JPH03290462A - Electrically conductive resin composition - Google Patents

Abstract

PURPOSE:To obtain an electrically conductive resin composition having excellent conductivity, antistatic property, heat resistance and moldability by blending a polyphenylene ether resin with a specific copolymer and conductive carbon at specific amounts. CONSTITUTION:The aimad composition obtained by blending 100 pts.wt. total of (A) 50-95wt.%, preferably 70-90wt.% polyphenylene ether resin [e.g. poly(2,6- dimethyl-1,4-phenylene) ether] and (B) 50-5wt.%, preferably 30-10wt.% copolymer of 30-95wt.% styrene compound and 70-5wt.% imide compound (e.g. maleic imide) of alpha,beta-unsaturated dicarboxylic acid with (C) 5-30 pts.wt., preferabiy 8-20 pts.wt. conductive carbon (e.g. acetylene carbon black) and (D) 0.1-20 pts.wt., preferably 1-15 pts.wt., preferably 1-15 pts.wt. 1,3-di-(4-piperidyl) propane.

Description

[Detailed description of the invention] [Industrial application field] The present invention has electrical conductivity and antistatic properties, and has excellent moldability as represented by melt flow index and heat resistance as represented by heat distortion temperature. The present invention relates to a conductive resin composition.

[Prior Art] As electronic devices become more densely packaged, IC components are mounted on through-hole boards and the like in order to further increase the density. However, if the IC component absorbs moisture, water vapor will be generated inside the IC when it is heated by the flow solder, causing blisters or cracks and damaging the IC component. For this reason, during mounting, it was necessary to provide a step of drying the IC component at a temperature of 120° C. or higher to remove moisture. Conventionally, the IC component drying process involves transferring IC components from conductive vinyl chloride resin or polystyrene resin trays to aluminum die-cast trays, drying them, and then transferring them to the trays again for shipment, which is a complicated process. It required a process. Therefore, as a simplification of the process and an alternative to expensive aluminum die-cast trays, 120'C
The adoption of heat-resistant trays for ICs made of resin that do not cause warping even in the above-mentioned IC drying process and have excellent dimensional stability is being considered. In addition, IC magazine cases, racks into which printed circuit boards are inserted, etc. are required to be heat resistant to 120°C or higher, and resin cases and resin ranks are being considered.

Heat-resistant resin #Jl is a strong acid material, for example, polyamide resin, polyester resin, etc. containing glass fiber, but since they are all crystalline resins, they have a large acid form shrinkage rate and poor dimensional stability. . Additionally, there are non-grade resins such as polycarbonate containing glass fibers, but the inclusion of glass fibers causes the molded products to warp and lack dimensional stability. Examples of highly heat-resistant non-grade resins include polyether sulfone, polyarylate, polyetherimide, etc., but these have poor moldability and are difficult to put to practical use.

[Problem to be solved by the invention]

The present invention provides a conductive resin composition that has conductivity and antistatic properties, has excellent heat resistance of 120''C or higher, and is excellent in moldability.

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors found that polyphenylene ether ml, styrene compounds and α
, a copolymer of β-unsaturated dicarboxylic acid with an imide compound,
It was discovered that a resin composition obtained by blending conductive carbon and 1.3-di(4-piperidyl)propane in a specific ratio and melt-kneading can be a distant relative of the above-mentioned results, and the present invention has been achieved. In the invention, (A) polyphenylene ether resin is 50 to 95% by weight.
(B) 50 to 5% by weight of a copolymer of a styrene compound and an α,β-unsaturated dicarboxylic acid compound (C) Based on 100 parts by weight of (A) + (B), conductive 1.3-di-(4-piperidyl)propane is 0.5 to 30 parts by weight (D) and 100 parts by weight of the above (A) + (B).
The polyphenylene ether resin constituting the conductive resin &lI paraboloid of the present invention, which provides a conductive resin composition consisting of 1 to 20 parts by weight, has the following general formula (where R1, R1, R3 and R4 are each independently a hydrogen atom, a halogen atom,
a hydrocarbon group, selected from the group consisting of a single-head hydrocarbon group, a hydrocarbon oxy group, and a non-hydrocarbon oxy group, where n represents the total number of heptad units, and is an integer of 20 or more)
It is a homopolymer or copolymer containing one or more units represented by

