JPH07133371A - Conductive resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which can give a molding excellent in conductivity, heat resistance and mechanical strengths and reduced in metal ion elution in ultrapure water by mixing a mixture comprising a thermoplastic resin and a specified metal alloy powder with conductive carbon black in a specified mixing ratio. CONSTITUTION:100 pts.wt. mixture comprising 10-90 pts.wt. thermoplastic resin which is desirably at least one member selected from among a polycarbonate, a polyphenylene sulfide, a polyamide and a polyolefin with 90-10 pts.wt. metal alloy powder having a mean particle diameter of 0.5-30/mum and being made of an Fe-base alloy having an Ni content of 3-28wt.%, a Cr content of 14-20wt.%, a C content of 0.08-0.5wt.%, a P content of 0.01-0.1 wt.% and an S content of 0.01-0.1wt.% is mixed with 1-10 pts.wt. conductive carbon black.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel conductive resin composition, and more specifically, molding having excellent conductivity, heat resistance, mechanical strength, and a small amount of metal ions eluted into ultrapure water. The present invention relates to a conductive resin composition which gives a body and has good moldability, which can be suitably used as a raw material for manufacturing semiconductor transport trays, electronic devices, electrical parts, medical instruments and the like.

[0002]

2. Description of the Related Art A large amount of a metal-based filler or an inorganic filler is blended with a thermoplastic resin in order to impart desired physical properties to the thermoplastic resin. For example, engineering plastics such as polycarbonate, polyphenylene sulfide, polyamide resin, high rigidity,
Metallic fillers in the form of fine particles have been blended for the purpose of imparting sound insulation performance, vibration damping performance and high specific gravity.

However, when an inorganic filler is added to plastic, impact resistance is unavoidably deteriorated, and when a metal filler is added, deterioration of resin physical properties and unstable conductivity due to metal occur. Depending on the metal, for example, in the case of stainless steel, magnetism and electrification are induced by the segregation of nickel in the component, and deterioration of the resin is promoted and physical properties deteriorate, so electrification and magnetism must be avoided. Its use has been limited as a material for use in, for example, electronic parts, electric parts, and medical parts, especially as a material for semiconductor carrying trays.

By the way, of the semiconductor carrying trays,
In addition to impact resistance, baking trays used during the semiconductor manufacturing process are required to have heat resistance to withstand baking and low elution of metal ions during washing with pure water. In regard to the above, good impact resistance and electrical conductivity are required, but a material that completely satisfies these requirements has not been known until now.

[0005]

DISCLOSURE OF THE INVENTION The present invention is non-magnetic and has conductivity, is excellent in heat resistance, impact resistance and dimensional stability, and has a small elution amount of metal ions in ultrapure water. The purpose of the present invention is to provide a novel conductive resin composition which can be suitably used as a material for a tray for carrying a semiconductor as well as a general electronic, electric component and medical component.

[0006]

The inventor of the present invention is
As a result of intensive research to develop a resin composition suitable as a material for electric parts, medical parts, etc., particularly as a material for a tray for carrying semiconductors, iron, nickel and chromium are the main components of a thermoplastic resin. By adding a certain amount of carbon, phosphorus, sulfur, by blending the resulting fine particle alloy of a specific composition with carbon black, it was found that the object can be achieved, the present invention based on this finding It came to eggplant.

That is, the present invention comprises (A) 10 to 90 parts by weight of a thermoplastic resin, (B) a nickel content of 3 to 28% by weight, a chromium content of 14 to 20% by weight, and a carbon content of 0.
A metal alloy having an average particle size of 0.5 to 30 μm of an iron-based alloy having a content of 08 to 0.5% by weight, a phosphorus content of 0.01 to 0.1% by weight, and a sulfur content of 0.01 to 0.1% by weight. Powder 90-10
(C) 1 to 10 parts by weight of conductive carbon black is blended with 100 parts by weight of a mixture of 100 parts by weight and a conductive resin composition.

