JPH11100475A - 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 6-12C α-olefin and a non-conjugated diene, has a halogen content of 0.1-10 wt.% and satisfies the following requirements (1) to (3); (1) the molar ratio of ethylene to the 6-12C α-olefin (ethylene/α-olefin) is 40/60 to 95/5, (2) the iodine value is 5-45 and (3) the Mooney viscosity (ML1+4 , 100 deg.C) is 15-350. 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]

TECHNICAL FIELD The present invention relates to a halogenated ethylene copolymer rubber and a rubber composition using the same.
More specifically, a halogenated ethylene copolymer rubber excellent in the balance of vulcanization characteristics, mechanical characteristics, and processing characteristics, and a copolymer of diene rubber, which is mainly composed of the copolymer rubber and a diene rubber. The present invention relates to a diene rubber compound having an excellent balance between sulfurability and processing characteristics.

[0002]

2. Description of the Related Art Ethylene / α-olefin / non-conjugated polyene copolymers are excellent in weather resistance, heat resistance, cold resistance, ozone resistance, etc., and are conventionally used for building materials, automobile parts, electric wire coating materials and the like. Widely used for Attempts have been made to make use of such excellent properties of the copolymer as a modifier for diene rubber.

However, the ethylene / α-olefin / non-conjugated polyene copolymer has a low vulcanization rate and poor co-vulcanizability with diene rubber because of a small number of unsaturated bonds in the molecule. A rubber composition having satisfactory mechanical strength has not been obtained. In addition, propylene is generally used as the α-olefin used in the ethylene / α-olefin / non-conjugated polyene copolymer, and such a copolymer has poor mechanical strength, flexibility, and processability. There is a problem that the balance is poor, the mechanical properties and the processability when blended with the diene rubber cannot be balanced, and a satisfactory modifying effect cannot be obtained.

Regarding the problem of vulcanization rate, for example, JP-A-63-4542 and JP-A-60-47040 disclose halogenating an ethylene / α-olefin / non-conjugated polyene copolymer. Improve the vulcanization speed,
It has been proposed to improve the mechanical strength of the composition.
However, the α-olefin used in these is a lower α-olefin having 3 to 4 carbon atoms, and as described above, the effect of modifying the diene rubber is insufficient.

Regarding the problem of balance between physical properties and processability, in recent years, proposals have been made regarding an ethylene / α-olefin / non-conjugated polyene copolymer using a metallocene catalyst. The metallocene catalyst has characteristics such as excellent copolymerizability of comonomers such as ethylene, α-olefin, and non-conjugated polyene, narrow molecular weight distribution of the obtained polymer, and uniform composition distribution. In addition, conventional EPDM
The vanadium-based catalyst which is a catalyst of (1) is characterized in that a comonomer (for example, a higher α-olefin) which has been difficult to polymerize is easily polymerized. The ethylene / higher α-olefin-based copolymer obtained in this way has an advantage of being superior in balance between mechanical strength, flexibility and processability as compared with the ethylene / propylene-based copolymer.

An example of halogenating an ethylene / α-olefin / non-conjugated polyene copolymer using a metallocene catalyst thus obtained is disclosed in JP-A-3-1815.
No. 05 and Japanese Patent Application Laid-Open No. 7-90018. However, the former uses propylene as the α-olefin, and is not practiced for higher α-olefins having 6 or more carbon atoms. On the other hand, the latter has a high chlorine content range of 20 to 40% by weight, and in such a high halogen content region, the processability and durability of the halogenated ethylene copolymer are extremely poor. In both cases, there is no description regarding the modification of diene rubber.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has been developed for co-vulcanization of ethylene / α-olefin / non-conjugated polyene copolymer with diene rubber and processing. It is an object of the present invention to provide a halogenated ethylene copolymer rubber having improved properties and a good balance of mechanical properties and processing properties. Also, the present invention provides a diene rubber with a halogenated ethylene copolymer rubber having an excellent balance of co-vulcanizability, mechanical properties and processing properties, thereby obtaining mechanical properties and dynamic resistance of the diene rubber. An object of the present invention is to provide a rubber composition having excellent weather resistance and ozone resistance without impairing mechanical fatigue.

