JPH09176402A - Heat-resistant rubber belt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat-resistant rubber belt which is excellent in resistances to heat aging and abrasion and has low-temp. softness by using a compsn. contg. a specific ethylene-α-olefin copolymer rubber obtd. by using a metallocene catalyst. SOLUTION: This belt is produced from a rubber compsn. contg. an ethylene-α-olefin copolymer rubber which is obtd. by randomly copolymerizing ethylene, a 3-12C α-olefin, and if necessary, a nonconjugated polyene in the presence of a metallocene catalyst and has a molar ratio of ethylene unit to the α-olefin unit of (60:40)-(80;20), an iodine value of 0-30, and an intrinsic viscosity (at 135 deg.C in decalin) of 1-3dl/g. Pref. the rubber compsn. contains two types of the copolymer rubber: one having an intrinsic viscosity higher than 0.95 times that of a linear ethylene-propylene copolymer having an ethylene content of 70mol% and the same wt. average mol.wt. as that of the copolymer rubber; and the other having an intrinsic viscosity of 0.2-0.95 times that of the ethylene- propylene copolymer. The compsn. can be easily processed on rolls, and the resultant belt is excellent in resistances to heat aging and abrasion and has low-temp. softness.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a heat resistant rubber belt,
More specifically, the present invention relates to a heat resistant rubber belt having excellent heat aging resistance, wear resistance and low temperature flexibility (cold resistance).

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene / propylene copolymer rubber (EPM) and ethylene / propylene / diene copolymer rubber (EPDM) do not have unsaturated bonds in the main chain, and therefore they are compared to general-purpose diene rubbers. It has excellent heat resistance and weather resistance and is used in many products such as automobile parts and industrial parts.

EPDM is obtained by introducing a diene component such as dicyclopentadiene or 5-ethylidene-2-norbornene into EPM in order to enable sulfur vulcanization. Is EP
Better than DM.

When sulfur vulcanization and peroxide vulcanization are compared, the thermal stability of the polysulfide bond formed in sulfur vulcanization is low, and therefore when heat aging resistance is required,
Peroxide vulcanization is selected.

Therefore, in the field where a heat-resistant rubber belt, a rubber hose, etc. have a long service life, and maintenance and inspection during the service period are to be minimized, that is, heat aging resistance is particularly required, the rubber is used as a rubber. EPM and peroxide vulcanization have been selected and used as the vulcanization system.

EPM is known to change the physical properties of the vulcanized rubber obtained depending on the ethylene content, molecular weight and the like. That is, the heat resistance is improved by increasing the ethylene content of the EPM, and the low temperature flexibility is improved by decreasing the ethylene content.

However, when the ethylene content is increased, the crystallinity develops, the inherent flexibility of the rubber is lost, and the roll processability also deteriorates. Therefore, heat aging resistance,
EP satisfying all of low temperature flexibility and roll processability
M is not used in products such as heat-resistant rubber belts and rubber hoses. These products use EPM with a low ethylene content, which emphasizes roll processability, and the heat-resistant aging required for the products. It cannot be said that the material has sufficient wear resistance and wear resistance.

Therefore, it has been desired to develop a heat resistant rubber belt which is excellent in low temperature flexibility as well as in heat aging resistance and abrasion resistance.

[0009]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and provides a heat resistant rubber belt which is excellent in heat aging resistance and abrasion resistance and is excellent in low temperature flexibility. Is intended.

[0010]

SUMMARY OF THE INVENTION The heat-resistant rubber belt according to the present invention contains ethylene, an α-olefin having 3 to 12 carbon atoms, and optionally an ethylene / α-olefin copolymer rubber (A) comprising a non-conjugated polyene. The ethylene / α-olefin-based copolymer rubber (A), which comprises a rubber composition formed by adding ethylene in the presence of a metallocene catalyst,
Obtained by random copolymerization of an α-olefin having 3 to 12 carbon atoms and, if necessary, a non-conjugated polyene, (1) (a) a unit derived from ethylene and (b) a carbon atom having 3 to 3 carbon atoms.
The unit derived from 12 α-olefins is 60/4
It is contained at a molar ratio of 0 to 80/20 [(a) / (b)], (2) has an iodine value of 0 to 30, and (3) has an intrinsic viscosity [η] measured in 135 ° C decalin. It is characterized by being 1 to 3 dl / g.

As the heat resistant rubber belt according to the present invention, a heat resistant belt made of the following rubber compositions (1) and (2) is preferable. (1) Ethylene consisting of ethylene, an α-olefin having 4 to 12 carbon atoms, and optionally a non-conjugated polyene
A rubber composition comprising an α-olefin-based copolymer rubber (A), wherein the ethylene / α-olefin-based copolymer rubber (A) contains ethylene and carbon in the presence of a metallocene catalyst. It is obtained by randomly copolymerizing an α-olefin having 4 to 12 atoms and a non-conjugated polyene as required, and (1) (a) a unit derived from ethylene and (b) a unit having 4 to 4 carbon atoms.
The unit derived from 12 α-olefins is 60/4
It is contained at a molar ratio of 0 to 80/20 [(a) / (b)], (2) has an iodine value of 0 to 30, and (3) has an intrinsic viscosity [η] measured in 135 ° C decalin. 1 to 3 dl / g, and (4) linear viscosity ethylene having an intrinsic viscosity [η] measured in the above (3) and the same weight average molecular weight (by light scattering method) as 70 mol%.・ Ratio of intrinsic viscosity [η] _{blank of} propylene copolymer [gη ^* (= [η] /
[Η] _blank )] is a value exceeding 0.95. (2) Ethylene consisting of ethylene, α-olefin having 3 to 12 carbon atoms and, if necessary, non-conjugated polyene
A rubber composition comprising an α-olefin copolymer rubber (A), wherein the ethylene / α-olefin copolymer rubber (A) contains ethylene and a carbon atom in the presence of a metallocene catalyst. An α-olefin of the formula 3 to 12 and, if necessary, a non-conjugated polyene in which only one carbon-carbon double bond that can be polymerized by the catalyst among carbon-carbon double bonds exists in one molecule. Obtained by random copolymerization, (1) (a) a unit derived from ethylene and (b) 3 carbon atoms.
Unit derived from α-olefin of 60 to 60 /
It is contained in a molar ratio of 40 to 80/20 [(a) / (b)], (2) has an iodine value of 0 to 30, and (3) has an intrinsic viscosity [η] measured in 135 ° C decalin. 1 to 3 dl / g, and (4) the intrinsic viscosity [η] measured in the above (3) and the ethylene content having the same weight average molecular weight (by light scattering method) as 70 mol% Ratio of chain ethylene / propylene copolymer to intrinsic viscosity [η] _blank [gη ^* (= [η] /
[Η] _blank )] is 0.2 to 0.95.

The heat resistant rubber belt according to the present invention is a vulcanized product of the above rubber composition.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The heat-resistant rubber belt according to the present invention will be specifically described below. The heat resistant rubber belt according to the present invention comprises a composition containing a specific ethylene / α-olefin copolymer rubber (A).

Ethylene / α-olefin copolymer rubber
(A) The ethylene / α-olefin copolymer rubber (A) used in the present invention comprises ethylene and α having 3 to 12 carbon atoms.
-It is obtained by randomly copolymerizing an olefin and a non-conjugated polyene, if necessary.

The above-mentioned ethylene / α-constituting the heat-resistant rubber belt composition (1) preferably used in the present invention.
The olefin-based copolymer rubber (A) has a linear molecular structure, and the ethylene / α-olefin-based copolymer weight which constitutes the heat-resistant rubber belt composition (2) preferably used in the present invention. The united rubber (A) has a long-chain branched type molecular structure.

[Α-Olefin] The number of carbon atoms is 3 to 1
Examples of the α-olefin of 2 include propylene and 1-
Butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1
-Hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl
-1-Pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene and combinations thereof.

Among these, the α-olefin constituting the linear ethylene / α-olefin copolymer rubber (A1) is preferably an α-olefin having 4 to 12 carbon atoms, and particularly 4 to 10 carbon atoms. Especially, 1-butene, 1-hexene, 1-octene, 1-decene and the like are preferably used.

The α-olefin constituting the long-chain branched type ethylene / α-olefin copolymer rubber (A2) is an α-olefin having 3 to 12 carbon atoms, especially 3 to 10 carbon atoms.
Olefins are preferred, especially 1-butene, 1-hexene, 1-
Octene and the like are preferably used.

[Non-conjugated polyene] linear ethylene / α
Examples of the non-conjugated polyene forming the olefin copolymer rubber (A1) include aliphatic polyene and alicyclic polyene.

Specific examples of such an aliphatic polyene include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4. -Hexadiene, 4-ethyl-1,4-hexadiene, 3-methyl-1,5
-Hexadiene, 3,3-Dimethyl-1,4-hexadiene, 5-
Methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-heptadiene, 1, 6-octadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-
1,4-octadiene, 5-methyl-1,5-octadiene, 6-
Methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 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, 4-methyl-1,4-nonadiene,
5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-
Nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7
-Nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-
1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 5-ethyl- 1,5-decadiene, 6-
Ethyl-1,5-decadiene, 6-methyl-1,6-decadiene,
6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-
Decadiene, 6-methyl-1,6-undecadiene, 9-methyl
-1,8- Undecadiene and the like.