The thermoplastic resin used as the component (A) in the composition of the present invention is not particularly limited and may be appropriately selected from those conventionally used as molding materials according to the purpose of use. Examples of such a thermoplastic resin include a polyolefin resin, a polyvinyl chloride resin, a polyamide resin, a polyester resin, a polyacetal resin, a polycarbonate resin, a polyaromatic ether or thioether resin, and a polyaromatic ester resin. Examples thereof include resins, polysulfone-based resins, styrene-based resins, acrylate-based resins and the like, among which polyolefins, polycarbonates, polyphenylene sulfides and aromatic polyamides are particularly preferable. Examples of polyolefins include polyethylene, polypropylene, and copolymers of ethylene with other α-olefins, with polypropylene being particularly preferred.

As the polycarbonate, a phosgene method in which 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is reacted with phosgene, a transesterification method in which bisphenol A is reacted with a carbonic acid diester such as diphenyl carbonate, etc. The bisphenol A-based polycarbonate obtained by the above method is preferable, but a part of bisphenol A may be 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane or 2,2
-Bis (4-hydroxy-3,5-dibromophenyl)
A modified bisphenol A-based polycarbonate substituted with propane or the like, a flame-retardant bisphenol A-based polycarbonate, or the like can also be used.

On the other hand, the polyphenylene sulfide has the formula:

[Chemical 1] Examples thereof include those having a repeating unit represented by

The polyphenylene sulfide has a paraphenylene group content of 70 mol% or more, preferably 80 mol% or more of the whole, and a solute of 0.4 g is added to 100 ml of the solvent α-chloronaphthalene.
The solution viscosity [η _{in h} ] obtained at 0 ° C is 0.05 deciliter / g or more, preferably 0.1 to 0.8 deciliter / g.
g is preferably used.

The polyphenylene sulfide may be a copolymer containing paraphenylene groups and 30 mol% or less of metaphenylene groups and orthophenylene groups, and these block copolymers are block copolymers. Polymers are preferred.

Further, the equation

[Chemical 2] (R in the formula is an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 4) and may contain one or more repeating units.

These polyphenylene sulfides may be substantially linear, branched, thermally crosslinked, or a mixture thereof.

On the other hand, as the aromatic polyamide, aromatic diamines such as m-xylylenediamine, p-phenylenediamine and m-phenylenediamine are condensed with aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid. The obtained product can be used.

In the composition of the present invention, the thermoplastic resin as the component (A) may be used alone or in combination of two or more kinds.

Next, in the composition of the present invention, the iron-based alloy used as the component (B) is an iron-based alloy containing nickel, chromium, and carbon as components, and further contains a trace amount of components. It contains phosphorus and sulfur.

The nickel content is in the range of 3 to 28% by weight, preferably 5 to 25% by weight, and the chromium content is in the range of 14 to 20% by weight, preferably 16 to 18% by weight. When the nickel content is less than 3% by weight, magnetism is likely to occur, and the reaction with the resin causes poor compatibility with the resin, resulting in a decrease in impact strength and an increase in the amount of warp. %, The deterioration of the resin is promoted, and the desired physical properties are not maintained. When it is 29% by weight or more, nickel in the metal alloy is precipitated to cause gelation of the resin and promote decomposition. Further, when the chromium content is less than 14% by weight, metal corrosion occurs, and when it exceeds 20% by weight, magnetism is likely to occur.

The iron-based alloy used in the composition of the present invention must have a carbon content of 0.08 to 0.5% by weight, preferably 0.10 to 0.40% by weight. If the content is more than 0.5% by weight, corrosion of the metal occurs, rust can be recognized on the molded product, and deterioration of physical properties is caused. If the content is less than 0.08% by weight, magnetism is likely to occur and the impact resistance is lowered.

On the other hand, the phosphorus content and the sulfur content are 0.0
1 to 0.1% by weight, with 0.1% by weight of these components.
If it exceeds 5% by weight, the physical properties of the resin are deteriorated, and if the amount of these components is too small, the strength tends to be insufficient.

In general, iron-based alloys contain, in addition to the above-mentioned components, trace elements such as molybdenum, as unavoidable components.
Silicon, manganese, copper, etc. may be contained, but in the present invention, those containing these unavoidable components can also be used unless there is a particular problem.

