JP2001131361A - Ethylene.alpha-olefin.triene copolymer rubber composition and vulcanized rubber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vulcanizable rubber composition having excellent scorch stability and giving a vulcanized rubber having excellent weather resistance, ozone resistance and thermal aging resistance without deteriorating the excellent mechanical properties, abrasion resistance and dynamic fatigue resistance of diene rubber. SOLUTION: The ethylene.α-olefintriene copolymer rubber composition contains an ethylene.α-olefin.triene copolymer rubber and a diene rubber. The ethylene.α-olefin.triene copolymer rubber is a random copolymer composed of ethylene, an α-olefin and a triene compound of formula (1) (R1 and R2 are each H, methyl or ethyl; and R3 and R4 are each methyl or ethyl) and having an ethylene/α-olefin molar ratio of 99/1 to 30/70, a triene compound content of 0.1-30 mol% and an intrinsic viscosity [η] of 0.1-10 dL/g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a vulcanizable ethylene / α-olefin / triene copolymer rubber composition containing an ethylene / α-olefin / triene copolymer rubber and a diene rubber and a vulcanized rubber thereof. In particular, a rubber composition excellent in scorch stability, without impairing the excellent mechanical properties of a diene rubber, wear resistance and dynamic fatigue resistance, weather resistance, ozone resistance and heat aging resistance The present invention relates to an ethylene / α-olefin / triene copolymer rubber composition capable of obtaining a vulcanized rubber excellent in vulcanizability and a vulcanized rubber obtained from the composition.

[0002]

2. Description of the Related Art An ethylene / propylene / diene rubber (hereinafter sometimes abbreviated as EPDM) such as an ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber is used for weather resistance, ozone resistance and heat aging. As a rubber having excellent properties, it is widely used in parts where automobile parts are subjected to static force, such as weather stripping, door glass run channels, and radiator hoses.

On the other hand, most of components requiring mechanical strength against dynamic fatigue, such as tires and vibration-isolating rubbers, are diene such as natural rubber (NR), styrene-butadiene rubber (SBR), and butadiene rubber (BR). A system rubber or a blend thereof is used.

[0004] In recent years, with the improvement in quality of automobiles, it has been desired to improve weather resistance and heat aging resistance of automobile parts. However, EPDM is excellent in weather resistance, ozone resistance and heat aging resistance, but has poor dynamic fatigue resistance.
Cannot be used alone for tires or anti-vibration rubber.

For this reason, much research has been conducted on blends of EPDM and diene rubbers in order to take advantage of these materials by blending them. The purpose of blending EPDM with a diene rubber is to achieve excellent mechanical properties, abrasion resistance, dynamic fatigue resistance and crack growth resistance of the diene rubber without practically deteriorating the properties thereof. It is to provide weather resistance and heat aging resistance.

[0006] As a method of blending EPDM and diene-based rubber, "Japanese Rubber Association, 51, 685 (197)
8) includes 1) polysulfide vulcanization, 2) peroxide vulcanization, 3) application of prevulcanized EPDM, 4) application of high iodine EPDM, 5) application of halogenated EPDM, 6)
The use of an accelerator having a long-chain alkyl group is described. In addition, the intrinsic viscosity measured in xylene at 70 ° C. is 3.
It is described that EPDM having a propylene content of 0 dl / g or more, a propylene content of 35% or less, and a high iodine value is good. However, even a blend of EPDM and a diene rubber obtained by the above method has insufficient co-vulcanizability, so that both properties are not sufficiently exhibited in the vulcanized rubber.

As a method for improving the co-vulcanizability of EPDM and a diene rubber, a method of copolymerizing another diene having a high vulcanization rate in place of a non-conjugated diene such as ethylidene norbornene used so far. Have been tried.

For example, Japanese Patent Application Laid-Open No. 8-31263 discloses that
A rubber composition comprising an ethylene / α-olefin / non-conjugated polyene copolymer rubber copolymerized with a branched polyene having a specific structural formula, and a diene rubber is described, and the rubber composition is vulcanized. It is described that vulcanized rubber excellent in weather resistance, ozone resistance and heat aging resistance can be obtained without impairing the excellent mechanical properties of diene rubber, abrasion resistance and dynamic fatigue resistance. ing. However, the ethylene
The α-olefin / non-conjugated polyene copolymer rubber has a high vulcanization rate and has an improved covulcanization property with a diene rubber, but has a problem of poor scorch stability.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a rubber composition having excellent scorch stability, which solves the problems associated with the prior art as described above. Ethylene / α- which can obtain a vulcanized rubber excellent in weather resistance, ozone resistance and heat aging resistance without impairing mechanical properties, wear resistance and dynamic fatigue resistance
An object of the present invention is to provide an olefin / triene copolymer rubber composition and a vulcanized rubber obtained from the composition.

[0010]

SUMMARY OF THE INVENTION The present invention provides the following ethylene
α-olefin / triene copolymer rubber composition and vulcanized rubber. (1) (A) Ethylene (a) and α having 3 to 20 carbon atoms
-A random copolymer rubber comprising an olefin (b) and a triene compound (c) represented by the following formula (1), wherein the structural unit derived from ethylene (a) has 3 carbon atoms
And the molar ratio (ethylene / α-olefin) to the structural unit derived from α-olefin (b) is from 99/1 to 3
0/70, ethylene having a content of structural units derived from the triene compound (c) of 0.1 to 30 mol% and an intrinsic viscosity [η] of 0.1 to 10 dl / g measured in decalin at 135 ° C. .Alpha.-olefin.triene copolymer rubber,
And (B) an ethylene / α-olefin / triene copolymer rubber composition containing a diene rubber.

Embedded image [In the formula (1), R ¹ and R ² each independently represent a hydrogen atom, a methyl group or an ethyl group, and R ³ and R ⁴ each independently represent a methyl group or an ethyl group. (2) The above (1), wherein the content of the ethylene / α-olefin / triene copolymer rubber (A) is 20 to 80% by weight and the content of the diene rubber (B) is 80 to 20% by weight. Rubber composition. (3) The rubber composition according to the above (1) or (2), comprising a reinforcing agent (C), a softening agent (D) or a vulcanizing agent (E). (4) A vulcanized rubber obtained by vulcanizing the rubber composition according to any one of (1) to (3).

In the present invention, the α-olefin having 3 to 20 carbon atoms (b) used as a monomer of the ethylene / α-olefin / triene copolymer rubber (A) includes propylene, 1-butene and 1- Pentene, 1-hexene,
3-methyl-1-butene, 3-methyl-1-pentene,
3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1
-Hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-
Heptene, 1-octene, 1-nonene, 1-decene, 1
-Undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene,
-Heptadecene, 1-octadecene, 1-nonadecene,
1-eicosene and the like. The α-olefin (b) can be used alone or in combination of two or more. The α-olefin (b) used as a monomer of the ethylene / α-olefin / triene copolymer rubber (A) is preferably an α-olefin having 3 to 8 carbon atoms, particularly propylene, 1-butene, 1- Hexene, 1-
Octene is preferred.

In the present invention, the triene compound (c) represented by the above formula (1) used as a monomer of the ethylene / α-olefin / triene copolymer rubber (A) is a compound which exists at the terminal of the molecule. It is a triene compound having one heavy bond and two double bonds (existing in the middle of a chain) other than at the terminal. One double bond present at the terminal is an ethylenic double bond, which is a double bond polymerizable with ethylene and an α-olefin. Is not involved in
-Remains in the side chain of the olefin / triene copolymer rubber (A).

Among the triene compounds (c) represented by the above formula (1), those in which R ³ and R ⁴ are both methyl groups are preferred, and ethylene obtained by using such a triene compound as a monomer raw material is preferred. The α-olefin / triene copolymer rubber (A) is particularly excellent in the balance between the vulcanization rate and scorch characteristics.

Specific examples of the triene compound (c) represented by the above formula (1) include the following compounds.

Embedded image

Among the above triene compounds (c), the first exemplified 4,8-dimethyl-1,4,8-decatriene (hereinafter sometimes abbreviated as DMDT) is preferred. Triene compound (c) represented by the formula (1)
May be a mixture of trans form and cis form,
The trans form alone or the cis form alone may be used. The triene compound (c) may be used alone or in combination of two or more.

The triene compound (c) represented by the formula (1) is a triene compound having a conjugated diene structure represented by the following formula (2) (hereinafter referred to as a conjugated diene structure-containing triene compound) and ethylene. It can be produced by reacting.

Embedded image (Equation (2), R ^1, R ^2, R ³ and R ⁴ are the same as R ^1, R ^2, R ³ and R ⁴ in each of the formulas (1).)

Specific examples of the conjugated diene structure-containing triene compound represented by the formula (2) include the following compounds.

Embedded image

In the reaction of the conjugated diene structure-containing triene compound represented by the formula (2) with ethylene, the temperature is usually 3
0-200 ° C, preferably 50-150 ° C, ethylene pressure is usually 0.05-9.8 MPa (0.5-100 kgf
/ Cm ² , gauge pressure), preferably 0.2 to 6.9 MP
a ( ^{2 to} 70 kgf / cm ² , gauge pressure) and the reaction time are usually preferably 0.5 to 30 hours. The reaction atmosphere may be an atmosphere of ethylene alone or an atmosphere containing an inert gas such as nitrogen or argon together with ethylene. It is not necessary to use a reaction solvent, but
May be used. As the reaction solvent, for example, hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, undecane, tridecane, toluene and xylene can be preferably used.

The reaction of the conjugated diene structure-containing triene compound represented by the formula (2) with ethylene is usually carried out in the presence of a catalyst. As the catalyst, a catalyst composed of a transition metal thiocyanate, an organic compound that can be a ligand of the transition metal of the salt, an organic aluminum compound, or the like can be used. Specific examples of the thiocyanate of the transition metal include Group 8 such as iron and ruthenium; Group 9 such as cobalt, rhodium and iridium; and nickel;
And a thiocyanate of a transition metal selected from the group consisting of Group 10 such as palladium.

Examples of the organic compound which can serve as the ligand include tri-o-tolylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, triphenylphosphine, bis (diphenylphosphino) methane, and 1,2-bis ( Phosphorus-containing compounds such as diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, triphenylphosphite, triphenylphosphine oxide, and triphenylphosphate; I can give it.

Examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, ethylaluminum dichloride, diethylaluminum ethoxide and the like.

In the ethylene / α-olefin / triene copolymer rubber (A), the structural unit derived from the triene compound (c) has a structure substantially represented by the following formula (3).

Embedded image (In the formula (3), R ^1, R ^2, R ³ and R ⁴ are the same as R ^1, R ^2, R ³ and R ⁴ in each of the formulas (1).)

It should be noted that the structural unit derived from the triene compound (c) in the ethylene / α-olefin / triene copolymer rubber (A) has a structure represented by the above formula (3). It can be confirmed by measuring the ¹³ C-NMR spectrum of the polymer.

