JP6859032B2 - Anti-vibration rubber composition and its uses - Google Patents

Description

The present invention relates to a composition for anti-vibration rubber and its use.

Ethylene-α-olefin rubbers such as ethylene-propylene copolymer rubber (EPR) and ethylene-propylene-diene copolymer rubber (EPDM) are versatile because they do not have unsaturated bonds in the main chain of their molecular structure. Compared to conjugated diene rubber, it has excellent heat aging resistance, weather resistance, and ozone resistance, and is widely used in applications such as automobile parts, electric wire materials, electronic / electrical parts, building civil engineering materials, and industrial material parts.
For example, anti-vibration rubber using EPDM is known (see, for example, Patent Documents 1 to 3).

Japanese Unexamined Patent Publication No. 11-293065 JP-A-2002-47363 International Publication No. 2015/12249

The vibration-proof characteristics (dynamic magnification) of the vibration-proof rubber fluctuate depending on the temperature, but it is difficult to predict it with conventional EPDM, especially at low temperatures.
According to the studies by the present inventors, it has been found that the conventionally known vibration-proof rubber made of EPDM shows an unexpected tendency of change in the region where the static spring constant is below room temperature. It was presumed that this was a factor that made it difficult to predict the anti-vibration characteristics, especially at low temperatures. Therefore, there is a problem that it is difficult to design so that the targeted anti-vibration characteristics can be exhibited in a wide temperature range.

Therefore, the subject of the present invention is a composition for anti-vibration rubber, which makes it easy to predict the anti-vibration characteristic (dynamic magnification) of the anti-vibration rubber in a certain temperature range, and an anti-vibration rubber formed by using the composition. To provide.

The present inventors have conducted diligent studies in order to solve the above problems. As a result, when an ethylene / α-olefin / non-conjugated polyene copolymer having a specific glass transition temperature is used, the change in the static spring constant (Ks) of the anti-vibration rubber in a certain temperature region is linear. ), And found that the above-mentioned problems could be solved, and completed the present invention.

That is, the present invention relates to, for example, the following [1] to [5].
[1]
Ethylene / α-olefin / non-conjugated including structural units derived from ethylene [A], structural units derived from α-olefin [B] having 4 to 20 carbon atoms, and structural units derived from non-conjugated polyene [C]. Contains polyene copolymer,
A composition for anti-vibration rubber having a glass transition temperature (Tg) of −70 to −50 ° C. as measured by differential scanning calorimetry (DSC) of the ethylene / α-olefin / non-conjugated polyene copolymer.

[2]
The anti-vibration rubber composition according to [1], wherein the ethylene / α-olefin / non-conjugated polyene copolymer satisfies the following (1) to (4).
(1) The molar ratio [[A] / [B]] of the structural unit derived from ethylene [A] to the structural unit derived from α-olefin [B] is 40/60 to 80/20.
(2) The content of the structural unit derived from the non-conjugated polyene [C] is 0.1 to 4.0 mol%, assuming that the total of the structural units of [A], [B] and [C] is 100 mol%. And
(3) Mooney viscosity ML _{(1 + 4) at} 125 ° C. 125 ° C. is 5 to 200.
(4) The B value represented by the following formula (i) is 1.20 or more.
B value = ([EX] + 2 [Y]) / [2 x [E] x ([X] + [Y])] ... (i)
[Here, [E], [X] and [Y] indicate the mole fractions of ethylene [A], α-olefin [B] having 4 to 20 carbon atoms, and unconjugated polyene [C], respectively. [EX] indicates the ethylene [A] -alpha-olefin [B] diad chain fraction having 4 to 20 carbon atoms. ]

[3]
The composition for anti-vibration rubber according to [1] or [2], wherein the glass transition temperature (Tg) of the ethylene / α-olefin / non-conjugated polyene copolymer measured by DSC is −70 to −60 ° C. Stuff.

[4]
An anti-vibration rubber formed by using the anti-vibration rubber composition according to any one of [1] to [3].

[5]
The anti-vibration rubber according to [4], which is at least one selected from a muffler hanger, a torsional damper, a change lever mount, a torsion rubber for a clutch, a centering bush, a tube damper, a torque bush, a suspension bush and an engine mount.

In the anti-vibration rubber formed by using the anti-vibration rubber composition of the present invention, the change of the static spring constant (Ks) in a constant temperature region is linear. Therefore, in the anti-vibration rubber composition of the present invention, it is easy to predict the anti-vibration characteristics (dynamic magnification) of the obtained anti-vibration rubber in a certain temperature range.

It is a figure which shows the static spring constant (Ks) of Example 1, 2 and Comparative Example 1. It is a figure which shows the dynamic spring constant (Kd) of Example 1, 2 and Comparative Example 1.

Hereinafter, modes for carrying out the present invention will be described.
The anti-vibration rubber composition of the present invention contains a specific ethylene / α-olefin / non-conjugated polyene copolymer described below. Hereinafter, the anti-vibration rubber composition containing a specific ethylene / α-olefin / non-conjugated polyene copolymer is also simply referred to as an anti-vibration rubber composition or composition.

[Composition for anti-vibration rubber]
The anti-vibration rubber composition of the present invention contains a specific ethylene / α-olefin / non-conjugated polyene copolymer described below. Hereinafter, this copolymer is also referred to as "ethylene-based copolymer A".

<< Ethylene / α-olefin / non-conjugated polyene copolymer >>
The ethylene / α-olefin / non-conjugated polyene copolymer used in the present invention is a structural unit derived from ethylene [A], that is, a structural unit derived from at least one type of α-olefin [B] having 4 to 20 carbon atoms. , And structural units derived from at least one non-conjugated polyene [C].

The ethylene / α-olefin / non-conjugated polyene copolymer used in the present invention has a glass transition temperature (Tg) of −70 to −50 ° C. as measured by differential scanning calorimetry (DSC). By using an ethylene / α-olefin / non-conjugated polyene copolymer having a glass transition temperature within the above range, the anti-vibration rubber formed by using the anti-vibration rubber composition of the present invention has a constant temperature range. Specifically, the change in the static spring constant (Ks) from −20 ° C. to 120 ° C. is linear. Therefore, the anti-vibration rubber composition of the present invention makes it easy to predict the anti-vibration characteristics (dynamic magnification) of the obtained anti-vibration rubber in a certain temperature range, and the anti-vibration rubber according to the desired physical properties of the anti-vibration rubber. The rubber composition is easy to design and is preferable.

The glass transition temperature (Tg) of the ethylene / α-olefin / non-conjugated polyene copolymer measured by DSC is −70 to −50 ° C., preferably −70 to −60 ° C. Within the above range, the change in the static spring constant from −20 ° C. to 120 ° C. is small, and the vibration isolation characteristics can be easily predicted, which is preferable.

It is preferable that the ethylene / α-olefin / non-conjugated polyene copolymer satisfies the following (1) to (4). When the following (1) to (4) are satisfied, rubber elasticity can be exhibited by cross-linking, which is preferable.
(1) The molar ratio [[A] / [B]] of the structural unit derived from ethylene [A] to the structural unit derived from α-olefin [B] is 40/60 to 80/20.
(2) The content of the structural unit derived from the non-conjugated polyene [C] is 0.1 to 4.0 mol%, assuming that the total of the structural units of [A], [B] and [C] is 100 mol%. And
(3) Mooney viscosity ML _{(1 + 4) at} 125 ° C. 125 ° C. is 5 to 200.
(4) The B value represented by the following formula (i) is 1.20 or more.

B value = ([EX] + 2 [Y]) / [2 x [E] x ([X] + [Y])] ... (i)
Here, [E], [X] and [Y] indicate the mole fractions of ethylene [A], α-olefin [B] having 4 to 20 carbon atoms, and non-conjugated polyene [C], respectively. EX] indicates the ethylene [A] -alpha-olefin [B] diad chain fraction having 4 to 20 carbon atoms.

The anti-vibration rubber obtained from the composition containing the ethylene-based copolymer A has a small change in anti-vibration characteristics at low temperatures, and it is easy to predict the anti-vibration characteristics in a wide temperature range. Can be demonstrated. Therefore, the anti-vibration rubber formed by using the composition of the present invention includes a muffler hanger, a torsional damper, a change lever mount, a torsion rubber for a clutch, a centering bush, a tube damper, a torque bush, a suspension bush, an engine mount and the like. Can be suitably used as.

The α-olefin [B] having 4 to 20 carbon atoms starts with 1-butene having 4 carbon atoms and having a linear structure without a side chain, 1-nonene having 9 carbon atoms, and 1-none having 10 carbon atoms. After decene, 1-nonadecene having 19 carbon atoms, 1-eicosene having 20 carbon atoms, and 4-methyl-1-pentene, 9-methyl-1-decene, 11-methyl-1-dodecene having a side chain, 12 -Ethyl-1-tetradecene and the like can be mentioned.

These α-olefins [B] can be used alone or in combination of two or more. Among these, α-olefins having 4 to 10 carbon atoms are preferable, 1-butene, 1-hexene, 1-octene and the like are particularly preferable, and 1-butene is particularly preferable.

Ethylene-propylene-non-conjugated polyene copolymers in which the α-olefin is propylene have insufficient rubber elasticity at low temperatures, and thus may have limited applications. On the other hand, since the ethylene-based copolymer A has a structural unit derived from an α-olefin [B] having 4 to 20 carbon atoms, it is excellent in rubber elasticity at a low temperature.

Specific examples of the non-conjugated polyene [C] include 1,4-hexadiene, 1,6-octadene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-. Chain non-conjugated diene such as 1,6-octadien; cyclohexadiene, dicyclopentadiene, methyltetrahydroinden, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5- Cyclic non-conjugated diene such as isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5- Norbornene, 2-propenyl-2,5-norbornene, 1,3,7-octatriene, 1,4,9-decatorien, 4,8-dimethyl-1,4,8-decatorien, 4-ethylidene-8-methyl Examples thereof include trienes such as -1,7-norbornene.

These non-conjugated polyenes [C] can be used alone or in combination of two or more.
Among these, chain non-conjugated diene such as 1,4-hexadiene, cyclic non-conjugated diene such as 5-ethylidene-2-norbornene, 5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene are preferable. Cyclic non-conjugated diene is preferable, and 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are particularly preferable.

Examples of the ethylene-based copolymer A include the following.
Ethylene / 1-butene / 1,4-hexadiene copolymer,
Ethylene / 1-pentene / 1,4-hexadiene copolymer,
Ethylene / 1-hexene / 1,4-hexadiene copolymer,
Ethylene 1-heptene 1,4-hexadiene copolymer,
Ethylene / 1-octene / 1,4-hexadiene copolymer,
Ethylene / 1-nonene / 1,4-hexadiene copolymer,
Ethylene / 1-decene / 1,4-hexadiene copolymer,
Ethylene / 1-butene / 1-octene / 1,4-hexadiene copolymer,
Ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer,
Ethylene 1-pentene 5-ethylidene-2-norbornene copolymer,
Ethylene / 1-hexene / 5-ethylidene-2-norbornene copolymer,
Ethylene 1-heptene 5-ethylidene-2-norbornene copolymer,
Ethylene / 1-octene / 5-ethylidene-2-norbornene copolymer,
Ethylene / 1-nonene / 5-ethylidene-2-norbornene copolymer,
Ethylene / 1-decene / 5-ethylidene-2-norbornene copolymer,
Ethylene / 1-butene / 1-octene / 5-ethylidene-2-norbornene copolymer,
Ethylene / 1-butene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer,
Ethylene / 1-pentene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer,
Ethylene / 1-hexene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer,
Ethylene, 1-heptene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene copolymer,
Ethylene / 1-octene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer,
Ethylene / 1-nonene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer,
Ethylene / 1-decene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer,
Ethylene, 1-butene, 1-octene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene copolymer.

As the ethylene-based copolymer A, one type or two or more types are used as required.
The ethylene-based copolymer A is
(1) The molar ratio [[A] / [B]] of the structural unit derived from ethylene [A] to the structural unit derived from α-olefin [B] is 40/60 to 80/20, preferably 40/60 to 80/20. It is in the range of 45/55 to 70/30, particularly preferably 50/50 to 70/30.

When the molar ratio of the structural unit derived from ethylene [A] and the structural unit derived from α-olefin [B] is within the above range, ethylene has an excellent balance between rubber elasticity at low temperature and tensile strength at room temperature. A system copolymer is obtained.

The ethylene-based copolymer A is
(2) The content of the structural unit derived from the non-conjugated polyene [C] is 0.1 to 4.0 mol%, assuming that the total of the structural units of [A], [B] and [C] is 100 mol%. , Preferably in the range of 0.5 to 3.3 mol%.

When the structural unit derived from the non-conjugated polyene [C] is in the above range, an ethylene-based copolymer having sufficient crosslinkability and flexibility can be obtained.
The ethylene-based copolymer A is
(3) Mooney Viscosity at 125 ° C. ML _{(1 + 4)} 125 ° C. is in the range of 5 to 200, preferably 8 to 150, and particularly preferably 8 to 100.

When the Mooney viscosity is in the above range, an ethylene-based copolymer showing good post-treatment (ribbon handling property) and having excellent rubber physical characteristics can be obtained.
The ethylene-based copolymer A is
(4) The B value is 1.20 or more, preferably 1.20 to 1.80, particularly preferably 1.22 to 1.40.

An ethylene-based copolymer having a B value of less than 1.20 has a large compression set at a low temperature, and an ethylene-based copolymer having an excellent balance between rubber elasticity at a low temperature and tensile strength at a normal temperature can be obtained. There is no risk.

The B value is an index showing the randomness of the copolymer chain distribution in the copolymer, and [E], [X], [Y], and [EX] in the above formula (i) are ¹³ The C-NMR spectrum was measured, and J. C. Randall [Macropolymers, 15, 353 (1982)], J. Mol. It can be obtained based on the report of Ray [Macropolymers, 10, 773 (1977)] et al.

<< Method for producing ethylene / α-olefin / non-conjugated polyene copolymer >>
The ethylene / α-olefin / non-conjugated polyene copolymer used in the present invention can be obtained by the following production method.