This iron-based alloy has an average particle size of 0.5 to 30 μm.
m, preferably 3 to 20 μm.
If the average particle diameter is less than 0.5 μm, impact strength and melt index are lowered, and magnetism is apt to occur, and if it exceeds 30 μm, impact strength is lowered. In order to obtain an alloy having such an average particle size, it is pulverized by a conventional method such as an atomizing method, a pulverizing method, a wet method or the like.

The metallic filler of the component (B) may be mixed with a fibrous filler as long as there is no particular problem. Further, if desired, it may be used after being surface-treated with a suitable surface-treating agent. As the surface treatment agent at this time, for example, a silane coupling agent, a titanate coupling agent,
Examples thereof include silica powder, silicone oil, higher fatty acids, higher alcohols and waxes.

In the composition of the present invention, the thermoplastic resin as the component (A) and the iron-based alloy as the component (B) are added in an amount of 10 to 90 parts by weight of the component (A) and 90 to 10 parts by weight of the component (B). In the range of 100 parts by weight, and the mixture is mixed with conductive carbon black 1 to 1 as the component (C).
Add 0 parts by weight.

If the amount of this thermoplastic resin is more than 90 parts by weight, the conductivity becomes poor and warpage or deformation occurs. Further, if this amount is less than 10 parts by weight, the melt index becomes small, the moldability deteriorates, and the impact strength also becomes low.

On the other hand, if the amount of carbon black is less than 1 part by weight, the conductivity will be insufficient, and if it exceeds 10 parts by weight, the melt index will be small, the moldability will be deteriorated, and the impact strength will be lowered.

The conductive carbon black used as the component (C) in the composition of the present invention generally has a specific surface area of 20 to 1800 m as measured by the low temperature nitrogen adsorption method and the BET method.
² / g and the pore volume are 1.5 to 10 cc / g as measured by the mercury porosimetry in the range of the pore radius of 30 to 7500Å, and the specific surface area is particularly 600 to 1200 m ² / g. Examples of such carbon black include channel black, acetylene black, carbon black produced by the furnace black method, and the like.

In the composition of the present invention, if desired, various additives usually used in resin compositions such as lubricants, colorants, stabilizers, antioxidants, ultraviolet absorbers, antistatic agents,
A flame retardant, a plasticizer, etc. can be blended.

The method for preparing the composition of the present invention is not particularly limited, and examples thereof include the above-mentioned component (A), component (B) and (C).
It can be prepared by melt-kneading the components and various additives used as necessary according to a conventional method to form a composite. Melt kneading can be performed by, for example, a method using a Henschel mixer, a single-screw or twin-screw extruder, a Banbury mixer, a roll or the like, and other conventional methods, but particularly, using a Henschel mixer, an extruder, a Banbury mixer. Is preferred

At this time, conductive carbon black may be blended with an appropriate amount of thermoplastic resin to prepare a masterbatch, which may then be used as a composite resin composition.

The resin composition of the present invention thus obtained usually has a specific gravity of 1.4 or more. For example, it may be a tray for carrying semiconductors (baking tray, carrying tray), electronic or electrical equipment. Parts, electromagnetic interference and electrostatic damage prevention materials, medical materials, various acoustic materials, sound insulation
It is suitable for applications such as damping material and building materials.

[0032]

The conductive resin composition of the present invention has a conductivity,
It is excellent in heat resistance and moldability, has high impact strength and mechanical strength, and has a small elution amount of metal ions in ultrapure water. Therefore, it is suitably used for various industrial materials, especially for semiconductor transport trays.

[0033]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. The alloy components in this are JIS G121
1 to G1228, Z2613 and G1204 were analyzed and measured.

The physical properties of the composition were evaluated as follows. (1) Melt index (g / 10 minutes) Determined in accordance with ASTM D1238 (275 ° C. or 230 ° C., load 2.16 kg). (2) Izod impact strength (kg · cm / cm) Determined according to ASTM D-256 (with notch). (3) Heat distortion temperature (° C.) Obtained in accordance with ASTM D-648 (load 18.6)
kg / cm ² ). (4) Volume resistivity (Ω · cm) Obtained in accordance with ASTM D-257. (5) Charging property (kV) A test piece (100 × 100 × 3.2 mm) was applied with a voltage of 10 k.
V was applied for 1 minute, and the electrification voltage was measured 5 seconds after the application was stopped. (6) Magnetization 10 g of a sample cube (about 3 × 3 × 3 mm) was placed on a polyethylene film having a thickness of 10 μm, and a magnet having a magnetic flux of 15,000 gauss was moved from the back surface of the film to remove the sample. The moving state was evaluated according to the following criteria. ◎ No movement ○ Less than 5% by weight of the whole moved △ 5 to 50% by weight of the whole moved × More than 50% by weight of the whole moved

