JPH04154856A - Electrically conductive rubber - Google Patents

Abstract

PURPOSE:To obtain an electrically conductive rubber excellent in dynamic fatigue resistance and electric conductivity by blending a specific higher alpha- olefinic copolymer rubber with an electric conductivity imparter in a specific amount. CONSTITUTION:The objective electrically conductive rubber is obtained by blending (A) 100 pts.wt. higher alpha-olefinic copolymer rubber, composed of a 6-12C higher alpha-olefin (e.g. hexene-1 or octene-1) and a nonconjugated diene (e.g. 6-methyl-1,6-octadiene) expressed by the formula (R<1> us 1-4C alkyl; R<2> and R<3> are H or 1-4C alkyl and R<2> and R<3> are not simultaneously H) and having 1.0-10.0dl/g, especially 3.0-8.0dl/g intrinsic viscosity (135 deg.C) and l-50, especially 4-20 iodine value with (B) 5-200 pts.wt., preferably 40-200 pts.wt. electric conductivity imparter (e.g. carbon black or metallic powder).

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a conductive rubber, and more particularly to a conductive rubber having excellent dynamic fatigue resistance and electrical conductivity.

Technical background of the invention Conductive rubber was initially used as an antistatic material, but
With the development of electronics technology, it has come to be used for a variety of applications such as contact materials and conductive adhesives.

Conductive rubber consists of semiconductor-based conductive rubber with a conductive molecular structure introduced into the rubber molecules, and dispersed composite conductive rubber with conductivity-imparting agents (conductive fillers) such as carbon black and metal particles dispersed in the rubber. It is broadly classified into sex rubber.

The above-mentioned dispersed composite conductive rubber is usually made by mixing silicone rubber with a large amount of carbon black, metal powder, fiber, etc., and the conductivity of the rubber is determined by the conductivity imparting agent in the rubber. It is expressed by contact and proximity at the atomic level.

As the above-mentioned metal, 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 uses are limited. Therefore, most of the conductive rubbers conventionally used in practical use use relatively inexpensive carbon black or carbon fiber as a conductivity imparting agent.

Incidentally, the conductive rubber as described above normally exhibits insulating properties when no pressure is applied, and when deformed and strained due to pressure or the like, the strained portions exhibit conductivity or semiconductivity. Conventionally, by utilizing such properties, conductive rubber has been widely used as a pressure-sensitive conductive material in pressure switches for electrical and electronic equipment.

Pressure switches for electrical and electronic equipment must have excellent dynamic fatigue resistance from the viewpoint of reliability of electrical and electronic equipment.
In other words, it is required to have a long repeated durability life. Therefore, conductive rubber used as a pressure switch material for electrical and electronic equipment is required to have excellent dynamic fatigue resistance.

OBJECTS OF THE INVENTION An object of the present invention is to provide a conductive rubber that has excellent dynamic fatigue resistance and conductivity as compared to conventional conductive rubbers.

Summary of the Invention The conductive rubber according to the present invention is composed of (A) a higher α-olefin having 6 to 12 carbon atoms and a non-conjugated diene represented by the following formula [I], and is prepared in a decalin solvent at 135°C. The intrinsic viscosity [η] measured at
．． It is in the range of 0 to 10.0617g, and the iodine value is 1 to
High-grade α-olefin copolymer rubber 1 in the range of 50
00 parts by weight, and 5 to 200 parts by weight of (B) a conductivity imparting agent.

In the formula, R1 is an alkyl group having 1 to 4 carbon atoms, R2 and R
3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, R and R3 are never both hydrogen atoms.

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 is made of a vulcanizate containing a specific higher α-olefin 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 is composed of a higher α-olefin and a non-conjugated diene.

The higher α-olefin used in the present invention has 6 carbon atoms.
-12 α-olefins, and specific examples include hexene-1, heptene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, and the like. In the present invention, the above higher α-olefins may be used alone or as a mixture of two or more. Above high class α-
Among the olefins, hexene-1, octene-1, and decene-1 are preferably used.

The content of higher α-olefin constituting the higher α-olefin copolymer rubber used in the present invention is 70 to 99.
99 mol%, preferably in the range of 80 to 99.9 mol%.

The non-conjugated diene used in the present invention has the following general formula [I
] is a non-conjugated diene.

(In the formula, R1 represents an alkyl group having 1 to 4 carbon atoms, and R2 and R3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, R and R3 are not both hydrogen atoms.) Specifically, non-conjugated dienes such as 6-
Methyl-116-octadiene, 7-methyl-1,6-
Octadiene, 6-ethyl-1,6-octadiene, 6
-broby-1, 6-octadiene, 6-butyl-1.
6-octadiene, 6-methyl-1,6-nonadiene,
7-Methyl-1,6-nonadiene, 6-ethyl-1,tononadiene, 7-ethyl-1,6-nonadiene, 6-methyl, 6-zocadien, 7-methyl-1,6-zocadien, 6-methyl -1,6-undecadiene and the like.

In the present invention, the above-mentioned non-conjugated dienes may be used alone or as a mixture of two or more.

Among the non-conjugated dienes mentioned above, 7-methyl-1,6-octadiene is preferably used.

The higher α-olefin copolymer rubber used in the present invention has an iodine value of 1 to 50, preferably 2 to 30, and more preferably 4 to 20. Generally, if the iodine value of the high-grade α-olefin copolymer rubber becomes too high, the resulting rubber composition tends to have low elongation and become brittle. On the other hand, if the iodine value of the high-grade α-olefin copolymer rubber becomes too low, the vulcanization rate of the resulting rubber composition will be slow, making it unusable.

The intrinsic viscosity [η] of the higher α-olefin copolymer rubber used in the present invention is 1.0 to 10.0 dl/g, preferably 2.0 to 9.0 dl/g, as measured in a decalin solvent at 135°C.
OdA'/g, more preferably 3.0-B, OdI/
It is g. When the above-mentioned intrinsic viscosity [η] exceeds 10 dl/g, the resulting rubber composition tends to be difficult to process, while when the intrinsic viscosity [η] is less than 1.0 dl/g, the resulting rubber composition tends to be difficult to process. The strength properties of objects tend to decrease.