Specifically, (a) a transition metal compound represented by the following general formula [I] (hereinafter, also referred to as “crosslinked metallocene compound”), (b) (b-1) organometallic compound, (b-2). ) Ethylene, carbon number in the presence of an olefin polymerization catalyst containing an organoaluminum oxy compound, (b-3) at least one compound selected from compounds that react with the transition metal compound (a) to form an ion pair. It can be produced by copolymerizing 4 to 20 α-olefins and non-conjugated polyenes.

（式［Ｉ］において、Ｙは炭素原子、ケイ素原子、ゲルマニウム原子およびスズ原子から
選ばれ、
Ｍはチタン原子、ジルコニウム原子またはハフニウム原子であり、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶は水素原子、炭素数１〜２０の炭化水素基、アリール基、置換アリール基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、
Ｒ¹からＲ⁶までの隣接した置換基は互いに結合して環を形成していてもよく、
Ｑはハロゲン原子、炭素数１〜２０の炭化水素基、アニオン配位子および孤立電子対で配位可能な中性配位子から同一のまたは異なる組合せで選ばれ、
ｎは１〜４の整数であり、
ｊは１〜４の整数である。）

(In formula [I], Y is selected from carbon, silicon, germanium and tin atoms.
M is a titanium atom, a zirconium atom or a hafnium atom,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, hydrocarbon groups with 1 to 20 carbon atoms, aryl groups, substituted aryl groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, An atom or substituent selected from a halogen atom and a halogen-containing group, which may be the same or different.
Adjacent substituents from R ¹ to R ⁶ may be bonded to each other to form a ring.
Q is selected from halogen atoms, hydrocarbon groups with 1 to 20 carbon atoms, anionic ligands and neutral ligands that can be coordinated with lone electron pairs in the same or different combinations.
n is an integer of 1 to 4
j is an integer of 1 to 4. )

<Cross-linked metallocene compound (a)>
The crosslinked metallocene compound (a) is represented by the above general formula [I]. Y, M, R ^{1 to} R ⁶ , Q and j in the formula [I] will be described below.
(Y, M, R ^{1 to} R ⁶ , Q, n and j)
Y is selected from a carbon atom, a silicon atom, a germanium atom and a tin atom, and is preferably a carbon atom.

M is a titanium atom, a zirconium atom or a hafnium atom, preferably a hafnium atom.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, aryl groups, substituted aryl groups, silicon-containing groups, nitrogen-containing groups, and oxygen-containing groups. , An atom or substituent selected from halogen atoms and halogen-containing groups, which may be the same or different. Further, ^{the adjacent substituents R 1} to R ⁶ may or may not be bonded to each other to form a ring.

Here, examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and a chain unsaturated hydrocarbon group having 2 to 20 carbon atoms. Cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms are exemplified. When ^{adjacent substituents R 1} to R ⁶ are bonded to each other to form a ring, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and the like are exemplified.

The alkyl group having 1 to 20 carbon atoms includes a linear saturated hydrocarbon group, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-heptyl group. , N-octyl group, n-nonyl group, n-decanyl group and other branched saturated hydrocarbon groups such as isopropyl group, isobutyl group, s-butyl group, t-butyl group, t-amyl group, neopentyl group, 3 -Methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-dipropylbutyl group, 1,1-dimethyl-2-methylpropyl Examples thereof include a group, a 1-methyl-1-isopropyl-2-methylpropyl group, and a cyclopropylmethyl group. The alkyl group preferably has 1 to 6 carbon atoms.

Examples of the cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornenyl group, and a 1-adamantyl group, which are cyclic saturated hydrocarbon groups. 3-Methylcyclopentyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 4 which are groups in which the hydrogen atom of the cyclic saturated hydrocarbon group, such as 2-adamantyl group, is replaced with a hydrocarbon group having 1 to 17 carbon atoms. Examples thereof include a −cyclohexylcyclohexyl group and a 4-phenylcyclohexyl group. The cyclic saturated hydrocarbon group preferably has 5 to 11 carbon atoms.

Examples of the chain unsaturated hydrocarbon group having 2 to 20 carbon atoms include an alkenyl group, an ethenyl group (vinyl group), a 1-propenyl group, a 2-propenyl group (allyl group), and a 1-methylethenyl group (isopropenyl group). Examples thereof include an ethynyl group, a 1-propynyl group, and a 2-propynyl group (propargyl group), which are alkynyl groups. The chain unsaturated hydrocarbon group preferably has 2 to 4 carbon atoms.

Examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms include a cyclopentadienyl group, a norbornyl group, a phenyl group, a naphthyl group, an indenyl group, an azulenyl group, a phenanthryl group, and an anthracenyl group, which are cyclic unsaturated hydrocarbon groups. , 3-Methylphenyl group (m-tolyl group), 4-methylphenyl group (p-tolyl group), which is a group in which the hydrogen atom of the cyclic unsaturated hydrocarbon group is replaced with a hydrocarbon group having 1 to 15 carbon atoms. , 4-Ethylphenyl group, 4-t-butylphenyl group, 4-cyclohexylphenyl group, biphenylyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group ( A benzyl group, which is a group in which the hydrogen atom of a linear hydrocarbon group or a branched saturated hydrocarbon group is replaced with a cyclic saturated hydrocarbon group having 3 to 19 carbon atoms or a cyclic unsaturated hydrocarbon group, such as a mesityl group. A Kumil group and the like are exemplified. The cyclic unsaturated hydrocarbon group preferably has 6 to 10 carbon atoms.

Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a dimethylmethylene group (isopropyridene group), an ethylmethylene group, a 1-methylethylene group, a 2-methylethylene group, and a 1,1-dimethylethylene group. Examples thereof include 1,2-dimethylethylene group and n-propylene group. The alkylene group preferably has 1 to 6 carbon atoms.

Examples of the arylene group having 6 to 20 carbon atoms include an o-phenylene group, an m-phenylene group, a p-phenylene group, and a 4,4'-biphenylylene group. The arylene group preferably has 6 to 12 carbon atoms.

As the aryl group, although it partially overlaps with the above-mentioned example of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, it is a substituent derived from an aromatic compound, such as a phenyl group, a 1-naphthyl group and a 2-naphthyl group. Examples thereof include a group, anthrasenyl group, phenanthrenyl group, tetrasenyl group, chrysenyl group, pyrenyl group, indenyl group, azulenyl group, pyrrolyl group, pyridyl group, furanyl group, thiophenyl group and the like. As the aryl group, a phenyl group or a 2-naphthyl group is preferable.

Examples of the aromatic compound include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysen, pyrene, pyrene, inden, azulene, pyrrole, pyridine, furan, and thiophene. Will be done.

The substituted aryl group partially overlaps with the above-mentioned example of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, but one or more hydrogen atoms of the aryl group are hydrocarbon groups having 1 to 20 carbon atoms. Examples thereof include a group substituted with a substituent selected from an aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, and specific examples thereof include a 3-methylphenyl group (m-tolyl group). ), 4-Methylphenyl group (p-tolyl group), 3-ethylphenyl group, 4-ethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, biphenylyl group, 4- (trimethylsilyl) Phenyl group, 4-aminophenyl group, 4- (dimethylamino) phenyl group, 4- (diethylamino) phenyl group, 4-morpholinylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-phenoxyphenyl Group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3- (trifluoromethyl) phenyl group, Examples thereof include 4- (trifluoromethyl) phenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 5-methylnaphthyl group, 2- (6-methyl) pyridyl group and the like. Will be done. Further, as the substituted aryl group, "electron donating group-containing substituted aryl group" described later can also be mentioned.

Examples of the silicon-containing group include alkyl groups such as trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, and triisopropylsilyl group, which are groups in which carbon atoms are replaced with silicon atoms in hydrocarbon groups having 1 to 20 carbon atoms. Examples thereof include arylsilyl groups such as silyl group, dimethylphenylsilyl group, methyldiphenylsilyl group and t-butyldiphenylsilyl group, pentamethyldisilanyl group and trimethylsilylmethyl group. The alkylsilyl group preferably has 1 to 10 carbon atoms, and the arylsilyl group preferably has 6 to 18 carbon atoms.

Examples of the nitrogen-containing group include an amino group, a nitro group, an N-morpholinyl group, and the above-mentioned hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing group in which the CH-structural unit is replaced with a nitrogen atom. A group in which the CH ₂ − structural unit is replaced with a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded, or a nitrogen atom or a nitrile group in which a hydrocarbon group having 1 to 20 carbon _{atoms is bonded to the −CH 3 structural unit.} Examples thereof include a dimethylamino group, a diethylamino group, a dimethylaminomethyl group, a cyano group, a pyrrolidinyl group, a piperidinyl group, a pyridinyl group and the like which are the groups replaced with. As the nitrogen-containing group, a dimethylamino group and an N-morpholinyl group are preferable.

Examples of the oxygen-containing group include a hydroxyl group, a above-mentioned hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a nitrogen-containing group in which the −CH ₂ − structural unit is replaced with an oxygen atom or a carbonyl group, or −. Methoxy group, ethoxy group, t-butoxy group, phenoxy group, trimethylsiloxy group, methoxyethoxy group, hydroxymethyl, which are groups in which the CH _{3 structural unit is replaced with an oxygen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded.} Group, methoxymethyl group, ethoxymethyl group, t-butoxymethyl group, 1-hydroxyethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group Group, n-2-oxabutylene group, n-2-oxapentylene group, n-3-oxapentylene group, aldehyde group, acetyl group, propionyl group, benzoyl group, trimethylsilylcarbonyl group, carbamoyl group, methylaminocarbonyl Examples thereof include a group, a carboxy group, a methoxycarbonyl group, a carboxymethyl group, an etocarboxymethyl group, a carbamoylmethyl group, a furanyl group, a pyranyl group and the like. As the oxygen-containing group, a methoxy group is preferable.

Examples of the halogen atom include fluorine, chlorine, bromine, and iodine, which are Group 17 elements.
Examples of the halogen-containing group include a trifluoromethyl group and a tribromo, which are groups in which a hydrogen atom is substituted with a halogen atom in the above-mentioned hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group or an oxygen-containing group. Examples thereof include a methyl group, a pentafluoroethyl group and a pentafluorophenyl group.

Q is selected from halogen atoms, hydrocarbon groups with 1 to 20 carbon atoms, anionic ligands and neutral ligands that can be coordinated with lone electron pairs in the same or different combinations.
Details of the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms are as described above. When Q is a halogen atom, a chlorine atom is preferable. When Q is a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group preferably has 1 to 7 carbon atoms.

Examples of the anion ligand include an alkoxy group such as a methoxy group, a t-butoxy group and a phenoxy group, a carboxylate group such as acetate and benzoate, and a sulfonate group such as mesylate and tosylate.

Examples of the neutral ligand capable of coordinating with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane and 1,2-dimethoxyethane. An ether compound and the like can be exemplified.
n is an integer of 1 to 4.
j is an integer of 1 to 4, preferably 2.
The above example with respect to the formula [I] is similarly applied in the following description.

The 2,3,6,7-tetramethylfluorenyl group contained in the crosslinked metallocene compound (a) represented by the general formula [I] has four substituents at the 2, 3, 6 and 7 positions. Therefore, it is presumed that the electronic effect is large, which produces a high-molecular-weight ethylene-based copolymer with high polymerization activity. On the other hand, since non-conjugated polyenes are generally bulkier than α-olefins, copolymerization of non-conjugated polyenes should not be bulky in the vicinity of the central metal of the polymerization catalyst, especially the metallocene compound which is the polymerization active point. It is presumed that it will lead to performance improvement. Since the four methyl groups contained in the 2,3,6,7-tetramethylfluorenyl group are not bulky as compared with other hydrocarbon groups, this contributes to high non-conjugated polyene copolymerization performance. It is thought that it is. From the above, in particular, the crosslinked metallocene compound represented by the above general formula [I] containing a 2,3,6,7-tetramethylfluorenyl group has a high molecular weight of the ethylene-based copolymer produced and a high non-conjugation. It is presumed that polyene copolymerization performance and high polymerization activity are simultaneously achieved at a high level in a well-balanced manner.

In the crosslinked metallocene compound (a) represented by the general formula [I], n is preferably 1. Such a crosslinked metallocene compound (a-1) is represented by the following general formula [V].

（式［Ｖ］において、Ｙ、Ｍ、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｑおよびｊの定義等は上述のとおりである。）

(In the formula [V], ^{the definitions of Y, M, R 1} , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Q and j are as described above.)

The crosslinked metallocene compound (a-1) has a simplified production process, a reduced production cost, and thus the crosslinked metallocene compound, as compared with the compound in which n in the general formula [I] is an integer of 2 to 4. The advantage of using the copolymer is that the production cost of the ethylene / α-olefin / non-conjugated polyene copolymer is reduced. Further, when ethylene, an α-olefin having 4 or more carbon atoms and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the crosslinked metallocene compound (a-1), the ethylene-based copolymer produced is produced. The advantage of increasing the molecular weight can also be obtained.

In the crosslinked metallocene compound (a-1) represented by the general formula [I], ^{it is preferable that R 1} , R ² , R ³ and R ⁴ are all hydrogen atoms. Such a crosslinked metallocene compound (a-2) is represented by the following general formula [VI].

（式［ＶＩ］において、Ｙ、Ｍ、Ｒ⁵、Ｒ⁶、Ｑおよびｊの定義等は上述のとおりである。）

(In the formula [VI], ^{the definitions of Y, M, R 5} , R ⁶ , Q and j are as described above.)

The crosslinked metallocene compound (a-2) is compared with a compound in which any one or more ^{of R 1} , R ² , R ³ and R ^{4 in the above general formula [V] is substituted with a substituent other than a hydrogen atom.} The manufacturing process is simplified, the manufacturing cost is reduced, and by using this crosslinked metallocene compound, the manufacturing cost of the ethylene / α-olefin / non-conjugated polyene copolymer is reduced. Further, when ethylene is copolymerized with an α-olefin having 4 or more carbon atoms and a non-conjugated polyene in the presence of an olefin polymerization catalyst containing the crosslinked metallocene compound (a-2), the polymerization activity is improved and ethylene produced is produced. The advantage of increasing the molecular weight of the system copolymer can also be obtained. At the same time, the advantage of improving the copolymerization performance of the non-conjugated polyene can be obtained.

In the crosslinked metallocene compound (a-2) represented by the general formula [VI], Y is more preferably a carbon atom. Such a crosslinked metallocene compound (a-3) is represented by the following general formula [VII].

