KR20010112733A - A polypropylene resin composition having excellent flowability, stiffness, and size stability - Google Patents

A polypropylene resin composition having excellent flowability, stiffness, and size stability Download PDF

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KR20010112733A
KR20010112733A KR1020000032157A KR20000032157A KR20010112733A KR 20010112733 A KR20010112733 A KR 20010112733A KR 1020000032157 A KR1020000032157 A KR 1020000032157A KR 20000032157 A KR20000032157 A KR 20000032157A KR 20010112733 A KR20010112733 A KR 20010112733A
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polypropylene
weight
resin composition
polypropylene resin
parts
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KR100620356B1 (en
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이영준
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유현식
삼성종합화학주식회사
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
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    • 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
    • C08K3/34Silicon-containing compounds
    • 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
    • C08K7/14Glass
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • 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
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • 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
    • C08K2201/002Physical properties
    • C08K2201/004Additives being defined by their length
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Abstract

A method for the production of a food acid includes the steps of combining fumaric acid with an organic acidic material in an aqueous medium to produce a mixture and drying the mixture to produce a food acid comprising a particulate material containing fumaric acid and the organic acidic material, the quantity of fumaric acid and the quantity of the organic acidic material being selected so that the fumaric acid makes up between about 5 % and 95 % of the particulate material.

Description

유동성, 강성 및 치수안정성이 우수한 폴리프로필렌 수지 조성물{A POLYPROPYLENE RESIN COMPOSITION HAVING EXCELLENT FLOWABILITY, STIFFNESS, AND SIZE STABILITY}Polypropylene resin composition excellent in fluidity, rigidity and dimensional stability {A POLYPROPYLENE RESIN COMPOSITION HAVING EXCELLENT FLOWABILITY, STIFFNESS, AND SIZE STABILITY}

본 발명은 유동성, 강성 및 치수안정성이 우수한 폴리프로필렌 수지 조성물에 관한 것으로서, 좀더 상세하게는 고결정성 폴리프로필렌 수지, 불포화카르본산이나 그 유도체에 의하여 변성된 변성폴리프로필렌, 무기 충진재로 유리섬유 및 운모를 포함하는 폴리프로필렌 수지 조성물에 관한 것이다.The present invention relates to a polypropylene resin composition having excellent fluidity, rigidity and dimensional stability, and more particularly, to a high crystalline polypropylene resin, a modified polypropylene modified by an unsaturated carboxylic acid or a derivative thereof, glass fiber and mica as an inorganic filler. It relates to a polypropylene resin composition comprising a.

폴리프로필렌 수지는 다른 폴리올레핀 소재에 비하여 강성, 내약품성, 성형성이 뛰어나 자동차 내장부품, 가전부품 등의 공업적 이용범위가 매우 넓은 소재이다. 그러나 폴리프로필렌 수지는 분자의 화학구조상 무극성을 나타내어, 2차 가공성, 특히 고체상태에서의 도장성 및 다른 소재와의 접착성이 열세하고 결정성 구조로 인해 치수안정성이 미흡하며, 내열성, 강성 또한 가전제품 재료로서 경쟁적으로 적용되는 폴리스티렌, 스티렌 아크릴로니트릴 공중합체 등의 다른 수지에 비하여 다소 열세이다.Polypropylene resin is excellent in rigidity, chemical resistance, and moldability compared to other polyolefin materials, and thus has a wide industrial application range for automobile interior parts and home appliance parts. However, polypropylene resin is non-polar in chemical structure of the molecule, so it is inferior in secondary processability, especially in solid state, paintability and adhesion to other materials, and poor dimensional stability due to crystalline structure, heat resistance and rigidity It is somewhat inferior to other resins, such as polystyrene and styrene acrylonitrile copolymers, which are competitively applied as product materials.

강성 및 내열성이 요구되는 자동차 및 전기전자 부품용으로 폴리프로필렌 수지에 무기 충진재 또는 다른 수지를 배합시킨 소재개발 방법이 제시되고 있다. 이와 관련하여 일본특허공개 소64-87645 및 소1-174550 등에 폴리프로필렌에 스티렌 중합체를 상용화제인 스티렌 부타디엔 블록 공중합체와 블랜딩하여 기계적 강도, 내열성 및 도장성을 개선시킨 조성물이 공개된 바 있으나, 기계적 물성의 향상 정도가 매우 낮고 비교적 고가의 상용화제를 사용하여 범용소재로 적용하기에 적절하지 못하다.A method of developing a material in which inorganic fillers or other resins are blended with polypropylene resins is proposed for automobiles and electrical and electronic parts requiring rigidity and heat resistance. In this regard, Japanese Patent Publications Nos. 64-87645 and 1-1-174550 have been disclosed to blend a styrene polymer in polypropylene with a styrene butadiene block copolymer, which is a compatibilizer, to improve mechanical strength, heat resistance and paintability. The improvement of physical properties is very low and it is not suitable to apply to general purpose materials using relatively expensive compatibilizer.

