JPH1135635A - Rubber for hermetically sealable packing and rubber composition for sealing mouth of capacitor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject rubber composition capable of exhibiting excellent hermetically sealing property, weatherability, creep resistance, etc., by including an ethylene α-olefin-polyene amorphous copolymer exhibiting a specific structure. SOLUTION: This rubber composition comprises (A) an ethylene-α-olefin- polyene amorphous copolymer, and the non-conjugated polyene comprises a norbornene compound having a chemical structure of formula I [(n) is an integer of 0-10; R<1> is H or 1-10C alkyl; R<2> is H or 1-5C alkyl] or formula II [R<3> is H or 1-10C alkyl]. The component A preferably satisfies the following items: (i) A molar ratio (ethylene/α-olefin) of ethylene to a 3-20C α-olefin is (50/50) to (90/10) and (ii) iodine value is 0.5-50 and (iii) intrinsic viscosity in decalin solution at 135 deg.C is 1-3 dL/g. A sealing rubber composition for sealing mouths of capacitors, excellent in hermetically sealing property, weather resistance, etc., can be expected thereby.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to sealability, weather resistance,
Hermetic sealant rubber composition with excellent chemical resistance, creep resistance, heat aging resistance, organic peroxide crosslinking efficiency and sealing properties, weather resistance, chemical resistance, creep resistance, heat aging resistance,
The present invention relates to a capacitor-sealing seal rubber composition having excellent organic peroxide crosslinking efficiency.

[0002]

2. Description of the Related Art Ethylene / propylene copolymer rubber (hereinafter sometimes referred to as EPR) and ethylene / propylene / non-conjugated diene copolymer rubber (hereinafter sometimes referred to as EPDM) have excellent weather resistance and heat resistance. Because of its excellent aging properties, water resistance, chemical resistance, and low temperature flexibility, it is used for household seal packing, hot water supply packing, industrial packing, and other sealed seal packing and condenser sealing seal packing. . Since it is desired that these parts maintain their sealing properties for a long time and do not undergo heat aging (environmental degradation), they are generally crosslinked using an organic peroxide.

As a method for preventing environmental degradation, Japanese Patent Application Laid-Open
As disclosed in JP-A-3-257114 and JP-A-63-291938, the heat aging resistance can be improved by using a specific antioxidant. However, there is a problem that the compression set of the vulcanized rubber is deteriorated and the sealing property cannot be maintained for a long time. In order to prevent this, there is a method of increasing the amount of the organic peroxide crosslinking agent used,
It is disadvantageous in terms of cost. On the other hand, it is generally known that increasing the diene content, which is a crosslinking site in EPDM, improves compression set. However, this method deteriorates heat aging resistance due to an increase in thermally unstable double bonds in the rubber.

[0004]

SUMMARY OF THE INVENTION Accordingly, a rubber composition for a hermetic seal packing excellent in hermeticity, weather resistance, chemical resistance, creep resistance, heat aging resistance, and organic peroxide crosslinking efficiency, and hermeticity and weather resistance are provided. It has been desired to develop a rubber composition for a capacitor-sealing seal which is excellent in heat resistance, chemical resistance (electrolyte solution), creep resistance, heat aging resistance and organic peroxide crosslinking efficiency.
The present invention improves the above-mentioned drawbacks, that is, the sealing composition, a rubber composition for a sealing seal packing excellent in organic peroxide crosslinking efficiency, and a sealing property, which are excellent in weather resistance, chemical resistance, creep resistance, heat aging resistance, and organic peroxide. An object of the present invention is to provide a rubber composition for a capacitor-sealing seal having excellent weather resistance, chemical resistance (electrolyte solution), creep resistance, heat aging resistance, and organic peroxide crosslinking efficiency.

[0005]

According to the present invention, there is provided an ethylene / α-olefin / polyene non-polymer comprising a polyene comprising at least one norbornene compound having a terminal vinyl group represented by the following general formula [1] or [2]. A rubber composition for a seal packing, comprising the crystalline copolymer (A):

Embedded image Wherein n is an integer of 0 to 10, R ¹ is hydrogen 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.

Embedded image Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Ethylene / α-olefin / polyene amorphous copolymer (A) used in the present invention
Is that (i) the molar ratio of ethylene to α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin) is 50/50.
(Ii) an iodine value of 0.5 to
(Iii) the intrinsic viscosity in a 135 ° C decalin solution is preferably in the range of 1 to 3 dL / g, or (iv) the molecular weight distribution (Mw) measured by GPC.
/ Mn) is from 3 to 50, and (V) random copolymer 10
The effective network chain density ν when press-crosslinking at 170 ° C. for 10 minutes with 0.01 mol of dicumyl peroxide to 0 g is 1.5 × 10 ²⁰ / cm ³ or more, and (Vi) 10
0.4 × 10 ⁶ d determined from the melt flow curve at 0 ° C.
Shear rate γ ₁ when showing yn / cm ² and 2.4 × 10 ⁶ dyn / c
The ratio γ ₂ / γ ₁ of the shear rate γ ₂ when showing m ² and the effective network chain density ν are represented by the general formula [I] 0.04 × 10 ⁻¹⁹ ≦ Log (γ ₂ / γ ₁ ) / ν ≦ 0.20x
It is preferable to be within the range satisfying 10 ⁻¹⁹ [I]. Further, the ethylene / α-olefin / polyene amorphous copolymer (A) used in the present invention includes the following compounds (H) and (I), ie, (H) VO (OR) _n X _3-n (provided that R is a hydrocarbon group,
X is halogen, a soluble vanadium compound represented by 0 ≦ n ≦ 3 or a vanadium compound represented by VX ₄ , and (I) R ′ _m AlX ′ _3-m (where R ′ is a hydrocarbon group,
X 'is a catalyst containing, as a main component, a halogen, an organoaluminum compound represented by 0 <m <3), most preferably the following compounds (J) and (K), that is, (J) VOCl ₃
A soluble vanadium compound represented by the formula:
(Et) ₂ Cl / Al (Et) _1.5 Cl _1.5 (where E
an organoaluminum compound represented by t (an ethoxy group) (the blend ratio is 1/5 or more); At a polymerization temperature of 30 to 60 ° C. and a polymerization pressure of 4
-12 kgf / cm ² , and ethylene and α-olefin and the general formula [I] under the conditions of 0.01 ≦ non-conjugated polyene / ethylene ≦ 0.2 and the supply amount (molar ratio) of ethylene and non-conjugated polyene
Alternatively, it is preferable to use an ethylene / α-olefin / polyene amorphous copolymer obtained by copolymerizing the norbornene compound represented by [II]. Further, the ethylene / α-olefin / polyene amorphous copolymer (A) used in the present invention may have an insoluble content of 1% or less after Soxhlet extraction (xylene, 3 hours, mesh: 325). preferable.

According to the present invention, there is also provided the above-mentioned ethylene α-
The organic peroxide (B) is used in an amount of 0.001 mole to 0.0 mole per 100 g of the olefin / polyene amorphous copolymer (A).
There is provided a vulcanizable rubber composition comprising 5 moles.

According to the present invention, the above-mentioned ethylene α-
The reinforcing agent and / or the inorganic filler is added to 10 parts by weight of the olefin / non-conjugated polyene random copolymer.
A rubber composition is provided which is contained in an amount of from about 200 parts by weight. According to the present invention, the reinforcing agent and / or the inorganic filler are 10 to 200 parts by weight, and the softening agent is 10 to 200 parts by weight based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer. A rubber composition is provided which is contained in an amount of part by weight. The filler preferably used in the present invention is talc or clay or silica or calcium carbonate, and the compounding amount is 10 to 200 parts by weight based on 100 parts by weight of the ethylene-α-olefin / VNB copolymer rubber. Is desirable. It is desirable to add 2 to 100 parts by weight of carbon black as long as the electrical characteristics are not deteriorated.

