JPH11100476A - Halogenated ethylenic copolymer rubber and vulcanizable rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a halogenated ethylenic copolymer rubber having balanced covulcanizability with diene rubbers and processing properties and obtain a diene rubber composition having excellent weather resistance and ozone resistance without deteriorating the mechanical properties and dynamic fatigue resistance of diene rubber by using the copolymer rubber. SOLUTION: This halogenated ethylenic copolymer rubber is composed of ethylene, a 3-12C α-olefin and a non-conjugated diene, has a halogen content of 0.1-40 wt.% and satisfies the following requirements (1) to (5); (1) the ethylene/α-olefin ratio is 40/60 to 95/5, (2) the iodine value is 5-45, (3) the Mooney viscosity (ML1+4 , 100 deg.C) is 15-350, (4) the molecular weight distribution (Mw/Mn) is 2.5-15 and (5) the branching index B is 0.60-0.95. The vulcanizable rubber composition is composed mainly of (A) 90-10 pts.wt. of the halogenated ethylenic copolymer rubber and (B) 10-90 pts.wt. of a diene rubber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a halogenated ethylene copolymer rubber and a vulcanizable rubber composition using the same, and more particularly, to a halogenated metallocene catalyst polymer having improved processing characteristics. Halogenated ethylene copolymer rubber with excellent processability and co-vulcanizability with diene rubber, and vulcanization characteristics, processability, physical properties and durability mainly composed of this copolymer rubber and diene rubber And a vulcanizable diene rubber compound having an excellent balance of

[0002]

2. Description of the Related Art Conventionally, ethylene / propylene / non-conjugated polyene copolymer (EPDM) has excellent weather resistance, heat resistance, cold resistance, ozone resistance, etc., and is used for building materials, automobile parts, electric wire coating materials. Widely used in such as. Attempts have been made to make use of such excellent properties of EPDM as a modifier for diene rubber.

[0003] However, originally, EPDM has poor dispersibility and compatibility with diene rubbers, and has poor co-vulcanizability due to a low vulcanization rate, and the resulting vulcanized product has poor mechanical strength. There is a problem of inferiority. Regarding the problem of the vulcanization rate, for example, JP-A-60-4542 and JP-A-60-60
-47040 discloses ethylene / α-olefin /
By halogenating the non-conjugated diene copolymer rubber,
It has been proposed to improve the vulcanization rate and improve the mechanical strength of the composition. However, with these methods,
The compatibility problem has not been solved, and the modifying effect is insufficient.

In recent years, EPs using metallocene catalysts have been developed.
A proposal for DM has been made. Metallocene catalysts
It has excellent copolymerizability of comonomers such as ethylene, α-olefin, and non-conjugated diene, and has a narrow molecular weight distribution of the obtained polymer and a uniform composition distribution. Further, the metallocene catalyst is characterized in that a comonomer (for example, a higher α-olefin) which is difficult to polymerize with a vanadium-based catalyst which is a conventional EPDM catalyst is easily polymerized.

[0005] For example, in Japanese Patent Publication No. 5-80493, the content, molecular weight distribution (Mw / Mn) of ethylene, α-olefin having 3 to 10 carbon atoms and non-conjugated diene,
The crystallinity, the B value related to the mole fraction of the α-olefin / ethylene chain, and the amount of the boiling methyl acetate soluble portion were specified, respectively, and the two tertiary carbon atoms adjacent to each other in the ¹³ C-NMR spectrum were determined. Low-crystalline ethylene-based random copolymers in which αβ and βγ signals based on methylene chains are not observed have been proposed.

[0006] However, EPDM obtained from these metallocene catalysts has the drawback that the molecular weight distribution is narrow and the processability is poor, and the EPDM does not mix well with the diene rubber at the time of kneading such as Banbury, resulting in poor processability. There's a problem.

On the other hand, the present inventors disclosed in Japanese Patent Laid-Open No. 9-4
No. 0718, the use of α, ω-diene represented by 1,9-decadiene makes it possible to obtain ethylene / α
-It has been proposed that the processability of olefin / non-conjugated diene based copolymers is improved. However, in the present invention,
No study has been conducted on the dispersibility and co-vulcanizability with diene rubber.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and is a halogenated ethylene copolymer rubber excellent in balance between co-vulcanizability with diene rubber and processing characteristics. By using this copolymer rubber, the mechanical properties of the diene rubber, without impairing the dynamic fatigue resistance, weather resistance, to provide a diene rubber composition excellent in ozone resistance. I do.

[0009]

According to the present invention, a halogen content of 0.1, which comprises ethylene, an α-olefin having 3 to 12 carbon atoms and a non-conjugated polyene, satisfies the following requirements:
４０40% by weight of a halogenated ethylene copolymer rubber. The molar ratio of ethylene to α-olefin having 3 to 12 carbon atoms (ethylene / α-olefin) is 40/60 to 95 /
5 Iodine value: ₁ to 45 Mooney viscosity (ML _{1 + 4} , 100 ° C.): 15 to 350 Ratio of polystyrene equivalent weight average molecular weight (Mw) to polystyrene equivalent number average molecular weight (Mn) determined by GPC (Mw / Mn) ) Is 3 to 15; the branching index B is 0.60 to 0.95. Further, the present invention provides (A) 90 to 10 parts by weight of the above-mentioned halogenated ethylene copolymer rubber, and (B) diene rubber 10 to 9 parts.
It is intended to provide a vulcanizable rubber composition (hereinafter also referred to as "rubber composition") containing 0 parts by weight [(A) + (B) = 100 parts by weight] as a main component.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The halogenated ethylene copolymer rubber of the present invention is an ethylene copolymer comprising ethylene, an α-olefin having 3 to 12 carbon atoms (hereinafter also referred to as “α-olefin”) and a non-conjugated polyene. It is a rubber obtained by halogenating rubber. Here, as the α-olefin, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 5-
Methyl-1-hexene, 1-octene, 1-nonene, 5
-Ethyl-1-hexene, 1-decene, 1-dodecene,
3-methyl-1-butene and the like.
-Hexene, 1-octene is used. These α-
The olefins can be used alone or as a mixture of two or more.

In the halogenated ethylene copolymer rubber, the molar ratio of ethylene to the α-olefin (ethylene / ethylene)
α-olefin) is in the range of 40/60 to 95/5, preferably 60/40 to 85/15 [the above requirement]. In this case, if the above molar ratio is less than 40/60, the mechanical strength is not sufficiently exhibited, while if it exceeds 95/5, the rubber elasticity is impaired.

As the non-conjugated polyene, any commonly used non-conjugated diene can be used, but it is convenient to divide it into two types depending on the presence or absence of the ability to form a branched chain in the produced copolymer rubber. One type is a non-conjugated diene that forms a branched chain in the produced copolymer rubber, and specific examples thereof include dicyclopentadiene, 2,5-norbornadiene, 5-vinyl-2-norbornene, and C6-C6. 2
And 0 aliphatic α, ω-dienes. Examples of the aliphatic α, ω-diene include 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, and 1,9-decadiene.

