JP2001279027A - Crosslinkable rubber composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a crosslinkable rubber composition having a high crosslinking rate, excellent in productivity of a crosslinked rubber molded product, capable of performing hot-air crosslinking with hot air vulcanization tank(HAV), ultrahigh frequency(UHF), etc., and excellent in characteristics such as scorch resistance, compression set properties, strength characteristics and heat, weather and abrasion resistances. SOLUTION: This crosslinkable rubber composition is crosslinkable with hot air and is capable of providing a crosslinked rubber sheet obtained by molding the composition into a sheetlike form and then crosslinking the molded sheet with the hot air without damaging the surface at all by pencil hardness tests with a pencil of HB hardness and having <=70% compression set after heat treatment at 150 deg.C for 22 h, <=1 dN.m scorch index and >=2.5 dN.m crosslinking torque. The composition comprises an ethylene-α-olefin.nonconjugated polyene random copolymer rubber, a cyclic polysiloxane compound having at least 2 SiH groups in one molecule, a catalyst and, as necessary, an alkenyl group-containing organopolysiloxane, a polyolefin resin and a reactional inhibitor. The cross-linked rubber molded product (including a foam) composed of the composition is used in applications such as an automotive weather strip.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinkable (vulcanizable) rubber composition and its use. More specifically, the present invention relates to a HAV (hot air vulcanizing tank), a UHF (ultraviolet) and a high crosslinking rate and excellent productivity. A crosslinkable rubber composition that is capable of hot-air cross-linking (ultra-high-frequency electromagnetic waves) and has excellent properties such as scorch resistance, compression set, strength properties, heat resistance, weather resistance, and wear resistance. For use.

[0002]

BACKGROUND OF THE INVENTION Ethylene / α-olefin / non-conjugated polyene random copolymer rubbers such as EPDM are generally excellent in weather resistance, heat resistance and ozone resistance, and are used for industrial parts for automobiles and industrial rubbers. It is used for products, electrical insulating materials, civil engineering and building materials, rubberized fabrics, etc.

[0003] Conventional ethylene / α-olefin / non-conjugated polyene random copolymer rubber has a drawback that its compression set is inferior to silicone rubber and the like. As a method of solving this drawback, a method of changing from sulfur vulcanization to peroxide crosslinking is effective. However, in this method, hot air crosslinking such as HAV (hot air vulcanizing tank) and UHF (ultra-high frequency electromagnetic wave) is performed. In this case, there is a disadvantage that the rubber surface does not crosslink or collapses (degradation), and the scratch resistance is extremely poor. This is because
This is because peroxides do not participate in crosslinking and the rubber surface comes into contact with oxygen, causing collapse.Steam resistance that blocks oxygen, crosslinking with lead, etc. improves the scratch resistance of the rubber surface, but , Disadvantageous in terms of production costs.

Japanese Patent Application Laid-Open No. 4-154855 discloses that
An olefin rubber composition comprising an EPDM / SiH / Pt-based compound capable of being crosslinked by hot air with HAV is disclosed, but the rubber composition was not sufficiently satisfactory in the scratch resistance and compression set. .

[0005] The present inventors have also proposed a specific ethylene
A rubber composition comprising a linear methyl hydrogen polysiloxane (B) and a chloroplatinic acid catalyst (C) used for an addition reaction type silicone rubber to an α-olefin / non-conjugated polyene random copolymer rubber (A) is as follows: A rubber composition which can be cross-linked by hot air cross-linking (HAV, UHF, etc.), which is excellent in production cost, and which is excellent in scratch resistance and compression set, has been found to be inferior in scorch resistance.

[0006] Therefore, ethylene / α-olefin / non-olefin, which can be cross-linked by hot air cross-linking (HAV, UHF, etc.) which is excellent in production cost, is excellent in scratch resistance, compression set, and scorch resistance. The emergence of a conjugated polyene random copolymer rubber composition has been desired.

Therefore, the inventors of the present application have proposed ethylene · α-
The olefin / non-conjugated polyene random copolymer rubber composition has been studied intensively, and the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) has a cyclic polysiloxane compound having at least two SiH groups in one molecule. A rubber composition comprising (B), a catalyst (C), and, if necessary, an alkenyl group-containing organopolysiloxane (D), a polyolefin resin (E), and a reaction inhibitor (F),
Hot air bridges with excellent production cost (HAV, UHF, etc.)
It was found that a molded article having excellent scorch resistance, scratch resistance and compression set could be produced, and the present invention was completed.

[0008]

SUMMARY OF THE INVENTION The crosslinkable rubber composition according to the present invention comprises
A rubber composition that can be cross-linked by hot air, and the cross-linked rubber sheet obtained by forming the rubber composition into a sheet and then hot-air cross-linking is free from scratches on the surface in a pencil hardness test using a HB pencil, and Compression set (CS) after heat treatment at 150 ° C. for 22 hours is 70% or less, and scorch index is 1d.
N · m or less, and the bridging torque (M _E ) is 2.5 dN ·
m or more.

The crosslinkable rubber composition according to the present invention includes, specifically, an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) and at least two SiH groups per molecule. A cyclic polysiloxane compound (B), a catalyst (C), an alkenyl group-containing organopolysiloxane (D) and / or a polyolefin resin (E) if necessary, and a reaction inhibitor (F) if necessary.
And containing.

[0010] Among such rubber compositions, a blend is obtained by microdispersing a polyolefin resin (E) in a molten state in an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A), The average dispersed particle diameter of the polyolefin resin (E) is 2 μm or less, and
The blend weight ratio [(E) / (A)] of the polyolefin resin (E) and the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is from 5/95 to 50/50.
Is preferable.

Further, the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is a non-conjugated polyene having at least one kind of a vinyl group having a terminal vinyl group represented by the following general formula [I] or [II].・ Α- having a structural unit derived from a norbornene-containing compound
Olefin / non-conjugated polyene random copolymer rubber (A
-2) or a non-conjugated polyene represented by the following general formula [I]
Or ethylene having a structural unit derived from at least one type of norbornene compound having a terminal vinyl group represented by [II] (a) and a non-conjugated polyene (b) represented by the following general formula [III]: α-olefin / non-conjugated polyene random copolymer rubber (A-
3) is preferred.

[0012]

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Wherein 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. ]

[0014]

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Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ]

[0016]

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[Wherein, R^FourIs a group having 1 to 10 carbon atoms.
A alkyl group;^Five, R⁶And R ⁷Is German
First, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
It is. ] The ethylene / α-olefin / non-conjugated poly
The enrandom copolymer rubber (A) comprises (i) ethylene and
Molar ratio to α-olefin having 3 to 20 carbon atoms (ethylene
(Lens / α-olefin) in the range of 40/60 to 95/5
(Ii) the iodine value is in the range of 0.5 to 50,
(Iii) Intrinsic viscosity measured with 135 ° C decalin solution
[Η] is in the range of 0.3 to 10 dl / g.

As the cyclic polysiloxane compound (B) having at least two SiH groups in one molecule used in the present invention, a compound represented by the following general formula [IV] or [V] is preferably used.

[0019]

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In the above general formulas [IV] and [V],
R ⁴ , R ⁵ , R ⁶ and R ⁷ are a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond and having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms. . R ⁵ , R ⁶
And R ⁷ may be the same group or different groups. Also, l, m and n are each 2 to
100.

As the catalyst (C), a platinum-based catalyst is preferably used. The crosslinkable rubber composition according to the present invention includes: automotive weather strip; automotive hose, water supply hose, gas hose; automotive anti-vibration rubber, railway anti-vibration rubber, industrial machinery anti-vibration rubber, construction Transmission belts, conveyor belts; automotive cup and seal materials, industrial machine seal materials; automotive weatherstrip sponges, architectural seal sponges or other foams; coated electric wires, electric wire joints, electrically insulating parts, Semiconductive rubber parts;
Rolls for OA equipment, industrial rolls; rubber products for household use; waterproof sheets for civil engineering construction;

The rubber composition according to the present invention, comprising the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer rubber (A), can be crosslinked at room temperature and is suitable for room temperature crosslinked rubber (RTV). It can be suitably used, and is also suitably used for reaction injection molding (RIM). Further, it can be used as a raw material for water-crosslinked rubber. Further, it can be used in the production of a thermoplastic elastomer, and can be used for modifying a thermoplastic resin or an engineering plastic.

The automotive weather strip, hose (automotive hose, water supply hose, gas hose), anti-vibration rubber (automobile anti-vibration rubber, railway anti-vibration rubber, industrial machinery anti-vibration rubber, Building seismic isolation rubber), belts (power transmission belts, conveyor belts), sealing materials (cup seals for automobiles, sealing materials for industrial machinery), foams (weather strip sponges for automobiles, sealing sponges for construction, and other Foam), covered electric wires, electric wire joints, electric insulating parts, semiconductive rubber parts, rolls for office automation equipment, industrial rolls, waterproofing sheets for civil engineering and construction, and household rubber products, the crosslinkable rubber composition according to the present invention. It is characterized by consisting of things.

It should be noted that the term "crosslinked rubber molded article" in the specification may refer to a non-foamed article alone or to both a non-foamed article and a foamed article.

[0025]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the crosslinkable rubber composition according to the present invention and its use will be specifically described.

The crosslinkable rubber composition according to the present invention is a rubber composition that can be crosslinked with hot air, and the crosslinked rubber sheet obtained by forming the rubber composition into a sheet and then crosslink with hot air is formed of HB. A pencil hardness test using a pencil showed no scratch on the surface, a compression set (CS) after heat treatment at 150 ° C. for 22 hours of 70% or less, and a scorch index of 1 dN.
M or less and the crosslinking torque (M _E ) is 2.5 dN
m or more.

The crosslinkable rubber composition according to the present invention, which exhibits the above-described physical properties, comprises an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A), and at least two SiH groups per molecule. It comprises a cyclic polysiloxane compound (B), a catalyst (C) and, if necessary, an alkenyl group-containing organopolysiloxane (D), a polyolefin resin (E), and a reaction inhibitor (F).

Ethylene / α-olefin / non-conjugated polyether
Non- random copolymer rubber (A) The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) used in the present invention comprises ethylene and
It is a random copolymer of an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene,
4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,
Examples thereof include 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. 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.

These α-olefins may be used alone or in combination of two or more. The non-conjugated polyene used in the present invention is, specifically, 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene , 4,5-dimethyl
Linear non-conjugated dienes such as -1,4-hexadiene and 7-methyl-1,6-octadiene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2 -Cyclic non-conjugated dienes such as norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene and dicyclopentadiene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene And trienes such as -3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene.

Among them, the following general formula [I] or [II]
The norbornene compound having a terminal vinyl group represented by

[0032]

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In the general formula [I], n is 0 to 10
R ¹ is a hydrogen atom or a carbon atom having 1 to 1
0 alkyl group, and as the alkyl group having 1 to 10 carbon atoms for R ¹ , specifically, a methyl group, an ethyl group,
Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, t-pentyl, neopentyl, hexyl, isohexyl, heptyl, Examples include an octyl group, a nonyl group, and a decyl group.

R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms of R ² include the alkyl groups having 1 to 5 carbon atoms among the specific examples of the above R ¹ .

[0035]

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In the general formula [II], R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group of R ³ include the same alkyl groups as the specific examples of the alkyl group of R ¹ .

