JPH10273565A - Bubber composition for damper material and damper material made therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rubber composition which can give a damper material excellent in strength, heat resistance, weather resistance, vibration-damping properties, vibration-deadening properties and dynamic fatigue resistance (flexural fatigue resistance) by using an unsaturated olefin copolymer having a specified iodine value and comprising ethylene, an aromatic vinyl compound and a nonconjugated polyene in a specified ratio. SOLUTION: This composition comprises an unsaturated olefin copolymer obtained from ethylene, an aromatic vinyl compound represented by the formula (wherein R<1> to R<3> are each H or a 1-8C alkyl; and n is 0-5), a nonconjugated polyene and optionally an α-olefin and having an ethylene/3-20C α-olefin ratio of 100/0 to 60/40 by mole, an (ethylene + α-olefin)/aromatic vinyl compound ratio of 90/10 to 50/50 by mole and an iodne value of 0.5-50. This composition can be used as a damper material even when it is in an unvulcanized state. However, it can exhibit its features most when it is used in a vulcanized state.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber composition for a damper material and a damper material, and more particularly, to strength characteristics, heat resistance, weather resistance, vibration damping, vibration damping and dynamic fatigue resistance (bending resistance). The present invention relates to a vulcanizable rubber composition for a damper material capable of obtaining a damper material having excellent fatigue properties and a damper material obtained by vulcanizing the rubber composition.

[0002]

2. Description of the Related Art In recent years, vibration and noise caused by transportation such as automobiles have become a problem. In addition, low vibration and low noise are required in fields such as automobiles, office equipment, and household electric appliances. Conventionally, as a means for reducing such noise and vibration, a method of suppressing transmission of vibration using a spring, a vibration-proof rubber, or the like has been frequently used.
The effect was not enough.

[0003] On the other hand, a method called vibration suppression for suppressing vibration itself has been conventionally performed. In this method, by attaching a damping material made of a viscoelastic body to a vibrating material,
This is a method of suppressing the occurrence of vibration. Examples of such vibration damping materials include polyester-based (JP-A-62-295949), polyamide-based (JP-A-56-159160), and epoxy resin-based (JP-A-58-23426). Various things have been proposed. A material having such characteristics is generally called a damper material. However, these materials did not sufficiently meet various requirements such as moldability, workability, and vibration damping performance.

[0004] Diene rubbers such as CR, IR and SBR are widely used for dampers because of their excellent properties such as vibration proofing, workability and strength. However, these diene rubbers are inferior in weather resistance and ozone resistance, and thus have a problem that their product life is short.

Further, US Pat. No. 4,645,793 discloses a blend of a diene rubber and an ethylene / α-olefin copolymer having improved weather resistance and ozone resistance. However, such a blend of a diene rubber and an ethylene / α-olefin copolymer has improved weather resistance and ozone resistance,
There are problems such as a decrease in strength and dynamic fatigue resistance (bending fatigue resistance).

[0006] Under such circumstances, vibration proof, workability,
There has been a demand for a damper material excellent in strength properties, weather resistance, ozone resistance and dynamic fatigue resistance, and a rubber composition for a damper material capable of obtaining such a damper material.

The inventors of the present invention have conducted intensive studies to obtain a rubber composition having the above-mentioned properties, and have found that ethylene and
It has been found that unsaturated olefin-based copolymers obtained from a specific polyene, an aromatic vinyl compound and, if necessary, an α-olefin having 3 to 20 carbon atoms satisfy the above properties. Thus, the present invention has been completed.

[0008]

An object of the present invention is to solve the problems associated with the prior art described above, and to provide strength characteristics, heat resistance, weather resistance, vibration damping, vibration damping and dynamic fatigue resistance. It is an object of the present invention to provide a rubber composition for a damper material from which a damper material excellent in (bending fatigue resistance) can be obtained, and a damper material obtained by vulcanizing the rubber composition.

[0009]

SUMMARY OF THE INVENTION The rubber composition for a damper material according to the present invention comprises:
(A) (i) ethylene, (ii) an aromatic vinyl compound represented by the following formula (I), and (iii) a non-conjugated polyene.
If necessary, (iv) an α-olefin having 3 to 20 carbon atoms, obtained from an α-olefin having 3 to 20 carbon atoms, and a structural unit derived from ethylene (i) and an α-olefin having 3 to 20 carbon atoms (iv). The molar ratio (ethylene / α-olefin) to the structural unit to be used is in the range of 100/0 to 60/40, and the structural unit derived from ethylene (i) and the number of carbon atoms are 3 to 20.
The molar ratio (ethylene + α-olefin / aromatic vinyl compound) of the total amount of the structural units derived from the α-olefin (iv) to the structural unit derived from the aromatic vinyl compound (ii) is 90/10 It is characterized by being composed of an unsaturated olefin copolymer having an iodine value in the range of 50/50 and 0.5 to 50.

[0010]

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(Wherein R ¹ , R ² and R ³ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n is an integer of 0 to 5) The rubber composition for a damper material according to the present invention comprises, in addition to the (A) unsaturated olefin copolymer, (B) a softening agent,
(C) at least one selected from fillers and (D) vulcanizing agents
Seed components can be included.

The damper material according to the present invention is characterized in that the rubber composition for a damper material is crosslinked. The damper material according to the present invention has an attenuation rate (tan) at 25 ° C.
δ) is usually 0.25 or more.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The rubber composition for a damper material and the damper material according to the present invention will be specifically described below.

The rubber composition for a damper material according to the present invention comprises:
(A) It consists of a specific unsaturated olefin copolymer. (A) Unsaturated olefin-based copolymer (A) Unsaturated olefin-based copolymer comprises (i) ethylene, (ii) an aromatic vinyl compound represented by the following formula (I), and (iii) ) Non-conjugated polyene and, optionally, (iv)
It is a random copolymer obtained from an α-olefin having 3 to 20 carbon atoms.

(Ii) As the aromatic vinyl compound, specifically, a compound represented by the following general formula (I) is used.

[0016]

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In the formula, R ¹ , R ² and R ³ may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Is an alkyl group.

N is an integer of 0 to 5, preferably 0 to 3. Examples of the aromatic vinyl compound as described above include styrene; o-methylstyrene, m-methylstyrene,
Mono- or polyalkylstyrenes such as p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene; methoxystyrene, ethoxystyrene, vinylbenzoic acid, methylvinylbenzoate, vinyl Benzyl acetate, hydroxystyrene,
Functional group-containing styrene derivatives such as o-chlorostyrene, p-chlorostyrene and divinylbenzene; 3-phenylpropylene, 4-phenylbutene, α-methylstyrene and the like. These aromatic vinyl compounds can be used alone or in combination of two or more.

(Iii) Examples of the non-conjugated polyene include 1,4-pentadiene, 1,4-hexadiene, 4-methyl-1,5-heptadiene, 5-methylene-2-norbornene, and 5-ethylidene-2-
Norbornene, 5-isopropenyl-2-norbornene, 2,5
-Norbornadiene, 1,6-cyclooctadiene, 2-ethylene-2,5-norbornadiene, 2-isopropenyl-2,5-norbornadiene, dicyclopentadiene, 1,6-octadiene, 1,7-octadiene, tricyclo A diene compound such as pentadiene, a non-conjugated triene or tetraene having one vinyl group in one molecule, and one diene compound in one molecule;
Non-conjugated triene or tetraene having five 5-norbornen-2-yl groups. The total number of carbon atoms per molecule of the non-conjugated triene or tetraene (when two or more non-conjugated trienes or tetraenes are contained, the average number of carbon atoms is not particularly limited), but is preferably 9 to 30. Pieces, more preferably 10 to 25
And particularly preferably 10 to 22. A non-conjugated triene or tetraene having a carbon atom number in such a range is advantageous because it is easy to handle such as purification. Here, "triene" means a hydrocarbon compound having three carbon-carbon double bonds (C = C) in one molecule, and "tetraene" means carbon-carbon double bond in one molecule.
It means a hydrocarbon compound having four carbon double bonds.
The carbon-carbon double bond has a carbon-
Carbon of a carbon double bond and a 5-norbornen-2-yl group
Contains carbon double bonds.

