JPH05287122A - Electrically conductive rubber - Google Patents

Abstract

(57) [Summary] [Structure] Specific higher α-olefins, specific α, ω-
A copolymer consisting of a diene and a specific non-conjugated diene, wherein the molar ratio of the higher α-olefin to the α, ω-diene, the content of the non-conjugated diene, and the intrinsic viscosity [η] are within a specific range. α-Olefin Copolymer Rubber (A) 1
A conductive rubber comprising a vulcanized product containing 00 parts by weight and 5 to 200 parts by weight of the conductivity-imparting agent (B). [Effect] The conductive rubber of the present invention has the effects of excellent dynamic fatigue resistance and excellent conductivity.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a conductive rubber, and more particularly to a conductive rubber having excellent dynamic fatigue resistance (flexing fatigue resistance) and excellent conductivity.

[0002]

BACKGROUND OF THE INVENTION Conductive rubber was initially used as an antistatic material, but with the development of electronic technology, it has come to be used for various purposes such as contact materials and conductive adhesiveness.

The conductive rubber is a dispersion obtained by dispersing a semiconductor-based conductive rubber having a conductive molecular structure introduced in the rubber molecule and a conductivity-imparting agent (conductive filler) such as carbon black or metal particles in the rubber. It is roughly classified into composite conductive rubber.

The above-mentioned dispersed composite type conductive rubber is usually silicone rubber or the like, powder of carbon black, metal or the like,
It is a rubber in which a large amount of fibers and the like are mixed, and the conductivity of the rubber is exhibited by the contact between the conductivity-imparting agents in the rubber and the proximity state at the atomic level.

As the above-mentioned metal, a noble metal such as gold or silver which does not deteriorate in characteristics over time is used. However,
These precious metals are expensive and therefore have limited uses. Therefore, most of the conductive rubbers that have been put to practical use conventionally use relatively inexpensive carbon black or carbon fiber as the conductivity-imparting agent.

By the way, the above-mentioned conductive rubber normally has an insulating property when not pressed, and has a property that when a deformation strain occurs due to a pressure or the like, the distorted portion exhibits conductivity or semi-conductivity. .. Conventionally, conductive rubber has been widely used as a pressure-sensitive conductive material in pressure switches of electric and electronic devices by utilizing such properties.

Pressure switches for electrical and electronic equipment are
From the viewpoint of the reliability of electronic devices, it is required to have excellent dynamic fatigue resistance, that is, to have long repeated durability life. Therefore, the conductive rubber as a pressure switch material for electric / electronic devices is required to have excellent dynamic fatigue resistance.

[0008] Therefore, the inventors of the present invention have conducted earnest research to obtain a conductive rubber having excellent dynamic fatigue resistance and excellent conductivity, and in the presence of a specific olefin polymerization catalyst, a specific higher α- When a higher α-olefin copolymer rubber obtained by copolymerizing an olefin, a specific α, ω-diene and a specific non-conjugated diene was added with a conductivity-imparting agent, this rubber was They have found that they are excellent and most suitable as conductive rubber, and have completed the present invention.

[0009]

OBJECT OF THE INVENTION It is an object of the present invention to provide a conductive rubber which is superior in dynamic fatigue resistance and conductivity as compared with conventional conductive rubbers.

[0010]

SUMMARY OF THE INVENTION The conductive rubber according to the present invention comprises (A) a higher α-olefin having 6 to 20 carbon atoms, an α, ω-diene represented by the following general formula [I], and the following general formula [ II] represented by a non-conjugated diene, wherein the higher α-olefin and the α, ω-diene have a molar ratio of 95/5 to 50/50 and a non-conjugated diene content of 0. 100 parts by weight of a higher α-olefin copolymer rubber having an intrinsic viscosity [η] of 01 to 30 mol% and a limiting viscosity [η] measured in decalin at 135 ° C. of 1.0 to 10.0 dl / g; ) A vulcanized product containing 5 to 200 parts by weight of a conductivity-imparting agent.

[0011]

[Chemical 3]

In the formula [I], n is an integer of 1 to 3 and R
¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

[0013]

[Chemical 4]

In the formula [II], n is an integer of 1 to 5,
R ³ represents an alkyl group having 1 to 4 carbon atoms, R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁴ and R ⁵ are both hydrogen atoms. Absent.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The conductive rubber according to the present invention will be specifically described below. The conductive rubber according to the present invention comprises a vulcanized product containing a specific higher α-olefin-based copolymer rubber (A) and a conductivity-imparting agent (B).

Higher α-Olefin Copolymer Rubber (A) The higher α-olefin copolymer rubber (A) used in the present invention comprises a specific higher α-olefin and a specific α, ω.
-A specific copolymer in which a diene and a specific non-conjugated diene are present in a specific ratio.

The higher α-olefin used in the present invention is a higher α-olefin having 6 to 20 carbon atoms,
Specifically, hexene-1, heptene-1, octene-
1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, nonadecene-1, eicosene-1,9-methyldecene- 1,
11-Methyldodecene-1, 12-ethyltetradecene-1 and the like can be mentioned.

In the present invention, the above-mentioned higher α-
The olefin may be used alone or as a mixture of two or more kinds. Of the above-mentioned higher α-olefins, hexene-1, octene-1, and decene-1 are particularly preferably used.

Α, ω-Diene The α, ω-diene used in the present invention is represented by the following general formula [I].

[0020]

[Chemical 5]

In the above general formula [I], n is 1 to 3
And R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
As the above α, ω-diene, specifically,
1,4-pentadiene, 1,5-hexadiene, 1,6
-Heptadiene, 3-methyl-1,4-pentadiene,
3-methyl-1,5-hexadiene, 3-methyl-1,
6-heptadiene, 4-methyl-1,6-heptadiene, 3,3-dimethyl-1,4-pentadiene, 3,4
-Dimethyl-1,5-hexadiene, 4,4-dimethyl-1,6-heptadiene, 4-ethyl-1,6-heptadiene and the like can be mentioned.

In the above-mentioned higher α-olefin copolymer rubber, when R ¹ and R ² are hydrogen atoms, the repeating unit derived from the α, ω-diene usually has the following structure: Formula [III] and / or formula [I
V] is considered to exist.

[0023]

[Chemical 6]

[0024]

[Chemical 7]

In the higher α-olefin copolymer rubber, the repeating units described above form a substantially linear structure in which they are randomly arranged. The structure of each of these repeating units can be confirmed by ¹³ C-NMR. here,
The substantially linear structure means that a branched chain structure may be formed, but it does not include a network crosslinked structure. The fact that the higher α-olefin copolymer rubber used in the present invention forms a substantially linear structure means that the copolymer rubber is completely dissolved in decalin at 135 ° C. It can be confirmed by not containing the polymer.

Non-Conjugated Diene The non-conjugated diene used in the present invention is represented by the following general formula [I
I].