[0008]

DETAILED DESCRIPTION OF THE INVENTION

[Function] The rubber composition for seal packing of the present invention contains an ethylene / α-olefin / polyene amorphous copolymer, and the non-conjugated polyene component is represented by the above formula [1] or [2]. It is a remarkable feature to select one composed of a norbornene compound having a chemical structure.

Various types of cyclic non-conjugated polyene such as those having a norbornene skeleton and those having a dicyclopentadiene skeleton are known, but 5-ethylidene-2-norbornene (ENB) and dicyclopentadiene When pentadiene (DCPD) is used, even if the iodine value of the copolymer falls within the range of the present invention, the permanent set is large and the heat aging resistance is extremely poor (see Comparative Examples 1 and 2 described later). ). This tendency is also observed when a linear polyene is used as the non-conjugated polyene (see Comparative Example 3 described later).

On the other hand, 5-methylene-2-norbornene (MND) and 5-vinyl-2-norbornene (V
When ND) is used, this rubber has a small permanent set and a remarkably excellent heat aging resistance (Examples 1 to 3 described later).
reference). This means that even if the iodine value is the same, that is, the content of the unsaturated bond in the copolymer is the same, the formula [1]
Alternatively, in the copolymer derived from the norbornene compound having the chemical structure of [2], it is considered that crosslinking with a peroxide is efficiently performed.

The following can be considered as a reason for this. That is, when a non-conjugated polyene is copolymerized, one ethylenic unsaturation participates in the copolymerization, and the remaining ethylenic unsaturation remains in the copolymer chain, but in the case of a cyclic non-conjugated polyene, There are cases where the remaining ethylenically unsaturated bond is in the ring and cases where it is outside the ring. It is considered that the ethylenically unsaturated bond outside the ring has a higher degree of freedom and is more reactive than the ethylenically unsaturated bond inside the ring. In the copolymer produced by the polymerization means of the present invention using the norbornene compounds having the chemical structures of the formulas [1] and [2], the proportion of ethylenically unsaturated bonds outside the ring is high, which is described above. Recognized as providing benefits.

The ethylene / α-olefin / polyene amorphous copolymer (A) used in the present invention satisfies the above requirements (i) to (iii), and preferably further satisfies (iv) to (Vi). Preferably, it is

The requirement (i) defines the composition ratio of ethylene (a) / α-olefin (b) in the copolymer. If the composition ratio is within the above range, the processability, Rubber characteristics, weather resistance, etc. can be maintained at a satisfactory level.

The requirement (ii) defines the content of unsaturated bonds in the copolymer derived from the non-conjugated polyene (c) by an iodine value, and this value is smaller than the above range. Is unfavorable because elongation becomes excessive and the permanent deformation rate increases. On the other hand, if it is too large, it is not preferable because the resistance to environmental degradation deteriorates and the cost becomes disadvantageous.

The requirement (iii) defines the molecular weight of the copolymer. If the intrinsic viscosity [η] is lower than the above range, physical properties such as mechanical properties are reduced, and the intrinsic viscosity [η] is lower than the above range. If it is too high, workability and the like tend to decrease.

The requirement (iv) defines the molecular weight distribution (Mw / Mn) of the copolymer to be used. Etc. are also good.

The requirement (V) stipulates the ease of peroxide crosslinking of the copolymer to be used or the degree of crosslinking obtained as an effective network chain density ν under a constant crosslinking condition (the measuring method will be described later). And this value is 1.5 × 10 ²⁰ pieces / cm
^If it is smaller than ³ , the elongation becomes excessive, and the creep and the permanent deformation rate increase, which is not preferable.

The requirement (Vi) indicates a balance between the shear stress dependence of the shear rate in the melt flow and the crosslinkability. The melt viscosity η is expressed by η = σ / γ, where γ is the shear rate and σ is the shear stress. The rate of increase of the shear rate per degree of increase is remarkably large, and among the central terms of the formula [I], the logarithmic value of the molecular shear rate ratio γ ₂ / γ ₁ is determined by the following equation. The value is large when the shear stress dependence of the shear rate is large, and small when the shear stress dependence is small. On the other hand, ν of the denominator represents the effective network chain density in the requirement (V), and the ratio of the two characteristic values in the range of the formula [I] indicates that the processability of the copolymer is high. It is important to maintain the heat aging resistance at an excellent level while maintaining the mechanical properties at an excellent level. That is, when this ratio is less than 0.04, workability tends to decrease, while when it exceeds 0.2, strength tends to decrease, permanent set increases, and heat aging resistance tends to decrease. .

The copolymer used in the present invention is obtained by copolymerizing ethylene (a), an α-olefin having 3 to 20 carbon atoms (b) and a non-conjugated polyene having a norbornene skeleton (c) in the above-mentioned quantitative ratio. It is manufactured at this time,
Using a catalyst comprising the soluble vanadium compound of the formula (H), particularly the soluble vanadium compound of the formula (J) and the organoaluminum compound of the formula (I), particularly the organoaluminum compound of the formula (K), 30-6
0 ° C., the polymerization pressure is 4 to 12 kgf / cm ² , and the supply amount (molar ratio) of ethylene and the non-conjugated polyene is in the range of 0.01 ≦ non-conjugated polyene / ethylene ≦ 0.2. Thereby, it can be manufactured so as to satisfy the requirements (i) to (Vi) at the same time.

[Ethylene / α-olefin / non-conjugated polyene random copolymer] The ethylene / α-olefin / non-conjugated polyene random copolymer according to the present invention comprises (a) ethylene and (b) a C3 or more carbon atom. It is a random copolymer of an α-olefin and (c) a norbornene compound represented by the general formula [I] or [II], and has the following configuration and characteristics.

The α-olefin of the above (b) is an α-olefin having 3 to 20 carbon atoms, and specifically, 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, 12-ethyl-tetradecene-1, and the like Is mentioned. These α-olefins may be used alone or
Used in combination of more than one species. Among them, α-olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene, 1-octene and the like are particularly preferably used.

The non-conjugated polyene (c) used in the present invention
Is a norbornene compound represented by the general formula [1] or [2].

Embedded image as well as

Embedded image In the formula, R ¹ is hydrogen or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ is a hydrogen atom or 1 to 5 carbon atoms.
10 alkyl groups.

As the alkyl group for R ¹ , specifically,
Specifically, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, t-pentyl, neopentyl Hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group and the like. Specific examples of the R ² alkyl group include the alkyl groups having 1 to 5 carbon atoms among the specific examples of the above R ¹ . Specific examples of the alkyl group for R ³ include the same alkyl groups as those described above for the alkyl group for R ¹ .

As the norbornene compound represented by the general formula [1] or [2], specifically, 5-methylene-
2-norbornene, 5-vinyl-2-norbornene, 5
-(2-propenyl) -2-norbornene, 5- (3-
Butenyl) -2-norbornene, 5- (1-methyl-2)
Propenyl) -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)
-Hexesyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,
2,3-trimethyl-4-pentenyl) -2-norbornene. Among them, 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.

In addition to 5-vinyl-2-norbornene, it can be used by mixing with the following non-conjugated polyene as long as the desired physical properties are not impaired. In particular,
1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-
Chain non-conjugated dienes such as hexadiene, 7-methyl-1,6-octadiene, methyltetrahydroindene,
5-ethylidene-2-norbornene, 5-methylene-2
Cyclic non-conjugated dienes such as -norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5
And trienes such as -norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, and 2-propenyl-2,2-norbornadiene.

