JP2001002896A - Conductive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive resin composition having low resistivity, and being excellent in moldability and molded appearance. SOLUTION: A conductive resin composition comprises (A) an epoxidized diene block copolymer, (B) a conductive filler and (C) a thermoplastic resin other than the epoxidized diene block copolymer. Alternatively, the composition comprises (A) the epoxidized diene block copolymer, (B) the conductive filler and (C) a thermoplastic elastomer other than the epoxidized diene block copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to electric, electronic, OA
The present invention relates to a conductive resin composition which can be used in the fields of equipment, automobiles, electric wires and the like, has a low resistivity, and has excellent moldability and appearance.

[0002]

2. Description of the Related Art Thermoplastic resins are widely used in electric, electronic, OA equipment, automobile fields and the like, taking advantage of their advantages such as light weight and ease of shaping. In particular, ABS resin or A
Hard resins containing S resin and PS resin are widely used in various fields because of their excellent mechanical strength, impact strength, heat resistance and dimensional stability.

[0003] On the other hand, a thermoplastic elastomer is a soft material that has recently attracted attention as an alternative material to a vulcanized rubber because a rubber elasticity can be obtained without a vulcanizing step.

[0004] In order to impart conductivity to these hard resins and thermoplastic elastomers, it is known to add a conductive filler such as carbon black or carbon fiber.

[0005] However, in the method of adding carbon black to the hard resin, the effect of reinforcing the strength and rigidity is small, and the impact strength is reduced. In addition, in the method of adding carbon fiber, strength, rigidity and other reinforcing effects are seen, but anisotropy is strong, and it is difficult to ensure dimensional accuracy.
In order to obtain sufficient conductivity, a large amount of addition is required, and there is also a problem in terms of cost.

On the other hand, soft conductive materials such as thermoplastic elastomers are used for conductive rollers and the like in the fields of OA equipment parts, automobiles, home electric parts, medical and food equipment parts, electric wires, miscellaneous goods and the like. As the conductive roller, a roller obtained by laminating a soft conductive material on a metal core material is generally used.

However, a composition obtained by adding a conductive filler to a thermoplastic elastomer has poor moldability and has problems in physical properties such as compression set. Therefore, as a soft conductive material, a rubber composition obtained by blending a conductivity imparting agent with a vulcanized rubber is widely used. However, vulcanized rubber requires complicated steps such as a vulcanizing step at the time of production, and materials that do not require these steps are desired.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a conductive resin composition having low resistivity, excellent moldability, and excellent molded appearance.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and have found that (A) an epoxidized diene-based block copolymer, (B) a conductive filler, and (C) an epoxy resin. A conductive resin composition comprising a thermoplastic resin other than the diene-based block copolymer was found, and the present invention was completed.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The diene block copolymer (A) as a raw material of the epoxidized diene block copolymer in the present invention is mainly composed of a polymer block mainly composed of a vinyl aromatic compound and a conjugated diene compound. A block copolymer comprising a polymer block, wherein the weight ratio of the vinyl aromatic compound to the conjugated diene compound (the weight ratio of the block copolymer) is from 5/95 to 90/10, and especially from 10/90 to
A weight ratio of 80/20 is preferred. The number average molecular weight of the block copolymer used in the present invention is 5,000 to 1,5.
00,000, preferably 10,000-800,00
0 and the molecular weight distribution [weight average molecular weight (Mw)]
(Mw / Mn)] and the number average molecular weight (Mn) is 10
It is as follows. The molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof. For example, XYX, YX
It is a vinyl aromatic compound (X) block-conjugated diene compound (Y) block copolymer having a structure such as -YX, (XY) 4Si, and XYXYX. Further, the unsaturated bond of the conjugated diene compound of the diene-based block copolymer may be partially hydrogenated.

Examples of the vinyl aromatic compound constituting the diene block copolymer include styrene, α-methylstyrene, vinyltoluene, p-tertiary butylstyrene, divinylbenzene, p-methylstyrene, 1,1-
One or more of diphenylstyrene and the like can be selected, and among them, styrene is preferable.

The conjugated diene compounds include, for example, butadiene, isoprene, 1,3-pentadiene,
2,3-dimethyl-1,3-butadiene, piperylene,
3-butyl-1,3-octadiene, phenyl-1,3
-One or two or more of butadiene and the like are selected, and among them, butadiene, isoprene and a combination thereof are preferable.

