and the structural unit derived from the non-conjugated polyene (a3) contains a structural unit derived from 5-vinyl-2-norbornene, and modified polybutadiene (B) An ethylene-based copolymer composition containing the same. [Chemical formula]

[0010] [2] The ethylene-based copolymer composition according to [1], wherein the ethylene-α-olefin-non-conjugated polyene copolymer (A) satisfies at least one of the following requirements (i) to (vi). (i) The molar ratio [(a1) / (a2)] of the structural unit derived from ethylene (a1) and the structural unit derived from α-olefin (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 ethylene-α-olefin-non-conjugated polyene copolymer (A). (iii) The weight average molecular weight (Mw) of the ethylene-α-olefin-non-conjugated polyene copolymer (A), the weight fraction of the structural unit derived from the non-conjugated polyene (weight fraction of (a3) (% by mass)), and the molecular weight of the non-conjugated polyene ((a3) molecular weight) satisfy the following formula (1). 4.5 ≦ Mw × (weight fraction of (a3) / 100) / (molecular weight of (a3)) ≦ 40 …(1) (iv) The complex viscosity η * (ω=0.1) (Pa·sec) at a frequency ω = 0.1 rad / s and the complex viscosity η * (ω=100) (Pa·sec) at a frequency ω = 100 rad / s, and the ratio P(η *(ω=0.1) / η * (ω=100) ) and the intrinsic viscosity [η] and the weight fraction of the structural unit derived from the non-conjugated polyene (a3) (weight fraction of (a3)) satisfy the following formula (2). P / ([η] 2.9 ) ≤ weight fraction of (a3) × 6 …(2) (v) The ratio of the weight average molecular weight (Mw) to the 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.

[0011] 〔3〕 The ethylene-based copolymer composition according to 〔1〕 or 〔2〕, wherein the modified polybutadiene (B) is maleic acid-modified polybutadiene. 〔4〕 The ethylene-based copolymer composition according to any one of 〔1〕 to 〔3〕, which contains 0.5 to 50 parts by mass of the modified polybutadiene (B) with respect to 100 parts by mass of the ethylene·α-olefin·non-conjugated polyene copolymer (A).

[0012] 〔5〕 The ethylene-based copolymer composition according to any one of 〔1〕 to 〔4〕, wherein the α-olefin (a2) is propylene. 〔6〕 The ethylene-based copolymer composition according to any one of 〔1〕 to 〔5〕, which is for a hose. 〔7〕 A crosslinked product of the ethylene-based copolymer composition according to any one of 〔1〕 to 〔6〕. 〔8〕 A hose product containing the crosslinked product according to 〔7〕. 〔9〕 The hose product according to 〔8〕, which is an automotive water-based hose product.

Advantages of the Invention

[0013] The ethylene-based copolymer composition of the present invention has good moldability and can produce a molded article with an excellent balance of insulation, coolant resistance, and heat aging resistance. For example, it can be suitably used for automotive water hoses. By using the ethylene-based copolymer composition of the present invention, it is possible to produce high-performance hose products, particularly hose products with an excellent balance of insulation, coolant resistance, and heat aging resistance.

Brief Description of the Drawings

[0014]

Figure 1

Modes for Carrying Out the Invention

[0015] Ethylene-based copolymer composition The ethylene-based copolymer composition of the present invention (hereinafter also referred to as "this composition") contains an ethylene·α-olefin·non-conjugated polyene copolymer (A) and a modified polybutadiene (B).

[0016] 《Ethylene·α-olefin·non-conjugated polyene copolymer (A)》 The ethylene·α-olefin·non-conjugated polyene copolymer (A) (hereinafter also referred to as "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).

[0017] Examples of the above 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, 1-eicosene, etc. 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 article having rubber elasticity can be obtained.

[0018] The above α-olefin (a2) may be used alone or in combination of two or more. That is, the above copolymer (A) contains a structural unit derived from at least one α-olefin (a2) having 3 to 20 carbon atoms, and may contain a structural unit derived from two or more α-olefins (a2) having 3 to 20 carbon atoms.

[0019] The above non-conjugated polyene (a3) is a compound containing two or more partial structures selected from the group consisting of the following general formulas (I) and (II) in total in the molecule, and contains 5-vinyl-2-norbornene (VNB).

[0020]

Chemical formula

[0021] Examples of the compound containing two or more partial structures selected from the group consisting of the above general formulas (I) and (II) in total in the molecule include 5-vinyl-2-norbornene (VNB), norbornadiene, 1,4-hexadiene, dicyclopentadiene, etc.

[0022] The above non-conjugated polyene (a3) may be used alone or in combination of two or more. When used alone, it is 5-vinyl-2-norbornene. When used in combination of two or more, it is a combination of 5-vinyl-2-norbornene and one or more compounds containing two or more substructures selected from the group consisting of the above general formulas (I) and (II) in total in the molecule. In the present invention, it is a preferred embodiment that the non-conjugated polyene (a3) is 5-vinyl-2-norbornene.

[0023] In the present invention, since the non-conjugated polyene (a3) contains 5-vinyl-2-norbornene, effects such as high availability, good reactivity with peroxides during the cross-linking reaction after polymerization, and easy improvement of the heat resistance of the polymer composition can be obtained.

[0024] In addition to the structural units derived from the above (a1), (a2), and (a3), the above copolymer (A) may further have a structural unit derived from a non-conjugated polyene (a4) containing only one substructure selected from the group consisting of the above general formulas (I) and (II) in the molecule.

[0025] 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, 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, 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene, and the like. 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 good mechanical properties can be easily obtained. The non-conjugated polyene (a4) may be used alone or in combination of two or more.

[0026] When the copolymer (A) contains a structural unit derived from the non-conjugated polyene (a4), the proportion is not particularly limited as long as the object of the present invention is not impaired. Usually, it is contained in a weight fraction of 0 to 20% by mass, preferably 0 to 8% by mass, more preferably about 0.01 to 8% by mass (provided that the total weight fraction of (a1), (a2), (a3), and (a4) is 100% by mass).

[0027] The above copolymer (A) may each contain structural units derived from one or more biomass-derived monomers (biomass-derived ethylene (a1), α-olefins (a2) having 3 to 20 carbon atoms, non-conjugated polyenes (a3), and non-conjugated polyenes (a4)). Further, the above copolymer (A) may each contain structural units derived from one or more chemical recycling-derived monomers (chemical recycling-derived ethylene (a1), α-olefins (a2) having 3 to 20 carbon atoms, non-conjugated polyenes (a3), and non-conjugated polyenes (a4)).

[0028] It is preferable that the above copolymer (A) satisfies at least one of the following requirements (i) to (vi), more preferably satisfies two or more, even more preferably satisfies three or more, still more preferably satisfies four or more, particularly preferably satisfies five or more, and most preferably satisfies all six.

[0029] (i) The molar ratio [(a1) / (a2)] of the structural units derived from ethylene (a1) to the structural units derived from α-olefin (a2) is 40 / 60 to 99.9 / 0.1. (ii) The weight fraction of the constitutional units derived from 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 constitutional units derived from non-conjugated polyene (a3) (weight fraction of (a3) (% by mass)), and the molecular weight of 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) The ratio P (η * (ω=0.1) (Pa·sec) at a frequency ω = 0.1 rad / s and the complex viscosity η * (ω=100) obtained by linear viscoelastic measurement (190 °C) using a rheometer, and the complex viscosity η * (ω=0.1) / η* (ω=100) ) and the intrinsic viscosity [η] and the weight fraction of the structural unit derived from the non-conjugated polyene (a3) (weight fraction of (a3)) satisfy the following formula (2). P / ([η] 2.9 ) ≤ weight fraction of (a3) × 6 …(2) (v) The ratio of the weight average molecular weight (Mw) to the 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.

[0030] ≪Requirement (i)≫ Requirement (i) specifies that the molar ratio of ethylene (a1) / α-olefin (a2) in the above 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, still more preferably 55 / 45 to 70 / 30, and particularly preferably 60 / 40 to 65 / 35.

[0031] By using the copolymer (A) that satisfies requirement (i), an ethylene-based copolymer composition excellent in rubber elasticity, mechanical strength, and flexibility can be obtained. The amount of ethylene (content of the structural unit derived from ethylene (a1)) and the amount of α-olefin (content of the structural unit derived from α-olefin (a2)) in the copolymer (A) can be 13 determined by C-NMR.

[0032] ≪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 above copolymer (A) (that is, in the total weight fraction of all structural units of 100% by mass). The weight fraction of the structural unit derived from this 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, still more preferably 0.5% by mass to 3.0% by mass, and particularly preferably 0.5% by mass to 2.0% by mass.

[0033] The copolymer (A) that satisfies requirement (ii) has sufficient hardness, excellent mechanical properties, and shows a fast crosslinking rate when crosslinked using a peroxide. The amount of non-conjugated polyene (a3) in the copolymer (A) (the content of the structural unit derived from non-conjugated polyene (a3)) can be determined by 13 13C-NMR.

[0034] ≪Requirement (iii)≫ Requirement (iii) specifies that in the above copolymer (A), the weight-average molecular weight (Mw) of the copolymer (A), the weight fraction of the structural unit derived from non-conjugated polyene (a3) in the copolymer (A) ((weight fraction of (a3): mass %), and the molecular weight of non-conjugated polyene (a3) ((molecular weight of (a3)) satisfy the above formula (1). The above formula (1) of requirement (iii) is preferably the following formula (1'). 4.5 ≦ Mw × (weight fraction of (a3) / 100) / (molecular weight of (a3)) ≦ 35 …(1')

[0035] When the above copolymer (A) satisfies requirement (iii), the content of the structural unit derived from non-conjugated polyene (a3) is appropriate, showing sufficient crosslinking performance, excellent crosslinking rate, and excellent mechanical properties, and an ethylene-based copolymer composition can be produced. Note that the weight-average molecular weight (Mw) of the copolymer (A) can be determined as a polystyrene-equivalent value measured by gel permeation chromatography (GPC).