[0008]

According to the present invention, a halogen content of 0.1, which comprises ethylene, an α-olefin having 6 to 12 carbon atoms and a non-conjugated polyene, and satisfies the following requirements:
10 to 10% by weight of a halogenated ethylene copolymer rubber. The molar ratio of ethylene to α-olefin having 6 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 Here, the halogen is preferably bromine. The present invention also relates to (A) the halogenated ethylene copolymer rubber 90 to
The present invention provides a vulcanizable rubber composition containing 10 parts by weight and (B) 10 to 90 parts by weight of a diene rubber (where (A) + (B) = 100 parts by weight).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The halogenated ethylene copolymer rubber used in the present invention is ethylene, α having 6 to 12 carbon atoms.
A rubber obtained by halogenating an olefin (hereinafter also referred to as “α-olefin”) and an ethylene copolymer rubber comprising a non-conjugated polyene. Here, as the α-olefin, for example, 1-hexene, 4-methyl-1-pentene, 1-heptene, 5-methyl-1-hexene, 1-octene, 1-nonene, 5-ethyl-1-hexene , 1-
Decene, 1-dodecene and the like, preferably 1-
Hexene and 1-octene, more preferably 1-octene, are used. These α-olefins can be used alone or in combination of two or more. The molar ratio of ethylene to the α-olefin (ethylene / α-olefin) in the halogenated ethylene copolymer rubber is as follows:
40/60 to 95/5, preferably 60/40 to 87
/ 13 [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.

[0010] Non-conjugated polyenes include, for example,
5-ethylidene-2-norbornene, dicyclopentadiene, tricyclopentadiene, 5-methyl-2,5-
Norbornadiene, 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, 1,7-octadiene, 1,4-hexadiene, 1,8-nonadiene, 1,
9-decadiene, 7-methyl-1,6-octadiene,
5,7-dimethyl-1,6-octadiene, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-
1,7-octadiene, 1,4,7-octatriene,
5-methyl-1,8-nonadiene, dicyclooctadiene, methylene norbornene, 5-vinyl-2-norbornene and the like. Of these non-conjugated polyenes,
Preferably, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene,
4-hexadiene, 7-methyl-1,6-octadiene, 5,7-dimethylene-1,6-octadiene, 1,
9-decadiene. These non-conjugated polyenes are 1
Species can be used alone or in combination of two or more.

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

Further, the Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the halogenated ethylene copolymer rubber (hereinafter also referred to as “Mooney viscosity”) is 15 to 350, preferably 2 to 350.
It is in the range of 0 to 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.

The weight average molecular weight (Mw) of the halogenated ethylene copolymer rubber in terms of polystyrene measured by gel permeation chromatography (GPC).
And the ratio [Mw / Mn (molecular weight distribution)] of the number average molecular weight (Mn) is preferably 1.5 to 15, more preferably 2.
It is in the range of 0-10.

The halogen content of the halogenated ethylene copolymer rubber is 0.1 to 10% by weight, preferably 0.3 to 5%.
% By weight. If it is less than 0.1% by weight, sufficient co-vulcanizability with the diene rubber cannot be obtained, while if it exceeds 10% by weight, processability deteriorates. 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 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,
aliphatic hydrocarbons such as n-decane and n-dodecane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene and xylene. These hydrocarbon solvents are
They can be used alone or in combination of two or more. Further, the raw material monomer can be used as a hydrocarbon solvent.

The polymerization catalyst used for producing the ethylene copolymer rubber used in the present invention includes, for example,
An olefin polymerization catalyst comprising a compound of a transition metal selected from V, Ti, Zr and Hf and an organometallic compound can be mentioned. The transition metal compound and the organometallic compound can be used alone or in combination of two or more. As a particularly preferred example of such an olefin polymerization catalyst, 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 can be mentioned. Hereinafter, the polymerization catalyst for producing the ethylene-based copolymer rubber 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 the 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 its 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 ratio of the components (E) and (F) used is usually from 1 / 0.5 to 1 / (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.

The above-mentioned ethylene copolymer rubber is halogenated to obtain the halogenated ethylene copolymer rubber of the present invention. 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 an 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 performed 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 an aqueous solution of caustic soda, washed with water, and then subjected to steam stripping to obtain a chlorinated or brominated ethylene copolymer rubber. Get.

