KR0174067B1 - Conductive Polysulfone Resin Composition - Google Patents

Conductive Polysulfone Resin Composition Download PDF

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KR0174067B1
KR0174067B1 KR1019950026802A KR19950026802A KR0174067B1 KR 0174067 B1 KR0174067 B1 KR 0174067B1 KR 1019950026802 A KR1019950026802 A KR 1019950026802A KR 19950026802 A KR19950026802 A KR 19950026802A KR 0174067 B1 KR0174067 B1 KR 0174067B1
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weight
resin
conductive
polysulfone resin
resin composition
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KR970010880A (en
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김환기
계형산
이효일
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김상응
주식회사삼양사
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06Polysulfones; Polyethersulfones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/06Elements
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/017Additives being an antistatic agent

Abstract

본 발명은 전도성 폴리설폰 수지 조성물에 관한 것으로, 방향족 폴리설폰수지 40∼80중량%와 폴리카보네이트 수지 60∼20중량%로 구성된 수지화합물 100중량부에 대해 카본화이바 5∼20중량부로 구성된 폴리설폰 수지 조성물에 관한 것으로, 전기 전도성, 치수정밀도, 기계적강도, 가공성 등이 우수하여 사출성형등 여러 가공방법에 의해 전도성 반도체 체(chip) 캐리어(carrier)에 적용할 수 있는 특징이 있다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive polysulfone resin composition, comprising: polysulfone resin composed of 5 to 20 parts by weight of carbon fiber with respect to 100 parts by weight of a resin compound composed of 40 to 80% by weight of aromatic polysulfone resin and 60 to 20% by weight of polycarbonate resin The present invention relates to a composition, which has excellent electrical conductivity, dimensional accuracy, mechanical strength, processability, and the like, and may be applied to a conductive semiconductor chip carrier by various processing methods such as injection molding.

Description

전도성 폴리설폰 수지 조성물Conductive Polysulfone Resin Composition

본 발명은 전도성 폴리설폰 수지 조성물에 관한 것으로, 좀 더 구체적으로는 방향족 폴리설폰 수지 40∼80중량%와 폴리카보네이트 수지 60∼20중량%로 구성된 수지화합물 100중량부에 대해 카본화이바 5∼20중량부로 구성된 전도성 폴리설폰 수지 조성물에 관한 것으로, 전기 전도성, 치수정밀도, 기계적강도, 가공성 등이 우수하여 사출성형등 여러 가공방법에 의해 전도성 반도체 체(chip) 캐리어(carrier)에 적용할 수 있는 특징이 있다.The present invention relates to a conductive polysulfone resin composition, more specifically, 5 to 20 weight percent carbon fiber based on 100 parts by weight of a resin compound composed of 40 to 80 weight% of aromatic polysulfone resin and 60 to 20 weight% of polycarbonate resin. The present invention relates to a conductive polysulfone resin composition composed of parts, and has excellent electrical conductivity, dimensional accuracy, mechanical strength, and workability, and thus can be applied to a conductive semiconductor chip carrier by various processing methods such as injection molding. have.

방향족 폴리설폰 수지에 전도성을 부여하기 위한 종래의 기술로는 일본특공 소53-61670호에 카본과 같은 전도성 물질을 첨가하여 전기저항이 1010Ω 이하의 값을 갖는 전도성 화합물을 제조하는 방법이 공지되어 있으나, 전도성 카본의 첨가량이 증가함에 따라 용융점도가 증가하여 용융화합물의 성형이 어려운 단점이 있었다.As a conventional technique for imparting conductivity to an aromatic polysulfone resin, a method of preparing a conductive compound having a value of 10 10 Ω or less by adding a conductive material such as carbon to Japanese Patent Application No. 53-61670 is known. However, as the addition amount of the conductive carbon increases, the melt viscosity increases, so that molding of the molten compound is difficult.

