JP2000063568A - Vulcanizable rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vulcanizable rubber composition excellent in processability, strength characteristic, weathering resistance, ozone resistance and thermal aging characteristics by making the composition include specific random copolymer rubber of ethylene, an α-olefin and a nonconjugated polyene, a diene-based rubber and an organic peroxide. SOLUTION: This vulcanizable rubber composition comprises (A) a random copolymer rubber of ethylene, an α-olefin and a nonconjugated polyene which consists of (i) ethylene, (ii) a 3-20C α-olefin (e.g. propylene, 1-butene, etc.), and (iii) at least one kind of a terminal vinyl group-containing norbornene compound of formula I [(n) is 0-10; R1 is H or a 1-10C alkyl; R2 is H or a 1-5C alkyl] or formula II (R3 is H or a 1-10C alkyl) (e.g. 5-methylene-2-norbornene, etc.), (B) a diene-based rubber (e.g. butadiene rubber, etc.), and (C) an organic peroxide (e.g. dicumyl peroxide, etc). The weight ratio of the components A and B (A/B) is 1/99-99/1, preferably 90/10-10/90.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in strength characteristics, heat resistance, weather resistance, vibration damping, vibration damping, wear resistance and dynamic fatigue resistance, and is used for automobile parts, general industrial parts, civil engineering building parts, The present invention relates to a vulcanizable rubber composition that can be suitably used for electric wires, electric insulating parts, and the like.

[0002]

2. Description of the Related Art Diene rubbers such as natural rubber, butadiene rubber (BR), styrene / butadiene copolymer rubber (SBR), and isoprene rubber are excellent in processability and strength characteristics, and therefore tires, automobile parts, It is often used for general industrial parts. Also, chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR)
Diene rubbers such as are widely used in civil engineering and construction parts such as belts and gaskets, automobile parts such as hoses and packings, and general industrial parts. However,
Since these diene rubbers are inferior in weather resistance, ozone resistance and heat aging resistance, there is a problem that their product life is short.

As a solution to this problem, US Pat.
645,793 discloses a blend of a diene rubber and an ethylene / α-olefin copolymer rubber. However, although a blend of such a diene rubber and an ethylene / α-olefin copolymer rubber has improved weather resistance and ozone resistance, its heat aging resistance is not improved and its strength characteristics are There are problems such as deterioration. In order to maintain the strength characteristics, it is necessary to improve the dispersibility of the diene rubber and the ethylene / α-olefin copolymer rubber, and the ethylene having the same vulcanization reactivity as the diene rubber is required. -It is necessary to improve the co-vulcanizability by using an α-olefin copolymer rubber.

[0004] As a measure for dispersibility, a kneading method has been studied, and JMMitshl; Rubber Che
The article by m. Technol., 50, 430 (1977) introduces an attempt to homogenize the dispersibility of a compound by making a masterbatch containing carbon black.
However, as a measure for co-vulcanizability, the vulcanization rate of EPDM is increased by pre-reacting with ethylene / propylene / diene copolymer rubber (EPDM). This method is well known as pendant sulfur. There is. However, the co-vulcanizability is insufficient and the strength characteristics cannot be maintained.

Further, an attempt to increase the vulcanization rate of EPDM is described in JP-A-6-128,428. In the attempt described in this publication, ethylene, propylene, and 7-methyl-as non-conjugated polyene were used.
Copolymerized with 1,6-octadiene. This EP
Although DM has a high vulcanization rate and is improved in co-vulcanization property with a diene rubber, further improvement in vulcanization rate is required. Thus, a vulcanizable rubber composition excellent in processability, strength characteristics (co-vulcanization), weather resistance, ozone resistance, and heat aging resistance has not been obtained so far.

[0006]

The present inventors obtain a vulcanizable rubber composition having excellent processability, strength characteristics (co-vulcanization), weather resistance, ozone resistance, and heat aging resistance. As a result of intensive research, ethylene, α-olefin / non-conjugated polyene random copolymer rubber composed of ethylene, α-olefin and a specific non-conjugated polyene, and a diene rubber,
It was found that a vulcanizable rubber composition excellent in the above properties can be obtained by using a composition containing an organic peroxide, and the present invention has been completed.

That is, the object of the present invention is to solve the above-mentioned problems, and to improve workability, strength characteristics (co-vulcanization), weather resistance, ozone resistance and heat aging resistance. An object is to provide an excellent vulcanizable rubber composition.

[0008]

The present invention is the following vulcanizable rubber composition. (1) (A) Ethylene (a-1), C3-C20 α-olefin (a-2), and at least one terminal vinyl group represented by the following formula (1) or (2) Ethylene / α-composed of norbornene compound (a-3)
Olefin / non-conjugated polyene random copolymer rubber,
A weight ratio of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) and the diene rubber (B) containing (B) a diene rubber and (C) an organic peroxide [ (A) / (B)] is 1/99 to 99
/ 1 vulcanizable rubber composition.

[Chemical 2] [In the formula (1), n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Formula (2)
In the above, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ] (2) Ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is << 1 >> ethylene (a-1)
And the molar ratio (ethylene / α-olefin) of the α-olefin (a-2) having 3 to 20 carbon atoms is 40/60 to 95 /
5, the iodine value is in the range of 0.5 to 50, and the intrinsic viscosity [η] measured in the decalin solution at 135 ° C. is in the range of 0.5 to 10 dl / g. The vulcanizable rubber composition according to (1) above. (3) Ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is << 1 >> ethylene (a-1).
And the molar ratio (ethylene / α-olefin) of the α-olefin (a-2) having 3 to 20 carbon atoms is 40/60 to 95 /
5), << 2 >> iodine value is in the range of 0.5 to 50, and << 3 >> intrinsic viscosity [η] measured in a 135 ° C decalin solution is in the range of 0.5 to 10 dl / g. Yes,
<< 4 >> The molecular weight distribution (Mw / Mn) measured by GPC is 3 to 50, and << 5 >> dicumyl peroxide is 0 relative to 100 g of ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). 17 using 0.01 mol
Effective network chain density ν when press-crosslinked at 0 ° C for 10 minutes
Is 1.5 × 10 ²⁰ pieces / cm ³ or more, and << 6 >> 100
0.4 × 10 ⁶ d obtained from the melt flow curve at ℃
Shear velocity γ ₁ when yn / cm ² is shown, and 2.4 × 10
⁶ ratio of the shear rate gamma ₂ when indicating a dyn / cm ^{₂ γ 2} / ^γ
₁ and the effective network chain density ν of << 5 >> is expressed by the following mathematical formula (I)

## EQU00002 ## The vulcanizable rubber composition according to the above (1) or (2), which satisfies 0.04 × 10 ^-19 ≤ Log (γ ₂ / γ ₁ ) / ν ≤ 0.20 × 10 ^-19 (I). (4) The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) has an insoluble content of 1 wt% or less after Soxhlet extraction (xylene, 3 hours, mesh: 325). A vulcanizable rubber composition according to any one of (1) to (3). (5) The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is a soluble vanadium compound represented by the following formula (3) or a vanadium halide compound represented by the following formula (4): Using a catalyst containing an organoaluminum compound represented by the following formula (5) as a main component, a polymerization temperature is 30 to 60 ° C., and a polymerization pressure is 4 to 12 k.
gf / cm ² (gauge pressure), the molar ratio of the supply amount of ethylene (a-1) and terminal vinyl group-containing norbornene compound (a-3) (terminal vinyl group-containing norbornene compound / ethylene) is 0.01 ≦ terminal Vinyl group-containing norbornene compound / ethylene (a-1), having 3 to 20 carbon atoms under the condition of satisfying ≦ 0.2
The vulcanizable rubber composition according to any one of (1) to (4) above, which is a copolymer of the α-olefin (a-2) and the terminal vinyl group-containing norbornene compound (a-3). . VO (OR ¹ ) _n X ¹ _3-n (3) VX ² ₄ (4) (In the formula (3), R ¹ is a hydrocarbon group, X ¹ is a halogen atom, and 0 ≦ n ≦ 3 is satisfied. In the formula (4), X ² is a halogen atom.) R ² _m AlX ³ _3-m (5) (In the formula (5), R ² is a hydrocarbon group and X ³ is a halogen atom. , 0 <m <3 is satisfied. (6) The diene rubber (B) is a butadiene rubber (BR),
Styrene / butadiene copolymer rubber (SBR), natural rubber (NR), isoprene rubber, chloroprene rubber (C
R), acrylonitrile butadiene rubber (NBR), acrylonitrile isoprene rubber (NIR), acrylonitrile butadiene isoprene rubber (NBIR), carboxylated NBR introduced with acrylic acid (XNBR) or a mixture thereof (1) to (5) above. A vulcanizable rubber composition according to any one of 1. (7) Organic peroxide (C) 0.001 to 100 g of ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) and diene rubber (B) in total of 100 g.
The vulcanizable rubber composition according to any one of (1) to (6) above, which contains 0.05 mol.

<< Ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) >> The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) used in the present invention is ethylene (a-1). ) And carbon number 3 to
A random copolymer rubber of 20 α-olefin (a-2) and at least one terminal vinyl group-containing norbornene compound (a-3) represented by the formula (1) or (2).

The α-olefin (a-2) used as a monomer for the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is an α-olefin having 3 to 20 carbon atoms.
It is an olefin (hereinafter may be simply referred to as α-olefin), and specific examples thereof include propylene, butene-1, 4-methylpentene-1, hexene-1, heptene-1, octene-1, nonene-1. , Decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, nonadecene-1, eicosene-1, 9-
Methyl-decene-1,11-methyl-dodecene-1,1,
2-ethyl-tetradecene-1 and the like. These α-olefins may be used alone or in combination of two or more. Of these, α-olefins having 3 to 10 carbon atoms are preferable, and particularly propylene, 1-butene, 1
-Hexene, 1-octene and the like are preferred.

Norbornene compound having a vinyl terminal group (a-3) used as a monomer for ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A)
Is a norbornene compound represented by the above formula (1) or (2). Specific examples of the alkyl group represented by R ¹ in the formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, C1-C10 alkyl group such as n-pentyl group, isopentyl group, t-pentyl group, neopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, nonyl group and decyl group, preferably 1-8 Can be given.

Specific examples of the alkyl group represented by R ² in the formula (1) include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t- Examples thereof include an alkyl group having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms such as a butyl group, an n-pentyl group, an isopentyl group, a t-pentyl group and a neopentyl group. In the formula (1), n is an integer of 0 to 10, preferably 0 to 8.

Specific examples of the alkyl group represented by R ³ in the formula (2) include the same as the alkyl group represented by R ^{1 in} the formula (1).

Specific examples of the terminal vinyl group-containing norbornene compound (a-3) represented by the above formula (1) or (2) include 5-methylene-2-norbornene and 5-
Vinyl-2-norbornene, 5- (2-propenyl)-
2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (1-methyl-2propenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (1-methyl- 3-butenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5
-(1-Methyl-4-pentenyl) -2-norbornene, 5- (2,3-dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-3-butenyl) -2-
Norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl-5-hexenyl) -2-norbornene, 5- (3,4-dimethyl-4-pentenyl)
-2-norbornene, 5- (3-ethyl-4-pentenyl), 5- (7-octenyl) -2-norbornene, 5
-(2-Methyl-6-heptenyl) -2-norbornene, 5- (1,2-dimethyl-5-hexecyl) -2-
Norbornene, 5- (5-ethyl-5-hexenyl)-
2-norbornene, 5- (1,2,3-trimethyl-4
-Pentenyl) -2-norbornene and the like. Among these, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5- (2-propenyl)-
2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene,
5- (5-hexenyl) -2-norbornene, 5- (6
-Heptenyl) -2-norbornene and 5- (7-octenyl) -2-norbornene are preferred. These may be used alone or in combination of two or more.

