JPH11335549A - Electrically conductive resin composition, semiconductor-packaging container, and ic tray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrically conductive resin compsn. having excellent heat resistance and molding processability and besides showing excellent appearance independently of the molding condition, and a molded product of a semiconductor-packaging container using the same. SOLUTION: An electrically conductive resin compsn. comprises (A) 100 pts.wt. of a resin compsn. contg. a polyphenylene ether resin, (B) 1-40 pts.wt. of a hydrogenated aromatic resin, (C) 3-40 pts.wt. of an A-B-A' type block- copolymeric elastomer in which A and A' are each a polymerized vinyl aromatic hydrocarbon block, and B is a polymerized conjugated-diene block and/or a hydrogenated, polymerized conjugated-diene block, and (D) 4-50 pts.wt. of an electrically conductive carbon black.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive resin composition having excellent conductivity, excellent heat resistance, excellent moldability, and a molded article having an excellent appearance regardless of molding conditions. Semiconductor packaging container obtained by

[0002]

2. Description of the Related Art As electronic devices are mounted at higher density, IC components are mounted on through-hole boards and the like in order to further increase the mounting density. However, if the IC component absorbs moisture when the IC component is mounted by the flow solder, water vapor is generated inside the IC during heating, causing blisters or cracks, and the IC component is damaged. Therefore, at the time of mounting, dry the IC parts at a temperature of 100 ° C or more in advance,
It is necessary to remove water. In this drying process, the surface specific resistance value is 10 ² Ω to 1 to prevent damage due to static electricity.
An IC tray made of a conductive material in a range of about 0 ¹⁰ Ω is used. Conventionally, this IC tray is made of a polypropylene resin composition having conductivity.
In recent years, a conductive resin composition having higher heat resistance has been required to shorten the drying time for the purpose of improving productivity.

[0003] In response to this problem, the present applicant has previously disclosed in
-180958, polyphenylene ether resin, styrene resin, conductive carbon, AB-
It has been disclosed that a conductive resin composition obtained by blending the A′-type hydrogenated block copolymer elastomer and the acid imide compound in a specific ratio is effective for the above problem. By this method, a resin composition having high heat resistance and a good balance of molding processability and mechanical properties can be obtained. However, when a molded product is obtained by injection molding, if injection speed is high, polyphenylene ether resin and ABA are obtained. 'In some cases, the mold-added block copolymer elastomer undergoes phase separation, causing blisters on a part of the surface of the molded article due to peeling.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to the above-mentioned problems, and it is possible to stably obtain a molded article having an excellent appearance without blisters on its surface regardless of molding conditions, and to obtain a moldable or mechanical property. It is an object of the present invention to provide a conductive resin composition which is not impaired and a semiconductor packaging container obtained as a molded product thereof. The present invention is specified by the following items [1] to [5]. [1] (A) 100 parts by weight of a resin composition containing a polyphenylene ether resin, (B) hydrogenated aromatic resin 1
A and A ′ are polymerized vinyl aromatic hydrocarbon blocks, and B is a polymerized conjugated diene block and / or conjugated diene book hydrogenated. A conductive resin composition comprising 3 to 40 parts by weight of a BA ′ type block copolymer elastomer and (D) 4 to 50 parts by weight of a conductive carbon black. [2] Component (A) is polyphenylene ether resin 50
The conductive resin composition according to [1], which is a resin composition comprising 100 to 100% by weight and 0 to 50% by weight of a styrene resin. [3] The conductive resin composition according to [1] or [2], wherein the component (B) is a hydride of a C9-based hydrocarbon resin. [4] A semiconductor packaging container molded from the conductive resin composition according to any one of [1] to [3]. [5] An IC tray formed from the conductive resin composition according to any one of [1] to [3].