[0027]

[Chemical 8]

In the above general formula [II], n is an integer of 1 to 5, R ³ represents an alkyl group having 1 to 4 carbon atoms, and R ⁴ and R ⁵ are hydrogen atoms or carbon atoms. 1 to
8 represents an alkyl group, and R ⁴ and R ⁵ are not both hydrogen atoms.

Specific examples of the non-conjugated diene as described above include 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene and 5-methyl-1,4-hexadiene. 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, 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, 7-methyl-
1,6-decadiene, 6-ethyl-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-
Examples include 1,8-decadiene and 9-methyl-1,8-undecadiene.

In the present invention, the above non-conjugated dienes may be used alone or as a mixture of two or more kinds. In addition to the non-conjugated dienes as described above, other copolymerizable monomers such as ethylene,
Propylene, butene-1, 4-methylpentene-1 and the like may be used as long as the object of the present invention is not impaired.

The molar ratio of the constituent unit derived from the higher α-olefin and the constituent unit derived from the α, ω-diene constituting the higher α-olefin copolymer rubber used in the present invention (higher α-olefin / α, ω-diene) is 5
0/50 to 95/5, preferably 60/40 to 90/1
0, more preferably 65/35 to 90/10. The value of the molar ratio is a value obtained by measurement by ¹³ C-NMR method.

In the present invention, higher α-olefins have α, ω
-By copolymerizing a diene, the processability of a higher α-olefin copolymer rubber can be improved. The content of the non-conjugated diene constituting the higher α-olefin copolymer rubber used in the present invention is 0.01 to 30 mol%, preferably 0.1 to 20 mol%, particularly preferably 0.1 to 30 mol%. It is within the range of 10 mol%. This characteristic value is a standard value when the higher α-olefin copolymer rubber used in the present invention is vulcanized with sulfur or peroxide.

The intrinsic viscosity [η] of the higher α-olefin copolymer rubber (A) used in the present invention measured in a decalin solvent at 135 ° C. is 1.0 to 10.0 dl / g, preferably 1. It is in the range of 5 to 7 dl / g. This characteristic value is a measure showing the molecular weight of the higher α-olefin copolymer rubber used in the present invention. When the molecular weight is in the above range, strength characteristics, weather resistance, ozone resistance, and heat aging are obtained. It is possible to obtain a copolymer excellent in properties such as properties, low temperature characteristics, and dynamic fatigue resistance.

The higher α-used in the present invention as described above
The olefin copolymer rubber (A) can be produced by the following method. The higher α-olefin copolymer rubber (A) used in the present invention is represented by the higher α-olefin having 6 to 20 carbon atoms and the above general formula [I] in the presence of an olefin polymerization catalyst. α, ω-diene,
It is obtained by copolymerizing with the non-conjugated diene represented by the general formula [II].

The olefin polymerization catalyst used in the present invention comprises a solid titanium catalyst component (a), an organoaluminum compound catalyst component (b) and an electron donor catalyst component (c).

FIG. 1 shows an example of a flow chart of a method for preparing an olefin polymerization catalyst component used in producing the higher α-olefin copolymer rubber used in the present invention. The solid titanium catalyst component (a) used in the present invention is
It is a highly active catalyst component containing magnesium, titanium, halogen and an electron donor as essential components.

Such solid titanium catalyst component (a) is
It is prepared by contacting the following magnesium compound, titanium compound, and electron donor. In the present invention, examples of the titanium compound used for preparing the solid titanium catalyst component (a) include Ti (OR) _g X
_4-g (R is a hydrocarbon group, X is a halogen atom, 0 ≦ g ≦
The tetravalent titanium compound represented by 4) can be mentioned.

More specifically, TiCl_Four, TiB
r_Four, TiI_Four Tetrahalogenated titanium such as; Ti
(OCH₃) Cl₃, Ti (OC₂H_Five) Cl₃, Ti (O
-n-C_FourH₉) Cl₃, Ti (OC₂H_Five) Br₃, Ti (O
-iso-C_FourH₉) Br₃ Trihalogenated alkoxy such as
Titanium; Ti (OCH₃)₂Cl₂, Ti (OC₂H_Five)₂C
l₂, Ti (O-n-C_FourH₉)₂Cl ₂, Ti (OC₂H_Five)₂
Br₂Dihalogenated dialkoxy titanium such as; Ti
(OCH₃)₃Cl, Ti (OC₂H_Five)₃Cl, Ti (O
-n-C_FourH₉)₃Cl, Ti (OC₂H_Five)₃Such as Br
Nohalogenated trialkoxy titanium; Ti (OC
H₃)_Four, Ti (OC₂H_Five)_Four, Ti (O-n-C_FourH₉)_Four,
Ti (O-iso-C_FourH₉)_Four, Ti (O-2-ethylhexyl
Le)_Four Such as tetraalkoxy titanium
You can

Of these, halogen-containing titanium compounds, particularly titanium tetrahalide, are preferred. Above all,
Titanium tetrachloride is particularly preferably used. These titanium compounds may be used alone or in combination of two or more. Furthermore, these titanium compounds are
It may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

Further, in the present invention, a trivalent titanium compound,
A tetravalent titanium compound is used, but a tetravalent titanium compound is particularly preferable. In the present invention, examples of the magnesium compound used for preparing the solid titanium catalyst component (a) include a reducing magnesium compound and a non-reducing magnesium compound.

Examples of the reducing magnesium compound include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of such a magnesium compound having a reducing property include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl. Magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, octyl butyl magnesium,
Butyl magnesium halide and the like can be mentioned. These magnesium compounds may be used alone or may form a complex compound with an organic aluminum compound described later. Further, these magnesium compounds may be liquid or solid.

Specific examples of the magnesium compound having no reducing property include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; magnesium methoxy chloride, magnesium ethoxy chloride, and magnesium isopropoxy chloride. Alkoxy magnesium halides such as butoxy magnesium chloride and octoxy magnesium chloride; Alkoxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; Ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium Alkoxy magnesium such as;
Examples thereof include allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; and magnesium carboxylates such as magnesium laurate and magnesium stearate.

The non-reducing magnesium compound may be a compound derived from the above-mentioned reducing magnesium compound or a compound derived during preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducible magnesium compound, for example, a reducible magnesium compound may be prepared from polysiloxane compounds, halogen-containing silane compounds, halogen-containing aluminum compounds, esters, alcohols, etc. It may be brought into contact with the compound.

In the present invention, in addition to the above-mentioned reducing magnesium compound and non-reducing magnesium compound, the magnesium compound may be a complex compound, a complex compound or another compound of the above magnesium compound and another metal. It may be a mixture with a metal compound. Further, it may be a mixture of two or more of the above compounds.

