KR100385242B1 - Polypropylene resin composition with improved surface hardness and scratch resistance properties - Google Patents
Polypropylene resin composition with improved surface hardness and scratch resistance properties Download PDFInfo
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- KR100385242B1 KR100385242B1 KR10-1999-0025110A KR19990025110A KR100385242B1 KR 100385242 B1 KR100385242 B1 KR 100385242B1 KR 19990025110 A KR19990025110 A KR 19990025110A KR 100385242 B1 KR100385242 B1 KR 100385242B1
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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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
- C08K5/00—Use of organic ingredients
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- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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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Abstract
본 발명은 표면경도 및 내스크래치성이 향상된 폴리프로필렌 수지 조성물에 관한 것으로서, 좀더 상세하게는 폴리프로필렌 수지, 무기필러인 월라스토나이트, 폴리프로필렌에 무수말레인산을 그라프트시킨 변성 폴리프로필렌, 분산제로 구성되는 표면경도 및 내스크래치성이 향상된 폴리프로필렌 수지 조성물에 관한 것이다.The present invention relates to a polypropylene resin composition having improved surface hardness and scratch resistance, and more specifically, to a polypropylene resin, wollastonite as an inorganic filler, and a modified polypropylene in which maleic anhydride is grafted to polypropylene. The present invention relates to a polypropylene resin composition having improved surface hardness and scratch resistance.
Description
본 발명은 표면경도 및 내스크래치성이 향상된 폴리프로필렌 수지 조성물에 관한 것으로서, 좀더 상세하게는 폴리프로필렌 수지와 침상형의 무기필러를 충진제로 사용하고, 무수말레인산을 그라프트시킨 변성 폴리프로필렌과 분산제를 함께 첨가하여 제조하므로써, 외관이 우수하고 성형가공성이 뛰어나며 치수안정성이 좋고 특히, 표면경도 및 내스크래치성이 향상된 폴리프로필렌 수지 조성물에 관한 것이다.The present invention relates to a polypropylene resin composition having improved surface hardness and scratch resistance, and more particularly, using a polypropylene resin and a needle-shaped inorganic filler as a filler, and using a modified polypropylene and a dispersant grafted with maleic anhydride. The present invention relates to a polypropylene resin composition having excellent appearance, excellent molding processability, good dimensional stability, and improved surface hardness and scratch resistance.
일반적으로 폴리프로필렌 수지 조성물은 가격대비 작업성 및 물성이 우수하여 사출 성형품의 재료로 널리 사용되고 있고, 내열특성, 굴곡강도, 인장강도 및 치수 안정성 등의 특성을 향상시킬 목적으로 무기필러나 기타 강화제 등을 첨가한 조성물을 개발하여 적용중이다. 특히 가격이 저렴하고 재생성이 우수한 탈크를 첨가한 폴리프로필렌 복합소재를 많이 사용하는데, 잘 알려진 바와 같이 탈크 함량이 늘어날수록 굴곡강성 및 내열성은 향상되지만 외관이 거칠어지고 표면경도 및 내스크래치성은 나빠지는 특성이 있으며, 이 때문에 탈크가 충진된 폴리프로필렌 수지를 적용한 자동차 내장재나 인테리어 생활용품 등 외관을 중요시하는 제품에서는 스크래치가 쉽게 나타나는 문제점이 있다.In general, the polypropylene resin composition is widely used as a material for injection molded products because of its excellent price-performance and physical properties, and inorganic fillers and other reinforcing agents for improving properties such as heat resistance, bending strength, tensile strength and dimensional stability. A composition to which is added is being developed and applied. In particular, polypropylene composites with talc added, which are inexpensive and have excellent regeneration, are used.As well known, as the talc content increases, flexural rigidity and heat resistance are improved, but the appearance becomes rough and surface hardness and scratch resistance deteriorate. And, because of this, there is a problem that scratches easily appear in products that emphasize the appearance, such as automotive interior materials or interior household goods to which the talc-filled polypropylene resin is applied.
