KR100792115B1 - Polypropylene Resin Composition With Excellent Strength And Heat Resistance - Google Patents
Polypropylene Resin Composition With Excellent Strength And Heat Resistance Download PDFInfo
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- 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
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- C08K7/00—Use of ingredients characterised by shape
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- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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Abstract
본 발명은 폴리프로필렌 수지 조성물에 관한 것으로, 보다 상세하게는 (A) 폴리프로필렌 36.0 ∼ 78.0 중량%, (B) 나일론 10.0 ∼ 30.0 중량%, (C) 유리섬유 10.0 ~ 30.0 중량%, (D) 상용화제로서 변성 폴리프로필렌 1.0 ~ 4.0 중량% 및 유기실란계 화합물 0.01∼2.0 중량%를 포함하는 폴리프로필렌 수지 조성물에 관한 것이며, 본 발명은 강도 및 내열성이 향상된 폴리프로필렌 수지 조성물을 제공할 수 있다.
The present invention relates to a polypropylene resin composition, and more specifically, (A) 36.0 to 78.0% by weight of polypropylene, (B) 10.0 to 30.0% by weight of nylon, (C) 10.0 to 30.0% by weight of glass fiber, (D) The present invention relates to a polypropylene resin composition comprising 1.0 to 4.0 wt% of modified polypropylene and 0.01 to 2.0 wt% of an organosilane compound as a compatibilizer, and the present invention can provide a polypropylene resin composition having improved strength and heat resistance.
나일론, 유리섬유(Glass Fiber), 폴리프로필렌, 강도, 내열성, 상용성, 블렌드Nylon, Glass Fiber, Polypropylene, Strength, Heat Resistant, Compatibility, Blend
Description
본 발명은 폴리프로필렌 수지 조성물에 관한 것으로, 보다 상세하게는 나일론, 유리섬유, 폴리프로필렌, 상용화제를 포함하는 폴리프로필렌 수지 조성물에 관한 것이다.The present invention relates to a polypropylene resin composition, and more particularly to a polypropylene resin composition comprising a nylon, glass fiber, polypropylene, compatibilizer.
폴리프로필렌 수지는 기계적 물성, 내약품성, 성형성이 뛰어나 자동차 내장부품, 가전부품, 산업자재 등의 공업적 이용범위가 매우 넓은 소재이다. 그러나, 폴리프로필렌은 화학구조상 무극성을 나타내어 2차 가공성, 특히 도장성 및 타 소재와의 접착성이 열세하고, 결정성 구조로 인하여 치수 안정성이 미흡하며, 강성, 내열성 또한 유사한 용도로 경쟁적으로 적용되는 폴리스티렌, 스티렌 아크릴로니트릴 공중합체 등의 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 is non-polar in chemical structure, so it is inferior in secondary processability, in particular paintability and adhesion to other materials, poor dimensional stability due to crystalline structure, and rigidity and heat resistance are also competitively applied for similar applications. It is slightly inferior to resins such as polystyrene and styrene acrylonitrile copolymers. 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, 강도 및 내열성 그리고 그 밖의 기계적 물성을 향상시키기 위해서 폴 리프로필렌 수지에 무기 충진재로서 유리섬유, 카본섬유, 위스커 등과 같은 침상형 충진재, 운석, 활석 등과 같은 판상형 충진재, 탄산칼슘, 알루미나 등과 같은 구상형 충진재 등을 이용한다. 특히, 유리섬유가 충전된 폴리프로필렌 수지는 고강도 및 고내열성을 갖는다. 또한, 유리섬유는 높은 이축율(aspect ratio)의 섬유상 구조로 인해 판상형 또는 구상형의 충진재에 비해 기계적 물성 향상 효과가 매우 뛰어나다.On the other hand, in order to improve the strength, heat resistance and other mechanical properties, polypropylene resin is used as an inorganic filler, acicular filler such as glass fiber, carbon fiber, whisker, plate-like filler such as meteorite and talc, spherical filler such as calcium carbonate and alumina. Mold filling materials are used. In particular, polypropylene resin filled with glass fibers has high strength and high heat resistance. In addition, the glass fiber is very excellent in improving the mechanical properties compared to the plate-shaped or spherical filler due to the high biaxial ratio (fiber) structure.
