JPH06145519A - Heat-resistant conductive resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition which is excellent in heat resistance, dimensional stability, and electrical conductivity and suitable for use as an IC tray. CONSTITUTION:The composition comprises 100 pts.wt. poly(phenylene sulfide), 10-40 pts.wt. conductive carbon black, and 60-100 pts.wt. glass ingredient consisting of 0-50wt.% glass fibers and 50-100wt.% glass flakes.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is a heat resistant conductive resin composition excellent in heat resistance, dimensional stability and conductivity.
More specifically, it has excellent dimensional stability when heated in a continuous high temperature range of 180 ° C or higher among plastic moldings, and it is a heat-resistant conductive material that is applied to fields requiring surface conductivity of less than 1 × 10 ⁶ Ω. It relates to a resin composition. In particular, the present invention is a heat-resistant conductive resin that is most suitable for injection molding materials used in process jigs and transfer containers for electronic components that are prone to trouble due to static electricity in semiconductor integrated circuits, semiconductor integrated circuit mounting boards, and the like, and that require heat treatment. It relates to a composition.

[0002]

2. Description of the Related Art Conventionally, for heat treatment jigs and containers for semiconductor integrated circuits, semiconductor integrated circuit mounting boards, etc., a polypropylene resin composition or a polyphenylene ether resin composition has been mixed with conductive carbon black or the like. Molded products are mainly used. However, the practical heat resistant temperature of these resin compositions is 125 ° C. for polypropylene resin compositions and 150 ° C. for modified polyphenylene ether resin compositions in the carrier for semiconductor integrated circuits generally called IC trays. It is set as the upper limit.

However, in recent years, the practical heat resistance temperature of the IC tray has been required to be 180 ° C. to 200 ° C., and in some cases, the conventional heat resistant conductive resin composition cannot handle it.

[0004]

On the other hand, the practical heat resistance temperature is
Polyethersulfone polymer is known as a resin that can withstand 180 ° C, and its characteristics are its mechanical properties and the temperature dependence of the linear expansion coefficient are extremely small. Are better. Further, the polyether sulfone polymer is also characterized by being excellent in solvent resistance as an amorphous resin and having solder resistance. The drawbacks of the polyethersulfone polymer as a molding material are:
It is pointed out that the melt viscosity is high even at high temperature molding exceeding 350 ° C, and the notch dependence of impact strength is large.

In the resin composition of the polyether sulfone polymer and the conductive carbon black, the drawbacks of the polyether sulfone polymer are promoted, and the fluidity at the time of molding and the impact strength of the molded product are significantly impaired. In many cases, a molded product that can withstand is not obtained. In addition, the polyethersulfone-based conductive resin composition is mixed with a polycarbonate polymer to ensure fluidity, or carbon fiber is used as a conductive filler to reduce flow loss and lower impact strength. Is being prevented.

[0006] However, the mixing of the polycarbonate polymer with the polyether sulfone resin composition causes a decrease in the practical heat resistance temperature, and the use of carbon fiber increases the directionality and warpage of the physical properties of the molded product. To do. In particular, a resin composition containing carbon fibers is not suitable because warp appears remarkably in a plate-shaped molded article such as an IC tray required by the present invention. Further, the polyether sulfone polymer and the carbon fiber are extremely expensive, and the resin composition obtained by blending them has a drawback that it is not widely accepted in the market.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have found that even if the conductive carbon black is made conductive, the decrease in fluidity and mechanical strength does not become a practical problem. Using a polyphenylene sulfide polymer that is considered to be inexpensive, it has excellent dimensional stability as an IC tray,
Moreover, the inventors have reached the invention of a heat-resistant conductive resin composition that can withstand practical heat resistance of 180 ° C. or higher.

[0008]

That is, the present invention provides a resin composition containing 100 parts by weight of a polyphenylene sulfide polymer, 10 to 40 parts by weight of conductive carbon black, and 60 to 100 parts by weight of a glass component. , The glass component blending ratio is 0 to 50% by weight of glass fiber, 50 to glass flake.
The heat-resistant conductive resin composition is 100% by weight.

