JP6709641B2 - Seal packing - Google Patents

Description

The present invention relates to a seal packing composition and its use.

Ethylene/α-olefin rubbers such as ethylene/propylene copolymer rubber (EPR) and ethylene/propylene/diene copolymer rubber (EPDM) do not have an unsaturated bond in the main chain of their molecular structure, and thus are widely used. Compared with conjugated diene rubber, it has excellent heat aging resistance, weather resistance, and ozone resistance, and is widely used for automobile parts, electric wire materials, electronic/electric parts, construction civil engineering materials, industrial material parts, and the like.

For example, it is known to obtain a rubber molding for sealing using EPDM (see, for example, Patent Document 1). Seal packing, which is a rubber molding for sealing, is used in various applications such as automobiles, industrial machinery, and electronic parts.However, since automobiles and industrial machinery are also used in cold regions, seal packing can be used at room temperature. In addition to the mechanical strength of, low temperature characteristics are required.

Conventionally, fluorocarbon rubber, butyl rubber, silicone rubber, etc. have been used as cell seal parts for fuel cells, but the use of ethylene/α-olefin/non-conjugated polyene rubber has been considered from the viewpoint of heat resistance and cost. There is. Since fuel cells are expected to be used in an extremely low temperature environment with the spread thereof, cell seal parts are required to have performance in a wide range of temperature environments from the operating temperature of the fuel cell to an extremely low temperature.

As a method for improving low-temperature flexibility and heat aging resistance of ethylene/propylene/diene copolymer rubber (EPDM), an α-olefin having 4 to 10 carbon atoms is used as an α-olefin to obtain ethylene and an α-olefin. An ethylene/α-olefin/non-conjugated polyene copolymer having excellent randomness has been proposed (Patent Document 2: JP-A-9-71617). In Example 4 of Patent Document 2, an ethylene/1-butene/ENB copolymer having a maximum B value represented by the following formula, which is an index showing the quality of randomness, was 1.12 was obtained. Is listed.

B value=[EX]/(2[E]×[X]) (i)
(In the formula (i), [E] and [X] represent the mole fractions of ethylene and the α-olefin having 4 to 20 carbon atoms, respectively, in the ethylene/α-olefin/non-conjugated polyene copolymer,
[EX] represents the diad chain fraction of ethylene/α-olefin having 4 to 20 carbon atoms. )

On the other hand, in Examples of Patent Document 3 (International Publication No. 2009/081794), a B value showing randomness by using a specific transition metal compound (bridged metallocene compound) (however, B value described in Patent Document 2 is used. However, it is disclosed that ethylene-propylene-ENB copolymers of 1.11 to 1.24 were obtained. Note that Patent Document 3 does not describe mechanical properties of the ethylene/propylene/ENB copolymer.

B value=(c+d)/[2×a×(e+f)]... [IV]
(In the formula [IV], a, e and f are the ethylene mole fraction, the α-olefin mole fraction and the non-conjugated polyene mole fraction in the ethylene/α-olefin/non-conjugated polyene copolymer, respectively, and c is Ethylene-α-olefin diad mole fraction, d is ethylene-non-conjugated polyene diad mole fraction.)

International Publication No. 2000/59962 JP, 9-71617, A International Publication No. 2009/081794

The conventionally-known EPDM seal packing does not have sufficient low-temperature characteristics, and the silicone rubber seal packing has excellent low-temperature characteristics, but it does not have sufficient strength at room temperature and is likely to break or tear. There was a problem that the sealability was impaired.

An object of the present invention is to provide a seal packing composition capable of forming a seal packing that achieves both low temperature characteristics and mechanical strength (strength/elongation), and a seal packing formed from the composition. ..

The present inventors diligently studied to solve the above problems. As a result, compared to the already proposed ethylene/α-olefin/non-conjugated polyene copolymer, the compression set at low temperature is small, and it has flexibility, and has rubber elasticity at low temperature and tensile strength at room temperature. The inventors have found that the above problems can be solved by using a specific ethylene/α-olefin/non-conjugated polyene copolymer excellent in balance with strength, and have completed the present invention.

That is, the present invention relates to, for example, the following [1] to [8].
[1]
It includes a structural unit derived from ethylene [A], a structural unit derived from an α-olefin [B] having 4 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [C], and the following (1) to (4 A composition for seal packing containing an ethylene/α-olefin/non-conjugated polyene copolymer satisfying (4). (1) The molar ratio [[A]/[B]] of the structural unit derived from ethylene [A] and 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% when the total of the structural units of [A], [B] and [C] is 100 mol %. (3) Mooney viscosity ML ₍₁₊₄₎ 125° C. at 125° C. is 5 to 200, and (4) B value represented by the following formula (i) is 1.20 or more.

B value=([EX]+2[Y])/[2×[E]×([X]+[Y])]...(i)
[Here, [E], [X], and [Y] represent the mole fractions of ethylene [A], α-olefin [B] having 4 to 20 carbon atoms, and non-conjugated polyene [C], respectively. [EX] represents ethylene [A]-C4-20 [alpha]-olefin [B] dyad chain fraction. ]

[2]
It includes a structural unit derived from ethylene [A], a structural unit derived from an α-olefin [B] having 4 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [C], and the following (1) to (4 A composition for seal packing containing an ethylene/α-olefin/non-conjugated polyene copolymer satisfying (4). (1) The molar ratio [[A]/[B]] of the structural unit derived from ethylene [A] and 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% when the total of the structural units of [A], [B] and [C] is 100 mol %. (3) Mooney viscosity ML ₍₁₊₄₎ 125° C. at 125° C. is 5 to 100, and (4) B value represented by the following formula (i) is 1.20 or more.

B value=([EX]+2[Y])/[2×[E]×([X]+[Y])]...(i)
[Here, [E], [X], and [Y] represent the mole fractions of ethylene [A], α-olefin [B] having 4 to 20 carbon atoms, and non-conjugated polyene [C], respectively. [EX] represents ethylene [A]-C4-20 [alpha]-olefin [B] dyad chain fraction. ]

[3]
The composition for seal packing according to [1] or [2], wherein the α-olefin [B] having 4 to 20 carbon atoms is 1-butene.

[4]
The ethylene/α-olefin/non-conjugated polyene copolymer is (a) a transition metal compound represented by the following general formula [I], and (b) (b-1) an organometallic compound,
In the presence of an olefin polymerization catalyst containing (b-2) an organoaluminum oxy compound, and (b-3) at least one compound selected from compounds that react with the transition metal compound (a) to form an ion pair. The composition for seal packing according to any one of [1] to [3], which is a polymer obtained by copolymerizing ethylene, ethylene, an α-olefin having 4 to 20 carbon atoms, and a non-conjugated polyene.

（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 the formula [I], Y is selected from a carbon atom, a silicon atom, a germanium atom and a tin atom,
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 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, An atom or a substituent selected from a halogen atom and a halogen-containing group, which may be the same or different,
Adjacent substituents R ¹ to R ⁶ may combine with each other to form a ring,
Q is the same or different combination selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anion ligand and a neutral ligand capable of coordinating with a lone pair of electrons,
n is an integer of 1 to 4,
j is an integer of 1 to 4. )

[5]
A seal packing formed using the composition for seal packing according to any one of [1] to [4].

[6]
The seal packing according to [5], which is a seal part for automobiles, a seal part for machines, a seal part for electronic/electric parts, a gasket for construction, a seal part for civil engineering building materials, or a seal part for fuel cells.

[7]
The seal packing according to [5] used for a hydrogen line.

[8]
The seal packing according to [7], wherein the crosslink density of the seal packing is 1.0×10 ^{16 to} 1.0×10 ²² pieces/cc.

According to the present invention, a seal packing composition capable of forming a seal packing excellent in low temperature characteristics such as low temperature flexibility and mechanical properties such as tensile strength, and a seal formed from the composition. Packing and can be provided.

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

[Composition for seal packing]
The seal packing 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 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], or a structural unit derived from at least one type of C 4-20 α-olefin [B]. And a structural unit derived from at least one non-conjugated polyene [C], and satisfy the following (1) to (4). (1) The molar ratio [[A]/[B]] of the structural unit derived from ethylene [A] and 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% when the total of the structural units of [A], [B] and [C] is 100 mol %. (3) Mooney viscosity ML ₍₁₊₄₎ 125° C. at 125° C. is 5 to 200, and (4) B value represented by the following formula (i) is 1.20 or more.

B value=([EX]+2[Y])/[2×[E]×([X]+[Y])]...(i)
Here, [E], [X], and [Y] represent the molar fractions of ethylene [A], α-olefin [B] having 4 to 20 carbon atoms, and non-conjugated polyene [C], respectively. EX] represents ethylene [A]-C4 to C20 α-olefin [B] dyad chain fraction.

The seal packing obtained from the composition containing the ethylene copolymer A has an excellent balance between rubber elasticity at low temperature and tensile strength at room temperature. Therefore, the seal packing composition containing the ethylene-based copolymer A can be used in cold regions, such as automobile seal parts, machine seal parts, electronic/electric part seal parts, construction gaskets, and civil engineering construction materials. It can be suitably used as a sealing part for a vehicle, a sealing part for a fuel cell, or the like.

The α-olefin [B] having 4 to 20 carbon atoms has a straight-chain structure with no side chain, starting with 1-butene having 4 carbon atoms, 1-nonene having 9 carbon atoms and 1-none having 10 carbon atoms. Via decene, 1-nonadecene having 19 carbon atoms, 1-eicosene having 20 carbon atoms, and 4-methyl-1-pentene having a side chain, 9-methyl-1-decene, 11-methyl-1-dodecene, 12 -Ethyl-1-tetradecene and the like.

These α-olefins [B] can be used alone or in combination of two or more. Of 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.

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

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

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

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.

The ethylene-based copolymer A may be used alone or in combination of two or more as necessary.
The ethylene-based copolymer A is
(1) The molar ratio [[A]/[B]] of the structural unit derived from ethylene [A] and the structural unit derived from α-olefin [B] is 40/60 to 80/20, preferably 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 is excellent in 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% when 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 ML _{(1+4) at} 125° C. 125° C. is 5 to 200. The upper limit of the Mooney viscosity is preferably 150, more preferably 125, even more preferably 100, particularly preferably 95, most preferably 80. The lower limit of the Mooney viscosity is preferably 8.

When the Mooney viscosity is within the above range, an ethylene-based copolymer having good post-treatment (ribbon handling property) and excellent rubber properties can be obtained.
The ethylene-based copolymer A is
(4) The B value is 1.20 or more, preferably 1.20 to 1.80, and 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 low temperature, and an ethylene-based copolymer having an excellent balance between rubber elasticity at low temperature and tensile strength at room temperature can be obtained. There is a possibility that it will not.

The B value is an index showing the randomness of the distribution of copolymerized monomer chains in the copolymer, and [E], [X], [Y], and [EX] in the above formula (i) are ¹³ The C-NMR spectrum was measured, and the J. C. Randall [Macromolecules, 15, 353 (1982)], J. Am. Ray [Macromolecules, 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 “bridged metallocene compound”), (b) (b-1) organometallic compound, (b-2) ) In the presence of an olefin polymerization catalyst containing an organoaluminum oxy compound and (b-3) at least one compound selected from compounds that react with the transition metal compound (a) to form an ion pair, ethylene, carbon number It can be prepared 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 the formula [I], Y is selected from a carbon atom, a silicon atom, a germanium atom and a tin atom,
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 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, An atom or a substituent selected from a halogen atom and a halogen-containing group, which may be the same or different,
Adjacent substituents R ¹ to R ⁶ may combine with each other to form a ring,
Q is the same or different combination selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anion ligand and a neutral ligand capable of coordinating with a lone pair of electrons,
n is an integer of 1 to 4,
j is an integer of 1 to 4. )

<Bridged metallocene compound (a)>
The bridged 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 each 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. An atom or a substituent selected from a halogen atom and a halogen-containing group, which may be the same or different. The adjacent substituents R ¹ to R ⁶ may be bonded to each other to form a ring, or may not be bonded to each other.