물성향상을 구현하기 위해 사용되는 무기 충진재와는 달리, 폴리아미드 수지중의 하나인 나일론을 폴리프로필렌 수지 조성물에 적용함으로써, 초고강도 및 고내열성을 갖게 할 수 있다. 따라서, 나일론 적용시의 상용성 문제만 해결된다면, 일반적인 기계적 물성의 향상과 더불어, 나일론이 지니고 있는 강인성, 내마모성, 내유성 등의 특성을 동시에 확보할 수 있다.
Unlike the inorganic fillers used to realize the physical property improvement, by applying nylon, one of the polyamide resins, to the polypropylene resin composition, it is possible to have ultra high strength and high heat resistance. Therefore, if only the compatibility problem in the application of nylon is solved, it is possible to secure the characteristics such as toughness, wear resistance, oil resistance, etc. that nylon has in addition to the improvement of general mechanical properties.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, 폴리프로필렌과 나일론ㆍ유리섬유를 혼합하고 이들의 상용화를 발현시키기 위하여 상용화제를 부가하여 혼합시킴으로써, 강도 및 내열성이 향상된 폴리프로필렌 수지 조성물을 제공함을 목적으로 한다. The present invention is to solve the above problems, by mixing a polypropylene and nylon and glass fibers and adding a compatibilizer to express their commercialization, thereby providing a polypropylene resin composition with improved strength and heat resistance The purpose.
즉, 본 발명은 폴리프로필렌 36.0 ~ 78.0 중량%, 나일론 10.0 ∼ 30.0 중량%, 유리섬유 10.0 ∼ 30.0 중량%, 상용화제로서 변성 폴리프로필렌 1.0 ~ 4.0 중량% 및 유기실란계 화합물 0.01∼2.0 중량%로 구성된 폴리프로필렌 수지 조성물 에 관한 것이다.
That is, the present invention is 36.0 to 78.0% by weight of polypropylene, 10.0 to 30.0% by weight of nylon, 10.0 to 30.0% by weight of glass fiber, 1.0 to 4.0% by weight of modified polypropylene as compatibilizer and 0.01 to 2.0% by weight of organosilane compound. It relates to a configured polypropylene resin composition.
이하, 본 발명을 보다 상세히 설명하고자 한다.
Hereinafter, the present invention will be described in more detail.
본 발명에서 제조된 폴리프로필렌 수지 조성물의 각 구성성분을 보다 상세히 설명하면 다음과 같다. Referring to each component of the polypropylene resin composition prepared in the present invention in more detail as follows.
본 발명의 (A) 성분인 폴리프로필렌 수지는 용융지수(MI)가 5~70g/10분(ASTM D1238, 230℃)이고, 결정성을 갖는 이소탁틱 폴리프로필렌 중합체가 바람직하다. 용융지수가 5g/10분 미만인 경우에는 부품의 성형성이 양호하지 못하여 생산성이 저하되는 반면, 용융지수가 70g/10분을 초과할 경우에는 충격강도가 급격히 저하된다.As for the polypropylene resin which is (A) component of this invention, melt index (MI) is 5-70g / 10min (ASTM D1238, 230 degreeC), and isotactic polypropylene polymer which has crystallinity is preferable. 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.
본 발명의 (B) 성분인 나일론은 폴리아미드 수지의 대표격인 나일론6, 나일론66 또는 둘의 혼합형인 나일론6/66으로서, 그 함량은 10.0 ~ 30.0 중량%가 바람직하다. 10.0 중량% 미만에서는 나일론의 성능발현이 미흡하며, 30.0 중량%를 초과할 경우에는 폴리프로필렌 수지와의 상분리가 두드러지게 되어 투입량을 증가시켜도 더 이상의 물성향상 효과를 기대하기 어렵다.Nylon as the component (B) of the present invention is nylon 6, nylon 66 or a mixed type of nylon 6/66 which is a representative of polyamide resin, and its content is preferably 10.0 to 30.0% by weight. If it is less than 10.0% by weight, the performance of the nylon is insufficient, and if it exceeds 30.0% by weight, the phase separation from the polypropylene resin becomes more prominent, so even if the input amount is increased, it is difficult to expect a further improvement in physical properties.