In the present invention, among these, magnesium compounds having no reducing property are preferable, and halogen-containing magnesium compounds are particularly preferable, and among these, magnesium chloride, alkoxy magnesium chloride, and allyloxy magnesium chloride are preferably used. Be done.

In the present invention, examples of the electron donor used in the preparation of the solid titanium catalyst component (a) include organic carboxylic acid esters and polyvalent carboxylic acid esters which will be described later. Specifically, they are represented by the following formula. And a compound having a skeleton of

[0047]

[Chemical 9]

[0048]

[Chemical 10]

[0049]

[Chemical 11]

[0050]

[Chemical 12]

In the above formula, R ¹ represents a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ and R ⁶ represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ Represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
At least one of R ³ and R ⁴ is preferably a substituted or unsubstituted hydrocarbon group. R ³ and R ⁴ may be connected to each other to form a ring structure. Examples of the substituted hydrocarbon group include substituted hydrocarbon groups containing a heteroatom such as N, O and S, and for example, -C-O-C.
-, - COOR, -COOH, -OH , -SO 3 H, -
Substituted hydrocarbon groups having a structure such as C—N—C— and —NH ₂ are mentioned.

Of these, a diester derived from a dicarboxylic acid in which at least one of R ¹ and R ² is an alkyl group having 2 or more carbon atoms is preferable. Specific examples of the polyvalent carboxylic acid ester, diethyl succinate, dibutyl succinate, diethyl methyl succinate, α-
Diisobutyl methyl glutarate, dibutyl methyl malonate, diethyl malonate, diethyl ethyl malonate, isopropyl diethyl malonate, diethyl butyl malonate,
Diethyl phenylmalonate, diethyl diethylmalonate, diethyl allyl malonate, diethyl diisobutylmalonate, diethyl dinormal butylmalonate, dimethyl maleate, monooctyl maleate, diisooctyl maleate, diisobutyl maleate, diisobutyl butyl maleate, butyl maleate Fatty acid polycarboxylic acid esters such as diethyl acidate, diisopropyl β-methylglutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisobutyl itaconate, diisooctyl citraconic acid, dimethyl citraconic acid; 1,2-cyclohexane Aliphatic polycarbonates such as diethyl carboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadicate Rubonic acid ester; monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate,
Monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, mononormal butyl phthalate, ethyl normal butyl phthalate, di-n-propyl phthalate,
Diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, Examples include aromatic polycarboxylic acid esters such as dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate; esters derived from heterocyclic polycarboxylic acids such as 3,4-furandicarboxylic acid.

Other examples of the polycarboxylic acid ester include diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, n-octyl sebacate, di-2-ethylhexyl sebacate and the like. The esters derived from the long-chain dicarboxylic acids of

Among these polyvalent carboxylic acid esters,
A compound having a skeleton represented by the above-mentioned general formula is preferable, more preferably an ester derived from phthalic acid, maleic acid, substituted malonic acid and the like and an alcohol having 2 or more carbon atoms, and phthalic acid and a carbon atom. Number 2
Diesters obtained by the reaction with the above alcohols are particularly preferable.

As the polyvalent carboxylic acid ester, it is not always necessary to use the polyvalent carboxylic acid ester as described above as a starting material, and the polyvalent carboxylic acid ester may be used in the process of preparing the solid titanium catalyst component (a). A compound capable of inducing an ester may be used to form a polyvalent carboxylic acid ester in the step of preparing the solid titanium catalyst component (a).

In the present invention, electron donors other than polyvalent carboxylic acids that can be used when preparing the solid titanium catalyst component (a) include alcohols, amines, amides, as described below. Ethers, ketones, nitriles, phosphines, stipines, arsines, phosphoramides, esters, thioethers,
Thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (aryloxy) silanes and other organosilicon compounds, organic acids, and amides of metals belonging to Groups I to IV of the periodic table And salts.

In the present invention, the solid titanium catalyst component (a) can be produced by bringing the above-mentioned magnesium compound (or metallic magnesium), electron donor and titanium compound into contact with each other. In order to produce the solid titanium catalyst component (a), a known method of preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound and an electron donor can be adopted. The above components may be contacted in the presence of other reaction agents such as silicon, phosphorus and aluminum.

The production method of these solid titanium catalyst components (a) will be briefly described below with some examples. (1) A method of reacting a magnesium compound or a complex compound composed of a magnesium compound and an electron donor with a titanium compound in a liquid phase. This reaction may be carried out in the presence of a grinding aid or the like. Further, when the reaction is performed as described above, the solid compound may be pulverized. Furthermore, when the reaction is carried out as described above, each component may be pretreated with an electron donor and / or a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound. In this method, the electron donor is used at least once. (2) A liquid magnesium compound having no reducing property,
A method of reacting a liquid titanium compound in the presence of an electron donor to deposit a solid titanium composite agent. (3) A method of further reacting a titanium compound with the reaction product obtained in (2). (4) In the reaction product obtained in (1) or (2),
A method of further reacting an electron donor and a titanium compound. (5) A solid compound obtained by pulverizing a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor in the presence of a titanium compound is treated with any of halogen, a halogen compound and an aromatic hydrocarbon. Method. In this method, the magnesium compound or the complex compound consisting of the magnesium compound and the electron donor may be crushed in the presence of a crushing aid or the like. Alternatively, the magnesium compound or the complex compound consisting of the magnesium compound and the electron donor may be pulverized in the presence of the titanium compound, pretreated with a reaction aid, and then treated with halogen or the like. Examples of the reaction aid include organic aluminum compounds and halogen-containing silicon compounds. In this method, the electron donor is used at least once. (6) A method of treating the compound obtained in (1) to (4) with halogen, a halogen compound, or an aromatic hydrocarbon. (7) A method of bringing a reaction product of a metal acid compound, dihydrocarbyl magnesium and a halogen-containing alcohol into contact with an electron donor and a titanium compound. (8) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxy magnesium, or aryloxy magnesium is reacted with an electron donor, a titanium compound, and / or a halogen-containing hydrocarbon.

Among the methods for preparing the solid titanium catalyst component (a) described in (1) to (8) above, a method using a liquid titanium halide during the catalyst preparation, a method using a titanium compound, or a titanium compound is used. When using the compound, a method using a halogenated hydrocarbon is preferable.

The amount of each of the above-mentioned components used for preparing the solid titanium catalyst component (a) varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of electron donor is about 1 mol per mol of the magnesium compound. 0.01-5
The titanium compound is present in an amount of about 0.01-500 moles, preferably 0.05-3, in an amount of about 0.05-2 moles.
Used in an amount of 00 mol.

The solid titanium catalyst component (a) thus obtained contains magnesium, titanium, halogen and an electron donor as essential components. In this solid titanium catalyst component (a), the halogen / titanium (atomic ratio) is about 4 to 200, preferably about 5 to 100,
The electron donor / titanium (molar ratio) is about 0.1-10,
Desirably, it is about 0.2 to about 6, and the magnesium / titanium (atomic ratio) is desirably about 1 to 100, preferably about 2 to 50.