The alicyclic polyene is preferably a polyene composed of an alicyclic portion having one unsaturated bond and a chain portion having an internal olefin bond,
For example, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene and the like can be mentioned.

In addition, trienes such as 2,3-diisopropylidene-5-norbornene and 2-ethylidene-3-isopropylidene-5-norbornene can be mentioned. Among these non-conjugated polyenes, methyl octadiene, 5-
Particularly preferred are ethylidene-2-norbornene, 1,4-hexadiene and the like.

These non-conjugated polyenes can be used alone or in combination of two or more kinds. In addition, long chain branched ethylene / α-olefin copolymer rubber (A
The non-conjugated polyene constituting 2) is a non-conjugated polyene in which only one carbon-carbon double bond polymerizable with a metallocene catalyst is present in one molecule among carbon-carbon double bonds. Such a non-conjugated polyene does not include a chain polyene having vinyl groups at both ends. When one of the two or more vinyl groups is a terminal vinyl group, the other vinyl group is preferably one having an internal olefin structure rather than a terminal.

Examples of such non-conjugated polyenes include aliphatic polyenes and alicyclic polyenes. As the aliphatic polyene, specifically, 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,
7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,
13-tetradecadiene, 1,5,9-decatriene, 3-methyl
-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-
Methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3,3-dimethyl-1,4-
Hexadiene, 3,4-dimethyl-1,5-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1, 5-heptadiene, 5-ethyl-1,5-heptadiene, 3-methyl-1,6
-Heptadiene, 4-methyl-1,6-heptadiene, 4,4-dimethyl-1,6-heptadiene, 4-ethyl-1,6-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1 , 4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-
Octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene,
6-ethyl-1,5-octadiene, 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, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 4-ethyl-1,4-nonadiene, 5-
Ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene,
6-methyl-1,5-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-
Nonadiene, 5-methyl-1,4-decadiene, 5-ethyl-1,4
-Decadiene, 5-methyl-1,5-decadiene, 6-methyl-
1,5-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl- 1,6-decadiene, 7-
Ethyl-1,6-decadiene, 7-methyl-1,7-decadiene,
8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 9-methyl-1,8
-Aliphatic polyenes such as undecadiene, vinyl cyclohexene, vinyl norbornene, ethylidene norbornene, dicyclopentadiene, cyclooctadiene, 2,5-
Norbornadiene, 1,4-divinylcyclohexane, 1,3-
Divinylcyclohexane, 1,3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, 1,5-diallyl Cyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-
Examples thereof include isopropenyl-4-vinylcyclohexane and 1-isopropenyl-3-vinylcyclopentane.

Specific examples of the aromatic polyene include divinylbenzene and vinylisopropenylbenzene. In the present invention, among these, non-conjugated polyenes having 7 or more carbon atoms are preferable, such as methyl octadiene (MOD) such as 7-methyl-1,6-octadiene and 5-ethylidene-2-norbornene. Ethylidene norbornene (ENB), vinyl norbornene,
Dicyclopentadiene (DCPD) and the like are preferably used.

These non-conjugated polyenes can be used alone or in combination of two or more kinds. [Linear ethylene / α-olefin copolymer rubber (A
Characteristics of 1)] The linear ethylene / α-olefin copolymer rubber (A1) preferably used in the present invention has the following characteristics. (1) Ethylene / α-olefin component ratio The linear ethylene / α-olefin copolymer rubber (A1) used in the present invention comprises (a) a unit derived from ethylene and (b) 4 carbon atoms. A unit derived from an α-olefin (hereinafter sometimes simply referred to as an α-olefin) of 60 to 40 to 80/20, preferably 65
/ 35-80 / 20, more preferably 65 / 35-7
It is contained in a molar ratio of 5/25 [(a) / (b)].

Use of a linear ethylene / α-olefin copolymer rubber having an ethylene component / α-olefin component ratio in the above range provides a heat-resistant rubber belt having excellent roll processability and heat aging resistance. A composition that can be obtained is obtained. (2) Iodine number In the linear ethylene / α-olefin copolymer rubber (A1) used in the present invention, the non-conjugated polyene component is an optional component, and the linear ethylene / α-olefin copolymer rubber is used. The iodine value, which is one index of the amount of the non-conjugated polyene component of the integrated rubber (A1), is 0 to 30, preferably 0 to 20, and more preferably 2 to 10.

This characteristic value is a standard when the ethylene / α-olefin copolymer rubber used in the present invention is crosslinked (vulcanized) with sulfur or an organic peroxide. (3) Intrinsic viscosity [η] Linear ethylene / α-olefin copolymer rubber (A
Intrinsic viscosity [η] measured in decalin at 135 ℃ of 1)
Is 1-3 dl / g, preferably 1.2-2.8 dl /
g, more preferably 1.5 to 2.5 dl / g.

This characteristic value is a scale showing the molecular weight of the ethylene / α-olefin copolymer rubber used in the present invention, and by combining with other characteristic values, weather resistance, ozone resistance, heat aging resistance. It is useful for obtaining a copolymer rubber having excellent properties such as properties, low temperature characteristics, and dynamic fatigue resistance. (4) gη ^* value is determined from the intrinsic viscosity [eta] of linear ethylene · alpha-olefin copolymer rubber as described above (A1) gη ^*
The value is above 0.95.

This gη ^* value is defined by the following equation. gη ^* = [η] / [η] _blank (where [η] is the intrinsic viscosity measured in (3) above, and [η] _blank is the ethylene / α-of the intrinsic viscosity [η]. The linear viscosity of a linear ethylene / propylene copolymer having the same weight average molecular weight (by a light scattering method) as that of the olefin copolymer rubber and an ethylene content of 70 mol% is the intrinsic viscosity.) The linear ethylene / α-olefin-based copolymer rubber has a rubber composition capable of providing a heat resistant rubber belt having excellent vulcanized physical properties such as strength.

[Characteristics of long-chain branched ethylene / α-olefin copolymer rubber (A2)] On the other hand, long-chain branched ethylene / α-olefin copolymer rubber (A2) preferably used in the present invention. Has the following characteristics. (1) Ethylene / α-olefin component ratio The long-chain branched ethylene / α-olefin copolymer rubber (A2) used in the present invention comprises (a) a unit derived from ethylene and (b) a carbon atom. A unit derived from the α-olefin of the number 3 to 12 (hereinafter, may be simply referred to as α-olefin), 60/40 to 80/20, preferably 65/35 to 80/20, and more preferably 65. / 3
It is contained at a molar ratio of 5 to 75/25 [(a) / (b)].

When a long-chain branched ethylene / α-olefin copolymer rubber having an ethylene component / α-olefin component ratio in the above range is used, a heat resistant rubber belt excellent in roll processability and heat aging resistance can be obtained. A composition that can be provided is obtained. (2) Iodine Value The iodine value of the long-chain branched ethylene / α-olefin copolymer rubber (A2) is 0 to 30, preferably 0 to 2.
It is 0, more preferably 2 to 10.

This characteristic value is a standard when the long chain branched ethylene / α-olefin copolymer rubber used in the present invention is crosslinked (vulcanized) with sulfur or an organic peroxide. (3) Intrinsic viscosity [η] The intrinsic viscosity [η] of the long-chain branched ethylene / α-olefin copolymer rubber (A2) measured in decalin at 135 ° C. is 1 to 3 dl / g, preferably 1 .2-2.8
dl / g, more preferably 1.5 to 2.5 dl / g. (4) gη ^* gη ^* values of long-chain branched ethylene · alpha-olefin copolymer rubber (A2) is 0.2 to 0.95, preferably 0.4 to 0.9, more preferably It is 0.5 to 0.85. This gη ^* value is obtained by the method described above.

When the gη ^* value of the ethylene / α-olefin copolymer rubber is 0.95 or less, it indicates that long chain branching is formed in the molecule. [Preparation Method of Ethylene / α-Olefin Copolymer Rubber (A)] The ethylene / α-olefin copolymer rubber (A) used in the present invention is a metrocene catalyst, for example, from Group IVB of the periodic table. In the presence of a catalyst consisting of a selected transition metal metallocene compound [A] and an organoaluminum oxy compound [B] or an ionizable ionic compound [C], ethylene and an α-olefin having 3 to 12 carbon atoms It is produced by random copolymerization with a non-conjugated polyene, if necessary.

The linear or long-chain branched ethylene / α-olefin copolymer rubber (A) as described above
Is ethylene in the presence of a specific metallocene catalyst,
It is produced by randomly copolymerizing an α-olefin having 3 to 12 carbon atoms and a non-conjugated polyene, if necessary.

The metallocene catalyst used in the present invention is
There is no particular limitation except that it contains the metallocene compound [A]. For example, a compound that forms an ion pair by reacting with the metallocene compound [A] and the organoaluminum oxy compound [B] and / or the metallocene compound [A] [ C]. Further, it may be formed from a metallocene compound [A], an organoaluminum oxy compound [B] and / or an organoaluminum compound [D] together with a compound [C] forming an ion pair.

The components used in forming the metallocene catalyst in the present invention will be described below. Metallocene Compound [A] The metallocene compound [A] used in the preparation of the ethylene / α-olefin copolymer rubber (A) used in the present invention has at least one ligand having a cyclopentadienyl skeleton. It is a transition metal compound of Group IVB of the periodic table. Examples of such transition metal compounds include transition metal compounds represented by the following general formula.