The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) used in the present invention is
Other monomers such as a non-conjugated polyene other than the terminal vinyl group-containing norbornene compound (a-3) represented by the formula (1) or (2) are copolymerized within a range not impairing the desired physical properties. Good. Specific examples of the non-conjugated polyene other than the terminal vinyl group-containing norbornene compound (a-3) include 1,4-hexadiene, 3-methyl-1,
Chain non-chain such as 4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene Conjugated diene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-
Methylene-2-norbornene, 5-isopropylidene-
Cyclic non-conjugated dienes such as 2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, dicyclopentadiene; 2,3-diisopropylidene-5-norbornene,
Examples thereof include triene such as 2-ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene.

The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) has the following << 1 >> to << 3 >>
Those having the characteristics of are preferable, and the following << 1 >>
Those having the characteristics of <6> are preferable. << 1 >> ethylene (a-1) / α-olefin (a-2)
Component ratio Ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) comprises a structural unit (a-1) derived from ethylene and a structural unit (a) derived from an α-olefin having 3 to 20 carbon atoms. -2) molar ratio [ethylene (a-
1) / α-olefin (a-2)] is 40/60 to 95.
/ 5, preferably 50/50 to 90/10, more preferably 55/45 to 85/15, particularly preferably 60 /.
It is preferably 40 to 80/20. Ethylene (a-
When the molar ratio of 1) / α-olefin (a-2) is within the above range, the crosslinking efficiency is good and the co-crosslinking property with the diene rubber (B) is also good. Further, it is also excellent in heat aging resistance, cold resistance and workability.

<< 2 >> Iodine Value The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) has an iodine value of 0.5 to 50 (g / 1).
00g), preferably 0.8-40 (g / 100g),
More preferably 1-30, particularly preferably 1.5-2
5 is desirable. When the iodine value is within the above range, the crosslinking efficiency is good and the co-crosslinking property with the diene rubber (B) is also good. Furthermore, in addition to being excellent in environmental deterioration resistance (= heat aging resistance), it is also advantageous in cost.

<< 3 >> Intrinsic Viscosity [η] The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) has an intrinsic viscosity [η] of 0 measured at 135 ° C. decalin (decahydronaphthalene). .5-1
0 dl / g, preferably 0.6 to 8 dl / g, more preferably 0.7 to 6 dl / g, and particularly preferably 0.8 to
It is preferably 5 dl / g. When the intrinsic viscosity [η] is in the above range, the co-crosslinking property and dispersibility with the diene rubber (B) are good, and the strength properties and processability are excellent.

<4> Molecular Weight Distribution The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) has a molecular weight distribution (weight average molecular weight Mw / number average molecular weight) measured by GPC (gel permeation chromatography). It is desirable that Mn) is 3 to 50, preferably 3.3 to 40, and more preferably 3.5 to 30. When the molecular weight distribution is within the above range, workability and strength properties are excellent.

<5> Crosslinking Density Ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is 100 g of ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) in dicumyl. 170 with 0.01 mol of peroxide
Effective network chain density ν when press-crosslinked at ℃ × 10 minutes is 1.5 × 10 ²⁰ / cm ³ or more, preferably 1.8 × 10
²⁰ pieces / cm ³ or more, more preferably 2.0 × 10 ²⁰ pieces / cm ³ or more is desirable. When the effective network chain density ν is in the above range, the co-crosslinking property with the diene rubber (B) is good.

<< 6 >> Log (γ ₂ / γ ₁ ) / ν Ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) was 0.4 × 10 obtained from the melt flow curve at 100 ° C. ⁶ and shear rate gamma ₁ when indicating a ^{dyn / cm 2, 2.4 × 10} 6 dyn / ratio of the shear rate gamma ₂ when indicating the cm ^{₂ γ 2} / ^γ _1, and the effective mesh of the "5" It is desirable that the chain density ν satisfies the following formula (I), preferably formula (I ′), and more preferably formula (I ″).

[ ^Formula 3] 0.04 × 10 ^-19 ≤ Log (γ ₂ / γ ₁ ) / ν ≤ 0.20 × 10 ^-19 … (I) 0.042 × 10 ^-19 ≤ Log (γ ₂ / γ ₁ ) / ν ≤ 0.19 × 10 ^-19 … (I ') 0.050 × 10 ^-19 ≦ Log (γ ₂ / γ ₁ ) / ν ≦ 0.18 × 10 ^-19 … (I ″) Log (γ ₂ / γ ₁ ) / ν is in the above range In this case, the dispersibility with the diene rubber (B) and the co-crosslinking property are good, and the processability is excellent.

In the present invention, the ethylene / α-olefin / non-conjugated polyene random polymer rubber (A) may be used alone or in combination of two or more kinds.

The ethylene / α-olefin / non-conjugated polyene random polymer rubber (A) comprises ethylene (a-1),
It can be produced by randomly copolymerizing the α-olefin (a-2) and the terminal vinyl group-containing norbornene compound (a-3) represented by the above formula (1) or (2) by a known method. . Ethylene having the characteristics of << 1 >> to << 3 >>, << 1 >> to << 6 >>, or that the insoluble content after Soxhlet extraction (xylene, 3 hours, mesh: 325) is 1% by weight or less. When producing the α-olefin / non-conjugated polyene random polymer rubber (A), the soluble vanadium compound represented by the formula (3) or the vanadium halide compound represented by the formula (4), and Using a catalyst containing an organoaluminum compound represented by the formula (5) as a main component, a polymerization temperature is 30 to 60 ° C., preferably 30 to 50 ° C., a polymerization pressure is 4 to 12 kgf / cm ² (gauge pressure), Preferably 5
~ 8kgf / cm ² (gauge pressure), ethylene (a-1)
The molar ratio (terminal vinyl group-containing norbornene compound / ethylene) of the supply amount of the vinyl ether group-containing norbornene compound (a-3) is 0.01 ≦, and the terminal vinyl group-containing norbornene compound / ethylene is ≦ 0.2, preferably 0.012 ≦. Under the condition that the terminal vinyl group-containing norbornene compound / ethylene ≦ 0.18, ethylene (a-1), carbon number 3-20
It can be easily produced by copolymerizing the α-olefin (a-2) with the terminal vinyl group-containing norbornene compound (a-3). In this case, ethylene (a
-1) and the C3-C20 α-olefin (a-2) have a molar ratio (ethylene / α-olefin) of 40 / 60-
The supply amounts of ethylene (a-1) and α-olefin (a-2) are adjusted so that the range is 95/5. The polymerization is preferably carried out in a hydrocarbon medium.

The soluble vanadium compound represented by the above formula (3) is a vanadium compound soluble in the hydrocarbon medium of the polymerization reaction system. The soluble vanadium compound may be an electron donor adduct. Examples of the hydrocarbon group represented by R ² in the soluble vanadium compound represented by the formula (3) include an alkyl group having 1 to 8 carbon atoms.

In the soluble vanadium compound represented by the above formula (3), the halogen atom represented by X ¹ is
Examples thereof include chlorine, bromine, iodine and fluorine. The soluble vanadium compounds represented by the above formula (3) may be used alone or in combination of two or more.

Specific examples of the soluble vanadium compound represented by the above formula (3) include VOCl ₃ and VO (OC
₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ Cl, VO (O-iso-
_{C 3 H 7) Cl 2,} VO (O-n-C 4 H 9) Cl 2, VO (OC
_{2 H 5) 3, VOBr 3} , VOCl 3, VO (O-n-C 4 H 9)
₃ and so on. Among these, VOCl ₃ and VO
(OC ₂ H ₅ ) Cl ₂ is preferred.

Examples of the halogen atom represented by X ² in the vanadium halide compound represented by the above formula (4) include chlorine, bromine, iodine and fluorine. The vanadium halide compound represented by the formula (4) is 1
They can be used alone or in combination of two or more. Further, the soluble vanadium compound represented by the formula (3) and the halogenated vanadium compound represented by the formula (4) can be used in combination.
Specific examples of the vanadium halide compound represented by the formula (4) include VCl _{4 and the} like.

In the organoaluminum compound represented by the above formula (5), examples of the hydrocarbon group represented by R ² include an alkyl group having 1 to 8 carbon atoms. In the organoaluminum compound represented by the formula (5), X ³
Examples of the halogen atom represented by include chlorine, bromine, iodine, fluorine and the like.

Specific examples of the organoaluminum compound represented by the above formula (5) include trialkylaluminums such as triethylaluminum and triisobutylaluminum; dialkylaluminum halides such as diethylaluminum chloride and diisobutylaluminum chloride; ethylaluminum. Examples include alkylaluminum sesquihalides such as sesquichloride, isobutylaluminum sesquichloride and n-hexylaluminum sesquichloride; alkylaluminum dihalides such as ethylaluminum dichloride, ethylaluminum dibromide and isobutylaluminum dichloride. Among these, halogen-containing organoaluminum compounds having an average composition in which m in the above formula (5) satisfies 1 ≦ m ≦ 2 are preferable. In addition to the organoaluminum compound represented by the formula (5) or instead of the organoaluminum compound, an organoaluminum in which a part of the hydrocarbon group represented by R ² in the formula (5) is substituted with hydrogen or an alkoxy group. Compounds can also be used. The organoaluminum compounds may be used alone or in combination of two or more.

Among the organoaluminum compounds represented by the above formula (5), Al (C ₂ H ₅ ) ₂ Cl and Al (C
₂ H ₅ ) _1.5 Cl _1.5 and mixtures thereof are especially preferred. Among them, Al (C ₂ H ₅ ) ₂ Cl and Al (C ₂ H ₅ ) _1.5
Cl _1.5 and Al (C ₂ H ₅ ) ₂ Cl / Al (C ₂ H ₅ ) _1.5
The molar ratio of Cl _1.5 is 1/5 to 10/1, preferably 1 /
A mixture containing 2 to 8/1 is desirable. When such a mixture is used, a polymer having a low insoluble content after Soxhlet extraction can be obtained, and for example, a polymer having an insoluble content of 1 wt% or less after Soxhlet extraction can be easily obtained.

The copolymerization reaction can be carried out in a hydrocarbon medium. Examples of the hydrocarbon medium include hexane, heptane, octane, kerosene, and other aliphatic hydrocarbons; cyclohexane, methylcyclohexane, and other alicyclic hydrocarbons; benzene, toluene, xylene, and other aromatic hydrocarbons, and the aforementioned polymerizable unsaturated hydrocarbons. Hydrocarbons can be exemplified. A mixed medium of two or more kinds may be used.

In the method for producing the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) used in the present invention, the copolymerization reaction is preferably carried out by a continuous method. The above formula (3) supplied to the polymerization reaction system at that time
Or a soluble vanadium compound represented by the formula (4)
The concentration of the vanadium halide compound represented by is 10 times or less, preferably 7 to 1 times the concentration of the soluble vanadium compound or the halogenated vanadium compound in the polymerization reaction system.
Double, more preferably 5 to 1, more preferably 3 to
It is desirable that the range is 1 time.

The ratio (Al / V) of aluminum atoms to vanadium atoms in the soluble vanadium compound or halogenated vanadium compound in the polymerization reaction system is 2 or more, preferably 2 to 50, more preferably 3 to 20. It is desirable to do. The soluble vanadium compound, the halogenated vanadium compound and the organoaluminum compound are usually diluted with the above hydrocarbon medium and supplied.

Here, the soluble vanadium compound or the halogenated vanadium compound is preferably diluted within the above concentration range, but the organoaluminum compound represented by the above formula (5) is, for example, 50 times or less the concentration in the polymerization reaction system. A method of adjusting the concentration to an arbitrary concentration and supplying it to the polymerization reaction system is adopted.

In the copolymerization reaction, the concentration of the soluble vanadium compound or halogenated vanadium compound in the copolymerization reaction system is usually 0.01 to 5 gram atom / liter, preferably 0.05 to 3 gram atom / vanadium atom. It is desirable to set it in the range of liter.

The copolymerization reaction is preferably carried out at a temperature of 30 to 60 ° C, preferably 30 to 50 ° C. The copolymerization reaction is usually carried out by a continuous method. In that case, ethylene (a-1) as a polymerization raw material, α-olefin (a-2) having 3 to 20 carbon atoms, norbornene compound containing a terminal vinyl group (a-3), soluble vanadium compound or vanadium halide as a catalyst component. The compound, the organoaluminum compound, and the hydrocarbon medium are continuously supplied to the polymerization reaction system, and the polymerization reaction mixture is continuously taken out from the polymerization reaction system.

