KR100187193B1 - Thermoplastic resin compositions - Google Patents
Thermoplastic resin compositions Download PDFInfo
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- KR100187193B1 KR100187193B1 KR1019960010030A KR19960010030A KR100187193B1 KR 100187193 B1 KR100187193 B1 KR 100187193B1 KR 1019960010030 A KR1019960010030 A KR 1019960010030A KR 19960010030 A KR19960010030 A KR 19960010030A KR 100187193 B1 KR100187193 B1 KR 100187193B1
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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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
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/06—Copolymers with vinyl aromatic monomers
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
Abstract
본 발명은 열가소성 수지 조성물에 관한 것으로서, 더욱 상세하게는 페닐말레이미드-스티렌-아크릴로니트릴 단량체를 공중합한 페닐말레이미드계 공중합체와 디엔계 고무질 중합체, 방향족비닐계 단량체, 아크릴레이트계 단량체 및 아크릴로니트릴 단량체를 그라프트공중합시킨 그라프트 공중합체로 이루어져 있어 내열성이 우수하고 중공성형용으로 적합한 특성이 있는 열가소성 수지 조성물에 관한 것이다.The present invention relates to a thermoplastic resin composition, and more particularly, to a phenylmaleimide copolymer copolymerized with a phenylmaleimide-styrene-acrylonitrile monomer, a diene rubber polymer, an aromatic vinyl monomer, an acrylate monomer, and an acryl. The present invention relates to a thermoplastic resin composition having a graft copolymer obtained by graft co-polymerization of a nitrile monomer, having excellent heat resistance and suitable properties for blow molding.
Description
본 발명은 열가소성 수지 조성물에 관한 것으로서, 더욱 상세하게는 페닐말레이미드-스티렌-아크릴로니트릴 단량체를 공중합한 페닐말레이미드계 공중합체와 디엔계 고무질 중합체, 방향족비닐계 단량체, 아크릴레이트계 단량체 및 아크릴로니트릴 단량체를 그라프트공중합시킨 그라프트 공중합체로 이루어져 있어 내열성이 우수하고 중공성형용으로 적합한 특성이 있는 열가소성 수지 조성물에 관한 것이다.The present invention relates to a thermoplastic resin composition, and more particularly, to a phenylmaleimide copolymer copolymerized with a phenylmaleimide-styrene-acrylonitrile monomer, a diene rubber polymer, an aromatic vinyl monomer, an acrylate monomer, and an acryl. The present invention relates to a thermoplastic resin composition having a graft copolymer obtained by graft co-polymerization of a nitrile monomer, having excellent heat resistance and suitable properties for blow molding.
일반적으로 중공성형용 수지로는 폴리에틸렌, 폴리프로필렌, 폴리비닐클로라이드 등의 범용수지가 주로 사용되어 왔다. 그러나, 이들 수지는 내열성이 취약하여 용기 또는 잡화 등과 같이 내열성이 요구되지 않는 소형품에 그 사용이 한정되어 왔다.In general, general purpose resins such as polyethylene, polypropylene, and polyvinyl chloride have been mainly used as the blow molding resin. However, these resins have been limited in their use in small articles that have poor heat resistance and do not require heat resistance such as containers or sundries.
최근에는 하이테크 중공성형 재료에 대한 대형화 및 내열성이 요구되면서 엔지니어링 플라스틱재인 변성 폴리페닐에테르, 폴리아마이드, 폴리카보네이트 엔지니어링 플라스틱 등을 자동차 에어스포일러(Air spoiler)용으로 사용하고 있으나, 이들 수지는 도장성이 나빠 도장시 프라이머(primer)처리를 하여야 하는 단점이 있으며, 또한 가격이 고가인 문제가 있다.Recently, due to the increase in size and heat resistance of high-tech blow molding materials, modified polyphenylethers, polyamides, and polycarbonate engineering plastics, which are engineering plastics, have been used for automotive air spoilers. There is a disadvantage in that the primer (primer) treatment when the coating is bad, and there is a problem that the price is expensive.