The ethylene / α-olefin / triene copolymer rubber (A) used in the present invention comprises ethylene (a)
Has a molar ratio (ethylene / α-olefin) of 99/1 to 30/70, preferably 95/5 to 5, a structural unit derived from α-olefin (b) having 3 to 20 carbon atoms. 60/40, more preferably 85/15
５０50/50. Since the ethylene / α-olefin / triene copolymer rubber (A) having a molar ratio of ethylene / α-olefin within the above range is used, the rubber elasticity is not impaired even at a low temperature, and the mechanical strength characteristics are excellent. A rubber composition from which a vulcanized rubber product can be obtained is obtained.

The ethylene / α-olefin / triene copolymer rubber (A) used in the present invention has a content of a structural unit derived from the triene compound (c) (hereinafter referred to simply as a content of the triene compound (c)). May be 0.1)
-30 mol%, preferably 0.3-20 mol%, more preferably 0.5-15 mol%. Since the ethylene / α-olefin / triene copolymer rubber (A) having the content of the triene compound (c) within the above range is used, a rubber composition having excellent covulcanizability with the diene rubber (B) can be obtained. can get.

The ethylene / α-olefin / triene copolymer rubber (A) used in the present invention has an intrinsic viscosity [η] of 0.1 to 10 dl / g measured in decalin (decahydronaphthalene) at 135 ° C. , Preferably 1 to 6 dl
/ G, more preferably 1.5 to 4.8 dl / g. Since the intrinsic viscosity [η] of the ethylene / α-olefin / triene copolymer rubber (A) having the above range is used, the blendability with the diene rubber (B) is good,
A rubber composition having excellent co-vulcanizability with the diene rubber (B) and excellent processability is obtained.

The ethylene / α-olefin / triene copolymer rubber (A) used in the present invention has an iodine value of 1 to 5
0, preferably 4 to 40, more preferably 10 to 30
It is desirable that When the ethylene / α-olefin / triene copolymer rubber (A) having an iodine value in the above range is used, the vulcanization rate is high and the co-vulcanizability with the diene rubber (B) is excellent. Moreover, a vulcanized rubber product excellent in heat aging resistance can be obtained.

In the ethylene / α-olefin / triene copolymer rubber (A) used in the present invention, the structural units derived from ethylene (a), α-olefin (b) and triene compound (c) are randomly arranged. And has a branched structure caused by the triene compound (c), and the main chain has a substantially linear structure. The fact that the ethylene / α-olefin / triene copolymer rubber (A) has a substantially linear structure and substantially does not contain a gel-like cross-linked polymer means that this copolymer rubber is dissolved in an organic solvent. However, it can be confirmed by substantially not containing an insoluble matter. For example, it can be confirmed that the ethylene / α-olefin / triene copolymer rubber (A) is completely dissolved in decalin at 135 ° C.

The ethylene / α-olefin / triene copolymer rubber (A) used in the present invention has a high vulcanization rate, is excellent in co-vulcanization with the diene rubber (B), and has good scorch stability. Are better. For example, when the third component is 4,8-dimethyl-1,4,8-decatriene (hereinafter, referred to as “decatriene”)
DMDT) (which may be abbreviated as DMDT) and 5-ethylidene-third compound in which the third component is not contained in the triene compound (c).
2-norbornene (hereinafter sometimes abbreviated as ENB)
Is compared with the ethylene / α-olefin / ENB copolymer rubber, which has the same iodine value as ethylene / α / olefin / ENB copolymer rubber.
-The vulcanization rate of the olefin / DMDT copolymer rubber (A) is twice or more faster.

Also, ethylene / α-olefin / DMDT
The copolymer rubber (A) has 4-ethylidene-8-methyl-, the third component of which is not contained in the triene compound (c).
Ethylene • α- which is 1,7-nonadiene (EMND)
It shows almost the same vulcanization rate as olefin / EMND copolymer rubber, but ethylene / α-olefin / DMDT copolymer rubber (A) has better ethylene / α-olefin / EMN
From D copolymer rubber, a longer t ₅ as measured by a method described later, has excellent scorch stability.

It should be noted that ethylene / α-olefin / ENB
Even if the copolymer rubber has a high ENB content, the effect of improving the vulcanization rate is lost when the ENB content exceeds 4 mol%.
The ethylene / α-olefin / DMDT copolymer rubber (A) can increase the vulcanization rate in proportion to the triene compound (c) content until the content of the triene compound (c) becomes 7 mol%.

Further, ethylene / α-olefin / ENB
When the iodine value is increased to increase the vulcanization rate, the low-temperature flexibility deteriorates in proportion to the increase in the vulcanization rate, but the ethylene / α-olefin / DMDT copolymer rubber (A) has no relation to the iodine value. Has excellent low temperature flexibility.

The ethylene / α-olefin / triene copolymer rubber (A) used in the present invention comprises ethylene (a),
It can be produced by copolymerizing an α-olefin having 3 to 20 carbon atoms (b) and the triene compound (c) represented by the formula (1) in the presence of a catalyst. As the catalyst, vanadium (V), zirconium (Z
r), a transition metal compound (d) such as titanium (Ti);
A catalyst comprising the organoaluminum compound (e) and / or the ionized ionic compound (f) can be preferably used.

Specific examples of the catalyst include (1) a titanium-based catalyst comprising a solid titanium catalyst component (d-1) and an organoaluminum compound (e-1), and (2) a soluble vanadium compound (d -2) and a vanadium-based catalyst comprising an organoaluminum compound (e-1), and (3)
A metallocene compound (d-3) of a transition metal selected from Group 4 of the periodic table and an organic aluminum oxy compound (e-
2) and / or ionized ionic compound (f-1)
And the like.

Of these, metallocene catalysts are preferred. The metallocene-based catalyst has a high activity, and the obtained ethylene / α-olefin / triene copolymer rubber (A) has a narrow molecular weight distribution and a narrow composition distribution.
The conversion of the triene compound (c) represented by is also high.

The solid titanium catalyst component (d-1) is prepared by contacting a titanium compound, a magnesium compound and an electron donor as described below. As the titanium compound, a trivalent titanium compound or a tetravalent titanium compound is used, and a tetravalent titanium compound is preferable. As the tetravalent titanium compound, for example, Ti (OR)
_j X _4-j (R is a hydrocarbon group, X is a halogen atom, 0 ≦ j ≦
The tetravalent titanium compound represented by 4) can be mentioned. Among these, a halogen-containing titanium compound is preferable, a titanium tetrahalide is more preferable, and titanium tetrachloride is particularly preferable.

The magnesium compound used for preparing the solid titanium catalyst component (d-1) may be a reducing magnesium compound or a non-reducing magnesium compound. Examples of the magnesium compound having a reducing property include a magnesium compound having a magnesium-carbon bond and a magnesium-hydrogen bond. As the magnesium compound having no reducibility, a compound derived from the magnesium compound having reducibility or a compound derived at the time of preparing the catalyst component can be used. Further, a complex compound, a complex compound of these magnesium compounds and other metals, or a mixture with other metal compounds can also be used. These magnesium compounds may be a mixture of two or more. The magnesium compound is preferably a non-reducing magnesium compound, more preferably a halogen-containing magnesium compound, and particularly preferably magnesium chloride, alkoxymagnesium chloride and allyloxymagnesium chloride.

Examples of the electron donor used for preparing the solid titanium catalyst component (d-1) include organic carboxylic acid esters and polyvalent carboxylic acid esters.
The solid titanium catalyst component (d-1) can be produced by contacting a titanium compound, a magnesium compound (or metallic magnesium) and an electron donor as described above. In order to produce the solid titanium catalyst component (d-1), a known method for preparing a highly active titanium catalyst component from a titanium compound, a magnesium compound and an electron donor can be employed. The above components may be brought into contact with each other in the presence of another reaction reagent such as silicon, phosphorus and aluminum.

As the organoaluminum compound (e-1) forming the titanium catalyst, a compound having at least one Al-carbon bond in a molecule can be used. Such compounds, for example, the formula _{^{(4) (R 1) m}} Al (OR 2) n H p X q ... (4) [In formula (4), R ¹ and R ² are typically 1 carbon atom Fifteen
, Preferably 1 to 4 hydrocarbon groups, which may be the same or different from each other. X is a halogen atom. m is 0 <m ≦ 3, n is 0 ≦ n <3, and p is 0 ≦ p <
3, q is a number satisfying 0 ≦ q <3, and m + n
+ P + q = 3. An organoaluminum compound represented by], or the formula ^{(5) (M 1) Al} (R 1) 4 ... (5) [Equation (5), M ¹ is Li, Na or K, R ¹ is formula (4) it is the same as R ^1. And a complex alkylated product of a Group 1 metal and aluminum.

In preparing the titanium-based catalyst, an electron donor can be used if necessary. Examples of such an electron donor include an organosilicon compound represented by the following formula (6) or (7). R _n Si (OR ′) _4-n (6) SiR ¹ R ² _m (OR ³ ) _3-m (7) [In the formula (6), R and R ′ are hydrocarbon groups, and n is 0 < n
<4. In the formula (7), R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group,
R ² is an alkyl group, a cyclopentyl group, or a cyclopentyl group having an alkyl group, R ³ is a hydrocarbon group, and m is a number satisfying 0 ≦ m ≦ 2. ]

In the above formula (7), examples of the cyclopentyl group having an alkyl group of R ¹ include a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl group, and a 2,3-dimethylcyclopentyl group. be able to.

The catalyst component forming the titanium-based catalyst includes α-
The olefin may be pre-polymerized. In the prepolymerization, it is desirable to prepolymerize the α-olefin in an amount of 0.1 to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g per 1 g of the titanium-based catalyst. The prepolymerization is preferably carried out under mild conditions by adding an α-olefin and the above-mentioned catalyst component to an inert hydrocarbon medium. The α-olefin used in the prepolymerization may be the same as or different from the α-olefin (b) used in the polymerization of the ethylene / α-olefin / triene copolymer rubber (A).

Examples of the soluble vanadium compound (d-2) forming the vanadium-based catalyst include a vanadium compound represented by the following formula (8) or (9). During _{VO (OR) a X b ...} (8) V (OR) c X d ... (9) [Formula (8) and (9), R is a hydrocarbon group, X is a halogen atom. a, b, c and d are each 0 ≦ a
≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦
It satisfies d ≦ 4, 3 ≦ c + d ≦ 4. ]

As the soluble vanadium compound (d-2), an electron donor adduct of a soluble vanadium compound obtained by contacting an electron donor can also be used.
As the organoaluminum compound (e-1) forming the vanadium catalyst, the same compound as the organoaluminum compound (e-1) forming the titanium catalyst can be used.