(I) (a) Ethylene / (b) α-Olefin Component Ratio The ethylene / α-olefin / non-conjugated polyene random copolymer provided by the present invention comprises (a) ethylene-derived units and ( b) a unit derived from an α-olefin having 3 to 20 carbon atoms (hereinafter sometimes simply referred to as an α-olefin) is 50/50 to 90/10, preferably 55/45 to
85/15, particularly preferably 60/40 to 80/20
[(A) / (b)].

(Ii) Iodine value The ethylene / α-olefin / non-conjugated polyene random copolymer used in the present invention has an iodine value of 0.5 to 50.
(g / 100 g), preferably 0.8 to 40 (g / 100 g), more preferably 1 to 30, particularly preferably 1.5 to 20. If this characteristic value is too small beyond the above range, the crosslinking efficiency is small, and if it is too large, the environmental degradation resistance is poor,
Further, it is not preferable because it is disadvantageous in terms of cost.

(Iii) Intrinsic viscosity The intrinsic viscosity [η] of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber measured at 135 ° C. in decalin is from 1 to 3 dl / g, preferably from 1.5 to 2.5 d.
It is preferred to use 1 / g copolymer rubber.

(Iv) Molecular weight distribution The molecular weight distribution (Mw / Mn) of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber is from 3 to 50, preferably from 3.3 to 40, more preferably 3.5.
~ 30.

(V) Crosslink density The effective network chain density ν of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber is 1.5 × 10 ²⁰ / cm ³ or more, preferably 1.8 × 10 ²⁰ / cm ³ or more, more preferably 2.0 × 10 ²⁰ / cm ³ or more.

(Vi) Log (γ ₂ / γ ₁ ) / ν The ratio of Log (γ ₂ / γ ₁ ) of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber to the effective network chain density ν is 0.04. × 10 ^{−19 to} 0.20 × 10 ⁻¹⁹ , preferably 0.042 × 10 ^{−19 to} 0.19 × 10 ⁻¹⁹ ,
More preferably, 0.050 × 10 ^{−19 to} 0.18 × 1
It is ^0-19 or more.

The ethylene / α-olefin /
The non-conjugated polyene random copolymer may be modified with a polar monomer, but this modified product will be described in detail.

[Production method of copolymer] In the present invention,
The specific ethylene / α-olefin / non-conjugated polyene random polymer as described above can be obtained by (a) ethylene, (b) α-olefin in the presence of a catalyst containing (H) and (I) as main components.
It is obtained by random copolymerizing an olefin and (C) a norbornene compound represented by the general formula [1] or [2].

The copolymerization is carried out at a polymerization temperature of 30 to 5 using a catalyst containing the following compounds (H) and (I) as main components.
It is preferable to carry out the reaction at 0 ° C., a polymerization pressure of 5 to 8 kgf / cm ² , and a supply amount (molar ratio) of ethylene and non-conjugated polyene of 0.01 ≦ non-conjugated polyene / ethylene ≦ 0.2. (H) VO (OR) _n X _3-n (where R is a hydrocarbon group, X is halogen, 0 ≦ n ≦ 3) or a soluble vanadium compound represented by VX ₄ : (I ) R ′ _m AlX ′ _3-m (where R ′ is a hydrocarbon group,
X 'is a halogen, and an organoaluminum compound represented by 0 <m <3).

When the following catalysts (J) and (K) are used, a polymer having an insoluble content of 1% or less after Soxhlet extraction with boiling xylene (3 hours, screen: 325 mesh) is obtained. Is particularly preferred. (J) Soluble vanadium compound represented by VOCl ₃ : (K) Al (Et) ₂ Cl / Al (Et) _1.5 Cl _1.5
(However, Et is an ethoxy group) an organoaluminum compound (the blend ratio is 1/5 or more).

In the copolymerization reaction, the soluble vanadium compound component used as a catalyst component is a vanadium compound component soluble in a hydrocarbon medium of the polymerization reaction system.
Specifically, the general formula VO (OR) _{n Xb} or V (OR)
_c X _d (where R is a hydrocarbon group, 0 ≦ a ≦ 3, 0 ≦ b ≦
3, 2 ≦ a + b ≦ 3, 0 ≦ e ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c
+ D.ltoreq.4), or an electron donor adduct thereof. More specifically, VOCl ₃ , VO (OC
₂ H ₃ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ Cl, VO (O
_{-Iso-C 3 H 7) Cl} 2, VO (O-n-C
_{2 H 5) Cl 2, VO} (OC 3 H 5) 3, VOBr 3,
VOCl ₃ , VO (On-C ₄ H ₉ ) ₃ , VCl _3.
2OC ₆ H ₁₂ OH can be exemplified.

The organoaluminum compound catalyst component used in the copolymerization reaction includes at least one A in the molecule.
Compounds having an l-carbon bond can be used. For example, (i) a compound represented by the general formula R ¹ mAl (OR ² ) nHpXq (where R ¹ and R ^{2 each} usually has 1 to 15 carbon atoms)
, Preferably 1 to 4 hydrocarbon groups, which may be the same or different, X is halogen, m
Is an organic aluminum compound represented by 0 <m ≦ 3, n is 0 ≦ n ≦ 3, p is 0 ≦ p ≦ 3, and q is a number of 0 ≦ q ≦ 3, and m + n + p + q = 3). (ii) the general formula M ¹ AlR ¹ ₄ (wherein M ¹ is Li, Na, a K, R ¹ is as defined above), and the like co-alkylated product of group 1 metal and aluminum represented by it can.

The following are examples of the organoaluminum compound belonging to the above (i). General formula R ¹ _m Al (OR ³ ) _3-n (where R ¹ and R ² are the same as above; m is preferably a number of 1.5 ≦ m ≦ 3). General formula R ¹ _m AlX _3-n (where R ¹ is the same as above; X is a halogen, m is preferably 0 <m <3). Formula R ¹ _m AlH _3-n (where R ¹ is the same as above. M is preferably 2 ≦ m <3)
Is). General formula R ¹ _m Al (OR ³ ) _n Xq (where R ¹ and R ³ are the same as above; X is halogen, 0
<M ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3
) Can be exemplified.

In the aluminum compounds belonging to (i), more specifically, trialkylaluminums such as triethylaluminum and tributylaluminum; trialkylaluminums such as triisopropylaluminum; dialkylaluminums such as diethylaluminum ethoxide and dibutylaluminum butoxide Aluminum alkoxide; ethylaluminum sesquiethoxide,
In addition to alkyl aluminum sesquialkoxides such as butyl aluminum sesquibutoxide, R ¹ _1.5 Al
(OR ¹ ) Partly alkoxylated alkylaluminum having an average composition represented by _1.5 or the like; dialkylaluminum halide such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; ethylaluminum sesquichloride, butylaluminum sesquichloride Partially halogenated alkylaluminums such as alkylaluminum sesquihalides, such as ethylaluminum sesquibromide, alkylaluminum dihalides, such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide;
Partially hydrogenated alkylaluminums such as dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, alkylaluminum dihydrides such as ethylaluminum hydride and propylaluminum dihydride; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide; Partially alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxy bromide can be exemplified.

As a compound similar to (i), an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom may be used. As such a compound, for example, And the like.

Examples of the compounds belonging to the above (ii) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . Among them, it is particularly preferable to use an alkyl aluminum halide, an alkyl aluminum dihalide or a mixture thereof.

The copolymerization reaction can be carried out in a hydrocarbon medium. Examples of the hydrocarbon medium include aliphatic hydrocarbons such as hexane, heptane, octane and kerosene, and quaternary groups such as cyclohexane and methylcyclohexane. Examples thereof include hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene, and the above-mentioned polymerizable unsaturated carbon. Even a mixed medium of two or more kinds may be used.

