JP2005344101A - Rubber composition and its application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber composition having an excellent extrusion moldability, a high vulcanization rate and excellent mechanical properties such as strength after vulcanization and its applications. <P>SOLUTION: The rubber composition is a random copolymer rubber of (a) ethylene, (b) a 3-20C α-olefin, (c) a non-conjugated polyene having only one carbon-carbon double bond polymerizable with a metallocene catalyst in the molecule and (d) a non-conjugated polyene having two carbon-carbon double bonds polymerizable with the catalyst in the molecule. The composition contains unit (a) and unit (b) in a molar ratio of 90/10-40/60 [(a)/(b)], unit (c) in an amount of 0.1-10 mole% and unit (d) in an amount of 0.1-3 mole%. The composition further contains an ethylenic copolymer rubber having a limiting viscosity number [η] in the range of 0.1-10 dl/g and a strength ratio D (Tαβ/Tαα) in<SP>13</SP>C-NMR spectrum of ≤0.5, and not less than one kind of component selected from a reinforcement material, a softener and a vulcanizing agent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an ethylene-based copolymer rubber, a vulcanizable rubber composition containing the copolymer rubber, and a method for producing the rubber, and more particularly to extrudability, heat aging resistance, and low temperature flexibility. The present invention relates to a novel ethylene copolymer rubber, a rubber composition, and a method for producing the rubber, which are excellent and have a high vulcanization speed and excellent mechanical properties.

  Conventionally, ethylene / propylene / polyene copolymer rubber has excellent weather resistance, ozone resistance, heat aging resistance, etc., and is widely used in automotive industrial materials, electric wire materials, construction / civil engineering materials, industrial materials, etc. It has been.

  As the ethylene / propylene / polyene copolymer rubber used in such applications, for example, it is desired that the rubber has excellent moldability, high vulcanization speed, and excellent vulcanization strength.

Such ethylene / propylene / polyene copolymer rubbers include ethylene / propylene / 5-ethylidene-2-norbornene (ENB) copolymer rubber, ethylene / propylene / dicyclopentadiene copolymer rubber, ethylene / propylene / 1 rubber. 1,4-hexadiene copolymer rubber and the like are known. Among these, ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber has a faster vulcanization rate than other unsaturated ethylene copolymer rubbers.

However, this ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber has a problem that it is inferior in extrusion moldability.
For this reason, the appearance of an ethylene-based copolymer rubber that is excellent in extrusion moldability, fast in vulcanization speed, and excellent in mechanical properties such as vulcanization strength is desired.

The applicant of the present application disclosed in Japanese Patent Laid-Open No. 5-262728 (Japanese Patent Application No. 4-27571) a random copolymer rubber comprising ethylene, α-olefin, and 7-methyl-1,6-octadiene (MOD). (I) ethylene / α-olefin (molar ratio) of 40/60 to 90/10, (ii) MOD content of 0.4 to 25 mol%, (iii) intrinsic viscosity at 135 ° C. decalin [Η] is 0.1 dl / g <[η] <8 dl / g, (iv) the intensity ratio D (Tαβ / Tαα) is 0.5 or less, (v) a B value of 1.00 to 1.50, (vi ) A ternary ethylene / α-olefin / diene copolymer rubber having a Tg of −53 ° C. was proposed.

  This terpolymer rubber is obtained in the presence of a transition metal catalyst comprising a Group IVB transition metal (zirconium compound) containing a ligand having a cyclopentadienyl skeleton and an organoaluminum oxy compound. A plurality of types of olefins were copolymerized with high activity, and had a narrow composition distribution and excellent low-temperature flexibility.

  However, this ternary copolymer rubber also has room for further improvement in terms of mechanical properties such as vulcanization strength, extrusion moldability, balance of vulcanization speed, flexibility at low temperatures, and heat aging resistance. there were.

Further, the applicant of the present application disclosed in JP-A-63-8408, ethylene, carbon number 3 to
An ethylene copolymer rubber obtained by random copolymerization of 10 α-olefins and polyenes 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB), (a) ethylene / α-olefin (molar ratio) of 50/50 to 95/5, (b) ENB and V
NB content molar ratio (ENB / VNB) is 1/1 to 45/1, (c) iodine value is 2 to 50, (d) 13
Intrinsic viscosity [η] measured in 5 ° C. decalylline is 0.7 to 6.0 dl / g, (e) Q value (Mw
An ethylene / α-olefin / polyene random copolymer rubber having a / Mn) greater than 6 was proposed.

  This copolymer rubber is obtained by random copolymerization of the above components in a hydrocarbon solvent in the presence of a soluble vanadium compound and an organoaluminum compound. The balance between vulcanization speed and vulcanization strength was good, and the shape retention was also good. However, there is room for further improvement in terms of vulcanization strength, flexibility at low temperatures, heat aging resistance, and the like.

For this reason, the appearance of an ethylene copolymer rubber that is excellent in extrusion moldability, fast in vulcanization speed, mechanical properties such as vulcanization strength, flexibility at low temperature, and excellent in heat aging resistance is desired. In addition, ethylene, α-olefin having 3 or more carbon atoms, non-conjugated polyene having only one polymerizable double bond in one molecule, and non-conjugated polyene having two polymerizable double bonds in one molecule. It has been desired to develop a method for producing a copolymer (rubber) that can polymerize α-olefin with high activity and high conversion.
Japanese Patent Application Laid-Open No. 5-262728 (Japanese Patent Application No. 4-27571) JP 63-8408 A

  The present invention seeks to solve the problems associated with the prior art as described above, and is excellent in extrusion moldability, fast in vulcanization speed, mechanical properties such as vulcanization strength, and flexibility at low temperatures. It is an object of the present invention to provide an ethylene copolymer rubber excellent in heat aging resistance, a rubber composition containing the copolymer rubber, and a method for producing the rubber.

The unsaturated ethylene copolymer rubber according to the present invention is
(a) ethylene, (b) an α-olefin having 3 to 20 carbon atoms, and (c) a carbon / carbon double bond that can be polymerized with a metallocene catalyst among carbon / carbon double bonds in one molecule. A non-conjugated polyene having only one, and (d) a non-conjugated polyene having two carbon / carbon double bonds that can be polymerized with the catalyst among the carbon / carbon double bonds,
A random copolymer rubber of
(i) a unit derived from ethylene (a) and a unit derived from an α-olefin having 3 to 20 carbon atoms (b) in a mole of 90/10 to 40/60 [(a) / (b)]. Contained in a ratio,
(ii) 0.1 to 10 units (c) derived from a non-conjugated polyene in which only one carbon / carbon double bond that can be polymerized with the catalyst is present in one molecule among carbon / carbon double bonds. Contained in an amount of mol%,
(iii) 0.1-3 mol of units (d) derived from non-conjugated polyene in which two carbon / carbon double bonds that can be polymerized with the catalyst among carbon / carbon double bonds are present in one molecule % In amount,
(iv) the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.1 to 10 dl / g;
(v) The intensity ratio D (Tαβ / Tαα) of Tαβ to Tαα in the ¹³ C-NMR spectrum is 0.5 or less.

In a preferred embodiment of the present invention, it is desirable that the ethylene copolymer rubber has a B value calculated from (vi) ¹³ C-NMR spectrum and the following formula of 1.0 to 2.0. .

B value = [P _OE ] / (2 · [P _E ] · [P _O ])
(Wherein [P _E ] is the mole fraction of the unit derived from (a) ethylene in the random copolymer rubber,
[ _PO ] is the content mole fraction of units derived from (b) α-olefin in the random copolymer rubber,
[P _OE ] is the ratio of the number of α-olefin / ethylene chains to the total number of dyad chains in the random copolymer rubber. ).

In addition, the ethylene copolymer rubber of the present invention has an intrinsic viscosity [η] measured in (iv) above and an ethylene content of 70 mol%, which is the same weight average molecular weight (according to the light scattering method). The gη ^* value (= [η] / [η] _Blank ) defined by the ratio of the chain ethylene / propylene copolymer to the intrinsic viscosity [η] _blank is preferably 0.9 or less.

In addition, the ethylene copolymer rubber of the present invention includes an intrinsic viscosity [η] measured in the above (iv) and gel permeation chromatography (GPC: 140 ° C., o-dichlorobenzene solvent) of this ethylene copolymer rubber. ) is determined by measuring the intrinsic viscosity of the ethylene content of 70 mol% of linear ethylene-propylene copolymer terms [η] _blank 'as the ratio g' (= [η
] / [Η] _blank ') is preferably 0.9 or less.

  The (b) α-olefin preferably has 4 or more carbon atoms, and the glass transition temperature Tg determined by DSC is −45 ° C. or lower, more preferably −50 ° C. or lower, particularly preferably −55 ° C. or lower. It is preferable that

In the method for producing an ethylene copolymer rubber according to the present invention, (a) ethylene and (b) 3 carbon atoms.
~ 20 α-olefin, and (c) a non-conjugated polyene having only one carbon / carbon double bond that can be polymerized with a metallocene catalyst among carbon / carbon double bonds in one molecule, and (d ) Among carbon / carbon double bonds, non-conjugated polyene having two carbon / carbon double bonds that can be polymerized with the catalyst,
The ethylene copolymer rubber as described above is produced by random copolymerization in the presence of a metallocene catalyst.

This metallocene catalyst preferably contains a metallocene compound represented by the following formula [III] or [IV].

[Wherein M is a transition metal of group IVB of the periodic table;
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 a halogen, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. Group,
R ¹³ and R ¹⁴ are each an alkyl group having 1 to 20 carbon atoms,
X ¹ and X ² are 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,
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 is 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)],

[Wherein M is a transition metal of group IVB of the periodic table;
R ²¹ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, an optionally halogenated alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or —NR ₂ , —SR, —OSiR ₃ , —SiR ₃ or —PR ₂ group (R is a halogen atom,
An alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms),
R ^{22 to} R ²⁸ are the same as R ²¹ described above, or adjacent R ^{22 to} R ²⁸ may form an aromatic ring or an aliphatic ring together with the atoms to which they are bonded,
X ³ and X ⁴ may be the same 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, an alkoxy group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. 10 aryl groups, aryloxy groups having 6 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, arylalkyl groups having 7 to 40 carbon atoms, alkylaryl groups having 7 to 40 carbon atoms, carbon atoms An arylalkenyl group of formula 8 to 40,
Z is

-Sn -, - O -, - S -, = SO, = SO 2, = NR 29, = CO, a = PR ²⁹ or = P (O) R ^29. (However, R ²⁹ and R ³⁰ may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, or 6 carbon atoms. C-10 aryl group, C6-C10 fluoroaryl group, C1-C10 alkoxy group, C2-C10 alkenyl group, C7-C40 arylalkyl group, carbon atom or arylalkenyl group or an alkylaryl group having 7 to 40 carbon atoms having 8 to 40, or the R ²⁹ and R ^30, may form a ring together with the atoms connecting them, respectively, M ² is , Silicon, germanium or tin atoms.)].

The rubber composition according to the present invention contains the above-described ethylene copolymer rubber and at least one component of the following (a), (b), and (c).
(a) a reinforcing agent in an amount of 300 parts by weight or less based on 100 parts by weight of the ethylene copolymer rubber;
(b) a softener in an amount of 200 parts by weight or less based on 100 parts by weight of the ethylene copolymer rubber;
(c) Vulcanizing agent.

The ethylene copolymer rubber according to the present invention as described above is excellent in extrusion moldability, has a high vulcanization speed, and is excellent in mechanical properties such as strength after vulcanization (vulcanization strength).
In the present specification, the term “ethylene-based copolymer rubber” is used in the meaning including both unvulcanized products and vulcanized products, unless it is contrary to the purpose. The rubber is also referred to as an ethylene copolymer or a copolymer.

  According to the present invention, an ethylene copolymer rubber excellent in extrusion moldability, fast in vulcanization speed, mechanical properties such as vulcanization strength, low temperature flexibility, heat aging resistance, etc., and the copolymer A rubber composition containing a combined rubber is obtained.

In addition, according to the method for producing an ethylene copolymer rubber according to the present invention, ethylene, α-olefin having 3 or more carbon atoms, and 1 in one molecule could not be achieved by the conventional production method.
A non-conjugated polyene having two polymerizable double bonds and a non-conjugated polyene having two polymerizable double bonds in one molecule with high activity and high conversion of α-olefin, Moreover, the copolymer can be copolymerized with excellent random copolymerization to obtain a high molecular weight copolymer. Moreover, since the manufacturing method of the ethylene copolymer rubber which concerns on this invention is excellent in the polymerization activity at high temperature, this copolymer rubber can be manufactured efficiently.

Hereinafter, the ethylene copolymer rubber according to the present invention, a vulcanizable rubber composition containing the copolymer rubber, and a method for producing the rubber will be specifically described.
[ Ethylene copolymer rubber ]
The ethylene copolymer rubber according to the present invention is
(a) ethylene, (b) an α-olefin having 3 to 20 carbon atoms, and (c) a carbon / carbon double bond that can be polymerized with a metallocene catalyst among carbon / carbon double bonds in one molecule. Randomization of only one non-conjugated polyene and (d) a non-conjugated polyene in which two carbon / carbon double bonds that can be polymerized with the catalyst are present in one molecule. It is a copolymer.

As the (ii) α-olefin having 3 to 20 carbon atoms used when forming such a random copolymer rubber, specifically,
Propylene, 1-butene, 1-pentene, 1-hexene, 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, 1-octene, 1-decene, 1-decene Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned, preferably propylene, 1-butene, 1-hexene and 1-octene are used, more preferably 1-butene, 1 Α-olefins having 4 or more carbon atoms such as -hexene and 1-octene are desirable. In particular, an ethylene copolymer rubber having an α-olefin having 4 or more carbon atoms tends to give a vulcanizate having good heat aging resistance, low temperature characteristics, and compression set. These α-olefins may be used alone or in combination of two or more.

In the present invention, the non-conjugated polyene is a non-conjugated polyene having only one carbon / carbon double bond that can be polymerized by a metallocene-based catalyst described later among carbon / carbon double bonds (c). )When,
Among carbon / carbon double bonds, non-conjugated polyene (d) having two carbon / carbon double bonds that can be polymerized with the catalyst is used in one molecule (hereinafter, both are simply referred to as “ Also called "non-conjugated polyene"),
Of these, the non-conjugated polyene (c) in which only one carbon / carbon double bond that can be polymerized with a metallocene catalyst is present in one molecule is a chain having both ends being vinyl groups (CH ₂ ═CH—). Polyene is not included. In such a non-conjugated polyene (c), when two or more carbon-carbon double bonds are present, only one carbon-carbon double bond exists as a vinyl group at the molecular end, The carbon / carbon double bond (C═C) is preferably present in the form of an internal olefin structure in the molecular chain (including the main chain and side chain). Examples of such non-conjugated polyene (c) include the following aliphatic polyenes and alicyclic polyenes.

Specific examples of the aliphatic non-conjugated polyene (c) include:
1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,7-nonadiene, 1,8-decadiene, 1,12-tetradecadiene,
3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-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,
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, 7-methyl-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,
Examples include 6-methyl-1,6-undecadiene and 9-methyl-1,8-undecadiene. In the present invention, these aliphatic polyenes can be used singly or in combination of two or more. Preferably, 7-methyl-1,6-octadiene is used.