The solid titanium catalyst component (a) contains a magnesium halide having a smaller crystal size than that of a commercially available magnesium halide, and usually has a specific surface area of about 50 m ² / g or more, preferably about 60-1, 000m
² / g, more preferably about 100 to 800 m ² / g. Since the solid titanium catalyst component (a) forms the catalyst component by integrating the above components, the composition thereof is not substantially changed by washing with hexane.

Such a solid titanium catalyst component (a) is
It can be used alone, or can be diluted with an inorganic compound or an organic compound such as a silicon compound, an aluminum compound or a polyolefin. When a diluent is used, it exhibits high catalytic activity even if it has a specific surface area smaller than that described above.

A method for preparing such a highly active titanium catalyst component is described, for example, in JP-A-50-108385.
50-126590, 51-20297, 51-28189, 51-64586, 51-92885, 51-1366
25, 52-87489, 52-100596, and
No. 52-147688, No. 52-104593, No. 53-2580, No. 53-40093, No. 53-40094, No. 53-430
No. 94, No. 55-135102, No. 55-135103,
55-152710, 56-811, 56-11908, 56-18606, 58-83006, 58-1387.
05 publication, 58-138706 publication, 58-138707 publication,
58-138708, 58-138709, 58-1387
No. 10, gazette 58-138715 gazette, gazette 60-23404 gazette, the same
No. 61-21109, No. 61-37802, No. 61-37803.

As the organoaluminum compound catalyst component (b) used in the present invention, a compound having at least one Al-carbon bond in the molecule can be used. Examples of such compounds include (i) the general formula (R ¹ ) _m Al (O (R ² )) _n H _p X _q (wherein, R ¹ and R ² usually have 1 to 15 carbon atoms). ,
It is preferably a hydrocarbon group containing 1 to 4 groups, which may be the same or different from each other. X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <
3 and q are numbers satisfying 0 ≦ q <3, and m +
an organic aluminum compound represented by the formula (n + p + q = 3), (ii) the general formula (M ¹ ) Al (R ¹ ) ₄ (wherein M ¹ is Li, Na, K, and R ¹ is the above (i). And a complex alkylated product of a group I metal represented by R ¹ ) and aluminum.

Examples of the organoaluminum compound belonging to the above (i) include the following compounds. Formula _{^{(R 1) n Al (O}} (R 2)) in _3-m (wherein, R ¹ R ¹ and R ² in the (i), R
Same as ² . m is a number preferably satisfying 1.5 ≦ m ≦ 3), the general formula ^{_{(R 1) m AlX 3-}} m ( wherein, R ¹ is the (i) the same .X is halogen and R ¹ in, m is a number preferably satisfying 0 <m <3), the general formula ^{_{(R 1) m AlH 3-}} m ( wherein, R ¹ is (i) above same .m preferably 2 ≦ a R ¹ in m <is a number satisfying 3), the general formula _{^{(R 1) m Al (oR}} 2) n X q ( wherein, R ¹ and R ² are the (i) R ¹ in, R
Same as ² . X is halogen, m is 0 <m ≦ 3, n is 0 ≦ n
<3, q is a number satisfying 0 ≦ q <3, and m + n + q
= 3) and the like.

Specific examples of the aluminum compound belonging to (i) above include trialkyl aluminum such as triethyl aluminum and tributyl aluminum; trialkenyl aluminum such as triisoprenyl aluminum; diethyl aluminum ethoxide and dibutyl aluminum butoxide. Dialkyl aluminum alkoxide; alkyl aluminum sesquialkoxide such as ethyl aluminum sesquiethoxide, butyl aluminum sesquibutoxide; (R ¹ ) _2.5 A
a partially alkoxylated alkylaluminum having an average composition such as 1 (O (R ² )) _0.5 ;
Dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide; alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide Partially halogenated alkyl aluminum such as alkyl aluminum dihalide; Dialkyl aluminum hydride such as diethyl aluminum hydride, dibutyl aluminum hydride; Alkyl aluminum dihydride such as ethyl aluminum dihydride, propyl aluminum dihydride Partially hydrogenated Kill aluminum; ethylaluminum ethoxy chloride, butyl aluminum butoxide cycloalkyl chloride, can be mentioned partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxy bromide.

As a compound similar to the aluminum compound belonging to the above (i), an organoaluminum compound in which two or more aluminums are bonded via an oxygen atom or a nitrogen atom can be mentioned. Such compounds include, for example, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ ,
_{(C 4 H 9) 2 AlOAl} (C 4 H 9) 2, (C 2 H 5) 2 Al
Examples thereof include N (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ and methylaminooxane.

The compounds belonging to (ii) above include L
Examples thereof include iAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . Among these, it is particularly preferable to use trialkylaluminum or alkylaluminum to which two or more kinds of aluminum compounds described above are bound.

The electron donor catalyst component (c) includes oxygen-containing compounds such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides and alkoxysilanes. An electron donor, a nitrogen-containing electron donor such as ammonia, amine, nitrile, or isocyanate, or a polyvalent carboxylic acid ester as described above can be used.

More specifically, carbon such as methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol. Alcohols having 1 to 18 atoms; phenol, cresol, xylenol, ethylphenol, propylphenol,
6 to 20 carbon atoms which may have a lower alkyl group, such as nonylphenol, cumylphenol and naphthol
Phenols; acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone, and other ketones having 3 to 15 carbon atoms;
Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, propionic acid. Ethyl, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, Cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, methyl malo Diisobutyl, cyclohexene carboxylic di -n- hexyl, nadic diethyl, tetrahydrophthalic acid diisopropyl, diethyl phthalate, diethyl phthalate, diisobutyl phthalate, di -
Organic acid esters having 2 to 30 carbon atoms, such as n-butyl, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate; acetyl chloride, benzoyl chloride, toluyl chloride, anise. 2 to 1 carbon atoms such as acid chloride
Acid halides of 5; methyl ether, ethyl ether,
Ethers having 2 to 20 carbon atoms such as isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine , Amines such as piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylenediamine; nitriles such as acetonitrile, benzonitrile and tolunitrile; acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride Be done.

As the electron donor (c), an organosilicon compound represented by the following general formula [II] can be used. R _n Si (OR ′) _4-n ... [1] (In the formula, R and R ′ are hydrocarbon groups, and n is 0 <n.
It is a number that satisfies <4. ) Specific examples of the organosilicon compound represented by the above general formula [1] include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane,
Diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-ο-tolyldimethoxysilane,
Bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane , Ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n
-Propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltoluethoxysilane, ethyltriethoxysilane,
Vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-
Aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyl Dimethoxysilane,
Ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxy silane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, etc. are used.