The average residence time in the copolymerization reaction varies depending on the kind of the polymerization raw material, the concentration of the catalyst component, the temperature, etc., but is usually 5 minutes to 5 hours, preferably 10 minutes to 3 hours. Is desirable. The pressure during the copolymerization reaction is usually maintained at 4 to 12 kgf / cm ² (gauge pressure), preferably 5 to 8 kgf / cm ² (gauge pressure), and in some cases, an inert gas such as nitrogen or argon is present. You may let me. Further, in order to adjust the molecular weight of the copolymer, a molecular weight modifier such as hydrogen can be appropriately present.

Ethylene (a-supplied to the copolymerization reaction
The supply ratio of 1) to the α-olefin (a-2) varies depending on the polymerization conditions, but is usually about 20/80 to 80/20 in molar ratio, while ethylene (a-1) and a terminal vinyl group are contained. The supply amount (molar ratio) with the norbornene compound (a-3) is preferably within the above range. The supply and mixing of the raw material olefins are controlled so that the ratio of each component in the produced ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) has the above composition. Further, the copolymerization reaction is carried out until the intrinsic viscosity of the produced ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) reaches the intrinsic viscosity.

The resulting copolymer solution obtained by the copolymerization reaction is a hydrocarbon medium solution of ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). The concentration of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) contained in the produced copolymer solution is usually 2 to 20% by weight, preferably 2 to 10% by weight. An ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is obtained by treating the resulting copolymer solution according to a conventional method.

In the present invention, ethylene / α-olefin /
The non-conjugated polyene random copolymer rubber (A) may be graft-modified with a polar monomer. Examples of the polar monomer include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or their derivatives, vinyl ester compounds, and chlorides. Examples include vinyl.

Examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3
-Hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy-propyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, Trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2- (6-hydroxyhexanoyloxy) ethyl acrylate and the like (meth ) Acrylic acid ester; 10-undecen-1-ol, 1
-Octen-3-ol, 2-methanol norbornene, hydroxystyrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, α-methylol acrylamide, 2- (meth) acroyloxyethyl acid phosphate, glycerin monoallyl ether, allyl alcohol, ant Roxyethanol, 2-
Examples thereof include butene-1,4-diol and glycerin monoalcohol.

Examples of the amino group-containing ethylenically unsaturated compound include --N (R ³¹ ) R ³² (wherein R ³¹ is a hydrogen atom, a methyl group or an ethyl group, and R ³² is a hydrogen atom or a carbon number of 1).
To 12, preferably an alkyl group having 1 to 8 carbon atoms, and a cycloalkyl group having 6 to 12 carbon atoms, preferably 6 to 8 carbon atoms. In addition, the above-mentioned alkyl group and cycloalkyl group may further have a substituent), and a vinyl-based monomer having at least one kind of an amino group or a substituted amino group.

Examples of such an amino group-containing ethylenically unsaturated compound include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate and methacrylic acid. Alkyl ester derivatives of acrylic acid or methacrylic acid such as phenylaminoethyl acid ester and cyclohexylaminoethyl methacrylate;
Vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine; allylamine derivatives such as allylamine, methacrylamine, N-methylacrylamine, N, N-dimethylacrylamide and N, N-dimethylaminopropylacrylamide; acrylamide , N-methylacrylamide and other acrylamide derivatives; p-aminostyrene and other aminostyrenes; 6-aminohexylsuccinimide, 2-aminoethylsuccinimide and the like.

As the epoxy group-containing ethylenically unsaturated compound, a monomer having at least one polymerizable unsaturated bond and at least one epoxy group in one molecule is used. Examples of such an epoxy group-containing ethylenically unsaturated compound include glycidyl acrylate, glycidyl methacrylate, mono and diglycidyl esters of maleic acid, mono and diglycidyl esters of fumaric acid, mono and diglycidyl esters of crotonic acid, Mono- and diglycidyl esters of tetrahydrophthalic acid, mono- and glycidyl esters of itaconic acid,
Mono- and diglycidyl esters of butenetricarboxylic acid, mono- and diglycidyl esters of citraconic acid,
Endocis-bicyclo [2.2.1] mono- and diglycidyl esters of hept5-ene-2,3-dicarboxylic acid (Nadic Acid ^™ ), endocis-bicyclo [2.
2.1] Dicarboxylic acid mono- and diglycidyl esters such as mono- and diglycidyl esters of hept-5-ene-2-methyl-2,3-dicarboxylic acid (methyl nadic acid ^TM ), mono- and glycidyl esters of allyl succinic acid ( In the case of monoglycidyl ester, the alkyl group has 1 to 12 carbon atoms, p-styrenecarboxylic acid alkylglycidyl ester, allylglycidyl ether, 2-
Methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,
4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-
1-Pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide and the like can be mentioned.

The aromatic vinyl compound is represented by the following formula CH ₂ = C (R ¹ ) -Y- (R ² ) _n (wherein Y is a benzene ring or a heterocycle, R ¹ is a hydrogen atom or a carbon number). 1 to 3 alkyl groups such as a methyl group, an ethyl group, a propyl group, and an isopropyl group.
² is a hydrocarbon group having 1 to 3 carbon atoms or a halogen atom, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group and a chlorine atom, a bromine atom or an iodine atom. n is usually an integer of 0 to 5, preferably 1 to 5. ).

As such an aromatic vinyl compound,
For example, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p
-Chlorostyrene, m-chlorostyrene, p-chloromethylstyrene, 4-vinylpyridine, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5
-Vinyl pyridine, 2-isopropenyl pyridine, 2-
Examples thereof include vinylquinoline, 3-vinylisoquinoline, N-vinylcarbazole and N-vinylpyrrolidone.

Examples of the unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid,
Tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2.2.1] hept-2-ene-5,6
-Unsaturated carboxylic acids such as dicarboxylic acids or their derivatives (for example, acid anhydrides, acid halides, amides, imides, esters, etc.).

Examples of this derivative include maleenyl chloride, maleenyl imide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic acid. Acid anhydride, dimethyl maleate, monomethyl maleate, ethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citracone, dimethyl tetrahydrophthalate, bicyclo [2.2.1] hept-2-
Dimethyl ene-5,6-dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth)
Examples thereof include acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate and aminopropyl methacrylate. Among these, (meth) acrylic acid, maleic anhydride, hydroxyethyl (meth) acrylate, glycidyl methacrylate and aminopropyl methacrylate are preferable.

Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearylate, benzoic acid. Examples thereof include vinyl, vinyl p-t-butylbenzoate, vinyl salicylate and vinyl cyclohexanecarboxylate.

The modified random copolymer rubber can be obtained by graft-polymerizing a polar monomer onto the above ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). Ethylene / α-olefin /
When the above polar monomer is graft-polymerized to the non-conjugated polyene random copolymer rubber (A), the polar monomer is 100 parts by weight of ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). To the department
It is usually used in an amount of 1 to 100 parts by weight, preferably 5 to 80 parts by weight.

This graft polymerization is usually carried out in the presence of a radical initiator. As the radical initiator, an organic peroxide or an azo compound can be used. Examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane,
2,5-Dimethyl-2,5-bis (t-butylperoxy) hexyne-3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) valalate, benzoyl peroxide , T
-Butylperoxybenzoate, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide and 2,4-dichlorobenzoyl peroxide, m-
Examples include toluyl peroxide.

Examples of the azo compound include azoisobutyronitrile and dimethylazoisobutyronitrile.

The radical initiator is preferably used in an amount of about 0.001 to 10 parts by weight with respect to 100 parts by weight of the copolymer rubber before modification. The radical initiator can be used as it is by mixing it with the random copolymer and the polar monomer, or can be used after being dissolved in a small amount of an organic solvent. The organic solvent can be used without particular limitation as long as it is an organic solvent capable of dissolving a radical initiator. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene; pentane, hexane, heptane, octane. , Aliphatic hydrocarbon solvents such as nonane and decane; alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane and decahydronaphthalene; chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and Chlorinated hydrocarbons such as tetrachloroethylene; methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-
Alcohol solvents such as butanol and tert-butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate; dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and di An ether solvent such as oxyanisole can be used.

When the polar monomer is graft-polymerized on the copolymer rubber before modification, a reducing substance may be used. When a reducing substance is used, the amount of polar monomer grafted can be improved. As a reducing substance, iron (I
I) ion, chromium ion, cobalt ion, nickel ion, palladium ion, sulfite, hydroxylamine, hydrazine, further -SH, SO ₃ H, -NHN
Examples thereof include compounds containing groups such as H ₂ and —COCH (OH) —.

Specific examples of such reducing substances include ferrous chloride, potassium dichromate, cobalt chloride,
Cobalt naphthenate, palladium chloride, ethanolamine, diethanolamine, N, N-dimethylaniline,
Examples thereof include hydrazine, ethyl mercaptan, benzenesulfonic acid, p-toluenesulfonic acid and the like. The reducing substance is based on 100 parts by weight of the copolymer rubber before modification,
Usually, it can be used in an amount of 0.001 to 5 parts by weight, preferably 0.1 to 3 parts by weight.

The graft modification can be carried out by a conventionally known method. For example, the copolymer rubber before modification is dissolved in an organic solvent, and then a polar monomer and a radical initiator are added to the solution, and the temperature is adjusted to 70 to 200 ° C. Preferably 80-19
At a temperature of 0 ° C., for 0.5 to 15 hours, preferably 1 to 10
It can be carried out by reacting for a time.

The above organic solvent is not particularly limited as long as it is an organic solvent capable of dissolving the copolymer rubber before modification. For example, aromatic hydrocarbon solvents such as benzene, toluene, xylene, pentane, hexane, heptane. Aliphatic hydrocarbon solvents such as and the like can be used.

It is also possible to produce a modified random copolymer rubber by reacting the copolymer rubber before modification with the polar monomer in the absence of solvent using an extruder or the like. This reaction is usually carried out at a temperature equal to or higher than the melting point of the copolymer rubber before modification, specifically at a temperature of 120 to 250 ° C. and usually for 0.5 to 10 minutes. The modified amount of the modified random copolymer rubber thus obtained (the amount of polar monomer grafted) is usually 0.1 to 50% by weight, preferably 0.2.
It is desirable that the content is ˜30% by weight.

<< Diene Rubber (B) >> The diene rubber (B) used in the present invention is a rubber having a double bond in the main chain, and known diene rubbers can be used without limitation. Specific examples of the diene rubber (B) include butadiene rubber (BR), styrene-butadiene copolymer rubber (SB
R), natural rubber (NR), isoprene rubber, chloroprene rubber (CR), acrylonitrile butadiene rubber (N
BR), acrylonitrile isoprene rubber (NIR),
Acrylonitrile butadiene isoprene rubber (NBI
R), and carboxylated NB introduced with acrylic acid
R (XNBR) and the like. Diene rubber (B)
As the natural rubber used as, the natural rubber specified by Green Book (International quality packaging standard for various grades of natural rubber) can be used.

As the isoprene rubber used as the diene rubber (B), isoprene rubber having a specific gravity of 0.91 to 0.94 and a Mooney viscosity (ML _{1 + 4} (100 ° C.)) of 30 to 120 is used. preferable. Diene rubber (B)
The specific gravity of SBR used as is 0.91 to 0.9
8, SBR having ML _{1 + 4} (100 ° C.) of 20 to 120 is preferably used. BR used as the diene rubber (B) has a specific gravity of 0.90 to 0.95 and ML _{1 + 4} (1
It is preferable to use BR having a temperature of 00 ° C. of 20 to 120.

CR used as the diene rubber (B)
The specific gravity is 1.1 to 1.3, ML _{1 + 4}(100 ℃) is 2
It is preferable to use CR which is 0 to 300. Diene
NBR used as the rubber (B) has a specific gravity of 0.9.
5 to 1.05, ML_{1 + 4}(100 ° C) is 20-300
It is preferable to use NBR. Diene rubber (B)
Can be used alone or in combination of two or more
It can also be used together.