본 발명의 (C) 성분인 유리섬유는 무기 충진재로서 평균입경이 5 ~ 15㎛, 바람직하게는 9 ~ 13㎛이고, 길이가 1 ~16㎛인 것의 사용이 가능하며, 그 함량은 10.0 ~ 30.0 중량%가 바람직하다. 유리섬유의 평균입경이 5㎛ 미만인 경우에는 혼 합하는 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. 본 발명에서의 유리섬유 함량이 10.0 중량% 미만일 때는 강성발현의 효과가 미흡하며, 30.0 중량% 초과일 때는 "휨"현상 등이 유발되어 외관상태가 양호하지 못하게 된다.Glass fiber as the component (C) of the present invention can be used as an inorganic filler having an average particle diameter of 5 ~ 15㎛, preferably 9 ~ 13㎛, length of 1 ~ 16㎛, the content of 10.0 ~ 30.0 Weight percent is preferred. If the average particle diameter of the glass fiber is less than 5 µm, it is broken during mixing, and the rigid expression effect is insufficient. If the average particle diameter is more than 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. When the glass fiber content of the present invention is less than 10.0% by weight, the effect of rigid expression is insufficient, and when the glass fiber content is higher than 30.0% by weight, the "warping" phenomenon is caused and the appearance is not good.
본 발명의 (D) 성분은 폴리프로필렌/나일론/유리섬유 블렌드의 혼련성 향상을 위한 상용화제로서, 구체적으로는 변성 폴리프로필렌 및 유기실란계 화합물을 복합적으로 사용한다. Component (D) of the present invention is a compatibilizer for improving the kneading property of the polypropylene / nylon / glass fiber blend, and specifically, a modified polypropylene and an organosilane-based compound are used in combination.
변성 폴리프로필렌은 폴리프로필렌을 불포화 카르복실산 또는 그 유도체에 의해 변성한 것으로, 그 함량은 1.0 ~ 4.0 중량%가 바람직하다. 변성 폴리프로필렌이 함량이 1.0 중량% 미만에서는 충진재와 폴리프로필렌 수지와의 계면 접착력을 충분히 유지할 수 없어 물성 향상 효과가 없으며, 4.0 중량%를 초과할 경우에는 투입량을 증가시켜도 더 이상의 물성 향상 효과는 기대하기 어렵다. The modified polypropylene is obtained by modifying polypropylene with an unsaturated carboxylic acid or derivatives thereof, and the content thereof is preferably 1.0 to 4.0% by weight. If the content of the modified polypropylene is less than 1.0 wt%, the interface adhesion between the filler and the polypropylene resin cannot be sufficiently maintained, and there is no effect of improving the physical properties. Difficult to do
유기실란계 화합물은 그 종류가 특별히 제한되지는 않으며, 본 발명에서는 한 개 또는 두 개의 아미노기를 포함하는 아미노실란계 화합물이 바람직하다. 적정량은 0.01 ~ 2.0 중량%이며, 보다 바람직하게는 0.05 ~ 1.0 중량%이다. 상기 범위를 벗어난 경우는 물성향상을 기대할 수 없다.The type of organosilane compound is not particularly limited, and in the present invention, an aminosilane compound containing one or two amino groups is preferable. The titration amount is 0.01 to 2.0 wt%, more preferably 0.05 to 1.0 wt%. If it is out of the above range, physical property improvement cannot be expected.