The other type of non-conjugated diene is a non-conjugated diene which does not form a branched chain in the produced copolymer rubber, and specific examples thereof include 5-ethylidene-2-norbornene and 5-methylene-2. -Norbornene, 5-isopropenyl-2-norbornene, 5- (1-butenyl)-
2-norbornene, cyclooctadiene, vinylcyclohexene, 1,5,9-cyclododecatriene, 6-methyl-4,7,8,9-tetrahydroindene, 2,
2'-dicyclopentenyl, trans-1,2-divinylcyclobutane, 2-methyl-1,4-hexadiene,
1,6-octadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene, 5,7-dimethyl-1,
Examples thereof include 6-octadiene, 3,6-dimethyl-1,7-octadiene, 1,4,7-octatriene, dicyclooctadiene, and methylene norbornene.

The above non-conjugated polyenes can be used alone or as a mixture of two or more.
It is preferred to use them by seed. Among these non-conjugated polyenes, those having a branch chain-forming ability include 1,9-
If decadiene or dicyclopentadiene does not have branching ability, 5-ethylidene-2-norbornene, 1,4-hexadiene, 7-methyl-1,6-octadiene, 5,7-dimethyl-1,6 -Octadiene is preferred.

The iodine value of the halogenated ethylene copolymer rubber of the present invention is in the range of 1 to 45, preferably 3 to 30 (the above requirement). If the iodine value is less than 1, the mechanical strength is poor, while if it exceeds 45, the rubber elasticity is impaired.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) (hereinafter also referred to as “Mooney viscosity”) of the halogenated ethylene copolymer rubber is 15 to 350, preferably 20 to 350.
-300 [the above requirements]. If the Mooney viscosity is less than 15, the mechanical strength is poor, while if it exceeds 350, the processing properties are poor.

Further, gel permeation chromatography (GPC) of the halogenated ethylene copolymer rubber
Weight average molecular weight (M
The ratio [Mw / Mn (molecular weight distribution)] between w) and the number average molecular weight (Mn) is in the range of 3 to 15, preferably 3.5 to 10 [the above requirement]. If Mw / Mn is less than 3, workability is poor, while if it exceeds 15, mechanical properties are impaired.

Further, the degree of branching index B of the halogenated ethylene copolymer rubber is 0.60 to 0.95, preferably,
It is in the range of 0.70 to 0.92 [the above requirement]. The value of the branching degree index B is determined by the intrinsic viscosity [η] of the unbranched model copolymer rubber and the weight average molecular weight in terms of polystyrene according to the viscosity-GPC method [Michio Kurata, Journal of the Rubber Society of Japan, (45) 1972]. Viscosity equation [η] = K determined by (Mw)
Using Mw (where K is a constant), the intrinsic viscosity [η] is calculated from Mw obtained by GPC measurement of the target copolymer rubber, and then the actual measurement [η] of the target copolymer rubber is calculated. Dividing by [η] calculated from the above viscosity formula gives the branching index B. Here, [η] is [η] determined at 120 ° C. in o-dichlorobenzene, and Mw is a value determined by GPC at 120 ° C. in o-dichlorobenzene. When the branching index is less than 0.60, the mechanical strength is poor. On the other hand, when it exceeds 0.95, the processing properties are poor, and when blended with a diene rubber, sufficient dynamic fatigue resistance and ozone resistance are obtained. Can not be obtained.

Further, the halogen content of the halogenated ethylene copolymer rubber of the present invention is 0.1 to 40% by weight, preferably 0.3 to 15% by weight, and more preferably 0.1 to 40% by weight.
It is 3 to 5% by weight. If the amount is less than 0.1% by weight, sufficient co-vulcanizability cannot be obtained when blended with the diene rubber, while if it exceeds 40% by weight, the processability deteriorates remarkably.
Examples of the halogen of the halogenated ethylene copolymer rubber of the present invention include chlorine and bromine as described above, and bromine is preferred from the viewpoint of the vulcanization rate.

The ethylene copolymer rubber used in the halogenated ethylene copolymer rubber of the present invention can be produced by an appropriate method such as a gas phase polymerization method, a solution polymerization method, and a slurry polymerization method. These polymerization operations can be carried out in a batch system or a continuous system. In the above solution polymerization method or slurry polymerization method, an inert hydrocarbon is usually used as a reaction medium. Such inert hydrocarbon solvents include, for example, n-pentane, n-hexane, n-heptane, n-octane, n-decane, n-
Aliphatic hydrocarbons such as dodecane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene and xylene. These hydrocarbon solvents can be used alone or
A mixture of more than one species can be used. Further, the raw material monomer can be used as a hydrocarbon solvent.

The ethylene copolymer rubber used in the present invention is produced by a metallocene catalyst comprising a metallocene compound and an organoaluminum compound or an ionic compound which reacts with the metallocene compound to form an ionic complex. Hereinafter, the metallocene-based catalyst will be described more specifically, but a polymerization catalyst other than the following may be used in some cases.

Examples of the metallocene catalyst include, for example,
A catalyst comprising the following components (C) and (D) or a catalyst comprising the following components (E) and (F) is exemplified. Component (C) is a transition metal compound represented by the following general formula (1). In the formula, M is a metal of Group 4 of the periodic table, (C ₅ R _m ) is a cyclopentadienyl group or a substituted cyclopentadienyl group, and each R may be the same or different and includes a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, or two adjacent carbon atoms are bonded. E is an atom having a non-bonded electron pair, R 'is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a carbon atom having 7 to 8 carbon atoms. 40 alkaryl groups or 7 to 7 carbon atoms
40 is an aralkyl group, R ″ is an alkylene group having 1 to 20 carbon atoms, dialkyl silicon or dialkyl germanium, and is a group that binds two ligands;
Is 1 or 0; when s is 1, m is 4; n is a number smaller than the valence of E by 2; when s is 0, m is 5,
n is a number less than the valence of E; when n ≧ 2, each R ′ may be the same or different; each R ′ may be bonded to form a ring; and Q is a hydrogen atom A halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, and p and q are 0 to 4
And satisfies the relationship 0 <p + q ≦ 4.

