JPH0976424A - Conductive composite plastic sheet and container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To markedly reduce the contamination of an IC caused by the falling- off of carbon black by the abrasion at a time of the contact with the IC by adding an olefinic resin to a conductive resin compsn. consisting of a thermoplastic resin and carbon black in a specific wt. ratio. SOLUTION: A sheet is produced by laminating a conductive resin compsn. consisting of a polystyrenic resin, carbon black and an olefinic resin to both surfaces of a sheet composed of a thermoplastic resin such as a polyphenylene ether resin. The conductive resin compsn. contains 5-50 pts.wt. of carbon black per 100 pts.wt. of a thermoplastic resin and 1-30 pts.wt. of the olefinic resin is added to 100 pts.wt. of the sum total amt. of the thermoplastic resin and carbon black. In this conductive composite plastic sheet, the surface intrinsic resistance value of the sheet having the conductive resin compsn. laminated thereto is 10<2> -10<10> Ω.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive composite plastic sheet suitable for semiconductor packaging, in which the contamination of IC or the like caused by the detachment of carbon black or the like due to abrasion at the time of contact with the IC or the like is remarkably reduced, and the same. The present invention relates to a conductive plastic container formed by molding a sheet.

[0002]

2. Description of the Related Art Conventionally, injection trays, vacuum forming trays, magazines, embossed carrier tapes, etc. have been used as packaging forms for ICs and electronic parts using ICs, and these packaging containers are damaged by static electricity. (1) a method of applying an antistatic agent on the surface of the packaging container, and (2) a method of applying a conductive paint,
(3) A method of dispersing an antistatic agent, (4) A method of dispersing a conductive filler, and the like are carried out.

However, the method (1) has a sufficient antistatic effect immediately after coating, but after a long time of use,
Stable performance cannot be obtained because the antistatic agent is liable to be released due to water outflow and abrasion. The surface resistivity is also 1
It is about 0 ⁹ to 10 ¹² Ω, which is unsuitable for IC packaging that requires a strict antistatic effect. The method (2) has the drawbacks that the coating is likely to be non-uniform during manufacture, and the anti-static effect is lost due to peeling off due to abrasion, destroying the IC and contaminating the lead portion of the IC. (3)
In the method (1), since it is necessary to add a large amount of antistatic agent, the physical properties of the resin are deteriorated, and the surface resistivity is greatly affected by humidity, so that stable performance cannot be obtained. As the conductive filler of the method (4), (a) fine metal powder,
Examples thereof include (b) carbon fiber and (c) carbon black. Among these, (a) fine metal powder and (b) carbon fiber can obtain sufficient conductivity even if added in a small amount, but the moldability is remarkably deteriorated, and it is difficult to disperse them uniformly, and the resin component is formed on the surface of the molded product. It is easy to form only a skin layer and it is difficult to obtain a stable surface resistivity.

On the other hand, (c) carbon black is
It is generally used because it is possible to disperse it evenly by studying the kneading conditions, etc., and it is easy to obtain a stable surface resistivity value, but it is necessary to add a large amount of carbon black, so fluidity is high. Also, there is a phenomenon that moldability decreases. Conventionally, as a resin for dispersing carbon black, polyvinyl chloride resin, polypropylene resin, polyethylene terephthalate resin, polystyrene resin and ABS resin are generally used, and polyphenylene ether resin is used for heat resistance at 100 ° C. or higher. Resin, polycarbonate resin, etc. are used. Among these resins, polystyrene resin for general use, and polyphenylene ether resin for heat resistance, there is no significant decrease in fluidity and moldability even if a large amount of carbon black is added compared to other resins, It is also excellent in cost. Further, as a method for improving the moldability and mechanical strength of a sheet obtained from these electrically conductive resins, and further improving the mechanical strength of a packaging container obtained by molding the sheet, JP-A-57 / 57
-205145, JP-A-62-18261 and the like are proposed. However, molded products of compositions obtained by adding a large amount of carbon black to these resins have a drawback that carbon black is easily detached from the surface of the molded product due to abrasion.

[0005]

SUMMARY OF THE INVENTION The present invention is intended to solve such a drawback, and is a sheet substrate made of at least one thermoplastic resin selected from polyphenylene ether resin, polystyrene resin or ABS resin. A sheet in which a conductive resin composition comprising a thermoplastic resin and carbon black selected from at least one type of polyphenylene ether resin, polystyrene resin or ABS resin is laminated on both surfaces of the conductive resin composition, Further, by containing an olefinic resin, a conductive composite plastic sheet and a sheet of the conductive composite plastic sheet in which the contamination of the IC or the like caused by the detachment of carbon black or the like due to abrasion at the time of contact with the IC or the like is significantly reduced, and the sheet are formed. It is an object of the present invention to provide a conductive plastic container having the following structure.

