KR20010002461A - Polyolefin resin composition containing chaff powder - Google Patents

Polyolefin resin composition containing chaff powder Download PDF

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Publication number
KR20010002461A
KR20010002461A KR1019990022277A KR19990022277A KR20010002461A KR 20010002461 A KR20010002461 A KR 20010002461A KR 1019990022277 A KR1019990022277 A KR 1019990022277A KR 19990022277 A KR19990022277 A KR 19990022277A KR 20010002461 A KR20010002461 A KR 20010002461A
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South Korea
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weight
polypropylene
resin composition
polyolefin resin
resin
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KR1019990022277A
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Korean (ko)
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김영원
채경석
김석원
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유현식
삼성종합화학 주식회사
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Priority to KR1019990022277A priority Critical patent/KR20010002461A/en
Publication of KR20010002461A publication Critical patent/KR20010002461A/en

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • 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
    • 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
    • C08L23/26—Compositions 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio

Abstract

PURPOSE: A polyolefin resin composition comprising polypropylene resin, chaff powder, adhesive resin and talc and having low specific gravity, excellent scratch resistance and impact resistance is provided, which can be applied for raw material for automobile parts, various vessels and building or industrial material. CONSTITUTION: The resin composition comprises 50 to 88% by weight of polypropylene resin having a melt index of 30 g/10min, 5 to 40% by weight of chaff powder and 2 to 10% by weight of modified polyolefin resin, additionally less than 30% by weight of talc. The modified resin is modified polypropylene resin by graft polymerization of polypropylene resin with maleic acid anhydride as a hydrophilic functional group.

Description

왕겨 가루가 첨가된 폴리올레핀 수지조성물{POLYOLEFIN RESIN COMPOSITION CONTAINING CHAFF POWDER}Polyolefin resin composition with chaff powder added {POLYOLEFIN RESIN COMPOSITION CONTAINING CHAFF POWDER}

본 발명은 왕겨가루가 첨가된 폴리올레핀 수지조성물에 관한 것으로서, 좀더 상세하게는 폴리프로필렌수지, 왕겨가루, 접착성수지 및 탈크로 이루어진 비중이 낮고 내긁힘성과 충격강도가 우수하여 자동차 부품 소재용으로 유용한 폴리올레핀 수지조성물에 관한 것이다.The present invention relates to a polyolefin resin composition to which chaff is added, and more specifically, low specific gravity consisting of polypropylene resin, chaff powder, adhesive resin and talc, and excellent scratch resistance and impact strength, which is useful for automobile parts. It relates to a polyolefin resin composition.

일반적으로 폴리프로필렌(polypropylene) 수지는 성능대비 가격이 저렴하고, 성형성이 우수하여 일반 생활용품 및 자동차용 소재로서 많이 사용되고 있다. 특히 자동차용 소재로는 폴리프로필렌 복합수지가 널리 사용되고 있는데 적용되는 부품의 요구특성에 따라 적용되는 소재의 종류도 달라진다. 높은 내충격성이 요구되는 외장부품의 경우는 폴리프로필렌과 고무의 복합수지가 주로 사용되며, 굴곡강성과 내열성이 요구되는 내장부품 또는 엔진룸부품의 경우는 폴리프로필렌과 탈크(Talc) 또는 유리섬유(Glass Fiber)의 복합수지 조성물이 주로 사용된다.In general, polypropylene (polypropylene) resin is a low price for performance, excellent moldability is used a lot as a general household goods and automotive materials. In particular, polypropylene composite resin is widely used as a material for automobiles, and the type of material to be applied varies according to the required characteristics of the parts to be applied. In the case of exterior parts requiring high impact resistance, polypropylene and rubber composite resins are mainly used.In case of interior parts or engine room parts requiring bending stiffness and heat resistance, polypropylene and talc or glass fiber ( The composite resin composition of Glass Fiber) is mainly used.

그러나, 자동차 내장부품용으로 주로 사용되는 폴리프로필렌과 탈크의 혼합된 복합수지는 탈크의 비중이 높아 차량의 중량이 무거워진다는 단점이 있으며, 탈크의 함량이 증가할수록 내긁힘성이 악화되며, 굴곡탄성율은 증가하나 충격강도가 낮아진다는 단점이 있다.However, a composite resin of polypropylene and talc, which is mainly used for automobile interior parts, has a disadvantage that heavy vehicle weight becomes high due to the high specific gravity of talc. As the content of talc increases, scratch resistance deteriorates and flexes. The elastic modulus increases but the impact strength is lowered.

