JPH0770386A - Conductive rubber - Google Patents

Abstract

(57) [Summary] [Structure] A copolymer of a specific higher α-olefin, a specific aromatic ring-containing vinyl monomer, and a specific non-conjugated diene, wherein the higher α-olefin and the aromatic ring-containing vinyl monomer To 100 parts by weight of a higher α-olefin copolymer rubber [I] having a molar ratio with a non-conjugated diene content and an intrinsic viscosity within specific ranges, and a conductivity-imparting agent [II] 5 to 200.
An electrically conductive rubber comprising a vulcanized product of a rubber composition containing 1 part by weight. [Effect] The conductive rubber of the present invention has 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 (flexural 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 in which a conductive molecular structure is introduced into rubber molecules 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 a rubber in which a large amount of carbon black, powder of metal or the like, fibers and the like are mixed in silicone rubber or the like, and the conductivity of the rubber is
It is exhibited by the contact between the conductivity-imparting agents in the rubber and the proximity state at the atomic level.

As the above metals, noble metals such as gold and silver, which do not deteriorate in characteristics over time, are used. However, since these precious metals are expensive, their use is limited. 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 is normally insulative when no pressure is applied, and when a deformation strain occurs due to pressure or the like, the strained portion has a property of being conductive or semi-conductive. . Conventionally, conductive rubber has been widely used as a pressure-sensitive conductive material for 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 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 extensive studies 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- A higher α-olefin-based copolymer rubber obtained by copolymerizing an olefin, a specific aromatic ring-containing vinyl monomer and a specific non-conjugated diene was added with a conductivity-imparting agent and vulcanized. The inventors have found that they are particularly excellent in properties and are most suitable as a conductive rubber, and have completed the present invention.

[0009]

SUMMARY 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 A conductive rubber according to the present invention comprises: [I] a higher α-olefin having 6 to 20 carbon atoms,
A higher α-olefin copolymer comprising an aromatic ring-containing vinyl monomer represented by the following general formula (i) and a non-conjugated diene represented by the following general formula (ii):
The molar ratio of the higher α-olefin to the aromatic ring-containing vinyl monomer is 95/5 to 30/70, the (B) non-conjugated diene content is 0.01 to 30 mol%, and the (C) 135
Intrinsic viscosity [η] measured in decalin at ℃ is 1.0-10d
It is characterized by comprising a vulcanized product of a rubber composition containing 100 parts by weight of a higher α-olefin copolymer rubber of 1 / g and [II] 5 to 200 parts by weight of a conductivity-imparting agent.

[0011]

[Chemical 3]

In the formula (i), n is an integer of 0 to 5 and R
¹ , R ² and R ³ 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 and R
⁴ represents an alkyl group having 1 to ⁴ carbon atoms, R ⁵ and R ⁶ represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁵ and R ⁶ are not both hydrogen atoms.

[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 rubber composition containing a specific higher α-olefin copolymer rubber [I] and a conductivity-imparting agent [II].

Higher α-Olefin Copolymer [I] The higher α-olefin copolymer rubber [I] used in the present invention is represented by a specific higher α-olefin and the following general formula (i). It is composed of an aromatic ring-containing vinyl monomer and a non-conjugated diene represented by the following general formula (ii).

[Higher α-olefin] The higher α-olefin used in the present invention is an α-olefin having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms.
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-methyl-decene-1, 11-methyl-dodecene-1, 12-ethyl-tetradecene-1 and the like.

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.

[Aromatic Ring-Containing Vinyl Monomer] The aromatic ring-containing vinyl monomer used in the present invention is represented by the following general formula (i).

[0020]

[Chemical 5]

(In the formula, n is an integer of 0 to 5, and R ¹ ,
R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ) Specific examples of the above aromatic ring-containing vinyl monomer include styrene, allylbenzene, and 4-phenylbutene.
-1,3-phenylbutene-1,4- (4-methylphenyl) butene-1,4- (3-methylphenyl) butene-1,4- (2-methylphenyl) butene-1,4- (4 -Ethylphenyl) butene-
1,4- (4-butylphenyl) butene-1,5-phenylpentene-1,4-phenylpentene-1,3-phenylpentene-
1,5- (4-methylphenyl) pentene-1,4- (2-methylphenyl) pentene-1,3- (4-methylphenyl) pentene-1,6-phenylhexene-1,5-phenylhexene- 1,
4-phenylhexene-1,3-phenylhexene-1,6- (4-
Methylphenyl) hexene-1,5- (2-methylphenyl)
Hexene-1,4- (4-methylphenyl) hexene-1,3-
(2-Methylphenyl) hexene-1,7-phenylheptene
-1,6-phenylheptene-1,5-phenylheptene-1,4-
Phenylheptene-1,8-phenyloctene-1,7-phenyloctene-1,6-phenyloctene-1,5-phenyloctene-1,4-phenyloctene-1,3-phenyloctene-
Examples include 1,10-phenyldecene-1.