As the norbornene compound represented by the general formula [I] or [II], specifically, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5-vinyl-2-norbornene,
(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 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, 5- (7-octenyl) -2- Norbornene is preferred. In the present invention, it is particularly preferred to use a combination of the norbornene compound having a terminal vinyl group represented by the above general formula [I] or [II] and a non-conjugated polyene represented by the following general formula [III].

[0038]

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In the general formula [III], R ⁴ is an alkyl group having 1 to 10 carbon atoms, and R ⁵ , R ⁶ and R
⁷ is each independently a hydrogen atom or a carbon atom number of 1 to
10 alkyl groups.

Examples of the alkyl group having 1 to 10 carbon atoms of R ⁴ , R ⁵ , R ⁶ and R ⁷ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group and an isobutyl group. Group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, t-pentyl group, neopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group and the like. .

Specific examples of the compound represented by the above general formula [III] include 1,4-hexadiene, 3-methyl-1,4
-Hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1 , 6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-
1,6-octadiene, 6-butyl-1,6-octadiene, 6-
Methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene,
6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonatadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, etc. Non-conjugated diene of the formula: methyltetrahydroindene, 5-ethylidene-2-
Norbornene, 5-isopropylidene-2-norbornene,
Cyclic non-conjugated dienes such as 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene and dicyclopentadiene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3- Isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 4-
Ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-
And trienes such as 1,4,8-decatriene.

Ethylene α comprising the above-mentioned components
-Olefin / non-conjugated polyene random copolymer (A)
Has the following characteristics. (I) Molar ratio of ethylene to α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin) Ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is obtained from (a) ethylene The unit derived from (b) a unit derived from an α-olefin having 3 to 20 carbon atoms (hereinafter sometimes simply referred to as an α-olefin) is 40/60 to 95/5, preferably 50/50 to
90/10, more preferably 55/45 to 85/1
5, particularly preferably in a molar ratio [(a) / (b)] of 60/40 to 80/20.

When the molar ratio is within the above range, a rubber composition which is excellent in heat aging resistance, strength characteristics and rubber elasticity and can provide a crosslinked rubber molded article excellent in cold resistance and processability is obtained. (Ii) Iodine value The iodine value of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is 0.5 to 50 (g / 100).
g), preferably 0.8 to 40 (g / 100 g), more preferably 1 to 30 (g / 100 g), particularly preferably 1.5 to 25 (g / 1 g).
00g).

When the iodine value is within the above range, a rubber composition having a high crosslinking efficiency can be obtained, and a crosslinked rubber molded article having excellent compression set and excellent environmental degradation resistance (= heat aging resistance). Is obtained. If the iodine value exceeds 50, it is disadvantageous in terms of cost, which is not preferable.

In the present invention, ethylene / α obtained by copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene represented by the above general formula [I] or [II]. -Olefin / non-conjugated polyene random copolymer rubber is preferred. Particularly preferred ethylene
α-olefin / non-conjugated polyene random copolymer rubber comprises ethylene, an α-olefin having 3 to 20 carbon atoms, a non-conjugated polyene represented by the above general formula [I] or [II], An ethylene / α-olefin / non-conjugated polyene random copolymer rubber obtained by simultaneously copolymerizing the non-conjugated polyene represented by [III].

In this case, the iodine value (x) derived from the non-conjugated polyene represented by the general formula [I] or [II] and the iodine value derived from the non-conjugated polyene represented by the general formula [III] Ratio [(x)
/ (Y)], from 1/50 to 50/1, preferably 1/3
0 to 30/1, more preferably 1/10 to 10/1,
Particularly preferably 1/5 to 5/1, most preferably 1/2.
It is desirably で 2/1.

The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) having this ratio [(x) / (y)] within the above range has an appropriate long-chain branching, and therefore has a low fluidity. Excellent, excellent in workability. In the present invention, when such an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is used, the degree of crosslinking is moderate, and the physical properties such as compression set are excellent, and
A crosslinked rubber molded article having excellent adhesiveness and oil resistance after aging can be obtained. (Iii) Intrinsic Viscosity The intrinsic viscosity [η] of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) measured in decalin at 135 ° C. is 0.3 to 10 dl / g, preferably 0.1 to 0.1 dl / g.
5 to 8 dl / g, more preferably 0.7 to 6 dl / g
g, particularly preferably 0.8 to 5 dl / g.

When the intrinsic viscosity [η] is within the above range, strength properties and compression set are excellent, and
A rubber composition capable of providing a crosslinked rubber molded article having excellent processability is obtained.

Among them, ethylene • α-having the following physical properties (iv) and (v) in addition to the physical properties (i) to (iii):
Olefin / non-conjugated polyene random copolymer rubber (A) is preferred. (Iv) Branching index determined by a dynamic viscoelasticity measuring device The branching index of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) determined by a dynamic viscoelasticity measuring device is 5 or more, preferably 7 or more. Above, more preferably 9 or more, particularly preferably 10 or more. If the value of the branching index is less than 5, the viscosity in the high shear rate region increases, and the flowability deteriorates, so that the roll processability and the extrusion processability deteriorate. (V) Molecular weight distribution (Mw / Mn) The molecular weight distribution (Mw / Mn) of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) measured by GPC is 3 to 100, preferably 3.3. ~ 7
5, more preferably 3.5 to 50.

When the molecular weight distribution (Mw / Mn) is within the above range, a rubber composition which is excellent in processability and can provide a crosslinked rubber molded article having excellent strength characteristics is obtained.
The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) used in the present invention has a polymerization temperature of 30 to 60 in the presence of a catalyst containing the following compounds (H) and (I) as main components. ° C, especially 30 to 59 ° C, polymerization pressure of 4 to 12 kgf / cm ² , especially 5 to 8 kgf / cm
^2. Under the condition of the molar ratio of the non-conjugated polyene and ethylene supplied (non-conjugated polyene / ethylene) of 0.01 to 0.2,
Ethylene, an α-olefin having 3 to 20 carbon atoms,
It can be obtained by random copolymerization with a norbornene compound having a terminal vinyl group represented by the above general formula [I], [II] or [III]. The copolymerization is preferably carried out in a hydrocarbon medium. (H) VO (OR) _n X _3-n
(Wherein, R is a hydrocarbon group, X is a halogen atom, and n is 0 or an integer of 1 to 3), or VX ₄ (X is a halogen atom). Vanadium compound represented.

The above-mentioned soluble vanadium compound (H) is a component soluble in a hydrocarbon medium of a polymerization reaction system, and specifically, has the general formula VO (OR) aXb or V (OR) c
Xd (wherein R is a hydrocarbon group and 0 ≦ a ≦ 3, 0
≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4,
Vanadium compounds represented by 3 ≦ c + d ≦ 4) or their electron donor adducts can be mentioned as typical examples.

More specifically, VOCl ₃ , 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 , VCl ₄ , VOCl ₃ ,
VO (On-C ₄ H ₉ ) ₃ and VCl ₃ .2OC ₆ H ₁₂ OH can be exemplified. (I) R ′ _m AlX ′ _3-m (R ′ is a hydrocarbon group and X ′
Is a halogen atom, and m is an integer of 1 to 3).

Specific examples of the organoaluminum compound (I) include trialkylaluminums such as triethylaluminum, tributylaluminum and triisopropylaluminum; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; ethoxide, alkyl sesquichloride alkoxides such as butyl sesquichloride butoxide; R ¹ _0.5 Al
(OR ¹ ) a partially alkoxylated alkylaluminum having an average composition represented by _0.5 or the like; a dialkylaluminum halide such as diethylaluminum chloride, dibutylaluminum chloride and 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 and butylaluminum dibromide; diethylaluminum hydride, dibutylaluminum hydride and the like Dialkyl aluminum hydride, ethyl aluminum dihydride, propyl alcohol Partially hydrogenated alkyl aluminum such as alkylaluminum dihydride such as ruminium dihydride; partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide Can be mentioned.

In the present invention, a soluble vanadium compound represented by VOCl ₃ among the above compound (H) and Al (OC ₂ H ₅ ) ₂ Cl among the above compound (I)
When a blend of / Al ₂ (OC ₂ H ₅ ) ₃ Cl ₃ (blend ratio is 1/5 or more) is used as a catalyst component, after Soxhlet extraction (solvent: boiling xylene, extraction time: 3 hours, mesh: 325) Is preferred because an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) having an insoluble content of 1% or less can be obtained.

As a catalyst used in the above copolymerization, a so-called metallocene catalyst such as disclosed in Japanese Patent Application Laid-Open No. 9-405
No. 86, the metallocene catalyst may be used.

Cyclic polysiloxane compound (B) Cyclic polysiloxane compound (B) used in the present invention
Reacts with the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) to act as a crosslinking agent. This cyclic polysiloxane compound (B) has a cyclic polysiloxane structure, and contains at least two, preferably three or more hydrogen atoms directly bonded to silicon atoms in one molecule, that is, SiH groups. It is necessary.

As such a cyclic polysiloxane compound (B), a compound represented by the following general formula [IV] or [V] is preferably used.

[0058]

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In the above general formulas [IV] and [V],
R ⁴ , R ⁵ , R ⁶ and R ⁷ are a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond and having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms. . R ⁵ , R ⁶
And R ⁷ may be the same group or different groups.

Specific examples of such a monovalent hydrocarbon group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-butyl -Alkyl groups such as pentyl group, isopentyl group, t-pentyl group, neopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, nonyl group and decyl group; aryl groups such as phenyl group, tolyl group and naphthyl group A halogen atom-substituted alkyl group such as a trifluoropropyl group. Among them, a methyl group, an ethyl group, a propyl group, a phenyl group, and a trifluoropropyl group are preferable, and a methyl group is particularly preferable.