The non-conjugated triene or tetraene includes three (for triene) or four (for tetraene) carbon-carbon double bonds (C =) including a vinyl group or a 5-norbornen-2-yl group. C), but the total number of hydrogen atoms directly bonded to carbon atoms adjacent to all carbon-carbon double bonds contained in one molecule of this non-conjugated triene or tetraene is not particularly limited. But,
Preferably 9-33, more preferably 12-33,
Particularly preferably, the number is 14 to 33. It is preferable that the total number of hydrogen atoms be in such a range, since a copolymer having a high crosslinking reaction rate can be obtained. When the non-conjugated triene or tetraene used is a mixture of two or more, the number of hydrogen atoms is indicated by an average of the number of these hydrogen atoms.

In the present invention, among the non-conjugated triene or tetraene, a non-conjugated triene or tetraene in which a vinyl group or a 5-norbornen-2-yl group is bonded to a methylene group (-CH _2- ) is preferable.

Among such non-conjugated trienes or tetraenes, compounds represented by the following general formula (II-a) or the following general formula (III-a) are preferable.

[0023]

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In the formula, p and q may be the same or different and are 0 or 1 (provided that p and q are not simultaneously 0). f is an integer of 0 to 5, preferably an integer of 0 to 2 (however, when p and q are both 1, they are not 0).

G is an integer of 1 to 6, preferably 1 to 6.
It is an integer of 3. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶
And R ⁷ may be the same or different and represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;
Preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, and R ⁷ is a hydrogen atom or a carbon atom number. Is an alkyl group of 1 to 3.

R ⁸ has a hydrogen atom or a carbon atom number of 1 to 1.
5 represents an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

R⁹Represents an atom having 1 to 5 hydrogen atoms and 1 to 5 carbon atoms.
Alkyl group or-(CH_Two)_n-CR ^Ten= CR¹¹R¹²In table
Wherein n is an integer of 1 to 5;^TenAnd
And R ¹¹May be the same or different from each other,
R 1 represents an alkyl group having 1 to 5 carbon atoms or¹²
Represents an alkyl group having 1 to 5 carbon atoms).
Preferably, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
Or-(CH_Two)_n-CR^Ten= CR¹¹R¹²Group represented by
(Where n is an integer of 1 to 3;^TenAnd R
¹¹May be the same or different from each other,
Or an alkyl group having 1 to 3 carbon atoms;¹²Is charcoal
Represents an alkyl group having 1 to 3 element atoms). However,
If p and q are both 1, then R⁹Is a hydrogen or carbon atom
It is an alkyl group having a number of 1 to 5.

[0028]

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(Where p, q, f, g, R ^{1 to} R ⁹ are
It has the same meaning as in the case of the general formula (II-a). (Iii) the non-conjugated polyene has the general formula (II-a) or
When the non-conjugated triene or tetraene represented by (III-a) is used, the rubber composition for a damper material has a high vulcanization rate, and the obtained damper material has excellent strength properties.

Specific examples of the non-conjugated triene or tetraene represented by the general formula (II-a) include the following compounds.

[0031]

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The non-conjugated triene or tetraene represented by the general formula (III-a) is specifically exemplified by the compound exemplified as the non-conjugated triene or tetraene represented by the general formula (II-a). Vinyl group is 5-norbornene
And compounds substituted with a 2-yl group.

Among the non-conjugated triene or tetraene represented by the general formula (II-a), the non-conjugated triene or tetraene represented by the following general formula (IV-a) is preferable.
This non-conjugated triene or tetraene is a compound in which p is 1 and q is 0 in the non-conjugated triene or tetraene represented by the general formula (II-a).

Among the non-conjugated trienes or tetraenes represented by the general formula (III-a), non-conjugated trienes or tetraenes represented by the following general formula (V-a) are preferable. The non-conjugated triene or tetraene is a compound in which p is 1 and q is 0 in the non-conjugated triene or tetraene represented by the general formula (III-a).

[0035]

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In the formula, f is an integer of 0 to 5, preferably 0 to 2. g is an integer of 1 to 6,
Preferably it is an integer of 1-3. R ¹ , R ² , R ⁵ , R
⁶ and R ⁷ may be the same or different from each other,
The same as the general formula (II-a), preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably R ¹ , R ² , R ⁵ and R ⁶ are hydrogen atoms and R ⁷ Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

R ⁸ is the same as in the above formula (II-a), and is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. is there.

R ⁹ is the same as in the above formula (II-a), and is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0039]

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Where f, g, R ¹ , R ² , R ⁵ -R ⁹
Has the same meaning as in the above formula (IV-a). (Iii) the non-conjugated polyene has the general formula (IV-a) or
When the non-conjugated triene or tetraene represented by (Va) is used, the rubber composition for a damper material has a high vulcanization rate, and the obtained damper material has excellent strength properties.

Specific examples of the non-conjugated triene or tetraene represented by the general formula (IV-a) include the following compounds.

[0042]

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[0043]

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[0044]

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[0045]

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Specific examples of the non-conjugated triene or tetraene represented by the general formula (V-a) include the vinyl group of the compound exemplified as the non-conjugated triene or tetraene represented by the general formula (IV-a). With a 5-norbornen-2-yl group.

In the present invention, (iii) the non-conjugated polyene is
The compound represented by the general formula (II-a) is more preferable, and the compound represented by the general formula (IV-a) is particularly preferable.

(Iii) The non-conjugated polyene has the general formula (I
When the non-conjugated triene or tetraene represented by Ia) is used, the rubber composition for a damper material has a high vulcanization rate, and the obtained damper material has excellent strength properties.

(Iii) The non-conjugated polyene has the general formula (I
When the non-conjugated triene or tetraene represented by Va) is used, the damper material obtained from the rubber composition for a damper material is particularly excellent in cold resistance, low-temperature characteristics, and vulcanization strength.

The non-conjugated triene or tetraene is
It may be a mixture of the trans form and the cis form, or may be the trans form alone or the cis form alone. These (iii) non-conjugated polyenes can be used alone or in combination of two or more.

The non-conjugated triene or tetraene represented by the general formula (II-a) or (III-a) is, for example,
It can be prepared by a conventionally known method as described in EP0691354A1 and WO96 / 20150. These (iii) non-conjugated polyenes can be used alone or in combination of two or more.

(Iv) Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene and 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-dodecene, 1-
Tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and the like, among which the number of carbon atoms is Four or more α-olefins are preferred, with 1-butene, 1-hexene, 1-octene and 1-decene being particularly preferred. These α-olefins can be used alone or in combination of two or more.

(A) The unsaturated olefin copolymer comprises:
A structural unit derived from ethylene (i), a structural unit derived from an aromatic vinyl compound (ii), a structural unit derived from a non-conjugated polyene (iii), and, if necessary, having 3 to 20 carbon atoms. (iii) structural units derived from an α-olefin (iv) are randomly arranged and bonded,
While having a branched structure caused by a non-conjugated polyene,
The main chain is a copolymer having a substantially linear structure. The fact that the copolymer has a substantially linear structure and does not substantially contain a gel-like crosslinked polymer means that the copolymer is dissolved in an organic solvent and contains substantially no insoluble matter. Can be confirmed by For example, when the intrinsic viscosity [η] is measured, it can be confirmed by the fact that the copolymer is completely dissolved in decalin at 135 ° C.