[0036] In the above copolymer (A), when "Mw × (weight fraction of (a3) / 100) / (molecular weight of (a3))" satisfies the above formula (1) or (1'), the degree of crosslinking is appropriate, and an ethylene-based copolymer composition with well-balanced excellent mechanical properties and heat aging resistance can be produced. If the value of "Mw × (weight fraction of (a3) / 100) / (molecular weight of (a3))" is too low, the crosslinkability may be insufficient and the crosslinking rate may be slow. If the value is too high, excessive crosslinking may occur and the mechanical properties may deteriorate.

[0037] ≪Requirement (iv)≫ Requirement (iv) is that the ratio P(η * (ω=0.1) (Pa·sec) at a frequency ω = 0.1 rad / s and the complex viscosity η * (ω=100) (Pa·sec) at a frequency ω = 100 rad / s of the above copolymer (A), obtained by linear viscoelastic measurement (190 °C) using a rheometer, and the limiting viscosity [η], and the weight fraction of the structural unit derived from the above non-conjugated polyene (a3) ((weight fraction of (a3): mass %) satisfy the above formula (2). The above formula (2) of Requirement (iv) is preferably the following formula (2'). * (ω=0.1) / η * (ω=100) ) and the limiting viscosity [η], and the weight fraction of the structural unit derived from the above non-conjugated polyene (a3) ((weight fraction of (a3): mass %) satisfy the above formula (2). The above formula (2) of Requirement (iv) is preferably the following formula (2'). P / ([η] 2.9 ) ≤ (weight fraction of (a3)) × 5.7 …(2')

[0038] Here, the ratio P(η * (ω=0.1) at a frequency ω = 0.1 rad / s and the complex viscosity η * (ω=100) at a frequency ω = 100 rad / s represents the frequency dependence of viscosity, and P / ([η] * (ω=0.1) / η * (ω=100) ), which corresponds to the left side of formula (2), shows a high value tendency when there are many long-chain branches although it is affected by short-chain branches and molecular weight. Generally, in an ethylene·α-olefin·non-conjugated polyene copolymer, the more the structural unit derived from the non-conjugated polyene is contained, the more the long-chain branches tend to be contained. However, the copolymer (A) of the present invention is considered to be able to satisfy the above formula (2) because it has fewer long-chain branches than a conventionally known ethylene·α-olefin·non-conjugated polyene copolymer. 2.9 ) shows a high value tendency when there are many long-chain branches although it is affected by short-chain branches and molecular weight. Generally, in an ethylene·α-olefin·non-conjugated polyene copolymer, the more the structural unit derived from the non-conjugated polyene is contained, the more the long-chain branches tend to be contained. However, the copolymer (A) of the present invention is considered to be able to satisfy the above formula (2) because it has fewer long-chain branches than a conventionally known ethylene·α-olefin·non-conjugated polyene copolymer.

[0039] In the present invention, the P value was determined by measuring with a viscoelasticity measuring device Ares (manufactured by Rheometric Scientific) under the conditions of 190°C, a strain of 1.0%, and varying the frequency. The ratio (η * ratio) was determined from the complex viscosity at 0.1 rad / s and the complex viscosity at 100 rad / s. The intrinsic viscosity [η] means the value measured in decalin at 135°C.

[0040] ≪Requirement (v)≫ Requirement (v) specifies that the ratio (molecular weight distribution; Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the above 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 in the range of 15 to 28, still more preferably in the range of 20 to 28, and particularly preferably in the range of 22 to 26.

[0041] When the above copolymer (A) satisfies requirement (v), since it contains an appropriate amount of low molecular weight components, the processability is good. The weight average molecular weight (Mw) and the number average molecular weight of the above copolymer (A) can be determined as polystyrene-converted numerical values measured by gel permeation chromatography (GPC).

[0042] ≪Requirement (vi)≫ Requirement (vi) specifies that the above number average molecular weight (Mn) of the copolymer (A) is 30,000 or less. The above number average molecular weight (Mn) is preferably in the range of 3,000 to 26,000, more preferably in the range of 6,000 to 23,000, still more preferably in the range of 7,000 to 18,000, and particularly preferably in the range of 8,000 to 12,000. When the above copolymer (A) satisfies requirement (vi), since it contains an appropriate amount of low molecular weight components, the processability is good.

[0043] In addition to satisfying one or more of the requirements (i) to (vi), the copolymer (A) preferably satisfies one or more of the requirements (vii) to (ix), more preferably satisfies two or more of them, and even more preferably satisfies all three of them. ≪Requirement (vii)≫ The copolymer (A) preferably satisfies the following formula (3) for the number of long-chain branches per 1000 carbon atoms (LCB 1000C ) obtained using 3D-GPC and the natural logarithm of the weight-average molecular weight (Mw), and more preferably satisfies the following formula (3'). LCB 1000C ≦1 - 0.07 × Ln(Mw) …(3) LCB 1000C ≦1 - 0.071 × Ln(Mw) …(3') The upper limit value of the long-chain branch content per unit carbon number of the copolymer (A) is specified by the above formula (3) or (3').

[0044] Such a copolymer (A) has a low proportion of long-chain branches contained therein, is excellent in curing characteristics when crosslinked using a peroxide, and can obtain an ethylene-based copolymer composition excellent in heat aging resistance.

[0045] Here, Mw and the number of long-chain branches per 1000 carbon atoms (LCB 1000C ) can be determined by a structural analysis method using 3D-GPC. In this specification, specifically, it was determined as follows. Using a 3D-high-temperature GPC device PL-GPC220 type (manufactured by Polymer Laboratories), the absolute molecular weight distribution was determined, and at the same time, the intrinsic viscosity was determined using a viscometer. The main measurement conditions are as follows. Detector: Differential refractometer / built-in GPC device Two-angle light scattering photometer PD2040 type (manufactured by Precison Detectors) Bridge-type viscometer PL-BV400 type (manufactured by Polymer Laboratories) Column: TSKgel GMH HR -H(S)HT × 2 pieces + TSKgel GMH HR-M(S) × 1 piece (All have an inner diameter of 7.8 mm φ and a length of 300 mm per piece) Temperature: 140 °C Mobile phase: 1,2,4-trichlorobenzene (containing 0.025% BHT) Injection volume: 0.5 mL Sample concentration: ca 1.5 mg / mL Sample filtration: Filtered through a sintered filter with a pore size of 1.0 μm In the above, the dn / dc value required for the determination of 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 injection 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).

[0047]

Equation

[0048] Also, the average values of g' were calculated from the following formulas (v-2), (v-3), and (v-4). The Trendline assuming only short-chain branches was determined for each sample.

[0049]

Equation

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

[0051] [Number] λ = BrNo / M …(V-6) LCB 1000C = λ × 14000 …(V-7) In formula (V-7), "14000" represents the molecular weight of 1000 units in methylene (CH 2 ) units.

[0052] The intrinsic viscosity [η] of the above copolymer (A) is preferably 0.1 to 5 dL / g, more preferably 0.5 to 5.0 dL / g, still 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. Also, the weight-average molecular weight (Mw) of the above 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.

[0053] The above copolymer (A) preferably satisfies both the above intrinsic viscosity [η] and weight-average molecular weight (Mw). In the above copolymer (A), as described above, the non-conjugated polyene (a3) contains VNB. It is more preferable that the non-conjugated polyene (a3) is VNB. That is, in the above formulas (1), (2) and formula (4) to be described later, etc., it is preferable that the "weight fraction of (a3)" is the "weight fraction of VNB" (mass%).

[0054] As described above, the copolymer (A) preferably further contains a structural unit derived from the non-conjugated polyene (a4) in a weight fraction of 0% by mass to 20% by mass (however, the total weight fraction of (a1), (a2), (a3), and (a4) is 100% by mass). In this case, it is preferable to satisfy the requirement (viii) below.

[0055] ≪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 of (a3) (% by mass))), the weight fraction of the structural unit derived from the non-conjugated polyene (a4) ((weight fraction of (a4) (% by mass))), 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) In formula (4), the content of the non-conjugated diene ((a3) and (a4) in total) in one molecule of the copolymer is specified.

[0056] When the copolymer (A) containing the structural unit derived from (a4) satisfies formula (4), an ethylene-based copolymer composition excellent in mechanical properties and heat aging resistance can be obtained. 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 the non-conjugated diene is too small, sufficient crosslinking may not occur and appropriate mechanical properties may not be obtained. If the value is too high, that is, if the content of the non-conjugated diene is too large, crosslinking may be excessive, mechanical properties may deteriorate, and heat aging resistance may also deteriorate.

[0057] ≪Requirement (ix)≫ The above copolymer (A) is not particularly limited, but the complex viscosity η at a frequency ω = 0.01 rad / s obtained by linear viscoelastic measurement (190 °C) using a rheometer * (ω=0.01) (Pa·sec), the complex viscosity η at a frequency ω = 10 rad / s * (ω=10) (Pa·sec), and the apparent iodine value derived from the non-conjugated polyene (a3) preferably 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)

[0058] Here, the complex viscosity η * (ω=0.01) and the complex viscosity η * (ω=10) are determined in the same manner as the complex viscosity η * (ω=0.1) and the complex viscosity η * (ω=100) in requirement (iv), except for the measurement frequency. The apparent iodine value derived from the non-conjugated polyene (a3) is determined by the following formula. Apparent iodine value derived from (a3) = weight fraction of (a3) × 253.81 / molecular weight of (a3)

[0059] In the above formula (5), the left side represents the shear rate dependence, which is an index of the long-chain branching amount, and the right side represents an index of the content of the non-conjugated polyene (a3) that has not been consumed as long-chain branches during polymerization. When the above copolymer (A) satisfies the above formula (5), it is preferable because the degree of long-chain branching is not too high. On the other hand, when the above formula (5) is not satisfied, it can be seen that a large proportion of the copolymerized non-conjugated polyene (a3) has been consumed for the formation of long-chain branches.