통상 균형잡힌 강도, 강성, 내충격성, 내열성, 성형성 및 2차 가공성이 뛰어나고, 특히 사출성형에 의한 성형이 곤란한 대형부품을 중공성형하기 위해서는 드로우-다운(draw-down)이 적어야 하고, 성형품의 표면외관성이 좋아야 하고, 도장성이 좋아야 하며, 특히 도장피막의 밀착성, 선영성이 좋아야 하며, 이밖에도 내약품성이 우수해야 한다.In general, in order to blow a large part that is excellent in balanced strength, stiffness, impact resistance, heat resistance, moldability, and secondary workability, and difficult to mold by injection molding, draw-down should be low. The surface appearance should be good, the paintability should be good, especially the adhesion of the coating film, the screening property should be good, and in addition, the chemical resistance should be excellent.
따라서, 본 발명자들은 상기와 같은 종래의 중공성형용 수지의 문제점을 해결하고, 특히 중공성형에 적합하면서 내열성이 우수한 열가소성 수지를 제조하기 위하여 연구노력한 결과, 분자량 분포가 넓으면서도 고분자량을 갖는 페닐말레이미드계 공중합체와 도장성과 외관이 우수한 그라프트 공중합체로서 디엔계 고무질 중합체, 방향족 비닐계 단량체, 아크릴레이트계 단량체 및 아크릴로니트릴 단량체로 이루어진 그라프트 중합체를 혼합하여 제조함으로써 본 발명을 완성하였다.Accordingly, the present inventors have solved the problems of the conventional blow molding resin as described above, and, in particular, have been researched to produce a thermoplastic resin having excellent heat resistance while being suitable for blow molding. As a result, phenylmaleic having a high molecular weight distribution and high molecular weight distribution The present invention has been completed by mixing a mid-based copolymer with a graft copolymer composed of a diene rubber polymer, an aromatic vinyl monomer, an acrylate monomer, and an acrylonitrile monomer as a graft copolymer having excellent paintability and appearance.
본 발명은 내열성이 우수하고 중공성형용으로서 우수한 물성을 갖는 열가소성 수지조성물을 제공하는 데 그 목적이 있다.An object of the present invention is to provide a thermoplastic resin composition having excellent heat resistance and excellent physical properties for blow molding.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 N-페닐말레이미드 단량체, 스티렌 단량체 및 아크릴로니트릴 단량체가 공중합된 페닐말레이미드계 공중합체와 그라프트 공중합체를 혼합하여 이루어진 열가소성 수지 조성물에 있어서, 상기 그라프트 공중합체는 디엔계 고무질 중합체 40∼70중량%, 방향족비닐계 단량체 20∼30중량%, 아크릴레이트계 단량체 1.0∼5.0중량% 및 아크릴로니트릴 단량체 10∼24중량%를 그라프트 공중합한 것임을 그 특징으로 한다.The present invention is a thermoplastic resin composition obtained by mixing a phenyl maleimide copolymer copolymerized with an N-phenylmaleimide monomer, a styrene monomer and an acrylonitrile monomer and a graft copolymer, wherein the graft copolymer is a diene rubber It is characterized by graft copolymerization of 40-70 weight% of polymers, 20-30 weight% of aromatic vinylic monomers, 1.0-5.0 weight% of acrylate monomers, and 10-24 weight% of acrylonitrile monomers.
이와같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명은 페닐말레이미드계 공중합체와 그라프트 공중합체를 혼합시켜 제조된 내열성이 우수한 중공성형용 열가소성 수지 조성물에 관한 것이다.The present invention relates to a thermoplastic resin composition for blow molding having excellent heat resistance prepared by mixing a phenylmaleimide copolymer and a graft copolymer.
본 발명에서 사용되는 페닐말레이미드계 공중합체는 N-페닐말레이미드 단량체 10∼25중량%, 스티렌 단량체 65∼85중량% 및 아크릴로니트릴 단량체 10∼20중량%를 공중합하여 제조된 것으로서, 이의 제조는 통상의 중합방법을 사용한다.The phenylmaleimide-based copolymer used in the present invention is prepared by copolymerizing 10 to 25% by weight of N-phenylmaleimide monomer, 65 to 85% by weight of styrene monomer and 10 to 20% by weight of acrylonitrile monomer. The conventional polymerization method is used.