Of these, ethyltriethoxysilane, n-
Propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis
Preferred are -p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane and diphenyldiethoxysilane.

Further, as the electron donor catalyst component (c), an organosilicon compound represented by the following general formula [2] can be used. SiR ¹ R ² _m (OR ³ ) _3-m ... [2] (In the formula, R ¹ is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R ² has an alkyl group, a cyclopentyl group and an alkyl group. A group selected from the group consisting of a cyclopentyl group, R ³ is a hydrocarbon group, and m is a number satisfying 0 ≦ m ≦ 2.) In the above formula [2], R ¹ is a cyclopentyl group or an alkyl group. And R ¹ is a cyclopentyl group having an alkyl group such as a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl group, and a 2,3-dimethylcyclopentyl group, in addition to the cyclopentyl group. Can be mentioned.

In the above formula [2], R ² is any one of an alkyl group, a cyclopentyl group or a cyclopentyl group having an alkyl group, and R ² is, for example, a methyl group, an ethyl group, a propyl group, An allyl group such as an isopropyl group, a butyl group and a hexyl group, or a cyclopentyl group exemplified as R ¹ and a cyclopentyl group having an alkyl group can be mentioned in the same manner.

In the above formula [2], R ³ is a hydrocarbon group, and examples of R ³ include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group.

Of these, it is preferable to use an organosilicon compound in which R ¹ is a cyclopentyl group, R ² is an alkyl group or a cyclopentyl group, and R ³ is an alkyl group, particularly a methyl group or an ethyl group.

Specific examples of such organosilicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane and cyclopentyltriethoxysilane; Dialkoxysilanes such as dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, di Cyclopentylmethylmethoxysilane,
Examples include monoalocoxysilanes such as dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane. Among these electron donors, organic carboxylic acid esters or organic silicon compounds are preferable, and organic silicon compounds are particularly preferable.

The olefin polymerization catalyst used in the present invention is formed from the solid titanium catalyst component (a) as described above, the organoaluminum compound catalyst component (b), and the electron donor catalyst component (c). In the present invention, the catalyst for olefin polymerization is used to produce higher α-olefins, α,
The ω-diene and the non-conjugated diene are polymerized. The olefin polymerization catalyst is used to prepolymerize α-olefins or higher α-olefins, and then the catalyst is used to The ω-diene and the non-conjugated diene can also be polymerized (main polymerization). During pre-polymerization, 0.1 to 500 per 1 g of olefin polymerization catalyst
g, preferably 0.3 to 300 g, particularly preferably 1 to
Prepolymerize α-olefins or higher α-olefins in an amount of 100 g.

In the prepolymerization, a catalyst having a much higher concentration than the catalyst concentration in the system in the main polymerization can be used.
The concentration of the solid titanium catalyst component (a) in the prepolymerization is
The amount is usually about 0.01 to 200 mmol, preferably about 0.1 to 100 mmol, and particularly preferably 1 to 50, in terms of titanium atom, per liter of an inert hydrocarbon medium described later.
It is desirable to set it in the millimolar range.

The amount of the organoaluminum catalyst component (b) is
0.1 to 500 g per 1 g of the solid titanium catalyst component (a),
The amount is preferably such that 0.3 to 300 g of a polymer is produced, and is usually about 0.1 to 100 mol, preferably about 0.1 per mol of titanium atom in the solid titanium catalyst component (a). An amount of 5 to 50 mol, particularly preferably 1 to 20 mol is desirable.

The electron donor catalyst component (c) is contained in an amount of 0.1 to 5 per mol of titanium atom in the solid titanium catalyst component (a).
It is preferably used in an amount of 0 mol, preferably 0.5 to 30 mol, particularly preferably 1 to 10 mol.

The prepolymerization is preferably carried out under mild conditions by adding an olefin or higher α-olefin and the above catalyst component to an inert hydrocarbon medium. Examples of the inert hydrogen medium used at this time include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Examples thereof include alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and mixtures thereof. Of these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons.
The olefin or higher α-olefin itself may be prepolymerized in a solvent, or may be prepolymerized in a substantially solvent-free state.

The higher α-olefin used in the prepolymerization may be the same as or different from the higher α-olefin used in the main polymerization described later. The reaction temperature in the prepolymerization is usually about −20 to + 100 ° C., preferably about −2.
It is desirable that the temperature is in the range of 0 to + 80 ° C, more preferably 0 to + 40 ° C.

In the prepolymerization, a molecular weight modifier such as hydrogen can be used. Such a molecular weight modifier has an intrinsic viscosity [η] of the polymer obtained by the prepolymerization measured in a decalin solvent at 135 ° C. of about 0.
It is desirable to use it in an amount of 2 dl / g or more, preferably about 0.5 to 10 dl / g.

The prepolymerization is carried out so that about 0.1 to 500 g, preferably about 0.3 to 300 g, particularly preferably 1 to 100 g of a polymer is produced per 1 g of the solid titanium catalyst component (a), as described above. It is desirable to do this. If the prepolymerization amount is too large, the production efficiency of the olefin polymer may decrease.

The prepolymerization can be carried out batchwise or continuously. The solid titanium catalyst component (a) or the solid titanium catalyst component (a) obtained by prepolymerizing the olefin polymerization catalyst as described above, the organoaluminum catalyst component (b), and the electron donor catalyst component ( in the presence of an olefin polymerization catalyst formed from
-Copolymerization (main polymerization) of olefin, α, ω-diene and non-conjugated diene.

In the copolymerization (main polymerization) of the higher α-olefin, the α, ω-diene and the non-conjugated diene, in addition to the above-mentioned olefin polymerization catalyst, olefin polymerization is performed as an organoaluminum compound catalyst component. The same component as the organoaluminum compound catalyst component (b) used in the production of the catalyst for use can be used. In the copolymerization (main polymerization) of higher α-olefins, α, ω-dienes and non-conjugated dienes, the electron donor catalyst component used in the production of the olefin polymerization catalyst was used. Components similar to the donor catalyst component (c) can be used. In addition, the organoaluminum compound and the electron donor used in the copolymer (main polymerization) of the higher α-olefin, the α, ω-diene, and the non-conjugated diene do not necessarily prepare the above olefin polymerization catalyst. It need not be the same as the organoaluminum compound and electron donor used in the process.

The copolymerization (main polymerization) of the higher α-olefin, the α, ω-diene and the non-conjugated diene is usually carried out in the liquid phase. As the reaction medium for the main polymerization, the above-mentioned inert hydrocarbon medium may be used, or an olefin which is liquid at the reaction temperature may be used.

