KR100706840B1 - Polycarbonate resin composition with improved flowability and impact-resistance - Google Patents

Polycarbonate resin composition with improved flowability and impact-resistance Download PDF

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KR100706840B1
KR100706840B1 KR1020010034408A KR20010034408A KR100706840B1 KR 100706840 B1 KR100706840 B1 KR 100706840B1 KR 1020010034408 A KR1020010034408 A KR 1020010034408A KR 20010034408 A KR20010034408 A KR 20010034408A KR 100706840 B1 KR100706840 B1 KR 100706840B1
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resin composition
polycarbonate resin
impact
present
weight
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KR20020096150A (en
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길현수
김성룡
김선웅
공태현
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주식회사 삼양사
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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
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters

Abstract

본 발명은 흐름성 및 내충격성이 향상된 폴리카보네이트 수지 조성물에 관한 것으로, 본 발명의 폴리카보네이트 수지 조성물은 폴리카보네이트 44.5~88.7 중량%, 유리섬유 10~40 중량%, 인계 가소제 0.2~5.0 중량%, 아크릴 고무계 충격보강제 1.0~10 중량% 및 열안정제 0.1~0.5 중량%로 이루어짐을 특징으로 한다.The present invention relates to a polycarbonate resin composition with improved flow and impact resistance, the polycarbonate resin composition of the present invention is 44.5 to 88.7 wt% polycarbonate, 10 to 40 wt% glass fiber, 0.2 to 5.0 wt% phosphorus plasticizer, It is characterized by consisting of 1.0 to 10% by weight of the acrylic rubber impact modifier and 0.1 to 0.5% by weight of the heat stabilizer.

Description

흐름성 및 내충격성이 향상된 폴리카보네이트 수지 조성물 {Polycarbonate resin composition with improved flowability and impact-resistance}Polycarbonate resin composition with improved flowability and impact-resistance

본 발명은 흐름성 및 내충격성이 향상된 폴리카보네이트(polycarbonate) 수지 조성물에 관한 것이다.The present invention relates to a polycarbonate resin composition having improved flow and impact resistance.

열가소성 수지 중 비스페놀 에이(Bisphenol A)의 폴리탄산에스테르 중합체인 폴리카보네이트는 뛰어난 내충격성, 전기적 성질 그리고 성형성을 가지며 넓은 온도 범위에서 그 물성을 유지할 수 있고 자기 소화성을 지닌 엔지니어링 플라스틱 소재로 다방면에 걸쳐 사용되고 있다.Polycarbonate, a polycarbonate ester polymer of bisphenol A, is an engineering plastic material with excellent impact resistance, electrical properties, and moldability, which can maintain its properties over a wide temperature range and is self-extinguishing. It is used.

이처럼 폴리카보네이트는 기계적 강성을 갖추고 있어 가전제품의 외장재 등 전기 전자 제품에 사용되나, 매우 높은 용융 점도를 가지고 있어 흐름성이 낮아 대형제품 및 복잡한 성형물 등에 적용하는데 어려움이 있다. 특히 강성을 증가시키기 위해 강화제로서 유리섬유를 첨가하는데, 유리섬유에 의해 흐름성이 더욱 저하되며 원래 우수했던 내충격성이 저하되고 제품 성형시 유리섬유가 표면에 돌출되어 깨끗한 외관을 얻기가 어려워지는 문제가 있다. As such, polycarbonate is used in electrical and electronic products such as exterior materials of home appliances due to its mechanical rigidity, but has a very high melt viscosity, which is difficult to apply to large products and complex moldings due to its low flowability. In particular, glass fiber is added as a reinforcing agent to increase rigidity, but the flowability is further reduced by the glass fiber, and the impact resistance, which was originally excellent, is lowered, and the glass fiber protrudes to the surface during product molding, making it difficult to obtain a clean appearance. There is.

이러한 문제점의 해결을 위해 폴리카보네이트의 용융 점도를 낮추기 위한 다 양한 첨가제들이 도입되었으나 일부를 제외하고는 그 효과가 그리 크지 않으며, 흐름성이 개선되는 경우 내충격성 등의 기계적 물성은 저하되는 것이 대부분이다.In order to solve this problem, various additives have been introduced to lower the melt viscosity of polycarbonate, but except for some of them, the effect is not so great. When the flowability is improved, mechanical properties such as impact resistance are mostly lowered. .