As a method for producing the block copolymer used in the present invention, any production method having the above-mentioned structure can be adopted. For example,
23798, JP-B-47-3252, JP-B-48-
No. 2423, Japanese Patent Application No. 49-105970, Japanese Patent Application No. 50
-27094, JP-B-46-32415, JP-A-5
According to the methods described in JP-A Nos. 9-166518, JP-B-49-36957, JP-B-43-17979, JP-B-46-32415, and JP-B-56-28925, a lithium catalyst or the like is used. A vinyl aromatic compound-conjugated diene compound block copolymer can be synthesized in an active solvent.

Further, JP-B-42-8704, JP-B-43-6636, or JP-A-59-133.
According to the method described in JP-A-203, hydrogenation can be carried out in an inert solvent in the presence of a hydrogenation catalyst to synthesize a partially hydrogenated block copolymer for use in the present invention.

The epoxidized diene-based block copolymer used in the present invention can be obtained by epoxidizing the above-mentioned diene-based block copolymer.

The epoxidized diene block copolymer in the present invention can be obtained by reacting the above block copolymer with an epoxidizing agent such as hydroperoxides and peracids in an inert solvent. Examples of peracids include formic acid, peracetic acid, and perbenzoic acid. In the case of hydroperoxides, a catalytic effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tertiary butyl hydroperoxide. . There is no strict limit on the amount of epoxidizing agent, and the optimal amount in each case depends on the particular epoxidizing agent used, the desired degree of epoxidation,
It is determined by variable factors such as the individual block copolymer used.

The obtained epoxidized diene block copolymer can be isolated by a suitable method, for example, a method of precipitating with a poor solvent, a method of throwing the polymer into hot water with stirring and distilling off the solvent, It can be performed by a direct desolvation method or the like.

The epoxy equivalent of the obtained epoxidized (hydrogenated) diene block copolymer is preferably from 200 to 1
It is in the range of 0000.

The compounding ratio of the epoxidized (hydrogenated) diene-based block copolymer is 0.1 to 30 parts by weight, preferably 0.1 to 30 parts by weight, per 100 parts by weight of the thermoplastic resin (C).
It is 20 parts by weight, more preferably 0.1 to 10 parts by weight.

The conductive filler (B) in the present invention comprises:
The resin composition of the present invention is used to exhibit suitable conductivity, and is exemplified below, but is not limited thereto. For example, carbon materials such as carbon black, graphite, and carbon fibers; metal powders such as aluminum and magnesium; metal materials such as metal fibers;

As the physical properties of carbon black, the average particle size of primary particles of carbon black is preferably from 5 to 300 nm, more preferably from 10 to 100 nm. If the particle size is extremely large, the specific surface area tends to be small, and the conductivity tends to be poor. On the other hand, if the particle size is extremely small, the dispersibility in the matrix resin tends to be poor. The amount of dibutyl phthalate (hereinafter referred to as DBP) lubrication is 1
0 to 1000 mL / 100 g is preferable, and 50 to 300 mL
More preferably, it is mL / 100 g. If the DBP lubrication amount is extremely small, sufficient conductivity tends not to be obtained. Furnace black and acetylene black are mentioned as carbon blacks satisfying these preferred conditions. Specifically, "Denka Black Granules" manufactured by Denki Kagaku Co., Ltd. and "Mitsubishi Conductive Carbon Black # 3600" manufactured by Mitsubishi Chemical Co., Ltd. Such as from the market.

The carbon fiber is generally produced by firing using cellulose fiber, acrylic fiber, lignin, petroleum or carbon-based special pitch as a raw material, and is made of various types such as flame-resistant, carbonaceous or graphite. There is no particular limitation on the base material. The average of the aspect ratio (fiber length / fiber diameter) of the carbon fiber is preferably 10 or more, and more preferably 50 or more. If the average of the aspect ratios is less than 10, the conductivity, strength, and rigidity decrease. Generally, the diameter of the carbon fiber is 3 to 15 μm. In order to adjust such an aspect ratio, any shape such as a chopped strand, a roving strand, and a milled fiber can be used. They can be used in combination.