Also, l, m and n each represent 2 to 1
00, preferably 2 to 50, more preferably 2 to 2
0, particularly preferably 2 to 10, most preferably 3 to 8. Specific examples of the compound represented by the above general formula [IV] or [V] include 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3 1,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9,11-hexamethylcyclohexasiloxane, 1,3,5,7,9,11,13-heptamethylcycloheptasiloxane , 1,3,5,7,9,11,13,15-octamethylcyclooctasiloxane, 1,3,5,7,9,11,13,15,17-nonamethylcyclononasiloxane, 1,3 , 5,7,9,11,13,15,17,19-Decamethylcyclodecasiloxane, 1,3,5-triethylcyclotrisiloxane, 1,3,5,7-tetraethylcyclotetrasiloxane, 1,3 1,5,7,9-pentaethylcyclopentasiloxane, 1,3,5,7,9,11-hexaethylcyclohexasiloxane, 1,3,5,7,9,11,13-heptaethylcycloheptasiloxane , 1,3,5,7,9,11,13,15-octaethylcyclo Octasiloxane, 1,3,5,7,9,11,13,15,17-nonaethylcyclononasiloxane, 1,3,5,7,9,11,13,15,17,19-decaethylcyclo Decasiloxane, 1,3,5-tripropylcyclotrisiloxane, 1,3,5,7-tetrapropylcyclotetrasiloxane, 1,3,5,7,9-pentapropylcyclopentasiloxane, 1,3,5 , 7,9,11-hexapropylcyclohexasiloxane, 1,3,5,7,9,11,13-heptapropylcycloheptasiloxane, 1,3,5,7,9,11,13,15-octa Propylcyclooctasiloxane, 1,3,5,7,9,11,13,15,17-nonapropylcyclononasiloxane, 1,3,5,7,9,11,13,15,17,
19-decapropylcyclodecasiloxane, 1,3,5-tributylcyclotrisiloxane, 1,3,5,7-tetrabutylcyclotetrasiloxane, 1,3,5,7,9-pentabutylcyclopentasiloxane, 1 , 3,5,7,9,11-hexabutylcyclohexasiloxane, 1,3,5,7,9,11,13-heptabutylcycloheptasiloxane, 1,3,5,7,9,11,13 1,15-octabutylcyclooctasiloxane, 1,3,5,7,9,11,13,15,17-nonabutylcyclononasiloxane, 1,3,5,7,9,11,13,15,17 ,
19-decabutylcyclodecasiloxane, 1,3,5-tripentylcyclotrisiloxane, 1,3,5,7-tetrapentylcyclotetrasiloxane, 1,3,5,7,9-pentapentylcyclopentasiloxane, 1,3,5,7,9,11-hexapentylcyclohexasiloxane, 1,3,5,7,9,11,13-heptapentylcycloheptasiloxane, 1,3,5,7,9,11, 13,15-octapentylcyclooctasiloxane, 1,3,5,7,9,11,13,
15,17-Nonapentylcyclononasiloxane, 1,3,5,7,9,
11,13,15,17,19-decapentylcyclodecasiloxane,
1,3,5-trihexylcyclotrisiloxane, 1,3,5,7-tetrahexylcyclotetrasiloxane, 1,3,5,7,9-pentahexylcyclopentasiloxane, 1,3,5,7, 9,11-hexahexylcyclohexasiloxane, 1,3,5,7,9,11,1
3-heptahexylcycloheptasiloxane, 1,3,5,7,9,
11,13,15-octahexylcyclooctasiloxane, 1,
3,5,7,9,11,13,15,17-nonahexylcyclononasiloxane, 1,3,5,7,9,11,13,15,17,19-decahexylcyclodecasiloxane, 1, 3,5-triphenylcyclotrisiloxane, 1,3,5,7-tetraphenylcyclotetrasiloxane,
1,3,5,7,9-pentaphenylcyclopentasiloxane, 1,
3,5,7,9,11-hexaphenylcyclohexasiloxane,
1,3,5,7,9,11,13-heptaphenylcycloheptasiloxane, 1,3,5,7,9,11,13,15-octaphenylcyclooctasiloxane, 1,3,5,7, 9,11,13,15,17-nonaphenylcyclononasiloxane, 1,3,5,7,9,11,13,15,17,19-decaphenylcyclodecasiloxane, 1,1,3,5, 5,7-tetramethylcyclotetrasiloxane, 1,1,3,5,5,7,9,9,11-hexamethylcyclohexasiloxane, 1,1,3,5,5,7,9,9, 1
1,13,13,15-octamethylcyclooctasiloxane, 1,
1,3,5,5,7,9,9,11,13,13,15,17,17,19-decamethylcyclodecasiloxane, 1,1,3,5,5,7-tetraethylcyclotetrasiloxane , 1,1,3,5,5,7,9,9,11-hexaethylcyclohexasiloxane, 1,1,3,5,5,7,9,9,11,13,13,15-
Octaethylcyclooctasiloxane, 1,1,3,5,5,7,9,
9,11,13,13,15,17,17,19-Decaethylcyclodecasiloxane, 1,1,3,5,5,7-tetrapropylcyclotetrasiloxane, 1,1,3,5,5, 7,9,9,11-hexapropylcyclohexasiloxane, 1,1,3,5,5,7,9,9,11,13,13,15-octapropylcyclooctasiloxane, 1,1,3, 5,5,7,9,9,11,1
3,13,15,17,17,19-decapropylcyclodecasiloxane, 1,1,3,5,5,7-tetrabutylcyclotetrasiloxane, 1,1,3,5,5,7,9, 9,11-hexabutylcyclohexasiloxane, 1,1,3,5,5,7,9,9,11,13,13,15-octabutylcyclooctasiloxane, 1,1,3,5,5, 7,9,9,11,13,13,1
5,17,17,19-decabutylcyclodecasiloxane, 1,1,3,
5,5,7-tetrapentylcyclotetrasiloxane, 1,1,3,
5,5,7,9,9,11-hexapentylcyclohexasiloxane, 1,1,3,5,5,7,9,9,11,13,13,15-octapentylcyclooctasiloxane, 1, 1,3,5,5,7,9,9,11,13,13,15,1
7,17,19-decapentylcyclodecasiloxane, 1,1,3,
5,5,7-tetrahexylcyclotetrasiloxane, 1,1,3,
5,5,7,9,9,11-hexahexylcyclohexasiloxane, 1,1,3,5,5,7,9,9,11,13,13,15-octahexylcyclooctasiloxane, 1, 1,3,5,5,7,9,9,11,13,13,15,1
7,17,19-decahexylcyclodecasiloxane, 1,1,3,
5,5,7-tetraphenylcyclotetrasiloxane, 1,1,3,
5,5,7,9,9,11-hexaphenylcyclohexasiloxane, 1,1,3,5,5,7,9,9,11,13,13,15-octaphenylcyclooctasiloxane, 1, 1,3,5,5,7,9,9,11,13,13,15,1
7,17,19-decaphenylcyclodecasiloxane and the like.

These compounds can be produced by a known method. Cyclic polysiloxane compound (B)
Is 0.1 to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A).
100 parts by weight, preferably 0.1 to 75 parts by weight, more preferably 0.1 to 50 parts by weight, even more preferably 0.2 to
To 30 parts by weight, even more preferably 0.2 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, most preferably 0.5 to 5 parts by weight. When the cyclic polysiloxane compound (B) is used in a proportion within the above range, a rubber composition which can form a crosslinked rubber molded article having an excellent compression set, an appropriate crosslink density, and excellent strength properties and elongation properties is obtained. Can be It is not preferable to use the cyclic polysiloxane compound (B) in a proportion exceeding 100 parts by weight, because it is disadvantageous in terms of cost.

The ratio of SiH groups to aliphatic unsaturated groups involved in the crosslinking of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) (SiH group / aliphatic unsaturated group) is 0%. .2-20, furthermore 0.5-1
It is preferably 0, particularly preferably 0.7 to 5.

Catalyst (C) The catalyst (C) used as an optional component in the present invention is an addition reaction catalyst, and has an alkenyl group of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) component. There is no particular limitation as long as it promotes the addition reaction (alkene hydrosilylation reaction) with the SiH group of the cyclic polysiloxane compound (B).
Addition catalysts composed of platinum group elements such as palladium-based catalysts and rhodium-based catalysts (Group 8 metals, Group 8 metal complexes,
Group 8 metal catalysts such as Group 8 metal compounds), among which platinum catalysts are preferred.

The platinum-based catalyst may be a known catalyst usually used for addition-curing type curing. For example, US Pat.
No. 970,150, a finely powdered metal platinum catalyst,
The chloroplatinic acid catalyst described in U.S. Pat. No. 2,823,218 and the platinum-hydrocarbon catalyst described in U.S. Pat. No. 3,159,601 and U.S. Pat. No. 159,662. Complex compounds, US Pat. No. 3,516,94
6, a complex compound of chloroplatinic acid and an olefin, and a complex of platinum and vinyl siloxane described in U.S. Pat. No. 3,775,452 and U.S. Pat. No. 3,814,780. And the like. More specifically, examples thereof include a simple substance of platinum (platinum black), chloroplatinic acid, a platinum-olefin complex, a platinum-alcohol complex, and a carrier in which a platinum carrier is supported on a carrier such as alumina or silica.

The palladium-based catalyst comprises palladium, a palladium compound, palladium chloride or the like.
The rhodium-based catalyst comprises rhodium, a rhodium compound, rhodium chlorate and the like.

Examples of the catalyst (C) other than those mentioned above include Lewis acids and cobalt carbonyl. Catalyst (C)
Is 0.1 to 100,00 with respect to the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A).
0 ppm by weight, preferably 0.1 to 10,000 weight p
pm, more preferably 1 to 5,000 ppm by weight, particularly preferably 5 to 1,000 ppm by weight.

When the catalyst (C) is used in a proportion within the above range, a rubber composition capable of forming a crosslinked rubber molded article having an appropriate crosslinking density and excellent strength and elongation properties is obtained. 1
It is not preferable to use the catalyst (C) at a ratio exceeding 0.00000 ppm by weight, because it is disadvantageous in terms of cost.

In the present invention, the catalyst (C)
To a non-crosslinked rubber molded article of a rubber composition containing no
A crosslinked rubber molded article can be obtained by irradiating a beam, an electron beam or the like. Alkenyl Group-Containing Organopolysiloxane (D) The alkenyl group-containing organopolysiloxane (D) used as required in the present invention is represented by the following average composition formula (1).

R ¹ _n SiO _{(4-n) / 2} (1) In the formula (1), R ¹ is the same or different unsubstituted or substituted monovalent hydrocarbon group, and n is 1 .98-
It is a positive number of 2.02.

As R ¹ , a monovalent hydrocarbon group having 1 to 10 carbon atoms, especially 1 to 8 carbon atoms, is preferable, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; Aliphatic saturated hydrocarbon groups such as cycloalkyl groups such as cyclohexyl groups, alkenyl groups such as vinyl group, allyl group, butenyl group and hexenyl group; aryl groups such as phenyl group and tolyl group; bonded to carbon atoms of these groups A chloromethyl group, a trifluoropropyl group, a cyanoethyl group, or the like, in which a part or all of the hydrogen atoms have been substituted with a halogen atom, a cyano group, or the like. More preferred groups are a methyl group, a vinyl group, a phenyl group, and a trifluoropropyl group.

It is necessary to have at least two alkenyl groups, preferably alkenyl groups having 2 to 8 carbon atoms, particularly preferably vinyl groups. The content of the alkenyl group in R ¹ is preferably 0.001 to 20 mol%, particularly preferably 0.025 to 6 mol%.

The alkenyl group-containing organopolysiloxane (D) represented by the above formula (1) is preferably basically linear, but has a different molecular structure such as linear or branched. One kind or a mixture of two or more kinds may be used.

The above-mentioned organopolysiloxane (D) has an average degree of polymerization of 100 to 20,000, especially 3,000 to 1,
It is preferably in the range of 0.000. In particular,

[0075]

Embedded image

(Where m is a positive integer and n is a positive number greater than or equal to 0),

[0077]

Embedded image

(Where m is a positive integer and p is 2 or more
A is -CH_Three Or -OH group. )
Or these main chains

[0079]

Embedded image

An example in which the above is introduced is exemplified. The above-mentioned organopolysiloxane (D) is synthesized by a method known per se. For example, details of the synthesis method of the alkenyl group-containing organopolysiloxane (D) are described in Japanese Patent Application No. 10-2980
No. 27778 describes a method for synthesizing silicone rubber.

In the present invention, the blend ratio [(A) / (D)] of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) and the alkenyl group-containing organopolysiloxane (D) is 2 / 98 to 98/2, preferably 3/97 to 97/3, more preferably 5/95 to 95/5. Within this range, a rubber capable of preparing a crosslinked rubber molded article having excellent scratch resistance, compression set, and abrasion resistance, and having low mold contamination and excellent strength properties when subjected to press crosslinking or injection crosslinking. A composition is obtained.