본 발명의 폴리프로필렌 수지 조성물에 있어서, 보강재, 충진재, 내열안정 제, 내후안정제, 대전방지제, 활제, 슬립제, 핵제, 난연제, 안료, 염료 등과 같은 통상의 각종 첨가제가 본 발명의 특징에 어긋나지 않는 범위 내에서 첨가될 수 있으며, 그 구체적인 예로 탈크, 탄소섬유, 탄산칼슘, 클레이, 실리카, 알루미나, 카본블랙, 수산화마그네슘, 제올라이트, 황산바륨 등이 있다.In the polypropylene resin composition of the present invention, conventional various additives such as reinforcing materials, fillers, heat stabilizers, weather stabilizers, antistatic agents, lubricants, slip agents, nucleating agents, flame retardants, pigments, dyes, etc. do not deviate from the characteristics of the present invention. It may be added in the range, specific examples thereof are talc, carbon fiber, calcium carbonate, clay, silica, alumina, carbon black, magnesium hydroxide, zeolite, barium sulfate 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.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명하나, 이러한 실시예들은 단지 설명의 목적을 위한 것으로 본 발명의 보호범위를 제한하는 것으로 해석되어서는 아니된다.
Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the protection scope of the present invention.
<실시예 및 비교예><Examples and Comparative Examples>
동일방향으로 회전하는 이축 압출기에 표 1에서 나타난 배합비로 폴리프로필렌, 나일론, 유리섬유, 변성 폴리프로필렌 및 유기실란계 화합물을 배합하고, 이들 100중량부에 대하여 0.7 중량부로 산화방지제 및 장기 내열 안정제를 투입한 후, 용융 혼합시키고 압출하여 펠렛(pellet)상의 블렌드(blend)물를 제조하고 80℃에서 진공 건조시켰다. 다만, 실시예 1, 2 및 비교예 1, 2에서는 혼련시의 온도를 240 ℃로 조절하고, 비교예 3, 4에서는 260℃로 조절하였다. 상기의 블렌드를 사출 성형하여 물성을 평가하고 그 결과를 표 1에 나타내었다. Compound the polypropylene, nylon, glass fiber, modified polypropylene and organosilane-based compound in the compounding ratio shown in Table 1 in the twin-screw extruder rotating in the same direction, and 0.7 parts by weight of the antioxidant and the long-term heat stabilizer After addition, the mixture was melt mixed and extruded to prepare a pellet-like blend, which was vacuum dried at 80 ° C. However, in Examples 1 and 2 and Comparative Examples 1 and 2, the temperature at the time of kneading was adjusted to 240 degreeC, and in Comparative Examples 3 and 4, it was adjusted to 260 degreeC. The blend was injection molded to evaluate physical properties and the results are shown in Table 1.
실시예 1에서는 나일론과 무기 충진재인 유리섬유의 도입이 물성향상에 중요한 역할을 하여, 나일론이 도입되지 않은 비교예 1의 유리섬유 강화 폴리프로필렌보다 강도 및 내열성이 상당히 높게 나왔다. 또한, 폴리프로필렌이 함유되지 않은 비교예 3의 경우와 대비해 볼 때에도, 동등이상의 결과를 나타내었다.In Example 1, the introduction of nylon and the glass fiber as an inorganic filler plays an important role in improving the physical properties, resulting in significantly higher strength and heat resistance than the glass fiber reinforced polypropylene of Comparative Example 1, in which nylon was not introduced. Moreover, when compared with the case of the comparative example 3 which does not contain a polypropylene, the result more than equivalent was shown.
실시예 2의 경우는 나일론이 도입되지 않은 비교예 2의 경우보다 강도, 내열성이 높게 나왔으며, 폴리프로필렌이 함유되지 않은 비교예 4의 경우와 물성이 비슷하게 나타났다.
In Example 2, strength and heat resistance were higher than those of Comparative Example 2, in which nylon was not introduced, and physical properties were similar to those of Comparative Example 4, in which polypropylene was not contained.