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, by blending a hydrogenated aromatic resin, a polyphenylene ether resin and A
It has been found that the compatibility of the -BA 'type block copolymer elastomer can be improved and the above-mentioned object can be achieved, and the present invention has been completed. That is, the present invention
(A) Resin composition 1 containing polyphenylene ether resin
00 parts by weight, (B) 1 to 40 parts by weight of a hydrogenated aromatic resin, (C) 3 to 40 parts by weight of an ABA ′ type block copolymer elastomer, (D) conductive carbon black 4 to
A conductive resin composition having excellent appearance without swelling due to exfoliation on the surface consisting of 50 parts by weight, which is stably obtained, and which does not impair molding processability, mechanical properties, etc., and molding the same. The present invention relates to the obtained semiconductor packaging container.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polyphenylene ether resin used in the present invention is a known method of oxidatively polymerizing a phenol compound represented by the formula (1) (formula 1) with oxygen or an oxygen-containing gas using an oxidative coupling catalyst. It is a polymer obtained by.

Embedded image (Wherein R1, R2, R3, R4 and R5 are each independently hydrogen, halogen, alkyl, halogenated alkyl,
It is selected from the group consisting of aryl and aryl halide, at least one of which is hydrogen. )

Specific examples of the above phenol compound include:
Phenol, o-, m-, or p-cresol, 2,
6-, 2,5-, 2,4- or 3,5-dimethylphenol, 2-methyl-6-phenylphenol, 2,6
-Diphenylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol, 2,3,5
-, 2,3,6- or 2,4,6-trimethylphenol, 3-methyl-6-t-butylphenol, thymol, 2-methyl-6-allylphenol and the like. The phenol compound may be a copolymer obtained by copolymerizing two or more kinds thereof, and two or more obtained homopolymers or copolymers may be mixed and used. Among the above phenol compounds, 2,6-dimethylphenol is particularly preferred. Therefore, in the present invention, poly (2,6-dimethyl-1,4-phenylene) ether obtained by polymerizing the same gives good results. .

The preferred molecular weight of the polyphenylene ether resin in the present invention is such that its intrinsic viscosity is 0.1.
3 to 0.7 dl / g, more preferably 0.35 to 0.5
dl / g (at 25 ° C. in chloroform). If it is less than 0.3 dl / g, the resulting composition may have poor mechanical strength, and if it exceeds 0.7 dl / g, the processability of the composition may be poor.

In the present invention, a polyphenylene ether resin may be used alone as the component (A), but a styrene resin may be added for the purpose of improving fluidity. In this case, the polyphenylene ether resin 50 to 10
The styrene resin is used in an amount of 0 to 50% by weight with respect to 0% by weight. If the styrene resin exceeds 50% by weight, I
In a molded body such as a C tray, dimensional shrinkage and warpage at a high temperature (130 ° C. or higher) increase, which is not suitable for the purpose of the present invention.

The styrenic resin used in the present invention comprises an aromatic vinyl compound represented by the formula (2) (formula 2), and is known in the art such as emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization. Obtained by polymerization according to the above method.

Embedded image (Wherein, R1 and R2, R3, R4, R5, R6 are each independently selected from the group consisting of hydrogen, halogen, alkyl, and alkyl halide).

Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, p-methylstyrene,
-Ethylstyrene, p-tert-butylstyrene, isopropenyltoluene and the like. Among these, styrene and α-methylstyrene are particularly preferred.

The styrenic resin used in the present invention may be a modified product obtained by polymerizing the above aromatic vinyl compound in the presence of a rubbery polymer and / or another copolymerizable monomer, if necessary. Can be used. Examples of the rubber-like polymer include diene rubber-like polymers represented by polybutadiene, butadiene-styrene copolymer, polyisoprene, and the like, or ethylene-propylene copolymer and ethylene-propylene-diene copolymer. Ethylene-α-olefin rubbery copolymer represented by, or,
Acrylic rubber mainly composed of acrylic acid ester, or isobutylene-isoprene copolymer or polyurethane rubber can be used, and among them, diene rubber such as polybutadiene or butadiene-styrene copolymer is preferably used. .