MLx In the formula, x is the valence of the transition metal atom M. M is a transition metal atom selected from Group IVB of the periodic table, and specifically, zirconium, titanium, and hafnium. Among them, zirconium is preferred.

L is a ligand that coordinates to the transition metal atom M, and at least one of these ligands L is a ligand having a cyclopentadienyl skeleton. Specific examples of the ligand L having a cyclopentadienyl skeleton coordinated to the transition metal atom M include a cyclopentadienyl group, a methylcyclopentadienyl group, and a dimethylcyclopentadienyl group. Alkyl-substituted cyclopentadienyl group such as trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, methylethylcyclopentadienyl group, hexylcyclopentadienyl group, or indenyl Group, 4,5,6,7-tetrahydroindenyl group, fluorenyl group and the like. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

The metallocene compound [A] used in the preparation of the linear ethylene / α-olefin copolymer rubber (A1) preferably used in the present invention is a compound represented by the following general formula [I]. Can be mentioned.

MLx ... [I] In the formula [I], M is a transition metal selected from Group IVB of the periodic table, specifically zirconium, titanium or hafnium, and x is an atom of the transition metal. Value.

L is a ligand that coordinates to a transition metal,
At least one of these ligands L is a ligand having a cyclopentadienyl skeleton, and this ligand having a cyclopentadienyl skeleton may have a substituent.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, hexylcyclopentadienyl group, methylbenzylcyclopentadienyl group, ethylhexylcyclopentadiene group. Examples thereof include an alkyl or cycloalkyl-substituted cyclopentadienyl group such as an enyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group.

These groups may be substituted with a halogen atom, a trialkylsilyl group or the like. Among these, an alkyl-substituted cyclopentadienyl group is particularly preferred.

When the compound represented by the formula [I] has two or more groups having a cyclopentadienyl skeleton as the ligand L, two groups having a cyclopentadienyl skeleton among them are: It may be bonded via an alkylene group such as ethylene and propylene, a substituted alkylene group such as isopropylidene and diphenylmethylene, a silylene group or a substituted silylene group such as dimethylsilylene, diphenylsilylene and methylphenylsilylene.

L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms,
Alkoxy group, aryloxy group, halogen atom, hydrogen atom or sulfonic acid-containing group (—SO ₃ ^Ra ) [wherein
^Ra is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group or an aryl group substituted with a halogen atom or an alkyl group. And the like.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include alkyl groups such as methyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group and aralkyl groups such as benzyl group.

The alkoxy group may, for example, be a methoxy group, an ethoxy group or an isopropoxy group.
Examples of the aryloxy group include a phenoxy group, and examples of the sulfonic acid-containing group (—SO ₃ ^Ra ) include a methanesulfonato group, a p-toluenesulfonato group, a trifluoromethanesulfonato group, and a p-chlorobenzenesulfonato group. Groups and the like.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. When the transition metal has a valence of 4, the metallocene compound represented by the above formula is more specifically represented by the following formula [II].

R ² _k R ³ _l R ⁴ _m R ⁵ _n M ... [II] In the formula [II], M is the above transition metal, and R ² is a group having a cyclopentadienyl skeleton (coordination). Child) and R ³ ,
R ⁴ and R ⁵ are independently the same as L except for a group having a cyclopentadienyl skeleton or a ligand having a cyclopentadienyl skeleton in the above general formula [I]. k is an integer of 1 or more, and k + 1 + m + n = 4.

Examples of the metallocene compound in which M is zirconium and at least two ligands having a cyclopentadienyl skeleton are bis (cyclopentadienyl) zirconium dichloride and bis (isopropylcyclopentadienyl). Zirconium dichloride,
Bis (indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium bis (methanesulfonate)
And the like. Other examples of such metallocene compounds are described in the specification of Japanese Patent Application No. 7-164362 filed by the present applicant.

A compound obtained by substituting the 1,3-position-substituted cyclopentadienyl group with a 1,2-position-substituted cyclopentadienyl group can also be used in the present invention. Further, in the above formula [II], at least two of R ² , R ³ , R ⁴ and R ⁵ , that is, R ² and R ³ are groups (ligands) having a cyclopentadienyl skeleton, and at least 2
The group can also be exemplified by a bridge-type metallocene compound in which an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group or the like is bonded. At this time, R ⁴ and R ⁵ are independently the same as L other than the ligand having the cyclopentadienyl skeleton described in the formula [I].

Examples of such bridge-type metallocene compounds include ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium bis (p-toluenesulfonate), isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride. , Dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, and the like. Other examples of such bridge-type metallocene compounds include Japanese Patent Application No. 7-
No. 164362.

Further, Japanese Patent Laid-Open No. 4-312043 shown by the following formula [A]
Metallocene compounds described in JP-A-268307. The metallocene has the formula [A]:

[0055]

Embedded image

[In the formula [A], M ¹ is IVB of the periodic table.
Group metals, specifically, for example, titanium, zirconium, and hafnium. R ¹ and R ² may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. An aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms
An alkenyl group having 7 to 40 carbon atoms, preferably 7 to
10 arylalkyl groups, 7 to 40 carbon atoms, preferably 7 to 12 alkylaryl groups, 8 carbon atoms
40, preferably 8 to 12 arylalkenyl groups, or a halogen atom, preferably a chlorine atom.

R ³ and R ^{4, which} may be the same or different from each other, are a hydrogen atom, a halogen atom, preferably a fluorine atom, a chlorine atom or a bromine atom, and an optionally halogenated carbon atom number 1 to 10, preferably 1 to 4 alkyl group, having 6 to 10 carbon atoms, preferably 6-8 aryl _{^{group, -NR 10 2, -SR 10,}} -OSiR 10 3, -
SiR ¹⁰ ₃ or —PR ¹⁰ ₂ group, where R ¹⁰ is a halogen atom, preferably a chlorine atom, or has 1 carbon atom.
Is an alkyl group having 10 to 10, preferably 1 to 3, or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms.

R ³ and R ⁴ are particularly preferably hydrogen atoms. R ⁵ and R ⁶ may be the same or different from each other, and preferably the same, R ⁵ and R 6
⁶ is R ³ and R with the proviso that it is not a hydrogen atom.
^It has the meaning described for ⁴ . R ⁵ and R ⁶ are
Preferably 1 to 1 optionally halogenated carbon atoms
Preferred is an alkyl group of 4, specifically a methyl group.

R ⁷ is the following:

[0060]

Embedded image

= BR ¹¹ , = AlR ¹¹ , -Ge-, -Sn
-, - O -, - S -, = SO, = SO 2, = NR 11, =
CO, = a PR ¹¹ or = P (O) R ^11, at that time, R ^11, R ¹² and R ^13, which may be the same or different from each other, a hydrogen atom, a halogen atom, 1 to carbon atoms
10, preferably 1 to 4 alkyl groups, more preferably a methyl group, a fluoroalkyl group having 1 to 10 carbon atoms, preferably CF ₃ group, having 6 to 10 carbon atoms, preferably 6 to 8 aryl group, A fluoroaryl group having 6 to 10 carbon atoms, preferably a pentafluorophenyl group,
An alkoxy group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly preferably a methoxy group, 2 to 10 carbon atoms,
Preferably 2-4 alkenyl groups, 7-7 carbon atoms
0, preferably 7 to 10 arylalkyl groups, 8 to 40 carbon atoms, preferably 8 to 12 arylalkenyl groups, or 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms.
R ¹¹ and R ¹² or R ¹¹ and R ¹³ may form a ring together with the atom to which they are bonded.

M ² is silicon, germanium or tin, preferably silicon or germanium. R ⁷ is = CR
^{11 R 12, = SiR 11 R} 12, = GeR 11 R 12, -O -, -
S -, = SO, it is preferred that = PR ¹¹ or = P (O) R ^11.

R ⁸ and R ⁹ may be the same or different from one another and have the same meaning as described for R ¹¹ . m and n may be the same as or different from each other, and are 0, 1 or 2, preferably 0 or 1.
And m + n is 0, 1 or 2, preferably 0 or 1.

Particularly preferred metallocene compounds satisfying the above conditions are shown in (i) to (iii) below.

[0065]

Embedded image

[In the above formulas (i), (ii) and (iii),
M ¹ is Zr or Hf, R ¹ and R ² are methyl groups or chlorine atoms, R ⁵ and R ⁶ are methyl groups,
An ethyl group or a trifluoromethyl group, R ⁸ and R
⁹ , R ¹⁰ and R ¹² have the meanings given above. The metallocene compound can be produced by a conventionally known method (see, for example, JP-A-4-268307).

In the present invention, a transition metal compound (metallocene compound) represented by the following formula [B] can also be used.

[0068]

Embedded image

In the formula [B], M represents a transition metal atom of Group IVB of the Periodic Table, specifically titanium, zirconium or hafnium. R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, or sulfur. A containing group, a nitrogen containing group or a phosphorus containing group is shown.

As the hydrocarbon group having 1 to 20 carbon atoms, alkyl group, alkenyl group, arylalkyl group,
An aryl group etc. are mentioned. The halogenated hydrocarbon group having 1 to 20 carbon atoms is a group obtained by substituting the above hydrocarbon group with a halogen atom.