The alicyclic polyene is composed of an alicyclic portion having one carbon / carbon double bond (unsaturated bond) and a chain portion having an internal olefin bond (carbon / carbon double bond). Specific examples include polyene, and specific examples include 5-ethylidene-2-norbornene (ENB), 5-propylidene-2-norbornene, 5-butylidene-2-norbornene, and the like. 5-ethylidene-2-norbornene (ENB) is preferably used.

Specific examples of other alicyclic polyenes include 2-methyl-2,5-norbornadiene and 2-ethyl-2,5-norbornadiene.
In the present invention, these non-conjugated polyenes (c) can be used singly or in combination of two or more.

Specific examples of the non-conjugated polyene (d) in which two carbon / carbon double bonds that can be polymerized by the catalyst among the carbon / carbon double bonds are present in one molecule include, for example, 5-vinyl- 5-alkenyl-2-norbornene such as 2-norbornene (VNB), 5-allyl-2-norbornene;
Alicyclic polyenes such as 2,5-norbornadiene, dicyclopentadiene (DCPD), norbornadiene, tetracyclo [4,4,0,1 ^2.5 , 1 ^7.10 ] deca-3,8-diene;
Examples include α, ω-dienes such as 1,7-octadiene and 1,9-decadiene.

Of these, 5-alkenyl-2-norbornene, dicyclopentadiene, 2,5-norbornadiene, 1,7-octadiene and 1,9-decadiene are preferable, and 5-vinyl-2-norbornene (VNB) is particularly preferable. Used.

The ethylene copolymer rubber according to the present invention (simply referred to as a copolymer or an ethylene copolymer) includes (a) ethylene, (b) α-olefin, (c) carbon Non-conjugated polyene in which only one carbon / carbon double bond that can be polymerized by the catalyst is present in a molecule, and (d) carbon that can be polymerized by the catalyst among carbon / carbon double bonds.・ Carbon double bond
Component units derived from each monomer ((a), (b), (c), (d)) of two non-conjugated polyenes present in one molecule are randomly arranged and bonded, While having a branched structure resulting from non-conjugated polyene, the main chain has a substantially linear structure. The fact that this copolymer (rubber) has a substantially linear structure and substantially no gel-like cross-linked structure means that the copolymer is dissolved in an organic solvent and substantially contains insoluble matter. This can be confirmed by the absence. For example, when the intrinsic viscosity [η] is measured, the copolymer can be confirmed by being completely dissolved in decalin at 135 ° C.
Component Unit Amount The ethylene copolymer rubber according to the present invention comprises (a) a component unit derived from ethylene (ethylene unit) and (b) a component unit derived from an α-olefin having 3 to 20 carbon atoms ( α-olefin unit) in a molar ratio ((a) / (b)) of 90/10 to 40/60, preferably 85/15 to 50/50, more preferably 82/18 to 55/45. Contains.

In the present invention, when the component (a) / component (b) (molar ratio) exceeds 90/10, it tends to be resinous, and when it is less than 40/60, the low-temperature characteristics tend to deteriorate.
In addition, in the ethylene-based copolymer rubber according to the present invention, (a) component unit amount derived from ethylene, and (b) component unit amount derived from α-olefin having 3 to 20 carbon atoms, Is not particularly limited as long as the above (a) component / (b) component (molar ratio) is satisfied. In the ethylene copolymer rubber according to the present invention, the total of ethylene units and α-olefin units is 100 mol%. (A) component units derived from ethylene, usually in an amount of 90 to 40 mol%, preferably 85 to 50 mol%, more preferably 82 to 55 mol%,
(b) The component unit derived from an α-olefin having 3 to 20 carbon atoms is usually contained in an amount of 10 to 60 mol%, preferably 15 to 50 mol%, more preferably 18 to 45 mol%. It is desirable.

In addition, in the ethylene copolymer rubber according to the present invention, (c) one carbon / carbon double bond that can be polymerized with a metallocene catalyst as described later is included in one molecule. It contains 0.1 to 10 mol%, preferably 0.2 to 8 mol%, more preferably 0.5 to 5 mol% of a component unit derived from a single non-conjugated polyene. If the amount of component unit (c) is less than 0.1 mol%, sulfur vulcanization tends to be difficult, and if it exceeds 10 mol%, the environmental aging resistance tends to decrease.

Further, in the ethylene copolymer rubber according to the present invention, (d) carbon / carbon double bonds that can be polymerized with a metallocene catalyst as described later among carbon / carbon double bonds are contained in one molecule. Contains 0.1 to 3 mol%, preferably 0.2 to 2.5 mol%, more preferably 0.3 to 2.0 mol% of component units derived from two non-conjugated polyenes present doing. When the amount of component unit (d) is less than 0.1 mol%, excellent extrudability tends to be difficult to develop, and when it exceeds 3 mol%, a gel-like crosslinked polymer tends to be formed.

In the ethylene-based copolymer rubber according to the present invention, the molar ratio of the component (c) to the component (c) (component (c) / component (d)) is 1/3 to 30/1, Preferably it is 1/2 to 20/1, more preferably 1/1 to 10/1. If it is out of the above range, the balance between the vulcanization speed and workability tends to be deteriorated.
Intrinsic viscosity [η]
In the present invention, the intrinsic viscosity [η] of ethylene copolymer rubber measured in decalin at 135 ° C. is 0.1 to 10 dl / g, preferably 0.5 to 5 dl / g, more preferably 0. In the range of 8-4 dl / g.

If the intrinsic viscosity is less than 0.1 dl / g, the strength after vulcanization (vulcanization strength) tends to be inferior, and if it exceeds 10 dl / g, the workability tends to be lowered.
Iodine value (IV value)
In the present invention, the iodine value of the ethylene copolymer rubber is preferably 0.5 to 50, preferably 1 to 40, particularly preferably 5 to 35.

The iodine-based ethylene copolymer rubber as described above has a high vulcanization speed and can be vulcanized at high speed.
D value (Tαβ / Tαα)
In the present invention, the D value, that is, the strength (area) ratio D (Tαβ / Tαα) of Tαβ to Tαα in the ¹³ C-NMR spectrum of the ethylene copolymer rubber (A) is 0.5 or less, particularly 0. .3 or less is desirable.

The strength ratio D value of the random copolymer rubber varies depending on the type of α-olefin constituting the random copolymer rubber.
Here, Tαβ and Tαα in the ¹³ C-NMR spectrum are the peak intensities of CH ₂ in units derived from α-olefins having 3 or more carbon atoms, and the positions relative to the tertiary carbon are different as shown below. Two types of CH ₂ are meant.

The strength ratio D of the random copolymer rubber can be determined as follows.
The ¹³ C-NMR spectrum of the random copolymer rubber is obtained by, for example, JE manufactured by JEOL Ltd.
Using an OL-GX270 NMR measuring apparatus, a mixed solution of hexachlorobutadiene / d ₆ -benzene = 2/1 (volume ratio) having a sample concentration of 5% by weight was mixed with d ₆ -benzene (128 ppm at 25 ° C. at 67.8 MHz. ) Measure with reference.

Analysis of the ¹³ C-NMR spectrum was basically performed according to the proposal of Lindeman Adams (Analysis Chemistry 43, p1245 (1971)) and JCRandall (Review Macromolecular Chemistry Physics, C29, 201 (1989)).

  Here, with respect to the intensity ratio D, (a) ethylene / (b) α-olefin (propylene) / (c) :( 5-ethylidene-2-norbornene (ENB)) / (d) :( 5-vinyl-2 -Norbornene (VNB)) A quaternary copolymer rubber will be described in more detail as an example.

In the ¹³ C-NMR spectrum of this copolymer rubber, a peak appearing at 45 to 46 ppm is assigned to Tαα, and a peak appearing at 32 to 33 ppm is assigned to Tαβ.
The intensity ratio D is calculated by the integral value (area) ratio of each peak portion.

  The strength ratio D thus determined is generally the ratio at which the 1,1-addition reaction occurs following the 1,2-addition reaction of propylene, or the 1,2-addition reaction occurs after the 2,1-addition reaction of propylene. It is considered as a measure of percentage. Therefore, the larger the intensity ratio D value, the more irregular the bonding direction of α-olefin (propylene). Conversely, the smaller the D value, the more regular the α-olefin bond direction, and the higher the regularity, the easier the molecular chains to assemble, and the vulcanized random copolymer rubber has superior strength and the like. This tends to be favorable.

In the present invention, as described later, ethylene (a), α-olefin (b) and two kinds of non-conjugated polyenes (c) and (d) are copolymerized using a specific Group IVB metallocene catalyst. Thus, it is preferable to obtain a random copolymer rubber having the strength ratio D of usually 0.5 or less. In the presence of a Group VB metallocene catalyst such as vanadium, for example, (a) ethylene, (b) propylene, (c): (5-ethylidene-2-norbornene (ENB)) and (d): (5 When -vinyl-2-norbornene (VNB)) is copolymerized, an ethylene / propylene / ENB / VNB quaternary copolymer rubber having a strength ratio D of 0.5 or less may not be obtained. The same applies to α-olefins other than propylene.
The B value ethylene copolymer rubber preferably has a B value of 1.0 to 2.0 determined from a ¹³ C-NMR spectrum and the following formula.

B value = [P _OE ] / (2 · [P _E ] · [P _O ])
(Wherein [P _E ] is the content of the unit derived from (a) ethylene in the random copolymer rubber.
Mole fraction,
[P _O ] is a monomer derived from (b) α-olefin in the random copolymer rubber.
Content mole fraction of
[P _OE ] is a function of the total number of dyad chains in the random copolymer rubber.
The ratio of α-olefin / ethylene chain number. )
This B value is an index representing the distribution state of ethylene and α-olefin in the copolymer rubber. JCRandall (Macromolecules, 15, 353 (1982)), J.Ray (Macromolecules, 10,773 (1977)) and others Based on the report.

  As the B value is larger, the block chain of ethylene or α-olefin becomes shorter, the distribution of ethylene and α-olefin is more uniform, and the composition distribution of the copolymer rubber is narrower. In addition, the composition distribution of the copolymer rubber becomes wider as the B value becomes smaller than 1.00, and such a copolymer rubber is compared with a copolymer rubber having a narrow composition distribution, for example, when vulcanized. The physical properties such as strength may not be sufficiently exhibited.

In the present invention, as described later, the B value is preferably 1. by copolymerizing ethylene, α-olefin, and two specific non-conjugated polyenes using a specific Group IVB metallocene catalyst. A random copolymer rubber of 0 to 2.0 has been obtained, but ethylene / α-olefin and non-conjugated polyene can be copolymerized in the presence of a titanium-based nonmetallocene catalyst. -It is impossible to obtain a quaternary copolymer rubber comprising an olefin and two kinds of non-conjugated polyenes and having a B value in the above range.
gη ^* value In the present invention, the ethylene copolymer rubber further comprises (iv) the intrinsic viscosity [η] of the ethylene copolymer rubber measured in decalin at 135 ° C. and the same weight average molecular weight. Gη ^* value (= [η] / [η] _Blank ) defined by the ratio of the intrinsic viscosity [η] _blank of a linear ethylene / propylene copolymer having an ethylene content of 70 mol% (by light scattering method) ) Is 0.9
Hereinafter, it is preferably 0.2 to 0.85, more preferably 0.4 to 0.8. When this gη ^* value exceeds 0.9, the amount of long chain branching in the molecule is small, and the processability tends to be lowered. For example, the shape retention property is lowered, the surface roughness value is increased, the extruded skin is deteriorated, and the amount of extrusion cannot be increased.

The above [η] _blank replaces the weight average molecular weight Mw obtained by the light scattering method for this ethylene / propylene / non-conjugated polyene quaternary copolymer (ethylene copolymer rubber) with the viscosity average molecular weight Mv, and the formula ( Calculated from I).

[Η] _Blank = 7.2 × 10 ⁻⁴ Mv ^0.667 ... (I)
g ′ Value The ethylene copolymer rubber of the present invention is measured by the above intrinsic viscosity [η] and gel permeation chromatography (GPC: 140 ° C., o-dichlorobenzene solvent) of the ethylene copolymer rubber. the obtained, the intrinsic viscosity of the ethylene content of 70 mol% linear ethylene-propylene copolymer terms [η] _blank 'as the ratio g' (= [η] / [η] blank ')
Is 0.9 or less, preferably 0.2 to 0.85, more preferably 0.4 to 0.8. When this g ′ value exceeds 0.9, the amount of long-chain branching in the molecule is small, and the processability tends to decrease. For example, the shape retention property is lowered, the surface roughness value is increased, the extruded skin is deteriorated, and the amount of extrusion cannot be increased.

For the above [η] _blank ′, first, GPC measurement of ethylene copolymer rubber is performed to obtain polystyrene-converted molecular weight M _i-PSt of each fraction.
Next, Mi _-PSt
Formula [η] _i-PSt · M _i-PSt = [η] _i-EPR · M _i-EPR , and [η] _i-PSt = 1.37 × 10 ⁻⁴ M _i-PSt ^0.686 ,
[Η] _i-EPR = 7.2 × 10 ⁻⁴ M _i-EPR ^0.667 is converted into EPR-converted molecular weight M _i-EPR using the formula:

Next, the converted M _i-EPR is converted into [η] _i-blank 'for each fraction according to the formula (II).
[Η] _i-blank '= 7.2 × 10 ⁻⁴ M _i-EPR ^0.667 (II)
Here, the subscript i indicates each fraction sorted by GPC. Next, the converted [η] _i-blank 'is calculated by the following equation (III) to obtain [η] _blank '.
[Η] _blank '= Σω _i · [η] _i-blank ' / Σω _i (III)
Here, ω represents a weight fraction. In this way, [η] _blank 'is calculated, and g' is obtained from the ratio with [η].

The ethylene copolymer rubber obtained by the present invention has a gη ^* value or g ′ value much smaller than 1 as described above, indicating that long chain branching is formed in the molecule. Such a random copolymer rubber is excellent in processability.

Tg value The ethylene copolymer rubber of the present invention has a glass transition temperature Tg determined by DSC (differential scanning calorimeter) of -45C or lower, preferably -50C or lower, particularly preferably -55. It is desirable that the temperature is not higher than ° C.

As described above, when an ethylene random copolymer rubber having a Tg of −45 ° C. or lower is used, a rubber composition capable of imparting a vulcanized rubber having excellent low-temperature flexibility can be obtained.
The ethylene copolymer rubber according to the present invention as described above is excellent in extrusion moldability, fast in vulcanization speed, and excellent in mechanical properties such as vulcanization strength.

  The ethylene copolymer rubber according to the present invention may be used in an unvulcanized state, or may be used in a vulcanized state by vulcanization by a vulcanization method as described later. When it is used in the above, its characteristics are further exhibited.

Further, the ethylene copolymer rubber according to the present invention may be used after being vulcanized alone, or may be used after being co-vulcanized with other rubber materials.
Since this ethylene copolymer rubber has a high vulcanization speed, it can be vulcanized in a shorter time or at a lower temperature than conventional ethylene copolymer rubber without using a large amount of vulcanizing agent. Sulfur rubber can be produced with high productivity.

  The ethylene copolymer rubber according to the present invention is particularly excellent in co-curability with diene rubbers such as natural rubber, styrene / butadiene rubber, isoprene rubber, butadiene rubber, nitrile rubber, and chloroprene rubber. Co-cured product of copolymer rubber and diene rubber has excellent mechanical properties, wear resistance, dynamic fatigue resistance, oil resistance, and weather resistance, ozone resistance, Excellent heat aging resistance.