[0006]

That is, the first aspect of the present invention
Of the invention, on both sides of a sheet substrate made of at least one kind of thermoplastic resin selected from polyphenylene ether resin, polystyrene resin or ABS resin, (A)
In a sheet obtained by laminating a conductive resin composition comprising at least one thermoplastic resin selected from polyphenylene ether resin, polystyrene resin or ABS resin, (B) carbon black and (C) olefin resin, A) The conductive resin composition is (B) carbon black 5 to 50 relative to 100 parts by weight of the thermoplastic resin (A).
1 part by weight to 30 parts by weight of (C) olefin resin per 100 parts by weight of the total amount of (A) thermoplastic resin and (B) carbon black, and (b) ) A conductive composite plastic sheet having a surface specific resistance value of 10 ² to 10 ¹⁰ Ω, which is obtained by laminating a conductive resin composition.

A second aspect of the present invention is that the (A) polyphenylene ether-based resin is provided on both sides of a sheet substrate made of at least one thermoplastic resin selected from polyphenylene ether-based resin, polystyrene-based resin or ABS-based resin. A conductive resin composition comprising a thermoplastic resin selected from at least one of a resin, a polystyrene resin or an ABS resin, (B) carbon black, (C) an olefin resin and (D) a compatibilizer is laminated. In the seat,
(A) The conductive resin composition is (A) thermoplastic resin 10
1 to 50 parts by weight of (B) carbon black per 0 parts by weight, and (C) olefinic resin 1 to 1 per 100 parts by weight of the total amount of the (A) thermoplastic resin and (B) carbon black. 30 parts by weight and (D) compatibilizer 1-30
The surface specific resistance value of the sheet containing (part by weight) the conductive resin composition is 10 ² to 10 ¹⁰ Ω.
Is a conductive composite plastic sheet of.

A third aspect of the present invention is that the compatibilizing agent (D) is a resin obtained by hydrogenating a styrene-diene block copolymer and / or a resin obtained by graft-copolymerizing styrene with a polyolefin. It is a conductive composite plastic sheet. A fourth invention of the present invention is a conductive plastic container obtained by molding the conductive composite plastic sheet of the first invention by pressure molding, vacuum molding, hot plate molding or the like. A fifth invention of the present invention is a conductive plastic container obtained by molding the conductive composite plastic sheet of the second invention by pressure molding, vacuum molding, hot plate molding or the like.

The present invention will be described in more detail below. In the present invention, at least one thermoplastic resin selected from polyphenylene ether-based resins, polystyrene-based resins or ABS-based resins is used for the base sheet and the conductive resin composition, respectively. The polyphenylene ether resin means a resin having a polyphenylene ether resin and a polystyrene resin as main components, and the content of the polyphenylene ether resin in the total amount of 100 parts by weight of the polyphenylene ether resin and the polystyrene resin is 28 to 86 parts by weight. If it is less than 28 parts by weight, sufficient mechanical properties as a polyphenylene ether resin cannot be obtained, and if it exceeds 86 parts by weight, the fluidity is lowered and molding process becomes difficult. The polyphenylene ether resin is US Pat. No. 338.
The homopolymers or copolymers described in 3435 are shown.

The polystyrene resin used in the present invention is a general polystyrene resin or an impact-resistant polystyrene resin and a resin containing a mixture thereof as a main component. ABS
The system resin means a resin containing a copolymer mainly composed of acrylonitrile-butadiene-styrene as a main component.

The carbon black (B) contained in the conductive resin composition in the present invention is furnace black, channel black, acetylene black, etc., and preferably has a large specific surface area and a small amount added to the resin is highly effective. The electrical conductivity of is obtained. For example, C. F. (S
upper Conductive Furnace),
E. FIG. C. F. (Electric Conductiv
e Furnace), Ketjen Black (Lion-trade name, manufactured by AKZO), and acetylene black. The amount of carbon black added is such that the surface resistivity can be 10 ² to 10 ¹⁰ Ω when laminated on the base material sheet, and (A) the thermoplastic resin 100.
5 to 50 parts by weight of (B) carbon black is preferable with respect to parts by weight. If the added amount is less than 5 parts by weight, sufficient conductivity cannot be obtained and the surface resistivity increases, and if it exceeds 50 parts by weight, the uniform dispersibility with the resin is deteriorated, the moldability is significantly reduced, Characteristic values such as strength are reduced. On the other hand, if the surface specific resistance value exceeds 10 ¹⁰ Ω, a sufficient antistatic effect cannot be obtained, and if the surface specific resistance value is less than 10 ² Ω, the power generation capability is too good and the IC may be destroyed.

