JPH08188710A - Electroconductive resin composition having good extruding property - Google Patents

Abstract

PURPOSE: To obtain the subject composition comprising a polyphenylene ether- based resin, an aromatic vinyl-based polymer, an olefinic polymer, etc., having good extruding property, impact resistance, antistatic property, moldability and heat resistance and suitable for members for IC members. CONSTITUTION: This composition comprises (A) 1-96wt.% polyphenylene ether- based resin, (B) 96-1wt.% aromatic vinyl compound-based polymer, (C) 0.1-30wt.% olefinic polymer (e.g. high density polyethylene), (D) 1-50wt.% conductivity- providing substance (e.g. carbon black). Furthermore, a homopolymer composed of a structural unit of formula I or formula II (R1 to R6 are each a monovalent residue such as a 1-4C alkyl, an aryl, a halogen or H) [e.g. poly(2,6-dimethyl-1,4- phenylene)ether] or a copolymer thereof is preferably used as the component A.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a conductive resin composition. More specifically, it relates to a resin composition having excellent extrudability, impact resistance, electrical conductivity, molding processability, and heat resistance. In particular,
The present invention relates to a resin composition having high utility as a composition for heat resistant trays for ICs.

[0002]

2. Description of the Related Art IC parts are heated to 100 ° C. or higher to cure the epoxy material to be encapsulated. If the IC parts absorb moisture, water vapor is generated inside the IC parts during heating, causing blisters or cracks. fall into disrepair. 100 to prevent this problem
Bake beforehand at a temperature above ℃. At this time, I
To protect C, an IC tray made of a conductive material having a surface resistance of 10 ⁸ Ω or less is used.

Conventionally, this tray is made of polystyrene resin,
It was made of polypropylene resin, etc., and it was thrown away, but in recent years, it has been reused to avoid environmental problems caused by throwing away, and the baking time can be shortened by increasing the temperature for the purpose of improving productivity. Therefore, a higher temperature type is required. As a molding material for IC members, JP-A-2-175754 discloses a heat distortion temperature of 130.
℃ or more, melt flow index 3g / 10 minutes (J
A molding material has been proposed which is based on IS-K7210, 300 ° C., 10 kg load) or more, has a surface resistance of the molded article of 10 ⁷ Ω or less, and contains at least 50% by weight or more of a polyphenylene ether resin. Specifically, as means for satisfying these physical properties, two methods have been proposed in which an acid imide compound is added to a polyphenylene ether resin / conductive carbon system or a polyphenylene ether resin having a low intrinsic viscosity is used.

Further, in Japanese Patent Application Laid-Open No. 2-180958, for an IC molded from a resin composition obtained by adding an ABA 'type hydrogenated block copolymer elastomer to a polyphenylene ether resin / conductive carbon system. Heat resistant trays have been proposed. Further, JP-A-62-10053
3 discloses a resin composition comprising a polyphenylene ether resin / ethylene copolymer / conductive carbon, and JP-A-3-37258 discloses a polyphenylene ether polymer / polystyrene polymer / carbon black / ethylene. -A method for producing a tray for transporting a semiconductor integrated circuit device, which is made of an acrylic ester copolymer resin, is described.

JP-A-3-143954 proposes a heat-resistant conductive resin composition having a composition obtained by adding a highly fluid polypropylene resin to the composition of JP-A-3-37258. In addition, polyphenylene ether polymer / styrene-butadiene block copolymer or hydrogenated product thereof /
The polyolefin resin composition is disclosed in JP-A-53-71115.
No. 8, JP-A-58-103557, JP-B-1
-2516, etc.

Generally, when carbon black is added to a resin, the extrudability and impact strength are lowered. Regarding the decrease in extrudability, strand breakage occurs due to surging, etc., and in the past it was necessary for people to re-strand the strand, or as an extreme example, the resin was clogged in the extruder and extrusion became impossible, Efforts have been made to reduce the fluidity (at the same time, lower the heat resistant temperature) until the fluidity becomes possible. Regarding the reduction of impact strength, efforts have been made to increase the impact resistance of the raw material resin so as to secure the strength that can be used as an absolute value even if the physical properties are deteriorated by the addition of carbon black.

