JP3209393B2 - Conductive composite plastic sheet and container - Google Patents

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 contamination of an IC or the like caused by detachment of carbon black or the like due to abrasion at the time of contact with the IC or the like is remarkably reduced. The present invention relates to a conductive plastic container formed by molding a sheet.

[0002]

2. Description of the Related Art Injection trays, vacuum forming trays, magazines, embossed carrier tapes, and the like have conventionally been used as packaging forms for ICs and electronic components using ICs. (1) a method of applying an antistatic agent to the surface of a packaging container, (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 have been implemented.

[0003] However, the method (1) shows a sufficient antistatic effect immediately after coating, but the method (1),
The antistatic agent is likely to be detached due to outflow due to moisture and abrasion, and stable performance cannot be obtained. The surface resistivity is also 1
0 is unsuitable for ⁹ to 10 ¹² Omega about a and packaging of IC that requires strict antistatic effect. The method (2) has the drawbacks that the coating tends to be non-uniform at the time of manufacture, and the anti-static effect is lost due to peeling off due to abrasion, thereby destroying the IC and contaminating the lead portion of the IC. (3)
In the method (1), it is necessary to add a large amount of an antistatic agent, so that the physical properties of the resin are reduced, and the surface specific resistance value is greatly affected by humidity, and stable performance cannot be obtained. As the conductive filler in the method (4), (a) metal fine powder,
(B) carbon fiber, (c) carbon black and the like. Among them, (a) fine metal powder and (b) carbon fiber can obtain sufficient conductivity by adding a small amount, but the moldability is remarkably deteriorated, it is difficult to disperse uniformly, and the resin component is present on the surface of the molded product. Only a skin layer is easily formed, and it is difficult to obtain a stable surface specific resistance value.

On the other hand, (c) carbon black is
It is generally used because it can be uniformly dispersed by examining the kneading conditions, etc., and it is easy to obtain a stable surface specific resistance value. And a phenomenon that the moldability decreases. Conventionally, resins for dispersing carbon black include polyvinyl chloride resins, polypropylene resins, polyethylene terephthalate resins, polystyrene resins and ABS resins for general use, and polyphenylene ether resins for heat resistance at 100 ° C. or higher. Resin, polycarbonate resin and the like are used. Among these resins, polystyrene resins are used for general purposes, and polyphenylene ether resins are used for heat resistance. It is also excellent in cost. Further, as a method for improving the moldability and mechanical strength of a sheet obtained from these conductive resins, and further improving the mechanical strength of a packaging container obtained by molding the sheet, JP-A-57-157
-205145, JP-A-62-18261 and the like have been proposed. However, molded articles of the composition obtained by adding a large amount of carbon black to these resins have a disadvantage that carbon black is easily detached from the surface of the molded article due to abrasion.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks and provides a sheet substrate made of at least one kind of thermoplastic resin selected from polyphenylene ether resin, polystyrene resin and ABS resin. In a sheet in which a conductive resin composition composed of a thermoplastic resin and carbon black selected from at least one kind of polyphenylene ether-based resin, polystyrene-based resin or ABS-based resin is laminated on both surfaces of the conductive resin composition, Further, by containing an olefin-based resin, a conductive composite plastic sheet which significantly reduces contamination of ICs and the like due to detachment of carbon black and the like due to abrasion at the time of contact with the ICs and the like, and molding the sheet. It is an object of the present invention to provide a conductive plastic container comprising:

[0006]

That is, the first aspect of the present invention is as follows.
The invention of (1) relates to a sheet substrate made of at least one kind of thermoplastic resin selected from polyphenylene ether-based resin, polystyrene-based resin and ABS-based resin,
In a sheet in which a conductive resin composition composed of 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, A) The conductive resin composition is (A) 100 parts by weight of the thermoplastic resin and (B) 5 to 50 carbon black.
(C) 1 to 30 parts by weight of the olefin resin (C) with respect to 100 parts by weight of the total amount of the thermoplastic resin (B) and the carbon black (B). ) A conductive composite plastic sheet in which the sheet on which the conductive resin composition is laminated has a surface specific resistance of 10 ² to 10 ¹⁰ Ω.