일본특허공개 평4-96948에는 폴리프로필렌 수지의 강성, 내열성, 내약품성을 향상시킬 목적으로 스티렌 아크릴로니트릴계 중합체를 상용화제인 산변성 폴리프로필렌과 블랜딩한 수지 조성물을 제시하고 있으나, 제조된 블랜드 수지의 기계적 강성이 높지 않다(FM=20,000kgf/㎠).Japanese Patent Laid-Open No. 4-96948 discloses a resin composition in which a styrene acrylonitrile-based polymer is blended with an acid-modified polypropylene as a compatibilizer for the purpose of improving the stiffness, heat resistance, and chemical resistance of a polypropylene resin. The mechanical rigidity of is not high (FM = 20,000kgf / cm 2).

이러한 단점을 해결하기 위해 일본특허공개 평3-126740에서는 폴리프로필렌 수지에 내열성이 우수한 나일론 수지와 무기충진재중 강도 및 내열성 향상효과가 큰 유리섬유를 산변성 폴리프로필렌과 블랜드한 수지 조성물이 제시되었다. 상기 조성물은 폴리프로필렌 대비 저점도의 나일론을 사용하여 제조된 수지 조성물의 매트릭스가 나일론이 되도록 하여 150∼170℃에서도 사용이 가능한 장점이 있다.In order to solve this drawback, Japanese Patent Laid-Open No. 3-126740 has proposed a resin composition in which a nylon resin having excellent heat resistance to a polypropylene resin and a glass fiber having a high effect of improving strength and heat resistance among inorganic fillers are blended with acid-modified polypropylene. The composition has an advantage that the matrix of the resin composition prepared by using a nylon having a lower viscosity than polypropylene can be used at 150 to 170 ° C.

그러나 전술한 조성물은 강성, 도장성, 내약품성 및 내열성이 우수한 반면 고가의 나일론 수지가 사용되어 범용소재로서의 한계를 지니고 있으며, 자동차 플라스틱 부품중 고강성 및 내열성 요구정도가 전술한 수지 물성보다 낮아도 적용이 가능한 부품이 대부분이다(예: FAN, FAN SHROUD, BLOWER FAN).However, the above-mentioned composition has excellent rigidity, paintability, chemical resistance and heat resistance, but has a limitation as a general-purpose material due to the use of expensive nylon resins, and is applicable even if the demand for high rigidity and heat resistance of the plastic parts of automobiles is lower than the aforementioned resin properties. Most of these parts are possible (eg FAN, FAN SHROUD, BLOWER FAN).

폴리프로필렌 수지의 기계적 물성, 특히 강성 및 내열성을 향상시키는 무기충진재로 널리 사용되는 것 중의 하나가 유리섬유이다. 유리섬유는 높은 이축율(aspect ratio)의 섬유상 구조로 인해 구상 또는 판상의 다른 무기 충진재에 비하여 기계적 물성의 향상 정도가 매우 탁월하다.Glass fiber is one of the widely used inorganic fillers to improve the mechanical properties of polypropylene resins, particularly rigidity and heat resistance. Glass fibers have a very good degree of improvement in mechanical properties compared to spherical or plate-shaped inorganic fillers due to their high aspect ratio fibrous structure.

일반적으로 유리섬유의 폴리프로필렌 수지내 충진량이 증가할수록 강성 및 내열성은 개선되지만 유리섬유의 높은 배향성으로 인해 제품 성형후 흐름방향과 흐름직각 방향 사이의 수축율차가 커져 최종 성형품의 휨(warpage)을 유발, 높은 치수안정성이 요구되는 회전기부품(fan류)에의 적용에 한계가 있고 외관이 나쁜 단점이 있다.In general, as the filling amount of glass fiber in polypropylene resin increases, the stiffness and heat resistance are improved, but due to the high orientation of glass fiber, the shrinkage difference between the flow direction and the flow direction after molding is increased, causing warpage of the final molded product. There is a limit to the application to the rotor parts (fans) that require high dimensional stability and has the disadvantage of poor appearance.