[ Production of ethylene copolymer rubber ]
The ethylene copolymer rubber according to the present invention as described above comprises (a) ethylene, (b) an α-olefin having 3 to 20 carbon atoms, and (c) a metallocene catalyst among carbon / carbon double bonds. A non-conjugated polyene having only one carbon / carbon double bond that can be polymerized in 1) and (d) a carbon / carbon double bond that can be polymerized with the catalyst among the carbon / carbon double bonds. It is preferably produced by random copolymerizing two non-conjugated polyenes present in one molecule in the presence of a metallocene catalyst.

  The metallocene catalyst used in the present invention is not particularly limited except that it contains the metallocene compound [A]. For example, the metallocene compound [A], the organoaluminum oxy compound [B] and / or the metallocene compound [A] It may be formed from a compound [C] that reacts to form an ion pair. Alternatively, the metallocene compound [A] may be formed from the organoaluminum compound [D] together with the organoaluminum oxy compound [B] and / or the compound [C] forming an ion pair.

Hereinafter, in the present invention, each component used when forming the metallocene catalyst will be described.
Metallocene compound [A]
Examples of the metallocene compound [A] used in the present invention include compounds represented by the following general formula [I].

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 the valence of the transition metal.

  L is a ligand coordinated to a transition metal, and at least one of these ligands L is a ligand having a cyclopentadienyl skeleton, and the coordination having this cyclopentadienyl skeleton The child may have a substituent.

As a ligand having a cyclopentadienyl skeleton, for example,
Cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n- or i-propylcyclopentadienyl group, n-, i-, sec-, t-, butylcyclopentadienyl group Hexylcyclopentadienyl group, octylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, methylethylcyclopentadienyl Enyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylhexylcyclopentadienyl group, methylbenzylcyclopentadienyl group, ethylbutylcyclopentadienyl group, ethylhexylcyclopentadienyl group, Methylcyclohexylcyclopentadi Alkyl or cycloalkyl substituted cyclopentadienyl groups such as alkenyl groups, further indenyl group, tetrahydroindenyl group and a fluorenyl group.

These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.
Of these, an alkyl-substituted cyclopentadienyl group is particularly preferable.
When the compound represented by the formula [I] has two or more groups having a cyclopentadienyl skeleton as the ligand L, the groups having two cyclopentadienyl skeletons are ethylene, propylene, etc. And a substituted alkylene group such as isopropylidene and diphenylmethylene, a substituted silylene group such as a silylene group or a dimethylsilylene group, a diphenylsilylene group, and a methylphenylsilylene group.

As L other than the ligand having a cyclopentadienyl skeleton, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a sulfonic acid-containing group (—SO ₃ R ^a ), a halogen atom or a hydrogen atom ( R ^a 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.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. More specifically,
Alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, octyl, decyl, dodecyl ,
A cycloalkyl group such as a cyclopentyl group and a cyclohexyl group,
Aryl groups such as phenyl and tolyl groups;
Examples include aralkyl groups such as benzyl group and neophyll group.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a pentoxy group, a hexoxy group, and an octoxy group. Can be mentioned.

Examples of aryloxy groups include phenoxy groups,
Examples of the sulfonic acid-containing group (—SO ₃ R ^a ) include a methane sulfonate group, a p-toluene sulfonate group, a trifluoromethane sulfonate group, and a p-chlorobenzene sulfonate group.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
When the valence of the transition metal is 4, for example, 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, R ² is a group (ligand) having a cyclopentadienyl skeleton, and R ³ , R ⁴ and R ⁵ are each independently cyclopentadienyl. It is the same as L other than the ligand having a cyclopentadienyl skeleton in the group having a skeleton or the general formula [I]. k is an integer of 1 or more, and k + l + m + n = 4.

Hereinafter, metallocene compounds including at least two ligands in which M is zirconium and has a cyclopentadienyl skeleton will be exemplified.
Bis (cyclopentadienyl) zirconium monochloride monohydride,
Bis (cyclopentadienyl) zirconium dichloride,
Bis (cyclopentadienyl) zirconium dibromide,
Bis (cyclopentadienyl) methylzirconium monochloride,
Bis (cyclopentadienyl) zirconium phenoxymonochloride,
Bis (methylcyclopentadienyl) zirconium dichloride,
Bis (ethylcyclopentadienyl) zirconium dichloride,
Bis (n-propylcyclopentadienyl) zirconium dichloride,
Bis (isopropylcyclopentadienyl) zirconium dichloride,
Bis (t-butylcyclopentadienyl) zirconium dichloride,
Bis (n-butylcyclopentadienyl) zirconium dichloride,
Bis (sec-butylcyclopentadienyl) zirconium dichloride,
Bis (isobutylcyclopentadienyl) zirconium dichloride,
Bis (hexylcyclopentadienyl) zirconium dichloride,
Bis (octylcyclopentadienyl) zirconium dichloride,
Bis (indenyl) zirconium dichloride,
Bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,
Bis (indenyl) zirconium dibromide,
Bis (cyclopentadienyl) zirconium dimethyl,
Bis (cyclopentadienyl) zirconium methoxychloride,
Bis (cyclopentadienyl) zirconium ethoxy chloride,
Bis (fluorenyl) zirconium dichloride,
Bis (cyclopentadienyl) zirconium bis (methanesulfonate),
Bis (cyclopentadienyl) zirconium bis (p-toluenesulfonate),
Bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonate),
Bis (methylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate),
Bis (ethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate),
Bis (propylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate),
Bis (butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate),
Bis (hexylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate),
Bis (1,3-dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate),
Bis (1-methyl-3-ethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate),
Bis (1-methyl-3-propylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate),
Bis (1-methyl-3-butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate),
Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride,
Bis (1-methyl-3-ethylcyclopentadienyl) zirconium dichloride,
Bis (1-methyl-3-propylcyclopentadienyl) zirconium dichloride,
Bis (1-methyl-3-butylcyclopentadienyl) zirconium dichloride,
Bis (1-methyl-3-hexylcyclopentadienyl) zirconium dichloride,
Bis (1-methyl-3-octylcyclopentadienyl) zirconium dichloride,
Bis (1-ethyl-3-butylcyclopentadienyl) zirconium dichloride,
Bis (trimethylcyclopentadienyl) zirconium dichloride,
Bis (tetramethylcyclopentadienyl) zirconium dichloride,
Bis (pentamethylcyclopentadienyl) zirconium dichloride,
Bis (methylbenzylcyclopentadienyl) zirconium dichloride,
Bis (ethylhexylcyclopentadienyl) zirconium dichloride,
Examples thereof include bis (methylcyclohexylcyclopentadienyl) zirconium dichloride.

A compound in which the 1,3-position substituted cyclopentadienyl group is substituted with a 1,2-position substituted cyclopentadienyl group can also be used in the present invention.
In the above formula [II], at least two of R ² , R ³ , R ⁴ and R ⁵ , for example, R ²
And R ³ is a group (ligand) having a cyclopentadienyl skeleton, and at least two groups are bonded via an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, or the like The metallocene compound can also be illustrated. In this case, R ⁴ and R ⁵ are independently the same as L other than the ligand having a cyclopentadienyl skeleton described in the formula [I].

As such a bridge-type metallocene compound,
Ethylenebis (indenyl) dimethylzirconium,
Ethylenebis (indenyl) zirconium dichloride,
Ethylene bis (indenyl) zirconium bis (trifluoromethanesulfonate),
Ethylene bis (indenyl) zirconium bis (methanesulfonate),
Ethylene bis (indenyl) zirconium bis (p-toluenesulfonate),
Ethylene bis (indenyl) zirconium bis (p-chlorobenzenesulfonate),
Ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride,
Isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride,
Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride,
Dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride,
Dimethylsilylene bis (dimethylcyclopentadienyl) zirconium dichloride,
Dimethylsilylene bis (trimethylcyclopentadienyl) zirconium dichloride,
Dimethylsilylenebis (indenyl) zirconium dichloride,
Dimethylsilylene bis (indenyl) zirconium bis (trifluoromethanesulfonate),
Dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,
Dimethylsilylenebis (cyclopentadienyl-fluorenyl) zirconium dichloride,
Diphenylsilylenebis (indenyl) zirconium dichloride,
And methylphenylsilylenebis (indenyl) zirconium dichloride.

Furthermore, metallocene compounds described in JP-A-4-268307 represented by the following formula [A] can be mentioned.
The metallocene has the formula [A]:

[In the formula [A], M ¹ is a group IVb, Vb or VIb group metal of the periodic table;
Specific examples include 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, an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, carbon 6-10 atoms, preferably 6-8 aryl groups, 6-10 carbon atoms, preferably 6-8 aryloxy groups, 2-10 carbon atoms, preferably 2-4 alkenyl groups, 7-7 carbon atoms 40 preferably an arylalkyl group having 7 to 10 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms, or a halogen atom, preferably a chlorine atom It is.

R ³ and R ⁴ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, preferably a fluorine atom, a chlorine atom or a bromine atom, or an optionally halogenated carbon atom of 1 to 10, preferably 1 to 4. Or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, —NR ¹⁰ ₂ , —SR ¹⁰ , —OSiR ¹⁰ ₃ , —SiR ¹⁰ ₃ or —PR ¹⁰ ₂ , wherein R ¹⁰ Is a halogen atom, preferably a chlorine atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, 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, preferably the same, and have the meanings described for R ³ and R ⁴ under the condition that R ⁵ and R ⁶ are not hydrogen atoms. R ⁵ and R ⁶ are preferably an optionally halogenated alkyl group having 1 to 4 carbon atoms, specifically, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group Or a trifluoromethyl group etc. are mentioned, A methyl group is preferable.

R ⁷ is:

= BR ¹¹ , = AlR ¹¹ , -Ge-, -Sn-, -O-, -S-, = SO, = SO ₂ , =
NR ¹¹ , ═CO, ═PR ¹¹ or ═P (O) R ¹¹ , wherein R ¹¹ , R ^12, and R ¹³ may be the same or different from each other, and are a hydrogen atom, a halogen atom, 10 preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, a fluoroalkyl group having 1 to 10 carbon atoms, preferably a CF ₃ group, an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, and 6 carbon atoms. 10 to 10 fluoroaryl groups, preferably pentafluorophenyl groups, 1 to 10 carbon atoms, preferably 1 to 4 alkoxy groups, particularly preferably methoxy groups, 2 to 10 carbon atoms, preferably 2 to 4 alkenyl groups, carbon atoms 7 to 40, 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 7 carbon atoms 12 alkylaryl groups, and “R ¹¹ and R ¹² ” or “R ¹¹ and R ¹³ ” may form a ring together with carbon atoms 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,
= Is preferably PR ¹¹ or = P (O) R ^11.

R ⁸ and R ⁹ may be the same or different from each other and have the same meaning as described for R ¹¹ .
m and n may be the same 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 metallocenes satisfying the above conditions are shown in the following (i) to (iii).

[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, ethyl groups Or it is a trifluoromethyl group, and R ⁸ , R ⁹ , R ¹¹ and R ¹² have the above-mentioned meanings. ]
Among the compounds represented by the formulas (i), (ii) and (iii), the following compounds are particularly preferable.

rac-ethylene (2-methyl-1-indenyl) ₂ -zirconium dichloride,
rac-dimethylsilylene (2-methyl-1-indenyl) ₂ -zirconium dichloride,
rac-dimethylsilylene (2-methyl-1-indenyl) ₂ -zirconium-dimethyl,
rac-ethylene- (2-methyl-1-indenyl) ₂ -zirconium-dimethyl,
rac-phenyl (methyl) silylene- (2-methyl-1-indenyl) ₂ -zirconium dichloride,
rac-diphenyl-silylene- (2-methyl-1-indenyl) ₂ -zirconium-dichloride,
rac-methylethylene- (2-methyl-1-indenyl) ₂ -zirconium dichloride,
rac-Dimethylsilylene- (2-ethyl-1-indenyl) ₂ -zirconium dichloride. Such a metallocene can be produced by a conventionally known method (for example, see JP-A-4-268307).

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

In the formula [B], M represents a transition metal atom of groups IVa, Va and VIa of the periodic table, and specifically, titanium, zirconium and 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 a sulfur-containing group. , A nitrogen-containing group or a phosphorus-containing group, specifically a halogen atom such as fluorine, chlorine, bromine, iodine;
Alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, adamantyl, alkenyl groups such as vinyl, propenyl, cyclohexenyl, and arylalkyls such as benzyl, phenylethyl, phenylpropyl A hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as a group, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, phenanthryl;
A halogenated hydrocarbon group in which a halogen atom is substituted for the hydrocarbon group;
Monohydrocarbon-substituted silyl such as methylsilyl, phenylsilyl, dihydrocarbon-substituted silyl such as dimethylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, Trihydrocarbon-substituted silyls such as tolylsilylsilyl and trinaphthylsilyl,
Silyl ethers of hydrocarbon-substituted silyls such as trimethylsilyl ether,
Silicon-substituted alkyl groups such as trimethylsilylmethyl, silicon-substituted aryl groups such as trimethylsilylphenyl,
Silicon-containing groups such as;
Oxygen-containing substituents such as hydroxy groups, alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, naphthoxy, and arylalkoxy groups such as phenylmethoxy, phenylethoxy;
A sulfur-containing group such as a substituent in which oxygen of the oxygen-containing group is substituted with sulfur;
Amino group, alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, arylamino group such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino or alkylarylamino Nitrogen-containing groups such as groups;
Phosphorus-containing groups such as phosphino groups such as dimethylphosphino and diphenylphosphino.

Among these, R ¹ is preferably a hydrocarbon group, particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl, and propyl. R ² is preferably hydrogen or a hydrocarbon group, 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 each independently represent 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, of which hydrogen It is preferably a hydrocarbon group or a halogenated hydrocarbon group. At least one of R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ may be bonded together to form a monocyclic aromatic ring together with the carbon atom. .

In addition, when there are two or more hydrocarbon groups or halogenated hydrocarbon groups, groups other than the group forming the 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 those described above for R ¹ and R ² .
Examples of ligands coordinated to M, which include 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 , are as follows: The following are examples.

Of these, those represented by the above formula (1) are preferred.
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.

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 substituted on the aromatic ring include the same groups as R ¹ and R ² described above.
X ¹ and X ² each independently 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, an oxygen-containing group or a sulfur-containing group; In terms of
Examples thereof include the same halogen atom as R ¹ and R ² , a hydrocarbon group having 1 to 20 carbon atoms, 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 , and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate, Sulfonate groups such as triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate, methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene sulfinate, trimethylbenzene Examples thereof include sulfinate groups such as sulfinate and pentafluorobenzene sulfinate.