In the present invention, the above-mentioned aromatic ring-containing vinyl monomer may be used alone, or may be used as a mixture of two or more kinds. Of the above aromatic ring-containing vinyl monomers, allylbenzene and 4-phenylbutene-1
Is preferred, and 4-phenylbutene-1 is particularly preferred. [Non-conjugated diene] The non-conjugated diene used in the present invention is
It is represented by the following general formula (ii).

[0023]

[Chemical 6]

(In the formula, n is an integer of 1 to 5, and R^FourIs
An alkyl group having 1 to 4 carbon atoms, R^FiveAnd R⁶Is hydrogen
A child or an alkyl group having 1 to 8 carbon atoms, R^Five
And R ⁶Neither is a hydrogen atom. ) Specific examples of the non-conjugated diene as described above include 4-me
Tyl-1,4-hexadiene, 5-methyl-1,4-hexadiene,
4-ethyl-1,4-hexadiene, 5-methyl-1,4-heptadie
5-ethyl-1,4-heptadiene, 5-methyl-1,5-hepta
Diene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5-he
Ptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,
4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyi
Ru-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-octa
Diene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-o
Ctadiene, 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-1,
8-decadiene, 9-methyl-1,8-undecadiene, etc.
You can

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 higher α-olefin and the aromatic ring-containing vinyl monomer constituting the higher α-olefin copolymer rubber [I] of the present invention (higher α-olefin / aromatic ring-containing vinyl monomer) is 30. / 70 to 95/5, preferably 40/60 to 90/10, more preferably 5
It is in the range of 0/50 to 80/20.

The value of the above molar ratio is a value obtained by measurement by the ¹³ C-NMR method. In the present invention, a higher α-olefin copolymer rubber [I] having excellent processability can be obtained by copolymerizing a higher α-olefin with an aromatic ring-containing vinyl monomer.

The content of the non-conjugated diene constituting the higher α-olefin copolymer [I] used in the present invention is 0.
01 to 30 mol%, preferably 0.1 to 20 mol%, particularly preferably 0.1 to 10 mol%, and the iodine value is 2 to 40, preferably 5 to 30. . This characteristic value is a standard value when the higher α-olefin copolymer rubber [I] of the present invention is vulcanized with sulfur or peroxide.

The higher viscosity α-olefin copolymer rubber [I] used in the present invention has an intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. of 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 [I] used in the present invention. When the molecular weight is in the above range, the weather resistance, ozone resistance, and heat aging resistance are high. It is possible to obtain a copolymer having excellent 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 [I] can be produced by the following method. The higher α-olefin copolymer rubber [I] 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. It is obtained by copolymerizing an aromatic ring-containing vinyl polymer and a non-conjugated diene represented by the general formula (ii).

The olefin polymerization catalyst used in the present invention is composed of, for example, 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 a magnesium compound, a titanium compound, and an electron donor as described below. 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 ₄ , TiBr ₄ ,
Titanium tetrahalides such as TiI ₄ ; Ti (OC
H ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (O-n-C ₄
H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O-iso-
Trihalogenated alkoxytitanium such as C ₄ H ₉ ) Br ₃ ;
Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ ,
_{Ti (O-n-C 4} H 9) 2 Cl 2, Ti (OC 2 H 5) 2 Br
Dihalogenated dialkoxy titanium such as ₂ ; Ti (OCH
₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (O-n-C _{4
H 9) 3 Cl, Ti (} OC 2 H 5) 3 monohalogenated trialkoxy titanium and _{Br; Ti (OCH 3) 4,} Ti
(OC ₂ H ₅ ) ₄ , Ti (O-n-C ₄ H ₉ ) ₄ , Ti (O-iso-
Examples thereof include tetraalkoxytitanium such as C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

Among these, halogen-containing titanium compounds,
In particular, titanium tetrahalide is preferable, and titanium tetrachloride is more preferably used. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

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 reducing magnesium compounds 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 organoaluminum compound described later. Further, these magnesium compounds may be liquid or solid.

Specific examples of the non-reducing magnesium compound 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 is 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, the magnesium compound is not limited to the above-mentioned reducing magnesium compound and non-reducing magnesium compound, but also a complex compound, a complex compound or another compound of the above-mentioned magnesium compound and another metal. It may be a mixture with a metal compound. Further, it may be a mixture of two or more kinds of the above compounds.