전술한 휨의 발생을 최소화하며 비교적 우수한 외관품을 구현할 수 있는 충진재로 운모가 있다. 운모는 비교적 저가이면서 소재가 지니는 색상이 다양하여(회색, 흰색, 황색, 암갈색) 착색 없이 각종 전기전자/자동차 소재로 활용도가 높은 충진재이다.There is a mica as a filler to minimize the occurrence of the warpage described above and to implement a relatively good appearance. Mica is a relatively inexpensive and versatile material (gray, white, yellow, dark brown), and is a filler that is widely used in various electric and electronic materials without coloring.

그러나 운모 충진재만으로는 고내열/고강성의 재료를 발현하는데 한계가 있고 충진재가 지니는 겉보기 밀도(BULK DENSITY)가 낮아 충진재 함량이 높은(예:40% 이상) 조성물 제조시 혼련기내 원료 피딩(FEEDING)이 어려워 작업성 및 생산성이 저하된다.However, the mica filler alone has a limit in expressing high heat / stiff materials and the low bulk density of the filler results in a high filler content (e.g., 40% or more). Difficult to reduce workability and productivity.

그리고, 상기 기술들의 경우 충진재를 추가함에 따라 수지의 유동성이 나빠져서 대형사출품이나 복잡한 자동차 부품의 성형시 플로우 마크, 미성형 등의 문제를 야기하게 된다.In addition, in the case of the above techniques, as the filler is added, the fluidity of the resin is deteriorated, which causes problems such as flow marks and unmolding when molding a large injection molding product or a complicated automobile part.

본 발명의 목적은 상기와 같은 문제점을 개선하여 유동성, 강성 및 치수안정성이 우수하고 비교적 제조가 용이하여 자동차 부품이나 전기전자부품에 적용할 수 있는 저가의 폴리프로필렌 수지 조성물을 제공하는 것이다.An object of the present invention is to provide a low-cost polypropylene resin composition that can be applied to automobile parts or electrical and electronic parts to improve the above problems by excellent fluidity, rigidity and dimensional stability and relatively easy to manufacture.

본 발명의 폴리프로필렌 수지 조성물은 고결정성 폴리프로필렌 수지 100중량부에 대하여 불포화카르본산 또는 그 유도체에 의하여 변성된 변성폴리프로필렌 0.1∼30중량부 및 유리섬유, 운모와 같은 무기 충진재 50∼85중량부로 이루어져 있다.The polypropylene resin composition of the present invention is 0.1 to 30 parts by weight of modified polypropylene modified by unsaturated carboxylic acid or its derivatives and 50 to 85 parts by weight of inorganic filler such as glass fiber and mica based on 100 parts by weight of high crystalline polypropylene resin. consist of.

본 발명에 사용되는 폴리프로필렌 수지는 용융지수(MI)가 80∼120g/10분(ASTM D1238, 230℃)이고, 핵자기공명법(Nuclear Magnetic Resnance)상의 입체규칙도 지수인 아이소택틱 펜타드 분율이 95% 이상이며, 겔투과크로마토그래피(GPC)법에 의한 중량평균 분자량(Mw)과 수평균 분자량(Mn)의 비율(Mw/Mn, 이하 분자량분포라 함)이 7∼12이다. 용융지수가 80g/10분 미만인 경우에는 대형 부품의 성형성이 양호하지 못하여 생산성이 저하되는 반면, 용융지수가 120g/10분을 초과하는 경우에는 충격강도가 급격히 저하된다. 그리고 아이소택틱 펜타드 분율이 95% 미만이면 내열도 및 강성이 낮아져서 고온에서 사용하는 복잡한 형상의 제품의 경우, 제품 사용중 휘거나 뒤틀리는 단점이 있다. 분자량 분포가 7 미만이면 같은 용융지수의 수지 조성물을 만들었을 때 용융흐름성이 나빠지고, 12를 초과하면 사출성형시 계량시간이 길어져 생산성이 저하된다.The polypropylene resin used in the present invention is an isotactic pentad having a melt index (MI) of 80 to 120 g / 10 minutes (ASTM D1238, 230 ° C.) and a stereoregularity index of Nuclear Magnetic Resnance. The fraction is 95% or more, and the ratio (Mw / Mn, hereinafter molecular weight distribution) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC) method is 7-12. If the melt index is less than 80g / 10min, the moldability of the large parts is not good, the productivity is lowered, while if the melt index is more than 120g / 10min, the impact strength is sharply lowered. When the isotactic pentad fraction is less than 95%, heat resistance and rigidity are lowered, and thus, in the case of a complicated shape product used at a high temperature, there is a disadvantage that the product is bent or twisted during use. If the molecular weight distribution is less than 7, when the resin composition of the same melt index is made, the melt flowability is poor, and if it exceeds 12, the metering time is increased during injection molding, and productivity is lowered.