Examples of the silicon-containing group include a monohydrocarbon-substituted silyl group, a dihydrocarbon-substituted silyl group, a trihydrocarbon-substituted silyl group, a hydrocarbon-substituted silyl silyl ether group, a silicon-substituted alkyl group, and a silicon-substituted aryl group. Can be mentioned.

Examples of the oxygen-containing group include a hydroxy group, an alkoxy group, an aryloxy group and an arylalkoxy group. Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing group is replaced with sulfur.

Examples of the nitrogen-containing group include an amino group, an alkylamino group, an arylamino group and an alkylarylamino group. Examples of the phosphorus-containing group include a phosphino group.

Of these, R ¹ is preferably a hydrocarbon group, and particularly preferably a methyl, ethyl or propyl hydrocarbon group having 1 to 3 carbon atoms. Also R ²
Is preferably hydrogen or a hydrocarbon group, and particularly preferably hydrogen or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl or propyl.

R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom or a carbon atom number of 1 to 20.
And a halogenated hydrocarbon group having 1 to 20 carbon atoms, among which hydrogen, a hydrocarbon group or a halogenated hydrocarbon group is preferable. R ³ and R ⁴ , R ⁴
And R ^5, at least one pair of R ⁵ and R ⁶ may form an aromatic ring of a single together with the carbon atoms to which they are attached rings.

When there are two or more kinds of hydrocarbon groups or halogenated hydrocarbon groups, the groups other than the group forming an aromatic ring may be bonded to each other to form a ring. When R ⁶ is a substituent other than an aromatic group, it is preferably a hydrogen atom.

Specific examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the halogenated hydrocarbon group having 1 to 20 carbon atoms include the same groups as R ¹ and R ² .

As a ligand coordinated to M, which contains a monocyclic aromatic ring formed by bonding at least one of R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ to each other, The following may be mentioned.

[0079]

Embedded image

Of these, the ligand represented by the above formula (1) is preferable. The aromatic ring may be substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

As the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon group having 1 to 20 carbon atoms, which are substituted on the aromatic ring, the same groups as the above R ¹ and R ² can be used. It can be illustrated.

X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group. Group, specifically R
Halogen atom similar to ¹ and R ² , ^{1 to 2} carbon atoms
Examples thereof include a hydrocarbon group having 0, a halogenated hydrocarbon group having 1 to 20 carbon atoms, and an oxygen-containing group.

Examples of the sulfur-containing group include the same groups as R ¹ and R ² , the sulfonate group and the sulfinate group. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent Tin-containing group, -O-, -CO-, -S-,
_{-SO -, - SO 2 -,} - NR 7 -, - P (R 7) -,
^{-P (O) (R 7)} -, - BR 7 - or -AlR ⁷ -
[Wherein R ⁷ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms]. Specifically, a divalent hydrocarbon group having 1 to 20 carbon atoms such as an alkylene group or an arylalkylene group; a halogenated hydrocarbon group obtained by halogenating the above divalent hydrocarbon group having 1 to 20 carbon atoms. A divalent silicon-containing group; a divalent germanium-containing group in which silicon in the divalent silicon-containing group is replaced with germanium; a divalent tin-containing group in which silicon in the divalent silicon-containing group is replaced with tin And R ⁷ is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms, which is the same as R ¹ and R ² .

Of these, a divalent silicon-containing group, a divalent germanium-containing group and a divalent tin-containing group are preferable, and a divalent silicon-containing group is more preferable,
Of these, an alkylsilylene group, an alkylarylsilylene group, and an arylsilylene group are particularly preferable.

Specific examples of the transition metal compound represented by the above formula [B] are shown below.

[0086]

[Chemical 6]

[0087]

Embedded image

[0088]

Embedded image

In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds may be used. The transition metal compound is usually used as a catalyst component for olefin polymerization as a racemate, but may be an R-type or S-type.

The indene derivative ligand of such a transition metal compound can be synthesized, for example, according to the following reaction route and using a conventional organic synthesis method.

[0091]

Embedded image

The transition metal compound used in the present invention can be synthesized from these indene derivatives by a known method, for example, the method described in JP-A-4-268307.

In the present invention, a transition metal compound (metallocene compound) represented by the following formula [C] can also be used.

[0094]

Embedded image

In the formula [C], M, R ¹ , R ² , R ³ ,
As R ⁴ , R ⁵ and R ⁶ , those similar to the case of the formula [B] can be mentioned. R ³ , R ⁴ , R ⁵ and R ⁶
Among them, two groups including R ³ are preferably alkyl groups, and R ³ and R ⁵ , or R ³ and R ⁶ are preferably alkyl groups. This alkyl group is preferably a secondary or tertiary alkyl group. The alkyl group may be substituted with a halogen atom or a silicon-containing group.
^And the substituents exemplified for R ² .

Of the groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ , the groups other than the alkyl group are preferably hydrogen atoms. As the hydrocarbon group having 1 to 20 carbon atoms,
A chain alkyl group and a cyclic alkyl group; an arylalkyl group and the like can be mentioned, and a double bond and a triple bond may be contained.

Two kinds of groups selected from R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a monocyclic or polycyclic ring other than the aromatic ring. As a halogen atom,
Specifically, the same groups as those for R ¹ and R ² can be exemplified.

Examples of X ¹ , X ² , Y and R ⁷ are the same as those of the above formula [B]. Metallocene compound (transition metal compound) represented by the above formula [C]
For example, rac-dimethylsilylene-bis (4,7-
Dimethyl-1-indenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis (2-methyl-4-phenylethyl-7-methyl-1-indenyl) zirconium dichloride, rac-di (i-propyl) silylene-bis (2-methyl-4)
-i-Propyl-7-methyl-1-indenyl) zirconium dichloride, rac-di (cyclohexyl) silylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl)
Zirconium dichloride, rac-methylphenylsilylene
-Bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride and the like. Other specific examples of such metallocene compounds are described in the specification of Japanese Patent Application No. 7-164362 filed by the present applicant.

In the present invention, a transition metal compound in which zirconium metal in the above compounds is replaced with titanium metal or hafnium metal can be used. The transition metal compound is usually used as a racemic compound, but may be used in R-form or S-form.

The indene derivative ligand of such a transition metal compound can be synthesized, for example, according to the same reaction route as described above and using a usual organic synthesis method. The transition metal compound (metallocene compound) represented by the above formula [C] can be synthesized from these indene derivatives by a known method, for example, a method described in JP-A-4-268307.

In the present invention, among the above metallocene compounds, the following general formula [III] or [I
The compound represented by V] is preferably used. General formula [I
The metallocene compound represented by the formula [II] is a part of the compound represented by the formula [C], and the metallocene compound represented by the general formula [IV] is a part of the compound represented by the formula [B]. Is.

[0102]

Embedded image

In the formula, M is a transition metal atom of Group IVB of the periodic table, specifically, titanium, zirconium,
Hafnium, particularly preferably zirconium. R ¹¹ and R ¹² R ¹¹ and R ¹² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with halogen, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, nitrogen. An alkyl group, an alkenyl group, an arylalkyl group, an aryl group etc. are mentioned as a C1-C20 hydrocarbon group which is a content group or a phosphorus content group.

These hydrocarbon groups include halogen atoms such as fluorine, chlorine, bromine and iodine, a trimethylsilyl group,
It may be substituted with an organic silyl group such as a triethylsilyl group and a triphenylsilyl group.

Examples of the oxygen-containing group include a hydroxy group, an alkoxy group, an allyloxy group and an arylalkoxy group. As the sulfur-containing group, a substituent in which oxygen of the oxygen-containing group is replaced with sulfur, a sulfonate group,
Examples thereof include a sulfinate group.

Examples of the nitrogen-containing group include an amino group, an alkylamino group, an arylamino group and an alkylarylamino group. Specific examples of the phosphorus-containing group include a dimethylphosphino group and a diphenylphosphino group.

Of these, R ¹¹ is preferably a hydrocarbon group, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as a methyl group, an ethyl group and a propyl group. R ¹² is preferably a hydrogen atom or a hydrocarbon group, particularly a hydrogen atom, a methyl group, an ethyl group,
The propyl group is preferably a hydrocarbon group having 1 to 3 carbon atoms.

R ¹³ and R ¹⁴ R ¹³ and R ¹⁴ have 1 carbon atom as exemplified above.
To 20 alkyl groups.

R ¹³ is preferably a secondary or tertiary alkyl group. R ¹⁴ may contain a double bond or a triple bond. X ¹ and X ² X ¹ and X ² represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing group as exemplified above. Group or sulfur-containing group, a halogen atom,
It is preferably 20 hydrocarbon groups.

Y Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group , -O-, -C
O -, - S -, - SO -, - SO 2 -, - NR 15 -, -
^{P (R 15) -, -} P (O) (R 15) -, - BR 15 - or -AlR ¹⁵ - [however, R ¹⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms , 1 carbon atom
To 20 halogenated hydrocarbon groups].

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include alkylene group and arylalkylene group. Examples of the halogenated hydrocarbon group include halogenated hydrocarbon groups obtained by halogenating the above divalent hydrocarbon group having 1 to 20 carbon atoms.

Examples of the divalent silicon-containing group include an alkylsilylene group, an alkylarylsilylene group, an arylsilylene group, an alkyldisilyl group, an alkylaryldisilyl group and an aryldisilyl group.