In the present invention, among these, a magnesium compound having no reducing property is preferable, and a halogen-containing magnesium compound is particularly preferable, and among these, magnesium chloride, alkoxy magnesium chloride, and allyloxy magnesium chloride are preferably used. To be

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 polycarboxylic acid esters described later, and they are specifically represented by the following formula. And a compound having a skeleton.

[0043]

[Chemical 7]

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 hetero atom such as N, O and S, and examples thereof include -COC- and-.
_{COOR, -COOH, -OH, -SO 3} H, -C-N
-C -, - and hydrocarbon group substituted with a structure such as NH _2.

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 polycarboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methyl glutarate, dibutyl methyl malonate, diethyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate, butyl. Diethyl malonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl allylmalonate, diethyl diisobutylmalonate,
Di-n-butylmalonate diethyl, dimethyl maleate, monooctyl maleate, diisooctyl maleate, diisobutyl maleate, diisobutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methyl glutarate, diallyl ethyl succinate, di-2 fumarate. -Fatty acid polycarboxylic acid esters such as ethylhexyl, diethyl itaconic acid, diisobutyl itaconic acid, diisooctyl citraconic acid, dimethyl citraconic acid; diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylic acid, diethyl tetrahydrophthalate, nadic Aliphatic polycarboxylic acid ester such as acid diethyl; monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, Ethyl isobutyl tartrate, mono-n-butyl phthalate, ethyl n-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, phthalic acid Di-2-ethylhexyl, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate,
Examples thereof include aromatic polycarboxylic acid esters such as 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 ester derived from the long-chain dicarboxylic acid 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,
Organosilicon compounds such as thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, and alkoxy (aryloxy) silanes, 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 reagents 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 and the like. Further, when the reaction is performed as described above, the solid compound may be pulverized. Furthermore, 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 when the reaction is carried out as described above. In addition,
In this method, the electron donor is used at least once. (2) 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 the reaction product obtained in (2) with a titanium compound. (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 composed of a magnesium compound and an electron donor in the presence of a titanium compound is treated with halogen, a halogen compound or an aromatic hydrocarbon. Method. In this method, the magnesium compound or the complex compound composed of the magnesium compound and the electron donor may be ground in the presence of a grinding aid. Alternatively, the magnesium compound or the complex compound composed 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) above 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 of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxy magnesium, or aryloxy magnesium 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 titanium is used. When using the compound, a method using a halogenated hydrocarbon is preferable.

The amount of each of the above-mentioned components used in 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 amount of the titanium compound is about 0.01 to 500 mol, preferably 0.05 to 30 mol, preferably in an amount of 0.05 to 2 mol.
Used in an amount of 0 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 4-200, preferably about 5-100,
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 about 1 to 100, preferably about 2 to 50.

The solid titanium catalyst component (a) contains magnesium halide having a smaller crystal size than that of commercially available magnesium halide, and usually has a specific surface area of about 50 m ² / g or more, preferably about 60 to 1000 m ^2. / G,
More preferably, it is 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
Although it can be used alone, it can also be used by diluting it 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.

The preparation method of such a high activity titanium catalyst component is described in, for example, JP-A-50-108385 and JP-A-5-108385.
0-126590, 51-20297, 51-28189, 51-64586, 51-92885, 51-13662.
No. 5, gazette 52-87489 gazette, gazette 52-100596 gazette, gazette 52
-147688, 52-104593, 53-2580, 53-40093, 53-40094, 53-43094
No. 55, No. 55-135102, No. 55-135103, No. 55
-152710, 56-811, 56-11908,
56-18606, 58-83006, 58-138705, 58-138706, 58-138707, 58-1.
38708, 58-138709, 58-138710, 58-138715, 60-23404, 61-2110
No. 9, No. 61-37802, No. 61-37803, and the like.

As the organoaluminum compound catalyst component (b) used in the present invention, a compound having at least one aluminum-carbon bond in the molecule can be used.
Such compounds include, for example, (a) general formula (R ¹ ) m Al (O (R ² )) n Hp Xq (wherein R ¹ and R ² have usually 1 to 15 carbon atoms, preferably Is a hydrocarbon group containing 1 to 4, which may be the same or different from each other, X represents a halogen atom, 0 <m ≦ 3, n is 0 ≦ n <3, and p is 0 ≦ p <3. , Q
Is a number 0 ≦ q <3, and m + n + p + q = 3
An organic aluminum compound represented by the formula: (b) a general formula (M ¹ ) Al (R ¹ ) ₄ (wherein M ¹ is Li, Na, K, and R ¹ is the same as above) Examples thereof include complex alkylated products of a Group 1 metal and aluminum.