[0060] Furthermore, the above copolymer (A) preferably contains a sufficient amount of structural units derived from non-conjugated polyene (a3), and it is more preferable that the weight fraction of the structural units derived from non-conjugated polyene (a3) in the copolymer ((weight fraction of (a3) (mass%))) and the weight average molecular weight (Mw) of the copolymer satisfy the following formula (6). 6 - 0.45×Ln(Mw) ≤ weight fraction of (a3) ≤ 10 …(6)

[0061] In addition, for the above copolymer (A), the number (n a3 ) of structural units derived from non-conjugated polyene (a3) per weight average molecular weight (Mw) is preferably 6 or more, more preferably 6 or more and 40 or less, still more preferably 7 or more and 39 or less, and particularly preferably 10 or more and 38 or less.

[0062] Such a copolymer (A) contains a sufficient amount of structural units derived from non-conjugated polyene (a3) such as VNB, has a low long-chain branch content, is excellent in curing characteristics when crosslinked using a peroxide, has good moldability, is excellent in the balance of physical properties such as mechanical properties, and is particularly excellent in heat aging resistance.

[0063] In addition, for the above copolymer (A), the number (n a4 ) of structural units derived from non-conjugated polyene (a4) per weight average molecular weight (Mw) is preferably 29 or less, more preferably 10 or less, and still more preferably less than 1.

[0064] Such a copolymer (A) has the content of structural units derived from non-conjugated polyene (a4) such as ENB suppressed within a range that does not impair the object of the present invention, is less likely to cause post-crosslinking, and has sufficient heat aging resistance.

[0065] Here, the number (n a3 ) of structural units derived from non-conjugated polyene (a3) or the number (n a4It can be determined by the following formula from the molecular weight of the non-conjugated polyene (a3) or (a4), the weight fraction of the structural unit derived from the non-conjugated polyene (a3) or (a4) in the copolymer ((weight fraction of (a3) or (a4) (mass%)), and the weight average molecular weight (Mw) of the copolymer (A). (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)

[0066] In the above copolymer (A), the number (n ) of each structural unit derived from the non-conjugated polyenes (a a3 ) and (n a4 ) both satisfy the above range, the copolymer (A) has a low long-chain branching content, excellent curing characteristics when crosslinked using a peroxide, good moldability, excellent physical property balance such as mechanical properties, and is less likely to cause post-crosslinking and is particularly excellent in heat aging resistance, so it is preferable.

[0067] <Preparation of copolymer (A)> The above copolymer (A) is a copolymer obtained by copolymerizing monomers composed of ethylene (a1), α-olefin (a2), non-conjugated polyene (a3), and optionally non-conjugated polyene (a4).

[0068] The above copolymer (A) may be prepared by any production method as long as it satisfies desired requirements such as one or more of the above requirements (i) to (vi), but it is preferably obtained by copolymerizing monomers in the presence of a metallocene compound, more preferably obtained by copolymerizing monomers in the presence of a catalyst system containing a metallocene compound, and even more preferably obtained by a method including a step (1) of copolymerizing in the presence of a polymerization catalyst containing a specific metallocene compound and a step (2) of deactivating the polymerization catalyst by adding an alcohol as a catalyst deactivator.

[0069] ≪Metallocene Compound≫ The above copolymer (A) is preferably 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 copolymerizing the monomers using such a polymerization catalyst system containing a metallocene compound, the long-chain branches contained in the resulting copolymer are suppressed, and the copolymer (A) satisfying the above requirements can be easily prepared.

[0070]

Chemical formula

[0071] As the hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms is preferable. Specifically, an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl (aryl) group having 6 to 20 carbon atoms or a substituted aryl (aryl) group, etc. may be mentioned. For example, methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, amyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, isopropylphenyl group, t-butylphenyl group, naphthyl group, biphenyl group, terphenyl group, phenanthryl group, anthracenyl group, benzyl group, cumyl group can be mentioned, and those containing an oxygen-containing group such as a methoxy group, an ethoxy group, a phenoxy group, a nitrogen-containing group such as a nitro group, a cyano group, an N-methylamino group, an N,N-dimethylamino group, an N-phenylamino group, a boron-containing group such as a borantriyl group, a diboranyl group, and a sulfur-containing group such as a sulfonyl group, a sulfenyl group are also mentioned as the hydrocarbon group.

[0072] In the above hydrocarbon group, a hydrogen atom may be substituted with a halogen atom. For example, a trifluoromethyl group, a trifluoromethylphenyl group, a pentafluorophenyl group, a chlorophenyl group, etc. can be mentioned.

[0073] Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, etc. For example, 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, a dimethyl(pentafluorophenyl)silyl group, etc. can be mentioned.

[0074] 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 the 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 the silicon-containing group, and R 6 and R 7 may be bonded to each other to form a ring, and R 10 and R 11 may be bonded to each other to form a ring. However, R 6 R 7 R 10 and R 11 are not all hydrogen atoms.

[0075] R 13 and R 14 each independently represent an aryl group. M 1 represents a zirconium atom. Y 1 represents a carbon atom or a silicon atom.

[0076] 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 pair of electrons, j represents an integer of 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different from each other.

[0077] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable. The hydrocarbon group is preferably a hydrocarbon group having 1 to 10 carbon atoms, and 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, a benzyl group, etc., and a methyl group, an ethyl group, and a benzyl group are preferable.

[0078] 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 can be mentioned.

[0079] 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.

[0080] Specific examples of neutral ligands capable of coordinating with lone pairs of electrons include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, or ethers such as tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane, etc.

[0081] Substituent R in the above formula [A1] 1 ~R 4 Examples of the cyclopentadienyl group having 1 ~R 4 include an unsubstituted cyclopentadienyl group in which R 1 ~R 4 are hydrogen atoms, a 3-monosubstituted cyclopentadienyl group such as 3-t-butylcyclopentadienyl group, 3-methylcyclopentadienyl group, 3-trimethylsilylcyclopentadienyl group, 3-phenylcyclopentadienyl group, 3-adamantylcyclopentadienyl group, 3-amylcyclopentadienyl group, 3-cyclohexylcyclopentadienyl group, etc., and a 3,5-disubstituted cyclopentadienyl group such as 3-t-butyl-5-methylcyclopentadienyl group, 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, 3-trimethylsilyl-5-methylcyclopentadienyl group, etc. However, it is not limited thereto. From the viewpoints of the ease of synthesis of metallocene compounds, production cost, and copolymerization ability of non-conjugated polyenes, an unsubstituted (R 1 ~R 4 are hydrogen atoms) cyclopentadienyl group is preferred.

[0082] Substituent R in the formula [A1] 5 ~R 12 Examples of the fluorenyl group having R 5 ~R 12 include an unsubstituted fluorenyl group in which R 2-substituted fluorenyl groups at the 2-position such as 2-methylfluorenyl group, 2-t-butylfluorenyl group, 2-phenylfluorenyl group, 4-substituted fluorenyl groups at the 4-position such as 4-methylfluorenyl group, 4-t-butylfluorenyl group, 4-phenylfluorenyl group, or 2,7-disubstituted fluorenyl groups at the 2,7- or 3,6-positions such as 2,7-di-t-butylfluorenyl group, 3,6-di-t-butylfluorenyl group, 2,3,6,7-tetrasubstituted fluorenyl groups such as 2,7-dimethyl-3,6-di-t-butylfluorenyl group, 2,7-diphenyl-3,6-di-t-butylfluorenyl group, or R represented by the following general formulas [V-I], [V-II], 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 examples include 2,3,6,7-tetrasubstituted fluorenyl groups, but are not limited thereto.

[0083]

Chemical formula

[0084]

Chemical formula

[0085] Specific examples of the compound represented by the above general formula [V-I] or [V-II] include an octamethyloctahydrodibenzofluorenyl group represented by formula [V-III], a tetramethyldodecahydrodibenzofluorenyl group represented by formula [V-IV], an octamethyltetrahydrodicyclopentapentafluorenyl group represented by formula [V-V], a hexamethyldihydrodicyclopentapentafluorenyl group represented by formula [V-VI], and a b,h-dibenzofluorenyl group represented by formula [V-VII].

[0086]

Chemical formula

[0087]

Chemical formula

[0088]

Chemical formula

[0089] [Chemistry]

[0090] [Chemistry]

[0091] All of the metallocene compounds represented by the above general formula [A1] containing these fluorenyl groups are excellent in the copolymerization ability of non-conjugated polyene, but when Y 1 is a silicon atom, transition metal compounds having a 2,7-disubstituted fluorenyl group, a 3,6-disubstituted fluorenyl group, a 2,3,6,7-tetrasubstituted fluorenyl group, and a 2,3,6,7-tetrasubstituted fluorenyl group represented by the above general formula [V-I] are particularly excellent. When Y is a carbon atom, R 5 to R 12 is an unsubstituted fluorenyl group in which R is a hydrogen atom, a 3,6-disubstituted fluorenyl group, a 2,3,6,7-tetrasubstituted fluorenyl group, and a metallocene compound having a 2,3,6,7-tetrasubstituted fluorenyl group represented by the above general formula [V-I] are particularly excellent.