The polyphenylene sulfide polymer used in the present invention may be any polymer whose monomer unit has the general formula shown in [Chemical Formula 1], and the secondary structure of the molecule may be a cross-linking type. It may be a chain high molecular weight type or a mixture of both.

The polyphenylene sulfide polymer used in the present invention is manufactured by Toray Phillips Co., Ltd.
It is available from Sustain, Kureha and Topren.

[0011]

[Chemical 1]

The conductive carbon black used in the present invention means acetylene black and furnace black referred to in the production method classification, and any conductive brand may be used as long as it has a conductive property as a resin composition.

Examples of acetylene black include Denka Black (Denki Kagaku Kogyo Co., Ltd.), and furnace blacks include Ketjen Black (Ketjen Black International) and Vulcan XC72.
(Cabot Corporation) and the like.

The amount of conductive carbon black used is determined by the conductivity (specifically, electrical resistivity) of the intended resin composition and the conductive performance of the carbon black itself to be applied. For example, the conductivity required for the IC tray is required to have a surface resistance value of less than 1 × 10 ⁶ Ω. In the present invention,
The conductive carbon black is 10 to 40 parts by weight based on 100 parts by weight of the polyphenylene sulfide polymer.

When the amount of carbon black used is less than 10 parts by weight, the surface resistance value of the molded article molded using the resin composition of the present invention cannot be satisfied, and when it exceeds 40 parts by weight, the fluidity and impact strength decrease. .

The glass component used in the present invention comprises glass fibers and glass flakes. The glass fibers used in the present invention have an average fiber diameter of less than 0.02 mm, an average fiber length of less than 0.1 mm, and more preferably an average fiber diameter.
It is less than 0.015 mm and the average fiber length is less than 0.05 mm.

An average fiber diameter of 0.02 mm and an average fiber length of 0.1 m
When it exceeds m 2, the orientation of glass fibers in the injection-molded article using the resin composition of the present invention appears strongly, and the absolute value of mechanical properties is improved, but the directionality and distribution become large, which is not preferable. Furthermore, in the case of a plate-shaped injection molded product such as an IC tray, warp appears remarkably and cannot be used.

Regarding the shape of the glass fiber, the cross section perpendicular to the length direction does not need to be substantially circular, and may be elliptical or may be a shape in which two or three circular parts are partially intersected. Nitto Boseki Co., Ltd. has announced a glass fiber having a cocoon cross section (intersection of two circles) as a glass fiber corresponding to these, but in any case, the fiber diameter and the fiber length may be within the above ranges. preferable.

Further, the glass fiber used in the present invention may be surface-treated with a coupling agent such as aminosilane or epoxysilane for the purpose of improving the adhesiveness with the resin composition, and it is easy to handle in the blending process. For the purpose of improving the above, a sizing agent such as urethane type or epoxy type may be used.

The glass flakes used in the present invention are adjacent flakes having an average maximum diameter of less than 1.0 mm, and have a smaller directionality than fibers, and are therefore advantageous in reducing warpage of injection molded products. . If the average maximum diameter exceeds 1.0 mm, the mold transferability in the fine structure portion of the injection-molded article tends to deteriorate and the weld strength of the thin portion tends to decrease, which is not preferable. For example, the average maximum diameter is 0.6 m from Nippon Sheet Glass Co., Ltd.
The m, 0.14 mm and 0.015 mm products that are surface-treated with a coupling agent and a sizing agent are commercially available.

The glass component used in the present invention is used in an amount of 60 to 100 parts by weight, preferably 70 to 90 parts by weight, based on 100 parts by weight of the polyphenylene sulfide polymer. .

If the glass component is less than 60 parts by weight, it is difficult to obtain sufficient heat resistance as a resin composition, specifically, to obtain a heat distortion temperature (JIS K-7207) of 200 ° C. or higher under a load of 18.5 kg. Furthermore, when the resin composition is injection-molded, the melt viscosity is too low to easily cause burrs on the molded product, and the reinforcing effect is insufficient, resulting in insufficient mechanical strength, which is not preferable.

On the other hand, when the glass component exceeds 100 parts by weight, the heat resistance, low burr resistance and mechanical properties of the resin composition are improved, but the melt viscosity becomes excessively high and injection molding becomes difficult.