<< Blend Ratio >> In the vulcanizable resin composition of the present invention, the weight ratio of ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) to the diene rubber (B) [ethylene The α-olefin / non-conjugated polyene random copolymer rubber (A) / diene rubber (B)] is (1/99) to (99/1), preferably (90/10) to (10/90). , Particularly preferably (8
5/15) to (30/70). When the blending amount of both is within the above range, the weather resistance, ozone resistance, and strength properties are excellent, and the properties originally possessed by the diene rubber (B) are not deteriorated. In addition, the processability is the same as the existing E with the same molecular weight.
It is extremely superior to PT. The reason for this is
Since the α-olefin / non-conjugated polyene random copolymer rubber (A) has a long-chain branched structure, the viscosity decreases in the high shear rate region such as during roll processing, so it is presumed that it has excellent processability. .

<< Organic Peroxide (C) >> As the organic oxide (C) used in the present invention, known organic peroxides used for vulcanization of rubber can be used without limitation. The compounding amount of the organic oxide (C) is 100 g of the total amount of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) and the diene rubber (B), and the organic peroxide (C). 0.001-0.05 mol, preferably 0.0
It is preferably from 02 to 0.03 mol. When the compounding amount of the organic oxide (C) is within the above range, a vulcanized rubber having excellent rubber elasticity and extensibility can be obtained.

Specific examples of the organic peroxide (C) include dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane and t-butylcumyl. Peroxide, di-t-amyl peroxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (benzoylperoxy) ) Hexane, 2,5-dimethyl-2,5-mono (t-butylperoxy) hexane,
Dialkyl peroxides such as α, α′-bis (t-butylperoxy-m-isopropyl) benzene; t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyvibrate, t-butylperoxymaleic acid , T-butylperoxy neodecanoate, t-butylperoxybenzoate, di-t-butylperoxyphthalate, 1,1-bis-t
Examples include peroxyesters such as -butylperoxy-3,3,5-trimethylcyclohexane; ketone peroxides such as dicyclohexanone peroxide; and mixtures thereof.

Above all, the temperature giving a half-life of 1 minute is 130
The organic peroxide (C) in the range of ℃ to 200 ℃ is preferable, and especially dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcuk. Millperoxide, di-t-amyl peroxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxine) hexyne-3,2,5-dimethyl-
2,5-mono (t-butylperoxy) hexane, 1,
1-Bis-t-butylperoxy-3,3,5-trimethylcyclohexane and the like are preferable.

The vulcanizable rubber composition of the present invention includes a reinforcing agent, an inorganic filler, a softening agent, an antioxidant (stabilizer), a processing aid, and a foaming system such as a foaming agent and a foaming aid. The compound, the plasticizer, the colorant, the other rubber compounding agent, the rubber, the resin and the like constituting the above can be compounded as other components. The type and content of the other components are appropriately selected according to the application, but among these, it is preferable to use a reinforcing agent, an inorganic filler, a softening agent, etc., which will be shown more specifically below.

Specific examples of the reinforcing agent include SRF and G
PF, FEF, MAF, HAF, ISAF, SAF, F
Carbon black such as T and MT, those obtained by surface-treating these carbon blacks with a silane coupling agent,
Examples thereof include silica, activated calcium carbonate, fine talc, and fine silicate. Specific examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc and clay.

The rubber composition contains a reinforcing agent and / or an inorganic filler as ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) and diene rubber (B).
Can be contained in an amount of up to 300 parts by weight, preferably up to 200 parts by weight, based on 100 parts by weight of the total. From the rubber composition containing such an amount of the reinforcing agent, a vulcanized rubber having improved mechanical properties such as tensile strength, tear strength and abrasion resistance can be obtained. When the inorganic filler is blended in the above amount, the hardness can be increased without impairing other physical properties of the vulcanized rubber, and the cost can be reduced.

As the softening agent, the softening agents conventionally blended in rubber are widely used. Specifically, petroleum-based softening agents such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt and petrolatum; coal tar, Coal tar softeners such as coal tar pitch; Fat oil softeners such as castor oil, linseed oil, rapeseed oil, coconut oil; waxes such as tall oil, sub, beeswax, carnauba wax, lanolin; ricinoleic acid, palmitin Fatty acids and fatty acid salts such as acids, barium stearate, calcium stearate and zinc laurate; synthetic polymer substances such as petroleum resin, atactic polypropylene and coumarone indene resin are used. Among these, petroleum-based softeners are preferable, and process oil is particularly preferable.

The rubber composition contains the above-mentioned softening agent in a total amount of 100 of ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) and diene rubber (B).
10 to 200 parts by weight, preferably 10 to 200 parts by weight
It can be contained in an amount of 150 parts by weight, particularly preferably 10 to 100 parts by weight.

This rubber composition exhibits excellent heat resistance and durability without the use of an antioxidant, but it is usually possible to extend the product life by using the antioxidant. The same as in the case of rubber. Examples of the antiaging agent used in this case include an amine antiaging agent, a phenol antiaging agent, and a sulfur antiaging agent.

Specific examples of the amine-based antioxidant include naphthylamine-based antioxidants such as phenyl-α-naphthylamine and phenyl-β-naphthylamine; p-
(P-Toluenesulfonylamide) -diphenylamine, 4,4- (α, α-dimethylbenzyl) diphenylamine, 4,4′-dioctyldiphenylamine, high temperature reaction product of diphenylamine and acetone, low temperature of diphenylamine and acetone Reaction products, low-temperature reaction products of diphenylamine with aniline and acetone, reaction products of diphenylamine with diisobutylene, octylated diphenylamine, dioctylated diphenylamine,
Diphenylamine anti-aging agents such as p, p'-dioctyl diphenylamine and alkylated diphenylamines;
N, N'-diphenyl-p-phenylenediamine, n-
Propyl-N'-phenyl-p-phenylenediamine,
N, N'-di-2-naphthyl-p-phenylenediamine, N-cyclohexyl-N'phenyl-p-phenylenediamine, N-phenyl-N '-(3-methacryloyloxy-2-hydroxypropyl) -p- Phenylenediamine, N, N'-bis (1-methylhebutyl) -p
-Phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-
Bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N- (1,3-dimethylbutyl) -N '
-Phenyl-p-phenylenediamine, phenyl, hexyl-p-phenylenediamine, phenyl, octyl-
Examples thereof include p-phenylenediamine anti-aging agents such as p-phenylenediamine.

Specific examples of the phenol anti-aging agent include styrenated phenol, 2,6-di-t-butyl-4-methylphenol and 2,6-di-t-butyl-p.
-Ethylphenol, 2,4,6-tri-t-butylphenol, butylhydroxyanisole, 1-hydroxy-3-methyl-4-isopropylbenzene, mono-t
-Butyl-p-cresol, mono-t-butyl-m-cresol, 2,4-dimethyl-6-t-butylphenol, butylated bisphenol A, 2,2'-methylene-
Bis- (4-methyl-6-t-butylphenol),
2,2'-methylene-bis- (4-ethyl-6-t-butylphenol), 2,2'-methylene-bis- (4-
Methyl-6-t-nonylphenol), 2,2'-isobutylidene-bis- (4,6-dimethylphenol),
4,4'-butylidene-bis- (3-methyl-6-t-
Butylphenol), 4,4'-methylene-bis-
(2,6-di-t-butylphenol), 2,2-thiobis- (4-methyl-6-t-butylphenol),
4,4'-thiobis- (3-methyl-6-t-butylphenol), 4,4'-thiobis- (2-methyl-6-
Butylphenol), 4,4'-thiobis- (6-t-
Butyl-3-methylphenol), bis (3-methyl-)
4-hydroxy-5-t-butylbenzene) sulfide, 2,2-thio [diethylbis-3- (3,5-di-
t-butyl-4-hydroxyphenol) propionate], bis [3,3-bis (4′-hydroxy-3′-)
t-butylphenol) butyric acid acid] glycol ester, bis [2- (2-hydroxy-5-methyl-3-t-butylbenzene) -4-methyl-6-t-butylphenyl] terephthalate, 1,3. 5-Tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) isocyanurate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydroxyamide) ), N-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenol) propionate, tetrakis [methylene- (3', 5'-di-
t-butyl-4-hydroxyphenyl) propionate] methane, 1,1′-bis (4-hydroxyphenyl) cyclohexane, mono (α-methylbenzene) phenol, di (α-methylbenzyl) phenol, tri (α-methyl) Benzyl) phenol, bis (2'-hydroxy-3'-t-butyl-5'-methylbenzyl) 4
-Methyl-phenol, 2,5-di-t-amylhydroquinone, 2,6-dibutyl-α-dimethylamino-p-
Cresol, 2,5-di-t-butylhydroquinone,
Examples thereof include diethyl ester of 3,5-di-t-butyl-4-hydroxybenzylphosphoric acid, catechol and hydroquinone.

Specific examples of the sulfur anti-aging agent include 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptomethylbenzimidazole and 2-mercaptomethylbenzimidazole. Zinc salt of mercaptomethylimidazole, dimyristyl thiodipropionate, dilauryl thiodipropionate, disterial thiodipropionate, ditridecyl thiodipropionate, pentaerythritol-tetrakis (β-lauryl-thiopropionate), etc. Can be given.

These anti-aging agents may be used alone or in two
A combination of two or more species can be used. The content of such an antioxidant is usually 0.1 to 1 with respect to a total of 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) and the diene rubber (B).
It is desirable that the amount is 0 parts by weight, preferably 0.5 to 5 parts by weight.

As the processing aid, those generally compounded with rubber as the processing aid can be widely used.
Specific examples include acids such as ricinoleic acid, stearic acid, palmitic acid and lauric acid, and salts of these higher fatty acids such as barium stearate, zinc stearate, calcium stearate or esters. Processing aids are ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) and diene rubber (B).
Can be appropriately used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less with respect to 100 parts by weight in total.

When the vulcanizable rubber composition of the present invention is vulcanized by heating, the vulcanization aid (polyfunctional monomer) is added in an amount of 0.5 to 2 with respect to 1 mol of the organic peroxide (C). It is preferable to use them in a molar amount, preferably in an approximately equimolar amount. Specific examples of the vulcanization aid include quinone dioxime compounds such as sulfur and p-quinone dioxime; (meth) acrylate compounds such as trimethylolpropane triacrylate, ethylene glycol dimethacrylate, and polyethylene glycol dimethacrylate. Allyl compounds such as diallyl phthalate and triallyl cyanurate;
Maleimide compounds such as m-phenylene bismaleimide; divinylbenzene and the like.

When the rubber composition contains a compound constituting a foaming system such as a foaming agent or a foaming aid, it can be foam-molded. As the foaming agent, a foaming agent generally used in foam-molding rubber can be widely used, and specifically, sodium bicarbonate, sodium carbonate,
Inorganic foaming agents such as ammonium bicarbonate, ammonium carbonate, ammonium nitrite; N, N'-dimethyl-N,
Nitroso compounds such as N'-dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine;
Azodicarbonamide, azobisisobutyronitrile,
Azocyclohexyl nitrile, azodiaminobenzene,
Azo compounds such as barium azodicarboxylate; sulfonyl hydrazide compounds such as benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), diphenylsulfone-3,3'-disulfonyl hydrazide; calcium azide, Examples thereof include azide compounds such as 4,4-diphenyldisulfonyl azide and p-toluenesulfonyl azide. Among these, nitroso compounds, azo compounds and azide compounds are preferable.

The blowing agent is 0.5 to 30 with respect to 100 parts by weight of the total of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) and the diene rubber (B).
It can be used in an amount of parts by weight, preferably 1 to 20 parts by weight. From the rubber composition containing the foaming agent in such an amount, a foam having an apparent specific gravity of 0.03 to 0.8 g / cm ³ can be produced.