Examples of the olefin resin (C) used in the present invention include polyethylene resins, polypropylene resins and blends of these with other resins. Among these, it is preferable to use a polyethylene resin. The polyethylene resin is classified into a low density polyethylene resin obtained by a high pressure polymerization method, a high density polyethylene resin obtained by a low pressure polymerization method, a linear low density polyethylene resin obtained by a low pressure solution polymerization method, and the like. In the present invention, when using a polyethylene resin alone, density and low-density polyethylene resin or a density of 0.930 g / cm ³ or less using a 0.945 g / cm @ 3 or less linear low density polyethylene resin Is preferred. Furthermore, a polyethylene resin and a compatibilizer can be used in combination, and in this case, it is preferable to use a high density polyethylene resin.

The melt flow index (measured according to JIS-K-7210) of the olefin resin (C) used in the present invention is 0.1 g / 10 minutes or more under the conditions of 190 ° C. and a load of 2.16 kg. Yes, if less than this value, polyphenylene ether resin, polystyrene resin, A
Kneading with the BS resin becomes difficult, and a good composition cannot be obtained. The addition amount of the olefin resin is preferably 1 to 30 parts by weight, particularly preferably 3 to 100 parts by weight based on 100 parts by weight of the total amount of the (A) thermoplastic resin and the (B) carbon black.
25 parts by weight. If the amount added is less than 1 part by weight, the effect is insufficient, and if it exceeds 30 parts by weight, it becomes difficult to uniformly disperse it in the polyphenylene ether resin, polystyrene resin, or ABS resin.

In the present invention, a polyphenylene ether resin of olefin resin, polystyrene resin or A
In order to make the dispersion in the BS resin more uniform, a compatibilizing agent can be used. As the compatibilizing agent, styrene is grafted to a resin obtained by hydrogenating a styrene-diene block copolymer and a polyolefin. It is preferable to use a resin selected from at least one kind of resin. The styrene-diene of the resin hydrogenated to the diene block copolymer used in the present invention is preferably butadiene or isoprene, and the polyolefin of the resin obtained by grafting styrene to the polyolefin is preferably polyethylene, polypropylene or an ethylene-vinyl acetate copolymer. .
Further, the addition amount of these compatibilizers is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the total amount of the (A) thermoplastic resin and (B) carbon black, and when it exceeds 30 parts by weight, it is a polyphenylene ether type. The dispersion of the olefin resin in the resin, polystyrene resin or ABS resin becomes too good, and the effect of suppressing the desorption of carbon black and the like is lost. If it is less than 1 part by weight, the effect is insufficient.

The melt flow index (measured according to JIS-K-7210) of the resin used as the compatibilizer in the present invention is 0.1 g / under a condition of 200 ° C. and a load of 5 kg.
It is preferably 10 minutes or more, and if it is less than this value, it becomes difficult to knead with a polyphenylene ether resin, a polystyrene resin, or an ABS resin.

In order to maintain sufficient molding processability, the conductive resin composition of the present invention is carbon so that the surface resistivity of the sheet laminated with the conductive resin composition is 10 ² to 10 ¹⁰ Ω. When filled with black, the melt flow index (measured according to JIS-K-7210) is 230 when the resin is polyphenylene ether resin.
C., load 10 kg, polystyrene resin 200.degree. C., load 5 kg, ABS resin 220.degree. C., load 10 kg, respectively.
It is preferably 1 g / 10 minutes or more.

Further, in the thermoplastic resin and conductive resin composition of the sheet base material, a lubricant, a plasticizer and a processing aid are added in order to improve the flow characteristics of the composition and the mechanical characteristics of the molded product, if necessary. It is possible to add various additives such as a reinforcing agent (resin modifier) and other resin components.

In order to produce the conductive composite plastic sheet of the present invention, first, all or part of the raw material of the conductive resin composition is kneaded and pelletized by using a known method such as a Banbury mixer and an extruder. The conductive resin composition thus obtained is formed into a sheet by a known method such as an extruder together with a thermoplastic resin which becomes a base sheet.