Examples of the divalent germanium-containing group include groups in which silicon in the divalent silicon-containing group is replaced with germanium. R ¹⁵ is the same halogen atom as described above, a hydrocarbon group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms.
20 halogenated hydrocarbon groups.

Of these, Y is preferably a divalent silicon-containing group or a divalent germanium-containing group,
It is more preferably a divalent silicon-containing group, and particularly preferably an alkylsilylene group, an alkylarylsilylene group, or an arylsilylene group.

Examples of the metallocene compound represented by the above general formula [III] include rac-dimethylsilylene-bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride and rac-dimethylsilylene-bis. (2,
7-dimethyl-4-sec-butyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-phenyldichloromethyl-1-indenyl) zirconium dichloride, rac-di (i- Propyl) silylene-
Bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-di (cyclohexyl) silylene-bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-Methylphenylsilylene-bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-diphenylsilylene
-Bis (2,7-dimethyl-4-t-butyl-1-indenyl) zirconium dichloride and the like. Other specific examples of such metallocene compounds are described in the specification of Japanese Patent Application No. 7-164362 filed by the present applicant.

Such a metallocene compound has an i-position at the 4-position.
A compound having a branched alkyl group such as a propyl group, a sec-butyl group and a tert-butyl group is particularly preferable. In the present invention, a racemate of the transition metal compound is generally used as a catalyst component for olefin polymerization, but an R-type or S-type may also be used.

The transition metal compound as described above can be prepared by a known method from an indene derivative, for example, JP-A-4-268307.
Can be synthesized by the method described in Japanese Patent Application Laid-Open No. H10-260, 1988. The compound represented by the following formula [IV] preferably used in the present invention is EP-549900 and Canada-20.
No. 84017.

[0118]

Embedded image

In the formula, M is a transition metal atom of Group IVB of the periodic table, specifically, titanium, zirconium,
Hafnium, particularly preferably zirconium. R ²¹ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, preferably a fluorine atom or a chlorine atom, and an optionally halogenated carbon atom number of 1 to 1.
0, preferably 1-4 alkyl groups, 6-1 carbon atoms
0, preferably 6-8 aryl group, -NR _2, -S
R, —OSiR ₃ , —SiR _3, or —PR ₂ groups (where R is a halogen atom, preferably a chlorine atom, an alkyl group having 1 to 10, preferably 1 to 3 carbon atoms, or 6 to 10 carbon atoms; Preferably 6 to 8 aryl groups).

R ^{22 to} R ^{28, which} may be the same or different, are the same atoms or groups as those of R ²¹ , and these R ^{22 to} R ²⁸ are the same.
^At least two adjacent groups out of ²⁸ may form an aromatic ring or an aliphatic ring together with their bonding atoms.

X ³ and X ⁴ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an OH group, an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. , Preferably an alkoxy group having 1 to 3 carbon atoms, an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, 2 to 10 carbon atoms, Preferably 2-4 alkenyl groups, 7-40 carbon atoms, preferably 7-10 arylalkyl groups, 7-40 carbon atoms, preferably 7-
A 12-alkylaryl group; and an arylalkenyl group having 8 to 40, preferably 8 to 12 carbon atoms.

[0122]

Embedded image

-Sn-, -O-, -S-, = SO, = S
O ₂ , ＮＲNR ²⁹ , ＣＯCO, ＰＲPR ²⁹ or ＰP (O) R
²⁹ . However, R ²⁹ and R ³⁰ may be the same or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly preferably a methyl group and 1 carbon atom. 10 to 10 fluoroalkyl group, preferably CF ₃ group, 6 to 10 carbon atom, preferably 6 to 8 aryl group, 6 to 10 carbon atom fluoroaryl group, preferably pentafluorophenyl group, 1-10, preferably 1-4 alkoxy groups, particularly preferably methoxy group, 2-1 carbon atom
0, preferably 2 to 4 alkenyl groups, 7 to 7 carbon atoms
It is an arylalkyl group having 40, preferably 7 to 10 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms, and an arylalkyl group having 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms.

R ²⁹ and R ³⁰ may form a ring together with the atom to which they are bonded. M ² is silicon, germanium or tin.

The above-mentioned alkyl group is a linear or branched alkyl group, and halogen (halogenated) is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, particularly preferably a fluorine atom or a chlorine atom. is there.

Among the compounds represented by the formula [IV], M is zirconium or hafnium,
R ²¹ is the same as each other and is an alkyl group having 1 to 4 carbon atoms, and R ^{22 to} R ²⁸ may be the same or different from each other and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X ³ and X ⁴ may be the same or different from each other, and are an alkyl group having 1 to 3 carbon atoms or a halogen atom;

[0127]

Embedded image

(M ² is silicon, R ²⁹ and R
³⁰ may be the same or different and are an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. ) Is preferable, and the substituents R ²² and R ²⁸ are a hydrogen atom, and R ^{23 to} R ²⁷ are more preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.

Further, M is zirconium, and R
²¹ is the same alkyl group having 1 to 4 carbon atoms from each other, R ²² and R ²⁸ are hydrogen atoms, R ²³ to R
²⁷ may be the same or different and has 1 to 4 carbon atoms
X ³ and X ^3
4 is a chlorine atom,

[0130]

Embedded image

(M ² is silicon, R ²⁹ and R ³⁰
May be the same or different, and have 1 carbon atom
An alkyl group having 4 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Is preferred, and in particular, M is zirconium, R ²¹ is a methyl group, and R ^{22 to} R
²⁸ is a hydrogen atom, X ³ and X ⁴ are chlorine atoms,

[0132]

Embedded image

(M ² is silicon, R ²⁹ and R ³⁰
May be the same or different and each is a methyl group or a phenyl group). Examples of the metallocene compound represented by the formula [IV] include rac-dimethylsilylene-bis {1- (2-methyl-4,5
-Benzoindenyl)} zirconium dichloride, rac-
Methylphenylsilylene-bis {1- (2-methyl-4,5-acenaphthocyclopentadienyl)} zirconium dichloride and the like can be mentioned. Another specific example of such a metallocene compound is disclosed in Japanese Patent Application No. 7-16436 filed by the present applicant.
No. 2 application specification.

Further, a compound in which zirconium in the above compound is replaced with titanium or hafnium can also be mentioned. In the present invention, a racemic metallocene compound represented by the formula [III] or [IV] is usually used as a catalyst component, but R-type or S-type can also be used.

The above metallocene compounds may be used in combination of two or more kinds. Next, the metallocene compound [A] used in the preparation of the long chain branched ethylene / α-olefin copolymer rubber (A2) preferably used in the present invention is represented by the following general formula [V]. Compounds.

[0136]

Embedded image

In the formula, M is a transition metal atom of Group IVB of the periodic table, specifically, titanium, zirconium,
Hafnium, particularly preferably zirconium. The substituent R ¹ R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, and examples thereof include an alkyl group and an alkenyl group.

Of these, an alkyl group in which the carbon bonded to the indenyl group is primary is preferable, and the number of carbon atoms is 1
To 4 are preferred, and a methyl group and an ethyl group are particularly preferred.

The substituents R ² , R ⁴ , R ⁵ , R ⁶ R ² , R ⁴ , R ⁵ and R ⁶ may be the same or different and are the same as hydrogen atom, halogen atom or R ¹ . It is a hydrocarbon group having 1 to 6 carbon atoms.

Here, the halogen atom is fluorine, chlorine, bromine or iodine. The substituent R ³ R ³ is an aryl group having 6 to 16 carbon atoms. The aryl group may be substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an organic silyl group.

The aryl group is preferably a phenyl group, a naphthyl group, an anthracenyl group or a phenanthryl group. Also, the aryl group has 1 carbon atom as a substituent.
Examples of the hydrocarbon group of to 20 include an alkyl group, an alkenyl group and an arylalkyl group.

The organic silyl group may, for example, be a trimethylsilyl group, a triethylsilyl group or a triphenylsilyl group. X ¹ and X ² X ¹ and X ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with halogen, an oxygen-containing group or a sulfur-containing group. Specifically, the same halogen atom and hydrocarbon group as described above can be mentioned.

Examples of the oxygen-containing group include a hydroxy group, an alkoxy group, an aryloxy group and an arylalkoxy group. Examples of the sulfur-containing group include a substituent obtained by substituting sulfur for oxygen in the oxygen-containing group, a sulfonate group, and a sulfinate group.

Of these, X ¹ and X ² are preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. YY is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, -O. -, -C
O -, - S -, - SO -, - SO 2 -, - NR 7 -, -
^{P (R 7) -, -} P (O) (R 7) -, - BR 7 - or -AlR ⁷ - (provided that, R ⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms , 1 carbon atom
To 20 halogenated hydrocarbon groups).

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include alkylene group and arylalkylene group. Examples of the halogenated hydrocarbon group include groups obtained by halogenating the above divalent hydrocarbon group having 1 to 20 carbon atoms.

Examples of the divalent silicon-containing group include an alkylsilylene group, an alkylarylsilylene group, an arylsilylene group, an alkyldisilyl group, an alkylaryldisilyl group and an aryldisilyl group.

Examples of the divalent germanium-containing group include groups obtained by substituting germanium for silicon in the divalent silicon-containing group. R ⁷ is the same halogen atom as described above, a hydrocarbon group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms.
20 halogenated hydrocarbon groups.

