KR100808722B1 - High conductive and stiff polypropylene resin composition - Google Patents
High conductive and stiff polypropylene resin composition Download PDFInfo
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- KR100808722B1 KR100808722B1 KR1020010083831A KR20010083831A KR100808722B1 KR 100808722 B1 KR100808722 B1 KR 100808722B1 KR 1020010083831 A KR1020010083831 A KR 1020010083831A KR 20010083831 A KR20010083831 A KR 20010083831A KR 100808722 B1 KR100808722 B1 KR 100808722B1
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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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
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Abstract
본 발명은 고강성 폴리프로필렌 수지 조성물에 관한 것으로, 더욱 상세하게는 폴리프로필렌 수지, 스테인레스스틸 섬유, 유리섬유, 상용화제를 포함하여 이루어진 전도성이 우수한 고강성 폴리프로필렌 수지 조성물에 관한 것이다.The present invention relates to a high rigid polypropylene resin composition, and more particularly, to a high rigid polypropylene resin composition having excellent conductivity including a polypropylene resin, stainless steel fiber, glass fiber, and a compatibilizer.
스테인레스스틸 섬유, 유리섬유, 폴리프로필렌, 전도성Stainless steel fiber, glass fiber, polypropylene, conductive
Description
본 발명은 고강성 폴리프로필렌 수지 조성물에 관한 것으로, 더욱 상세하게는 폴리프로필렌 수지, 스테인레스스틸 섬유, 유리섬유, 상용화제를 포함하여 이루어진 전도성이 우수한 고강성 폴리프로필렌 수지 조성물에 관한 것이다.The present invention relates to a high rigid polypropylene resin composition, and more particularly, to a high rigid polypropylene resin composition having excellent conductivity including a polypropylene resin, stainless steel fiber, glass fiber, and a compatibilizer.
폴리프로필렌 수지는 기계적 물성, 내약품성, 성형성이 뛰어나 자동차 내장부품, 가전부품, 산업자재 등의 공업적 이용범위가 매우 넓은 소재이다. 그러나, 폴리프로필렌은 분자의 화학 구조상 무극성을 나타내어, 2차 가공성, 특히 고체 상태에서의 도장성 및 다른 소재와의 접착성이 열세하고 결정성 구조로 인하여 치수 안정성이 미흡하며, 강성ㆍ내열성 또한 유사한 용도로 경쟁적으로 적용되는 폴리스티렌, 스티렌 아크릴로니트릴 공중합체 등의 다른 수지보다 다소 열세하다. 이러한 이유로, 자동차 및 전기전자 부품용으로 폴리프로필렌 수지에 무기 충진재 또는 타 수지를 배합시킨 소재의 개발방법이 제시되고 있다.Polypropylene resin has excellent mechanical properties, chemical resistance, and moldability, and thus has a wide range of industrial applications such as automobile interior parts, home appliances parts, and industrial materials. However, polypropylene exhibits a polarity due to the chemical structure of the molecule, which is inferior in secondary workability, especially in the solid state, paintability and adhesion to other materials, poor dimensional stability due to the crystalline structure, and stiffness and heat resistance are similar. It is somewhat inferior to other resins, such as polystyrene and styrene acrylonitrile copolymers, which are competitively applied for the purpose. For this reason, a method of developing a material in which an inorganic filler or another resin is mixed with a polypropylene resin for automobiles and electric and electronic parts has been proposed.