It is also possible to use a foaming auxiliary together with the foaming agent, and when the foaming auxiliary is used in combination, it is effective in lowering the decomposition temperature of the foaming agent, promoting decomposition, and making the bubbles uniform. Examples of such foaming aids include organic acids such as salicylic acid, phthalic acid, stearic acid, and oxalic acid, and urea or its derivatives. The foaming aid is 0.01 to 10 parts by weight, preferably 0.1 to 100 parts by weight of the total of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) and the diene rubber (B). It can be used in amounts of up to 5 parts by weight.

The vulcanizable rubber composition of the present invention can be used as a blend with other known rubbers within a range not impairing the object of the present invention. Examples of such other rubber include silicone rubber, ethylene / propylene random copolymer rubber (EPR), and ethylene / α-olefin other than the above ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A).・ Non-conjugated polyene copolymer,
Examples include EPDM.

Further, if a styrene resin (PS) and an acrylonitrile / styrene resin (AS) are blended for the purpose of improving impact resistance, the grafting efficiency is higher than that of the existing EPT and the grafting is easy, which is preferable. Also, T
Even if it is used as a raw material of PO, the efficiency of the organic peroxide is higher than that of the existing EPT, which is preferable.

The vulcanizable rubber composition of the present invention comprises an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A), a diene rubber (B) and an organic peroxide (C), and the above-mentioned compounds. It can be prepared from other components such as by a general method for preparing a rubber compound.
For example, using an internal mixer such as a Banbury mixer, a kneader or an intermix, the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) and the diene rubber (B) and other components are mixed with 80 After kneading at a temperature of ~ 170 ° C for 3 ~ 10 minutes,
After adding an organic peroxide (C) and, if necessary, a vulcanization aid and the like, and using a roll such as an open roll or a kneader, the mixture is kneaded at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes and then dispensed. It can be prepared by In this way, a ribbon-shaped or sheet-shaped rubber composition (blended rubber) is usually obtained. When the kneading temperature in the above internal mixers is low, the organic peroxide (C), vulcanization aid, foaming agent and the like can be kneaded at the same time.

To obtain a vulcanized product (vulcanized rubber) from the vulcanizable rubber composition of the present invention, an unvulcanized rubber composition as described above is usually used in an extruder, calender roll, press,
It can be obtained by preforming into a desired shape by various molding methods such as an injection molding machine and a transfer molding machine, and simultaneously with molding, introducing the molded product into a vulcanization tank and heating it for vulcanization.

When the above vulcanizable rubber composition is vulcanized by heating, a heating tank in a heating form such as hot air, a fluidized bed of glass beads, UHF (ultra high frequency microwave), steam, LCM (hot molten salt tank), etc. It is preferable to heat at a temperature of 150 to 270 ° C. for 1 to 30 minutes.

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

The vulcanizate obtained from the vulcanizable rubber composition of the present invention has processability, strength characteristics (co-vulcanizability), weather resistance,
It has excellent ozone resistance and heat aging resistance, so it can be used for tires, anti-vibration rubber, vibration cover materials, radiator hoses,
Fuel hoses, brake and fuel equipment systems, cover materials such as lamp sockets, automobile industrial parts such as wiper blades, rubber rolls, conveyor belts, transmission belts, timing belts, industrial rubber parts such as hydraulic hoses, electric wires, electrical insulation parts , Electrical / electronic parts such as semi-conductive parts, anode caps, condenser packing, rubberized cloth, roofing sheets, gas hoses, water packing, civil engineering and building supplies such as water hoses, rain gear, rubber bands, shoes, rubber gloves, latex, It can be widely used for household products such as golf balls, heat insulating materials, cushioning materials, and sealing materials.

[0088]

The vulcanizable rubber composition of the present invention contains a specific ethylene / α-olefin / non-conjugated polyene random copolymer rubber, a diene rubber and an organic peroxide, and contains ethylene / α- Since the weight ratio of the olefin / non-conjugated polyene random copolymer rubber (A) and the diene rubber is within a specific range, processability, strength characteristics (co-vulcanizability), weather resistance, ozone resistance, and heat resistance Has excellent aging properties.

[0089]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the excellent effects of the present invention will be described with reference to Examples, but the present invention is not limited to these Examples. The measuring method is as follows.

<< Composition >> The composition of the copolymer was measured by the ¹³ C-NMR method. << Iodine value >> Obtained by a titration method. << Intrinsic viscosity [η] >> The intrinsic viscosity [η] was measured in decalin at 135 ° C. << Molecular weight distribution >> Weight average molecular weight Mw determined by GPC
It was expressed by the ratio of / number average molecular weight Mn. << γ ₂ / γ ₁ >> Obtain the melt flow curve at 100 ℃,
Shear rate γ ₁ when 0.4 × 10 ⁶ dyn / cm ² is shown
And shear rate γ when 2.4 × 10 ⁶ dyn / cm ² is shown
The ratio with ₂ was calculated. L / D = 60 mm / 3 mm << effective mesh chain density >> JIS K 6258 (1993)
Year), soak in toluene at 37 ℃ for 72 hours, and fl
The effective network chain density ν (pieces / cm ³ ) was calculated from the ory-Rehner equation from the following equation. ν (pieces / cm ³ ) = {ν _R + ln (1-ν _R ) + μν _R ² } /
{−V ₀ (ν _R ^1/3 −ν _R / 2)} [ν (pieces / cm ³ ): Effective network chain density, pure rubber 1c
Number of effective network chains in m ³ ν _R : Volume fraction of pure rubber to volume of pure rubber (volume of pure rubber + volume of absorbed solvent) in swollen vulcanized rubber μ: Rubber-solvent interaction constant (0.49) V ₀ : Preparation of molecular volume sample of solvent: 0.01 mol of dicumyl peroxide was added to 100 g of random copolymer, and kneading temperature was 5
Kneading was carried out at 0 ° C. using an 8-inch open roll by the method described in SRIS, and the obtained sample was 170
It was prepared by press vulcanization at 0 ° C for 10 minutes. [Relationship between γ ₂ / γ ₁ and Crosslink Density] Log (γ ₂ / γ ₁ ) / ν
Was calculated.

<< Amount of insoluble matter after Soxhlet extraction >> As a pretreatment, about 5 g of the sample was sandwiched between luminers and 160 ± 5.
A sheet having a thickness of 0.5 mm is prepared using a hand press at ℃. Cut out 1 to 2 g and cut into a size of 1 mm square or less. A stainless steel basket is weighed, and the weight at this time is A. Place the above sample in a stainless steel basket at 1 ± 0.
Take 1 g and weigh. The weight at this time is B. Then place the zeolite and xylene in a 300 ml flat bottom flask.
Add 00 ml. Next, cooling water for the condenser is passed and nitrogen for sealing is flowed. Next, mesh 3
Set the Soxhlet extractor with a filter of 25 and start the reflux. Next, the reflux rate is set to 4 to 6 minutes,
Extract for 3 hours. After the reflux is completed, the sample is taken out, replaced with room temperature n-heptane and acetone, and dried under reduced pressure at 105 ° C. for 1 hour. After allowing to cool for 1 hour, the sample is weighed, and the weight at this time is defined as C. From these weights, the amount of insoluble matter after Soxhlet extraction is calculated based on the following formula. Insoluble content after Soxhlet extraction (% by weight) = {(C-
B) / (B-A)} × 100

Production Example 1 Using a stainless steel polymerization vessel (stirring speed = 250 rpm) having a substantial internal volume of 100 liter and equipped with stirring blades, ternary ethylene / propylene / 5-vinyl-2-norbornene was continuously used. Polymerization was carried out. 60 liter / hr of hexane and 3.7 kg / h of ethylene in the liquid phase from the side of the polymerizer
r, propylene at 9.3 kg / hr, and 5-vinyl-2-norbornene at a rate of 480 g / hr,
Further, hydrogen was 40 liter / hr, VOCl ₃ as a catalyst was 45 mmol / hr, Al (C ₂ H ₅ ) ₂ Cl was 225 mmol / hr, and Al (C ₂ H ₅ ) _1.5 Cl _1.5 was 45.
It was continuously fed at a rate of mmol / hr. The copolymerization reaction was performed at 40 ° C.

The copolymerization reaction was carried out under the above conditions to obtain ethylene.
-Propylene-5-vinyl-2-norbornene copolymer
Was obtained as a uniform solution state. Is the polymerization solution below the polymerization vessel?
It was continuously withdrawn from the flask and a small amount of methanol was added to the polymerization solution.
Is added to stop the polymerization reaction and steam stripping
After separating the copolymer from the solvent by aging treatment,
It was vacuum dried for 48 hours. Thus obtained
The ethylene / propylene molar ratio of the copolymer is 68/3
2. Intrinsic viscosity [η] is 1.98 dl / g, 5-vinyl-
The 2-norbornene content was 10.0 in iodine value.
Γ determined from the melt flow curve of this copolymer ₂/ Γ₁
Is 139.2, effective network chain density ν is 31.2 × 10¹⁹Individual
/ Cm³, Log (γ₂/ Γ₁) / Ν is 0.069 × 10
^-19Met. Conditions and results are shown in Table 1 and Table 2.
You

Production Examples 2 to 4 Copolymerization was performed in the same manner as in Production Example 1 except that the conditions shown in Table 1 were changed to obtain copolymers shown in Table 2.

[0095]

[Table 1] _{* 1 VOCl 3 -Al (C 2} H 5) 2 Cl / Al (C 2 H 5) 1. 5 Cl 1. 5 * 2 VO (OC 2 H 5) Cl 2 -Al (C 2 H 5) 1. _{5 Cl 1 5 * 3 Et:} . C 2 H 5 * 4 C 3: propylene * 5 VNB: 5-vinyl-2-norbornene ENB: 5-ethylidene-2-norbornene

[0096]

[Table 2] * 1 Ethylene / propylene molar ratio in the copolymer * 2 Effective network chain density ν: Unit is × 10 ¹⁹ / cm ³ * 3 Log (γ ₁ / γ ₂ ) / ν: Unit is × 10 ^-19 / Cm ³

Example 1 First, the compounding agents shown in Table 3 were kneaded with a Banbury mixer having a capacity of 1.7 liters (manufactured by Kobe Steel, Ltd.). The kneading method was as follows. First, an ethylene / α-olefin / non-conjugated polyene random copolymer rubber was masticated for 30 seconds, then zinc white, stearic acid, carbon black, and oil as a softening agent were added and kneaded for 2 minutes. After that, raise the ram to clean it, and knead for another 1 minute,
It discharged at 0 degreeC and the compound (1-1) was obtained. This kneading was performed at a filling rate of 70%. Further, the compounding ingredients shown in Table 4 were kneaded in the same manner as above to obtain a compounded matter (2-1).

75 parts by weight of the above-mentioned compound (1-1) and 25 parts by weight of the compound (2-1) were used for 8 inch rolls (surface temperature of front roll 50 ° C., surface temperature of rear roll 50 ° C., Front roll speed 16 rpm, rear roll speed 18 rp
m) and a 100% dicumyl peroxide product (Mitsui Chemicals, Inc., trade name Mitsui DCP, trademark) 1.
After adding 35 parts by weight and kneading for 3 minutes, the mixture was dispensed into a sheet and pressed at 160 ° C. for 20 minutes to prepare a vulcanized sheet having a thickness of 2 mm.

The vulcanized sheet was subjected to a tensile test, a hardness test, a permanent set test, an ozone resistance test, an oil resistance test and a heat aging resistance test. Further, the co-crosslinking property was calculated from the tensile strength of the tensile test (see FIG. 1). In addition, JIS K63
In accordance with 01, the sample for compression set measurement at 160 ° C
It was vulcanized for 25 minutes. A compression set test was performed using this sample. These measuring methods are as follows. The results are shown in Table 5 and Table 8.

According [0100] (1) Tensile properties JIS K 6301, measurement temperature 25 ° C., subjected to tensile test at a tensile rate of 500 mm / min conditions, elongation (E _B) and strength at break of the vulcanized sheet (T _B) It was measured. (2) Hardness test According to JIS K6301, spring hardness (Hs,
The JIS A hardness) was determined. (3) Permanent strain In accordance with JIS K6301, the permanent strain (Ts) was determined. (4) Compression set In conformity with JIS K6301. The compression set (C _s ) of the test piece aged at 120 ° C. for 22 hours was determined.