[0007] The second invention of the present invention relates to a method for preparing a polyphenylene ether-based resin on both surfaces of a sheet substrate comprising at least one kind of thermoplastic resin selected from a polyphenylene ether-based resin, a polystyrene-based resin and an ABS-based resin. A conductive resin composition comprising a thermoplastic resin selected from at least one of a resin, a polystyrene resin and an ABS resin, (B) carbon black, (C) an olefin resin and (D) a compatibilizer is laminated. In the sheet,
(A) The conductive resin composition is (A) a thermoplastic resin 10
0 parts by weight, (B) 5 to 50 parts by weight of carbon black, and (C) 1 to 10 parts by weight of (C) olefinic resin to 100 parts by weight of the total amount of the thermoplastic resin and (B) carbon black. 30 parts by weight and (D) compatibilizer 1 to 30
Parts by weight, and (b) the sheet laminated with the conductive resin composition has a surface specific resistance of 10 ² to 10 ¹⁰ Ω.
Is a conductive composite plastic sheet.

The third invention of the present invention is directed to the second invention, wherein the compatibilizing agent 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 forming the conductive composite plastic sheet of the first invention by pressure forming, vacuum forming, hot plate forming 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 air pressure molding, vacuum molding, hot plate molding or the like.

Hereinafter, the present invention will be described in more detail. In the present invention, at least one kind of thermoplastic resin selected from polyphenylene ether-based resin, polystyrene-based resin and ABS-based resin is used for the base sheet and the conductive resin composition, respectively. The polyphenylene ether-based resin refers to a resin having a polyphenylene ether resin and a polystyrene-based 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-based resin is 28 to 86 parts by weight. If the amount is less than 28 parts by weight, sufficient mechanical properties as a polyphenylene ether-based resin cannot be obtained. If the amount exceeds 86 parts by weight, the fluidity is reduced and molding processing becomes difficult. The polyphenylene ether resin is described in US Pat.
The homopolymer or copolymer described in No. 3435 is shown.

The polystyrene resin used in the present invention refers to a resin mainly composed of a general polystyrene resin or impact-resistant polystyrene resin and a mixture thereof. ABS
The term "based resin" means a resin mainly composed of a copolymer mainly composed of three components of acrylonitrile-butadiene-styrene.

The carbon black (B) contained in the conductive resin composition of the present invention is furnace black, channel black, acetylene black, or the like, and preferably has a large specific surface area and a small amount of addition to the resin. Is obtained. For example, C. F. (S
upper Conductive Furnace),
E. FIG. C. F. (Electric Conductiv
e Furnace), Ketjen Black (trade name, manufactured by Lion-AKZO) and acetylene black. The amount of carbon black added is such that the surface specific resistance value can be set to 10 ² to 10 ¹⁰ Ω in a state of being laminated on the base sheet, and (A) the thermoplastic resin 100
(B) 5 to 50 parts by weight of carbon black is preferred based on 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. If the surface specific resistance value is less than 10 ² Ω, the power generation capability is so good that the IC may be broken.

The olefin resin (C) used in the present invention includes polyethylene resins, polypropylene resins and blends of these with other resins. Among these, it is particularly preferable to use a polyethylene resin. The polyethylene resins are classified into low-density polyethylene resins obtained by high-pressure polymerization, high-density polyethylene resins obtained by low-pressure polymerization, and linear low-density polyethylene resins obtained by low-pressure solution polymerization. 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. In this case, it is preferable to use a high-density polyethylene resin.

The olefin resin (C) used in the present invention has a melt flow index (measured according to JIS-K-7210) of not less than 0.1 g / 10 minutes at 190 ° C. under 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 30 parts by weight, based on 100 parts by weight of the total amount of the thermoplastic resin (A) and the carbon black (B).
25 parts by weight. If the added amount 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 the polyphenylene ether-based resin, polystyrene-based resin, and ABS-based resin.

