KR930008196B1 - Polyphenylene sulfide resin composition - Google Patents

Polyphenylene sulfide resin composition Download PDF

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KR930008196B1
KR930008196B1 KR1019900009818A KR900009818A KR930008196B1 KR 930008196 B1 KR930008196 B1 KR 930008196B1 KR 1019900009818 A KR1019900009818 A KR 1019900009818A KR 900009818 A KR900009818 A KR 900009818A KR 930008196 B1 KR930008196 B1 KR 930008196B1
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polyphenylene sulfide
resin composition
sulfide resin
weight
density polyethylene
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KR1019900009818A
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KR920000873A (en
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김광태
김정락
박병식
황창익
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제일합섬 주식회사
이수환
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions 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
    • C08L81/04—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene

Abstract

The polyphenylene sulphide resin composition is composed of 15-70 wt.% of polyphenylene sulphide resin having 1000-5000 melt flow index, 5-35 wt.% of glass fiber, 10-75 wt.% of nodular molten silica having 1-5 μm average particle size, 0.05-5 wt.% of bismuth oxide, and 0.4-7 wt.% of low density polyethylene (LDPE) having 0.91-0.93 density. The resin composition has a good mol work ability, abrasion-resistance and dimensional stability, is useful as an engineering plastic in the field of electric, electronic and automobile parts.

Description

폴리페닐렌 설파이드 수지 조성물Polyphenylene sulfide resin composition

본 발명은 성형가공성, 기계적 강도 및 전기적 특성이 양호하면서 내마모성 및 치수안정성이 우수한 폴리페닐렌설파이드 수지 조성물에 관한 것이다.The present invention relates to a polyphenylene sulfide resin composition having good molding processability, mechanical strength and electrical properties while being excellent in wear resistance and dimensional stability.

폴리페닐렌 설파이드 수지는 내열성, 내약품성, 난연성, 강성이 우수한 엔지니어링 플라스틱으로서 최근에 전기, 전자 부품 및 자동차 부품 등의 분야에서 주목받고 있으며 그 수요가 꾸준히 신장되고있다.Polyphenylene sulfide resin is an engineering plastic having excellent heat resistance, chemical resistance, flame retardancy, and rigidity, and has recently been attracting attention in the fields of electric, electronic parts, and automobile parts, and its demand is steadily expanding.

그러나, 폴리페닐렌 설파이드 수지 단독으로는 연성이 작고 취약하므로, 강도, 강성, 인성, 내열성 등의 엔지니어링 플라스틱으로서 요구되는 성능을 대폭 개선시킬 목적으로 통상 수지에 유리섬유나 탄소섬유등의 섬유상 강화제를 첨가시키거나 여기에 덧붙여 치수안정성 및 성형품의 외관, 제품의 가격 절감을 위하여 다양한 무기물 충진제를 첨가시키고 있다.However, polyphenylene sulfide resin alone has a small ductility and weakness. Therefore, fibrous reinforcing agents such as glass fibers and carbon fibers are usually applied to resins for the purpose of greatly improving the performance required as engineering plastics such as strength, rigidity, toughness and heat resistance. In addition, various inorganic fillers are added for dimensional stability, appearance of molded products, and cost reduction of products.

이러한 폴리페닐렌 설파이드 조성물은 전기, 전자부품, 자동차 부품, 화학기계부품등 다양하게 산업 전반에 걸쳐 더욱 소형화, 정밀화되는 추세와 함께 그 요구 특성도 더욱 엄격해지고 있다.Such polyphenylene sulfide compositions are becoming more compact and refined throughout various industries such as electrical, electronic parts, automobile parts, and chemical mechanical parts, and their demanded characteristics are becoming more stringent.

이렇게 최근 각 분야의 부품에 요구되는 특성은 내열성, 성형성, 기계적 강도, 전기적 특성, 내습성과 함께 내마모성, 치수안정성이 높은 소재의 출현을 요구하고 있다. 특히 유리 섬유만의 단독 강화 제품의 경우 기계적 강도 및 내열성은 뛰어나나 성형시 수지의 흐름방향과 횡방향에서의 선팽창 계수의 이방성이 커서 성형품의 치수안정성 및 잔류 응력의 문제점을 내재하고 있다.As such, the characteristics required for components in each field require the appearance of materials having high wear resistance and dimensional stability along with heat resistance, moldability, mechanical strength, electrical properties, and moisture resistance. In particular, the glass fiber alone reinforcement products have excellent mechanical strength and heat resistance, but the anisotropy of the linear expansion coefficient in the flow direction and the transverse direction of the resin during molding causes problems of dimensional stability and residual stress of the molded article.