[0092] In the present invention, in the metallocene compound represented by the above general formula [A1], when Y 1 is a silicon atom and all of R 5 to R 12 are hydrogen atoms, R 13 and R 14 are 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, both R 6 and R 11 are t-butyl groups, and when R 5 , R 7 , R 8 , R 9 , R 10 , R 12 are not t-butyl groups, R 13 and R 14 are selected from groups other than a benzyl group and a silicon-substituted phenyl group; Y 1 is a carbon atom, and when R 5 to R 12 are all hydrogen atoms, R 13 , R 14 is selected from groups other than methyl group, isopropyl group, t-butyl group, isobutyl group, phenyl group, p-t-butylphenyl group, p-n-butylphenyl group, silicon-substituted phenyl group, 4-biphenyl group, p-tolyl group, naphthyl group, benzyl group, cyclopentyl group, cyclohexyl group, xylyl group; Y 1 is a carbon atom, and R 6 and R 11 are a common group selected from t-butyl group, methyl group or phenyl group, and when R 5 , R 7 , R 8 , R 9 , R 10 and R 12 are different groups or atoms, R 13 , R 14 is selected from groups other than methyl group, phenyl group, p-t-butylphenyl group, p-n-butylphenyl group, silicon-substituted phenyl group, benzyl group; Y 1 is a carbon atom, and when 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 are different groups or atoms from R 6 , R 13 , R 14 is selected from groups other than methyl group and phenyl group; Y 1 is a carbon atom, and when the site composed of fluorenyl group and R 5 ~R 12 is b,h-dibenzofluorenyl or a,i-dibenzofluorenyl, it is preferable that R 13 , R 14 are selected from groups other than methyl group and phenyl group.

[0093] 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 thereby. 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-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, Diphenylsilylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, Diphenylsilylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, Diphenylsilylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentapentafluorenyl)zirconium dichloride, Diphenylsilylene(cyclopentadienyl)(hexamethyldihydrodicyclopentapentafluorenyl)zirconium dichloride, Diphenylsilylene(cyclopentadienyl)(b,h-dibenzofluorenyl)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)(octamethyltetrahydrodicyclopentaphenalenyl)zirconium dichloride, Di(p-tolyl)silylene(cyclopentadienyl)(hexamethyldihydrodicyclopentaphenalenyl)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)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, Di(m-tolyl)silylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentapentafluorenyl)zirconium dichloride, Di(m-tolyl)silylene(cyclopentadienyl)(hexamethyldihydrodicyclopentapentafluorenyl)zirconium dichloride, Di(m-tolyl)silylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride etc. can be mentioned.

[0094] 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)(octamethyltetrahydrodicyclopentapentafluorenyl)zirconium dichloride, Diphenylmethylene(cyclopentadienyl)(hexamethyldihydrodicyclopentapentafluorenyl)zirconium dichloride, Diphenylmethylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, Di(p-tolyl)methylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, 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)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, Di(p-tolyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, Di(p-tolyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentaphenalenyl)zirconium dichloride, Di(p-tolyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentaphenalenyl)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)(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)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, Di(m-tolyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentapentalenyl)zirconium dichloride, Di(m-tolyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentapentalenyl)zirconium dichloride, Di(m-tolyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, Di(p-t-butylphenyl)methylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride, Di(p-t-butylphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butylfluorenyl)zirconium dichloride, Di(p-t-butylphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butylfluorenyl)zirconium dichloride, Di(p-t-butylphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, Di(p-t-butylphenyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, Di(p-t-butylphenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentapentalenyl)zirconium dichloride, Di(p-t-butylphenyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentapentalenyl)zirconium dichloride, Di(p-t-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)(octamethyltetrahydrodicyclopentaphenalenyl)zirconium dichloride, Di(4-biphenyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentaphenalenyl)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-butyl fluorenyl)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-butylfluorenyl)zirconium dichloride, Di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, Di(p-chlorophenyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, Di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentaphenalenyl)zirconium dichloride, Di(p-chlorophenyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentaphenalenyl)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)(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)(octamethyltetrahydrodicyclopentaphenalenyl)zirconium dichloride, Di(m-chlorophenyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentapentafluorenyl)zirconium dichloride, Di(m-chlorophenyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride, Di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, Di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(2,7-di-t-butylfluorenyl)zirconium dichloride, Di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(3,6-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)(octameth lutetetrahydrodicyclopentapentafluorenyl)zirconium dichloride, Di(m-trifluoromethylphenyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentapentafluorenyl)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(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, Di(2-naphthyl)methylene(cyclopentadienyl)(tetramethyldodecahydrodibenzofluorenyl)zirconium dichloride, Di(2-naphthyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentaphenalenyl)zirconium dichloride, Di(2-naphthyl)methylene(cyclopentadienyl)(hexamethyldihydrodicyclopentaphenalenyl)zirconium dichloride, Di(2-naphthyl)methylene(cyclopentadienyl)(b,h-dibenzofluorenyl)zirconium dichloride etc. can be mentioned.

[0095] As an example of the structural formula of these metallocene compounds, the structural formulas of di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride (the following (A)) and di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride (the following (B)) are shown below.

[0096]

Chemical formula

[0097] The metallocene compound represented by the above formula [A1], which can be preferably used for the preparation of the above copolymer (A), can be produced by any method without particular limitation. For example, it can be produced according to the methods described in J. Organomet. Chem., 63, 509 (1996), WO2005 / 1 00410, WO2006 / 123759, WO01 / 27124, JP-A-2004-168744, JP-A-2004-175759, JP-A-2000-212194, etc.

[0098] ≪Catalyst Containing Metallocene Compound≫ Examples of the polymerization catalyst that can be preferably used for the production of the above copolymer (A) include those containing the above-mentioned metallocene compound [A1] and capable of copolymerizing monomers.

[0099] Preferably, (a) the metallocene compound represented by the general formula [A1], and (b) at least one compound selected from (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) a compound that reacts with the metallocene compound (a) to form an ion pair (hereinafter also referred to as an "ionizing ionic compound"), and further, if necessary, (c) a particulate carrier. The polymerization catalyst composed of the above components will be described specifically below.

[0100] ≪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).

[0101] (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 represented by the following general formulas [VII] to [IX] are used. (b-1a) General formula: R a 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 the formula.

[0102] 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. (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 alkylate of a Group 1 metal of the periodic table and aluminum.

[0103] Examples of such compounds include LiAl(C 2 H 5 ) 4 and LiAl(C 7 H 15 ) 4 and the like. (b-1c) General formula: R a R b M 3 …[IX] (In formula [IX], 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, and M 3 is Mg, Zn or Cd.) A dialkyl compound having a Group 2 or Group 12 metal of the periodic table represented by

[0104] Among the above organometallic compounds (b-1), organoaluminum compounds such as triethylaluminum, triisobutyl aluminum, tri-n-octylaluminum are preferred. Also, such organometallic compounds (b-1) may be used alone or in combination of two or more.

[0105] (b-2) Organoaluminum oxy compound The organoaluminum oxy compound (b-2) may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687.

[0106] Conventionally known aluminoxanes can be produced, for example, by the following methods 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 crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerium(I) chloride hydrate, etc., to react the adsorbed water or crystal water with the organoaluminum compound. (2) A method in which water, ice or steam is directly allowed to act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0107] Note that the aluminoxane may contain a small amount of an organometallic component. Also, after distilling off the solvent or unreacted organoaluminum compound from the recovered solution of the aluminoxane, it may be redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

[0108] Examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above (b-1a).

[0109] Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and among them, trimethylaluminum and triisobutylaluminum are particularly preferred. The above organoaluminum compounds are used alone or in combination of two or more.

[0110] Also, the benzene-insoluble organoaluminum oxy compound, which is one embodiment of the organoaluminum oxy compound (b-2) used in the present invention, has an Al component dissolved in benzene at 60 °C of usually 10% by mass or less, preferably 5% by mass or less, particularly preferably 2% by mass or less in terms of Al atoms based on 100% by mass of benzene, that is, those insoluble or hardly soluble in benzene are preferred.

[0111] Examples of the organoaluminum oxy compound (b-2) used in the present invention also include organoaluminum oxy compounds containing boron represented by the following general formula [X].

[0112]

Chemical formula

[0113] The organoaluminum oxy compound containing boron represented by the general formula [X] is General formula: R 1 -B(OH) 2 …[XI] (In formula [XI], R1 represents the same group as R1 in the general formula [X].) and an alkylboronic acid represented by an organoaluminum compound are reacted in an inert solvent under an inert gas atmosphere at a temperature of -80°C to room temperature for 1 minute to 24 hours to produce it.

[0114] 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, 3,5-bis(trifluoromethyl)phenylboronic acid, and the like.

[0115] Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These may be used alone or in combination of two or more.

[0116] Examples of the organoaluminum compound that reacts with such an alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to (b-1a). Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferred. The above-mentioned organoaluminum oxy compound (b-2) is used singly or in combination of two or more.

[0117] (b-3) Ionizing ionic compound Examples of the ionizing 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, USP5321106, etc. Further, heteropoly compounds and isopoly compounds can also be included. Such ionizing ionic compounds (b-3) are used singly or in combination of two or more.

[0118] Specifically, examples of the Lewis acid include BR 3 (R is a phenyl group which may have a substituent such as fluorine, a methyl group, a trifluoromethyl group or the like, or fluorine) compounds represented by and examples thereof include 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, tris(3,5-dimethylphenyl)boron, etc. Examples of the ionic compound include compounds represented by the following general formula [XII].

[0119]

Chemical formula

[0120] Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri(methylphenyl)carbonium cation, and tri(dimethylphenyl)carbonium cation.

[0121] 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; dialkylammonium cations such as di(isopropyl)ammonium cation and dicyclohexylammonium cation.

[0122] Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri(methylphenyl)phosphonium cation, and tri(dimethylphenyl)phosphonium cation.

[0123] R 1+ Preferably, it is a carbonium cation, an ammonium cation, etc., and particularly preferably a triphenylcarbonium cation, an N,N-dimethylanilinium cation, or an N,N-diethylanilinium cation.