따라서 이런 문제점을 해결하기 위하여 여러가지 방법이 제안되고 있다. 예를 들어 아미노계 실란 커플링제가 처리된 무기 필러 및 에폭사이드 관능기를 갖는 α,β-불포화산의 에스테르로 변성시킨 에틸렌-α-올레핀 공중합체 고무를 이용하여 폴리프로필렌 매트릭스/고무 성분/무기충진제간의 결합력을 향상시키는 것을 주제로 한 특허(한국특허 공개 제 97-3307호), 에폭사이드 관능기를 갖는 α,β-불포화산의 에스테르로 변성시킨 에틸렌-α-올레핀 공중합체 고무, 그리고 불포화 카본산 또는 그 유도체로 변성된 폴리올레핀을 이용하여 폴리프로필렌 매트릭스/고무 성분간의 결합력을 향상시킴으로써 내긁힘성 및 내충격 강도를 보완하는 것을 주제로 한 특허(한국특허 공개 제 90-641호) 등이 있으나, 이들의 경우 고무 성분이 첨가됨에 따라 굴곡강성이 저하됨과 동시에 수지의 흐름성이 급격히 저하되는 문제점이 있다. 그리고 유리섬유 혹은 박편상의 마이카를 사용하여 내긁힘성을 향상시키는 특허(일본 특개소 제53-118055호)가 있으나, 유리섬유 및 박편상의 마이카를 사용하는 경우 수지의 흐름성 저하와 성형품의 표면외관이 불량하다는 문제점이 있으며, 매트릭스로 사용되는 폴리프로필렌 수지의 에틸렌 함유량을 특정범위로 한정하여 내긁힘성을 개선한 방법(일본 특개소 56-88447호)이 있으나 폴리프로필렌의 에틸렌 함유량을 제한하는 경우는 충격을 흡수하는 역할을 하는 에틸렌의 함량이 감소함에 따라 충격강도가 떨어지는 단점이 있었다.Therefore, various methods have been proposed to solve this problem. For example, a polypropylene matrix / rubber component / inorganic filler using an ethylene-α-olefin copolymer rubber modified with an inorganic filler treated with an amino-based silane coupling agent and an ester of an α, β-unsaturated acid having an epoxide functional group. Patent (Korean Patent Publication No. 97-3307) which aims at improving the binding force between livers, the ethylene-alpha-olefin copolymer rubber modified with the ester of the alpha, beta-unsaturated acid which has an epoxide function, and unsaturated carboxylic acid Or there is a patent (Korean Patent Publication No. 90-641) and the like to compensate for the scratch resistance and impact strength by improving the binding force between the polypropylene matrix / rubber component using a polyolefin modified with its derivatives, but these In the case that the rubber component is added, there is a problem in that the bending rigidity is lowered and the flowability of the resin is sharply lowered. In addition, there is a patent (Japanese Patent Application No. 53-118055) which improves scratch resistance by using glass fiber or flaky mica. However, when glass fiber and flaky mica are used, the flow of resin decreases and the surface appearance of the molded article. There is a problem that this is poor, there is a method to improve the scratch resistance by limiting the ethylene content of the polypropylene resin used as the matrix to a specific range (Japanese Patent Laid-Open No. 56-88447), but when limiting the ethylene content of the polypropylene The disadvantage was that the impact strength is lowered as the content of ethylene, which serves to absorb shock, decreases.
본 발명의 목적은 상기와 같은 문제점을 개선하기 위한 것으로서, 무기필러로 월라스토나이트(Wollastonite)를 사용하고, 폴리프로필렌과 월라스토나이트 사이의 접착성을 증가시키기 위해 극성 관능기를 갖고 있는 무수말레인산을 그라프트시킨 변성 폴리프로필렌을 첨가하고, 무기필러의 함량이 높아짐에 따라 무기필러의 뭉침 현상이 발생하여 소재물성 특성이 균일하지 않고 외관이 나빠지는 현상을 방지하기 위하여 적정 분산제를 사용하므로써 사출성형시 가공성이 좋고 가공후 외관이 우수하며 치수 안정성과 열적 물성, 기계적 물성이 양호하고 특히, 표면경도 및 스크래치성이 향상된 폴리프로필렌 수지 조성물을 제공하는 것이다.An object of the present invention is to improve the above problems, using wollastonite as an inorganic filler, maleic anhydride having a polar functional group to increase the adhesion between polypropylene and wollastonite. When the grafted modified polypropylene is added and the content of the inorganic filler increases, the aggregation of the inorganic filler occurs, so that the material properties are not uniform and the appearance is deteriorated. The present invention provides a polypropylene resin composition having good processability and excellent post-processing appearance, having good dimensional stability, thermal properties, and mechanical properties, and particularly having improved surface hardness and scratch resistance.