(7) Warp Amount (mm) A flat plate-shaped test piece (200 × 200 × 3 mm) was heated to the following temperature in a gear oven, and then the maximum warped portion was measured to obtain the value. PA, PP system 120 ° C PC system 130 ° C PPS, PPE system 150 ° C PS system 100 ° C PVC system 70 ° C

(8) Total elution amount of metal ions (ppb) After 10 g of the pellet was left in 100 ml of ion-exchanged water at 80 ° C. for 7 days, the pellet-removed ion-exchanged water was subjected to ICP (dielectric coupling plasma) emission spectroscopy. Analyzer [Seiko Denshi Kogyo KK, SPS1500
UR] to determine the total amount of metal ions.

Examples 1 to 5 and Comparative Examples 1 and 2 Polycarbonate (Taflon FN-3 manufactured by Idemitsu Petrochemical Co., Ltd.
000, density 1.20 g / cm ³ ), Ni 13% by weight, chromium 18% by weight, carbon 0.26% by weight, phosphorus 0.
Contains 07% by weight and 0.05% by weight of sulfur and has an average particle size of 8
5 parts by weight of carbon black (Ketchen Black EC manufactured by Lion) was added to 100 parts by weight of the iron-based alloy powder of μm mixed in different amounts, and the mixture was premixed, and then the twin-screw extruder ( Ikegai Iron Works, PCM45)
Was kneaded and extruded at 220 to 320 ° C. and cut with a pelletizer to prepare pellets. Physical properties of the conductive resin composition thus obtained were determined and are shown in Table 1.

[0038]

[Table 1]

As is clear from this table, when the amount of the polycarbonate exceeds 90 parts by weight, the conductivity decreases and the amount of warpage increases, and when the amount is less than 10 parts by weight, the melt index decreases. Becomes smaller and molding becomes difficult, and the amount of metal ions eluted increases.

Examples 6 and 7, Comparative Examples 3 and 4 A conductive resin composition was prepared in the same manner as in Example 3, except that the addition amount of carbon black was changed.
The physical properties of this product are shown in Table 2.

[0041]

[Table 2]

As is clear from this table, when the amount of the conductive carbon black is less than 1 part by weight per 100 parts by weight of the total amount of the resin and the alloy powder, the conductivity is lowered, and this amount is 1
When it is more than 0 parts by weight, moldability and impact resistance are deteriorated.

Examples 8 to 11 Polyphenylene sulfide (MI 340 g / 10 min at 315 ° C., 5 kg load, relative at 20.6 ° C. in α-chlornaphthalene at a concentration of 0.4 g / 100 ml, measured using an Ubbelohde viscometer. Viscosity 0.24dl /
g) and the alloy powder used in Example 1 were mixed in different amounts, and 5 parts by weight of conductive carbon black was added to 100 parts by weight of the mixture, and the conductive composition was prepared in the same manner as in Example 1. Was prepared. The physical properties of this product are shown in Table 3.

[0044]

[Table 3]

As is clear from this table, all the resin compositions show good impact resistance, electrical conductivity and thermal stability,
Small elution amount of metal ions.

Examples 12 to 14 and Comparative Examples 5 and 6 In Example 3, iron-based alloy powders having different carbon contents were used, and the other procedures were performed in the same manner to prepare conductive resin compositions. The physical properties of this product are shown in Table 4.

[0047]

[Table 4]

As is clear from this table, when the carbon content in the iron-based alloy is less than 0.08% by weight, impact resistance is low and magnetism occurs, and when it is more than 0.5% by weight, metal ions are produced. The amount of elution increases significantly.