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

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

In order to maintain sufficient moldability, the conductive resin composition according to the present invention is formed so that a sheet laminated with the conductive resin composition has a surface specific resistance of 10 ² to 10 ¹⁰ Ω. When filled with black, the melt flow index (measured according to JIS-K-7210) is 230 when the polyphenylene ether resin is used.
0 ° C., a load of 10 kg, a polystyrene resin at 200 ° C., a load of 5 kg, and an ABS resin at a temperature of 220 ° C., a load of 10 kg.
It is preferably at least 1 g / 10 minutes.

Further, a lubricant, a plasticizer, and a processing aid may be added to the thermoplastic resin and the conductive resin composition of the sheet substrate, if necessary, to improve the flow characteristics of the composition and the mechanical properties of the molded product. Various additives such as a reinforcing agent (resin modifier) and other resin components can be added.

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

When kneading the conductive resin composition, it is possible to knead the raw materials all together.
It is also possible to knead the styrene-based resin and carbon black, or the styrene-based resin and the olefin-based resin separately, and to knead the kneaded material step by step, for example, to knead the kneaded material at once. Furthermore, it is also possible to simultaneously knead the pellets obtained by separately kneading when extruding into a sheet, or to knead the non-olefin resin in advance, for example, and to add this when extruding into a sheet. is there.

As a method of laminating the conductive resin composition on the base sheet, each of them is separately formed into a sheet or a film by an extruder and then stepwise formed by a heat laminating method, a dry laminating method, an extrusion laminating method or the like. It is also possible to obtain sheets which are collectively laminated by a multilayer 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
It 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 preferably 80% or less on both surfaces. If the total thickness is less than 0.1 mm, the strength as a packaging container obtained by forming a sheet is insufficient, and the thickness is 3.0 mm.
If it exceeds 300, it will be difficult to form such as compressed air forming, vacuum forming, hot plate forming and the like. Further, if the conductive resin composition layer is only on one side of the sheet, or if the ratio of the conductive resin composition layer to the total thickness is less than 2% on one side, the surface specific resistance value of the packaging container obtained by molding the sheet becomes extremely high, so that it is sufficient. If the combined plastic sheet does not have a sufficient antistatic effect and exceeds 80% on both surfaces, the properties such as the mechanical strength of the composite plastic sheet deteriorate.

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

[0023]

The present invention will be described in more detail with reference to the following examples. Examples 1 to 7 The raw materials shown in Table 1 were used, weighed at the raw material composition ratios shown in Table 2, and uniformly mixed by 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 carried out at a ratio of the base sheet to the total thickness. Each conductive resin composition is extruded 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 T die having a width of 500 mm to obtain a sheet having a total thickness of 300 μm. Further, the obtained composite sheet is vacuum formed and QFP 14 mm × 20 mm / 64p
The obtained vacuum molded tray for IC packaging and the embossed carrier tape were obtained. Tables 6 and 7 show the evaluation results. In each of the examples, the carbon black did not fall off and was good.

Comparative Examples 1 to 4 In the same manner as in the examples, the raw materials shown in Table 1 were used, each was weighed at the raw material composition ratio shown in Table 3, and uniformly mixed by a high-speed mixer. 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. As in the example, a sheet having a total thickness of 300 μm was obtained. Further, the obtained sheet was vacuum-formed to obtain the same vacuum-forming tray for IC packaging and embossed carrier tape as in the examples. Tables 6 and 7 show the evaluation results.

Each evaluation was performed by the following method. (1) Surface specific resistance The distance between the electrodes was 10 mm using a Lorester surface resistance meter (manufactured by Mitsubishi Yuka), and any 10 points on the surface of the sheet sample were measured. For the vacuum forming tray and embossed carrier tape, The central 10 points on the inner bottom surface of the pocket were measured, and the logarithmic average value of each was taken as the surface resistivity. (2) Break Point Strength and Tensile Elasticity The No. 2 test piece was measured at a tensile speed of 10 mm / min according to JIS-K-7113 for the sheet sample.