왕겨가루를 이용한 혼합 조성물에 관한 미합중국 특허 제4,866,110호에는 왕겨가루와 유리섬유, 탈지처리한 왕겨, 가죽 분말, 암면 등을 밀폐된 얇은 판위에 투입하여 자동차 도어트림(Door Trim)을 압축성형한 제품이 있는데 사출성형 및 압출성형에는 유동성이 좋지 않아 부적합하며, 비중이 높으며 성형품의 외관이 불량하다는 단점이 있었다.U.S. Patent No. 4,866,110, which relates to a mixed composition using rice hull powder, is a product in which the door trim is compressed by inserting rice hull powder, fiberglass, degreasing chaff, leather powder, and rock wool into a closed thin plate. There are disadvantages in that injection molding and extrusion molding are inadequate due to poor fluidity, high specific gravity, and poor appearance of molded products.

그리고, 일본국 공개특허 제77-42008호에는 열가소성 수지의 착색안료로서 왕겨가루를 이용한 기술이 있는데, 이 제품은 내열성이 부족하고 수축이 심하다는 단점이 있었다.In Japanese Patent Laid-Open No. 77-42008, there is a technique using chaff powder as a coloring pigment of a thermoplastic resin, which has a disadvantage of insufficient heat resistance and severe shrinkage.

본 발명의 목적은 상기와 같은 문제점을 개선하기 위한 것으로서, 폴리프로필렌과 탈크 혼합물의 물성을 개선한 왕겨 가루가 첨가된 폴리올레핀 수지조성물을 제공하는 것이다.An object of the present invention is to improve the above problems, to provide a polyolefin resin composition to which chaff powder is added to improve the physical properties of the polypropylene and talc mixture.

본 발명의 폴리올레핀 수지조성물은 폴리프로필렌 50~88중량%, 왕겨가루 5~40중량%, 탈크 30중량% 이하, 무수말레인산이 그라프트된 변성 폴리올레핀 수지 2~10중량%로 이루어진 것을 특징으로 한다.Polyolefin resin composition of the present invention is characterized in that consisting of 50 to 88% by weight of polypropylene, 5 to 40% by weight of chaff powder, talc 30% by weight or less, 2 to 10% by weight of modified polyolefin resin grafted maleic anhydride.

왕겨가루는 190℃이상의 고열을 받을 경우 왕겨가루 내에 존재하는 식용 오일 성분과 불포화지방산, 팔미틱산 등의 각종의 휘발성분이 용융수지 내에서 기화하여 제품의 외관을 손상시키고 심한 수축이 발생하므로 혼합물 제조온도 및 성형품 제조온도를 190℃ 이하로 조절해야 한다.When rice hulls are subjected to a high temperature of 190 ℃ or higher, various volatile components such as edible oils and unsaturated fatty acids and palmitic acid in the rice husk are vaporized in the molten resin, which damages the appearance of the product and causes severe shrinkage. And the molded article manufacturing temperature should be controlled to 190 ℃ or less.

따라서 본 발명의 폴리올레핀 수지조성물에 있어서, 폴리프로필렌은 혼합물 제조온도 및 성형품 제조온도를 190℃ 이하로 조절하기 위하여 폴리프로필렌 수지의 용융지수(Melt Index)가 30g/10분 이상인 것을 사용하였다. 폴리프로필렌 수지의 용융지수가 30g/10분 이상의 것이 적합하며 그 미만에서는 흐름성이 저하되어 컴파운딩 및 사출공정에서 자체 마찰열에 의한 실린더 내부온도가 상승함으로 인해 왕겨가루 내에 존재하는 휘발성분이 기체화되면서 성형품의 외관을 저하시킨다. 폴리프로필렌의 함량은 50~88중량%로서 50% 미만일 경우 또한 흐름성이 저하되어 성형품의 외관이 저하된다.Therefore, in the polyolefin resin composition of the present invention, a polypropylene resin having a melt index (Melt Index) of 30 g / 10 minutes or more was used to adjust the mixture preparation temperature and the molded article manufacturing temperature to 190 ° C. or less. The melt index of polypropylene resin is more than 30g / 10min, and below that, the flowability is deteriorated. As the internal temperature of the cylinder increases due to the frictional heat during compounding and injection process, the volatile components present in the rice husk are vaporized. Deteriorates the appearance of the molded article. If the content of polypropylene is 50 to 88% by weight and less than 50%, the flowability is also lowered, which lowers the appearance of the molded article.

