JPH0831230A - Semiconductor aromatic polysulfone resin composition - Google Patents

Abstract

PURPOSE:To provide a semiconductive aromatic polysulfone resin composition having stable semiconductivity and excellent in mass productivity, moldability, heat resistance and dimensional accuracy, etc. CONSTITUTION:This resin composition comprises 100 parts by weight of a resin composition consisting of 10-95wt.% aromatic polysulfone resin and 5-90wt.% polyphenylene sulfide resin and 10-50 pts.wt. of carbon black, the amount of DBP absorbed by the carbon black being 100-300cc/100g, the nitrogen adsorption ratio surface area of the carbon black being 10-100m<2>/g. A molding of the resin composition achieves performance such that its surface resistivity value is in the range 10<5>-10<12>OMEGA.

Description

Detailed Description of the Invention

[0001]

[Industrial application] Resin compositions with antistatic function can be applied to many fields such as home appliances, office automation equipment, IC related fields, such as malfunction and function deterioration due to static electricity, and prevention of dirt adhesion due to dust. Can be expected. In particular, since the aromatic polysulfone resin used in the present invention has high heat resistance and dimensional stability, specific examples of its characteristics include carriers and trays used in the baking process of IC manufacturing.

[0002]

2. Description of the Related Art Polymer compounds are moldable, mass-producible and lightweight.
It is suitable for all fields due to its excellent efficiency and cost.
Conventional polymer compounds have surface resistance of 10
^Fifteen-10 ¹⁷Stores static electricity due to the nature of Ω and insulator
However, it has a drawback that it is easily charged. High charged
As obstacles due to child compounds, dust and dirt adsorption, electric shock
Discomfort due to, electronics such as AV equipment / OA equipment
Examples include malfunctions and damage of ICs in products.

As a general antistatic method for polymer compounds to avoid such obstacles, there are a surface treatment method and a kneading method. The surface treatment method is a method of preventing electrification by treating the surface of the molded body with a conductive paint, plating, vapor deposition of metal, spraying / coating of a surfactant and the like.
However, the number of processes increases, large-scale equipment is required, and the cost increases. In addition, there are drawbacks such as peeling and loss of the antistatic agent due to washing with water and rubbing.

As a method of solving these drawbacks and exhibiting a permanent antistatic effect, there is a method of kneading a surfactant, a hydrophilic polymer, carbon black, a conductive filler and the like into a polymer compound. Surfactants and hydrophilic polymers have an antistatic effect by diffusing static electricity accumulated by moisture absorption by ionic conduction, but do not exhibit an antistatic effect when the operating temperature is high or the humidity is low. In addition, when the molding temperature is high, such as super engineering plastic, the surfactant and hydrophilic polymer are thermally decomposed,
The antistatic effect cannot be exhibited.

As a typical method for imparting conductivity, there is a method of adding carbon black, especially what is called conductive carbon. However, the Japan Adhesive Association magazine Vol.
23, No. As described on pages 3,103 to 111 (1987), when carbon black is added to a polymer compound, conductivity does not appear while the amount of addition is small, but when the amount of addition exceeds a certain level, the conductivity rapidly increases. The phenomenon that the conductivity rises occurs. It is considered that this is because the carbon black itself is a powder having a low resistance value, so that contact between the carbon blacks starts in the polymer. Moreover, the formation of the conductive mechanism is greatly influenced by the aggregation state and orientation of carbon black. That is, the surface resistance value changes depending on the molding conditions, and the surface resistance value differs depending on the gate portion of the molded product or the portion such as the flow front end. For this reason, it is difficult to change the resistance value of the polymer step by step, and in particular, it is necessary to manufacture a polymer composition and a molded product having a conductivity of about 10 ⁷ to 10 ¹² Ω which is an antistatic level with high productivity. Is extremely difficult.

Therefore, the volume resistivity of 10 ¹ to 10 is disclosed in JP-A 1-268759 and 1-268760.
^{The addition of 6} Ωcm metal filler is proposed. Examples of metal fillers include reduction products of potassium titanate whiskers, nickel-coated products of mica, and conductive ZnO and antimony trioxide surfaces obtained by heat treatment by adding a treatment agent mainly containing aluminum to zinc oxide. Treated products and the like are mentioned, but since these have a large specific gravity, the function is not exhibited unless added in a large amount as a simple substance. For this reason, it has been proposed to use carbon black, graphite, titanium carbide, metal powder, etc., which have a low volume resistivity, in combination with the actual product, because the filler in the processed product is expensive and the amount added is large. Is few.