(A) The unsaturated olefin copolymer is
The molar ratio (ethylene / α-olefin) of the structural unit derived from ethylene (i) to the structural unit derived from α-olefin having 3 to 20 carbon atoms (iv) is 100/0.
６０60/40, preferably 100/0 to 70/30, more preferably 100/0 to 80/20, and the structural unit derived from ethylene (i) and the number of carbon atoms are 3 to
The molar ratio (ethylene + α-olefin / aromatic vinyl compound) of the total amount of the structural units derived from the α-olefin (iv) to the structural unit derived from the aromatic vinyl compound (ii) is 90/10 ~ 50/50, preferably 8
5/15 to 55/45, preferably 80/20 to 60 /
It is desirable to be in the range of 40.

A structural unit derived from ethylene (i),
Molar ratio with constituent units derived from α-olefin (iv) having 3 to 20 carbon atoms (ethylene / α-olefin)
Is in the range of 100/0 to 60/40, the damper material obtained from the rubber composition for a damper material of the present invention has excellent low-temperature properties. In addition, the damper material obtained when the proportion of the structural unit derived from the aromatic vinyl compound (ii) is within the above range has excellent vibration damping properties. (A) The unsaturated olefin copolymer preferably has an iodine value in the range of usually 0.5 to 50, preferably 3 to 50, more preferably 4 to 40. (A) When the iodine value of the unsaturated olefin-based copolymer is within the above range, the rubber composition for a damper material has a high vulcanization rate.

The (A) unsaturated olefin copolymer preferably has a crystallinity calculated from the melting point peak measured by a differential scanning calorimeter of 15% or less, preferably 10% or less. The intrinsic viscosity [η] measured in a decalin solution at 135 ° C. is desirably in the range of 0.1 to 10 dl / g, preferably 1 to 5 dl / g.

In the unsaturated olefin copolymer (A) used in the present invention, the ratio of the constituent units constituting a chain structure in which two or more constituent units derived from an aromatic vinyl compound are continuous is the same as that of the aromatic vinyl compound. It is desirably 1% or less, preferably 0.1% or less, based on the structural unit derived from the compound. The content ratio of a chain structure in which two or more structural units derived from an aromatic vinyl compound are continuous is ¹³ C—N
It can be determined by MR.

In the above (A) unsaturated olefin-based copolymer, (iii) the non-conjugated polyene has the general formula (I)
When represented by Ia), in the unsaturated olefin-based copolymer (A), the structural unit derived from the non-conjugated triene or tetraene has a structure represented by the following general formula (II-b) Have.

[0059]

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(Where p, q, f, g, R ^{1 to} R ⁹ are
It has the same meaning as in the case of the general formula (II-a). Further, (iii) when the non-conjugated polyene is represented by the general formula (III-a), a structural unit derived from the non-conjugated triene or tetraene in the unsaturated olefin-based copolymer (A). Has a structure represented by the following general formula (III-b).

[0061]

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(Where p, q, f, g, R ^{1 to} R ⁹ are
It has the same meaning as in the case of the general formula (II-a). Further, (iii) the non-conjugated polyene has the general formula (IV-a)
When represented by the formula, in the unsaturated olefin-based copolymer (A), the structural unit derived from the non-conjugated triene or tetraene has a structure represented by the following general formula (IV-b) ing.

[0063]

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Wherein f, g, R ¹ , R ² , R ⁵ -R ⁹
Has the same meaning as in formula (IV-a). And (iii) when the non-conjugated polyene is represented by the general formula (V-a), in the unsaturated olefin-based copolymer (A), a structural unit derived from the non-conjugated triene or tetraene. Has a structure represented by the following general formula (V-b).

[0065]

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Where f, g, R ¹ , R ² , R ⁵ -R ⁹
Has the same meaning as in formula (IV-a). Note that (iii) the structural unit derived from the non-conjugated polyene is
The fact that the unsaturated olefin copolymer (A) has each of the above structures can be confirmed by measuring the ¹³ C-NMR spectrum of the copolymer.

Next, a method for producing the unsaturated olefin copolymer (A) will be described. The unsaturated olefin-based copolymer (A) used in the present invention comprises, for example, (i) ethylene and (i) in the presence of a metallocene catalyst (a).
i) an aromatic vinyl compound, (iii) a non-conjugated polyene,
If necessary, it can be produced by copolymerizing (iv) an α-olefin having 3 to 20 carbon atoms.

As the metallocene catalyst (a), metallocene-based catalysts conventionally used as single-site catalysts and metallocene-based catalysts similar thereto can be used without limitation. In particular, metallocene compounds of transition metals (transition metal A catalyst comprising the compound (b) and the organic aluminum oxy compound (c) and / or the ionized ionic compound (d) is preferably used.

As the metallocene compound (b), IUP
Family number 1 according to the revised version of the AC Inorganic Chemistry Nomenclature (1989)
A metallocene compound of a transition metal selected from Group 4 of the periodic table (long-period type) of the elements represented by Nos. To 18, specifically, a metallocene compound represented by the following general formula (1).

MLx (1) In the formula (1), M is a transition metal selected from Group 4 of the periodic table, specifically, zirconium, titanium or hafnium, and x is the valence of the transition metal. .

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

Examples of the ligand having a cyclopentadienyl skeleton include, for example, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n- or i-propylcyclopentadienyl group, n-,
i-, sec- or t-butylcyclopentadienyl group, hexylcyclopentadienyl group, octylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group , Pentamethylcyclopentadienyl group, methylethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylhexylcyclopentadienyl group, methylbenzylcyclopentadienyl group, ethyl Alkyl or cycloalkyl-substituted cyclopentadienyl groups such as butylcyclopentadienyl group, ethylhexylcyclopentadienyl group, methylcyclohexylcyclopentadienyl group, and further indenyl group, 4,5,6,7-tetrahydroindenyl group , Fluo And a phenyl group.

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

When the metallocene compound (b) represented by the formula (1) has two or more groups having a cyclopentadienyl skeleton as the ligand L, a group having two cyclopentadienyl skeletons among them The two are linked via an alkylene group such as ethylene and propylene, a substituted alkylene group such as isopropylidene and diphenylmethylene, a silylene group or a dimethylsilylene group, a diphenylsilylene group, and a substituted silylene group such as a methylphenylsilylene group. Is also good.

Examples of L other than the ligand having a cyclopentadienyl skeleton include a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a sulfonic acid-containing group (—SO ₃ R ¹ ), and halogen. Atoms or hydrogen atoms (here, R ¹ 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, an aralkyl group and the like. More specifically, a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, alkyl group such as dodecyl group, cyclopentyl group And an aryl group such as a phenyl group and a tolyl group; an aralkyl group such as a benzyl group and a neophyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group,
Examples include 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.

Examples of the aryloxy group include a phenoxy group. Examples of the sulfonic acid-containing group (—SO ₃ R ¹ ) include a methanesulfonato group, a p-toluenesulfonato group, a trifluoromethanesulfonato group, and a p-chlorobenzenesulfonato 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 (b) represented by the formula (1) is more specifically represented by the following general formula (2).