In the copolymerization (main polymerization) of a higher α-olefin, an α, ω-diene and a non-conjugated diene, the solid titanium catalyst component (a) is converted into titanium atom per liter of polymerization volume, It is usually used in an amount of about 0.001 to about 1.0 mmol, preferably about 0.005 to 0.5 mmol. Further, the organoaluminum catalyst component (b)
Is generally about 1 to 2,000 mol, preferably about 5 to about 5 mol of metal atom in the organoaluminum compound catalyst component (b), relative to 1 mol of titanium atom in the solid titanium catalyst component (a).
It is used in an amount such that it is 500 mol. Further, the electron donor catalyst component (c) is usually about 0.005 mol per 1 mol of metal atom in the organoaluminum compound catalyst component (b).
It is used in an amount of 1 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.05 to 1 mol.

If hydrogen is used during the main polymerization, the molecular weight of the resulting polymer can be adjusted. In the present invention, the polymerization temperature of the higher α-olefin, the α, ω-diene and the non-conjugated diene is usually about 20 to 200 ° C, preferably about 40 to 100 ° C, and the pressure is usually atmospheric pressure to 100
kg / cm ^{2 It is} preferably set to normal pressure to 50 kg / cm ² . In the copolymerization (main polymerization) of higher α-olefin, α, ω-diene, and non-conjugated diene, polymerization is
It can be carried out by any of a batch system, a semi-continuous system and a continuous system. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

Conductivity imparting agent (B) The conductivity imparting agent (B) used in the present invention is a conventionally known conductivity imparting agent (conductivity filler), specifically,
Examples thereof include carbon black, carbon fiber, metal powder and metal fiber. These conductivity-imparting agents are used alone or in combination. Carbon black is preferred in the present invention.

In the present invention, the conductivity-imparting agent (B)
Is the above-mentioned higher α-olefin copolymer rubber (A) 1
5 to 200 parts by weight, preferably 40 to 100 parts by weight
Used in amounts of up to 200 parts by weight.

The conductive rubber according to the present invention is prepared by blending 5 to 200 parts by weight of the conductivity-imparting agent (B) with 100 parts by weight of the above-mentioned higher α-olefin copolymer rubber (A). However, it may contain an auxiliary agent used in the vulcanization reaction, for example, a metal activator, a compound having an oxymethylene structure, and an anti-scorch agent. Further, the conductive rubber according to the present invention, a reinforcing agent for rubber,
The addition of additives such as a filler, a softening agent, an antiaging agent, and a processing aid further improves the moldability during the production of the conductive rubber. Therefore, in the present invention, it is preferable to use the above additives.

Manufacturing Method of Conductive Rubber The conductive rubber according to the present invention is preferably manufactured, for example, by the following method.

That is, a vulcanizing agent is added to a rubber compound containing the above-mentioned higher α-olefin copolymer rubber (A) and the conductivity-imparting agent (B) to effect vulcanization.
The conductive rubber according to the present invention is obtained.

Vulcanization is performed by adding a vulcanizing agent to the higher α-olefin copolymer rubber (A) and the conductivity-imparting agent (B), but the vulcanizing agent is added before molding. Good.
Sulfur vulcanization and organic peroxide vulcanization are effective as vulcanization methods for the higher α-olefin copolymer rubber (A).

Specific examples of sulfur compounds used in sulfur vulcanization include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dimethyldithiocarbamate. .. Of these, sulfur is preferably used. Sulfur compounds are
It 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 higher α-olefin copolymer rubber (A).

When a sulfur compound is used as a vulcanizing agent, it is preferable to use a vulcanization accelerator together. Specific examples of the vulcanization accelerator include N-cyclohexyl-2-
Benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, N, N-
Diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole, 2- (2,4-
Dinitrophenyl) mercaptobenzothiazole, 2-
Thiazole compounds such as (2,6-diethyl-4-morpholinothio) benzothiazole and dibenzyldithiazyl disulfide; diphenylguanidine, triphenylguanidine, diorthotolylguanidine, orthotriyl-by-
Guanidine compounds such as guanide and diphenylguanidine phthalate; acetaldehyde-aniline reaction products, butyraldehyde-aniline condensates, hexamethylenetetramine, aldehyde amines such as acetaldehyde ammonia, or aldehyde-ammonia compounds; 2
-Imidazoline compounds such as mercaptoimidazoline;
Thiourea compounds such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorsotolylthiourea; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide Thiuram compounds such as zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate,
Examples thereof include dithioate-based compounds such as sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium diethyldithiocarbamate; and compounds such as xanthate-based compounds such as zinc dibutylxanthate.

These vulcanization accelerators are contained in an amount of 0.1 to 100 parts by weight of the higher α-olefin copolymer rubber (A).
It is used in an amount of 20 parts by weight, preferably 0.2 to 10 parts by weight.

Specific examples of the organic peroxide-based vulcanizing agent used for vulcanizing the organic peroxide include dicumyl peroxide and 2,5-dimethyl-2,5-di (tert-butylperoxy). ) Hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-
2,5-di (tert-butylperoxy) hexyne-3,
Examples thereof include di-tert-butyl peroxide, di-tert-butylperoxy-3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide and the like. Among them, dicumyl peroxide, di-tert-butyl peroxide and di-tert-butylperoxy-3,3,5-trimethylcyclohexane are preferably used. These organic peroxides are used alone or in combination of two or more.

In the present invention, the above-mentioned organic peroxide vulcanizing agent is a higher α-olefin copolymer rubber (A) 1
It is usually used in an amount of 0.0003 to 0.05 mol, preferably 0.001 to 0.03 mol, relative to 00 g, but the optimum amount thereof should be appropriately determined according to the required physical property values. Is desirable.

In the present invention, when an organic peroxide is used as a vulcanizing agent, it is desirable to use a vulcanizing auxiliary together. Specific examples of the vulcanization aid include sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; Maleimide compounds, such as divinylbenzene. Such a vulcanization aid is used in an amount of 0.5 to 2 mol, preferably about equimolar, relative to 1 mol of the organic peroxide used.

Further, in the production of the conductive rubber according to the present invention, the following vulcanization aid is further used in combination with the higher α-olefin copolymer rubber (A) together with the above vulcanization agent. It is preferable to add them simultaneously.

Examples of the vulcanization aid which is preferably used in combination with the vulcanizing agent include a metal activator, a compound having an oxymethylene structure, an anti-scorch agent and the like. Specific examples of the metal activator include magnesium oxide, zinc white, zinc carbonate, higher fatty acid zinc, red lead, litharge, calcium oxide and the like. These metal activators are higher α-olefin copolymer rubbers (A)
3 to 15 parts by weight, preferably 5 to 100 parts by weight
Used in an amount of from 10 to 10 parts by weight.

In order to cope with various rubber processing steps, it is desirable to add a compound having an oxymethylene structure and a scorch inhibitor. Specific examples of the compound having an oxymethylene structure used in the present invention include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol. These compounds having an oxymethylene structure are usually used in an amount of 0.1 to 100 parts by weight with respect to 100 parts by weight of the higher α-olefin copolymer rubber (A).
It is used in an amount of 10 parts by weight, preferably 1-5 parts by weight.