In the constitution of the glass component, it is preferable that the glass fiber is 0 to 50% by weight and the glass flake is 50 to 100% by weight. If the glass fiber content exceeds 50% by weight, the amount of warp in a plate-shaped molded article such as an IC tray increases, which is not preferable.

In the present invention, even if the glass flakes are used alone, sufficient heat resistance required for the resin composition,
It is possible to obtain mechanical properties and fluidity, and it is not always necessary to use it in combination with glass fiber. However, in the present invention, when the constitution of the glass component is limited to the single use of glass flakes, the method for producing the resin composition is limited. On the other hand, in the resin composition using glass fibers together, the higher the ratio of glass fibers, the easier the stranding becomes, and the pellets can be cut with a normal strand cutter.

Further, in the present invention, various coupling agents may be additionally used in addition to the surface treatment of the glass component for the purpose of improving the adhesion between the polyphenylene sulfide polymer and the glass component. Further, in the present invention, various lubricants may be used for the purpose of improving lubricity at the time of melt-kneading in an extruder for obtaining a heat resistant conductive resin composition and improving releasability at the time of injection molding. However, in the present invention, since the processing temperature of the resin composition is 300 ° C. or higher, it is preferable that the various additives are thermally stable at 300 ° C. or higher.

[0027]

EXAMPLES The present invention will be described in detail below based on examples. The "parts" and "%" shown in Tables 1 and 2 below are based on weight.

Example 1 Polyphenylene sulfide polymers listed in Table 1,
Carbon black, glass components (glass fibers, glass flakes) and other additives are adjusted to respective compounding ratios, and then the polyphenylene sulfide polymer, the glass components and the lubricant are put into a mixer having a high-speed rotating blade to mix. While doing so, a liquid coupling agent was continuously added little by little and mixed for about 3 minutes. Next, the mixed raw material and carbon black were put into a tumbler mixer, mixed for about 3 minutes, fed to a twin-screw extruder in the same direction and melt-kneaded at a temperature of 260 to 310 ° C. to obtain pellets. Samples for evaluation of various physical properties and IC trays with an average wall thickness of 1.5 mm for practical evaluation are unfilled and overfilled using an injection molding machine maintained at a cylinder temperature of 330 ° C and a mold surface temperature of 120 ° C ± 5 ° C. It was produced in consideration of avoiding. Tables 3 and 4 show the measurement results of various physical property evaluation samples and practical evaluation IC trays.

Examples 2 to 9 and Comparative Examples 1 to 6 Polyphenylene sulfide polymers, carbon black, glass components (glass fiber,
The same operation as in Example 1 was carried out except that the glass flakes) and other additives were mixed in respective proportions to prepare samples for evaluating various physical properties and trays for practical evaluation. Tables 3 to 6 show the measurement results of various physical property evaluation samples and practical evaluation IC trays.
It was shown to.

1) Various raw materials are as follows. (1) Polyphenylene sulfide polymer: Toprene T-1 Co., Ltd .: non-crosslinked type, melt viscosity 300 poise (300
℃, 20kg), Mn = 6000, Mw = 20000, Mw / Mn = 3.3 T-2: Weak cross-linking type, melt viscosity 600 poise (300
℃, 20kg), Mn = 10000, Mw = 31000, Mw / Mn = 3.1 LN-2: Linear high molecular weight type, Mw = 39500 (2) Carbon black acetylene black (AB): Denki Kagaku Kogyo Co., Ltd., product Name, Denka Black Furnace Black (FB): Ca Black Co., Ltd., trade name, Vulcan XC72

(3) Glass component Glass fiber (PAF401): average fiber diameter 0.01 mm
Average fiber length 0.03 mm, aminosilane / urethane surface treatment, Nitto Boseki Co., Ltd. glass fiber (HIS powder): cocoon cross section, average fiber diameter 0.018 mm, average fiber length 0.03 mm, aminosilane /
Urethane-based surface treatment, Nitto Boseki Co., Ltd. glass flakes (REFG101): average maximum diameter of 0.
6 mm, aminosilane / epoxysilane surface treatment, Nippon Sheet Glass Co., Ltd. glass flakes (REFG301): average maximum diameter of 0.
14 mm, aminosilane / epoxysilane surface treatment, Nippon Sheet Glass Co., Ltd. (4) Coupling agent (A-189): γ-mercapto
Propyl trimethoxysilane, manufactured by Nippon Unicar Co., Ltd. (5) Lubricant (Hoechst wax E): montanic acid ester, manufactured by Hoechst Japan Co., Ltd.