Specific examples of component (C) include bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) ) Zirconium diphenyl, dimethylsilylbis (cyclopentadienyl) zirconium dichloride, dimethylsilylbis (cyclopentadienyl) zirconium dimethyl, methylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (cyclopentadienyl) zirconium dichloride, bis (Indenyl) zirconium dichloride, bis (indenyl) zirconium dimethyl, dimethylsilylbis (indenyl) zirconium dichloride, methylenebis (indenyl) zircon Umujikurorido, bis (4,
5,6,7-tetrahydroindenyl) zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, dimethylsilylbis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride , Dimethylsilylbis (4,5
6,7-tetrahydro-1-indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadiene) Enyl) zirconium dimethyl, dimethylsilylbis (3-methyl-1-cyclopentadienyl) zirconium dichloride, methylenebis (3-methyl-1-cyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium Dichloride, dimethylsilylbis (3-t-butyl-1-cyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (2,4-dimethyi) 1-cyclopentadienyl)
Zirconium dichloride, bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (2,3,5-trimethyl-1-cyclopentadienyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, dimethyl Silylbis (fluorenyl) zirconium dichloride, (fluorenyl) (cyclopentadienyl) zirconium dichloride, dimethylsilyl (fluorenyl) (cyclopentadienyl) zirconium dichloride, isopropylene (fluorenyl) (cyclopentadienyl) zirconium dichloride, (t -Butylamide) (1, 2, 3,
4,5-pentamethylcyclopentadienyl) zirconium dichloride, dimethylsilyl (t-butylamide)
(2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, methylene (t-butylamide) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, (Phenoxy) (1,2,3,4,5-pentamethylcyclopentadienyl) zirconium dichloride, dimethylsilyl (o-phenoxy) (2,3,4,5-tetramethyl-
1-cyclopentadienyl) zirconium dichloride,
Methylene (o-phenoxy) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, ethylene (o-phenoxy) (2,3,4,5
-Tetramethyl-1-cyclopentadienyl) zirconium dichloride, bis (dimethylamido) zirconium dichloride, bis (diethylamido) zirconium dichloride, bis (di-t-butylamido) zirconium dichloride, dimethylsilylbis (methylamido) zirconium dichloride, dimethylsilyl Examples include bis (t-butylamide) zirconium dichloride, and compounds in which zirconium in these compounds is replaced with titanium or hafnium, but is not limited thereto. The above transition metal compounds can be used alone or in combination of two or more.

The component (D) is an aluminoxane compound having a unit represented by the following general formula (2), and although the chemical structure is not necessarily clear, a linear, cyclic or cluster compound, Alternatively, it is presumed to be a mixture of these compounds. -[Al (R) -O]-... (2) wherein R is an alkyl group having 1 to 20 carbon atoms, and 6 to 4 carbon atoms.
An aryl group having 0, an alkaryl group having 7 to 40 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, preferably a methyl group, an ethyl group, an isobutyl group, and particularly preferably a methyl group. The aluminoxane compound can be produced by a known method involving a reaction between water and the organoaluminum compound having at least one R group.
The ratio of the components (C) and (D) used is usually from 1/1 to 1 / 100,000, preferably from 1 to 100,000 in terms of the molar ratio of the transition metal to the aluminum atom (transition metal / aluminum atom). / 5 to 1 / 50,000.

Next, the component (E) is a transition metal alkyl compound represented by the following general formula (3). In the formula, M is a metal of Group 4 of the periodic table, (C ₅ R _m ) is a cyclopentadienyl group or a substituted cyclopentadienyl group, each R may be the same or different, and represents a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, or two adjacent carbon atoms are bonded. E is an atom having a non-bonded electron pair, R 'is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a carbon atom having 7 to 8 carbon atoms. 40 alkaryl groups or 7 to 7 carbon atoms
40 is an aralkyl group, R ″ is an alkylene group having 1 to 20 carbon atoms, dialkyl silicon or dialkyl germanium, and is a group that binds two ligands;
Is 1 or 0; when s is 1, m is 4; n is a number smaller than the valence of E by 2; when s is 0, m is 5,
n is a number less than the valence of E, and when n ≧ 2, each R ′ may be the same or different, and each R ′ may be bonded to form a ring; C1-C20 alkyl group, C6-C40 aryl group, C7-C
An alkaryl group of 40 or an aralkyl group of 7 to 40 carbon atoms, p and q are integers of 0 to 3,
<P + q ≦ 4.

Specific examples of component (E) include bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diethyl, bis (cyclopentadienyl) zirconium diisobutyl, and bis (cyclopentadienyl) Zirconium diphenyl, bis (cyclopentadienyl) zirconium di {bis (trimethylsilyl) methyl}, dimethylsilylbis (cyclopentadienyl) zirconium dimethyl, dimethylsilylbis (cyclopentadienyl) zirconium diisobutyl, methylenebis (cyclopentadienyl) ) Zirconium dimethyl, ethylene bis (cyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, bis (indenyl) zirconium diisobutyl, dimethyl Rubis (indenyl) zirconium dimethyl, methylenebis (indenyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dimethyl, bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, dimethylsilylbis (4,5,6,7 -Tetrahydro-1-indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-
Tetrahydro-1-indenyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (3-methyl-1-cyclopentadienyl) zirconium dimethyl, bis (t-
Butylcyclopentadienyl) zirconium dimethyl,
Dimethylsilylbis (3-t-butyl-1-cyclopentadienyl) zirconium dimethyl, bis (1,3-dimethylcyclopentadienyl) zirconium dimethyl,
Bis (1,3-dimethylcyclopentadienyl) zirconium diisobutyl, dimethylsilylbis (2,4-dimethyl-1-cyclopentadienyl) zirconium dimethyl, methylenebis (2,4-dimethyl-1-cyclopentadienyl) Zirconium dimethyl, ethylene bis (2,4-dimethyl-1-cyclopentadienyl) zirconium dimethyl, bis (1,2,4-trimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (2,3,5-trimethyl) -1-cyclopentadienyl) zirconium dimethyl, bis (fluorenyl) zirconium dimethyl, dimethylsilylbis (fluorenyl) zirconium dimethyl, (fluorenyl)
(Cyclopentadienyl) zirconium dimethyl, dimethylsilyl (fluorenyl) (cyclopentadienyl)
Zirconium dimethyl, isopropylene (fluorenyl) (cyclopentadienyl) zirconium dimethyl,
(T-butylamide) (1,2,3,4,5-pentamethylcyclopentadienyl) zirconium dimethyl, dimethylsilyl (t-butylamide) (2,3,4,5-
Tetramethyl-1-cyclopentadienyl) zirconium dimethyl, methylene (t-butylamide) (2,3
4,5-tetramethyl-1-cyclopentadienyl) zirconium dimethyl, (phenoxy) (1,2,3
4,5-pentamethylcyclopentadienyl) zirconium dimethyl, dimethylsilyl (o-phenoxy)
(2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dimethyl, methylene (o-phenoxy) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dimethyl, Bis (dimethylamido) zirconium dimethyl, bis (diethylamido) zirconium dimethyl, bis (di-t-butylamido) zirconium dimethyl, dimethylsilylbis (methylamido) zirconium dimethyl, dimethylsilylbis (t-butylamido) zirconium dimethyl and the like, and compounds thereof Compounds obtained by substituting zirconium therein with titanium or hafnium include, but are not limited to. The above transition metal alkyl compounds can be used alone or in combination of two or more.

The transition metal alkyl compound may be synthesized and used in advance, or may be a transition metal halide in which R ″ in the above general formula (3) is substituted with a halogen atom, and trimethylaluminum, triethylaluminum, diethylaluminum. It may be formed by bringing an organic metal compound such as monochloride, triisobutylaluminum, methyllithium, and butyllithium into contact in a reaction system.