The content of the non-conjugated diene constituting the higher α-olefin copolymer rubber used in the present invention is in the range of 0.01 to 30 mol%, preferably 0.1 to 20 mol%.

The composition of the high-grade α-olefin copolymer rubber is 13C-N.
Measure by MR method.

The higher α-olefin copolymer rubber used in the present invention can be produced, for example, by the following method.

The higher α-olefin copolymer rubber used in the present invention is obtained by copolymerizing a higher α-olefin and a nonconjugated diene in the presence of an olefin polymerization catalyst.

The olefin polymerization catalyst used in the above copolymerization is
It is formed from 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 flowchart of a method for preparing a catalyst component for olefin polymerization used in the production of a higher α-olefin copolymer rubber in the present invention.

The solid titanium catalyst component [A] is a highly active catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components.

Such a solid titanium catalyst component [A] is prepared by contacting a magnesium compound, a titanium compound, and an electron donor as described below.

Examples of the titanium compound used for preparing the solid titanium catalyst component (A) include Ti(OR) gX4-g (R is a hydrocarbon group, X is)
Examples include tetravalent titanium compounds having 10 gene atoms and 0≦g≦4. More specifically, Tic/
, TiBr STi I4; T + (OCHa ) CII 3, Ti(OC2H
5) Trihalogenated alkoxytitanium such as C13, Ti(On-CH) C13, T I (OC2H5) Br3, Ti(Oiso C4H9) Br3; Ti(O′CH3)2CI! 2, T'+(QCH) CA'2, Ti(On-C4H!+)2 G' 2, TI(QC
Dihalogenated dialkoxytitaniums such as 2Ha)2Br2; Ti(OCH3)3C1, Ti(OC2H5)3C1.

Ti(On-C4H9') 3CI! , Ti(OC2H
5) Monohalogenated trialkoxytitanium such as 3Br; T + (OCH3) 4, T I (OC2Hs) 4, T + (On-C4H9) 4 Ti (Oiso-C4H9) 4 T i (0-2- Examples include tetraalkoxytitanium such as ethylhexyl)4.

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

Examples of the magnesium compound used in the preparation of the solid titanium catalyst component [A] include magnesium compounds that have reducing properties and magnesium compounds that do not have reducing properties.

Here, as a magnesium compound having reducing properties,
For example, magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond can be mentioned. Specific examples of magnesium compounds having such reducing properties include dimethylmagnesium, diethylmagnesium,
Dipropylmagnesium, dibutylmagnesium, cyamylmagnesium, dit\xylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, amylmagnesium chloride, butylethoxymagnesium, ethylbutylmagnesium, octyl Examples include butylmagnesium and butylmagnesium halide. These magnesium compounds may be used alone or may form a complex compound with an organoaluminum compound described below. Moreover, these magnesium compounds may be liquid or solid.

Specific examples of non-reducing magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, and butochimochloride. Alkoxymagnesium halides such as magnesium, octoxymagnesium chloride; alkoxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; ethoxymagnesium,
isopropoxymagnesium, butoxymagnesium,
Examples include alkoxymagnesiums such as n-octoxymagnesium and 2-ethylhexoxymagnesium; allyloxymagnesiums such as phenoxymagnesium and dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate; I can do it.

These non-reducing magnesium compounds may be compounds derived from the above-mentioned reducing magnesium compounds or compounds derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound can be derived from a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, etc. All you have to do is bring it into contact with a compound.

In addition to the above-mentioned magnesium compounds having reducing properties and non-reducing properties, magnesium compounds include complex compounds, composite compounds, or mixtures of the above-mentioned magnesium compounds with other metals, or other metal compounds. You can. Furthermore, a mixture of two or more of the above compounds may be used.

Among these, magnesium compounds that do not have reducibility are preferred, particularly preferred are magnesium compounds containing oxides, and among these, magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride are preferably used.

Examples of the electron donor used in the preparation of the solid titanium catalyst component [A] include organic carboxylic acid esters, preferably polyhydric carboxylic acid esters, and specifically, compounds having a skeleton represented by the following formula: .

R-C-COOR6 In the above formula, R1 represents a substituted or unsubstituted hydrocarbon group, RSR and R represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and R3 and R4 represent a hydrogen atom, a substituted or Represents an unsubstituted hydrocarbon group. Note that at least one of R3 and R4 is preferably a substituted or unsubstituted hydrocarbon group. Furthermore, R 1 and R 4 may be connected to each other to form a cyclic structure. Examples of the substituted hydrocarbon group include substituted hydrocarbon groups containing different atoms such as N, O, and S, such as -C-O-C-1-COOR, -COOH.

Examples include substituted hydrocarbon groups having structures such as -OH, -3o3H, -C-N-C-1-NH2, and the like.

Among these, diesters derived from dicarboxylic acids in which at least one of R and H is an alkyl group having 2 or more carbon atoms are preferred.

Specific examples of polyvalent carboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methylsuccinate,
Diisobutyl α-methylglutarate, dibutylmethyl malonate, diethyl malonate, diethyl ethyl malonate,
Diethyl isopropyl malonate, diethyl butyl malonate, diethyl phenyl malonate, diethyl diethyl malonate, diethyl allyl malonate, diethyl diisobutyl malonate, diethyl di-n-butyl malonate, dimethyl maleate, monooctyl maleate, diisooctyl maleate, maleic acid Diisobutyl acid, diisobutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethylsuccinate, di-2-ethylhexyl fumarate, diethyl itaconate, diisobutyl ita, diisobutyl conate, diisooctyl citraconate, dimethyl citraconate, etc. aliphatic polycarboxylic acid esters such as diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadic acid, monoethyl phthalate, phthalate. Dimethyl acid, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, mono-normal butyl phthalate, ethyl normal-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-1-phthalate Butyl, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, didecyl phthalate, benzylbutyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, trimellitate Examples include aromatic polycarboxylic acid esters such as dibutyl acid, and esters derived from heteroarticulated polycarboxylic acids such as 3,4-furandicarboxylic acid.