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, and a divalent tin content. group, -O -, - CO -, - S -, - SO -, - SO 2 -, - NR 7 -, - P (R 7) -, - P (O) (R 7) -, - BR 7 — Or —AlR ⁷ — [wherein R ⁷ is 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], specifically,
Alkylene groups such as methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene, A divalent hydrocarbon group having 1 to 20 carbon atoms such as an arylalkylene group such as diphenylmethylene and diphenyl-1,2-ethylene;
A halogenated hydrocarbon group obtained by halogenating the divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene;
Methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p- Alkylsilylene such as chlorophenyl) silylene, alkylarylsilylene, arylsilylene groups, alkyldisilylene such as tetramethyl-1,2-disilylene, tetraphenyl-1,2-disylylene, alkylaryldisilylene, aryldisilylene groups, etc. A divalent silicon-containing group;
A divalent germanium-containing group obtained by replacing the silicon of the divalent silicon-containing group with germanium;
A divalent tin-containing group substituent in which the silicon of the divalent silicon-containing group is substituted with tin, and the like,
R ⁷ is the same halogen atom as R ¹ and R ² , a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

  Of these, a divalent silicon-containing group, a divalent germanium-containing group, and a divalent tin-containing group are preferred, and a divalent silicon-containing group is more preferred. Of these, alkylsilylene and alkylarylsilylene are particularly preferred. Arylsilylene is preferred.

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

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

  Such an indene derivative ligand of a transition metal compound can be synthesized, for example, by a general organic synthesis method using the following reaction route.

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

In the formula [C], examples of M, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ include the same as those in the formula [B].
Of R ³ , R ⁴ , R ⁵ and R ⁶ , two groups including R ³ are preferably alkyl groups, and R ³ and R ⁵ , or R ³ and R ⁶ are alkyl groups. Is preferred. 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. Examples of the halogen atom and silicon-containing group include the substituents exemplified for R ¹ and R ² .

Of the groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ , the group other than the alkyl group is preferably a hydrogen atom.
Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, Linear, branched and cyclic alkyl groups such as nonyl, dodecyl, eicosyl, norbornyl, adamantyl;
Examples thereof include arylalkyl groups such as benzyl, phenylethyl, phenylpropyl, and tolylmethyl, and may contain a double bond or a triple bond.

Two 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.
Specific examples of the halogen atom include the same groups as R ¹ and R ² .

Examples of X ¹ , X ² , Y and R ⁷ are the same as those in the formula [B].
Specific examples of the metallocene compound (transition metal compound) represented by the above formula [C] are shown below.

rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,4,7-trimethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,4,6-trimethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,5,6-trimethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,4,5,6-tetramethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,4,5,6,7-pentamethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-n-propyl-7-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (4-i-propyl-7-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-i-propyl-6-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-methyl-6-i-propyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-i-propyl-5-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4,6-di (i-propyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4,6-di (i-propyl) -7-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-i-butyl-7-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-sec-butyl-7-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4,6-di (sec-butyl) -1-indenyl) dirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-tert-butyl-7-methyl-1-indenyl) zirconium dichloride,
rac-Dimethylsilylene-bis (2-methyl-4-cyclohexyl-7-methyl-1-indenyl)
Zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-benzyl-7-methyl-1-indenyl) zirconium dichloride,
rac-Dimethylsilylene-bis (2-methyl-4-phenylethyl-7-methyl-1-indenyl)
Zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-phenyldichloromethyl-7-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-chloromethyl-7-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-trimethylsilylmethyl-7-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-trimethylsiloxymethyl-7-methyl-1-indenyl) zirconium dichloride,
rac-diethylsilylene-bis (2-methyl-4-i-propyl-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 (n-butyl) 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,
rac-diphenylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride,
rac-diphenylsilylene-bis (2-methyl-4-di (i-propyl) -1-indenyl) dirconium dichloride,
rac-di (p-tolyl) silylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride,
rac-di (p-chlorophenyl) silylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dibromide,
rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dimethyl,
rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium methyl chloride,
rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium-bis (methanesulfonate)
rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium-bis (p-phenylsulfinato),
rac-dimethylsilylene-bis (2-methyl-3-methyl-4-i-propyl-6-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-ethyl-4-i-propyl-6-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-phenyl-4-i-propyl-6-methyl-1-indenyl) zirconium dichloride.

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

Such an indene derivative ligand of a transition metal compound can be synthesized, for example, by a common organic synthesis method using the same reaction route as described above.
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, the method described in JP-A-4-268307.

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

In formula [D], examples of M, R ¹ , X ¹ , X ² and Y include the same as those in formula [B] or formula [C].
Among these, R ¹ is preferably a hydrocarbon group, and particularly preferably a hydrocarbon group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl.

X ¹ and X ² are preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
R ² represents an aryl group having 6 to 16 carbon atoms, specifically,
Phenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, perinaphthenyl (phenalenyl), aceanthrylenyl and the like. Of these, phenyl and naphthyl are preferable. These aryl groups may be substituted with the same halogen atom as R ¹ , a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Specific examples of the transition metal compound (metallocene compound) represented by the above formula [D] are shown below.
rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (α-naphthyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (1-anthracenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (2-anthracenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (9-anthracenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (9-phenanthryl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (p-fluorophenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (pentafluorophenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (p-chlorophenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (m-chlorophenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (o-chlorophenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (o, p-dichlorophenyl) phenyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (p-bromophenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (p-tolyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (m-tolyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (o-tolyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (o, o'-dimethylphenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (p-ethylphenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (pi-propylphenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (p-benzylphenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (p-biphenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (m-biphenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (p-trimethylsilylphenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4- (m-trimethylsilylphenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-ethyl-4-phenyl-1-indenyl) zirconium dichloride,
rac-diphenylsilylene-bis (2-ethyl-4-phenyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-phenyl-4-phenyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-n-propyl-4-phenyl-1-indenyl) zirconium dichloride,
rac-diethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride,
rac-di- (i-propyl) silylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride,
rac-di- (n-butyl) silylene-bis (2-methyl-4-phenyl-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,
rac-diphenylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride,
rac-di (p-tolyl) silylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride,
rac-di (p-chlorophenyl) silylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride,
rac-methylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride,
rac-ethylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride,
rac-dimethylgermyl-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride,
rac-dimethyltin-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dibromide,
rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dimethyl,
rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium methyl chloride,
rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium chloride SO ₂ Me,
rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium chloride OSO ₂ Me and the like.

In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above compound can also be used.
Such a transition metal compound represented by the formula [D] can be prepared, for example, according to Journal of Organometallic Chem. In this way, it can be manufactured.

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 a sulfur-containing group. Represents a nitrogen-containing group or a phosphorus-containing group,
R ² represents an aryl group having 6 to 16 carbon atoms, specifically,
Phenyl, α-naphthyl, β-naphthyl, anthracenyl, phenatryl, pyrenyl, acenaphthyl, perinaphthenyl (phenalenyl), aceanthrylenyl and the like.

Such a transition metal compound [D] is usually used as a racemate, but R-form or S-form can also be used.
In the present invention, a metallocene compound represented by the following formula [E-1] can also be used.

L ^a MX ₂ ... [E-1]
(M is a group IV or lanthanide series metal of the periodic table;
L ^a is a derivative of a delocalized π bond group and imparts restraint geometrical shape to the metal M active site,
X is each independently hydrogen, halogen or a hydrocarbon group, silyl group or germanyl group containing 20 or less carbon, silicon or germanium. )
Among the compounds represented by the formula [E-1], specifically, a compound represented by the following formula [E-2] is preferable.

M is titanium, zirconium or hafnium, and X is the same as described above.
Cp is a substituted cyclopentadienyl group having a π bond to M and having a substituent Z, or a derivative thereof.

Z is oxygen, sulfur, boron or an element from Group IVA of the periodic table (eg silicon, germanium, tin);
Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and Z and Y may form a condensed ring.

As such a compound represented by the formula [E-2], specifically,
(Dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane)
Titanium dichloride,
((T-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) titanium dichloride,
(Dibenzyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) titanium dichloride,
(Dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane)
Dibenzyl titanium,
(Dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane)
Dimethyl titanium,
((T-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) dibenzyltitanium,
((Methylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) dineopentyl titanium,
((Phenylphosphide) (tetramethyl-η ⁵ -cyclopentadienyl) methylene) diphenyltitanium,
(Dibenzyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) dibenzyltitanium,
(Dimethyl (benzylamide) (η ⁵ -cyclopentadienyl) silane) di (trimethylsilyl) titanium,
(Dimethyl (phenylphosphide)-(tetramethyl-η ⁵ -cyclopentadienyl) silane) dibenzyltitanium,
((Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) dibenzyltitanium,
(2-η ^5- (tetramethyl-cyclopentadienyl) -1-methyl-ethanolate (2-)) dibenzyltitanium,
(2-η ^5- (tetramethyl-cyclopentadienyl) -1-methyl-ethanolate (2-)) dimethyl titanium,
(2-((4a, 4b, 8a, 9,9a-η) -9H-fluoren-9-yl) cyclohexanolate (2-)) dimethyl titanium,
(2-((4a, 4b, 8a, 9,9a-η) -9H-fluoren-9-yl) cyclohexanolate (2-)) dibenzyltitanium and the like.

In the present invention, the above metallocene compounds can be used in combination of two or more.
In the above description, the titanium compound is exemplified as the 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.
In the present invention, the metallocene compounds [E-1] and [E-2] are preferably zirconocene compounds having a central metal atom of zirconium and a ligand containing at least two cyclopentadienyl skeletons. Used. In the metallocene compound [II], the central metal atom is preferably titanium.

In the present invention, among the metallocene compounds as described above, it is easy to control the degree of long-chain branching over a wide range, and activity, conversion of α-olefin, molecular weight of the produced polymer, randomness, In view of the polymerization temperature, a compound represented by the following general formula [III] or [IV] is particularly preferably used.

  The metallocene compound represented by the general formula [III] is a part of the compound represented by the above formula [C], and the metallocene compound represented by the general formula [IV] is a compound represented by the above formula [B]. Is part of.

In the formula, M is a transition metal atom of Group IVB of the periodic table, specifically, titanium, zirconium or hafnium, and 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 a halogen, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. Group,
Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, Alkyl groups such as cyclohexyl group, octyl group, nonyl group, dodecyl group, eicosyl group, norbornyl group, adamantyl group,
Alkenyl groups such as vinyl, propenyl, and cyclohexenyl;
Arylalkyl groups such as benzyl group, phenylethyl group, phenylpropyl group,
Phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, α- or β-naphthyl group, methylnaphthyl group, anthracenyl group, phenanthryl group, benzylphenyl group, pyrenyl group, Examples include aryl groups such as acenaphthyl group, phenalenyl group, aceantrirenyl group, tetrahydronaphthyl group, indanyl group, and biphenylyl group.

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

As the oxygen-containing group, specifically,
Alkoxy groups such as hydroxy group, methoxy group, ethoxy group, propoxy group, butoxy group,
Allyloxy groups such as phenoxy group, methylphenoxy group, dimethylphenoxy group, naphthoxy group,
Examples thereof include arylalkoxy groups such as phenylmethoxy group and phenylethoxy group.

As the sulfur-containing group, specifically,
A substituent obtained by substituting oxygen of the oxygen-containing group with sulfur,
Methyl sulfonate group, trifluoromethane sulfonate group, phenyl sulfonate group, benzyl sulfonate group, p-toluene sulfonate group, trimethyl benzene sulfonate group, triisobutyl benzene sulfonate group, p-chlorobenzene Sulfonate groups, sulfonate groups such as pentafluorobenzene sulfonate,
Examples thereof include sulfinate groups such as methyl sulfinate group, phenyl sulfinate group, benzene sulfinate group, p-toluene sulfinate group, trimethylbenzene sulfinate group and pentafluorobenzene sulfinate.

As the nitrogen-containing group, specifically,
Alkyl groups such as amino group, methylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dicyclohexylamino group,
Examples thereof include arylamino groups such as phenylamino group, diphenylamino group, ditolylamino group and dinaphthylamino group, and alkylarylamino groups such as methylphenylamino 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 of a methyl group, an ethyl group, or a propyl group.

R ¹² is preferably a hydrogen atom or a hydrocarbon group, and particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group.
R ¹³ and R ¹⁴
R ¹³ and R ¹⁴ are alkyl groups having 1 to 20 carbon atoms as exemplified above.

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 may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms as exemplified above, or a halogenated carbonization having 1 to 20 carbon atoms. A hydrogen group, an oxygen-containing group or a sulfur-containing group, preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

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- , -CO -, - S -, - SO -, - SO 2 -, - NR 15 -, - P (R 15) -, - P (O) (R 15) -, - BR 15 - or -AlR ¹⁵ —Wherein R ¹⁵ is 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 alkoxy group, specifically,
Methylene group, dimethylmethylene group, 1,2-ethylene group, dimethyl-1,2-ethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,2-cyclohexylene group, 1,4- A divalent hydrocarbon group having 1 to 20 carbon atoms such as an alkylene group such as a cyclohexylene group, an arylalkylene group such as a diphenylmethylene group and a diphenyl-1,2-ethylene group;
A halogenated hydrocarbon group obtained by halogenating the divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene;
Methylsilylene group, dimethylsilylene group, diethylsilylene group, di (n-propyl) silylene group, di (i-propyl) silylene group, di (cyclohexyl) silylene group, methylphenylsilylene group, diphenylsilylene group, di (p- Alkyldialkylene such as (tolyl) silylene group, alkylsilylene group such as di (p-chlorophenyl) silylene, alkylarylsilylene group, arylsilylene group, tetramethyl-1,2-disilyl group, tetraphenyl-1,2-disilyl group, etc. A divalent silicon-containing group such as a silyl group, an alkylaryldisilyl group, an aryldisilyl group;
Examples thereof include a divalent germanium-containing group in which silicon of the divalent silicon-containing group is replaced with germanium.

R ¹⁵ is the same hydrogen atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, or halogenated hydrocarbon group having 1 to 20 carbon atoms as described above.
Among these, Y is preferably a divalent silicon-containing group, a divalent germanium-containing group, more preferably a divalent silicon-containing group, an alkylsilylene group, an alkylarylsilylene group, an arylsilylene. Particularly preferred is a group.

Specific examples of the metallocene compound represented by the general formula [III] are shown below.
rac-dimethylsilylene-bis (2,7-dimethyl-4-ethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,7-dimethyl-4-n-propyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,7-dimethyl-4-n-butyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,7-dimethyl-4-sec-butyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,7-dimethyl-4-t-butyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,7-dimethyl-4-n-pentyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,7-dimethyl-4-n-hexyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,7-dimethyl-4-cyclohexyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,7-dimethyl-4-methylcyclohexyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,7-dimethyl-4-phenylethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,7-dimethyl-4-phenyldichloromethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,7-dimethyl-4-chloromethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,7-dimethyl-4-trimethylsilylmethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,7-dimethyl-4-trimethylsiloxymethyl-1-indenyl) zirconium dichloride,
rac-diethylsilylene-bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride,
rac-di (i-propyl) silylene-bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride,
rac-di (n-butyl) 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-methylphenylsilylene-bis (2,7-dimethyl-4-t-butyl-1-indenyl) zirconium dichloride,
rac-diphenylsilylene-bis (2,7-dimethyl-4-t-butyl-1-indenyl) zirconium dichloride,
rac-diphenylsilylene-bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride,
rac-diphenylsilylene-bis (2,7-dimethyl-4-ethyl-1-indenyl) zirconium dichloride,
rac-di (p-tolyl) silylene-bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride,
rac-di (p-chlorophenyl) silylene-bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride,
rac-Dimethylsilylene-bis (2-methyl-4-i-propyl-7-ethyl-1-indenyl) zirconium dibromide
rac-dimethylsilylene-bis (2,3,7-trimethyl-4-ethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,3,7-trimethyl-4-n-propyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,3,7-trimethyl-4-n-butyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,3,7-trimethyl-4-sec-butyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,3,7-trimethyl-4-t-butyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,3,7-trimethyl-4-n-pentyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,3,7-trimethyl-4-n-hexyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,3,7-trimethyl-4-cyclohexyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,3,7-trimethyl-4-methylcyclohexyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,3,7-trimethyl-4-trimethylsilylmethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,3,7-trimethyl-4-trimethylsiloxymethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,3,7-trimethyl-4-phenylethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,3,7-trimethyl-4-phenyldichloromethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,3,7-trimethyl-4-chloromethyl-1-indenyl) zirconium dichloride,
rac-diethylsilylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride,
rac-di (i-propyl) silylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride,
rac-di (n-butyl) silylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride,
rac-di (cyclohexyl) silylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride,
rac-methylphenylsilylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride,
rac-methylphenylsilylene-bis (2,3,7-trimethyl-4-t-butyl-1-indenyl) zirconium dichloride,
rac-diphenylsilylene-bis (2,3,7-trimethyl-4-t-butyl-1-indenyl) zirconium dichloride,
rac-diphenylsilylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride,
rac-diphenylsilylene-bis (2,3,7-trimethyl-4-ethyl-1-indenyl) zirconium dichloride,
rac-di (p-tolyl) silylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride,
rac-di (p-chlorophenyl) silylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dimethyl,
rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium methyl chloride,
rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium-bis (methanesulfonate)
rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium-bis (p-phenylsulfinato),
rac-dimethylsilylene-bis (2-methyl-3-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-ethyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-phenyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) titanium dichloride,
rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) hafnium dichloride and the like.