The component (F) is an ionic compound represented by the following general formula (4). In the formula, [L] ^{k +} is a Bronsted acid or a Lewis acid, M ′ is an element belonging to Groups 13 to 15 of the periodic table, and A ₁ to
_An is a hydrogen atom, a halogen atom, and a carbon number of 1 to 2, respectively.
0 alkyl group, C1-C30 dialkylamino group, C1-C20 alkoxyl group, C6-C40
An aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms, an aralkyl group having 7 to 40 carbon atoms, a halogen-substituted hydrocarbon group having 1 to 40 carbon atoms,
An acyloxy group or an organic metalloid group having 1 to 20 carbon atoms, k is an ionic value of L, an integer of 1 to 3,
Is an integer of 1 or more, and q = (k × p).

Specific examples of component (F) include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, methyl (di-n-butyl) ammonium tetraphenylborate, tetraphenylborate Dimethylanilinium borate, methylpyridinium tetraphenylborate, methyl tetraphenylborate (2-
Cyanopyridinium), methyl tetraphenylborate (4-cyanopyridinium), trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, tetrakis Methyl (penta-fluorophenyl) borate (di-n-butyl) ammonium, dimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, methyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate ), Methyl tetrakis (pentafluorophenylphenyl) borate (4-cyanopyridinium),
Tetrakis [bis (3,5-di-trifluoromethyl)
Phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, silver tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, and the like, but are not limited thereto. The above ionic compounds can be used alone or in combination of two or more.

The use ratio of the component (E) and the component (F) is usually from 1 / 0.5 to molar ratio [(E) / (F)].
1/20, preferably in the range of 1 / 0.8 to 1/10. The metallocene-based catalyst used in producing the ethylene-based copolymer rubber used in the present invention may be used by supporting at least a part of those components on a suitable carrier. The type of carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used. In addition, there is no particular limitation on the loading method, and a known method may be appropriately used.

By halogenating the above-mentioned ethylene copolymer rubber, the halogenated ethylene copolymer rubber of the present invention can be obtained. The production method is not particularly limited, but is usually produced as follows.

That is, the chlorination is carried out by pulverizing the above-mentioned ethylene copolymer rubber into fine particles and bringing them into contact with molecular chlorine gas, or by bringing the fine particles into aqueous suspension and contacting them with molecular chlorine gas. Or n-hexane, n-
Dissolve the above copolymer rubber in hydrocarbons such as heptane or carbon tetrachloride, tetrachloroethylene, halogenated hydrocarbons such as chlorobenzene, to form a uniform solution state,
Contact with molecular chlorine gas or furfuryl chloride, N-chlorosuccinimide, 1,3-dichloro-
It is carried out by a method of adding 5,5-dimethylhydantoindobenzenebenzene dichloride or the like. In addition, bromination, as in the case of chlorination in a homogeneous solution state, the copolymer rubber is dissolved in a hydrocarbon or halogenated hydrocarbon,
It is carried out by contacting with molecular bromine or by using an organic brominating agent such as N-bromosuccinimide. During the halogenation reaction, ultraviolet rays may be irradiated or a peroxide may be added to accelerate the reaction.

After the halogenation reaction, the treatment is carried out as follows. In the case of chlorination in a solid phase, after the reaction is completed, excess chlorine is expelled through nitrogen gas to obtain a chlorinated ethylene copolymer rubber. After the chlorination reaction in the suspended state, the reaction product is washed with water and dried to obtain a chlorinated ethylene copolymer rubber. Furthermore, after the chlorination or bromination reaction in the solution state, for example, the reaction product is neutralized with a sodium hydroxide aqueous solution, washed with water, and then washed.
A chlorinated or brominated ethylene-based copolymer rubber is obtained by steam stripping.

An acid acceptor, an antioxidant and a metal deactivator are added to these halogenated ethylene copolymer rubbers in an amount of about 0.05 to 2 parts by weight based on 100 parts by weight of the copolymer rubber. Is preferred. Here, the acid acceptor may be an organic acid salt of a metal belonging to Group IIA of the periodic table, for example, magnesium stearate, calcium stearate, manaceite, hydrotalcite, epoxidized soybean oil, epoxy acid absorbent, etc. As an inhibitor, di-t
-Butylhydroxytoluene, tetrakis [methylene (3,5-di-t-butyl-4-hydroxy) hydrocinnamate] methane, d, l-α-tocopherol, phenyl-β-naphthylamine, triphenylamine,
Examples of metal deactivators such as 1,4-benzoquinone include tris (nonylphenyl) phosphite, isopropyl citrate, pentaerythritol, tetrakis (2,
4-di-t-butylphenyl) 4,4'-biphenylene-di-phosphite and the like are used.

A vulcanizing agent is added to the halogenated ethylene copolymer rubber of the present invention, and if necessary, a vulcanization accelerator, a vulcanization aid, a reinforcing agent / filler for rubber, and a softener. A vulcanizate can be obtained by blending an acid acceptor, an antioxidant, and the like with a method used in the production of ordinary vulcanized rubber.
Further, the halogenated ethylene copolymer rubber of the present invention may be made of another rubber or resin such as another type of ethylene / α-olefin / non-conjugated polyene copolymer, ethylene / α-olefin copolymer, polyethylene, or polypropylene. One or more kinds may be used in combination.

Next, the rubber composition of the present invention comprises the above (A)
The main component is a halogenated ethylene copolymer rubber and (B) a diene rubber. Here, examples of the (B) diene rubber include natural rubber, styrene-butadiene rubber, polybutadiene rubber, acrylonitrile-butadiene rubber, polyisoprene rubber, polynorbornene rubber, and hydrogenated polymers thereof, and are preferable. Is
Natural rubber, styrene-butadiene rubber, polybutadiene rubber, and polyisoprene rubber are used. The hydrogenation rate of the hydrogenated polymer is usually 20 to 99%, preferably 50 to 95%. These (B) diene rubbers can be used alone or in combination of two or more. (B) The Mooney viscosity of the diene rubber is 10 to 10.
200 is preferable, and 20 to 100 is more preferable. If it is less than 10, the mechanical strength is inferior, while if it exceeds 200, the processing characteristics are inferior, which is not preferable.

The compounding ratio of the (A) halogenated ethylene copolymer rubber and (B) diene rubber in the rubber composition of the present invention is 90 to 10 parts by weight of component (A), preferably 80 to 20 parts by weight. Parts, more preferably 60 to 20 parts by weight, component (B) 10 to 90 parts by weight, preferably 20 to 8 parts by weight.
0 parts by weight, more preferably 40 to 80 parts by weight [however, (A) + (B) = 100 parts by weight]. If the amount of the component (A) exceeds 90 parts by weight (the amount of the component (B) is less than 10 parts by weight), the mechanical strength of the vulcanized rubber may be insufficient, and on the other hand, less than 10 parts by weight [the component (B) Is 9
0 parts by weight], the ozone resistance of the vulcanized rubber decreases.

In obtaining a vulcanizate from the rubber composition of the present invention, the intended use of the vulcanizate, in addition to (A) the halogenated ethylene copolymer rubber and (B) the diene rubber,
Depending on the performance based on it, the types and amounts of rubber reinforcing agents, fillers, softeners, acid acceptors, antioxidants, and vulcanization of vulcanizing agents, vulcanization accelerators, vulcanization aids, etc. The type and amount of the compounds constituting the system and the step of producing the vulcanizate are appropriately selected.