Other copolymerizable monomers include vinyl cyanide monomers, maleic acid and maleic anhydride, and derivatives or acrylates thereof. Specifically, acrylonitrile, methacrylonitrile, and the like as the vinyl cyanide monomer, maleic esters such as dibutyl maleate as the maleic acid derivative, and N as the maleic anhydride derivative
N-substituted maleimides such as -phenylmaleimide, and methyl acrylate, methyl methacrylate, and the like as acrylates are preferred. The above-mentioned aromatic vinyl compound, rubbery polymer and other copolymerizable monomers may be used alone or in combination.
More than one species can be used. Further, two or more kinds of the obtained polymers may be mixed and used.

In the present invention, the content of the rubbery polymer in the styrene resin is preferably 80% by weight or less, more preferably 5 to 70% by weight. In order to increase the impact strength of the composition, it is preferable that the rubber-like polymer is contained in an amount of 5% by weight or more. The matrix component excluding the rubber-like polymer gives good results when at least 50% by weight, more preferably at least 70% by weight of the matrix component is an aromatic vinyl compound represented by the formula (2). When the amount of the aromatic vinyl compound is less than 50% by weight, the compatibility with the polyphenylene ether resin may be obtained, and the mechanical strength and the surface appearance may be impaired, which is not preferable. In the present invention, so-called high-impact polystyrene obtained by grafting styrene onto polybutadiene is particularly preferably used.

The (B) hydrogenated aromatic resin used in the present invention is a hydride of an aromatic resin. Examples of the aromatic resin include a C9-based hydrocarbon resin, a C5 / C9-based hydrocarbon resin, a cumarone-indene resin, a terpene-styrene resin, and a styrene-based resin.

Here, the C9 hydrocarbon resin is a C9 fraction obtained by cracking naphtha (for example, styrene,
Indene, vinyl toluene, α-methylstyrenes, etc.)
Refers to a petroleum resin obtained by cationic polymerization of C5 / C
The ninth hydrocarbon resin is a C9 fraction and a C5 fraction obtained by cracking naphtha (for example, isoprene, pentadiene, cyclopentadiene, dicyclopentadiene, etc.).
And petroleum resins obtained by copolymerizing Coumarone-indene resin is a thermoplastic resin obtained by copolymerizing coumarone, indene, styrene and the like contained in solvent naphtha (boiling point 150 to 200 ° C.), which is a light fraction in coke oven gas, as a raw material oil. Refers to resin. The terpene-styrene resin is a resin obtained by copolymerizing a terpene-based polymerization component such as pinene, dipentene, limonene and styrene at an arbitrary ratio. The styrene resin is the same as that described for the component (A).

In the present invention, hydrides of these resins can be used alone or in combination of two or more.
In particular, among these hydrogenated aromatic resins, a C9-based resin having a high aromatic content in the resin and a large effect of improving the compatibility with a polyphenylene ether resin or an ABA ′ type block copolymer elastomer described later. It is particularly preferred to use hydrides of hydrocarbon resins.

Further, the hydrogenated aromatic resin (B) used in the present invention comprises 30 to 10 of aromatic aromatic rings of the aromatic resin.
0% is hydrogenated. Preferably 50 of the aromatic ring
~ 98% is hydrogenated. If the hydrogenation ratio of the aromatic ring is less than 30%, the residual ratio of the aromatic ring in the resin increases, and the heat resistance of the composition decreases, which is not preferable. When at least 30% of the aromatic ring is hydrogenated, generally, the olefinic double bond of the hydrogenated aromatic resin is completely hydrogenated.

The softening point of the hydrogenated aromatic resin used in the present invention is preferably in the range of 80 to 180 ° C. More preferably, it is 100 to 160 ° C. If the softening point is lower than 80 ° C., the heat resistance of the composition may decrease, which is not preferable. On the other hand, when the temperature exceeds 180 ° C., the melt viscosity of the composition becomes high, and the moldability decreases, which is not preferable. Examples of these hydrogenated aromatic resins include those sold by Arakawa Chemical Industries, Ltd. under the trade name of Alcon.