상기 페닐말레이미드계 공중합체의 조성에 있어서, N-페닐말레이미드 단량체의 함량이 10중량% 미만이면 최종 목적물의 내열성이 만족스럽지 못하고, 25중량%를 초과하여 사용하면 성형성이 저하되고 제조비용이 상승하는 문제가 있다. 그리고, 스티렌 단량체의 함량이 65중량% 미만이면 성형성이 저하되고 제조비용이 상승하는 문제가 있으며, 85중량%를 초과하면 성형가공시 가스의 다량 발생으로 외관이 불량해지는 문제가 있다. 또한, 아크릴로니트릴 단량체의 함량이 상기 범위를 벗어나면 내열성 및 내화학성이 떨어져 도장시에 문제가 된다.In the composition of the phenyl maleimide copolymer, when the content of the N-phenyl maleimide monomer is less than 10% by weight, the heat resistance of the final target product is not satisfactory, and when used in excess of 25% by weight, the moldability is lowered and the manufacturing cost There is a rising problem. In addition, if the content of the styrene monomer is less than 65% by weight, there is a problem that the moldability is lowered and the manufacturing cost is increased. When the content of the styrene monomer is more than 85% by weight, the appearance is poor due to the generation of a large amount of gas during the molding process. In addition, when the content of the acrylonitrile monomer is out of the above range, heat resistance and chemical resistance are poor, which causes a problem during coating.
상기와 같은 조성으로 이루어진 페닐말레이미드계 공중합체는 중량평균 분자량이 130,000∼210,000인 것이 바람직하고, 중량평균 분자량과 수평균분자량의 비율(중량평균분자량/수평균분자량)은 2.5∼4.5로 구성되는 것이 좋다. 만약, 중량평균 분자량이 130,000 미만이면 중공성형시 파리손(parison) 강도가 낮아 드로우-다운이 커져 중공성형이 곤란하며, 중량평균 분자량이 210,000을 초과하면 중공성형이 곤란하거나 후가공시 표면의 평활성과 처리시간이 길어지는 문제가 있다. 또한, 중량평균 분자량/수평균분자량의 비율이 2.5∼4.5인 것이 성형품의 표면이 평활하고 중공성형시 용융균열(melt fracture)이 발생하지 않는다. 이때, 분자량의 조절은 중합분자량 조절제인 머캅탄류, 예를 들면 t-도데실머캅탄 또는 n-도데실머캅탄을 사용한다.The phenylmaleimide-based copolymer having the above composition preferably has a weight average molecular weight of 130,000 to 210,000, and the ratio (weight average molecular weight / number average molecular weight) of the weight average molecular weight and the number average molecular weight is 2.5 to 4.5. It is good. If the weight average molecular weight is less than 130,000, the blow-down strength is low during blow molding, so the draw-down becomes large, and blow molding is difficult. If the weight average molecular weight exceeds 210,000, the blow molding is difficult or the surface smoothness is reduced. There is a problem that the processing time becomes long. In addition, the ratio of the weight average molecular weight / number average molecular weight is 2.5 to 4.5, the surface of the molded article is smooth and no melt fracture occurs during blow molding. At this time, the control of molecular weight uses mercaptans which are polymerization molecular weight regulators, for example, t-dodecyl mercaptan or n-dodecyl mercaptan.
한편, 본 발명에서 상기 페닐말레이미드계 공중합체와 혼합되는 그라프트 공중합체는 디엔계 고무질 중합체 40∼70중량%, 방향족비닐계 단량체 20∼30중량%, 아크릴레이트계 단량체 1.0∼5.0중량% 및 아크릴로니트릴 단량체 10∼24중량%를 그라프트 공중합한 것이다.On the other hand, in the present invention, the graft copolymer mixed with the phenylmaleimide copolymer is 40 to 70% by weight of the diene rubber polymer, 20 to 30% by weight of the aromatic vinyl monomer, 1.0 to 5.0% by weight of the acrylate monomer and It is graft copolymerized 10 to 24 weight% of acrylonitrile monomers.