（式［ＶＩＩ］において、Ｍ、Ｒ⁵、Ｒ⁶、Ｑおよびｊの定義等は上述のとおりである。）
該架橋メタロセン化合物（ａ−３）は、例えば下式［ＶＩＩＩ］のような簡便な方法で合成することが可能である。

(In the formula [VII], ^{the definitions of M, R 5} , R ⁶ , Q and j are as described above.)
The crosslinked metallocene compound (a-3) can be synthesized by a simple method such as the following formula [VIII].

（式［ＶＩＩＩ］において、Ｍ、Ｒ⁵、Ｒ⁶の定義等は上述のとおりである。）

(In the formula [VIII], ^{the definitions of M, R 5} , R ^{6 and} the like are as described above.)

In the above formula [VIII], R ⁵ and R ⁶ contain a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen. an atom or substituent selected from the group, each may be the same or different, is a substituent which may be bonded to each other to form a ring, the general formula R ⁵ -C (= O) -R ^Since various ketones representing such conditions represented by 6 are commercially available from general reagent manufacturers, it is easy to obtain a raw material for the crosslinked metallocene compound (a-3). Even if such a ketone is not commercially available, the ketone can be easily synthesized by, for example, the method by Olah et al. [Heterocycles, 40, 79 (1995)]. As described above, the crosslinked metallocene compound (a-3) has a simpler and easier manufacturing process than a compound in which Y in the general formula [V] is selected from a silicon atom, a germanium atom and a tin atom, and the manufacturing cost is low. Further reduction is obtained, and by using this crosslinked metallocene compound, there is an advantage that the production cost of the ethire-based copolymer is reduced. Further, when ethylene, an α-olefin having 4 or more carbon atoms and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the crosslinked metallocene compound (a-3), the ethylene-based copolymer produced is produced. The advantage of further increasing the polymer weight can also be obtained.

In the crosslinked metallocene compound (a-3) represented by the general formula [VII], R ⁵ and R ⁶ are preferably groups selected from an aryl group and a substituted aryl group. When ethylene is copolymerized with an α-olefin having 4 or more carbon atoms and a non-conjugated polyene in the presence of an olefin polymerization catalyst containing the crosslinked metallocene compound, the polymerization activity is further improved and the ethylene-based copolymer produced is further further improved. The advantage of high molecular weight can be obtained. At the same time, the advantage of improving the copolymerization performance of the non-conjugated polyene can be obtained.

In the crosslinked metallocene compound (a-3) represented by the general formula [VII], ^{it is more preferable that R 5} and R ⁶ are the same group selected from an aryl group and a substituted aryl group. By selecting R ⁵ and R ⁶ in this way, the process of synthesizing the crosslinked metallocene compound is simplified, the production cost is further reduced, and by using this crosslinked metallocene compound, the production cost of the ethylene-based copolymer is reduced. The advantage of being reduced is obtained.

In the crosslinked metallocene compound (a-3) represented by the general formula [VII], ^{it is more preferable that R 5} and R ⁶ are the same substituted aryl group. When ethylene, an α-olefin having 4 or more carbon atoms and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the crosslinked metallocene compound, there is an advantage that the produced ethylene-based copolymer has a higher molecular weight. can get.

In the crosslinked metallocene compound (a-3) represented by the above general formula [VII], in R ⁵ and R ⁶ , one or more hydrogen atoms of the aryl group have a substituent constant σ of Hammett's rule of −0.2 or less. In the case of a substituted aryl group substituted with the electron-donating substituent of the above, and having a plurality of the electron-donating substituents, the electron-donating substituents may be the same or different, and the electron may be different. In addition to the donor substituent, it may have a substituent selected from a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, and the substituent may be used. When a plurality of groups are provided, each substituent may be the same or different, preferably a substituted aryl group (hereinafter, also referred to as “electron donating group-containing substituted aryl group”). When ethylene, an α-olefin having 4 or more carbon atoms and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing the crosslinked metallocene compound, there is an advantage that the produced ethylene-based copolymer has a higher molecular weight. can get.

An electron donating group having a Hammett equation substituent constant σ of −0.2 or less is defined and exemplified as follows. Hammett's law is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's law include σp when substituted at the para position of the benzene ring and σm when substituted at the meta position, and these values can be found in many general documents. For example, the literature by Hansch and Taft [Chem. Rev. , 91, 165 (1991)] provide a detailed description of a very wide range of substituents. However, the values of σp and σm described in these documents may differ slightly depending on the documents even if they are the same substituent. In the present invention, in order to avoid confusion caused by such a situation, Hansch and Taft's literature [Chem. Rev. , 91, 165 (1991)], Table 1 (pages 168-175) is defined as the substituent constants σp and σm of Hammett's law. In the present invention, an electron-donating group having a Hammett equation substituent constant σ of −0.2 or less means that σp is −0 when the electron-donating group is substituted at the para-position (4th position) of the phenyl group. It is an electron-donating group of .2 or less, and when substituted with the meta-position (3rd position) of the phenyl group, it is an electron-donating group having σm of −0.2 or less. Further, when the electron donating group is substituted at the ortho position (2-position) of the phenyl group, or when it is substituted at an arbitrary position of an aryl group other than the phenyl group, σp is −0.2 or less. It is an electron donating group of.

As electron-donating substituents having a substituent constant σp or σm of -0.2 or less according to Hammett's rule, p-amino group (4-amino group), p-dimethylamino group (4-dimethylamino group), p- Nitrogen-containing groups such as diethylamino group (4-diethylamino group) and m-diethylamino group (3-diethylamino group), oxygen-containing groups such as p-methoxy group (4-methoxy group) and p-ethoxy group (4-ethoxy group) Examples thereof include a group, a tertiary hydrocarbon group such as a pt-butyl group (4-t-butyl group), and a silicon-containing group such as a p-trimethylsiloxy group (4-trimethylsiloxy group). The electron-donating substituents having a Hammett law substituent constant σp or σm of −0.2 or less as defined in the present invention are described in the literature by Hansch and Taft [Chem. Rev. , 91, 165 (1991)], but is not limited to the substituents described in Table 1 (pages 168-175). Substituents that are not described in the literature but whose substituent constant σp or σm when measured based on Hammett's law will be in the range are the substituents of Hammett's law defined in the present invention. It is included in the electron donating group having a constant σp or σm of −0.2 or less. Examples of such a substituent include a p-N-morpholinyl group (4-N-morpholinyl group) and an m-N-morpholinyl group (3-N-morpholinyl group).

In the electron-donating group-containing substituted aryl group, when a plurality of electron-donating substituents are substituted, each electron-donating substituent may be the same or different, and the number of carbon atoms other than the electron-donating substituent may be different. Substituents selected from 1 to 20 hydrocarbon groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups may be substituted, and when a plurality of the substituents are substituted. Each substituent may be the same or different, but the sum of the electron-donating substituent contained in one substituted aryl group and the substituent constant σ of each Hammett rule of the substituent is −0.15 or less. Is preferable. Examples of such substituted aryl groups include m, p-dimethoxyphenyl group (3,4-dimethoxyphenyl group) and p- (dimethylamino) -m-methoxyphenyl group (4- (dimethylamino) -3-methoxyphenyl). Group), p- (dimethylamino) -m-methylphenyl group (4- (dimethylamino) -3-methylphenyl group), p-methoxy-m-methylphenyl group (4-methoxy-3-methylphenyl group) , P-methoxy-m, m-dimethylphenyl group (4-methoxy-3,5-dimethylphenyl group) and the like are exemplified.

Examples of the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the nitrogen-containing group, the oxygen-containing group, the halogen atom and the halogen-containing group that the electron-donating group-containing substituted aryl group may have are the above-mentioned atoms. Alternatively, specific examples of substituents can be given.

As a result of diligent studies on various cross-linked metallocene compounds (a), the applicant has identified R ⁵ and R ⁶ in the cross-linked metallocene compound (a-3) represented by the above general formula [VII], particularly according to Hammett's rule. An olefin polymerization catalyst containing the crosslinked metallocene compound (a-3) when one or more electron-donating substituents having a substituent constant σ of −0.2 or less are substituted for an electron-donating group-containing substituted aryl group. For the first time, it has been found that when ethylene, an α-olefin having 4 or more carbon atoms and a non-conjugated polylocene are copolymerized in the presence of ethylene, the molecular weight of the produced ethylene-based copolymer is further increased.

In the coordinate polymerization of an olefin using an organic metal complex catalyst such as the crosslinked metallocene compound (a-3), the molecular chain of the olefin polymer produced grows by repeatedly polymerizing the olefin on the central metal of the catalyst ( Growth reaction), it is known that the molecular weight of the olefin polymer increases. On the other hand, in a reaction called chain transfer, the molecular chain of the olefin polymer is dissociated from the central metal of the catalyst, so that the growth reaction of the molecular chain is stopped, and therefore the increase in the molecular weight of the olefin polymer is also stopped. Are known. From the above, the molecular weight of the olefin polymer is characterized by the ratio of the frequency of the growth reaction to the frequency of the chain transfer reaction, which is peculiar to the organic metal complex catalyst that produces the olefin polymer. That is, the larger the ratio between the frequency of the growth reaction and the frequency of the chain transfer reaction, the higher the molecular weight of the olefin polymer produced, and conversely, the smaller the ratio, the lower the molecular weight. Here, the frequency of each reaction can be estimated from the activation energy of each reaction, and it is considered that the reaction with low activation energy has a high frequency and the reaction with high activation energy has a low frequency. It is thought that it can be done. In general, it is known that the frequency of the growth reaction in olefin polymerization is sufficiently higher than the frequency of the chain transfer reaction, that is, the activation energy of the growth reaction is sufficiently lower than the activation energy of the chain transfer reaction. There is. Thus, activation energy subtracted values of the activation energy from growth reaction of chain transfer reaction (hereinafter, Delta] E _C) is positive, the frequency of the propagation reaction in comparison with the frequency of chain transfer this value is larger is larger Therefore, it is presumed that the molecular weight of the resulting olefin polymer will be high. The validity of the estimation of the molecular weight of the olefin polymer performed in this way is supported by, for example, the calculation results of Raine et al. [Organometallics, 30, 1350 (2011)]. In the crosslinked metallocene compound (a-3) represented by the above general formula [VII], R ⁵ and R ⁶ are particularly one electron-donating substituent having a substituent constant σ of Hammett's rule of −0.2 or less. One or more substituted in the case of the electron-donating group containing a substituted aryl group, said Delta] E _C increases, crosslinked metallocene compound (a-3) an olefin polymerization in the presence of a catalyst ethylene and number 4 or more carbon containing It is presumed that the molecular weight of the ethylene-based copolymer produced when the α-olefin and the non-conjugated polyene are copolymerized increases.

In the crosslinked metallocene compound (a-3) represented by the general formula [VII], the ^{electron-donating substituent contained in R 5} and R ⁶ is a group selected from a nitrogen-containing group and an oxygen-containing group. More preferred.

In the crosslinked metallocene compound (a-3) represented by the general formula [VII], R ⁵ and R ⁶ are substituted phenyls containing a group selected from a nitrogen-containing group and an oxygen-containing group as the electron-donating substituent. It is more preferably a group. For example, when synthesizing according to the method of the above formula [VIII], various benzophenones used as raw materials are commercially available from general reagent manufacturers, so that the raw materials can be easily obtained, the manufacturing process is simplified, and the manufacturing cost is further reduced. By using this crosslinked metallocene compound, it is possible to obtain the advantage that the production cost of the ethylene-based copolymer is reduced.

Here, examples of the substituted phenyl group containing a group selected from the nitrogen-containing group and the oxygen-containing group as the electron-donating substituent include an o-aminophenyl group (2-aminophenyl group) and a p-aminophenyl group (4). -Aminophenyl group), o- (dimethylamino) phenyl group (2- (dimethylamino) phenyl group), p- (dimethylamino) phenyl group (4- (dimethylamino) phenyl group), o- (diethylamino) phenyl Group (2- (diethylamino) phenyl group), p- (diethylamino) phenyl group (4- (diethylamino) phenyl group), m- (diethylamino) phenyl group (3- (diethylamino) phenyl group), o-methoxyphenyl group (2-methoxyphenyl group), p-methoxyphenyl group (4-methoxyphenyl group), o-ethoxyphenyl group (2-ethoxyphenyl group), p-ethoxyphenyl group (4-ethoxyphenyl group), o-N -Morphorinylphenyl group (2-N-morpholinylphenyl group), p-N-morpholinylphenyl group (4-N-morpholinylphenyl group), m-N-morpholinylphenyl group (3) -N-morpholinylphenyl group), o, p-dimethoxyphenyl group (2,4-dimethoxyphenyl group), m, p-dimethoxyphenyl group (3,4-dimethoxyphenyl group), p- (dimethylamino) -M-methoxyphenyl group (4- (dimethylamino) -3-methoxyphenyl group), p- (dimethylamino) -m-methylphenyl group (4- (dimethylamino) -3-methylphenyl group), p- Examples thereof include a methoxy-m-methylphenyl group (4-methoxy-3-methylphenyl group), a p-methoxy-m, m-dimethylphenyl group (4-methoxy-3,5-dimethylphenyl group) and the like.

In the crosslinked metallocene compound (a-3) represented by the general formula [VII], R ⁵ and R ⁶ are electron-donating substitutions at the meta-position and / or para-position for the bond with the carbon atom as Y. A substituted phenyl group containing a group selected from a nitrogen-containing group and an oxygen-containing group as the group is more preferable. For example, when synthesized according to the method of the above formula [VIII], the synthesis becomes easier, the manufacturing process is simplified, the manufacturing cost is further reduced, and thus the crosslinked metallocene is easier than when the group is substituted at the ortho position. The use of the compound has the advantage of reducing the production cost of the ethylene-based copolymer.

In the crosslinked metallocene compound (a-3) represented by the general formula [VII], R ⁵ and R ⁶ are electron-donating substitutions at the meta-position and / or para-position for the bond with the carbon atom as Y. In the case of a substituted phenyl group containing a nitrogen-containing group as a group, the nitrogen-containing group is more preferably a group represented by the following general formula [II].