(5) Aging property According to JIS K 6301, the vulcanized sheet was put in an oven at 120 ° C. for 96 hours to be aged, and then a measurement temperature was set to 25.
Conduct a tensile test under conditions of ℃ and pulling speed of 500 mm / min.
Elongation at break of the vulcanized sheet (E _B), the strength (T _B) and hardness (H _A) was measured, the tensile strength retention A _R (T _B), elongation retention ratio A _R (E _B) And hardness change (A _H ) were calculated. (6) Ozone resistance test According to JIS K6301, ozone concentration 80 pph
m, measurement temperature 40 ° C., extension rate 0 to 20%, frequency 5 Hz
Under the conditions of 1 day, 2 days, 4 days after the start of the test,
After 7 days and 10 days, the state of crack generation after each lapse of time was observed and evaluated. (7) Oil resistance test The oil resistance test was carried out according to the dipping test specified in JIS K6301, and the volume change rate (ΔV,%) of the test piece was obtained.
In addition, JIS No. 3 oil was used as a test oil. The test conditions are 100 ° C. and 72 hours.

(8) The weight% of the co-crosslinkable ethylene / α-olefin / non-conjugated polyene random copolymer rubber compound (1) is x, and the weight% of the diene rubber compound (2) is y. Where x + y = 10
It is 0%. Further, the tensile strength of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber compound (1) after crosslinking was A ₀ , and the tensile strength of the diene rubber compound (2) after crosslinking was B _0. The co-crosslinkability (%) was calculated from the formula.

## EQU00004 ## Co-crosslinkability (%) = {Strength of compounded mixture of compound (1) and compound (2) in the ratio of x: y} × 100 / {(A ₀
× x / 100) + (B ₀ × y / 100)}

[0103]

[Table 3] * 1: Ethylene / propylene-5-vinyl-2-norbornene copolymer rubber of Production Example 1 in Tables 1 and 2 * 2: Sakai Chemical Industry Co., Ltd., Zinc Hua No. 3 * 3: NOF Corporation ), Tsubaki (trademark) * 4: Tokai Carbon Co., Ltd., Seast 3 (trademark) * 5: Nippon Sun Oil Co., Ltd., Sunpar 2280 (trademark)

[0104]

[Table 4] * 1: Acrylonitrile butadiene rubber, manufactured by Nippon Zeon Co., Ltd., 1042AL (trademark), Mooney viscosity (ML
_{1 + 4} (100 ° C.)) = 46, nitrile content = 33.5 mol%, iodine value = about 200 g / 100 g * 2: Sakai Chemical Industry Co., Ltd., Zinc Hua No. 1 * 3: NOF Corporation Tsubaki (trademark) * 4: Tokai Carbon Co., Ltd., Seast 3 (trademark) * 5: New Japan Rika Co., Ltd., Sanso Sizer nDOP
(Trademark)

Example 2 As shown in Table 5, Example 1 was repeated except that the amount of the compound (1-1) was changed to 50 parts by weight and the amount of the compound (2-1) was changed to 50 parts by weight.
I went the same way. The results are shown in Table 5 and Table 8.

Example 3 As shown in Table 5, Example 1 was changed except that the compound (1-1) was changed to 25 parts by weight and the compound (2-1) was changed to 75 parts by weight.
I went the same way. The results are shown in Table 5 and Table 8.

Comparative Example 1 As shown in Table 5, Example 1 was repeated except that the compound (2-1) was not used and only the compound (1-1) was used in an amount of 100 parts by weight.
I went the same way. The results are shown in Table 5 and Table 8.

Comparative Example 2 As shown in Table 5, Example 1 was used except that the compound (1-1) was not used and only 100 parts by weight of the compound (2-1) was used.
I went the same way. The results are shown in Table 5 and Table 8.

Comparative Example 3 The polymer shown in Production Example 3 in Tables 1 and 2 was used in place of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) used in Example 1. ,
A compound (1-2) was obtained in the same manner as in Example 1. As shown in Table 6, the same procedure as in Example 1 was carried out except that only 100 parts by weight of this formulation (1-2) was used. The results are shown in Table 6 and Table 9.

Comparative Example 4 As shown in Table 6, Example 1 was repeated except that the amount of the compound (1-2) was changed to 75 parts by weight and the amount of the compound (2-1) was changed to 25 parts by weight.
I went the same way. The results are shown in Table 6 and Table 9.

Comparative Example 5 As shown in Table 6, Example 1 was changed except that the amount of the compound (1-2) was changed to 50 parts by weight and the amount of the compound (2-1) was changed to 50 parts by weight.
I went the same way. The results are shown in Table 6 and Table 9.

Comparative Example 6 As shown in Table 6, Example 1 was changed except that the amount of the compound (1-2) was changed to 25 parts by weight and the amount of the compound (2-1) was changed to 75 parts by weight.
I went the same way. The results are shown in Table 6 and Table 9.

Comparative Example 7 As shown in Table 6, the same procedure as in Comparative Example 5 was carried out except that the amount of dicumyl peroxide was changed to 2.7 parts by weight. The results are shown in Table 6 and Table 9.

Comparative Example 8 As shown in Table 7, instead of dicumyl peroxide,
The same procedure as in Comparative Example 1 was carried out except that 1.5 parts by weight of sulfur and 1.2 parts by weight of N-cyclohexyl-2-benzothiazyl sulfenamide (manufactured by Sanshin Chemical Co., Ltd., Sancella CM, trademark) were blended. It was The results are shown in Tables 7 and 10.

Comparative Example 9 As shown in Table 7, instead of dicumyl peroxide,
The same procedure as in Example 1 was performed except that 1.5 parts by weight of sulfur and 1.2 parts by weight of N-cyclohexyl-2-benzothiazyl sulfenamide (manufactured by Sanshin Chemical Co., Ltd., Sancella CM, trademark) were blended. It was The results are shown in Tables 7 and 10.

Comparative Example 10 As shown in Table 7, instead of dicumyl peroxide,
Example 2 was repeated except that 1.5 parts by weight of sulfur and 1.2 parts by weight of N-cyclohexyl-2-benzothiazyl sulfenamide (manufactured by Sanshin Kagaku Co., Ltd., Sancella CM, trademark) were blended. It was The results are shown in Tables 7 and 10.

Comparative Example 11 As shown in Table 7, instead of dicumyl peroxide,
The same procedure as in Example 3 was performed except that 1.5 parts by weight of sulfur and 1.2 parts by weight of N-cyclohexyl-2-benzothiazyl sulfenamide (manufactured by Sanshin Chemical Co., Ltd., Sancella CM, trademark) were blended. It was The results are shown in Tables 7 and 10.

Comparative Example 12 As shown in Table 7, instead of dicumyl peroxide,
Same as Comparative Example 2 except that 1.5 parts by weight of sulfur and 1.2 parts by weight of N-cyclohexyl-2-benzothiazyl-sulfenamide (manufactured by Sanshin Kagaku Co., Ltd., Sancella CM, trademark) were blended. It was The results are shown in Tables 7 and 10.

[0119]

[Table 5] * 1 DCP ₁₀₀ : Dicumyl peroxide 100% by weight concentration product * 2 CZ: N-cyclohexyl-2-benzothiazyl sulfenamide * 3 160 ° C, 20 minutes vulcanization * 4 120 ° C x 22 hr

[0120]

[Table 6] * 1 DCP ₁₀₀ : Dicumyl peroxide 100% by weight concentration product * 2 CZ: N-cyclohexyl-2-benzothiazyl sulfenamide * 3 160 ° C, 20 minutes vulcanization * 4 120 ° C x 22 hr

[0121]

[Table 7] * 1 DCP ₁₀₀ : Dicumyl peroxide 100% by weight concentration product * 2 CZ: N-cyclohexyl-2-benzothiazyl sulfenamide * 3 160 ° C, 20 minutes vulcanization * 4 120 ° C x 22 hr

[0122]

[Table 8] * 1 Heat aging resistance: Gear oven, 120 ° C, 96h * 2 Ozone resistance: 40 ° C, 80pphm, 20%, n = 2 * 3 Oil resistance: JIS No. 3 oil, 100 ° C x 70h

[0123]

[Table 9] * 1 Heat aging resistance: Gear oven, 120 ° C, 96h * 2 Ozone resistance: 40 ° C, 80pphm, 20%, n = 2 * 3 Oil resistance: JIS No. 3 oil, 100 ° C x 70h

[0124]

[Table 10] * 1 Heat aging resistance: Gear oven, 120 ° C, 96h * 2 Ozone resistance: 40 ° C, 80pphm, 20%, n = 2 * 3 Oil resistance: JIS No. 3 oil, 100 ° C x 70h

The above results are summarized in Table 11.

[Table 11] * 1 See Figure 1 for co-crosslinking properties. Figure 1 is a horizontal axis "EPT / NBR (%)", the vertical axis is the "measured T _B / calculated T _B (MPa)" is a graph showing the co-crosslinking property. From FIG. 1, it is clear that the rubber composition of VNB-EPT / NBR / organic peroxide is excellent in co-crosslinking property. The evaluation criteria in Table 11 are as follows.

[0126] Co-crosslinkable ◎: Found T _B / calculated T _B = 80~100% ○: Found T _B / calculated T _B = 75~90% △: Found T _B / calculated T _B = 70~85% ×: Found T _B / calculated T _B = 50 to 80% compression set ◎: C _s is less than 10% ○: C _s is less than 5% 20% △: C _s or more and less than 20% 50% ×: C _s is 50% or more Heat aging resistance ◎: A _R (E _B ) is 90% or more ○: A _R (E _B ) is 70% or more and less than 90% Δ: A _R (E _B ) is 50% or more and less than 70% ×: A _R (E _B ) is less than 50% Oil resistance ◎: ΔV is 30 to 100% ○: ΔV is 40 to 200% Δ: ΔV is 50 to 250% ×: ΔV is 100% or more Ozone resistance ◎: 96 hours Subsequent judgment is “None” ○: 96 hours later is “A-4” or more Δ: 96 hours later is “B-4” or more ×: 96 hours later is “disconnect”

As can be seen from Table 11, the examples are excellent in all of the co-crosslinking property, compression set, heat aging resistance, oil resistance and ozone resistance, but the above formula (1) or (2) Comparative example using 5-ethylidene-2-norbornene not included (organic peroxide / ENB-EPT)
Is poor in co-crosslinking property except heat aging resistance and ozone resistance, compression set, and oil resistance as compared with the examples, and is not included in the formula (1) or (2). -Comparative example using norbornene and sulfur instead of organic peroxide (sulfur / ENB-EPT)
Of all the characteristics are worse than those of the examples.

Example 4 First, the compounding agents shown in Table 12 were kneaded with a Banbury mixer having a capacity of 1.7 liter "manufactured by Kobe Steel Ltd.". The kneading method was as follows. First, an ethylene / α-olefin / non-conjugated polyene random copolymer rubber was masticated for 30 seconds, then zinc white, stearic acid, carbon black and oil as a softening agent were added and kneaded for 2 minutes. After that, raise the ram to clean it, and knead for another 1 minute,
It was discharged at 0 ° C. to obtain a compound (1-3). This kneading was performed at a filling rate of 70%. Moreover, the compounding agents shown in Table 13 were kneaded in the same manner as above to obtain a compound (2-2).

80 parts by weight of the above-mentioned compound (1-3) and 20 parts by weight of the compound (2-2) were mixed with an 8-inch roll (surface temperature of front roll: 50 ° C., surface temperature of rear roll: 50 ° C., Front roll speed 16 rpm, rear roll speed 18 rp
m-), 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane 40% concentration product (Trigonox 29/40, Kayaku Akzo Co., Ltd.)
6 parts by weight and 2 parts by weight of ethylene glycol dimethacrylate were added and kneaded for 3 minutes, then dispensed into a sheet and pressed at 160 ° C. for 15 minutes to prepare a vulcanized sheet having a thickness of 2 mm.