[0007]

Under the above circumstances, the object of the present invention is to provide good impact resistance, moldability, conductivity and heat resistance, and particularly as an IC member article composition. It is intended to provide an excellent resin composition.

[0008]

Means for Solving the Problems That is, the present invention is: (I) 1 to 96% by weight of polyphenylene ether resin
From (II) 96 to 1% by weight of the aromatic vinyl compound polymer, (III) 0.1 to 30% by weight of the olefin polymer, (IV) and 1 to 50% by weight of the conductivity imparting substance. And a molded article, especially an IC
It is a member for use.

That is, the inventor of the present invention added an olefin polymer to a polyphenylene ether resin, an aromatic vinyl polymer, and a conductivity-imparting substance to obtain extrudability, impact strength, conductivity, molding processability, The present invention has been accomplished by finding a resin composition having excellent heat resistance. The polyphenylene ether resin used in the present invention is represented by the repeating unit shown below, and a homopolymer or a copolymer whose structural unit is represented by the following formula [a] or [b] is used. it can.

[0010]

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(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are monovalent residues such as an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen and hydrogen, and R ₅ , R ₆ are not hydrogen at the same time) Representative examples of homopolymers of polyphenylene ether resins include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-6-ethyl 1). , 4-
Phenylene) ether, poly (2,6-diethyl-1,
4-phenylene) ether, poly (2-ethyl-6-n)
-Propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ether, poly (2-methyl-6-n-butyl-1,4-)
(Phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl) -1,4
Examples thereof include homopolymers such as -phenylene) ether and poly (2-methyl-6-chloroethyl-1,4-phenylene) ether.

The polyphenylene ether copolymer is 2,
Copolymer of 6-dimethylphenol and 2,3,6-trimethylphenol or copolymer of o-cresol or 2,3,6-trimethylphenol and o-
It includes a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure such as a copolymer with cresol.

Further, the polyphenylene ether resin used in the present invention may contain various other phenylene ether units which have been conventionally proposed to be present in the polyphenylene ether resin as long as the object of the present invention is not violated. It may be included as a partial structure. As an example of what is proposed to coexist in a small amount, Japanese Patent Application No. 63-12698 and Japanese Patent Application Laid-Open No. 63-3012 are given.
No. 22, a 2- (dialkylaminomethyl) -6-methylphenylene ether unit, and
2- (N-alkyl-N-phenylaminomethyl) -6
-Methylphenylene ether unit and the like.
In addition, those in which diphenoquinone or the like is bonded in the main chain of the polyphenylene ether resin are also included.

Further, for example, Japanese Patent Laid-Open No. 2-276823.
Lines 7-10 from the top of the page except the figure in the upper right column of page 9
Description up to line 16 in the upper left column of the page, JP-A-63-10805
No. 9, page 8, upper left column, line 4 to lower left column, line 1 and JP-A No. 59-59724, page 2, lower left column, lower line 4 to lower right column, third line. Also included are the exemplified polyphenylene ethers modified with compounds having carbon-carbon double bonds.

Among these polyphenylene ether resins, polyphenylene ether modified with a compound having a carbon-carbon double bond is preferable. Styrene as a compound having a carbon-carbon double bond, having 9 or more carbon atoms 22
The following alkyl or alkenyl or aralkyl or acrylic acid ester and / or methacrylic acid ester with a cycloalkyl group are preferable.

The polyphenylene ether resin used in the present invention has a number average molecular weight of 1,000 to 100,
It is preferably 000. A more preferable range is
It is about 6,000 to 60,000. In the present invention, the number average molecular weight is a polystyrene equivalent number average molecular weight obtained by gel permeation chromatography using a calibration curve of standard polystyrene.

The amount of the polyphenylene ether resin added is 1 to 96% by weight, preferably 40 to 95% by weight, more preferably 50 to 90% by weight. Next, the aromatic vinyl compound-based polymer used in the present invention is styrene, α
-Homopolymers such as methylstyrene and vinyltoluene, copolymers thereof, and copolymers with other ethylenically unsaturated monomers. Further, a vinyl aromatic polymer in which these resins are reinforced with an elastomer may be used.