（式［ＩＩ］において、Ｒ⁷およびＲ⁸は水素原子、炭素数１〜２０の炭化水素基、ケイ素含有基、酸素含有基およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、互いに結合して環を形成していてもよく、Ｎの右に描かれた線はフェニル基との結合を表す。）

(In the formula [II], R ⁷ and R ⁸ are atoms or substituents selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group and a halogen-containing group, and they may be the same. They may be different or bonded to each other to form a ring, and the line drawn to the right of N represents the bond with the phenyl group.)

Specific examples of the above-mentioned substituents can be mentioned as examples of the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the oxygen-containing group and the halogen-containing group as R ⁷ and R ^8.
Such a crosslinked metallocene compound (a-4) is represented by the following general formula [IX].

（式［ＩＸ］において、Ｍ、Ｑおよびｊの定義等は上述のとおりである。Ｒ⁷、Ｒ⁸およびＲ¹⁰は水素原子、炭素数１〜２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる置換基であり、それぞれ同一でも異なっていてもよく、Ｒ⁷、Ｒ⁸およびＲ¹⁰のうちの隣接した置換基は互いに結合して環を形成していてもよく、ＮＲ⁷Ｒ⁸はハメット則の置換基定数σが−０．２以下の窒素含有基であり、該窒素含有基が複数個存在する場合にはそれぞれの窒素含有基は互いに同一でも異なっていてもよく、ｎは１〜３の整数であり、ｍは０〜４の整数である。）

(In the formula [IX], the definitions of M, Q and j are as described above. R ⁷ , R ⁸ and R ¹⁰ are hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups and nitrogen-containing groups. It is a substituent selected from a group, an oxygen-containing group, a halogen atom and a halogen-containing group, and may be the same or different from ^{each other. Adjacent substituents of R 7} , R ⁸ and R ¹⁰ are bonded to each other and ring. NR ⁷ R ⁸ is a nitrogen-containing group having a substituent constant σ of Hammett's rule of −0.2 or less, and when a plurality of the nitrogen-containing groups are present, each nitrogen-containing group is formed. May be the same or different from each other, n is an integer of 1 to 3 and m is an integer of 0 to 4.)

In the crosslinked metallocene compound (a-3) represented by the general formula [VII], R ⁵ and R ⁶ are electron-donating substitutions at the meta-position and / or para-position for the bond with the carbon atom as Y. In the case of a substituted phenyl group containing an oxygen-containing group as a group, the oxygen-containing group is more preferably a group represented by the following general formula [III].

（式［ＩＩＩ］において、Ｒ⁹は水素原子、炭素数１〜２０の炭化水素基、ケイ素含有基、窒素含有基およびハロゲン含有基から選ばれる原子または置換基であり、Ｏの右に描かれた線はフェニル基との結合を表す。）

(In formula [III], R ⁹ is an atom or substituent selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group and a halogen-containing group, and is drawn to the right of O. The line represents the bond with the phenyl group.)

Specific examples of the above-mentioned substituents can be mentioned as examples of the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the nitrogen-containing group and the halogen-containing group as R ^9.
Such a crosslinked metallocene compound (a-5) is represented by the following general formula [X].

（式［Ｘ］において、Ｍ、Ｑおよびｊの定義等は上述のとおりである。Ｒ⁹およびＲ¹⁰は水素原子、炭素数１〜２０の炭化水素基、ケイ素含有基、窒素含有基、酸素含有基、ハロゲン原子およびハロゲン含有基から選ばれる原子または置換基であり、それぞれ同一でも異なっていてもよく、Ｒ¹⁰の隣接した置換基は互いに結合して環を形成していてもよく、ＯＲ⁹はハメット則の置換基定数σ−０．２以下の酸素含有基であり、該酸素含有基が複数個存在する場合にはそれぞれの酸素含有基は互いに同一でも異なっていてもよく、ｎは１〜３の整数であり、ｍは０〜４の整数である。）

(In the formula [X], the definitions of M, Q and j are as described above. R ⁹ and R ¹⁰ are hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen. It is an atom or a substituent selected from a containing group, a halogen atom and a halogen-containing group, and may be the same or different from ^{each other, and adjacent substituents of R 10} may be bonded to each other to form a ring, OR. ^{Reference numeral 9} is an oxygen-containing group having a substituent constant of σ-0.2 or less according to Hammett's rule, and when a plurality of the oxygen-containing groups are present, the oxygen-containing groups may be the same or different from each other, and n is It is an integer of 1 to 3, and m is an integer of 0 to 4.)

The crosslinked metallocene compound (a) represented by the general formula [I], the crosslinked metallocene compound (a-1) represented by the general formula [V], and the crosslinked metallocene compound represented by the general formula [VI] ( a-2), the crosslinked metallocene compound (a-3) represented by the general formula [VII], the crosslinked metallocene compound (a-4) represented by the general formula [IX], or the above general formula [X]. In the crosslinked metallocene compound (a-5) represented, M is more preferably a hafnium atom. Further of the ethylene-based copolymer produced when ethylene is copolymerized with α-olefin having 4 or more carbon atoms and a non-conjugated polyene in the presence of an olefin polymerization catalyst containing the crosslinked metallocene compound in which M is a hafnium atom. The advantages of higher molecular weight and improved copolymerization performance of non-conjugated polyene can be obtained.

(Example of crosslinked metallocene compound (a), etc.)
As such a crosslinked metallocene compound (a),
[Dimethylmethylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [diethylmethylene (eta ⁵ - cyclopentadienyl) (eta ⁵ - 2,3,6,7-tetramethyl-fluorenyl)] hafnium dichloride, [di -n- butyl methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenylmethoxycarbonyl} yl)] hafnium dichloride, [dicyclopentyl methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [dicyclohexyl methylene (eta ⁵ - cyclopenta dienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride,
[Cyclopentylidene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [cyclohexylidene (eta ⁵ - cyclopentadienyl) (eta ⁵ -2,3,6,7-tetramethyl-fluorenyl)] hafnium dichloride,
[Diphenylmethylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [di-1-naphthylmethylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [di-2-naphthylmethylene (eta ⁵ - cyclopentadienyl) (eta ^5-2,3,6,7- Tetramethylfluorenyl)] Hafnium dichloride,
[Bis (3-methylphenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [bis (4-methylphenyl) methylene ( eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [bis (3,4-dimethylphenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [bis (4-n-hexyl-phenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ^5-2,3, 6,7-tetramethyl-fluorenyl)] hafnium dichloride, [bis (4-cyclohexyl-phenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)} ] hafnium dichloride, [bis (4-t- butylphenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride,
[Bis (3-methoxyphenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [bis (4-methoxyphenyl) methylene ( eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [bis (3,4-dimethoxyphenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [bis (4-methoxy-3-methylphenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ⁵ -2, 3,6,7- tetramethyl fluorenyl) hafnium dichloride, [bis (4-methoxy-3,4-dimethylphenyl) methylene (eta ⁵ - cyclopentadienyl) (η ⁵ -2,3,6, 7-tetramethyl-fluorenyl)] hafnium dichloride, [bis (4-ethoxyphenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)} hafnium dichloride, [bis (4-phenoxyphenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [bis {4- (trimethylsiloxy ) phenyl} methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride,
[Bis {3- (dimethylamino) phenyl} methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [bis {4- (dimethyl amino) phenyl} methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [bis (4-N-morpholinium sulfonyl phenyl) (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride,
[Bis {4- (trimethylsilyl) phenyl} methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride,
[Bis (3-chlorophenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [bis (4-chlorophenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [bis (3-fluorophenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ⁵ - 2,3,6,7-tetramethyl-fluorenyl)] hafnium dichloride, [bis (4-fluorophenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl} fluorenyl)] hafnium dichloride, [bis {3- (trifluoromethyl) phenyl} methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)} hafnium dichloride, [bis {4- (trifluoromethyl) phenyl} methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride,
[Methylphenylmethylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [methyl (4-methylphenyl) methylene (eta ⁵ - cyclopenta dienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [methyl (4-methoxyphenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ^5-2,3 , 6,7-tetramethyl-fluorenyl)] hafnium dichloride, [methyl {4- (dimethylamino) phenyl} methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl} fluorenyl)] hafnium dichloride, [methyl (4-N-morpholinium sulfonyl) methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)} hafnium Dichloride,
[Dimethylsilylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [diethyl silylene (eta ⁵ - cyclopentadienyl) (eta ⁵ - 2,3,6,7-tetramethyl-fluorenyl)] hafnium dichloride, [dicyclohexyl silylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)} hafnium dichloride, [diphenylsilylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [di (4-methylphenyl) silylene (eta ⁵ - cyclo Pentazienyl) (η 5-2, ^{3, 6, 7-} tetramethylfluorenyl)] Hafnium dichloride,
[Dimethyl gel Mi Len (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, [diphenyl gel Mi Len (eta ⁵ - cyclopentadienyl) (eta ⁵ -2,3,6,7-tetramethyl-fluorenyl)] hafnium dichloride,
[1- (η ⁵ - cyclopentadienyl) -2- (η ⁵ -2,3,6,7- tetramethyl fluorenyl) ethylene] hafnium dichloride, [1- (η ⁵ - cyclopentadienyl) -3- (η ⁵ -2,3,6,7- tetramethyl fluorenyl) propylene] hafnium dichloride, [1- (η ⁵ - cyclopentadienyl) -2- (η ⁵ -2,3,6 , 7-tetramethyl-fluorenyl) -1,1,2,2-tetramethyl silylene] hafnium dichloride, [1- (η ⁵ - cyclopentadienyl) -2- (η ⁵ -2,3,6, 7-Tetramethylfluorenyl) phenylene] hafnium dichloride, and compounds in which the hafnium atom of these compounds is replaced with a zirconium atom or a compound in which a chloro ligand is replaced with a methyl group are exemplified, but a crosslinked metallocene compound (A) is not limited to these examples.

<Production method of crosslinked metallocene compound>
The crosslinked metallocene compound can be produced by a known method, and the production method is not particularly limited. As a manufacturing method, for example, J. Organomet. Chem. , 63, 509 (1996), WO2006123759, WO01 / 27124, JP2004-168744, JP2004-175759, JP2000-212194, which are publications related to the application by the present applicant. It can be produced by the method described in the publication.

<Preferable form when the crosslinked metallocene compound is used as a catalyst for an ethylene / α-olefin / non-conjugated polyene copolymer>
Next, a preferable form when the crosslinked metallocene compound is used as a catalyst for an ethylene / α-olefin / non-conjugated polyene copolymer (olefin polymerization catalyst) will be described.

When the crosslinked metallocene compound is used as an olefin polymerization catalyst component, the catalyst is
(A) The crosslinked metallocene compound represented by the general formula [I] and
At least one selected from (b) (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) a compound that reacts with a crosslinked metallocene compound (a) to form an ion pair. Seed compound and
Further if necessary
(C) Consists of a particulate carrier.
Hereinafter, each component will be specifically described.

<(B-1) Organometallic compound>
As the organometallic compound (b-1) used in the present invention, specifically, the organometallic compounds of Groups 1, 2 and 12 and 13 of the Periodic Table as shown in the following general formulas [VII] to [IX]. Is used.

(B-1a) formula _{^{R a m Al (OR b)}} n H p X q ··· [VII]
(In the formula [VII], ^Ra and R ^b may be the same or different from each other, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, where X represents a halogen atom and m. Is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3). ..

Such compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trin-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methyl. Examples thereof include aluminum dichloride, dimethylaluminum chloride, and diisobutylaluminum hydride.

(B-1b) General formula M ² AlR ^a ₄ ... [VIII]
(In the formula [VIII], M ² represents Li, Na or K, and ^Ra is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.) A complex alkylated product of a group metal and aluminum.
Examples of such compounds include LiAl (C ₂ H ₅ ) ₄ , LiAl (C ₇ H ₁₅ ) _{4, and the} like.

(B-1c) General formula R ^a R ^b M ³ ... [IX]
(In the formula [IX], ^Ra and R ^b may be the same or different from each other, and represent hydrocarbon groups 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).

Among the above-mentioned organometallic compounds (b-1), organoaluminum compounds such as triethylaluminum, triisobutylaluminum, and trin-octylaluminum are preferable. Further, such an organometallic compound (b-1) may be used alone or in combination of two or more.

<(B-2) Organoaluminium oxy compound>
The (b-2) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or is a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. You may.

Conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method in which an organic aluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension of the above, and adsorbed water or water of crystallization is reacted with the organic aluminum compound.
(2) A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method 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.

The aluminoxane may contain a small amount of an organometallic component. Further, the solvent or unreacted organoaluminum compound may be distilled and removed from the recovered solution of aluminoxane, and then redissolved in the solvent or suspended in a poor solvent of aluminoxane.

Specific examples of the organoaluminum compound used when preparing alminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to (b-1a) above.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum and triisobutylaluminum are particularly preferable.
The above-mentioned organoaluminum compounds are used alone or in combination of two or more.

Further, in the benzene-insoluble organoaluminum oxy compound which is one aspect of the (b-2) organoaluminum oxy compound used in the present invention, the Al component dissolved in benzene at 60 ° C. is based on 100% by weight of benzene in terms of Al atom. Usually, it is 10% by weight or less, preferably 5% by weight or less, particularly preferably 2% by weight or less, that is, one which is insoluble or sparingly soluble in benzene is preferable.

As the (b-2) organoaluminum oxy compound used in the present invention, an organoaluminum oxy compound containing boron represented by the following general formula [X] can also be mentioned.

〔式［Ｘ］中、Ｒ¹は炭素数が１〜１０の炭化水素基を示し、Ｒ²〜Ｒ⁵は、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子、炭素数が１〜１０の炭化水素基を示す。〕

[In the formula [X], R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, and R ^{2 to} R ⁵ may be the same or different from each other, and have a hydrogen atom, a halogen atom, and 1 to 10 carbon atoms. It shows 10 hydrocarbon groups. ]

The organoaluminum oxy compound containing boron represented by the general formula [X] includes alkylboronic acid represented by the following general formula [XI] and
R ¹ −B (OH) ₂ … [XI]
(In the formula [XI], R ¹ represents the same group as ^{R 1} in the general formula [X].)
It can be produced by reacting the organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.

Specific 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, and n-hexylboronic acid. Acids, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like can be mentioned.

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

Specific examples of the organoaluminum compound to be reacted with such alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to (b-1a).

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more. The above-mentioned (b-2) organoaluminum oxy compound is used alone or in combination of two or more.