As the anti-scorch agent, a known anti-scorch agent can be used, and specific examples thereof include maleic anhydride and salicylic acid. The above-mentioned scorch inhibitor is generally used in an amount of 0.2 to 5 parts by weight, preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the higher α-olefin copolymer rubber (A). Be done.

When the conductive rubber according to the present invention contains additives such as a rubber reinforcing agent, a filler, a softening agent, an antiaging agent and a processing aid, the property as a conductive rubber is further improved. These additives may be appropriately mixed before or after vulcanization of the higher α-olefin copolymer rubber (A).

Specific examples of the rubber reinforcing agent used in combination with the vulcanizing agent include finely divided silicic acid, and short fibers such as cotton, polyester, nylon, aramid, and glass.

As the filler, specifically, light calcium carbonate, heavy calcium carbonate, talc, clay, silica and the like are used. These reinforcing agents and fillers are
Higher α-olefin copolymer rubber (A) 10
It is blended in an amount of up to 300 parts by weight, preferably up to 200 parts by weight, based on 0 part by weight.

As the softening agent, a softening agent generally used for rubber can be used. Specifically, petroleum-based softening agents such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petrolatum; coal. Coal tar type softeners such as tar and coal tar pitch; Fat oil type 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 or fatty acid salts thereof such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate, zinc laurate; petroleum resin, atactic polypropylene, coumarone indene Synthetic polymeric substances such as resins; dioctyl phthalate, dioctyl adipate,
Examples thereof include ester plasticizers such as dioctyl sebacate.

The blending amount of these softening agents can be appropriately selected depending on the use of the vulcanized product, but the blending amount is usually higher α-
The maximum amount is 100 parts by weight, preferably the maximum amount is 70 parts by weight, based on 100 parts by weight of the olefin copolymer rubber (A).

Further, by using an antioxidant, the material life of the conductive rubber according to the present invention can be extended. This is the same as in the case of normal rubber. Specific examples of the antioxidant used in this case include aromatic secondary amine stabilizers such as phenylnaphthylamine and N, N'-di-2-naphthylphenylenediamine; dibutylhydroxytoluene, tetrakis [methylene] (3,5
-Di-t-butyl-4-hydroxy) hydrocinnamate]
Phenolic stabilizers such as methane; bis [2-methyl-4-
A thioether stabilizer such as (3-n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide;
Examples thereof include dithiocarbamate-based stabilizers such as nickel dibutyldithiocarbamate. These antioxidants may be blended alone or in combination of two or more.

Such an anti-aging agent is added in an amount of 0.1 parts by weight per 100 parts by weight of the higher α-olefin copolymer rubber (A).
It is used in an amount of 1 to 5 parts by weight, preferably 0.5 to 3 parts by weight.

As the processing aid, compounds used in the processing of ordinary rubber can be used, and specifically, ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, calcium stearate,
Examples thereof include higher fatty acids, salts thereof and esters thereof such as zinc stearate and esters of the above acids.

These processing aids are usually used in an amount of about 1 per 100 parts by weight of the higher α-olefin copolymer rubber (A).
It is used in an amount of 0 parts by weight or less, preferably about 1 to 5 parts by weight.

Further, in the present invention, in the conductive rubber composition, natural rubber, in the range not impairing the object of the present invention,
Diene rubbers such as SBR, IR and BR, and other types of rubbers such as EPDM and chlorosulfonated polyethylene can also be blended.

The conductive rubber according to the present invention can be obtained, for example, by preparing and molding a rubber compound by the following method. That is, the higher α-olefin-based copolymer rubber (A), the conductivity-imparting agent (B), and necessary additives such as a reinforcing agent, a filler, and a softening agent are mixed with a mixer such as a Banbury mixer. After kneading at a temperature of 80 to 170 ° C. for about 3 to 10 minutes, a vulcanizing agent and a vulcanization aid are additionally mixed using rolls such as open rolls, and a roll temperature of about 40 to 80 ° C. for about 5 to 30. The mixture is kneaded for a minute and then dispensed to prepare a ribbon-shaped or sheet-shaped rubber compound.

Then, the rubber compound prepared as described above is molded by using a roll machine, a calender molding machine, an extrusion molding machine or the like, and the molded product is heated to 130 to 220.
Vulcanization is performed by heating at 1 ° C for 1 to 60 minutes to form a conductive rubber.

The conductive rubber can be obtained by molding and vulcanizing the above rubber compound in a mold using a press molding machine or an injection molding machine. In this case, the mold temperature is usually 130 to 220 ° C., and the time required for vulcanization is 1 to 60 minutes.

The conductive rubber produced as described above is excellent in dynamic fatigue resistance (flexing fatigue resistance) and also in conductivity.

[0122]

Since the conductive rubber according to the present invention is composed of a vulcanized product containing a specific higher α-olefin copolymer rubber and a conductivity-imparting agent in a specific ratio, dynamic fatigue resistance is improved. It has the effect of excellent conductivity and excellent conductivity.

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

[0124]

Example 1 [Preparation of Solid Titanium Catalyst Component (a)] 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated and reacted at 130 ° C. for 2 hours to form a uniform solution. 21.3 g of phthalic anhydride was added to this solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in this homogeneous solution. After cooling the homogeneous solution thus obtained to room temperature, 75 ml of titanium tetrachloride 2 kept at -20 ° C
The entire amount was added dropwise to 00 ml over 1 hour. After the completion of charging, the temperature of this mixed solution was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.22 g of diisobutyl phthalate was added, and the mixture was kept at the same temperature for 2 hours with stirring. After the completion of the reaction for 2 hours, the solid portion was collected by hot filtration, and the solid portion was resuspended in 275 ml of titanium tetrachloride, and then heated and reacted again at 110 ° C. for 2 hours. After completion of the reaction, hot filtration is performed again to collect a solid portion, and 1
It was sufficiently washed with 10 ° C. decane and hexane until no free titanium compound was detected in the washing liquid. The titanium catalyst component (a) prepared by the above operation was stored as a decane slurry, and a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component (a) thus obtained was 2.5% by weight of titanium and 6% of chlorine.
5% by weight, 19% by weight of magnesium and 13.5% by weight of diisobutyl phthalate. [Polymerization] Using a 4-liter glass polymerization vessel equipped with a stirring blade, the copolymerization reaction of octene-1, 1,5-hexadiene, and 7-methyl-1,6-octadiene was continuously carried out. It was