또한, 일본특공 소68-98632호에서는 방향족 폴리설폰 수지와 폴리페닐렌 설파이트 수지로 구성된 수지화합물과 그래스화이버, 카본화이버, 흑연, 삼산화안티몬, 바륨설페이트 등의 충진제(Filler)로 구성된 성형 수지 화합물이 알려져 있으나, 사출성형등에 의한 가공방법이 고려되지 않았으며, 전기전도성을 갖는 성형품에 대한 언급이 없다.In addition, Japanese Patent Publication No. 68-98632 discloses a resin compound composed of an aromatic polysulfone resin and a polyphenylene sulfite resin, and a molding resin compound composed of fillers such as grass fibers, carbon fibers, graphite, antimony trioxide, and barium sulfate. Although it is known, processing by injection molding and the like has not been considered, and there is no mention of a molded article having electrical conductivity.

또한, 미국특허 5,173,524호에 방향족 폴리설폰 수지와 폴리페닐렌설파이트 수지 화합물에 전도성 카본을 사용하여 전도성, 열안정성 및 기계적 강도가 좋은 화합물이 알려져 있으나, 이 화합물은 폴리페닐렌설파이트 수지의 결정성 때문에 성형시 성형수축이 발생하여 치수 정밀도가 떨어지는 단점이 있다.In addition, US Pat. No. 5,173,524 discloses a compound having good conductivity, thermal stability, and mechanical strength by using conductive carbon in an aromatic polysulfone resin and a polyphenylene sulfite resin compound, but this compound is due to the crystallinity of the polyphenylene sulfite resin. Molding shrinkage occurs during molding, which has the disadvantage of poor dimensional accuracy.

따라서, 본 발명의 목적은 치수정밀도, 기계적 강도 및 가공성이 우수하여 사출성형 등의 여러 가공공정에 적용할 수 있는 전도성 폴리설폰 수지 조성물을 제공하는데 있다.Accordingly, it is an object of the present invention to provide a conductive polysulfone resin composition which is excellent in dimensional accuracy, mechanical strength and processability, which can be applied to various processing processes such as injection molding.

본 발명을 좀 더 구체적으로 설명하면 다음과 같다.The present invention is described in more detail as follows.

방향족 폴리설폰 수지 40∼80중량%와 폴리카보네이트 수지 60∼20중량%로 구성된 수지를 용융압출기의 1차 투입구에 투입하고 수지 화합물 100중량부에 대해 전도성 카본화이바 5∼20중량부를 2차 투입구에 투입하여 용융 혼련함으로써 전도성 폴리설폰 수지 조성물을 제조하게 되나, 본 발명은 폴리설폰 수지와 폴라카보네이트 수지를 먼저 믹서(Mixer)에서 프리믹싱(Pre-mixing) 한 다음 2축 압출기의 1차 투입구에 투입하고, 카본화이버를 2차 투입구에 투입하여 제조한다.A resin consisting of 40 to 80% by weight of aromatic polysulfone resin and 60 to 20% by weight of polycarbonate resin is introduced into the primary inlet of the melt extruder, and 5 to 20 parts by weight of conductive carbon fiber to the secondary inlet relative to 100 parts by weight of the resin compound. The conductive polysulfone resin composition is prepared by melting and kneading, but in the present invention, the polysulfone resin and the polycarbonate resin are first pre-mixed in a mixer and then introduced into a primary inlet of a twin screw extruder. Then, the carbon fiber is put into the secondary inlet to manufacture.

또한, 제조시에 혼련효과를 크게 하기 위하여 2축 용융압출기의 니딩블럭(Kneading block)수를 늘렸고, 초기 전단력을 크게 하여 1차 투입된 수지 혼합물이 2차 투입구에 도달할 시에는 완전히 용융될 수 있도록 스크루 배열(Screw Configuration)을 조절하였다.In addition, in order to increase the kneading effect during manufacturing, the number of kneading blocks of the biaxial melt extruder was increased, and the initial shearing force was increased so that the resin mixture introduced into the primary can be completely melted when reaching the secondary inlet. Screw Configuration was adjusted.

이 수지 조성물의 가공시에 압출기의 가공온도는 250∼320℃, 스크루 회전속도는 150∼500rpm으로 하였다.At the time of processing this resin composition, the processing temperature of the extruder was 250-320 degreeC, and the screw rotation speed was 150-500 rpm.