The amount of the hydrogenated aromatic resin in the present invention is 1 to 40 parts by weight, preferably 3 to 40 parts by weight, based on the composition.
30 parts by weight. If the amount is less than 1 part by weight, the effect of improving the compatibility between the polyphenylene ether resin and the ABA 'type block copolymer elastomer described below is small, and the molding processability may be insufficient, and 40 parts by weight. If the ratio exceeds the above, the heat resistance and the mechanical strength may decrease, which is not preferable.

The (A) ABA 'type block copolymer elastomer used in the present invention comprises vinyl aromatic hydrocarbon polymers A and A' blocks and a conjugated diene polymer B block. Examples of vinyl aromatic hydrocarbons include styrene, α-methylstyrene, vinyl toluene, vinyl xylene, ethyl vinyl xylene, vinyl naphthalene, and mixtures thereof. A and A ′ may be the same or different, and examples of the conjugated diene compound include 1,3 butadiene, isoprene, and a mixture thereof. Further, a product obtained by hydrogenating a conjugated diene polymer B block can be suitably used in the present invention. Examples of the ABA′-type block copolymer elastomer used in the present invention include those sold by Kuraray Co., Ltd. under the trade name of Septon and Shell Chemical Co., Ltd. under the trade name of Clayton. . These can be used alone or in combination of two kinds.

The amount of the ABA 'type block copolymer elastomer used in the present invention is 3 to 4 with respect to the composition.
0 parts by weight, preferably 5 to 30 parts by weight. If the amount is less than 3 parts by weight, the effect of improving the impact resistance may be insignificant.
If the amount exceeds the weight part, the compatibility with the polyphenylene ether resin, the rigidity and the like may decrease, which is not preferable.

The conductive carbon black (D) used in the present invention is used for the purpose of imparting conductivity by dispersing it in the composition and greatly reducing the surface resistance of the resin molded product. Furnace black, acetylene and the like are used. Black or the like is preferably used. For example, Ketjen Black EC sold by Lion, Conductex sold by Colombian Carbon, SEAST sold by Tokai Carbon, and CA in the United States
There is a product name such as Vulcan sold by BOT. These may be used alone or in combination of two or more.

The amount of conductive carbon black added is 4 to 50 parts by weight, preferably 6 to 40 parts by weight, based on the composition. If less than 4 parts by weight, the conductivity may be insufficient,
If the amount exceeds 50 parts by weight, the moldability and mechanical strength may be reduced, and it is difficult to obtain a good molded body, which is not preferable.

The method for producing the resin composition is not limited. For example, it can be performed by a method in which components to be used are collectively mixed by a mixer such as a Henschel mixer or a tumbler mixer, and extruded and granulated. This resin composition contains other thermoplastic resins and elastomers, or lubricants, pigments, stabilizers, flame retardants and other additives, or metal powders, glass fibers, carbon fibers, etc. as long as the properties are not impaired. A material, mica, talc, or the like can be appropriately used depending on the purpose and application. From the conductive resin composition of the present invention, IC
The method for forming the tray is not particularly limited, and a method using a usual injection molding machine, a method using a melt press, or the like is used.

[0026]

EXAMPLES The present invention will now be described specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. The following components were used as components in Examples and Comparative Examples. (A) Polyphenylene ether resin (hereinafter abbreviated as PPE) manufactured by GEM Polymer Co., Ltd. (Liquid intrinsic viscosity measured in chloroform at 25 ° C. is 0.47 dl / g)
And polystyrene (hereinafter abbreviated as GPPS) and high-impact polystyrene were used as the styrene-based resin. As polystyrene, a trade name of Nippon Polystyrene Co., Ltd., Nippon Polysty G440K, as high impact polystyrene, Nippon Polystyrene Co., Ltd.
Manufactured by Nippon Polysty H550R. (B)
As hydrogenated aromatic resins, Alcon P-100 (softening point 100 ° C.) and A-Rankawa Chemical Industries, Ltd.
140 (softening point 140 ° C.) was used. (C) Sepaton 8004 (trade name of Kuraray Co., Ltd.)
(Abbreviated as SEPS)). (D) As conductive carbon black, Lion Corporation
Ketjen EC (trade name) and SEAST-116 (trade name) manufactured by Tokai Carbon Co., Ltd. were used.