The average of the aspect ratios of the carbon fibers can be determined, for example, by placing the molded body on a glass plate in a state of being dissolved in a solvent and using an image analyzer (TOSIX-i, an image processing R & D system manufactured by Toshiba Corporation). It can be performed using: The surface of the carbon fiber may be subjected to a surface treatment, for example, an epoxy treatment, a urethane treatment, an oxidation treatment, or the like, in order to increase the affinity with the resin, as long as the properties of the composition of the present invention are not impaired. As such carbon fiber, for example, Vesfight HTA-C6 from Toho Rayon Co., Ltd.
Commercially available as -SR.

The graphite preferably has a scale shape. As graphite having a flake shape, either natural graphite, which is graphite as a mineral name, or artificial graphite obtained by heat-treating amorphous carbon at about 3000 ° C. to artificially orient micrographite crystals having an irregular arrangement. One or both can be mixed and used. The average particle size of the flake-shaped graphite is preferably at least 120 mesh, more preferably at least 200 mesh. When the average particle size is less than 120 mesh, the effect of improving anisotropy and the conductivity are reduced.

The average particle size of the flaky graphite can be determined by, for example, a Tyler standard sieve. The surface of graphite having a flake shape is subjected to a surface treatment, for example, an epoxy treatment, a urethane treatment, an oxidation treatment, etc., in order to increase the affinity with the resin as long as the properties of the composition of the present invention are not impaired. Good. Nippon Sheet Glass Co., Ltd. has provided carbon flake # 5 as such scaly graphite.
It is commercially available as 85.

The mixing ratio of these conductive fillers is 2 to 200 parts by weight based on 100 parts by weight of the thermoplastic resin other than (C) the epoxidized diene-based block copolymer.
Preferably it is 4 to 50 parts by weight, more preferably 5 to 20 parts by weight.

The thermoplastic resin other than the epoxidized diene block copolymer (C) other than the epoxidized diene block copolymer in the present invention is not particularly limited as long as it is a moldable resin. For example, in the case of a hard conductive resin, a styrene resin, a polyolefin resin such as polyethylene or polypropylene, an aromatic polycarbonate resin, a polyamide resin, a polyphenylene ether resin, a polyethylene terephthalate (PET), a polybutylene terephthalate (PBT) or the like. And the like. Preferably, an aromatic polycarbonate resin alone, or a methacrylic acid ester, an acrylic acid ester, an aromatic monovinyl compound and a vinyl cyanide compound in the presence of an aromatic polycarbonate resin and a diene rubber component. A rubber-containing thermoplastic resin obtained by copolymerizing at least two kinds of vinyl monomers selected from the group consisting of compounds, and / or an aromatic vinyl monomer and a vinyl cyanide monomer are copolymerized. A thermoplastic resin obtained by blending with a thermoplastic resin is exemplified.

The aromatic polycarbonate resin is an aromatic polycarbonate produced by a known phosgene method or a melting method (see, for example, JP-A-63-215763 and JP-A-2-124934). The polycarbonate resin is composed of a carbonate component and a diphenol component. Examples of the precursor for introducing the carbonate component include phosgene and diphenyl carbonate. Suitable diphenols include, for example, 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A); 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane; -Bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane;
1-bis (4-hydroxyphenyl) decane; 1,4-
Bis (4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclododecane; 1,1
-Bis (3,5-dimethyl-4-hydroxyphenyl)
4,4-dihydroxydiphenyl ether; 4,4-thiodiphenol; 4,4-dihydroxy-3,3-dichlorodiphenyl ether;
-Dihydroxy-2,5-dihydroxydiphenyl ether and the like. These can be used alone or in combination. In addition, it is also possible to use a compound having three or more phenolic hydroxyl groups.

A rubber obtained by copolymerizing at least two kinds of vinyl monomers selected from the group consisting of methacrylates, acrylates, aromatic monovinyl compounds and vinyl cyanide compounds in the presence of a diene rubber component. Specific examples of the contained thermoplastic resin include ABS resin, MBS
Resins. The butadiene rubber in the rubber-containing thermoplastic resin includes, for example, polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer and the like.