Other examples of polyvalent carboxylic acid esters include long chain dicarboxylic acids such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, n-octyl sebacate, and di-2-ethylhexyl sebacate. Mention may be made of esters derived from.

Among these polyhydric carboxylic acid esters, compounds having a skeleton represented by the above-mentioned general formula are preferred, and compounds derived from phthalic acid, maleic acid, substituted malonic acid, etc. and an alcohol having 2 or more carbon atoms are more preferred. Preferred are esters, and particularly preferred are diesters obtained by the reaction of phthalic acid and an alcohol having 2 or more carbon atoms.

These polyvalent carboxylic acid esters do not necessarily need to be used as starting materials, and these polyvalent carboxylic acid esters can be derived in the process of preparing the solid titanium catalyst component [A]. A polyhydric carboxylic acid ester may be produced in the preparation step of the solid titanium catalyst component [A] using a compound that can be used.

Electron donors other than polyhydric carboxylic acids that can be used when preparing the solid titanium catalyst [A] include alcohols, amines, amides, ethers, ketones, and nitriles as described below. phosphines, stipines, arsines, phosphoramides, esters, thioethers, thioesters, acid anhydrides, acidolides, aldehydes, alcoholates, alkoxy (
Examples include organosilicon compounds such as (aryloxy)silanes, organic acids, and amides and salts of metals belonging to Groups 1 to 2 of the periodic table.

The solid titanium catalyst component [A] can be produced by bringing the above-described magnesium compound (or metal magnesium), an electron donor, and a titanium compound into contact with each other. In order to produce the solid titanium catalyst component [A], a known method for preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound, and an electron donor can be employed. Note that the above components include, for example, silicon,
The contact may be made in the presence of other reaction reagents such as phosphorus and aluminum.

Several examples of methods for producing these solid titanium catalyst components [A] will be briefly described below.

(1) A method of reacting a magnesium compound or a complex compound consisting 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.

Moreover, when reacting as described above, a solid compound may be pulverized. Furthermore, when reacting 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. Note that in this method, the above electron donor is used at least once.

(2) a liquid magnesium compound that does not have reducing properties;
A method in which a solid titanium complex is precipitated by reacting a liquid titanium compound in the presence of an electron donor.

(3) A method in which the reaction product obtained in (2) is further reacted with a titanium compound.

(4) The reaction product obtained in (1) or (2),
A method for further reacting an electron donor and a titanium compound.

(5) A solid material 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 either a halogen, a halogen compound, or an aromatic hydrocarbon. Method. In this method, a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor may be ground in the presence of a grinding aid or the like. Also,
A magnesium compound or a complex compound consisting of a magnesium compound and an electron donor may be ground in the presence of a titanium compound, then pretreated with a reaction aid, and then treated with a halogen or the like. Note that examples of the reaction aid include organoaluminum compounds and halogen-containing silicon compounds.

Note that in this method, an electron donor is used at least once.

(6) A method of treating the compound obtained in (1) to (4) above with a halogen, a halogen compound, or an aromatic hydrocarbon.

(7) A method of contacting a contact reaction product of a metal oxide, dihydrocarbylmagnesium, and a halogen-containing alcohol 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, alkoxymagnesium, or aryloxymagnesium with an electron donor, a titanium compound, and/or a halogen-containing hydrocarbon.

Solid titanium catalyst component [A] listed in (1) to (8) above
Among the preparation methods, a method using liquid titanium halide during catalyst preparation, a method using a titanium compound after use, or a method using a halogenated hydrocarbon when using a titanium compound are preferred.

The amount of each of the above-mentioned components used when preparing the solid titanium catalyst component [Al varies depending on the preparation method and cannot be unconditionally defined, but for example, the amount of electron donor per mole of magnesium compound is about 0.01 to In an amount of 5 mol, preferably 0.05 to 2 mol, the titanium compound is about 0.0
It is used in an amount of 1 to 500 mol, preferably 0.05 to 300 mol.

It can be done.

The solid titanium catalyst component thus obtained [Al is
Contains magnesium, titanium, halogen and electron donor as essential components.

In this solid titanium catalyst component [Al, the halogen/titanium (atomic ratio) is about 4 to 200, preferably about 5 to 10
0, and the electron donor/titanium (molar ratio) is about 0.
1-10. It is preferably about 0.2 to about 6, and the magnesium/titanium (atomic ratio) is preferably about 1 to 100, preferably about 2 to 50.

This solid titanium catalyst component [Al contains magnesium halide with a small crystal size compared to commercially available magnesium halide, and usually has a specific surface area of about 5 Onf/
g or more, preferably about 60 to 1000 n-r/g, more preferably about 100 to 800 rrr/g. Since the solid titanium catalyst component (Al) is a catalyst component formed by the above-mentioned components, its composition is not substantially changed by hexane washing.

Although such a solid titanium catalyst component [Al can be used alone, it can also be used diluted with an inorganic or organic compound such as a silicon compound, an aluminum compound, or a polyolefin. In addition,
When a diluent is used, high catalytic activity is exhibited even if the specific surface area is smaller than the above-mentioned specific surface area.

Regarding the preparation method of such a highly active titanium catalyst component, see, for example, JP-A-50-108385 and JP-A-50-108385.
-126590 publication, 51-20297 publication, 51-28189 publication, 51-64586 publication,
Publication No. 51-92885, No. 51-! No. 36625, No. 52-87489, No. 52- ] D'
No. 0596, No. 52-147688, No. 52
-104593 publication, 53-2511i1 publication,
Publication No. 53-4N93, Publication No. 53-40094,
No. 53-43094, No. 55-135102, No. 55-135103, No. 55-15271
Publication No. 0, Publication No. 56-811, Publication No. 56-11908
No. 56-18606, No. 5g-8300
No. 6, No. 5B-138705, No. 5g-13
No. 8706, No. 5fl-1387117, No. 511-13117011, No. 58-13870
Publication No. 9, Publication No. 5g-138710, Publication No. 58-1
No. 38715, No. 60-23404, No. 61
-21109 Publication, Publication No. 61-37802, Publication No. 6
1-37803, etc.