[0124] Examples of the ionic compound also include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

[0125] Specific examples of the trialkyl-substituted ammonium salts include, for example, triethylammonium tetra(phenyl)borate, tripropylammonium tetra(phenyl)borate, tri(n-butyl)ammonium tetra(phenyl)borate, trimethylammonium tetra (p-tolyl)borate, trimethylammonium tetra(o-tolyl)borate, tri(n-butyl)ammonium tetra(pentafluorophenyl)borate, tripropylammonium tetra(o,p-dimethylphenyl)borate, tri(n-butyl)ammonium tetra(N,N-dimethylphenyl)borate, tri(n-butyl)ammonium tetra(p-trifluoromethylphenyl)borate, tri(n-butyl)ammonium tetra(3,5-ditrifluoromethylphenyl)borate, tri(n-butyl)ammonium tetra(o-tolyl)borate, and the like.

[0126] Specific examples of the N,N-dialkylanilinium salts include, for example, N,N-dimethylanilinium tetra(phenyl)borate, N,N-diethylanilinium tetra(phenyl)borate, N,N,2,4,6-pentamethylanilinium tetra(phenyl)borate, and the like.

[0127] Specific examples of the dialkylammonium salts include, for example, di(1-propyl)ammonium tetra(pentafluorophenyl)borate, dicyclohexylammonium tetra(phenyl)borate, and the like.

[0128] Furthermore, examples of the ionic compounds include triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N,N-diethylanilinium pentaphenylcyclopentadienyl complex, boron compounds represented by the following formula [XIII] or [XIV], and the like. In the following formula, Et represents an ethyl group.

[0129] [Chemistry]

[0130] [Chemistry]

[0131] Specific examples of borane compounds include, for example 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, bis[tri(n-butyl)ammonium] dodeca chlorododecaborate; salts of metal borane anions such as tri(n-butyl)ammonium bis(dodecahydrido dodecaborate) cobaltate(III), bis[tri(n-butyl)ammonium] bis(dodecahydrido dodecaborate) nickelate(III), and the like.

[0132] Specific examples of the carborane compound include, for example, 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-dicarboundecaborane, 2,7-dicarboundecaborane, undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri(n-butyl)ammonium 1-carbadodecaborate, tri(n-butyl)ammonium-1-carbaundecaborate, tri(n-butyl)ammonium-1-carbadodecaborate, tri(n-butyl)ammonium-1-trimethylsilyl-1-carbadodecaborate, tri(n-butyl)ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium-6-carbadodecaborate, tri(n-butyl)ammonium-7-carbaundecaborate, tri(n-butyl)ammonium-7,8-dicarboundecaborate, tri(n-butyl)ammonium-2,9-dicarboundecaborate, tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-8-ethyl-7,9-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-8-allyl-7,9-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarboundecaborate, tri(n-butyl)ammonium undecahydride-4,6-dibromo-7-carbaundecaborate, and salts of anions such as these; Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)ferrate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)cobaltate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)nickelate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)cuprate(III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)aurate(III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)ferrate(III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)chromate(III), tri(n-butyl)ammonium bis(tribromooctahydride-7,8-dicarbaundecaborate)cobaltate(III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)chromate(III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)manganate(IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)cobaltate(III), bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)nickelate(IV), and salts of metal carborane anions such as these are exemplified.

[0133] Heteropoly compounds are atoms selected from silicon, phosphorus, titanium, germanium, arsenic, and tin, and one or It consists of two or more kinds of atoms. Specifically, phosphovanadate, germanovanadate, arsenovanadate, phosphoniobate, germanoniobate, silicomolybdic acid, phosphomolybdic acid, titanomolybdic acid, germanomolybdic acid, arsenomolybdic acid, stannomolybdic acid, phosphotungstic acid, germanotungstic acid, stannotungstic acid, phosphomolybdovanadate, phosphotungstovanadate, germanotungstovanadate, phosphomolybdotungstovanadate, germanomolybdotungstovanadate, phosphomolybdotungstic acid, phosphomolybdoniobate, 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 can be used, but it is not limited to this.

[0134] Among the ionized 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.

[0135] In the present invention, when using 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 ionized ionic compound (b-3) such as triphenylcarbenium tetrakis(pentafluorophenyl)borate, it can exhibit very high polymerization activity in the production of the copolymer (A).

[0136] (c) particulate carrier In the present invention, the (c) particulate carrier used as needed is an inorganic compound or an organic compound and is a granular or fine particulate solid. As the inorganic compound, a porous oxide, an inorganic halide, clay, a clay mineral or an ion-exchangeable layered compound is preferable. Specific examples thereof include those described in WO2015 / 122495 pamphlet.

[0137] The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as they are, or may be used after being subjected to treatments such as ball milling and sieving. Further, they may be used after newly adding and adsorbing water or performing heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more kinds.

[0138] Among these, preferable ones are clay or a clay mineral, and particularly preferable ones are montmorillonite, vermiculite, hectorite, teniolite, and synthetic mica. Examples of the organic compound include granular or fine particulate solids having a particle size in the range of 10 to 300 μm. Specifically, (co)polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, (co)polymers produced mainly from vinylcyclohexane and styrene, and modified products thereof can be exemplified.

[0139] The metallocene catalyst used in the present invention can further contain a specific organic compound component (d) as necessary, together with a metallocene compound (a), at least one compound (b) selected from an organometallic compound (b-1), an organoaluminum oxy compound (b-2), and an ionized ionic compound (b-3), and a carrier (c) used as necessary.

[0140] (d) Organic compound component In the present invention, the organic compound component (d) is used for the purpose of improving polymerization performance and physical properties of the produced polymer as necessary. Examples of such an organic compound include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates, but are not limited thereto. ​

[0141] <<Method for Producing and Conditions of the Copolymer (A)>> The above-mentioned copolymer (A) can be produced by copolymerizing monomers composed 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).

[0142] When copolymerizing such monomers, the usage and addition order of each component constituting the above-mentioned polymerization catalyst can be arbitrarily selected, and the following methods (1) to (5) are exemplified. (1) A method of adding the metallocene compound (a) alone to the polymerization reactor. (2) A method of adding the metallocene compound (a) and the compound (b) to the polymerization reactor in an arbitrary order. (3) A method of adding a catalyst component in which the metallocene compound (a) is supported on a carrier (c) and the compound (b) to the polymerization reactor in an arbitrary order. (4) A method of adding a catalyst component in which the compound (b) is supported on a carrier (c) and the metallocene compound (a) to the polymerization reactor in an arbitrary order. (5) A method of adding a catalyst component in which the metallocene compound (a) and the compound (b) are supported on a carrier (c) to the polymerization reactor.

[0143] In each of the above methods (2) to (5), at least two of the metallocene compound (a), the compound (b), and the carrier (c) may be contacted in advance. In each of the above methods (4) and (5) in which the compound (b) is supported, the non-supported compound (b) may be added in an arbitrary order if necessary. In this case, the compound (b) may be the same as or different from the compound (b) supported on the carrier (c).

[0144] Further, the solid catalyst component in which the metallocene compound (a) is supported on the above-mentioned carrier (c) and the solid catalyst component in which the metallocene compound (a) and the compound (b) are supported on the carrier (c) may be prepolymerized with an olefin, and a catalyst component may be further supported on the prepolymerized solid catalyst component.

[0145] The above copolymer (A) can be preferably obtained by copolymerizing monomers in the presence of the above polymerization catalyst. When carrying out the polymerization of olefins using the polymerization catalyst as described above, the metallocene compound (a) is usually 10 -12 ~10 -2 mol, preferably 10 -10 ~10 -8 mol per liter of the reaction volume.

[0146] Compound (b-1) is used in an amount such that the molar ratio [(b-1) / M] of compound (b-1) to all transition metal atoms (M) in the metallocene compound (a) is usually 0.01 to 50000, preferably 0.05 to 10000. Compound (b-2) is used in an amount such that the molar ratio [(b-2) / M] of the aluminum atom in compound (b-2) to all transition metals (M) in the metallocene compound (a) is usually 10 to 50000, preferably 20 to 10000. Compound (b-3) is used in an amount such that the molar ratio [(b-3) / M] of compound (b-3) to the transition metal atom (M) in the metallocene compound (a) is usually 1 to 20, preferably 1 to 15.

[0147] 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, but preferably has a step of obtaining the following polymerization reaction solution.

[0148] The step of obtaining the polymerization reaction solution means using an aliphatic hydrocarbon as a polymerization solvent, and the above metallocene catalyst, preferably Y 1 bonded to in the general formula [A1] 13 R 14 is a phenyl group, or a phenyl group substituted by an alkyl group or a halogen group, and R 7 R 10In the presence of a polymerization catalyst containing a transition metal compound having an alkyl substituent, ethylene (a1), an α-olefin (a2) having 3 to 20 carbon atoms, a non-conjugated polyene (a3), and optionally a non-conjugated polyene (a4) are copolymerized to obtain a polymerization reaction solution of a copolymer (A).

[0149] Examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Specifically, 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 can be mentioned. They can be used alone or in combination of two or more. In addition, the olefin itself can also be used as a solvent. Among these, hexane is preferable from the viewpoint of separation and purification from the obtained copolymer (A).

[0150] The polymerization temperature is usually in the range of -50 to +200°C, preferably in the range of 0 to +150°C, more preferably in the range of +70 to +110°C, and depends on the achievable molecular weight and polymerization activity of the metallocene catalyst system used. A higher temperature (above +70°C) is desirable from the viewpoints of catalyst activity, copolymerizability, and productivity.

[0151] The polymerization pressure is usually under 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. The polymerization reaction can be carried out by any of the batch, semi-continuous, and continuous methods. Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions. In the present invention, among these, it is preferable to adopt a method in which the monomers are continuously supplied to the reactor for copolymerization.

[0152] The reaction time (average residence time when the copolymerization is carried out by a continuous method) varies depending on conditions such as the catalyst concentration and the polymerization temperature, but is usually from 0.5 minutes to 5 hours, preferably from 5 minutes to 3 hours, more preferably from 10 minutes to 2 hours.