Examples of the methacrylic acid ester and acrylic acid ester include lower alkyl esters of methacrylic acid and acrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl acrylate. Examples of the aromatic monovinyl compound include styrene, α-methylstyrene, halogenated styrene, vinyltoluene and the like. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. The rubber-containing thermoplastic resin may be produced by any one of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be one-stage copolymerization or multi-stage copolymerization. Further, two or more copolymers may be used in combination.

The thermoplastic resin obtained by copolymerizing an aromatic vinyl monomer and a vinyl cyanide monomer is a resin generally referred to as an AS resin. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, halogenated styrene, vinyltoluene and the like, and preferably styrene and α-methylstyrene. Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile. Further, other vinyl monomers copolymerizable with these, such as methyl methacrylate,
Maleimide or the like can be copolymerized.

In the case of a soft conductive resin, a thermoplastic elastomer can be used. For example, a styrene-based thermoplastic elastomer, a polyolefin-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, and the like can be given. Among them, styrene-based thermoplastic elastomers and polyolefin-based thermoplastic elastomers are preferred from the viewpoint of low hardness.

Preferred examples of the styrene thermoplastic elastomer used in the present invention include hydrogenated styrene / butadiene block copolymers, hydrogenated styrene / isoprene block copolymers, and mixtures thereof. And styrene / conjugated diene block copolymer as a basic component. As the hydrogenated product of the styrene / conjugated diene block copolymer, the conjugated diene is a polymer block consisting of butadiene alone, isoprene alone, or a mixture of isoprene and butadiene, specifically, styrene / butadiene / styrene. A hydrogenated product of a block copolymer (hereinafter sometimes simply referred to as "hydrogenated S-B-S"), a hydrogenated product of a styrene-isoprene-styrene block copolymer (hereinafter simply referred to as "hydrogenated S-B-S"). IS).) Or styrene-isoprene-butadiene.
A hydrogenated product of a styrene block copolymer (hereinafter sometimes simply referred to as “hydrogenated S-BI-S”) may be mentioned.

The hydrogenated styrene / conjugated diene block copolymer has a weight average molecular weight of 50,000 to 50,000.
500,000, preferably 120,000 to 450,
000, particularly preferably 150,000 to 400,000.
0, styrene content is 5 to 50% by weight, preferably 8 to
45% by weight, particularly preferably 10 to 40% by weight, 1,2
A block copolymer having a microstructure of less than 50%, preferably less than 45% and a degree of hydrogenation of 95% or more, preferably 97% or more, is used.

The hydrogenated styrene-conjugated diene block copolymer having a weight-average molecular weight of less than 50,000 tends to have poor rubber elasticity and mechanical strength, and those having a weight-average molecular weight exceeding 500,000 tend to have poor moldability. Becomes

Further, hydrogenated SIS and hydrogenated S-BI
-S is disclosed in JP-A-2-102212 and JP-A-3-1321.
No. 88114, i.e., styrene and isoprene or isoprene-butadiene are converted to 100
Parts by weight, 0.01 to 0.2 parts by weight of an alkyllithium compound as an initiator and 0.04 to 0.8 parts by weight of a coupling agent, and 0.1 to 100 parts by weight of an initiator.
It is obtained by sequentially polymerizing in an inert catalyst at -20 to 80 ° C. for 1 to 50 hours in the presence of ４００400 parts by weight of a Lewis base, and then hydrogenating isoprene or isoprene-butadiene block. Examples of commercially available products include "Clayton G" manufactured by Shell Japan, "Septon" and "High Blur" manufactured by Kuraray Co., Ltd., "Toughtec" manufactured by Asahi Kasei Kogyo Co., Ltd., and "Dynaron" manufactured by Nippon Synthetic Rubber Co., Ltd.

Styrene-based thermoplastic elastomers containing a hydrogenated styrene / conjugated diene block copolymer as a base are described, for example, in Mitsubishi Chemical Corporation.
"Lavalon", Shell Japan Co., Ltd. "Clayton G Compound", Kuraray Co., Ltd. "Septon Compound", Asahi Kasei Kogyo Co., Ltd. "Tuftec Compound E Series, S Series" and the like.