Further, in Japanese Patent Laid-Open No. 5-117446, carbon fibers that have been subjected to an oxidation treatment, carbon fibers obtained by making the firing temperature less than 800 ° C. and the progress of carbonization incomplete, fibrates of germanium, etc. Fiber whose resistance value is controlled to 10 ^-1 to 10 ³ Ωcm, or volume specific resistance value is 10
^The volume resistivity value is 10 ⁵ to 10 by adding general conductive carbon fiber having a conductivity of ^-1 Ωcm or less, aluminum, steel, copper or the like having high conductivity to the polymer.
Fiber-containing polymer compounds controlled at ¹³ Ωcm have been proposed. However, in recent semiconductor manufacturing fields, since the distance between pins has become narrower due to the higher density of integrated circuits, the progress of surface mounting technology, and the increase in the number of pins, trays and carriers molded with the fiber-containing polymer compound described above have been used. If it is used, the carbon fibers protruding from the surface of the molded product come into contact with the pins to cause a short circuit, and the integrated circuit is easily broken. This is because the carbon fiber itself is a strong conductive material, so that the pin of the charged IC comes into contact with the carbon fiber, an overcurrent flows, or the pins are short-circuited via the carbon fiber. For this reason, semiconductor manufacturers are demanding polymer compounds and molded products that have an antistatic effect and have a small variation in surface resistance value without using a conductive material as a conductive material.

[0008]

DISCLOSURE OF THE INVENTION The object of the present invention is to prevent the destruction of an integrated circuit due to a short circuit, to provide an inexpensive, stable antistatic surface resistance value, mass productivity, heat resistance, flame retardancy, mechanical strength, It is intended to provide a semiconductive resin composition having excellent dimensional accuracy, moldability and the like.

[0009]

Means for Solving the Problems The inventors of the present invention have made earnest studies on the above problems, and as a result, they have been achieved by combining a specific resin composition and a specific carbon black. That is, the present invention
DBP (dibutyl phthalate) based on 100 parts by weight of a resin composition comprising 10 to 95% by weight of an aromatic polysulfone resin and 5 to 90% by weight of a polyphenylene sulfide resin.
This is achieved by a semiconductive aromatic polysulfone resin composition containing 10 to 50 parts by weight of carbon black having an oil absorption of 100 to 300 cc / 100 g and a nitrogen adsorption specific surface area of 10 to 100 m ² / g or less. The aromatic polysulfone resin used in the present invention means (1) (Chemical formula 1) or
(2) A resin having a repeating unit represented by (Chemical Formula 2).

[0010]

Embedded image

[0011]

Embedded image This resin is a polymer of the type obtained by subjecting an alkali phenolate group, an aromatic halogen group activated by an electron-withdrawing sulfone to a condensation reaction in an aprotic polar solvent, and having an arylene bond (aromatic Group bond), an ether bond, and a sulfone bond are linear polymers having three essential bond units. These aromatic polysulfone resins are disclosed, for example, in Japanese Examined Patent Publication Nos. 40-10067 and 42-7.
It can be easily produced by the method described in Japanese Patent Publication No. 799, Japanese Patent Publication No. 47-617, etc. As typical commercial products, (1)
Examples of the aromatic polyether sulfone resin having a repeating unit represented by: ULTRASON-E (manufactured by BASF, Germany, trade name), RADEL (manufactured by AMOCO, USA), etc., and the repeating unit represented by (2) As the aromatic polysulfone resin to have, ULTRASON-S (trade name of BASF, Germany), UDEL (AMOCO of the United States)
Company name, trade name) and the like.

The polyphenylene sulfide resin used in the present invention is a resin represented by the general formula (3).

[0013]

Embedded image The polyphenylene sulfide resin used in the present invention contains 60 mol% of the repeating structural unit represented by (3).
Including the above, the composing copolymer component is a meta bond,
Even if it contains an ether bond, a sulfone bond, a biphenyl bond, etc., it does not matter as long as it does not significantly affect the crystallinity and stretch orientation of the polymer.

The polyphenylene sulfide resin can be produced by a method of reacting a halogen-substituted aromatic compound with an alkali sulfide (US Pat. No. 2,513,188, Japanese Examined Patent Publication No. 45-3368) and the like, followed by crosslinking to obtain a high molecular weight compound. The converted product is called a cross-linked polyphenylene sulfide. Further, a method of obtaining a linear polymer having a high molecular weight by allowing an oxide or hydroxide of an alkaline earth metal to coexist during the polymerization (JP-A-60-55029, JP-A-60-55030). No.) etc., and is called linear polyphenylene sulfide. A typical commercially available product is Ryton P-6 as a cross-linked polyphenylene sulfide resin.
(Ranku Phillips Petroleum, trade name). Examples of the linear polyphenylene sulfide resin include Fortron W-205 (trade name, manufactured by Kureha Chemical Industry Co., Ltd.). As the polyphenylene sulfide resin used in the present invention, either a cross-linked or linear polyphenylene sulfide resin may be used, or two types may be mixed.