Polyolefin Resin (E) The polyolefin resin (E) used as required in the present invention is a thermoplastic resin, and specifically, high-density polyethylene (HDPE), medium-density polyethylene (MDP)
E), ethylene homopolymer (polyethylene) such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE) or ethylene with 3 to 2 carbon atoms
0, preferably a crystalline ethylene / α-olefin copolymer composed of 3 to 8 α-olefins; polypropylene such as propylene homopolymer, propylene block copolymer, and propylene random copolymer; propylene, 1-butene , 4-methyl-1-pentene, 1-hexene, 1-heptene,
3-20, preferably 3-8 carbon atoms such as 1-octene
And α-olefin crystalline homopolymers or copolymers.

The melting point of these polyolefin resins (E) is 250 ° C. or less. Among them, polyethylene and polypropylene are preferable, and polypropylene is particularly preferable. When a foaming agent is compounded in the rubber composition according to the present invention, the polyolefin resin (E) may have 3 carbon atoms.
Crystalline α-olefin homopolymers or copolymers, preferably polypropylenes, of α-olefins having a Vicat softening point of 130 ° C. or higher, preferably 140 ° C.
It is desirable that the temperature is not less than ° C.

In the present invention, the blend ratio of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) and the polyolefin resin (E) [(E) /
(A)] is 5/95 to 50/50, preferably 10/95.
90 to 40/60. If the polyolefin resin (E) is used at a blend ratio within this range, rubber elasticity can be maintained.

The polyolefin resin (E) such as polyethylene has the effect of increasing the product hardness equivalent to that of carbon black with respect to the reinforcing agent and the filler, as well as lowering the viscosity of the compound at the processing temperature and improving the processability. Used as an effective compounding material.

[0086] The amount of the blended polypropylene was a total amount of the polypropylene and ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) of 1
When the amount is 50 parts by weight or less relative to 00 parts by weight, the obtained compound is such that the copolymer rubber (A) phase becomes sea,
A so-called sea-island structure in which the polypropylene phase becomes islands. The island phase of polypropylene serves as a reinforcing agent, and has an effect of melting at a temperature higher than the melting point to lower the compound viscosity and improve the fluidity.

In the present invention, the method of mixing the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) with the polyolefin resin (E) includes a Banbury mixer, an internal mixer usually used as a rubber kneading machine, A method of kneading at a temperature equal to or higher than the melting point of the polyolefin resin (B) using a mixer, a kneader, an open roll, or the like may be used. However, there is a high possibility that a poorly kneaded product of the polyolefin resin (E) becomes a foreign substance. /
02316 [Ethylene / α in an extruder
-The olefin / non-conjugated polyene copolymer rubber (A) and the polyolefin resin (E) are sufficiently melted, and the polyolefin resin (E) is micro-mixed in the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A). Blending until dispersed].

Reaction Inhibitor (F) Examples of the reaction inhibitor (F) used as an optional component together with the catalyst (C ) in the present invention include benzotriazole, ethynyl group-containing alcohols (such as ethynylcyclohexanol), acrylonitrile, amide Compound (for example,
N, N-diallylacetamide, N, N-diallylbenzamide, N, N, N ', N'-tetraallyl-o-phthalic diamide, N,
N, N ', N'-tetraallyl-m-phthalic diamide, N, N, N',
N'-tetraallyl-p-phthalic diamide, etc.), sulfur,
Examples include phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, organic peroxides such as tetramethyltetravinylcyclotetrasiloxane, and hydroperoxide.

The reaction inhibitor (F) is an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) 1
0 to 50 parts by weight, usually 0.000 parts by weight to 00 parts by weight
1 to 50 parts by weight, preferably 0.0001 to 30 parts by weight, more preferably 0.0001 to 20 parts by weight, further preferably 0.0001 to 10 parts by weight, particularly preferably 0.0001 to 5 parts by weight. Used in

The reaction inhibitor (F) is used in an amount of 50 parts by weight or less.
When a rubber composition is used, a rubber composition having a high crosslinking speed and excellent productivity of a crosslinked rubber molded article can be obtained. It is not preferable to use the reaction inhibitor (F) in a proportion exceeding 50 parts by weight, because it is disadvantageous in terms of cost.

Other Ingredients The crosslinkable rubber composition according to the present invention can be used without being crosslinked. However, when it is used as a crosslinked product such as a crosslinked rubber molded article or a crosslinked rubber foam molded article, The characteristics can be exhibited.

In the crosslinkable rubber composition according to the present invention,
Depending on the intended use of the crosslinked product, etc., conventionally known rubber reinforcing agents, inorganic fillers, softeners, antioxidants, processing aids, vulcanization accelerators, organic peroxides, crosslinking aids, foaming agents, Foaming aid,
Additives such as a colorant, a dispersant, and a flame retardant can be blended within a range that does not impair the purpose of the present invention.

The above-mentioned rubber reinforcing agent is used for the tensile strength of the crosslinked rubber,
It has the effect of increasing mechanical properties such as tear strength and wear resistance. As such a rubber reinforcing agent, specifically,
SRF, GPF, FEF, HAF, ISAF, SAF,
Examples thereof include carbon blacks such as FT and MT, and carbon blacks which have been surface-treated with a silane coupling agent, finely divided silica, silica, and the like.

Specific examples of silica include fumed silica,
Precipitated silica and the like. These silicas may be surface-treated with a reactive silane such as hexamethyldisilazane, chlorosilane, alkoxysilane, or a low-molecular-weight siloxane. The specific surface area of silica (BED method) is preferably 50 m ² / g or more, more preferably 100 to 400 m ² / g.

The type and amount of the rubber reinforcing agent can be appropriately selected depending on the application, but the amount of the rubber reinforcing agent is usually the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) 100 For parts by weight,
Up to 300 parts by weight, preferably up to 200 parts by weight.

Specific examples of the above-mentioned inorganic filler include light calcium carbonate, heavy calcium carbonate, talc, clay and the like. The type and amount of these inorganic fillers can be appropriately selected depending on the application, but the amount of the inorganic filler is usually 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). In contrast, it is at most 300 parts by weight, preferably at most 200 parts by weight.

As the above-mentioned softener, a softener usually used for rubber can be used. Specifically, petroleum softening agents such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, petrolatum; coal tar softening agents such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, Fatty oil-based softeners such as coconut oil; tall oil; sub; waxes such as beeswax, carnauba wax and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate, zinc laurate; Synthetic polymer substances such as resin, atactic polypropylene, and coumarone indene resin can be used. Among them, a petroleum softener is preferably used, and particularly, a process oil is preferably used.

The amount of these softeners is appropriately selected depending on the use of the crosslinked product. Examples of the anti-aging agent include amine-based, hindered phenol-based, or sulfur-based anti-aging agents, and as described above, these anti-aging agents are used within a range that does not impair the object of the present invention. Can be

The amine antioxidants used in the present invention include diphenylamines and phenylenediamines. Specific examples of the diphenylamines include p- (p-toluenesulfonylamide) -diphenylamine, 4,4 ′-(α, α-dimethylbenzyl) diphenylamine, 4,4′-dioctyl diphenylamine,
High-temperature reaction product of diphenylamine and acetone, low-temperature reaction product of diphenylamine and acetone, low-temperature reaction product of diphenylamine and aniline and acetone, reaction product of diphenylamine and diisobutylene, octylated diphenylamine, dioctylated diphenylamine,
p, p'-Dioctyl diphenylamine, alkylated diphenylamine and the like.

Specific examples of phenylenediamines include N, N'-diphenyl-p-phenylenediamine, n-isopropyl-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 -P- such as methylpentyl) -p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, phenylhexyl-p-phenylenediamine, phenyloctyl-p-phenylenediamine
And phenylenediamines.

Of these, 4,4 '-(α, α-dimethylbenzyl) diphenylamine and N, N'-di-2-naphthyl-p-phenylenediamine are particularly preferred. These compounds can be used alone or in combination of two or more.

The hindered phenolic antioxidants used in the present invention include (1) 1,1,3-tris
-(2-methyl-4-hydroxy-5-t-butylphenyl) butane, (2) 4,4'-butylidenebis- (3-methyl-6-t-butylphenol), (3) 2,2-thiobis ( 4-methyl-6-t
-Butylphenol), (4) 7-octadecyl-3- (4'-
Hydroxy-3 ', 5'-di-t-butylphenyl) propionate, (5) tetrakis- [methylene-3- (3', 5'-di-t
-Butyl-4'-hydroxyphenyl) propionate] methane, (6) pentaerythritol-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl) propionate], (7) triethylene glycol-bis [3-
(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], (8) 1,6-hexanediol-bis [3-
(3,5-di-t-butyl-4-hydroxyphenyl) propionate], (9) 2,4-bis (n-octylthio) -6- (4-
Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, (10) tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, (11) 2 , 2-thio-
Diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], (12) N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy) -Hydrocinnamide, (13) 2,4-bis [(octylthio) methyl] -o-cresol, (14) 3,5-di-t-butyl-4-hydroxybenzyl-phosphonate-diethyl ester,
(15) Tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, (16) octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate, (17) 3,9-bis [2- ｛3-
(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy {-1,1-dimethylethyl] -2,4-8,10-tetraoxaspiro [5,5] undecane it can. Among them, the phenol compounds (5) and (17) are particularly preferred.

As the sulfur-based anti-aging agent used in the present invention, a sulfur-based anti-aging agent usually used for rubber is used. Specifically, imidazole-based aging such as 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptomethylbenzimidazole, and zinc salt of 2-mercaptomethylimidazole Inhibitors: dimyristyl thiodipropionate, dilauryl thiodipropionate, distearyl thiodipropionate, ditridecyl thiodipropionate, pentaerythritol
-Tetrakis- (β-lauryl-thiopropionate)
And other aliphatic thioether-based antioxidants. Among these, 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptomethylbenzimidazole, pentaerythritol-tetrakis- (β-lauryl-thiopropio Is preferred.

As the processing aids described above, compounds used in ordinary rubber processing can be used. Specifically, higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid and lauric acid; salts of higher fatty acids such as barium stearate, zinc stearate and calcium stearate; ricinoleic acid, stearic acid, palmitic acid and lauric acid And higher fatty acid esters.

Such processing aids are usually ethylene
It is 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 α-olefin / non-conjugated polyene random copolymer rubber (A), but is appropriately optimized according to required physical properties. It is desirable to determine the amount.

In the present invention, both the addition crosslinking and the radical crosslinking may be carried out using an organic peroxide in addition to the above-mentioned catalyst (C). Organic peroxide is ethylene
It is used in an amount of about 0.1 to 10 parts by weight based on 100 parts by weight of the α-olefin / non-conjugated polyene random copolymer rubber (A). As the organic peroxide, a conventionally known organic peroxide that is usually used at the time of rubber crosslinking can be used.

When an organic peroxide is used, it is preferable to use a crosslinking assistant together. As a crosslinking aid,
Specifically, sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; maleimide compounds; Is mentioned. Such a crosslinking assistant is used in an amount of 0.5 to 2 mol, preferably about equimolar, based on 1 mol of the organic peroxide used.

As the above foaming agents, specifically, sodium bicarbonate, sodium carbonate, ammonium bicarbonate,
Inorganic blowing agents such as ammonium carbonate and ammonium nitrite; nitroso compounds such as N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine; azodicarbonamide, azobisiso Azo compounds such as butyronitrile, azocyclohexylnitrile, azodiaminobenzene, and barium azodicarboxylate; benzenesulfonylhydrazide, toluenesulfonylhydrazide, p, p'-oxybis (benzenesulfonylhydrazide), diphenylsulfone-3,3'- Sulfonyl hydrazide compounds such as disulfonyl hydrazide; calcium azide, 4,4-diphenyldisulfonyl azide,
and azide compounds such as p-toluenesulfonyl azide.

These foaming agents are ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) 10
0.5 to 30 parts by weight, preferably 1 to 0 parts by weight
It is used in a proportion of up to 20 parts by weight. When the foaming agent is used in the above ratio, a foam having a specific gravity of 0.03 to 0.8 g / cm ³ can be produced. However, it is possible to appropriately determine an optimal amount according to required physical properties. desirable.

If necessary, a foaming agent may be used in combination.
A foaming aid may be used. The foaming aid acts to lower the decomposition temperature of the foaming agent, promote the decomposition, and make the air 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.

These foaming auxiliaries are ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) 1
It is used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 00 parts by weight, but it is desirable to appropriately determine an optimum amount according to required physical properties.

In the crosslinkable rubber composition according to the present invention, it can be blended with other known rubbers as long as the object of the present invention is not impaired. Such other rubbers include natural rubber (NR) and isoprene rubber (I
R), butadiene rubber (B)
R), conjugated diene rubbers such as styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), and chloroprene rubber (CR).

Further, conventionally known ethylene / α-olefin-based copolymer rubbers can also be used, for example, ethylene / propylene-random copolymer (EPR), and the above-mentioned ethylene / α-olefin / non-conjugated polyene random copolymer rubber. Ethylene / α-olefin / polyene copolymers other than (A) (eg, EPDM) can be used.

Rubber Composition and Use Thereof The crosslinkable rubber composition according to the present invention comprises the above-mentioned ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A), cyclic polysiloxane compound (B), catalyst (C) and, if necessary, an alkenyl group-containing organopolysiloxane (D), a polyolefin resin (E), and a reaction inhibitor (F).

[0115] Among the above rubber compositions, a blend is obtained by microdispersing a polyolefin resin (E) in a molten state in an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). The blend weight ratio [(E) / (A)] of (E) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) is 5
The rubber composition having a ratio of / 95 to 50/50 is particularly excellent in maintaining rubber elasticity of a rubber product.

The term “micro-dispersion” as used herein means the average dispersed particle diameter of the polyolefin resin (E) (measured particle number: 40), which can be measured from a photograph magnified 10,000 times with a transmission electron microscope.
Is preferably 2 μm or less. In the present invention, the average particle diameter of the dispersed particles is referred to as “average dispersed particle diameter”.

In the present invention, the polyolefin resin (E) is an α-olefin having 3 to 20 carbon atoms, preferably 3 to 8 carbon atoms.
In the case of a crystalline homopolymer or copolymer of an olefin,
Ethylene-alpha-olefin-nonconjugated polyene copolymer rubber (A) an intrinsic viscosity measured at 135 ° C. in decalin [eta] _A and an intrinsic viscosity measured at 135 ° C. in decalin of the polyolefin resin (E) [η] _B Ratio ([η] _A /
[Η] _B ) is usually 1 ± 0.14, preferably 1 ± 0.1
It is desirably 2. When the ratio of the intrinsic viscosity is within the above range, the island stability of the polyolefin resin (E) in the rubber phase is exhibited, and the stability is determined by the heat, flow, and shearing force in the ordinary kneading step. It is not affected at all. As the intrinsic viscosity ratio approaches 1, the microdispersion of the polyolefin resin (E) in the rubber phase becomes very good.

As described above, among the crosslinkable rubber compositions according to the present invention, a preferable rubber composition is one in which the polyolefin resin (E) is an ethylene homopolymer or a crystalline ethylene / α-olefin copolymer. A rubber composition and the following rubber composition. (1) Ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A), cyclic polysiloxane compound (B) having at least two SiH groups in one molecule, catalyst (C), polyolefin resin And (E) a rubber composition comprising:
-A blend in which the polyolefin resin (E) is micro-dispersed in the molten state in the olefin / non-conjugated polyene random copolymer rubber (A), and the average dispersed particle diameter of the polyolefin resin (E) is 2 μm or less. And polyolefin resin (E) and ethylene / α-olefin /
A crosslinkable rubber composition, wherein the blend weight ratio [(E) / (A)] with the non-conjugated polyene random copolymer rubber (A) is 5/95 to 50/50. (2) Ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A), cyclic polysiloxane compound (B) having at least two SiH groups in one molecule, catalyst (C), alkenyl group A rubber composition comprising an organopolysiloxane (D) and a polyolefin resin (E), wherein the rubber composition comprises an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A)
It is a blend in which a polyolefin resin (E) is micro-dispersed in a molten state, and the polyolefin resin (E)
Is 2 μm or less, and the blend weight ratio of the polyolefin resin (E) and the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) [(E) / (A)] Is from 5/95 to 50/50. (3) Ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A), cyclic polysiloxane compound (B) having at least two SiH groups in one molecule, catalyst (C), alkenyl group A rubber composition comprising an organopolysiloxane (D), a polyolefin resin (E), and a reaction inhibitor (F), wherein the rubber composition is an ethylene / α-olefin / non-conjugated polyene random. It is a blend in which the polyolefin resin (E) is micro-dispersed in a molten state in the copolymer rubber (A), and the average dispersed particle size of the polyolefin resin (E) is 2 μm.
And the blend weight ratio [(E) / (A)] of the polyolefin resin (E) and the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is 5
/ 95 to 50/50, a crosslinkable rubber composition.

The aspect ratio (major axis / minor axis) of the dispersed particles of the polyolefin resin (E) is preferably 5 or less, more preferably 3 to 1. When the aspect ratio is 5 or less, the microdispersion of the polyolefin resin (E) particles is good.

The crosslinkable rubber composition according to the present invention includes a weatherstrip for automobiles; a hose for automobiles, a hose for water supply, and a hose for gas; , Seismic isolation rubber for buildings; power transmission belts, conveyor belts; cup and seal materials for automobiles, seal materials for industrial machinery; weather strip sponges for automobiles
Sealing sponge or other foam for building; covered wire, wire joint, electrical insulating part, semiconductive rubber part; roll for office automation equipment, industrial roll; waterproof sheet for civil engineering and construction; It is preferably used.

Examples of the automobile weather strip include a door weather strip, a trunk weather strip, a luggage weather strip, a roof side rail weather strip, a sliding door weather strip, a ventilator weather strip, a sliding loop panel weather strip, a front window weather strip, Rear window weather strip, quarter window weather strip, lock pillar weather strip, door glass outer weather strip, door glass inner weather strip, dam wind shield, clath run channel, bracket for door mirror, seal head lamp, seal cowl top, etc. Can be

Examples of the automobile hose include a brake hose, a radiator hose, a heater hose, and an air cleaner hose. Examples of the automobile anti-vibration rubber include an engine mount, a liquid seal engine mount, a damper pulley, a chain damper,
Carburetor mount, torsion damper, strut mount, rubber bush, bumper rubber, helper rubber, spring seat, shock absorber, air spring, body mount, bumper guard, muffler support, rubber coupling, center bearing support,
Rubbers for clutches, differential mounts, suspension bushes, sliding bushes, cushion struts, stoppers, handle dampers, radiator supporters, muffler hangers, and the like.

Examples of the railroad anti-vibration rubber include slab mats, ballast mats, track mats and the like. Examples of the anti-vibration rubber for industrial machines include an expansion joint, a flexible joint, a bush, and a mount.

Examples of the transmission belt include a V belt, a flat belt, and a toothed belt. Examples of the transport belt include a light transport belt, a cylindrical belt, a rough top belt, a transport belt with a flange, a transport belt with a U-shaped guide, and a transport belt with a V guide.

As the above-mentioned automobile cup sealing material,
For example, master cylinder piston cup, wheel cylinder piston cup, constant velocity joint boot, pin boot, dust cover, piston seal, packing, O
A ring, a diaphragm, and the like can be given.

Examples of the industrial machine sealing material include a condenser packing, an O-ring, a packing and the like. As the weather strip sponge for automobiles, for example, door weather strip sponge,
Examples include a bonnet weatherstrip sponge, a trunk room weatherstrip sponge, a sunroof weatherstrip sponge, a ventilator weatherstrip sponge, and a corner sponge.

Examples of the building seal sponge include a gasket, an air tight, a joint material, a seal sponge at a door stop, and the like. Examples of the other foam include a sponge for protecting a hose, a sponge for a cushion, a heat insulating sponge, an insulation pipe, and the like.

Examples of the rolls for OA equipment include a charging roll, a transfer roll, a developing roll, and a paper feed roll. Examples of the industrial roll include an iron-making roll, a paper-making roll, and a printing wire roll.

Examples of the household rubber products include rain gear, rubber bands, shoes, rubber gloves, latex products, golf balls and the like. Among the waterproofing sheets for civil engineering and construction, as the waterproofing sheet for construction, a roofing sheet and the like are mentioned, and as the waterproofing sheet for civil engineering, a waterproofing sheet for a reservoir, a rubber treatment plant and the like. Water-stop sheet for use.

Further, the crosslinkable rubber composition according to the present invention can be crosslinked at ordinary temperature and is suitably used for reaction injection molding (RIM). It is suitably used as a raw material for water-crosslinked rubber. Furthermore, it can be used in the production of thermoplastic elastomers, and can also be used to modify thermoplastic resins and engineering plastics.

The weather strip for automobiles, hoses (hoses for automobiles, hoses for water supply, and hoses for gas), anti-vibration rubbers (anti-vibration rubber for automobiles, anti-vibration rubber for railways, anti-vibration rubber for industrial machinery, Building seismic isolation rubber), belts (power transmission belts, conveyor belts), sealing materials (cup seals for automobiles, sealing materials for industrial machinery), foams (weather strip sponges for automobiles, sealing sponges for construction, and other Foams), covered electric wires, electric wire joints, electrical insulating parts, semiconductive rubber parts, rolls for office automation equipment, industrial rolls, waterproof sheets for civil engineering and construction, and household rubber products can be crosslinked according to the present invention described above. Made of a natural rubber composition.

Preparation of Rubber Composition and Crosslinked Rubber Molded Article
As manufactured above, crosslinkable rubber composition according to the present invention, most if it can be used even while uncrosslinked, using as a cross-linking, such as cross-linked rubber molded product or crosslinked rubber foam molded body The characteristics can be exhibited.

In order to produce a crosslinked product from the crosslinkable rubber composition according to the present invention, an uncrosslinked compounded rubber is prepared once, as in the case of vulcanizing (crosslinking) a general rubber. Crosslinking may be performed after molding the compounded rubber into an intended shape.

As a cross-linking method, any of a method of heating using a cross-linking agent (cyclic polysiloxane compound (B)) or a method of irradiation with light, γ-ray, or electron beam may be adopted.

First, the crosslinkable rubber composition according to the present invention is prepared, for example, by the following method. That is,
The crosslinkable rubber composition according to the present invention can be mixed with an ethylene / α-olefin / non-conjugated polyene random copolymer by using an internal mixer (closed mixer) such as a Banbury mixer, a kneader or an intermix, preferably an extruder. The polymer rubber (A) and, if necessary, the polyolefin resin (E), and further additives such as a rubber reinforcing agent, an inorganic filler, and a softening agent were kneaded preferably at a temperature of 80 to 170 ° C for 3 to 10 minutes. Then, using a roll such as an open roll or a kneader, add the cyclic polysiloxane compound (B), the catalyst (C), and if necessary, the reaction inhibitor (F), a foaming agent, and a foaming assistant. It can be prepared by mixing, kneading at a roll temperature of 80 ° C. or lower for 1 to 30 minutes, and then dispensing.

In the present invention, an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A)
Rubber reinforcing agents, inorganic fillers, etc. can be kneaded at high temperatures, but if the cyclic polysiloxane compound (B) and catalyst (C) are kneaded at high temperatures at the same time, crosslinking (scorch) may occur. Therefore, when the cyclic polysiloxane compound (B) and the catalyst (C) are added simultaneously, 8
It is preferable to knead at 0 ° C. or less. When one of the cyclic polysiloxane compound (B) and the catalyst (C) is added, kneading can be performed even at a high temperature exceeding 80 ° C. In addition, it is also preferable in some cases to use cooling water for the heat generated by kneading.

When the kneading temperature in the internal mixer is low, the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) and, if necessary, the polyolefin resin (E) and An antioxidant, a colorant, a dispersant, a flame retardant, a foaming agent, and the like may be simultaneously kneaded together with the siloxane compound (B), a rubber reinforcing agent, an inorganic filler, a softener, and the like. Polyolefin resin (E)
When kneading is used, it is necessary to knead at a temperature not lower than the melting point of the polyolefin resin (E).

The crosslinkable rubber composition according to the present invention prepared as described above can be prepared by various molding methods using an extruder, a calender roll, a press, an injection molding machine, a transfer molding machine and the like. The molded product can be crosslinked at the same time as molding or by introducing the molded product into a vulcanizing tank. A crosslinked product can be obtained by heating at a temperature of 120 to 270 ° C. for 1 to 30 minutes, or by irradiating light, γ-ray, or electron beam by the method described above. In this crosslinking step, a mold may be used, or the crosslinking may be performed without using a mold. When a mold is not used, the steps of molding and crosslinking are usually performed continuously. As a heating method in the vulcanization tank, a heating tank such as hot air, a fluidized bed of glass beads, UHF (ultra-high frequency electromagnetic wave), and steam can be used.

[0139]

The crosslinkable rubber composition according to the present invention comprises:
High crosslinking speed, excellent productivity of crosslinked rubber molded product, HA
V, UHF and other hot air crosslinks are possible, and crosslinked rubber moldings (including foams) having excellent properties such as scorch resistance, compression set, strength properties, heat resistance, weather resistance and abrasion resistance ) Can be provided.

Since the crosslinkable rubber composition according to the present invention or the crosslinked rubber molded article obtained from the composition has the above-mentioned effects, weather strips for automobiles; hoses for automobiles; hoses for water supply; Hoses such as hoses; anti-vibration rubber for automobiles, anti-vibration rubber for railways, anti-vibration rubber for industrial machinery, anti-vibration rubber for construction, etc .; belts for transmission belts, conveyor belts, etc .; cups and seals for automobiles Materials, sealing materials for industrial machinery, etc .; weather strip sponges for automobiles, sealing sponges for construction, other sponges for hose protection, foam for cushion sponges, heat insulating sponges, insulation pipes, etc .;
Wire joints, electrical insulation parts, semiconductive rubber parts; OA
Rolls for equipment, industrial rolls; waterproof sheets for construction, waterproof sheets for civil engineering; household goods such as rain gear, rubber bands, shoes, rubber gloves, latex products, golf balls, etc .; for modifying plastics, for thermoplastic elastomers, water Widely used for crosslinked rubber, thermoplastic resin modifier, engineering plastic modifier, etc.

[0141]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Incidentally, the composition, iodine value, intrinsic viscosity [η], molecular weight distribution (M
w / Mn) and branching index were measured or obtained by the following methods. (1) Composition of copolymer rubber The composition of the copolymer was measured by ¹³ C-NMR method. (2) Iodine value of copolymer rubber The iodine value of the copolymer rubber was determined by a titration method. (3) Intrinsic viscosity [η] The intrinsic viscosity [η] of the copolymer rubber was measured in 135 ° C decalin. (4) Molecular Weight Distribution (Mw / Mn) The molecular weight distribution of the copolymer rubber was determined by the ratio (Mw) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC.
w / Mn). For GPC, GMH-HT and GMH-HTL manufactured by Tosoh Corporation were used for the column, and orthodichlorobenzene was used for the solvent. (5) Branching index Complex viscosity η ^{* of} EPR having no long-chain branching (4 samples with different molecular weights) using a dynamic viscoelasticity tester
Was measured.

0.01 rad / sec and 8 rad / sec
The complex viscosity η ^* at the time of c is obtained, and the complex viscosity η
_The vertical axis is _1L ^* (0.01 rad / sec), and the complex viscosity η
_2L ^* (8 rad / sec) is plotted on the horizontal axis to create a reference line, and η _2L ^* = 1 × on an extension of that line
Η _1L0 ^* at 10 ³ / Pa · s was measured.

Next, similarly for the target sample,
The complex viscosity η ^* at 0.01 rad / sec and 8 rad / sec is determined, and the complex viscosity η _1B ^* (0.01 rad
/ Sec) on the vertical axis, the complex viscosity η _2B ^* (8 rad / sec).
c) is plotted on the horizontal axis. This plot has a value larger than that of the reference line, and the longer the long-chain branching, the greater the distance from the reference line.

Next, the reference line is translated so as to pass over this plot, and the complex viscosity η ₂ ^* = 1 × 10 ³ / P
The intersection η _1B0 ^* with a · s was measured. The values of η _1L0 ^* and η _1B0 ^* measured as described above were applied to the following equation to calculate the branching index.

Branching index = (log η _1L0 ^* _−log η _1B0 ^* ) × 10 The above measurement conditions are as follows. -Reference samples: 4 types of EPR manufactured by Mitsui Chemicals, Inc., Tuffmer P-0280, P-048
0, P-0680, P-0880 (trade name) ・ Dynamic Viscoelasticity Tester (RDS): Rheometric
Company s Sample: A 2 mm sheet is punched out into a circle with a diameter of 25 mm for use.・ Temperature: 190 ° C. ・ Strain rate: 1% ・ Frequency dependence: 0.001 to 500 rad / sec

[0147]

[Production Example 1] [Production of ethylene-propylene / 5-vinyl-2-norbornene random copolymer rubber (A-1)] A stainless steel polymerization vessel having a substantial inner volume of 100 liters equipped with stirring blades (stirring speed = Using 250 rpm), terpolymerization of ethylene, propylene and 5-vinyl-2-norbornene was continuously performed. 60 liters of hexane, 3.7 kg of ethylene, 8.0 kg of propylene, and 48 parts of 5-vinyl-2-norbornene per hour were added to the liquid phase from the side of the polymerization vessel.
At a rate of 0 g, 50 Nl of hydrogen, 48 mmol of VOCl ₃ as catalyst and 2 mL of Al (Et) ₂ Cl
40 mmol of Al (Et) _1.5 Cl _1.5 were continuously fed at a rate of 48 mmol.

When the copolymerization reaction was carried out under the conditions described above, an ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A-1) was obtained in a uniform solution state.

Thereafter, a small amount of methanol was added to the polymerization solution continuously withdrawn from the lower part of the polymerization vessel to stop the polymerization reaction, and the polymer was separated from the solvent by steam stripping. Vacuum drying was performed for hours.

Table 1 shows the physical properties of the ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A-1) obtained as described above.

[0151]

[Production Example 2] [Ethylene / propylene / 5-vinyl-2-no
Rubornene and 5-ethylidene-2-norbornene random
Production of polymer rubber (A-2)] Substantially equipped with stirring blades
100 liter stainless steel polymerization vessel (stirring speed
= 250 rpm) to continuously feed ethylene and propylene.
Len, 5-vinyl-2-norbornene and 5-ethylidene-2-no
A quaternary copolymerization with rubornene was performed. From the side of the polymerization vessel
60 liters of hexane and 3.0 parts of ethylene per hour were added to the liquid phase.
kg, 8.5 kg of propylene, 5-vinyl-2-norvol
370 g of nene and 47 of 5-ethylidene-2-norbornene
At a rate of 0 g and 50 Nl of hydrogen as catalyst
VOCl _Three90 mmol, Al (Et)_Two420 for Cl
Mmol, Al (Et)_1.5Cl_{1. Five}Of 120 mmol
Feeded continuously at speed.

When the copolymerization reaction is carried out under the above-described conditions, the ethylene / propylene / 5-vinyl-2-norbornene / 5-ethylidene-2-norbornene random copolymer rubber (A-2) becomes uniform. Obtained in solution.

Thereafter, a small amount of methanol was added to the polymerization solution continuously withdrawn from the lower part of the polymerization vessel to stop the polymerization reaction, and the polymer was separated from the solvent by steam stripping. Vacuum drying was performed for hours.

Ethylene / propylene / 5-vinyl-2-norbornene / 5-ethylidene-2-norbornene random copolymer rubber (A-2) obtained as described above
Table 1 shows the physical properties of the compound.

[0155]

[Production Examples 3 and 4] In Production Example 1, by changing the polymerization conditions as shown in Table 1, ethylene-propylene / 5-ethylidene-2-norbornene random copolymer rubber (A-3) having different properties was prepared. -Propylene dicyclopentadiene random copolymer rubber (A-4) was obtained. Table 1 shows the physical properties of the obtained copolymer rubbers (A-3) and (A-4).

[0156]

[Table 1]

[0157]

Example 1 First, ethylene-propylene-5-
Vinyl-2-norbornene random copolymer rubber (A-
1) 100 parts by weight and carbon black [trade name Asahi #
60 G, manufactured by Asahi Carbon Co., Ltd.] and 20 parts by weight of a softener [trade name: Diana Process Oil ^™ PW-380, manufactured by Idemitsu Kosan Co., Ltd.] [Made by Steel Works Ltd.] to produce a rubber compound (1-a).

The kneading method is as follows.
5-vinyl-2-norbornene random copolymer rubber (A-
1) was masticated for 30 seconds, and then carbon black and a softener were added and kneaded for 2 minutes. Thereafter, the ram was lifted and cleaned, kneaded for another 1 minute, and discharged at about 130 ° C. to obtain a rubber compound (1-a). This kneading was performed at a filling rate of 70%.

Next, the rubber compound (1-a)
To 180 parts by weight, 4.8 parts by weight of 1,3,5,7-tetramethylcyclotetrasiloxane (B-1) and 0.1 part by weight of ethynylcyclohexanol (F-1) as a reaction control agent were added to give 6 parts. Inch roll (front roll surface temperature 30 ° C, rear roll surface temperature 30 ° C, front roll rotation speed 18rpm,
The mixture was kneaded for 10 minutes, and then 0.075 parts by weight of isopropyl alcohol solution (C-1) having a chloroplatinic acid concentration of 2% by weight was added to a 6 inch roller.
(The surface temperature of the front roll is 30 ° C and the surface temperature of the rear roll is 3
The mixture was added at 0 ° C. at a rotation speed of the front roll of 18 rpm and a rotation speed of the rear roll at 15 rpm) and mixed for 5 minutes. A 2 mm sheet was formed.

The rubber compound (1-b) containing a cross-linking agent before the heat curing was subjected to a 6-inch roll (front roll surface temperature 30 ° C., rear roll surface temperature 30 ° C., front roll rotation speed 18 rpm, A 2 mm thick sheet was formed at a roll rotation speed of 15 rpm, and then pressed at 40 ° C. for 6 minutes using a 50-ton press forming machine to prepare a 2 mm thick uncrosslinked sheet. This uncrosslinked sheet was left in a 200 ° C. atmosphere HAV (hot air vulcanizing tank) for 5 minutes to produce a crosslinked sheet without pressure.

The obtained crosslinked sheet was subjected to a tensile test, a heat aging resistance test, a scratch resistance test, a compression set test and a hardness test according to the following methods. According (1) Tensile test JIS K6251, measurement temperature 23 ° C., subjected to tensile test at a tensile rate of 500 mm / min conditions to measure the intensity T _B and elongation E _B at break of the crosslinked sheet. (2) Heat aging test A heat aging test was performed in accordance with JIS K6257. That is, the crosslinked sheet is placed in an oven at 150 ° C. for 7 minutes.
After aging for 2 hours, a tensile test was performed at a measurement temperature of 23 ° C. and a tensile speed of 500 mm / min, and the elongation and strength at break of the crosslinked sheet were measured.
_R (T _B ) and elongation retention A _R (E _B ) were calculated. (3) Scratch resistance test Immediately after taking out from the HAV (hot air vulcanizing tank), the surface of the crosslinked sheet was scratched with a HB pencil, the scratched state was visually observed, and the scratch resistance was evaluated in four steps. Was. <Four-stage evaluation of scratch resistance> A: No scratch on surface B: Slight scratch on surface C: Scratched D: Extremely severe scratch (4) Compression set test JIS According to K6250, the produced crosslinked sheets were laminated, and a compression set test was performed in accordance with JIS K6262. This test condition is 150 ° C. × 22 hrs. (5) Hardness test Hardness _HA was measured according to JIS K6253.

Table 2 shows the results. Furthermore, to determine the scorch index and crosslinking torque (M _E) by using the rubber compound (1-b). (6) Scorch Index Crosslinking Degree Measuring Instrument [Alpha Technology Acquisition Inc. Made, brand name RHEOMETER MDR20
00], the torque S and the minimum torque S′MIN after 20 minutes at 100 ° C. were measured, and the scorch index was calculated by the following equation.

(Scorch index) = (Torque S after 20 minutes)
-(Minimum torque S'MIN) The results are shown in Table 2. (7) cross-linked torque (M _E) the degree of cross-linking measuring [alpha technology Aku tinkering Deployment Inc. Made, brand name RHEOMETER MDR20
00], the torque after 20 minutes at 160 ° C. was measured. The measured torque was used as the crosslinking torque (M _E ).

Table 2 shows the results.

[0165]

Example 2 In Example 1, the ethylene-propylene / 5-vinyl-2-norbornene random copolymer rubber (A-1) used in Example 1 was replaced with ethylene-propylene / 5-vinyl-2. -The same procedure was performed as in Example 1 except that the norbornene / 5-ethylidene-2-norbornene random copolymer rubber (A-2) was used.

Table 2 shows the results.

[0167]

Example 3 In Example 1, 100 parts by weight of the ethylene-propylene / 5-vinyl-2-norbornene random copolymer rubber (A-1) used in Example 1 was replaced with ethylene-propylene / 5- 30 parts by weight of vinyl-2-norbornene random copolymer rubber (A-1) and dimethylpolysiloxane having a vinyl group [average degree of polymerization: 8000, both ends of which are encapsulated with dimethylvinylsilyl group; Mol%] 70 (D-1), except that 70 parts by weight was used.

The results are shown in Table 2.

[0169]

Embodiment 4 First, ethylene / propylene / 5-vinyl-2
-A weight ratio [(E-1) / of a norbornene random copolymer rubber (A-1) and a polyethylene (E-1) [made by Mitsui Chemicals, Inc., trade name Ultzex ^™ 20200J].
(A-1)] and the number of rotations of the screw of the extruder and polyethylene (E-
1) By controlling the supply amount, the mixture was adjusted by a twin-screw kneading extruder to obtain a blend (I). The temperature inside the extruder was 180 ° C.

Next, the average dispersed particle diameter of polyethylene (E-1) in the obtained blend (I) was measured by using an electron microscope [trade name: H-8100 (200 KV), manufactured by
Using Hitachi, Ltd.], the average dispersion particle size was 0.01 μm.
m or less.

<Preparation of Sample> The above blend (I)
Trim the pellet of 0.1μ with a microtome.
m or less, and a thin film piece was dyed with ruthenic acid. Next, carbon was vapor-deposited on the thin film piece to obtain a sample for an electron microscope.

Also, 120 parts by weight of the blend (I) obtained as described above, 40 parts by weight of carbon black [Asahi # 60G, manufactured by Asahi Carbon Co., Ltd.], a softening agent [Idemitsu Kosan Co., Ltd. ), Diana Process Oil ^TM PW-
[380] 20 parts by weight were kneaded with a 1.7 liter Banbury mixer [BB-2 type mixer manufactured by Kobe Steel Ltd.] to prepare a rubber compound (4-a).

[0173] The kneading method is as follows.
The mixture was masticated for 2 seconds, and then carbon black and a softener were added and kneaded for 2 minutes. Thereafter, the ram was raised and cleaned, kneaded for another 1 minute, and discharged at about 130 ° C. to obtain a rubber compound (4-a). This kneading has a filling rate of 70%
Performed in

Next, the rubber compound (4-a) 1
80 parts by weight of 6 inch roll (surface temperature of front roll 30
° C, surface temperature of the rear roll 30 ° C, number of rotations of the front roll 18
rpm, the rotation speed of the rear roll is 15 rpm)
1,3,5,7-tetramethylcyclotetrasiloxane (B-
1) 4.8 parts by weight, 0.1 part by weight of ethynylcyclohexanol (F-1) as a reaction control agent, chloroplatinic acid concentration 2
Wt% isopropyl alcohol solution (C-1) 0.0
75 parts by weight were added and mixed for 10 minutes. From the obtained rubber compound (4-b), compression molding was performed at 160 ° C. for 10 minutes to form a sheet having a thickness of 2 mm.

The rubber compound (4-b) containing a cross-linking agent before the heat curing was subjected to a 6-inch roll (front roll surface temperature 30 ° C., rear roll surface temperature 30 ° C., front roll rotation speed 18 rpm, rear roll speed 18 rpm). A 2 mm thick sheet was formed at a roll rotation speed of 15 rpm, and then pressed at 40 ° C. for 6 minutes using a 50-ton press forming machine to prepare a 2 mm thick uncrosslinked sheet. It was left in an atmosphere HAV (hot air vulcanizing tank) for 5 minutes to produce a crosslinked sheet without pressure.

With respect to the obtained crosslinked sheet, a tensile test, a heat aging resistance test, a scratch resistance test, a compression set test and a hardness test were performed in accordance with the above methods. Further, using the rubber compound (4-b), in the same manner as in Example 1,
The scorch index and the crosslinking torque (M _E ) were determined.

Table 2 shows the results.

[0178]

Example 5 In Example 4, polyethylene (E-
In the same manner as in Example 4 except that polypropylene (E-2) (trade name: F337D, manufactured by Grand Polymer Co., Ltd.) was used instead of 1).

The average dispersed particle diameter of the polypropylene (E-2) in the obtained blend (II) was measured by using an electron microscope [trade name: H-8100 (200 KV), manufactured by
Using a sample manufactured by Hitachi, Ltd.], the average dispersed particle was 0.5 μm.
m, and the aspect ratio was 1.7. Table 2 shows the results.

[0180]

Comparative Example 1 In Example 1, C ₆ H ₅ was used instead of 1,3,5,7-tetramethylcyclotetrasiloxane (B-1).
_{Si- (OSi (CH 3) 2} H) except for using organohydrogensiloxane represented by _3, it was carried out in the same manner as in Example 1. Table 2 shows the results.

[0181]

Comparative Example 2 In Example 1, ethylene-propylene / 5-ethylidene-2 was used instead of the ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A-1) used in Example 1. -Performed in the same manner as in Example 1 except that the norbornene random copolymer rubber (A-3) was used. Table 2 shows the results.

[0182]

Comparative Example 3 In Example 1, an ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A
In the same manner as in Example 1 except that ethylene-propylene-dicyclopentadiene random copolymer rubber (A-4) was used instead of -1). Table 2 shows the results.

[0183]

Comparative Example 4 In Example 1, 1,3,5,7-tetramethylcyclotetrasiloxane (B-1) and a chloroplatinic acid concentration of 2
3.5% by weight of dicumyl peroxide 40% concentration product [Mitsui Chemicals Co., Ltd., Mitsui DCP-40C] instead of the isopropyl alcohol solution (C-1) and ethynylcyclohexanol (F-1) by weight%. The procedure was performed in the same manner as in Example 1 except that some parts were added. Table 2 shows the results.

[0184]

Comparative Example 5 In Example 1, 1,3,5,7-tetramethylcyclotetrasiloxane (B-1) and chloroplatinic acid concentration 2
Weight of isopropyl alcohol solution (C-1) and ethynylcyclohexanol (F-1), 1.5 parts by weight of sulfur, 2-mercaptobenzothiazole [manufactured by Sanshin Chemical Industry Co., Ltd., trade name: Suncellar M] 0.5 parts by weight,
Other than adding 1.0 part by weight of tetramethylthiuram disulfide [manufactured by Sanshin Chemical Industry Co., Ltd., trade name: Suncellar TT], 5 parts by weight of zinc white, and 1 part by weight of stearic acid,
Performed in the same manner as in Example 1. Table 2 shows the results.

[0185]

[Table 2]

[0186]

[Table 3]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/08 C08L 23/08 83/05 83/05 83/07 83/07 H01B 3/28 H01B 3 / 28 9/00 9/00 A (72) Inventor: Yasushi Arino 3rd Chikusa Kaigan, Ichihara-shi, Chiba Mitsui Chemicals, Inc. (72) Inventor Masaaki Kawasaki 3rd Chikashikaigan, Ichihara-shi, Chiba Mitsui Chemicals F term in the Company (reference) FA08Z FD010 FD020 FD030 FD14X FD14Y FD140 FD146 FD147 FD150 FD208 FD320 GC00 GJ02 GL00 GM00 GN00 GQ00 5G305 AA02 AA04 AA14 AB15 AB24 AB28 AB36 BA26 CA01 CA08 CA26 CA47 CA51

Claims (60)

[Claims] 1. A rubber composition which can be cross-linked by hot air. A cross-linked rubber sheet obtained by forming the rubber composition into a sheet and then cross-linking with hot air has a scratch on its surface in a pencil hardness test using a HB pencil. It has no compression set, and has a compression set (CS) of 70% or less after heat treatment at 150 ° C. for 22 hours, a scorch index of 1 dN · m or less, and a crosslinking torque (M
_E ) is 2.5 dN · m or more. 2. A rubber composition comprising: an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A); a cyclic polysiloxane compound (B) having at least two SiH groups in one molecule; 2. A catalyst comprising a catalyst (C).
3. The crosslinkable rubber composition according to item 1. 3. The rubber composition according to claim 1, wherein the rubber composition is an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A),
3. An alkenyl group-containing organopolysiloxane (D) in addition to the cyclic polysiloxane compound (B) having at least two iH groups in one molecule and the catalyst (C). The crosslinkable rubber composition according to the above. 4. A rubber composition comprising: an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A); a cyclic polysiloxane compound (B) having at least two SiH groups per molecule; A rubber composition comprising a catalyst (C) and a polyolefin resin (E), wherein the rubber composition comprises: an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) It is a blend in which the polyolefin resin (E) is micro-dispersed in a molten state. The polyolefin resin (E) has an average dispersed particle diameter of 2 μm or less, and the polyolefin resin (E) and ethylene / α-olefin / non-conjugated. Blend weight ratio with polyene random copolymer rubber (A) [(E) / (A)] is 5 / 95-50
The crosslinkable rubber composition according to claim 1, wherein the composition is / 50. 5. A rubber composition comprising: an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A); and a cyclic polysiloxane compound (B) having at least two SiH groups in one molecule. A rubber composition comprising a catalyst (C), an alkenyl group-containing organopolysiloxane (D), and a polyolefin resin (E), wherein the rubber composition comprises an ethylene / α-olefin / non-conjugated polyene random. It is a blend in which a polyolefin resin (E) is micro-dispersed in a molten state in a copolymer rubber (A). The polyolefin resin (E) has an average dispersed particle size of 2 μm or less, and a polyolefin resin (E). ) And ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) in a blend weight ratio [(E) / (A)] of 5/95 to 50/50.
The crosslinkable rubber composition according to claim 1, wherein 6. A rubber composition comprising: an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A); a cyclic polysiloxane compound having at least two SiH groups in one molecule (B); A rubber composition comprising a catalyst (C), an alkenyl group-containing organopolysiloxane (D), a polyolefin resin (E), and a reaction inhibitor (F). It is a blend of polyolefin resin (E) micro-dispersed in a molten state in α-olefin / non-conjugated polyene random copolymer rubber (A). The polyolefin resin (E) has an average dispersed particle size of 2 μm or less. And the blend weight ratio [(E) / (A)] of the polyolefin resin (E) and the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is / 95-50 / 50
The crosslinkable rubber composition according to claim 1, wherein 7. The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is a non-conjugated polyene having at least one terminal vinyl group represented by the following general formula [I] or [II]. Ethylene and α-olefins having structural units derived from norbornene compounds
The crosslinkable rubber composition according to any one of claims 2 to 6, which is a non-conjugated polyene random copolymer rubber (A-2); Wherein 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. , Embedded image [Wherein, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms]. 8. The ethylene / α-olefin / non-conjugated polyolefin.
Rien random copolymer rubber (A) is a non-conjugated polyene
A small amount represented by the following general formula [I] or [II].
At least a kind of norbornene compound containing a terminal vinyl group
The structural unit derived from (a) and the following general formula [III]
Structural unit derived from non-conjugated polyene (b) represented
, Α-olefin and non-conjugated polyene having
Characterized by being a copolymer rubber (A-3)
A crosslinkable rubber composition according to any one of claims 2 to 7.
Object;Wherein n is an integer of 0 to 10,¹Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
And R^TwoIs a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
Yes], embedded image[Wherein, R^ThreeRepresents a hydrogen atom or an atom having 1 to 10 carbon atoms.
A alkyl group],[Wherein, R^FourIs an alkyl group having 1 to 10 carbon atoms.
R^Five, R⁶And R ⁷Are each independently a hydrogen source
Or an alkyl group having 1 to 10 carbon atoms]. 9. The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) comprises (i) a molar ratio of ethylene to an α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin). ) Is in the range of 40/60 to 95/5, (ii) the iodine value is in the range of 0.5 to 50, and (iii) the intrinsic viscosity [η] of the decalin solution measured at 135 ° C. is 0.3. The crosslinkable rubber composition according to any one of claims 2 to 8, wherein the composition is in the range of 10 to 10 dl / g. 10. The crosslinkable rubber composition according to claim 2, wherein the catalyst (C) is a platinum-based catalyst. 11. The crosslinkable rubber composition according to claim 1, which is used in the production of a weather strip for an automobile. 12. A weather strip for a vehicle, wherein the weather strip for a vehicle is a door weather strip, a trunk weather strip,
Luggage weather strip, roof side rail weather strip, sliding door weather strip, ventilator weather strip, sliding loop panel weather strip, front window weather strip, rear window weather strip, quarter window weather strip, lock pillar weather strip, door glass outer weather The crosslinkable rubber composition according to claim 11, which is a strip, a door glass inner weather strip, a dam windshield, a glass run channel, a bracket for a door mirror, a seal head lamp, or a seal cowl top. 13. The crosslinkable rubber composition according to any one of claims 1 to 10, which is used in the production of an automobile hose, a water supply hose, or a gas hose. 14. The crosslinkable rubber composition according to claim 13, wherein said automobile hose is a brake hose, a radiator hose, a heater hose or an air cleaner hose. 15. The method according to any one of claims 1 to 10, wherein the rubber is used in the manufacture of rubber for automobiles, rubber for railways, rubber for industrial machines, or rubber for building isolation. The crosslinkable rubber composition according to the above. 16. The anti-vibration rubber for an automobile includes an engine mount, a liquid seal engine mount, a damper pulley, a chain damper, a carburetor mount, a torsion damper, a strut mount, a rubber bush, a bumper rubber, a helper rubber, a spring seat, and a shock absorber. , Air spring, body mount, bumper guard, muffler support, rubber coupling, center bearing support, clutch rubber, differential mount, suspension bush, sliding bush, kushon strut bar, stopper, handle damper, radiator supporter or muffler hanger The crosslinkable rubber composition according to claim 15, characterized in that: 17. The railway anti-vibration rubber comprises a slab mat,
The crosslinkable rubber composition according to claim 15, which is a ballast mat or a track mat. 18. The vibration isolating rubber for an industrial machine is an expansion joint, a flexible joint, a bush, or a mount.
3. The crosslinkable rubber composition according to item 1. 19. The crosslinkable rubber composition according to claim 1, which is used in the production of a power transmission belt or a conveyor belt. 20. The transmission belt according to claim 19, wherein the transmission belt is a V belt, a flat belt or a toothed belt.
3. The crosslinkable rubber composition according to item 1. 21. The belt for light conveyance, wherein the belt for light conveyance is:
The crosslinkable rubber composition according to claim 19, which is a cylindrical belt, a rough top belt, a transport belt with a flange, a transport belt with a U-shaped guide, or a transport belt with a V guide. 22. The crosslinkable rubber composition according to any one of claims 1 to 10, which is used in the production of an automobile cup seal material or an industrial machine seal material. 23. The automobile cup / sealant is a master cylinder piston cup, a wheel cylinder piston cup, a constant velocity joint boot, a pin boot, a dust cover, a piston seal, a packing, an O-ring, or a diaphragm. A crosslinkable rubber composition according to claim 22. 24. The crosslinkable rubber composition according to claim 22, wherein the industrial machine sealing material is a capacitor packing, an O-ring or a packing. 25. A weather strip sponge for an automobile,
The crosslinkable rubber composition according to any one of claims 1 to 10, which is used in the production of a building seal sponge or other foam. 26. The vehicle weather strip sponge according to claim 2, wherein the automotive weather strip sponge is a door weather strip sponge, a bonnet weather strip sponge, a trunk room weather strip sponge, a sunroof weather strip sponge, a ventilator weather strip sponge, or a corner sponge.
6. The crosslinkable rubber composition according to 5. 27. The crosslinkable rubber composition according to claim 25, wherein the architectural seal sponge is a gasket, air tight, joint material or door stop seal sponge. 28. The sponge for protecting a hose, a sponge for a cushion, a heat insulating sponge, or an insulation pipe according to claim 25.
3. The crosslinkable rubber composition according to item 1. 29. The crosslinkable rubber composition according to claim 1, which is used in the production of covered electric wires, electric wire joints, electrically insulating parts and semiconductive rubber parts. 30. A roll for use in the production of rolls for OA equipment or industrial rolls.
A crosslinkable rubber composition according to any one of the above. 31. A roll for an OA device, comprising: a charging roll;
The crosslinkable rubber composition according to claim 30, which is a transfer roll, a development roll, or a paper feed roll. 32. The crosslinkable rubber composition according to claim 30, wherein the industrial roll is a roll for making iron, a roll for making paper, or a roll for printing electric wires. 33. The crosslinkable rubber composition according to claim 1, which is used in the production of a waterproof sheet for civil engineering and construction. 34. The crosslinkable rubber composition according to claim 1, which is used in the production of household rubber products. 35. The household rubber product is a rain gear, rubber band,
35. The crosslinkable rubber composition according to claim 34, which is a shoe, a rubber glove, a latex product or a golf ball. 36. The crosslinkable rubber composition according to claim 1, which is capable of crosslinking at room temperature. 37. The crosslinkable rubber composition according to claim 1, which is used for reaction injection molding (RIM). 38. The crosslinkable rubber composition according to claim 1, which is used for a room temperature crosslinked rubber (RTV). 39. The crosslinkable rubber composition according to claim 38, wherein the rubber composition for room temperature crosslinked rubber (RTV) is used as a building sealant or adhesive. 40. The crosslinkable rubber composition according to claim 1, which is used in producing a thermoplastic elastomer. 41. The crosslinkable rubber composition according to claim 1, which is used for modifying an engineering plastic. 42. An automotive weather strip comprising the crosslinkable rubber composition according to any one of claims 1 to 10. 43. A hose comprising the crosslinkable rubber composition according to any one of claims 1 to 10. 44. The hose according to claim 43, wherein the hose is an automobile hose, a water supply hose, or a gas hose. 45. An anti-vibration rubber comprising the crosslinkable rubber composition according to claim 1. Description: 46. An anti-vibration rubber according to claim 45, wherein said anti-vibration rubber is an anti-vibration rubber for automobiles, anti-vibration rubber for railways, anti-vibration rubber for industrial machines, or anti-vibration rubber for buildings. Rubber. 47. A belt comprising the crosslinkable rubber composition according to any one of claims 1 to 10. 48. The belt according to claim 47, wherein said belt is a transmission belt or a conveyor belt. 49. A sealing material comprising the crosslinkable rubber composition according to any one of claims 1 to 10. 50. The sealing material according to claim 49, wherein said sealing material is a cup sealing material for automobiles or a sealing material for industrial machines. 51. A foam comprising the crosslinkable rubber composition according to any one of claims 1 to 10. 52. The foam according to claim 51, wherein the foam is a weatherstrip sponge for automobiles or a seal sponge for construction. 53. A covered electric wire which is covered with a covering comprising the crosslinkable rubber composition according to any one of claims 1 to 10. 54. An electric wire joint comprising the crosslinkable rubber composition according to any one of claims 1 to 10. 55. An electrically insulating component comprising the crosslinkable rubber composition according to any one of claims 1 to 10. 56. A semiconductive rubber part comprising the crosslinkable rubber composition according to any one of claims 1 to 10. 57. A roll for OA equipment, comprising the crosslinkable rubber composition according to any one of claims 1 to 10. 58. An industrial roll comprising the crosslinkable rubber composition according to any one of claims 1 to 10. 59. A waterproof sheet for civil engineering and construction comprising the crosslinkable rubber composition according to any one of claims 1 to 10. A household rubber product comprising the crosslinkable rubber composition according to any one of claims 1 to 10.