본 발명의 폴리올레핀 수지조성물에 있어서, 왕겨가루는 탈크와 같이 필러로 사용되는 성분으로서 비중이 0.5g/cm3이하로서 탈크가 2.2g/cm3이상인데 비해 비중 감소효과가 탁월하다. 왕겨가루로 톱밥, 쌀 및 보리와 같은 곡류의 껍질을 분쇄한 것이 사용가능하다. 왕겨가루 혼합물은 충격강도 및 내긁힘성이 동일한 함량의 탈크 혼합물 보다 우수하고 다른 기계적 물성은 동등 수준이다. 왕겨가루는 5~40중량% 범위가 적합하며 첨가량이 이보다 많을 경우 혼합물의 흐름성이 저하되는 동시에 휘발성분이 발생하여 사출 및 압출성형에 적합하지 않고, 이보다 작을 경우에는 비중 감소효과를 원하는 만큼 기대하기 어렵다.In the polyolefin resin composition of the present invention, rice hull powder is the talc has a specific gravity as a component as below 0.5g / cm 3 is used as a filler such as talc 2.2g / cm 3 or higher specific gravity reduction effect is excellent compared. Crushed grain husks such as sawdust, rice and barley can be used with rice flour. The rice hull powder mixture has better impact strength and scratch resistance than the talc mixture of the same content, and other mechanical properties are equivalent. Rice husk powder is suitable in the range of 5 to 40% by weight, and if the amount is more than this, the flowability of the mixture decreases and volatiles are generated, which is not suitable for injection and extrusion molding. it's difficult.

본 발명의 폴리올레핀 수지조성물에 있어서, 폴리프로필렌과 혼합되어 자동차용 소재로서 가장 일반적으로 사용되는 무기필러인 탈크는 30중량% 이하가 사용된다. 그 함량이 증가할수록 굴곡탄성율은 증가하나 충격강도는 낮아지고 내긁힘성 또한 나빠지는 것은 이미 문헌 또는 경험을 통하여 널리 알려진 사실이다. 따라서 적용되는 부품의 성능과 환경조건에 적합하게 그 함량이 결정되는데, 일반적으로 사용되는 양은 10중량%, 20중량%, 30중량%이다.In the polyolefin resin composition of the present invention, talc, which is an inorganic filler most commonly used as a vehicle material by mixing with polypropylene, is used in an amount of 30% by weight or less. As the content increases, the flexural modulus increases, but the impact strength decreases and the scratch resistance worsens. Therefore, the content is determined according to the performance and environmental conditions of the parts to be applied, the amount generally used is 10% by weight, 20% by weight, 30% by weight.

왕겨가루와 폴리프로필렌 수지와는 상용성이 없어서 왕겨가루의 함량이 증가할수록 물성이 감소하므로 본 발명의 폴리올레핀 수지조성물에 있어서, 왕겨가루와 폴리프로필렌 수지와의 상용성 증가를 위해 사용되는 변성 폴리올레핀은 폴리프로필렌 수지에 친수성 관능기인 무수말레인산(MAH)을 그라프트 중합시킨 변성 폴리프로필렌으로서, 폴리프로필렌 수지와 무기 필러로 첨가한 왕겨가루 및 탈크입자와 폴리프로필렌과의 접착성을 향상시키는 역할을 한다. 변성 폴리프로필렌은 2~10중량%가 사용되며, 첨가량이 2중량% 미만일때는 효과를 기대할 수 없고, 10중량%를 초과하여 과량 첨가시에는 제조원가가 상승하며 폴리프로필렌 수지 자체의 기본물성을 저하시킨다.In the polyolefin resin composition of the present invention, the modified polyolefin used for increasing the compatibility of the chaff powder with the polypropylene resin is not compatible with the chaff powder and the polypropylene resin. A modified polypropylene obtained by graft polymerization of maleic anhydride (MAH), which is a hydrophilic functional group, on a polypropylene resin, and serves to improve adhesion between chaff powder and talc particles added to a polypropylene resin and an inorganic filler and polypropylene. The modified polypropylene is used in 2 to 10% by weight, the effect can not be expected when the addition amount is less than 2% by weight, the production cost increases when the excess amount is added in excess of 10% by weight and lowers the basic physical properties of the polypropylene resin itself .

본 발명은 하기 실시예와 비교예에 의하여 보다 구체적으로 이해될 수 있고, 하기의 실시예에 의해 본 발명을 예시하기 위한 것에 지나지 않으며 본 발명의 보호범위를 제한하고자 하는 것은 아니다.The present invention can be understood in more detail by the following examples and comparative examples, which are intended to illustrate the invention by the following examples and are not intended to limit the protection scope of the present invention.