본 발명에 사용된 폴리설폰 수지는 비에이에스에프(BASF)사의 울트라손(UltrasonR)을 사용하였으며, 그 사용량이 80중량%를 초과하면 가공온도가 높아 가공성이 어렵고, 40중량% 미만에서는 열안정성이 떨어져 성형된 사출품의 열안정성이 좋지 않다.Polysulfone resin used in the present invention was used as Ultrason (Ultrason R ) of BASF, when the amount of use exceeds 80% by weight, the processing temperature is high and difficult to process, less than 40% by weight thermal stability The thermal stability of this injection molded article is poor.

폴리카보네이트 수지는 주식회사 삼양사 제품 트리렉스(TrirexR)를 사용하였는데, 이 수지는 점도 평균 분자량이 20,000∼30,000인 것을 사용하였다.As the polycarbonate resin, Trirex R manufactured by Samyang Co., Ltd. was used, and a resin having a viscosity average molecular weight of 20,000 to 30,000 was used.

본 발명에 사용된 폴리카보네이트 수지의 사용량이 60중량%를 초과하면 수지의 분자쇄 운동이 용이하고 열안정성이 낮아 성형된 사출품은 열처리(baking)에 의해 성형품의 얇은 부분이 손상되어 치수안정성이 떨어진다. 또 20중량% 미만일 경우에는 가공성의 불량으로 가공이 잘 안되는 결함이 있다.When the amount of the polycarbonate resin used in the present invention exceeds 60% by weight, the molded resin molded product is easy to carry out molecular chain movement and has low thermal stability, so that the thin part of the molded product is damaged by baking, resulting in poor dimensional stability. . If the amount is less than 20% by weight, there is a defect that the machining is poor due to poor workability.

본 발명에 사용된 카본화이버는 토레이(toray)사의 도레이카(toraycaR)를 사용하였는데, 그 사용량이 수지화합물 100부에 대해 5중량부 미만에서는 전기전도성이 낮아, 먼지 등의 오염물의 표면흡착이 발생하여 반도체의 성능을 저하시키며, 그 사용량이 20중량부를 초과하면 용융점도의 상승이 커서 흐름서이 크게 저하되어 가공성이 낮아진다. 그리고, 전도성을 향상시키기 위하여 저도성 카본을 첨가하여 수지의 표면저항을 감소시켰으며, 전도성 카본의 종류로는 퍼니스블랙, 채널블랙, 써멀블랙을 모두 포함한다. 전기전도성은 수지 조성물에 카본화이버의 사용 또는 전도성 카본의 사용으로도 충분히 얻을 수 있으며, 다른 전도성 충진제도 전도성 증가의 목적으로 첨가될 수 있다. 본 발명 폴리설폰 수지 조성물은 전도성 이외에도 다른 여러가지 특성을 부여하기 위해 클라스화이바(G/F), 충격보강제, 난연제등 여러가지 첨가제도 사용할 수 있다.Carbon fiber used in the present invention used toray (Torayca R ) of Toray (Toray), when the amount is less than 5 parts by weight based on 100 parts of the resin compound, the electrical conductivity is low, the surface adsorption of contaminants such as dust When the amount of use exceeds 20 parts by weight, the melt viscosity rises and the flow rate is greatly reduced, resulting in poor workability. In addition, the surface resistance of the resin was reduced by adding low conductivity carbon in order to improve conductivity, and the types of conductive carbon include furnace black, channel black, and thermal black. Electrical conductivity can also be sufficiently obtained by using carbon fibers or conductive carbon in the resin composition, and other conductive fillers can be added for the purpose of increasing conductivity. The polysulfone resin composition of the present invention may also use various additives such as classifiers (G / F), impact modifiers, and flame retardants in order to impart various other properties in addition to conductivity.

상술한 바와 같이 본 발명에 따른 전도성 수지 조성물은 종래의 수지 조성물에 비하여 좋은 전기전도성, 치수정밀도, 내열성, 가공성이 향상되어 반도체 체(Chip) 캐리어용 수지의 용도 및 전기, 전자 하우징용 소재의 광범위한 산업분야에 매우 유용하게 사용될 수 있다.As described above, the conductive resin composition according to the present invention has improved electrical conductivity, dimensional accuracy, heat resistance, and workability as compared with the conventional resin composition, and thus has a wide range of uses for resins for semiconductor chip carriers and materials for electrical and electronic housings. It can be very useful in the industrial field.