한편, 강성 및 내열성 그리고 그 밖의 기계적 물성을 향상시키기 위해서 폴리프로필렌 수지에 무기 충진재로서 유리섬유ㆍ카본섬유ㆍ위스커 등과 같은 침상형 충진재, 운석ㆍ활석 등과 같은 판상형 충진재, 탄산칼슘ㆍ알루미나 등과 같은 구상형 충진재 등을 이용한다. 특히, 유리섬유가 충전된 폴리프로필렌 수지는 고강성 및 높은 내열성이 요구되는 제품에 주로 이용되어지고 있다. 또한, 유리섬유는 높은 이축율(aspect ratio)의 섬유상 구조로 인해 구상 또는 판상의 다른 무기 충진재에 비해 기계적 물성 향상 효과가 매우 뛰어나다.On the other hand, in order to improve rigidity, heat resistance and other mechanical properties, polypropylene resins are used as inorganic fillers, needle-like fillers such as glass fibers, carbon fibers, and whiskers, plate-like fillers such as meteorites and talc, and spherical types such as calcium carbonate and alumina. Filler is used. In particular, polypropylene resin filled with glass fibers is mainly used for products requiring high rigidity and high heat resistance. In addition, the glass fiber has an excellent effect of improving mechanical properties compared to other inorganic fillers having a spherical or plate shape due to the high biaxial rate (fibrous) structure.
물성향상을 구현하기 위해 사용되는 무기 충진재와는 달리 스테인레스스틸 섬유는 우수한 전도 특성을 소유한 첨가제로서, 이를 폴리프로필렌 수지에 적용하여 전도성 폴리프로필렌 수지 조성물의 구현이 가능하다. 등방수축 특성을 가진 스테인레스스틸 섬유는 성형 수축율 뿐만 아니라 강성 및 그 외 기계적 물성에 미치는 악영향도 미비하여, 특수 목적으로 제조된 폴리프로필렌 수지 조성물에 우수한 전도성을 동시에 부여할 수 있다.Unlike the inorganic fillers used to implement the physical property improvement, stainless steel fiber is an additive possessing excellent conductive properties, and it is possible to implement the conductive polypropylene resin composition by applying it to a polypropylene resin. Stainless steel fibers having isotropic shrinkage properties are not only adversely affect the stiffness and other mechanical properties as well as the molding shrinkage, it can simultaneously impart excellent conductivity to the polypropylene resin composition prepared for a special purpose.
본 발명의 목적은 상기와 같은 폴리프로필렌 수지가 갖는 문제점을 해결함과 동시에 전도 특성을 부여하기 위하여, 폴리프로필렌 수지, 스테인레스스틸 섬유, 유리섬유를 혼합하고, 소량의 상용화제 및 기타 첨가제를 추가적으로 혼합시킴으로써, 전도성이 우수한 고강성 폴리프로필렌 수지 조성물을 제공하는 것이다.An object of the present invention is to solve the problems of the polypropylene resin as described above, and to impart conductive properties, to mix a polypropylene resin, stainless steel fibers, glass fibers, and additionally mixed a small amount of compatibilizers and other additives This is to provide a highly rigid polypropylene resin composition having excellent conductivity.
본 발명의 폴리프로필렌 수지 조성물은 (A) 폴리프로필렌 수지 26.0∼79.0중량%, (B) 스테인레스스틸 섬유 10.0∼40.0중량%, (C) 유리섬유 10.0∼30.0중량% 및 (D) 상용화제 1.0∼4.0중량%를 포함하여 이루어지는 것을 특징으로 한다. The polypropylene resin composition of the present invention comprises (A) 26.0 to 77.9% by weight of polypropylene resin, (B) 10.0 to 40.0% by weight of stainless steel fiber, (C) 10.0 to 30.0% by weight of glass fiber, and (D) 1.0 to 3% compatibilizer. It comprises a 4.0% by weight.