Suitable examples of the olefin-based thermoplastic elastomer used in the present invention include olefin-based copolymer rubbers such as ethylene-propylene copolymer rubber (EPM) and ethylene-propylene-non-conjugated diene copolymer rubber ( (EPDM) or other elastomers of amorphous random copolymers containing olefins as the main component, or those containing heat-treated elastomers cross-linked mainly by radicals as a basic component, in the presence of organic peroxides Can be mentioned. Specific examples of the olefin copolymer rubber include the above-mentioned ethylene / propylene copolymer rubber (EPM) and ethylene / 1-butene copolymer rubber (EP
M), ethylene-propylene-butene copolymer rubber, ethylene-hexene copolymer, ethylene-heptene copolymer, ethylene-octene copolymer, ethylene-4-methylpentene-1 copolymer and non-conjugated diene Aliphatic butenes such as butene-1,1,4-hexadiene,
Ethylidene norbornene, 5-methylnorbornene, 5
-Ethylene / propylene / non-conjugated diene copolymer rubber using vinyl norbornene, dicyclopentadiene, dicyclooctadiene and the like.

These copolymers or copolymer rubbers include random copolymers, block copolymers, graft copolymers,
Any of the alternating copolymers may be used, and the production method and shape are not particularly limited. These olefin-based copolymer rubbers may be used alone or in combination of a plurality of components. These olefin copolymer rubbers have a weight average molecular weight of 50,000 to 1,000,000, preferably 60,000 to 800,000, particularly preferably 80,000.
00 to 500,000, ethylene content of 30 to 90% by weight, preferably 40 to 80% by weight, Mooney viscosity ML
_{1 + 4} (100 ° C) is 5 to 400, preferably 10 to 35
It is preferable to use 0 copolymer rubber. When the weight average molecular weight of the ethylene-propylene copolymer rubber is less than the above range, rubber elasticity, mechanical strength tends to be inferior, and those whose weight average molecular weight exceeds the above range,
It tends to be inferior in moldability.

The olefin-based thermoplastic elastomers contained as the olefin-based copolymer rubber base are, for example, "Thermolan" manufactured by Mitsubishi Chemical Corporation, "Milastomer" manufactured by Mitsui Petrochemical Industry Co., Ltd., and Sumitomo Chemical. It can be obtained from the market as "Sumitomo TPE" manufactured by Kogyo Co., Ltd. or "Santoprene" manufactured by Advanced Elastomer Systems.

The conductive resin composition of the present invention can be produced by mixing the above components with a mixer such as a tumbler, a V-type blender, a Nauta mixer, a Banbury mixer, a kneading roll, and an extruder. In the production of the conductive resin composition of the present invention, the method of mixing the components and the order of mixing are not particularly limited. As a general method, all components are preliminarily mixed with a tumbler, a V blender, etc.
This is a method of uniformly melting and mixing with an extruder, but it is also possible to use a method of melting and mixing the remaining components into two or more kinds of molten mixtures of these components depending on the shape of the components.

In the resin composition of the present invention, in addition to the above-mentioned components, any additives may be used, if necessary, such as a releasing agent, an antistatic agent, a light stabilizer, an antioxidant, as long as the properties are not impaired. Agents, reinforcing agents, softeners, foaming agents, dyes and pigments, inorganic fillers and the like can be added.

Examples of the releasing agent include pentaerythritol tetrastearate, pentaerythritol tetraperargonate, stearyl stearate, behenyl behenate, stearyl mono-, di- or triglyceride, sorbitan monostearate, paraffin wax, beeswax, polywax Examples thereof include dimethylsiloxane and phenyl group-containing dimethylsiloxane.

Examples of the antistatic agent include glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, mono- or diglyceride maleic anhydride, graphite, metal powder and the like.

Examples of the light stabilizer include 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole and 2- (3-tert-butyl-5-methyl-).
2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl]- 2H-benzotriazole, 2,2′-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2′-p
-Phenylenebis (3,1-benzoxazin-4-one), polyalkylene naphthalate and the like.

Antioxidants include phosphoric acid and phosphoric acid esters such as, for example, trimethyl phosphate; phosphorous acid and phosphites such as, for example, tris (2,4-di-tertbutylphenyl) phosphite; Erythritol tetrakis (3-mercaptopropionate) pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropiolate, octadecyl-3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenephosphonite and the like.