As the organoaluminum compound catalyst component [B], a compound having at least one Al-carbon bond in the molecule can be used. Such compounds include, for example, (1) (wherein R and R2 are hydrocarbon groups containing usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and these may be the same or different from each other. X represents a halogen atom, 0 m≦3, and n is 0≦.

n<3, p is a number of 0≦p<3, q is a number of 0≦q<3, and m + n + p + q = 3)
Examples include organoaluminum compounds represented by the following formula, and complex alkylated products with Group 1 metal aluminum represented by the formula (wherein Ml is Li, Na, or Ni, and R1 is the same as above).

Examples of the organic aluminum compounds belonging to (i) above include the following compounds.

- Formula R1lllAl (OR2) -m (wherein R and R2 are the same as above. m is preferably 1
．． 5≦m≦3), - Formula R1, AlX3-I
11 (wherein R1 is the same as above, X is halogen, m is preferably O<m<3), - formula RIIIAI
! H3-[11 (wherein, R1 is the same as above. m is preferably 2≦m<3
), general formula RIIIAl (OR2) Xq ] (wherein, R and R2 are the same as above.
<m≦3.0≦n<3.0≦q<3, m −1−n
+ q = 3).

More specifically, the aluminum compounds belonging to (i) include trialkylaluminum such as triethylaluminum and tributylaluminium; trialkenylaluminum such as triisoprenylaluminum; dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide. ; Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
, 5 0.5 Partially alkoxylated alkylaluminum with homogeneous composition; Dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide: ethylaluminum sesquipromide, butylaluminum sesquipromide, ethylaluminum Alkylaluminum sesquihalides such as sesquipromide; partially halogenated alkyl aluminum such as alkyl aluminum cybarides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide; diethyl aluminum hydride, dibutyl aluminum hydride, etc. dialkylaluminum hydrides; other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, probylaluminum dihydride; ethylaluminum ethoxy chloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide Mention may be made of partially alkoxylated and halogenated alkyl aluminums such as.

Compounds similar to (i) include organoaluminum compounds in which two or more aluminum atoms are bonded via oxygen atoms or nitrogen atoms. Examples of such compounds include (CH') Al0Al (
(,R5)2,(CH) AAOAA (C4H
9) 2,2H5 Methylaluminoxane, etc. can be mentioned.

Compounds belonging to (ii) above include LiAl1
CC2H3)4, LIAII(C7H15)4, etc. can be mentioned.

Among these, it is particularly preferable to use trialkylaluminum or alkylaluminum in which two or more of the above-mentioned aluminum compounds are combined.

As the electron donor catalyst component [C], oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides, alkoxysilanes, etc. Nitrogen-containing electron donors such as , ammonia, amines, nitriles, isocyanates, or polyhydric carboxylic acid esters as described above can be used. More specifically, methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, cumyl alcohol, isopropylbenzyl alcohol Alcohols with 1 to 18 carbon atoms; phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol,
Phenols with 6 to 20 carbon atoms that may have a lower alkyl group such as cumylphenol and naphthol; Ketones with 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, and benzoquinone; acetaldehyde , propionaldehyde, octylaldehyde, benzaldehyde,
2-1 carbon atoms such as tolualdehyde and naphthaldehyde
Aldehydes of 5; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, croton ethyl acid, 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 ethylbenzoate, methyl anisate, n-butyl maleate , diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate,
Organic acid esters with 2 to 30 carbon atoms such as diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate; acetyl Acid halides with 2 to 15 carbon atoms such as chloride, benzoyl chloride, toluyl chloride, and anisyl chloride; 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, and diphenyl ether ethers; acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylenediamine; Nitriles such as acetonitrile, benzonitrile, and tolnitrile; acid anhydrides such as acetic anhydride, phthalic anhydride, and benzoic anhydride are used.

Further, as the electron donor catalyst component [C], an organosilicon compound represented by the following general formula [I] can also be used.

RS i (OR') 4-, l...
[I] [wherein R and R′ are hydrocarbon groups, and 0<
n<4] Examples of the organosilicon compound represented by the above general formula [I] include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane,
Dimethyljethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, i-butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyljethoxysilane, bis0-) Lyldimethoxysilane, bis-m-)lyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p
4lyldiethoxysilane, bisethyl phenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltoluethoxysilane,
Ethyltriethoxysilane, vinyltriethoxysilane, turtle-butyltriethoxysilane, n-butyltriethoxysilane, 1so-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyl Triisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane,
2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy(xllyloxy)silane, vinyltris(β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyl Tetraethoxydisiloxane and the like are used.

Among them, ethyltriethoxysilane, n-propyltriethoxysilane, (-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane,
Vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis p-tolyldimethoxysilane, p-)lylmethyldimethoxysilane, dicyclo/\xyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2- Norbornanemethyldimethoxysilane and diphenyljethoxysilane are preferred.

Further, as the electron donor catalyst component [C], an organosilicon compound represented by the following general formula [n] can also be used.

[Wherein, R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, R2 is a group selected from the group consisting of an alkyl group, a cyclopentyl group, and a cyclopentyl group having an alkyl group, and R3 is a hydrocarbon group, m is 0≦m≦2. ] In the above formula [U], R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R1 includes, in addition to the cyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl group, a 2-ethylcyclopentyl group, and a cyclopentyl group. , 3-dimethylcyclopentyl group and other alkyl group-containing cyclopentyl groups.

Further, in formula [II], R2 is an alkyl group, a cyclopentyl group, or a cyclopentyl group having an alkyl group, and R2 is, for example, a methyl group, an ethyl group, a butyl group, an isopropyl group, An alkyl group such as a butyl group or a hexyl group, or a cyclopentyl group exemplified as R1 and a cyclopentyl group having an alkyl group can be similarly mentioned.