본 발명의 수지 조성물에 있어서, (A) 폴리프로필렌 수지는 용융지수(MI)가 5∼70g/10분(ASTM D1238, 230℃)인 것이 바람직하다. 용융지수가 5g/10분 미만인 경우에는 부품의 성형성이 양호하지 못하여 생산성이 저하되는 반면, 용융지수가 70g/10분을 초과할 경우에는 충격강도가 급격히 저하된다. 상기 폴리프로필렌 수지는 호모폴리머, 임팩트 코폴리머, 이소탁틱 코폴리머중에서 단독 혹은 두개 이상 선택하는 것이 바람직하다.In the resin composition of the present invention, the polypropylene resin (A) preferably has a melt index (MI) of 5 to 70 g / 10 minutes (ASTM D1238, 230 ° C). If the melt index is less than 5g / 10min, the moldability of the parts is not good, the productivity is lowered, while if the melt index exceeds 70g / 10min, the impact strength is sharply lowered. Preferably, the polypropylene resin is selected from homopolymers, impact copolymers, and isotactic copolymers alone or in two or more.
본 발명의 수지 조성물에 있어서, (B) 스테인레스스틸 섬유는 10.0∼40.0중량%가 바람직하다. 10.0중량% 미만인 경우에는 스테인레스스틸 섬유의 성능발현이 만족스럽지 못하며, 40.0중량%를 초과할 경우에는 전도성 올레핀계 수지 조성물로서의 경제성이 떨어지게 된다.In the resin composition of this invention, 10.0-40.0 weight% of (B) stainless steel fiber is preferable. If it is less than 10.0% by weight, the performance expression of the stainless steel fiber is not satisfactory, and if it exceeds 40.0% by weight, the economic efficiency of the conductive olefin resin composition is inferior.
본 발명의 수지 조성물에 있어서, (C) 유리섬유는 무기 충진재로서 평균입경이 5∼15㎛, 바람직하게는 9∼13㎛이고, 길이가 1∼16㎛인 것을 사용하는 것이 바람직하고, 함량은 기계적 물성을 고려하여 10.0∼30.0중량%가 바람직하다. 유리섬유의 평균입경이 5㎛ 미만인 경우에는 혼합하는 동안에 깨지게 되어 강성발현 효과가 미흡해지며, 15㎛를 초과할 경우에는 기계적 강도를 얻을 수 없음과 동시에 성형품의 변형이 악화되어 외관 상태가 불량해진다. 본 발명에서의 유리섬유 길이는 특정길이로의 제한없이 상업적으로 쉽게 구할 수 있는 것이라면 사용이 가능하며, 혼련 작업성 측면에서 통상 1∼8㎛정도 길이의 쵸핑된 스트랜드(chopped strand)의 사용이 바람직하다.In the resin composition of the present invention, the glass fiber (C) preferably has an average particle diameter of 5 to 15 µm, preferably 9 to 13 µm, and a length of 1 to 16 µm as the inorganic filler, and the content thereof is 10.0 to 30.0 wt% is preferable in consideration of mechanical properties. If the average particle diameter of the glass fiber is less than 5 µm, it breaks during mixing and the rigid expression effect is insufficient. If the average particle diameter exceeds 15 µm, the mechanical strength cannot be obtained and the deformation of the molded product is deteriorated, resulting in poor appearance. . The glass fiber length in the present invention can be used as long as it can be easily obtained commercially without limitation to a specific length, and in terms of kneading workability, the use of chopped strands having a length of about 1 to 8 μm is preferable. Do.
본 발명의 수지 조성물에 있어서, (D) 상용화제의 함량은 1.0∼4.0중량%가 바람직하다. 상용화제의 함량이 1.0중량% 미만인 경우에는 충진재와 폴리프로필렌 수지와의 계면 접착력을 충분히 유지할 수 없어 물성향상에 기여도가 없으며, 4.0중량%를 초과할 경우에는 투입량을 증가시켜도 더 이상의 물성향상 효과는 기대하기 어렵다. 상기 상용화제는 폴리프로필렌과 유리섬유와의 혼련성 향상을 위해 배합되는 것으로서, 폴리프로필렌을 불포화 카르복실산 또는 그 유도체에 의해 변성한 변성 폴리프로필렌, 폴리프로필렌-말레익 언하이드리드 그라프트 공중합체(PP-g-MA) 또는 실란계 화합물이 바람직하다. In the resin composition of the present invention, the content of the (D) compatibilizer is preferably 1.0 to 4.0% by weight. If the content of the compatibilizer is less than 1.0% by weight, the interfacial adhesion between the filler and the polypropylene resin cannot be maintained sufficiently, and thus, there is no contribution to the improvement of the physical properties. It's hard to expect The compatibilizer is formulated to improve kneading of polypropylene and glass fiber, and is a modified polypropylene and polypropylene-maleic unhydride graft copolymer in which polypropylene is modified with an unsaturated carboxylic acid or a derivative thereof. Preference is given to (PP-g-MA) or silane compounds.