Examples of the reinforcing agent include metal fibers, silicon nitride fibers, potassium titanate whiskers, boron fibers, aromatic polyamide fibers, aromatic polyester fibers, carbon fibers, glass beads, glass flakes, titanium oxide,
Examples include alumina, silica, asbestos, talc, clay, mica, and quartz powder.

Examples of the softening agent include a softening agent for hydrocarbon rubber. The hydrocarbon rubber softener is a mixture of an aromatic ring, a naphthene ring, and paraffin, and has a paraffin chain carbon number of 50% of the total carbon.
The oil occupying the above is called paraffinic oil, the oil having 30 to 45% of naphthenic ring carbon is called naphthenic oil, and the oil having more than 30% aromatic carbon is called aromatic oil. It is classified. Among them, it is preferable to use paraffin oil.

[0050]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
However, unless the present invention exceeds the gist,
It is not limited to the example. [Preparation of Epoxidized Diene Block Copolymer] (Preparation Example 1) A stirrer, a reflux condenser, and a thermometer are provided.
Polystyrene-polybutadiene in a jacketed reactor
-Block copolymer of polystyrene [styrene / butadi
En weight ratio = 40/60] 300 g, ethyl acetate 150
0 g was charged and dissolved. Then 30% acetic acid of peracetic acid
165 g of an ethyl solution was continuously dropped, and stirred at 40 ° C. for 3 hours.
The epoxidation reaction was performed for hours. Return the reaction solution to room temperature
Out of the reactor, add a large amount of methanol and
Precipitate the precipitate, filter, wash with water, dry, epoxy
A modified block copolymer was obtained. Epoxidized die obtained
The copolymer block copolymer is referred to as copolymer A (copolymer A).
Epoxy equivalent 490). (Example 2 of adjustment) Equipped with a stirrer, a reflux condenser, and a thermometer
Polystyrene-polybutadiene in a jacketed reactor
-Block copolymer of polystyrene [styrene / butadi
En weight ratio = 20/80] 300 g, cyclohexane 3
000g was charged and dissolved, and the temperature was 60 ° C, as a hydrogenation catalyst.
Di-P-tolylbis (1-cyclopentadienyl) tita
Ium / cyclohexane solution (concentration 1 mmol / litre)
40 ml) and n-butyllithium solution (concentrated)
8 mmol and 0 ° C,
A mixture mixed under a hydrogen pressure of 2.0 kg / cm2 is added,
The reaction was performed at a hydrogen partial pressure of 2.5 kg / cm 2 for 60 minutes.
The resulting partially hydrogenated polymer solution was dried under reduced pressure to remove the solvent.
It was removed (80% hydrogenation rate of the whole butadiene portion). This part
1500 g of cyclohexane is added to 300 g of the hydrogenated polymer.
The preparation was dissolved. Then 30% by weight of peracetic acid in ethyl acetate
200 g of the solution was dropped continuously, and the mixture was stirred at 40 ° C for 3 hours.
A poxidation reaction was performed. Return the reaction solution to room temperature
Take out from the reactor and add a large amount of methanol to polymer
Precipitate, filter, wash with water, dry,
A lock copolymer was obtained. The obtained epoxidized diene base
The lock copolymer is referred to as copolymer B (epoxidation of copolymer).
460). (Adjustment Example 3) Equipped with a stirrer, a reflux condenser, and a thermometer
Polystyrene-polyisoprene in a jacketed reactor
-Block copolymer of polystyrene [styrene / isop
Weight ratio = 30/70] 300 g, cyclohexane 2
Charge and dissolve 500g, nickel catalyst as hydrogenation catalyst
To a hydrogen partial pressure of 15 kg / cm2 and a temperature of 150 ° C.
For 3 hours. The resulting partially hydrogenated polymer solution is
The solvent was removed by drying under reduced pressure.
85%). To 300 g of this partially hydrogenated polymer, cyclo