In the method for producing an ethylene random copolymer of the present invention, the copolymerization reaction is carried out by a continuous method. At this time, the concentration of the soluble vanadium compound supplied to the polymerization reaction system is 10 times or less, preferably 7 to 1 times, more preferably 5 to 1 times, and more preferably 3 to 1 times the concentration of the soluble vanadium compound in the polymerization reaction system. The range is one time.

The ratio of aluminum atoms to vanadium atoms (Al / V) in the polymerization reaction system is 2 or more, preferably 2 to 50, particularly preferably 3 to 20. The soluble vanadium compound and the organoaluminum compound are each usually supplied after being diluted with the hydrocarbon medium. Here, the soluble vanadium compound is desirably diluted to the above concentration range, but a method is employed in which the organoaluminum compound is adjusted to an arbitrary concentration of, for example, 50 times or less the concentration in the polymerization reaction system and supplied to the polymerization reaction system. Is done.

In the copolymerization reaction, the concentration of the soluble vanadium compound in the copolymerization reaction system is usually in the range of 0.01 to 5 gram atoms / liter, preferably 0.05 to 3 gram atoms / liter as vanadium atoms. .

The copolymerization reaction is carried out at a temperature of 30 to 60 ° C., particularly 30 to 50 ° C. The copolymerization reaction is usually carried out by a continuous method. In that case, ethylene as a polymerization raw material,
α-olefin and norbornene-based polyene compound, soluble vanadium compound component of catalyst component, organoaluminum compound component and hydrocarbon medium are continuously supplied to the polymerization reaction system, and the polymerization reaction mixture is continuously released from the assembly reaction system. You. The average residence time during the copolymerization reaction varies depending on the type of polymerization raw material, the concentration and temperature of the catalyst component,
Usually, it is in the range of 5 minutes to 5 hours, preferably 10 minutes to 3 hours. The pressure during the copolymerization reaction is usually 4-1.
The pressure is maintained at ² kgf / cm ² , particularly 5 to 8 kg / cm ² , and in some cases, an inert gas such as nitrogen or argon may be present. Further, in order to adjust the molecular weight of the copolymer, a molecular weight modifier such as hydrogen may be appropriately present.

The supply ratio of ethylene and α-olefin supplied to the copolymerization varies depending on the polymerization conditions, but is usually about 20/80 to 80/20 in molar ratio.
The supply amount (molar ratio) of ethylene and non-conjugated polyene is preferably in the range of 0.01 ≦ non-conjugated polyene / ethylene ≦ 0.2. The supply and mixing of the starting olefin are controlled so that the proportion of each component in the generated ethylene-based random copolymer becomes the composition of the ethylene-based random copolymer of the present invention. The copolymerization reaction is carried out until the intrinsic viscosity of the resulting ethylene-based random copolymer reaches the intrinsic viscosity specified in the present invention.

The resulting copolymer solution obtained by the copolymerization reaction is a hydrocarbon medium solution of the ethylene random copolymer. The concentration of the ethylene random copolymer contained in the resulting copolymer solution is usually in the range of 2.0 to 20.0% by weight, preferably 2.0 to 10.0% by weight. The ethylene-based random copolymer of the present invention can be obtained by treating the resulting copolymer solution according to a conventional method.

[Modified random copolymer] In the present invention, the above-mentioned ethylene / α-olefin / non-conjugated polyene random copolymer may be graft-modified with a polar monomer. Examples of the polar monomer include a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid or a derivative thereof, a vinyl ester compound, and a chloride. Vinyl and the like.

Examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate, 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) acrylates such as meth) acrylate, polyethylene glycol mono (meth) acrylate, and 2- (6-hydroxyhexanoyloxy) ethyl acrylate; 10-undecene-1-ol; 1-octen-3-ol; -Methanol norbornene, hydroxystyrene, hydroxyethyl vinyl ether,
Hydroxybutyl vinyl ether, α-methylol acrylamide, 2- (meth) acryloyloxyethyl acid phosphate, glycerin monoallyl ether,
Allyl alcohol, allyloxyethanol, 2-butene-1,4-diol and glycerin monoalcohol.

The amino group-containing ethylenically unsaturated compound is represented by the following formula: (Wherein, R ³¹ is a hydrogen atom, a methyl group or an ethyl group, and R ³² is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and 6 to 12 carbon atoms, preferably 6 to 8. The alkyl group and the cycloalkyl group may further have a substituent.) Or a vinyl group having at least one kind of a substituted amino group. Monomers can be mentioned. Examples of such an amino group-containing ethylenically unsaturated compound include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, and phenylamino methacrylate. Alkyl or methacrylic acid alkyl ester derivatives such as ethyl and cyclohexylaminoethyl methacrylate, N
Vinylamine derivatives such as -vinyldiethylamine, N-acetylvinylamine, allylamine derivatives such as allylamine, methacrylamine, N-methylacrylamine, N, N-dimethylacrylamide, N, N-dimethylaminopropylacrylamide, acrylamide, Acrylamide derivatives such as N-methylacrylamide; aminostyrenes such as p-aminostyrene; 6-aminohexylsuccinimide; 2-aminoethylsuccinimide;

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. Such epoxy group-containing ethylenically unsaturated compounds include, for example, glycidyl acrylate, glycidyl methacrylate, etc., 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,
Mono- and diglycidyl esters of endo-cis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid ^™ ), endo-cis-bicyclo [2,
2,1] mono- and diglycidyl esters of hept-5-ene-2-methyl-2,3-dicarboxylic acid (methylnadic acid ^TM ), mono- and alkylglycidyl esters of dicarboxylic acids such as mono- and glycidyl esters of allylsuccinic acid ( In the case of monoglycidyl ester, the alkyl group has 1 to 12 carbon atoms, alkyl glycidyl ester of p-styrene carboxylic acid, allyl glycidyl 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.

The aromatic vinyl compound has the following formula: (In the formula, Φ is a phenyl group, and R ¹ is each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, or an isopropyl group. R ² is a carbon atom. 1 to 3 hydrocarbon groups or halogen atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a chlorine atom, a bromine atom, and an iodine atom, where n is usually 0 to 5, preferably It is an integer of 1 to 5.). Examples of such an aromatic vinyl compound include 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-vinylpyridine, 2-isopropenylpyridine, 2-vinylquinoline, 3-vinylisoquinoline,
N-vinyl carbazole and N-vinyl pyrrolidone.

Examples of 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 ] Unsaturated carboxylic acids such as hept-2-ene-5,6-dicarboxylic acid and derivatives thereof (for example, acid anhydrides, acid halides, amides, imides, esters and the like). Examples of the derivative include maleenyl chloride, maleenyl imide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride. Dimethyl maleate, monomethyl maleate, ethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo [2,
2,1] hept-2-ene-5,6-dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate, aminopropyl methacrylate and the like. It is. Among these, (meth) acrylic acid, maleic anhydride, hydroxyethyl (meth) acrylate, glycidyl methacrylate, and aminopropyl methacrylate are preferred.

Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate,
Examples thereof include vinyl persatic acid, vinyl laurate, vinyl stearate, vinyl benzoate, pt-butyl vinyl benzoate, vinyl salicylate, vinyl chlorohexanecarboxylate, and the like.

[Preparation of Modified Random Copolymer] The modified random copolymer is obtained by graft-polymerizing a polar monomer to the above random copolymer.
When grafting the above-mentioned polar monomer to the random copolymer, the polar monomer is usually 1 to 100 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the random copolymer. Used in quantity.

The graft polymerization is usually performed 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, and 2,5-dimethyl-2,5. -Bis (t-butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) bararate, benzoyl peroxide, t-butylperoxide Oxybenzoate, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide and 2,4-dichlorobenzoyl peroxide, m-toluyl peroxide Oxide and the like. Examples of the azo compound include azoisobutyronitrile and dimethylazoisobutyronitrile. The radical initiator is desirably used in an amount of about 0.001 to 10 parts by weight based on 100 parts by weight of the random copolymer.