Of these, Y is preferably a divalent silicon-containing group or a divalent germanium-containing group,
It is more preferably a divalent silicon-containing group, and particularly preferably an alkylsilylene group, an alkylarylsilylene group, or an arylsilylene group.

Examples of the metallocene compound represented by the above general formula [V] include rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- ( p-chlorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-biphenyl) -1-indenyl) zirconium dichloride,
rac-dicyclohexylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-
Methylphenylsilylene-bis (2-methyl-4-phenyl
-1-indenyl) zirconium dichloride and the like. Other specific examples of such metallocene compounds are described in the specification of Japanese Patent Application No. 7-164362 filed by the present applicant. Moreover, the compound which changed zirconium in the above compounds to titanium and hafnium can also be mentioned.

In the present invention, the racemate of the above metallocene compound is usually used as the catalyst component, but R type or S type can also be used. In the present invention, two or more kinds of the above metallocene compounds can be used in combination.

Such metallocene compounds are described in Journal
of Organometallic Chem. 288 (1985), pp. 63-67, European Patent Application Publication No. 0,320,762.

In addition to the metallocene compound represented by the above general formula [V], a metallocene compound represented by the following general formula [VI] can be given. L ^a MX ₂ [VI] (M is a metal of Group IV or lanthanide series of the periodic table, L ^a is a derivative of a delocalized π-bonding group, and is bound to a metal M active site. (Given a geometric shape, X is independently a hydrogen atom, a halogen atom or a hydrocarbon group containing 20 or less carbon atoms, a silicon atom or a germanium atom, a silyl group or a germyl group.) Among the compounds represented by the formula [VI], specifically, the compound represented by the following formula [VII] is preferable.

[0153]

Embedded image

M is titanium, zirconium or hafnium, and X is the same as above. Cp is π in M
A substituted cyclopentadienyl group or a derivative thereof which is bonded and has a substituent Z.

Z is oxygen, sulfur, boron or an element of Group IVA of the periodic table, Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and Z and Y form a condensed ring. You may.

Examples of such a compound represented by the formula [VII] include (dimethyl (t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silane) titanium dichloride and ((t-butylamido) (tetra Methyl-
η ⁵ -Cyclopentadienyl) -1,2-ethanediyl) dibenzyl titanium, ((phenylphosphido) (tetramethyl-η ⁵ -cyclopentadienyl) methylene) diphenyl titanium, (dimethyl (phenylphosphide)- (Tetramethyl-η ⁵ -cyclopentadienyl) silane) dibenzyl titanium, (2-η ^5- (tetramethyl-cyclopentadienyl) -1-methyl-ethanolate (2-)) dimethyl titanium and the like. . Another specific example of such a metallocene compound is disclosed in Japanese Patent Application No. 7-164362 filed by the present applicant.
No. application specification.

In the present invention, the metallocene compounds represented by the above formula [VI] can be used in combination of two or more kinds. In the above description, a titanium compound is exemplified as a metallocene compound, but a compound in which titanium is replaced with zirconium or hafnium can also be exemplified.

These compounds may be used alone or in combination of two or more. Among the metallocene compounds described above, the metallocene compound represented by the general formula [V] is preferably used in the preparation of the long-chain branched ethylene / α-olefin copolymer rubber (A2).

Organoaluminum Oxy Compound [B] The organoaluminum oxy compound [B] used in the present invention may be a conventionally known aluminoxane, and as disclosed in JP-A-2-78687. Benzene-insoluble organoaluminum oxy compound may be used.

Reaction with the metallocene compound [A] produces ions
Compound [C] that forms a pair As compound [C] that reacts with metallocene compound [A] used in the present invention to form an ion pair, it is described in Table 1-
501950 gazette, special table 1-502036 gazette,
JP-A-3-179005, JP-A-3-179900
No. 6, JP-A-3-207703, JP-A-3-207703
The Lewis acid, the ionic compound, the borane compound, and the carborane compound described in 207704, US-547718, etc. can be mentioned.

As the Lewis acid, Mg-containing Lewis acid, A
Examples thereof include l-containing Lewis acids and B-containing Lewis acids, and among them, B-containing Lewis acids are preferable. As the Lewis acid containing a boron atom, specifically, compounds represented by the following general formula can be exemplified.

BR ¹ R ² R ³ (In the formula, R ¹ R ² and R ³ are each independently a phenyl group which may have a substituent such as a fluorine atom, a methyl group and a trifluoromethyl group. Or a fluorine atom.) As the compound represented by the above general formula, tris (pentafluorophenyl) boron is particularly preferable.

The ionic compound used in the present invention is a salt composed of a cationic compound and an anionic compound. In the present invention, an ionic compound having an organic boron compound anion is preferable.

The compound [C] which reacts with the above metallocene compound [A] to form an ion pair is described in detail in the specification of Japanese Patent Application No. 7-164362 filed by the present applicant. ing.

Organoaluminum Compound [D] The organoaluminum compound [D] used in the present invention is
For example, it can be represented by the following general formula (a).

R ⁵ _n AlX _3-n ... (a) (In the formula, R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 1.
3. In the above formula (a), R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group or an aryl group.

In the present invention, the organoaluminum compound is
It is also possible to use two or more types in combination. The organoaluminum compound [D] used in the present invention is described in detail in the specification of Japanese Patent Application No. 7-164362 filed by the present applicant.

The specific metallocene catalyst used in the present invention contains the above metallocene compound [A]. For example, as described above, the metallocene compound [A] is used.
And an organic aluminum oxy compound [B]. It may be formed from a metallocene compound [A] and a compound [C] which reacts with the metallocene compound [A] to form an ion pair. Further, together with the metallocene compound [A], an organic aluminum oxy compound [B] is used. And a compound [C] which reacts with the metallocene compound [A] to form an ion pair. In these embodiments, it is particularly preferable to further use an organic aluminum compound [D] in combination.

In the present invention, the above metallocene compound [A]
Is generally used in an amount of about 0.00005 to 0.1 mmol, preferably about 0.0001 to 0.05 mmol, in terms of transition metal atoms per liter of polymerization volume.

Organoaluminum oxy compound [B]
Is usually about 1 to 10,000 moles, preferably 10 to 10 moles of aluminum atoms per mole of transition metal atom.
It can be used in an amount such that it is 5,000 mol.

In the compound [C] which reacts with the metallocene compound [A] to form an ion pair, the boron atom is usually about 0.5 to 20 mol, preferably 1 to 1 mol of the transition metal atom. It is used in an amount such that it is 10 mol.

Further, the organoaluminum compound [D] is
It is usually about 0-1,000 mol, preferably about 0-500 mol, per 1 mol of boron atoms in the compound [C] forming an aluminum atom or an ion pair in the organic aluminum oxy compound [B]. Such amounts are used as needed.

Using the metallocene catalyst as described above,
Ethylene, an α-olefin having 3 to 12 carbon atoms,
If necessary, a non-conjugated polyene is copolymerized to obtain an ethylene / α-olefin copolymer rubber with excellent polymerization activity.

Even if ethylene, an α-olefin having 3 to 12 carbon atoms and a non-conjugated polyene are copolymerized with a Group VB group transition metal compound type catalyst such as a vanadium type catalyst, sufficient polymerization is achieved. Copolymer rubber cannot be obtained because it is active.

In addition, when producing, for example, EPDM using a Group VB transition metal compound-based catalyst, the type of non-conjugated polyene is often limited to norbornene ring-containing polyenes such as ENB.

On the other hand, when a metallocene catalyst is used as in the present invention, the non-conjugated polyene is not limited to norbornene ring-containing polyenes, and various polyenes such as those mentioned above, such as 7-methyl-1,6. -Chain non-conjugated polyenes such as methyl octadiene (MOD) such as octadiene can also be copolymerized.

In the present invention, ethylene and 3 to 10 carbon atoms are used.
The above-mentioned metallocene compound [A] constituting the metallocene catalyst, the organoaluminum oxy compound [B], and the compound forming an ion pair when the α-olefin of 12 and the non-conjugated polyene are copolymerized as necessary. [C],
Furthermore, the organoaluminum compound [D] may be separately supplied to the polymerization reactor, or a metallocene catalyst containing the metallocene compound [A] may be prepared in advance and then subjected to the copolymerization reaction.

When preparing the metallocene catalyst,
A hydrocarbon solvent which is inert to the reaction with the catalyst component can be used. Specific examples of the inert hydrocarbon solvent include aliphatic solvents such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene. Hydrocarbon, cyclopentane, cyclohexane, alicyclic hydrocarbons such as methylcyclopentane, benzene, toluene, aromatic hydrocarbons such as xylene, ethylene chloride, chlorobenzene,
Halogenated hydrocarbons such as dichloromethane can be used. These hydrocarbon solvents can be used alone or in combination.

The metallocene compound [A], the organoaluminum oxy compound [B], the compound [C] forming an ion pair and the organoaluminum compound [D] are usually
Mixing contact can be performed at 100 to 200 ° C, preferably -70 to 100 ° C.

In the present invention, ethylene and 3 to 10 carbon atoms are used.
The copolymerization of the α-olefin of 12 with a non-conjugated polyene, if necessary, is usually 40 to 200 ° C., preferably 50 to 200 ° C.
150 ° C., particularly preferably 60 to 120 ° C., atmospheric pressure to
100 kg / cm ^2, preferably atmospheric pressure to 50 kg / cm ^2, particularly preferably be carried out under the conditions of atmospheric pressure 30 kg / cm ^2.