<Compound that reacts with (b-3) transition metal compound (a) to form an ion pair>
Examples of the compound (b-3) (hereinafter, referred to as “ionized ionic compound”) that reacts with the crosslinked metallocene compound (a) to form an ion pair include JP-A-1-501950 and JP-A-1-502306. Luisic acid and ionic compounds described in JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106 and the like. , Bolan compounds and carborane compounds and the like. Further, heteropoly compounds and isopoly compounds can also be mentioned. Such an ionized ionic compound (b-3) is used alone or in combination of two or more.

Specifically, examples of the Lewis acid include compounds represented by BR ₃ (R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group, trifluoromethyl group). For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris ( Examples thereof include p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.
Examples of the ionic compound include compounds represented by the following general formula [XII].

（式［ＸＩＩ］中、Ｒ¹⁺としては、Ｈ⁺、カルボニウムカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンなどが挙げられる。Ｒ²〜Ｒ⁵は、互いに同一でも異なっていてもよく、有機基、好ましくはアリール基または置換アリール基である。）

(In the formula [XII], ^examples of R 1+ include H ⁺ , carbonium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptyrienyl cations, and ferrosenium cations having transition metals. ^{2 to} R ⁵ may be the same or different from each other and are an organic group, preferably an aryl group or a substituted aryl group.)

Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenyl carbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

Specifically, the ammonium cation is a trialkylammonium cation such as a trimethylammonium cation, a triethylammonium cation, a tripropylammonium cation, a tributylammonium cation, or a tri (n-butyl) ammonium cation;
N, N-dialkylanilinium cations such as N, N-dimethylanilinium cations, N, N-diethylanilinium cations, N, N, 2,4,6-pentamethylanilinium cations;
Examples thereof include dialkylammonium cations such as di (isopropyl) ammonium cations and dicyclohexylammonium cations.

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

As R ¹⁺ , carbonium cations, ammonium cations and the like are preferable, and triphenylcarbonium cations, N, N-dimethylanilinium cations and N, N-diethylanilinium cations are particularly preferable.

Further, as the ionic compound, a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, a dialkylammonium salt, a triarylphosphonium salt and the like can also be mentioned.

Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl). Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra ( N, N-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenyl) boron, tri (n) -Butyl) ammonium tetra (o-tolyl) boron and the like can be mentioned.

Specifically, as the N, N-dialkylanilinium salt, for example, N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N, 2,4,6 -Pentamethylanilinium tetra (phenyl) boron and the like.

Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrosenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Cyclopentadienyl complex, N, N-diethylanilinium pentaphenylcyclopentadienyl complex, boron compound represented by the following formula [XIII] or [XIV], and the like can also be mentioned.

（式中、Ｅｔはエチル基を示す。）

(In the formula, Et represents an ethyl group.)

（式中、Ｅｔはエチル基を示す。）

(In the formula, Et represents an ethyl group.)

Specifically, as a borane compound, for example, decaborane;
Bis [tri (n-butyl) ammonium] nonabolate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate , Anionic salts such as bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachloro dodecaborate;
Metal borane anions such as tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III) Examples include salt.

Specific examples of the carborane compound include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecabolan, dodecahydride-1-phenyl-1,3-dicarbanonaborane, and dodecahydride-. 1-Methyl-1,3-dicarbanonaborane, Undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecabolane, 2,7-dicarbundecabolane, Undeca Hydlide-7,8-dimethyl-7,8-dicarbaundecabolan, dodecahydride-11-methyl-2,7-dicarbaundecabolan, tri (n-butyl) ammonium 1-carbadecabolate, tri ( n-Butyl) ammonium-1-carbundecaborate, tri (n-butyl) ammonium-1-carbadodecaborate, tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaboleate, tri (n-butyl) ) Ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium-6-carbadecabolate, tri (n-butyl) ammonium-7-carbundecaborate, tri (n-butyl) ammonium-7,8 -Dicarbundecaborate, tri (n-butyl) ammonium-2,9-dicarbundecaborate, tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbundecaborate, tri (n-) Butyl) ammonium undecahydride-8-ethyl-7,9-dicarbundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) Ammonium undecahydride-8-allyl-7,9-dicarbundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecarbolate, tri (n-butyl) ammonium unde Anion salts such as decahydride-4,6-dibromo-7-carbundecaborate; tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonabolate) cobaltate (III), tri. (N-Butyl) Ammonite Bis (Undeca Hydlide-7,8-Dicarba Undecaborate) Telate (III), Tri (n-Butyl) Ammonium Bis (Undeca Hydride-7,8-Dicarba Undecaborate) Ko Baltoate (III), Tri (n-Butyl) Ammonium Bis (Undeca Hydride-7,8-Dicarba Undecaborate) Nickate (III), Tri (n-Butyl) Ammonium Bis (Undeca Hydride-7) , 8-Dicarbaundecaborate) Copper acid salt (III), Tri (n-butyl) ammonium bis (Undecahydride-7,8-dicarbaundecaborate) Hydrochloride (III), Tri (n-butyl) Ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbundecaborate) iron acid salt (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-) Dicarbaundecaborate) Chromate (III), Tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbundecaborate) Cobalate (III), Tris [tri (n-butyl) Ammonium] Bis (Undeca Hydlide-7-Carbaundecaborate) Chromate (III), Bis [Tri (n-butyl) Ammonium] Bis (Undeca Hydride-7-Carbaundecaborate) Manganate (IV) ), Bis [tri (n-butyl) ammonium] bis (Undecahydride-7-carbaundecarbolate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (Undecahydride-7-) Examples include salts of metal carborane anions such as carboundecaborate) nickelate (IV).

Heteropoly compounds consist of atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphobanadic acid, germanovanadic acid, arsenic vanadic acid, linniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungsonic acid, germanotungsic acid, tin tungsic acid, phosphomolybed vanadic acid, lintangstovanadic acid, germanotangstovanadic acid, lysmolybed tonguestovanadic acid, germanomolybdo tonguestovanadic acid, phosphomolybed tungstate , Phosphomolybdoniobic acid, and salts of these acids, such as Periodic Table Group 1 or Group 2 metals, specifically lithium, sodium, potassium, rubidium, cesium, berylium, magnesium, calcium, strontium, barium. , And organic salts such as triphenylethyl salt can be used, but this is not the case.

(B-3) Among the ionized ionic compounds, the above-mentioned ionic compounds are preferable, and among them, triphenylcarbenium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are used. More preferred.

(B-3) Ionized Ionic compounds are used alone or in combination of two or more.
When the transition metal compound (a) represented by the general formula [I] is used as a catalyst, an organometallic compound (b-1) such as triisobutylaluminum, an organoaluminum oxy compound (b-2) such as methylaluminoxane, or When used in combination with an ionized ionic compound (b-3) such as triphenylcarbenium tetrakis (pentafluorophenyl) borate, it exhibits extremely high polymerization activity in the production of ethylene / α-olefin / non-conjugated polyene copolymers.

The catalyst for olefin polymerization is selected from the transition metal compound (a), (b-1) organometallic compound, (b-2) organoaluminum oxy compound, and (b-3) ionized ionic compound. The carrier (c) can also be used, if necessary, together with at least one compound (b).

<(C) Carrier>
In the present invention, the carrier (c) used as needed is an inorganic compound or an organic compound, and is a solid in the form of granules or fine particles.

Of these, as the inorganic compound, a porous oxide, an inorganic halide, clay, a clay mineral or an ion-exchange layered compound is preferable.
As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _2, etc., or a composite or a mixture containing these is used. For example, natural or synthetic zeolite, SiO _2- MgO, SiO _2- Al ₂ O ₃ , SiO _2- TiO ₂ , SiO _2- V ₂ O ₅ , SiO _2- Cr ₂ O ₃ , SiO _2- TiO _2- MgO, etc. Can be used. Of these, those _{containing SiO 2} and / or Al ₂ O ₃ as main components are preferable. Although the properties of such a porous oxide differ depending on the type and production method, the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m. It is desirable that ^{the pore volume is in the range of 2} / g, preferably 100 to 700 m ² / g, and the pore volume is in ^{the range of 0.3 to 3.0 cm 3 / g.} Such a carrier is used by firing at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr _{2 and the} like are used. The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a product obtained by dissolving an inorganic halide in a solvent such as alcohol and then precipitating it in the form of fine particles with a precipitant. Clay is usually composed mainly of clay minerals. Further, the ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak bonding force, and the contained ions can be exchanged. Most clay minerals are ion-exchange layered compounds. Further, as these clays, clay minerals, and ion-exchange layered compounds, not only naturally produced ones but also artificial synthetic compounds can be used.

Further, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as _{hexagonal fine packing type, antimony type, CdCl 2} type and CdI _{2 type can be used.} It can be exemplified. Such clays and clay minerals include kaolin, bentonite, knot clay, gailome clay, alophen, hisingel stone, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokudei stone group, parigolskite, kaolinite, nacrite, and dicite. , and the like halloysite, the ion-exchange layered _{compounds, α-Zr (HAsO 4)} 2 · H 2 O, α-Zr (HPO 4) 2, α-Zr (KPO 4) 2 · 3H 2 O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO ₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄₎ ) ₂ , γ-Ti (NH ₄ PO ₄ ) ₂ · H ₂ O and other crystalline acidic salts of polyvalent metals.

Such clays, clay minerals or ion-exchange layered compounds preferably have a pore volume of 0.1 cc / g or more with a radius of 20 Å or more measured by a mercury intrusion method, preferably 0.3 to 5 cc / g. Especially preferable. Here, the pore volume is measured in the range of a pore radius of 20 to 30,000 Å by a mercury intrusion method using a mercury porosimeter.

When a carrier having a radius of 20 Å or more and a pore volume smaller than 0.1 cc / g is used as a carrier, it tends to be difficult to obtain high polymerization activity.
It is also preferable to chemically treat clay and clay minerals. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment removes impurities on the surface and increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkaline treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. Further, in the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative and the like can be formed, and the surface area and the interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in a state in which the layers are expanded by utilizing the ion-exchange property and exchanging the exchangeable ions between the layers with another large bulky ion. Such bulky ions play a supporting role in supporting the layered structure, and are usually called pillars. Further, the introduction of another substance between the layers of the layered compound in this way is called intercalation. Guest compounds to be intercalated include cationic inorganic compounds such as _{TiCl 4} , ZrCl _4, and metal alkoxides such as _{Ti (OR) 4} , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) _3. R is a hydrocarbon group, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ and other metal hydroxide ions And so on. These compounds are used alone or in combination of two or more. Further, when these compounds were intercalated, they were _{obtained by hydrolyzing metal alkoxides such as Si (OR) 4} , Al (OR) ₃ , and Ge (OR) ₄ (R is a hydrocarbon group or the like). Polymers, colloidal inorganic compounds such as _{SiO 2 can coexist.} In addition, examples of pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then heating and dehydrating them.

Clays, clay minerals, and ion-exchange layered compounds may be used as they are, or may be used after treatments such as ball milling and sieving. Further, it may be used after newly adding and adsorbing water or heat dehydration treatment. Further, it may be used alone or in combination of two or more.

Of these, preferred are clays or clay minerals, with particular preference being montmorillonite, vermiculite, hectorite, teniolite and synthetic mica.
Examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specifically, a (co) polymer or vinylcyclohexane or styrene produced mainly of an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene can be used. Examples thereof include (co) polymers produced as main components and variants thereof.

The olefin polymerization catalyst used in the present invention is composed of a crosslinked metallocene compound (a), (b-1) an organometallic compound, (b-2) an organoaluminum oxy compound, and (b-3) an ionized ionic compound. It can also include at least one compound (b) of choice and a carrier (c) used as needed.

<Method of polymerizing monomers in the presence of a catalyst for ethylene / α-olefin / non-conjugated polyene copolymer>
When copolymerizing ethylene, α-olefin, and non-conjugated polyene, the usage and the order of addition of each component constituting the polymerization catalyst are arbitrarily selected, and the following methods are exemplified.
(1) A method of adding the compound (a) alone to a polymerizer.
(2) A method of adding the compound (a) and the compound (b) to a polymerizer in an arbitrary order.
(3) A method of adding the catalyst component in which the compound (a) is supported on the carrier (c) and the compound (b) to the polymerizer in an arbitrary order.
(4) A method of adding the catalyst component in which the compound (b) is supported on the carrier (c) and the compound (a) to the polymerizer in an arbitrary order.
(5) A method of adding a catalyst component in which the compound (a) and the compound (b) are supported on the carrier (c) to a polymerizer.

In each of the above methods (2) to (5), at least two of the 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 compound (b) in which the compound (b) is not supported may be added in any order, if necessary. In this case, the compound (b) may be the same as or different from the compound (b) supported on the carrier (c).

Further, in the solid catalyst component in which the compound (a) is supported on the carrier (c) and the solid catalyst component in which the compound (a) and the compound (b) are supported on the carrier (c), olefins are prepolymerized. Alternatively, the catalyst component may be further supported on the prepolymerized solid catalyst component.

In the method for producing an ethylene / α-olefin / non-conjugated polyene copolymer, ethylene, α-olefin, and non-conjugated polyene are present in the presence of the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer catalyst. Ethylene / α-olefin / non-conjugated polyene copolymer can be produced by copolymerizing the above.

In the present invention, it can be carried out by any of a liquid phase polymerization method such as solution (dissolution) polymerization and suspension polymerization, or a gas phase polymerization method.
Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, cyclopentane, cyclohexane, and methylcyclopentane. Aliphatic hydrocarbons such as benzene, toluene, xylene and other aromatic hydrocarbons, ethylene chloride, chlorobenzene, dichloromethane and other halogenated hydrocarbons, and may be used alone or in combination of two or more. Can be done. Moreover, the olefin itself can also be used as a solvent.

When polymerizing ethylene or the like using the above-mentioned copolymer catalyst, the compound (a) is usually 10 ^-12 to ^10-2 mol, preferably 10 ^-10 to 10 per liter of reaction volume. It is used in an amount such that it becomes ^{-8 mol.}

Compound (b-1) usually has a molar ratio [(b-1) / M] of compound (b-1) to all transition metal atoms (M) in compound (a) of 0.01 to 50,000. It is preferably used in an amount such that it is 0.05 to 10000. The molar ratio [(b-2) / M] of the aluminum atom in the compound (b-2) to the total transition metal (M) in the compound (a) is usually 10 to 10 in the compound (b-2). It is used in an amount such that it is 50,000, preferably 20,000 to 10,000. The molar ratio [(b-3) / M] of the compound (b-3) to the transition metal atom (M) in the compound (a) is usually 1 to 20, preferably 1 to 20. It is used in an amount such that it becomes 1 to 15.