[0153] The molecular weight of the resulting copolymer (A) can also be adjusted by introducing hydrogen into the polymerization system or by changing the polymerization temperature. Furthermore, it can also be adjusted by the amount of the compound (b) used. Specifically, examples include triisobutylaluminum, methylaluminoxane, diethylzinc, etc. When adding hydrogen, the appropriate amount is about 0.001 to 100 NL per 1 kg of olefin.

[0154] Also, the molar ratio of the charged ethylene (a1) to the above α-olefin (a2) (ethylene (a1) / α-olefin (a2)) is preferably from 40 / 60 to 99.9 / 0.1, more preferably from 50 / 50 to 90 / 10, still more preferably from 55 / 45 to 85 / 15, and most preferably from 55 / 45 to 78 / 22.

[0155] The charged amount of the non-conjugated polyene (a3) is usually from 0.07 to 10% by mass, preferably from 0.1% by mass to 8.0% by mass, more preferably from 0.5% by mass to 5.0% by mass, based on 100% by mass of the total of ethylene (a1), α-olefin (a2), and non-conjugated polyene (a3) (total monomer charged amount).

[0156] In the present invention, after the step (1) of carrying out copolymerization in the presence of the polymerization catalyst, it is preferable to include a step (2) of adding a catalyst deactivator to deactivate the polymerization catalyst. As the catalyst deactivator, alcohols can be used, methanol or ethanol is preferable, and ethanol is particularly preferable.

[0157] In the step (2), by adding the catalyst deactivator in an amount of preferably 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 based on the organometallic compound (b-1), a slightly modified catalyst with a catalyst deactivator such as ethanol is generated, and as a result of moderately polymerizing low molecular weight components, a copolymer (A) with a moderately broad molecular weight distribution can be obtained. On the other hand, if the addition amount of the catalyst deactivator is too large, almost no modified catalyst is generated, and almost no polymerization of low molecular weight components occurs, so the molecular weight distribution of the resulting copolymer (A) tends to be narrow. Also, if no catalyst deactivator is added or the addition amount 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 resulting copolymer (A) tends to be too high.

[0158] 《Modified polybutadiene (B)》 The modified polybutadiene (B), which is one of the components constituting the ethylene-based copolymer composition of the present invention, is a polybutadiene modified with an unsaturated carboxylic acid and / or its derivative. Since this composition contains the modified polybutadiene (B) in addition to the copolymer (A), it has good moldability and can produce molded articles such as hoses with excellent balance of insulation, coolant resistance, and heat aging resistance.

[0159] Examples of the unsaturated carboxylic acid or its derivative include unsaturated carboxylic acids or unsaturated dicarboxylic acids such as acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, and endo-cis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid (nadic acid (trademark)), and derivatives such as acid halides, amides, imides, acid anhydrides, and esters of these acids. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, maleic acid, nadic acid, and their acid anhydrides are more preferred, and maleic anhydride is particularly preferred.

[0160] The modified polybutadiene (B) according to the present invention may be a commercially available product. For example, maleic anhydride-modified polybutadiene is manufactured and sold under the trade names such as Ricon130MA8, Ricon130MA13, Ricon130MA20, Ricon131MA5, Ricon131MA10, Ricon131MA17, Ricon131MA20, Ricon184MA6, etc. by Cray Valley.

[0161] 〈Other polymers〉 The ethylene-based copolymer composition of the present invention may contain other polymers other than the ethylene·α-olefin·non-conjugated polyene copolymer (A) and the modified polybutadiene (B).

[0162] Examples of other polymers include ethylene·α-olefin copolymers other than the ethylene·α-olefin·non-conjugated polyene copolymer (A). The α-olefin is usually an α-olefin having 3 to 20 carbon atoms, and among them, α-olefins having 3 to 10 carbon atoms such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, etc. are preferable, and propylene and 1-butene are particularly preferable.

[0163] Specific examples of the ethylene·α-olefin copolymer which is another polymer preferably include an ethylene·propylene copolymer and an ethylene·1-butene copolymer. When the composition contains other polymers, the content ratio of the other polymers is preferably 100 parts by mass or less, more preferably 30 to 70 parts by mass, and still more preferably 50 to 60 parts by mass with respect to a total of 100 parts by mass of the copolymer (A), the modified polybutadiene (B), and the other polymers.

[0164] <Ethylene-based copolymer composition> The ethylene-based copolymer composition of the present invention contains the ethylene·α-olefin·non-conjugated polyene copolymer (A) and the modified polybutadiene (B). In this composition, based on 100 parts by mass of the ethylene·α-olefin·non-conjugated polyene copolymer (A), the modified polybutadiene (B) is preferably contained in the range of 0.5 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, still more preferably 1 to 10 parts by mass, and particularly preferably 5 to 10 parts by mass. Also, the proportion of the copolymer (A) in this composition is generally 10% by mass or more and 90% by mass or less, preferably 13 to 75% by mass, more preferably 17 to 50% by mass, and still more preferably 20 to 30% by mass.

[0165] When the blending amount of the modified polybutadiene (B) in this composition is within the above range, the moldability is good, and a molded article such as a hose having an excellent balance of insulation, coolant resistance, and heat aging resistance can be produced. The hose product obtained by using this is excellent in the balance of insulation, coolant resistance, and heat aging resistance, and is suitable for automotive water hoses and the like, so it is preferable.

[0166] In addition to the ethylene·α-olefin·non-conjugated polyene copolymer (A) and the modified polybutadiene (B) of the present invention, and optionally other polymers, the ethylene-based copolymer composition may contain a softening agent, a filler, a crosslinking agent, and other additives, such as a processing aid, an activator, a moisture absorbent, and further a heat stabilizer, a weather stabilizer, an antistatic agent, a colorant, a lubricant, and a thickener.

[0167] This composition can be prepared by kneading the ethylene·α-olefin·non-conjugated polyene copolymer (A) and the modified polybutadiene (B) and other components optionally blended at a desired temperature using a kneader such as a mixer, a kneader, or a roll.

[0168] <Crosslinking agent> Examples of the crosslinking agent include crosslinking agents generally used when crosslinking rubber, such as organic peroxides, phenolic resins, hydrosilicone compounds, amino resins, quinones or their derivatives, amine compounds, azo compounds, epoxy compounds, isocyanate compounds, etc. Among these, organic peroxides are preferred.

[0169] Examples of the organic peroxide 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-butylperoxybenzoate, ert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide, etc.

[0170] 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, n-butyl-4,4-bis(tert-butylperoxy)valerate are preferred, and among them, 2,5-di-(tert-butylperoxy)hexane and 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane are most preferred.

[0171] When an organic peroxide is used as a crosslinking agent, its compounding 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 with respect to 100 parts by mass in total of the ethylene·α-olefin·non-conjugated polyene copolymer (A), the modified polybutadiene (B), and other polymers that require crosslinking if necessary. When the compounding amount of the organic peroxide is within the above range, the copolymer composition exhibits excellent crosslinking properties, which is preferable.

[0172] Also, when an organic peroxide is used as a crosslinking agent, it is preferable to use a crosslinking aid in combination. Examples of the crosslinking aid include sulfur; quinone dioxime-based crosslinking aids such as p-quinone dioxime; acrylic crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; allyl crosslinking aids such as diallyl phthalate and triallyl isocyanurate; maleimide-based crosslinking aids; divinylbenzene; metal oxides such as zinc oxide (for example, two types of zinc oxide (JIS standard (K-1410)), manufactured by Hakusuitech Co., Ltd.), magnesium oxide, and activated zinc white (for example, "META-Z102" (trade name: manufactured by Inoue Sekkai Kogyo Co., Ltd.) and other zinc oxides). The compounding amount of the crosslinking aid is usually 0.5 to 10 moles, preferably 0.5 to 7 moles, and more preferably 1 to 7 moles with respect to 1 mole of the organic peroxide.

[0173] <Softening agent> Specific examples of the softening agent include petroleum-based softening agents such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, petrolatum, etc.; coal tar-based softening agents such as coal tar; fatty oil-based softening agents such as castor oil, linseed oil, rapeseed oil, soybean oil, coconut oil, etc.; waxes such as beeswax, carnauba wax, etc.; fatty acids or their salts such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, etc.; naphthenic acid, pine oil, rosin or its derivatives; synthetic polymer substances such as terpene resin, petroleum resin, coumarone-indene resin, etc.; ester-based softening agents such as dioctyl phthalate, dioctyl adipate, etc.; and others such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oil, tall oil, factice, etc. Petroleum-based softening agents are preferred, and process oil is particularly preferred.

[0174] The compounding amount of the softening agent in the present composition is generally 2 to 100 parts by mass, preferably 10 to 100 parts by mass, more preferably 15 to 50 parts by mass, still more preferably 20 to 40 parts by mass, based on 100 parts by mass in total of the ethylene·α-olefin·non-conjugated polyene copolymer (A), modified polybutadiene (B), and other polymers optionally compounded.

[0175] 〈Inorganic filler〉 Specific examples of the inorganic filler include one or more of light calcium carbonate, heavy calcium carbonate, talc, clay, etc. Among these, heavy calcium carbonate such as "Whiton SB" (trade name: Shiraishi Calcium Co., Ltd.) is preferred.

[0176] When the copolymer composition contains an inorganic filler, the compounding amount of the inorganic filler is usually 2 to 50 parts by mass, preferably 5 to 50 parts by mass, based on 100 parts by mass in total of the ethylene·α-olefin·non-conjugated polyene copolymer (A), modified polybutadiene (B), and other polymers optionally compounded. When the compounding amount is within the above range, the kneading processability of the copolymer composition is excellent, and an OA equipment roll excellent in mechanical properties can be obtained.