The following compounds can be exemplified as the organoaluminum compound belonging to the above (a). General formula (R ¹ ) n Al (O (R ² )) _3-m (wherein R ¹ and R ² are the same as above. M is preferably a number of 1.5 ≦ m ≦ 3), Formula (R ¹ ) m AlX _3-m (wherein R ¹ is the same as described above, X is halogen, and m is preferably 0 <m <3), general formula (R ¹ ) m AlH _3-m ( In the formula, R ¹ is the same as above, and m is preferably 2 ≦ m <3.
Of the general formula (R ¹ ) m Al (OR ² ) n Xq (wherein R ¹ and R ² are the same as above. X is halogen, 0
<M ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3
And the like.

Specific examples of the aluminum compound belonging to (a) 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; ethyl aluminum sesquiethoxide,
Alkyl aluminum sesquialkoxides such as butyl aluminum sesquibutoxide, (R ¹ ) _2.5 Al (O
(R ² )) Partially alkoxylated alkylaluminum having an average composition represented by _0.5 or the like; Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; Ethylaluminum sesquichloride, butylaluminum sesquichloride Alkyl aluminum sesquihalides such as ethyl aluminum sesquibromide; partially halogenated alkyl aluminums such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; diethyl aluminum hydride, dibutyl aluminum hydride Dialkyl aluminum hydride such as; ethyl aluminum dihydride, Partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ropylaluminium dihydride; partially alkoxylated and halogenated such as ethylaluminum ethoxy chloride, butylaluminum butoxycyclolide, ethylaluminum ethoxy bromide Alkyl aluminum can be mentioned.

Examples of the compound similar to the above (a) include an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom. Examples of such a compound include (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 AlN (C 2 H 5) Al (C
₂ H ₅ ) ₂ , methylaminooxane and the like can be mentioned.

As the compound belonging to (b) above, Li
Al (C₂H_Five)_Four, LiAl (C₇H ₁₅)_FourGive up
be able to. Among these, especially trialkylal
Minium or two or more aluminum compounds mentioned above
It is preferable to use an alkylaluminum having a bound substance.
Good

Examples of the electron donor catalyst component (c) include oxygen-containing alcohols 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 the 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, methylmalon Diisobutyl, cyclohexene carboxylic di -n- hexyl, nadic diethyl, tetrahydrophthalic acid diisopropyl, diethyl phthalate, diethyl phthalate, diisobutyl phthalate, di -n
-Butyl, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate and other organic acid esters having 2 to 30 carbon atoms;
Acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride; number of carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether 2 to 20 ethers; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine, etc. Amines; nitriles such as acetonitrile, benzonitrile, tolunitrile; acid anhydrides such as acetic anhydride, phthalic anhydride, benzoic anhydride, etc. are used.

As the electron donor (c), an organosilicon compound represented by the following general formula [1] can be used. Rn 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-o-tolyl Dimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane,
Dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane Silane, 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-norbornanemethyldimethoxysilane,
Ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxy silane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane and the like are used.

Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bisp -
Tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane,
Diphenyldiethoxysilane is preferred.

Further, as the electron donor catalyst component (c),
It is also possible to use an organosilicon compound represented by the following general formula [2]. 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 is an alkyl group, a cyclopentyl group or an alkyl group. It is 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. R ¹ has 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. A cyclopentyl group can be mentioned.

Further, in the 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 or an isopropyl group. Group, butyl group, allyl group such as hexyl group, or R ¹
The cyclopentyl group and the cyclopentyl group having an alkyl group exemplified as can be mentioned in the same manner.

In the 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.

Among 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,
Examples thereof include monoalocoxysilanes such as dicyclopentylmethylmethoxysilane, 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). According to the present invention, the olefin polymerization catalyst is used to polymerize a higher α-olefin, an aromatic ring-containing vinyl monomer, and a non-conjugated diene. -After prepolymerizing an olefin, a higher α-olefin, an aromatic ring-containing vinyl monomer, and a non-conjugated diene can be polymerized (main polymerization) using this catalyst.

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
It is usually about 0.01 to 200 mmol, preferably about 0.1 to 100 mmol, and particularly preferably 1 to 5 in terms of titanium atom per liter of an inert hydrocarbon medium described later.
It is desirable to set it in the range of 0 mmol.