실시예 1∼5Examples 1-5

표 1에 나타낸 조성에 따라 폴리프로필렌(삼성종합화학주식회사, Grade명 BI750T), 왕겨를 분쇄한 가루(평균입자 크기: 0.01mm~0.1mm), 탈크 및 변성 폴리올레핀(MAH-g-PP, 삼성종합화학주식회사, Grade명 CP4673)을 드라이 블랜딩(Dry Blending)한 다음 트윈스크류(Twin Screw) 압출기에 투입하여 압출하면서 펠렛상으로 제조하였다. 상기의 변성 폴리올레핀은 폴리프로필렌 수지에 무수말레인산을 함침시키고 반응개시제로서 과산화물인 다이큐밀퍼옥사이드(dicumyl peroxide)를 혼합한 다음 압출기내에서 반응을 시켜 펠렛형상으로 제조하였다. 이때 무수말레인산의 결합율은 0.3중량% 이상이었다.According to the composition shown in Table 1, polypropylene (Samsung Chemical Co., Ltd., Grade name BI750T), ground chaff powder (average particle size: 0.01mm ~ 0.1mm), talc and modified polyolefin (MAH-g-PP, Samsung General) Chemical Co., Ltd., grade name CP4673) was dry blended (Dry Blending) and then put into a twin screw extruder to produce a pellet while extruded. The modified polyolefin was prepared in a pellet form by impregnating maleic anhydride in a polypropylene resin, mixing peroxide dicumyl peroxide as a reaction initiator, and then reacting in an extruder. At this time, the bonding ratio of maleic anhydride was 0.3% by weight or more.

각 조성물을 사출기를 이용하여 시편을 제조한 다음 하기와 같은 방법으로 아이조드 충격강도, 굴곡탄성율, 인장강도, 밀도, 내긁힘성을 측정하였으며, 그 결과를 표 1에 나타내었다.Each composition was prepared by using an injection molding machine, and then the Izod impact strength, flexural modulus, tensile strength, density, and scratch resistance were measured by the following method, and the results are shown in Table 1 below.

물성시험방법Property test method

ASTM D256로 아이조드 충격강도(노치부)를, ASTM D790로 굴곡탄성율을, ASTM D638로 인장강도를, ASTM D1505로 밀도를 측정하였으며, 내긁힘성은 사출기를 이용하여 두께 2mm의 시트(sheet)를 제조한 다음 24시간이 경과후 수평왕복시 마모시험기를 이용하여 1회 왕복으로 긁은 다음 긁힘의 정도를 육안으로 판별하였다.Izod impact strength (notch) was measured by ASTM D256, flexural modulus was measured by ASTM D790, tensile strength was measured by ASTM D638, and density was measured by ASTM D1505. After 24 hours, the reciprocating wear test machine was used for one round trip and the degree of scratching was visually determined.

비교예 6∼9Comparative Examples 6-9

표 1에 나타낸 조성에 따라 폴리프로필렌(삼성종합화학주식회사, Grade명 BI750T), 왕겨를 분쇄한 가루(평균입자 크기: 0.01mm~0.1mm), 탈크 및 변성 폴리올레핀(MAH-g-PP, 삼성종합화학주식회사, Grade명 CP4673)을 드라이 블랜딩(Dry Blending)한 다음 트윈스크류(Twin Screw) 압출기에 투입하여 압출하면서 펠렛상으로 제조하였고, 각 조성물을 사출기를 이용하여 시편을 제조한 다음, 실시예 1과 동일한 방법으로 물성시험을 실시하였으며, 그 결과를 표 1에 나타내었다.According to the composition shown in Table 1, polypropylene (Samsung Chemical Co., Ltd., Grade name BI750T), ground chaff powder (average particle size: 0.01mm ~ 0.1mm), talc and modified polyolefin (MAH-g-PP, Samsung General) Chemical Co., Ltd., grade name CP4673) was dry blended and then extruded into a twin screw extruder to prepare pellets, and each composition was prepared by using an injection molding machine, Example 1 The physical properties were tested in the same manner as shown in Table 1 below.