R ² _k R ³ _l R ⁴ _m R ⁵ _n M (2) In the formula (2), M is a transition metal similar to the transition metal of the formula (1), preferably zirconium or titanium. ^Two
Is a group (ligand) having a cyclopentadienyl skeleton, and R ³ , R ⁴ and R ⁵ may be the same or different from each other, and may have a group having a cyclopentadienyl skeleton or the above-mentioned general formula (1) The same applies to L except for the ligand having a cyclopentadienyl skeleton in the above). k is an integer of 1 or more, and k + 1 + m + n = 4.

Further, examples of the bridge type metallocene compound include a metallocene compound represented by the following formula [A]. The metallocene has the formula [A]:

[0082]

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In the formula [A], M ¹ is a metal belonging to Group IVB of the periodic table, and specifically, for example, titanium, zirconium,
Hafnium can be mentioned.

R ¹ and R ² may be the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms;
~ 3 alkoxy groups, 6-10 carbon atoms, preferably 6 carbon atoms
To 8 aryl groups, having 6 to 10 carbon atoms, preferably 6 to
8 aryloxy groups, alkenyl groups having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms; arylalkyl groups having 7 to 40 carbon atoms, preferably 7 to 10 carbon atoms; alkyls having 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms Aryl group, 8 carbon atoms
-40, preferably 8-12 arylalkenyl groups, or halogen atoms, preferably chlorine atoms.

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

R ³ and R ⁴ are particularly preferably hydrogen atoms. R ⁵ and R ⁶ may be the same or different and are preferably the same, and have the meanings described for R ³ and R ⁴ , provided 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,
Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a trifluoromethyl group, and a methyl group is preferable.

R ⁷ is as follows:

[0088]

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= BR¹¹, = AlR¹¹, -Ge-, -Sn
-, -O-, -S-, = SO, = SO _Two, = NR¹¹, =
CO, = PR¹¹Or = P (O) R¹¹Where R
¹¹, R^{1 Two}And R¹³May be the same or different
And preferably a hydrogen atom, a halogen atom, and a carbon number of 1 to 10.
Is an alkyl group of 1-4, more preferably a methyl group, carbon
A fluoroalkyl group having 1 to 10 atoms, preferably CF_Three
Group, aryl having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms
Group, preferably a fluoroaryl group having 6 to 10 carbon atoms
Is a pentafluorophenyl group, preferably having 1 to 10 carbon atoms.
Or 1-4 alkoxy groups, particularly preferably methoxy
Group, alkenyl having 2 to 10, preferably 2 to 4 carbon atoms
Group, aryl having 7 to 40 carbon atoms, preferably 7 to 10 carbon atoms
An alkyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms;
An arylalkenyl group or a group having 7 to 40 carbon atoms
Or 7 to 12 alkylaryl groups;
¹¹And R¹²"Or" R¹¹And R¹³"Means
May form a ring together with the atom to which it is bonded.

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

R ⁸ and R ⁹ may be the same or different and have the same meaning as described for R ¹¹ . m and n may be the same or different 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).

[0093]

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[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, and R ⁵ and R ⁶ are methyl groups. , An ethyl group or a trifluoromethyl group, and R ⁸ , R ⁹ , R ¹⁰ and R ¹² have the above-mentioned meaning. Among the compounds represented by the formulas (i), (ii) and (iii), the following compounds are particularly preferred.

Rac-dimethylmethylenebis (indenyl) zirconium dichloride, rac-dimethylmethylenebis (2-methyl-1-indenyl) zirconium dichloride, rac-diphenylmethylenebis (2-methyl-
1-indenyl) zirconium dichloride, 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 Mechiru-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 as the bridge type metallocene compound.

[0097]

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[B] In the formula [B], M represents a transition metal atom of Group IVB of the periodic table, and specifically, titanium, zirconium and hafnium.

R ¹ and R 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, a silicon-containing group,
Oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group, specifically, halogen atom such as fluorine, chlorine, bromine, iodine; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl , Dodecyl, eicosyl, norbornyl, alkyl groups such as adamantyl, vinyl, propenyl, alkenyl groups such as cyclohexenyl, benzyl, phenylethyl, arylalkyl groups such as phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, Propylphenyl, biphenyl, naphthyl,
A hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as methylnaphthyl, anthracenyl, and phenanthryl; a halogenated hydrocarbon group in which a halogen atom is substituted on the hydrocarbon group; a monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl; Dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl, trihydrocarbons such as trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl Substituted silyl, silyl ether of hydrocarbon-substituted silyl such as trimethylsilyl ether, silicon-substituted alkyl group such as trimethylsilylmethyl, silicon-substituted aryl group such as trimethylsilylphenyl, etc. Oxygen-containing groups such as hydroxy groups, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; allyloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; and arylalkoxy groups such as phenylmethoxy and phenylethoxy. A sulfur-containing group such as a substituent in which the oxygen of the oxygen-containing group is substituted by sulfur; an amino group, an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, a phenylamino group; A nitrogen-containing group such as an arylamino group or an alkylarylamino group such as diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino; dimethylphosphino;
It is a phosphorus-containing group such as a phosphino group such as diphenylphosphino.

Among them, R ¹ is preferably a hydrocarbon group, particularly methyl, ethyl and propyl having 1 carbon atom.
It is preferably from 3 to 3 hydrocarbon groups. 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 and 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; Among them, hydrogen, a hydrocarbon group or a halogenated hydrocarbon group is preferable. R ³ and R ⁴ , R ⁴ and R ⁵ ,
At least one pair of R ⁵ and R ⁶ may form a monocyclic aromatic ring together with the carbon atom to which they are bonded.

When there are two or more hydrocarbon groups or halogenated hydrocarbon groups other than the group forming an aromatic ring, these groups 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, a hydrocarbon group having 1 to 20 carbon atoms, and a 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 the ligand coordinated to M, including a monocyclic aromatic ring formed by combining at least one of R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ , are as follows. Some examples are shown below.

[0104]

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

Examples of the halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a halogenated hydrocarbon group having 1 to 20 carbon atoms which are substituted on the aromatic ring include the same groups as those described above for R ¹ and R ^2. .

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. And specifically, R ¹ and R
² the same halogen atom, hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing groups can be exemplified.

Examples of the sulfur-containing group include the same groups as those described above for R ¹ and R ² and methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate and trimethylbenzenesulfonate. Sulfonate groups such as phonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate , Trimethylbenzenesulfinate, pentafluorobenzenesulfinate and the like.

Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, 2
Divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-, -CO-, -S-, -SO-,-
^{_{SO 2 -, - NR 7 -}} , - P (R 7) -, - P (O)
^{(R 7) -, - BR} 7 - or -AlR ⁷ - [However,
R ⁷ represents 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, methylene, dimethylmethylene, 1,2-ethylene, Dimethyl-1,2-ethylene, 1,3-trimethylene,
Divalent having 1 to 20 carbon atoms such as alkylene groups such as 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene, and arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene. A halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene; methylsilylene, dimethylsilylene, diethylsilylene, di (n-
Alkyl silylenes such as propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene, aryl Silylene group,
Tetramethyl-1,2-disilylene, tetraphenyl-1,2-
A divalent silicon-containing group such as an alkyldisilylene such as disilylene, an alkylaryldisilylene, or an aryldisilylene group; a divalent germanium-containing group obtained by substituting silicon of the divalent silicon-containing group with germanium; A divalent tin-containing group substituent in which silicon of the silicon-containing group is substituted with tin, and the like. R ⁷ is the same halogen atom as R ¹ or R ² , a hydrocarbon group having 1 to 20 carbon atoms, a carbon number 1
To 20 halogenated hydrocarbon groups.