Among these, compounds having a branched alkyl group such as i-propyl group, sec-butyl group, and tert-butyl group at the 4-position are particularly preferable.
In the present invention, a racemate of the transition metal compound is usually used as an olefin polymerization catalyst component, but an R-type or S-type can also be used.

The transition metal compound as described above can be synthesized from an indene derivative by a known method, for example, a method described in JP-A-4-268307.
The compound represented by the following formula [IV] preferably used in the present invention is described in the specifications of EP-549900 and Canada-2084017.

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

R ^{22 to} R ²⁸ may be the same or different and are the same atom or group as R ^21, and at least two adjacent groups of R ^{22 to} R ²⁸ together with the atoms to which they are bonded, An aromatic ring or an aliphatic ring may be formed.

X ³ and X ⁴ may be the same or different from each other;
Hydrogen atom, halogen atom, OH group,
An alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms,
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,
An alkenyl group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms,
An arylalkyl group having 7 to 40 carbon atoms, preferably 7 to 10 carbon atoms,
An alkylaryl group having 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms,
It is an arylalkenyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms.

  Z is

-Sn -, - O -, - S -, = SO, = SO 2, = NR 29, = CO, a = PR ²⁹ or = P (O) R ^29.
However, R ²⁹ and R ³⁰ may be the same or different from each other,
Hydrogen atom, halogen atom,
An alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly preferably a methyl group,
A fluoroalkyl group having 1 to 10 carbon atoms, preferably a CF ₃ group,
An aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms,
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,
An alkenyl group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms,
An arylalkyl group having 7 to 40 carbon atoms, preferably 7 to 10 carbon atoms,
An arylalkenyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms,
It is an alkylaryl group having 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms.

R ²⁹ and R ³⁰ may each form a ring together with the atoms 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 the halogen (halogenated) is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and particularly preferably a fluorine atom or a chlorine atom.

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;
R ^{22 to} R ²⁸ may be the same as or different from each other, and are 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,
Z is

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

Furthermore, M is zirconium,
R ²¹ is the same alkyl group having 1 to 4 carbon atoms,
R ²² and R ²⁸ are hydrogen atoms;
R ^{23 to} R ²⁷ may be the same or different,
An alkyl group having 1 to 4 carbon atoms or a hydrogen atom,
X ³ and X ⁴ are both chlorine atoms,
Z is

(M ² is silicon, and R ²⁹ and R ³⁰ may be the same or different from each other, and are an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.)
Are preferred, especially
M is zirconium,
R ²¹ is a methyl group;
R ^{22 to} R ²⁸ are hydrogen atoms;
X ³ and X ⁴ are chlorine atoms,
Z is

A compound in which M ² is silicon and R ²⁹ and R ³⁰ may be the same or different from each other and is a methyl group or a phenyl group is preferable.
Several examples of such metallocene compounds represented by the formula [II] are shown below.

rac-dimethylsilylene-bis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4,5-acenaphthocyclopentadienyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,3-6-trimethyl-4,5-benzoindenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-methyl-4,5-acenaphthocyclopentadienyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (4,5-benzoindenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2,6-dimethyl-4,5-benzoindenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2,3-6-trimethyl-4,5-benzoindenyl)} zirconium dichloride and the like.

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

The above metallocene compounds can be used in combination of two or more. The metallocene compound as described above can also be used in contact with a particulate carrier compound.
The carrier _{compound, Si O 2, Al 2 O} 3, B 2 O 3, MgO, ZrO 2, CaO, Ti
Inorganic carrier compounds such as O ₂ , ZnO, Zn ₂ O, SnO ₂ , BaO, and ThO, resins such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and styrene-divinylbenzene copolymer Can be used. These carrier compounds can also be used in combination of two or more.

These metallocene compounds may be diluted with hydrocarbons or halogenated hydrocarbons.
Next, when forming a metallocene catalyst (a catalyst comprising a metallocene compound of a transition metal selected from Group IV of the periodic table and an organoaluminum oxy compound and / or a compound forming an ion pair) in the present invention. The organoaluminum oxy compound and the compound forming an ion pair will be described.

Organoaluminum oxy compound [B]
The organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound.

  Such a conventionally known aluminoxane is specifically represented by the following general formula.

(In the above general formula, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group, an ethyl group, particularly preferably a methyl group, and m is 2 or more, preferably It is an integer of 5-40.)
Here, the aluminoxane is an alkyloxyaluminum unit represented by the formula (OAl (R ¹ )) and an alkyloxyaluminum unit represented by the formula (OAl (R ² )) [wherein R ¹ and R ² are R And R ¹ and R ² represent different groups, and may be formed from mixed alkyloxyaluminum units.

A conventionally well-known aluminoxane is manufactured, for example with the following method, and is normally collect | recovered as a solution of an aromatic hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of recovering a solution of an aromatic hydrocarbon solvent by adding an organoaluminum compound such as trialkylaluminum to the aromatic hydrocarbon solvent in which is suspended.

  (2) A method in which water (water, ice, or water vapor) is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover the solution as an aromatic hydrocarbon solvent solution.

Of these methods, the method (1) is preferably employed.
Examples of the organoaluminum compound used when producing the aluminoxane solution include the organoaluminum compounds described below.

  The benzene-insoluble organoaluminum oxy compound used in the present invention is, for example, a method in which an aluminoxane solution is brought into contact with water or an active hydrogen-containing compound, or a method in which the above organoaluminum compound is brought into contact with water. Etc.

The benzene-insoluble organoaluminum oxy-compound used in the present invention, the compound was analyzed by infrared spectroscopy (IR), the absorbance at around 1220 cm ^-1 and (D _1220), the absorbance at around 1260 cm ^-1 (D ₁₂₆₀ ) (D ₁₂₆₀ / D ₁₂₂₀ ) is 0.09.
The ratio is preferably 0.08 or less, particularly preferably in the range of 0.04 to 0.07.

  The benzene-insoluble organoaluminum oxy compound as described above is presumed to have an alkyloxyaluminum unit represented by the following formula.

In the formula, R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms. As such hydrocarbon group, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, cyclohexyl group, A cyclooctyl group etc. can be illustrated. Among these, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

  This benzene-insoluble organoaluminum oxy compound may contain an oxyaluminum unit represented by the following formula in addition to the alkyloxyaluminum unit represented by the above formula.

In the formula, R ⁸ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, a halogen, or a hydrogen atom.
R ⁸ and R ⁷ in the above formulas represent different groups.

  In the case of containing an oxyaluminum unit, an organoaluminumoxy compound having an alkyloxyaluminum unit containing an alkyloxyaluminum unit in a proportion of 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more is desirable. .

The organoaluminum oxy compound used in the present invention may contain a small amount of a metal organic compound component other than aluminum.
Compound [C] which forms an ion pair by reacting with metallocene compound [A]
Examples of the compound [C] that forms an ion pair by reacting with the metallocene compound [A] used in the present invention include JP-A-1-501950, JP-A-1-502036, and JP-A-3-179005. Examples include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and US-547718. be able to.

  Examples of the Lewis acid include Mg-containing Lewis acid, Al-containing Lewis acid, and B-containing Lewis acid. Among these, B-containing Lewis acid is preferable. Specific examples of the Lewis acid containing a boron atom include compounds represented by the following general formula.

BR ¹ R ² R ³
(In the formula, R ¹ R ² and R ³ each independently represent a phenyl group which may have a substituent such as a fluorine atom, a methyl group or a trifluoromethyl group, or a fluorine atom.)
Specific examples of the compound represented by the above general formula include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, and tris (4-fluoromethylphenyl). ) Boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like. Of these, tris (pentafluorophenyl) boron is particularly preferred.

  The ionic compound used in the present invention is a salt composed of a cationic compound and an anionic compound. The anion functions to cationize the metallocene compound [A] by reacting with the metallocene compound [A] and to stabilize the transition metal cation species by forming an ion pair. Examples of such anions include an organic boron compound anion, an organic arsenic compound anion, an organoaluminum compound anion, and the like, and an anion that is relatively bulky and stabilizes the transition metal cation species is preferable. Examples of the cation include a metal cation, an organometallic cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation. Specific examples include triphenylcarbenium cation, tributylammonium cation, N, N-dimethylammonium cation, and ferrocenium cation.

In the present invention, an ionic compound having an organoboron compound anion is preferred. In particular,
Triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron, Tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, Trialkyl-substituted ammonium salts such as tri (n-butyl) ammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (4-fluorophenyl) boron,
N, N such as N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron -Dialkylanilinium salts,
Dialkyl ammonium salts such as di (n-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron,
Examples include triarylphosphonium salts such as triphenylphosphonium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, tri (dimethylphenyl) phosphonium tetra (phenyl) boron, and the like. .

In the present invention, as the ionic compound containing a boron atom, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) Borate can also be mentioned.

Moreover, the ionic compound containing the following boron atoms can also be illustrated. (The counter ion in the ionic compounds listed below is tri (n-butyl) ammonium, but is not limited thereto.)
Anionic salts such as bis [tri (n-butyl) ammonium] nonaborate,
Bis [tri (n-butyl) ammonium] decaborate,
Bis [tri (n-butyl) ammonium] undecaborate,
Bis [tri (n-butyl) ammonium] dodecaborate,
Bis [tri (n-butyl) ammonium] decachlorodecaborate,
Bis [tri (n-butyl) ammonium] dodecachlorododecaborate,
Tri (n-butyl) ammonium-1-carbadecaborate,
Tri (n-butyl) ammonium-1-carbaundecaborate,
Tri (n-butyl) ammonium-1-carbadodecaborate,
Examples include tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, and the following borane compounds and carborane compounds. it can. These compounds are used as Lewis acids and ionic compounds.

Examples of the salt of borane compound, carborane complex compound, and carborane anion include decaborane (14),
7,8-dicarboundecaborane (13),
2,7-dicarboundecaborane (13),
Undecahydride-7,8-dimethyl-7,8-dicarbaoundecaborane,
Dodecahydride-11-methyl-2,7-dicarbaundecaborane,
Tri (n-butyl) ammonium 6-carbadecaborate (14),
Tri (n-butyl) ammonium 6-carbadecaborate (12),
Tri (n-butyl) ammonium 7-carbaundecaborate (13),
Tri (n-butyl) ammonium 7,8-dicarbaundecaborate (12),
Tri (n-butyl) ammonium 2,9-dicarbaundecaborate (12),
Tri (n-butyl) ammonium dodecahydride-8-methyl 7,9-dicarboundeborate,
Tri (n-butyl) ammonium undecahydride 8-ethyl-7,9-dicarbaundecaborate,
Tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate,
Tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate,
Tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate,
And tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate.

Examples of carborane compounds and carborane salts include:
4-carbanonaborane (14),
1,3-dicarbanonaborane (13),
6,9-dicarbadecarborane (14),
Dodecahydride-1-phenyl-1,3-dicarbanonaborane,
Dodecahydride-1-methyl-1,3-dicarbanonaborane,
And undecahydride-1,3-dimethyl-1,3-dicarbanonaborane.

Furthermore, the following compounds can also be illustrated. (The counter ion in the ionic compounds listed below is tri (n-butyl) ammonium, but is not limited thereto.)
Metal carborane salts and metal borane anions such as tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III),
Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (ferrate) (III),
Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III),
Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) nickelate (III),
Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaoundecaborate) cubrate (cuprate) (III),
Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (metal salt) (III),
Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecarboxylate) ferrate (III),
Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundeborate) chromate (chromate) (III),
Tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III),
Tri (n-butyl) ammonium bis (dodecahydride dicarbadodecaborate) cobaltate (III),
Bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickelate (III),
Tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III),
Bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) manganate (IV),
Bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III),
And bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV).

Two or more of the above compounds [C] can be used in combination.
Organoaluminum compound [D]
The organoaluminum compound [D] used in the present invention can be represented, for example, 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 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, specifically, a methyl group, an ethyl group, an n-propyl group, Examples thereof include isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, and tolyl group.

As such an organoaluminum compound, specifically,
Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum,
Alkenyl aluminum such as isoprenyl aluminum,
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide,
Alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide,
Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide,
Examples thereof include alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.

Further, as the organoaluminum compound [D], a compound represented by the following formula (b) can also be used.
R ⁵ _n AlY _3-n (b)
(Wherein, R ⁵ is the same as R ⁵ in the formula (a), Y is -OR ⁶ group, -OSiR ⁷ ₃ group, -OAlR ⁸ ₂ group, -NR ⁹ ₂ group, -SiR ¹⁰ ₃ groups or -N (R ¹¹ ) AlR ¹² ₂ groups,
n is 1-2,
R ⁶ , R ⁷ , R ⁸ and R ¹² are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl group, phenyl group and the like,
R ⁹ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc.
R ¹⁰ and R ¹¹ are a methyl group, an ethyl group, and the like. )
Specific examples of such an organoaluminum compound include the following compounds.

(i) Compounds represented by R ⁵ _n Al (OR ⁶ ) _3-n , such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide and the like.
(ii) a compound represented by R ⁵ _n Al (OSiR ⁷ ₃ ) _3-n , such as (C ₂ H ₅ ) ₂ Al (OSi (CH ₃ ) ₃ ),
(Iso-C ₄ H ₉ ) ₂ Al (OSi (CH ₃ ) ₃ ),
(Iso-C ₄ H ₉ ) ₂ Al (OSi (C ₂ H ₅ ) ₃ ) and the like.

(iii) a compound represented by R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n , such as (C ₂ H ₅ ) ₂ Al (OAl (C ₂ H ₅ ) ₂ ),
Such as _{(iso-C 4 H 9)} 2 Al (OAl (iso-C 4 H 9) 2).