본 발명의 표면경도 및 스크래치성이 향상된 폴리프로필렌 수지 조성물은 폴리프로필렌 수지 50~87.9중량%, 무기필러인 월라스토나이트 10~40중량%, 폴리프로필렌에 무수말레인산을 그라프트시킨 변성폴리프로필렌 2~10중량%, 분산제 0.1~1중량%로 이루어지는 것을 특징으로 한다.Polypropylene resin composition with improved surface hardness and scratchability of the present invention is modified polypropylene 2 ~ 50 ~ 87.9% by weight of polypropylene resin, 10 to 40% by weight of the inorganic filler wollastonite, grafted maleic anhydride to polypropylene It consists of 10 weight% and 0.1-1 weight% of a dispersing agent.
본 발명에서 사용되는 폴리프로필렌 수지는 용융지수가 5~40g/10분(ASTM D1238, 230℃)인 호모 폴리프로필렌 또는 에틸렌 함량이 25몰% 이하인 블록 공중합체 또는 랜덤공중합체 또는 이들의 혼합물이 바람직하며, 용융지수가 5g/10분 미만인 경우 사출성형 가공성이 저하되고, 40g/10분을 초과하는 경우 충격강도가 현저히 저하되며, 폴리프로필렌중의 에틸렌 함량이 25몰%을 초과하는 경우 강성이 저하된다.The polypropylene resin used in the present invention is preferably a homopolypropylene having a melt index of 5 to 40 g / 10 minutes (ASTM D1238, 230 ° C) or a block copolymer or a random copolymer having a ethylene content of 25 mol% or less, or a mixture thereof. When the melt index is less than 5g / 10min, the injection molding processability is lowered, and when the melt index is more than 40g / 10min, the impact strength is significantly lowered, and when the ethylene content of the polypropylene exceeds 25 mol%, the rigidity is lowered. do.
본 발명에서 사용되는 무기필러인 월라스토나이트는 10∼40중량% 첨가되는 것이 바람직하며, 월라스토나이트 함유량이 10중량% 미만인 경우에는 내열성, 인장강도 및 굴곡강도등의 물성향상 효과가 적으며, 40중량%를 넘으면 사출성형시 흐름 자국이 발생하여 외관이 나빠지며 충격강도가 저하된다. 또한 월라스토나이트는 화학조성이 CaSiO3, 모어경도 4∼5, 융점이 1500℃ 이상이고 에스펙비(aspect ratio)가 2∼50이며 침상형의 입자모양을 갖고 평균 입자 크기는 3∼50마이크로미터(㎛)인 것이 적당하다. 에스펙비가 2 미만인 경우에는 강성이 저하하는 문제점이 있고 50을 초과하는 경우 외관 및 충격 물성 저하의 문제점이 있으며, 평균 입자 크기가 3마이크로미터 미만일 경우 압출 가공시 입자 뭉침에 의한 생산성이 떨어지고 50마이크로미터를 초과하는 경우 외관 및 충격물성 저하의 문제이 발생하여 외관이 나빠지며 충격강도가 저하된다.Wollastonite, the inorganic filler used in the present invention, is preferably added in an amount of 10 to 40% by weight. When the content of the wollastonite is less than 10% by weight, the effect of improving physical properties such as heat resistance, tensile strength and flexural strength is small. If it exceeds 40% by weight, flow marks are generated during injection molding, resulting in deterioration of appearance and impact strength. In addition, wollastonite has a chemical composition of CaSiO 3 , a molar hardness of 4 to 5, a melting point of 1500 ° C. or more, an aspect ratio of 2 to 50, a needle-like particle shape, and an average particle size of 3 to 50 micrometers. (Μm) is appropriate. If the ratio is less than 2, there is a problem that the rigidity is lowered, and if it exceeds 50, there is a problem of appearance and impact properties deterioration. If the average particle size is less than 3 micrometers, productivity due to agglomeration of particles during extrusion is reduced and 50 microns. If the meter is exceeded, problems of appearance and impact property deteriorate, resulting in deterioration of appearance and impact strength.