2) The measuring methods of various physical property evaluation samples were as follows. (1) Volume resistivity: Based on SRIS-2301 standard. (2) Heat distortion temperature: Based on JIS K-7207. Load 18.5kg
f (3) Melt flow rate: Compliant with JIS K-7210. temperature
310 ℃, load 5kg (4) Izod impact strength: In accordance with JIS K-7110. 1/8
Inch, notched (5) Tensile elongation: Compliant with JIS K-7113. (6) Tensile strength: In accordance with JIS K-7113.

3) The method for measuring the IC tray for practical evaluation was as follows. (1) Injection moldability: When molding IC trays for practical evaluation with a screw type injection molding machine with a mold clamping pressure of 220 tons, insufficient filling due to higher viscosity of the resin composition used within the capacity range of the molding machine. Also, it was determined whether or not the generation of burrs due to the low viscosity can be controlled. Insufficient filling and burrs can be controlled: ○ Insufficient filling and burrs are difficult to control: × (2) Surface resistance between two points: 3119 DIGITAL M manufactured by Hioki Co., Ltd.
Ω Hi TESTER with a measurement voltage of 250 V
The surface resistance between two points of each of the seven sets (a) to (g) of the three IC trays shown in (3) was measured, and the average value was obtained.

(3) Bending fracture load: As shown in FIG. 3, an IC tray is installed at a predetermined position on a metal fixing jig,
A load average value of three IC trays was calculated, in which a metal indenter having a semicircular cross section was extended in the short direction of the central portion of the tray to continuously increase the load, and the tray was broken. (4) Molding shrinkage: Cylinder temperature 330 ℃, mold surface temperature
This is the shrinkage ratio with respect to the mold standard when the IC tray is injection molded at 120 ± 5 ° C, and the external dimensions were measured with a caliper with an accuracy of 0.01 mm to obtain the average value of 5 IC trays.

(5) Heat shrinkage ratio: Five IC trays were stacked, left in an oven set at 180 ° C. for 48 hours, and subsequently cooled at room temperature for 12 hours, before being treated for one cycle. The shrinkage ratio of the external dimensions after the treatment with respect to the external dimensions of was measured with a caliper with an accuracy of 0.01 mm to obtain the average value of 5 IC trays. (6) Warpage amount: The height before and after the treatment corresponding to the heating / cooling cycle of (5) is shown in Fig. 4 at the points (1) to (9)
Five trays were measured with a height gauge equipped with a pressure terminal with an accuracy of 0.01 mm, and the average value of the warp amount was obtained from the difference between the maximum value and the minimum value.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

[Table 4]

[0040]

[Table 5]

[0041]

[Table 6]

[0042]

As described above, the heat-resistant and conductive resin composition of the present invention can be used as a plastic molded article in a plastic molding.
It provides good dimensional stability and conductivity of less than 1 × 10 ⁶ Ω even with heat treatment in the high temperature range of 0 ° C or higher, especially in semiconductor integrated circuits and semiconductor integrated circuit mounting boards. It is most suitable as an injection molding material for process jigs for electronic parts and transport containers that require heat treatment.

[Brief description of drawings]

FIG. 1 is a front view and a side view of an IC tray used for measurement.

FIG. 2 is an IC showing a portion where a surface resistance value between two points is measured.
It is a front view of a tray.

3A and 3B are a front view and a side view of an IC tray showing bending fracture load measurement points.

FIG. 4 is a front view of an IC tray showing a portion where a warp amount is measured.

[Explanation of symbols]

 1. IC tray 2. fixing jig

Claims (1)

[Claims] 1. A polyphenylene sulfide polymer 100.
A resin composition comprising 10 parts by weight, 10 to 40 parts by weight of conductive carbon black, and 60 to 100 parts by weight of a glass component, wherein the blending ratio of the glass component is 0 to 50% by weight of glass fiber,
A heat-resistant conductive resin composition comprising 50 to 100% by weight of glass flakes.