[0177] <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 talc, fine powder silicic acid, etc. Among these, carbon black is preferred. When blending a reinforcing material, it 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 80 parts by mass with respect to a total of 100 parts by mass of the ethylene·α-olefin·non-conjugated polyene copolymer (A), the modified polybutadiene (B), and other polymers blended as necessary.

[0178] <Antioxidant (stabilizer)> By blending an antioxidant (stabilizer) into the copolymer composition according to the present invention, the lifespan of the molded body to be formed therefrom can be extended. Such antioxidants include conventionally known antioxidants, for example, amine-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants, etc. There are.

[0179] Furthermore, as antioxidants, aromatic secondary amine-based antioxidants such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine; phenol-based antioxidants such as dibutylhydroxytoluene and tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane; thioether-based antioxidants such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide; dithiocarbamate-based antioxidants such as nickel dibutyldithiocarbamate; sulfur-based antioxidants such as 2-mercaptobenzoyl imidazole, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dilauryl thiodipropionate, and distearyl thiodipropionate, etc. can be mentioned.

[0180] These anti-aging agents can be used alone or in combination of two or more. The compounding amount 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 still more preferably 5.0 to 10 parts by mass with respect to 100 parts by mass in total of the ethylene·α-olefin·non-conjugated polyene copolymer (A), the modified polybutadiene (B), and other polymers compounded as required. By setting it within such a range, there is no bloom on the surface of the molded body obtained from the resulting copolymer composition, and the occurrence of vulcanization inhibition can be further suppressed.

[0181] 〈Processing Aids〉 As the processing aids according to the present invention, those generally compounded with rubber as processing aids can be widely used.

[0182] Specific examples of the processing aids include ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, zinc stearate, calcium stearate, esters, etc. Among these, stearic acid is preferred.

[0183] The compounding amount of the processing aids 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 still more preferably 2.0 parts by mass or less with respect to 100 parts by mass in total of the ethylene·α-olefin·non-conjugated polyene copolymer (A), the modified polybutadiene (B), and other polymers compounded as required.

[0184] 〈Activators〉 Specific examples of the activators include amines such as di-n-butylamine, dicyclohexylamine, and monoethanolamine; activators such as diethylene glycol, polyethylene glycol, lecithin, triallyl trimellitate, and zinc compounds of aliphatic carboxylic acids or aromatic carboxylic acids; zinc peroxide preparations; cetadecyltrimethylammonium bromide, synthetic hydrotalcite, special quaternary ammonium compounds, etc.

[0185] The compounding amount of the active agent is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass, based on 100 parts by mass in total of the ethylene·α-olefin·non-conjugated polyene copolymer (A), the modified polybutadiene (B), and other polymers compounded as required.

[0186] 〈Humectant〉 Specific examples of the humectant include calcium oxide, silica gel, sodium sulfate, molecular sieve, zeolite, white carbon, and the like.

[0187] The compounding amount of the humectant is usually 0.5 to 15 parts by mass, preferably 1.0 to 12 parts by mass, based on 100 parts by mass in total of the ethylene·α-olefin·non-conjugated polyene copolymer (A), the modified polybutadiene (B), and other polymers compounded as required.

[0188] 《Crosslinked product》 The crosslinked product of the ethylene-based copolymer composition of the present invention is obtained by crosslinking the present composition. To produce a crosslinked product from the present composition, in the same manner as when vulcanizing general rubber, an unvulcanized rubber composition is prepared by the method described above, and then, after molding this rubber composition into a desired shape, vulcanization may be carried out. The unvulcanized rubber composition prepared as described above can be molded and vulcanized by various molding methods, but its characteristics can be most exerted when molded and vulcanized by mold molding such as compression molding, injection molding, and casting molding.

[0189] In the case of compression molding, for example, a pre-weighed unvulcanized rubber composition is put into a mold, and after closing the mold, heating is carried out at a temperature of 120 to 270°C for 30 seconds to 120 minutes, whereby the target crosslinked product can be obtained.

[0190] In the case of injection molding, for example, a ribbon-shaped or pellet-shaped rubber composition is supplied to a pot by a screw in a preset amount. Subsequently, the preliminarily heated rubber composition is sent into a mold by a plunger within 1 to 20 seconds. After injecting the rubber composition, it is heated at a temperature of 120 to 270 °C for 30 seconds to 120 minutes, whereby the target crosslinked product is obtained.

[0191] In the case of injection molding, for example, a pre-weighed rubber composition is placed in a pot and injected into a mold by a piston within 1 to 20 seconds. After injecting the rubber composition, it is heated at a temperature of 120 to 270 °C for 30 seconds to 120 minutes, whereby the target crosslinked product is obtained.

[0192] 《Uses of the ethylene copolymer composition》 The present composition and its crosslinked product can be made into products for various uses by being molded into a desired shape.

[0193] The present composition is excellent in moldability such as extrudability, and its molded body and crosslinked molded body are excellent in the balance of heat aging resistance, insulation, coolant resistance, etc. Therefore, the present composition can be suitably used for hoses, and hose products having excellent performance can be obtained from the present composition. The hose product according to the present invention is excellent in the balance of insulation, coolant resistance, and heat aging resistance, and thus is particularly useful as an automotive water system hose product such as a rubber hose used in a coolant system for cooling the battery and motor of an electric vehicle.

Examples

[0194] Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0195] Measurement and evaluation methods The evaluation methods for each physical property in the following examples and comparative examples are as follows. · Characteristics of the copolymer <Composition of ethylene·α-olefin·non-conjugated polyene copolymer> The weight fraction (mass %) of each constitutional unit of the ethylene·α-olefin·non-conjugated polyene copolymer was determined by 13 the measured values by C-NMR. The measured values were obtained by measuring the C-NMR spectrum of the copolymer using an ECX400P type 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 integration number of 8000 times. 13

[0196] <Iodine value> The iodine value of the ethylene·α-olefin·non-conjugated polyene copolymer was determined by titration. Specifically, it was measured by the following method. 0.5 g of the ethylene·α-olefin·non-conjugated polyene copolymer was dissolved in 60 ml of carbon tetrachloride, a small amount of Wijs reagent and 20% potassium iodide solution were added, and it was titrated with 0.1 mol / L sodium thiosulfate solution. Near the end point, a starch indicator was added, and it was titrated until the light purple color disappeared while stirring well. The number of grams of iodine was calculated as the amount of halogen consumed per 100 g of the sample.

[0197] <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 in terms of polystyrene measured by gel permeation chromatography (GPC). The measuring apparatus and conditions are as follows. Also, the molecular weight was calculated based on the calibration curve prepared using commercially available monodisperse polystyrene and the conversion method. Apparatus: Gel permeation chromatograph Alliance GP2000 type (manufactured by Waters), Analyzer: Empower2 (manufactured by Waters), Column: TSKgel GMH6-HT×2 + TSKgel GMH6-HTL×2 (7.5 mm I.D.×30 cm, manufactured by 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: 400 μL, Sampling time interval: 1 s, Column calibration: Monodisperse polystyrene (manufactured by Tosoh Corporation), Molecular weight conversion: Old method EPR conversion / Calibration method considering viscosity.

[0198] <Intrinsic viscosity> The intrinsic viscosity [η] was measured using a fully automatic intrinsic viscosity meter manufactured by Separation Co., Ltd. at a temperature of 135 °C and a measurement solvent of decalin.

[0199] <Complex viscosity η * > As a rheometer, a viscoelasticity measuring device Ares (manufactured by Rheometric Scientific) was used, and the complex viscosity η at a frequency ω = 0.01 rad / s, a temperature of 190 °C, and a strain of 1.0% * (ω=0.01) and the complex viscosity η at a frequency ω = 0.1 rad / s * (ω=0.1) and the complex viscosity η at a frequency ω = 10 rad / s * (ω=10) and the complex viscosity η at a frequency ω = 100 rad / s * (ω=100) (all in units of Pa·sec) were measured. Also, from the obtained results, η * (ω=0.1) and η * (ω=100) and the ratio of the complex viscosities of η * ratio), the P value (η * (ω=0.1) / η * (ω=100) ) was calculated.

[0200] <Number of long-chain branches per 1000 carbon atoms (LCB 1000c )> Number of long-chain branches (LCB 1000c ) was measured by the method described above.

[0201] · Physical properties of crosslinked bodies (vulcanized rubber) <Hardness test (Durometer A hardness)> In accordance with JIS K 6253, the hardness of the sheet (Type A durometer, HA) was measured using six 2-mm vulcanized rubber sheets with smooth surfaces. The flat parts were stacked to a thickness of approximately 12 mm. However, specimens with foreign matter, air bubbles, or scratches were not used. Also, the dimensions of the measurement surface of the specimen were set to a size such that the tip of the pressing needle could be measured at a position more than 12 mm away from the edge of the specimen.

[0202] <Tensile test> The vulcanized rubber sheets obtained in the examples and comparative examples were punched out to prepare No. 3 dumbbell test specimens described in JIS K 6251 (2001). Using these test specimens, a tensile test was conducted in accordance with the method specified in the same JIS K6251 under the conditions of a measurement temperature of 25°C and a tensile speed of 500 mm / min, and the 100% modulus (M100), tensile break point stress (TB), and tensile break point elongation (EB) were measured.

[0203] <Heat resistance aging> Regarding the 2-mm thick vulcanized rubber sheets prepared in the examples, etc., a heat resistance aging test was conducted in accordance with JIS K 6257 by holding at 150°C for 504 hours. The hardness, tensile break point stress, and tensile break point elongation of the sheet after the heat resistance aging test were measured in the same manner as in the above [Hardness test] items and the above [Tensile test] items.

[0204] From the difference in hardness before and after the heat resistance aging test, AH (shore-A) was obtained, and from the tensile break point stress (TB) and tensile break point elongation (EB) before and after the heat resistance aging test, the change rates after the test with respect to the values before the heat resistance aging test were obtained as Ac(TB) and Ac(EB), respectively.