The amount of the organoaluminum catalyst component (b) is
The amount may be such that 0.1 to 500 g, preferably 0.3 to 300 g of polymer is produced per 1 g of the solid titanium catalyst component (a), and it is per mol of titanium atom in the solid titanium catalyst component (a). The amount is usually about 0.1 to 100 mol, preferably about 0.5 to 50 mol, particularly preferably 1 to 20 mol.

The electron donor catalyst component (c) is used 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 in this case 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 preliminary polymerization, a molecular weight modifier such as hydrogen can be used. Such a molecular weight modifier has an intrinsic viscosity [η] of a polymer obtained by prepolymerization measured in a decalin solvent at 135 ° C. of about 0.2 or less.
It is desirable to use it in an amount of 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 the 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 an olefin, an aromatic ring-containing vinyl monomer, and a non-conjugated diene is performed.

In the copolymerization (main polymerization) of the higher α-olefin, the aromatic ring-containing vinyl monomer and the non-conjugated diene, in addition to the above olefin polymerization catalyst, olefin polymerization as an organoaluminum compound catalyst component is carried out. The same component as the organoaluminum compound catalyst component (b) used when producing the catalyst for use can be used. Also high-class α
-An electron donor catalyst used in producing an olefin polymerization catalyst as an electron donor catalyst component in the copolymerization (main polymerization) of an olefin, an aromatic ring-containing vinyl monomer, and a non-conjugated diene The same component as the 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 aromatic ring-containing vinyl monomer and the non-conjugated diene do not necessarily prepare the above-mentioned 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 aromatic ring-containing vinyl monomer 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 the higher α-olefin, the aromatic ring-containing vinyl monomer and the non-conjugated diene, the solid titanium catalyst component (a) is converted into titanium atom per 1 liter of polymerization volume, Usually, it is 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 the organoaluminum compound catalyst component (b) based on 1 mol of titanium atom in the solid titanium catalyst component (a).
The metal atom therein is usually used in an amount of about 1 to 2000 mol, preferably about 5 to 500 mol. Further, the electron donor catalyst component (c) is usually about 0.001 to 10 mol, preferably 0.01 to 2 mol, per mol of the metal atom in the organoaluminum compound catalyst component (b).
It is particularly preferably used in an amount of 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 aromatic ring-containing vinyl monomer and the non-conjugated diene is usually about 20 to 20.
0 ° C., to preferably about 40 to 100 ° C., the pressure is usually preferably atmospheric pressure to 100 kg / cm ² is set to the normal pressure to 50 kg / cm ^2. In the copolymerization (main polymerization) of the higher α-olefin, the aromatic ring-containing vinyl monomer and the non-conjugated diene, the polymerization 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 [II] The conductivity-imparting agent [II] used in the present invention is a conventionally known conductivity-imparting agent, specifically, carbon black,
Examples thereof include carbon fiber, metal powder and metal fiber. These conductivity-imparting agents are used alone or in combination. In the present invention, carbon black is preferred.

In the present invention, the conductivity imparting agent [II]
Is the above-mentioned higher α-olefin copolymer rubber [I] 1
5 to 200 parts by weight, preferably 4 to 00 parts by weight
It is used in a proportion of 0 to 200 parts by weight.

The conductive rubber according to the present invention has the above-mentioned high grade α.
-It is composed of a vulcanized product obtained by mixing 5 to 200 parts by weight of the conductivity-imparting agent [II] with 100 parts by weight of the olefin copolymer rubber [I]. An agent, for example, a metal activator, a compound having an oxymethylene structure, and an anti-scorch agent may be contained.

When the conductive rubber according to the present invention contains additives such as a rubber reinforcing agent, a filler, a softening agent, an anti-aging agent and a processing aid, the moldability in the production of the conductive rubber is improved. Are even better. 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, the vulcanization is carried out by adding a vulcanizing agent to a rubber compound containing the above-mentioned higher α-olefin copolymer rubber [I] and the conductivity-imparting agent [II] to carry out vulcanization. To obtain the conductive rubber.

Vulcanization is carried out by adding a vulcanizing agent to a rubber compound comprising a higher α-olefin copolymer rubber [I] and a conductivity-imparting agent [II]. It is better to do it before molding. Sulfur vulcanization and organic peroxide vulcanization are effective as vulcanization methods for the higher α-olefin copolymer rubber [I].

Specific examples of the sulfur compound used in sulfur vulcanization include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dimethyldithiocarbamate. To be Of these, sulfur is preferably used. Sulfur compounds are
The higher α-olefin copolymer rubber [I] 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.