When kneading the conductive resin composition, it is possible to knead the raw materials all at once.
It is also possible to knead the styrene resin and the carbon black, the styrene resin and the olefin resin separately, and knead the kneaded product at once to carry out the kneading stepwise. Furthermore, pellets obtained by kneading separately can be kneaded at the same time when forming a sheet by an extruder, or, for example, it is also possible to pre-knead other than an olefin resin and add this when forming a sheet by an extruder. is there.

As a method for laminating the conductive resin composition on the base sheet, each of them is separately molded into a sheet or film by an extruder, and then a heat lamination method, a dry lamination method, an extrusion lamination method or the like is used in a stepwise manner. It is also possible to laminate the sheets together, or it is possible to obtain a sheet laminated together by a multi-layer coextrusion method using a feed block, a multi-manifold die or the like.

The overall thickness of the sheet of the present invention is 0.1 to
The thickness is 3.0 mm, and the conductive resin composition layer needs to be laminated on both sides of the base sheet. The ratio of the thickness of the conductive resin composition to the total thickness is 2 on each side.
% Or more and 80% or less on both sides is preferable. If the total wall thickness is less than 0.1 mm, the strength as a packaging container obtained by molding a sheet will be insufficient, and the thickness will be 3.0 mm.
If it exceeds the above range, forming such as pressure forming, vacuum forming, hot plate forming becomes difficult. Further, if the conductive resin composition layer is provided only on one side of the sheet, or if the ratio of the total thickness of the sheet is less than 2% on one side, the surface resistivity of the packaging container obtained by molding the sheet becomes remarkably high. If the total of both surfaces exceeds 80%, the properties such as mechanical strength as the composite plastic sheet will be deteriorated.

The electrically conductive composite plastic sheet of the present invention is suitable for semiconductor packaging, and further, an electrically conductive composite plastic obtained by forming the sheet by a known sheet forming method such as pressure forming, vacuum forming, hot plate forming. The container is used as a semiconductor packaging container. Specifically, the plastic container is a vacuum forming tray for packaging ICs, a magazine, an embossed carrier tape, electronic parts using ICs, a vacuum forming tray for packaging electronic devices, and the like.

[0023]

EXAMPLES The present invention will now be described in more detail with reference to examples. Examples 1 to 7 The raw materials shown in Table 1 were used, and the raw material composition ratios shown in Table 2 were weighed and uniformly mixed with a high-speed mixer.
The mixture was kneaded using a mm-vent type twin-screw extruder and pelletized by a strand cut method to obtain a conductive resin composition. Next, the combination of the base sheet and the conductive resin composition layer shown in Table 4 was performed at a ratio of the base sheet to the total thickness. Extruding each conductive resin composition with a φ65 mm extruder (L / D = 28) so that both sides of the base sheet have substantially the same thickness,
The sheets were laminated by a feed block method using a φ40 mm extruder (L / D = 26) and a 500 mm wide T die to obtain a sheet having an overall wall thickness of 300 μm. Furthermore, the obtained composite sheet is vacuum-formed and QFP 14 mm × 20 mm / 64 p
A vacuum forming tray for IC packaging and an embossed carrier tape of the same were obtained. The evaluation results are shown in Tables 6 and 7. In each of the examples, the carbon black was not removed and was good.

Comparative Examples 1 to 4 In the same manner as in Examples, the raw materials shown in Table 1 were used, the respective raw material composition ratios shown in Table 3 were weighed and uniformly mixed with a high speed mixer, and then a φ45 mm vent type was used. The mixture was kneaded using a twin-screw extruder and pelletized by a strand cut method to obtain a conductive resin composition. Next, the combination of the base sheet and the conductive resin composition layer shown in Table 5 was performed at the ratio of the base sheet to the total thickness. A sheet having a total thickness of 300 μm was obtained as in the example. Further, the obtained sheet was vacuum-molded to obtain a vacuum-molding tray for IC packaging and an embossed carrier tape similar to those in the examples. The evaluation results are shown in Tables 6 and 7.

Each evaluation was carried out by the following method. (1) Specific surface resistance With a Lorester surface resistance meter (manufactured by Mitsubishi Petrochemical Co., Ltd.), the distance between the electrodes was set to 10 mm, the sheet sample was measured at any 10 points on the surface, and the vacuum forming tray and embossed carrier tape were measured. The central portion of the inner bottom surface of the pocket portion was measured at 10 points, and the logarithmic average value thereof was taken as the surface specific resistance value. (2) Strength at Break Point, Tensile Elastic Modulus Sheet No. 2 test pieces were measured at a pulling speed of 10 mm / min according to JIS-K-7113.