Examples of the rubber reinforcing agent and filler that can be used in the present invention include SAF carbon black, ISAF
Carbon black, HAF carbon black, FEF carbon black, GPF carbon black, SRF carbon black, FT carbon black, MT carbon black, acetylene carbon black, Ketjen black, heavy calcium carbonate, white powder, light calcium carbonate, ultrafine activity Calcium carbonate, special calcium carbonate, basic magnesium carbonate, magnesium carbonate, natural silicic acid, synthetic silicic anhydride, synthetic hydrous silicic acid, synthetic calcium silicate, synthetic magnesium silicate, synthetic aluminum silicate, aluminum hydroxide, water Magnesium oxide,
Magnesium oxide, kaolin clay, calcined clay, pyrolite clay, kaolin, silanized clay, sericite, talc, fine talc, calcium silicate (wollastonite, zonotonite, petal calcium silicate), diatomaceous earth, aluminum silicate, Silicic anhydride,
Mica, magnesium silicate, asbestos, PFM (P
processed Mineral Fiber), sepiolite, potassium titanate, elestadite, gypsum fiber, glass balun, silica balun, fly ash balun, silas balun, carbon-based balun, phenolic resin, urea-based resin, styrene-based resin, organic balun such as vinylidene chloride-based resin , Alumina, barium sulfate, aluminum sulfate, calcium sulfate, molybdenum disulfide, graphite, glass fiber (chopped strand, roping, milled glass fiber, glass flake), cut fiber, rock fiber, micro fiber, carbon fiber, aromatic polyamide fiber , Potassium titanate fiber, tackified fire, ebonite powder, wood powder, ceramic, rubber powder, recycled rubber, red bean, cyanine green, etc. These can be used alone or in combination of two or more. The amount of the above rubber reinforcing agent and filler is 100 parts by weight of a rubber component (hereinafter also referred to as "rubber component") composed of (A) a halogenated ethylene copolymer rubber and (B) a diene rubber of the present invention. To 10 to 200 parts by weight, preferably 10 to 10 parts by weight
0 parts by weight.

The softeners usable in the present invention include, for example, petroleum softeners such as aromatic, naphthenic and paraffinic oils; castor oil, cottonseed oil, linseed oil, rapeseed oil, soybean oil, palm oil, and the like. Oil, peanut oil,
Plant softeners such as wax wax; black sub, white sub, candy sub;
Fatty acids and fatty acid salts such as barium stearate, calcium stearate and zinc laurate; rigid polymer substances such as petroleum resin, atactic polypropylene, coumarone indene resin and polyester resin; or polyester plasticizer such as dioctyl phthalate; , Microcrystalline wax, silicone oil, modified silicone oil and the like. The softener weakens the intermolecular force of the rubber, facilitates processing, assists in the dispersion of carbon black, white carbon, etc. to be compounded as a filler, or lowers the hardness of the vulcanized rubber, resulting in flexibility and elasticity. It is used for the purpose of increasing The above softeners can be used alone or in combination of two or more. The amount of the softener is 10
It is usually 10 to 130 parts by weight, preferably 20 to 100 parts by weight, based on 0 parts by weight.

The acid acceptors that can be used in the present invention include organic acids of metals of Group IIA of the periodic table, such as magnesium stearate, calcium stearate, manaceite, hydrotalcite, epoxidized soybean oil, and epoxy acid absorbent. In addition to these, metal oxides such as magnesium and lead, and metal hydroxides are widely used.

The antioxidants which can be used in the present invention include:
Naphthylamine, diphenylamine, p-phenylenediamine, quinoline, hydroquinone derivative, mono, bis, tris, polyphenol, thiobisphenol, hindered phenol, phosphite, imidazole, nickel dithiocarbamate And phosphoric acid-based antioxidants. These can be used alone or in combination of two or more.

The vulcanizate obtained from the rubber composition of the present invention is usually used in the same manner as vulcanizing general rubber.
It is manufactured by preparing an unvulcanized compounded rubber once, then molding the compounded rubber into an intended shape, and then performing vulcanization. Here, as the vulcanizing agent, an organic peroxide, sulfur, a sulfur compound, a sulfur-containing organic vulcanizing agent, a triazine-based compound, and the like are used, and the use of sulfur and a sulfur compound is particularly preferable.

As the above-mentioned organic peroxide, 1,1-di-
t-butylperoxy-3,3,5-trimethylcyclohexane, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,
5-di-methyl-2,5-di (t-butylperoxy)
Hexane, 2,5-di-methyl-2,5-di (t-butylperoxy) hexyne, 1,3-bis (t-butylperoxy-isopropyl) benzene, t-butylperoxy-isopropyl carbonate, acetyl Cyclohexylsulfonyl peroxide, isobutyl peroxide, di-isopropylperoxydicarbonate, di-allylperoxydicarbonate, di-n-propylperoxydicarbonate, di- (2-ethoxyethyl) peroxydicarbonate, di ( (Methoxyisopropyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneohexanate, di (3-methyl-3-methyloxybutyl) peroxydicarbonate, t-butylperoxyneodeca Ne , T-hexyl peroxyneodecanoate, t- butyl peroxy hexanate,
2,4-dichlorobenzoyl peroxide, t-hexylperoxypivalate, t-butylperoxypivalate, 3,3,5-trimethylhexanoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide , Cumyl peroxy octate, acetyl peroxide, t-butyl peroxy (2-ethyl hexanate), benzoyl peroxide, t-butyl peroxy isobutyrate,
1,1-bis (t-butylperoxy) cyclohexane, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylperoxy3,
3,5-trimethylhexanate, cyclohexanone peroxide, t-butylperoxyallyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,2-bis (t-butylperoxy) Octane, t-butyl peroxyacetate, 2,
2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butyldiperoxyisophthalate, methyl ethyl ketone per Oxide, α, α′-bis (t-butylperoxy-
m-isopropyl) hexane, di-isopropylbenzene-hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2,5-dimethylhexane-2,5-
Examples include dihydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide and the like.

Further, a sulfur-based vulcanizing agent (sulfur / sulfur compound)
Examples thereof include powdered sulfur, sulfur white, highly dispersible sulfur, insoluble sulfur, precipitated sulfur, surface-treated sulfur, colloidal sulfur, sulfur chloride, sulfur monochloride, sulfur dichloride, and the like. Also,
As the sulfur-containing organic vulcanizing agent, morpholine disulfide,
Alkylphenol disulfides, thiuram disulfide, N, N'-dithio-bis (hexahydro-2H-
Azepinone-2), 2- (4'-morpholinodithio) benzothiazole and the like. Further, as the triazine-based compound, 2,4,6-trimercapto-S-
Triazine, 2-di-n-butylamino-4,6-dimercapto-S-triazine and the like. The above vulcanizing agents can be used alone or in combination of two or more.

The amount of these vulcanizing agents is 10
The amount is usually 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight with respect to 0 parts by weight.