The radical initiator can be used as it is by mixing it with the random copolymer and the polar monomer, but can also be used after dissolving it in a small amount of an organic solvent. As the organic solvent, any organic solvent capable of dissolving a radical initiator can be used without any particular limitation. Examples thereof include aromatic hydrocarbon solvents such as benzene, toluene and xylene, pentane, hexane, heptane, and 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-propynol, iso-propanol, n-butanol, sec-butanol and t
alcohol solvents such as ert-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 dioxyanisole An ether solvent such as

When grafting a polar monomer onto the random copolymer, a reducing substance may be used.
When a reducing substance is used, the graft amount of a polar monomer can be improved. Iron (II) as a reducing substance
Ion, chromium ion, cobalt ion, nickel ion, palladium ion, sulfite, hydroxyamine,
Hydrazine, more -SH, SO ₃ H, -NHN
Compounds containing groups such as H ₂ and —COCH (OH) — are exemplified. As such a reducing substance, specifically, ferrous chloride, potassium dichromate, cobalt chloride,
Cobalt naphthenate, palladium chloride, ethanolamine, diethanolamine, N, N-dimethylaniline,
Hydrazine, ethyl mercaptan, benzenesulfonic acid, p-toluenesulfonic acid and the like can be mentioned. In the present invention, the reducing substance is used in an amount of usually 0.001 to 5 parts by weight, preferably 0.1 to 100 parts by weight of the random copolymer.
It can be used in an amount of up to 3 parts by weight.

The graft modification of the random copolymer with a polar monomer can be carried out by a conventionally known method. For example, the random copolymer is dissolved in an organic solvent, and then the polar monomer and a radical initiator are added to the solution. 70
At a temperature of from 200 to 200 ° C, preferably from 80 to 190 ° C.
The reaction can be carried out for 5 to 15 hours, preferably 1 to 10 hours. The organic solvent is not particularly limited as long as it is an organic solvent capable of dissolving the random copolymer. Examples thereof include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and aliphatic hydrocarbons such as pentane, hexane, and heptane. A system solvent or the like can be used.

A modified random copolymer can also be produced by reacting a random copolymer with a polar monomer without using a solvent using an extruder or the like. This reaction is usually performed at a temperature equal to or higher than the melting point of the random copolymer, specifically, from 120 to 2
It is usually desirable to carry out at a temperature of 50 ° C. for usually 0.5 to 10 minutes.

The amount of modification (graft amount of polar momer) of the modified random copolymer thus obtained is usually 0.1.
It is desirably 1 to 50% by weight, preferably 0.2 to 30% by weight.

[Vulcanizable Rubber Composition] The ethylene / α-olefin / polyene random copolymer of the present invention can be used as it is in an unvulcanized state. Characteristics can be exhibited.
The copolymer according to the present invention can be vulcanized by a method of heating using a vulcanizing agent or a method of irradiating an electron beam without using a vulcanizing agent.

The ethylene / α-olefin / polyene random copolymer of the present invention may contain other components as appropriate according to the purpose. In this rubber composition, the ethylene / α-olefin / polyene random copolymer is used. The copolymer is
It is desirable that the content is 20% by weight or more, preferably 25% by weight or more in the whole rubber composition. Further, as other components, for example, a compound constituting a foaming system such as a reinforcing agent, an inorganic filler, a softener, an antioxidant (stabilizer), a processing aid, a foaming agent, a foaming aid, a plasticizer, Various chemicals such as coloring agents and other rubber compounding agents can be exemplified. The type and content of the other components are appropriately selected depending on the application. Among them, it is particularly preferable to use a reinforcing agent, an inorganic filler, a softening agent, and the like, which will be described below more specifically.

[Reinforcing Agent and Inorganic Filler] As the reinforcing agent, specifically, SRF, GPF, FEF, MAF, H
Examples thereof include carbon blacks such as AF, ISAF, SAF, FT, and MT, those obtained by subjecting these carbon blacks to surface treatment with a silane coupling agent, silica, activated calcium carbonate, fine talc, and fine silicates.

Specific examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc, clay and the like.

The rubber composition may contain a reinforcing agent and / or an inorganic filler in an amount of 10 to 200 parts by weight, preferably 10 to 180 parts by weight, based on 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A). It can be contained in an amount. From a rubber composition containing such an amount of a 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.

[Softeners] As softeners, softeners conventionally compounded in rubbers are widely used, and specific examples include petroleum softeners such as process oils, lubricating oils, paraffin, liquid paraffin, petroleum asphalt, and petrolatum. Agents, coal tar softeners such as coal tar and coal tar pitch, fatty oil softeners such as castor oil, linseed oil, rapeseed oil and coconut oil, waxes such as tall oil, sub, beeswax, carnauba wax, lanolin , Ricinoleic acid, palmitic acid, barium stearate, calcium stearate,
Fatty acids and fatty acid salts such as zinc laurate, petroleum resins, synthetic high molecular substances such as atactic polypropylene and coumarone indene resin are used. Of these, petroleum softeners are preferred, and process oils are particularly preferred. The rubber composition is prepared by adding the above softener to the ethylene / α-olefin / polyene copolymer (A) 100
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.

[Antiaging Agent] The rubber or rubber composition exhibits excellent heat resistance and durability even without using an antiaging agent. Is possible as in the case of ordinary rubber. Antioxidants used in this case include:
Examples include amine antioxidants, phenol antioxidants, and sulfur antioxidants.

Examples of the amine-based antioxidant include naphthylamine-based antioxidants such as phenyl-α-naphthylamine and phenyl-β-naphthylamine;
(P-toluenesulfonylamide) -diphenylamine, 4,4- (α, α-dimethylbenzyl) diphenylamine, 4,4′-dioctyldiphenylamine, high-temperature reaction product of diphenylamine and acetone, low-temperature reaction of diphenylamine and acetone Reaction product, low-temperature reaction product of diphenylamine and aniline with acetone, reaction product of diphenylamine and diisobutylene, octylated diphenylamine, dioctylated diphenylamine,
diphenylamine-based antioxidants such as p, p'-dioctyldiphenylamine and alkylated diphenylamine;
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-methylheptyl) -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-
and p-phenylenediamine-based antioxidants such as p-phenylenediamine. Specific examples of the phenolic antioxidant include styrenated phenol, 2,6
-Di-t-butyl-4-methylphenol, 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
-Thio-bis- (4-methyl-6-t-butylphenol), 4,4'-thio-bis- (3-methyl-6-t-
Butylphenol), 4,4'-thio-bis- (2-methyl-6-butylphenol), 4,4'-thio-bis- (6-t-butyl-3-methylphenol), bis (3-methyl- 4-hydroxy-5-t-butylbenzene) sulfide, 2,2-thio [diethyl-bis-3-
(3,5-di-t-butyl-4-hydroxyphenol) propionate], bis [3,3-bis (4′-hydroxy-3′-t-butylphenol) butyric 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'-hexamethylene-bis (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-methyl Benzyl) phenol, tri (α-methylbenzyl) phenol, bis (2′-hydroxy-3′-t-butyl-5′-methylbenzyl) 4-methyl-phenol, 2,5-di-t-
Amyl hydroquinone, 2,6-di-butyl-α-dimethylamino-p-cresol, 2,5-di-t-butylhydroquinone, diethyl ester of 3,5-di-t-butyl-4-hydroxybenzylphosphoric acid , Catechol,
Hydroquinone and the like can be mentioned.