The polymerization temperature of ethylene or the like using such a copolymer catalyst is usually in the range of −50 to + 200 ° C., preferably in the range of 0 to + 200 ° C., more preferably in the range of + 80 to + 200 ° C., and is used together. Although it depends on the reached molecular weight and polymerization activity of the polymer catalyst system, it is desirable from the viewpoint of productivity that the temperature is higher (+ 80 ° C. or higher).

The polymerization pressure is usually under normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out by any of batch type, semi-continuous type and continuous type. Further, it is also possible to carry out the polymerization in two or more stages having different reaction conditions.

The molecular weight of the obtained ethylene-based copolymer A can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can be adjusted according to the amount of compound (b) used. Specific examples thereof include triisobutylaluminum, methylaluminoxane, and diethylzinc. When hydrogen is added, the amount thereof is appropriately about 0.001 to 100 NL per 1 kg of olefin.

<< Other ingredients >>
The anti-vibration rubber composition of the present invention contains the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer (ethylene-based copolymer A), and preferably contains a cross-linking agent as another component. ..

Further, the anti-vibration rubber composition of the present invention contains other additives such as a cross-linking aid, a vulcanization accelerator, a vulcanization aid, a softening agent, a reinforcing agent, an antiaging agent, and an inorganic filling, depending on the purpose. Agents, processing aids, activators, hygroscopic agents, heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, colorants, lubricants, thickeners, foaming agents, foaming aids and polymers other than ethylene-based copolymer A ( It may contain at least one selected from (other polymers). Also. Each additive may be used alone or in combination of two or more.

For the anti-vibration rubber according to the present invention, the ethylene-based copolymer A and other components to be blended as needed are kneaded at a desired temperature using, for example, a kneader such as a mixer, a kneader, or a roll. Can be prepared by Since the ethylene-based copolymer A has excellent kneadability, the anti-vibration rubber composition can be satisfactorily prepared.

Specifically, using a conventionally known kneader such as a mixer or a kneader, the ethylene-based copolymer A and, if necessary, other components are mixed at a predetermined temperature and time, for example, 80 to 200 ° C. for 3 to 30 minutes. After kneading, other components used as needed, such as a cross-linking agent, are added to the obtained kneaded product, and a roll is used at a predetermined temperature and time, for example, at a roll temperature of 30 to 80 ° C. By kneading for ~ 30 minutes, the anti-vibration rubber composition of the present invention can be prepared.

<Crosslinking agent, crosslinking aid, vulcanization accelerator and vulcanization aid>
Examples of the cross-linking agent include rubbers such as organic peroxides, phenol resins, sulfur compounds, hydrosilicone compounds, amino resins, quinone or derivatives thereof, amine compounds, azo compounds, epoxy compounds and isocyanate compounds. Examples thereof include cross-linking agents generally used for cross-linking. Of these, organic peroxides and sulfur compounds (hereinafter also referred to as "vulcanizing agents") are suitable.

Examples of the organic peroxide include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-di- (tert-butylperoxy) hexane, and 2,5-dimethyl-2,5-di-(. tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexin-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- Examples thereof include butylperoxybenzoate, ert-butylperoxyisopropyl carbonate, diacetylperoxide, lauroyl peroxide and tert-butylcumyl peroxide.

When an organic peroxide is used as the cross-linking agent, the amount thereof in the anti-vibration rubber composition is generally 0.1 to 20 parts by mass, preferably 0.% by mass, based on 100 parts by mass of the ethylene-based copolymer A. It is 2 to 15 parts by mass, more preferably 0.5 to 10 parts by mass. When the blending amount of the organic peroxide is within the above range, there is no bloom on the surface of the obtained anti-vibration rubber, and the anti-vibration rubber composition exhibits excellent cross-linking properties, which is preferable.

When an organic peroxide is used as the cross-linking agent, it is preferable to use a cross-linking aid in combination. Examples of the cross-linking aid include sulfur; a quinone-dioxym-based cross-linking aid such as p-quinone dioxime; an acrylic cross-linking aid such as ethylene glycol dimethacrylate and trimethylolpropantrimethacrylate; diallyl phthalate and triallyl isocyanurate. Allyl-based cross-linking aids such as; Maleimide-based cross-linking aids; Divinylbenzene; Zinc oxide (for example, ZnO # 1 and zinc oxide 2 types (JIS standard (K-1410)), manufactured by Huxitec Co., Ltd.), magnesium oxide, etc. Examples thereof include metal oxides such as zinc oxide (for example, zinc oxide such as "META-Z102" (trade name; manufactured by Inoue Lime Industry Co., Ltd.)).

When a cross-linking aid is used, the blending amount of the cross-linking aid in the anti-vibration rubber composition is usually 0.5 to 10 mol, preferably 0.5 to 7 mol, based on 1 mol of the organic peroxide. More preferably, it is 1 to 6 mol.

Examples of the sulfur-based compound (sulfurizing agent) include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate.

When a sulfur-based compound is used as the cross-linking agent, the amount thereof in the anti-vibration rubber composition is usually 0.1 to 10 parts by mass, preferably 0.12, based on 100 parts by mass of the ethylene-based copolymer A. It is ~ 7.0 parts by mass, more preferably 0.15 to 5.0 parts by mass. When the blending amount of the sulfur-based compound is within the above range, there is no bloom on the surface of the obtained anti-vibration rubber, and the anti-vibration rubber composition exhibits excellent cross-linking properties.

When a sulfur-based compound is used as the cross-linking agent, it is preferable to use a vulcanization accelerator in combination.
Examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, N, N'-diisopropyl-2-benzothiazolesulfenamide, 2 -Mercaptobenzothiazole (for example, Sunseller M (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), 2- (4-morpholinodithio) penzothiazole (for example, Noxeller MDB-P (trade name; manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)) (Manufactured by)), 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole and dibenzothiazyldisulfide (for example, Sunseller DM (trade name; 3) (Shinkagaku Kogyo Co., Ltd.)) and other thiazole-based vulcanization accelerators; guanidine-based vulcanization accelerators such as diphenylguanidine, triphenylguanidine and diorsotrilguanidine; acetaldehyde / aniline condensate and butylaldehyde / aniline condensate, etc. Sulfenamide-based vulcanization accelerator; imidazoline-based vulcanization accelerator such as 2-mercaptoimidazolin; tetramethylthium monosulfide (for example, Sunseller TS (trade name: manufactured by Sanshin Chemical Industry Co., Ltd.)), tetramethylthiuram disulfide (for example) , Suncella TT (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.), tetraethylthiuram disulfide (for example, Suncella TET (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), tetrabutyltiuram disulfide (for example, Suncella TBT (trade name; (Sanshin Chemical Industry Co., Ltd.)) and dipentamethylene thiuram tetrasulfide (for example, Sunseller TRA (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)) and other thiuram-based vulcanization accelerators; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate , Zinc dibutyldithiocarbamate (eg, Sunseller PZ, Sunseller BZ and Sunseller EZ (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)) and dithioate-based vulcanization accelerators such as telluryl diethyldithiocarbamate; ethylenethiourea (eg, Sunseller). BUR (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.), Sunseller 22-C (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), N, N'-diethylthiourea and N, N'-dibutylthiourea and other thiourea-based additions Sulfenamide accelerators; examples include zantate-based vulcanization accelerators such as zinc dibutylxatogenate.

When a vulcanization accelerator is used, the blending amount of these vulcanization accelerators in the anti-vibration rubber composition is generally 0.1 to 20 parts by mass, preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the ethylene-based copolymer A. It is 0.2 to 15 parts by mass, more preferably 0.5 to 10 parts by mass. When the blending amount of the vulcanization accelerator is within the above range, the anti-vibration rubber composition exhibits excellent cross-linking characteristics without blooming on the surface of the obtained anti-vibration rubber.

When a sulfur-based compound is used as the cross-linking agent, a vulcanization aid can be used in combination.
Examples of the vulcanization aid include zinc oxide (for example, ZnO # 1 and zinc oxide 2 types, manufactured by Huxitec Co., Ltd.), magnesium oxide, and zinc oxide (for example, "META-Z102" (trade name; Inoue Lime Industry). Zinc oxide) such as (manufactured by Co., Ltd.).
When a vulcanization aid is used, the blending amount of the vulcanization aid in the anti-vibration rubber composition is usually 1 to 20 parts by mass with respect to 100 parts by mass of the ethylene-based copolymer A.

<Softener>
Examples of the softening agent include petroleum-based softening agents such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and vaseline; Fatty oil-based softeners such as soybean oil and palm oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin or derivatives thereof; synthetic polymer substances such as terpene resin, petroleum resin and kumaron inden resin; dioctyl Ester-based softeners such as phthalate and dioctyl adipate; other examples include microcrystallin wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oil, tall oil, and sub (factis), among which petroleum-based softening. Agents are preferred, process oils are particularly preferred. Examples of the process oil include paraffin-based process oils (for example, "Diana Process Oil PW-380" (trade name; manufactured by Idemitsu Kosan Co., Ltd.)).

When the anti-vibration rubber composition contains a softening agent, the blending amount of the softening agent is generally 2 to 100 parts by mass, preferably 10 to 100 parts by mass with respect to 100 parts by mass of the ethylene copolymer A. is there.

<Reinforcing agent>
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, and differential silicic acid.

As the carbon black, for example, carbon such as SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, MT can be used. Examples of carbon black include the trade names of Tokai Carbon Co., Ltd., Seest GV, Seest G-SVH, Seest G-116, Seest G-SO, Seest G-S, Seest G-FY, and Seest G-TA. ..

Examples of silica include fumes silica, precipitated silica and the like. These silicas may be surface-treated with a reactive silane such as mercaptosilane, aminosilane, hexamethyldisilazane, chlorosilane, alkoxysilane, or a low molecular weight siloxane.

When the anti-vibration rubber composition contains a reinforcing agent, the amount of the reinforcing agent to be blended is generally 5 to 150 parts by mass, preferably 5 to 100 parts by mass with respect to 100 parts by mass of the ethylene-based copolymer A. is there.

<Anti-aging agent (stabilizer)>
By adding an anti-aging agent (stabilizer) to the anti-vibration rubber composition of the present invention, the life of the anti-vibration rubber to be formed can be extended. Examples of such an anti-aging agent include conventionally known anti-aging agents such as amine-based anti-aging agents, phenol-based anti-aging agents, and sulfur-based anti-aging agents.

Examples of the anti-aging agent include aromatics such as phenylbutylamine and N, N'-di-2-naphthyl-p-phenylenediamine (for example, Nocrack White (trade name; manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.)). Second amine anti-aging agent; phenol-based anti-aging agent such as dibutylhydroxytoluene, tetrakis [methylene (3,5-di-t-butyl-4-hydroxy) hydrocinnamate] methane; bis [2-methyl-4 -(3-n-alkylthiopropionyloxy) -5-t-butylphenyl] thioether-based anti-aging agents such as sulfide; dithiocarbamate-based anti-aging agents such as nickel dibutyldithiocarbamate; 2-mercaptobenzoylimidazole, 2-mercapto Sulfur-based benzoimidazole (for example, "Sandant MB" (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), zinc salt of 2-mercaptobenzoimidazole, dilaurylthiodipropionate, distearylthiodipropionate, etc. There are anti-aging agents and the like.

When the anti-vibration rubber composition contains an anti-aging agent, the blending amount of the anti-aging agent is usually 0.3 to 10 parts by mass, preferably 0 with respect to 100 parts by mass of the ethylene-based copolymer A. It is .5-7.0 parts by mass. When the blending amount of the antiaging agent is within the above range, there is no bloom on the surface of the obtained anti-vibration rubber, and the occurrence of vulcanization inhibition can be further suppressed.

<Inorganic filler>
Examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc, clay, etc. Among these, heavy calcium carbonate such as "Whiten SB" (trade name; Shiraishi Calcium Co., Ltd.) Is preferable.

When the anti-vibration rubber composition contains an inorganic filler, the blending amount of the inorganic filler is usually 2 to 50 parts by mass, preferably 5 to 50 parts by mass with respect to 100 parts by mass of the ethylene-based copolymer A. It is 50 parts by mass. When the blending amount of the inorganic filler is within the above range, the kneading processability of the anti-vibration rubber composition is excellent, and the anti-vibration rubber having excellent mechanical properties can be obtained.

<Processing aid>
As the processing aid, for example, those generally blended in rubber as a processing aid can be widely used.

Specific examples of the processing aid include fatty acids such as ricinoleic acid, stearic acid, palmitic acid and lauric acid, fatty acid salts such as barium stearate, zinc stearate and calcium stearate, and esters. Of these, stearic acid is preferred.

When the anti-vibration rubber composition contains a processing aid, the blending amount of the processing aid is usually 10 parts by mass or less, preferably 8.0 parts by mass, based on 100 parts by mass of the ethylene-based copolymer A. It is as follows.

<Activator>
Activators include, for example, amines such as di-n-butylamine, dicyclohexylamine, monoeranolamine; zinc compounds of diethylene glycol, polyethylene glycol, lecithin, trialilute melilate, aliphatic carboxylic acid or aromatic carboxylic acid. Activators; Zinc peroxide modifiers; Cutadecyltrimethylammonium bromide, synthetic hydrotalcites, special quaternary ammonium compounds. Examples of polyethylene glycol include PEG # 4000, which is a trade name manufactured by Lion Corporation.

When the anti-vibration rubber composition contains an activator, the amount of the activator blended is usually 0.2 to 10 parts by mass, preferably 0.3, based on 100 parts by mass of the ethylene-based copolymer A. ~ 5 parts by mass.

<Hydraulic agent>
Examples of the hygroscopic agent include calcium oxide, silica gel, sodium sulfate, molecular sieve, zeolite, and white carbon.

When the anti-vibration rubber composition contains a hygroscopic agent, the blending amount of the hygroscopic agent is usually 0.5 to 15 parts by mass, preferably 1. It is 0 to 12 parts by mass.