본 발명에 사용되는 변성폴리프로필렌은 폴리프로필렌을 불포화카르본산 또는 그 유도체에 의하여 변성시킨 것이다. 폴리프로필렌의 예로는 폴리프로필렌 단독 중합체, 에틸렌/프로필렌 공중합체 고무, 프로필렌/α-올레핀 비공역 디엔화합물 공중합체(예:EPDM) 등이다. 상기 α-올레핀으로는 에틸렌, 부텐-1, 헵텐-1, 헥센-1,4-메틸펜텐 등이 있고, 이들은 단독 또는 2종 이상을 혼합하여 사용할 수 있다. 상기 폴리프로필렌을 변성시키기 위한 불포화카르본산으로는 아크릴산, 메타크릴산, 말레인산, 푸마르산, 이타콘산, 크로톤산, 디트라콘산, 소르빈산, 인 그리카산 등이 있으며, 불포화카르본산 유도체는 산무수물, 에스테르, 아미드, 이미드, 금속염 등으로서, 이들의 예로는 무수말레인산, 무수이타콘산, 무수디트라콘산, 아크릴산 메틸, 메타크릴산 메틸, 아크릴산 에틸, 아크릴산 부틸, 말레인산 모노 에테르/에스테르, 아크릴 아미드, 말레인산 모노 아미드, N-부틸 말레이미드, 아크릴산 나트륨, 메타크릴산 나트륨 등이 있다.The modified polypropylene used in the present invention is obtained by modifying polypropylene with unsaturated carboxylic acid or derivatives thereof. Examples of polypropylenes are polypropylene homopolymers, ethylene / propylene copolymer rubbers, propylene / α-olefin nonconjugated diene compound copolymers such as EPDM. Examples of the α-olefins include ethylene, butene-1, heptene-1, hexene-1,4-methylpentene and the like, and these may be used alone or in combination of two or more thereof. The unsaturated carboxylic acid for modifying the polypropylene includes acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, ditraconic acid, sorbic acid, phosphoric acid, and the like. , Amides, imides, metal salts and the like, examples of which are maleic anhydride, itaconic anhydride, ditraconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, maleic acid monoether / ester, acrylamide, maleic acid Monoamide, N-butyl maleimide, sodium acrylate, sodium methacrylate, and the like.

상기 불포화카르본산 또는 그 유도체로서 폴리프로필렌을 변성시키는 경우, 상기 물질을 단독으로 또는 2종 이상을 혼합하여 사용할 수 있다. 폴리프로필렌을 변성시키는 방법은 특별히 제한되지 않고 종래의 공지된 방법을 이용할 수 있으며, 이는 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있다. 예를 들어, 폴리프로필렌을 적당한 유기용매에 용해시켜 불포화카르본산 및/또는 그 유도체와 라디칼 발생제를 첨가하여 혼련가공하는 방법이나 또는 상기의 각 성분을 압출기에 공급하여 그라프트 공중합을 행하는 방법이 이용될 수 있다.When modifying polypropylene as the unsaturated carboxylic acid or derivatives thereof, the above materials may be used alone or in combination of two or more thereof. The method for modifying the polypropylene is not particularly limited and may be a conventionally known method, which can be easily carried out by those skilled in the art. For example, polypropylene is dissolved in a suitable organic solvent and kneaded by adding unsaturated carboxylic acid and / or its derivatives and a radical generator, or graft copolymerization is performed by feeding each of the above components into an extruder. Can be used.

본 발명에 사용되는 변성폴리프로필렌에서 불포화카르본산 또는 그 유도체의 부가량은 변성폴리프로필렌의 중량 기준으로 0.01∼10중량%가 바람직하다. 0.01중량% 미만으로 사용되는 경우에는 강성 및 내열성이 열세해지며, 10중량%를 초과하여 사용되는 경우에는 충격강도가 낮아지며, 비용이 증가하게 되는 단점이 있다.In the modified polypropylene used in the present invention, the amount of unsaturated carboxylic acid or derivative thereof is preferably 0.01 to 10% by weight based on the weight of the modified polypropylene. When used in less than 0.01% by weight is inferior in rigidity and heat resistance, when used in excess of 10% by weight has a disadvantage in that the impact strength is lowered, the cost increases.