상기 그라프트 공중합체 조성에 있어서, 디엔계 고무질 중합체로는 그 입자크기가 800∼2,000Å인 소입경의 디엔계 고무질 중합체 40∼60중량%와 그 입자크기가 3,000∼5,000Å인 대입경의 디엔계 고무질 중합체 40∼60중량%를 혼합시킨 혼합물을 사용하는 데, 이는 가공시 표면광택 및 중공성형성을 향상시킬 수 있다. 본 발명에서 사용할 수 있는 디엔계 고무질 중합체의 구체적인 예로는 1,3-부타디엔, 1,4-부타디엔, 이소프렌, 클로로프렌 또는 2-페닐-1,3-부타디엔이 있다. 이와 같은 디엔계 고무질 중합체의 함량이 전체 그라프트 공중합체 조성 중 40중량% 미만이면 충격강도등의 물성이 저하되는 문제가 있고, 70중량%를 초과하여 첨가하면 충격강도는 향상되나 성형품의 외관이 불량해지는 문제가 있다.In the graft copolymer composition, as the diene rubber polymer, a diene rubber polymer having a particle size of 800 to 2,000 kPa 40 to 60% by weight of a diene rubber polymer and a particle size of 3,000 to 5,000 kPa A mixture of 40 to 60% by weight rubbery polymer is used, which can improve surface gloss and hollowness during processing. Specific examples of diene rubber polymers that can be used in the present invention include 1,3-butadiene, 1,4-butadiene, isoprene, chloroprene or 2-phenyl-1,3-butadiene. If the content of the diene rubber polymer is less than 40% by weight of the graft copolymer composition, there is a problem that physical properties such as impact strength are lowered.When the content of the diene rubber polymer is added in excess of 70% by weight, the impact strength is improved, but the appearance of the molded article is improved. There is a problem of becoming poor.
그리고, 그라프트 공중합체 조성 중 방향족비닐계 단량체로는 스티렌, α-메틸스티렌 또는 이들의 혼합물을 사용하며, 그 함량이 20중량% 미만이면 유동성 저하로 인한 성형불량의 문제가 있고, 30중량%를 초과하면 충격강도 및 내화학약품성이 저하되는 문제가 있다. 또한, 아크릴레이트계 단량체는 내화학성이 우수한 특성을 갖는 것으로서 표면광택, 도장성의 향상을 위해 첨가하며, 이의 구체적인 화합물로는 메틸 메타크릴레이트, 메틸 아크릴레이트 또는 에틸 아크릴레이트가 있다. 이의 사용량이 상기 범위를 벗어나면 도장성이나 선영성이 떨어지는 문제가 있다. 그리고, 아크릴로니트릴 단량체의 함량이 10중량% 미만이면 성형시 가스발생 및 변색 등의 문제가 있다.In addition, styrene, α-methylstyrene, or a mixture thereof is used as the aromatic vinyl monomer in the graft copolymer composition. If the content is less than 20% by weight, there is a problem of poor molding due to fluidity deterioration, and 30% by weight. If it exceeds, there is a problem that the impact strength and chemical resistance is lowered. In addition, the acrylate-based monomer is excellent in chemical resistance and is added to improve surface gloss and paintability, and specific compounds thereof include methyl methacrylate, methyl acrylate or ethyl acrylate. If the amount of use thereof is out of the above range, there is a problem that paintability or sunscreen is inferior. And, if the content of acrylonitrile monomer is less than 10% by weight there is a problem such as gas generation and discoloration during molding.
상기와 같은 페닐말레이미드계 공중합체와 그라프트 공중합체를 혼합하여 본 발명의 열가소성 수지 조성물을 제조하는 데, 이때 페닐말레이미드계 공중합체와 그라프트 공중합체의 혼합비는 30 : 70∼70 : 30 중량비로서 열가소성 수지 조성물 중에 페닐말레이미드 공중합체의 함량이 30중량% 미만이면 내열성이 저하되는 문제가 있고, 70중량%를 초과하여 첨가되면 가공성의 저하로 성형불량 및 충격강도 등이 저하되는 문제가 있다.The phenylmaleimide-based copolymer and the graft copolymer are mixed to produce the thermoplastic resin composition of the present invention, wherein the mixing ratio of the phenylmaleimide-based copolymer and the graft copolymer is 30:70 to 70:30. If the content of the phenylmaleimide copolymer in the thermoplastic resin composition is less than 30% by weight, the heat resistance may be lowered. If the content of the phenylmaleimide copolymer is less than 30% by weight, the addition of more than 70% by weight may result in deterioration in moldability and impact strength. have.