1500 g of hexane was charged and dissolved. Then peracetic acid
150 g of a 30% by weight ethyl acetate solution was continuously dropped, and stirred.
The epoxidation reaction was performed at 40 ° C. for 3 hours with stirring. reaction
Return the solution to room temperature and take it out of the reactor.
The polymer was precipitated by filtration, washed with water after filtration and dried.
Thus, an epoxy-modified block copolymer was obtained. Got
The epoxidized diene block copolymer is referred to as copolymer C.
(The epoxy equivalent of the copolymer is 750). [Evaluation method] Preparation of test pieces: each material was kneaded using a twin-screw kneading extruder.
And then pelletized. Then inject using these pellets
Using a molding machine, test specimen (100 mm x 100 mm x 2 mm)
Was molded. Volume resistivity: "R" manufactured by Advantest Corporation as an electrode
12702A ”, using a digital camera manufactured by Advantest Inc.
Measured with ultra-high resistance / micro ammeter "R8340A"
did. Molded appearance: The appearance of the test piece was visually observed. Hardness: Condition JI according to the measurement standard of JIS K6301
Measured in SA. Compression set: After 7 pieces of the above test pieces were brought into close contact with each other,
Polished to a thickness of 12.7mm, diameter 29mm
Into a right circular cylinder to form a test specimen for measuring compression set.
Done. This test piece for measuring compression set and thickness 9.52
mm spacer with a measuring device (compressed by Kobunshi Keiki Co., Ltd.)
Attached to a permanent strain tester (based on JIS K6301),
The specimen was compressed 25%. 22 hours at 70 ° C in this state
Heated. Next, the test piece was allowed to stand at room temperature (25 ° C.).
After a lapse of 0 minutes, the thickness was measured. From the measured thickness,
The compression set value was determined from the following equation. CS = (t₀-T₁) /
(T ₀-T_Two) × 100 (CS: compression set value (%), t
₀: Original thickness of test piece (mm), t₁： Test piece from compression device
Take out, thickness (mm) after 30 minutes, t_Two:spacer
(Example 1) Polycarbonate (trade name; Panlite L)
1225 [manufactured by Teijin Chemicals Limited]) 100 parts by weight, carbon fiber
Wei (trade name: Vesfight HTA-C6-SR [Toho Re
-Yon Co., Ltd.] 10 parts by weight, graphite (trade name: CARBON
Flake # 585 [Nippon Sheet Glass Co., Ltd.]) 10 weight
Part, epoxidized diene block copolymer (copolymer
A) After mixing 5 parts by weight with a tumbler, a twin screw extruder
And the test piece was molded by an injection molding machine. Evaluation
Table 1 shows the results. (Example 2) Polycarbonate (trade name; Panlite L)
1225 (manufactured by Teijin Chemicals Limited)) 60 parts by weight, ABS tree
Fat (trade name: Sebian 510 [Daicel Chemical Industries, Ltd.)
40% by weight, carbon fiber (trade name: Vesfight H)
TA-C6-SR [Toho Rayon Co., Ltd.]) 10 weight
Part, graphite (trade name: carbon flake # 585 [Nippon plate
Glass Co., Ltd.] 10 parts by weight, epoxidized diene-based
5 parts by weight of a block copolymer (copolymer B) with a tumbler
After mixing, pelletize with a twin screw extruder and use an injection molding machine
Test specimens were formed. Table 1 shows the evaluation results. (Comparative Example 1) Polycarbonate (trade name; Panlite L)
1225 [manufactured by Teijin Chemicals Limited]) 100 parts by weight, carbon fiber
Wei (trade name: Vesfight HTA-C6-SR [Toho Re
-Yon Co., Ltd.] 10 parts by weight, graphite (trade name: CARBON
Flake # 585 [Nippon Sheet Glass Co., Ltd.]) 10 weight
After mixing the parts with a tumbler, pelletize with a twin screw extruder
The test pieces were molded using an injection molding machine. Table 1 shows the evaluation results.
Shown in