The metallocene compound (d-3) forming the metallocene-based catalyst is a metallocene compound of a transition metal selected from Group 4 of the periodic table, and specifically has the following formula (1)
0). MLx (10) [In the formula (10), M is a transition metal selected from Group 4 of the periodic table, x is the valence of the transition metal M, and L is a ligand. ]

In the formula (10), specific examples of the transition metal represented by M include zirconium, titanium and hafnium. In equation (10),
L is a ligand that coordinates to the transition metal, and at least one of these ligands L is a ligand having a cyclopentadienyl skeleton. The ligand having a cyclopentadienyl skeleton may have a substituent.

Examples of the ligand L having a cyclopentadienyl skeleton include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n- or i-propylcyclopentadienyl group,
n-, i-, sec- or t-butylcyclopentadienyl group, dimethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylbenzylcyclopentadienyl group, etc. An alkyl or cycloalkyl-substituted cyclopentadienyl group; further, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, a fluorenyl group and the like. The group having a cyclopentadienyl skeleton may be substituted with a halogen atom, a trialkylsilyl group, or the like.

When the compound represented by the formula (10) has two or more groups having a cyclopentadienyl skeleton as the ligand L, two of the groups having the cyclopentadienyl skeleton are It may be bonded via an alkylene group such as ethylene and propylene; a substituted alkylene group such as isopropylidene and diphenylmethylene; and a substituted silylene group such as a silylene group or a dimethylsilylene group, a diphenylsilylene group, and a methylphenylsilylene group.

The ligand L other than a ligand having a cyclopentadienyl skeleton (a ligand having no cyclopentadienyl skeleton) includes a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group and an aryloxy group. , A sulfonic acid-containing group (—SO
₃ ^Ra ), a halogen atom or a hydrogen atom (where ^Ra is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, or an aryl group substituted with a halogen atom or an alkyl group). can give.

Examples of the hydrocarbon group having 1 to 12 carbon atoms of the ligand L include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. More specifically,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
t-butyl group, pentyl group, hexyl group, octyl group,
Alkyl groups such as decyl group and dodecyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neophyl group.

Examples of the alkoxy group of the ligand L include a methoxy group, an ethoxy group and an n-propoxy group. Examples of the aryloxy group include a phenoxy group. Examples of the sulfonic acid-containing group (—SO ₃ R ^a ) include a methanesulfonato group, a p-toluenesulfonato group, a trifluoromethanesulfonato group, and a p-chlorobenzenesulfonato group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

The metallocene compound represented by the above formula (10) is more specifically represented by the following formula (11) when the valence of the transition metal is 4, for example. R ² _k R ³ _l R ⁴ _m R ⁵ _n M (11) [In the formula (11), M is a transition metal of the formula (10), and R ² is a group having a cyclopentadienyl skeleton (ligand) , R ³ ,
R ⁴ and R ⁵ are each independently a group (ligand) having or not having a cyclopentadienyl skeleton. k is an integer of 1 or more, and k + 1 + m + n = 4. ]

In the following, when M is zirconium and the ligand having a cyclopentadienyl skeleton is at least 2
The metallocene compound (d-3) is included. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1, 3-dimethylcyclopentadienyl) zirconium dichloride and the like. 1 above
A compound in which a 3-position substituted cyclopentadienyl group is substituted with a 1,2-position substituted cyclopentadienyl group can also be used.

The metallocene compound (d-3) includes R ² , R ³ , R ⁴ and R ^{5 in the} above formula (11).
At least two, for example, R ² and R ³ is a group having a cyclopentadienyl skeleton (ligand), at least two groups of the alkylene group, substituted alkylene group, such as silylene group or substituted silylene group Bridge-type metallocene compounds linked via an intermediary can also be used. At this time, R ⁴ and R ⁵ are independently represented by the formula (1)
This is the same as the ligand L other than the ligand having a cyclopentadienyl skeleton described in 0).

As such a bridge type metallocene compound (d-3), ethylenebis (indenyl)
Dimethyl zirconium, ethylene bis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride,
Diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl)
Zirconium dichloride and the like can be mentioned.

As the metallocene compound (d-3), JP-A-4-268307 represented by the following formula (12)
And the metallocene compounds described in the above.

Embedded image

In the equation (12), M ¹ is 4 in the periodic table.
Group metals, specifically, titanium, zirconium, and hafnium. In the formula (12), R ¹ and R ² are a hydrogen atom; an alkyl group having 1 to 10, preferably 1 to 3 carbon atoms; an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms; An aryl group having 10, preferably 6 to 8 carbon atoms;
Aryloxy group having 8 to 8 carbon atoms; alkenyl group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms;
An arylalkyl group having 10 to 10 carbon atoms; an alkylaryl group having 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms;
Preferably 8 to 12 arylalkenyl groups; or halogen atoms, preferably chlorine atoms. R ¹ and R ²
May be the same or different.

In the formula (12), R ³ and R ⁴ are each a hydrogen atom; a halogen atom, preferably a fluorine atom, a chlorine atom or a bromine atom;
-10, preferably 1-4 alkyl groups; 6-1 carbon atoms
0, preferably C6-8 aryl _{^{group; -N (R 10) 2,}} -
^{SR 10, -OSi (R 10)} 3, -Si (R 10) 3 or -P
(R ¹⁰ ) ₂ groups. R ¹⁰ is a halogen atom, preferably a chlorine atom; an alkyl group having 1 to 10, preferably 1 to 3 carbon atoms; or an aryl group having 6 to 10, preferably 6 to 8 carbon atoms. R ³ and R ⁴ may be the same or different from each other. R ³ and R ⁴ are particularly preferably hydrogen atoms.

In the formula (12), R ⁵ and R ⁶ are the same as R ³ and R ⁴ except for a hydrogen atom. R ⁵ and R ⁶ may be the same or different from each other, and are preferably the same. R ⁵ and R ⁶ are preferably an optionally halogenated alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group or a trifluoromethyl And a methyl group.

In the formula (12), R ⁷ is

Embedded image= BR¹¹, = AlR¹¹, -Ge-, -Sn-, -O-,
-S-, = SO, = SO _Two, = NR¹¹, = CO, = PR
¹¹Or = P (O) R¹¹It is. R above¹¹, R¹²And R
¹³Is a hydrogen atom; a halogen atom; having 1 to 10 carbon atoms, preferably
Or 1 to 4 alkyl groups, more preferably a methyl group;
A fluoroalkyl group having 1 to 10 carbon atoms, preferably CF
_ThreeGroup; aryl having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms
A fluoroaryl group having 6 to 10 carbon atoms, preferably
Pentafluorophenyl group; having 1 to 10 carbon atoms, preferably
Is 1-4 alkoxy groups, particularly preferably a methoxy group;
An alkenyl group having 2 to 10, preferably 2 to 4 carbon atoms;
Arylalkyl having a prime number of 7 to 40, preferably 7 to 10
A group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms
Alkenyl group; or 7 to 40 carbon atoms, preferably 7-1
2 alkylaryl groups. "R¹¹And R¹²Or
"R¹¹And R¹³"Means the atoms to which they are attached
Together they may form a ring. R¹¹, R¹²And R
¹³May be the same or different.

The above M ² is silicon, germanium or tin, preferably silicon or germanium. In the formula (12), R ⁷ is: = CR ¹¹ R ¹² , = SiR ^{11
R 12, = GeR 11 R 1} 2, -O -, - S -, = SO, = P
Preferably, R ¹¹ or ＰP (O) R ¹¹ .

In the formula (12), R ⁸ and R ⁹ are the same as R ¹¹ described above. R ⁸ and R ⁹ may be the same or different from each other. In the formula (12), m and n are each 0, 1, or 2, preferably 0 or 1, and m + n is 0, 1, or 2, preferably 0 or 1. m and n may be the same or different from each other.

The metallocene compound (d-3) represented by the formula (12) includes the following compounds. ra
c-Ethylene (2-methyl-1-indenyl) 2-zirconium-dichloride, rac-dimethylsilylene (2-methyl-1-indenyl) 2-zirconium-dichloride. Metallocene compound (d-3) represented by formula (12)
Can be produced by a known method (for example, JP-A-4-268307).

As the metallocene compound (d-3), a metallocene compound represented by the following formula (13) can be used.

Embedded image In the formula (13), M represents a transition metal atom of Group 4 of the periodic table, specifically, titanium, zirconium, hafnium, or the like.

In the formula (13), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a C 1-20
A halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. Specific examples of R ¹ and R ² include halogen atoms such as fluorine, chlorine, bromine, and iodine; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, and adamantyl. Alkyl groups, vinyl, propenyl, alkenyl groups such as cyclohexenyl, benzyl, phenylethyl, arylalkyl groups such as phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl,
C1-20 hydrocarbon groups such as aryl groups such as propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl and phenanthryl; halogenated hydrocarbon groups having 1 to 20 carbon atoms in which the above hydrocarbon groups are substituted with halogen atoms A monohydrocarbon-substituted silyl such as methylsilyl or phenylsilyl, a dihydrocarbon-substituted silyl such as dimethylsilyl or diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl , Tritolylsilyl, trinaphthylsilyl and other hydrocarbon-substituted silyls such as trimethylsilylether, silyl ethers of hydrocarbon-substituted silyls, and silicon-substituted alkyl groups such as trimethylsilylmethyl. Silicon-containing groups such as silicon-substituted aryl groups such as tylsilylphenyl; hydroxy groups, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; allyloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; phenylmethoxy, phenyl An oxygen-containing group such as an arylalkoxy group such as ethoxy; a sulfur-containing group such as a substituent in which the oxygen of the oxygen-containing group is substituted by sulfur; an amino group, methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexyl A nitrogen-containing group such as an alkylamino group such as amino, an arylamino group such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino, or an alkylarylamino group; Phosphino,
And phosphorus-containing groups such as phosphino groups such as diphenylphosphino.

Among these, R ¹ is preferably a hydrocarbon group, particularly preferably an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or propyl. Also R ²
Is preferably hydrogen or a hydrocarbon group, particularly preferably hydrogen or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or propyl.

In the formula (13), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated carbon atom having 1 to 20 carbon atoms. Shows a hydrogen group. Among them, hydrogen, a hydrocarbon group or a halogenated hydrocarbon group is preferable. R
^At least one pair of ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶
Together with the carbon atom to which they are attached, they may form a monocyclic aromatic ring. When there are two or more hydrocarbon groups or halogenated hydrocarbon groups, the groups other than the groups forming the aromatic ring may be bonded to each other to form a ring. When R ⁶ is a substituent other than an aromatic group, it is preferably a hydrogen atom.

In R ³ , R ⁴ , R ⁵ and R ⁶ of the formula (13), the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon group having 1 to 20 carbon atoms include
The same thing can be mentioned as ¹ and R ^2.

In the formula (13), X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a carbon atom having 1 to 2 carbon atoms.
0 represents a hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group. Specific examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, the halogenated hydrocarbon group having 1 to 20 carbon atoms, and the oxygen-containing group are the same as those described above for R ¹ and R ² .