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

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

[0112]

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[0113]

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[0114]

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

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

[0117]

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The 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 as the bridge type metallocene compound.

[0120]

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[C] In the formula [C], M, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as those in the above formula [B]. No.

Of R ³ , R ⁴ , R ⁵ and R ⁶ , R ³
Is preferably an alkyl group,
Preferably, R ³ and R ⁵ , or R ³ and R ⁶ are alkyl groups. This alkyl group is preferably a secondary or tertiary alkyl group. Also, this alkyl group is
A halogen atom, which may be substituted with a silicon-containing group,
Examples of the halogen atom and the silicon-containing group include the substituents exemplified for R ¹ and R ² .

Among the groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ , the groups other than the alkyl group are preferably hydrogen atoms. 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, A chain alkyl group and a cyclic alkyl group such as nonyl, dodecyl, eicosyl, norbornyl and adamantyl; an arylalkyl group such as benzyl, phenylethyl, phenylpropyl and tolylmethyl; and the like, including a double bond and a triple bond May be.

Further, 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. As a halogen atom,
Specifically, the same groups as those for R ¹ and R ² can be exemplified.

As X ¹ , X ² , Y and R ⁷ , those similar to the above formula [B] can be mentioned. The metallocene compound (transition metal compound) represented by the formula [C] below
Here is a specific example.

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) diruconium dichloride, ra
c-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) diconium 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, r
ac-dimethylsilylene-bis (2-methyl-4-chloromethyl-
7-methyl-1-indenyl) zirconium dichloride, ra
c-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-4,6-di (i-propyl) -1-
(Indenyl) diruconium 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, r
ac-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 (methanesulfonato), 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 compounds may be used. The transition metal compound is usually used as a racemic compound, but may be used in R-form or S-form.

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

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

[0130]

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[D] In the formula [D], M, R ¹ , X ¹ , X ² and Y are the same as those in the formula [B] or the formula [C]. Can be

Among them, R ¹ is preferably a hydrocarbon group, 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, phenalenyl (perinaphthenyl), aceanthrenyl and the like. It is. Of these, phenyl and naphthyl are preferred. These aryl groups may be substituted with the same halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms as in R ¹ .

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 muscidochloride, ra
c-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) diruconium 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-dimethylgermylene-bis ( 2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethyltin-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethyl Rylene - 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 bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride OSO ₂ Me - ₂ Me, rac- dimethylsilylene.

In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds can also be used. The transition metal compound represented by the formula [D] is described in Journa
l of Organometallic Chem. 288 (1985), pp. 63-67, EP-A-0,320,762 and examples, for example, as follows.

[0136]

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The transition metal compound [D] is usually used as a racemic compound, but may be used in the R or S form.

In the present invention, the metallocene compound (b)
As the metallocene compound represented by the following general formula (3). L ¹ M ² Z ¹ ₂ (3) (wherein, M ² is a metal belonging to Group 4 of the periodic table or a lanthanide series, L ¹ is a derivative of a delocalized π-bonded group,
The metal M ² active site has a constrained geometry,
¹ may be the same or different from each other, and represent a hydrogen atom,
A hydrocarbon, silyl or germyl group containing a halogen atom or up to 20 carbon, silicon or germanium atoms. ) The metallocene compound (b) represented by the formula (3)
Among them, a metallocene compound represented by the following general formula (4) is preferable.

[0139]

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In the formula (4), M ³ is titanium, zirconium or hafnium, and Z ¹ is the same as described above. C
p is a cyclopentadienyl group, a substituted cyclopentadienyl group, or a derivative thereof, which is π-bonded to M ³ in an η ⁵ bonding mode.

W ¹ is oxygen, sulfur, boron or an element of group 14 of the periodic table, or a group containing these elements, and V ¹ is a ligand containing nitrogen, phosphorus, oxygen or sulfur.

W ¹ and V ¹ may form a condensed ring.
Also, Cp and W ¹ may form a condensed ring. Preferred examples of the group represented by Cp in the general formula (4) include a cyclopentadienyl group, an indenyl group, a fluorenyl group and a saturated derivative thereof, and these form a ring with the metal atom (M ³ ). I do. Each carbon atom in the cyclopentadienyl group may be the same or different group selected from the group consisting of a hydrocarbyl group and a substituted hydrocarbyl group, and one or more carbon atoms may be a halogen atom, a hydrocarbyl-substituted group. Substituted by a metalloid group, and the metalloid is one of the Periodic Tables of the Elements
Selected from group 4 and halogen atoms. Also, one or more substituents may together form a fused ring. Preferred hydrocarbyl and substituted hydrocarbyl groups which can be substituted with at least one hydrogen atom in the cyclopentadienyl group contain 1 to 20 carbon atoms and are a linear or branched alkyl group, cyclic hydrocarbon group, alkyl-substituted cyclic group. Includes hydrocarbon groups, aromatic groups and alkyl-substituted aromatic groups. Preferred organic metalloid groups are 1
It includes mono-, di- and tri-substituted organic metalloid groups of Group 4 elements, each of the hydrocarbyl groups being from 1 to 20.
Contains carbon atoms. Specific examples of preferred organic metalloid groups include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, phenyldimethylsilyl, methyldiphenylsilyl, triphenylsilyl, triphenylgermyl, and trimethylgermyl.

Specific examples of Z ^{1 in} the general formula (4) include hydride, halo, alkyl, silyl, germyl, aryl, amide, aryloxy, alkoxy,
Examples include phosphide, sulfide, acyl, pseudo halide such as cyanide, azide, acetylacetonate or a mixture thereof, which may be the same or different from each other.

Specific examples of the compound represented by the general formula (4) include (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) titanium dichloride and (( t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) silane) titanium dichloride.

As the metallocene compound (b), a metallocene compound represented by the above general formula (3) is particularly preferred in view of polymerization activity and heat resistance of a molded article. The metallocene compounds (b) described so far may be used alone or in combination of two or more.

The metallocene compound (b) used in the present invention
May be used after being diluted with a hydrocarbon or a halogenated hydrocarbon. Next, the organoaluminum oxy compound (c) and the ionized ionic compound (d) used when forming the metallocene catalyst (a) will be described.

The organoaluminum oxy compound (c) used in the present invention may be a conventionally known aluminoxane (c)
Or a benzene-insoluble organic aluminum oxy compound (c) as exemplified in JP-A-2-78687.

Aluminoxane (c) is produced, for example, by the following method, and is usually recovered as a solution in a hydrocarbon solvent. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as trialkylaluminum to an aromatic hydrocarbon solvent in which is suspended and reacting the resulting mixture to recover a solution of the aromatic hydrocarbon solvent.

(2) Water (water, ice or steam) is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran, and is recovered as a solution of an aromatic hydrocarbon solvent. how to.

(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a hydrocarbon medium such as decane, benzene or toluene.

As the ionized ionic compound (d),
Lewis acids, ionic compounds, borane compounds, and carborane compounds can be exemplified. These ionized ionic compounds (d) are disclosed in JP-A-1-501950, JP-A-1-502036, and JP-A-3-17.
No. 9005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and USP-5321106.

As the Lewis acid used as the ionized ionic compound (d), BR ₃ (where R is the same or different and may have a substituent such as fluorine, methyl, trifluoromethyl, etc.) A phenyl group or fluorine), for example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoro Methylphenyl) boron, tris (pentafluorophenyl) boron and the like.