상기와 같이 페닐말레이미드계 공중합체와 디엔계 고무질 중합체, 방향족비닐계 단량체, 아크릴레이트계 단량체 및 아크릴로니트릴 단량체로 이루어진 그라프트 공중합체를 혼합시켜 제조된 본 발명의 열가소성 수지 조성물은 내열성 및 도장성 등이 우수하고, 중공성형 특성이 우수하므로 대형 중공성형 분야에서 유용하게 사용될 수 있다.As described above, the thermoplastic resin composition of the present invention prepared by mixing a phenylmaleimide copolymer with a diene rubber polymer, an aromatic vinyl monomer, an acrylate monomer, and an acrylonitrile monomer is mixed. Excellent properties, such as excellent blow molding properties can be useful in the field of large blow molding.
이하, 본 발명을 실시예에 의거하여 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited by the Examples.
제조예 A : 페닐말레이미드계 공중합체의 제조Preparation Example A: Preparation of Phenylmaleimide Copolymer
질소치환된 반응기에 사용된 전체 단량체 함량 100중량부에 대하여 순수 200중량부, 라우릴황산나트륨 2 중량부를 첨가하고 교반시키면서 50℃까지 승온시킨 다음, 여기에 순수 10중량부에 과황산칼륨 2 중량부를 용해시킨 수용액을 첨가하였다. 그리고, 다음 표 1에 나타낸 바와 같이 N-페닐말레이미드, 스티렌, 아크릴로니트릴과 t-도데실머캅탄을 전체 투입량중 5%를 1시간에 걸쳐 투입한 후, 반응기 내부의 온도를 70℃로 상승시킨 다음, 5시간에 걸쳐 나머지 9%를 연속 투입하였다. 투입이 완료된 후 중합온도를 80℃로 승온하여 5시간 동안 숙성시켜 중합을 완료시켰다.200 parts by weight of pure water and 2 parts by weight of sodium lauryl sulfate were added to 100 parts by weight of the total monomer content used in the nitrogen-substituted reactor, and the temperature was raised to 50 ° C while stirring, and then 10 parts by weight of pure persulfate 2 parts by weight of pure water. The dissolved aqueous solution was added. As shown in Table 1 below, 5% of the total amount of N-phenylmaleimide, styrene, acrylonitrile and t-dodecyl mercaptan was added over 1 hour, and then the temperature inside the reactor was increased to 70 ° C. The remaining 9% was continuously added over 5 hours. After the addition was completed, the polymerization temperature was raised to 80 ℃ and aged for 5 hours to complete the polymerization.
중합이 완료된 다음 공중합체의 일부를 채취하고, 가스크로마토그래피를 이용하여 미반응 단량체를 정량하여 최종 중합율을 산출하였으며, 최종품의 라텍스를 염석 건조시켜 만든 파우더 1.5mg 을 채취하여 테트라하이드로퓨란 10ml에 용해시킨 후 일본 쇼덱스(Shodex)사 가스투과크로마토그래피(GPC : Gas Permeation Chromatography)를 사용하여 중량평균분자량(Mw) 및 분자량 분포(D)를 측정하였으며, 그 결과를 다음 표 1에 나타내었다.After the completion of the polymerization, a part of the copolymer was collected, and the final polymerization rate was calculated by quantifying the unreacted monomers using gas chromatography, and 1.5 mg of powder made by salt-drying the latex of the final product was taken and then, 10 ml of tetrahydrofuran was collected. After dissolving, the weight average molecular weight (Mw) and the molecular weight distribution (D) were measured using Gas Permeation Chromatography (GPC) from Shodex, Japan, and the results are shown in Table 1 below.