The sulfur-containing groups include the above-mentioned R ¹ , R ²
And the same groups as above, and methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzene Sulfonate groups such as sulfonate and pentafluorobenzene sulfonate; methyl sulfinate, phenyl sulfinate, benzene sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, pentafluorobenzene sulfinate and the like And the like.

In the formula (13), Y represents 1 to 2 carbon atoms.
0 divalent hydrocarbon group, divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-,- CO-,-
S -, - SO -, - SO 2 -, - NR 7 -, - P (R 7)
-, - P (O) ( R 7) -, - BR 7 - or -AlR ⁷ -
(However, R ⁷ is a hydrogen atom, a halogen atom, a carbon number of 1 to
20 hydrocarbon groups and halogenated hydrocarbon groups having 1 to 20 carbon atoms).

In the formula (13), specific examples of Y include methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, Divalent hydrocarbon groups having 1 to 20 carbon atoms such as alkylene groups such as 1,2-cyclohexylene and 1,4-cyclohexylene, and arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene; chloromethylene The above carbon number 1-20 such as
A halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group: methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenyl Alkylsilylene such as silylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene, arylsilylene group, tetramethyl-1,2-disilylene,
A divalent silicon-containing group such as an alkyldisilylene such as tetraphenyl-1,2-disilylene, an alkylaryldisilylene, or an aryldisilylene group; divalent germanium obtained by substituting silicon for the above-mentioned divalent silicon-containing group with germanium A group containing a divalent tin-containing group in which silicon of the above-mentioned divalent silicon-containing group is substituted with tin;
⁷ is the same halogen atom as R ¹ and R ^2, and has 1 to 2 carbon atoms.
0 hydrocarbon group and halogenated hydrocarbon group having 1 to 20 carbon atoms.

Among these, a divalent silicon-containing group, a divalent germanium-containing group, and a divalent tin-containing group are preferable, and a divalent silicon-containing group is more preferable. Preferred are silylene, alkylarylsilylene, and arylsilylene.

In the formula (13), at least one of R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ is bonded to each other and contains a monocyclic aromatic ring. Examples of the ligand to be placed include those represented by the following formulas (14) to (16).

[0075]

Embedded image [In the formulas (14) to (16), Y is the same as the formula (13). ]

As the metallocene compound (d-3), a transition metal compound represented by the following formula (17) can also be used.

Embedded image [In the formula (17), M, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as those in the above formula (13). ]

In the formula (17), among R ³ , R ⁴ , R ⁵ and R ⁶ , two groups including R ³ are preferably alkyl groups, and R ³ and R ⁵ or R ³ Preferably, R ⁶ is an alkyl group. This alkyl group is preferably a secondary or tertiary alkyl group. The alkyl group may be substituted with a halogen atom or a silicon-containing group. Examples of the halogen atom or the silicon-containing group include R ¹ ,
The substituents exemplified for R ² can be mentioned.

In R ³ , R ⁴ , R ⁵ and R ^{6 in} the formula (17), the group other than the alkyl group is preferably a hydrogen atom. As the hydrocarbon group having 1 to 20 carbon atoms,
Methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl,
Chain alkyl groups and cyclic alkyl groups such as octyl, nonyl, dodecyl, eicosyl, norbornyl, and adamantyl; and arylalkyl groups such as benzyl, phenylethyl, phenylpropyl, and tolylmethyl; May be included.

Further, R ³ , R ⁴ , R ⁵ and R ⁶ in the formula (17) are such that two kinds of groups selected therefrom are bonded to each other to form a monocyclic or polycyclic ring other than an aromatic ring. Is also good. Examples of the halogen atom include the same as those described above for R ¹ and R ² . X ¹ , X ² and Y are the same as those in the above formula (13).

Specific examples of the metallocene compound (d-3) represented by the formula (17) are shown below. rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2,4,7-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,
4,6-trimethyl-1-indenyl) zirconium dichloride.

A transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds can also be used. The transition metal compound is usually used as a racemic compound,
Molds can also be used.

As the metallocene compound (d-3) represented by the formula (17), the following compounds can be used. R ¹ is preferably a hydrocarbon group, particularly preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl or butyl.

X ¹ and X ² are preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ³
Represents an aryl group having 6 to 16 carbon atoms, and specifically,
Phenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl (perinaphthenyl), aceanthrenyl and the like. Of these, phenyl and naphthyl are preferred. These aryl groups are the same as the above-mentioned R ¹ , a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a carbon group having 1 to 20 carbon atoms.
It may be substituted by 20 halogenated hydrocarbon groups.

Specific examples of such a transition metal compound (metallocene compound) are shown below. rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4
-Phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-
(Α-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4
-(Β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-
4- (1-anthracenyl) -1-indenyl) zirconium dichloride and the like. In the above compounds, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal can also be used.

As the metallocene compound (d-3),
A compound represented by the following formula (18) can also be used. L ^a MX ₂ ... in (18) [formula (18), M is a metal of group 4 of the periodic table or lanthanum series. L ^a is a derivative of a delocalized π bond group and is a group imparting a constraint geometric shape to the metal M active site. X is each independently hydrogen, halogen or 20
The following carbon, silicon or germanium containing hydrocarbon groups, silyl groups or germyl groups. ]

Among the compounds represented by the formula (18), a compound represented by the following formula (19) is preferable.

Embedded image

In the formula (19), M is titanium, zirconium or hafnium, and X is the same as in the formula (18). Cp
Is a substituted cyclopentadienyl group having a π bond to M and having a substituent Z. Z is oxygen, sulfur, boron or an element of Group 14 of the periodic table (for example, silicon, germanium or tin), Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and forms a condensed ring with Z and Y May be.

Examples of the compound represented by the formula (19) include (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) titanium dichloride and ((t-butylamide) (tetra Methyl-η ⁵
-Cyclopentadienyl) -1,2-ethanediyl) titanium dichloride. Further, in the above metallocene compounds, compounds in which titanium is replaced by zirconium or hafnium can also be mentioned.

The metallocene compound (d-3) represented by the formula (18) or (19) has a ligand in which the central metal atom is zirconium and has at least two cyclopentadienyl skeletons. Zirconocene compounds are preferably used.

As the metallocene compound (d-3), a transition metal compound of Group 4 of the periodic table represented by the following formula (20) can also be used.

Embedded image

In the formula (20), M is a transition metal atom belonging to Group 4 of the periodic table, specifically, titanium, zirconium or hafnium, and preferably zirconium. R ^{1 in the} formula (20) may be the same or different, and at least one of them has 11 to 2 carbon atoms.
A aryl group having 0, an arylalkyl group having 12 to 40 carbon atoms, an arylalkenyl group having 13 to 40 carbon atoms, an alkylaryl group having 12 to 40 carbon atoms or a silicon-containing group, or a group represented by R ¹ At least two adjacent groups together with the carbon atoms to which they are attached form one or more aromatic or aliphatic rings. In this case, the ring formed by R ¹ is a 4 to 20 carbon atoms in all including carbon atoms to which R ¹ is attached.

Examples of the case where at least two adjacent groups among the groups represented by R ¹ in the formula (20) together with the carbon atoms to which they are attached form one or more aromatic or aliphatic rings. Condensed phenyl group, condensed cyclohexyl group, condensed cyclopentadienyl group, condensed dihydrocyclopentadienyl group, condensed indenyl group, condensed tetrahydroindenyl group, condensed fluorenyl group, condensed tetrahydrofluorene And a condensed octahydrofluorenyl group. These groups may be substituted with a chain alkyl group, a cyclic alkyl group, a halogen atom, a halogen-substituted alkyl group, an aryl group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, or a phosphorus-containing group.

An aryl group, an arylalkyl group, an arylalkenyl group, an alkylaryl group and an aromatic ring;
R ¹ other than R ¹ to form an aliphatic ring is a hydrogen atom, a halogen atom, an alkyl group or a silicon-containing group having 1 to 10 carbon atoms.

The aryl group having 11 to 20 carbon atoms includes
Biphenylyl, anthryl, phenanthryl and the like. Examples of the arylalkyl group having 12 to 40 carbon atoms include phenanthrylmethyl, phenanthrylethyl, phenanthrylpropyl and the like. C13-
Examples of the 40 arylalkenyl groups include vinylphenanthryl. Examples of the alkylaryl group having 12 to 40 carbon atoms include methylphenanthryl, ethylphenanthryl, and propylphenanthryl. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, hexyl,
Cyclohexyl, octyl, nonyl and the like can be mentioned.

Examples of the silicon-containing group include methylsilyl, phenylsilyl, dimethylsilyl, diethylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl,
Examples include groups such as tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tolylsilyl, and trinaphthylsilyl. Note that the above alkyl group, aryl group, arylalkyl group, arylalkenyl group, and alkylaryl group may be substituted with halogen.

In the formula (20), R ² may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 2 to 10 carbon atoms. An alkenyl group, an arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or It is a phosphorus-containing group.

Further, at least two adjacent groups among the groups represented by R ² in the formula (20) together with the carbon atoms to which they are bonded form one or more aromatic or aliphatic rings. You may. In this case, the ring formed by R ² is a 4 to 20 carbon atoms in all including carbon atoms to which R ² is attached, an aromatic ring, R ² other than R ² that forms an aliphatic ring Is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or a silicon-containing group.

A group in which two groups represented by R ² in the formula (20) form one or more aromatic or aliphatic rings is a fluorenyl group represented by the following formula (21) The embodiment having the structure as described above is also included.

Embedded image

Examples of the alkyl group having 1 to 10 carbon atoms and the halogen atom include the same groups and atoms as described above. As the aryl group having 6 to 20 carbon atoms, phenyl,
Biphenylyl, α- or β-naphthyl, anthryl,
Phenanthryl and the like. Examples of the arylalkyl group having 7 to 40 carbon atoms include benzyl, phenylethyl, phenylpropyl, phenanthrylmethyl, phenanthrylethyl, and phenanthrylpropyl. Examples of the arylalkenyl group having 8 to 40 carbon atoms include styryl and vinylphenanthryl.

Examples of the alkylaryl group having 7 to 40 carbon atoms include tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, methylnaphthyl, methylphenanthryl, ethylphenanthryl, propylphenanthryl and the like. . 2 to 1 carbon atoms
Examples of the alkenyl group of 0 include vinyl, propenyl, cyclohexenyl and the like. Examples of the silicon-containing group include the same groups as described above. As the oxygen-containing group,
Examples include a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy and butoxy, an allyloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, and an arylalkoxy group such as phenylmethoxy and phenylethoxy.

Examples of the sulfur-containing group include a substituent in which oxygen of the above-mentioned oxygen-containing group is substituted by sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, Trimethylbenzenesulfonate,
Sulfonate groups such as triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzene And sulfinate groups such as sulfinate and pentafluorobenzene sulfinate.