Here, as the hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, a chain unsaturated hydrocarbon group having 2 to 20 carbon atoms, Examples thereof include cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms. Further, 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 is a linear saturated hydrocarbon group such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group. , N-octyl group, n-nonyl group, n-decanyl group and the like, which are 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 group Group, 1-methyl-1-isopropyl-2-methylpropyl group, cyclopropylmethyl group and the like. The alkyl group preferably has 1 to 6 carbon atoms.

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

The chain unsaturated hydrocarbon group having 2 to 20 carbon atoms is an alkenyl group such as ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), 1-methylethenyl group (isopropenyl group). And the like, an alkynyl group such as an ethynyl group, a 1-propynyl group, a 2-propynyl group (propargyl group) and the like are exemplified. 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 cyclopentadienyl group, norbornyl group, phenyl group, naphthyl group, indenyl group, azulenyl group, phenanthryl group, and 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 a hydrogen atom of a 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 a hydrogen atom of a linear hydrocarbon group or a branched saturated hydrocarbon group such as a mesityl group) is replaced with a cyclic saturated hydrocarbon group having 3 to 19 carbon atoms or a cyclic unsaturated hydrocarbon group, A cumyl group etc. are illustrated. The number of carbon atoms in the cyclic unsaturated hydrocarbon group is preferably 6-10.

Examples of the alkylene group having 1 to 20 carbon atoms include methylene group, ethylene group, dimethylmethylene group (isopropylidene group), ethylmethylene group, 1-methylethylene group, 2-methylethylene group, 1,1-dimethylethylene group, Examples 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 o-phenylene group, m-phenylene group, p-phenylene group and 4,4'-biphenylylene group. The carbon number of the arylene group is preferably 6-12.

The aryl group partially overlaps with the above-mentioned examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, but is a substituent derived from an aromatic compound such as phenyl group, 1-naphthyl group, and 2-naphthyl. Examples thereof include groups, anthracenyl groups, phenanthrenyl groups, tetracenyl groups, chrysenyl groups, pyrenyl groups, indenyl groups, azulenyl groups, pyrrolyl groups, pyridyl groups, furanyl groups and thiophenyl groups. The aryl group is preferably a phenyl group or a 2-naphthyl group.

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

The substituted aryl group partially overlaps with the above-described examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, but one or more hydrogen atoms contained in the aryl group have 1 to 20 carbon atoms, Examples thereof include groups 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 specifically, 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 include 4-(trifluoromethyl)phenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 5-methylnaphthyl group, and 2-(6-methyl)pyridyl group. To be done. Further, examples of the substituted aryl group also include “electron donating group-containing substituted aryl group” described later.

The silicon-containing group is an alkyl group such as a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group or a triisopropylsilyl group, which is a hydrocarbon group having 1 to 20 carbon atoms in which carbon atoms are replaced by silicon atoms. Examples thereof include a silyl group, a dimethylphenylsilyl group, a methyldiphenylsilyl group, an arylsilyl group such as a t-butyldiphenylsilyl group, a pentamethyldisilanyl group, and a 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, a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing group described above, in which a ═CH— structural unit is replaced with a nitrogen atom, A group in which a CH ₂ — structural unit is replaced by a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bound, or a —CH ₃ structural unit is a nitrogen atom or a nitrile group to which a hydrocarbon group having 1 to 20 carbon atoms is bound. Examples thereof include dimethylamino group, diethylamino group, dimethylaminomethyl group, cyano group, pyrrolidinyl group, piperidinyl group, and pyridinyl group. 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 hydrocarbon group having 1 to 20 carbon atoms described above, a silicon-containing group or a nitrogen-containing group in which a —CH ₂ — structural unit is replaced with an oxygen atom or a carbonyl group, or — A methoxy group, an ethoxy group, a t-butoxy group, a phenoxy group, a trimethylsiloxy group, a methoxyethoxy group, a hydroxymethyl, which is a group in which a CH ₃ structural unit is replaced by 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 ethcarboxymethyl group, a carbamoylmethyl group, a furanyl group and a pyranyl group. A methoxy group is preferred as the oxygen-containing group.

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

Q is selected from the same or different combinations from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anion ligand and a neutral ligand capable of coordinating with a lone electron pair.
The 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 anionic ligands include alkoxy groups such as methoxy group, t-butoxy group and phenoxy group, carboxylate groups such as acetate and benzoate, and sulfonate groups 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 etc. can be illustrated.
n is an integer of 1 to 4.
j is an integer of 1 to 4, preferably 2.
In addition, the above-mentioned exemplification regarding the formula [I] is similarly applied to the following description.

The 2,3,6,7-tetramethylfluorenyl group contained in the bridged 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 an electronic effect is large, and thereby a high polymerization activity and a high molecular weight ethylene-based copolymer are produced. On the other hand, since generally non-conjugated polyene becomes bulky compared to α-olefin, a polymerization catalyst for polymerizing this, particularly a copolymer of non-conjugated polyene is preferable in the vicinity of the central metal of the metallocene compound which is a polymerization active point. It is estimated that this will lead to improved performance. The four methyl groups contained in the 2,3,6,7-tetramethylfluorenyl group are not bulky as compared with other hydrocarbon groups and the like, which 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 an ethylene copolymer produced and a high non-conjugation. It is presumed that polyene copolymerization performance and high polymerization activity are simultaneously realized at a high level and in good balance.

In the bridged metallocene compound (a) represented by the general formula [I], n is preferably 1. Such a bridged 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 bridged metallocene compound (a-1) has a simplified manufacturing process and reduced manufacturing cost as compared with the compound in which n in the general formula [I] is an integer of 2 to 4, and thus this bridged metallocene compound is used. The use thereof has an advantage that the production cost of the ethylene/α-olefin/non-conjugated polyene copolymer is reduced. Furthermore, 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-1), the resulting ethylene-based copolymer is The advantage of high molecular weight is also obtained.

In the bridged metallocene compound (a-1) represented by the general formula [V], R ¹ , R ² , R ³ and R ⁴ are preferably all hydrogen atoms. Such a bridged 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 bridged metallocene compound (a-2) has a structure 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 advantage is that the production process is simplified, the production cost is reduced, and by using the crosslinked metallocene compound, the production cost of the ethylene/α-olefin/non-conjugated polyene copolymer is reduced. Furthermore, in the case of copolymerizing ethylene 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 is produced. The advantage of high molecular weight of the copolymer is also obtained. At the same time, the advantage of improving the copolymerization performance of the non-conjugated polyene is also obtained.

In the bridged metallocene compound (a-2) represented by the above general formula [VI], Y is more preferably a carbon atom. Such a bridged 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 bridged metallocene compound (a-3) can be synthesized, for example, by a simple method represented by 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 and R ⁶ are as described above.)

In the above formula [VIII], 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, oxygen-containing groups, halogen atoms and halogen-containing groups. An atom or a substituent selected from the groups, which may be the same or different, and which may be bonded to each other to form a ring, are represented by the general formula R ⁵ —C(═O)—R. Various ketones represented by ⁶ which satisfy such conditions are commercially available from general reagent manufacturers, and thus the raw material of the bridged metallocene compound (a-3) is easily available. 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 simple and easy manufacturing process as compared with a compound in which Y in the general formula [V] is selected from a silicon atom, a germanium atom and a tin atom, and has a low manufacturing cost. Further, it is possible to obtain the advantage that the production cost of the ethylenic copolymer is reduced by using the crosslinked metallocene compound. 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-3), the resulting ethylene-based copolymer is The advantage of higher molecular weight is also obtained.

In the bridged metallocene compound (a-3) represented by the general formula [VII], R ⁵ and R ⁶ are preferably a group 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 bridged metallocene compound, the polymerization activity is further improved and the ethylene-based copolymer produced is further improved. The advantage of high molecular weight is obtained. At the same time, the advantage of improving the copolymerization performance of the non-conjugated polyene is also obtained.

In the bridged metallocene compound (a-3) represented by the above general formula [VII], R ⁵ and R ⁶ are more preferably the same groups selected from an aryl group and a substituted aryl group. By selecting R ⁵ and R ⁶ in this way, the synthesis process of the bridged metallocene compound is simplified and the production cost is further reduced, and by using the bridged metallocene compound, the production cost of the ethylene-based copolymer is reduced. Is reduced.

In the bridged 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 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 cross-linked metallocene compound, there is an advantage of further increasing the molecular weight of the produced ethylene copolymer. can get.

In the bridged metallocene compound (a-3) represented by the above general formula [VII], R ⁵ and R ⁶ have one or more hydrogen atoms of the aryl group and a substituent constant σ of Hammett rule of −0.2 or less. A substituted aryl group substituted with an electron-donating substituent, wherein each electron-donating substituent may be the same or different, Other than the donative 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. When it has a plurality of groups, each substituent is preferably a substituted aryl group which may be the same or different (hereinafter also referred to as “electron-donating group-containing 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 cross-linked metallocene compound, there is an advantage of further increasing the molecular weight of the produced ethylene copolymer. can get.

The electron donating group having a Hammett's rule substituent constant σ of −0.2 or less is defined and exemplified as follows. Hammett's rule is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives in 1935 L. et al. P. The rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by the 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 literatures. For example, the article by Hansch and Taft [Chem. Rev. , 91, 165 (1991)] for a very wide range of substituents. However, the values of σp and σm described in these documents may be slightly different depending on the documents even if they are the same substituents. In the present invention, in order to avoid the confusion caused by such a situation, for all the substituents mentioned, the reference by Hansch and Taft [Chem. Rev. , 91, 165 (1991)], Table 1 (pages 168-175) is defined as the substituent constants σp and σm of Hammett's rule. In the present invention, an electron-donating group having a Hammett's rule substituent constant σ of −0.2 or less means σp of −0 when the electron-donating group is substituted at the para position (4th position) of a phenyl group. .2 or less, and when substituted at the meta position (3 position) of the phenyl group, [sigma]m is -0.2 or less. When the electron-donating group is substituted at the ortho position (2-position) of the phenyl group or at any position of the aryl group other than the phenyl group, σp is −0.2 or less. Is an electron-donating group.

As the electron-donating substituent having a Hammett's rule substituent constant σp or σm of −0.2 or less, 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 groups, tertiary hydrocarbon groups such as p-t-butyl group (4-t-butyl group), and silicon-containing groups such as p-trimethylsiloxy group (4-trimethylsiloxy group). The electron-donating substituent having a Hammett's rule substituent constant σp or σm of −0.2 or less as defined in the present invention is described by Hansch and Taft [Chem. Rev. , 91, 165 (1991)], Table 1 (pages 168-175). Even if the substituent is not described in the literature, the substituent whose substituent constant σp or σm when measured based on the Hammett's rule is in the range is a substituent of the Hammett's rule 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 a m-N-morpholinyl group (3-N-morpholinyl group).

