KR100440917B1 - Low-gloss thermoplastic resin composition using copolymer having cyclic iminoether branch as mattifying agent - Google Patents
Low-gloss thermoplastic resin composition using copolymer having cyclic iminoether branch as mattifying agent Download PDFInfo
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- KR100440917B1 KR100440917B1 KR1019960024162A KR19960024162A KR100440917B1 KR 100440917 B1 KR100440917 B1 KR 100440917B1 KR 1019960024162 A KR1019960024162 A KR 1019960024162A KR 19960024162 A KR19960024162 A KR 19960024162A KR 100440917 B1 KR100440917 B1 KR 100440917B1
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- 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
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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Abstract
Description
본 발명은 저광택 열가소성 수지 조성물에 관한 것으로서, 더욱 상세하게는 폴리카보네이트(이하, PC라 함)수지와 아크릴로니트릴-부타디엔-스티렌 공중합체(이하, ABS라 함)수지의 혼합시에 사이클릭이미노에테르 관능기를 곁가지로 갖는 공중합체를 소광제로 사용함으로써 기계적 강도, 내열성 및 충격강도 등의 저하없이 현저한 소광효과를 나타낼 수 있는 열가소성 수지 조성물에 관한 것이다.The present invention relates to a low-gloss thermoplastic resin composition, and more particularly, to a cyclic resin when mixing a polycarbonate (hereinafter referred to as PC) resin and an acrylonitrile-butadiene-styrene copolymer (hereinafter referred to as ABS) resin. The present invention relates to a thermoplastic resin composition capable of exhibiting a significant matting effect without deterioration in mechanical strength, heat resistance and impact strength by using a copolymer having a minoether functional group as a matting agent.
일반적으로 열가소성 수지의 성형품, 특히 PC와 ABS 혼합수지는 높은 표면광택도를 나타내며 이는 플라스틱 성형품의 장점이 되기도 하지만 특정용도에서는 시각장애를 유발하는 등 단점으로 작용하기도 한다. 예를들어, 자동차 내장재, 컴퓨터 터미널, 사무기기 및 전기·전자제품의 하우징 등의 용도에서는 시각장애 효과의 제거 및 고급스런 분위기의 연출을 위하여 저광택의 표면이 요구된다.In general, molded products of thermoplastics, in particular, PC and ABS mixed resins exhibit high surface gloss, which may be an advantage of plastic molded products, but may also cause disadvantages such as causing visual impairment in certain applications. For example, in applications such as automobile interiors, computer terminals, office equipment, and housings of electrical and electronic products, low gloss surfaces are required for eliminating visual impairment effects and creating a luxurious atmosphere.
이와같은 요구에 부응하기 위한 수지성형품의 표면광택을 줄이기 위한 방법으로 미국특허 제 4,460,733 호 및 제 4,987,174 호에는 실리카, 실리케이트 또는 알루미나 등의 무기충진제를 첨가하는 방법이 개시된 바 있으나, 그 소광효과가 미미하고 소광효과의 증대를 위해서 첨가제의 함량을 늘렸을 때 충격강도와 같은 기계적 물성이 저하되며 유동성이 급격히 감소하는 치명적 단점을 나타내었다. 이와 같은 문제점을 해결하기 위해서 고분자량의 유기소광제를 첨가하는 방법이 제안된 바 있으나, 충격강도 뿐만 아니라 열변형온도나 광안정성 등 다른 중요한 물성의 저하를 유발시키는 문제점을 가지고 있었다.As a method for reducing the surface gloss of resin molded articles to meet such demands, US Pat. Nos. 4,460,733 and 4,987,174 disclose methods of adding inorganic fillers such as silica, silicate, or alumina, but the matting effect thereof is insignificant. In addition, when the additive content is increased to increase the matting effect, mechanical properties such as impact strength are lowered, and fluidity decreases rapidly. In order to solve such a problem, a method of adding a high molecular weight organic quencher has been proposed, but it has a problem of inducing not only impact strength but also other important physical properties such as heat deformation temperature and light stability.