Examples of the nitrogen-containing group include an amino group, an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino. And an arylamino group or an alkylarylamino group. Examples of the phosphorus-containing group include dimethylphosphino and diphenylphosphino.

Among them, R ² is preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl. Preferable examples of the fluorenyl group having R ² as such a substituent include a 2,7-dialkyl-fluorenyl group. In this case, the alkyl group of the 2,7-dialkyl includes a C ¹ to C 5 alkyl group. Alkyl group. Further, R ¹ and R ² described above may be the same or different from each other.

R ³ and R ^{4 in} the formula (20) may be the same or different from each other, and have the same hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms and 6 to 20 carbon atoms as described above.
Aryl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, arylalkenyl group having 8 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, silicon-containing group, and oxygen-containing group , A sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. Of these, at least one of R ³ and R ⁴ is preferably an alkyl group having 1 to 3 carbon atoms.

X ¹ and X ^{2 in} the formula (20) may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon having 1 to 20 carbon atoms. Group, an oxygen-containing group, a sulfur-containing group or a nitrogen-containing group, or a conjugated diene residue formed from X ¹ and X ² , specifically, a halogen atom, an oxygen-containing group, a sulfur-containing group and a nitrogen-containing group. Examples of the group include the same atoms and groups as described above.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, and adamantyl; vinyl,
Alkenyl groups such as propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, α- or β-naphthyl, methylnaphthyl, anthryl, And aryl groups such as phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like. Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen.

[0107] X ¹ and Examples of the conjugated diene residue formed by X ² Prefecture, eta ^{4-1,4-diphenyl-1,3-butadiene,} eta ⁴ -1,3-butadiene, eta ^4-1,4 - dibenzyl-1,3-butadiene, eta ^{4-1-phenyl-1,}
3-pentadiene, eta ^{4-3-methyl-1,3-pentadiene,} eta ^4-1,4-bis (trimethylsilyl) -
1,3-butadiene, 2,3-dimethylbutadiene, η
^{4-2,4-hexadiene,} isoprene, and the like. The conjugated diene residue formed from X ¹ and X ² includes 1,3-butadiene, 2,4-hexadiene, 1-
The residues of phenyl-1,3-pentadiene and 1,4-diphenylbutadiene are preferable, and these residues may be further substituted with a hydrocarbon group having 1 to 10 carbon atoms. Among these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfur-containing group is preferable.

In the formula (20), Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, or a divalent germanium. -Containing group, divalent tin-containing group, -O-, -CO-, -S-,-
_{SO -, - SO 2 -,} - NR 5 -, - P (R 5) -, - P
(O) (R ⁵ ) —, —BR ⁵ — or —AlR ⁵ — (where R ⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon having 1 to 20 carbon atoms) Group)
And specifically, methylene, dimethylmethylene,
1,2-ethylene, dimethyl-1,2-ethylene, 1,
3-trimethylene, 1,4-tetramethylene, 1,2-
Alkylene groups such as cyclohexylene and 1,4-cyclohexylene, diphenylmethylene, diphenyl-1,2
-1 carbon atom such as an arylalkylene group such as ethylene
To 20 divalent hydrocarbon groups; halogenated hydrocarbon groups obtained by halogenating the above divalent hydrocarbon groups having 1 to 20 carbon atoms such as chloromethylene; methylsilylene, dimethylsilylene, diethylsilylene, di (n- Propyl) silylene,
Alkyl silylene such as di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene, arylsilylene group, tetra Methyl-1,
Divalent silicon-containing groups such as alkyldisilylenes such as 2-disilylene and tetraphenyl-1,2-disilylene, alkylaryldisilylenes and aryldisilylene groups;
A divalent germanium-containing group in which silicon of the divalent silicon-containing group is substituted with germanium; a divalent tin-containing group in which silicon of the divalent silicon-containing group is substituted with tin.

Among these divalent groups, those represented by the formula (20)
It is preferable that the shortest connecting part of -Y- represented by is composed of one or two atoms. R ⁵ is the same halogen atom, hydrocarbon group having 1 to 20 carbon atoms, or halogenated hydrocarbon group having 1 to 20 carbon atoms as described above.

Among these, Y is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent silicon-containing group or a divalent germanium-containing group, and is preferably a divalent silicon-containing group. Is more preferable, and alkylsilylene, alkylarylsilylene or arylsilylene is particularly preferable.

Further, as the metallocene compound (d-3), a transition metal compound represented by the following formula (22) can also be used.

Embedded image

In the formula (22), M is a transition metal atom belonging to Group 4 of the periodic table, specifically, titanium, zirconium or hafnium, and preferably zirconium. R ^{6 in the} formula (22) may be the same or different from each other, and may be a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms,
0, an alkenyl group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, and a phosphorus-containing group. Specifically, as the halogen atom and the alkyl group having 1 to 10 carbon atoms, those represented by the formula (20) The same groups as those described for R ¹ in the above formula (1) can be used.
It may be mentioned the same as R ² in 0).

Examples of the aryl group having 6 to 10 carbon atoms include phenyl, α- and β-naphthyl. Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, propenyl, cyclohexenyl and the like.

The above alkyl group and alkenyl group may be substituted with halogen. Among them, R ⁶ is preferably an alkyl group, an aryl group or a hydrogen atom, particularly methyl, ethyl, n-propyl, i-propyl, a hydrocarbon group having 1 to 3 carbon atoms, phenyl, α-naphthyl, It is preferably an aryl group such as β-naphthyl or a hydrogen atom.

R ^{7 in the} formula (22) may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, a C 1 -C 1
An alkyl group having 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms,
An alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group,
It is an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and specific examples thereof include the same as R ² in the formula (20).

The above alkyl group, aryl group, alkenyl group, arylalkyl group, arylalkenyl group and alkylaryl group may be substituted by halogen.

Of these, R ⁷ is preferably a hydrogen atom or an alkyl group, particularly a hydrogen atom or a carbon atom having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl and tert-butyl. Is preferred. Further, R ⁶ and R ⁷ may be the same or different from each other.

One of R ⁸ and R ^{9 in} the formula (22) is an alkyl group having 1 to 5 carbon atoms, and the other is the same hydrogen atom and halogen atom as R ² in the formula (20).
It is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group.

Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, propyl, butyl, pentyl and the like. Among these, it is preferable that one of R ⁸ and R ⁹ is an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl and propyl, and the other is a hydrogen atom.

[0120] Formula X ¹ and X ² in (22), X ¹ in may be the same or different from each other, the equation (20)
And the same hydrogen atom, halogen atom and carbon number 1 as X ²
20 hydrocarbon groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing groups, sulfur-containing groups or nitrogen-containing groups,
Or a conjugated diene residue formed from X ¹ and X ² . Of these, halogen atoms or C1-20
Is preferred.

Y in the formula (22) is the same as Y in the formula (20), a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, and a divalent hydrocarbon group. Silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-, -CO-, -S-, -SO-, -SO
^{_{2 -, - NR 5 -,}} - P (R 5) -, - P (O) (R 5)
—, —BR ⁵ — or —AlR ⁵ —, wherein R ⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Among them, Y is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent silicon-containing group or a divalent germanium-containing group, and preferably a divalent silicon-containing group. Is more preferable, and alkylsilylene, alkylarylsilylene or arylsilylene is particularly preferable.

The metallocene compound (d-3) is used alone or in combination of two or more. Further, the metallocene compound (d-3) may be used after being diluted with a hydrocarbon or a halogenated hydrocarbon. Further, the metallocene compound (d-3) can be used in contact with a particulate carrier compound.

Examples of the carrier compound for supporting the metallocene compound (d-3) include SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ and Mg.
O, ZrO ₂ , CaO, TiO ₂ , ZnO, SnO ₂ , BaO,
And inorganic carrier compounds such as ThO; polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-
Resins such as pentene and styrene / divinylbenzene copolymer can be used. These carrier compounds are used alone or in combination of two or more.

Next, the organoaluminum oxy compound (e-2) and the ionized ionic compound (f-1) used for forming the metallocene catalyst will be described.
The organic aluminum oxy compound (e-2) may be a known aluminoxane or a benzene-insoluble organic aluminum oxy compound (e-2).

Such a known aluminoxane is specifically represented by the following formula (23) or (24).

Embedded image [In the formulas (23) and (24), R is a methyl group,
It is a hydrocarbon group such as an ethyl group, a propyl group and a butyl group, preferably a methyl group, an ethyl group, particularly preferably a methyl group, and m is an integer of 2 or more, preferably 5 to 40. ]

In the formula (23) or (24), aluminoxane is an alkyloxyaluminum unit represented by the formula (OAl (R ¹ )) and an alkyloxyaluminum unit represented by the formula (OAl (R ² )) [wherein, R ¹ and R ² can be exemplified the same hydrocarbon group as R, R ¹
And R ² represent different groups]. The organic aluminum oxy compound (e-2) may contain a small amount of an organic compound component of a metal other than aluminum.

Ionized ionic compound (sometimes referred to as ionic ionized compound or ionic compound) (f
Examples of -1) include Lewis acids, ionic compounds, borane compounds and carborane compounds.
Examples of the Lewis acid include a compound represented by BR ₃ (R is a phenyl group or a fluorine which may have a substituent such as fluorine, a methyl group, and a trifluoromethyl group). Specific examples of Lewis acids include trifluoroboron, triphenylboron, tris (4-
Fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, Tris (3,5-dimethylphenyl) boron and the like.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Examples of the trialkyl-substituted ammonium salt as the ionic compound include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, and tri (n-butyl) ammonium tetra (phenyl) boron. Examples of the dialkylammonium salt as an ionic compound include di (1-propyl) ammonium tetra (pentafluorophenyl) boron, dicyclohexylammonium tetra (phenyl) boron, and the like.

As the ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl)
Examples thereof include borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and ferrocenium tetra (pentafluorophenyl) borate.

Examples of the borane compounds include decaborane (9); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, and bis [tri (n-butyl) ammonium]
Salts of metal borane anions such as bis (dodeca hydride dodecaborate) nickelate (III) and the like can be mentioned.

Examples of the carborane compound include 4-carbanonaborane (9), 1,3-dicarbanonaborane (8), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate. ) Salts of metal carborane anions such as nickelate (IV).

The above-mentioned ionized ionic compound (f)
-1) is used alone or in combination of two or more. Further, the organic aluminum oxy compound (e-2) and the ionized ionic compound (f-1) can be used by being supported on the carrier compound. When forming the metallocene catalyst, the organic aluminum oxy compound (e-2) or the ionized ionic compound (f-
1) together with the organoaluminum compound (e-1)
May be used.

In order to produce the ethylene / α-olefin / triene copolymer rubber (A) used in the present invention, ethylene (a) is added in the presence of the above-mentioned titanium catalyst, vanadium catalyst or metallocene catalyst. , Α-olefin (b) and triene compound (c) represented by the above formula (1) are usually copolymerized in a liquid phase. In this case, a hydrocarbon solvent is generally used, but an α-olefin (b) may be used as the solvent.