When an organic peroxide is used as the vulcanizing agent, sulfur, p-quinonedioxime, p-benzoquinonedioxime, p,
p'-Dibenzoylquinone dioxime, N-methyl-
N'-4-dinitroaniline, N, N'-m-phenylenedimaleimide, dipentamethylenethiuram pentasulfide, dinitrosobenzene, divinylbenzene, triallyl cyanurate, triallyl isocyanurate, triazine thiol, ethylene glycol dimethacrylate , Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, trimethylolpropane triacrylate, erythritol tetramethacrylate, trimethylolpropane trimethacrylate, diallyl melamine, trimethacrylate, Dimethacrylate, divinyl adipate, vinyl butyrate, Rustearate, liquid polybutadiene rubber, liquid polyisoprene rubber, liquid styrene-butadiene rubber, liquid acrylonitrile-butadiene rubber, magnesium diacrylate, calcium diacrylate, aluminum acrylate, zinc acrylate, stannas acrylate, zinc methacrylate, magnesium methacrylate And a co-crosslinking agent such as zinc dimethacrylate. These co-crosslinking agents can be used alone or in combination of two or more. The compounding amount of the co-crosslinking agent is usually 0.5 to 20 parts by weight based on 100 parts by weight of the rubber component.

When a sulfur vulcanizing agent is used as the vulcanizing agent, a vulcanization accelerator can be used. Examples of such a vulcanization accelerator include aldehyde ammonia such as hexamethylenetetramine and acetaldehyde / ammonia; n-butyraldehyde-aniline condensate, butyraldehyde-monobutylamine condensate, heptaldehyde-aniline condensation And aldehyde amines such as tricrotonylidene tetramine condensate; diphenyl guanidine, di-o-tolyl guanidine, ortho tolyl biguanide, dicatechol and boric acid dioritol, tolyl and guanidine salts such as boric acid; 2-mercaptoimidazoline Imidazolines such as 2-mercaptobenzothiazole, 2-mercaptothiazoline, dibenzothiazyl disulfide, zinc salt of 2-mercaptobenzothiazole, and 2-mercaptobenzothiazole Potassium salt, cyclohexylamine salt of 2-mercaptobenzothiazole, 2- (2,4
Dinitrophenylthio) benzothiazole, 2- (N,
Thiazoles such as N-diethylthio-carbamoylthio) benzothiazole, 2- (4'-morpholino-dithio) benzothiazole, 4-morpholino-2-benzotheazyl disulfide; N-cyclohexyl-2-benzothiazole sulfenamide; N, N-dicyclohexyl-2-benzothiazyl sulfenamide, N-
Oxydiethylene-2-benzothiazyl sulfenamide, N, N-diisopropyl-2-benzothiazyl.
Sulfenamides such as sulfenamide and Nt-butyl-2-benzothiazyl sulfenamide; thiocarbanide, ethylene thiourea (2-mercaptoimidazoline), diethyl thiourea, dibutyl thiourea, mixed alkyl thiourea Thioureas such as tolylmethylthiourea and dilaurylthiourea; sodium dimethyl dithiocarbamate, sodium diethyldithiocarbamate, sodium di-n-butylcarbamate, lead dimethyldithiocarbamate, lead diamyldithiocarbamate, diamil. Zinc dithiocarbamate, zinc zinc zinc dithiocarbamate, zinc zinc di-n-butyldithiocarbamate, zinc zinc dibenzyldithiocarbamate, zinc zinc N-pentamethylenedithiocarbamate, ethylphenate Zinc dithiocarbamate, selenium dimethyldithiocarbamate, selenium diethyldithiocarbamate, tellurium diethyldithiocarbamate, cadmium diethyldithiocarbamate, copper dimethyldithiocarbamate, iron dimethyldithiocarbamate, bismuth dimethyldithiocarbamate, dimethyl Dithiocarbamate salts such as piperidine dithiocarbamate, pipecoline methylpentamethylene dipicarbamate, and activated dithiocarbamate; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, active tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram .Disulfide, N, N'-dimethyl-
Thiurams such as N, N'-diphenylthiuram disulfide, dipentamethylenethiuram disulfide, dipentamethylenethiuram tetrasulfide, mixed alkyl thiuram disulfide; sodium isopropyl xanthate, isopropyl zinc xanthate, butyl. Xanthates such as zinc xanthate; 4,4'-dithiodimorpholine, aminodialkyldithiophosphate, zinc-o, on-butyl phosphorodithioate, 3-mercaptoimidazoline-thione-2, thioglycolic acid ester And the like.
These vulcanization accelerators can be used alone or in combination of two or more. The amount of the vulcanization accelerator is usually 0.1 to 20 parts by weight, based on 100 parts by weight of the rubber component.
Preferably it is 0.2 to 10 parts by weight.

[0049] In addition to the above vulcanizing agents and vulcanization accelerators, vulcanization accelerating auxiliaries can be added as required. Such vulcanization accelerating aids include, for example, magnesium oxide, zinc white, activated zinc white, surface-treated zinc white, zinc carbonate, composite zinc white, composite active zinc white, surface-treated magnesium oxide, calcium hydroxide, electrode Metal oxides such as fine calcium hydroxide, lead monoxide, litharge, lead red, lead white; organic acids such as stearic acid, oleic acid, lauric acid, zinc stearate, calcium stearate, potassium stearate, sodium stearate ( Salts) and the like, and zinc white and stearic acid are particularly preferable.
These vulcanization accelerators can be used alone or in combination of two or more. The amount of the vulcanization accelerator is
It is usually 0.5 to 20 parts by weight based on 100 parts by weight of the rubber component.

The rubber composition of the present invention further comprises an ultraviolet absorber, a light stabilizer, a flame retardant, an antistatic agent, a conductive plasticizer, a liquid rubber, a functional group-containing oligomer, a colorant, an oil resistance improver, A foaming agent, an anti-scorch agent, a tackifier, a dewatering agent, an activator, a wax, a coupling agent, a mastication accelerator, an antibacterial agent, a foaming aid, a processing aid, and the like can be arbitrarily compounded.

In preparing the rubber composition of the present invention, a conventionally known kneading machine, extruder, vulcanizing apparatus and the like can be used. The method and order of compounding the filler, plasticizer, vulcanizing agent and the like mixed together with the (A) halogenated ethylene copolymer rubber and (B) diene rubber of the present invention are not particularly limited. After mixing the halogenated ethylene copolymer rubber and the diene rubber, a filler, a softener, and the like using a mixer or the like, a method of adding a vulcanizing agent or the like using a roll or the like may be used.

Next, vulcanization is carried out by, for example, placing the rubber composition of the present invention in a mold and raising the temperature, or vulcanizing with an extruder by a method usually used for the production of vulcanized rubber. And vulcanization by heating in a vulcanization tank and vulcanizing, whereby a vulcanized rubber can be produced. The rubber composition of the present invention can be suitably used for applications such as tires, anti-vibration rubber, window frames, various weather strips, civil engineering materials, and rubber rolls.

[0053]

The present invention will now be described more specifically with reference to examples. However, the present invention is not limited to these embodiments. The percentages and parts in the examples are on a weight basis unless otherwise specified. The measurement and evaluation in Examples and Comparative Examples were performed by the following methods.