The ionic compound used as the ionized ionic compound (d) is a salt comprising a cationic compound and an anionic compound. The anion functions to cationize the metallocene compound (b) by reacting with the metallocene compound (b), thereby stabilizing 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, and an organic aluminum compound anion, and those which are relatively bulky and stabilize transition metal cation species are preferable. Examples of the cation include a metal cation, an organic metal cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation. More specifically, triphenylcarbenium cation, tributylammonium cation,
N, N-dimethylammonium cation, ferrocenium cation and the like.

Of these, ionic compounds containing a boron compound as an anion are preferred. Specific examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and trialkylammonium salts. Reel phosphonium salts and the like can be mentioned.

Examples of the above trialkyl-substituted ammonium salts include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) ) Boron and the like.

The N, N-dialkylanilinium salt includes, for example, N, N-dimethylanilinium tetra (phenyl) boron. Examples of the dialkylammonium salt include di (n-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Examples of the triarylphosphonium salt include triphenylphosphonium tetra (phenyl) boron, tri (methylphenyl) phosphoniumtetra (phenyl) boron, and tri (dimethylphenyl) phosphoniumtetra (phenyl) ) Boron and the like.

Examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and ferrocenium tetra (pentafluorophenyl) borate. You can also mention.

Examples of the borane compound used as the ionized ionic compound (d) include the following compounds. Decaborane (14); salts of anions such as bis [tri (n-butyl) ammonium] nonaborate and bis [tri (n-butyl) ammonium] decaborate; and tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobalt Acid salt (III),
And salts of metal borane anions such as bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III).

Examples of the carborane compound used as the ionized ionic compound (d) include 4-carbanonaborane (1
4) salts of anions such as 1,3-dicarbanonaborane (13); and tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III); Metal carborane anion salts such as (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) ferrate (III).

The above-mentioned ionized ionic compound (d) can be used alone or in combination of two or more. Metallocene catalyst (a) used in the present invention
May further contain the following organoaluminum compound (e) in addition to the above components, if necessary.

As the organoaluminum compound (e) optionally used, for example, an organoaluminum compound represented by the following general formula (5) can be mentioned. (R ⁶ ) _n AlX _3-n (5) In the formula (5), R ⁶ is a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and X is a halogen atom or a hydrogen atom. And n is 1-3.

Examples of such a hydrocarbon group having 1 to 15 carbon atoms include an alkyl group, a cycloalkyl group and an aryl group. Specifically, a methyl group, an ethyl group, an n-propyl group, Examples thereof include an isopropyl group and an isobutyl group.

Specific examples of such an organoaluminum compound include the following compounds. Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, tri n-butyl aluminum,
Triisobutylaluminum, in trialkylaluminum, formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein such tri sec- butyl aluminum, x, y, z are located in the positive number , Z ≧ 2x) alkenyl aluminum such as isoprenyl aluminum, dialkyl aluminum halide such as dimethyl aluminum chloride and diisobutyl aluminum chloride, dialkyl aluminum hydride such as diisobutyl aluminum hydride and dialkyl aluminum alkoxide such as dimethyl aluminum methoxide And dialkyl aluminum aryloxides such as diethylaluminum phenoxide.

(I) ethylene, (ii) aromatic vinyl compound and (iii) non-conjugated polyene, if necessary (iv)
The α-olefin may be copolymerized by any of a batch method and a continuous method. When carrying out the copolymerization by a continuous method, the metallocene catalyst (a) is used in the following concentrations.

That is, the concentration of the metallocene compound (b) in the polymerization system is usually 0.00005 to 1.0 mmol / liter (polymerization volume), and preferably 0.0001 to 1.0 mmol / liter (polymerization volume).
0.5 mmol / l.

The organic aluminum oxy compound (c)
Is a ratio of aluminum atom to metallocene compound (b) in the polymerization system (Al / transition metal) of 0.1 to 1000.
It is supplied in an amount of 0, preferably 1 to 5000.

The molar ratio of the ionized ionic compound (d) to the metallocene compound (b) in the polymerization system (the ionized ionic compound (d)
/ Metallocene compound (b)) in an amount of 0.1 to 20, preferably 1 to 10.

When the organoaluminum compound (e) is used, it is usually supplied in an amount of about 0 to 5 mmol / L (polymerization volume), preferably about 0 to 2 mmol / L.

Production of unsaturated olefin copolymer
The copolymerization reaction is usually carried out at a temperature of -30 to + 250 ° C,
Preferably, 0-200 ° C, pressure exceeds 0-80kg /
cm ^Two(Gauge pressure), preferably exceeding 0 to 50 kg
/ Cm^Two(Gauge pressure).

The reaction time (average residence time when the copolymerization is carried out by a continuous method) varies depending on conditions such as the catalyst concentration and the polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes to 10 minutes. 1.5 hours.

In producing the unsaturated olefin-based copolymer, (i) ethylene, (ii) an aromatic vinyl compound and (iii) a non-conjugated polyene, and if necessary, (iv) α-
The olefin is supplied to the polymerization system in such an amount that a copolymer having the above specific composition is obtained. Further, upon copolymerization, a molecular weight regulator such as hydrogen may be used.

As described above, (i) ethylene, (ii)
When an aromatic vinyl compound, (iii) a non-conjugated polyene and, if necessary, (iv) an α-olefin are copolymerized, the copolymer is usually obtained as a polymerization solution containing the same. This polymerization solution is treated by a conventional method to obtain an unsaturated olefin copolymer. Since the unsaturated olefin-based copolymer has a high damping rate, it has excellent vibration damping performance, vibration damping performance, and the like.

In the present invention, two or more kinds of unsaturated olefin copolymers (A) having different compositions may be used as a mixture. Thereby, the damping characteristics can be exhibited in a wide temperature range.

The rubber composition for a damper material according to the present invention can be used as a damper material even when unvulcanized.
When the composition is vulcanized and used as a vulcanizate, its properties can be exhibited most.

In order to produce a vulcanizate from the rubber composition for a damper material according to the present invention, an unvulcanized compounded rubber is prepared once, and then the vulcanizate is prepared as in the case of vulcanizing ordinary rubber. Vulcanization may be performed after molding the compounded rubber into an intended shape. As the vulcanization method, any of a method using a vulcanizing agent and a method of irradiating an electron beam may be adopted.

When a method using a vulcanizing agent is employed as the vulcanizing method, the unvulcanized compounded rubber is an unsaturated olefin copolymer (A), a vulcanizing agent, and if necessary, a vulcanizing agent. It can be prepared by mixing and kneading a sulfur accelerator, a vulcanization aid, a filler, a softener and the like.

When the method of irradiating an electron beam is employed as the vulcanization method, the unvulcanized compounded rubber is added to the unsaturated olefin-based copolymer (A) with a filler, a softening agent and the like, if necessary. Can be prepared by mixing and kneading.

The amount of the unsaturated olefin copolymer (A) in the unvulcanized compounded rubber can be appropriately selected depending on the intended performance and use of the vulcanized product, but is usually at least 20% by weight, preferably at least 20% by weight. Is 25% by weight or more.

As the softening agent (B) used in preparing the unvulcanized compounded rubber, a softening agent conventionally compounded in rubber is widely used. Specifically, paraffinic oil, naphthenic oil , Aromatic oils and other process oils, lubricating oils, paraffin, liquid paraffin, petroleum asphalt, petroleum softeners such as petrolatum; coal tar, coal tar softeners such as coal tar pitch;
Fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, and coconut oil; tall oil; sub; waxes such as beeswax, carnauba wax, and lanolin; Fatty acids such as zinc and fatty acid salts; and synthetic high molecular substances such as petroleum resins, atactic polypropylene, and coumarone indene resins. Among them, a petroleum softener is preferably used, and particularly, a process oil is preferably used. The amount of these softeners can be appropriately selected depending on the use of the vulcanizate, but is usually 150 parts by weight or less, preferably 10 to 100 parts by weight, per 100 parts by weight of the unsaturated olefin copolymer (A). Parts by weight.