Examples of such hydrocarbon solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and kerosene and halogen derivatives thereof; alicyclic hydrocarbons such as cyclohexane, methylcyclopentane and methylcyclohexane. Hydrogen and its halogen derivatives; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, and their halogen derivatives are used. These solvents may be used in combination.

Ethylene (a), α-olefin (b),
The triene compound (c) may be copolymerized by a batch method or a continuous method. When the copolymerization is carried out by a batch method, the catalyst is used in the following concentration.

When a titanium catalyst comprising the solid titanium catalyst component (d-1) and the organoaluminum compound (e-1) is used, the solid titanium catalyst component (d-1)
Is converted to titanium atoms per liter of polymerization volume,
Usually, it is used in an amount of about 0.001 to about 1.0 mmol, preferably about 0.005 to 0.5 mmol. The organoaluminum compound (e-1) is usually used in an amount of about 10 to 500 mol as a metal atom in the organoaluminum compound (e-1) per 1 mol of the titanium atom in the solid titanium catalyst component (d-1). Preferably, it is used in an amount of 20 to 200 mol. When using an electron donor,
Usually about 0.001 to 10 mol, preferably 0.1 to 1 mol, per 1 mol of metal atom in the organoaluminum compound (e-1).
It is used in an amount of from 0.01 to 2 mol, particularly preferably from 0.05 to 1 mol.

When a vanadium catalyst comprising a soluble vanadium compound (d-2) and an organoaluminum compound (e-1) is used, the concentration of the soluble vanadium compound in the polymerization system is usually 0.01 to 5%. Mmol / liter
(Polymerization volume), preferably 0.05 to 3 mmol / lite
r. It is desirable that the soluble vanadium compound (d-2) is supplied at a concentration of 10 times or less, preferably 1 to 7 times, more preferably 1 to 5 times the concentration of the soluble vanadium compound present in the polymerization system. The organoaluminum compound (e-1) is supplied in an amount of 2 or more, preferably 2 to 50, more preferably 3 to 20 in terms of a molar ratio of aluminum atoms to vanadium atoms (Al / V) in the polymerization system. .

The soluble vanadium compound (d-2) and the organoaluminum compound (e-1) are usually supplied after being diluted with the hydrocarbon solvent, liquid ethylene or the triene compound (c). At this time, the soluble vanadium compound (d-2) is desirably diluted to the above concentration, but the organoaluminum compound (e-1) is adjusted to an arbitrary concentration of, for example, 50 times or less the concentration in the polymerization system. Desirably, it is supplied into the polymerization system.

When a metallocene catalyst comprising a metallocene compound (d-3) and an organic aluminum oxy compound (e-2) or an ionized ionic compound (f-1) is used, the metallocene catalyst in the polymerization system is used. Compound (d
The concentration of (-3) is usually 0.00005 to 0.1 mmol / liter (polymerization volume), preferably 0.0001 to 0.1.
05 mmol / liter. The organoaluminum oxy compound (e-2) has a molar ratio of aluminum atom to transition metal in the metallocene compound in the polymerization system (Al
/ Transition metal) from 1 to 10,000, preferably from 10 to 50
It is supplied in a quantity of 00.

In the case of the ionized ionic compound (f-1), the molar ratio of the ionized ionic compound (f-1) to the metallocene compound (d-3) in the polymerization system (the ionized ionic compound (f-1) / Metallocene compound (d-
3)) is supplied in an amount of 0.5 to 20, preferably 1 to 10. When the organoaluminum compound (e-1) is used, it is used in an amount of usually about 0 to 5 mmol / liter (polymerization degree), preferably about 0 to 2 mmol / liter.

When monomers such as ethylene (a), α-olefin (b), and triene compound (c) are copolymerized in the presence of the titanium-based catalyst, the copolymerization reaction usually takes place at a temperature of -20 to + 150 ° C, preferably 0 to
120 ° C., more preferably 0-100 ° C. and a pressure of 0
Over 7.8 MPa (80 kgf / cm ² , gauge pressure), preferably over 0 and 4.9 MPa (50 k
gf / cm ² , gauge pressure) or less.

When monomers such as ethylene (a), α-olefin (b), and triene compound (c) are copolymerized in the presence of the vanadium-based catalyst, the copolymerization reaction usually takes place at a temperature of -50 to + 100C, preferably -3
0 to + 80 ° C, more preferably -20 to + 60 ° C,
When the pressure exceeds 0 and reaches 4.9 MPa (50 kgf / cm ² ,
Gauge pressure) or less, preferably more than 0 and 2.0 MPa
(20 kgf / cm ² , gauge pressure).

When monomers such as ethylene (a), α-olefin (b) and triene compound (c) are copolymerized in the presence of the above-mentioned metallocene catalyst, the temperature of the copolymerization reaction is usually- 20 to + 150 ° C, preferably 0 to
120 ° C., more preferably 0-100 ° C. and a pressure of 0
Over 7.8 MPa (80 kgf / cm ² , gauge pressure), preferably over 0 and 4.9 MPa (50 k
gf / cm ² , gauge pressure) or less.

In the copolymerization, ethylene (a), α-olefin (b), and triene compound (c), and other monomers used as necessary, are ethylene / α-olefin / triene copolymers having the above specific composition. The rubber (A) is supplied to the polymerization system in such an amount that a rubber (A) can be obtained. In the copolymerization, a molecular weight regulator such as hydrogen may be used.

When ethylene (a), α-olefin (b) and triene compound (c) are copolymerized as described above, ethylene / α-olefin / triene copolymer rubber (A) usually It is obtained as a polymerization solution containing.
This polymerization liquid is treated by a conventional method to obtain an ethylene / α-olefin / triene copolymer rubber (A).

The diene rubber (B) used in the present invention
Is a rubber containing a double bond in the main chain, and a known diene rubber can be used without limitation. Specifically, natural rubber (N
R), isoprene rubber (IR), butadiene rubber (B
R), conjugated diene rubbers such as styrene / butadiene rubber (SBR) and chloroprene rubber (CR). As the diene rubber (B), an isoprene rubber having a balanced mechanical strength, that is, a natural rubber (NR) and an isoprene rubber (IR) are preferably used.

As the diene rubber (B), commercially available products can be used. For example, RSS # 1 (natural rubber), Sumitomo SBR
1502 (trademark, manufactured by Sumitomo Chemical Co., Ltd.), Diene 350
(Polybutadiene rubber, trade name, manufactured by Asahi Kasei Corporation). The diene rubber (B) may be used alone or as a mixture of two or more.

In the rubber composition of the present invention, the content of the ethylene / α-olefin / triene copolymer rubber (A) is from 20 to 80% by weight, preferably from 25 to 75% by weight.
More preferably, the content of the diene rubber (B) is 20 to 80% by weight, preferably 25 to 70% by weight, and more preferably 25 to 70% by weight.
It is desirably 75% by weight, more preferably 30 to 70% by weight.

When the contents of the ethylene / α-olefin / triene copolymer rubber (A) and the diene rubber (B) are within the above ranges, the vulcanizable rubber composition is excellent in scorch stability. In addition, a rubber composition capable of obtaining a vulcanized rubber excellent in weather resistance, ozone resistance and heat aging resistance without impairing the excellent mechanical properties, wear resistance and dynamic fatigue resistance inherent in diene rubber. You can get things.

The rubber composition of the present invention can be used in an unvulcanized state, but when it is used as a vulcanized rubber (vulcanized product), more excellent properties can be exhibited. That is, the ethylene / α-olefin / triene copolymer rubber (A) constituting the rubber composition of the present invention has a function of improving properties such as weather resistance, ozone resistance and heat aging resistance of the vulcanized rubber. In addition, the diene rubber (B) has a function of improving properties such as mechanical properties, abrasion resistance, and dynamic fatigue resistance of the vulcanized rubber. A vulcanized rubber excellent in properties, abrasion resistance, dynamic fatigue resistance, weather resistance, ozone resistance and heat aging resistance can be obtained. The rubber composition of the present invention is a vulcanizable rubber composition, and is vulcanized by a method of heating using a vulcanizing agent or a method of irradiating an electron beam without using a vulcanizing agent. Can be obtained.

The rubber composition of the present invention comprises, in addition to the essential components of the ethylene / α-olefin / triene copolymer rubber (A) and the diene rubber (B), a reinforcing agent (C), a softener (D) and It may further contain at least one additive selected from the group consisting of the vulcanizing agent (E).

As the reinforcing agent (C) used in the present invention, a known reinforcing agent compounded in a known rubber can be used without limitation. Specifically, SRF, GPF, FEF, MA
Carbon blacks such as F, HAF, ISAF, SAF, FT, and MT; those obtained by surface-treating these carbon blacks with a silane coupling agent; silica, activated calcium carbonate, fine talc, fine silica, and the like.

The content of the reinforcing agent (C) is 300 parts by weight or less, preferably 10 to 300 parts by weight, more preferably 10 to 200 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). Is the ratio of When the content of the reinforcing agent (C) is in the above range, a vulcanized rubber having excellent mechanical properties such as tensile strength, tear strength and abrasion resistance can be obtained.

As the softening agent (D) used in the present invention, a known softening agent blended in a known rubber can be used without any limitation. Specifically, process oils, lubricating oils, paraffin, liquid paraffin, petroleum asphalt , Petroleum softening agents such as petrolatum; coal tar softening agents such as coal tar and coal tar pitch; fatty oil softening agents such as castor oil, linseed oil, rapeseed oil and coconut oil; tall oil, sub, beeswax, Waxes such as carnauba wax and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate, and zinc laurate; and synthetic polymer materials such as petroleum resins, atactic polypropylene, and coumarone indene resins. can give. Of these, petroleum softeners are preferred, and process oils are particularly preferred.

The content of the softener (D) is 200 parts by weight or less, preferably 10 to 200 parts by weight, more preferably 10 to 150 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). Is the ratio of

When vulcanizing the rubber composition of the present invention by heating, a vulcanizing agent (E) is usually blended into the rubber composition. If necessary, compounds constituting the vulcanization system such as a vulcanization accelerator and a vulcanization aid can be blended.

As the vulcanizing agent (E), sulfur, sulfur compounds, organic peroxides and the like can be used.
The form of sulfur is not particularly limited, and for example, powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like can be used.

Examples of the sulfur compound include sulfur chloride, sulfur dichloride, polymer polysulfide, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dimethyldithiocarbamate and the like.

Examples of the organic peroxide used as the vulcanizing agent (E) include dicumyl peroxide, di-tert-butyl peroxide, di-tert-butylperoxy-3,3,5-trimethylcyclohexane, and t-butylcumyl. Peroxide, di-t-amyl peroxide, 2,5-dimethyl-
2,5-di (t-butylperoxin) hexyne-3,
2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane, α, α′-bis (t-butylperoxy-m Alkyl peroxides such as -isopropyl) benzene and t-butyl hydroperoxide;
t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate,
Peroxyesters such as t-butylperoxymaleic acid, t-butylperoxyneodecanoate, t-butylperoxybenzoate and di-t-butylperoxyphthalate; ketone peroxides such as dicyclohexanone peroxide; These may be used in combination of two or more.