그러나 이러한 선팽창계수의 이방성을 줄이는 방법으로서 비교적 적은 충진제를 첨가하는 방법이 고려되고 있지만 이러한 방법에 의하면 선팽창계수의 이방성은 개선되더라도 기계적 강도 및 내열성이 떨어지는 점을 극복할 수가 없다. 일본 특개소 제57-63355호에서는 폴리페닐렌 수지에 마이카 및 유리섬유로 이루어진 조성물이 제시되어 있는데 이 조성물은 선팽창계수의 이방성도 작고 성형성, 내열성 및 기계적 강도는 양호하지만, 마모특성이 측면에서는 이를 해결하지 못하고 있다.However, although a method of adding a relatively small filler is considered as a method of reducing the anisotropy of the linear expansion coefficient, the method cannot overcome the point that the mechanical strength and the heat resistance are poor even though the anisotropy of the linear expansion coefficient is improved. Japanese Patent Application Laid-Open No. 57-63355 discloses a composition consisting of mica and glass fibers in a polyphenylene resin, which has a low anisotropy of coefficient of linear expansion and good moldability, heat resistance and mechanical strength, but in terms of wear characteristics. This is not solved.

따라서, 본 발명자들은 위와 같은 문제점들을 해결하고자 연구한 결과 폴리페닐렌 설파이드 수지에 유리섬유, 구상실리카, 산화비스무스 및 저밀도 폴리에틸렌으로 이루어진 조성물이 성형가공성, 기계적강도 및 전기적 특성이 양호하고 내마모성 및 선팽창계수의 이방성이 적음을 알게되어 본 발명을 완성하게 되었다.Accordingly, the present inventors have studied to solve the above problems, the composition consisting of glass fiber, spherical silica, bismuth oxide and low density polyethylene in the polyphenylene sulfide resin has good molding processability, mechanical strength and electrical properties, wear resistance and coefficient of linear expansion It was found that the anisotropy of less than to complete the present invention.

즉 본 발명은,That is, the present invention,

(A) 폴리페닐렌 설파이드 수지 15~70중량%(A) 15 to 70% by weight of polyphenylene sulfide resin

(B) 유리섬유 5~35중량%(B) 5 to 35 wt% glass fiber

(C) 구상(球狀) 용융 실리카 10~75중량%(C) 10 to 75% by weight of spherical fused silica

(D) 산화 비스무스 0.05~5중량%(D) bismuth oxide 0.05 to 5% by weight

(E) 저밀도 폴리에틸렌 0.4~7중량%(E) 0.4-7% by weight of low density polyethylene

를 주요성분으로 하는 폴리페닐렌 설파이드 수지 조성물임을 특징으로 한다.It is characterized in that the polyphenylene sulfide resin composition having a main component.

이하 본 발명에 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명에 사용된 수지는 미경화 또는 부분 경화된 멜트인덱스(ASTM D-1238, 316℃, 5Kg)가 500~10,000인 수지, 더욱 좋게는 멜트 인덱스가 1000~5000인 것이 효과적이다. 멜트 인덱스가 500이하인 것은 본 조성물의 가공시 유동성이 좋지 못하며 10,000이상인 것은 성형품의 물성이 매우 좋지 못하다.The resin used in the present invention is an resin having an uncured or partially cured melt index (ASTM D-1238, 316 ° C., 5Kg) of 500 to 10,000, more preferably a melt index of 1000 to 5000. If the melt index is 500 or less, the fluidity during processing of the present composition is not good, and if it is 10,000 or more, the physical properties of the molded product are very poor.

본 발명에 있어서 사용된 섬유상 강화제는 대표적으로 유리섬유로서 그 길이가 3mm, 직경이 13μm의 촙트 스트랜드(Chopped Strand)로서 그 함량은 5~35중량%가 적당하며, 5중량% 미만일 경우는 충분한 기계적 성질을 얻지 못하므로 좋지 않다. 또한 35%이상의 다량의 유리섬유를 함유한 PPS수지 조성물은 기계적 강도가 우수하고 비용절감의 장점이 있으나 선팽창 계수의 이방성의 발생이 크고 표면이 평활하지 못할 뿐 아니라 외관이 좋지 않다.The fibrous reinforcement used in the present invention is typically a glass fiber, 3mm in length, 13μm chopped strand (Chopped strand), the content is suitable 5 ~ 35% by weight, if less than 5% by weight is sufficient mechanical Not good because it doesn't get temper. In addition, PPS resin composition containing a large amount of glass fibers of more than 35% has the advantages of excellent mechanical strength and cost reduction, but the anisotropy of the coefficient of linear expansion is large, the surface is not smooth and the appearance is not good.

본 발명에 있어 사용된 구상 실리카는 Aspect Ration(L/S)가 1~1.5의 것이 좋다.The spherical silica used in the present invention preferably has an aspect ratio (L / S) of 1 to 1.5.