Although this copolymerization reaction can be carried out by various polymerization methods, it is preferably carried out by solution polymerization. At this time, the above-mentioned hydrocarbon solvent can be used as the polymerization solvent.

The copolymerization can be carried out by any of batch method, semi-continuous method and continuous method, but continuous method is preferred. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

Further, ethylene / α-used in the present invention
The olefin-based copolymer rubber can be obtained by the method as described above, and the molecular weight of the copolymer rubber can be adjusted by changing the polymerization conditions such as the polymerization temperature, and the hydrogen (molecular weight modifier It can also be adjusted by controlling the amount used.

Composition for Heat-Resistant Rubber Belt The composition for heat-resistant rubber belt used in the present invention is the above-mentioned ethylene / α-olefin copolymer rubber (A).
Auxiliary agent used in the vulcanization reaction,
For example, it may contain a metal activator, a compound having an oxymethylene structure, and an anti-scorch agent.

When the composition for a heat resistant rubber belt used in the present invention contains additives such as a reinforcing agent for rubber, a filler, a softening agent, an antiaging agent and a processing aid, the property as a heat resistant rubber belt is obtained. Further improve. Therefore, in the present invention, it is preferable to use the above-mentioned additives.

Heat Resistant Rubber Belt The heat resistant rubber belt according to the present invention is a vulcanized product formed from the above composition for heat resistant rubber belt.

The heat resistant rubber belt according to the present invention is preferably manufactured by the following method, for example. That is, a heat-resistant rubber belt according to the present invention is obtained by adding a vulcanizing agent to the ethylene / α-olefin-based copolymer rubber (A) as described above and performing vulcanization.

Vulcanization is carried out by adding a vulcanizing agent to the ethylene / α-olefin copolymer rubber (A), and it is preferable to add the vulcanizing agent before molding. Also, ethylene / α
-Sulfur vulcanization and organic peroxide vulcanization are effective as vulcanization methods for the olefin copolymer rubber (A). In particular, organic peroxide vulcanization is preferable from the viewpoint of heat aging resistance.

Specific examples of the sulfur compound used in sulfur vulcanization include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dimethyldithiocarbamate. To be Of these, sulfur is preferably used. The sulfur compound is 0.1 to 10 parts by weight, preferably 0.5 to 10 parts by weight based on 100 parts by weight of the ethylene / α-olefin copolymer rubber (A).
Used in an amount of 5 parts by weight.

When a sulfur compound is used as a vulcanizing agent, it is preferable to use a vulcanization accelerator together. Specific examples of vulcanization accelerators include N-cyclohexyl-2-benzothiazole sulfenamide and N-oxydiethylene-2.
-Benzothiazole sulfenamide, N, N-diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl- 4-morpholinothio) benzothiazole, dibenzothiazyl disulfide and other thiazole compounds; diphenylguanidine, triphenylguanidine, diorsonitrile guanidine, orthonitrile biguanide, diphenylguanidine phthalate and other guanidine compounds; acetaldehyde-aniline reaction product, Butyraldehyde-aniline condensate, hexamethylenetetramine, aldehyde amines such as acetaldehyde ammonia, or aldehyde-ammonia compounds; imidazoline compounds such as 2-mercaptoimidazoline; thiocarbani Compounds such as thiourea compounds such as dode, diethyl thiourea, dibutyl thiourea, trimethyl thiourea, diorsotolyl thiourea; tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, pentamethylene thiuram tetrasulfide. Thiuram compounds such as zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, dimethyldithiocarbamate Dithioate compounds such as tellurium; xanthate compounds such as zinc dibutylxanthate; A compound such as zinc white may be mentioned.

These vulcanization accelerators are used in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the ethylene / α-olefin copolymer rubber (A). Used.

The organic peroxide used in the vulcanization of the organic peroxide may be any compound that is usually used in the vulcanization of rubber. For example, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylhydroperoxide, t-butylcumyl peroxide, benzoyl peroxide, 2,5-Dimethyl-2,5-di (t-butylperoxine) hexyne-3,2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5
-Mono (t-butylperoxy) -hexane, α, α'-
Bis (t-butylperoxy-m-isopropyl) benzene and the like can be mentioned. Among them, dicumyl peroxide, di-t-butylperoxide and di-t-butylperoxy-3,3,5-trimethylcyclohexane are preferably used. These organic peroxides are used alone or in combination of two or more, and 0.0003 to 0.05 mol per 100 g of ethylene / α-olefin copolymer rubber (A),
It is preferably used in a proportion of 0.001 to 0.03 mol, but it is desirable to appropriately determine the optimum amount according to the required physical property values.

When an organic peroxide is used as a vulcanizing agent, it is preferable to use a vulcanizing auxiliary together. Specific examples of the vulcanization aid include 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; Other maleimide compounds include divinylbenzene. Such a vulcanization aid is used in an amount of 0.1 to 2 mol, preferably about equimolar, relative to 1 mol of the organic peroxide used.

Further, in the production of the heat resistant rubber belt according to the present invention, it is preferable to further use a vulcanization aid such as a metal activator, a compound having an oxymethylene structure and a scorch inhibitor.

Specific examples of the metal activator include magnesium oxide, zinc white, zinc carbonate, higher fatty acid zinc, red lead, litharge, calcium oxide and the like. These metal activators are used in an amount of 1 to 15 parts by weight based on 100 parts by weight of the ethylene / α-olefin copolymer rubber (A),
It is preferably used in an amount of 3 to 10 parts by weight.

Further, in order to deal with various rubber processing steps, it is desirable to add a compound having an oxymethylene structure and a scorch inhibitor. Specific examples of the compound having an oxymethylene structure used in the present invention include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol. These compounds having an oxymethylene structure are used in an amount of 0.1 to 1 with respect to 100 parts by weight of the ethylene / α-olefin copolymer rubber (A).
It is used in an amount of 0 parts by weight, preferably 1 to 5 parts by weight.

As the scorch inhibitor, known scorch inhibitors can be used, and specific examples thereof include maleic anhydride and salicylic acid. These scorch inhibitors are used in an amount of 0.2 to 5 parts by weight, preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the ethylene / α-olefin copolymer rubber (A).

The heat resistant rubber belt according to the present invention is further improved in properties as a heat resistant rubber belt by containing additives such as a rubber reinforcing agent, a filler, a softening agent, an antiaging agent and a processing aid. These additives may be appropriately mixed with the ethylene / α-olefin-based copolymer rubber (A) before or after vulcanization.

As the rubber reinforcing agent, specifically, SR
F, GPF, FEF, HAF, ISAF, SAF, F
Various carbon blacks such as T and MT, finely divided silicic acid, and various short fibers such as glass short fibers, cotton short fibers, polyester short fibers, nylon short fibers, and aramid short fibers.

Specific examples of the filler include light calcium carbonate, heavy calcium carbonate, talc, clay, silica and the like. The type and blending amount of these rubber reinforcing agents and fillers can be appropriately selected depending on the application, but the blending amount is usually up to 300 parts by weight with respect to 100 parts by weight of ethylene / α-olefin copolymer rubber (A). Department,
Preferably up to 200 parts by weight, particularly preferably up to 10 parts by weight
0 parts by weight.

As the softening agent, a softening agent 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; petroleum resins, atactic polypropylene, cumarone indene resins Synthetic plastics such as dioctyl phthalate, dioctyl agitate, dioctyl sebacate and the like. The blending amount of these softening agents can be appropriately selected depending on the use of the vulcanized product, but the blending amount is usually 150 parts by weight at the maximum with respect to 100 parts by weight of the ethylene / α-olefin copolymer rubber (A), It is preferably at most 100 parts by weight, particularly preferably at most 50 parts by weight.

As the anti-aging agent, an anti-aging agent usually used for rubber is 0.1 to 5 parts by weight, preferably 100 parts by weight of ethylene / α-olefin copolymer rubber (A). It may be used in an amount of 0.5 to 3 parts by weight.

As the processing aid, a processing aid usually used for rubber is used in an amount of 10 parts by weight or less, preferably 1 to 5 parts by weight, based on 100 parts by weight of the ethylene / α-olefin copolymer rubber (A). It may be used in parts.

Further, in the present invention, in the composition for heat resistant rubber belts, natural rubber, diene rubbers such as SBR, IR and BR, EPD, etc. are used in the range which does not impair the object of the present invention.
Other types of rubber such as M can also be compounded.

The heat resistant rubber belt according to the present invention can be obtained, for example, by preparing and molding a rubber compound by the following method. That is, by using a mixer such as a Banbury mixer, necessary additives such as ethylene / α-olefin copolymer rubber (A), a reinforcing agent, a filler, and a softening agent are added at a temperature of 80 to 170 ° C. for about 3 to After kneading for 10 minutes, a roll such as an open roll is used to additionally mix a vulcanizing agent and, if necessary, a vulcanization accelerator or a vulcanization aid, and a roll temperature of 40 to 80 ° C. for 5 to 30 After kneading for a minute, the mixture is dispensed to prepare a ribbon-shaped or sheet-shaped compounded rubber.

Alternatively, the ethylene / α-olefin copolymer rubber (A) and the above-mentioned additives are added in an amount of about 80-100.
It is fed directly into the extruder heated to 0 ° C and the residence time is about 0.
By taking 5 to 5 minutes, a rubber compound in pellet form can be prepared.