Examples of the sulfur-based antioxidants include 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, and zinc salt of 2-mercaptomethylbenzimidazole. , 2-mercaptomethylimidazole zinc salt, dimistyl thiodipropionate, dilauryl thiodipropionate, disterial thiodipropionate, ditridecyl thiodipropionate, pentaerythritol-tetrakis- (β-lauryl- Thiopropionate) and the like.

These antioxidants can be used alone or in combination of two or more. The amount of such an antioxidant is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A). It is desirable to use parts by weight.

[Processing Aids] As processing aids, those generally blended with rubber as processing aids 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 and esters. Processing aids are ethylene, α-olefin,
It can be suitably used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the polyene copolymer.

[Vulcanizing Agent] When the rubber composition is vulcanized by heating, a vulcanizing system such as a vulcanizing agent, a vulcanization accelerator and a vulcanization aid is usually included in the rubber composition. Compound the compound. As the vulcanizing agent, sulfur, sulfur-based compounds, organic peroxides and the like can be used. Among these, an organic peroxide which is a vulcanizing agent having excellent heat aging resistance is preferable.

The form of sulfur is not particularly limited, and for example, powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like can be used. Specific examples of the sulfur-based compound include sulfur chloride, sulfur dichloride, polymer polysulfide, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dimethyldithiocarbamate.

As the organic peroxide, specifically,
Dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide,
Di-t-amyl peroxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxin) hexyne-3,2,5-dimethyl-
2,5-di (benzoylperoxy) hexane, 2,5
-Dimethyl-2,5-mono (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-
Dialkyl peroxides such as isopropyl) benzene; t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxybivalate, t-butylperoxymaleic acid, t-butylperoxyneodecano Ethate, t-butyl peroxybenzoate, di-t-butyl peroxyphthalate, 1,1
Peroxyesters such as -bis-t-butylperoxy-3,3,5-tri-methylcyclohexane; ketone peroxides such as dicyclohexanone peroxide; and mixtures thereof. Among them,
Organic peroxides having a half-life of 1 minute at a temperature in the range of 130 ° C. to 200 ° C. are preferred, and in particular, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3. , 5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide, t-butyl hydroperoxide,
2,5-dimethyl-2,5-di (t-butylperoxin) hexyne-3, 2,5-dimethyl-2,5-mono (t-butylperoxy) hexane, 1,1-bis-t
Organic peroxides such as -butylperoxy-3,3,5-tri-methylcyclohexane are preferably used.

When the vulcanizing agent is sulfur or a sulfur compound, 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A) is used. When it is an organic peroxide in an amount of parts by weight, 0.001 to 0.05 mol, preferably 0.002 to 0.02 mol, per 100 g of the ethylene / α-olefin / polyene copolymer (A). Is desirably used in an appropriate amount.

[Vulcanization Accelerator] When sulfur or a sulfur compound is used as the vulcanization agent, it is preferable to use a vulcanization accelerator in combination. As the vulcanization accelerator, specifically,
Sulfenamide compounds such as N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene-2-benzothiazolesulfenamide, N, N-diisopropyl-2-benzothiazolesulfenamide, 2-mercaptobenzo Thiazole, 2-
(2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio)
Benzothiazole, dibenzothiazyl disulfide, 2
A thiazole compound such as-(4'-morpholinodithio) benzothiazole, a guanidine compound such as diphenylguanidine, triphenylguanidine, diorsonitrile guanidine, orthonitrile biguanide, diphenylguanidine phthalate, an acetaldehyde-aniline reactant, butyraldehyde -Aniline condensate, aldehyde amine or aldehyde-ammonia compound such as hexamethylenetetramine, acetaldehyde ammonia, imidazoline compound such as 2-mercaptoimidazoline (ethylenethiourea), thiocarbanilide,
Thiourea compounds such as diethylthiourea, dibutylthiourea, trimethylthiourea, and diorthotolylthiourea, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide,
Thiuram compounds such as pentamethylenethiuram tetrasulfide, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, dimethyldithiocarbamate Examples thereof include dithioate compounds such as selenium and tellurium dimethyldithiocarbamate, xanthate compounds such as zinc dibutylxanthate, and zinc white. Vulcanization accelerators such as those described above are ethylene / α-olefin /
0.1 parts by weight based on 100 parts by weight of the polyene copolymer (A)
It is desirable to use in an amount of from 20 to 20 parts by weight, preferably from 0.2 to 10 parts by weight.

[Vulcanization Aid (Polyfunctional Monomer)]
When an organic peroxide is used as the vulcanizing agent, the vulcanizing aid (polyfunctional monomer) is used in an amount of 0.5 to 2 mol, preferably approximately equimolar, to 1 mol of the organic peroxide. Is preferred. Specific examples of the vulcanization aid include sulfur, quinone dioxime compounds such as p-quinone dioxime, (meth) acrylate compounds such as trimethylolpropane triacrylate and polyethylene glycol dimethacrylate, diallyl phthalate, triaryl Examples include allyl compounds such as allyl cyanurate, maleimide compounds such as m-phenylene bismaleimide, divinylbenzene, and the like. In the present invention, among the above vulcanizing agents, it is preferable to use sulfur or a sulfur-based compound, particularly sulfur, because the excellent properties of the rubber composition can be exhibited.

[Foaming agent] When the rubber composition contains a compound constituting a foaming system such as a foaming agent and a foaming aid,
It can be foam molded. As the foaming agent, foaming agents generally used when foaming rubber can be widely used, and specifically, sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite and the like Inorganic blowing agent, N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N '
A nitroso compound such as dinitrosopentamethylenetetramine, an azo compound such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate, benzenesulfonylhydrazide, toluenesulfonylhydrazide, p, p'-oxybis (benzenesulfonylhydrazide), diphenylsulfone-3,3'-
Sulfonyl hydrazide compounds such as disulfonyl hydrazide; and azide compounds such as calcium azide, 4,4-diphenyldisulfonyl azide, and p-toluenesulfonyl azide. Of these, nitroso compounds, azo compounds and azide compounds are preferred. The blowing agent is ethylene / α-olefin / polyene copolymer 10
0.5 to 30 parts by weight, preferably 1 to 0 parts by weight,
It can be used in an amount of 20 parts by weight. From the rubber composition containing the foaming agent in such an amount, an apparent specific gravity of 0.0
It is possible to produce a foam 3~0.8g / cm ^3.

A foaming aid can be used together with the foaming agent. When the foaming aid is used in combination, the foaming agent has effects such as lowering the decomposition temperature, accelerating the decomposition, and making the bubbles uniform. Examples of such a foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid and oxalic acid, urea and derivatives thereof. The foaming aid is used in an amount of 0.0 to 100 parts by weight of the ethylene / α-olefin / polyene copolymer.
It can be used in an amount of 1 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

[Other Rubbers] The rubber composition according to the present invention comprises:
As long as the object of the present invention is not impaired, it can be used by blending with other known rubbers. Examples of such other rubbers include natural rubber (NR), isoprene rubber such as isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-
Butadiene rubber (NBR), chloroprene rubber (CR)
And conjugated diene rubbers. Further, conventionally known ethylene / α-olefin copolymer rubbers can also be used, for example, ethylene / propylene random copolymer (EPR), ethylene / α-olefin other than the above-mentioned ethylene / α-olefin / polyene copolymer. -A polyene copolymer, for example, EPDM can be used.

The vulcanizable rubber composition according to the present invention can be prepared from an ethylene / α-olefin / polyene copolymer and other components as described above by a general method for preparing a rubber compound. it can. For example, using an internal mixer such as a Banbury mixer, a kneader or an intermix, ethylene / α-olefin /
After kneading the polyene copolymer and other components at a temperature of 80 to 170 ° C. for 3 to 10 minutes, if necessary, a vulcanizing agent,
It can be prepared by adding a vulcanization accelerator or a vulcanization aid, kneading at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes using a roll such as an open roll or a kneader, and then dispensing. it can. In this way, a rubber composition (compounded rubber) usually in the form of a ribbon or sheet is obtained. When the kneading temperature in the above internal mixers is low, a vulcanizing agent, a vulcanization accelerator, a foaming agent and the like can be kneaded at the same time.

