JPS59155419A - Electroconductive resin composition - Google Patents

Abstract

PURPOSE:An electroconductive resin composition having an electrical conductivity <=10<8>OMEGA, containing an unsaturated polyester resin or an epoxy ester resin and grafted fine carbon powder. CONSTITUTION:An electroconductive resin composition containing 100pts.wt. unsaturated polyester resin and/or epoxy resin, and 50-400pts.wt. grafted fine carbon powder prepared by graft-polymerizing a polyester with fine carbon powder. This composition may be mixed with, if necessary, a curing catalyst such as benzoyl peroxide, a mold release such as stearic acid or zinc stearate, a filler such as calcium carbonate or glass powder, a thermoplastic resin such as polyethylene or polyvinyl acetate, a reinforcing material such as glass fiber or an organic fiber, or the like. The grafted fine carbon powder can be obtained by reacting alkali-treated carbon black with an epoxy compound and a dicarboxylic acid anhydride.

Description

[Detailed description of the invention] The present invention relates to a conductive resin composition.

Generally, unsaturated polyester resins or epoxy ester resins exhibit a high two-volume resistivity of 1014 to 1016 Ω, and are used for electrically insulating parts such as electrically insulating varnishes, casting resin compositions, and molding materials.

On the other hand, when applying electrostatic coating to molded products using unsaturated polyester resin or epoxy ester resin to improve appearance, the volume resistivity of the coated object is desired to be 1 Ω-c'm or less. . Furthermore, in electronic related fields, due to static electricity in cases and housings.

A case where the LSI is destroyed or malfunctions.

9 volume resistivity to 108 for the purpose of preventing static electricity in the housing.
It is considered to be less than Ω-σ, and unlike conventional electrical insulation, unsaturated polyester resins or epoxy ester resins are required to have electrical conductivity.

Graphite coating and copper mirror method are methods for imparting conductivity.

Silver mirror method, conductive lacquer coating, chemical plating deposition.

There are methods such as adhesion of conductive films, but these methods are difficult in themselves and have the disadvantage of increasing the number of steps.

Furthermore, these methods are far from perfect, as the conductive film formed may peel off from the base, and the peeled off material may fall onto the circuit board, causing a short circuit in the electrical circuit.

Therefore, generally, as a relatively simple method, a method of adding unsaturated polyester resin or epoxy ester resin carbon fine powder is used. However, when fine carbon powder is added to unsaturated polyester resin or epoxy ester resin, the growing radicals are captured by the functional groups such as phenol and quinone present on the fine carbon powder, and the fine carbon powder acts as a curing inhibitor. It shows the working metal, inhibits three-dimensional curing, and causes curing failure. Therefore, the amount of carbon fine powder to be added is limited to 100 parts by weight of unsaturated polyester resin or epoxy ester resin.

If the amount added is 20 parts by weight or less, it is necessary to obtain a conductivity of only about 2 volume resistivity of 10 9 Ω-2.

However, carbon fine powder is industrially inexpensive and can easily be imparted with conductivity by simply adding and mixing it with unsaturated polyester resin or epoxy ester resin, so styrene, methacrylic acid, etc. can be added to the phenol and quinones on the surface of carbon fine powder. Efforts have been made to craft-polymerize vinyl monomers to neutralize the active sites that inhibit the curing of unsaturated polyester resins or epoxy ester resins.

However, when these fine carbon powders grafted with vinyl monomers are added to unsaturated polyester resins or epoxy ester resins, it is extremely difficult to add them to the unsaturated polyester resins or epoxy ester resins.

As a result of studies, the present inventors have found that in a resin composition containing an unsaturated polyester resin and/or an epoxy ester resin imparted with conductivity, a grafted carbon fine powder obtained by graft polymerizing polyester onto a carbon fine powder is used. By this, the above-mentioned drawbacks are improved and 108Ω-an
It has been found that a conductive unsaturated polyester resin composition having the following conductivity can be obtained.

The present invention relates to a conductive resin composition containing 50 to 400 parts of grafted carbon fine powder, which is obtained by grafting 24 carbon fibers onto carbon fine powder.

The composition of the present invention may contain benzoyl peroxide, t-butyl peroxybenzoate, t-
Curing catalysts such as butyl peroxy octoate, release agents such as stearic acid, zinc stearate, and calcium stearate, fillers such as calcium carbonate, clay, talc, and glass powder, and thermoplastics such as polystyrene, polyvinyl acetate, and polyethylene. It may also contain reinforcing materials such as resin, glass fiber, and organic fiber.

Examples of fine carbon powder to which polyester is graft-polymerized include natural gas, coal gas, generator gas, heavy oil, and pitch oil7. naphthalene, anthracene.

Fine carbon powder obtained by subjecting acetylene or the like to endothermic decomposition, incomplete combustion, etc. can be used.

The grafted carbon fine powder used in the present invention is obtained by reacting carbon black treated with an alkali, an epoxy compound, and a dicarboxylic acid anhydride.