상기 변성폴리프로필렌은 그 자체만으로 사용될 수 있지만, 변성되지 않은 폴리프로필렌을 적정량 함유할 수도 있다. 변성폴리프로필렌은 폴리프로필렌 중합체 100중량부에 대하여 0.1∼30중량부의 양으로 첨가된다. 변성폴리프로필렌의 함량이 0.1중량부 미만인 경우에는 충진재와 폴리프로필렌 수지의 계면접착력을 충분히 유지할 수 없어 물성향상에 기여도가 없고, 30중량부를 초과하는 경우에는 투입량을 증가시켜도 더이상 물성향상 효과가 발현되지 않는다.The modified polypropylene may be used by itself, but may also contain an appropriate amount of unmodified polypropylene. The modified polypropylene is added in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the polypropylene polymer. If the content of the modified polypropylene is less than 0.1 part by weight, the interfacial adhesion between the filler and the polypropylene resin cannot be sufficiently maintained, and there is no contribution to the improvement of the physical properties. If the content exceeds 30 parts by weight, the effect of improving the physical properties is no longer expressed even if the input amount is increased. Do not.

본 발명에서 사용되는 무기 충진재는 폴리프로필렌 수지에 대하여 50∼85중량부가 사용되는데, 무기 충진재의 함량이 50중량부 미만인 경우에는 치수안정성 및 강성이 저하되고, 85중량부를 초과하는 경우에는 동재료의 압출혼련 제조가 용이하지 않으며 충격 강도가 저하되고 성형품의 비중이 지나치게 높아져서 범용소재로서의 경제적인 장점이 사라진다. 무기 충진재는 유리섬유 및 운모가 이용되며, 유리섬유의 경우 평균입경이 10∼15μ이고 길이가 3∼6mm인 재료가 바람직하게 사용된다. 유리섬유의 입경이 15μ를 넘거나 길이가 6mm를 초과하는 경우 외관이 불량해지며, 비용이 증가하게 되고, 입경이 10μ미만 또는 길이가 3mm미만인 경우에는 기계적 강도가 저하하게되는 단점이 있다. 운모의 경우 평균입경이 40∼50μ이고 최대입경이 100μ인 재료가 바람직하다. 운모의 입경이 최대치보다 큰 경우 육안으로 운모입자가 관찰되어 다소 외관이 안좋고 물성이 저하된다. 무기 충진재중 유리섬유의 함량은 폴리프로필렌 중합체에 대하여 45중량부를 넘지 않는 것이 바람직하며 45중량부를 초과하는 경우에는 성형품의 외관이 나빠지고 동재료의 압출혼련 제조시 작업성이 나빠진다. 운모 함량은 유리섬유 100중량부에 대하여 50∼800중량부가 바람직하며 50중량부 미만인 경우에는 동 수지 조성물의 휨(warpage) 방지 효과가 없고, 800중량부를 초과하는 경우에는 유리섬유 상대함량이 낮아져서 동 소재가 얻고자 하는 고강성이 발현되지 않는다.The inorganic filler used in the present invention is 50 to 85 parts by weight based on the polypropylene resin, when the content of the inorganic filler is less than 50 parts by weight dimensional stability and stiffness is lowered, when the content of the inorganic filler exceeds 85 parts by weight of the copper material Extrusion kneading is not easy to manufacture, the impact strength is lowered and the specific gravity of the molded article is too high to eliminate the economic advantages as a general-purpose material. As the inorganic filler, glass fiber and mica are used, and in the case of glass fiber, a material having an average particle diameter of 10 to 15 mu and a length of 3 to 6 mm is preferably used. If the particle diameter of the glass fiber exceeds 15μ or 6mm in length, the appearance is poor, the cost increases, and if the particle diameter is less than 10μ or less than 3mm in length, there is a disadvantage that the mechanical strength is lowered. In the case of mica, a material having an average particle diameter of 40 to 50 µ and a maximum particle diameter of 100 µ is preferable. If the particle size of the mica is larger than the maximum value, the mica particles are observed with the naked eye. The content of the glass fiber in the inorganic filler is preferably not more than 45 parts by weight relative to the polypropylene polymer. When the content of the glass fibers is more than 45 parts by weight, the appearance of the molded product is deteriorated and the workability is poor during the extrusion kneading of the copper material. The mica content is preferably 50 to 800 parts by weight based on 100 parts by weight of glass fiber, and less than 50 parts by weight has no effect of preventing warpage of the resin composition. The high rigidity that the material is trying to obtain is not expressed.

본 발명의 수지 조성물에는 보강재, 충진재, 내열안정재, 내후안정제, 대전방지제, 활제, 슬립제, 핵제, 난연제, 안료, 염료 등과 같은 각종 첨가제가 본 발명의 특징에 어긋나지 않는 범위내에서 첨가될 수 있고, 이러한 구체적인 예로서, 탈크, 탄소섬유, 탄산칼슘, 황산바륨 등이 있다.To the resin composition of the present invention, various additives such as reinforcing materials, fillers, heat stabilizers, weather stabilizers, antistatic agents, lubricants, slip agents, nucleating agents, flame retardants, pigments, dyes, and the like may be added within a range not contrary to the characteristics of the present invention. Specific examples thereof include talc, carbon fiber, calcium carbonate, barium sulfate and the like.