본 발명에서 사용되는 변성폴리프로필렌은 폴리프로필렌에 무수말레인산을 그라프트시킨 것으로 무수말레인산의 결합율이 0.3중량% 이상이고, 2∼10중량% 첨가되는 것이 바람직하다. 본 발명의 수지 조성물에 변성폴리프로필렌을 2중량% 미만 첨가하면 폴리프로필렌과 월라스토나이트의 접착 효과가 떨어지고, 10중량%를 초과하여 첨가하는 경우에는 제조원가가 상승되고 폴리프로필렌 수지 자체의 기본물성이 저하된다.The modified polypropylene used in the present invention is obtained by grafting maleic anhydride to polypropylene, and the bonding ratio of maleic anhydride is 0.3% by weight or more, preferably 2 to 10% by weight. When less than 2% by weight of modified polypropylene is added to the resin composition of the present invention, the adhesion effect between polypropylene and wollastonite is reduced, and when it is added in excess of 10% by weight, the manufacturing cost is increased and the basic properties of the polypropylene resin itself are increased. Degrades.
본 발명에서 사용되는 분산제는 0.1∼1중량% 첨가되는 것이 바람직하며, 분산제가 0.1중량% 미만인 경우에는 무기필러의 충분한 분산효과가 얻어지지 않으며,1중량%를 넘으면 첨가제의 탄화나 성형후 과량의 첨가제가 성형제품의 표면에 이송되므로써 최종 성형품의 외관을 저하시킨다. 본 발명의 분산제로는 분산 또는 촉매 잔사 중화의 목적으로 사용되는 칼슘스테아레이트(calcium stearate), 징크스테아레이트(zinc stearate), 마그네슘스테아레이트(magnesium stearate) 등을 사용할 수 있다.It is preferable that the dispersant used in the present invention is added in an amount of 0.1 to 1% by weight. When the dispersant is less than 0.1% by weight, sufficient dispersing effect of the inorganic filler is not obtained. The additives are transferred to the surface of the molded product, thereby degrading the appearance of the final molded product. As the dispersant of the present invention, calcium stearate, zinc stearate, magnesium stearate, or the like used for the purpose of dispersion or neutralization of the catalyst residue may be used.
본 발명에 따른 조성물의 제조방법에 대하여는 종래 폴리프로필렌 수지 조성물의 제조에 사용되고 있는 방법을 사용하고, 필요에 따라 각종 첨가성분을 니더, 롤, 밤바리 믹서 등의 혼련기와 싱글(single) 또는 트윈(twin) 스크류(screw) 압출기 등에의 투입에 의하여 제조가 가능하다.The method for producing a composition according to the present invention is conventionally used in the production of a polypropylene resin composition, and if necessary, various additives may be added to kneaders such as kneaders, rolls, chestnut mixers, and the like. twin) It is possible to manufacture by inserting into a screw extruder or the like.
본 발명은 하기 실시예 및 비교예에 의하여 보다 구체적으로 이해될 수 있고, 하기의 실시예는 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, the following examples are only for illustrating the present invention and are not intended to limit the protection scope of the present invention.
실시예 및 비교예Examples and Comparative Examples
하기 표 1 및 표 2에 나타낸 비율에 따라 각 원료를 실시예 및 비교예 모두 믹서 혼련를 사용하여 혼합한 후, 트윈스크류 압출기로 용융혼련하여 각 조성물을 펠렛상으로 제조하고, 사출기(140톤)를 이용하여 테스트 시편을 제조한 후 규정의 방법에 따라 평가를 실시하였다.In accordance with the ratios shown in Table 1 and Table 2, each of the raw materials in the Examples and Comparative Examples were mixed using mixer kneading, and then melt-kneaded in a twin screw extruder to prepare each composition in pellet form, and an injection machine (140 tons) was prepared. After the test specimens were prepared, the evaluation was carried out according to the prescribed method.