(iv) a compound represented by R ⁵ _n Al (NR ⁹ ₂ ) _3-n , such as (CH ₃ ) ₂ Al (N (C ₂ H ₅ ) ₂ ),
(C ₂ H ₅ ) ₂ Al (NH (CH ₃ )),
(CH ₃ ) ₂ Al (NH (C ₂ H ₅ )),
(C ₂ H ₅ ) ₂ Al [N (Si (CH ₃ ) ₃ ) ₂ ],
(Iso-C ₄ H ₉ ) ₂ Al [N (Si (CH ₃ ) ₃ ) ₂ ] and the like.

(v) a compound represented by R ⁵ _n Al (SiR ¹⁰ ₃ ) _3-n , such as (iso-C ₄ H ₉ ) ₂ Al (Si (CH ₃ ) ₃ ).
In the present invention, among these, R ⁵ ₃ Al, R ⁵ _n Al (OR ⁶ ) _{3 -n} , R ⁵ _n Al (OA
An organoaluminum compound represented by 1R ⁸ ₂ ) _3-n can be mentioned as a suitable example, and a compound in which R ⁵ is an isoalkyl group and n = 2 is particularly preferred. These organoaluminum compounds can be used in combination of two or more.

  The metallocene-based catalyst used in the present invention includes the metallocene compound [A] as described above, and can be formed from, for example, the metallocene compound [A] and the organoaluminum oxy compound [B] as described above. . Further, it may be formed from a metallocene compound [A] and a compound [C] (ionic compound) that reacts with the metallocene compound [A] to form an ion pair, and together with the metallocene compound [A], an organic aluminum The compound [C] in which the oxy compound [B] and the metallocene compound [A] react to form an ion pair can be used in combination. In these embodiments, it is particularly preferable to further use an organoaluminum compound [D].

  In the present invention, the metallocene compound [A] is usually about 0.00005 to 0.1 mmol, preferably about 0.0001 to 0.05 mmol in terms of transition metal atom per liter of polymerization volume. Used in quantity.

  The organoaluminum oxy compound [B] is used in such an amount that the aluminum atom is usually about 1 to 10,000 mol, preferably 10 to 5,000 mol, per 1 mol of the transition metal atom. it can.

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

  Furthermore, the organoaluminum compound [D] is usually about 0 to 1,000 moles per mole of boron atoms in the compound [C] forming an aluminum atom or ion pair in the organoaluminum oxy compound [B], Preferably, it is used as needed in an amount of about 0 to 500 mol.

  Using the metallocene catalyst as described above, when ethylene, an α-olefin having 3 to 20 carbon atoms, and two kinds of non-conjugated polyenes are copolymerized, (a) ethylene · ( b) α-olefin, (c) non-conjugated polyene, (d) non-conjugated polyene quaternary ethylene copolymer rubber (ethylene copolymer rubber) can be obtained.

  In addition, using a Group VB transition metal compound-based catalyst such as a vanadium-based catalyst, ethylene, an α-olefin having 3 to 20 carbon atoms, and the above-mentioned two types of non-conjugated polyenes (c) (d) are used together. Even when polymerized, it may not be possible to obtain a copolymer rubber with sufficient polymerization activity.

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

In the present invention, when ethylene (a), an α-olefin (b) having 3 to 20 carbon atoms, and two non-conjugated polyenes (c) and (d) are copolymerized, a metallocene catalyst is used. The metallocene compound [A], the organoaluminum oxy compound [B], the compound forming an ion pair [
C], and further, organoaluminum compound [D] may be separately supplied to the polymerization reactor, or a metallocene catalyst containing metallocene compound [A] is prepared in advance and then used for the copolymerization reaction. Also good.

  Further, when preparing the metallocene catalyst, a hydrocarbon solvent that is inactive with the catalyst component can be used. Specifically, as the inert hydrocarbon solvent, propane, butane, pentane, hexane, heptane, Aliphatic hydrocarbons such as octane, decane, dodecane, kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylene chloride, chlorobenzene, dichloromethane, etc. The halogenated hydrocarbons 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 mixed at −100 to 200 ° C., preferably −70 to 100 ° C. Can be made.

In the present invention, a quaternary copolymerization reaction of ethylene (a), an α-olefin (b) having 3 to 20 carbon atoms, and two kinds of non-conjugated polyene (c) and non-conjugated polyene (d), Usually 40 to 200 ° C., preferably 50 to 150 ° C., particularly preferably 60 to 120 ° C., further preferably 70 to 120 ° C., atmospheric pressure to 100 kg / cm ^2, preferably atmospheric pressure to 50 kg / cm ^2, particularly preferably Can be carried out under atmospheric pressure to 30 kg / cm ² .

  This copolymerization reaction can be carried out by various polymerization methods, but is preferably carried out by solution polymerization. In this case, as the polymerization solvent, the above hydrocarbon solvents can be used, and an α-olefin such as propylene may be used as the solvent.

  Copolymerization can be carried out by any of batch, semi-continuous and continuous methods, but is preferably carried out continuously. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

  The reaction time (average residence time when copolymerization is carried out in a continuous process) varies depending on conditions such as catalyst concentration and polymerization temperature, but is usually 5 minutes to 5 hours, preferably 10 minutes to 3 hours. Degree.

  The ethylene copolymer rubber used in the present invention can be obtained by the above-described method. The molecular weight of the ethylene copolymer rubber can be adjusted by changing the polymerization conditions such as the polymerization temperature. It can also be adjusted by controlling the amount of hydrogen (molecular weight regulator) used.

In the present invention, the organoaluminum oxy compound or the ionic compound can be used by being supported on the carrier compound described above.
When ethylene (a), α-olefin (b) and non-conjugated polyenes (c) and (d) are copolymerized as described above, an ethylene copolymer rubber is usually obtained as a polymerization liquid containing the same. . This polymerization solution is treated by a conventional method to obtain an ethylene copolymer rubber.

[ Graft-modified product of ethylene copolymer rubber ]
The ethylene copolymer rubber according to the present invention can be modified and used by graft polymerization of a polar monomer to the ethylene copolymer rubber.

The graft-modified ethylene copolymer rubber (also referred to as graft-modified ethylene copolymer rubber) of the present invention is prepared by the above ethylene copolymer rubber in the presence or absence of a radical initiator. It can be obtained by reacting with a polar monomer as described later.

  Examples of polar monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or their derivatives, vinyl ester compounds, vinyl chloride. Etc.

Specifically, hydroxyl-containing ethylenically unsaturated compounds include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy-propyl ( (Meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, (Meth) acrylic esters such as butanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2- (6-hydroxyhexanoyloxy) ethyl acrylate; 10-undecen-1-ol, 1-octene-3 - , 2-methanol norbornene, hydroxystyrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylol acrylamide, 2- (meth) acryloyloxyethyl acid phosphate, glycerin monoallyl ether, allyl alcohol, allyloxyethanol, 2 -Butene-1,4-diol, glycerin monoalcohol and the like.

  An amino group-containing ethylenically unsaturated compound is a compound having an ethylenic double bond and an amino group, and as such a compound, a vinyl-based unit having at least one amino group or substituted amino group represented by the following formula: A polymer can be mentioned.

In the formula, R ¹ is a hydrogen atom, a methyl group or an ethyl group, and R ² is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and 6 to 12 carbon atoms, preferably 6 carbon atoms. ˜8 cycloalkyl groups. The above alkyl group and cycloalkyl group may further have a substituent.

  Specific examples of such an amino group-containing ethylenically unsaturated compound include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, Alkyl ester derivatives of acrylic acid or methacrylic acid such as phenylaminoethyl methacrylate and cyclohexylaminoethyl methacrylate; vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine; allylamine, methacrylamine, N-methyl Allylamine derivatives such as acrylic amine, N, N-dimethylacrylamine, and N, N-dimethylaminopropylacrylamine; acrylamide derivatives such as acrylamide and N-methylacrylamide; p-aminostyrene Which amino styrenes; 6-aminohexyl succinimide and 2-aminoethyl succinimide is used.

The epoxy group-containing ethylenically unsaturated compound is a monomer having at least one unsaturated bond polymerizable in one molecule and at least one epoxy group. As such an epoxy group-containing ethylenically unsaturated compound, specifically, Is glycidyl acrylate, glycidyl methacrylate, etc.
Mono and diglycidyl esters of maleic acid, mono and diglycidyl esters of fumaric acid, mono and diglycidyl esters of crotonic acid, mono and diglycidyl esters of tetrahydrophthalic acid, mono and diglycidyl esters of itaconic acid, butenetricarboxylic acid Mono- and diglycidyl esters, mono- and diglycidyl esters of citraconic acid, mono- and diglycidyl esters of endo-cis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (nadic acid ^TM ), endo -Dicarboxylic acids such as mono- and diglycidyl esters of cis-bicyclo [2.2.1] hept-5-ene-2-methyl-2,3-dicarboxylic acid (methyl nadic acid ^TM ), mono- and diglycidyl esters of allyl succinic acid Mono and dialkyl glycidyl esters (monoglycidyl C 1-12 of alkyl group in the case of ester, alkyl glycidyl ester of p-styrene carboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1- Butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, Examples thereof include vinylcyclohexene monoxide.

  Examples of the aromatic vinyl compound include compounds represented by the following formula.

In the above formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group. it can. R ³ represents a hydrocarbon group having 1 to ³ carbon atoms or a halogen atom, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a chlorine atom, a bromine atom, and an iodine atom. Can do. N represents an integer of usually 0 to 5, preferably 1 to 5.

Specific examples of such aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-chlorostyrene, m-chlorostyrene and p-chloro. Methylstyrene, 4-vinylpyridine, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, 2-isopropenylpyridine, 2-vinylquinoline, 3-vinylisoquinoline, N-vinyl Examples thereof include carbazole and N-vinylpyrrolidone.

Unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept-2 -Unsaturated carboxylic acids such as ene-5,6-dicarboxylic acid, or acid anhydrides or derivatives thereof (for example, acid halides, amides, imides, esters, etc.). Specific examples of the compound include maleenyl chloride, maleenylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid Acid anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5,6 Examples thereof include dimethyl dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate and aminopropyl methacrylate. Among these, (meth) acrylic acid, maleic anhydride, hydroxyethyl (meth) acrylate, glycidyl methacrylate, and aminopropyl methacrylate are preferable.

  Examples of vinyl ester compounds include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, pt -Vinyl butyl benzoate, vinyl salicylate, vinyl cyclohexanecarboxylate and the like.

The polar monomer is usually used in an amount of 0.1 to 100 parts by weight, preferably 0.5 to 80 parts by weight with respect to 100 parts by weight of the ethylene copolymer rubber.
Examples of the radical initiator include organic peroxides and azo compounds.

Specific examples of organic peroxides include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, and 2,5-dimethyl. -2,5-bis (t-butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) valerate, benzoyl peroxide, t-Butylperoxybenzoate, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide and 2,4-dichlorobenzoyl peroxide And m-toluyl peroxide. Examples of the azo compound include azoisobutyronitrile and dimethylazoisobutyronitrile.

Such a radical initiator is generally desirably used in an amount of 0.001 to 10 parts by weight with respect to 100 parts by weight of the ethylene copolymer rubber.
The radical initiator can be used as it is by mixing it with an ethylene copolymer rubber and a polar monomer, but it can also be used by dissolving the radical initiator in a small amount of an organic solvent. As an organic solvent used here, if it is an organic solvent which can melt | dissolve a radical initiator, it can be used without limitation in particular. Such organic solvents include aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane; cyclohexane, methylcyclohexane and decahydronaphthalene. Alicyclic hydrocarbon solvents such as: chlorobenzene, dichlorobenzene, trichlorobenzene, chlorinated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene; methanol, ethanol, n-propanol, iso-propanol Alcohol solvents such as n-butanol, sec-butanol and tert-butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate; Chirueteru, diethyl ether, di -n- amyl ether, and ether solvents such as tetrahydrofuran and dioxy anisole.

  In the present invention, when the ethylene copolymer rubber is graft-modified, a reducing substance may be used. The reducing substance has an action of improving the graft amount in the obtained graft-modified ethylene copolymer rubber.

Reducing substances include iron (II) ion, chromium ion, cobalt ion, nickel ion, palladium ion, sulfite, hydroxylamine, hydrazine, etc., as well as -SH
, —SO ₃ H, —NHNH ₂ , —COCH (OH) — and the like.

  Specific examples of such reducing substances include ferrous chloride, potassium dichromate, cobalt chloride, cobalt naphthenate, palladium chloride, ethanolamine, diethanolamine, N, N-dimethylaniline, hydrazine, and ethyl mercaptan. Benzenesulfonic acid, p-toluenesulfonic acid, and the like.

The reducing substance is usually used in an amount of 0.001 to 5 parts by weight, preferably 0.1 to 3 parts by weight, with respect to 100 parts by weight of the ethylene copolymer rubber. Graft modification of the ethylene copolymer rubber can be performed by a conventionally known method. For example, the ethylene copolymer rubber is dissolved in an organic solvent, and then a polar monomer and a radical initiator are added to the solution. At a temperature of 200 ° C., preferably 80-190 ° C., for 0.5-15 hours, preferably 1
It is carried out by reacting for 10 hours.

The organic solvent used when graft-modifying the ethylene copolymer rubber can be used without particular limitation as long as it is an organic solvent that can dissolve the ethylene copolymer rubber.
Examples of such an organic solvent include the above-described aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, and heptane.

  Further, the graft-modified ethylene copolymer rubber can be produced by reacting the ethylene copolymer rubber and the polar monomer in the absence of a solvent using an extruder or the like. The reaction temperature is usually above the melting point of the ethylene copolymer rubber, specifically in the range of 120 to 250 ° C. The reaction time under such temperature conditions is usually 0.5 to 10 minutes.

  The graft amount of the graft group derived from the polar monomer in the graft-modified ethylene copolymer rubber thus prepared is usually 0.1 to 50% by weight, preferably 0.2 to 30% by weight. Is in range.

  The modified ethylene copolymer rubber thus obtained is excellent in adhesion to metals and polar resins. Moreover, the impact resistance and low temperature impact resistance can be improved by blending the modified ethylene copolymer rubber with a polar resin.

  Further, a molded body obtained by molding a modified ethylene copolymer rubber (modified ethylene random copolymer) is excellent in printability and paintability on the surface of the molded body. In addition, a resin composition having improved filler dispersibility can be obtained by blending the modified ethylene copolymer rubber (modified ethylene random copolymer) with a filler such as glass fiber and an inorganic compound in polyolefin. Can be obtained. In this way, it is possible to obtain a resin composition that retains the advantages of blending a filler and has improved mechanical strength.

[ Vulcanizable rubber composition ]
The rubber composition according to the present invention containing the ethylene copolymer rubber as described above is a vulcanizable rubber composition (hereinafter also referred to as a vulcanizable rubber composition) and remains unvulcanized. However, it can also be used, but when used as a vulcanizate, more excellent characteristics can be expressed.

The vulcanizable rubber composition according to the present invention can be vulcanized by a method of heating using a vulcanizing agent or a method of irradiating an electron beam without using a vulcanizing agent.
The vulcanizable rubber composition according to the present invention can contain other components as appropriate in accordance with the purpose together with the ethylene copolymer rubber, but the ethylene copolymer rubber is contained in the total rubber composition. It is desirable to contain it in an amount of not less than wt%, preferably not less than 25 wt%. When the content of the ethylene copolymer rubber in the rubber composition is within this range, good physical properties as a rubber composition are manifested.