본 발명의 수지 조성물을 제조하는 방법에 있어서는 압출기를 사용한 재료혼련이 바람직하며, 보편적으로 알려진 폴리프로필렌 수지 조성물을 제조하는 가공조건을 이용할 수 있다. 단, 유리섬유와 운모는 충진재가 지니는 형상을 충분히 유지하기 위하여 사이드 호퍼 피딩(SIDE HOPPER FEEDING)이 필수적이다.In the method for producing the resin composition of the present invention, material kneading using an extruder is preferable, and processing conditions for producing a generally known polypropylene resin composition can be used. However, in order to sufficiently maintain the shape of the filler and glass fiber and mica, side hopper feeding is essential.

본 발명은 하기의 실시예에 의하여 보다 구체적으로 이해될 수 있으며, 하기의 실시예는 본 발명을 예시하기 위한 예에 지나지 않는 것으로 본 발명의 보호범위를 제한하고자 하는 것은 아니다.The present invention can be understood in more detail by the following examples, the following examples are only examples for illustrating the present invention and are not intended to limit the protection scope of the present invention.

실시예Example

하기의 실시예 1∼2는 본 방법에 따른 실시예이며, 비교예 1∼4는 본 발명과 비교하기 위한 것이다. 실시예와 비교예에 대한 각 성분들의 함량과 각 실시예 및 비교예에 따른 제조수지 조성물의 물성결과를 표 1에 나타내었다.Examples 1 to 2 below are examples according to the present method, and Comparative Examples 1 to 4 are for comparison with the present invention. Table 1 shows the physical properties of the resin compositions according to the Examples and Comparative Examples and the contents of the components for the Examples and Comparative Examples.

표 1의 실시예 1∼2와 비교예 1∼4에 사용된 각 성분에 대한 설명은 다음과 같다.Description of each component used in Examples 1-2 of Table 1 and Comparative Examples 1-4 is as follows.

1) 폴리프로필렌 : 용융지수(MI)가 100g/10분(230)인 폴리프로필렌 단독 중합체1) Polypropylene: Polypropylene homopolymer with melt index (MI) of 100 g / 10 min (230)

2) 변성 폴리프로필렌 : 반응된 무수말레인산을 폴리프로필렌 중량기준 0.2% 이상 포함하는 용융지수가 40g/10분인 폴리프로필렌 단독 중합체2) Modified polypropylene: Polypropylene homopolymer having a melt index of 40 g / 10 minutes containing 0.2% or more of reacted maleic anhydride based on the polypropylene weight.

3) 무기 충진재 :3) Inorganic Filler:

- 유리섬유 : 평균입경 10μ, 길이 3mm인 실란으로 표면처리된 섬유-Glass fiber: Fiber treated with silane with average particle diameter of 10μ and length of 3mm

- 운모 : 평균입경 40∼50μ인 갈색 운모(표면처리 안됨)-Mica: Brown mica with average particle diameter of 40-50μ (no surface treatment)

표 1의 성분을 JSW TEX44ALPHA 2축 혼련압출기에서 운모와 유리섬유는 측면공급하고 기타 원료수지, 변성 폴리프로필렌 및 첨가제는 믹서를 사용하여 혼합, 호퍼에 한번에 모두 투입시키고 용융혼련하여 동 재료를 제조한 후 삼성클뢰크너 FCM-110(형체력=110톤)으로 사출하여 ASTM규격에서 정하는 시편을 제작하였다.In the JSW TEX44ALPHA twin-screw kneading extruder, mica and glass fiber are supplied side by side, and other raw materials, modified polypropylene and additives are mixed and mixed by using a mixer at once, and melt-kneaded to prepare copper materials. Afterwards, it was injected into Samsung Klockner FCM-110 (cutting force = 110 tons) to produce specimens specified in ASTM standards.

각 시험물성별 시험조건은 다음과 같다.Test conditions for each test property are as follows.

1) MI(Melt flow index)1) MI (Melt flow index)

ASTM D1238의 방법에 따라 230℃, 2.16kg하중에서 측정하였다.According to the method of ASTM D1238 it was measured at 230 ℃, 2.16kg load.

2) 스파이랄 플로우2) spiral flow

110톤 사출기에서 235℃에서 스파이랄 금형에 사출하여 사출된 시편의 길이를 측정하였다.The length of the injected specimen was measured by injection into a spiral mold at 235 ° C. in a 110 ton injection machine.