As the filler (C) used when preparing the unvulcanized compounded rubber, specifically, SRF, GPF,
FEF, MAF, HAF, ISAF, SAF, FT, M
Carbon blacks such as T; those obtained by subjecting these carbon blacks to a surface treatment with a silane coupling agent; silica; activated calcium carbonate; fine talc; fine silica; The amount of these fillers can be appropriately selected depending on the use of the vulcanized product, but is usually 300 parts by weight or less, preferably 10 to 300 parts by weight, per 100 parts by weight of the unsaturated olefin-based copolymer (A). Parts by weight, more preferably 10 to 200 parts by weight.

As the (D) vulcanizing agent used when preparing an unvulcanized compounded rubber, a sulfur compound and an organic peroxide can be exemplified. In particular, when a sulfur compound is used, the performance of the vulcanized product can be best exhibited.

Specific examples of the sulfur compound include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dimethyldithiocarbamate and the like. Of these, sulfur is preferably used. The sulfur compound is 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 unsaturated ethylene-based copolymer (A).

When a sulfur compound is used as a vulcanizing agent, it is preferable to use a vulcanization accelerator in combination, and specific examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazolesulfenamide (CBS). , N-oxydiethylene
2-benzothiazolesulfenamide, N, N-diisopropyl-2-benzothiazolesulfenamide, 2-mercaptobenzothiazole (MBT), 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2 Thiazole compounds such as 2,6-diethyl-4-morpholinothio) benzothiazole and dibenzothiazyldisulfide; diphenylguanidine (DPG), triphenylguanidine,
Guanidine compounds such as diornitrile guanidine, orthonitrile biguanide, diphenylguanidine phthalate; aldehyde amine or aldehyde-ammonia compounds such as acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde ammonia; Imidazoline compounds such as -mercaptoimidazoline; thiourea compounds such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea; tetramethylthiuram monosulfide; tetramethylthiuram disulfide (TMTD);
Thiuram compounds such as tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate (ZnBDC), zinc ethylphenyldithiocarbamate, butylphenyl Dithioacid salt compounds such as zinc dithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate and tellurium dimethyldithiocarbamate; xanthate compounds such as zinc dibutylxanthogenate; and compounds such as zinc white.

These vulcanization accelerators are used in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the unsaturated olefin copolymer (A).
It is used in an amount of 0 parts by weight, preferably 0.2 to 10 parts by weight.

As the organic peroxide, those conventionally used for peroxide vulcanization of rubber are widely used, for example, dicumyl peroxide, di-t-butyl peroxide,
Di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl hydroperoxide, t-butylcumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-di (t-butyl Peroxin) hexyne-3,2,5-
Dimethyl-2,5-di (benzoylperoxy) hexane,
2,5-dimethyl-2,5-mono (t-butylperoxy) -hexane, α, α′-bis (t-butylperoxy-m-isopropyl) benzene and the like. Among them, dicumyl peroxide, di-t-butyl peroxide and di-t-butylperoxy-3,3,5-trimethylcyclohexane are preferably used. These organic peroxides can be used alone or in combination of two or more. Organic peroxide is an unsaturated olefin copolymer (A) 100 g
0.0003 to 0.05 mol, preferably 0.1 to 0.3 mol.
It is used in the range of 001 to 0.03 mol.

When an organic peroxide is used as the vulcanizing agent, it is preferable to use a vulcanizing aid in combination. Specific examples of the vulcanizing aid include sulfur; quinone dioximes such as p-quinone dioxime. Methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; other maleimide compounds; and divinylbenzene. Such a vulcanization aid is used in an amount of 0.5 to 2 mol, preferably about equimolar, per 1 mol of the organic peroxide used.

In the present invention, a rubber reinforcing agent, an antioxidant, a processing aid, and the like can be further blended with the unvulcanized compounded rubber. It can be appropriately selected according to the performance of the vulcanized product.

The method for producing the vulcanizate is not particularly limited, but specifically, for example, the following method is employed. When a method using a vulcanizing agent is adopted as the vulcanizing method, the unsaturated olefin-based copolymer (A), if necessary, a filler, a softening agent, etc. are mixed in a mixer such as a Banbury mixer to 80 to 170. After kneading at a temperature of 3 ° C. for 3 to 10 minutes, a vulcanizing agent and, if necessary, a vulcanization accelerator or a vulcanization aid are additionally mixed using a roll such as an open roll. After kneading for ~ 30 minutes, the mixture is dispensed to prepare an unvulcanized compound rubber in a ribbon or sheet form. The unvulcanized compounded rubber thus prepared is formed into an intended shape by an extruder, a calender roll, or a press.
Heat at a temperature of 70 ° C. for 1 to 30 minutes, or introduce the molded product into a vulcanization tank,
A vulcanizate is obtained by heating for 0 minutes. Vulcanization may be performed in a mold or without a mold.
When a mold is not used, the steps of molding and vulcanization are usually performed continuously. As the heating method in the vulcanizing tank, hot air,
A heating tank such as a fluidized bed of glass beads, UHF (ultra-high frequency electromagnetic wave), and steam can be used.

When the electron beam irradiation method is employed as the vulcanization method, a mixer such as a Banbury mixer is used to add the unsaturated olefin-based copolymer (A) and, if necessary, a filler and a softening agent. 3-1 at 80-170 ° C
After kneading for 0 minutes, using a roll such as an open roll, kneading at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes, and then dispensing, a ribbon-shaped or sheet-shaped unvulcanized compounded rubber is prepared. The unvulcanized compounded rubber thus prepared is molded into an intended shape by an extruder, a calender roll, or a press, and a vulcanized product is obtained by irradiating an electron beam. Irradiation of electron beam is 0.1-10M
eV (mega electron volts), preferably 0.3 to
An electron having an energy of 2 MeV and an absorbed dose of 0.
5-35 Mrad (Megarad), preferably 0.5-
It is desirable to perform so as to be 10 Mrad.

The vulcanizates thus obtained are excellent in heat resistance, weather resistance and dynamic fatigue resistance, as well as in vibration damping properties, vibration damping properties and strength properties. Damping rate (tan) at 25 ° C. after crosslinking the rubber composition for a damper material of the present invention.
δ) is 0.25 or more, preferably 0.3 or more, more preferably 0.4 or more. The higher the value of tan δ, the better the vibration damping characteristics.

The damper material according to the present invention is formed from the above rubber composition for a damper material or a vulcanized product of the composition. Note that the damper material is a material for reducing the amplitude of impact or vibration by a method of dissipating energy, and includes a damping material, a vibration proof material, a sound insulating material, and the like.

When the damper material according to the present invention is used for, for example, a damping steel sheet, another resin may be blended with the above-mentioned ethylene / aromatic vinyl compound copolymer. Other resins include polyethylene, polypropylene, polystyrene, and modified products thereof. When other resins are blended, the moldability is improved.

The damper material of the present invention may contain a compounding agent such as an antioxidant, a processing aid, a heat stabilizer, a weather stabilizer, an antistatic agent, a lubricant, a flame retardant or the like within a range not to impair the object of the present invention. Can be blended.