표 1Table 1

상기 표 1에서 알 수 있듯이 폴리프로필렌 50~88중량%, 왕겨가루 5~40중량%, 탈크 30중량% 이하, 변성 폴리올레핀 수지 2~10중량%로 이루어진 본 발명의 폴리올레핀 수지조성물을 사용함으로써 비중이 낮고 내긁힘성, 인장강도 및 충격강도 등의 물성이 모두 우수한 결과를 얻을 수 있었다. 특히, 왕겨가루가 40중량% 함유된실시예 3의 경우 필러 총량(왕겨가루 + 탈크)이 40중량%로서 동일한 실시예 4 보다도 굴곡탄성율, 충격강도 등이 더 우수하여, 탈크보다 왕겨가루를 사용할 경우 물성이 더 우수하다는 것을 알 수가 있었다.As can be seen in Table 1, specific gravity is obtained by using the polyolefin resin composition of the present invention consisting of 50 to 88% by weight of polypropylene, 5 to 40% by weight of chaff, 5 to 40% by weight of talc, and 2 to 10% by weight of modified polyolefin resin. Low and excellent physical properties such as scratch resistance, tensile strength and impact strength were all obtained. In particular, in the case of Example 3 containing 40% by weight of chaff powder, the total amount of filler (chaff powder + talc) is 40% by weight, which is superior in flexural modulus, impact strength, etc., than in Example 4, so that chaff powder is used than talc. It was found that the physical properties are better.

이상에서 볼 수 있는 바와 같이, 본 발명에 의하여 제조된 수지조성물은 사출성형, 압출성형, 압축성형이 용이하고 비중이 가벼우며 내긁힘성과 충격강도 등의 물성이 우수한 효과를 가져 자동차 내장부품용 소재 및 각종 용기류, 건축 및 산업자재용으로도 적용이 가능하다.As can be seen from the above, the resin composition prepared by the present invention is easy to injection molding, extrusion molding, compression molding, light weight, light weight and excellent effects such as scratch resistance and impact strength material for automotive interior parts It is also applicable to various containers, construction and industrial materials.

Claims (4)

폴리프로필렌 50~88중량%, 왕겨가루 5~40중량%, 변성 폴리올레핀 수지 2~10중량%로 이루어진 것을 특징으로 하는 폴리올레핀 수지조성물.A polyolefin resin composition comprising 50 to 88% by weight of polypropylene, 5 to 40% by weight of chaff powder, and 2 to 10% by weight of modified polyolefin resin. 제1항에 있어서, 폴리프로필렌의 용융지수(Melt Index)가 30g/10분 이상인 것을 특징으로 하는 폴리올레핀 수지조성물.The polyolefin resin composition according to claim 1, wherein the polypropylene has a melt index of 30 g / 10 minutes or more. 제1항에 있어서, 변성올레핀은 폴리프로필렌 수지에 친수성 관능기인 무수말레인산을 그라프트 중합시킨 변성 폴리프로필렌인 것을 특징으로 하는 폴리올레핀 수지조성물.The polyolefin resin composition according to claim 1, wherein the modified olefin is a modified polypropylene obtained by graft polymerization of maleic anhydride as a hydrophilic functional group on a polypropylene resin. 제1항에 있어서, 추가로 탈크 30중량% 이하를 더 포함하는 것을 특징으로 하는 폴리올레핀 수지조성물.The polyolefin resin composition according to claim 1, further comprising 30 wt% or less of talc.
KR1019990022277A 1999-06-15 1999-06-15 Polyolefin resin composition containing chaff powder KR20010002461A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101332208B1 (en) * 2011-10-25 2013-11-22 손승재 Natural ingredient sheet composition use for rice husk and method thereof
CN105713299A (en) * 2016-04-28 2016-06-29 江苏德威新材料股份有限公司 Temperature-resistant 125-DEG C irradiation-free polypropylene modified material

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JPS57105433A (en) * 1980-12-22 1982-06-30 Asahi Chem Ind Co Ltd Thermoplastic resin composition
JPH06220234A (en) * 1993-01-26 1994-08-09 Calp Corp Composite resin composition for cellular cushioning material
JPH07118464A (en) * 1993-10-26 1995-05-09 Sumitomo Seika Chem Co Ltd Rice hull-containing resin composition

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JPS57105433A (en) * 1980-12-22 1982-06-30 Asahi Chem Ind Co Ltd Thermoplastic resin composition
JPH06220234A (en) * 1993-01-26 1994-08-09 Calp Corp Composite resin composition for cellular cushioning material
JPH07118464A (en) * 1993-10-26 1995-05-09 Sumitomo Seika Chem Co Ltd Rice hull-containing resin composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101332208B1 (en) * 2011-10-25 2013-11-22 손승재 Natural ingredient sheet composition use for rice husk and method thereof
CN105713299A (en) * 2016-04-28 2016-06-29 江苏德威新材料股份有限公司 Temperature-resistant 125-DEG C irradiation-free polypropylene modified material
CN105713299B (en) * 2016-04-28 2018-06-19 江苏德威新材料股份有限公司 A kind of 125 DEG C of heatproof exempts from irradiated polypropylene modified material

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