Specific examples of comonomers include α-methylstyrene, acrylonitrile, methacrylonitrile, acrylic acid esters, methacrylic acid esters,
Examples include maleic anhydride, N-alkylmaleimides, N-arylmaleimides, vinyloxazoline and the like. Further, as an example of the aromatic vinyl compound copolymer, a block copolymer composed of an aromatic vinyl compound and a conjugated diene,
And hydrogenated products thereof, aromatic vinyl compound-maleic anhydride copolymer, aromatic vinyl compound-acrylonitrile copolymer, aromatic vinyl compound-acrylonitrile-conjugated diene copolymer, aromatic vinyl compound-methyl methacrylate copolymer Examples include coalescence.

Among the above examples of the aromatic vinyl compound copolymer, the preferred one is a block copolymer comprising at least one vinyl aromatic compound polymer block A and at least one olefin compound polymer block B. The content of the vinyl aromatic compound polymer block A in the block copolymer is 10% by weight or more and 90% by weight or less, and the degree of unsaturation of the olefin compound in the olefin compound polymer block B is 20% by weight. It is a hydrogenated product of a block copolymer comprising an aromatic vinyl compound and a conjugated diene in an amount of not more than%.

The olefin compound polymer block of the block copolymer is a monoolefin such as ethylene, propylene, 1-butene or isobutylene, or a conjugated diolefin such as butadiene, isoprene or 1,3-pentadiene, or 1,4. A polymer block in which one or more olefin compounds selected from non-conjugated diolefins such as hexadiene, norbornene and norbornene derivatives are polymerized or copolymerized, and the degree of unsaturation of the block is 20 % Or less.

The olefin compound polymer block may be randomly copolymerized with a vinyl aromatic compound as long as its characteristics are not impaired. These block copolymers may be used as they are or after being modified by a conventionally known method such as maleic anhydride. In addition, these aromatic vinyl compound-based polymers are used alone or in combination of two or more.

Examples of the olefin polymer used in the present invention include high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, polybutene, ionomer resin and olefin copolymer. As the ionomer resin, an ionomer resin of a metal having a valence of 2 or more is more effective than that of a metal having a valence of 1. In the conductive resin composition of the present invention, the addition amount of the olefin-based polymer needs to be suppressed so that the heat distortion temperature is not lowered in the final composition, and the extrudability, impact resistance and conductivity are improved. It is necessary to add the amount until the effect appears,
It is 0.1 to 30% by weight, preferably 1 to 20% by weight, more preferably 3 to 15% by weight.

The conductivity-imparting substance used in the present invention is carbon black for conductivity, coloring, rubber, graphite, carbon fiber, zinc oxide, barium sulfate, aluminum borate, titanium oxide, titanium black, tin oxide, titanic acid. Examples thereof include potassium and aluminum. These conductivity-imparting agents are added in an amount of
It is 1 to 50% by weight, more preferably 5 to 40% by weight. Carbon black is particularly excellent in terms of cost.

An antistatic agent, an inorganic filler, various stabilizers, a plasticizer, a flame retardant, a pigment, etc. are appropriately added to the conductive resin composition of the present invention within a range not impairing its characteristics according to a known method. Can be used. The method for producing the resin composition of the present invention is not particularly limited, but known methods such as extrusion by a twin-screw extruder can be used. or,
The method for molding the heat resistant tray for IC from the resin composition of the present invention is not particularly limited, and a commonly used method such as injection molding or melt pressing may be used.

In the present invention, the IC member refers to a resin molded body having conductivity for the purpose of preventing the IC from being damaged by static electricity. For example, IC tray, IC magazine,
A member relating to the manufacture and transportation of ICs such as IC embossed carrier tape, chip tray, chip tray cover, and antistatic film for chip tray.

[0026]

EXAMPLES The present invention will be specifically described below with reference to examples. The physical properties were measured under the following conditions. Viscosity of polymer: 0.5% chloroform solution was measured using an Ubbelohde viscous tube at 30 ° C. to obtain ηsp /
Represented by c.

Melt flow rate: 300 ° C., 10 k
Measure with g load. Heat distortion temperature; in accordance with ASTM D-648, load 1
It is measured at 8.6 kg / cm ² . Izod impact strength; measured according to ASTM D-256.