Α-Olefin content (mol%) was measured by ¹³ C-NMR method. However, the content (mol%) of ethylene and α-olefin in each of Examples and Comparative Examples is a value when the total amount of these is 100 mol%. The iodine value was measured by an infrared absorption spectrum method. Mooney viscosity (ML _{1 + 4} , 100 ° C.) Measured under the conditions of measurement temperature of 100 ° C., preheating of 1 minute, and measurement of 4 minutes in accordance with JIS K6300. It was measured by GPC in Mw / Mn o-dichlorobenzene at 135 ° C. The branching index B o-dichlorobenzene solvent was used, and the sample concentration was 0.15.
%, 135C, 150CV type GPC manufactured by Waters
Was measured by The halogen content was measured by X-ray fluorescence analysis.

Roll workability Roll workability was determined by the following five-step evaluation. 5; The rubber band is completely adhered to the roll, and the bank rotates smoothly. 4: The rubber band sometimes separates from the roll surface from the top of the roll to the bank. 3: The rubber band is considerably apart from the roll surface from the top of the roll to the bank. 2: The rubber band does not adhere to the roll surface and hangs down, and the roll processing cannot be performed unless the rubber band is touched. 1; The rubber band does not adhere to the roll surface at all and hangs down. Unless the rubber band is touched, the roll processing cannot be performed.

The cohesiveness of the plastmill The discharge amount of the rubber compound during kneading of the plastmill was calculated as follows.
The following four grades evaluated. ◎: Excellent discharge amount ○: Good discharge amount Δ: The unity of the discharged rubber is slightly poor. X: The discharged rubber is not collected.

Vulcanization behavior Using a Curastometer V type manufactured by Nippon Synthetic Rubber Co., Ltd., a maximum torque M was obtained from a vulcanization curve at 160 ° C. for 30 minutes.
H was determined. Tensile test According to JIS K6301, a tensile strength TB (MPa) and an elongation at break EB (%) were measured using a No. 3 type test piece at a measurement temperature of 25 ° C. and a tensile speed of 500 mm / min. According to the hardness test JIS K6301, the spring hardness HS (J
IS A hardness) was measured.

Compression set was measured at 70 ° C. for 22 hours in accordance with JIS K6301. Heat aging resistance Measured under the following conditions in accordance with JIS K6301. Aging conditions: 160 ° C., 70 hours, in an air oven Breaking strength retention [AR (TB)], breaking elongation retention [A
R (EB)]

Elongation Fatigue Test (Crack Growth) A No. 1 type dumbbell test piece described in JIS K6301 was prepared, and an elongation rate of 75% was measured for 10 test pieces in which a crack was previously formed in the longitudinal center of the test piece. Elongation fatigue under conditions of temperature 30 ° C and rotation speed 300 cpm,
The average value of the number of cycles until the test piece was cut was determined. (Crack Initiation) A test piece in which a crack was not previously formed in the test piece was subjected to the test under the same conditions as above except that the elongation rate was 100%, and the average value of the number of cycles at the time of cutting the test piece was obtained. Ozone resistance test According to JIS K6301, ozone concentration 50 pph
The crack generation time was measured under the conditions of m, 40 ° C., and elongation rate of 50%, and was used as an index of ozone resistance. The test period was 14 days.

Reference Example 1 (Production of Ethylene Copolymer Rubber) 1.45 liters of purified toluene was placed in a 3 liter stainless steel autoclave sufficiently purged with nitrogen.
Octene in 450 ml, 7-methyl-1,6
-45 ml of octadiene and 1.7 ml of 1,9-decadiene were added, and after heating to 30 ° C,
While continuously supplying ethylene at a rate of 14 normal liters / minute, the internal pressure of the container was adjusted to 5 kg / cm ² . Separately, isopropylene (fluorenyl) (cyclopentadienyl) zirconium dichloride dissolved in 3.0 ml of purified toluene was placed in a 50 ml glass flask containing a magnetic stirrer and sufficiently purged with nitrogen. Was added, and 1.5 mmol of triisobutylaluminum dissolved in 6.0 ml of purified toluene was added thereto, and the mixture was stirred and reacted at room temperature for 30 minutes. Next, 3.6 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate dissolved in 7.2 ml of purified toluene was added, and the mixture was stirred at room temperature for 20 minutes to be reacted to obtain a polymerization catalyst.

This polymerization catalyst was added to the above autoclave to initiate polymerization. During the reaction, keep the temperature at 30 ° C, and continuously supply ethylene, while keeping the internal pressure of the vessel at 5 kg.
/ Cm ² and polymerization was carried out for 15 minutes. Then
After adding a small amount of methanol to stop the reaction,
The mixture was dissolved by steam stripping and dried on a 6-inch roll to obtain 155 g of a polymer. This polymer is
28. Ethylene content 71.5 mol%, 1-octene content
5 mol%, iodine value 15.5, Mooney viscosity 45, Mw
/ Mn 5.5, ethylene of branching index B = 0.835 /
1-octene / 7-methyl-1,6-octadiene /
1,9-decadiene random copolymer (hereinafter referred to as “EODM
(1) ").

Example 1 (Production of Halogenated Ethylene Copolymer Rubber) 150 g of the EODM (1) obtained in Reference Example 1 was dissolved in 4.0 liter of n-hexane, and this was dissolved in a reflux condenser, a stirrer and Charged into a glass reaction vessel equipped with a thermometer,
The temperature was kept at 50 to 60 ° C and the mixture was stirred. In addition, bromine n-
A hexane solution (5.6 g as bromine) was added dropwise, stirred for 1 hour, neutralized by adding a dilute aqueous sodium hydroxide solution, and the solvent was removed by steam stripping. 145 g of polymer were obtained. The polymer thus obtained had an iodine value of 12.5, a Mooney viscosity of 46, Mw / Mn of 5.5,
A brominated ethylene / 1-octene / 7-methyl-1,6-octadiene / 1,9-decadiene random copolymer having a branching index B = 0.835 and a bromine content of 2.0% (hereinafter referred to as “Br-EODM”) (1) ").

Example 2 (Preparation and evaluation of rubber composition) Natural rubber, brominated ethylene / 1 prepared according to Example 1
-Octene / 7-methyl-1,6-octadiene / 1,
9-decadiene random copolymer [Br-EODM
(1)] A rubber compound having the composition shown in Table 1 comprising a filler, a vulcanizing agent, a stabilizer and the like was kneaded at 70 ° C. for 20 minutes using a 6-inch open roll. The kneaded rubber compound was press-vulcanized at 160 ° C. for 15 minutes to produce a vulcanized rubber sheet having a thickness of 2 mm. Using this sheet, mechanical properties were measured. Table 2 shows the results.