In other words, from the top of the polymerization vessel, octene-1,
A hexane solution of 1,5-hexadiene and 7-methyl-1,6-octadiene was added in the polymerization vessel at an octene-1 concentration of 200 g / liter and a 1,5-hexadiene concentration of 3
The concentration of titanium in the polymerization vessel was 2.1 liters per hour, and the hexane slurry solution of the solid titanium catalyst component (a) as a catalyst was 9 g / liter and the concentration of 7-methyl-1,6-octadiene was 10 g / liter. Is 0.4 liter per hour, and a hexane solution of triisobutylaluminum is 1 liter per hour so that the aluminum concentration in the polymerization vessel is 8 mmol / liter. The hexane solution had a silane concentration of 2.6 mmol / m in the polymerization vessel.
It was continuously fed into each of the polymerization vessels at a rate of 0.5 liter per hour so as to be 1 liter. On the other hand, the polymerization solution in the polymerization vessel was continuously withdrawn from the lower portion of the polymerization vessel so as to always have a volume of 2 liters. Further, from the upper part of the polymerization vessel, hydrogen was supplied at a rate of 1 liter / hour and nitrogen was supplied at a rate of 50 liter / hour. The copolymerization reaction was carried out at 50 ° C. by circulating warm water in a jacket attached outside the polymerization vessel.

Next, a small amount of methanol was added to the polymerization solution extracted from the lower part of the polymerization vessel to stop the copolymerization reaction, and this polymerization solution was poured into a large amount of methanol to precipitate the copolymer. After the copolymer was thoroughly washed with methanol, it was dried under reduced pressure at 140 ° C for a whole day and night.
A 1,5-hexadiene / 7-methyl-1,6-octadiene copolymer was obtained at a rate of 90 g / h.

Octene-1 constituting the obtained copolymer
And 1,5-hexadiene molar ratio (octene-1 /
1,5-hexadiene) was 68/32, and the 7-methyl-1,6-octadiene content was 3.1 mol%. The intrinsic viscosity [η] of the copolymer measured in decalin at 135 ° C. was 4.8 dl / g.

The above polymerization conditions are shown in Table 1.

[0129]

[Table 1]

(Production of Vulcanized Rubber) Octene-1.multidot. Produced by the above method as a higher α-olefin copolymer rubber (A) using an 8-inch open roll.
1,5-Hexadiene / 7-methyl-1,6-octadiene copolymer rubber (1-a) was compounded and kneaded according to Table 2 to obtain an unvulcanized compounded rubber. The roll surface temperature at this time is 50 ° C. for both the front roll and the rear roll, and the rotation number of the roll is 16 rpm for the front roll and 18 for the rear roll.
It was rpm.

[0131]

[Table 2]

The above compounded rubber was vulcanized by a press heated to 160 ° C. for 20 minutes, and the vulcanized rubber sheet obtained was subjected to the following tests. The test items are as follows. [Test items] Tensile test, bending test, specific volume resistivity [Test method] Tensile test, bending test is JIS K 63
It was measured according to 01.

That is, in the tensile test, the tensile strength (T
_B ) and elongation (E _B ) were measured. In the bending test, resistance to crack growth was examined with a DeMatcher test machine. That is, the number of times of bending until the crack became 15 mm was measured.

Volume resistivity is measured according to ASTM D257
Was measured according to. The results are shown in Table 3.

[0135]

Example 2 In Example 1, the copolymer rubber (1-
Instead of a), as shown in Table 1, hexene-1,1,5-hexadiene-7 obtained by copolymerization in the same manner as in Example 1 except that the higher α-olefin and the polymerization conditions were changed. The same procedure as in Example 1 was carried out except that the methyl-1,6-octadiene copolymer rubber (1-b) was used.

The results are shown in Table 3.

[0137]

Example 3 In Example 1, the copolymer rubber (1-
Instead of a), as shown in Table 1 above, decene-1,1,6-heptadiene-7 obtained by copolymerization in the same manner as in Example 1 except that the higher α-olefin and the polymerization conditions were changed. -Methyl-1,6-octadiene copolymer rubber (1
Example 1 was repeated except that -c) was used.

The results are shown in Table 3.

[0139]

Example 4 The procedure of Example 1 was repeated, except that the amount of acetylene black was changed to 100 parts by weight.

The results are shown in Table 3.

[0141]

Example 5 Example 1 was repeated except that the amount of acetylene black was changed to 200 parts by weight.

The results are shown in Table 3.

[0143]

Example 6 In Example 1, instead of acetylene black, Ketjen Black EC [surface area (nitrogen adsorption method) 1000 m ² / g, average particle diameter (nitrogen adsorption method) 30 μm]
m; manufactured by Lion Akzo Co., Ltd.] was used in the same manner as in Example 1 except that 5 parts by weight was used.

The results are shown in Table 3.

[0145]

[Embodiment 7] In Embodiment 6, Ketjen Black E
Example 6 was repeated except that the amount of C was changed to 40 parts by weight.

The results are shown in Table 3.

[0147]

COMPARATIVE EXAMPLE 1 The procedure of Example 1 was repeated except that the amount of acetylene black was changed to 250 parts by weight, but kneading was difficult and the desired vulcanized rubber could not be obtained. It was

[0148]

Comparative Example 2 In Example 6, Ketjen Black E
Example 6 was repeated except that the amount of C was changed to 2 parts by weight.

The results are shown in Table 3.

[0150]

Comparative Example 3 The procedure of Example 1 was repeated except that silicone rubber was used in place of the higher α-olefin copolymer rubber.

The results are shown in Table 3.

[0152]

[Table 3]

[0153]

[Table 4]

[Brief description of drawings]

FIG. 1 is a flow chart showing a process for preparing an olefin polymerization catalyst used in the production of the higher α-olefin copolymer rubber used in the present invention.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical indication location H01B 1/20 Z 7244-5G (72) Inventor Kawasaki Masaaki Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture 6-1-2 Mitsui Petrochemical Co., Ltd. (72) Inventor Toshimasa Takada 6-1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Co., Ltd.

Claims (1)

[Claims] 1. A higher α-olefin having 6 to 20 carbon atoms, an α, ω-diene represented by the following general formula [I]:
And a non-conjugated diene represented by the following general formula [II], wherein the molar ratio of the higher α-olefin to the α, ω-diene is 9:
5/5 to 50/50 with a non-conjugated diene content of 0.0
1 to 30 mol% and 100 parts by weight of a higher α-olefin copolymer rubber having an intrinsic viscosity [η] measured in 135 ° C decalin of 1.0 to 10.0 dl / g; ) A conductive rubber comprising a vulcanized product containing 5 to 200 parts by weight of a conductivity-imparting agent; [In the formula, n is an integer of 1 to 3, and R ¹ and R ² are
Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms], [In the formula, n is an integer of 1 to 5 and R ³ is 1 carbon atom.
Represents to 4 alkyl groups, R ⁴ and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁴
Neither R ⁵ nor R ⁵ is a hydrogen atom].