고분자량의 유기소광제를 첨가하는 방법중에서는 글리시딜 관능기를 갖는 중합체를 첨가하는 방법이 제안된 바 있으며, 그 예로는 미국특허 제 5,026,777 호, 제 4,902,745 호, 제 5,354,796 호, 제 4,885,336 호, 제 5,369,172 호, 제 5,369,154 호, 제 4,994,416 호, 제 5,430,101 호 제 5,336,111 호 및 제 5,395,889 호 등이 있다. 그러나 상기한 고분자량의 유기소광제는 가공중에 가교반응을 유발하여 유동성을 악화시키는 문제점과 함께 가공조건에 의해 광택도의 변화가 심하다는 단점이 있다.Among the methods of adding a high molecular weight organic quencher, a method of adding a polymer having a glycidyl functional group has been proposed, and examples thereof include US Pat. Nos. 5,026,777, 4,902,745, 5,354,796, 4,885,336, 5,369,172, 5,369,154, 4,994,416, 5,430,101 5,336,111 and 5,395,889. However, the high molecular weight organic quencher has a problem that the glossiness is severely changed by the processing conditions together with the problem of deteriorating fluidity by causing a crosslinking reaction during processing.
따라서, 본 발명자는 상기와 같은 종래의 열가소성 수지의 문제점을 해결하기 위하여, 높은 표면광택 특성을 보이는 PC와 ABS의 혼합물에 사이클릭이미노에테르(cyclic iminoether) 관능기를 곁가지로 갖는 공중합체를 첨가한 결과 기계적 강도, 열변형온도 및 충격강도 등의 저하없이 현저한 소광효과를 나타낸다는 것을 알게되어 본 발명을 완성하였다.Accordingly, the present inventors have added a copolymer having a cyclic iminoether functional group to a mixture of PC and ABS that exhibits high surface gloss characteristics in order to solve the problems of the conventional thermoplastic resin as described above. As a result, the present invention was found to exhibit a remarkable matting effect without deterioration in mechanical strength, heat deformation temperature, impact strength, and the like.
본 발명은 수지의 기계적 강도, 열변형온도 및 충격강도 등 물성의 저하없이 우수한 소광효과를 나타낼 수 있는 열가소성 수지 조성물을 제공하는 데 그 목적이 있다.An object of the present invention is to provide a thermoplastic resin composition that can exhibit an excellent matting effect without deterioration of physical properties such as mechanical strength, heat deformation temperature and impact strength of the resin.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 PC수지와 ABS수지를 주성분으로 하고 소광제로서 공중합체 수지가 첨가된 열가소성 수지 조성물에 있어서, 상기 주성분 수지 100 중량부에 대하여 다음 구조식의 공중합체를 0.5∼20 중량부 함유하는 것을 그 특징으로 한다.The present invention relates to a thermoplastic resin composition containing a PC resin and an ABS resin as a main component and to which a copolymer resin is added as a quencher, wherein the copolymer containing 0.5 to 20 parts by weight of the copolymer of the following structural formula is contained with respect to 100 parts by weight of the main component resin. It features.
상기 식에서, R1, R2, R3및 R4는 메틸기 또는 수소원자이고; R5는 C1∼2의 알킬기, 할로겐 원자 또는 수소원자이고; R6은 C1∼2의 알킬기, 아릴, 알킬아릴 또는 수소원자이고; n은 0 또는 1이고; a, b, c 및 d는 반복단위 개수 비를 나타내는 것으로 a는 1∼50%, b는 0∼99%, c는 0∼50%, d는 0∼50%이며, 단, a+b+c+d는 100%이다.Wherein R 1 , R 2 , R 3 and R 4 are methyl groups or hydrogen atoms; R 5 is C 1-2 alkyl group, halogen atom or hydrogen atom; R 6 is a C 1-2 alkyl group, aryl, alkylaryl or hydrogen atom; n is 0 or 1; a, b, c and d represent the ratio of the number of repeating units, where a is 1 to 50%, b is 0 to 99%, c is 0 to 50%, and d is 0 to 50%, provided that a + b + c + d is 100%.