입도는 0.8~100μm로서 특시 평균 입도가 1~50μm가 전체가 80%이상인 것이 좋다. 이 구상 실리카의 첨가량은 10~75%가 적당하며, 10%미만일 경우는 양호한 내마모성을 얻지 못하며, 75%를 초과할 경우에는 성형가공성이 나빠진다. 또한 본 발명에 있어서 사용되는 산화 비스무스로는 BiO2, Bi2O3, Bi2O5등이 있는데 특히 Bi2O3가 효과적이다. 이 산화 비스무스는 전체조성물 중 0.05~5%가 좋다. 0.05% 미만일 때는 그 내습특성, 따라서 전기적 특성이 향상 효과가 적으며 5% 이상일 경우는 조성물의 용융시의 유동성이 떨어지는 단점이 있다.The particle size is 0.8 to 100 μm, and the average particle size of 1 to 50 μm is preferably 80% or more. The addition amount of this spherical silica is 10 to 75% is suitable, when less than 10% does not obtain good wear resistance, when it exceeds 75%, moldability is poor. In addition, bismuth oxides used in the present invention include BiO 2 , Bi 2 O 3 , Bi 2 O 5, and the like, and Bi 2 O 3 is particularly effective. This bismuth oxide is preferably 0.05 to 5% of the total composition. If less than 0.05%, the moisture resistance, and therefore the electrical properties have little effect of improving, and if more than 5% has a disadvantage in that the fluidity at the time of melting the composition.

또한 본 발명의 조성물은 저밀도 폴리에틸렌 소량을 함유한다. 이 물질은 본 발명의 조성물과 같이 고충 진제품을 가공할때 그 가공성을 양호하게 할 목적으로 사용된다. 여기서 사용되는 저밀도 폴리에틸렌은 그 밀도가 0.91~0.93의 것들이 적당하다.The composition of the present invention also contains a small amount of low density polyethylene. This material is used for the purpose of improving the processability when processing a high filling product like the composition of the present invention. The low density polyethylene used here is suitably those whose density is 0.91-0.93.

이러한 가공성을 높이기 위해 스테아릭 아연과 같은 포화지방산 염이나 다른 에틸렌계 공중합체를 사용할 수도 있다.Saturated fatty acid salts such as stearic zinc or other ethylene copolymers may be used to enhance this processability.

본 발명의 폴리페닐렌 설파이드 수지 조성물은 그 특성을 저해하지 않은 범위에서 각종 강화제 및 무기 충전제를 첨가할 수 있다. 가령, 탄소섬유, 보론 섬유, 아스팔트섬유, 금속 섬유 등의 보강제 및 클레이, 마이카, 실리카, 글라스 비스, 알루미나, 탄산 칼슘, 황산칼슘, 규산칼슘, 산화아연, 산화티탄, 산화철 등의 충전제를 혼용, 배합하는 것도 가능하다. 그 함량은 전 조성물에 대하여 10~30중량%의 범위에서 충전시키는 것이 좋다.The polyphenylene sulfide resin composition of this invention can add various strengthening agents and inorganic fillers in the range which does not impair the characteristic. For example, reinforcing agents such as carbon fiber, boron fiber, asphalt fiber, metal fiber, and fillers such as clay, mica, silica, glass bis, alumina, calcium carbonate, calcium sulfate, calcium silicate, zinc oxide, titanium oxide, iron oxide, etc. It is also possible to mix. The content is preferably filled in the range of 10 to 30% by weight based on the total composition.

또한 용도에 따라 다양한 첨가제를 사용할 수 있는데 그 함량은 총 조성중 10중량%이내가 적당하다. 대표적인 첨가제로는 열안정제, 산화방지제, 자외선 흡수제, 활제, 가공 조제, 연료 안료 등의 착색제, 금형 부식방지제 등의 통상의 첨가제를 1종 이상 첨가할 수 있다.In addition, a variety of additives can be used depending on the application, the content of which is suitable within 10% by weight of the total composition. As a typical additive, one or more conventional additives such as color stabilizers such as heat stabilizers, antioxidants, ultraviolet absorbers, lubricants, processing aids, fuel pigments, and mold corrosion inhibitors may be added.

이하 본 발명을 실시예에 의거하여 상세히 설명한다.Hereinafter, the present invention will be described in detail with reference to Examples.