The method for producing polyphenylene ether resin is not particularly limited, but US Pat. No. 3,306,874 and US Pat.
No. 75, No. 3257357 and No. 3257358
It can be produced by the reaction of phenols according to the method described in No. These phenols include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6 dibutylphenol, 2,6-dilaurylphenol, 2,
6-dipropylphenol, 2.6-diphenylphenol, 2-methyl-6-nitylphenol, 2-methyl-6-cyclohexylphenol, 2-methyl6-medoxyphenol, 2-methyl-6-butylphenol,
Examples include, but are not limited to, 2,6-simethoxyphenol, 2,3,6-)limethylphenol, 2,3,5,6-titramethylphenol, and 2,6-diethoxyphenol. do not have. In the present invention, the preferred polyphenylene ether resin is poly(2,6
-Simethyl-1,4-phenylene) ether.

Styrene compounds forming a copolymer of a styrene compound and an imide compound of an α,β unsaturated dicarboxylic acid used in the present invention include styrene, α-methylstyrene, 0-methylstyrene, p-methylstyrene, etc. can be given.

The imide compound of α,β unsaturated dicarboxylic acid is represented by the following formula (wherein R+, Rz and R3 represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a phenyl group, a phenylene group, or an alkylene group). sell. Specifically, maleimide, N-methylmaleimide, N-
Cyclohexy0 lumaleimide, N-phenylmaleimide, N-
(p-hydroxyphenyl)maleimide, N-benzylmaleimide, etc. In the copolymer of the styrene compound of the present invention and an imide compound of an α,β unsaturated dicarboxylic acid, the styrene compound and the α,β unsaturated The ratio of imide compounds of dicarboxylic acid is 30% of styrene compounds.
~95% by weight, and 70~5% by weight of the imide compound of α, β unsaturated dicarboxylic acid, and its number average molecular weight is 10,000 or less as measured by gel permeation chromatography (GPC) and standard polystyrene standards. preferable.

The ratio of the polyphenylene ether resin of the present invention to the copolymer of a styrene compound and an imide compound of α, β unsaturated dicarboxylic acid is 50 to 9.
5% by weight, 50-5% by weight of a copolymer of a styrene compound and an imide compound of α,β-unsaturated dicarboxylic acid, the preferred range being 70-90% by weight of polyphenylene ether resin,
It is a copolymer of a styrene compound and an imide compound of α,β unsaturated dicarboxylic acid in an amount of 30 to 10% by weight. If the polyphenylene ether resin is less than 50% by weight, the heat resistance will be insufficient, and if it exceeds 95% by weight, the fluidity will be poor and a good molded product will not be obtained.

In the present invention, the conductive carbon is a carbon that imparts high conductivity and significantly reduces the surface resistance of the resin when filled into the resin, and acetylene black, furnace black, etc. are preferably used. Specific examples of furnace black include commercially available products such as Ketschen Black EC (trade name of Akzo, Netherlands), Asahi MS-500 (trade name of Asahi Carbon Corporation), and Palkan XC72 (trade name of CABOT, USA).

The amount of conductive carbon contained is 5 to 30 parts by weight, preferably 8 to 20 parts by weight, per 100 parts by weight of components (A) and (B). If it is less than 5 parts by weight, the conductivity will be insufficient, and if it exceeds 30 parts by weight, fluidity and mechanical strength will decrease, making it difficult to obtain a good molded product.

In the present invention, 1,3-di-(4-piperidyl)propane is commercially available and is 0.1 to 20 parts by weight, preferably 1 part by weight, per 100 parts by weight of components (A) + (B). Contains ~15 parts by weight. If it is less than 0.1 part by weight, fluidity will be poor and it will be difficult to obtain a good molded product. If it exceeds 20 parts by weight, heat resistance will decrease.