The carbon black having a DBP (dibutyl phthalate) oil absorption of 100 to 300 cc / 100 g and a nitrogen adsorption specific surface area of 10 to 100 m ² / g used in the present invention may be one generally available on the market. Alternatively, two or more kinds may be used in combination. The DBP (dibutyl phthalate) oil absorption is measured by the JIS K6221 rubber carbon black test method, and the nitrogen adsorption specific surface area is measured by the method of ASTM D3037.

Typical commercially available carbon blacks are Diablack (trade name, manufactured by Mitsubishi Kasei Co.) and Sta.
tex (Columbian, USA, trade name), Vu
lcan (manufactured by Cabot, Inc., trade name), Seast (manufactured by Tokai Carbon Co., trade name) and the like.

The surface resistance value in the present invention means JIS
It is measured by the K-6911 method, and in the experiment of the present invention, it was measured by a measuring instrument Hiresta (trade name, manufactured by Mitsubishi Petrochemical Co., Ltd.) corresponding to JIS K-6911.

In the present invention, the compounding ratio of the aromatic polysulfone resin and the polyphenylene sulfide resin is 10 to 95% by weight of the aromatic polysulfone resin, preferably 20.
~ 95% by weight, polyphenylene sulfide resin 90-5
% Resin composition, preferably 80 to 5% by weight
DBP oil absorption is 100 to 300c with respect to 00 parts by weight
c / 100 g, preferably 100-200 cc / 100
10 to 5 carbon black having a nitrogen adsorption specific surface area of 10 to 100 m ² / g, preferably 10 to 80 m ² / g.
It is 0 part by weight, preferably 10-40 parts by weight.

When the content of the aromatic polysulfone resin is less than 10% by weight, the heat resistance is remarkably lowered. When it exceeds 95% by weight, moldability is deteriorated and the surface resistance value becomes unstable. When the amount of carbon black added is less than 10 parts by weight, the surface resistance value is insufficient, and when it exceeds 50 parts by weight, moldability and mechanical strength are deteriorated, and a good molded product cannot be obtained. In addition, carbon black having an oil absorption of DBP, that is, dibutyl phthalate of less than 100 cc / 100 g, has little structure development, so if it is not added in a large amount, conductivity will not be exhibited, and thus moldability and mechanical properties will deteriorate. Will end up. Also, 300cc / 100g
It is difficult to industrially produce carbon black that exceeds the limit. Even if the DBP oil absorption is within the above preferred range,
When the nitrogen adsorption specific surface area exceeds 100 m ² / g, the carbon black is so-called conductive carbon, and conductivity starts to be expressed with a small addition amount, but as described above, the antistatic level, that is, the surface resistance value is 10 ⁷ ~ 10 ¹²
It is extremely difficult to manufacture a polymer composition and a molded product having a conductivity of about Ω with high productivity. If the nitrogen adsorption specific surface area is less than 10 m ² / g, it will be difficult to industrially manufacture.

The semiconductive aromatic polysulfone resin composition of the present invention has a semiconductive property without being influenced by molding conditions by adding a blend of an aromatic polysulfone resin and a polyphenylene sulfide resin and a specific carbon black. It was found that a certain surface resistance value of about 10 ⁵ to 10 ¹² Ω is stably expressed. This means that in the conventional carbon black-added product, the surface resistance value of the partial portion deviates from the above range even if the amount of carbon black added and the molding conditions are adjusted each time the shape of the molded product changes. The present invention is well within the above range, has the characteristics of being versatile enough to be used for molded articles having different shapes and being excellent in mass productivity.

The method for producing the semiconductive aromatic polysulfone resin composition of the present invention is not particularly limited, and a commonly known method can be adopted. Aromatic polysulfone resin, polyphenylene sulfide resin, carbon black are uniformly mixed with the above composition ratio using a high-speed stirrer, and then melt-kneaded into pellets by a single-screw or multi-screw extruder with sufficient kneading capacity. To be done.

Further, various elastomers may be added. As the elastomer, an ABA 'type block copolymer elastomer is used. Here, A and A ′ are polymerized vinyl aromatic hydrocarbon blocks, and B is a polymerized conjugated diene block or a polymerized conjugated diene block hydrogenated. For the same purpose, a glycidyl group-containing copolymer consisting of an α-olefin and a glycidyl ester of an α, β unsaturated acid, a core / shell type elastomer, a polyester elastomer and the like can be mentioned. These elastomers may be used alone or in combination. Depending on the purpose, coloring agents such as pigments and dyes, reinforcing materials such as glass fibers, metal fibers and carbon fibers, fillers such as metal oxides, talc, mica and calcium carbonate, antioxidants, UV absorbers, lubricants. A flame retardant, an additive such as hydrotalcites, a release agent such as a fluororesin or a silicone resin, and carbon black, graphite, metal powder, an antistatic agent and the like other than those claimed in the claims can be added.