[실시예 1~3][Examples 1-3]

폴리페닐렌 설파이드 수지(A)로 "라이톤" V-1 그레이드(미국 필립스 피트로울리엄사)와 (B) 유리섬유로서 촙트 스트랜드(Chopped Strand)[일동방적(주) 3PE-945)] (C) 구상 용융 실리카((日) 전지화학공업 덴까 용융 실리카 FB-44) (D) 산화비스무스(플루카사 ; Bi2O3)) 및 (E) 저밀도 폴리에틸렌 (한양화학 MB9400 ; 밀도 0.916) 0.5중량%를 표 1에 예시된 조성으로 혼합하여 45mm 직경의 동방향 2축 압출기에 의해 용융, 펠리트화 하였다. 얻어진 펠리트를 130℃에서 3시간 건조 후 5온스 사출성형기를 이용하여 실린더 온도 300~340℃, 금형온도 120℃에서 사출성형하여 굴곡강도 시편, 열변형온도 측정용 시편, 원판시편을 제작하여 그 물성을 측정하였다. 그 결과를 표 1에 표시하였다."Lyton" V-1 grade (A Philips Pittoulium, USA) with polyphenylene sulfide resin (A) and Chopped Strand (3PE-945 Co., Ltd.) as glass fiber] C) Spherical fused silica ((Japan) Battery Chemical Industry Denka Fused Silica FB-44) (D) Bismuth oxide (Flukas, Bi 2 O 3 )) and (E) Low density polyethylene (Hanyang Chemical MB9400; Density 0.916) 0.5 wt. The% was mixed in the composition illustrated in Table 1 and melted and pelletized by a 45 mm diameter coaxial twin screw extruder. After drying the obtained pellets at 130 ° C. for 3 hours, injection molding was carried out at a cylinder temperature of 300 to 340 ° C. and a mold temperature of 120 ° C. using a 5 ounce injection molding machine to prepare flexural strength specimens, specimens for measuring thermal deformation temperature, and disc specimens. Physical properties were measured. The results are shown in Table 1.

굴곡 강도는 ASTM D-790, 체적 고유저항은 ASTM D-257, 내마모성은 ASTM D-1044, 선팽창계수는 ASTM D-696에 준하여 측정하였다.Flexural strength was measured according to ASTM D-790, volume resistivity, ASTM D-257, abrasion resistance, ASTM D-1044, and linear expansion coefficient according to ASTM D-696.

[비교 실시예 1,2]Comparative Examples 1 and 2

실시예 1~3에서 사용된 동일한 폴리페닐렌 설파이드 수지 V-1과 유리섬유에 (C)와 (D) 대신에 탄산칼슘(임화성 : 林化成, 크리스톤-S) 또는 탈크(일신, NA-400P)를 사용하여 실시예와 동일한 방법으로 용융, 혼련하여 펠리트화한 후 성형하여 그 물성을 측정하였다.In the same polyphenylene sulfide resin V-1 and glass fibers used in Examples 1 to 3, instead of (C) and (D), calcium carbonate (Impurity: Crescent-S) or talc (Ishinshin, NA) -400P) was melted, kneaded and pelletized in the same manner as in Example, and then molded and measured for physical properties.

[표 1]TABLE 1

Figure kpo00001
Figure kpo00001

주 : 1) PPS : 폴리페닐렌 설파이드Note: 1) PPS: Polyphenylene sulfide

2) LDPE : 저밀도 폴리 에틸렌2) LDPE: Low Density Polyethylene

Claims (1)

하기 (A)(B)(C)(D)(E)의 성분으로 구성됨을 특징으로 하는 폴리 페닐렌 설파이드 수지 조성물.The polyphenylene sulfide resin composition which consists of a component of following (A) (B) (C) (D) (E). (A) 멜트 플로우지수가 1000~5000인 폴리페닐렌 설파이드수지 15~70중량%(A) 15 to 70% by weight of polyphenylene sulfide resin having a melt flow index of 1000 to 5000 (B) 유리섬유 5~35중량%(B) 5 to 35 wt% glass fiber (C) 평균입도가 1~5μm 구상(球狀) 용융 실리카 10~75중량%(C) 10 ~ 75% by weight of spherical fused silica with an average particle size of 1 ~ 5μm (D) 산화 비스무스 0.05~5중량%(D) bismuth oxide 0.05 to 5% by weight (E) 밀도범위가 0.91~0.93인 저밀도 폴리에틸렌 0.4~7중량%(E) 0.4-7 wt% low density polyethylene with a density range of 0.91-0.93
KR1019900009818A 1990-06-30 1990-06-30 Polyphenylene sulfide resin composition KR930008196B1 (en)

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Publication number Priority date Publication date Assignee Title
CN103254482A (en) * 2012-02-17 2013-08-21 辽宁辽杰科技有限公司 Creep resistance continuous glass fiber reinforced polyethylene prepreg tape and preparation method thereof

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KR100342167B1 (en) * 2000-02-26 2002-07-02 주식회사 비에스텍 Silicone of printing coating method
KR100491408B1 (en) * 2002-01-24 2005-05-25 서청길 Sublimation Transfer Paper on Cotton Fabrics

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103254482A (en) * 2012-02-17 2013-08-21 辽宁辽杰科技有限公司 Creep resistance continuous glass fiber reinforced polyethylene prepreg tape and preparation method thereof

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