Further, in formula [n], R3 is a hydrocarbon group, and R
Examples of 3 include alkyl groups, cycloalkyl groups,
Examples include hydrocarbon groups such as aryl groups and aralkyl groups.

Among these, R1 is a cyclopentyl group, and R2
It is preferred to use organosilicon compounds in which R is an alkyl group or a cyclopentyl group and R3 is an alkyl group, especially a methyl group or an ethyl group.

Examples of such organosilicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and cyclopentyltriethoxysilane; dicyclopentyldimethoxy Dialkoxysilanes such as silane, bis(2-methylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxysilane, dicyclopentyljethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxy Examples include monoalkoxysilanes such as silane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane. Among these electron donors, organic carboxylic acid esters or organic silicon compounds are preferred, and organic silicon compounds are particularly preferred.

The olefin polymerization catalyst used in the production of high-grade α-olefin copolymer rubber consists of the solid titanium catalyst component [A] as described above, the organoaluminum compound catalyst component [B], and the electron donor [C ] This olefin polymerization catalyst is used to polymerize higher α-olefins and non-conjugated dienes, but this olefin polymerization catalyst is used to prepolymerize α-olefins or higher α-olefins. After this, a higher α-olefin and a non-conjugated diene can be polymerized (main polymerization) using this catalyst. per gram of olefin polymerization catalyst during prepolymerization,
The α-olefin or higher α-olefin is prepolymerized in an amount of 0.1 to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g.

In the prepolymerization, a catalyst can be used at a much higher concentration than the catalyst concentration in the system in the main polymerization.

The concentration of solid titanium catalyst component [A] in prepolymerization is:
Normally about 0.01 to 200 mmol, preferably about 0.01 to 200 mmol, in terms of titanium atoms, per inert hydrocarbon medium 11 described below.
．． It is in the range from 1 to 100 mmol, particularly preferably from 1 to 50 mmol.

The amount of organoaluminum catalyst component [B] is 0.1 to 500 g, preferably 0.1 to 500 g, per Ig of solid titanium catalyst component [A].
The amount may be such that 3 to 300 g of polymer is produced, and is usually about 0.1 to 100 mol, preferably about 0.5 to 5 mol, per 1 mol of titanium atoms in the solid titanium catalyst component [A].
The amount is 0 mol, particularly preferably 1 to 20 mol.

The electron donor catalyst component [C] is a solid titanium catalyst component [A
] It is used in an amount of 0.1 to 50 mol, preferably 0.5 to 30 mol, particularly preferably 1 to 10 mol, per mol of titanium atoms in .

Prepolymerization is preferably carried out under mild conditions by adding the olefin or higher α-olefin and the above catalyst components to an inert hydrocarbon medium.

Examples of the inert hydrocarbon 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 include alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and mixtures thereof. Among these inert hydrocarbon media, it is particularly preferred to use aliphatic hydrocarbons. Incidentally, the prepolymerization can be carried out using the olefin or higher α-olefin itself as a solvent, or the prepolymerization can be carried out substantially in the absence of a solvent.

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 during prepolymerization is usually about -20 to +100°C.
, preferably in the range of about -20 to +80'C1, more preferably in the range of 0 to +40'C1.

In addition, in the prepolymerization, a molecular weight regulator such as hydrogen can also be used. Such a molecular weight modifier is 1
The intrinsic viscosity [η] of the polymer obtained by prepolymerization measured in a decalin solvent at 35°C is about 0.2 dl/g or more, preferably about 0.2 dl/g or more. 5-10 dl! It is desirable to use the amount such that /g.

The prepolymerization is carried out using the solid titanium catalyst component [A] as described above.
About 0.1 to 500 g per Ig, preferably about 0.3 to 3
00 g, particularly preferably 1 to 100 g of polymer. If the amount of prepolymerization is too large, the production efficiency of the olefin polymer may decrease.

Prepolymerization can be carried out batchwise or continuously.

The olefin polymerization catalyst was prepolymerized as described above, and the obtained solid titanium catalyst component [A], organoaluminum catalyst component [B], and electron donor catalyst component [
Copolymerization (main polymerization) of a higher α-olefin and a nonconjugated diene is carried out in the presence of an olefin polymerization catalyst formed from C].

During copolymerization (main polymerization) of a higher α-olefin and a nonconjugated diene, in addition to the above-mentioned olefin polymerization catalyst, the organic aluminum compound used in producing the olefin polymerization catalyst is added as an organoaluminum compound catalyst component. Those similar to the aluminum compound catalyst component [B] can be used. In addition, in the copolymerization (main polymerization) of a higher α-olefin and a non-conjugated diene, the electron donor catalyst component [C] used in producing the olefin polymerization catalyst is used as an electron donor catalyst component. Something similar can be used. In addition, copolymerization (main polymerization) of higher α-olefin and non-conjugated diene
The organoaluminum compound and electron donor used in this step are not necessarily the same as those used in preparing the olefin polymerization catalyst described above.

Copolymerization (main polymerization) of a higher α-olefin and a nonconjugated diene is usually carried out in a liquid phase.

In the copolymerization (main polymerization) of a higher α-olefin and a nonconjugated diene, the solid titanium catalyst component [A] has a polymerization volume I
It is usually used in an amount of about 0.001 to about 1.0 mmol, preferably about 0.005 to 0.1 mmol, calculated as titanium atom per I. In addition, in the organoaluminum compound catalyst component [B], the metal atoms in the organoaluminum compound catalyst component [B] are usually about 1 to 2000 mol, preferably about 1 to 2000 mol, per 1 mol of titanium atoms in the solid titanium catalyst component [A]. is used in an amount of about 5 to 500 moles.

Further, the electron donor catalyst component [C] is usually about 0.001 to 10 mol, preferably about 0.01 to 10 mol, per mol of metal atom in the organoaluminum compound catalyst component [B].
The amount used is such that it is 2 mol, particularly preferably about 0.05 to 1 mol.

If hydrogen is used during the main polymerization, the molecular weight of the resulting polymer rubber can be adjusted.