It is preferable that the epoxy compound and the dicarboxylic acid anhydride are reacted in reduced amounts. Carbon black is treated with an alkali such as potassium hydroxide, sodium hydroxide, lithium hydroxide, etc., but it is preferable to treat the carboxyl groups of carbon black with an aqueous potassium hydroxide solution.

The dicarboxylic acid anhydride is maleic anhydride.

Phthalic anhydride or the like is used, and in some cases, trinolitic anhydride, pyromellitic anhydride, etc. may be used in combination. In addition, as epoxy compounds, epichlorohydrin,
Allyl glycidyl ether.

Glycidyl methacrylate, various epoxy resins, etc. can be used.

As various epoxy resins, novolac type epoxy resins, bisphenol type epoxy mmL alicyclic epoxy resins, etc., which will be described later, can be used.

As the epoxy compound, it is preferable to use a compound represented by the general formula RICHCH2N2 (wherein R+ is an alkyl group, an alkenyl group, or a phenyl group, and these may be halogenated). Grafted carbon fine powder can also be obtained by reacting alkali-treated carbon black and lactone.

As the lactone, β-gropiolactone, α-butyrolactone, spirodilactone, etc. can be used.

In the alkali treatment of carbon black, one equivalent or more of alkali is usually used per equivalent of carboxyl group of carbon black. The value of fL< is 2 to 5 times the equivalent. The reaction temperature is preferably 50 to 100°C for 3 to 10 hours. At this time, it is preferable to use a solvent in which an alkali is dissolved.

For example, water, alcohols such as methanol, ethanol, etc. can be used, but are not limited thereto.

To react the thus treated carbon black, epoxy compound, and dicarboxylic acid anhydride, 1. Usually, 10 oz of the treated carbon black is reacted with io'' moles or more of each of the epoxy compound and carboxylic acid anhydride. Preferably, 10 to 103 moles of the epoxy compound and the carboxylic acid anhydride are reacted in equal amounts and the treated carbon black is preferably reacted with the epoxy compound and the carboxylic anhydride.

The reaction temperature is preferably 100 to 150°C, and a solvent such as toluene or xylene may be used at this time.

The preferred reaction time is 0.5 to 4 hours.

In order to react the treated carbon black with lactone, 9 usually reacts 10 −1 mol or more of lactone with respect to 100 J of treated carbon black.

Preferably, 10 to 103 moles are reacted. The reaction temperature is preferably 40-80°C, and the reaction time is 0.5-80°C.
4 hours is a good time. There is no problem even if the above-mentioned solvents are used.

is desirable. When the ratio is less than 10, curing of the unsaturated polyester resin tends to be inhibited.

The unsaturated polyester resin in the present invention includes unsaturated dicarboxylic acids such as maleic anhydride, itaconic acid, and citraconic acid; glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, and neopentyl glycol; Polyhydric alcohols such as trihydric alcohols such as trimethylolpropane and pentaerythritol, if necessary.
Unsaturated polyesters obtained by reacting saturated dicarboxylic acids such as terephthalic acid, inophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, adipic acid, and sepatic acid;
Styrene, divinylbenzene, t
-Butylstyrene.

It is obtained by dissolving it in copolymerizable monomers such as vinyltoluene, diallyl phthalate, chlorostyrene, vinyl acetate, acrylic esters, methacrylic esters, and other crosslinking monomers.

Epoxy ester resins include novolac type epoxy resin and bisphenol type epoxy resin.

A product obtained by reacting an epoxy resin such as an alicyclic epoxy resin with an unsaturated basic acid and/or an unsaturated polybasic acid and dissolving it in the above-mentioned copolymerizable monomer is used.

As a novolac type epoxy resin, DEN manufactured by Dow Company is used.
-438, DEN-431, Shell Chemical Ep-152
, Ep-154, etc.

Bisphenol type epoxy resins include Ep-828, Ep-1001, Ep-1004 manufactured by Shell Chemical Co., Ltd., and Araldye 6094 manufactured by Ciba Corporation. Examples include Araldite 6097.

As the alicyclic epoxy resin, vinylcyclohexene
Dioxide (trade name: Chitsonox 206), dicyclopentadiene dioxide (Chitsonox 207X)
), 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexane carboxylate (Chissonox 201), and the like.

Examples of unsaturated basic acids to be reacted with the epoxy resin include acrylic acid, methacrylic acid, and crotonic acid.

cinnamic acid, etc. Maleic acid, maleic anhydride, fumaric acid, etc. can be used as the cleaved unsaturated polybasic acid. - The reaction of the epoxy resin with the unsaturated basic acid or unsaturated polybasic acid is carried out by known methods.

In the present invention, both the unsaturated polyester resin and the epoxy ester resin may be used, or either one may be used.

In the present invention, the amount of grafted carbon fine powder added is 1 1 of unsaturated polyester resin and/or epoxy ester resin.
The amount is in the range of 50 to 400 parts by weight, but if the amount is less than 50 parts by weight, the resulting composition will have sufficient electrical conductivity with a volume resistivity of 108Ω-(7) or less. Not shown. If the amount added exceeds 400 parts by weight,
The crosstalk with the unsaturated polyester resin deteriorates, causing problems in moldability.