When a sulfur compound is used as a vulcanizing agent, it is preferable to use a vulcanization accelerator together. Specific examples of vulcanization accelerators include N-cyclohexyl-2-benzothiazole sulfenamide and N-oxydiethylene.
-2-benzothiazole sulfenamide, N, N-diisopropyl-2-benzothiazole sulfenamide, 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl)
Thiazole compounds such as mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole and dibenzothiazyl disulfide; diphenylguanidine, triphenylguanidine, diorsonitrile guanidine, orthonitrile biguanide, diphenyl Guanidine compounds such as guanidine phthalate; acetaldehyde-aniline reaction products, butyraldehyde-aniline condensates, aldehyde amines such as hexamethylenetetramine, acetaldehyde ammonia, or aldehyde-ammonia compounds; imidazoline compounds such as 2-mercaptoimidazoline; thiocarbanilide, diethyl Thiourea, dibutyl thiourea, trimethyl thiourea,
Thiourium-based compounds such as diorthotolylthiourea; thiuram-based compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, diethyldithiocarbamate Dithioate compounds such as zinc, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, tellurium dimethyldithiocarbamate; zinc dibutylxanthate, etc. Xanthate compounds; zinc white and the like.

These vulcanization accelerators are used in an amount of 0.1 to 2 per 100 parts by weight of the higher α-olefin copolymer rubber [I].
It is used in an amount of 0 parts by weight, preferably 0.2 to 10 parts by weight.

The organic peroxide used in the vulcanization of organic peroxide may be any of those usually used in the vulcanization of rubber. Specifically, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy
-3,3,5-Trimethylcyclohexane, t-butyl hydroperoxide, t-butyl cumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5 -Dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-Dimethyl-2,5-di (t-butylperoxy) -hexane, α, α'-bis (t-butylperoxy-m-isopropyl) Examples include benzene.
Among them, dicumyl peroxide, di-t-butyl peroxide and di-t-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 [I] 1
It is used in an amount of 0.0003 to 0.05 mol, preferably 0.001 to 0.03 mol with respect to 00 g, and the optimum amount thereof can be appropriately determined according to the required physical property values. desirable. In the present invention, when an organic peroxide is used as a vulcanizing agent, it is preferable to use a vulcanizing auxiliary together. Specific examples of the vulcanization aid include sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; 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 added to the higher α-olefin copolymer rubber [I] together with the above vulcanizing agent. It is preferable to add.

Examples of the vulcanization aid which is preferably used together with the vulcanizing agent include metal activators, compounds having an oxymethylene structure, and scorch inhibitors.
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 rubber [I] 10
3 to 15 parts by weight, preferably 5 to 10 parts by weight, relative to 0 parts by weight
Used in parts by weight.

Further, in order to deal with various rubber processing steps, it is desirable to add a compound having an oxymethylene structure and a scorch inhibitor. Specific examples of the compound having an oxymethylene structure used in the present invention include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol. The compound having an oxymethylene structure is used in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the higher α-olefin copolymer rubber [I].

As the anti-scorch agent, known anti-scorch agents can be used, and specific examples thereof include maleic anhydride and salicylic acid. These scorch inhibitors are used in an amount of 0.2 to 5 parts by weight, preferably 0.3 to 3 parts by weight, based on 100 parts by weight of the higher α-olefin copolymer rubber [I].

The conductive rubber according to the present invention has more excellent properties as a conductive rubber when it contains additives such as a rubber reinforcing agent, a filler, a softening agent, an antiaging agent and a processing aid. These additives may be appropriately mixed with the higher α-olefin copolymer rubber [I] before or after vulcanization.

Specific examples of the rubber reinforcing 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, etc. are used. These reinforcing materials and fillers are added in an amount of at most 300 parts by weight, preferably at most 200 parts by weight, based on 100 parts by weight of the higher α-olefin copolymer rubber [I].

As the softening agent, a softening agent usually used for rubber can be used. Specifically, petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petrolatum; coal tar-based softeners such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, Fatty oil softeners such as coconut oil;
Tall oil; Sub; Waxes such as beeswax, carnauba wax, lanolin; Fatty acids such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate, zinc laurate or fatty acid salts thereof; Petroleum resin, atactic polypropylene, coumarone indene Examples thereof include synthetic polymeric substances such as resins; ester-based plasticizers such as dioctyl phthalate, dioctyl adipate, and 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 100 parts by weight at the maximum with respect to 100 parts by weight of the higher α-olefin copolymer rubber [I]. And preferably up to 70 parts by weight.