About this vulcanized sheet, tensile test, hardness test, permanent set test, ozone resistance test, heat aging resistance test,
An Akron abrasion test was conducted. Further, the co-crosslinking property was calculated from the tensile strength of the tensile test. Furthermore, JIS K630
According to 1, the sample for compression set measurement was vulcanized at 160 ° C. for 20 minutes. A compression set test was performed using this sample. These measuring methods are as follows.
The results are shown in Tables 14 and 16.

(1) Tensile properties The same as in Example 1. (2) Hardness test Same as in Example 1. (3) Permanent distortion Same as in Example 1. (4) Compression set In conformity with JIS K6301. The compression set (C _s ) was determined for the test piece aged at 135 ° C for 72 hours and the test piece left to stand at -25 ° C for 70 hours.

(5) Aging characteristics According to JIS K 6301, the vulcanized sheet was put in an oven at 135 ° C. for 72 hours for aging, and then measured at a measurement temperature of 25.
Conduct a tensile test under conditions of ℃ and pulling speed of 500 mm / min.
Elongation at break of the vulcanized sheet (E _B), the strength (T _B) and hardness (H _A) was measured, the tensile strength retention A _R (T _B), elongation retention ratio A _R (E _B) And hardness change (A _H ) were calculated. (6) Ozone resistance test Same as in Example 1. (7) Akron abrasion test Conforms to JIS k6264 Complies with ASTM D1630 (8) Co-crosslinkability Same as in Example 1.

[0133]

[Table 12] * 1: Ethylene / propylene-5-vinyl-2-norbornene copolymer rubber of Production Example 2 in Tables 1 and 2 * 2: Sakai Chemical Industry Co., Ltd., Zinc Hua No. 3 * 3: NOF Corporation ), Tsubaki (trademark) * 4: Tokai Carbon Co., Ltd., Seast SO (trademark) * 5: Nikko Kyokushi Co., Ltd., P-200 (trademark)

[0134]

[Table 13] * 1: Butadiene rubber, Ubekosan Co., Ltd., Ubepol 150 (trademark), Mooney viscosity (ML _{1 + 4} (100 ° C))
= 43, 1,4 cis content = 98 mol% * 2: Sakai Chemical Industry Co., Ltd., Zinc Hua No. 3 * 3: NOF Corporation, Tsubaki (trademark) * 4: Tokai Carbon Co., Ltd. , Seast SO (trademark) * 5: P-200 (trademark) manufactured by Nikko Kyoseki Co., Ltd.

Example 5 As shown in Table 14, 50 parts by weight of the compound (1-3),
The same procedure as in Example 4 was carried out except that the amount of the compound (2-2) was changed to 50 parts by weight. The results are shown in Tables 14 and 16.

Example 6 As shown in Table 14, 20 parts by weight of the compound (1-3),
The same procedure as in Example 4 was carried out except that the amount of the compound (2-2) was changed to 80 parts by weight. The results are shown in Tables 14 and 16.

Comparative Example 13 As shown in Table 14, the same procedure as in Example 4 was carried out except that the compound (2-2) was not used and only the compound (1-3) was used in an amount of 100 parts by weight. The results are shown in Tables 14 and 16.

Comparative Example 14 As shown in Table 14, the same procedure as in Example 4 was carried out except that the compound (1-3) was not used and only the compound (2-2) was used in an amount of 100 parts by weight. The results are shown in Tables 14 and 16.

Comparative Example 15 The polymer shown in Production Example 4 of Table 1 and Table 2 was used in place of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) used in Example 4. ,
A compound (1-4) was obtained in the same manner as in Example 4. Table 15
As shown in, the same procedure as in Example 4 was carried out except that only 100 parts by weight of this formulation (1-4) was used. The results are shown in Table 15.
And shown in Table 17.

Comparative Example 16 As shown in Table 15, 80 parts by weight of the compound (1-4),
The same procedure as in Example 4 was carried out except that the amount of the compound (2-2) was changed to 20 parts by weight. The results are shown in Tables 15 and 17.

Comparative Example 17 As shown in Table 15, 50 parts by weight of the compound (1-4),
The same procedure as in Example 4 was carried out except that the amount of the compound (2-2) was changed to 50 parts by weight. The results are shown in Tables 15 and 17.

Comparative Example 18 As shown in Table 15, 20 parts by weight of the compound (1-4),
The same procedure as in Example 4 was carried out except that the amount of the compound (2-2) was changed to 80 parts by weight. The results are shown in Tables 15 and 17.

[0143]

[Table 14] * 1 TBPTMC: 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane * 2 EGDMA: ethylene glycol dimethacrylate * 3 160 ° C, 15 minutes vulcanization * 4 135 ° C x 72hr * 5- 25 ° C x 70 hours

[0144]

[Table 15] * 1 TBPTMC: 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane * 2 EGDMA: ethylene glycol dimethacrylate * 3 160 ° C, 15 minutes vulcanization * 4 135 ° C x 72hr * 5- 25 ° C x 70 hours

[0145]

[Table 16] * 1 Heat aging resistance: Gear oven, 135 ° C x 72h * 2 Ozone resistance: 40 ° C, 80pphm, 20%, n = 2

[0146]

[Table 17] * 1 Heat aging resistance: Gear oven, 135 ° C x 72h * 2 Ozone resistance: 40 ° C, 80pphm, 20%, n = 2

Example 7 First, the compounding ingredients shown in Table 18 were kneaded with a Banbury mixer having a capacity of 1.7 liter "manufactured by Kobe Steel, Ltd.". The kneading method was as follows. First, an ethylene / α-olefin / non-conjugated polyene random copolymer rubber was masticated for 30 seconds, then zinc white, stearic acid, carbon black and oil as a softening agent were added and kneaded for 2 minutes. After that, raise the ram to clean it, and knead for another 1 minute,
It was discharged at 0 ° C. to obtain a compound (1-5). This kneading was performed at a filling rate of 70%. Further, the compounding agents shown in Table 19 were kneaded in the same manner as above to obtain a compound (2-3).

70 parts by weight of the above-mentioned compound (1-5) and 30 parts by weight of the compound (2-3) were used for 8 inch rolls (surface temperature of front roll 50 ° C., surface temperature of rear roll 50 ° C., Front roll speed 16 rpm, rear roll speed 18 rp
m) and wrapped with dicumyl peroxide (Mitsui DCP
40C, manufactured by Mitsui Chemicals, Inc., 4 parts by weight, and added 3
After kneading for 1 minute, dispense into a sheet and store at 160 ℃ for 30 minutes.
The sheet was pressed for a minute to prepare a vulcanized sheet having a thickness of 2 mm.

The vulcanized sheet was subjected to a tensile test, a hardness test, a permanent set test, an ozone resistance test, an oil resistance test, a heat aging resistance test, and an Akron abrasion resistance test. Further, the co-crosslinking property was calculated from the tensile strength of the tensile test. Furthermore, JI
A sample for compression set measurement was vulcanized at 160 ° C. for 35 minutes in accordance with SK6301. A compression set test was performed using this sample. These measuring methods are as follows. The results are shown in Table 20 and Table 22.

(1) Tensile properties The same as in Example 1. (2) Hardness test Same as in Example 1. (3) Permanent distortion Same as in Example 1. (4) Compression set In conformity with JIS K6301. The compression set (C _s ) of the test piece aged at 100 ° C. for 22 hours was determined.

(5) Aging Property According to JIS K 6301, the vulcanized sheet was put in a tubular tube at 110 ° C. for 48 hours to be aged, and then a tensile test was conducted at a measuring temperature of 25 ° C. and a pulling speed of 500 mm / min. , elongation at break of the vulcanized sheet (E _B), the strength (T _B) and hardness (H _a) was measured, the tensile strength retention a _R (TB),
The elongation retention A _R (EB) and the change in hardness (A _H ) were calculated. (6) Ozone resistance test Same as in Example 1. (7) Oil resistance test The oil resistance test was carried out according to the dipping test specified in JIS K6301, and the volume change rate (ΔV,%) of the test piece was obtained.
In addition, JIS No. 3 oil was used as a test oil. The test conditions are 40 ° C. and 48 hours. (8) Akron abrasion test Same as Example 4. (9) Co-crosslinkability Same as in Example 1.

[0152]

[Table 18] * 1: Ethylene / propylene / 5-vinyl-2-norbornene copolymer rubber of Production Example 1 in Tables 1 and 2 * 2: Sakai Chemical Industry Co., Ltd., Zinc Hua No. 3 * 3: NOF Corporation ), Tsubaki (trademark) * 4: Tokai Carbon Co., Ltd., Seast 3 (trademark) * 5: Nippon San Oil Co., Ltd., Sansen 4240 (trademark)

[0153]

[Table 19] * 1: Styrene butadiene rubber, manufactured by Nippon Zeon Co., Ltd.
1502 (trademark), Mooney viscosity (ML _{1 + 4} (100
)) = 42, bound styrene = 23.5% * 2: Sakai Chemical Industry Co., Ltd., Zinc Hua No. 3 * 3: NOF Corporation, Tsubaki (trademark) * 4: Tokai Carbon Co., Ltd. Made by Seast 3 (trademark) * 5: Made by Nippon San Oil Co., Ltd., Sansen 4240 (trademark)

Example 8 As shown in Table 20, 50 parts by weight of the compound (1-5),
The same procedure as in Example 7 was carried out except that the amount of the compound (2-3) was changed to 50 parts by weight. The results are shown in Table 20 and Table 22.

Example 9 As shown in Table 20, 30 parts by weight of the compound (1-5),
Example 7 was carried out in the same manner as in Example 7 except that the amount of the compound (2-3) was changed to 70 parts by weight. The results are shown in Table 20 and Table 22.

Comparative Example 19 As shown in Table 20, the procedure of Example 7 was repeated except that the compound (2-3) was not used and only the compound (1-5) was used in an amount of 100 parts by weight. The results are shown in Table 20 and Table 22.

Comparative Example 20 As shown in Table 20, the same procedure as in Example 7 was carried out except that the compound (1-5) was not used and only the compound (2-3) was used in an amount of 100 parts by weight. The results are shown in Table 20 and Table 22.

Comparative Example 21 The procedure of Comparative Example 21 was repeated except that the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) used in Example 7 was replaced by the polymer of Production Example 3 in Tables 1 and 2. A compound (1-6) was obtained in the same manner as in Example 7. As shown in Table 21, the same procedure as in Example 7 was carried out except that only 100 parts by weight of this formulation (1-6) was used. The results are shown in Tables 21 and 23.

Comparative Example 22 As shown in Table 21, 70 parts by weight of the compound (1-6),
It carried out like Example 7 except having changed the compound (2-3) into 30 weight part. The results are shown in Tables 21 and 23.

Comparative Example 23 As shown in Table 21, 50 parts by weight of the compound (1-6),
The same procedure as in Example 7 was carried out except that the amount of the compound (2-3) was changed to 50 parts by weight. The results are shown in Tables 21 and 23.

Comparative Example 24 As shown in Table 21, 30 parts by weight of the compound (1-6),
Example 7 was carried out in the same manner as in Example 7 except that the amount of the compound (2-3) was changed to 70 parts by weight. The results are shown in Tables 21 and 23.

[0162]

[Table 20] * 1 DCP ₄₀ : 40% by weight dicumyl peroxide concentration product * 2 Vulcanized at 160 ° C for 30 minutes * 3 100 ° C x 22 hr

[0163]

[Table 21] * 1 DCP ₄₀ : 40% by weight dicumyl peroxide concentration product * 2 Vulcanized at 160 ° C for 30 minutes * 3 100 ° C x 22 hr

[0164]

[Table 22] * 1 Heat aging resistance: Tubular, 110 ° C, 48h * 2 Ozone resistance: 40 ° C, 80pphm, 20%, n = 2 * 3 Oil resistance: JIS No. 3 oil, 40 ° C x 48h

[0165]

[Table 23] * 1 Heat aging resistance: Tubular, 110 ° C, 48h * 2 Ozone resistance: 40 ° C, 80pphm, 20%, n = 2 * 3 Oil resistance: JIS No. 3 oil, 40 ° C x 48h

Example 10 First, the compounding agents shown in Table 24 were kneaded with a Banbury mixer having a capacity of 1.7 liters (manufactured by Kobe Steel, Ltd.). The kneading method was as follows. First, an ethylene / α-olefin / non-conjugated polyene random copolymer rubber was masticated for 30 seconds, then zinc white, carbon black and oil as a softening agent were added and kneaded for 2 minutes. After that, raise the ram to clean, knead for another 1 minute, and discharge at about 120 ° C.
A formulation (1-7) was obtained. This kneading was performed at a filling rate of 70%. Further, the compounding agents shown in Table 25 were kneaded in the same manner as above to obtain a compound (2-4).