In the substituted aryl group containing an electron-donating group, when a plurality of the electron-donating substituents are substituted, the electron-donating substituents may be the same or different, and the number of carbon atoms in addition to the electron-donating substituent may be different. 1 to 20 hydrocarbon groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups may be substituted, if a plurality of the substituents are substituted. The respective substituents may be the same or different, but the sum of the electron-donating substituents contained in one substituted aryl group and the substituent constant σ of each of the substituents according to Hammett's rule is −0.15 or less. Is preferred. Examples of such a substituted aryl group include m,p-dimethoxyphenyl group (3,4-dimethoxyphenyl group), p-(dimethylamino)-m-methoxyphenyl group (4-(dimethylamino)-3-methoxyphenyl group. 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.

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 which the electron-donating group-containing substituted aryl group may have are those atoms described above. Alternatively, specific examples of the substituent can be given.

As a result of diligent studies on various bridged metallocene compounds (a), the present applicant has determined that R ⁵ and R ⁶ in the bridged metallocene compound (a-3) represented by the above general formula [VII], particularly Hammett's rule When an electron-donating group-containing substituted aryl group in which one or more electron-donating substituents having a substituent constant σ of −0.2 or less is substituted, an olefin polymerization catalyst containing the bridged metallocene compound (a-3) It was found for the first time that the molecular weight of the ethylene-based copolymer produced when copolymerizing ethylene with an α-olefin having 4 or more carbon atoms and a non-conjugated polyene in the presence thereof is further increased.

In the coordination polymerization of an olefin with an organometallic complex catalyst such as a bridged metallocene compound (a-3), the olefin polymer is repeatedly polymerized on the central metal of the catalyst, so that the molecular chain of the produced olefin polymer grows ( Growth reaction), the molecular weight of the olefin polymer is known to increase. 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 accordingly, 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 unique to the organometallic complex catalyst that produces it. That is, the larger the ratio of the growth reaction frequency to the chain transfer reaction frequency, 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 the reaction with a low activation energy has a high frequency, and conversely, the reaction with a high activation energy has a low frequency. It is thought that it can be done. Generally, it is known that the frequency of growth reaction in olefin polymerization is sufficiently higher than the frequency of chain transfer reaction, that is, the activation energy of growth reaction is sufficiently lower than the activation energy of chain transfer reaction. There is. Therefore, the value obtained by subtracting the activation energy of the growth reaction from the activation energy of the chain transfer reaction (hereinafter ΔE _C ) becomes positive, and the larger this value, the greater the frequency of the growth reaction compared to the frequency of the chain transfer reaction. It is estimated that the molecular weight of the resulting olefin polymer becomes high. The validity of the estimation of the molecular weight of the olefin polymer carried out in this way is supported by, for example, the calculation result of Lane et al. [Organometallics, 30, 1350 (2011)]. In the bridged metallocene compound (a-3) represented by the above general formula [VII], R ⁵ and R ⁶ are, in particular, an electron-donating substituent having a Hammett's rule substituent constant σ of −0.2 or less. When one or more substituted electron-donating group-containing substituted aryl groups are used, the above ΔE _C increases, and ethylene and carbon atoms having 4 or more carbon atoms are present in the presence of an olefin polymerization catalyst containing the bridged metallocene compound (a-3). It is presumed that the ethylene-based copolymer produced when the α-olefin and the non-conjugated polyene are copolymerized has a high molecular weight.

In the bridged 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 preferable.

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

Here, the substituted phenyl group containing a group selected from a nitrogen-containing group and an oxygen-containing group as the electron-donating substituent is an o-aminophenyl group (2-aminophenyl group), 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 -Morpholinylphenyl 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) and a p-methoxy-m,m-dimethylphenyl group (4-methoxy-3,5-dimethylphenyl group).

In the bridged metallocene compound (a-3) represented by the general formula [VII], R ⁵ and R ⁶ are the electron-donating substituents at the meta position and/or para position relative to 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 a group is more preferable. For example, in the case of synthesizing according to the method of the above formula [VIII], the synthesis becomes easier as compared with the case where the group is substituted at the ortho position, the manufacturing process is simplified, the manufacturing cost is further reduced, and this bridged metallocene is further synthesized. The use of the compound has the advantage of reducing the production cost of the ethylene copolymer.

In the bridged metallocene compound (a-3) represented by the general formula [VII], R ⁵ and R ⁶ are the electron-donating substituents at the meta position and/or para position relative to the bond with the carbon atom as Y. When it is 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 an atom or a substituent 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, each of which may be the same. They may be different or may be bonded to each other to form a ring, and the line drawn to the right of N represents a bond with a phenyl group.)

Specific examples of these substituents can be given as 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 bridged 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. A substituent selected from a group, an oxygen-containing group, a halogen atom and a halogen-containing group, which may be the same or different and adjacent substituents of R ⁷ , R ⁸ and R ¹⁰ are bonded to each other to form a ring. NR ⁷ R ⁸ is a nitrogen-containing group having a Hammett's rule substituent constant σ of −0.2 or less. When a plurality of nitrogen-containing groups are present, each of the nitrogen-containing groups is 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 bridged metallocene compound (a-3) represented by the general formula [VII], R ⁵ and R ⁶ are the electron-donating substituents at the meta position and/or para position relative to the bond with the carbon atom as Y. When it is 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 the formula [III], R ⁹ is an atom or a 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 depicted on the right of O. The broken line represents the bond with the phenyl group.)

Specific examples of these substituents can be given as 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 bridged 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 a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, oxygen. An atom or a substituent selected from a containing group, a halogen atom and a halogen containing group, which may be the same or different, and the adjacent substituents of R ¹⁰ may be bonded to each other to form a ring, OR ⁹ is an oxygen-containing group having a Hammett's rule substituent constant σ-0.2 or less, and when a plurality of oxygen-containing groups are present, the respective oxygen-containing groups may be the same or different, and n is It is an integer of 1 to 3, and m is an integer of 0 to 4.)

The bridged metallocene compound (a) represented by the general formula [I], the bridged metallocene compound (a-1) represented by the general formula [V], and the bridged metallocene compound represented by the general formula [VI] ( a-2), the bridged metallocene compound (a-3) represented by the general formula [VII], the bridged metallocene compound (a-4) represented by the general formula [IX] or the general formula [X]. In the represented bridged metallocene compound (a-5), M is more preferably a hafnium atom. 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 above-mentioned bridged metallocene compound in which M is a hafnium atom, the resulting ethylene-based copolymer is further added. The advantages of higher molecular weight and improved copolymerization performance of non-conjugated polyene are obtained.

(Exemplary examples of the bridged metallocene compound (a))
As such a bridged metallocene compound (a),
[Dimethylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [diethylmethylene (η ⁵ -Cyclopentadienyl) (η ^5- 2,3,6,7-Tetramethylfluorenyl)] hafnium dichloride, [di-n-butylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorene Nil)] hafnium dichloride, [dicyclopentylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [dicyclohexylmethylene (η ⁵ -cyclopenta) Dienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride,
[Cyclopentylidene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [Cyclohexylidene (η ⁵ -Cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethyl-fluorenyl)] hafnium dichloride,
[Diphenylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [di-1-naphthylmethylene (η ⁵ -cyclopentadienyl) (Η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [di-2-naphthylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7- Tetramethylfluorenyl)] hafnium dichloride,
[Bis(3-methylphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis(4-methylphenyl)methylene( η ⁵ -Cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis(3,4-dimethylphenyl)methylene (η ⁵ -cyclopentadienyl) (Η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis(4-n-hexylphenyl)methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,3 6,7-Tetramethylfluorenyl)] hafnium dichloride, [bis(4-cyclohexylphenyl)methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl) ] Hafnium dichloride, [bis(4-t-butylphenyl)methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride,
[Bis(3-methoxyphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis(4-methoxyphenyl)methylene( η ⁵ -Cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis(3,4-dimethoxyphenyl)methylene (η ⁵ -cyclopentadienyl) (Η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis(4-methoxy-3-methylphenyl)methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2 3,6,7-Tetramethylfluorenyl)]hafnium dichloride, [bis(4-methoxy-3,4-dimethylphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ −2,3,6, 7-Tetramethylfluorenyl)]hafnium dichloride, [bis(4-ethoxyphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)]hafnium Dichloride, [bis(4-phenoxyphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis{4-(trimethylsiloxy) )Phenyl}methylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride,
[Bis{3-(dimethylamino)phenyl}methylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis{4-(dimethyl Amino)phenyl}methylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis(4-N-morpholinylphenyl)(η ⁵ -cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride,
[Bis{4-(trimethylsilyl)phenyl}methylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride,
[Bis(3-chlorophenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis(4-chlorophenyl)methylene(η ⁵ -Cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [bis(3-fluorophenyl)methylene (η ⁵ -cyclopentadienyl) (η ^5- 2,3,6,7-Tetramethylfluorenyl)] hafnium dichloride, [bis(4-fluorophenyl)methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethyl Fluorenyl)] hafnium dichloride, [bis{3-(trifluoromethyl)phenyl}methylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium Dichloride, [bis{4-(trifluoromethyl)phenyl}methylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride,
[Methylphenylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [methyl(4-methylphenyl)methylene (η ⁵ -cyclopenta) Dienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [methyl(4-methoxyphenyl)methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3 ,6,7-Tetramethylfluorenyl)]hafnium dichloride, [methyl {4-(dimethylamino)phenyl}methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethyl Fluorenyl)] hafnium dichloride, [methyl (4-N-morpholinylphenyl) methylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium Dichloride,
[Dimethylsilylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [diethylsilylene (η ⁵ -cyclopentadienyl) (η ^5- 2,3,6,7-Tetramethylfluorenyl)] hafnium dichloride, [dicyclohexylsilylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium Dichloride, [diphenylsilylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [di(4-methylphenyl)silylene (η ⁵ -cyclo Pentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride,
[Dimethylgermylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride, [Diphenylgermylene (η ⁵ -Cyclopentadienyl) (η ⁵ -2,3,6,7-tetramethyl-fluorenyl)] hafnium dichloride,
[1-(η ⁵ -Cyclopentadienyl)-2-(η ⁵ -2,3,6,7-tetramethylfluorenyl)ethylene] hafnium dichloride, [1-(η ⁵ -Cyclopentadienyl) -3-(η ⁵ -2,3,6,7-tetramethylfluorenyl)propylene] hafnium dichloride, [1-(η ⁵ -cyclopentadienyl)-2-(η ⁵ -2,3,6 ,7-Tetramethylfluorenyl)-1,1,2,2-tetramethylsilylene]hafnium dichloride, [1-(η ⁵ -cyclopentadienyl)-2-(η ⁵ -2,3,6, Examples include 7-tetramethylfluorenyl)phenylene]hafnium dichloride, and compounds in which a hafnium atom of these compounds is replaced with a zirconium atom or a chloro ligand is replaced with a methyl group. (A) is not limited to these examples.

<Method for producing crosslinked metallocene compound>
The bridged 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), WO 2006/123759, WO 01/27124, JP 2004-168744 A, JP 2004-175759 A, JP 2000-175759 A, which are the publications filed by the present applicant. It can be manufactured by the method described in Japanese Patent No. 212194.

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

When using a bridged metallocene compound as an olefin polymerization catalyst component, the catalyst is
(A) a bridged metallocene compound represented by the general formula [I],
At least one selected from (b) (b-1) organometallic compounds, (b-2) organoaluminum oxy compounds, and (b-3) compounds that react with the bridged metallocene compound (a) to form ion pairs. Seed compounds,
If necessary,
(C) A particulate carrier.
Hereinafter, each component will be specifically described.