다음의 실시예 및 비교예는 본 발명을 좀 더 구체적으로 설명하는 것이지만, 본 발명의 범주를 한정하는 것은 아니다.The following examples and comparative examples illustrate the present invention more specifically, but do not limit the scope of the present invention.

[실시예 1∼4, 비교예 1∼4][Examples 1-4, Comparative Examples 1-4]

표 1에서 기재된 바와 같이 폴리설폰수지, 폴리카보네이트 수지 및 카본화이버의 사용량을 변경하여 250∼320℃의 온도와 회전수 350rpm으로 용융 혼련용 압출기(Twin Screw Extruder)로 혼련압출하여 성형용 펠렛을 제조한 다음, 120℃에서 4시간 열품건조한 후 300℃의 온도에서 사출기로 전도성 수지 시편 및 반도체 체 캐리어를 성형하여 각각의 물성을 측정하였다.As described in Table 1, the amount of polysulfone resin, polycarbonate resin and carbon fiber was changed and kneaded and extruded using a twin screw extruder at a temperature of 250 to 320 ° C. and a rotational speed of 350 rpm to manufacture molding pellets. Then, after thermal drying at 120 ° C for 4 hours, the conductive resin specimen and the semiconductor sieve carrier were molded by an injection molding machine at a temperature of 300 ° C to measure their respective properties.

상기 실시예 및 비교예에서 각각 제조된 전도성 수지 조성물의 시편에 대한 물성측정 결과를 표 1에 나타내었는 바, 각각의 물성은 ASTM 규격에 의하여 (1) 인장강도는 ASTM D638, (2) 열변형온도는 ASTM D648, (3) 용융지수의 값은 ASTM D1238, (4) 치수정밀도의 측정은 380×150×1T의 시편을 시사출하여 15℃, 습도 60%에서 48시간 방치후 사출시의 크기와 변화한 후의 비(Ratio)와, (5) 성형 시편의 표면저항 값은 23℃, 수분률 50%에서 표면저항계로 측정하였으며, 반도체 체 캐리어는 형체력 220톤의 사출기에서 실린더 온도 320℃, 금형온도 150℃의 온도에서 성형하였으며 표면저항값과 낙추 충격 강도를 측정하였다.The physical property measurement results for the specimens of the conductive resin compositions prepared in Examples and Comparative Examples, respectively, are shown in Table 1, and the physical properties of each of the (1) tensile strength of ASTM D638, (2) Temperature is ASTM D648, (3) Melt Index is ASTM D1238, (4) Dimensional accuracy is measured by injecting a specimen of 380 × 150 × 1T, and leaving it at 15 ℃ and 60% humidity for 48 hours before injection. The ratio of Ratio and (5) the surface resistance of the molded specimens were measured with a surface ohmmeter at 23 ° C and 50% moisture content, and the semiconductor sieve carrier was measured at a cylinder temperature of 320 ° C and a mold at an injection machine of 220 ton clamping force. Molding was performed at a temperature of 150 ° C. and surface resistance and fall impact strength were measured.

Claims (1)

방향족 폴리설폰수지 40∼80중량%와 폴리카보네이트 수지 60∼20중량%로 구성된 수지화합물 100중량부에 대하여, 카본파이버 5∼20중량부로 구성됨을 특징으로 하는 전도성 폴리설폰 수지 조성물.A conductive polysulfone resin composition comprising 5 to 20 parts by weight of carbon fiber with respect to 100 parts by weight of a resin compound composed of 40 to 80% by weight of an aromatic polysulfone resin and 60 to 20% by weight of a polycarbonate resin.
KR1019950026802A 1995-08-28 1995-08-28 Conductive Polysulfone Resin Composition KR0174067B1 (en)

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KR101295715B1 (en) * 2012-07-17 2013-08-16 유한회사 아이엘에스 Heat radiation composition for reflecing board and cover of lighting apparatus coating having shielding electronic wave and lighting apparatus cover

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