본 발명의 폴리프로필렌 수지 조성물에는 상기 (A), (B), (C), (D)의 성분 외에 보강재ㆍ충진재ㆍ내열안정제ㆍ내후안정제ㆍ대전방지제ㆍ활제ㆍ슬립제ㆍ핵제ㆍ난연제ㆍ안료ㆍ염료 등과 같은 통상의 각종 첨가제가 본 발명의 특징에 어긋나지 않는 범위 내에서 첨가될 수 있으며, 이의 구체적인 예로 탈크ㆍ탄소섬유ㆍ탄산칼슘ㆍ클레이ㆍ실리카ㆍ알루미나ㆍ카본블랙ㆍ수산화마그네슘ㆍ제올라이트ㆍ황산바륨 등이 있다.In the polypropylene resin composition of the present invention, in addition to the components (A), (B), (C) and (D), reinforcing materials, fillers, heat stabilizers, weather stabilizers, antistatic agents, lubricants, slip agents, nucleating agents, flame retardants, pigments Various conventional additives such as dyes and the like may be added within the scope of the present invention. Specific examples thereof include talc, carbon fiber, calcium carbonate, clay, silica, alumina, carbon black, magnesium hydroxide, zeolite, and sulfuric acid. Barium and the like.
본 발명의 수지 조성물을 제조하는 방법에 있어서는 단축 또는 이축 압출기를 사용한 혼련이 바람직하며, 보편적으로 알려진 폴리프로필렌 수지 조성물을 제조하는 가공조건을 이용하고, 폴리프로필렌 융점 이상에서의 배합이 가능하다. 단, 무기 충진재인 유리섬유의 형상을 충분히 유지시키기 위하여, 압출기 도중에서의 유리섬유의 동시 또는 개별투입이 필수적이다.In the method for producing the resin composition of the present invention, kneading using a single screw or twin screw extruder is preferable, and mixing at or above the polypropylene melting point is possible using processing conditions for producing a polypropylene resin composition which is generally known. However, in order to sufficiently maintain the shape of the glass fiber as the inorganic filler, simultaneous or individual injection of the glass fiber during the extruder is essential.
실시예Example
본 발명의 실시예에서는, 이축 압출기를 사용하여 통상의 용융 블렌드법에 따라 폴리프로필렌 수지, 스테인레스스틸 섬유, 유리섬유, 상용화제, 기타 첨가제로부터 폴리프로필렌 수지/스테인레스스틸 섬유/유리섬유 수지 조성물을 제조하고, 이를 충분히 건조시킨 후 사출 성형하여 이들의 전도성 및 강성 등을 검토하고자 한다.In an embodiment of the present invention, a polypropylene resin / stainless steel fiber / glass fiber resin composition is prepared from polypropylene resin, stainless steel fiber, glass fiber, compatibilizer, and other additives according to a conventional melt blending method using a twin screw extruder. After sufficiently drying it, injection molding is to examine their conductivity and stiffness.
본 발명은 하기의 실시예에 의하여 보다 구체적으로 이해될 수 있으며, 하기의 실시예들은 단지 설명의 목적을 위한 것으로 본 발명을 제한하는 것으로 해석 되어서는 안 된다.The invention can be understood in more detail by the following examples, which are only for the purpose of description and should not be construed as limiting the invention.