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명은 소광제로서 사이클릭이미노에테르기를 곁가지로 갖는 공중합체를 첨가함으로써 우수한 소광효과를 나타내는 열가소성 수지 조성물에 관한 것이다.The present invention relates to a thermoplastic resin composition exhibiting excellent matting effect by adding a copolymer having a cyclic imino ether group as a matting agent.
본 발명에서 PC수지는 주성분 수지중 10∼90 중량%로 함유되는 바, 바람직하기로는 20∼80 중량%이다. 만일, 그 함량이 10 중량% 미만이면 내열성이 나쁘고, 90 중량%를 초과하면 최종 조성물의 용융점도의 상승으로 가공성이 좋지 않게 된다.In the present invention, the PC resin is contained in 10 to 90% by weight of the main component resin, preferably 20 to 80% by weight. If the content is less than 10% by weight, the heat resistance is bad, and if the content exceeds 90% by weight, the workability is not good due to the increase of the melt viscosity of the final composition.
그리고, 본 발명에서의 PC는 점도분자량이 15,000∼30,000의 것을 사용하는 것이 바람직한 바, 그 점도분자량이 15,000 미만이면 기계적 물성이 극히 나쁘고, 30,000을 초과하는 경우에는 수지의 가공에 문제를 초래한다.In the present invention, it is preferable that a viscosity molecular weight of 15,000 to 30,000 is used in the PC. If the viscosity molecular weight is less than 15,000, the mechanical properties are extremely bad, and if the viscosity exceeds 30,000, a problem occurs in processing of the resin.
한편, ABS수지는 디엔계 고무의 존재하에서 시안화비닐화합물과 방향족비닐화합물을 중합시켜 얻은 그라프트 공중합체로서, 주성분 수지중 10∼90 중량%로 함유되는데 그 함량이 10 중량% 미만이면 내충격성 및 가공성의 개선효과가 미약하고, 90 중량%를 초과하면 내열성이 저하된다.On the other hand, ABS resin is a graft copolymer obtained by polymerizing a vinyl cyanide compound and an aromatic vinyl compound in the presence of a diene rubber, and is contained in 10 to 90% by weight of the main component resin, and if the content is less than 10% by weight, the impact resistance and The improvement effect of workability is insignificant, and when it exceeds 90 weight%, heat resistance will fall.
또한, 본 발명에서 새롭게 사용하고 있는 상기 구조식의 공중합체는 비닐계 단량체들이 고분자 주쇄의 성분을 이루며 사이클릭이미노에테르(cyclic iminoether)를 곁가지로 갖는 공중합체로서 괴상, 현탁 또는 유화중합 등과 같은 일반적인 비닐계 단량체들의 중합방법에 의하여 얻을 수 있다.In addition, the copolymer of the structural formula newly used in the present invention is a copolymer in which the vinyl monomers form a component of the polymer main chain and have a cyclic iminoether aside, such as a bulk, suspension or emulsion polymerization. It can be obtained by a polymerization method of vinyl monomers.
상기 구조식으로 나타내는 공중합체의 효과적인 함량은 상기 주성분수지 100 중량부에 대하여 0.5∼20 중량부이며, 그 함량이 0.5 중량부 미만이면 소광효과가 불충분하고, 20 중량부를 초과하면 유동성과 기계적 물성의 약화를 초래하고 가격이 상승한다.The effective amount of the copolymer represented by the above structural formula is 0.5 to 20 parts by weight based on 100 parts by weight of the main component resin, the content is less than 0.5 parts by weight of the matting effect is insufficient, if the content exceeds 20 parts by weight weakened fluidity and mechanical properties Causes the price to rise.