Surface Resistance Surface resistivity is measured according to ASTM D-257. Peeling Using a 1/8 inch thick dumbbell test piece (tab gate),
The gate part is torn and the following three grades are evaluated. Those that do not peel off are indicated by O, those that peel off slightly are indicated by Δ, and those that peel off are indicated by X.

Extrudability The strand emerging from the die during extrusion using an extruder was observed and the surging property was visually evaluated.
Judge in stages. Good ones are indicated by ◯, slightly poor ones by Δ, and poor ones by x.

[0030]

Example 1 As a polyphenylene ether resin, poly (2,6-dimethyl-1,4phenylene) ether (hereinafter abbreviated as PPE) was prepared according to US Pat. No. 4,788,277.
In the presence of dibutylamine according to the method described in Japanese Patent Application No. 62-77570, 2,6-
It is produced by oxidative coupling polymerization of xylenol. P
PE has ηsp / c = 0.55 and ηsp / c = 0.50.
42 items are made.

PPE (ηsp / c = 0.55), stearyl acrylate, styrene-butadiene block copolymer hydrogenated product (manufactured by Asahi Kasei Kogyo KK, trade name Tuftec H)
1081), carbon black (Lion Co., Ltd., trade name Ketjen Black EC600JD), high density polyethylene (Asahi Kasei Co., Ltd., trade name Suntec-H)
DJ 310) and a stabilizer (equal weight mixture of ZnO and ZnS) were mixed in an amount ratio shown in Table 1 to obtain 300 in a twin-screw extruder.
Melt-knead at ℃ and pelletize. The pellets are molded by an injection molding machine under the condition of 330 ° C., a test piece is prepared and evaluated.

[0032]

[Example 2] The same procedure as in Example 1 was carried out except that the high-density polyethylene in Example 1 was changed to low-density polyethylene (trade name: Suntec-LD M7620S, manufactured by Asahi Kasei Corporation).

[0033]

[Comparative Example 1] The same procedure as in Example 1 was carried out except that the high density polyethylene in Example 1 was replaced with a hydrogenated styrene-butadiene block copolymer.

[0034]

[Table 1]

[0035]

Example 3 PPE (ηsp / c = 0.42), stearyl acrylate, high-impact polystyrene (manufactured by Asahi Chemical Industry Co., Ltd., trade name Stylon H9009), hydrogenated styrene-butadiene block copolymer (Asahi Chemical Industry ( Co., Ltd., trade name Tuftec H1081), styrene-
Butadiene block copolymer hydrogenated product (Asahi Kasei Co., Ltd.)
Manufactured by Tuftec H1061), carbon black (produced by Denki Kagaku Kogyo Co., Ltd., trade name Denka Black), high density polyethylene (produced by Asahi Kasei Kogyo Co., Ltd., trade name Suntec HD J310), stabilizers (ZnO and ZnS). Of the same weight) are mixed at the ratio shown in Table 2, melt-kneaded in a twin-screw extruder at 300 ° C., and pelletized. The pellets are molded by an injection molding machine under the condition of 330 ° C., a test piece is prepared and evaluated.

[0036]

Example 4 In Example 3, the high-density polyethylene was replaced by an ionomer resin (Mitsui DuPont Polychemical Co., Ltd.).
The same operation as in Example 3 was carried out except that the product name was changed to Himilan 1554).

[0037]

Comparative Example 2 The procedure of Example 3 is repeated except that the high density polyethylene is not added.

[0038]

[Table 2]

[0039]

INDUSTRIAL APPLICABILITY The molding material of the present invention is superior in extrudability, impact resistance and conductivity, and is also excellent in molding processability and heat resistance as compared with the conventional conductive resin composition. It is remarkably excellent as a component article composition.

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Claims (3)

[Claims] 1. (I) Polyphenylene ether resin 1 to 1
96% by weight, and (II) aromatic vinyl compound-based polymer 9
6 to 1% by weight, and (III) olefin polymer 0.1
˜30% by weight, (IV) and the conductivity-imparting substance 1-5
A resin composition comprising 0% by weight. 2. A resin molded product molded from the resin composition according to claim 1. 3. A member for IC molded from the resin composition according to claim 1.