[표 1]TABLE 1
* 중량평균 분자량 / 수평균 분자량* Weight average molecular weight / Number average molecular weight
제조예 B : 그라프트 공중합체의 제조Preparation Example B: Preparation of Graft Copolymer
질소치환된 반응기에 순수 100 중량부 및 올레인산나트륨 0.5 중량부를 투입하고 교반하면서 반응기 내부온도를 70℃로 승온시킨 후, 5시간에 걸쳐서 다음 표 2에 나타낸 고무질 중합체, 스티렌, 메틸메타크릴레이트 및 아크릴로니트릴을 첨가하여 중합하였다.100 parts by weight of pure water and 0.5 parts by weight of sodium oleate were added to a nitrogen-substituted reactor, and the temperature of the reactor was raised to 70 ° C. while stirring, and the rubbery polymers, styrene, methyl methacrylate, and acrylic shown in the following Table 2 over 5 hours. Polymerization was carried out by the addition of ronitrile.
[표 2]TABLE 2
실시예 1∼6 및 비교예 1∼5Examples 1-6 and Comparative Examples 1-5
상기 제조예 및 제조비교예에 따라 제조된 페닐말레이미드계 공중합체와 그라프트중합체를 다음 표 3에 나타낸 바와 같은 비율로 배합한 후 염석하여 응고시킨 다음, 활제, 산화방지제 및 착색제를 첨가한 후 압출기로 용융혼련하여 펠렛을 얻었다. 얻어진 펠렛을 각종 시험편금형이 부착된 사출성형기로 제작한 후 물성을 측정하였으며, 그 결과는 다음 표 3에 나타낸 바와 같다. 또한, 중공성형기(일본프라코(주)DA-75형)를 사용하여 실린더 온도 210 ℃에서 원통형을 성형하였다. 이때, 1.5M, 3.5kg의 파리손(parison)은 30초이상 동안 드로우-다운이 없을 때 중공성형을 판정하였다. 또한, 대량샘플을 제작하여 자동차 에어스포일러(Air spoiler)를 성형하고 우레탄 도장을 실시하였다. 이때, 도장온도는 100℃이며, 2시간 이상 건조하였으며, 도장성, 성형품의 변형유무 및 광택도(반사각 60。, 표면광택)를 측정한 결과를 다음 표 3에 나타내었다.The phenylmaleimide-based copolymer and the graft polymer prepared according to Preparation Examples and Comparative Examples were mixed at a ratio as shown in the following Table 3, and then solidified by salting, followed by addition of a lubricant, an antioxidant, and a coloring agent. Melt kneading was carried out with an extruder to obtain pellets. The obtained pellets were manufactured by injection molding machine with various test specimen molds, and physical properties thereof were measured. The results are shown in Table 3 below. In addition, the cylindrical shape was shape | molded at the cylinder temperature of 210 degreeC using the blow molding machine (Japan-Praco DA-75 type | mold). At this time, 1.5M, 3.5kg of parison (parison) was determined blow molding when there is no draw-down for more than 30 seconds. In addition, a large sample was produced to mold an automobile air spoiler and perform urethane coating. At this time, the coating temperature is 100 ℃, dried for 2 hours or more, the results of measuring the paintability, deformation of the molded article and glossiness (reflection angle 60 °, surface gloss) is shown in Table 3 below.
여기서, 열변형온도는 ASTM D648에 의거한 방법으로 측정하였으며, 광택도는 ASTM D513에 의거한 방법으로 측정하였다.Here, the heat distortion temperature was measured by the method according to ASTM D648, glossiness was measured by the method according to ASTM D513.
[표 3]TABLE 3
(주) 1) 중공성형이 우수한 것의 순으로 ◎ ○ △ × ××,(Note) 1) In order of excellent blow molding ◎ ○ △ × × ×,
2) 변형량이 적은 것의 순으로 ◎ ○ △ × ××,2) In order of decreasing deformation amount ◎ ○ △ × × ×,
3) 광택도는 숫자가 높을수록 평활하고 도장성이 우수함3) The glossiness is smoother with higher number and excellent paintability
상기 표 3의 결과로부터 본 발명에 따라 제조된 열가소성 수지 조성물은 열변형온도가 높고 중공성형성이 우수하며 도장성이 우수함을 알 수 있다.From the results of Table 3, it can be seen that the thermoplastic resin composition prepared according to the present invention has a high heat deformation temperature, excellent hollow formability, and excellent paintability.
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