An acid acceptor, an antioxidant, and a metal deactivator are added to the halogenated ethylene copolymer rubber 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, such as magnesium stearate, calcium stearate, manaceite, hydrotalcite, epoxidized soybean oil, epoxy acid absorbent, and the like. As the agent, 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, a softening agent A vulcanizate can be obtained by blending an agent, an acid acceptor, an antioxidant, and the like, and using a method commonly used for the production of 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 mixing 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, in addition to (A) a halogenated ethylene copolymer rubber and (B) a diene rubber, the intended use of the vulcanizate is as follows.
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 and 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; 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 usable in the present invention include organic acids of metals belonging to Group IIA of the periodic table, such as magnesium stearate, calcium stearate, manaceite, hydrotalcite, epoxidized soybean oil, epoxy acid absorbents 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 when 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, sulfur compounds, sulfur-containing organic vulcanizing agents, triazine compounds and the like are used, but the use of sulfur and sulfur compounds is particularly preferred.

As the 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 'may be used in combination with the organic peroxide.
-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, dimethacrylate Methacrylate, divinyl adipate, vinyl butyrate, vinyl stearate, liquid polybutadiene rubber, liquid polyisoprene rubber, liquid styrene-butadiene rubber, liquid acrylonitrile-butadiene rubber, magnesium diacrylate, calcium diacrylate,
Co-crosslinking agents such as aluminum acrylate, zinc acrylate, stannath acrylate, zinc methacrylate, magnesium methacrylate, and zinc dimethacrylate can be blended. 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 100 parts by weight of the rubber component.
20 parts by weight.

When a sulfur vulcanizing agent is used as a 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.

[0045] In addition to the above vulcanizing agents and vulcanization accelerators, vulcanization accelerating auxiliaries can be added, if necessary. 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 a method commonly used in the production of vulcanized rubber, for example, by placing the rubber composition of the present invention in a mold and raising the temperature, or by using an extruder. 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.

[0049]

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.

The 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 halogen content was measured by X-ray fluorescence analysis.

The cohesiveness of the plastmill The discharge amount of the rubber compound at the time of kneading the plastmill is 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.

Tensile test According to JIS K6301, using a No. 3 type test piece, at a measuring temperature of 25 ° C. and a tensile speed of 500 mm / min, the tensile strength TB (MPa) and the tensile elongation EB (%) were determined. It was measured. According to the hardness test JIS K6301, the spring hardness (JIS
A hardness).

The heat aging resistance was measured under the following conditions in accordance with JIS K6301. Aging conditions: 160 ° C., 70 hours, retention of breaking strength in air oven [Ar (T _B )], retention of elongation at break [Ar (E
_B ))

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.
-450 ml of octene, 5-ethylidene-2
-After adding 45 ml of norbornene and raising the temperature to 30 ° C, the internal pressure of the vessel was adjusted to 5 kg / cm ² while continuously supplying ethylene at a rate of 14 normal liters / minute. 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. Then, 3.6 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate dissolved in 7.2 ml of purified toluene was added,
The mixture was reacted by stirring at room temperature for 20 minutes to obtain a polymerization catalyst.

The 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
/Mn2.5 ethylene / 1-octene / 5-ethylidene-2-norbornene random copolymer rubber (hereinafter referred to as "EO
DM (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 (5.7 g as bromine) was added dropwise, stirred for 1 hour, neutralized by adding a dilute aqueous solution of sodium hydroxide, and the solvent was removed by steam stripping. 145 g of polymer were obtained. The polymer thus obtained has an iodine value of 12.5, a Mooney viscosity of 46, Mw / Mn of 2.5,
Brominated ethylene / 1-octene / 5 with 2.0% bromine content
-Ethylidene-2-norbornene random copolymer rubber (hereinafter also 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 / 5-ethylidene-2-norbornene random copolymer rubber Br-EODM (1), filler, vulcanizing agent,
A rubber compound of the following formulation comprising 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.

[0059]

[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, instead of 5-ethylidene-2-norbornene, non-conjugated polyene was replaced by 7-methyl-1,
Reference Example 1 except that 45 ml of 6-octadiene was used.
By operating in the same manner as described above, the ethylene content was 71.5 mol%,
An ethylene / 1-octene / 7-methyl-1,6-octadiene random copolymer rubber having an octene content of 28.5 mol%, an iodine value of 15.5, a Mooney viscosity of 45, and a Mw / Mn of 2.5 (hereinafter referred to as “EODM (2 ) "). In Example 3, bromine having an iodine value of 13.5 and a bromine content of 2.0% was operated in the same manner as in Example 1 except that this EODM (2) was used as the brominated ethylene copolymer rubber. Ethylene / 1-octene / 7-methyl-1,6-octadiene random copolymer rubber (hereinafter referred to as “Br-EODM”).
(2) ").