  Other components include, for example, reinforcing agents, inorganic fillers, softeners, antioxidants (stabilizers), processing aids, foaming agents, compounds that constitute foaming systems such as foaming aids, plasticizers, Examples include various agents such as colorants, flame retardants, and other rubber compounding agents. The type and content of the other components are appropriately selected depending on the use, but among these, it is particularly preferable to use a reinforcing agent, an inorganic filler, a softening agent, and the like, which will be described more specifically below. .

Reinforcing agents and inorganic fillers Specific examples of reinforcing agents include carbon blacks such as SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, and MT, and these carbon blacks as silane coupling agents. Surface treated with silica, silica, activated calcium carbonate, fine powder talc, fine powder silicic acid and the like.

Specific examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc, and clay.
In the rubber composition according to the present invention, the reinforcing agent and / or the inorganic filler is usually 300 parts by weight or less, preferably 10 to 300 parts by weight, and more preferably 10 parts by weight with respect to 100 parts by weight of the ethylene copolymer rubber. It can contain in the quantity of -200 weight part.

From the rubber composition containing such a reinforcing agent, a vulcanized rubber having improved mechanical properties such as tensile strength, tear strength and abrasion resistance can be obtained.
When the inorganic filler is blended in the above amount, the hardness can be increased without deteriorating other physical properties of the vulcanized rubber, and the cost can be reduced.

Softeners As softeners, softeners conventionally blended in rubber are widely used. Specifically, petroleum softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petroleum jelly are used. ,
Coal tar softeners such as coal tar and coal tar pitch,
Fatty oil softeners such as castor oil, linseed oil, rapeseed oil, coconut oil,
Waxes such as tall oil, sub, beeswax, carnauba wax, lanolin,
Fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate, zinc laurate,
Synthetic polymer materials such as petroleum resin, atactic polypropylene and coumarone indene resin are used.

Of these, petroleum-based softeners are preferable, and process oil is particularly preferable.
In the rubber composition according to the present invention, the softening agent as described above is usually 200 parts by weight or less, preferably 10 to 200 parts by weight, more preferably 10 to 150 parts by weight with respect to 100 parts by weight of the ethylene copolymer rubber. Parts, particularly preferably 10 to 100 parts by weight.

Antioxidant The rubber composition according to the present invention preferably contains an antioxidant because the material life can be extended. Specifically, as this antioxidant,
Aromatic secondary amine stabilizers such as phenylnaphthylamine, 4,4 ′-(α, α-dimethylbenzyl) diphenylamine, N, N′-di-2-naphthyl-p-phenylenediamine,
Phenolic stabilizers such as 2,6-di-t-butyl-4-methylphenol and tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane ,
Thioether stabilizers such as bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide,
Benzimidazole stabilizers such as 2-mercaptobenzimidazole,
Dithiocarbamate stabilizers such as nickel dibutyldithiocarbamate,
Examples include quinoline stabilizers such as a polymer of 2,2,4-trimethyl-1,2-dihydroquinoline. Two or more of these can be used in combination.

  Such an antioxidant can be appropriately used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less, particularly preferably 3 parts by weight or less, based on 100 parts by weight of the ethylene copolymer rubber.

Processing aids As processing aids, those generally blended into rubber as processing aids can be widely used. Specific examples include acids such as ricinoleic acid, stearic acid, palmitic acid and lauric acid, and salts of these higher fatty acids such as barium stearate, zinc stearate, calcium stearate or esters.

The processing aid can be appropriately used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the ethylene copolymer rubber.
Vulcanizing agent When the rubber composition according to the present invention is vulcanized by heating, a vulcanizing system such as a normal vulcanizing agent, a vulcanization accelerator, and a vulcanizing auxiliary is added to the rubber composition. The constituent compounds are blended.

As the vulcanizing agent, sulfur, a sulfur-based compound, an organic peroxide, or the like can be used.
The form of sulfur is not particularly limited, and for example, powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like can be used.

  Specific examples of the sulfur compound include sulfur chloride, sulfur dichloride, polymer polysulfide, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dimethyldithiocarbamate.

Moreover, as an organic peroxide, specifically,
Dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide, 2,5-dimethyl -2,5-di (t-butylperoxin) hexyne-3,2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butyl) Peroxy) -hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, alkyl peroxides such as t-butyl hydroperoxide,
t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxymaleic acid, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, di- -Peroxyesters such as t-butyl peroxyphthalate,
Examples include ketone peroxides such as dicyclohexanone peroxide. Two or more of these may be used in combination.

  Of these, organic peroxides having a one-minute half-life temperature of 130 ° C. to 200 ° C. are preferred. Specifically, dicumyl peroxide, di-t-butyl peroxide, di-t-butyl peroxy-3 1,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide, t-butyl hydroperoxide and the like are preferable.

In the present invention, among various vulcanizing agents as described above, it is preferable to use sulfur or a sulfur-based compound, particularly sulfur, because a rubber composition having excellent characteristics can be obtained.
When the vulcanizing agent is sulfur or a sulfur compound, it can be used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the ethylene copolymer rubber.

  When the vulcanizing agent is an organic peroxide, it can be used in an amount of 0.0003 to 0.05 mol, preferably 0.001 to 0.03 mol, per 100 g of the ethylene copolymer rubber. .

Vulcanization accelerator When sulfur or a sulfur compound is used as the vulcanizing agent, it is preferable to use a vulcanization accelerator in combination.

Specifically, as a vulcanization accelerator,
Sulfenamide compounds such as N-cyclohexyl-2-benzothiazole sulfenamide (CBS), N-oxydiethylene-2-benzothiazole sulfenamide, N, N-diisopropyl-2-benzothiazole sulfenamide,
Thiazole compounds such as 2-mercaptobenzothiazole (MBT), 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole, dibenzothiazyl disulfide,
Guanidine compounds such as diphenylguanidine, triphenylguanidine, diorthonitrile guanidine, orthonitrile biguanide, diphenylguanidine phthalate,
Aldehyde amines or aldehyde-ammonia compounds such as acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde ammonia,
Imidazoline compounds such as 2-mercaptoimidazoline, thiourea compounds such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea,
Thiuram compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide, dipentamethylenethiuram tetrasulfide (DPTT),
Dithioacid salts such as zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium dimethyldithiocarbamate Compounds,
Xanthates such as zinc dibutylxanthate,
Examples include zinc white.

The vulcanization accelerator as described above is 0.1 to 0.1 parts per 100 parts by weight of the ethylene copolymer rubber.
It is desirable to use 20 parts by weight, preferably 0.2 to 10 parts by weight.
Vulcanization aid When an organic peroxide is used as the vulcanization agent, the vulcanization aid (polyfunctional monomer) is preferably 0.5 to 2 moles per mole of the organic peroxide. Are preferably used together in approximately equimolar amounts.

As a vulcanization aid, specifically,
Quinonedioxime compounds such as sulfur and p-quinonedioxime,
(Meth) acrylate compounds such as trimethylolpropane triacrylate and polyethylene glycol dimethacrylate,
Allyl compounds such as diallyl phthalate and triallyl cyanurate, maleimide compounds such as m-phenylene bismaleimide,
Examples include divinylbenzene.

Foaming agent The rubber composition according to the present invention can be foam-molded when it contains a compound constituting a foaming system such as a foaming agent and a foaming aid.

As the foaming agent, foaming agents generally used for foam molding of rubber can be widely used. Specifically, sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, etc. Inorganic blowing agents, nitroso compounds such as N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine,
Azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate, benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), diphenyl Examples thereof include sulfonyl hydrazide compounds such as sulfone-3,3′-disulfonylhydrazide, azide compounds such as calcium azide, 4,4-diphenyldisulfonyl azide, and p-toluenesulfuronyl azide.

Of these, nitroso compounds, azo compounds, and azide compounds are preferred. The foaming agent is 0.5 to 30 parts by weight, preferably 1 to 2 parts per 100 parts by weight of the ethylene copolymer rubber.
It can be used in an amount of 0 parts by weight. From the rubber composition containing the foaming agent in such an amount, a foam having an apparent specific gravity of 0.03 to 0.8 g / cm ³ can be produced.

  Further, a foaming aid can be used together with the foaming agent. When the foaming aid is used in combination, there are effects such as a reduction in the decomposition temperature of the foaming agent, acceleration of decomposition, and uniformization of bubbles. Examples of such foaming aids include organic acids such as salicylic acid, phthalic acid, stearic acid, and oxalic acid, urea, and derivatives thereof.

The foaming assistant can be used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the ethylene copolymer rubber.
Other rubbers The rubber composition according to the present invention may contain other known rubbers as long as the object of the present invention is not impaired.

  Examples of such other rubbers include isoprene-based rubbers such as natural rubber (NR) and isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), and chloroprene rubber. Mention may be made of conjugated diene rubbers such as (CR).

  Further, a conventionally known ethylene / α-olefin copolymer rubber may be used. For example, an ethylene / propylene random copolymer (EPR), an ethylene copolymer other than the ethylene copolymer rubber, such as EPDM, may be used. Can be used.

The vulcanizable rubber composition according to the present invention can be prepared from an ethylene copolymer rubber and other components as described above by a general method for preparing a rubber compound. For example, using an internal mixer such as a Banbury mixer, a kneader, or an intermix, the ethylene copolymer rubber and other components are kneaded at a temperature of 80 to 170 ° C. for 3 to 10 minutes, and if necessary. Add vulcanizing agent, vulcanization accelerator or vulcanizing aid, knead at roll temperature of 40-80 ° C for 5-30 minutes using rolls such as open roll or kneader, and then dispense. Can be prepared. Thus, a rubber composition (blended rubber) usually in the form of a ribbon or sheet is obtained. When the kneading temperature in the internal mixer is low, a vulcanizing agent, a vulcanization accelerator, a foaming agent, and the like can be kneaded at the same time.

[ Vulcanized rubber ]
The vulcanized product (vulcanized rubber) of the rubber composition according to the present invention is usually an unvulcanized rubber composition as described above, usually an extrusion molding machine, a calender roll, a press, an injection molding machine, a transfer molding machine, etc. It can be obtained by preforming into a desired shape by various molding methods, vulcanizing at the same time as molding or by introducing the molded product into a vulcanizing tank and heating, or irradiating with an electron beam.

  When the rubber composition is vulcanized by heating, a heating tank having a heating form such as hot air, glass bead fluidized bed, UHF (ultra high frequency electromagnetic wave), steam, LCM (hot molten salt tank) is used. It is preferable to heat at a temperature of ˜270 ° C. for 1 to 30 minutes.

  Further, when vulcanizing by electron beam irradiation without using a vulcanizing agent, an electron beam having an energy of 0.1 to 10 MeV, preferably 0.3 to 2 MeV is absorbed into the preformed rubber composition. Irradiation may be performed so that the dose is 0.5 to 35 Mrad, preferably 0.5 to 10 Mrad.

In molding and vulcanization, a mold may be used or a mold may not be used.
When a mold is not used, the rubber composition is usually molded and vulcanized continuously.
Vulcanized rubber molded and vulcanized as described above includes weather strips, door glass run channels, window frames, radiator hoses, brake parts, wiper blades, anti-vibration rubber and other automotive industry parts, rubber rolls, belts, packings and hoses. It can be used for industrial rubber products such as, electrical insulating materials such as anode caps and grommets, construction gaskets, civil engineering materials such as civil engineering sheets, and rubberized fabrics.

A vulcanized foam obtained by heating and foaming a rubber compound containing a foaming agent can be used for applications such as a heat insulating material, a cushioning material, and a sealing material.
[Example]
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

The measurement conditions are as follows.
[i] Specific gravity measurement:
A test piece of 20 mm × 20 mm is punched from the upper part of the vulcanized tubular sponge, and the surface dirt is wiped off with alcohol. This test piece was attached to an automatic hydrometer (manufactured by Toyo Seiki Seisakusho: Model M-1) in an atmosphere of 25 ° C., and the specific gravity was measured from the difference in mass between air and pure water.
[ii] Tensile test:
The upper part of the vulcanized tube-like sponge was punched in the length direction with a No. 3 type dumbbell described in JIS K 6301 (1989) to obtain a test piece. Using the test piece, a tensile test was performed at a measurement temperature of 25 ° C. and a tensile speed of 500 mm / min in accordance with the method defined in paragraph 3 of JIS K 6301, and the tensile breaking stress T _B (kg / cm ² ) And tensile elongation at break E _B (%).

Except for punching out the vulcanized rubber sheet and punching out with the No. 3 dumbbell, a test piece was obtained in the same manner as described above, and the tensile breaking point stress T _B (kg / cm ² ) and the tensile breaking point elongation E _B (%) Was measured.
[ii] Compression set test:
The vulcanized tubular sponge is cut to 30 mm and attached to a compression set measuring mold. The test piece was compressed so that its height was ½ that before the load was applied, and the mold was heat treated in a gear oven at 70 ° C. for 200 hours. After cooling for 30 minutes, the height of the test piece was measured, and the compression set was calculated by the following formula.

t ₀ : Height of the test piece before the test t ₁ : Height of the test piece after heat-treating the test piece and allowing it to cool for 30 minutes t ₂ : Height of the test piece attached to the measurement mold [ In the case of Example 4, Examples 6 to 8 and Comparative Example 2]
In the compression set test, low temperature compression set (CS) after 22 hours at −40 ° C. was determined according to JIS K 6301.

In any case, the lower the low temperature compression set, the better the low temperature flexibility.
[iv] Measurement of shape retention:
The ratio of the height and width of the cross-section of the vulcanized tubular sponge was measured and used as the shape retention rate.

L: Height of tubular sponge D: Width of tubular sponge
[v] Surface roughness measurement:
The surface roughness of the sponge was expressed by quantifying the irregularities on the upper surface of the sponge using a stylus type surface roughness measuring instrument. Actually, the tubular sponge rubber obtained as described above is cut into a length of 50 mm, and the total height (h ₁₎ of the convex portions from the highest to the tenth in the extracted portion.
) Minus the total height (h ₂ ) of the recesses from the lowest to the tenth (h ₁ −h ₂ )
The value calculated by dividing by 10 was taken as the surface roughness of the sponge rubber.
[vi] Hardness test (Hs hardness):
Hardness test is based on JIS K 6301, spring hardness Hs (JISA hardness)
Was measured.
[vii] Aging test:
Aging test was performed 168 hours air heating aging test at 125 ° C., retention for the physical properties before aging, i.e. tensile strength retention _{[A R (T B)]} , retention of elongation [A _R (E _B)] and The change in hardness [A _H ] (JIS A) was determined.
[viii] Evaluation of extrudability:
The compounded rubber was extruded at an extrusion speed of 30 m / min using an extruder equipped with a circular die having a diameter of 3 mm (cylinder temperature 70 ° C, head temperature 80 ° C, die temperature 90 ° C). It was evaluated by. The amount of compounded rubber extruded for 10 seconds was taken as the amount of extrusion.

[Criteria for five-step evaluation of extrusion properties]
The evaluation at each stage was performed in accordance with ASTM D 2230-77 scoring standard B for surface skin smoothness, with 5 being the highest and 1 being the lowest (causing melt fracture during extrusion).
[ix] Glass transition temperature Tg:
The glass transition temperature Tg of the ethylene copolymer rubber was measured with a differential scanning calorimeter (DSC). This glass transition temperature is an index of low temperature flexibility of the ethylene copolymer rubber.