[Vulcanized Rubber] The vulcanized product (vulcanized rubber) of the rubber composition according to the present invention is obtained by subjecting the unvulcanized rubber composition as described above to an extrusion molding machine, a calender roll, a press, or the like. It is preformed into a desired shape by various molding methods such as injection molding machines and transfer molding machines, and is vulcanized by heating at the same time as molding or by introducing the molded product into a vulcanization tank, or by irradiating an electron beam. Can be obtained.

When the above rubber composition is vulcanized by heating, a heating tank of a heating form such as hot air, a fluidized bed of glass beads, UHF (ultra-high frequency electromagnetic wave), steam, or LCM (hot molten salt tank) is used. At a temperature of 150 to 270 ° C.
Heating for 30 minutes is preferred.

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

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

The vulcanized rubber molded and vulcanized as described above is useful as a hermetic seal packing in various building structures, various machines, various electric products, various vehicles, various containers and the like.

[0089]

EXAMPLES 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 measurements in the following examples were performed as follows. [Composition] The composition of the copolymer was measured by ¹³ C-NMR method. [Iodine value] It was determined by a titration method. [Intrinsic viscosity] The intrinsic viscosity [η] was measured at 135 ° C in decalin. [Molecular weight distribution] Weight average molecular weight Mw determined by GPC
/ Number average molecular weight Mn. [Γ ₂ / γ _1] at 100 ° C. Melt flow - Ca - determine the blanking shows shear rate gamma ₁ and 2.4 × 10 ⁶ dyn / cm ² at the time showing a 0.4 × 10 ⁶ dyn / cm ² The ratio of the shear rate γ ₂ at that time was determined. L / D = 60 mm / 3 mm [Effective mesh chain density] JIS K 6258 (1993)
Year), immerse in toluene at 37 ° C for 72 hours,
The effective network chain density was calculated from the ory-Rehner equation. ν _R : volume fraction of pure rubber with respect to the volume of pure rubber in the swollen vulcanized rubber (volume of pure rubber + volume of absorbed solvent), μ: rubber-solvent interaction constant (0.49) V ₀ : Solvent molecular volume ν (pieces / cm ³ ): effective network chain density. Number of effective network chains in 1 cm ^{3 of} pure rubber Preparation of sample: To 100 g of random copolymer, 0.01 mol of dicumyl peroxide was added, and at a kneading temperature of 50 ° C., 8-inthiopun roll was used. Kneading was performed according to the method described in SRIS, and the obtained sample was
Produced 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 determined by calculation.

[0092]

[Table 1]

[0093]

[Table 2]

Example 1 An ethylene / α-olefin / polyene amorphous copolymer (Example 1) produced under the conditions shown in Table 1 and having the composition and physical properties shown in Table 1 was used. Using a 1.7 liter Banbury mixer, the compounding ingredients shown in Table 2 were used in an amount of 140 to 1
The mixture was kneaded at a temperature of 50 ° C. for 5 minutes to obtain a blend (1).

[0095]

[Table 3] * 1: Ethylene / propylene / 5-vinyl-2-norbornene copolymer rubber (1) Copolymer rubber described in Table 2 Ethylene / propylene (molar ratio) = 74/26 Intrinsic viscosity measured in decalin at 135 ° C. [ η] = 1.97dl / g Iodine value = 3.1 # 35 (trademark) * 5: Fujitalc Co., Ltd., LMG-100 * 6: polyethylene glycol, molecular weight = 4000 * 7: Ouchi Shinko Chemical Co., Ltd., Nocrack MB (trademark)

Next, the compound (1) was wound around an 8-inch open roll (manufactured by Nippon Roll Co., Ltd.), and a compounding agent was added on the open roll so as to have a compounding formula shown in Table 3 below. After kneading for 3 minutes, take out the sheet and thickness 3
mm sheet was obtained. At this time, the roll surface temperature was 50 ° C. for the front roll and 60 ° C. for the rear roll.

[0097]

[Table 4] * 9: Mitsui Petrochemical Industries, Ltd., Mitsui DCP-40C (trademark) Dicumyl peroxide (concentration: 40%) * 10: Seiko Chemical Co., Ltd., Hicross M (trademark)

The compound (2) obtained as described above was heated at a mold temperature of 180 ° C. for 10 minutes using a press molding machine (manufactured by Kotaki Seiki Co., Ltd.) to obtain a vulcanized sheet having a thickness of 2 mm. And used for measurement of modulus, tensile properties, crosslink density, and aging properties.

The measuring methods are as follows. (1) Modulus According to JIS K 6301, a tensile test was performed under the conditions of a measurement temperature of 25 ° C., a tensile speed of 50 mm / min and 100 mm / min, and a modulus M ₂₅ when the vulcanized sheet was stretched by 50% was measured. (2) in accordance Tensile properties JIS K 6301, measurement temperature 25 ° C., subjected to tensile test at a tensile rate of 500 mm / min condition was measured elongation E _B and strength T _B at break of the vulcanized sheet. (3) Effective network chain density (index of crosslinking density) According to JIS K 6301, the vulcanized sheet was immersed in toluene at 37 ° C, and the effective network chain density was calculated from the following equation. υ _R : Volume fraction of pure rubber to volume of pure rubber swollen in swollen vulcanized rubber (volume of pure rubber + volume of absorbed solvent) μ: interaction constant between rubber and solvent (0.49) V ₀ : molecular volume of the solvent ν (pieces / cm ³ ): effective network chain concentration. The number of effective mesh chains in 1 cc of pure rubber. (4) Compression set (CS) Conforms to JIS (5) Aging properties According to JIS K6301, the vulcanized sheet is placed in an oven at 175 ° C. for 168 hours to age, and then measured at a temperature of 2
A tensile test was performed at 5 ° C. and a tensile speed of 500 mm / min, and the elongation and strength at break of the vulcanized sheet were measured. The tensile strength retention A _R (T _B ) and the elongation retention A _R (E _B ) was calculated. (6) Formability (a) Rollability The kneaded material kneaded by the above method was left at room temperature for 24 hours. Using an 8-inch open roll, 1.5 kg of the kneaded material was maintained at a roll temperature of 50 ° C. and a roll gap of 5 mm, the state of winding around the roll was observed, and the roll workability was evaluated on a 5-point scale. [Five-level evaluation] 5 The rubber band is completely adhered to the roll, and the band is rotating smoothly. 4... The band sometimes separates from the roll surface from the top of the roll to the bank. 3 The band separates from the roll surface from the top of the roll to between the banks. 2 ... The band does not adhere to the roll surface, and the roll cannot be processed without hand. 1 ··· The band hangs down without adhering to the roll surface at all and cannot be rolled without hand. Table 4 shows the results.

Example 2 In Example 1, the ethylene-propylene-
Instead of 5-vinyl-2-norbornene copolymer rubber (1), the following ethylene / propylene / 5-vinyl-2-norbornene copolymer rubber (2) produced under the conditions shown in Table 1
The procedure was performed in the same manner as in Example 1 except that Ethylene / propylene / 5-vinyl-2-norbornene copolymer rubber (2): ethylene / propylene (molar ratio) = 75/25 Intrinsic viscosity [η] measured in 135 ° C. decalin = 1.8
3dl / g Iodine value = 10.9 The results are shown in Table 4.