(3) Presence or absence of carbon dropout For the sheet sample, QFP 14 mm ×
20mm / 64pin IC is pressed with a load of 100g, and stroke is reciprocated 100 times with 15mm, then I
The lead portion of C was observed with a microscope. For vacuum forming trays and embossed carrier tapes, the same IC is installed in the pockets and the stroke is 30 mm and the speed is 40 minutes per minute.
Vibrate 200,000 times in the plane direction at 0 reciprocating speed, then I
The C lead portion was observed with a microscope. Both evaluations were made based on the presence or absence of black deposits such as carbon black on the lead portion. (4) MFI Regarding the conductive resin compositions of each Example and Comparative Example JIS
-Measurement was performed according to K-7210.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

[0030]

[Table 4]

[0031]

[Table 5]

[0032]

[Table 6]

[0033]

[Table 7]

[0034]

As described above, the polyphenylene ether resin, the polystyrene resin, or the polyphenylene ether resin, the polystyrene resin or the sheet base material made of at least one thermoplastic resin selected from the polyphenylene ether resin, the polystyrene resin or the ABS resin is provided on both sides. In a sheet in which a conductive resin composition composed of a thermoplastic resin selected from at least one kind of ABS resin and carbon black is laminated, by adding an olefin resin to the conductive resin composition, IC It is possible to obtain a conductive composite plastic sheet and a conductive plastic container formed by molding the sheet, in which the contamination of IC and the like caused by the detachment of carbon black due to abrasion when contacting the sheet is significantly reduced.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B32B 27/20 B32B 27/20 Z 27/28 27/28 27/30 27/30 B C08J 7 / 04 CEZ C08J 7/04 CEZD C08K 3/04 KFV C08K 3/04 KFV C08L 23/00 LCC C08L 23/00 LCC 25/06 LEH 25/06 LEH LQS LQS 55/02 LMB 55/02 LMB LME LME 71/12 LQN 71/12 LQN LQP LQP

Claims (5)

[Claims] 1. Both sides of a sheet substrate made of at least one kind of thermoplastic resin selected from polyphenylene ether resin, polystyrene resin or ABS resin,
A sheet in which a conductive resin composition comprising (A) at least one kind of thermoplastic resin selected from polyphenylene ether resin, polystyrene resin or ABS resin, (B) carbon black and (C) olefin resin is laminated. In (a), the conductive resin composition is (B) carbon black 5 per 100 parts by weight of (A) thermoplastic resin.
To 50 parts by weight, and 1 to 30 parts by weight of the (C) olefin resin per 100 parts by weight of the total amount of the (A) thermoplastic resin and the (B) carbon black, and (B) A conductive composite plastic sheet characterized in that the sheet having the conductive resin composition laminated thereon has a surface specific resistance value of 10 ² to 10 ¹⁰ Ω. 2. Both sides of a sheet substrate made of at least one kind of thermoplastic resin selected from polyphenylene ether resin, polystyrene resin or ABS resin,
(A) a polyphenylene ether-based resin, a thermoplastic resin selected from at least one of a polystyrene-based resin or an ABS-based resin, (B) carbon black, (C) an olefin-based resin, and (D) a conductive agent containing a compatibilizer. In a sheet laminated with a resin composition, (a) the conductive resin composition contains (B) 5 to 50 parts by weight of carbon black per 100 parts by weight of the thermoplastic resin (A), and (A) 1 to 30 parts by weight of the (C) olefin resin and 1 to 30 parts by weight of the compatibilizer (D) per 100 parts by weight of the total amount of the thermoplastic resin and the (B) carbon black, and ) A conductive composite plastic sheet, characterized in that the surface resistivity of the sheet laminated with the conductive resin composition is 10 ² to 10 ¹⁰ Ω. 3. The conductive material according to claim 2, wherein the compatibilizing agent (D) is a resin obtained by hydrogenating a styrene-diene block copolymer and / or a resin obtained by graft-copolymerizing styrene with a polyolefin. Composite plastic sheet. 4. A conductive plastic container obtained by molding the conductive composite plastic sheet according to claim 1 by pressure forming, vacuum forming, hot plate forming, or the like. 5. A conductive plastic container obtained by molding the conductive composite plastic sheet according to claim 2 by pressure forming, vacuum forming, hot plate forming, or the like.