<(b-1) Organometallic compound>
As the (b-1) organometallic compound used in the present invention, specifically, the organometallic compounds of Groups 1, 2 and 12 and 13 of the periodic table as represented by 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], R ^a and R ^b may be the same or different and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, 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). .

Examples of such compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methyl Examples thereof include aluminum dichloride, dimethyl aluminum chloride and diisobutyl aluminum hydride.

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

(B-1c) formula ^{R a R b M 3 ··· [} IX]
(In the formula [IX], R ^a and R ^b may be the same or different and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd. A dialkyl compound having a metal of Group 2 or Group 12 of the periodic table represented by the formula:

Among the above-mentioned organometallic compounds (b-1), organoaluminum compounds such as triethylaluminum, triisobutylaluminum and tri-n-octylaluminum are preferable. Moreover, such an organometallic compound (b-1) may be used individually by 1 type, and may be used in combination of 2 or more type.

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

The 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, ceric chloride hydrate, etc. A method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension of, and reacting the adsorbed water or crystal water with the organoaluminum compound.
(2) A method in which water, ice, or water vapor is allowed to directly act 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 organic metal component. Further, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent or suspended in the poor solvent for the aluminoxane.

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

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

The (b-2) organoaluminum oxy compound used in the present invention is a benzene-insoluble organoaluminum oxy compound. It is usually 10% by weight or less, preferably 5% by weight or less, and particularly preferably 2% by weight or less, that is, those which are insoluble or sparingly soluble in benzene are preferable.

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

〔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, R ^{2 to} R ⁵ may be the same or different from each other, and a hydrogen atom, a halogen atom, and a carbon number of 1 to 10 hydrocarbon groups are shown. ]

The organoaluminum oxy compound containing boron represented by the general formula [X] is an alkylboronic acid represented by the following general formula [XI],
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 an organoaluminum compound in an inert solvent in 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-hexylboron. Acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis(trifluoromethyl)phenylboronic acid and the like can be mentioned.

Of 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 an alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (b-1a) above.

Of these, trialkyl aluminum and tricycloalkyl aluminum are preferable, and trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum are particularly preferable. These may be used alone or in combination of two or more. The organoaluminum oxy compound (b-2) as described above may be used alone or in combination of two or more.

<(b-3) Compound that reacts with the transition metal compound (a) to form an ion pair>
Examples of the compound (b-3) that reacts with the crosslinked metallocene compound (a) to form an ion pair (hereinafter referred to as “ionized ionic compound”) include JP-A-1-501950 and JP-A-1-502036. Lewis acids and ionic compounds described in JP-A No. 3-179005, JP-A No. 3-179006, JP-A No. 3-207703, JP-A No. 3-207704, USP-5321106, etc. , Borane compounds and carborane compounds. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned. Such ionized ionic compounds (b-3) may be used alone or in combination of two or more.

Specific examples of the Lewis acid include compounds represented by BR ₃ (R is a phenyl group which may have a substituent such as fluorine, a methyl group and a trifluoromethyl group or fluorine). , 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 cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. ^{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 triphenylcarbonium cation, tri(methylphenyl)carbonium cation, tri(dimethylphenyl)carbonium cation, and other trisubstituted carbonium cations.

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

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

R ¹⁺ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N,N-dimethylanilinium cation or an N,N-diethylanilinium cation.

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

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

Specific examples of the N,N-dialkylanilinium salt include, 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 dialkyl ammonium 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, ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium pentaphenyl Examples also include a cyclopentadienyl complex, an N,N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula [XIII] or [XIV].

（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.)

Specific examples of the borane compound include decaborane; bis[tri(n-butyl)ammonium]nonaborate, bis[tri(n-butyl)ammonium]decaborate, bis[tri(n-butyl)ammonium]undecaborate, bis Anion salts such as [tri(n-butyl)ammonium]dodecaborate, bis[tri(n-butyl)ammonium]decachlorodecaborate, bis[tri(n-butyl)ammonium]dodecachlorododecaborate; tri(n -Butyl)ammonium bis(dodecahydrido dodecaborate)cobaltate (III), bis[tri(n-butyl)ammonium]bis(dodecahydridododecaborate)nickelate (III) and other salts of metal borane anions Can be mentioned.

Specific examples of the carborane compound include, for example, 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecaborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride. 1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaunadecaborane, 2,7-dicarbaunadecaborane, Undeca hydride-7,8-dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborane, tri(n-butyl)ammonium 1-carbadecaborate, tri( n-Butyl)ammonium-1-carbaundecaborate, tri(n-butyl)ammonium-1-carbadodecaborate, tri(n-butyl)ammonium-1-trimethylsilyl-1-carbadecaborate, tri(n-butyl) ) Ammonium bromo-1-carbadodecaborate, tri(n-butyl)ammonium-6-carbadecaborate, tri(n-butyl)ammonium-7-carbaundecaborate, tri(n-butyl)ammonium-7,8 -Dicarbaundecaborate, tri(n-butyl)ammonium-2,9-dicarbaundecaborate, tri(n-butyl)ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri(n-) Butyl)ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri(n-butyl) Ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri(n-butyl)ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri(n-butyl)ammoniumun Anion salts such as decahydride-4,6-dibromo-7-carbaundecaborate;
Tri(n-butyl)ammonium bis(nonahydride-1,3-dicarbanonaborate)cobaltate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate) Ferrate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarboundecaborate)cobaltate (III), tri(n-butyl)ammonium bis(undecahydride-7) ,8-Dicarbaundecaborate)nickelate (III), tri(n-butyl)ammonium bis(undecahydride-7,8-dicarbaundecaborate)cuprate (III), tri(n-butyl) Ammonium bis(undecahydride-7,8-dicarbaundecaborate)aurate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) Ferrate (III), tri(n-butyl)ammonium bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)chromate (III), tri(n-butyl)ammonium bis( Tribromooctahydride-7,8-dicarbaundecaborate)cobaltate (III), tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)chromate (III) , Bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborate)manganate (IV), bis[tri(n-butyl)ammonium]bis(undecahydride-7-cal Examples thereof include salts of metal carborane anions such as boundecaborate)cobaltate (III) and bis[tri(n-butyl)ammonium]bis(undecahydride-7-carboundecaborate)nickelate (IV). Be done.

The heteropoly compound is composed of an atom selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorous Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid, phosphomolybdotungstic acid , Phosphorus molybdo niobate, and salts of these acids, such as metals of Group 1 or 2 of the Periodic Table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium. Etc., and organic salts such as triphenylethyl salt can be used, but not limited thereto.

(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 preferable. More preferable.

(B-3) The ionized ionic compound may be 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 the ionized ionic compound (b-3) such as triphenylcarbenium tetrakis(pentafluorophenyl)borate is used in combination, a very high polymerization activity is exhibited in the production of ethylene/α-olefin/non-conjugated polyene copolymer.

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

<(c) Carrier>
In the present invention, the carrier (c) optionally used is an inorganic compound or an organic compound, and is a granular or fine particle solid.

Of these, the inorganic compound is preferably a porous oxide, an inorganic halide, clay, a clay mineral, or an ion-exchange layered compound.
As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ or the like, or a compound or mixture containing them 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. Among these, those containing SiO ₂ and/or Al ₂ O ₃ as the main components are preferable. The properties of such a porous oxide differ depending on the type and production method, but 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. ² /g, preferably 100 to 700 m ² /g, and a pore volume 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 or the like is used. The inorganic halide may be used as it is, or may be used after being crushed by a ball mill or a vibration mill. It is also possible to use the one prepared by dissolving the inorganic halide in a solvent such as alcohol and then depositing it in the form of fine particles with a depositing agent.

Clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with each other with weak bonding forces, and the ions contained therein can be exchanged. Most clay minerals are ion-exchangeable layered compounds. Further, these clays, clay minerals, and ion-exchange layered compounds are not limited to naturally occurring compounds, and artificial synthetic products can also be used.

In addition, clay, clay minerals, or ion-exchangeable layered compounds include clay, clay minerals, and ionic crystalline compounds having a layered crystal structure such as hexagonal close packing type, antimony type, CdCl ₂ type, and CdI ₂ type. It can be illustrated. Such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hissingelite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdee group, palygorskite, kaolinite, nakrite, dickite. , Halloysite, and the like, and as the ion-exchange layered compound, 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} ), crystalline acid salts of polyvalent metals such as γ-Ti(NH ₄ PO ₄ ) ₂ ·H ₂ O, and the like.

Such clay, clay mineral or ion-exchangeable layered compound preferably has a pore volume of 20 cc or more and a radius of 0.1 cc/g or more, measured by mercury porosimetry, preferably 0.3 to 5 cc/g. Particularly preferred. Here, the pore volume is measured in the range of the pore radius of 20 to 30000Å by the mercury intrusion method using a mercury porosimeter.

When a carrier having a pore volume with a radius of 20 Å or more and 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 and a treatment for affecting the crystal structure of clay 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. Alkali treatment destroys the crystal structure of clay and causes a change in the structure of clay. Further, in the salt treatment and the organic substance treatment, an ionic complex, a molecular complex, an organic derivative and the like can be formed to change the surface area and the interlayer distance.

The ion-exchangeable layered compound may be a layered compound in which the interlayer is expanded by utilizing the ion-exchange property and exchanging the interlayer exchangeable ion with another large bulky ion. Such bulky ions play a pillar-like role for supporting the layered structure, and are usually called pillars. Further, such introduction of another substance between the layers of the layered compound is called intercalation. As the guest compound to be intercalated, a cationic inorganic compound such as TiCl ₄ , ZrCl ₄ or the like, a metal alkoxide (such as Ti(OR) ₄ , Zr(OR) ₄ , PO(OR) ₃ or 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 may be used alone or in combination of two or more. In addition, when these compounds were intercalated, they were obtained by hydrolyzing a metal alkoxide (R is a hydrocarbon group, etc.) such as Si(OR) ₄ , Al(OR) ₃ , Ge(OR) _4, etc. A polymer, a colloidal inorganic compound such as SiO ₂ and the like can be allowed to coexist. Examples of the pillars include oxides produced by intercalating the above metal hydroxide ions between layers and then heating and dehydrating them.

The clay, clay mineral, and ion-exchange layered compound may be used as they are, or may be used after treatment such as ball milling and sieving. Further, it may be used after newly adsorbing and adsorbing water, or after heat dehydration treatment. Furthermore, they may be used alone or in combination of two or more.

Among these, preferred are clays and clay minerals, and particularly preferred are 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, (co)polymers or vinylcyclohexane or styrene produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene are used. The (co)polymer produced as a main component, and those modified compounds can be illustrated.

The olefin polymerization catalyst used in the present invention comprises a crosslinked metallocene compound (a), (b-1) an organometallic compound, (b-2) an organoaluminumoxy compound, and (b-3) an ionized ionic compound. It is also possible to include at least one compound (b) selected and a carrier (c) used as necessary.

<Method of polymerizing monomers in the presence of catalyst for ethylene/α-olefin/non-conjugated polyene copolymer>
When copolymerizing ethylene, an α-olefin, and a non-conjugated polyene, the usage and addition order 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 polymerization vessel.
(2) A method of adding the compound (a) and the compound (b) to the polymerization vessel in any 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 polymerization vessel in any 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 polymerization vessel in any 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 polymerization vessel.