Example 3 In Example 1, the ethylene propylene
The following ethylene-propylene / 5-vinyl-2-norbornene copolymer rubber (3) produced under the conditions shown in Table 1 in place of the 5-vinyl-2-norbornene copolymer rubber (1)
The procedure was performed in the same manner as in Example 1 except that Ethylene / propylene / 5-hydroxy-2-norbornene copolymer rubber (3): ethylene / propylene (molar ratio) = 75/25 Intrinsic viscosity [η] measured in 135 ° C decalin = 2.1 Iodine value = 8 Table 4 shows the results.

Comparative Example 1 In Example 1, the ethylene propylene
Except that instead of the 5-vinyl-2-norbornene copolymer rubber (1), the following ethylene-propylene-DCPD copolymer rubber (ratio -1) produced under the conditions shown in Table 1, was used. Performed in the same manner as in Example 1. Ethylene / propylene / DCPD copolymer rubber (ratio-
1): Ethylene / propylene (molar ratio) = 66/34 Intrinsic viscosity [η] measured at 135 ° C. in decalin = 1.8.
5dl / g Iodine value = 12.0 The results are shown in Table 3.

Comparative Example 2 In Example 1, the ethylene propylene
Except that instead of the 5-vinyl-2-norbornene copolymer rubber (1), the following ethylene-propylene-ENB copolymer rubber (ratio-2) produced under the conditions shown in Table 1, was used. Performed in the same manner as in Example 1. Ethylene / propylene / ENB copolymer rubber (ratio-
2): Ethylene / propylene (molar ratio) = 66/34, intrinsic viscosity [η] measured at 135 ° C. in decalin = 1.9
8dl / g iodine value = 13.0 The results are shown in Table 4.

Comparative Example 3 In Example 1, the ethylene propylene
The procedure was performed in the same manner as in Example 1 except that the following ethylene-propylene / 1,4-hexadiene copolymer rubber (ratio -3) was used instead of the 5-vinyl-2-norbornene copolymer rubber (1). Was. Ethylene / propylene / 1,4 hexadiene copolymer rubber (ratio-3): Ethylene / propylene (molar ratio) = 67/33 Iodine value = 12.0 Ratio-3: DuPont 1040 (trademark) Table 4 shows the results.

[Table 5]

[0105]

EFFECT OF THE INVENTION The vulcanizable rubber composition according to the present invention containing an ethylene / α-olefin / non-conjugated polyene random copolymer has a sealing property, weather resistance, chemical resistance, creep resistance and heat aging. To provide a sealed sealing rubber composition having excellent sealing properties, organic peroxide crosslinking efficiency, and a capacitor-sealing seal rubber composition having excellent sealing properties, weather resistance, chemical resistance, heat aging resistance, and organic peroxide crosslinking efficiency. be able to.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 3/34 C08K 3/34 5/00 5/00 5/01 5/01 5/14 5/14 C08L 23/08 C08L 23/08 23 / 16 23/16 C09K 3/10 C09K 3 / 10Z (72) Inventor Tetsuo Tojo 3rd Chigusa Beach, Ichihara-shi, Chiba Mitsui Oil Chemicals Co., Ltd.

Claims (9)

[Claims] 1. An ethylene / α-olefin / polyene polyene comprising at least one kind of norbornene compound having a terminal vinyl group represented by the following general formula [1] or [2]:
A rubber composition for a seal packing, comprising a polyene amorphous copolymer (A): Wherein n is an integer of 0 to 10, R ¹ is hydrogen 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. 2] [Wherein, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms]. 2. An ethylene / α-olefin / polyene amorphous copolymer (A) comprising: (i) a molar ratio of ethylene to an α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin) of 50; / 50-9
(Ii) iodine value in the range of 0.5 to 50, (iii) intrinsic viscosity in decalin solution at 135 ° C. of 1 to 3
2. The rubber composition for a seal packing according to claim 1, wherein the rubber composition is in the range of dL / g. 3. An ethylene / α-olefin / polyene amorphous copolymer (A) comprising: (i) a molar ratio of ethylene to an α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin) of 50 / 50-9
(Ii) iodine value in the range of 0.5 to 50, (iii) intrinsic viscosity in decalin solution at 135 ° C. of 1 to 3
(iv) the molecular weight distribution (Mw / Mn) measured by GPC is 3 to 5;
And (V) 100 g of the random copolymer.
An effective network chain density ν of 1.5 × 10 ²⁰ when press-crosslinked at 170 ° C. for 10 minutes using 0.01 mol of oxide.
And the number / cm ³ or more, melt flow at 100 ℃ (Vi) - 0 determined from Bed - mosquito.
Shear speed γ ₁ when showing 4 × 10 ⁶ dyn / cm ² and 2.4 ×
The ratio γ ₂ / γ ₁ of the shear rate γ ₂ when showing 10 ⁶ dyn / cm ² and the effective network chain density ν are represented by the general formula [III]: 0.04 × 10 ⁻¹⁹ ≦ Log (γ ₂ / γ ₁₎ ) /Ν≦0.20×
The rubber composition for a seal packing according to claim 1, wherein the rubber composition satisfies 10 ^-19 [III]. 4. Using a catalyst containing the following compounds (H) and (I) as main components, a polymerization temperature of 30 to 60 ° C., a polymerization pressure of 4 to 12 kgf / cm ² , and a supply amount of ethylene and a non-conjugated polyene. (Molar ratio) under the condition of 0.01 ≦ non-conjugated polyene / ethylene ≦ 0.2, ethylene, α-olefin and general formula [I]
4. The rubber composition for a seal packing according to claim 3, wherein an ethylene / α-olefin / polyene amorphous copolymer obtained by copolymerizing a norbornene compound represented by [II] is used. H) Soluble vanadium compound represented by VO (OR) _n X _3-n (where R is a hydrocarbon group, X is halogen, 0 ≦ n ≦ 3) or vanadium compound represented by VX ₄ : (I) R ' _m AlX' _3-m (where R 'is a hydrocarbon group, X'
Is a halogen, and an organoaluminum compound represented by 0 <m <3). 5. Soxhlet extraction (xylene, 3 hours,
The insoluble matter after the mesh: 325) is 1% or less.
4. The rubber composition for a seal packing according to item 1. 6. Using a catalyst containing the following compounds (J) and (K) as main components, a polymerization temperature of 30 to 60 ° C., a polymerization pressure of 4 to 12 kgf / cm ² , and a supply amount of ethylene and a non-conjugated polyene. (Molar ratio) under the condition of 0.01 ≦ non-conjugated polyene / ethylene ≦ 0.2, ethylene, α-olefin and general formula [I]
4. The rubber composition for a seal packing according to claim 3, wherein an ethylene / α-olefin / polyene amorphous copolymer obtained by copolymerizing a norbornene compound represented by [II] is used. J) Soluble vanadium compound represented by VOCl ₃ : (K) Al (Et) ₂ Cl / Al ₂ (Et) _1.5 Cl
_An organoaluminum compound represented by _1.5 (where Et is an ethoxy group) (the blend ratio is 1/5 or more). 7. An organic peroxide of 0.1 g per 100 g of the amorphous ethylene / α-olefin / polyene copolymer (A).
The vulcanizable rubber composition according to any one of claims 1 to 6, wherein 001 mol to 0.05 mol is blended. 8. The method according to claim 1, wherein the reinforcing agent and / or the inorganic filler are contained in an amount of 10 to 200 parts by weight based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer. Item 7. The rubber composition according to Item 6. 9. An amount of 10 to 200 parts by weight of a reinforcing agent and / or an inorganic filler and 10 to 200 parts by weight of a softening agent based on 100 parts by weight of an ethylene / α-olefin / non-conjugated polyene random copolymer. The rubber composition according to claim 6, wherein the rubber composition is contained.