[0205] <Water resistance> In accordance with the method defined in JISD2602, water was used as the immersion solution, and a water resistance test was conducted under the conditions of 150°C ± 1°C for 168 hours. The hardness, tensile break point stress, and tensile break point elongation were measured in the same manner as in the above [Hardness test] items and the above [Tensile test] items. From the difference in hardness before and after the water resistance test, AH (shore - A) was determined. From the tensile breaking point stress (TB) and tensile breaking point elongation (EB) before and after the water resistance test, the change rates after the test with respect to the values before the water resistance test were determined as Ac(TB) and Ac(EB), respectively. Also, from the volumes before and after the water resistance test, the volume change rate (ΔV) was determined.

[0206] <Coolant resistance> As an index of hot water resistance, evaluation was carried out using a coolant used in automobile radiator cooling water. The evaluation coolant was prepared by diluting a commercially available automobile radiator coolant liquid (manufactured by FUCHS, MAINTAIN FRICOFIN V long - life coolant) to 90% by volume with distilled water. According to the method defined in JIS D2602, using the above - mentioned evaluation coolant as the immersion solution, immersion was carried out under the conditions of 135°C ± 1°C for 168 hours, and the volume change rate (ΔV (%)) was determined from the volumes before and after immersion.

[0207] <Oil resistance> Regarding the 2 - mm - thick vulcanized rubber sheet prepared in Examples etc., an oil resistance test was carried out by immersing it in a test oil (IRM901) adjusted to 150°C for 72 hours according to JIS K 6258. The volume change rate (ΔV (%)) was determined from the volumes before and after the oil resistance test.

[0208] <Electrical properties (volume resistivity)> A volume resistivity test was carried out in accordance with the Japan Rubber Association Standard Specification (SRIS) 2304 (1971) to measure the volume resistivity of the cross - linked body. The average value is shown in the table.

[0209] [Production Example 1] (Production of copolymer (A - 1)) Using the continuous polymerization apparatus shown in Figure 1, the ethylene - propylene - VNB copolymer (A - 1) was produced as follows. Into a polymerization reactor C with a volume of 300 liters, 58.3 L / hr of a dehydrated and purified hexane solvent was introduced from pipe 6, and 4.5 mmol / hr of triisobutylaluminum (TiBA) was introduced from pipe 7. (C 6 H 5 )3 CB(C 6 F 5 ) 4 was continuously supplied at 0.150 mmol / hr, and di(p-tolyl)methylene(cyclopentadienyl)(octamethyl octahydrodibenzofluorenyl)zirconium dichloride was continuously supplied at 0.030 mmol / hr. At the same time, ethylene was continuously supplied into the polymerization reactor C at 6.6 kg / hr, propylene at 9.3 kg / hr, hydrogen at 18 liters / hr, and VNB at 340 g / hr through pipes 2, 3, 4, and 5 respectively, 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.

[0210] The solution of the ethylene·propylene·VNB copolymer produced in the polymerization reactor C was continuously discharged at a flow rate of 88.0 liters / hr through pipe 8, heated to 170 °C (the pressure rose to 4.1 MPaG), and supplied to the phase separator D. At this time, ethanol, which is a polymerization inhibitor, was continuously introduced into pipe 8 in an amount 0.1 mol times that of TiBA in the liquid component withdrawn from the polymerization reactor C.

[0211] In the phase separator D, the solution of the ethylene·propylene·VNB copolymer was separated into a concentrated phase (lower phase part) containing most of the ethylene·propylene·VNB copolymer and a dilute phase (upper phase part) containing a small amount of polymer.

[0212] The separated concentrated phase was led to the heat exchanger K at 85.4 liters / hr through pipe 11, and further led into the hopper E, where the solvent was evaporated and separated, and the ethylene·propylene·VNB copolymer was obtained in an amount of 7.8 kg / hr.

[0213] The physical properties of the obtained ethylene·propylene·VNB copolymer (A-1) were evaluated as described above. The results are shown in Table 1. The molecular weight distribution of the obtained copolymer (A-1) showed bimodality.

[0214]

Table 1

[0215] [Example 1] As the first step, using a BB-4 type Banbury mixer (manufactured by Kobe Steel, Ltd.), 69 parts by mass of the ethylene·propylene·VNB copolymer (A-1) obtained in Production Example 1 and 40 parts by mass of an ethylene·propylene·ethylidene norbornene copolymer (ENB-EPT, manufactured by Mitsui Chemicals, Inc., trade name: Mitsui EPT 0045, Mooney viscosity (ML (1+4) 100 °C): 40, ethylene content: 51% by weight) were kneaded for 1 minute, and then to this, 5 parts by mass of active zinc white (vulcanization accelerator, META-Z 102, manufactured by Inoue Lime Industry Co., Ltd.), 80 parts by mass of talc (Mistron Vapor Talc, manufactured by Nippon Mistron Co., Ltd.), 62 parts by mass of carbon black 1 (Asahi #60UG, manufactured by Asahi Carbon Co., Ltd.), 16 parts by mass of carbon black 2 (SRF, Asahi #50G, manufactured by Asahi Carbon Co., Ltd.), 31 parts by mass of paraffin-based process oil (Diana Process PW-380, manufactured by Idemitsu Kosan Co., Ltd.), 3 parts by mass of a primary antioxidant (Irganox 1010, manufactured by BASF), 6 parts by mass of a secondary antioxidant (Santant MB, manufactured by Sanshin Chemical Industry Co., Ltd.), and 1 part by mass of stearic acid were added and kneaded at 140 °C for 2 minutes. Then, the ram was raised for cleaning, and further kneading was performed for 1 minute, and the kneaded product was discharged at about 150 °C to obtain a formulation for the first step.

[0216] Next, as the second step, the formulation obtained in the first step was wound around a 6-inch roll (manufactured by Nippon Roll Co., Ltd., surface temperature of the front roll 50 °C, surface temperature of the rear roll 50 °C, rotational speed of the front roll 16 rpm, rotational speed of the rear roll 18 rpm), and to this, 8.5 parts by mass of Perhexa 25B-40 (manufactured by NOF Corporation: 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 40% masterbatch), which is an organic peroxide, and 5 parts by mass of maleic acid-modified polybutadiene (Ricon 13MA17, manufactured by Cray Valley) were added and kneaded for 10 minutes to obtain an uncrosslinked rubber formulation.

[0217] This uncrosslinked rubber formulation was separated into a sheet form, and using a 100-ton press molding machine, sheet-shaped and block-shaped crosslinked bodies were respectively prepared under the crosslinking conditions shown in Table 2, and the measurement of each property was performed. The results are shown in Table 2.

[0218] [Comparative Example 1] In the second stage of Example 1, a rubber composition and a crosslinked product were produced in the same manner as in Example 1, except that maleic acid-modified polybutadiene (Ricon 13MA17, manufactured by Cray Valley) was not blended, and further evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

[0219] [Table 2] [Explanation of Symbols]

[0220] C Polymerization Reactor D Phase Separator E Hopper F Pump G Heat Exchanger H Heat Exchanger

Claims

1. A copolymer composition comprising 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 two or more partial structures selected from the group consisting of the following general formulas (I) and (II) in one molecule, wherein the structural unit derived from the non-conjugated polyene (a3) contains a structural unit derived from 5-vinyl-2-norbornene, an ethylene-α-olefin-non-conjugated polyene copolymer (A), and modified polybutadiene (B) An ethylene-based copolymer composition containing the same. 【Chemical Formula 1】

2. The ethylene-based copolymer composition according to Claim 1, wherein the ethylene-α-olefin-non-conjugated polyene copolymer (A) satisfies at least one of the following requirements (i) to (vi). (i) The molar ratio [(a1) / (a2)] of the structural unit derived from ethylene (a1) to the structural unit derived from α-olefin (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 ethylene-α-olefin-non-conjugated polyene copolymer (A). (iii) The weight average molecular weight (Mw) of the ethylene-α-olefin-non-conjugated polyene copolymer (A), the weight fraction of the structural unit derived from the non-conjugated polyene (a3) ((weight fraction of (a3) (% by mass))), 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) The ratio P(η * / η (ω=0.1) ) of the complex viscosity η * (Pa·sec) at a frequency ω = 0.1 rad / s obtained by linear viscoelastic measurement (at 190 °C) using a rheometer to the complex viscosity η (ω=100) (Pa·sec) at a frequency ω = 100 rad / s, the limiting viscosity [η], and the weight fraction of the structural unit derived from the non-conjugated polyene (a3) (weight fraction of (a3)) satisfy the following formula (2). * (ω=0.1) (Pa·sec) and the complex viscosity η (ω=100) * (ω=100) (Pa·sec), and the limiting viscosity [η], and the weight fraction of the structural unit derived from the non-conjugated polyene (a3) (weight fraction of (a3)) satisfy the following formula (2). * (ω=0.1) / η (ω=0.1) * (ω=100) ), the limiting viscosity [η], and the weight fraction of the structural unit derived from the non-conjugated polyene (a3) (weight fraction of (a3)) satisfy the following formula (2). P / ([η] 2.9 ) ≤ (weight fraction of (a3)) × 6 …(2) (v) The ratio (molecular weight distribution; Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (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-based copolymer composition according to Claim 1, wherein the modified polybutadiene (B) is maleic acid-modified polybutadiene.

4. The ethylene-based copolymer composition according to Claim 1, containing 0.5 to 50 parts by mass of the modified polybutadiene (B) with respect to 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (A).

5. The ethylene-based copolymer composition according to Claim 1, wherein the α-olefin (a2) is propylene.

6. The ethylene-based copolymer composition according to Claim 1, which is for a hose.

7. A crosslinked product of the ethylene-based copolymer composition according to any one of Claims 1 to 6.

8. A hose product containing the crosslinked product according to Claim 7.

9. The hose product according to Claim 8, which is an automotive water-based hose product.

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