<Blowing agent and foaming aid>
The anti-vibration rubber formed by using the anti-vibration rubber composition of the present invention may be a non-foamed material or a foamed material. When the anti-vibration rubber is a foam, it is preferable that the anti-vibration rubber composition contains a foaming agent.

As the foaming agent, any commercially available foaming agent is preferably used. Examples of such foaming agents include inorganic foaming agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, and ammonium nitrite; N, N'-dinitrosoterephthalamide, N, N'-dinitroso. Nitroso compounds such as pentamethylenetetramine; azo compounds such as azodicarboxylicamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonylhydrazide, toluenesulfonylhydrazide, p, p'- Oxybis (benzenesulfonylhydrazide) Sulfonylhydrazide compounds such as diphenylsulphon-3,3'-disulfonylhydrazide; azide compounds such as calcium azide, 4,4'-diphenyldisulfonyl azide and paratoluenemalhonyl azide can be mentioned. Of these, azo compounds, sulfonyl hydrazide compounds, and azide compounds are preferably used.

When the anti-vibration rubber composition contains a foaming agent, the blending amount of the foaming agent is appropriately selected depending on the performance required for the anti-vibration rubber produced from the anti-vibration rubber composition, but ethylene is used. It is usually used in a ratio of 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass with respect to 100 parts by mass of the system copolymer A.

Further, if necessary, a foaming aid may be used in combination with the foaming agent. The addition of the foaming aid is effective in controlling the decomposition temperature of the foaming agent and homogenizing the bubbles. Specific examples of the foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid and oxalic acid, urea and its derivatives.

When the anti-vibration rubber composition contains a foaming aid, the blending amount of the foaming aid is usually 1 to 100 parts by mass, preferably 2 to 80 parts by mass with respect to 100 parts by mass of the foaming agent. Used in proportion.

<Other polymers>
The anti-vibration rubber composition of the present invention may contain other polymers in addition to the ethylene-based copolymer A. Other polymers that need to be crosslinked include, for example, natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, acrylic rubber, silicone rubber, fluororubber, urethane rubber and other crosslinkable rubbers. Can be mentioned. Other polymers that do not require cross-linking include, for example, block copolymers of styrene and butadiene (SBS), polystyrene-poly (ethylene-butylene) -polystyrene (SEBS), polystyrene-poly (ethylene-propylene) -polystyrene ( Sstyrene-based thermoplastic elastomer (TPS) such as SEPS), olefin-based thermoplastic elastomer (TPO), vinyl chloride-based elastomer (TPVC), ester-based thermoplastic elastomer (TPC), amide-based thermoplastic elastomer (TPA), urethane-based heat Examples thereof include elastomers such as plastic elastomer (TPU) and other thermoplastic elastomers (TPZ). When another polymer is used, it can be blended in an amount of usually 100 parts by mass or less, preferably 80 parts by mass or less, based on 100 parts by mass of the ethylene-based copolymer A.

[Vibration-proof rubber]
The anti-vibration rubber of the present invention is formed by using the above-mentioned anti-vibration rubber composition.
As a method for producing an anti-vibration rubber from the anti-vibration rubber composition of the present invention, for example, the anti-vibration rubber composition is molded into a desired anti-vibration rubber shape, and at the same time as or after the molding, the above-mentioned Examples thereof include a method of cross-linking the composition.

The ethylene / α-olefin / non-conjugated polyene copolymer used in the present invention has a glass transition temperature (Tg) of −70 to −50 ° C. as measured by differential scanning calorimetry (DSC). By using an ethylene / α-olefin / non-conjugated polyene copolymer having a glass transition temperature within the above range, the anti-vibration rubber formed by using the anti-vibration rubber composition of the present invention has a constant temperature range. Specifically, the change in the static spring constant (Ks) from −20 ° C. to 120 ° C. is linear. Therefore, the anti-vibration rubber composition of the present invention makes it easy to predict the anti-vibration characteristics (dynamic magnification) of the obtained anti-vibration rubber in a certain temperature range, and the anti-vibration rubber according to the desired physical properties of the anti-vibration rubber. The rubber composition is easy to design and is preferable.

Examples of the method of cross-linking treatment include a method of cross-linking by heating a composition containing a cross-linking agent as a composition for anti-vibration rubber, and a method of cross-linking the composition for anti-vibration rubber by irradiating an electron beam. There is a method of processing.

That is, the anti-vibration rubber of the present invention is formed by molding a composition for anti-vibration rubber into an intended shape using a molding machine such as an extrusion molding machine, a calendar roll, a press, an injection molding machine, or a transfer molding machine. At the same time, or by introducing the molded product into a vulcanization tank and heating it at 120 to 270 ° C. for 1 to 30 minutes, or by cross-linking by irradiating an electron beam, it can be prepared.

A mold may be used for the cross-linking, or the cross-linking may be carried out without using the mold. When a mold is not used, the molding and cross-linking steps are usually carried out continuously. As a heating method in the vulcanization tank, means such as hot air, a fluidized bed of glass beads, UHF (ultra high frequency electromagnetic wave), and steam can be used.

When an electron beam is used as the cross-linking method without using a cross-linking agent, an energy of usually 0.1 to 10 MeV, preferably 0.3 to 2 MeV is applied to the anti-vibration rubber composition formed into a predetermined shape. The electron beam may be irradiated so that the absorbed dose is usually 0.5 to 35 Mrad, preferably 0.5 to 10 Mrad.

The vibration-proof rubber of the present invention can be suitably used as a vibration-proof rubber for automobiles, a vibration-proof rubber for machinery, a vibration-proof rubber for electronic / electrical parts, a vibration-proof rubber for construction, and a vibration-proof rubber for civil engineering and building materials. ..
Specific examples of the anti-vibration rubber of the present invention include a muffler hanger, a torsional damper, a change lever mount, a torsion rubber for a clutch, a centering bush, a tube damper, a torque bush, a suspension bush and an engine mount.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the following examples and the like, "parts" means "parts by mass" unless otherwise specified.

<< Ethylene / α-olefin / non-conjugated polyene copolymer >>
[Glass transition temperature (Tg)]
The glass transition temperature (Tg) of the ethylene / α-olefin / non-conjugated polyene copolymer was determined by DSC measurement under the following conditions.

Using a differential scanning calorimeter [SII RDC220], a sample of about 10 mg was heated from 30 ° C. to 200 ° C. at a heating rate of 50 ° C./min under a nitrogen atmosphere, and held at that temperature for 10 minutes. Further, the temperature was cooled to −100 ° C. at a temperature lowering rate of 10 ° C./min, held at that temperature for 5 minutes, and then raised to 200 ° C. at a temperature rising rate of 10 ° C./min.

The glass transition temperature (Tg) is perceived as the DSC curve bends due to the change in specific heat and the baseline moves in parallel during the second temperature rise. The temperature at the intersection of the tangent of the baseline, which is lower than this bending, and the tangent of the point where the inclination is maximum at the bending portion is defined as the glass transition temperature (Tg).

[Molar quantity of each structural unit]
The molar amount of the structural unit derived from ethylene [A], the structural unit derived from α-olefin [B], and the structural unit derived from the non-conjugated polyene [C] of the ethylene / α-olefin / non-conjugated polyene copolymer is , ¹ Obtained by intensity measurement with an H-NMR spectrum meter.

[Moony Viscosity]
_{The Mooney viscosity ML (1 + 4)} 125 ° C. of the ethylene / α-olefin / non-conjugated polyene copolymer was measured according to JIS K6300 (1994) using a Mooney viscosity meter (SMV202 type manufactured by Shimadzu Corporation). ..

[B value]
Using o-dichlorobenzene-d ₄ / benzene-d ₆ (4/1 [v / v]) as the measurement solvent, at a measurement temperature of 120 ° C., ¹³ C- of an ethylene / α-olefin / non-conjugated polyene copolymer. The NMR spectrum (100 MHz, ECX400P manufactured by JEOL Ltd.) was measured, and the B value was calculated based on the following formula (i).
B value = ([EX] + 2 [Y]) / [2 x [E] x ([X] + [Y])] ... (i)
Here, [E], [X] and [Y] indicate the mole fractions of ethylene [A], α-olefin [B] having 4 to 20 carbon atoms and unconjugated polyene [C], respectively, and [EX]. ] Indicates the ethylene [A] -alpha-olefin [B] diad chain fraction having 4 to 20 carbon atoms.

The glass transition temperature, the molar amount of each structural unit, the Mooney viscosity ML _{(1 + 4)} 125 ° C., and the B value are all obtained in the synthetic example described later, which are ethylene, α-olefin, and non-ethylene before oil expansion. The conjugated polyene copolymer was measured.

[Synthesis of transition metal compounds]
[Bis (4-methoxyphenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)} Synthesis of hafnium dichloride (catalyst -a1) (i) 6 , 6-Synthesis of 6-bis (4-methoxyphenyl) fulvene 8.28 g (115 mmol) of lithium cyclopentadienyl and 200 ml of dehydrated THF (tetrahydrofuran) were added to a 500 ml three-necked flask under a nitrogen atmosphere. 13.6 g (119 mmol) of DMI (1,3-dimethyl-2-imidazolidinone) was added while cooling in an ice bath, and the mixture was stirred at room temperature for 30 minutes. Then, 25.3 g (105 mol) of 4,4'-dimethoxybenzophenone was added, and the mixture was stirred under heating under reflux for 1 week. While cooling in an ice bath, 100 ml of water was gradually added, 200 ml of dichloromethane was further added, and the mixture was stirred at room temperature for 30 minutes. The resulting two-layer solution was transferred to a 500 ml separatory funnel and the organic layer was washed 3 times with 200 ml of water. After drying over anhydrous magnesium sulfate for 30 minutes, the solvent was distilled off under reduced pressure to obtain an orange-brown solid. Separation was performed by silica gel chromatograph (700 g, hexane: ethyl acetate = 4: 1) to obtain a red solution. The solvent was distilled off under reduced pressure to obtain 9.32 g (32.1 mmol, 30.7%) of 6,6-bis (4-methoxyphenyl) fulvene as an orange solid. Identification of 6,6-bis (4-methoxyphenyl) fulvene was ^{performed by 1} H-NMR spectrum. The measured values are shown below.
^{1 1} H-NMR spectrum (270 MHz, CDCl ₃ ): δ / ppm 7.28-7.23 (m, 4H), 6.92-6.87 (m, 4H), 6.59-6.57 (m) , 2H), 6.30-6.28 (m, 2H), 3.84 (s, 6H)

(Ii) Synthesis of bis (4-methoxyphenyl) (cyclopentadienyl) (2,3,6,7-tetramethylfluorenyl) methane Under a nitrogen atmosphere, 2,3,6,7- in a 100 ml three-mouthed flask 500 mg (2.25 mmol) of tetramethylfluorene and 40 ml of dehydrated t-butyl methyl ether were added. While cooling in an ice bath, 1.45 ml (2.36 mmol) of an n-butyllithium / hexane solution (1.63M) was gradually added, and the mixture was stirred at room temperature for 18 hours. After adding 591 mg (2.03 mmol) of 6,6-bis (4-methoxyphenyl) fulvene, the mixture was heated under reflux for 3 days. 50 ml of water was gradually added while cooling in an ice bath, and the obtained solution was transferred to a 300 ml separatory funnel. After adding 50 ml of dichloromethane and shaking several times, the aqueous layer was separated, and the organic layer was washed 3 times with 50 ml of water. After drying over anhydrous magnesium sulfate for 30 minutes, the solvent was distilled off under reduced pressure. The obtained solid was washed with a small amount of diethyl ether to obtain a white solid. Further, the solvent of the washing liquid was distilled off under reduced pressure, and the obtained solid was washed with a small amount of diethyl ether to collect a white solid, which was combined with the previously obtained white solid. The solid was dried under reduced pressure and 793 mg (1.55 mmol, 76.0%) of bis (4-methoxyphenyl) (cyclopentadienyl) (2,3,6,7-tetramethylfluorenyl) methane was added. Obtained. Identification of bis (4-methoxyphenyl) (cyclopentadienyl) (2,3,6,7-tetramethylfluorenyl) methane was performed on the FD-MS spectrum. The measured values are shown below.
FD-MS spectrum: M / z 512 (M ⁺ )

(Iii) [bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl)
Under nitrogen atmosphere of (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} hafnium dichloride, bis 100ml Schlenk tube (4-methoxyphenyl) (cyclopentadienyl) (2,3,6 , 7-Tetramethylfluorenyl) methane 272 mg (0.531 mmol), dehydrated toluene 20 ml and THF 90 μl (1.1 mmol) were added sequentially. While cooling in an ice bath, 0.68 ml (1.1 mmol) of an n-butyllithium / hexane solution (1.63M) was gradually added, and the mixture was stirred at 45 ° C. for 5 hours to obtain a red solution. The solvent was distilled off under reduced pressure, and 20 ml of dehydrated diethyl ether was added to prepare a red solution again. 164 mg (0.511 mmol) of hafnium tetrachloride was added while cooling in a methanol / dry ice bath, and the mixture was stirred for 16 hours while gradually raising the temperature to room temperature to obtain a yellow slurry. The solid obtained by distilling off the solvent under reduced pressure was brought into a glove box, washed with hexane, and then extracted with dichloromethane. The solvent was distilled off under reduced pressure, and the obtained solid was dissolved in a small amount of dichloromethane, hexane was added, and the solid was recrystallized at −20 ° C. The precipitated solid is collected, washed with hexane, and dried under reduced pressure to give a yellow solid [bis (4-methoxyphenyl) methylene (η ⁵ -cyclopentadienyl) (η 5-2, ^{3, 6).} , 7-Tetramethylfluorenyl)] Hafnium dichloride 275 mg (0.362 mmol, 70.8%) was obtained. [Bis (4-methoxyphenyl) methylene (eta ⁵ - cyclopentadienyl) (eta ^{5-2,3,6,7-tetramethyl-fluorenyl)]} Identification of hafnium dichloride ¹ H-NMR spectrum and FD- The MS spectrum was used. The measured values are shown below.
^{1 1} H-NMR spectrum (270 MHz, CDCl ₃ ): δ / ppm 7.87 (s, 2H), 7.80-7.66 (m, 4H), 6.94-6.83 (m, 4H), 6.24 (t, J = 2.6Hz, 2H), 6.15 (s, 2H), 5.65 (t, J = 2.6Hz, 2H), 3.80 (s, 6H), 2. 47 (s, 6H), 2.05 (s, 6H)
FD-MS spectrum: M / z 760 (M ⁺ )
The chemical formula of the obtained catalyst-a1 is shown below.