When the antioxidant is blended with the higher α-olefin copolymer rubber [I], the material life of the conductive rubber according to the present invention can be extended. This is
It is similar to the case of normal rubber. Specific examples of the antioxidant used in this case include aromatic secondary amine-based stabilizers such as phenylnaphthylamine and N, N'-di-2-naphthylphenylenediamine; dibutylhydroxytoluene, tetrakis [methylene] Phenolic stabilizers such as (3,5-di-t-butyl-4-hydroxy) hydrocinnamate] methane; bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butyl Examples thereof include thioether stabilizers such as phenyl] sulfide; and dithiocarbamate stabilizers such as nickel dibutyldithiocarbamate. These antioxidants are blended alone or in combination of two or more.

Such an anti-aging agent is added in an amount of 0.1% by weight based on 100 parts by weight of the higher α-olefin copolymer rubber [I].
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, zinc stearate, esters of these acids, higher fatty acids,
Examples thereof include salts and esters thereof.

These processing aids are usually used in an amount of 1 part based on 100 parts by weight of the higher α-olefin copolymer rubber [I].
It is used in an amount of 0 parts by weight or less, preferably 1 to 5 parts by weight. Further, in the present invention, natural rubber and SB are contained in the composition for conductive rubber within the range not impairing the object of the present invention.
Diene rubbers such as R, 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, by using a mixer such as a Banbury mixer, necessary additives such as higher α-olefin copolymer rubber [I], conductivity imparting agent [II], reinforcing agent, filler and softening agent are added at 80 to 170 ° C. At a temperature of 3-10
After kneading for a minute, a vulcanizing agent and, if necessary, a vulcanization accelerator or vulcanization aid are additionally mixed using rolls such as an open roll, and the mixture is mixed at a roll temperature of 40 to 80 ° C for 5 The mixture is kneaded for 30 minutes and then dispensed to prepare a ribbon-shaped or sheet-shaped rubber compound.

Then, the rubber compound prepared as described above is generally molded by using a roll machine, a calender molding machine, an extruder or the like, and the molded product is heated at 130 to 220 ° C. for 1 to 60 minutes. And vulcanize 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.

[0113]

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, it has a dynamic fatigue resistance. It has the effect of excellent conductivity and excellent conductivity.

[0114]

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

[0115]

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 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, 200 ml of titanium tetrachloride having 75 ml maintained at -20 ° C.
The entire amount was added dropwise into the flask over 1 hour. After charging,
The temperature of this mixed solution was raised to 110 ° C. over 4 hours, and 1
When the temperature reached 10 ° C, diisobutyl phthalate 5.2
2 g was added and the mixture was kept at the same temperature for 2 hours with stirring. After completion of the reaction for 2 hours, a solid portion was collected by hot filtration,
This solid portion was resuspended in 275 ml of titanium tetrachloride, and then heated and reacted again at 110 ° C. for 2 hours. After the reaction was completed, the solid portion was collected again by hot filtration, and thoroughly washed with decane and hexane at 110 ° C. 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, 65% by weight of chlorine, 19% by weight of magnesium and 13.5% by weight of diisobutylphthalate. (Polymerization) Using a 4-liter glass polymerization vessel equipped with a stirring blade, hexene-1,4-phenylbutene-1,
A copolymerization reaction with 7-methyl-1,6-octadiene was performed.

That is, from the top of the polymerization vessel, hexene-1,4-
A hexane solution of phenylbutene-1 and 7-methyl-1,6-octadiene was added to the polymerization vessel at a hexene-1 concentration of 132 g /
Liter, 4-phenylbutene-1 concentration 39g / liter,
2.1 liter / hour so that the concentration of 7-methyl-1,6-octadiene was 10 g / liter, and a hexane slurry solution of the solid titanium catalyst component (a) was used as a catalyst so that the titanium concentration in the polymerization vessel was 0.04 mmol. / Liter,
0.4 liter / hour, a hexane solution of triisobutylaluminum is 1 liter / hour so that the aluminum concentration in the polymerization vessel is 4 mmol / liter, and a hexane solution of trimethylmethoxysilane is 1: 1 in the polymerization vessel. 0.5 hourly so that it becomes 3 millimoles / liter
It was continuously fed into the polymerizer at a rate of 1 liter. On the other hand, the polymerization solution in the polymerization vessel from the bottom of the polymerization vessel is always 2
It was continuously withdrawn so as to obtain liter. Also, from the top of the polymerization vessel, 0.8 liters of hydrogen and 5 hours of nitrogen are supplied.
Supplied with 0 liter. The copolymerization reaction is carried out by circulating warm water through a jacket attached to the outside of the polymerization vessel.
Performed at 0 ° C.