In each of the 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 methods (4) and (5) in which the compound (b) is supported, the unsupported compound (b) may be added in any order, if necessary. In this case, the compound (b) may be the same as or different from the compound (b) supported on the 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), olefin is 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, in the presence of the above-mentioned catalyst for ethylene/α-olefin/non-conjugated polyene copolymer, ethylene, α-olefin and non-conjugated polyene are added. An ethylene/α-olefin/non-conjugated polyene copolymer can be produced by copolymerizing the above.

In the present invention, any of liquid phase polymerization methods such as solution (dissolution) polymerization and suspension polymerization or gas phase polymerization methods can be carried out.
Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and aliphatic hydrocarbons such as kerosene, cyclopentane, cyclohexane, methylcyclopentane. Alicyclic hydrocarbons such as benzene, aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. Use alone or in combination of two or more. You can Also, the olefin itself can 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 1 liter of reaction volume. ^{-Used in} an amount to give ^-8 mol.

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

Further, the polymerization temperature of ethylene or the like using such a copolymer catalyst is usually -50 to +200°C, preferably 0 to +200°C, more preferably +80 to +200°C. The higher temperature (+80° C. or higher) is preferable from the viewpoint of productivity, though it depends on the ultimate molecular weight and the polymerization activity of the polymer catalyst system.

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

The molecular weight of the resulting ethylene-based polymer can also be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature. Further, it can be adjusted depending on the amount of the compound (b) used. Specific examples 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 seal packing composition of the present invention contains the above-mentioned ethylene/α-olefin/non-conjugated polyene copolymer (ethylene-based copolymer A), and preferably contains a crosslinking agent as another component.

The seal packing composition of the present invention may contain another polymer 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. Is 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 ( Styrene-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 of the elastomer include a thermoplastic elastomer (TPU) and other thermoplastic elastomers (TPZ). The other polymer can be added 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 copolymer A.

Further, the seal packing composition of the present invention contains other additives depending on the purpose, for example, a crosslinking aid, a vulcanization accelerator, a vulcanization aid, a softening agent, a reinforcing agent, an antioxidant, an inorganic filler. , A processing aid, an activator, a hygroscopic agent, a heat resistance stabilizer, a weather resistance stabilizer, an antistatic agent, a colorant, a lubricant, a thickener, a foaming agent and a foaming auxiliary agent may be contained. .. Also. Each additive may be used alone or in combination of two or more.

The composition for seal packing according to the present invention contains the ethylene-based copolymer A and other components optionally blended at a desired temperature using a kneader such as a mixer, a kneader, or a roll. It can be prepared by kneading. Since the ethylene-based copolymer A has excellent kneading properties, it is possible to favorably prepare the seal packing composition.

Specifically, using a conventionally known kneading machine such as a mixer or a kneader, the ethylene 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, the resulting kneaded product is optionally added with other components such as a cross-linking agent and the like, and is used at a predetermined temperature and time using a roll, for example, at a roll temperature of 30 to 80° C. The composition for seal packing of the present invention can be prepared by kneading for about 30 minutes.

<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 its derivatives, amine compounds, azo compounds, epoxy compounds, and isocyanate compounds. The cross-linking agent generally used in cross-linking may be mentioned. Among these, organic peroxides and sulfur compounds (hereinafter also referred to as “vulcanizing agent”) are preferable.

Examples of the organic peroxide include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(. tert-Butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3,1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert) -Butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert- Butyl peroxybenzoate, ert-butyl peroxy isopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide.

When an organic peroxide is used as the cross-linking agent, the amount of the compound in the seal packing composition is such that the ethylene copolymer A and other polymer that needs to be cross-linked (such as cross-linkable rubber) In general, the amount is 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass in total. When the compounding amount of the organic peroxide is within the above range, there is no blooming on the surface of the obtained seal packing and the composition for seal packing exhibits excellent crosslinking properties, which is preferable.

When an organic peroxide is used as a crosslinking agent, it is preferable to use a crosslinking auxiliary together. Examples of the crosslinking aid include sulfur; quinonedioxime crosslinking aids such as p-quinonedioxime; acrylic crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; 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 two types (JIS standard (K-1410)), manufactured by Hakusui Tech Co., Ltd.), magnesium oxide, Examples thereof include metal oxides such as zinc white (for example, zinc oxide such as “META-Z102” (trade name; manufactured by Inoue Lime Industry Co., Ltd.)).

When a crosslinking aid is used, the amount of the crosslinking aid in the seal packing composition is usually 0.5 to 10 mol, preferably 0.5 to 7 mol, based on 1 mol of the organic peroxide. It is preferably 1 to 6 mol.

Examples of the sulfur-based compound (vulcanizing 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 of the compound in the seal packing composition is set to that of the ethylene-based copolymer A and other polymer (cross-linkable rubber or the like) that needs to be cross-linked. It is usually 0.3 to 10 parts by mass, preferably 0.5 to 7.0 parts by mass, and more preferably 0.7 to 5.0 parts by mass with respect to 100 parts by mass in total. When the blending amount of the sulfur-based compound is within the above range, there is no blooming on the surface of the obtained seal packing, and the seal packing composition exhibits excellent crosslinking properties.

When a sulfur compound is used as a crosslinking agent, it is preferable to use a vulcanization accelerator together.
Examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, N,N′-diisopropyl-2-benzothiazolesulfenamide, 2 -Mercaptobenzothiazole (for example, Sunceller M (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)), 2-(4-morpholinodithio) benzthiazole (for example, Nocceller MDB-P (trade name; Ouchi Shinko Chemical Industry Co., Ltd.) )), 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio)benzothiazole and dibenzothiazyl disulfide (for example, Sancellar DM (trade name; (Shin Chemical Industry Co., Ltd.)) and other thiazole vulcanization accelerators; guanidine vulcanization accelerators such as diphenylguanidine, triphenylguanidine and diorsotolylguanidine; acetaldehyde/aniline condensate and butyraldehyde/aniline condensate Aldehyde amine-based vulcanization accelerators; 2-mercaptoimidazoline and other imidazoline-based vulcanization accelerators; tetramethylthiuram monosulfide (for example, Sansel TS (trade name; Sanshin Chemical Industry Co., Ltd.)), tetramethylthiuram disulfide (for example, , Sansera TT (trade name; Sanshin Chemical Industry Co., Ltd.), tetraethyl thiuram disulfide (for example, Sansera TET (trade name; Sanshin Chemical Industry Co., Ltd.)), tetrabutyl thiuram disulfide (for example, Sansera TBT (trade name; Sanshin Chemical Industry Co., Ltd.) and dipentamethylene thiuram tetrasulfide (for example, Sancella TRA (trade name; Sanshin Chemical Industry Co., Ltd.)) and other thiuram vulcanization accelerators; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate. , Zinc dibutyldithiocarbamate (for example, Sancella PZ, Sancella BZ and Sancella EZ (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.)) and dithioate vulcanization accelerators such as tellurium diethyldithiocarbamate; ethylenethiourea (for example, Sancella BUR (trade name; Sanshin Chemical Industry Co., Ltd.), Sansera 22-C (trade name; Sanshin Chemical Industry Co., Ltd.)), thiourea-based additives such as N,N'-diethylthiourea and N,N'-dibutylthiourea Sulfurization accelerators: Zanthate-based vulcanization accelerators such as zinc dibutylxatogenate can be mentioned.

When a vulcanization accelerator is used, the amount of these vulcanization accelerators contained in the composition for seal packing is such that the ethylene-based copolymer A and other polymers that need to be cross-linked (crosslinkable It is generally 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, based on 100 parts by mass in total of rubber and the like. When the blending amount of the vulcanization accelerator is within the above range, the resulting seal packing does not bloom on the surface thereof, and the seal packing composition exhibits excellent crosslinking properties.

When a sulfur compound is used as the crosslinking agent, a vulcanization aid can be used in combination.
Examples of the vulcanization aid include, for example, zinc oxide (for example, ZnO#1/zinc oxide two types, manufactured by Hakusui Tech Co., Ltd.), magnesium oxide, zinc oxide (for example, “META-Z102” (trade name; Inoue Lime Industry). (Manufactured by KK) and zinc oxide).

When a vulcanization aid is used, the amount of the vulcanization aid in the composition for seal packing is such that the ethylene copolymer A and other polymers that are blended as required (such as crosslinkable rubber) 1) to 20 parts by mass with respect to 100 parts by mass in total.

<Softener>
Examples of the softening agent include petroleum-based softening agents such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and petrolatum; coal tar-based softening agents such as coal tar; castor oil, linseed oil, rapeseed oil, large oil Fatty oil softeners such as soybean oil and coconut oil; waxes such as beeswax and carnauba wax; naphthenic acid, pine oil, rosin or its derivatives; synthetic polymer substances such as terpene resin, petroleum resin, coumarone indene resin; dioctyl Ester-based softeners such as phthalate and dioctyl adipate; Others include microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oil, tall oil, and sub (factice). Among these, petroleum-based softening Agents are preferred and process oils are particularly preferred.

When the composition for seal packing contains a softening agent, the blending amount of the softening agent is the total of the ethylene-based copolymer A and other polymer (elastomer, crosslinkable rubber, etc.) components blended as necessary. It is generally 2 to 100 parts by mass, preferably 10 to 100 parts by mass, relative to 100 parts by mass.

<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.

When the composition for seal packing contains a reinforcing agent, the amount of the reinforcing agent is the total of the ethylene copolymer A and other polymers (elastomer, crosslinkable rubber, etc.) to be added as necessary. It is generally 5 to 150 parts by mass, preferably 5 to 100 parts by mass, relative to 100 parts by mass.

<Anti-aging agent (stabilizer)>
By incorporating an antioxidant (stabilizer) into the composition for seal packing of the present invention, the life of the seal packing formed from the composition can be extended. As such an antiaging agent, there are conventionally known antiaging agents such as amine antiaging agents, phenol antiaging agents, and sulfur antiaging agents.

Examples of the antiaging agent include aromatic secondary amine antiaging agents such as phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine; dibutylhydroxytoluene, tetrakis[methylene(3,5-diene) -T-butyl-4-hydroxy)hydrocinnamate]methane and other phenolic antioxidants; bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide and the like Thioether anti-aging agent; dithiocarbamate anti-aging agent such as nickel dibutyl dithiocarbamate; 2-mercaptobenzoylimidazole, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dilaurylthiodipropionate, distearyl There are sulfur type antiaging agents such as thiodipropionate.

When the composition for seal packing contains an anti-aging agent, the amount of the anti-aging agent to be added is such that the ethylene copolymer A and other polymer (elastomer, crosslinkable rubber, etc.) to be added as necessary are added. It is usually 0.3 to 10 parts by mass, preferably 0.5 to 7.0 parts by mass, based on 100 parts by mass in total. When the blending amount of the antioxidant is within the above range, there is no bloom on the surface of the obtained seal packing, and it is possible to further suppress the occurrence of vulcanization inhibition.

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

When the composition for seal packing contains an inorganic filler, the amount of the inorganic filler to be blended is such that the ethylene copolymer A and another polymer to be blended as necessary (elastomer, crosslinkable rubber, etc.) It is usually 2 to 50 parts by mass, preferably 5 to 50 parts by mass with respect to 100 parts by mass in total. When the compounding amount of the inorganic filler is within the above range, the composition for seal packing has excellent kneading processability, and a seal packing having excellent mechanical properties can be obtained.

<Processing aid>
As the processing aid, for example, those generally blended with rubber as the 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, esters and the like. Of these, stearic acid is preferred.

When the composition for seal packing contains a processing aid, the amount of the processing aid to be added depends on the amount of the ethylene copolymer A and other polymer (elastomer, crosslinkable rubber, etc.) to be added as necessary. It is usually 10 parts by mass or less, preferably 8.0 parts by mass or less, based on 100 parts by mass in total.