[0051]

[Table 1]

(Example 3) Styrene-based thermoplastic elastomer (trade name: Lavalon T331C [Mitsubishi Chemical Corporation)
), 20 parts by weight of carbon black (trade name: Denka Black Granules [manufactured by Denki Kagaku Co., Ltd.]), and 2 parts by weight of an epoxidized diene-based block copolymer (copolymer C). The pellet was formed by a machine and a test piece was formed by an injection molding machine. Table 2 shows the evaluation results. (Example 4) Styrene-based thermoplastic elastomer (trade name: Lavalon T331C [manufactured by Mitsubishi Chemical Corporation]) 100
20 parts by weight of carbon black (trade name: Denka Black Granules [manufactured by Denki Kagaku Co., Ltd.]) and 5 parts by weight of an epoxidized diene block copolymer (copolymer C) are pelletized by a twin screw extruder. Specimens were molded using an injection molding machine.
Table 2 shows the evaluation results. (Comparative Example 2) Styrene-based thermoplastic elastomer (trade name: Lavalon T331C [manufactured by Mitsubishi Chemical Corporation]) 100
Parts by weight, carbon black (trade name: Denka Black Granules [manufactured by Denki Kagaku]) 20 parts by weight, ethylene-glycidyl methacrylate copolymer (trade name: Bond First E [manufactured by Sumitomo Chemical Co., Ltd.]) 5 parts by weight Was pelletized by a twin-screw extruder and a test piece was molded by an injection molding machine, and the evaluation results are shown in Table 2. Comparative Example 3 Styrene-based thermoplastic elastomer (trade name: Lavalon T331C [manufactured by Mitsubishi Chemical Corporation) ]) 100
20 parts by weight of carbon black (trade name: Denka Black Granules [manufactured by Denki Kagaku Co., Ltd.]) were pelletized by a twin-screw extruder, and a test piece was molded by an injection molding machine. Table 2 shows the evaluation results.

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[Table 2]

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Industrial Applicability The conductive resin composition of the present invention has low volume resistivity and low compression set, is excellent in moldability and appearance, and can be used in the fields of electricity, electronics, OA equipment, automobiles and the like.

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Claims (13)

[Claims] 1. A conductive resin composition comprising (A) an epoxidized diene-based block copolymer, (B) a conductive filler, and (C) a thermoplastic resin other than the epoxidized diene-based block copolymer. 2. The conductive resin composition according to claim 1, wherein the thermoplastic resin other than (C) the epoxidized diene-based block copolymer is an aromatic polycarbonate resin. 3. A thermoplastic resin other than (C) an epoxidized diene-based block copolymer, comprising a methacrylic acid ester, an acrylic acid ester, an aromatic monovinyl compound and a cyano-based resin in the presence of an aromatic polycarbonate resin and a diene-based rubber component. Rubber-containing thermoplastic resin obtained by copolymerizing at least two types of vinyl monomers selected from the group consisting of vinyl cyanide compounds, and / or copolymerization of aromatic vinyl monomers and vinyl cyanide monomers The conductive resin composition according to claim 1, wherein the resin is a thermoplastic resin. 4. The conductive material according to claim 1, wherein the thermoplastic resin (C) other than the epoxidized diene-based block copolymer is a thermoplastic elastomer other than the epoxidized diene-based block copolymer. Resin composition. 5. The conductive resin composition according to claim 4, wherein the thermoplastic elastomer is a styrene-based thermoplastic elastomer and / or an olefin-based thermoplastic elastomer. 6. The conductive resin composition according to claim 1, wherein (B) the conductive filler comprises at least one of carbon black, carbon fiber, and graphite. 7. The conductive resin composition according to claim 6, wherein the primary particles of carbon black have an average particle size of 5 to 300 nm. 8. The conductive resin composition according to claim 6, wherein the carbon black has a dibutyl phthalate oil supply amount of 10 to 1000 mL / 100 g. 9. The carbon fiber according to claim 6, wherein the average of the aspect ratio (fiber length / fiber diameter) is 10 or more.
3. The conductive resin composition according to item 1. 10. The graphite has a scale shape and an average particle size of 1
The conductive resin composition according to claim 6, wherein the conductive resin composition is graphite having a mesh size of 20 mesh or more. (A) An epoxidized diene-based block copolymer comprises a polymer block mainly composed of vinyl aromatic in the same molecule and a polymer block mainly composed of a conjugated diene compound partially containing epoxy. The conductive resin composition according to claim 1, comprising a polymer block mainly composed of a hydrogenated conjugated diene compound partially containing epoxy. 12. The conductive resin composition according to claim 11, wherein the epoxy equivalent of (A) the epoxidized diene-based block copolymer is from 200 to 10,000. 13. Component (A) is 0.1 to 30 parts by weight, and component (B) is 2 to 100 parts by weight of a thermoplastic resin other than the epoxidized diene-based block copolymer (C).
The conductive resin composition according to any one of claims 1 to 12, wherein the amount is 200 parts by weight.