Of these, the one-minute half-life temperature was 130
Organic peroxide having a temperature of from 200 ° C to 200 ° C is preferred, specifically, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide , Di-t-amyl peroxide, t-butyl hydroperoxide and the like.

In the present invention, among various vulcanizing agents as described above, it is preferable to use sulfur or a sulfur compound, particularly sulfur, since a rubber composition having excellent properties can be obtained.

When the vulcanizing agent (E) is sulfur or a sulfur compound, the total of the components (A) and (B) is 1
It can be used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 00 parts by weight. Further, when the vulcanizing agent (E) is an organic peroxide, the amount of 0.0003 to 100 g of the total of the components (A) and (B)
It can be used in a proportion of 0.05 mol, preferably 0.001 to 0.03 mol.

When sulfur or a sulfur compound is used as the vulcanizing agent (E), it is preferable to use a vulcanization accelerator in combination. As the vulcanization accelerator, N-cyclohexyl-
2-benzothiazolesulfenamide (CBS), N
Sulfenamide-based compounds such as -oxydiethylene-2-benzothiazolesulfenamide, N, N-diisopropyl-2-benzothiazolesulfenamide;
2-mercaptobenzothiazole (MBT), 2-
(2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio)
Thiazole compounds such as benzothiazole and dibenzothiazyl disulfide; guanidine compounds such as diphenylguanidine, triphenylguanidine, diorthonitrileguanidine, orthonitrile biguanide, diphenylguanidine phthalate; acetaldehyde-aniline reactant, butyraldehyde-aniline condensation Aldehyde amines such as hexamethylenetetramine and acetaldehyde ammonia or aldehyde-ammonia compounds; imidazoline compounds such as 2-mercaptoimidazoline; thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea, etc. Thiourea compounds; tetramethylthiuram monosulfide, tetramethylthiuram disulfide (T TD), thiuram-based compounds such as tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide, dipentamethylenethiuram tetrasulfide (DPTT); zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, di-n-butyldithiocarbamate Zinc salts such as zinc, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, tellurium dimethyldithiocarbamate; xanthate compounds such as zinc dibutylxanthogenate; can give.

The vulcanization accelerator described above is used in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the total of the components (A) and (B).
It is desirable to use 0 parts by weight, preferably 0.2 to 10 parts by weight.

When an organic peroxide is used as the vulcanizing agent (E), the vulcanizing aid (polyfunctional monomer) is used in an amount of 0.5 to 2 mol, preferably 0.5 to 2 mol, per mol of the organic peroxide. It is preferable to use them together in an approximately equimolar ratio.

Examples of the vulcanization aid include sulfur; quinone dioxime compounds such as p-quinone dioxime; (meth) acrylate compounds such as trimethylolpropane triacrylate and polyethylene glycol dimethacrylate;
Allyl compounds such as diallyl phthalate and triallyl cyanurate; maleimide compounds such as m-phenylene bismaleimide; and divinylbenzene.

The rubber composition of the present invention contains a stabilizer such as an inorganic filler, an antioxidant and a light stabilizer, a processing aid, a compound constituting a foaming system such as a foaming agent and a foaming aid, and a plasticizer. Various other components such as a coloring agent, a foaming agent, a flame retardant, and other rubber compounding agents can be compounded. The type and content of other components are appropriately selected depending on the application.

Examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc, clay and the like. The amount of the inorganic filler is usually 300 parts by weight or less, preferably 10 to 300 parts by weight, more preferably 10 to 200 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). It is desirable to do. When the amount of the inorganic filler is within the above range, the hardness can be increased without impairing other physical properties of the vulcanized rubber, and the cost can be reduced.

The rubber composition of the present invention preferably contains an antioxidant since the material life can be extended.
As this antioxidant, phenylnaphthylamine,
Aromatic secondary amine stabilizers such as 4,4 ′-(α, α-dimethylbenzyl) diphenylamine and N, N′-di-2-naphthyl-p-phenylenediamine; 2,6-di-t
Phenolic stabilizers such as -butyl-4-methylphenol, tetrakis- [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane; bis [2-methyl- Thioether stabilizers such as 4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide; benzimidazole stabilizers such as 2-mercaptobenzimidazole; dithiocarbamate salts such as nickel dibutyldithiocarbamate Stabilizer; 2,2,4-trimethyl-1,
And quinoline-based stabilizers such as a polymer of 2-dihydroquinoline. These may be used in combination of two or more. Such an antioxidant comprises component (A) and component (B)
It can be appropriately used in a proportion of 5 parts by weight or less, preferably 3 parts by weight or less based on 100 parts by weight of the total of the components.

As processing aids, those generally used in rubbers as processing aids can be widely used.
Specific examples include higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid and lauric acid; salts or esters of these higher fatty acids, for example, barium stearate, zinc stearate, calcium stearate and the like. The processing aid comprises a total of 1 component (A) and 1 component (B).
It can be suitably used in a proportion of 10 parts by weight or less, preferably 5 parts by weight or less with respect to 00 parts by weight.

When the rubber composition of the present invention contains a compound constituting a foaming system such as a foaming agent and a foaming aid, it can be foam-molded. As the foaming agent, foaming agents generally used when foaming rubber can be widely used, and specifically, sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite and the like Inorganic blowing agent, N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-
Nitroso compounds such as dinitrosopentamethylenetetramine, azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azo compounds such as azodiaminobenzene, barium azodicarboxylate, benzenesulfonylhydrazide, toluenesulfonylhydrazide, p, p Sulfonyl hydrazide compounds such as' -oxybis (benzenesulfonyl hydrazide) and diphenylsulfone-3,3'-disulfonyl hydrazide; azide compounds such as calcium azide, 4,4-diphenyldisulfonyl azide and p-toluenesulfonyl azide; can give.

Of these, nitroso compounds, azo compounds and azide compounds are preferred. The foaming agent is 0.5 to 30 parts by weight based on 100 parts by weight of the ethylene copolymer rubber,
Preferably, it can be used in a proportion of 1 to 20 parts by weight. From the rubber composition containing the foaming agent in such an amount, a foam having an apparent specific gravity of 0.03 to 0.8 g / cm ³ can be produced.

A foaming aid can be used together with the foaming agent. When the foaming aid is used in combination, there are effects such as lowering the decomposition temperature of the foaming agent, accelerating the decomposition, and making the bubbles uniform. Examples of such a foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid and oxalic acid, urea and derivatives thereof. The foaming aid comprises the component (A) and the component (B)
It can be used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total components.

The rubber composition of the present invention may contain other known rubbers as long as the object of the present invention is not impaired.
Such other rubbers include (A) component and (B)
Rubbers other than the components include, for example, ethylene / α-olefin copolymer rubbers such as ethylene / propylene random copolymer (EPR).

The rubber composition of the present invention comprises an ethylene / α-olefin / triene copolymer rubber (A) and a diene rubber (B), and optionally a reinforcing agent (C) and a softening agent (D). And at least one additive selected from the group consisting of vulcanizing agents (E) and, if necessary, other components as described above, which can be prepared by a general rubber compound preparation method. . For example, using an internal mixer such as a Banbury mixer, a kneader or an intermix, ethylene / α-
After kneading the olefin / triene copolymer rubber (A), diene rubber (B), reinforcing agent (C), softener (D) and other components at a temperature of 80 to 170 ° C. for 3 to 10 minutes, necessary Then, a vulcanizing agent (E), a vulcanization accelerator or a vulcanization aid is added, and the mixture is kneaded with a roll such as an open roll or a kneader at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes. After that, it can be prepared by fractionation. In this way, a rubber composition (compounded rubber) usually in the form of a ribbon or sheet is obtained. When the kneading temperature in the above internal mixers is low, the vulcanizing agent (E), the vulcanization accelerator, the foaming agent and the like can be kneaded at the same time.

The vulcanized rubber of the present invention can be obtained by subjecting the unvulcanized rubber composition of the present invention as described above to various molding methods such as an extrusion molding machine, a calender roll, a press, an injection molding machine and a transfer molding machine. It is a vulcanized rubber obtained by preforming into a desired shape, simultaneously with molding, or by introducing a molded product into a vulcanization tank and heating, or vulcanizing by irradiating an electron beam.

In the case of vulcanizing the rubber composition of the present invention by heating, HAV (hot air), PCM (glass bead fluidized bed), UHF (ultra-high frequency electromagnetic wave), steam, LCM
(Hot-melting salt tank) or other heating tank.
It is preferable to heat at a temperature of 0 to 270 ° C for 1 to 30 minutes.

When vulcanization is performed by electron beam irradiation without using a vulcanizing agent, the preformed rubber composition is added to the vulcanizate in an amount of 0.1%.
An electron beam having an energy of from 10 to 10 MeV, preferably from 0.3 to 2 MeV, is irradiated with an absorbed dose of 0.5 to 35 Mra.
d, preferably 0.5 to 10 Mrad.

In molding and vulcanization, a mold may be used, or a mold may not be used. When a mold is not used, the rubber composition is usually continuously molded and vulcanized.

The ethylene / α-olefin / triene copolymer rubber composition of the present invention obtained by blending the ethylene / α-olefin / triene copolymer rubber (A) and the diene rubber (B) is a rubber alloy. The vulcanized rubber product obtained from such a rubber composition is an existing E
The dynamic fatigue resistance, which was a drawback of PDM, and the weather resistance, ozone resistance, and heat aging resistance, which were drawbacks of the diene rubber (B), were greatly improved.

Therefore, the ethylene / α-olefin / triene copolymer rubber composition and the vulcanized rubber of the present invention have excellent mechanical properties, abrasion resistance, dynamic fatigue resistance, weather resistance, ozone resistance and heat aging resistance. For example, it can be suitably used in fields where such is required, for example, automotive parts, specifically, seal rubber parts, vibration-proof rubber, tire sidewalls, tire treads, and the like.

[0183]

The ethylene / α-olefin / triene copolymer rubber composition of the present invention is a specific ethylene / α-olefin / copolymer of a specific triene compound (c).
Triene copolymer rubber (A) and diene rubber (B)
Since it contains a rubber composition having excellent scorch stability, excellent mechanical properties of a diene rubber, without impairing abrasion resistance and dynamic fatigue resistance, weather resistance,
A vulcanized rubber having excellent ozone resistance and heat aging resistance can be obtained.

Since the vulcanized rubber of the present invention is obtained by vulcanizing the rubber composition of the present invention, it does not impair the excellent mechanical properties, abrasion resistance and dynamic fatigue resistance of the diene rubber. Excellent weather resistance, ozone resistance and heat aging resistance.