<Activator>
Examples of the activator include amines such as di-n-butylamine, dicyclohexylamine, and monoeranolamine; diethylene glycol, polyethylene glycol, lecithin, triaryl meritolate, aliphatic carboxylic acid or aromatic carboxylic acid zinc compounds, and the like. Activators; zinc peroxide preparations; ktadecyl trimethyl ammonium bromide, synthetic hydrotalcite, special quaternary ammonium compounds.

When the composition for seal packing contains an activator, the amount of the activator is 100 in total of the ethylene copolymer A and other polymers (elastomer, crosslinkable rubber, etc.) optionally blended. It is usually 0.2 to 10 parts by mass, preferably 0.3 to 5 parts by mass with respect to parts by mass.

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

When the composition for seal packing contains a hygroscopic agent, the amount of the hygroscopic agent is the total of the ethylene copolymer A and other polymers (elastomer, crosslinkable rubber, etc.) to be blended as necessary. It is usually 0.5 to 15 parts by mass, preferably 1.0 to 12 parts by mass with respect to 100 parts by mass.

<Foaming agent and foaming aid>
The seal packing formed by using the rubber composition for seal packing 1 of the present invention may be a non-foamed body or a foamed body. When the seal packing is a foam, the rubber composition 1 for seal packing preferably 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 pentamethylene tetramine; azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexyl nitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'- Sulfonyl hydrazide compounds such as oxybis(benzenesulfonyl hydrazide)diphenyl sulfone-3,3′-disulphonyl hydrazide; azide compounds such as calcium azide, 4,4′-diphenyl disulfonyl azide and paratoluene malonyl azide. Among them, an azo compound, a sulfonyl hydrazide compound, and an azide compound are preferably used.

When the rubber composition for seal packing 1 contains a foaming agent, the blending amount of the foaming agent is appropriately selected depending on the performance required for the seal packing manufactured from the rubber composition for seal packing 1. Generally 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the ethylene copolymer A and other polymers (elastomer, crosslinkable rubber, etc.) blended as necessary. Used in proportion.

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

When the rubber composition 1 for seal packing contains a foaming aid, the compounding 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.

[Physical properties of composition for seal packing]
By using the composition for seal packing of the present invention, it is possible to form a seal packing having excellent mechanical properties at room temperature and low temperature properties.

By using the composition for seal packing of the present invention, it is possible to obtain a seal packing having excellent low temperature flexibility as compared with the case of using the conventional EPDM, and it is possible to obtain cold resistance as compared with the case of using silicone rubber. It is possible to obtain a seal packing having excellent properties.

[Seal packing]
The seal packing of the present invention is formed from the composition for seal packing described above.
As a method for producing a seal packing from the composition for seal packing of the present invention, for example, the composition 1 (uncrosslinked composition) is molded into a desired seal packing shape, and at the same time as or after the molding, A method of crosslinking the composition is mentioned.

Examples of the method for performing the crosslinking treatment include a method of using a composition containing a crosslinking agent as the seal packing composition, a method of crosslinking treatment by heating, and a crosslinking treatment by irradiating the seal packing composition with an electron beam. There is a method.

That is, the seal packing of the present invention, the composition for seal packing, using a molding machine such as an extrusion molding machine, a calender roll, a press, an injection molding machine, a transfer molding machine, is molded into an intended shape, and at the same time as molding. Alternatively, it can be prepared by introducing the molded product into a vulcanization tank and heating it at 120 to 270° C. for 1 to 30 minutes, or by crosslinking by irradiation with an electron beam.

A mold may be used for the cross-linking, or the cross-linking may be performed without using the mold. When a mold is not used, the molding and crosslinking 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 without using a cross-linking agent as a cross-linking method, the seal packing composition molded into a predetermined shape usually has an energy of 0.1 to 10 MeV, preferably 0.3 to 2 MeV. The electron beam may be irradiated so that the absorbed dose is usually 0.5 to 35 Mrad, preferably 0.5 to 10 Mrad.

INDUSTRIAL APPLICABILITY The seal packing of the present invention can be suitably used as a seal part for automobiles, a seal part for machines, a seal part for electronic/electrical parts, a gasket for construction, a seal part for civil engineering building materials, and a seal part for fuel cells.

Specific examples of the seal packing of the present invention include a brake master cylinder cup for a hydraulic brake, a brake wheel cylinder cup, a brake hydraulic pressure control seal packing, and a brake O-ring, a clutch cylinder cup for a clutch, and a condenser. Examples include packing and gaskets for sealing fuel cells.

The seal packing of the present invention is also preferably a seal packing used for hydrogen lines. At a hydrogen station that supplies hydrogen to a fuel cell vehicle or the like, there are many hydrogen lines through which hydrogen passes. The seal packing of the present invention can be suitably used as a seal packing used in such a hydrogen line.

Since a large amount of hydrogen is stored at the hydrogen station, it is necessary to store it in a compressor at high pressure. Further, when supplying hydrogen from the hydrogen station, it is necessary to send out at high pressure and high speed, and at this time, the temperature of hydrogen rises. In order to prevent the temperature inside the hydrogen tank of a fuel cell vehicle or the like from rising too high, it is necessary to store hydrogen at a low temperature at the hydrogen station, for example, at about -40°C. Therefore, the seal packing used for the hydrogen line is required to have a low-temperature sealing property. The seal packing of the present invention has both low temperature characteristics and mechanical strength (strength/elongation), and can be suitably used for hydrogen lines.

Further, in the seal packing of the present invention, particularly in the seal packing used for the hydrogen line, the cross-link density of the seal packing is preferably 1.0×10 ^{16 to} 1.0×10 ²² pieces/cc, and 1.0× It is more preferably 10 ^{18 to} 1.0×10 ²¹ pieces/cc, and particularly preferably 1.0×10 ^{19 to} 1.0×10 ²¹ pieces/cc. The crosslink density ν can be calculated by the following Flory-Rehner equation (1) using equilibrium swelling.

V _R in the formula (1) was obtained by extracting the seal packing with toluene under the condition of 37° C.×72 h.

As described above, the ethylene/α-olefin/non-conjugated polyene copolymer contained in the seal packing composition of the present invention has a structural unit derived from the α-olefin [B] having 4 to 20 carbon atoms. The crosslinked product of the ethylene/α-olefin/non-conjugated polyene copolymer (α-olefin having 4 to 20 carbon atoms) has a hydrogen content higher than that of the ethylene/propylene/non-conjugated polyene copolymer (EPDM). The present inventors have found that the permeability is low. As the polymer, a cross-linked product of the ethylene/α-olefin/non-conjugated polyene copolymer having a structural unit derived from an α-olefin [B] having a side chain larger than propylene and having 4 to 20 carbon atoms is a polymer. Those skilled in the art expect that hydrogen permeability will increase because chains easily form chains, and in fields such as hydrogen line seal packings through which hydrogen passes at high pressure, EPDM cross-linked products can be used as the ethylene/α Those skilled in the art do not consider changing to a cross-linked product of an olefin/non-conjugated polyene copolymer (α-olefin having 4 to 20 carbon atoms). However, contrary to the expectation, the present inventors have found that the crosslinked product of the ethylene/α-olefin/non-conjugated polyene copolymer (α-olefin having 4 to 20 carbon atoms) is more than the crosslinked product of EPDM. It was found that the hydrogen permeability was low. The reason why the hydrogen permeability of the crosslinked product of the ethylene/α-olefin/non-conjugated polyene copolymer (the carbon number of the α-olefin is 4 to 20) is low is not clear. -When comparing a cross-linked product of an olefin/non-conjugated polyene copolymer (α-olefin having 4 to 20 carbon atoms) and a cross-linked product of EPDM at the same density, the ethylene/α-olefin/non-conjugated polyene copolymer It was speculated that a crosslinked polymer (α-olefin having 4 to 20 carbon atoms) may be more likely to be crystallized and that the crosslink density may be equal to or higher than that of EPDM due to the mobility of the molecular chain. ..

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 description of Examples and the like, "parts" means "parts by mass" unless otherwise specified.

<Ethylene/α-olefin/non-conjugated polyene copolymer>
[Molar amount 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 non-conjugated polyene [C] of the ethylene/α-olefin/non-conjugated polyene copolymer is , ¹ H-NMR spectrum meter.

[Moonie 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 viscometer (SMV202 type manufactured by Shimadzu Corporation). ..

[B value]
Using o-dichlorobenzene-d ₄ /benzene-d ₆ (4/1 [v/v]) as a measurement solvent, at a measurement temperature of 120° C., ¹³ C-of the ethylene/α-olefin/non-conjugated polyene copolymer was obtained. 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×[E]×([X]+[Y])]...(i)
Here, [E], [X] and [Y] represent the mole fractions of ethylene [A], α-olefin [B] having 4 to 20 carbon atoms and non-conjugated polyene [C], respectively, and [EX] ] Shows ethylene [A]-C4-20 alpha-olefin [B] dyad chain fraction.

(Limited viscosity)
The intrinsic viscosity [η] of the ethylene/α-olefin/non-conjugated polyene copolymer is a value measured at 135°C using a decalin solvent.

Specifically, about 20 mg of an ethylene/α-olefin/non-conjugated polyene copolymer was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135°C. To this decalin solution, 5 ml of decalin solvent was added and diluted, and then the specific viscosity ηsp was measured in the same manner. This dilution operation was repeated twice more, and the value of ηsp/C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity (see the following formula).
[Η]=lim(ηsp/C) (C→0)”

[Synthesis of transition metal compound]
Synthesis of [bis(4-methoxyphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride (catalyst-a1) (i) 6 Synthesis of 6,6-bis(4-methoxyphenyl)fulvene Under a nitrogen atmosphere, 8.28 g (115 mmol) of lithium cyclopentadienide and 200 ml of dehydrated THF (tetrahydrofuran) were added to a 500 ml three-necked flask. 13.6 g (119 mmol) of DMI (1,3-dimethyl-2-imidazolidinone) was added while cooling with an ice bath, and the mixture was stirred at room temperature for 30 minutes. After that, 25.3 g (105 mol) of 4,4′-dimethoxybenzophenone was added, and the mixture was stirred under heating under reflux for 1 week. 100 ml of water was gradually added while cooling with an ice bath, 200 ml of dichloromethane was further added, and the mixture was stirred at room temperature for 30 minutes. The obtained bilayer solution was transferred to a 500 ml separating 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 chromatography (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. The 1,6-bis(4-methoxyphenyl)fulvene was identified by ¹ H-NMR spectrum. The measured values are shown below.
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-necked 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 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 with an ice bath, and the resulting solution was transferred to a 300 ml separating funnel. After adding 50 ml of dichloromethane and shaking the mixture 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, the obtained solid was washed with a small amount of diethyl ether to collect a white solid, and the white solid was combined with the previously obtained white solid. This 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 by FD-MS spectrum. The measured values are shown below. FD-MS spectrum: M/z 512 (M ⁺ ).