Then, the rubber compound prepared as described above is molded into a belt by using a roll machine, a calender molding machine, an extruder, etc.
Vulcanization is performed by heating at 220 ° C. for 1 to 60 minutes to obtain a heat resistant rubber belt.

Further, the above rubber compound can be molded and vulcanized in a mold using a press molding machine or an injection molding machine to obtain a heat resistant rubber belt. In this case, the mold temperature is usually 130 to 220 ° C., and the time required for vulcanization is 1 to 60 minutes.

The heat-resistant rubber belt according to the present invention thus obtained is made of synthetic fiber cloth, natural fiber cloth, or steel fiber cloth.
A composite rubber belt can be obtained by laminating cords, glass cords, etc. as a reinforcing material. Moreover, a composite rubber belt can be obtained by laminating such a reinforcing material with the above rubber compound, compounding it, and then vulcanizing it.

The heat resistant rubber belt produced as described above is excellent in heat aging resistance, abrasion resistance and low temperature flexibility.

[0211]

The heat-resistant rubber belt according to the present invention is an ethylene / α-olefin prepared by using a metallocene catalyst and comprising ethylene, an α-olefin having 3 to 12 carbon atoms and, if necessary, a non-conjugated polyene. The composition comprises a copolymer rubber (A), the molar ratio of the ethylene component unit to the α-olefin component unit having 3 to 12 carbon atoms, iodine value and intrinsic viscosity [η]. Is in a specific range, so it has excellent roll processability and
It excels in heat aging resistance and abrasion resistance as well as low temperature flexibility (cold resistance).

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. The ethylene / α-olefin copolymer rubbers used in Examples and Comparative Examples are as shown in Table 1.

[0213]

[Table 1]

[0214]

Example 1 The ethylene / 1-butene copolymer rubber [copolymer (1)] shown in Table 1 was compounded according to Table 2 to obtain an unvulcanized compounded rubber.

That is, the above copolymer (1), zinc white, stearic acid, HAF carbon black, paraffin type process oil, polyethylene glycol and an antioxidant were added to a Banbury mixer [Kobe Co., Ltd.] having a capacity of 1.7 liters. Kneading for 5 minutes at a steel mill, and then allowed to stand for 1 day at room temperature. Dicumyl peroxide (vulcanizing agent) and ethylene glycol dimethacrylate (vulcanizing aid) were added to the kneaded material thus obtained by an open roll and kneaded to give a compounded rubber, and a thickness of about 2 mm A compounded rubber sheet of was obtained. The roll surface temperature at this time is 50 for the front roll.
C. and the rear roll was 50.degree. Further, the roll rotation speed was 16 rpm for the front roll and 18 rpm for the rear roll.

[0216]

[Table 2]

The compounded rubber sheet obtained as described above was press-vulcanized at 170 ° C. for 10 minutes to obtain a vulcanized rubber sheet. The following tests were conducted on the obtained vulcanized rubber sheet. The results are shown in Table 3.

[1] Roll processability test An 8 inch open roll having a roll width of 20 inches was used to visually observe the state of winding of the compound around the roll when adding and kneading the vulcanizing agent and the vulcanization aid.

[2] Tensile test JIS K 6301 (198) was prepared by punching out a vulcanized rubber sheet.
No. 3 type dumbbell test piece described in 9 years) was prepared, and the test piece was used in accordance with the method defined in the same JIS K 6301 paragraph 3, measurement temperature 25 ° C., tensile speed 500
A tensile test was carried out under the condition of mm / min to measure the 300% modulus (M ₃₀₀ ), the tensile stress at break T _B and the elongation at break E _B.

[3] Hardness Test In the hardness test, the spring hardness H _S (JIS A hardness) was measured according to JIS K 6301 (1989).

[4] Aging test In the aging test, an air heating aging test was carried out at 175 ° C. for 240 hours, and the retention ratio to the physical properties before aging, that is, the tensile strength retention ratio A _R (T _B ), the elongation retention ratio A _R ( E _B ).

[5] Abrasion test For the abrasion test, a Taber abrasion test was performed according to JIS K 6264. That is, the amount of wear after 1000 times with a load of 250 gf was obtained.

[6] Low Temperature Twist Test (Gehman Torsion Test) The low temperature twist test was carried out according to JIS K 6301 to determine T ₁₀ [° C.]. This temperature is an indicator of the low temperature flexibility of the vulcanized rubber.

(Test Conditions) Twisting constant of twisted wire: 0.5 gf · cm / degree Immersion time: 10 minutes Twisting time: 5 seconds

[0225]

Examples 2 to 5 The same as Example 1 except that the copolymers (2) to (5) shown in Table 1 above were used instead of the copolymer (1). I went to.

The results are shown in Table 3.

[0227]

Comparative Example 1 In Example 1, instead of the copolymer (1), the molar ratio of ethylene and propylene (ethylene / propylene) was 58/42, and the Muni-viscosity [ML _{1 + 4} (1
00 ° C.]] is 40, the iodine value is 0, and the intrinsic viscosity [η] measured in decalin at 135 ° C. is 1.9 dl / g. An ethylene / propylene copolymer [hereinafter abbreviated as EPM (1)] is used. The same procedure as in Example 1 was carried out except that it was omitted.

The results are shown in Table 3.

[0229]

COMPARATIVE EXAMPLE 2 In Example 1, instead of the copolymer (1), the molar ratio of ethylene and propylene (ethylene / propylene) was 72/28, and the Muni-viscosity [ML _{1 + 4} (1
00 ° C.), an iodine value of 0, an intrinsic viscosity [η] measured in decalin at 135 ° C. of 1.9 dl / g is an ethylene / propylene copolymer [hereinafter abbreviated as EPM (2)]. The same procedure as in Example 1 was carried out except that it was omitted.

The results are shown in Table 3.

[0231]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C08L 23:18) B29K 23:00 (72) Inventor Tetsuo Tojo 3 Chikusaigan, Ichihara, Chiba Prefecture Address Mitsui Sekiyu Kagaku Kogyo Co., Ltd.

Claims (3)

[Claims] 1. A rubber composition comprising ethylene, an α-olefin having 3 to 12 carbon atoms, and optionally an ethylene / α-olefin copolymer rubber (A) comprising a non-conjugated polyene. The ethylene / α-olefin-based copolymer rubber (A) is obtained by randomizing ethylene, an α-olefin having 3 to 12 carbon atoms, and optionally a non-conjugated polyene in the presence of a metallocene catalyst. Obtained by copolymerization, (1) (a) a unit derived from ethylene and (b) a carbon atom number of 3 to
The unit derived from 12 α-olefins is 60/4
It is contained at a molar ratio of 0 to 80/20 [(a) / (b)], (2) has an iodine value of 0 to 30, and (3) has an intrinsic viscosity [η] measured in 135 ° C decalin. A heat-resistant rubber belt, which is 1 to 3 dl / g. 2. A rubber composition comprising ethylene, an α-olefin having 4 to 12 carbon atoms, and optionally an ethylene / α-olefin copolymer rubber (A) comprising a non-conjugated polyene. The ethylene / α-olefin-based copolymer rubber (A) is obtained by randomizing ethylene, an α-olefin having 4 to 12 carbon atoms, and optionally a non-conjugated polyene in the presence of a metallocene catalyst. Obtained by copolymerization, (1) (a) a unit derived from ethylene and (b) 4 to 4 carbon atoms.
The unit derived from 12 α-olefins is 60/4
It is contained at a molar ratio of 0 to 80/20 [(a) / (b)], (2) has an iodine value of 0 to 30, and (3) has an intrinsic viscosity [η] measured in 135 ° C decalin. 1 to 3 dl / g, and (4) linear viscosity ethylene having an intrinsic viscosity [η] measured in the above (3) and the same weight average molecular weight (by light scattering method) as 70 mol%.・ Ratio of intrinsic viscosity [η] _{blank of} propylene copolymer [gη ^* (= [η] /
[Η] _blank )] is a value exceeding 0.95, The heat resistant rubber belt according to claim 1. 3. A rubber composition comprising ethylene, an α-olefin having 3 to 12 carbon atoms, and optionally an ethylene / α-olefin copolymer rubber (A) comprising a non-conjugated polyene. The ethylene / α-olefin-based copolymer rubber (A) comprises ethylene, an α-olefin having 3 to 12 carbon atoms, and optionally a carbon-carbon double bond in the presence of a metallocene catalyst. Among them, the carbon-carbon double bond that can be polymerized by the catalyst is obtained by random copolymerization with a non-conjugated polyene having only one molecule in one molecule, and (1) (a) a unit derived from ethylene And (b) 3 carbon atoms
Unit derived from α-olefin of 60 to 60 /
It is contained in a molar ratio of 40 to 80/20 [(a) / (b)], (2) has an iodine value of 0 to 30, and (3) has an intrinsic viscosity [η] measured in 135 ° C decalin. 1 to 3 dl / g, and (4) the intrinsic viscosity [η] measured in the above (3) and the ethylene content having the same weight average molecular weight (by light scattering method) as 70 mol% Ratio of chain ethylene / propylene copolymer to intrinsic viscosity [η] _blank [gη ^* (= [η] /
The heat resistant rubber belt according to claim 1, wherein [η] _blank )] is 0.2 to 0.95.