The damper material according to the present invention can be used in various applications, for example, various machines and devices that generate vibration and noise due to rotational motion and reciprocating motion, their housings, structures such as bridge floors, conduits for water, gas and the like. Types, air conditioning ducts, various vehicles,
It is used as a damping material for ships and railway vehicles, a damping material for precision machinery, a damping material for audio equipment, and a vibration damping material.

[0196]

The damper material according to the present invention has excellent strength properties, vibration damping properties and weather resistance.

[0197]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0198]

[Production Example 1] [Polymerization of ethylene / styrene / EMND copolymer]
The 5-liter autoclave was sufficiently purged with nitrogen, and hexane 310 ml, styrene 170 ml, 4-ethylidene
8 ml of -8-methyl-1,7-nonadiene (EMND) was charged. Next, the temperature inside the system was raised to 40 ° C. while stirring, and ethylene was introduced so as to be 10 kg / cm ² . next,
In a separate reactor, 9.2 mmol of methylaluminoxane (3% by weight toluene solution, manufactured by Tosoh Akzo Co., Ltd.) and titanium (dimethyl (t-butylamido) tetramethyl-η ⁵ -cyclopentadienyl) silane synthesized by a known method After adding 0.018 mmol of dichloride and stirring for 15 minutes, the mixture was introduced into an autoclave and polymerization was started. During this polymerization, ethylene was polymerized for 30 minutes while continuously supplying ethylene at 10 kg / cm ² . The polymerization was terminated by adding 5 ml of methanol.

After completion of the polymerization, the mixture was added to 1 liter of methanol to precipitate a polymer. The precipitated polymer was further washed twice with 1 liter of methanol and dried in vacuum at 130 ° C. for 12 hours. The obtained ethylene styrene
The molar ratio of ethylene and styrene (ethylene / styrene) constituting the EMND copolymer (copolymer (a)) was 79 /
21. The iodine value is 18 and 135 ° C.
The intrinsic viscosity [η] measured in decalin is 1.7 dl / g
And the glass transition temperature was 1 ° C.

[0200]

[Production Example 2] [Polymerization of ethylene / styrene / EMND copolymer] According to the method described in Production Example 1, the molar ratio of ethylene to styrene (ethylene / styrene) was 62/38 and the iodine value was 12 An ethylene-styrene-EMND copolymer (copolymer (b)) having an intrinsic viscosity [η] of 1.1 dl / g measured in decalin at 135 ° C. and a glass transition temperature of 10 ° C. Manufactured.

[0201]

[Production Example 3] [Polymerization of ethylene / styrene / EMND copolymer] In Production Example 1, (dimethyl (t-butylamido) tetramethyl-η ⁵ -cyclopentadienyl) silane) titanium dichloride was synthesized by a known method. Was performed in the same manner as in Production Example 1 except that isopropylidene-bis (indenyl) zirconium dichloride was used.
D copolymer (copolymer (c)) was produced. The molar ratio of ethylene to styrene (ethylene / styrene) constituting the obtained ethylene / styrene / EMND copolymer (copolymer (c)) was 77/23. The iodine value is 17, the intrinsic viscosity [η] measured in decalin at 135 ° C. is 1.5 dl / g, and the glass transition temperature is 4
° C.

[0202]

Example 1 The copolymer (a) produced in Production Example 1, zinc white, stearic acid, FEF carbon black, naphthenic oil, vulcanization accelerator (CBS) and sulfur were blended according to Table 1, and an open roll was prepared. (Front roll / rear roll: 70
/ 70 ° C, 16/18 rpm) to obtain an unvulcanized compounded rubber.

The unvulcanized compounded rubber thus obtained was heated by a press heated to 160 ° C. for 20 minutes to produce a vulcanized sheet, and the following tests were performed. Table 1 shows the results.

[Tensile test] Tensile strength (TB) and elongation (EB) were measured according to JIS K6301.

[Hardness test] JIS A hardness (HS) was measured according to JIS K6301. [Ozone resistance test] The ozone resistance test was performed in an ozone test tank under the conditions that the ozone concentration was 80 ppm and the elongation was 80%.
%, Temperature was 40 ° C., and time was 96 hours. Evaluation of ozone resistance is based on JIS K
6301. The evaluation criteria for the surface state are as follows, for example, displayed as “C-5”.

Number of cracks A: small number of cracks B: large number of cracks C: size and depth of infinite number of cracks 1: those that cannot be seen with the naked eye but can be seen with a magnifying glass of 10 times magnification 2: those that can be seen with the naked eye 3 ... Cracks that are deep and relatively large (less than 1 mm) 4… Cracks that are deep and large (1 mm or more and less than 3 mm) 5… Cracks or cuts that are likely to be 3 mm or more [Vibration control] RDSII manufactured by Rheometrics Using,
The dynamic viscoelasticity at 25 ° C. was measured at a frequency of 2.5 rad / sec, and the attenuation rate (tan δ) was measured. The larger the tan δ, the better the vibration damping property.

[0207]

Example 2 In Example 1, the copolymer (b) produced in Production Example 2 was used instead of the copolymer (a), and the composition of each component was changed as shown in Table 1. Except for the above, a vulcanized sheet was prepared and tested in the same manner as in Example 1. Table 1 shows the results.

[0208]

Comparative Example 1 In Example 1, an ethylene / propylene / 5-ethylidene-2-norbornene copolymer (ethylene / propylene (molar ratio): 68) was used in place of the copolymer (a).
/ 32), intrinsic viscosity [η]; 1.7 dl / g, iodine value; 12) (copolymer (d)), except that the composition of each component was changed as described in Table 1. A vulcanized sheet was prepared and tested in the same manner as in Example 1. Table 1 shows the results.

[0209]

Example 3 The procedure of Example 1 was repeated except that the copolymer (c) produced in Production Example 3 was used as the copolymer. Table 1 shows the results.

[0210]

[Table 1]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 3/30 C08K 3/30 5/01 5/01 5/098 5/098 C08L 23/16 C08L 23/16 F16F 15/08 F16F 15/08 D // (C08F 210/02 212: 04 236: 20) (72) Inventor Tetsuo Higashijo 3 Chigusa Kaigan, Ichihara-shi, Chiba Mitsui Chemicals, Inc.

Claims (4)

[Claims] (A) (i) ethylene, (ii) an aromatic vinyl compound represented by the following formula (I), (iii) a non-conjugated polyene, and if necessary, (iv) the number of carbon atoms. Is a 3 to 20 α-olefin, and a molar ratio of a structural unit derived from ethylene (i) and a structural unit derived from an α-olefin (iv) having 3 to 20 carbon atoms (ethylene / α-olefin) in the range of 100/0 to 60/40, and ethylene (i)
And the molar ratio of the structural unit derived from the aromatic vinyl compound (ii) to the total amount of the structural unit derived from the α-olefin (iv) having 3 to 20 carbon atoms and the structural unit derived from the aromatic vinyl compound (ii) -Olefin / aromatic vinyl compound)
A rubber composition for a damper material, comprising an unsaturated olefin copolymer having an iodine value in the range of 90/10 to 50/50 and an iodine value in the range of 0.5 to 50; ] (In the formula, R ¹ , R ² and R ³ may be the same or different from each other, and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n is an integer of 0 to 5.) 2. In addition to (A) the unsaturated olefin-based copolymer, it contains at least one component selected from (B) a softener, (C) a filler, and (D) a vulcanizing agent. Claim 1
4. The rubber composition for a damper material according to item 1. 3. A damper material obtained by crosslinking the rubber composition for a damper material according to claim 1 or 2. 4. The decay rate (tan δ) at 25 ° C. is 0.
The damper material according to claim 3, which is 25 or more.