그밖에, 본 발명의 수지 조성물에는 일반적인 플라스틱 수지 조성물에 사용되는 여러 유형의 첨가제들이 추가되어질 수 있다. 예를들면, 산화방지제, 열안정제, 광안정제, 활제, 난연제, 가소제, 대전방지제, 항균제, 충격보강제, 착색제 또는 이형제 등이 포함된다.In addition, various types of additives used in the general plastic resin composition may be added to the resin composition of the present invention. For example, antioxidants, heat stabilizers, light stabilizers, lubricants, flame retardants, plasticizers, antistatic agents, antibacterial agents, impact modifiers, colorants or release agents and the like.
상기와 같은 조성의 성분들을 이용하여 열가소성 수지 성형물을 제조하는 방법은, 이들 조성을 210∼250 ℃의 온도에서 이축용융혼련 압출기로 혼련압출하여 성형용 펠렛을 제조한 후 이를 열풍건조하고 사출성형기로 성형한다.Method for producing a thermoplastic resin molding using the components of the composition as described above, by kneading and extruding these compositions in a twin-screw melt kneading extruder at a temperature of 210 ~ 250 ℃ to produce a pellet for molding and hot-air dried and molded into an injection molding machine do.
상술한 바와 같은 본 발명에 의한 열가소성 수지 조성물은 내열성, 내충격성이 우수하고 제반물성이 균형을 이루며 별도공정의 추가없이도 표면광택을 현저히 감소시켜 시각장애 효과의 감소 및 우아한 분위기가 연출되므로 자동차의 내장재, 사무기기나 전기·전자제품들의 외장재와 같은 분야에 매우 유용하게 사용될 수 있다.As described above, the thermoplastic resin composition according to the present invention has excellent heat resistance and impact resistance, balances various physical properties, and significantly reduces surface gloss without adding a separate process, thereby reducing visual impairment effects and creating an elegant atmosphere. It can be very useful in fields such as office equipment or exterior materials of electrical and electronic products.
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.
실시예 1~5, 비교예 1~3Examples 1-5, Comparative Examples 1-3
다음 표에 나타낸 조성 및 함량으로 210∼250℃의 온도에서 이축용융혼련 압출기로 혼련압출하여 성형용 펠렛을 제조하고, 120℃에서 5시간 열풍건조한 후 230∼260℃의 온도로 사출성형하여 시편을 성형하고 각각의 물성을 평가하였으며, 그 결과는 다음 표와 같다.The pellets for molding were prepared by kneading and extruding with a twin screw melt kneading extruder at a temperature of 210 to 250 ° C. according to the composition and content shown in the following table.Then, the specimen was formed by injection molding at a temperature of 230 to 260 ° C. Molding and evaluation of the respective properties, the results are shown in the following table.
여기서, 각각의 물성평가는 ASTM 규격에 의하되 표면광택도의 측정은 ASTM D-523에 의한 60° 각도에서의 측정치로서, 내충격성은 ASTM D-526에 의한 1/8 인치 아이조드 시편의 충격강도로서, 기계적 성질은 ASTM D-638 및 D-792에 의한 인장강도와 굴곡강도·굴곡탄성율로서, 그리고 내열성은 ASTM D-648에 의하되 18.6kg의 하중을 적용하여 측정 및 평가하였다.Here, each property evaluation is based on ASTM standards, but the measurement of surface glossiness is measured at an angle of 60 ° according to ASTM D-523, and the impact resistance is the impact strength of the 1/8 inch Izod specimen according to ASTM D-526. Mechanical properties were measured by tensile strength and flexural strength and flexural modulus according to ASTM D-638 and D-792, and heat resistance was measured and evaluated by applying a load of 18.6kg according to ASTM D-648.