(Iii) Synthesis of [bis(4-methoxyphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)] hafnium dichloride 100 ml Schlenk under nitrogen atmosphere 272 mg (0.531 mmol) of bis(4-methoxyphenyl)(cyclopentadienyl)(2,3,6,7-tetramethylfluorenyl)methane, 20 ml of dehydrated toluene and 90 μl (1.1 mmol) of THF were sequentially placed in the tube. Was added. 0.68 ml (1.1 mmol) of n-butyllithium/hexane solution (1.63M) was gradually added while cooling with an ice bath and 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 give a red solution again. 164 mg (0.511 mmol) of hafnium tetrachloride was added while cooling with a methanol/dry ice bath, and the mixture was stirred for 16 hours while gradually warming to room temperature, whereby a yellow slurry was obtained. 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 solid obtained by distilling off the solvent under reduced pressure was dissolved in a small amount of dichloromethane, hexane was added, and the mixture was recrystallized at -20°C. The precipitated solid was collected, washed with hexane and dried under reduced pressure to give [bis(4-methoxyphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,3,6 as yellow solid. , 7-Tetramethylfluorenyl)] hafnium dichloride (275 mg, 0.362 mmol, 70.8%) was obtained. [Bis(4-methoxyphenyl)methylene(η ⁵ -cyclopentadienyl)(η ⁵ -2,3,6,7-tetramethylfluorenyl)]hafnium dichloride was identified by ¹ H-NMR spectrum and FD- It was performed by MS spectrum. The measured values are shown below.

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=2.6 Hz, 2H), 6.15 (s, 2H), 5.65 (t, J=2.6 Hz, 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]
Polymerization reaction of ethylene, 1-butene and 5-ethylidene-2-norbornene (ENB) was continuously carried out at 95° C. using a polymerization vessel having a volume of 300 L equipped with a stirring blade.
Hexane (feed rate: 31 L/h) was used as a polymerization solvent, and ethylene feed rate was 3.8 kg/h, 1-butene feed rate was 7 kg/h, ENB feed rate was 390 g/h and hydrogen continuously. It was continuously fed to the polymerization reactor so that the feed rate was 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 fed to the polymerization vessel at a feed rate of 0.020 mmol/h. Further, as co-catalysts _{(C 6 H 5) 3 CB} (C 6 F 5) 4 (CB-3) The feed rate 0.100 mmol / h, triisobutylaluminum (TiBA) the feed rate 10 mmol / h as the organoaluminum compound Were continuously fed to the polymerization reactor.

Thus, 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 liquid extracted from the lower part of the polymerization vessel to stop the polymerization reaction, and the ethylene/1-butene/ENB copolymer was separated from the solvent by steam stripping treatment. It was dried under reduced pressure overnight.

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 properties of the obtained EBDM-1 were measured by the methods described above. The results are shown in Table 1.

[Synthesis Examples 2 to 6]
Ethylene/1-butene/ENB copolymer (EBDM-2) of Synthesis Example 2 and ethylene/1 of Synthesis Example 3 were prepared in the same manner as in Synthesis Example 1 except that the polymerization conditions were changed as described in Table 1. -Butene/ENB copolymer (EBDM-3), ethylene/1-butene/ENB copolymer of Synthesis Example 4 (EBDM-4), ethylene/1-butene/ENB copolymer of Synthesis Example 5 (EBDM-) 5), an ethylene/1-butene/ENB copolymer (EBDM-6) of Synthesis Example 6 was obtained. The results are shown in Table 1.

[Example 1]
<<Composition for seal packing>>
Using MIXTRON BB MIXER (manufactured by Kobe Steel, Ltd., BB-2 type, volume 1.7 L, rotor 2WH), 100 parts of EBDM-1 obtained in Synthesis Example 1 was zinc oxide as a crosslinking aid. (ZnO #1/Zinc oxide 2 types (JIS standard (K-1410), manufactured by Hakusui Tech Co., Ltd.) 5 parts, stearic acid 1 part as a processing aid, carbon black "Asahi #60G" as a reinforcing agent ( Trade name: Asahi Carbon Co., Ltd. 40 parts, as an anti-aging agent, Sandant MB (2-mercaptobenzimidazole, Sanshin Chemical Industry Co., Ltd.) 2 parts, as an anti-aging agent Irganox 1010 (dibutyl) Hydroxytoluene, tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane, manufactured by BASF) were blended in an amount of 1 part and then kneaded to obtain a blend 1.

The kneading conditions were such that the rotor rotation speed was 40 rpm, the floating weight pressure was 3 kg/cm ² , the kneading time was 5 minutes, and the kneading discharge temperature was 144° C.
Then, after confirming that the temperature of the compound 1 reached 40° C., a kayak mill D-40C (dicumyl peroxide 40 mass %, as a crosslinking agent (vulcanizing agent) was added to the compound 1 by using a 6-inch roll. Kayaku Akzo) was added at a compounding amount of 6.8 parts and kneaded to obtain compound 2 (composition for seal packing).

The kneading conditions were as follows: roll temperature: front roll/rear roll=50° C./50° C., roll peripheral speed: front roll/rear roll=18 rpm/15 rpm, roll gap: 3 mm, blending time: 8 minutes, blending Got 2.

[Unvulcanized physical property test 1: Mooney viscosity]
The Mooney viscosity ML ₍₁₊₄₎ 100° C. of the 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 vulcanized properties]
Vulcanization measuring device: MDR2000 (manufactured by ALPHA TECHNOLOGIES) was used to measure the vulcanization induction time (TS1) and the vulcanization rate (TC90) of the compound 2 as follows.

The torque change obtained under the conditions of constant temperature and constant shear rate was measured.
The time from the minimum torque value to the torque increase of 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 taken as TC90 (min). The measurement conditions were a temperature of 180° C. and a time of 15 minutes. The smaller the TC90, the faster the vulcanization rate.

<<Evaluation of vulcanized products (crosslinked products)>>
The compound 2 was crosslinked with a press molding machine at 180° C. for 10 minutes to prepare a sheet (vulcanized product) having a thickness of 2 mm.

The obtained sheet was subjected to hardness test, tensile test, calculation of crosslink density, heat aging resistance test, Gehman twist test, TR test, low temperature flexibility test and storage elastic modulus test by the following methods.

The compound 2 was vulcanized at 180° C. for 13 minutes by using a press molding machine in which a cylindrical mold was set to prepare a right cylindrical test piece having a thickness of 12.7 mm and a diameter of 29 mm and compressed. A test piece (vulcanized product) for permanent set (CS) test was obtained.

The compression set was evaluated by the following method using the obtained test piece for compression set (CS) test.
The results are shown in Table 3.

[Hardness test: hardness (Durometer-A)]
Regarding the hardness of the sheet, the description of “Hardness test” in item 7 of “Physical test method for thermosetting polyurethane elastomer molded article” of JIS K7312 (1996) and JIS K6253 (2006) “Vulcanized rubber and thermoplastic rubber- The hardness was measured in accordance with the description of test type A in “Durometer hardness test” in item 6 of “Determination of hardness”.

[Tensile test: modulus, stress at tensile break, elongation at tensile break]
The sheet modulus, tensile stress at break and elongation at break were measured by the following methods.
The sheet was punched out to prepare a No. 3 type dumbbell test piece described in JIS K 6251 (1993), and using this test piece, a measurement temperature of 25° C. was measured according to the method specified in JIS K 6251 paragraph 3. A tensile test was performed under the conditions of a tensile speed of 500 mm/min, and a tensile stress (25% modulus (M25)) when the elongation rate was 25% and a tensile stress (50% modulus (M50) when the elongation rate was 50%. )), tensile stress when the elongation is 100% (100% modulus (M100)), tensile stress when the elongation is 200% (200% modulus (M200)), tensile stress at break (TB) And tensile elongation at break (EB) were measured.

[Calculation of crosslink density]
The crosslink density ν of the sheet was calculated from the following Flory-Rehner equation (1) using equilibrium swelling.
V _R in the formula (1) was obtained by extracting a crosslinked 2 mm sheet with toluene under the condition of 37° C.×72 h.

[Heat resistance aging test]
According to JIS K 6257, the sheet was subjected to a heat aging test of holding it at 150° C. for 168 h. The hardness, tensile stress at break and tensile elongation at break of the sheet after the heat aging test are the same as those in the item [Hardness (Durometer-A)] and the item [Modulus, tensile stress at break, tensile elongation at break]. It was measured by the method.

AH (Duro-A) was determined from the difference in hardness before and after the heat aging test, and after the test against the value before the heat aging test from the tensile break point stress (TB) and the tensile break point elongation (EB) before and after the heat aging test. The rate of change was calculated as Ac(TB) and Ac(EB), respectively.

[Gehman twist test (low temperature twist test)]
In the low temperature twist test, T ₂ (° C.), T ₅ (° C.) and T ₁₀ (° C.) of the sheet were measured using a Gehman twist tester according to JIS K6261 (1993). These temperatures are indicators of the low temperature flexibility of the vulcanized rubber. For example, the lower T ₂ is, the better the low temperature flexibility is.

[TR test (low temperature elastic recovery test)]
According to JIS K6261, the sheet was subjected to a TR test (low temperature elastic recovery test) to measure cold resistance.

The test measures the recoverability of stretched sheets by freezing the stretched sheets and continuously increasing the temperature. (Temperatures at which the length of the test piece shrinks (recovers) by 10%, 30%, 50%, and 70% by the temperature rise are indicated as TR10, TR30, TR50, and TR70, respectively.) TR10 (unit: °C) It can be judged that the lower is the better the cold resistance.

[Low temperature flexibility test: tan δ-Tg (low temperature flexibility)]
A strip sample having a width of 10 mm, a thickness of 2 mm and a length of 30 mm was prepared from the sheet.
Using this sample, the temperature dispersion of viscoelasticity (-70°C to 25°C) was measured by RDS-II manufactured by Rheometrics under the conditions of 0.5% strain and 1 Hz frequency. tan δ-Tg (° C.) was derived by reading the peak temperature from the temperature dependence curve of tan δ.

[Storage elastic modulus test: Storage elastic modulus (-40°C)]
The sheet was measured using RDS-II manufactured by Rheometrics in a torsion mode (torsion) between a width of 10 mm and a length of 38 mm at a heating rate of 2°C/min from -100°C to 100°C at 10 Hz. , And the value of the storage elastic modulus G′(Pa) at −40° C. was obtained.

[Compression set]
With respect to the test piece for measuring compression set (CS), the compression set was measured according to JIS K6262 (1997) after treatment at 125° C. for 72 hours and then at 0° C., −40° C. or −50° C. for 22 hours.

[Examples 2 to 10]
Example 1 was repeated except that the type of EBDM and the amount of carbon black "Asahi #60G" were changed as described in Table 2, and Formulation 1 and Formulation 2 were prepared for each of Examples 2 to 10. Got

A sheet was prepared in the same manner as in Example 1 and subjected to a hardness test, a tensile test, a calculation of a crosslink density, a heat aging resistance test, a Gehman twist test, a TR test, a low temperature flexibility test, and a storage elastic modulus test. .. In addition, a compression set (CS) test specimen was prepared in the same manner as in Example 1, and the compression set was measured. The results are shown in Table 3.
Table 2 shows the types of EBDM and the amount of carbon black "Asahi #60G" in each example.

[Comparative Examples 1 and 2]
EBDM-1 was changed to EPDM 14030 (Comparative Example 1) and EP331 (Comparative Example 2), the same procedure as in Example 1 was performed to obtain Formulation 1 and Formulation 2 for Comparative Examples 1 and 2, respectively. It was

A sheet was prepared in the same manner as in Example 1 and subjected to a hardness test, a tensile test, a calculation of a crosslink density, a heat aging resistance test, a Gehman twist test, a TR test, a low temperature flexibility test, and a storage elastic modulus test. .. In addition, a compression set (CS) test specimen was prepared in the same manner as in Example 1, and the compression set was measured. The results are shown in Table 4.