The polymerization temperature of higher α-olefin and non-conjugated diene is usually about 20 to 200°C, preferably about 40 to 100°C, and the pressure is usually normal pressure to 100 kg/ci, preferably normal pressure to 50 kg/ci. Set to C[lf. In the copolymerization (main polymerization) of a higher α-olefin and a nonconjugated diene, the polymerization can be carried out in any of a batch method, a semi-continuous method, and a continuous method. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

Conductivity imparting agent (B) As the conductivity imparting agent (B) used in the present invention, conventionally known conductivity imparting agents (conductive fillers), specifically,
Examples include carbon black, carbon fiber, metal powder, and metal fiber. These conductivity imparting agents may be used alone or in combination.

Carbon black is preferred in the present invention.

In the present invention, the conductivity imparting agent (B) is used in an amount of 5 to 200 parts by weight, preferably 40 to 200 parts by weight, based on 100 parts by weight of the above-mentioned higher α-olefin copolymer rubber (A). used.

The conductive rubber according to the present invention is a vulcanized product obtained by blending 5 to 200 parts by weight of a conductivity imparting agent (B) with 100 parts by weight of the above-described high α-olefin copolymer rubber (A). An auxiliary agent used in the vulcanization reaction,
For example, it may contain a metal activator, a compound having an oxymethylene structure, and a scorch inhibitor. Furthermore, when the conductive rubber according to the present invention contains additives such as rubber reinforcing agents, fillers, softeners, anti-aging agents, and processing aids,
Moldability during the production of conductive rubber is further improved. Therefore, in the present invention, it is preferable to use the above additives.

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

That is, the conductive rubber according to the present invention is produced by molding and vulcanizing a rubber compound containing the above-mentioned high α-olefin copolymer rubber (A) and conductivity imparting agent (B). obtain.

Vulcanization is carried out by adding a vulcanizing agent to the higher α-olefin copolymer rubber (A) and the conductivity imparting agent (B), but it is preferable to add the vulcanizing agent before molding.

Further, as a method of vulcanizing the high-grade α-olefin copolymer rubber, sulfur vulcanization and organic peroxide vulcanization are effective.

Specifically, sulfur compounds used in sulfur vulcanization include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide,
Examples include tetramethylthiuram disulfide and selenium dimethyldithiocarbamate. Among them, sulfur is preferably used. The amount of the sulfur compound is 0.0% per 100 parts by weight of the higher α-olefin copolymer rubber (A).
It is used in an amount of 1 to 10 parts by weight, preferably 0.5 to 5 parts by weight.

Further, when a sulfur compound is used as a vulcanizing agent, it is preferable to use a vulcanization accelerator together. Specifically, the vulcanization accelerators include N-cyclohexyl-2-benzothiasheet 1 sulfenamide, N-oxydiethylene-2
-benzothiazolesulfenamide, N,N-diisopropyl-2-benzothiazolesulfenamide, 2
-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,
Thiazole-based compounds such as 6-ethyl-4-morpholinothio)benzothiazole and dibendithiazyl disulfide; guanidine-based compounds such as diphenylguanidine, triphenylguanidine, diorthotolylguanidine, orthotolyl-bi-guanide, diphenylguanidine-futa, and late; Compounds; Aldehyde amines or aldehyde-ammonia compounds such as acetaldehyde-aniline reactants, butyraldehyde-aniline condensates, hexamethylenetetramine, acetaldehyde ammonia; imidacillin compounds such as 2-mercaptoimidacillin; thiocarbamic acid, jethi Thiourea-based compounds such as ruthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea; tetramethylthiuram monosulfide, tetramethylthiuram disulfide,
Thiuram compounds such as tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, zinc di-n-butyldithiocarbamate,
Examples include dithioate salt compounds such as zinc ethyl phenyl dithiocarbamate, zinc butylphenyl dithiocarbamate, sodium dimethyl dithiocarbamate, selenium dimethyl dithiocarbamate, and tellurium diethyldithiocarbamate; compounds such as xanthate compounds such as zinc dibutyl xanthate. be able to.

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

Specifically, the organic peroxide vulcanizing agent used in organic peroxide vulcanization includes dicumyl peroxide, 2.
5-dimethyl-2,5-di(rerl-butylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5
-di(tetj-butylperoxy)hexyne-3, di-1crt-butylperoxide, di-terj-butyl/lz/lzoxy-3.3.5-1'limethylcyclohexane, tel-butylhydroperoxide, etc. can. Among them, dicumyl peroxide,
Di1erl-butyl peroxide and di-tert-butylperoxy-3,3,5-)limethylcyclohexane are preferably used.

In the present invention, the above-mentioned organic peroxide vulcanizing agent is usually 3 x 10' to 5 x 10 -2 mol, preferably 1 x 10 -2 mol, preferably 1
They may be used singly or in a mixture of two or more at a ratio of x10-3 to 3x10-2 moles.

In the present invention, when an organic peroxide is used as a vulcanizing agent, it is desirable to use a vulcanizing aid in combination. 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, Examples include maleimide compounds and divinylbenzene. Such a vulcanization aid is used in a proportion of 0.5 to 2 mol, preferably about equimolar, per 1 mol of the organic peroxide vulcanizing agent used.

Furthermore, in producing the conductive rubber according to the present invention, the following vulcanization aid is added to the high-grade α-olefin copolymer rubber (A) in combination with the above-mentioned vulcanizing agent. is preferable.

Examples of vulcanization aids that are preferably used in combination 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, and calcium oxide. These metal activators include higher α-olefin copolymer rubber (A)1.
00 parts by weight, 3 to 15 parts by weight, preferably 5 to 15 parts by weight
It is preferable to use it in a proportion of 10 parts by weight.

Additionally, in order to cope with various rubber processing steps, it is desirable to add a compound having an oxyethylene structure and a scorch inhibitor.

Specific examples of the compound having an oxyethylene structure used in the present invention include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol.

These compounds are usually 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 (A).

As the scorch inhibitor, a known scorch inhibitor can be used, and specific examples include maleic anhydride and salicylic acid. The above-mentioned scorch inhibitor is usually a high-grade α-olefin copolymer rubber (A
)1. It is used in a proportion of 0.2 to 5 parts by weight, preferably 0.3 to 3 parts by weight, based on the amount of OOM.