Examples 15 to 19 and Comparative Examples 7 and 8 The same as Example 3 except that the iron-based alloys having nickel contents of 2% by weight and 29% by weight were used. To prepare a conductive resin composition. The physical properties of this product were determined, and the results are shown in Table 5.

As is clear from this table, when the nickel content is 2% by weight, the magnetism is high and the Izod impact value is low, and when the nickel content is 29% by weight, the Izod impact value and the heat deformation temperature are low, and the warp amount is large. And the amount of metal ions eluted increases.

[0051]

[Table 5]

Comparative Examples 9 and 10 A conductive resin composition was prepared in the same manner as in Example 3 except that the iron-based alloys having chromium contents of 11% by weight and 23% by weight were used. Was prepared. The physical properties of this product were determined, and the results are shown in Table 6. The former all showed good physical properties, but lacked corrosion resistance and increased the elution amount of metal ions, and could not be put to practical use. It was also found that the latter has high magnetism and the object of the present invention cannot be achieved.

[0053]

[Table 6]

Examples 20 to 22 and Comparative Examples 11 and 12 Conductive resin compositions were prepared in the same manner as in Example 3 except that the iron-based alloys in Example 3 having different average particle diameters were used. The physical properties of The results are shown in Table 7.

[0055]

[Table 7]

As is clear from this table, when an iron-based alloy having an average particle size of less than 0.5 μm is used, magnetism is likely to occur and the amount of warpage is large, and the average particle size is more than 30 μm. When used, the impact resistance is low and the amount of metal ions eluted is large.

Examples 23 to 26, Comparative Examples 13 to 16 In order to investigate the effect of the phosphorus and sulfur contents in the iron-based alloy, the phosphorus or sulfur contents in the iron-based alloy in Example 3 were changed. A conductive resin composition was prepared in the same manner as in Example 3 except that the above was used. The physical properties of this product were determined, and the results are shown in Table 8.

[0058]

[Table 8]

Example 27 Polypropylene (made by Idemitsu Petrochemical, J-465H, density 0.90) was used in place of the polycarbonate used in Example 3.
A conductive resin composition was prepared in the same manner as in Example 3 except that g / cm ³ ) was used. The physical properties of this product were determined to be MI 7.2 g / 10 min, and an Izod impact value of 4.1.
kg · cm / cm, heat distortion temperature 134 ° C., volume resistivity 7.2 × 10 ⁴ Ω · cm, magnetic susceptibility 0.10 kV, warpage amount 0.49 mm, metal ion elution amount 39 ppb.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shuhei Komura 1-277 Kanda Izumi-cho, Chiyoda-ku, Tokyo Within 277 Calup Industry Co., Ltd. (72) Inventor Masatoshi Akatsuka 1-277 Kanda Izumi-cho, Chiyoda-ku, Tokyo Within 277 Calpe Industry Co., Ltd. (72) In-house Hideo Okawa 1-277 Kanda Izumi-cho, Chiyoda-ku, Tokyo Within Calpe Industry Co., Ltd. ( 72) Inventor Yoshihisa Kato 10 Ryugu-cho, Minato-ku, Aichi Prefecture Daido Steel Co., Ltd. (72) Inventor Hirotoshi Kawato 3-1-1 Marunouchi, Chiyoda-ku, Tokyo Idemitsu Material Co., Ltd. (72) Inventor Yasuhiko Ozawa 1-63-3 Jobandai, Itabashi-ku, Tokyo Tojo Design and Project Co., Ltd.

Claims (2)

[Claims] 1. (A) 10 to 90 parts by weight of a thermoplastic resin, (B) nickel content of 3 to 28% by weight, chromium content of 14 to 20% by weight, carbon content of 0.08 to 0.5% by weight. %, Phosphorus content 0.01-0.1% by weight, sulfur content 0.01-0.1% by weight, average particle size of 0.5-
A conductive resin composition, wherein (C) 1 to 10 parts by weight of conductive carbon black is mixed with 100 parts by weight of a mixture consisting of 90 to 10 parts by weight of a metal alloy powder having a size of 30 μm. 2. The conductive resin composition according to claim 1, wherein the thermoplastic resin is at least one selected from polycarbonate, polyphenylene sulfide, polyamide and polyolefin.