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. The copolymer was thoroughly washed with methanol and then dried under reduced pressure at 140 ° C for a whole day and night to obtain hexene-1,4-phenylbutene-1,7-methyl-1,6-octadiene copolymer at a rate of 122 g / hr. It was

With hexene-1 which constitutes the obtained copolymer
The molar ratio with 4-phenylbutene-1 (hexene-1 / 4-phenylbutene-1) is 75/25, and the iodine value is 9.4.
Met. The intrinsic viscosity [η] measured in decalin at 135 ° C was 5.7 dl / g.

The above polymerization conditions are shown in Table 1.

[0120]

[Table 1]

(Production of Vulcanized Rubber) Hexene-1,4-phenylbutene-1, .e. Produced by the above method as higher α-olefin copolymer rubber (i) using an 8-inch open roll. 7-Methyl-1,6-octadiene copolymer rubber (1-a) was compounded according to Table 2 and kneaded to obtain an unvulcanized compounded rubber. The kneading time at this time is 15 minutes,
The roll surface temperature is 50 for both the front and rear rolls.
℃, and the rotation speed of the front roll is 16 rp
m, the rear roll was 18 rpm.

[0122]

[Table 2]

The above rubber compound 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 item) 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 tensile strength (T _B), was measured elongation (E _B).

In the bending test, the resistance to crack growth was examined with a DeMatcher tester. That is, the crack is 15 mm
The number of times of flexing was measured. The volume resistivity is
Measured according to ASTM D257.

The results are shown in Table 3.

[0126]

Example 2 In Example 1, the copolymer rubber (1-a)
Instead of, as shown in Table 1 above, hexene obtained by copolymerization in the same manner as in Example 1 except that the polymerization conditions were changed.
The procedure of Example 1 was repeated except that -1,4-phenylbutene-1,7-methyl-1,6-octadiene copolymer rubber (1-b) was used.

The results are shown in Table 3.

[0128]

Example 3 In Example 1, the copolymer rubber (1-a)
In place of the above, as shown in Table 1 above, octene-1,4-phenylbutene-1,7- was obtained by copolymerization in the same manner as in Example 1 except that the higher α-olefin and the polymerization conditions were changed.
The procedure of Example 1 was repeated except that the methyl-1,6-octadiene copolymer rubber (1-c) was used.

The results are shown in Table 3.

[0130]

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

The results are shown in Table 3.

[0132]

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

The results are shown in Table 4.

[0134]

Example 6 In Example 1, instead of acetylene black, Ketjen Black EC [surface area (nitrogen adsorption method) 1000 m ² / g, average particle size (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 4.

[0136]

Example 7 In Example 6, Ketjen Black E
The same procedure as in Example 6 was repeated except that the amount of C was changed to 40 parts by weight.

The results are shown in Table 4.

[0138]

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

The results are shown in Table 5.

[0140]

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

The results are shown in Table 5.

[0142]

Comparative Example 3 The procedure of Example 1 was repeated, except that a silicone rubber was used instead of the higher α-olefin copolymer rubber [I].

The results are shown in Table 5.

[0144]

[Table 3]

[0145]

[Table 4]

[0146]

[Table 5]

[Brief description of drawings]

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaaki Kawasaki Aki 6-1-2, Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd.

Claims (1)

[Claims] 1. [I] A higher α-o having 6 to 20 carbon atoms.
Refine and aromatic ring represented by the following general formula (i)
Vinyl monomers and non-copolymers represented by the following general formula (ii)
It is a higher α-olefin copolymer consisting of a diene.
(A) higher α-olefin and aromatic ring-containing vinyl
The molar ratio with the nomer is 95/5 to 30/70,
(B) The content of non-conjugated diene is 0.01 to 30 mol%.
(C) Intrinsic viscosity measured in decalin at 135 ° C
Higher α-olefin based copolymers with [η] of 1.0 to 10 dl / g
Rubber set containing 100 parts by weight of united rubber and 5 to 200 parts by weight of [II] conductivity-imparting agent
Conductive rubber characterized by comprising a vulcanized product;(In the formula, n is an integer of 0 to 5, and R¹, R²And R³
Are each independently a hydrogen atom or a carbon atom number of 1 to 8.
Represents an alkyl group of),(In the formula, n is an integer of 1 to 5, and R^FourHas 1 carbon atom
Represents an alkyl group of ~ 4, R^FiveAnd R⁶Is a hydrogen atom
Or represents an alkyl group having 1 to 8 carbon atoms, R ^FiveAnd
And R⁶Are not both hydrogen atoms).