3) 충격강도3) impact strength

ASTM D256에 의거하여 상온에서 노취시편으로 측정하였다.In accordance with ASTM D256 it was measured by the notched specimens at room temperature.

4) 굴곡탄성률4) Flexural modulus

ASTM D770에 의거하여 상온에서 측정하였다.It was measured at room temperature in accordance with ASTM D770.

5) 수축율5) Shrinkage

두께가 2mm, 가로와 세로폭이 각각 100mm인 시트를 사출성형, 상온 48시간 경과후 흐름방향과 흐름직각 방향의 치수를 측정하였다.Sheets having a thickness of 2 mm and widths of 100 mm each were measured by injection molding and measured in a flow direction and a right angle direction after 48 hours at room temperature.

실시예 1과 비교예 1Example 1 and Comparative Example 1

초고유동성을 지니는 실시예 1이 비교예 1 대비 유동성을 나타내는 스파이랄플로우 지수가 높아 대형품 성형에 유리함.Example 1 having ultra high fluidity has a high spiral flow index indicating fluidity compared to Comparative Example 1, which is advantageous for forming a large product.

실시예 1과 비교예 2Example 1 and Comparative Example 2

고결정성 폴리프로필렌을 수지 조성물로 하는 실시예 1이 비교예 2 대비 흐름성 및 강성이 탁월함.Example 1 using the high crystalline polypropylene as a resin composition is excellent in flowability and rigidity compared to Comparative Example 2.

실시예 1과 비교예 3Example 1 and Comparative Example 3

운모와 유리섬유 보강재를 혼합사용하는 실시예 1이 운모를 단독으로 사용하는 비교예 3 대비 강성이 탁월함.Example 1 using a mixture of mica and glass fiber reinforcement is superior in rigidity compared to Comparative Example 3 using mica alone.

실시예 2와 비교예 4Example 2 and Comparative Example 4

변성 폴리프로필렌을 포함하는 실시예 2가 변성 폴리프로필렌을 사용하지 않는 비교예 4 대비 강성이 우수함.Example 2 comprising a modified polypropylene is superior in rigidity compared to Comparative Example 4 does not use a modified polypropylene.

이상의 실시예 및 비교예에서 볼 수 있는 바와 같이, 본 발명에 의하여 제조된 폴리프로필렌 수지 조성물은 유동성, 강성 및 치수안정성이 우수하여 자동차부품이나 전기전자부품 등에 적합하다.As can be seen from the above examples and comparative examples, the polypropylene resin composition prepared according to the present invention is excellent in fluidity, rigidity and dimensional stability, and is suitable for automobile parts, electrical and electronic parts, and the like.

본 발명의 단순한 변형 또는 변경이 이 분야의 당업자에 의하여 용이하게 실시될 수 있지만, 이러한 변형이나 변경은 모두 본 발명의 보호 범위에 속하는 것으로 이는 첨부된 특허청구범위에 의하여 명확해질 수 있다.Simple modifications or variations of the present invention may be readily made by those skilled in the art, but such modifications or changes are all within the protection scope of the present invention, which may be clarified by the appended claims.

Claims (6)