(3) Presence or absence of carbon detachment The surface of the sheet sample is QFP 14 mm ×
A 20 mm / 64 pin IC is pressed with a load of 100 g and reciprocated 100 times with a stroke of 15 mm.
The lead part of C was observed with a microscope. For the vacuum forming tray and embossed carrier tape, the same IC is mounted in the pocket portion and the stroke is 30 mm and the speed is 40 min.
Vibration in the plane direction 200,000 times at a speed of 0 reciprocations.
The C lead was observed with a microscope. The evaluation was based on the presence or absence of black deposits such as carbon black on the lead portions. (4) MFI JIS for conductive resin compositions of Examples and Comparative Examples
The 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, a polyphenylene ether-based resin, a polystyrene-based resin, or a polyphenylene ether-based resin is provided on both surfaces of a sheet substrate made of at least one kind of thermoplastic resin selected from a polyphenylene ether-based resin, a polystyrene-based resin, and an ABS-based resin. In a sheet in which a conductive resin composition comprising a thermoplastic resin selected from at least one of ABS resins and carbon black is laminated, an olefin resin is further added to the conductive resin composition. It is possible to obtain a conductive composite plastic sheet in which contamination of an IC or the like caused by detachment of carbon black due to abrasion at the time of contact with a conductive plastic container and a conductive plastic container obtained by molding the sheet are significantly reduced.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-63-299923 (JP, A) JP-A-57-205145 (JP, A) JP-A-6-305084 (JP, A) JP-A-7-205 21834 (JP, A) JP-A-58-31749 (JP, A) JP-A-3-87097 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35 / 00 B65D 65/40 B65D 85/86-85/90 H01B 1/20-1/24 WPI / L (QUESTEL)

Claims (5)

(57) [Claims] At least one selected from a polyphenylene ether resin, a polystyrene resin and an ABS resin.
On both sides of a sheet substrate made of various types of thermoplastic resin,
(A) at least one thermoplastic resin selected from polyphenylene ether-based resin, polystyrene-based resin or ABS-based resin, (B) carbon black, and (C) melt flow index at 190 ° C. under a load of 2.16 kg according to JIS- 0.1 g / in the measurement according to K-7210
In a sheet in which a conductive resin composition comprising an olefin resin for 10 minutes or more is laminated, the olefin resin
Is low density polyethylene resin, high density polyethylene resin,
Linear low density polyethylene resin, polypropylene resin
Or a blend of these and another resin, wherein (A) the conductive resin composition contains (B) 5 to 50 parts by weight of carbon black with respect to 100 parts by weight of the thermoplastic resin (A), and A sheet comprising (C) 1 to 30 parts by weight based on 100 parts by weight of the total amount of the thermoplastic resin (A) and the carbon black (B), and (b) a conductive resin composition laminated thereon. A conductive composite plastic sheet having a surface specific resistance of 10 ² to 10 ¹⁰ Ω. 2. At least one selected from a polyphenylene ether resin, a polystyrene resin and an ABS resin.
On both sides of a sheet substrate made of various types of thermoplastic resin,
(A) a thermoplastic resin selected from at least one of a polyphenylene ether-based resin, a polystyrene-based resin and an ABS-based resin, (B) carbon black, and (C) a melt flow index of 190 ° C. under a load of 2.16 kg.
0.1 g / 1 in measurement according to IS-K-7210
Or 0 minutes olefinic resin and (D) consisting of a compatibilizer conductive resin composition in a sheet obtained by laminating, the O
Refining resin is low density polyethylene resin, high density poly
Ethylene resin, linear low-density polyethylene resin, polyp
Propylene-based resins or blends of these with other resins
What, (i) with respect to the conductive resin composition (A) 100 parts by weight of the thermoplastic resin (B) Carbon Black 5-50
(C) 1 to 30 parts by weight of (C) an olefin resin and (D) 1 to 30 parts by weight based on 100 parts by weight of the total amount of the thermoplastic resin (B) and the carbon black (B). Parts by weight and (b) a sheet laminated with the conductive resin composition has a surface specific resistance of 10
A conductive composite plastic sheet having a resistance of ² to 10 ¹⁰ Ω. 3. The conductive material according to claim 2, wherein (D) the compatibilizer 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 comprising the conductive composite plastic sheet according to any one of claims 1 to 3. 5. A semiconductor packaging container comprising the conductive composite plastic sheet according to any one of claims 1 to 3.