(3) (3)
상기 구조식에서, R1=메틸이고, R=R3=R4=R5=수소이고, R6=메틸이고, n=0이고, 반복단위 개수 비로서 a, b, c 및 d가 각각 a= 5%, b= 70%, c= 21%, d= 4%인 공중합체Wherein R 1 = methyl, R = R 3 = R 4 = R 5 = hydrogen, R 6 = methyl, n = 0 and a, b, c and d are each a = 5%, b = 70%, c = 21%, d = 4%
(4) 상기 구조식에서 R1=R2=R3=R4=R5=수소이고, R6=메틸이고, n=1이고, 반복단위 개수 비로서 a, b, c 및 d가 각각 a= 5%, b= 70%, c= 25%, d= 0%인 공중합체(4) wherein R 1 = R 2 = R 3 = R 4 = R 5 = hydrogen, R 6 = methyl, n = 1 and a, b, c and d are each a = 5%, b = 70%, c = 25%, d = 0%
(5) YOSHINOX-SR, 일본 동도화성 제품(5) YOSHINOX-SR, Japan Dodo Chemical
상기 표의 결과로부터 본 발명에서와 같이 상기 구조식의 공중합체를 소광제로서 첨가한 경우 충격강도, 인장강도, 굴곡강도, 굴곡탄성율 및 열변형온도 등 물성의 저하가 없으면서도 표면광택이 현저하게 감소함을 알 수 있다.From the results of the table, when the copolymer of the above structural formula is added as a matting agent as in the present invention, the surface gloss is remarkably reduced without deterioration of physical properties such as impact strength, tensile strength, flexural strength, flexural modulus and heat deformation temperature. It can be seen.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019960024162A KR100440917B1 (en) | 1996-06-26 | 1996-06-26 | Low-gloss thermoplastic resin composition using copolymer having cyclic iminoether branch as mattifying agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019960024162A KR100440917B1 (en) | 1996-06-26 | 1996-06-26 | Low-gloss thermoplastic resin composition using copolymer having cyclic iminoether branch as mattifying agent |
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| Publication Number | Publication Date |
|---|---|
| KR980002149A KR980002149A (en) | 1998-03-30 |
| KR100440917B1 true KR100440917B1 (en) | 2004-11-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1019960024162A KR100440917B1 (en) | 1996-06-26 | 1996-06-26 | Low-gloss thermoplastic resin composition using copolymer having cyclic iminoether branch as mattifying agent |
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| Country | Link |
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| KR (1) | KR100440917B1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0375941A2 (en) * | 1988-12-27 | 1990-07-04 | General Electric Company | Low gloss thermoplastic blends |
| US5274034A (en) * | 1991-06-19 | 1993-12-28 | General Electric Company | Polycarbonate polystyrene composition |
| KR960001022A (en) * | 1994-06-12 | 1996-01-25 | 성재갑 | Thermoplastic resin composition with excellent moldability and low gloss |
| KR100204463B1 (en) * | 1996-06-28 | 1999-06-15 | 김윤 | Thermoplastic resin compositions |
| KR100245948B1 (en) * | 1994-08-31 | 2000-03-02 | 성재갑 | Low gloss, high thermal stable and light stable thermoplastic resin composition |
-
1996
- 1996-06-26 KR KR1019960024162A patent/KR100440917B1/en not_active IP Right Cessation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0375941A2 (en) * | 1988-12-27 | 1990-07-04 | General Electric Company | Low gloss thermoplastic blends |
| US5274034A (en) * | 1991-06-19 | 1993-12-28 | General Electric Company | Polycarbonate polystyrene composition |
| KR960001022A (en) * | 1994-06-12 | 1996-01-25 | 성재갑 | Thermoplastic resin composition with excellent moldability and low gloss |
| KR100245948B1 (en) * | 1994-08-31 | 2000-03-02 | 성재갑 | Low gloss, high thermal stable and light stable thermoplastic resin composition |
| KR100204463B1 (en) * | 1996-06-28 | 1999-06-15 | 김윤 | Thermoplastic resin compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| KR980002149A (en) | 1998-03-30 |
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