[Synthesis Example 1]
A polymerization reaction of ethylene, 1-butene and 5-ethylidene-2-norbornene (ENB) was continuously carried out at 95 ° C. using a polymerizer having a volume of 300 L equipped with a stirring blade.
Using hexane (feed amount: 31 L / h) as the polymerization solvent, the ethylene feed amount was 3.8 kg / h, the 1-butene feed amount was 7 kg / h, the ENB feed amount was 390 g / h, and hydrogen. The feed amount was continuously supplied to the polymerizer so as to be 3 NL / h.

While maintaining the polymerization pressure at 1.6 MPaG and the polymerization temperature at 95 ° C., the catalyst −a1 was used as the main catalyst and continuously supplied to the polymerizer so as to have a feed amount of 0.020 mmol / h. In addition, (C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ (CB-3) as a cocatalyst has a feed amount of 0.100 mmol / h, and triisobutylaluminum (TiBA) as an organoaluminum compound has a feed amount of 10 mmol / h. Each was continuously supplied to the polymerizer so as to be.

In this way, a solution containing 14% by mass of an ethylene / 1-butene / ENB copolymer formed from ethylene, 1-butene and ENB was obtained. A small amount of methanol was added to the polymerization reaction solution extracted from the lower part of the polymer to stop the polymerization reaction, and the ethylene / 1-butene / ENB copolymer was separated from the solvent by steam stripping treatment, and then at 80 ° C. It was dried under reduced pressure all day and night.

By the above operation, an ethylene / 1-butene / ENB copolymer (EBDM-1) formed from ethylene, butene and ENB was obtained at a rate of 4.5 kg / h.
The physical characteristics of the obtained EBDM-1 were measured by the method described above. The results are shown in Table 1.
EBDM-1 was oil-expanded with Diana Process (registered trademark) PW-100 (manufactured by Idemitsu Kosan Co., Ltd.) at a ratio of 100:30 to obtain oil-expanded EBDM-1.

[Example 1]
<< Composition for anti-vibration rubber >>
Using MIXTRON BB MIXER (manufactured by Kobe Steel Co., Ltd., BB-2 type, volume 1.7 L, rotor 2WH), 130 parts of oil-expanded EBDM-1 (converted to EBDM-1) obtained in Synthesis Example 1 (100 parts by mass), 5 parts of zinc oxide (META-Z102, manufactured by Inoue Lime Industry Co., Ltd.) as a vulcanization aid, 1 part of stearic acid as a processing aid, and Nocrack White (an anti-aging agent). N, N'-di-2-naphthyl-p-phenylenediamine, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) as an anti-aging agent, Sandant MB (2-mercaptobenzimidazole, Sanshin Kagaku Kogyo Co., Ltd.) 2 parts of PEG # 4000 (polyethylene glycol, manufactured by Lion Co., Ltd.) as an activator. 46 parts of Siest G-SO (FTF carbon black, manufactured by Tokai Carbon Co., Ltd.) as a reinforcing agent, and 28 parts of Diana process oil PW-380 (paraffin-based process oil, manufactured by Idemitsu Kosan Co., Ltd.) as a softening agent. After blending, kneading was performed to obtain Formulation 1.

The kneading conditions were a rotor rotation speed of 40 rpm, a floating weight pressure of 3 kg / cm ² , a kneading time of 5 minutes, and a kneading discharge temperature of 144 ° C.
Next, after confirming that the temperature of the compound 1 reached 40 ° C., a 6-inch roll was used to add Suncella TT (tetramethylthiuram disulfide, manufactured by Sanshin Chemical Industry Co., Ltd.) to the compound 1 as a vulcanization accelerator. ) As a vulcanization accelerator, Suncella TRA (dipentamethylene thiuram tetrasulfide, manufactured by Sanshin Kagaku Kogyo Co., Ltd.) as a vulcanization accelerator, Sunseller BZ (zinc dibutyldithiocarbamate, 1 part of Sanshin Chemical Industry Co., Ltd.), 1 part of Sunseller M (2-mercaptobenzothiazole, manufactured by Sanshin Chemical Industry Co., Ltd.) as a vulcanization accelerator, Suncella 22-C (ethylenethiourea) as a vulcanization accelerator , Sanshin Kagaku Kogyo Co., Ltd.) was added in an amount of 0.5 parts and sulfur was added in an amount of 0.2 parts as a vulcanizing agent and kneaded to obtain Formulation 2 (composition for vibration-proof rubber).

The kneading conditions are that the roll temperature is front roll / rear roll = 50 ° C./50 ° C., the roll peripheral speed is front roll / rear roll = 18 rpm / 15 rpm, the roll gap is 3 mm, and the kneading time is 8 minutes. I got the thing 2.

[Unvulcanized physical characteristics test 1: Mooney viscosity]
The Mooney viscosity ML _{(1 + 4)} 125 ° C. of Formulation 2 was measured using a Mooney viscometer (SMV202 type manufactured by Shimadzu Corporation) according to JIS K6300 (1994).

[Unvulcanized physical property test 2: Evaluation of vulcanization characteristics]
Vulcanization measuring device: Using MDR2000 (manufactured by ALPHA TECHNOLOGIES), the vulcanization rate of Formulation 2 (tc90) was measured as follows.

The torque changes obtained under the conditions of constant temperature and constant shear rate were measured.
The time from the minimum torque value to the increase of torque by 1 point (1 dNm) was defined as the vulcanization induction time (TS1; minutes).

The time required to reach a torque of 90% of the difference between the maximum torque value (S'Max) and the minimum torque value (S'Min) was defined as tk90 (min). The measurement conditions were a temperature of 170 ° C. and a time of 20 minutes. The smaller the tc90, the faster the vulcanization rate.

<< Evaluation of vulcanized product (crosslinked product) >>
The formulation 2 was crosslinked at 170 ° C. for 10 minutes using a press molding machine to prepare a sheet (vulcanized product) having a thickness of 2 mm.

The obtained sheet was subjected to a hardness test, a tensile test, a crosslink density calculation, and a heat aging test by the following methods.
Vulcanize the formulation 2 at 170 ° C. for 15 minutes using a press molding machine in which a columnar mold is set to prepare a right-cylindrical test piece having a thickness of 12.7 mm and a diameter of 29 mm, and compressing the mixture. A test piece (vulcanized product) for a permanent strain (CS) test was obtained.

Using the obtained test piece for compression set (CS) test, the set piece of compression set was evaluated by the following method.
Further, a test piece was prepared in the same manner as the compression set for the compression set (CS) test piece, and a static spring test piece and a dynamic spring test piece were obtained.

Using the obtained test piece for static spring test, the static spring constant was determined by the following method.
Using the obtained test piece for dynamic spring test, the dynamic spring constant was determined by the following method.
For some temperatures for which the spring test was performed, the dynamic magnification (dynamic spring constant / static spring constant) was obtained from the static spring constant and the dynamic spring constant.
The results are shown in Table 2.

[Hardness test: Hardness (Durometer-A)]
Regarding the hardness of the sheet, the description of "Hardness test" in Section 7 of "Physical test method for thermosetting polyurethane elastomer molded product" of JIS K7312 (1996) and JIS K6253 (2006) "Vulcanized rubber and thermoplastic rubber-" The measurement was performed in accordance with the description of test type A in "Durometer hardness test" in Section 6 of "How to determine hardness".

[Tensile test: tensile breaking point stress, tensile breaking point elongation]
The tensile breaking point stress and the tensile breaking point elongation of the sheet were measured by the following methods.
A sheet was punched out to prepare a No. 3 dumbbell test piece described in JIS K 6251 (1993), and this test piece was used to measure a temperature of 25 ° C. according to the method specified in JIS K 6251 (3). A tensile test was carried out under the condition of a tensile speed of 500 mm / min, and the tensile breaking point stress (TB) and the tensile breaking point elongation (EB) were measured.

[Calculation of crosslink density]
The cross-linking density ν of the sheet was calculated from the Flory-Rehner equation (a) using the following equilibrium swelling.
V _R in the formula (a) were determined by toluene extraction in the conditions of 37 ° C. × 72h a 2mm sheet crosslinked.

[Heat aging test]
The sheet was subjected to a heat aging test in which the sheet was held at 170 ° C. for 70 hours according to JIS K 6257. The hardness, tensile breaking point stress, and tensile breaking point elongation of the sheet after the heat aging test can be obtained by the same method as in the item of [Hardness (Durometer-A)] and the item of [Tension breaking point stress, tensile breaking point elongation]. Measured at.

AH (Duro-A) was obtained from the difference in hardness before and after the heat aging test, and from the tensile breaking point stress (TB) and tensile breaking point elongation (EB) before and after the heat aging test, after the test with respect to the values before the heat aging test. The rate of change of was determined as Ac (TB) and Ac (EB), respectively.

[Compressive permanent strain]
For the test piece for measuring compression set, the compression set after treatment at 120 ° C. for 70 hours was measured according to JIS K6262 (1997).

[Static spring constant (Ks)]
Measured according to JIS K 6386: 1999 "Vibration-proof rubber-rubber material" 7.9.1 dynamic magnification.

The testing machine used is Instron's dual column desktop universal test system 5996, the testing machine capacity is load cell type 50 kN, the test temperature is 23 ° C, -20 ° C (-20 ° C ± 2 ° C x 30 minutes or more state adjustment), 80. There are four types: ° C (80 ° C ± 2 ° C x 15 minutes or more state adjustment) and 120 ° C (120 ° C ± 2 ° C x 15 minutes or more state adjustment). The amount of strain is 3 mm, the calculation range is the compression displacement of 1.5 mm to 2.5 mm during the third compression (main test), but the zero displacement point is the rising point of the load-deflection curve during the third compression (main test). The test was conducted.
Ks at each temperature is shown in FIG.

[Dynamic spring constant (Kd)]
After measuring the static spring constant, the measurement was carried out under the following conditions using a sample whose state was adjusted at 23 ° C. ± 2 ° C. and 50 ± 5% RH × 16 hours or more.

The testing machine used is a servo pulser EHF-EM020K1-020-1A manufactured by Shimadzu Corporation, the testing machine capacity is load cell type 1kN, 20kN, the deformation method is compression method, and the test temperature is 23 ° C, -20 ° C (-20 ° C). There are three types: ± 2 ° C x 30 minutes or more state adjustment) and 80 ° C (80 ° C ± 2 ° C x 15 minutes or more state adjustment), with an average deflection of 1.25 mm (10% of the initial thickness of the test piece). The deflection amplitude was ± 0.5 mm, the frequency was 15 Hz, and the data was calculated by data processing (FFT method), and data was collected about 30 seconds after the start of the test (450th time at 15 Hz).
The Kd of each temperature is shown in FIG.
The dynamic ratio (Kd / Ks) was obtained by dividing the dynamic spring constant by the static spring constant.

[Example 2]
Seast G-SO (FTF carbon black, manufactured by Tokai Carbon Co., Ltd.) was changed from 46 parts to 52 parts, except that Diana process oil PW-380 (paraffin-based process oil, manufactured by Idemitsu Kosan Co., Ltd.) was not used. , The same procedure as in Example 1 was carried out to obtain Formulation 1 and Formulation 2.
Each physical property was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Comparative Example 1]
130 parts of oil-expanded EBDM-1 was changed to 148 parts of Mitsui EPT (registered trademark) 4100E (manufactured by Mitsui Chemicals, Inc.) (100 parts by mass in terms of EPT), and Diana process oil PW-380 (paraffin type). The same procedure as in Example 1 was carried out except that the process oil (manufactured by Idemitsu Kosan Co., Ltd.) was changed from 28 parts to 18 parts to obtain Formulation 1 and Formulation 2.

Each physical property was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.
The Mitsui EPT (registered trademark) 4100E is manufactured by Mitsui Chemicals, Inc., has an ethylene content of 57% by mass, an ENB content of 7.3% by mass, a Mooney viscosity (ML _{(1 + 4)} 125 ° C.) 74, and an oil spread amount of 48 parts by mass. It is an ethylene / propylene / ENB copolymer (relative to 100 parts by mass of EPT).

Claims (4)

Ethylene / α-olefin / non-conjugated including structural units derived from ethylene [A], structural units derived from α-olefin [B] having 4 to 20 carbon atoms, and structural units derived from non-conjugated polyene [C]. Contains polyene copolymer,
Ri wherein the ethylene-alpha-olefin-nonconjugated polyene copolymer differential scanning calorimetry of the glass transition temperature measured by (DSC) (Tg) is -70 to -60 ° C. der,
The α- olefin [B] is 1-butene, wherein the non-conjugated polyene [C] is Ru 5-ethylidene-2-norbornene der, vibration damping rubber composition. The anti-vibration rubber composition according to claim 1, wherein the ethylene / α-olefin / non-conjugated polyene copolymer satisfies the following (1) to (4).
(1) The molar ratio [[A] / [B]] of the structural unit derived from ethylene [A] to the structural unit derived from α-olefin [B] is 40/60 to 80/20.
(2) The content of the structural unit derived from the non-conjugated polyene [C] is 0.1 to 4.0 mol%, assuming that the total of the structural units of [A], [B] and [C] is 100 mol%. And
(3) Mooney viscosity ML _{(1 + 4) at} 125 ° C. 125 ° C. is 5 to 200.
(4) The B value represented by the following formula (i) is 1.20 or more.
B value = ([EX] + 2 [Y]) / [2 x [E] x ([X] + [Y])] ... (i)
[Here, [E], [X] and [Y] indicate the mole fractions of ethylene [A], α-olefin [B] having 4 to 20 carbon atoms, and unconjugated polyene [C], respectively. [EX] indicates the ethylene [A] -alpha-olefin [B] diad chain fraction having 4 to 20 carbon atoms. ] An anti-vibration rubber formed by using the anti-vibration rubber composition according to claim 1 or 2. The anti-vibration rubber according to claim 3 , which is at least one selected from a muffler hanger, a torsional damper, a change lever mount, a torsion rubber for a clutch, a centering bush, a tube damper, a torque bush, a suspension bush and an engine mount.

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