[0023]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The surface resistance values described in Examples and Comparative Examples were measured by the following method. (1) Injection molding machine used PS20E2ASE (manufactured by Nissei Plastic Industry Co., Ltd.) (2) Molded product Vertical 80 mm × Horizontal 40 mm ×
A 2 mm thick flat plate mold structure uses a three-plate mold, and after dropping it into the resin reservoir with a pin gate, adopts a film gate in the longitudinal direction. (3) Surface resistance meter Hiresta (manufactured by Mitsubishi Petrochemical Co., Ltd.) JIS K-6911 compliant evaluation method The above flat plate was subjected to injection molding at a resin temperature of 360 ° C., a mold temperature of 150 ° C., and an injection speed of 20% and 80%. Dozens of sheets were molded under one molding condition, left at a temperature of 23 ° C. and a humidity of 50% RH for 48 hours, and then arbitrarily extracted 3 sheets. For each, 3 points on the gate side, center, and tip were measured with a surface resistance meter. It was measured that the range of the minimum value to the maximum value of the surface resistance value was within the range of 10 ⁵ to 10 ¹² Ω, which is the semi-conductive range, even if the molding conditions were changed. The carbon blacks used in Examples and Comparative Examples are shown in Table 1.

The DBP (dibutyl phthalate) oil absorption of carbon black and the nitrogen adsorption specific surface area were measured by the following methods. DBP oil absorption: JIS K6221 Carbon black test method for rubber Nitrogen adsorption specific surface area: ASTM D3037

Examples 1 to 4 ULTRASON-E1010P (BAS, Germany) was used as the aromatic polysulfone resin.
Company F's trade name, abbreviated as PES below, Ryton E-1880 as a polyphenylene sulfide resin (trade name of Toray Phillips Petroleum Co., abbreviated as PPS below), carbon black N-550U (US Co
Lumbian, trade name) is blended in the ratio shown in Table 2, and kneaded and pelletized in the range of 330 ° C to 340 ° C.
The results of measuring the surface resistance value after molding under the above conditions are shown in Table 2.
Shown in

Examples 5 to 6 The same as Examples 1 to 4 except that the type of carbon black was changed, and the results are shown in Table 2.

Comparative Examples 1 to 3 The same as Examples 1 to 4 except that the composition ratios shown in Table 3 were used, and the results are shown in Table 3. Even if the amount of Ketjen EC added is changed to PES alone,
It can be seen that the surface resistance value is out of range.

Comparative Examples 4 to 6 The same as Examples 1 to 4 except that the composition ratios shown in Table 3 were used, and the results are shown in Table 3. Compared to Comparative Examples 1 to 3, the matrix resin is PES.
It can be seen that the blending of / PPS causes the conductivity to start to be expressed with a small amount of carbon black added, but the range of the surface resistance value is out of the range.

Comparative Examples 7 to 9 The same as Examples 1 to 4 except that the kind of carbon black was changed, and the results are shown in Table 4. In the case of carbon black other than the claims of the present invention, the range of the surface resistance value is out of the range as in Comparative Examples 4 to 6.

[Comparative Example 10] The same as Examples 1 to 4 except that the composition ratios shown in Table 4 were used, and the results are shown in Table 4. Even if a large amount of carbon black within the scope of the claims of the present invention is added, the matrix resin does not exhibit conductivity when it is a PES simple substance, and further addition causes an increase in melt viscosity, which is not preferable in molding processing. .

Comparative Examples 11 to 12 The same as Examples 1 to 4 except that the kind of carbon black was changed, and the results are shown in Table 4. With carbon blacks other than those claimed in the present invention, conductivity is not exhibited as in Comparative Example 10.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

[0035]

[Table 4]

[0036]

EFFECTS OF THE INVENTION The composition according to the present invention has stable semiconductivity while using inexpensive carbon black as a conductive material, has no troubles due to the conductive material rising, and has mass productivity, moldability and heat resistance. A semiconductive aromatic polysulfone resin composition having excellent properties and dimensional accuracy can be provided at low cost.

Exploiting the above characteristics, it is expected to develop applications such as jigs, carriers and trays used in manufacturing processes in the electronic and electrical fields.

Claims (2)

[Claims] 1. A DBP oil absorption of 100 to 300 cc / 100 g and a nitrogen adsorption specific surface area per 100 parts by weight of a resin composition comprising 10 to 95% by weight of an aromatic polysulfone resin and 5 to 90% by weight of a polyphenylene sulfide resin. 10 to 100 m ² / g of carbon black is 10 to 50
A semi-conductive aromatic polysulfone resin composition comprising parts by weight. 2. A semiconductive aromatic polysulfone resin composition according to claim 1, which has a surface resistance of 10 ⁵ to 10.
A molded product having a performance within the range of 10 ¹² Ω.