ADVANTAGE OF THE INVENTION The present invention provides a conductive resin composition that exhibits sufficient conductivity.

Next, Examples and Comparative Examples of the present invention will be shown. In Examples and Comparative Examples, "1 part" indicates parts by weight. Furthermore, what is the grafting rate?

Weight of carbon black before reaction means.

Example 1 To 40 parts of fine carbon powder (channel black), 500 parts of KOH aqueous solution (9, OX 10'' mol/1) was added.

Processed at 70℃ for 6 hours with stirring to remove fine carbon powder.
Separate and wash with water. This treated carbon fine powder was sufficiently dried at 100°C.

3 parts of this treated carbon fine powder was reacted with 10 parts of maleic anhydride and 14 parts of glycidyl methacrylate for 120°C for 3 hours, and the resulting grafted carbon fine powder was separated. The grafting rate was 50%.

50 parts of this grafted carbon fine powder was stirred and dispersed in 50 parts of unsaturated polyester resin PS-9130 (manufactured by Hitachi Chemical), 2 parts of benzoyl peroxide paste was added, and the mixture was molded into a predetermined mold. At the inner.

It was heat cured at 80°C. The volume resistivity (according to JIS K 6911, the same applies hereinafter) of this cured product is 1×
It was 1050-σ.

Example 2 Using the same treated carbon fine powder as in Example 1, 3 parts of this carbon fine powder was reacted with 20 parts of epichlorohydrin and 15 parts of phthalic anhydride at 120°C for 3 hours, and the resulting grafted carbon fine powder was classified by F. did. The grafting rate was 30.

70 parts of this grafted carbon fine powder, 30 parts of unsaturated polyester resin PS-913, and 1 part of benzoyl peroxide were dispersed in 9 parts, poured into a mold, and cured at 80°C. The volume resistivity of the cured product was 1 x 1030-.

Example 3 Using the same treated carbon fine powder as in Example 1, this carbon fine powder 3
50 parts of β-propiolactone was reacted with 50 parts of β-propiolactone at 50° C. for 3 hours, and the resulting fine grafted carbon powder was separated. The grafting rate was 140φ.

60 parts of fine conografted carbon powder, 10 parts of epoxy ester resin (PS-6100 manufactured by Hitachi Chemical), and 2 parts of benzoyl peroxide were mixed and dispersed, poured into a mold, and cured at 80°C.

The volume resistivity of the cured product was I x 10'Ω-m.

Comparative Example A mixture of 100 parts of oil furnace black, 315 parts of styrene, 200 parts of methyl isobutyl ketone, and 3 parts of 2.2'-azobisisobutylonitrile was heated to 80 parts under a nitrogen atmosphere.
Polymerization was carried out at ℃ for 5 hours. This composition was then poured into excess methanol to separate the solid content to obtain a vinyl polymer-grafted carbon fine powder. The grafting rate was 50%. 50 parts of this vinyl polymer grafted carbon fine powder, 50 parts of unsaturated polyester resin PS-913, 50 parts
Two parts of tipenzoyl bioxide paste were mixed and cured by heating at 80° C. in a predetermined mold. When the inside of the mold was opened after 2 hours, phase separation between the grafted carbon fine powder and the unsaturated polyester resin had occurred.

Continuing from page 1 ■Int, C1, 3 identification code Internal office reference number (C
08L' 63/10 67100) 6911-4J
Inventor Etsushi Iwami 4-13-1 Higashimachi, Hitachi City, Hitachi Chemical Co., Ltd., Yamazaki Factory 0 Inventor Yukishi Arayo, Hitachi Chemical Co., Ltd. Yamazaki Factory, 4-13-1 Higashimachi, Hitachi City 0 Norio Tsubo, Igarashi City, Niigata City, Igarashi Ninomachi, Niigata City, Igarashi District Staff R8502, Shira Shirasaka, Niigata City, Niigata City, Igarashi, Niigata City 6646 Road Kamikaoka House No. 0 0 Meiji Sone, Niigata City, Niigata City, Souga City, Niigata City 50. Inventor Akihiro Yamada 3-303, Sekiya Matsunami-cho, Niigata City Procedural amendment (spontaneous) April 6, 1980, Gupa Ki- To the Commissioner of the Patent Office 1, Indication of the case 1988 Patent Application No. 3oop No. 2 No. 2 Name of the invention Conductive resin composition 3 Relationship with the person making the amendment 11-1 Name of the patent applicant (4
45) Hitachi Chemical Co., Ltd. (''・1 Representative)
Correct the text ``human stell resin'' to ``epoxy ester resin.''

2) On the second line from the bottom of page 11, the text "1 channel black" has been corrected to "channel blank."

Claims (1)

[Claims] 1. 100 parts by weight of unsaturated polyester resin and/or epoxy ester resin and 50 parts by weight of grafted carbon fine powder obtained by graft polymerization of polyester onto carbon fine powder - 4
A conductive resin composition containing 00 parts by weight.