[0064]

[Table 1]

* 1) RSS # 1 * 2) Diana Process Oil PW manufactured by Idemitsu Kosan Co., Ltd.
-380 * 3) Diphenylguanidine * 4) Dipentamethylenethiuram tetrasulfide

Example 3 In Reference Example 1, the non-conjugated polyene was replaced with 5-ethylidene-butane instead of 7-methyl-1,6-octadiene.
Except for using 2-norbornene, the same operation as in Reference Example 1 was carried out to obtain an ethylene content of 72.0 mol%, a 1-octene content of 28.0 mol%, an iodine value of 14.5, a Mooney viscosity of 52, and an Mw / Mn of 5. .4, an ethylene / 1-octene / 5-ethylidene-2-norbornene / 1,9-decanediene random copolymer having a branching index B = 0.845 (hereinafter also referred to as “EODM (2)”) was obtained. . Next, an iodine value of 11.1 was obtained in the same manner as in Example 1 except that this EODM (2) was used as an ethylene copolymer rubber.
5. A brominated ethylene / 1-octene / 5-ethylidene-2-norbornene / 1,9-decanediene random copolymer having a bromine content of 2.0% (hereinafter referred to as "Br-EODM").
(2) "). Next, a rubber composition was obtained in the same manner as in Example 2 except that the above-mentioned Br-EODM (2) was used as the brominated ethylene copolymer rubber. Table 2 shows the results.

Comparative Example 1 A polymer was obtained in the same manner as in Reference Example 1, except that 1,9-decadiene was not used. This polymer has an ethylene content of 71.0 mol%, a 1-octene content of 29.0 mol%, an iodine value of 15.0, a Mooney viscosity of 47, Mw / Mn of 2.8, and a branching index B = 0.97.
8 ethylene / 1-octene / 7-methyl-1,6-octadiene random copolymer (hereinafter referred to as “EODM (3)”
). Then, the same operation as in Example 1 was carried out except that this EODM (3) was used as the ethylene copolymer rubber, to obtain an iodine value of 13 and a branching index B of 0.9.
78, a brominated ethylene / 1-octene / 7-methyl-1,6-octadiene random copolymer having a bromine content of 2.0% (hereinafter also referred to as "Br-EODM (3)").
Next, as the brominated ethylene copolymer rubber, the above Br
-A rubber composition was obtained in the same manner as in Example 2 except that EODM (3) was used. Table 2 shows the results.

Example 4 A bromine having an iodine value of 10 and a bromine content of 4.7% was prepared in the same manner as in Example 3 except that 12.0 g of bromine in n-hexane was dropped as bromine. Ethylene / 1-octene / 5-ethylidene-2-norbornene /
1,9-decadiene random copolymer (hereinafter referred to as "Br-E
ODM (4) "). Next, a rubber composition was obtained in the same manner as in Example 2 except that the above-mentioned Br-EODM (4) was used as the brominated ethylene copolymer rubber.

Example 5 The procedure of Example 3 was repeated, except that 1.4 g of bromine in n-hexane was dropped as bromine, and the same operation was carried out to obtain a brominated ethylene / 1 with an iodine value of 14 and a bromine content of 0.4%. -Octene / 5-ethylidene-2-norbornene / 1,9-decadiene random copolymer (hereinafter referred to as "Br-EODM").
(5) "). Next, a rubber composition was obtained in the same manner as in Example 2, except that the above-mentioned Br-EODM (5) was used as the brominated ethylene copolymer rubber.

Comparative Example 2 A brominated ethylene / 1-octene / 5-ethylidene-2 having a bromine content of 45% was operated in the same manner as in Example 3 except that 115 g of bromine in n-hexane was dropped as bromine. -Norbornene / 1,9-decadiene random copolymer (hereinafter also referred to as "Br-EODM (6)") was obtained. Next, a rubber composition was obtained in the same manner as in Example 2, except that this Br-EODM (6) was used as the brominated ethylene copolymer rubber. Table 3 shows the results.

Comparative Example 3 In Example 3, brominated ethylene / 1-octene / 5
-Instead of ethylidene-2-norbornene / 1,9-decadiene random copolymer, ethylene / 1 before bromination
-Octene / 5-ethylidene-2-norbornene / 1,
A rubber composition was obtained in the same manner as in Example 3, except that the 9-decadiene random copolymer EODM (2) was used. Table 3 shows the results.

Example 6 In Example 3, a diene rubber and Br-EODM were used.
A rubber composition was obtained in the same manner as in Example 2, except that the blending number of (2) was changed to 45 parts and 55 parts, respectively. Table 4 shows the results.

Comparative Example 4 In Example 3, diene rubber and Br-EODM were used.
A rubber composition was obtained in the same manner as in Example 2, except that the blending number of (2) was changed to 95 parts and 5 parts, respectively. Table 4 shows the results.

Comparative Example 5 In Example 3, diene rubber and Br-EODM were used.
A rubber composition was obtained in the same manner as in Example 2 except that the number of parts of (2) was changed to 5 parts and 95 parts, respectively. Table 4 shows the results.

In Table 2, Examples 2 to 3 are rubber compositions of the present invention, which are excellent in processability, vulcanization characteristics, mechanical strength, heat aging resistance and dynamic fatigue resistance. On the other hand, Comparative Example 1 is an example in which Mw / Mn is small and the branching index is too high, and is inferior in workability.

In Table 3, Examples 3 to 5 are rubber compositions of the present invention.
The durability is excellent, and it can be seen that the halogenated ethylene copolymer rubber of the present invention is excellent in the effect of modifying a diene rubber. Comparative Example 2 was an example in which the halogen content was too large, and the kneading was difficult because the cohesion by the halogen was too strong. Comparative Example 3 is a non-halogenated example, but is inferior in co-vulcanizability with a diene rubber and inferior in mechanical strength and durability.

In Table 4, the results are shown in Examples 3 and 6
Is a rubber composition of the present invention, and has improved heat aging resistance and ozone resistance as compared with Comparative Example 4 in which the blending amount of the halogenated ethylene copolymer rubber is too small. Comparative Example 5
Is an example where the compounding amount of the halogenated ethylene copolymer rubber is too large, and the mechanical strength and the dynamic fatigue properties are remarkably inferior.

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

The halogenated ethylene copolymer rubber of the present invention has excellent covulcanizability with diene rubber, and provides a rubber composition having excellent processing characteristics and durability. Therefore, the rubber composition of the present invention is very suitably used for applications such as tires, prevention rubbers, and OA rolls.

Claims (2)

[Claims] 1. A halogenated ethylene copolymer rubber comprising ethylene, an α-olefin having 3 to 12 carbon atoms and a non-conjugated polyene and having a halogen content of 0.1 to 40% by weight which satisfies the following requirements: The molar ratio of ethylene to α-olefin having 3 to 12 carbon atoms (ethylene / α-olefin) is 40/60 to 95 /
5 Iodine value: ₁ to 45 Mooney viscosity (ML _{1 + 4} , 100 ° C.): 15 to 350 Ratio of polystyrene equivalent weight average molecular weight (Mw) to polystyrene equivalent number average molecular weight (Mn) determined by GPC (Mw / Mn) ) Is 3 to 15 and the branching degree index B is 0.60 to 0.95. 2. (A) 90 to 10 parts by weight of the halogenated ethylene copolymer rubber according to claim 1, (B) 10 to 90 parts by weight of a diene rubber [(A) + (B) = 100 parts by weight] V. A vulcanizable rubber composition comprising: