JPH10175440A - Rubber composite for weather strip - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition having high hardness, excellent mechanical characteristics such as strength and compressive permanent strain, and excellent low temperature characteristic, by containing a specific copolymer (A) and/or a specific copolymer (B), a vulcanizing agent and/or a cross linking agent in the composition. SOLUTION: Ethylene/high class α-olefin/noncopolyene random copolymer (A) in which the mole ratio of ethylene and α-olefin (high class α-olefin) of the number of carbon 6-12 is 82/18-95/5, the iodine value is 5-45, the Mooney viscosity (ML1+4, 100 deg.C) is 10-350, and a ratio (Mw/Mn) of the polystyrene converted weight mean molecular weight (Mw) to the polystyrene converted number mean molecular weight (Mn) is 2-15, and ethylene/propylene/high class α-olefin/nonconjugation polyene random copolymer (B) in which the mole ratio of ethylene/propylene + high class α olefin is 82/18-95/5, the mole ratio of propylene/high class α-olefin is 1/99-50/50, the iodine value 5-45, the Mooney viscosity is 10-350, and the ratio of Mw/Mn is 2-15, are individually or mixingly used, and a vulcanizing agent and/or a cross linking agent are contained therein.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a rubber composition for a weatherstrip, and more particularly, to a rubber composition for a weatherstrip excellent in hardness, mechanical strength, low-temperature properties and the like.

[0002]

2. Description of the Related Art Conventionally, ethylene / α-olefin / non-conjugated diene copolymers have excellent weather resistance, heat resistance, cold resistance, ozone resistance, etc., and are used as building materials, automotive parts, electric wire coating materials, and the like. Although widely used, it has heretofore been difficult to impart further excellent mechanical properties such as high hardness and high strength to the composition without deteriorating the inherent characteristics of the copolymer. For example, by using an ethylene / α-olefin / non-conjugated diene copolymer having a high ethylene content, using a large amount of a vulcanizing agent and a large amount of a reinforcing agent, and blending a small amount of a softening agent or a plasticizer, a high level can be obtained. A method for obtaining a vulcanized rubber having a hardness is known. However, in such a method, the Mooney viscosity of the unvulcanized rubber composition becomes very large,
There is a problem that kneading by a Banbury mixer and processing by a roll become difficult, fluidity at the time of extrusion molding and injection molding is reduced, and elongation at break and compression set are also reduced in physical properties. A method of blending an ethylene / α-olefin / non-conjugated diene copolymer with a polystyrene resin to increase the hardness has also been proposed, but in this case, there is a problem that the mechanical strength of the vulcanized rubber is reduced. In addition, any of these methods has a problem in that the intrinsic properties of the ethylene / α-olefin / non-conjugated diene copolymer such as cold resistance and heat resistance are impaired. Further, 65 to 85% by weight of ethylene, 1 to 25% by weight of α-olefin and 10 to 18% by weight of a non-conjugated diene.
Rubber composition comprising sulfur blended with ethylene / α-olefin / non-conjugated diene copolymer rubber consisting of
No. 450), ethylene, α having 3 to 10 carbon atoms.
The respective contents of olefin and non-conjugated diene, intrinsic viscosity, molecular weight distribution (Mw / Mn), crystallinity, B value related to the mole fraction of α-olefin-ethylene chain, and the amount of soluble methyl boiling acetate. A low-crystalline ethylene random copolymer in which no αβ and βγ signals based on the methylene chain between two adjacent tertiary carbon atoms are identified in the ¹³ C-NMR spectrum (JP-B 5-8049)
No. 3) has been proposed. However, mechanical properties such as modulus, tensile strength, elongation at break, and hardness of these copolymer rubbers and vulcanized rubbers obtained from the copolymers have been studied. / Α-olefin / non-conjugated diene copolymers have not been studied in terms of their overall characteristics, and the methods described in the above-mentioned publications show that ethylene / α-olefins are excellent in both mechanical properties and cold resistance. The technical problem of obtaining a / non-conjugated diene copolymer composition has not been solved yet.

[0003]

SUMMARY OF THE INVENTION The object of the present invention was made in view of the above-mentioned circumstances in the prior art. The object of the present invention is to provide high hardness, mechanical properties such as strength and compression set and low temperature. An object of the present invention is to provide a rubber composition for a weatherstrip excellent in both properties and properties.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a composition containing a specific ethylene copolymer has an excellent property balance. They have found and completed the present invention. The gist of the present invention consists of a rubber composition for a weatherstrip comprising the following copolymer (A) and / or copolymer (B) and a vulcanizing agent and / or a crosslinking agent. Copolymer (A): (1) Molar ratio of ethylene to α-olefin having 6 to 12 carbon atoms (ethylene / α-olefin having 6 to 12 carbon atoms)
(2) iodine value is in the range of 5-45, (3) Mooney viscosity (M
(L1 + 4, 100 ° C.) is in the range of 10 to 350, (4)
The ratio (Mw / Mn) between the weight average molecular weight (Mw) in terms of polystyrene and the number average molecular weight (Mn) in terms of polystyrene determined by GPC is in the range of 2 to 15. Ethylene / α-olefin having 6 to 12 carbon atoms / non- Conjugated polyene random copolymer. Copolymer (B): (1) The molar ratio of ethylene to propylene and the total amount of α-olefins having 6 to 12 carbon atoms (ethylene / (propylene + α-olefins having 6 to 12 carbon atoms)) is 82 /
(2) The molar ratio of propylene to α-olefin having 6 to 12 carbon atoms (propylene / α-olefin having 6 to 12 carbon atoms) is 1/99 to 50.
/ 50, (3) iodine value is in the range of 5-45, (4) Mooney viscosity (ML1 + 4, 100 ° C) is in the range of 10-350, (5) determined by GPC The ratio (Mw / Mn) between the weight average molecular weight (Mw) in terms of polystyrene and the number average molecular weight (Mn) in terms of polystyrene is in the range of 2 to 15 ethylene / propylene / α-olefin having 6 to 12 carbon atoms / non-conjugated Polyene random copolymer.

The copolymer (A) and the copolymer (B) constituting the rubber composition for a weatherstrip of the present invention are described below.
Will be described sequentially. Copolymer (A) The copolymer (A) is ethylene, an α-olefin having 6 to 12 carbon atoms (hereinafter referred to as “higher α-olefin”),
And a non-conjugated polyene. Examples of the higher α-olefin in the copolymer (A) include 1-hexene, 4-methyl-1-pentene, 1-heptene, 5-methyl-1-hexene, 1-octene,
-Nonene, 5-ethyl-1-hexene, 1-decene, 1
-Dodecene and the like. These higher α-olefins can be used alone or in combination of two or more. Molar ratio of ethylene to higher α-olefin in copolymer (A) (ethylene / higher α-olefin)
Is 82/18 to 95/5, preferably 85/15 to 9
It is in the range of 3/7. In this case, the molar ratio is 82/1
If it is less than 8, mechanical strength is not sufficiently exhibited, and 95
If / 5 is exceeded, rubber elasticity is impaired. The non-conjugated polyene in the copolymer (A) includes, for example, 5
-Vinyl-2-norbornene, 5-ethylidene-2-norbornene, 2,5-norbornadiene, dicyclopentadiene, 5-propylidene-2-norbornene, 1,
Cyclic polyenes such as 4-dicyclohexadiene, 1,4-dicyclooctadiene and 1,5-dicyclooctadiene; 1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,6-octadiene; 7-methyl-1,6
Linear polyenes such as -octadiene, 3,7-dimethyl-1,6-octadiene, and 5,7-dimethyl-1,6-octadiene; and preferably 5-ethylidene-.
2-norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene are used. These non-conjugated polyenes can be used alone or in combination of two or more. Also, together with the non-conjugated polyene, 1,5
-Hexadiene, 2-methyl-1,5-hexadiene,
Α, ω such as 1,7-octadiene and 1,9-decadiene
-One or more chain dienes may be used in combination. The iodine value of the copolymer (A) is in the range of 5-45, preferably 10-35. In this case, if the iodine value is less than 5, the mechanical strength is poor, and if it exceeds 45, the rubber elasticity is impaired. The Mooney viscosity (ML1 + 4, 100 ° C.) (hereinafter simply referred to as “Mooney viscosity”) of the copolymer (A) is in the range of 10 to 350, preferably 20 to 300. Further, the ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight (Mw) to the polystyrene-equivalent number average molecular weight (Mn) of the copolymer (A) measured by GPC (gel permeation chromatography) is 2 to 2.
It is in the range of 15 and preferably in the range of 2 to 10. In the present invention, the copolymer (A) can be used alone or in combination of two or more.

Copolymer (B) The copolymer (B) is a copolymer comprising ethylene, propylene, a higher α-olefin and a non-conjugated polyene. In the copolymer (B), the molar ratio of ethylene to the total amount of propylene and higher α-olefin (ethylene /
(Propylene + higher α-olefin)) is 82/18
９５95/5, preferably 85/15８５92/8. In this case, if the molar ratio is less than 82/18, the mechanical strength is not sufficiently exhibited, and if it exceeds 95/5, the rubber elasticity is impaired. The molar ratio of propylene to higher α-olefin (propylene / higher α-olefin) in the copolymer (B) is in the range of 1/99 to 50/50, preferably 1/99 to 25/75. As the higher α-olefin in the copolymer (B), for example,
1-hexene, 4-methyl-1-pentene, 1-heptene, 5-methyl-1-hexene, 1-octene, 1-nonene, 5-ethyl-1-hexene, 1-decene, 1-dodecene, and the like. Can be These higher α-olefins are
They can be used alone or in combination of two or more. In the copolymer (B), the molar ratio of ethylene to the total amount of propylene and higher α-olefin (ethylene /
(Propylene + α-olefin having 6 to 12 carbon atoms)
Is 82/18 to 95/5, preferably 85/15 to 9
It is in the range of 2/8. In this case, the molar ratio is 82/1
If it is less than 8, mechanical strength is not sufficiently exhibited, and 95
If / 5 is exceeded, rubber elasticity is impaired. As the non-conjugated polyene in the copolymer (B), for example, 5-
Vinyl-2-norbornene, 5-ethylidene-2-norbornene, 2,5-norbornadiene, dicyclopentadiene, 5-propylidene-2-norbornene, 1,4
Cyclic non-conjugated polyenes such as -dicyclohexadiene, 1,4-dicyclooctadiene and 1,5-dicyclooctadiene; 1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,6-octadiene , 7-methyl-1,
Examples include chain polyenes such as 6-octadiene, 3,7-dimethyl-1,6-octadiene, and 5,7-dimethyl-1,6-octadiene, and preferably 5-ethylidene-2-norbornene and dicyclopentadiene. , 7-methyl-1,6-octadiene are used. These non-conjugated polyenes can be used alone or in combination of two or more. Further, together with the non-conjugated polyene,
One or more kinds of α, ω-chain dienes such as 5-hexadiene, 2-methyl-1,5-hexadiene, 1,7-octadiene and 1,9-decadiene can be used in combination. The iodine value of the copolymer (B) is in the range of 5-45, preferably 10-35. In this case, if the iodine value is less than 5, the mechanical strength is poor, and if it exceeds 45, the rubber elasticity is impaired. The Mooney viscosity of the copolymer (B) is 10 to 350, preferably 20 to 300.
In the range. Further, the ratio (Mw / Mn) of Mw to Mn in the copolymer (B) is 2 to 15, preferably 2
-10. In the present invention, the copolymer (B)
Can be used alone or in combination of two or more.

Production of copolymer (A) and copolymer (B)
The copolymer (A) and the copolymer (B) are produced by a gas phase polymerization method,
It can be produced by an appropriate method such as a solution polymerization method or a slurry polymerization method. These polymerization operations can be carried out in a batch system or a continuous system. In the solution polymerization method or the slurry polymerization method, an inert hydrocarbon is usually used as a reaction medium, and in some cases, a raw material monomer can be used as a reaction medium. Examples of the inert hydrocarbon medium include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane and dodecane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatics such as benzene, toluene and xylene. Hydrocarbons and the like. These inert hydrocarbon media can be used alone or in combination of two or more.

The polymerization catalyst used for producing the copolymer (A) and the copolymer (B) of the present invention is, for example, a compound of a transition metal selected from vanadium, titanium, zirconium and hafnium and an organic metal. An olefin polymerization catalyst comprising a compound can be mentioned. The transition metal compound and the organometallic compound can be used alone or in combination of two or more. As a particularly preferred example of such an olefin polymerization catalyst, a metallocene catalyst comprising a metallocene compound and an organoaluminum compound or an ionic compound which reacts with the metallocene compound to form an ionic complex can be mentioned. Hereinafter, the metallocene-based catalyst for producing the copolymers (A) and (B) will be described more specifically, but other polymerization catalysts may be used in some cases. Examples of the metallocene catalyst include a catalyst comprising the following components (a) and (b) or a catalyst comprising the following components (c) and (d). Component (a) is a transition metal compound represented by the following general formula [I]. R in _{''s (C 5 R m)} p (R' n E) q MQ 4-pq ... [1] equation, M is the Group 4 metal of the periodic table, (C ₅ R _m) are A cyclopentadienyl group or a substituted cyclopentadienyl group, each R may be the same or different, and includes a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, Is an alkaryl group of -40 or an aralkyl group of 7-40 carbon atoms, or two adjacent carbon atoms are bonded to form a 4- to 8-membered carbon ring, and E has a non-bonded electron pair R ′ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms, or
40 is an aralkyl group, R '' is an alkylene group having 1 to 20 carbon atoms, dialkylsilicon or dialkylgermanium, which is a group binding two ligands,
Is 1 or 0, and when s is 1, m is 4 and n is E
Is two less than the valence of, and when s is 0, m is 5
Wherein n is one less than the valence of E, and when n ≧ 2, each R ′ may be the same or different, and each R ′ may be bonded to form a ring, and Q is Hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, 6 to 40 carbon atoms
An alkaryl group having 7 to 40 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, and p and q are 0
４4 and satisfies the relationship 0 <p + q ≦ 4.

Specific examples of component (a) include bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) ) Zirconium diphenyl, dimethylsilylbis (cyclopentadienyl) zirconium dichloride, dimethylsilylbis (cyclopentadienyl) zirconium dimethyl, methylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (cyclopentadienyl) zirconium dichloride, bis (Indenyl) zirconium dichloride, bis (indenyl) zirconium dimethyl, dimethylsilylbis (indenyl) zirconium dichloride, methylenebis (indenyl) zircon Umujikurorido, bis (4,
5,6,7-tetrahydroindenyl) zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, dimethylsilylbis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride , Dimethylsilylbis (4,5
6,7-tetrahydro-1-indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadiene) Enyl) zirconium dimethyl, dimethylsilyl bis (3-methyl-1-cyclopentadienyl) zirconium dichloride, methylene bis (3-methyl-1-cyclopentadienyl) zirconium dichloride, bis (tertiary butylcyclopentadienyl) Zirconium dichloride, dimethylsilylbis (3-tert-butyl-1-cyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (2,4-di Chill-1-cyclopentadienyl) zirconium dichloride, bis (1,2,4-trimethyl cyclopentadienyl) zirconium dichloride, dimethyl silyl bis (2,3,5-trimethyl -1
-Cyclopentadienyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, dimethylsilylbis (fluorenyl) zirconium dichloride,
(Fluorenyl) (cyclopentadienyl) zirconium dichloride, dimethylsilyl (fluorenyl) (cyclopentadienyl) zirconium dichloride, isopropylene (fluorenyl) (cyclopentadienyl) zirconium dichloride, (tertiary butylamide) (1,
2,3,4,5-pentamethylcyclopentadienyl)
Zirconium dichloride, dimethylsilyl (tertiary butylamide) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, methylene (tertiary butylamide) (2,3,4,5-tetra Methyl-1-cyclopentadienyl) zirconium dichloride, (phenoxy) (1,2,3,4,5-pentamethylcyclopentadienyl) zirconium dichloride, dimethylsilyl (o-phenoxy) (2,3,4, 5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, methylene (o-phenoxy) (2,3
4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, ethylene (o-phenoxy)
(2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dichloride, bis (dimethylamido) zirconium dichloride, bis (diethylamide)
Zirconium dichloride, bis (di-tert-butylamido) zirconium dichloride, dimethylsilylbis (methylamide) zirconium dichloride, dimethylsilylbis (tertiary-butylamido) zirconium dichloride and the like, and compounds in which zirconium in these compounds is replaced with titanium or hafnium But
It is not limited to these. The transition metal compounds can be used alone or in combination of two or more.

The component (b) is an aluminoxane compound having a structural unit represented by the following general formula [2], and although the chemical structure is not necessarily clear, a linear, cyclic or cluster compound Or a mixture of these compounds. -[Al (R) -O]-... [2] wherein R is an alkyl group having 1 to 20 carbon atoms, and 6 to 4 carbon atoms.
An aryl group having 0, an alkaryl group having 7 to 40 carbon atoms, or an aralkyl group having 7 to 40 carbon atoms, preferably a methyl group, an ethyl group, an isobutyl group, and particularly preferably a methyl group. The aluminoxane compound can be produced by a known method via a reaction between water and the organoaluminum compound having at least one R group. The use ratio of the component (a) and the component (b) is usually from 1: 1 to 1:10 in a molar ratio between the transition metal and the aluminum atom.
0000, preferably in the range of 1: 5 to 1: 50,000.

Next, the component (c) is a transition metal alkyl compound represented by the following general formula [3]. R ″ s (C ₅ R _m ) _p (R ′ _n E) _q MR ″ ′ _4-pq ... [3] In the formula, M is a metal of Group 4 of the periodic table, and (C ₅ R _m ) is a cyclopentadienyl group or a substituted cyclopentadienyl group, and each R may be the same or different and includes a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, Is an alkaryl group having 7 to 40 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, or two adjacent carbon atoms are bonded to form a 4- to 8-membered carbocyclic ring; Wherein R ′ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms, or
40 is an aralkyl group, R '' is an alkylene group having 1 to 20 carbon atoms, dialkylsilicon or dialkylgermanium, which is a group binding two ligands,
Is 1 or 0, and when s is 1, m is 4 and n is E
Is two less than the valence of, and when s is 0, m is 5
Wherein n is a number less than the valence of E, and when n ≧ 2, each R ′ may be the same or different, and each R ′ may be bonded to form a ring; '' Represents 1 to 2 carbon atoms
An alkyl group having 0, an aryl group having 6 to 40 carbon atoms, an alkaryl group having 7 to 40 carbon atoms or an aralkyl group having 7 to 40 carbon atoms, p and q are integers of 0 to 3, and 0 < The relationship of p + q ≦ 4 is satisfied.

Specific examples of component (c) include bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diethyl, bis (cyclopentadienyl) zirconium diisobutyl, and bis (cyclopentadienyl) Zirconium diphenyl, bis (cyclopentadienyl) zirconium di {bis (trimethylsilyl) methyl}, dimethylsilylbis (cyclopentadienyl) zirconium dimethyl, dimethylsilylbis (cyclopentadienyl) zirconium diisobutyl, methylenebis (cyclopentadienyl) ) Zirconium dimethyl, ethylene bis (cyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, bis (indenyl) zirconium diisobutyl, dimethyl Rubis (indenyl) zirconium dimethyl, methylenebis (indenyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dimethyl, bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, dimethylsilylbis (4,5,6,7 -Tetrahydro-1-indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-
Tetrahydro-1-indenyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (3-methyl-1-cyclopentadienyl) zirconium dimethyl, bis (third
Tert-butylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (3-tert-butyl-1-cyclopentadienyl) zirconium dimethyl, bis (1,
3-dimethylcyclopentadienyl) zirconium dimethyl, bis (1,3-dimethylcyclopentadienyl)
Zirconium diisobutyl, dimethylsilylbis (2,
4-dimethyl-1-cyclopentadienyl) zirconium dimethyl, methylenebis (2,4-dimethyl-1-cyclopentadienyl) zirconium dimethyl, ethylenebis (2,4-dimethyl-1-cyclopentadienyl)
Zirconium dimethyl, bis (1,2,4-trimethylcyclopentadienyl) zirconium dimethyl, dimethylsilylbis (2,3,5-trimethyl-1-cyclopentadienyl) zirconium dimethyl, bis (fluorenyl) zirconium dimethyl, dimethyl Silylbis (fluorenyl) zirconium dimethyl, (fluorenyl)
(Cyclopentadienyl) zirconium dimethyl, dimethylsilyl (fluorenyl) (cyclopentadienyl)
Zirconium dimethyl, isopropylene (fluorenyl) (cyclopentadienyl) zirconium dimethyl,
(Tertiary butylamide) (1,2,3,4,5-pentamethylcyclopentadienyl) zirconium dimethyl,
Dimethylsilyl (tertiary butylamide) (2,3,4
5-tetramethyl-1-cyclopentadienyl) zirconium dimethyl, methylene (tertiary butylamide)
(2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dimethyl, (phenoxy) (1,
2,3,4,5-pentamethylcyclopentadienyl)
Zirconium dimethyl, dimethylsilyl (o-phenoxy) (2,3,4,5-tetramethyl-1-cyclopentadienyl) zirconium dimethyl, methylene (o-phenoxy) (2,3,4,5-tetramethyl- 1-cyclopentadienyl) zirconium dimethyl, bis (dimethylamido) zirconium dimethyl, bis (diethylamido) zirconium dimethyl, bis (di-tert-butylamido) zirconium dimethyl, dimethylsilylbis (methylamido) zirconium dimethyl, dimethylsilylbis (dimethyl Tertiary butyl amide) zirconium dimethyl,
Examples include compounds in which zirconium in these compounds is replaced with titanium or hafnium, but is not limited thereto. The transition metal alkyl compounds can be used alone or in combination of two or more. The transition metal alkyl compound may be synthesized and used in advance, or may be a transition metal halide in which R ″ in the general formula [3] is substituted with a halogen atom, and trimethylaluminum, triethylaluminum, diethylaluminum monochloride. And an organometallic compound such as triisobutylaluminum, methyllithium or butyllithium in the reaction system.

The component (d) is an ionic compound represented by the following general formula [4]. ([L] ^{k +} ) _p ([M'A ¹ A ² ... A ⁿ ] ^- ) _q ... [4] wherein [L] ^{k +} is a Bronsted acid or a Lewis acid, and M 'is periodic table is the 13 to 15 group elements, a ¹ ~
^An is a hydrogen atom, a halogen atom, and a carbon number of 1 to 2, respectively.
0 alkyl group, C1-C30 dialkylamino group, C1-C20 alkoxy group, C6-C40 aryl group, C6-C40 aryloxy group, C7-C40 alka A reel group, an aralkyl group having 7 to 40 carbon atoms, a halogen-substituted hydrocarbon group having 1 to 40 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, or an organic metalloid group; Is an integer, p is an integer of 1 or more, and q = (k × p). Specific examples of component (d) include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tributylammonium tetraphenylborate, methyl (dibutyl) ammonium tetraphenylborate, dimethylanilinium tetraphenylborate,
Methylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium), methyl tetraphenylborate (4-cyanopyridinium), trimethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl)
Triethylammonium borate, tributylammonium tetrakis (pentafluorophenyl) borate, methyl (dibutyl) ammonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, tetrakis ( Methyl pentafluorophenyl) borate (2-
Cyanopyridinium), methyl tetrakis (pentafluorophenylphenyl) borate (4-cyanopyridinium), dimethylanilinium tetrakis [bis (3,5-di-trifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, silver tetraphenylborate And ferrocenium tetrakis (pentafluorophenyl) borate and the like, but are not limited thereto. The ionic compounds can be used alone or in combination of two or more. The use ratio of the component (c) and the component (d) is usually 1: 0.5 to 1:20 in a molar ratio ((c) :( d)).
Preferably it is in the range of 1: 0.8 to 1:10. The metallocene catalyst can be used by supporting at least a part of the components on a suitable carrier. The type of such a carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used. There is no particular limitation on the supporting method, and a known method may be appropriately employed.

Vulcanizing Agent and Crosslinking Agent Further, the vulcanizing agent and the crosslinking agent used in the present invention will be described. As the vulcanizing agent, for example, powder sulfur,
Sulfur such as precipitated sulfur, colloidal sulfur, and insoluble sulfur; inorganic vulcanizing agents such as sulfur chloride, selenium, and tellurium; and sulfur-containing organic compounds such as morpholine disulfide, alkylphenol disulfide, thiuram disulfide, and dithiocarbamate. These vulcanizing agents can be used alone or in combination of two or more. The compounding amount of the vulcanizing agent is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight based on 100 parts by weight of the copolymer (A) and / or the copolymer (B). is there. Further, a vulcanization accelerator can be used together with the vulcanizing agent. Such vulcanization accelerators include, for example, aldehyde ammonias such as hexamethylenetetramine; guanidines such as diphenylguanidine, di (o-tolyl) guanidine, o-trilupiguanide; thiocarbanilide, di (o- Thioureas such as tolyl) thiourea, N, N'-diethylthiourea, tetramethylthiourea, trimethylthiourea, dilaurylthiourea; mercaptobenzothiazole, dibenzothiazole disulfide, 2- (4-morpholinothio) benzothiazole,
Thiazoles such as 2- (2,4-dinitrophenyl) -mercaptobenzothiazole and (N, N'-diethylthiocarbamoylthio) benzothiazole; N-tert-butyl-2-benzothiazylsulfene Amides, N, N '
Sulfenamides such as -dicyclohexyl-2-benzothiazylsulfenamide, N, N'-diisopropyl-2-benzothiazylsulfenamide, N-cyclohexyl-2-benzothiazylsulfenamide; tetramethylthiuram Thiurams such as disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide; zinc dimethylthiocarbamate, zinc diethylthiocarbamate;
Carbamates such as zinc di-n-butylthiocarbamate, zinc ethylphenyldithiocarbamate, sodium dimethyldithiocarbamate, copper dimethyldithiocarbamate, tellurium dimethylthiocarbamate and iron dimethylthiocarbamate; zinc butylthioxanthate; Xanthates and the like. These vulcanization accelerators can be used alone or in combination of two or more. The amount of the vulcanization accelerator is determined by the amount of the copolymer (A)
And / or 100 parts by weight of copolymer (B),
Usually, it is 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight. Further, in addition to the vulcanizing agent and the vulcanization accelerator, a vulcanization acceleration auxiliary may be added as necessary. Examples of such vulcanization accelerating aids include metal oxides such as magnesium oxide, zinc white, litharge, leadtan, lead white; stearic acid, oleic acid, and organic acids such as zinc stearate. Particularly preferred are zinc white and stearic acid. These vulcanization accelerators can be used alone or in combination of two or more. The amount of the vulcanization accelerator is usually 0.5 to 20 parts by weight based on 100 parts by weight of the copolymer (A) and / or the copolymer (B). Next, as the crosslinking agent, for example, 1,1
Di-tert-butylperoxy-3,3,5-trimethylcyclohexane, di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide,
Organic peroxides such as 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and 1,3-bis (tert-butylperoxy-isopropyl) benzene are exemplified. These crosslinking agents can be used alone or in combination of two or more. The amount of the crosslinking agent to be added is generally 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the copolymer. In addition, a crosslinking aid can be used together with the crosslinking agent. Examples of such a crosslinking aid include sulfur and sulfur compounds such as dipentamethylenethiuram tetrasulfide; ethylene di (meth) acrylate, polyethylene di (meth)
Polyfunctional monomers such as acrylate, divinylbenzene, diallyl phthalate, triallyl cyanurate, metaphenylene bismaleimide, and toluylene bismaleimide; oxime compounds such as p-quinone oxime and p, p'-benzoylquinone oxime; Can be These crosslinking assistants can be used alone or in combination of two or more. The compounding amount of the crosslinking aid is determined according to the copolymer (A).
And / or 100 parts by weight of copolymer (B),
Usually, it is 0.5 to 20 parts by weight.

Other Additives In addition to fillers, softeners and foaming agents, a plasticizer, a lubricant,
Various other additives, such as a tackifier, an antioxidant, and an ultraviolet absorber, may be added. Examples of the filler include SRF, FEF, HAF, ISAF, SAF, F
Carbon black such as T and MT; white carbon;
Inorganic fillers such as fine particle magnesium silicate, calcium carbonate, magnesium carbonate, clay, talc and the like can be mentioned. These fillers can be used alone or in combination of two or more. The amount of the filler is usually 10 to 200 parts by weight, preferably 10 to 1 part by weight, per 100 parts by weight of the copolymer (A) and / or the copolymer (B).
00 parts by weight. Examples of the softening agent include, for example, process oils such as aromatic oils, naphthenic oils, and paraffin oils that are generally used for rubber; vegetable oils such as palm oil; and synthetic oils such as alkylbenzene-based oils. Of these, process oils are preferred, and paraffin oil is particularly preferred. The softeners can be used alone or in combination of two or more. The amount of the softening agent is usually 10 to 130 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the copolymer (A) and / or the copolymer (B). Examples of the foaming agent include inorganic foaming agents such as ammonium carbonate, sodium bicarbonate, and anhydrous sodium nitrate; dinitrosopentamethylenetetramine, N, N′-dimethyl-N,
Organic foaming agents such as N'-dinitrosoterephthalamide, benzenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), 3,3'-disulfone hydrazide diphenyl sulfone, azoisobutyronitrile, azobisformamide and the like. Can be Further, a foaming aid such as a urea-based, organic acid-based, or metal salt-based foam may be used together with these foaming agents. These foaming agents and foaming assistants can be used alone or in combination of two or more. Further, the rubber composition for a weatherstrip of the present invention may comprise butyl rubber, natural rubber, polyisoprene rubber, polybutadiene rubber, styrene / butadiene copolymer, acrylonitrile-butadiene copolymer, and other types of ethylene / α-olefin / non-conjugated. Diene copolymer,
One or more other rubbers or resins such as ethylene / α-olefin polymers, polyethylene, and polypropylene can be used as a mixture.

[0016] In preparing the weather strip rubber composition for the preparation of compositions and vulcanization present invention may be used conventionally known kneader, extruder, the vulcanizing apparatus or the like. A vulcanizing agent and / or a cross-linking agent mixed with the copolymer (A) and / or the copolymer (B),
The method and order of blending the filler and the plasticizer are not particularly limited. For example, using a Banbury mixer or the like, the copolymer (A) and / or the copolymer (B), the filler, and the plasticizer are used. And then adding a vulcanizing agent and / or a cross-linking agent using a roll or the like.
Next, in the method used for normal vulcanized rubber production, for example,
Either vulcanize by placing the rubber composition in a mold and raising the temperature, or by vulcanizing by heating in a vulcanization tank after molding into an arbitrary shape using an extruder, Vulcanized rubber can be manufactured. The rubber composition for a weatherstrip of the present invention can be suitably used for applications such as sponge products for automobiles and glass runs.

[0017]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be described more specifically with reference to the following examples. However, the present invention
The present invention is not limited to these embodiments. The measurement and evaluation in Examples and Comparative Examples were performed by the following methods. (A) Propylene content and higher α-olefin content (mol%) were measured by ¹³ C-NMR method. However, the content (mol%) of ethylene, propylene and higher α-olefin is
The values are shown assuming that the total amount of these is 100 mol%. (Ii) Iodine value It was measured by an infrared absorption spectrum method. (C) Mooney viscosity Measured at a measurement temperature of 100 ° C., a preheating time of 1 minute, and a measurement time of 4 minutes in accordance with JIS K6300. (D) using a Mw / Mn o-dichlorobenzene solvent at 135 ° C.
Measured by C. (E) Tensile test The tensile strength TB (MPa) and elongation at break EB (%) were measured using a No. 3 type test piece at a measurement temperature of 25 ° C. and a tensile speed of 500 mm / min in accordance with JIS K6301. It was measured. (F) Hardness test According to JIS K6301, the spring hardness (JIS
-A hardness) was measured. (G) Compression set test Based on JIS K6301, it was measured at 70 ° C. for 22 hours. (H) Low-temperature torsion test (German temperature) T5 (° C.) was measured according to JIS K6301.

[0018]

【Example】

Example 1 (Production of copolymer (A)) Content 2 sufficiently substituted with nitrogen
500 ml of purified toluene, 500 ml of 1-hexene, 10 ml of dicyclopentadiene, and 6 mmol of methylaluminoxane in terms of aluminum atoms dissolved in 4 ml of purified toluene were added to a 1 liter stainless steel autoclave.
After the temperature was raised to 0 ° C., the pressure was increased with ethylene to make the ethylene partial pressure 4 kg / cm ² . Then, purified toluene 1.
1.2 μmol of dicyclopentadienyl zirconium dichloride dissolved in 2 ml was added to initiate the polymerization. During the reaction, the temperature was kept at 40 ° C., and the reaction was carried out for 30 minutes while continuously supplying ethylene so that the ethylene partial pressure was kept at 4 kg / cm ² . After the reaction,
The polymer solution was poured into 2 liters of methanol to precipitate a polymer, and the precipitated polymer was separated by filtration and dried under reduced pressure to obtain 104 g of a polymer. This polymer has an ethylene content of 85.2 mol% and a 1-hexene content of 1
4.8 mol%, iodine value 16, Mooney viscosity 45, Mw
/ Mn 3.2 was an ethylene / 1-hexene / dicyclopentadiene copolymer. This copolymer is called copolymer
(A-1). (Preparation and evaluation of composition) The copolymer (A-1) and each component obtained by removing the vulcanizing agent component from the components shown in Table 1 were subjected to rotation speed using a Labo Plastomill (content: 250 ml). 60
The mixture was kneaded at 60 ° C. for 150 seconds to obtain a compound (i). Next, the vulcanizing agent component was added to the compound (i) and kneaded with a 10-inch roll maintained at 50 ° C. for 5 minutes to obtain a compound (ii). Next, the compound (ii) was heated by heating at 160 ° C.
Heating was performed for 30 minutes under a press pressure of 150 kgf / cm ² to prepare a vulcanized sheet of 120 × 120 × 2 mm and a sample for compression set test, and various characteristics were evaluated. As a result, the composition using the copolymer (A-1) was high in hardness and excellent in both mechanical properties such as strength and compression set and low-temperature properties. Table 2 shows the evaluation results.

Example 2 (Production of copolymer (A)) Instead of 1-hexene and dicyclopentadiene, 1-octene and 5-ethylidene-2-norbornene (hereinafter referred to as "ENB") were used, respectively.
122 g of a polymer was obtained in the same manner as in Example 1, except that ethylenebis (indenyl) zirconium dichloride was used instead of dicyclopentadienylzirconium dichloride. This polymer had an ethylene content of 84.7 mol% and a 1-octene content of 15.3.
Mol%, iodine value 18, Mooney viscosity 52, Mw / Mn
2.3 ethylene / 1-octene / ENB copolymer. This copolymer is referred to as copolymer (A-2). (Preparation and evaluation of composition) Compound (i) and compound (ii) were prepared and various properties were evaluated in the same manner as in Example 1 except that copolymer (A-2) was used. As a result, the composition using the copolymer (A-2) has high hardness,
It was excellent in both mechanical properties such as strength and compression set and low-temperature properties. Table 2 shows the evaluation results.

Example 3 (Production of copolymer (A))
To a liter stainless steel autoclave, 850 ml of purified toluene, 150 ml of 1-decene, 15 ml of 1,4-hexadiene, and 6 mmol of methylaluminoxane were added, and after the temperature was raised to 40 ° C, pressure was applied with ethylene. 4 kg / c ethylene partial pressure
It was m ^2. Separately, dimethylsilyl (tertiary butylamide) (2,3,3) dissolved in 1.2 ml of purified toluene was placed in a 50 ml-volume glass flask containing a magnetic stirrer and sufficiently purged with nitrogen. 4,5
-Tetramethyl-1-cyclopentadienyl) titanium dichloride (1.2 μmol) and triisobutylaluminum dissolved in purified toluene (2.4 ml) were added thereto, and the mixture was stirred and reacted at room temperature for 30 minutes. Thereafter, 6 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate dissolved in 6 ml of purified toluene was added, and the mixture was stirred and reacted at room temperature for 20 minutes to synthesize a polymerization catalyst. This polymerization catalyst was added to the above-described autoclave to start polymerization. During the reaction, the reaction was carried out for 15 minutes while maintaining the temperature at 40 ° C. and continuously supplying ethylene so that the ethylene partial pressure was maintained at 4 kg / cm ² . After completion of the reaction, the polymer solution was poured into 2 liters of methanol to precipitate a polymer, and the precipitated polymer was separated by filtration and dried under reduced pressure to obtain 118 g of a polymer. This polymer has an ethylene content of 82.8 mol%, 1
Ethylene / 1-decene / decene content 17.2 mol%, iodine value 14, Mooney viscosity 50, Mw / Mn 2.2
It was a 1,4-hexadiene copolymer. This copolymer is referred to as copolymer (A-3). (Preparation and evaluation of composition) Compound (i) and compound (ii) were prepared and various properties were evaluated in the same manner as in Example 1 except that copolymer (A-3) was used. As a result, the composition using the copolymer (A-3) has a high hardness,
It was excellent in both mechanical properties such as strength and compression set and low-temperature properties. Table 2 shows the evaluation results.

Example 4 (Production of copolymer (A))
700 ml of purified toluene, 300 ml of 1-octene, 12 ml of ENB, and 6 mmol of methylaluminoxane in terms of aluminum atoms dissolved in 5 ml of purified toluene were added to a 1 liter stainless steel autoclave, and the temperature was raised to 30 ° C. Thereafter, the internal pressure of the container was adjusted to 4 kg / cm ² while continuously supplying ethylene at a rate of 14 normal liters / minute. Next, 1.2 μmol of ethylenebis (indenyl) zirconium dichloride dissolved in 1.5 ml of toluene was added to initiate polymerization. During the reaction, keep the temperature at 30 ° C, while continuously supplying ethylene,
The polymerization was carried out for 15 minutes while maintaining the pressure in the vessel at 4 kg / cm ² . After that, the reaction was stopped by adding a small amount of methanol, and then dissolved by steam stripping.
Drying was performed with an inch roll to obtain 131 g of a polymer. This polymer has an ethylene content of 91.5 mol%, 1
-An ethylene / 1-octene / ENB random copolymer having an octene content of 8.5 mol%, an iodine value of 15, a Mooney viscosity of 112, and Mw / Mn of 2.3. This copolymer is referred to as a copolymer (A-4). (Preparation and Evaluation of Composition) (Preparation and Evaluation of Composition) Preparation of Compound (i) and Compound (ii) in the same manner as in Example 1 except that the copolymer (A-4) was used. Various characteristics were evaluated. As a result, the composition using the copolymer (A-4) was high in hardness and excellent in both mechanical properties such as strength and compression set and low-temperature properties. Table 2 shows the evaluation results.

Example 5 (Production of copolymer A) In a 2-liter stainless steel autoclave sufficiently purged with nitrogen, purified toluene 700 ml, 1-octene 300 ml, ENB 12 ml, purified toluene 5 ml After adding 6 mmol of methylaluminoxane in terms of aluminum atoms dissolved therein and raising the temperature to 30 ° C., 14 normal liters / min of ethylene and 0.1 mol of hydrogen were added.
While continuously supplying at a rate of 6 normal liters / minute,
The pressure inside the container was adjusted to 4 kg / cm ² . Then, 1.2 μmol of ethylenebis (indenyl) zirconium dichloride dissolved in 4.5 ml of toluene was added to initiate polymerization. Keep the temperature at 30 ° C during the reaction,
While continuously supplying ethylene, the internal pressure of the container is set to 4 kg / c.
While maintaining the pressure at m ² , polymerization was carried out for 15 minutes. Thereafter, a small amount of methanol was added to stop the reaction, then the mixture was dissolved by steam stripping and dried with a 6-inch roll to obtain 118 g of a polymer. This polymer has an ethylene content of 90.5 mol%, a 1-octene content of 9.5 mol%, an iodine value of 14, a Mooney viscosity of 49, and Mw / Mn.
2.1 ethylene / 1-octene / ENB random copolymer. This copolymer is referred to as copolymer (A-5). (Preparation and Evaluation of Composition) Compound (i) and compound (ii) were prepared and various properties were evaluated in the same manner as in Example 1 except that the copolymer (A-5) was used. As a result, the composition using the copolymer (A-5) was high in hardness and excellent in both mechanical properties such as strength and compression set and low-temperature properties. Table 2 shows the evaluation results.

Example 6 (Production of Copolymer A) In a stainless steel autoclave having a content of 2 liters and sufficiently purged with nitrogen, 870 ml of purified toluene, 130 ml of 1-octene, 7-methyl-1,6-octadiene were prepared. Was added to 15 ml of purified toluene dissolved in 5 ml of purified toluene, and 6 mmol of methylaluminoxane in terms of aluminum atoms was added. While supplying continuously, the internal pressure of the container was adjusted to 5 kg / cm ² . Then, 2.0 μmol of isopropylene (fluorenyl) (cyclopentadienyl) zirconium dichloride dissolved in 4.5 ml of toluene was added to initiate polymerization. Keep the temperature at 50 ° C during the reaction,
While supplying ethylene continuously, the internal pressure of the container is 5 kg / c.
While maintaining the pressure at m ² , polymerization was carried out for 20 minutes. Thereafter, a small amount of methanol was added to stop the reaction, then the mixture was dissolved by steam stripping and dried with a 6-inch roll to obtain 88 g of a polymer. This polymer has an ethylene content of 88.5 mol%, a 1-octene content of 11.5 mol%, an iodine value of 13.5, a Mooney viscosity of 46, Mw /
Ethylene / 1-octene / 7-methyl with Mn of 2.1
It was a 1,6-octadiene random copolymer. This copolymer is referred to as copolymer (A-6). (Preparation and Evaluation of Composition) Compound (i) and compound (ii) were prepared and various properties were evaluated in the same manner as in Example 1 except that copolymer (A-6) was used. As a result, the composition using the copolymer (A-6) was high in hardness and excellent in both mechanical properties such as strength and compression set and low-temperature properties. Table 3 shows the evaluation results.

Example 7 (Production of copolymer A) In a 2-liter stainless steel autoclave sufficiently purged with nitrogen, 870 ml of purified toluene, 130 ml of 1-octene, 7-methyl-1,6-octadiene were prepared. Was added to 15 ml, 1.8 ml of 1,9-decadiene, and 6 mmol of methylaluminoxane in terms of aluminum atom dissolved in 5 ml of purified toluene.
After the temperature was raised to 14 ° C., 14 normal liters of ethylene /
The pressure inside the vessel was adjusted to 5 kg / cm ² while continuously supplying hydrogen at a rate of 1 normal liter / minute. Then, 2.0 μmol of isopropylene (fluorenyl) (cyclopentadienyl) zirconium dichloride dissolved in 4.5 ml of toluene was added to initiate polymerization. During the reaction, the polymerization was carried out for 20 minutes while maintaining the temperature at 50 ° C. and continuously supplying ethylene while maintaining the internal pressure of the vessel at 5 kg / cm ² . Thereafter, a small amount of methanol was added to stop the reaction, then the mixture was dissolved by steam stripping, and dried with a 6-inch roll.
g of polymer were obtained. This polymer has an ethylene content of 8
9 mol%, 1-octene content 11 mol%, iodine value 1
It was an ethylene / 1-octene / 7-methyl-1,6-octadiene / 1,9-decadiene random copolymer having a 3.5, a Mooney viscosity of 83 and an Mw / Mn of 5.4. This copolymer is referred to as copolymer (A-7). (Preparation and evaluation of composition) Compound (i) and compound (ii) were prepared and various properties were evaluated in the same manner as in Example 1 except that copolymer (A-7) was used. As a result, the composition using the copolymer (A-7) was high in hardness and excellent in both mechanical properties such as strength and compression set and low-temperature properties. Table 3 shows the evaluation results.

Example 8 (Production of copolymer A) In a 2-liter stainless steel autoclave sufficiently purged with nitrogen, 870 ml of purified toluene, 130 ml of 1-octene, 10 ml of ENB, 1,9- After adding 3.6 mmol of methylaluminoxane in terms of aluminum atom dissolved in 3.6 ml of decadiene and 5 ml of purified toluene and raising the temperature to 50 ° C., 14 normal liters / minute of ethylene and 1 normal liter / minute of hydrogen were added. 5kg while the container is continuously supplied at the speed of
/ Cm ² . Then isopropylene (fluorenyl) dissolved in 4.5 ml of toluene
(Cyclopentadienyl) zirconium dichloride2.
0 μmol was added to initiate the polymerization. During the reaction, the polymerization was carried out for 20 minutes while maintaining the temperature at 50 ° C. and continuously supplying ethylene while maintaining the internal pressure of the vessel at 5 kg / cm ² . Thereafter, a small amount of methanol was added to stop the reaction, then the mixture was dissolved by steam stripping, and dried with a 6-inch roll to obtain 89 g of a polymer. This polymer has an ethylene content of 88 mol%, a 1-octene content of 12 mol%, an iodine value of 16.5 and a Mooney viscosity of 10 mol.
5, ethylene / 1-octene / EN with Mw / Mn 5.8
B / 1,9-decadiene random copolymer. This copolymer is referred to as copolymer (A-8). (Preparation and evaluation of composition) Compound (i) and compound (ii) were prepared and various properties were evaluated in the same manner as in Example 1 except that copolymer (A-8) was used. As a result, the composition using the copolymer (A-8) was high in hardness and excellent in both mechanical properties such as strength and compression set and low-temperature properties. Table 3 shows the evaluation results.

Example 9 (Production of copolymer (B))
600 ml of purified toluene, 400 ml of 1-octene, 15 ml of ENB, and 6 mmol of methylaluminoxane in terms of aluminum atom dissolved in 5 ml of purified toluene were added to a 1 liter stainless steel autoclave, and the temperature was raised to 30 ° C. Thereafter, the inner pressure of the container was adjusted to 4 kg / cm ² while continuously supplying ethylene at a rate of 12 normal liters / minute and propylene at a rate of 2 normal liters / minute. Next, 1.2 μmol of ethylenebis (indenyl) zirconium dichloride dissolved in 1.5 ml of toluene was added to initiate polymerization. During the reaction, the temperature was kept at 30 ° C, and while the monomer was continuously supplied, the internal pressure of the container was set at 4k.
g / cm ² , and the reaction was carried out for 15 minutes. Thereafter, a small amount of methanol was added to stop the reaction, then the mixture was dissolved by steam stripping and dried with a 6-inch roll to obtain 115 g of a polymer. This polymer has an ethylene content of 84 mol% and a propylene content of 3.5.
Mol%, 1-octene content 12.5 mol%, molar ratio of propylene to higher α-olefin 21.9 / 78.1,
Ethylene / propylene / 1 having a molar ratio of 87.5 / 12.5 to the total amount of ethylene and propylene and 1-octene, an iodine value of 16, a Mooney viscosity of 95, and a Mw / Mn of 2.2.
-Octene / ENB random copolymer. This copolymer is referred to as copolymer (B-1). (Preparation and Evaluation of Composition) Compound (i) and compound (ii) were prepared and various properties were evaluated in the same manner as in Example 1 except that the copolymer (B-1) was used. As a result, the composition using the copolymer (B-1) was high in hardness and excellent in both mechanical properties such as strength and compression set and low-temperature properties. Table 3 shows the evaluation results.

Example 10 (Preparation of Copolymer (B)) In place of 1-octene, 1-
Except that hexene was used, 11
2 g of polymer were obtained. This polymer has an ethylene content of 83.6 mol%, a propylene content of 3.6 mol%, a 1-hexene content of 12.8 mol%, a molar ratio of propylene to higher α-olefin of 22/78, ethylene and propylene and 1-hexene. Molar ratio to the total amount of 87.2 / 12.
8, iodine value 15, Mooney viscosity 102.5, Mw / M
ethylene / propylene / 1-hexene / EN of n2.2
B was a random copolymer. This copolymer is referred to as copolymer (B-2). (Preparation and evaluation of composition) Compound (i) and compound (ii) were prepared and various properties were evaluated in the same manner as in Example 1 except that copolymer (B-2) was used. As a result, the composition using the copolymer (B-2) was high in hardness and excellent in both mechanical properties such as strength and compression set and low-temperature properties. Table 3 shows the evaluation results.

Comparative Examples 1 to 3 Instead of the copolymer (A-1), a comparative copolymer (ethylene / propylene / non-conjugated polyene copolymer shown in Table 4) obtained by a known polymerization method was used. Except for using C-1) to (C-3), a composition was prepared and various properties were evaluated in the same manner as in Example 1. As a result, the compositions using these copolymers were low in hardness and inferior in low-temperature characteristics, and were not satisfactory as a material for weatherstrip. Table 5 shows the evaluation results.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

[0033]

[Table 5]

[0034]

The rubber composition for a weatherstrip of the present invention has high hardness, and is excellent in both mechanical properties such as strength and compression set and low-temperature properties. Therefore, the weatherstrip rubber composition of the present invention has a high property balance as a material for weatherstrips such as sponge products for automobiles and glass runs.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Fumio Tsutsumi, Inventor Nippon Gosei Rubber Co., Ltd. 2-1-1-24 Tsukiji, Chuo-ku, Tokyo

Claims (1)

[Claims] 1. A weather strip rubber composition comprising the following copolymer (A) and / or copolymer (B) and a vulcanizing agent and / or a crosslinking agent. Copolymer (A): (1) Molar ratio of ethylene to α-olefin having 6 to 12 carbon atoms (ethylene / α-olefin having 6 to 12 carbon atoms)
(2) iodine value is in the range of 5-45, (3) Mooney viscosity (M
(L1 + 4, 100 ° C.) is in the range of 10 to 350, (4)
The ratio (Mw / Mn) between the weight average molecular weight (Mw) in terms of polystyrene and the number average molecular weight (Mn) in terms of polystyrene determined by GPC is in the range of 2 to 15. Ethylene / α-olefin having 6 to 12 carbon atoms / non- Conjugated polyene random copolymer. Copolymer (B): (1) The molar ratio of ethylene to propylene and the total amount of α-olefins having 6 to 12 carbon atoms (ethylene / (propylene + α-olefins having 6 to 12 carbon atoms)) is 82 /
(2) The molar ratio of propylene to α-olefin having 6 to 12 carbon atoms (propylene / α-olefin having 6 to 12 carbon atoms) is 1/99 to 50.
/ 50, (3) iodine value is in the range of 5-45, (4) Mooney viscosity (ML1 + 4, 100 ° C) is in the range of 10-350, (5) determined by GPC The ratio (Mw / Mn) between the weight average molecular weight (Mw) in terms of polystyrene and the number average molecular weight (Mn) in terms of polystyrene is in the range of 2 to 15 ethylene / propylene / α-olefin having 6 to 12 carbon atoms / non-conjugated Polyene random copolymer.