실시예 및 비교예에서의 수지의 물성측정은 다음과 같은 방법으로 행하였다.The physical property measurement of resin in the Example and the comparative example was performed by the following method.
1) 인장강도1) tensile strength
ASTM D638의 방법으로, 상온에서 측정하였다(kg/㎠).By the method of ASTM D638, measured at room temperature (kg / ㎠).
2) 굴곡탄성율2) Flexural modulus
ASTM D790의 방법으로, 상온에서 측정하였다(kg/㎠) By the method of ASTM D790, measured at room temperature (kg / ㎠)
3) 열변형온도 3) Heat deflection temperature
ASTM D648의 방법으로, 18.5kg의 하중하에 측정하였다(℃)By the method of ASTM D648, measured under a load of 18.5 kg (° C.)
4) 체적고유저항 4) Volume specific resistance
ASTM D257의 방법으로, 상온에서 측정하였다(ohmㆍcm)Measured at room temperature by the method of ASTM D257 (ohmcm)
실시예 1Example 1
동일방향으로 회전하는 이축 압출기에 폴리프로필렌 수지 56.0중량%와 스테인레스스틸 섬유 10.0중량%, 유리섬유 30.0중량%, 그리고 변성 폴리프로필렌 4.0중 량% 및 상기 성분들의 합계 100중량부에 대해 기타 첨가제 0.5중량부를 투입한 후, 용융 혼합시키고 압출하여 펠렛상의 수지 조성물을 제조하고 80℃에서 진공 건조시켰다. 이와 같이 제조된 열가소성 폴리프로필렌 수지 조성물로 사출 성형하여 물성을 평가한 결과, 비교예 1에 대비하여 스테인레스스틸 섬유 도입에 의한 전도 특성의 두드러진 향상으로 체적고유저항 값이 매우 낮았으며, 그 외 기계적 물성 측면에서도 동등이상의 수준을 보였다. 그 구체적인 결과를 하기 표 1에 나타내었다.56.0 wt% polypropylene resin, 10.0 wt% stainless steel fiber, 30.0 wt% glass fiber, and 4.0 wt% modified polypropylene and 0.5 wt% of other additives based on 100 parts by weight of the components in a twin screw extruder rotating in the same direction After the addition, the mixture was melt mixed and extruded to prepare a pellet-shaped resin composition, which was vacuum dried at 80 deg. As a result of evaluating the physical properties by injection molding with the thermoplastic polypropylene resin composition prepared as described above, the volume specific resistance was very low due to the remarkable improvement of the conduction characteristics by the introduction of stainless steel fiber in comparison with Comparative Example 1, and other mechanical properties. In terms of level, the results were equal. The specific results are shown in Table 1 below.
실시예 2Example 2
전도성 첨가제인 스테인레스스틸 섬유를 20.0중량%로 증량하고, 폴리프로필렌 수지를 46중량%로 배합한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 고강성 폴리프로필렌 수지 조성물을 제조하였다. 이와 같이 제조된 고강성 폴리프로필렌 수지 조성물을 사출성형하여 물성을 평가한 결과, 실시예 1의 폴리프로필렌 수지 조성물보다 전도성 및 기계적 물성이 모두 우수하였다. 그 구체적인 결과를 하기 표1에 나타내었다.A highly rigid polypropylene resin composition was prepared in the same manner as in Example 1, except that the stainless steel fiber, which is a conductive additive, was increased to 20.0 wt% and the polypropylene resin was blended at 46 wt%. As a result of evaluating the physical properties by injection molding the highly rigid polypropylene resin composition prepared as described above, both the conductivity and the mechanical properties were superior to the polypropylene resin composition of Example 1. The specific results are shown in Table 1 below.