<물성시험방법><Property Test Method>
1. 표면경도 : ASTM D785Surface Hardness: ASTM D785
(표면경도(R-Scale) 95 이상일때 자동차 내장재 적용에 적합 판정함)(Suitable for application of automotive interior materials when surface hardness (R-Scale) is 95 or more)
2. 내스크래치성 : 연필경도 Test2. Scratch resistance: pencil hardness test
(연필경도 2B 이상일때 자동차 내장재 적용에 적합 판정함)(It is judged to be suitable for automobile interior materials when pencil hardness is over 2B)
3. 외관 : 300 ×90 ×3mm 사출시편을 제작하여 흐름자국 및 표면 거칠기 등을 육안으로 판정함3. Appearance: 300 × 90 × 3mm injection specimens are produced to visually determine flow traces and surface roughness.
4. 인장강도 : ASTM D6384. Tensile Strength: ASTM D638
5. 굴곡탄성율 : ASTM D7905. Flexural modulus: ASTM D790
6. 아이조드 충격강도 : ASTM D2566. Izod impact strength: ASTM D256
* 1)삼성종합화학(주), BJ700* 1) Samsung General Chemical Co., Ltd., BJ700
2)평균입자크기 12㎛2) Average particle size 12㎛
3)삼성종합화학(주), CP4673T3) Samsung General Chemical Co., Ltd., CP4673T
* 1)삼성종합화학(주), BJ700* 1) Samsung General Chemical Co., Ltd., BJ700
2)평균입자크기 10㎛2) Average particle size 10㎛
3)평균입자크기 200㎛3) Average particle size 200㎛
4)평균입자크기 12㎛4) Average particle size 12㎛
5)삼성종합화학(주), CP4673T5) Samsung General Chemical Co., Ltd., CP4673T
상기 표 1과 2에서 알 수 있는 바와 같이 본 발명의 실시예는 비교예에 비하여 표면경도와 내스크래치 특성이 우수함을 알 수 있다.As can be seen in Tables 1 and 2 it can be seen that the embodiment of the present invention is superior in surface hardness and scratch resistance than the comparative example.
이상에서 볼 수 있는 바와 같이, 본 발명에 의하여 제조된 폴리프로필렌 수지 조성물은 폴리프로필렌 수지에 침상형 무기필러인 월라스토나이트를 사용하고, 폴리프로필렌 수지와 월라스토나이트간의 접착력을 향상시키기 위해서 무수말레인산을 그라프트시킨 변성 폴리프로필렌을 첨가하고, 분산제를 사용하여 수지 조성물내 무기필러의 분산성을 향상시켜 사출성형 가공후 제품의 전반적인 물성을 향상시키고, 외관이 우수하며, 특히 표면경도 및 내스크래치 특성이 뛰어난 효과를 갖는다.As can be seen from the above, the polypropylene resin composition produced according to the present invention uses wollastonite, which is a needle-shaped inorganic filler, to improve the adhesion between polypropylene resin and wollastonite in polypropylene resin. Graft modified polypropylene is added, and the dispersant improves the dispersibility of the inorganic filler in the resin composition, thereby improving the overall physical properties of the product after injection molding processing, excellent appearance, especially surface hardness and scratch resistance This has an excellent effect.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-1999-0025110A KR100385242B1 (en) | 1999-06-29 | 1999-06-29 | Polypropylene resin composition with improved surface hardness and scratch resistance properties |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-1999-0025110A KR100385242B1 (en) | 1999-06-29 | 1999-06-29 | Polypropylene resin composition with improved surface hardness and scratch resistance properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20010004447A KR20010004447A (en) | 2001-01-15 |
| KR100385242B1 true KR100385242B1 (en) | 2003-05-27 |
Family
ID=19596644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR10-1999-0025110A KR100385242B1 (en) | 1999-06-29 | 1999-06-29 | Polypropylene resin composition with improved surface hardness and scratch resistance properties |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100385242B1 (en) |
-
1999
- 1999-06-29 KR KR10-1999-0025110A patent/KR100385242B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010004447A (en) | 2001-01-15 |
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