Comparative Example 1 Example 1 was repeated except that a commercially available EPDM (Mooney viscosity: 65, ethylene / propylene molar ratio: 67/33, iodine value: 15.0) was used as the ethylene copolymer rubber. In the same manner as described above, a brominated ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber having a bromine content of 2.0% (hereinafter also referred to as "Br-EPDM (1)") was obtained. In Comparative Example 1, a rubber composition was obtained in the same manner as in Example 2, except that this Br-EPDM (1) was used as the brominated ethylene copolymer rubber.
Table 2 shows the results.

Example 4 A bromine having an iodine value of 10 and a bromine content of 4.7% was obtained in the same manner as in Example 1 except that 12.0 g of bromine in n-hexane was dropped as bromine. An ethylene / 1-octene / 5-ethylidene-2-norbornene random copolymer rubber (hereinafter also referred to as "Br-EODM (3)") was obtained. In Example 4, except that Br-EODM (3) was used as the brominated ethylene copolymer rubber,
By operating in the same manner as in Example 2, a rubber composition was obtained. Table 2 shows the results.

Example 5 A bromine having an iodine value of 15 and a bromine content of 0.4% was obtained in the same manner as in Example 1, except that 1.4 g of bromine in n-hexane was dropped as bromine. An ethylene / 1-octene / 5-ethylidene-2-norbornene random copolymer rubber (hereinafter also referred to as "Br-EODM (4)") was obtained. In Example 4, a rubber composition was obtained in the same manner as in Example 2, except that this Br-EODM (4) was used as the brominated ethylene copolymer rubber. Table 2 shows the results.

Comparative Example 2 A bromine having an iodine value of 3 and a bromine content of 11.2% was prepared in the same manner as in Example 1, except that 28.0 g of bromine in n-hexane was dropped as bromine. An ethylene / 1-octene / 5-ethylidene-2-norbornene copolymer rubber (hereinafter, also referred to as "Br-EODM (5)") was obtained. In Comparative Example 2, a rubber composition was obtained in the same manner as in Example 2, except that this Br-EODM (5) was used as the brominated ethylene copolymer rubber. Table 3 shows the results
Shown in

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

Example 6 In Example 2, 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 (1) was changed to 45 parts and 55 parts, respectively. Table 4 shows the results.

Comparative Example 4 In Example 2, the 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 (1) was changed to 95 parts and 5 parts, respectively. Table 4 shows the results.

Comparative Example 5 In Example 2, 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 (1) was changed to 5 parts and 95 parts, respectively. Table 4 shows the results.

As is clear from Table 2, Examples 2 to 3
Is a rubber composition of the present invention, which is superior to Comparative Example 1 in workability and dynamic fatigue properties. Moreover, as is clear from Table 3, Examples 4 and 5 are rubber compositions of the present invention,
As compared with Comparative Examples 2 and 3, the mechanical strength was excellent, and it was found that the diene rubber had an excellent effect of modifying. On the other hand, Comparative Example 2 was an example in which the halogen content was too large, and the cohesion by the halogen was too strong, so that kneading was difficult. Comparative Example 3 is an example in which halogen was not added, and was inferior in co-vulcanizability with a diene rubber and markedly reduced in mechanical strength. Furthermore, as is clear from Table 4, Example 6 is the rubber composition of the present invention, and has improved ozone resistance as compared with Comparative Example 5 in which the amount of the halogenated ethylene copolymer rubber is too small. Comparative Example 6 is an example in which the amount of the halogenated ethylene copolymer rubber is too large, and the mechanical strength is remarkably inferior.

[0071]

[Table 2]

[0072]

[Table 3]

[0073]

[Table 4]

[0074]

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 (3)

[Claims] 1. A halogenated ethylene copolymer rubber comprising ethylene, an α-olefin having 6 to 12 carbon atoms and a non-conjugated polyene and having a halogen content of 0.1 to 10% by weight satisfying the following requirements. The molar ratio of ethylene to α-olefin having 6 to 12 carbon atoms (ethylene / α-olefin) is 40/60 to 95 /
5 Iodine value is _{1 to} 45 Mooney viscosity (ML _{1 + 4} , 100 ° C) 15 to 350 2. The halogenated ethylene copolymer rubber according to claim 1, wherein the halogen is bromine. 3. (A) 90 to 10 parts by weight of a halogenated ethylene copolymer rubber according to claim 1 or 2, (B) 10 to 90 parts by weight of a diene rubber (provided that (A) + (B) =
100 parts by weight] as a main component.