실시예 3Example 3
전도성 첨가제인 스테인레스스틸 섬유를 30.0중량%로 증량하고, 폴리프로필렌 수지를 36중량%로 배합한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 고강성 폴리프로필렌 수지 조성물을 제조하였다. 이와 같이 제조된 고강성 폴리프로필렌 수지 조성물을 사출성형하여 물성을 평가한 결과, 실시예 2의 폴리프로필렌 수지 조성물보다 전도성 및 기계적 물성이 모두 우수하였다. 그 구체적인 결과를 하기 표 1에 나타내었다. A highly rigid polypropylene resin composition was prepared in the same manner as in Example 1, except that the stainless steel fiber, which is a conductive additive, was increased to 30.0 wt% and the polypropylene resin was blended at 36 wt%. As a result of evaluating the physical properties by injection molding the highly rigid polypropylene resin composition prepared as described above, both the conductivity and the mechanical properties were superior to the polypropylene resin composition of Example 2. The specific results are shown in Table 1 below.
비교예 1Comparative Example 1
전도성 첨가제인 스테인레스스틸 섬유를 사용하지 않고 폴리프로필렌 수지 66.0중량%, 유리섬유 30.0중량%, 변성 폴리프로필렌 4.0중량% 및 기타 첨가제를 투입한 후, 상기 실시예 1과 동일한 방법으로 고강성 폴리프로필렌 수지 조성물을 제조하였다. 이와 같이 제조된 고강성 폴리프로필렌 수지 조성물을 사출성형하여 물성을 평가하고, 그 결과를 하기 표 1에 나타내었다.After using 66.0% by weight of polypropylene resin, 30.0% by weight of glass fiber, 4.0% by weight of modified polypropylene, and other additives without using stainless steel fiber as a conductive additive, a highly rigid polypropylene resin was prepared in the same manner as in Example 1. The composition was prepared. The high-rigidity polypropylene resin composition thus prepared was injection molded to evaluate physical properties, and the results are shown in Table 1 below.
주) *불포화 카르복실산에 의해 변성된 변성 폴리프로필렌 Note) * modified polypropylene modified by unsaturated carboxylic acid
이상의 실시예 및 비교예에서 볼 수 있는 바와 같이, 본 발명에 의하여 제조된 폴리프로필렌 수지 조성물은 전도성 및 강성이 우수하다.As can be seen from the above examples and comparative examples, the polypropylene resin composition prepared by the present invention is excellent in conductivity and rigidity.
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| KR20150066264A (en) * | 2013-12-06 | 2015-06-16 | 주식회사 엘지화학 | Conductive propylene based thermoplastic resin composition having less amount of TVOCs and improved mechanical properties |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR910008563A (en) * | 1989-10-31 | 1991-05-31 | 이헌조 | How to display the top line of the auto-input to indicate the coverage for the "√" mark |
| JPH0639930A (en) * | 1992-03-20 | 1994-02-15 | Lantor Bv | Reinforced conductive plastic |
| KR19990082602A (en) * | 1996-02-16 | 1999-11-25 | 이데미쓰세끼유가가꾸가부시끼가이샤 | Manufacturing method and lightweight molded article of fiber reinforced thermoplastic resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR910008563A (en) * | 1989-10-31 | 1991-05-31 | 이헌조 | How to display the top line of the auto-input to indicate the coverage for the "√" mark |
| JPH0639930A (en) * | 1992-03-20 | 1994-02-15 | Lantor Bv | Reinforced conductive plastic |
| KR19990082602A (en) * | 1996-02-16 | 1999-11-25 | 이데미쓰세끼유가가꾸가부시끼가이샤 | Manufacturing method and lightweight molded article of fiber reinforced thermoplastic resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20150066264A (en) * | 2013-12-06 | 2015-06-16 | 주식회사 엘지화학 | Conductive propylene based thermoplastic resin composition having less amount of TVOCs and improved mechanical properties |
| KR101675624B1 (en) | 2013-12-06 | 2016-11-11 | 주식회사 엘지화학 | Conductive propylene based thermoplastic resin composition having less amount of TVOCs and improved mechanical properties |
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