When the conductive rubber according to the present invention contains rubber reinforcing agents, fillers, softeners, anti-aging agents, processing aids, etc., its properties as a conductive rubber will be better.

These additives may be mixed into the higher α-olefin copolymer rubber (A) and the conductivity imparting agent (B) at an appropriate time before or after vulcanization.

Rubber reinforcing agents used in conjunction with vulcanizing agents, etc.
Specific examples include finely divided silicic acid and short fibers such as cotton, polyester, nylon, and glass.

Specifically, light calcium carbonate, heavy calcium carbonate, talc, clay, etc. are used as the filler.

These reinforcing agents and fillers are generally blended in an amount of 200 parts by weight or less, preferably 150 parts by weight or less, based on 100 parts by weight of the higher α-olefin copolymer rubber (A).

Examples of softeners include process oils, lubricating oils, paraffin, liquid paraffin, petroleum asphalt, petroleum-based substances such as petrolatum, coal tars such as coal tar and coal tar pitch, castor oil, linseed oil, and rapeseed oil. Oil, fatty oil such as coconut oil, tall oil, waxes such as wax, beeswax, carnauba wax, lanolin, fatty acids or their metal salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate, petroleum resin, atactic acid. Synthetic polymer substances such as polypropylene and coumaron indene resin, ester plasticizers such as dioctyl phthalate, dioctyl adipate, and dioctyl sebacate, other microcrystalline waxes, sub(factice), liquid polybutadiene, modified liquid polybutadiene, liquid thiocol, etc. can be mentioned.

These softeners are generally 70 parts by weight or less per 1.00 parts by weight of the higher α-olefin copolymer rubber (A),
It is preferably blended in an amount of 50 parts by weight or less.

Further, by using an anti-aging agent, it is possible to extend the material life of the conductive rubber according to the present invention. This is the same as in the case of ordinary rubber.

Specifically, the anti-aging agents used in this case include aromatic secondary amine 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 comethane, bis[2-
methyl-4-(3-n-alkylthiopropionyloxy)-5-1-butylphenyl], thioether stabilizers such as sulfide, dithiocarbamate stabilizers such as nickel dibutyldithiocarbamate, etc. alone or in combination of two or more. Formulated in combination.

Such anti-aging agents are used in a proportion of usually 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the high α-olefin copolymer rubber (A). .

As processing aids, compounds commonly used in rubber processing can be used, specifically, = 54-ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, calcium stearate,
Zinc stearate 1. ] esters of diantacids l, );
Examples include higher fatty acids, their salts, and their esters.

These processing aids are usually used in an amount of about 10 parts by weight or less, preferably about 1 to 5 parts by weight, based on 100 parts by weight of the higher α-olefin copolymer rubber (A). .

In addition, in the present invention, natural rubber, IR, CR,
Other rubbers such as diene rubber such as NBR and EPDM1-chlorosulfonated polyethylene may 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, higher α-olefin copolymer rubber (A),
After kneading the conductivity imparting agent (B) and necessary additives such as reinforcing agents, fillers, and softeners using a mixer such as a Banbury mixer at a temperature of about 80 to 170°C for about 3 to 10 minutes. , a vulcanizing agent, and a vulcanizing aid are additionally mixed using rolls such as an open roll, and the roll temperature is approximately 40 to 80.
The rubber compound is prepared in the form of a ribbon or sheet by kneading and dispensing for about 5 to 30 minutes at °C.

Next, the rubber compound prepared as described above is fractionated using a roll machine, a calendar machine, an extrusion molding machine, etc., and is heated to 130 to 220°C to perform vulcanization.

Effects of the Invention The conductive rubber according to the present invention is composed of a vulcanizate containing a specific high-grade α-olefin copolymer rubber and a conductivity imparting agent in a specific ratio, so it is different from conventional conductive rubber. It has superior dynamic fatigue resistance and electrical conductivity compared to other materials.

(The following is a blank space) The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 (Preparation of solid titanium catalyst component) 95.2 g of anhydrous magnesium chloride, 442 ml of decane
and 390.6 g of 2-ethylhexyl alcohol at 1
After heating the reaction at 30°C for 2 hours to obtain a homogeneous solution,
3 g of phthalic anhydride 2 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 obtained in this way to room temperature, this homogeneous solution 75
The entire amount was added dropwise over 1 hour to 200 ml of titanium tetrachloride maintained at -20°C. After charging, the temperature of this mixed liquid was raised to 110°C over 4 hours, and then heated to 110°C.
When the temperature reached 0℃, diisobutyl phthalate 5.22
g was added thereto, and the mixture was kept at the same temperature for 2 hours with stirring. After the completion of the 2-hour reaction, the solid portion was collected by hot filtration, and this solid portion was resuspended in 275 ml of titanium tetrachloride, and then the heating reaction was performed again at 110-57°C for 2 hours. Ta. After the reaction was completed, the solid portion was collected again by hot filtration and thoroughly washed with decane and hexane at 10° C. until no free titanium compound was detected in the washing liquid. The solid titanium catalyst component prepared by the above procedure was stored as a decane slurry.
A portion of this is dried for the purpose of investigating the catalyst composition. The composition of the solid titanium catalyst component thus obtained was 2.2% by weight of titanium, 58.1% by weight of chlorine, and 19% by weight of magnesium.
．． 2% by weight and 10.7% by weight of diisobutyl phthalate.

(Polymerization) Decane was added to a 500 ml polymerization vessel equipped with a stirring blade.
2 ml, 100 ml of octene-1. ? -Methyl-1
, 6-octadiene (8 ml) was charged. The temperature of this solution was raised to 50° C., and hydrogen and nitrogen were continuously introduced into the solution at a rate of IOA and 50 A per hour, respectively.