[0185]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. The copolymer rubbers used in the examples and comparative examples are as follows. Incidentally t ₅ is a scorch stability index measured by the method described in Note shown in Table 1.

<< Ethylene / α-olefin / triene copolymer rubber (A) >> (A-1) Ethylene / propylene / 4,8-dimethyl-
1,4,8-decatriene copolymer rubber (hereinafter referred to as DMD
Ethylene / propylene (molar ratio): 70/30 Triene content: 0.65 mol% Intrinsic viscosity [η] measured in decalin at 135 ° C .: 2.
72 dl / g-Iodine value: 10 (A-2) Ethylene propylene 4,8-dimethyl-
1,4,8-decatriene copolymer rubber (hereinafter referred to as DMD
Ethylene / propylene (molar ratio): 60/40 Triene content: 1.77 mol% Intrinsic viscosity [η] measured in decalin at 135 ° C .: 2.
16dl / g-Iodine value: 25 (A-3) Ethylene propylene 4,8-dimethyl-
1,4,8-decatriene copolymer rubber (hereinafter referred to as DMD
Ethylene / propylene (molar ratio): 56/44 Triene content: 2.92 mol% Intrinsic viscosity [η] measured in decalin at 135 ° C: 1.
92 dl / g-Iodine value: 39 (A-4) Ethylene propylene 4,8-dimethyl-
1,4,8-decatriene copolymer rubber (hereinafter referred to as DMD
Ethylene / propylene (molar ratio): 54/46 Triene content: 3.72 mol% Intrinsic viscosity [η] measured at 135 ° C in decalin: 1.
63dl / g-Iodine value: 48 (A-5) Ethylene propylene-5-ethylidene-2
-Norbornene copolymer rubber (hereinafter abbreviated as ENB-EPT)-ethylene / propylene (molar ratio): 64/36-5-ethylidene-2-norbornene content: 1.45
Mol% · intrinsic viscosity [η] measured in decalin at 135 ° C: 2.
18dl / g ・ Iodine value: 21 << diene rubber (B) >> (B-1) Natural rubber (NR) ・ RSS # 1, rib smoked sheet

Examples 1 to 4 Unvulcanized compounded rubber was obtained according to the composition shown in Table 1. That is,
(A) component, (B) component, zinc flower No. 1, stearic acid,
FEF carbon black [Asahi # 60HG (trademark), manufactured by Asahi Carbon Co., Ltd.], naphthenic process oil [Sansen 4240 (trademark), manufactured by Nippon Sun Oil Co., Ltd.], and an anti-aging agent [Nocrack 810-NA (trademark) ), Manufactured by Ouchi Shinko Chemical Industry Co., Ltd.] to a 1.7 liter Banbury mixer [manufactured by Kobe Steel Ltd.] and kneaded. This kneading was performed at a filling rate of 70%. Next, a vulcanization accelerator [Noxeller CZ (trademark), manufactured by Ouchi Shinko Chemical Industry Co., Ltd.] and sulfur are added to the obtained kneaded material, and an 8-inch roll (pre-roll / post-roll: 65 ° C / 65 ° C) is added. To obtain a compounded rubber.

With respect to the compounded rubber obtained as described above, a physical property test of the unvulcanized rubber was carried out, and t ₉₀ (90%
The time required for vulcanization) was determined. Table 3 shows the results. Further, a sheet of the compounded rubber obtained as described above was taken out and subjected to (t ₉₀ +
For 2 minutes), a 2 mm thick vulcanized rubber sheet was prepared by heating and pressing, and various tests were performed. Tables 3 and 4 show the results.
Shown in

Comparative Example 1 A compounded rubber was obtained in the same manner as in Example 1 with the compounding shown in Table 2, and the physical properties of unvulcanized rubber and vulcanized rubber were measured using this compounded rubber in the same manner as in Example 1. . The results are shown in Tables 5 and 6.

[0190]

[Table 1]

[0191]

[Table 2]

Notes to Tables 1 and 2 * 1 RSS # 1: Natural rubber (NR) * 2 Carbon black: FEF carbon black, Asahi # 60HG (trademark), manufactured by Asahi Carbon Co., Ltd. * 3 Process oil: Sansen 4240 (Trademark), manufactured by Nippon Sun Oil Co., Ltd. * 4 Antioxidant: Nocrack 810-NA (trademark),
Ouchi Shinko Chemical Co., Ltd. * 5 Vulcanization accelerator: Noxeller CZ (trademark), Ouchi Shinko Chemical Co., Ltd.

[0193]

[Table 3]

[0194]

[Table 4]

[0195]

[Table 5]

[0196]

[Table 6]

Notes on Tables 3 to 6 * 1 Performed according to JIS K 6300. Mooney viscometer manufactured by Shimadzu Corporation (model SMV-
202, Trademark), the change in Mooney viscosity was measured at 125 ° C., and the time from the start of the measurement to a rise of 5 points from the minimum viscosity (Vm) was determined, and the scorch time t
₅ (minutes). The scorch time t ₅ shows a longer scorch that stability is good. * 2 Cured meter (CURELASTMETE manufactured by Nippon Synthetic Rubber Co., Ltd.) performed according to JIS K6253.
R) Measure the change in torque at 150 ° C. using a mold 3 and determine the difference between the minimum value ML and the maximum value MH of the torque obtained from the vulcanization curve as ME (MH−ML = ME), and reach a 90% ME value. The time (t ₉₀ (minutes)) to obtain was determined as the vulcanization rate. t ₉₀ indicates that the faster the vulcanization rate a short period of time.

* 3 Tensile test: A vulcanized rubber sheet was punched out to prepare a No. 3 dumbbell test piece described in JIS K 6253, and this test piece was used to prepare a dumbbell test piece.
According to the method specified in 6253, a tensile test was performed under the conditions of a measurement temperature of 25 ° C. and a tensile speed of 500 mm / min.
The% modulus (M ₁₀₀ ), 200% modulus (M ₂₀₀ ), 300% modulus (M ₃₀₀ ), stress at break (T _B ), and elongation at break (E _B ) were measured. In addition, about the test piece which was heat-treated at 80 ° C for 1 hour,
The tensile test was performed to measure the tensile stress at break (T _B ) and the elongation at break (E _B ).

* 4 Hardness test: Spring hardness H _A (JIS A hardness) was measured in accordance with JIS K6253. Further, the above hardness test was performed on a test piece heat-treated at 80 ° C. for 1 hour, and the spring hardness H _A (JIS
A hardness).

* 5 Heat aging resistance: JIS K6253
A tensile test and a hardness test were performed on the test pieces before and after the heat treatment in accordance with the air heat aging test specified in, and the tensile strength at break (T _B ), the elongation at break (E _B ), and J
The IS A hardness (H _S ) was measured, and the rate of change of the stress at break (T _B ) [A _C (T _B )] and the elongation at break (E _B ) were measured.
Rate of change [A _C (E _B )] and JIS A hardness (H _S )
The difference [AH] was determined. The test conditions are as follows. Test temperature: 100 ° C Test time (heat treatment time): 96 hours

* 6 Elongation fatigue test (Monsanto fatigue test): JIS K 6253
No. 1 type dumbbell test piece described in Example 1 was prepared, and a 2 mm scratch was made at the longitudinal center of the test piece. The elongation rates of the 20 test pieces were 40%, 80%, and 1%, respectively.
The strain was subjected to elongation fatigue under the conditions of a measurement temperature of 40 ° C. and a rotation speed of 300 rpm, and the average value of stress at the time of dumbbell breakage and the average value of the number of times of breakage were measured.

* 7 Crack growth test (dematcher bending test): According to ASTM D 813, the resistance to crack growth was examined using a dematcher tester. That is, the number of bends until a crack was generated and the number of bends until the test piece was completely cut were measured (measuring temperature: 40 ° C., rotation speed: 300 rpm).

* 8 The degree of co-vulcanization was determined by the following equation.
It was used as an index of vulcanizability. Co-vulcanization degree (%) = ΔT_B(blend) / [T_B(DMDT) × a + T_B(N
R) × b]｝ × 100 In the above formula, T_B(blend) is ethylene-α-olef
In-triene copolymer rubber (A) and diene rubber
Of the vulcanized rubber sheet obtained from the rubber composition containing (B)
Tensile breaking stress (T_B), T_B(DMDT) is ethylene
Refined triene copolymer rubber (A)
Tensile stress at break (T _B), T_B(NR) is
Vulcanized rubber sheet obtained from diene rubber (B) alone
A represents ethylene / α-olefin / to
The weight fraction of the liene copolymer rubber (A), b is a diene rubber
Represents the weight fraction of the system (B), and a + b = 1.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masaaki Kawasaki 3 Chigusa Coast, Ichihara City, Chiba Prefecture Mitsui Chemicals Co., Ltd. F-term (reference) 4F070 AA05 AA06 AA08 AA09 AA13 AA16 AC05 AC20 AC50 AE01 AE02 AE08 BA02 FB06 GA06 GC03 GC04 4J002 AC01X AC03X AC06X AC08X AC09X AE053 AG003 BA013 BB05W BB133 BB15W BB17W BB19W BK003 DA036 DA046 DE236 DJ016 DJ046 EA016 EF056 EG046 EK006 EK036 EK046 EV046 EV156 EV166 FB096 FD016 FD023 FD026 FD146 FD150 GN01 4J100 AA01Q AA02P AA03Q AA04Q AA08Q AA15Q AA16Q AA17Q AA19Q AA21Q AS21R CA05 JA28

Claims (4)

[Claims] (A) ethylene (a) having 3 to 2 carbon atoms
A random copolymer rubber comprising an α-olefin (b) of 0 and a triene compound (c) represented by the following formula (1), wherein the structural unit derived from ethylene (a) has 3 to 20 carbon atoms.
Has a molar ratio (ethylene / α-olefin) of 99/1 to 30/7 with a structural unit derived from α-olefin (b).
0, ethylene / α having a content of structural units derived from the triene compound (c) of 0.1 to 30 mol% and an intrinsic viscosity [η] of 0.1 to 10 dl / g measured in decalin at 135 ° C. Ethylene-α-olefin containing olefin-triene copolymer rubber and (B) diene rubber
Triene copolymer rubber composition. Embedded image [In the formula (1), R ¹ and R ² each independently represent a hydrogen atom, a methyl group or an ethyl group, and R ³ and R ⁴ each independently represent a methyl group or an ethyl group. ] 2. The composition according to claim 1, wherein the content of the ethylene / α-olefin / triene copolymer rubber (A) is 20 to 80% by weight and the content of the diene rubber (B) is 80 to 20% by weight. Rubber composition. 3. The rubber composition according to claim 1, comprising a reinforcing agent (C), a softening agent (D) or a vulcanizing agent (E). 4. A vulcanized rubber obtained by vulcanizing the rubber composition according to any one of claims 1 to 3.