75 parts by weight of the above-mentioned compound (1-7) and 25 parts by weight of the compound (2-4) were mixed with an 8-inch roll (the surface temperature of the front roll was 50 ° C., the surface temperature of the rear roll was 50 ° C., Front roll speed 16 rpm, rear roll speed 18 rp
m) and wrapped with dicumyl peroxide (Mitsui DCP
40 C, 1.88 parts by weight of Mitsui Chemicals Co., Ltd., and kneading for 3 minutes, and then dispensed into a sheet form and 150 ° C.
And pressed for 40 minutes to prepare a vulcanized sheet having a thickness of 2 mm.

This vulcanized sheet was subjected to a tensile test, a hardness test, a permanent set test, an ozone resistance test, an oil resistance test and a heat aging resistance test. Further, the co-crosslinking property was calculated from the tensile strength of the tensile test. Furthermore, the sample for compression set measurement was vulcanized at 150 ° C. for 45 minutes according to JIS K6301. A compression set test was performed using this sample. These measuring methods are as follows. The results are shown in Table 26.

(1) Tensile properties The same as in Example 1. (2) Hardness test Same as in Example 1. (3) Permanent distortion Same as in Example 1. (4) Compression set In conformity with JIS K6301. The compression set (C _s ) of the test piece aged at 100 ° C. for 70 hours was determined.

(5) Aging characteristics According to JIS K 6301, the vulcanized sheet is
Put the tube in the tuber for 96 hours and age it, then measure the temperature.
Conduct a tensile test at 25 ° C and a tensile speed of 500 mm / min.
Elongation at break of vulcanized sheet (E_B), Strength (T_B) Oh
And hardness (H_A) Is measured and the tensile strength retention rate A_R(T_B),
Elongation retention rate A_R(E_B) And hardness change (A _H) Is calculated
It was (6) Ozone resistance test Conforms to JIS K6301, ozone concentration 1000pp
hm, measurement temperature 40 ° C, extension rate 0 to 20%, frequency 5H
Each time after 1 day and 2 days after starting the test
The state of crack generation at the time of was observed and evaluated. (7) Oil resistance test Compliant with the immersion test specified in JIS K6301
Then, the volume change rate (ΔV,%) of the test piece was obtained.
In addition, JIS No. 3 oil was used as a test oil. Test condition
Is 70 ° C. for 48 hours. (8) Co-crosslinking property Same as Example 1.

[0171]

[Table 24] * 1: Ethylene / propylene-5-vinyl-2-norbornene copolymer rubber of Production Example 1 in Tables 1 and 2 * 2: Sakai Chemical Industry Co., Ltd., Zinc Hua No. 3 * 3: Tokai Carbon Co., Ltd. ), Seast 3 (trademark) * 4: Sun Sun Oil Co., Ltd., Sunsen 4240 (trademark)

[0172]

[Table 25] * 1: Chloroprene rubber * 2: Sakai Chemical Industry Co., Ltd., Zinc Hua No. 3 * 3: Tokai Carbon Co., Ltd., Seast 3 (trademark) * 4: Nippon San Oil Co., Ltd., Sansen 4240 (trademark) )

Example 11 As shown in Table 26, 50 parts by weight of the compound (1-7),
The same procedure as in Example 10 was carried out except that the amount of the compound (2-4) was changed to 50 parts by weight. The results are shown in Table 26.

Example 12 As shown in Table 26, 25 parts by weight of the compound (1-7),
The same procedure as in Example 10 was repeated except that the amount of the compound (2-4) was changed to 75 parts by weight. The results are shown in Table 26.

Comparative Example 25 As shown in Table 26, the procedure of Example 10 was repeated, except that the compound (2-4) was not used and only the compound (1-7) was used in an amount of 100 parts by weight. The results are shown in Table 26.

Comparative Example 26 As shown in Table 26, the same procedure as in Example 10 was carried out except that the compound (1-7) was not used and only the compound (2-4) was used in an amount of 100 parts by weight. The results are shown in Table 26.

Comparative Example 27 Instead of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) used in Example 10, Table 1 was used.
And the compound (1-8) was obtained in the same manner as in Example 10 except that the polymer of Production Example 3 in Table 2 was used. Table 27
As shown in, the same procedure as in Example 10 was carried out except that only 100 parts by weight of this formulation (1-8) was used. The results are shown in Table 2.
7 shows.

Comparative Example 28 As shown in Table 27, 75 parts by weight of the compound (1-8),
The same procedure as in Example 10 was carried out except that the amount of the compound (2-4) was changed to 25 parts by weight. The results are shown in Table 27.

Comparative Example 29 As shown in Table 27, 50 parts by weight of the compound (1-8),
The same procedure as in Example 10 was carried out except that the amount of the compound (2-4) was changed to 50 parts by weight. The results are shown in Table 27.

Comparative Example 30 As shown in Table 27, 25 parts by weight of the compound (1-8),
The same procedure as in Example 10 was repeated except that the amount of the compound (2-4) was changed to 75 parts by weight. The results are shown in Table 27.

[0181]

[Table 26] * 1 DCP ₁₀₀ : 100% by weight dicumyl peroxide concentration product * 2 150 ° C, 40 minutes vulcanization * 3 100 ° C x 70hr * 4 Heat aging resistance: tubular, 150 ° C, 96h * 5 Ozone resistance: 40 ° C, 1000 pphm, 20%, n = 2 * 6 Oil resistance: JIS No. 3 oil, 70 ° C x 48h

[0182]

[Table 27] * 1 DCP ₁₀₀ : 100% by weight dicumyl peroxide concentration product * 2 150 ° C, 40 minutes vulcanization * 3 100 ° C x 70hr * 4 Heat aging resistance: tubular, 150 ° C, 96h * 5 Ozone resistance: 40 ° C, 1000 pphm, 20%, n = 2 * 6 Oil resistance: JIS No. 3 oil, 70 ° C x 48h

[Brief description of drawings]

FIG. 1 is a graph showing the results of examples and comparative examples.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yoshiharu Kikuchi             Mitsui Chemicals Co., Ltd. 3 Chikusaigan, Ichihara, Chiba Prefecture             Inside the company (72) Inventor Taku Kanda             Mitsui Chemicals Co., Ltd. 3 Chikusaigan, Ichihara, Chiba Prefecture             Inside the company (72) Inventor Masaaki Kawasaki             Mitsui Chemicals Co., Ltd. 3 Chikusaigan, Ichihara, Chiba Prefecture             Inside the company F-term (reference) 4J002 AC01X AC02X AC03X AC06X                       AC07X AC08X AC09X AC10X                       BB15W BN06W CD20W EK016                       EK036 EK056 EK066 FD010                       FD020 FD070 FD146 FD150                       FD320 GC00 GC01 GJ02                       GL00 GM00 GM01 GN00 GN01                       GQ00 GQ01

Claims (7)

[Claims] 1. (A) ethylene (a-1) and having 3 carbon atoms
~ 20 ethylene-containing an α-olefin (a-2) and at least one norbornene compound having a terminal vinyl group represented by the following formula (1) or (2) (a-3):
α-olefin / non-conjugated polyene random copolymer rubber, (B) diene rubber, and (C) organic peroxide, and the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A)
And the weight ratio of the diene rubber (B) [(A) /
(B)] is a vulcanizable rubber composition having a ratio of 1/99 to 99/1. [Chemical 1] [In the formula (1), n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Formula (2)
In the above, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ] 2. An ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) comprises << 1 >> ethylene (a-1) and an α-olefin (a-2) having 3 to 20 carbon atoms. Molar ratio (ethylene / α-olefin) is in the range of 40/60 to 95/5, << 2 >> iodine value is in the range of 0.5 to 50, << 3 >> measured in decalin solution at 135 ° C. The vulcanizable rubber composition according to claim 1, having an intrinsic viscosity [η] of 0.5 to 10 dl / g. 3. An ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) comprises a << 1 >> ethylene (a-1) and an α-olefin (a-2) having 3 to 20 carbon atoms. Molar ratio (ethylene / α-olefin) is in the range of 40/60 to 95/5, << 2 >> iodine value is in the range of 0.5 to 50, << 3 >> measured in decalin solution at 135 ° C. Intrinsic viscosity [η] is in the range of 0.5 to 10 dl / g, << 4 >> Molecular weight distribution (Mw / Mn) measured by GPC is 3 to 50, << 5 >> Ethylene / α-olefin / non When 100 g of the conjugated polyene random copolymer rubber (A) was subjected to press-crosslinking with 0.01 mol of dicumyl peroxide at 170 ° C. for 10 minutes, the effective network chain density ν was 1.5 × 10 ^20.
1 / cm ³ or more, and << 6 >> found from the melt flow curve at 100 ° C.
The shear rate γ ₁ when showing 4 × 10 ⁶ dyn / cm ² ,
Shear rate γ ₂ when 2.4 × 10 ⁶ dyn / cm ² is shown
With the ratio γ ₂ / γ ₁ and the effective network chain density ν of << 5 >> above
Is a vulcanizable rubber according to claim 1 or 2, satisfying the following mathematical formula (I): 0.04 × 10 ^-19 ≦ Log (γ ₂ / γ ₁ ) / ν ≦ 0.20 × 10 ^-19 (I) Composition. 4. The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) has an insoluble content of 1% by weight or less after Soxhlet extraction (xylene, 3 hours, mesh: 325). The vulcanizable rubber composition according to any one of 1 to 3. 5. The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is a soluble vanadium compound represented by the following formula (3) or a vanadium halide compound represented by the following formula (4). And a catalyst containing an organoaluminum compound represented by the following formula (5) as a main component, using a polymerization temperature of 30 to 60 ° C. and a polymerization pressure of 4
~ 12 kgf / cm ² (gauge pressure), ethylene (a-
1) and a terminal vinyl group-containing norbornene compound (a-3)
Ethylene (a-1), the number of carbon atoms is 3 to 3 under the condition that the molar ratio of the supply amount of (terminal vinyl group-containing norbornene compound / ethylene) satisfies 0.01 ≤ terminal vinyl group-containing norbornene compound / ethylene ≤ 0.2 20
The vulcanizable rubber composition according to any one of claims 1 to 4, which is a copolymer of the α-olefin (a-2) and the norbornene compound having a terminal vinyl group (a-3). VO (OR ¹ ) _n X ¹ _3-n (3) VX ² ₄ (4) (In the formula (3), R ¹ is a hydrocarbon group, X ¹ is a halogen atom, and 0 ≦ n ≦ 3 is satisfied. In the formula (4), X ² is a halogen atom.) R ² _m AlX ³ _3-m (5) (In the formula (5), R ² is a hydrocarbon group and X ³ is a halogen atom. , 0 <m <3 is satisfied.) 6. The diene rubber (B) is a butadiene rubber (BR) or a styrene-butadiene copolymer rubber (SB).
R), natural rubber (NR), isoprene rubber, chloroprene rubber (CR), acrylonitrile butadiene rubber (N
BR), acrylonitrile isoprene rubber (NIR),
Acrylonitrile butadiene isoprene rubber (NBI
R), carboxylated NBR introduced with acrylic acid (X
NBR) or a mixture thereof.
A vulcanizable rubber composition according to any one of 1. 7. An organic peroxide (C) based on 100 g of a total of ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) and diene rubber (B).
7. 1 to 6 containing 0.001 to 0.05 mol.
A vulcanizable rubber composition according to any one of 1.