EPDM 14030 is manufactured by Mitsui Chemicals, Inc., Mooney viscosity (ML ₍₁₊₄₎ 125° C.)=17, Mooney viscosity (ML ₍₁₊₄₎ 100° C.)=26, ethylene content=51 mass %, ENB content. =8.1% by mass of ethylene/propylene/ENB copolymer.

EP331 is manufactured by JSR Corporation, Mooney viscosity (ML ₍₁₊₄₎ 125° C.)=23, Mooney viscosity (ML ₍₁₊₄₎ 100° C.)=35, ethylene content=47%, ENB content=11.1. It is an ethylene/propylene/ENB copolymer with 3% and an oil extension of 0 (PHR).

[Comparative Examples 3 to 6]
The silicone rubber compound comprises 100 parts by mass of silicone rubber and 2 parts by mass of an off-white paste (manufactured by Shin-Etsu Chemical Co., Ltd.) containing about 25% of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane. Roll temperature is front roll/rear roll=30° C./30° C., roll peripheral speed is front roll/rear roll=18 rpm/15 rpm, roll gap is 3 mm, kneading time is 8 minutes, and silicone rubber compound (compound The obtained compound was evaluated for Mooney viscosity and vulcanization characteristics in the same manner as in Example 1.

This compound was crosslinked with a press molding machine at 180° C. for 10 minutes to prepare a sheet (vulcanized product) having a thickness of 2 mm, and the obtained sheet was subjected to a hardness test in the same manner as in Example 1. A tensile test, a heat aging resistance test, a Gehman twist test, a TR test, a low temperature flexibility test and a storage elastic modulus test were performed.

Further, using a press molding machine in which a cylindrical mold is set, vulcanization is performed at 180° C. for 13 minutes to prepare a right cylindrical test piece having a thickness of 12.7 mm and a diameter of 29 mm, and the compression set ( A test piece (vulcanized product) for CS) test was obtained, and the compression set was measured in the same manner as in Example 1.

As the silicone rubber, KE-941-U (density (23° C.) 1.11 g/cm ³ ) (Comparative Example 3), KE-951-U (density (23° C.) 1.14 g/cm ³ ) ( Comparative Example 4), KE-971-U (density (23° C.) 1.30 g/cm ³ ) (Comparative Example 5), KE-981-U (density (23° C.) 1.42 g/cm ³ ) (Comparative Example) 6) (all manufactured by Shin-Etsu Chemical Co., Ltd.) were used.
The results are shown in Table 4.

Comparing the example with the comparative example using EPDM (comparative examples 1 and 2), it is found that in the example 1 and the comparative examples 1 and 2 having similar hardness, T ₂ (° C.) and T ₅ (in the Gehman twist test). ° C.) and T ₁₀ (° C.) is lower in the sheet obtained in example 1 was found to be excellent in low-temperature flexibility, from T-R test results (especially the result of TR10), in example 1 It can be seen that the obtained sheet has better cold resistance.

In addition, when the example and the comparative example using the silicone rubber compound (comparative examples 3 to 6) are compared, the results of the TR test (particularly the result of TR10) are found between the example and the comparative example having similar hardness. From the results, it can be seen that the sheets obtained in the examples are more excellent in cold resistance, and that TB and EB also tend to be better.

[Synthesis example 7]
An ethylene/1-butene/ENB copolymer (EBDM-7) of Synthesis Example 7 was obtained in the same manner as in Synthesis Example 1 except that the polymerization conditions were changed as described in Table 5. The results are shown in Table 5.

[Example 11]
<<Composition for seal packing>>
Using MIXTRON BB MIXER (manufactured by Kobe Steel, Ltd., BB-2 type, volume 1.7 L, rotor 2WH), the ethylene/1-butene/ENB copolymer (EBDM-7) 100 obtained in Synthesis Example 7 was used. Paraffin-based process oil "Diana Process Oil PW-100" (trade name; manufactured by Idemitsu Kosan Co., Ltd.) as a softening agent was mixed in an amount of 40 parts, and then kneaded to obtain a mixture A (140 parts). Oil-extended EPDM-7) was obtained.

The kneading conditions were a rotor rotation speed of 40 rpm and a floating weight pressure of 3 kg/cm ^2. After kneading EPDM-7 for 1 minute, a softening agent was added and kneading was continued for 5 minutes. The kneading discharge temperature was 150°C.

Using 6-inch rolls, 140 parts of oil-extended EPDM-7 (formulation A) was added to KAYAKUMIL D-40C (dicumyl peroxide 40% by mass, manufactured by Kayaku Akzo) as a crosslinking agent (vulcanizing agent). Was added in a compounding amount of 6.8 parts and kneaded to obtain a compound B (composition for seal packing).

The kneading conditions were as follows: roll temperature: front roll/rear roll=50° C./50° C., roll peripheral speed: front roll/rear roll=18 rpm/15 rpm, roll gap: 3 mm, blending time: 8 minutes, blending B (composition for seal packing) was obtained.

<<Preparation of sheet>>
The compound B (composition for seal packing) was crosslinked with a press molding machine at 180° C. for 10 minutes to prepare a sheet (vulcanized product) having a thickness of 2 mm.

[Gas permeability test]
In the gas permeability test, according to ASTM D 1434, the gas permeability of the sheet (vulcanized product) was measured with a differential pressure gas permeation tester (manufactured by Toyo Seiki Co., Ltd.) to be 100% as the test gas (permeation gas). % Hydrogen, 100% oxygen, 100% nitrogen, 100% carbon dioxide was used, and the temperature was 23° C. and the humidity was 0%.
Table 6 shows the gas permeability of each test gas.

[Comparative Example 7]
EBDM-7 was changed to EPDM (Mitsui EPT (registered trademark) 3072EM, ethylene/propylene/ENB copolymer), and the same procedure as in Example 11 was carried out to prepare a sheet (vulcanized product) having a thickness of 2 mm, and the gas was used. The permeability was evaluated.
Table 6 shows the gas permeability of each test gas.

[Example 12]
<<Composition for seal packing>>
Using a 6 inch roll, KAYAKUMIL D-40C (dicumyl peroxide 40% by mass, manufactured by Kayaku Akzo) as a cross-linking agent (vulcanizing agent) was added to 100 parts of EBDM-7 at a compounding amount of 6.8 parts. And kneaded to obtain a blend C (composition for seal packing).

The kneading conditions were as follows: roll temperature: front roll/rear roll=50° C./50° C., roll peripheral speed: front roll/rear roll=18 rpm/15 rpm, roll gap: 3 mm, blending time: 8 minutes, blending C (composition for seal packing) was obtained.

<<Preparation of sheet (unvulcanized)>>
EBDM-7 was hot pressed at 190° C. for 10 minutes using a press molding machine, and then cold pressed at 10° C. for 5 minutes using a water-cooled press molding machine to obtain a sheet (unvulcanized) having a thickness of 2 mm. Was prepared.

<<Preparation of sheet (vulcanized product)>>
The compound C (composition for seal packing) was crosslinked with a press molding machine at 180° C. for 10 minutes to prepare a sheet (vulcanized product) having a thickness of 2 mm.

[Gas permeability test]
In the gas permeability test, according to ASTM D 1434, the gas permeability of the sheet was measured using a differential pressure method gas permeation tester (manufactured by Toyo Seiki Co., Ltd.) with a test gas (permeation gas) of 100% hydrogen and 100%. It measured using oxygen, 100% nitrogen, and 100% carbon dioxide at a temperature of 23° C. and a humidity of 0%.
The gas permeability of each test gas is shown in Table 7.

[Comparative Example 8]
EBDM-7 was changed to EPDM (Mitsui EPT (registered trademark) 3072EM, ethylene/propylene/ENB copolymer), and the same procedure as in Example 12 was performed to obtain a sheet (unvulcanized product) having a thickness of 2 mm and a thickness of 2 mm. A sheet (vulcanized product) was prepared and gas permeability was evaluated.
The gas permeability of each test gas is shown in Table 7.

From Example 12 and Comparative Example 8, the EBDM vulcanizate had a lower gas permeability including the hydrogen permeability than the EPDM vulcanizate. The lower gas permeability of the EBDM vulcanizate than that of the EPDM vulcanizate was an unexpected effect as described above. Therefore, the seal packing formed by using the seal packing composition of the present invention is excellent in the sealing property of gas such as hydrogen gas.

Claims (5)

It includes a structural unit derived from ethylene [A], a structural unit derived from an α-olefin [B] having 4 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [C], and the following (1) to (4 A seal packing used for a hydrogen line, comprising a cross-linked product of a seal packing composition containing an ethylene/α-olefin/non-conjugated polyene copolymer satisfying the above requirement.
(1) The molar ratio [[A]/[B]] of the structural unit derived from ethylene [A] and 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% when the total of the structural units of [A], [B] and [C] is 100 mol %. And
(3) Mooney viscosity at 125° C. ML ₍₁₊₄₎ 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×[E]×([X]+[Y])]...(i)
[Here, [E], [X], and [Y] represent the mole fractions of ethylene [A], α-olefin [B] having 4 to 20 carbon atoms, and non-conjugated polyene [C], respectively. [EX] represents ethylene [A]-C4-20 [alpha]-olefin [B] dyad chain fraction. ] It includes a structural unit derived from ethylene [A], a structural unit derived from an α-olefin [B] having 4 to 20 carbon atoms, and a structural unit derived from a non-conjugated polyene [C], and the following (1) to (4 A seal packing used for a hydrogen line, comprising a cross-linked product of a seal packing composition containing an ethylene/α-olefin/non-conjugated polyene copolymer satisfying the above requirement.
(1) The molar ratio [[A]/[B]] of the structural unit derived from ethylene [A] and 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% when the total of the structural units of [A], [B] and [C] is 100 mol %. And
(3) Mooney viscosity at 125° C. ML ₍₁₊₄₎ 125° C. is 5 to 100,
(4) The B value represented by the following formula (i) is 1.20 or more.
B value=([EX]+2[Y])/[2×[E]×([X]+[Y])]...(i)
[Here, [E], [X], and [Y] represent the mole fractions of ethylene [A], α-olefin [B] having 4 to 20 carbon atoms, and non-conjugated polyene [C], respectively. [EX] represents ethylene [A]-C4-20 [alpha]-olefin [B] dyad chain fraction. ] Having 4 to 20 carbon atoms α- olefin [B] is Shirupakki down according to claim 1 or 2 is 1-butene. The ethylene/α-olefin/non-conjugated polyene copolymer is
(A) a transition metal compound represented by the following general formula [I],
(B) (b-1) organometallic compound,
In the presence of an olefin polymerization catalyst containing (b-2) an organoaluminum oxy compound, and (b-3) at least one compound selected from compounds that react with the transition metal compound (a) to form an ion pair. ethylene, a polymer obtained by copolymerizing α- olefin and non-conjugated polyene having 4 to 20 carbon atoms, Shirupakki down according to any one of claims 1 to 3.

(In the formula [I], Y is selected from a carbon atom, a silicon atom, a germanium atom and a tin atom,
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 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, An atom or a substituent selected from a halogen atom and a halogen-containing group, which may be the same or different,
Adjacent substituents R ¹ to R ⁶ may combine with each other to form a ring,
Q is the same or different combination selected from a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an anion ligand and a neutral ligand capable of coordinating with a lone pair of electrons,
n is an integer of 1 to 4,
j is an integer of 1 to 4. ) The crosslinking density of the seal packing is 1.0 × 10 ¹⁶ ~1.0 × 10 ²² cells is / cc, seal packing according to any one of claims 1-4.