* Temperature cycle in Tg measurement by DSC The sample was heated from room temperature (25 ° C.) to 180 ° C. at a rate of 20 ° C./min and kept at this temperature (180 ° C.) for 2 minutes, and then the sample was −20 ° C. The sample was cooled to −80 ° C. at a rate of / min and held at this temperature (−80 ° C.) for 2 minutes, and then the sample was again heated at a rate of 20 ° C./min to determine the glass transition temperature Tg of the sample .

  Using a 4-liter glass polymerizer equipped with a stirring blade, quaternary co-polymerization of ethylene, propylene, 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB) A polymerization reaction was performed.

  That is, first, dehydrated and purified toluene was added in an amount of 1.2 liters per hour from the top of the polymerization vessel to a toluene solution of (1,3-dimethylcyclopentadienyl) zirconium dichloride (Zr: 0.1 mmol). / Liter) in a quantity of 0.4 liters per hour, methylaluminoxane (MAO) in toluene (Al: 33.3 mmol / l) in a quantity of 1.2 liters per hour in a mixed toluene solution of ENB and VNB ( The total of ENB and VNB: 21.7 ml / liter, ENB / VNB = 5.5 (volume ratio)) was continuously fed at a rate of 1.2 liters per hour.

Further, ethylene was continuously fed into the polymerization vessel from the upper part of the polymerization vessel at a rate of 200 liters per hour and propylene at a rate of 200 liters per hour.
This copolymerization reaction was performed at 20 ° C. so that the average residence time of the reaction mixture was 30 minutes (that is, the polymerization scale was 2 liters).

The obtained polymer solution was continuously withdrawn from the lower part of the polymerization vessel, and a small amount of methanol was added thereto to stop the polymerization reaction.
The obtained polymer solution was poured into a large excess of methanol (compared to the amount of methanol required to stop the polymerization reaction), so that the polymer was precipitated and collected by filtration.

  The polymer was then mixed with a stabilizer [30 mg of “Irganox 1010” manufactured by Ciba Geigy and 60 mg of “Mark 329K” (manufactured by Asahi Denka)] per 100 g of polymer, and then dried at 120 ° C. under reduced pressure overnight.

By the above operation, an ethylene / propylene / ENB / VNB quaternary copolymer was obtained in an amount of 116 g / hour.
The obtained copolymer had a molar ratio of ethylene units to propylene units of 71/29, a molar ratio of ENB units to VNB units (ENB units / VNB units) of 5.8, and an intrinsic viscosity [ η] is 2.7 dl / g, the iodine value (IV value) is 19.5, the intensity ratio of Tαβ to Tαα (Tαβ / Tαα) in the ¹³ C-NMR spectrum is less than 0.01, and gη ^{* The} value was 0.55, the g ′ value was 0.61, the glass transition temperature Tg was −46 ° C., and the B value was 1.1.

Next, the ethylene / propylene / ENB / VNB quaternary copolymer and the active zinc white, stearic acid, dimethyl distearyl ammonium chloride, carbon black and oil shown in Table 1 were kneaded using a 1.7 liter Banbury mixer. did.

  Next, using a 14-inch roll (F / B = 50/50 ° C.), the vulcanizing agent and other components (residue) other than the components shown in Table 1 were kneaded as described above. The compounded rubber (rubber composition) was obtained by adding to the kneaded product and kneading.

  Next, this compounded rubber was extruded into a tube shape by extruding it at a die temperature of 80 ° C. and a cylinder temperature of 60 ° C. using a 60 mm extruder equipped with a tube die (inner diameter: 10 mm, wall thickness: 1 mm).

The surface roughness of the unvulcanized tubular molded body was 8.
The resulting molded body was vulcanized in a hot air vulcanization tank at 220 ° C. for 6 minutes to obtain a sponge rubber.

When the physical properties of the obtained sponge-like vulcanized rubber were measured,
Its specific gravity (density) is 0.49 (g / cm ³ ),
The tensile stress at break (T _B ) is 24 kg / cm ² ,
The tensile elongation at break (E _B ) is 270%,
Compression set is 28%,
The shape retention was 83%.

The results are also shown in Table 4.
In addition, Tables 2 to 3 show the synthesis conditions of the ethylene / propylene / ENB / VNB quaternary copolymer.

  Table 1 also shows the composition of the rubber composition.

In Example 1, a copolymerization reaction was carried out in the same manner as in Example 1 except that the raw materials and reaction conditions were changed as shown in Tables 2 to 3.
Moreover, about the obtained copolymer, the rubber composition was prepared similarly to Example 1 and the vulcanization | cure property was calculated | required.

The results are shown in Table 4.
The tensile test, hardness test, and compression set test of Example 4 were performed in the same manner as Example 6 described later, and the results are shown in Table 8.
[Comparative Example 1]

An ethylene / propylene / ENB copolymer having an ethylene content of 70 mol%, an iodine value of 22 and an intrinsic viscosity [η] of 2.7 dl / g was converted to VO (OC ₂ H ₅ ) Cl ₂ / (C ₂ It was synthesized by a known method using H ₅ ) _1.5 AlCl _1.5 catalyst.

Using this ethylene / propylene / ENB copolymer, a rubber composition was prepared in the same manner as in Example 1, vulcanized, and various physical properties were measured in the same manner as in Example 1. The results are also shown in Table 4.
The abbreviations in the table are as follows.
MAO: methylaluminoxane, VNB: 5-vinyl-2-norbornene, ENB: 5-ethylidene-2-norbornene, NBD: norbornadiene, OCPD: dicyclopentadiene,
MOD: 7-methyl-1,6-octadiene.
Diene-1:
Non-conjugated polyene (c) in which only one carbon / carbon double bond that can be polymerized with a metallocene catalyst exists in one molecule.
Diene-2:
Non-conjugated polyene (d) in which two carbon / carbon double bonds that can be polymerized with a metallocene catalyst are present in one molecule.

A stainless steel autoclave with an internal volume of 2 liters that has been sufficiently purged with nitrogen, hexane in an amount of 0.6 liter, 1-octene (octene-1) in an amount of 0.4 liter, and ENB in an amount of 1
VNB was charged in an amount of 0,2 ml and 2.5 ml, respectively.

Next, ethylene was introduced until 8 kg / cm ² -G.
Thereafter, 1 mmol of triisobutylaluminum and 0.004 mmol of rac-dimethylsilylenebis {1- (4-isopropyl-2,7-dimethylindenyl)} zirconium dichloride and 1.2 mmol of methylaluminoxane (MAO) (in terms of aluminum atoms) ) Was premixed in toluene and pressurized with nitrogen to initiate the polymerization.

Thereafter, only ethylene was continuously supplied to keep the total pressure at 8 kg / cm ² -G, and polymerization was carried out at 70 ° C. for 1 hour.
After stopping the polymerization by adding a small amount of methanol into the system, the unreacted monomer was purged.

The polymer solution was precipitated by putting the obtained polymer solution into a large excess of methanol (compared to the amount of methanol necessary to stop the polymerization reaction).
The polymer was collected by filtration, mixed with stabilizers [30 mg of “Irganox 1010” Ciba Geigy and 60 mg “Mark 329K” (Asahi Denka)] per about 100 g of polymer, and then dried at 120 ° C. under reduced pressure overnight.

As a result, the molar ratio of ethylene units to 1-octene units (ethylene units / 1-octene units) was 74.9 / 25.1, and the molar ratio of ENB units to VNB units (ENB units / VNB units) was 4.5, intrinsic viscosity [η] is 2.2 dl / g, iodine value is 12.5, and intensity ratio D value of Tαβ to Tαα in the ¹³ C-NMR spectrum (Tαβ / T
αα) is less than 0.01, gη ^* value is 0.58, g ′ value is 0.64, glass transition temperature Tg is −58 ° C., and B value is 1.1. A 1-octene / ENB / VNB copolymer was obtained in an amount of 56 g / hour.

  Next, a compounded rubber (rubber composition) was obtained in the same manner as in Example 1 using the copolymer and the compounding agents shown in Table 5 below.

  This compounded rubber was extruded using a 60 mm extruder equipped with a flat plate die (dimensions: height 2 mm, width 30 mm) at a head temperature of 80 ° C., a die temperature of 70 ° C., and a cylinder temperature of 60 ° C. to form a sheet. Molded into.

The extruded skin of the unvulcanized sheet-like molded product was 4, and the extrusion amount was 180 cm / 10 seconds.
Next, this unvulcanized sheet-like molded body was vulcanized at 160 ° C. for 10 minutes to obtain a crosslinked rubber sheet having a thickness of 2 mm.

Various physical property tests were performed using the crosslinked rubber sheet.
When the physical properties of the obtained crosslinked rubber sheet were measured,
The tensile stress at break (T _B ) is 80 kg / cm ² ,
The tensile elongation at break (E _B ) is 540%,
Hs hardness is 64,
Of the heat aging resistance, the tensile strength retention A _R (T _B ) is 103%,
The elongation retention rate A _R (E _B ) is 99%,
The change in hardness A _H is +2,
The compression set (low temperature flexibility) was 10%.

The results are also shown in Table 8.
In addition, Tables 6 to 7 show the synthesis conditions of the ethylene / 1-octene / ENB / VNB quaternary copolymer.

In Example 6, an ethylene copolymer rubber was produced in the same manner as in Example 6, except that the amount of ENB was changed to 15 ml and the amount of VNB was changed to 3.5 ml.
As a result, the molar ratio of ethylene units to octene-1 units (ethylene units / octene-1 units) was 75.5 / 24.5, and the molar ratio of ENB units to VNB units (ENB units / VNB units). ) Is 4.7, the intrinsic viscosity [η] is 2.0 dl / g, the iodine value (IV value) is 16.5, and the intensity ratio D (Tαβ to Tαα in the ¹³ C-NMR spectrum is D ( Tαβ / Tαα) is less than 0.01, the gη ^* value is 0.52, the g ′ value is 0.59, the glass transition temperature Tg is −57 ° C., and the B value is 1.1. An ethylene / octene-1 / ENB / VNB copolymer (rubber) was obtained in an amount of 48 g / hr.

Using this copolymer, a rubber composition was prepared in the same manner as in Example 6, and the physical properties were determined.
The results are shown in Table 8.
Moreover, the synthesis conditions of this copolymer are shown together in Tables 6-7.

In Example 6, an ethylene copolymer rubber was produced in the same manner as in Example except that octene-1 was changed to butene-1 and butene-1 was charged in 0.24 Nl.
As a result, the molar ratio of ethylene units to butene-1 units (ethylene units / butene-1 units) was 78/22, and the molar ratio of ENB units to VNB units (ENB units / VNB units) was 3 , The intrinsic viscosity [η] is 2.1 dl / g, the iodine value (IV value) is 14.5, and the intensity ratio D of Tαβ to Tαα in the ¹³ C-NMR spectrum (Tαβ / Tαα) Is less than 0.01,
The gη ^* value is 0.53, the g ′ value is 0.58, the glass transition temperature Tg is −55 ° C., and the B value is 1.1. A coalescence (rubber) was obtained with a yield of 65 g / hr.

Using this copolymer, a rubber composition was prepared in the same manner as in Example 6, and the physical properties were determined.
The results are shown in Table 8.
Moreover, the synthesis conditions of this copolymer are shown together in Tables 6-7.
[Comparative Example 2]

In Example 6, instead of using only ENB as the diene and using 1-octene, propylene was charged at an initial pressure of 5 kg / cm ² · G, and then ethylene was added at 8 k.
An ethylene / propylene / ENB copolymer rubber was produced in the same manner as in Example 6 except that the polymerization temperature was changed to 70 ° C. and the polymerization temperature was changed to 80 ° C. until g / cm ² · G.

As a result, the molar ratio of ethylene units to propylene units (ethylene units / propylene units) was 70/30, the intrinsic viscosity [η] was 2.1 dl / g, and the iodine value (IV value) was 14. Yes, the intensity ratio D of Tαβ to Tαα in the ¹³ C-NMR spectrum (Tα
β / Tαα) is less than 0.01, the gη ^* value is 0.97, the g ′ value is 0.98, the glass transition temperature Tg is −49 ° C., and the B value is 1.1. An ethylene / propylene / ENB terpolymer (rubber) was obtained in an amount of 40 g / hour.

Using this copolymer, a rubber composition was prepared in the same manner as in Example 6, and the physical properties were determined.
The results are shown in Table 8.
Moreover, the synthesis conditions of this copolymer are shown together in Tables 6-7.

Claims (14)

(a) ethylene, (b) an α-olefin having 3 to 20 carbon atoms, and (c) a carbon / carbon double bond that can be polymerized with a metallocene catalyst among carbon / carbon double bonds in one molecule. Randomization of only one non-conjugated polyene and (d) a non-conjugated polyene in which two carbon / carbon double bonds that can be polymerized with the catalyst are present in one molecule. A copolymer rubber,
(i) a unit derived from ethylene (a) and a unit derived from an α-olefin having 3 to 20 carbon atoms (b) in a mole of 90/10 to 40/60 [(a) / (b)]. Contained in a ratio,
(ii) 0.1 to 10 units (c) derived from a non-conjugated polyene in which only one carbon / carbon double bond that can be polymerized with the catalyst is present in one molecule. Contained in an amount of mol%,
(iii) 0.1-3 mol of units (d) derived from non-conjugated polyene in which two carbon / carbon double bonds that can be polymerized with the catalyst among carbon / carbon double bonds are present in one molecule % In amount,
(iv) the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.1 to 10 dl / g;
(v) an ethylene copolymer rubber having an intensity ratio D (Tαβ / Tαα) of Tαβ to Tαα in a ¹³ C-NMR spectrum of 0.5 or less;
At least one or more of the following (a), (b), (c);
A rubber composition characterized by comprising:
(a) a reinforcing agent in an amount of 300 parts by weight or less based on 100 parts by weight of the ethylene copolymer rubber;
(b) a softener in an amount of 200 parts by weight or less based on 100 parts by weight of the ethylene copolymer rubber;
(c) Vulcanizing agent. In the ethylene copolymer rubber, a unit derived from 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 (c) When,
Among the carbon-carbon double bonds, the molar ratio of the unit (d) derived from the non-conjugated polyene in which two carbon-carbon double bonds polymerizable with the catalyst exist in one molecule (component (c) / The rubber composition according to claim 1, wherein component (d) is 1/3 to 30/1.   3. The rubber composition according to claim 1, wherein (b) the α-olefin has 4 or more carbon atoms in the ethylene copolymer rubber.   The rubber composition according to any one of claims 1 to 3, wherein the ethylene copolymer rubber has a glass transition temperature Tg determined by DSC of -45 ° C or lower.   The rubber composition according to any one of claims 1 to 4, comprising a foaming agent in an amount of 0.5 to 30 parts by weight with respect to 100 parts by weight of the ethylene copolymer rubber.   A vulcanized rubber obtained by vulcanizing the rubber composition according to any one of claims 1 to 5.   A vulcanized foam obtained by vulcanizing and foaming the rubber composition according to claim 6.   An automotive industrial part comprising the vulcanized rubber according to claim 6.   An industrial rubber part comprising the vulcanized rubber according to claim 6.   An electrical insulating material comprising the vulcanized rubber according to claim 6.   A civil engineering and building material article comprising the vulcanized rubber according to claim 6.   A heat insulating material comprising the vulcanized foam according to claim 7.   A cushion material comprising the vulcanized foam according to claim 7.   A sealing material comprising the vulcanized foam according to claim 7.