After raising the temperature to 50°C, 0.625 mmol of triisobutylaluminum, 0.21 mmol of trimethylethoxysilane, and 0.0125 mmol of solid titanium catalyst component in terms of titanium atoms were charged to initiate polymerization. 50
After polymerization was carried out at .degree. C. for 30 minutes, a small amount of isobutyl alcohol was added to stop the polymerization, and the polymerization solution was poured into a large amount of methanol to precipitate a copolymer.

Next, the precipitated copolymer was collected and dried under reduced pressure at 12.0°C overnight to give 1g of octene-1.7 at 15°C.
-Methyl-1,6-octadiene copolymer was obtained.

The intrinsic viscosity [η] of the obtained copolymer measured in decalin at 135°C was 3.0 dl! /g, and the iodine value (1
v) is 20, octene-1 and 7-methyl-1,6
-octadiene (octene-1/7-methyl-1,6-octadiene) was 91/9.

The above polymerization conditions are shown in Table 1.

Vulcanized rubber test pieces were prepared according to the following procedure and subjected to the following tests.

First, using an 8-inch open roll (manufactured by Nippo Roll Co., Ltd.), the compounded rubber was separated by kneading according to the recipe shown in Table 2.
A compounded rubber sheet with a thickness of about 2 mUl was obtained.

The above kneading time was 15 minutes, and the surface temperature of the rolls was 50°C (front roll/back roll) and 150°C.

Table 2 Octene-1,7-methyl-1,6-octadiene copolymer rubber 100.0 Acetylene black 140.0 Dicumyl peroxide 0,8 Triallylisocyanurate 1,51) Surface area (
Nitrogen adsorption method) 61rrf/g, average particle size (nitrogen adsorption method)
490 people, 1 of the above compounded rubber sheets manufactured by Denki Kagaku Kogyo ■
Vulcanization was performed at 60° C. for 30 minutes to obtain a vulcanized rubber.

The tensile strength and elongation of the obtained vulcanized rubber were determined according to 113 and 6301, and ^STM D 257
The specific volume resistivity was determined according to the following. Furthermore, this vulcanized rubber was subjected to a bending test to evaluate its dynamic fatigue resistance. The bending test was performed using a dematcher testing machine to examine resistance to crack growth. That is, the number of bending times until the crack became 15 mm was measured.

The results are shown in Table 3.

Example 2 In Example 1, octene-1,7-methyl-1,6
- Instead of the octadiene copolymer rubber, hexene obtained by copolymerizing in the same manner as in Example 1 except using a higher α-olefin and changing the polymerization conditions as shown in Table 1 above.
A vulcanized rubber was obtained in exactly the same manner as in Example 1, except that door methyl-1,6-octadiene copolymer rubber was used.
We conducted the evaluation.

The results are shown in Table 3.

Example 3 62 In Example 1, octene-1.7-methyl-1,6
-4-Methylpentene-octenate 7-1 obtained by copolymerizing in the same manner as in Example 1 except using a higher α-olefin and changing the polymerization conditions as shown in Table 1 above instead of the octadiene copolymer rubber. A vulcanized rubber was obtained and evaluated in exactly the same manner as in Example 1, except that methyl-1,6-octadiene copolymer rubber was used.

The results are shown in Table 3.

Example 4 In Example 1, the amount of acetylene black was changed to 60
Vulcanized rubber was obtained and evaluated in exactly the same manner as in Example 1, except that the parts by weight were changed.

The results are shown in Table 3.

Example 5 In Example 1, the amount of acetylene black was changed to 10
A vulcanized rubber was obtained and evaluated in exactly the same manner as in Example 1, except that the amount was 0 parts by weight.

The results are shown in Table 3.

Example 6 63 In Example 1, the amount of acetylene black was 20
A vulcanized rubber was obtained and evaluated in exactly the same manner as in Example 1, except that the amount was 0 parts by weight.

The results are shown in Table 3.

Example 7 In Example 1, instead of 40 parts by weight of acetylene black, Ketchien black EC [surface area (nitrogen adsorption method) 1,000 rrf/g, average particle size (nitrogen adsorption method) 30
μm1 manufactured by Lion Akzo Co., Ltd.] was used in an amount of 5 parts by weight.
Vulcanized rubber was obtained in exactly the same manner as in Example 1 and evaluated.

The results are shown in Table 3.

Example 8 A vulcanized rubber was obtained and evaluated in exactly the same manner as in Example 7, except that the amount of Ketchen Black EC was changed to 40 parts by weight.

The results are shown in Table 3.

Comparative Example 1 In Example 1, the amount of acetylene black was 25
An attempt was made to obtain a vulcanized rubber in the same manner as in Example 1 except that the amount was 0 parts by weight, but kneading was difficult and no vulcanized rubber suitable for testing could be obtained.

Comparative Example 2 A vulcanized rubber was obtained and evaluated in exactly the same manner as in Example 7, except that the amount of Ketchen Black EC was changed to 2 parts by weight.

The results are shown in Table 3.

Comparative Example 3 In Example 1, octene-1,7-methyl-1,6
- Vulcanized rubber was obtained and evaluated in exactly the same manner as in Example 1, except that silicone rubber was used instead of the octadiene copolymer rubber.

The results are shown in Table 3.

AA -

[Brief explanation of drawings]

FIG. 1 is a flowchart showing the steps for preparing an olefin polymerization catalyst used in the production of a higher α-olefin copolymer rubber in the present invention. Patent applicant Mitsui Petrochemical Industries Co., Ltd. Agent Patent attorney Shun Suzuki -67=

Claims (1)

[Scope of Claims] 1) (A) Consists of a higher α-olefin having 6 to 12 carbon atoms and a non-conjugated diene represented by the following general formula [I], and the limit measured in a decalin solvent at 135°C Viscosity [η] is 1
．． It is in the range of 0 to 10.0 dl/g, and the iodine value is 1 to
High-grade α-olefin copolymer rubber 1 in the range of 50
00 parts by weight, and (B) 5 to 200 parts by weight of a conductivity imparting agent; ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] In the formula, R^1 represents an alkyl group having 1 to 4 carbon atoms, and R^2 and R^3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.However, R^2 and R^3 are both hydrogen atoms. (It is never the case.)