(주) (week)
*폴리프로필렌 : 하이 아이소탁틱 폴리프로필렌, 삼성종합화학, 용융지수(MI)는 5~70g/10분* Polypropylene: High isotactic polypropylene, Samsung General Chemical, Melt Index (MI) is 5 ~ 70g / 10min
*나일론 : KN Series, 코오롱, 저/중/고점도* Nylon: KN Series, Kolon, Low / Medium / High Viscosity
*유리섬유 : 글라스파이버, (주)금강, 입경 9~13㎛/길이 1~16㎛* Glass fiber: Glass fiber, Geum steel Co., Ltd., particle size 9 ~ 13㎛ / length 1 ~ 16㎛
*변성 폴리프로필렌 : 폴리프로필렌-말레익 언하이드리드 그라프트 공중합체, 삼성* Modified polypropylene: Polypropylene-maleic hydride graft copolymer, Samsung
종합화학 Comprehensive Chemistry
*유기실란계 화합물(1) : 알파-아미노프로필트리메톡시실란Organic silane compound (1): alpha-aminopropyl trimethoxysilane
*유기실란계 화합물(2) : 베타-메타크릴옥시프로필트리메톡시실란Organic silane compound (2): beta-methacryloxypropyl trimethoxysilane
<물성측정방법><Measurement of Properties>
1) 밀도1) density
ASTM D1505의 방법으로 상온에서 측정하였다.It was measured at room temperature by the method of ASTM D1505.
2) 비캇(Vicat) 연화온도2) Vicat Softening Temperature
ASTM D1525의 방법으로 측정하였다.It was measured by the method of ASTM D1525.
3) 인장강도 및 신율3) Tensile strength and elongation
ASTM D638의 방법으로 상온에서 측정하였다.It was measured at room temperature by the method of ASTM D638.
4) 굴곡탄성율4) Flexural modulus
ASTM D790의 방법으로 상온에서 측정하였다.It was measured at room temperature by the method of ASTM D790.
이상에서 상세히 설명한 바와 같이, 본 발명은 강도 및 내열성이 향상된 폴리프로필렌 수지 조성물을 제공할 수 있다.As described in detail above, the present invention can provide a polypropylene resin composition with improved strength and heat resistance.
Claims (4)
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| KR1020010086362A KR100792115B1 (en) | 2001-12-27 | 2001-12-27 | Polypropylene Resin Composition With Excellent Strength And Heat Resistance |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US11365295B2 (en) | 2018-06-05 | 2022-06-21 | Toyota Jidosha Kabushiki Kaisha | Fiber-reinforced resin composition and method of producing the same |
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| CN102558681B (en) * | 2011-12-30 | 2013-09-18 | 福建晟扬管道科技有限公司 | Trenchless corrugated pipe special for electric power and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60104136A (en) * | 1983-11-09 | 1985-06-08 | Chisso Corp | Glass fiber-reinforced polypropylene composition |
| JPS6466268A (en) * | 1987-09-08 | 1989-03-13 | Nissan Motor | Resin molding material |
| JPH06179784A (en) * | 1992-12-14 | 1994-06-28 | Tosoh Corp | Polypropylene composition |
| KR940014657A (en) * | 1992-12-29 | 1994-07-19 | 하기주 | Glass Fiber Reinforced Polyamide Resin Composition |
| KR20010040964A (en) * | 1998-02-13 | 2001-05-15 | 마크 에프. 웍터 | Polymer nanocomposite composition |
-
2001
- 2001-12-27 KR KR1020010086362A patent/KR100792115B1/en not_active IP Right Cessation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60104136A (en) * | 1983-11-09 | 1985-06-08 | Chisso Corp | Glass fiber-reinforced polypropylene composition |
| JPS6466268A (en) * | 1987-09-08 | 1989-03-13 | Nissan Motor | Resin molding material |
| JPH06179784A (en) * | 1992-12-14 | 1994-06-28 | Tosoh Corp | Polypropylene composition |
| KR940014657A (en) * | 1992-12-29 | 1994-07-19 | 하기주 | Glass Fiber Reinforced Polyamide Resin Composition |
| KR20010040964A (en) * | 1998-02-13 | 2001-05-15 | 마크 에프. 웍터 | Polymer nanocomposite composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11365295B2 (en) | 2018-06-05 | 2022-06-21 | Toyota Jidosha Kabushiki Kaisha | Fiber-reinforced resin composition and method of producing the same |
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