용융지수가 80∼120g/10분, 핵자기공명법상의 입체 규칙도 지수인 아이소택틱 펜타드 분율이 95% 이상, 겔투과크로마토그래피(GPC)법에 의한 분자량분포(Mw/Mn)가 7∼12인 폴리프로필렌 수지 100중량부, 불포화카르본산 또는 그 유도체에 의하여 변성된 변성폴리프로필렌 0.1∼30 중량부, 무기 충진재로 유리섬유 및 운모를 50∼85중량부 포함하는 폴리프로필렌 수지 조성물.Melt index is 80-120g / 10min, isotactic pentad fraction, which is the stereoregularity index in nuclear magnetic resonance method, is 95% or more, and molecular weight distribution (Mw / Mn) is 7 by gel permeation chromatography (GPC) method. A polypropylene resin composition comprising 100 parts by weight of a polypropylene resin of 12 to 12, 0.1 to 30 parts by weight of modified polypropylene modified by unsaturated carboxylic acid or a derivative thereof, and 50 to 85 parts by weight of glass fiber and mica as an inorganic filler. 제 1항에 있어서, 상기 변성폴리프로필렌은 폴리프로필렌 단독 중합체, 에틸렌/프로필렌 공중합체 고무, 프로필렌/α-올레핀 비공역 디엔화합물 공중합체를 불포화카르본산이나 또는 그 유도체에 의하여 변성한 것을 특징으로 하는 폴리프로필렌 수지 조성물.The method of claim 1, wherein the modified polypropylene is characterized in that the polypropylene homopolymer, ethylene / propylene copolymer rubber, propylene / α-olefin non-conjugated diene compound copolymer modified with unsaturated carboxylic acid or derivatives thereof Polypropylene resin composition. 제 2항에 있어서, 불포화카르본산 또는 그 유도체는 무수말레인산, 무수이타콘산, 무수디트라콘산, 아크릴산 메틸, 메타크릴산 메틸, 아크릴산 에틸, 아크릴산 부틸, 말레인산 모노에테르/에스테르, 아크릴 아미드, 말레인산 모노 아미드, N-부틸 말레이미드, 아크릴산 나트륨, 메타크릴산 나트륨인 것을 특징으로 하는 폴리프로필렌 수지 조성물.The unsaturated carboxylic acid or derivatives thereof according to claim 2 are maleic anhydride, itaconic anhydride, ditraconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, maleic acid monoether / ester, acrylamide, maleic acid mono. Amide, N-butyl maleimide, sodium acrylate, sodium methacrylate, The polypropylene resin composition characterized by the above-mentioned. 제 1항에 있어서, 상기 변성폴리프로필렌에 부가되는 불포화카르본산 또는그 유도체의 양은 변성폴리프로필렌의 중량 기준으로 0.01∼10중량%인 것을 특징으로 하는 폴리프로필렌 수지 조성물.The polypropylene resin composition according to claim 1, wherein the amount of unsaturated carboxylic acid or derivative thereof added to the modified polypropylene is 0.01 to 10% by weight based on the weight of the modified polypropylene. 제 1항에 있어서, 상기 무기 충진재중 유리섬유는 평균입경이 10∼15μ이고 길이가 3m∼6mm이며, 운모는 평균입경이 40∼50μ이고, 최대입경이 100μ인 것을 특징으로 하는 폴리프로필렌 수지 조성물.The polypropylene resin composition according to claim 1, wherein the glass fiber of the inorganic filler has an average particle diameter of 10 to 15 µm and a length of 3 m to 6 mm, and a mica has an average particle diameter of 40 to 50 µ and a maximum particle diameter of 100 µ. . 제 1항에 있어서, 유리섬유와 운모의 혼합비는 유리섬유 100중량부에 대하여 운모가 50∼800중량부인 것을 특징으로 하는 폴리프로필렌 수지 조성물.The polypropylene resin composition according to claim 1, wherein the mixing ratio of the glass fiber and mica is 50 to 800 parts by weight of mica based on 100 parts by weight of glass fiber.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040008806A (en) * 2002-07-19 2004-01-31 현대자동차주식회사 Polypropylene resin composition for automobil thinwall bumper cover
KR101526742B1 (en) * 2013-12-17 2015-06-05 현대자동차주식회사 A resin composition of carbon fiber reinforced polypropylene with excellent molding property
KR101650143B1 (en) * 2015-11-09 2016-08-23 한보일렉트(주) Antistatic compositions for coating pipe

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JPH06179784A (en) * 1992-12-14 1994-06-28 Tosoh Corp Polypropylene composition
JPH06207063A (en) * 1993-01-13 1994-07-26 Sekisui Chem Co Ltd Injection molding resin composition
JPH08143739A (en) * 1994-11-17 1996-06-04 Tonen Corp Fiber-reinforced polypropylene composition
JPH0959450A (en) * 1995-08-28 1997-03-04 Tonen Corp Mica-reinforced polypropylene resin composition
KR100465177B1 (en) * 1996-12-28 2005-04-06 삼성토탈 주식회사 Polypropylene resin composition with excellent rigidity, heat resistance and dimension stability
JP3321059B2 (en) * 1997-12-18 2002-09-03 日本ポリケム株式会社 Glass fiber reinforced polypropylene resin composition
KR19990066058A (en) * 1998-01-21 1999-08-16 남창우 Polypropylene resin composition excellent in paintability

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040008806A (en) * 2002-07-19 2004-01-31 현대자동차주식회사 Polypropylene resin composition for automobil thinwall bumper cover
KR101526742B1 (en) * 2013-12-17 2015-06-05 현대자동차주식회사 A resin composition of carbon fiber reinforced polypropylene with excellent molding property
US9499689B2 (en) 2013-12-17 2016-11-22 Hyundai Motor Company Carbon fiber reinforced polypropylene resin composition with excellent molding property
KR101650143B1 (en) * 2015-11-09 2016-08-23 한보일렉트(주) Antistatic compositions for coating pipe

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