Examples 1 to 10 and Comparative Examples 1 to 7 The above components were weighed at the ratios shown in Tables 1 to 4 and thoroughly mixed with a tumbler mixer.
The mixture was melt-kneaded using a twin-screw extruder having a length of 2 m to obtain a pellet-shaped heat-resistant conductive resin composition. A test piece and a practical evaluation IC tray were formed from the pellets using an injection molding machine, and evaluation was performed using the obtained test piece and a practical evaluation IC tray. The results are shown in Tables 1 to 4. The evaluation was performed according to the following method. (1) Izod impact strength (hereinafter abbreviated as IZOD,
The unit is J / m.) It was based on JIS K-7110. Test specimen thickness: 3.
2 mm. (2) Heat deflection temperature (hereinafter abbreviated as deflection temperature, unit is ° C.) JIS K-7207 was followed. Bending stress: 18.2
MPa. Heat deflection temperature is 130 ° C as heat resistance evaluation
The above was passed. (3) Surface resistance of molded article (hereinafter abbreviated as resistance, unit is Ω) The surface resistance of a flat molded article of 80 × 40 × 2 mm is measured with a surface high resistance meter (manufactured by Yuka Denshi Co., Ltd. And the relative humidity was 50%.
As an evaluation, a range of 10 2 to 10 10 Ω was accepted. (4) Molding processability Using an injection molding machine with a mold clamping force of 100 tons, 200 × 140 at a cylinder temperature of 330 ° C. and a mold temperature of 110 ° C.
× Form an IC tray with a wall pressure of 2 mm, injection speed 80 mm
/ Sec. When molding was possible at a rate / sec, and x when molding was difficult. (5) Swelling due to peeling Using an injection molding machine with a mold clamping force of 100 tons, cylinder temperature 330 ° C, mold temperature 110 ° C, injection speed 80 mm /
A 200 × 140 × 2 mm wall thickness IC tray was molded under the conditions of s and 120 mm / sec, and the surface of the molded product was visually observed. No blistering was caused by peeling. × (hereinafter, referred to as
Injection speed of 80 mm / sec is blister-1 and injection speed is 12
0 mm / sec is abbreviated as blister-2).

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Table 3]

[0031]

[Table 4] Note: * 1 indicates that the test piece and the IC tray could not be molded because the melt viscosity was too high, and the physical properties, moldability, and blistering due to delamination could not be evaluated.

[0032]

As described above, the present invention provides a conductive resin composition which is excellent in heat resistance and molding processability and has an excellent appearance regardless of molding conditions. Made it possible to provide.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 25:04) (72) Inventor Shoji Yoshimura 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemicals, Inc.

Claims (5)

[Claims] (A) 100 parts by weight of a resin composition containing a polyphenylene ether resin, (B) 1 to 40 parts by weight of a hydrogenated aromatic resin, (C) A and A ′ are polymerized vinyl aromatic carbonized B is a hydrogen block, B is a hydrogenated hydrogenated conjugated diene block and / or conjugated diene book, 3 to 40 parts by weight of an ABA 'type block copolymer elastomer, (D) A conductive resin composition containing 4 to 50 parts by weight of a conductive carbon black. 2. Component (A) comprising 50 to 100% by weight of a polyphenylene ether resin and 0 to 50% by weight of a styrene resin
The conductive resin composition according to claim 1, which is a resin composition comprising: 3. The conductive resin composition according to claim 1, wherein the component (B) is a hydride of a C9 hydrocarbon resin. 4. A semiconductor packaging container molded from the conductive resin composition according to claim 1. 5. An IC tray formed from the conductive resin composition according to claim 1.