In the present invention, it is also possible to add various elastomers and the like. Specifically, high-impact polystyrene, styrene-butadiene rubber, styrene-butadiene-step 1 block copolymer elastomer and its butadiene portion hydrogenated, ethylene-propylene rubber, ethylene-propylene-she 7S base Examples include copolymer elastomers, methyl methacrylate-ethyl acrylate core-shell type elastomers, etc. (A)+
It is preferably 1 to 20 parts by weight per 100 parts by weight of component (B).

There are no particular limitations on the method for producing the conductive resin composition of the present invention, and generally known methods can be employed. That is, a polyphenylene ether resin, a copolymer of a styrene compound and an imide compound of α,β unsaturated dicarboxylic acid, conductive carbon, and 1,3-di-(4-piperidyl)propane are mixed using a high-speed stirrer or the like. After uniformly mixing, the mixture is melt-kneaded and pelletized using a single-screw or multi-screw extruder with sufficient cross-mixing capacity. Depending on the purpose, we also use pigments, dyes, reinforcing agents such as glass fiber, metal fiber, and carbon fiber, fillers such as talc and calcium carbonate, antioxidants,
Ultraviolet absorbers, lubricants, flame retardants, antistatic agents, and the like can be added.

[Example] The present invention will be described in more detail with reference to Examples below. The characteristics of the resin U acid products described in Examples and Comparative Examples were evaluated according to the following method (1) Melt flow index (molding processability) Load: 10 kg, temperature: 300
Measured at °C in accordance with JIS-7210.

(2) Heat distortion temperature (heat resistance) JIS-72 at bending stress 18.56 kg/c+4
Measured in accordance with 07.

(3) Surface resistance of the molded product A 100 mm square, 1 mm thick flat plate was formed into a bottom shape by injection molding, and a surface resistance meter (manufactured by Mitsubishi Yuka Co., Ltd., product name: Resistit) was used.
Measured at

Examples 1 to 3 Polyphenylene ether resin manufactured by CGEM Polymer Co., Ltd., intrinsic viscosity 0.5 in chloroform at 25°C], α,
Copolymer of β-unsaturated dicarboxylic acid with imodo compound (80% by weight of styrene, 20% by weight of N-methylmaleimide), Ketchen Black EC as III carbon
(manufactured by Niakshi in the Netherlands), hydrogenated as an elastomer (
Styrene-butadiene-styrene) block copolymer [
Manufactured by Shell Chemical Co., Ltd., trade name Fleton G-1650)
), 1,3-di-(4-piperidyl)propane (manufactured by Toka Kagaku Co., Ltd.) were blended in the proportions shown in Table 1, and 270-3
The mixture was kneaded at 00°C and pelletized. Test pieces were molded from the pellets by injection molding, and the evaluation results are shown in Table 1.

Examples 4 to 5 In Examples 1 to 3, 90% by weight of styrene,
The procedure was the same as in Examples 1 to 3 except that 10% by weight of N-phenylmaleimide was used and ethylene-propylene rubber (manufactured by JSR Corporation, trade name: EPO2F) was used as the elastomer. It is shown in Table 1.

Example 6 In Examples 4 to 5, 75% by weight of styrene was used as a copolymer of α, β unsaturated dicarboxylic acid with an imide compound;
The same procedure was used except that 25% by weight of N-cyclohexylmaleimide was used, and the results are shown in Table 1.

Comparative Examples 1 to 5 Examples 1 to 6 were the same except that the blending ratio was changed, and the results are shown in Table 1. If the blending ratio is outside the range specified in the present invention, moldability, heat resistance, and surface resistance will be significantly reduced, and the product will not have sufficient practical value.

〔Effect of the invention〕

The conductive resin assembly t2'J#J of the present invention has excellent moldability, thermal properties, and electrical conductivity, and has great practical value.

Endurance

Claims (1)

[Scope of Claims] 1) (A) 50 to 95% by weight of polyphenylene ether resin, (B) 50 to 5% by weight of copolymer of styrene compound and imide compound of α,β unsaturated dicarboxylic acid ( C) 5 to 30 parts by weight of conductive carbon (D) per 100 parts by weight of (A) + (B), and 1,3- parts by weight per 100 parts by weight of (A) + (B). Di-(4-piperidyl)propane is 0.1
-20 parts by weight of a conductive resin composition.