그러므로 강성을 증가시키기 위해 유리섬유가 첨가되어도 흐름성과 내충격성을 저하시키지 않고 성형시 깨끗한 외관을 얻게 함으로써, 폴리카보네이트의 장점은 최대한 살리고 약점은 보완된 수지 조성물에 대한 발명은 아직 과제로 남아있다.Therefore, even if the glass fiber is added to increase the rigidity to obtain a clean appearance during molding without deteriorating flowability and impact resistance, the invention for the resin composition that maximizes the advantages of the polycarbonate and the weaknesses are still a problem.

본 발명에서는 상기 과제를 달성하기 위해 인계 가소제를 사용하여 흐름성을향상시키고, 아크릴 고무계의 충격보강제를 첨가하여 내충격성을 보완하며, 더 나아가 제품 형성시 깨끗한 외관을 얻을 수 있는 폴리카보네이트 수지 조성물을 제공하는데 목적이 있다.In the present invention, in order to achieve the above object by using a phosphorus-based plasticizer to improve the flow properties, by adding an impact modifier of the acrylic rubber-based impact resistance, furthermore a polycarbonate resin composition that can obtain a clean appearance when forming a product The purpose is to provide.

본 발명은 우수한 흐름성을 가지면서도 내충격성이 보강된 폴리카보네이트 수지 조성물에 관한 것으로, 본 발명의 폴리카보네이트 수지 조성물은 폴리카보네이트 44.5~88.7 중량%, 유리섬유 10~40 중량%, 인계 가소제 0.2~5.0 중량%, 아크릴 고무계 충격보강제 1.0~10 중량% 및 열안정제 0.1~0.5 중량%로 이루어짐을 특징으로 한다.The present invention relates to a polycarbonate resin composition having excellent flowability and reinforced impact resistance, the polycarbonate resin composition of the present invention is 44.5 to 88.7% by weight of polycarbonate, 10 to 40% by weight of glass fiber, 0.2 ~ phosphorus plasticizer 5.0 wt%, acrylic rubber impact modifier 1.0-10 wt% and the heat stabilizer is characterized in that consisting of 0.1 to 0.5 wt%.

본 발명의 폴리카보네이트는 비스페놀 에이의 중합체로, 점도 평균 분자량은 15,000~35,000인 것이 바람직하며, 15,000 미만일 경우 강도가 취약하고, 35,000을 초과하면 가공온도가 높아져 성형에 어려움이 있다. Polycarbonate of the present invention is a polymer of bisphenol A, the viscosity average molecular weight is preferably 15,000 ~ 35,000, when less than 15,000, the strength is weak, when it exceeds 35,000, the processing temperature is high, there is difficulty in molding.                     

본 발명의 유리섬유는 폴리카보네이트 수지 조성물의 강성을 보완하기 위해 첨가되는 것으로, 고분자 사이에서 매우 강한 결합력을 유지하여 기계적 특성과 내마모성을 향상시키며, 내구성과 유연성을 지니고 있어 플라스틱 가공시 단단한 틀이 제작될 수 있게 한다. 본 발명의 유리섬유는 전체 수지 조성물 중에 10~40 중량%로 사용되며, 10 중량% 미만이면 요구되는 강성이 나타나지 않고, 40 중량%를 초과하면 수지의 가공이 어렵다.The glass fiber of the present invention is added to supplement the rigidity of the polycarbonate resin composition, maintains a very strong bonding force between the polymer to improve the mechanical properties and wear resistance, and has a durability and flexibility to produce a rigid mold during plastic processing To be possible. Glass fiber of the present invention is used in 10 to 40% by weight of the total resin composition, less than 10% by weight does not appear the required stiffness, and exceeds 40% by weight is difficult to process the resin.

본 발명의 인계 가소제는 폴리카보네이트 수지 조성물의 흐름성을 향상시키기 위한 것으로, 하기 화학식 1의 구조를 가진 인산 에스테르 화합물이다.The phosphorus plasticizer of the present invention is for improving the flowability of the polycarbonate resin composition, and is a phosphate ester compound having a structure represented by the following general formula (1).

Figure 112001031202160-pat00005
Figure 112001031202160-pat00005

상기 화학식에서 Ar1~Ar4는 크레실, 페닐, 자이렌, 프로필페닐 및 부틸페닐로 구성되는 군에서 선택된 하나이며, R은 아릴렌이고, n은 0~5의 정수이다. Ar 1 to Ar 4 in the above formula is one selected from the group consisting of cresyl, phenyl, xylene, propylphenyl and butylphenyl, R is arylene, n is an integer of 0-5.

본 발명에서는 상기와 같이 치환된 인계 가소제를 두 가지 이상 혼합하여 사용할 수도 있다. In the present invention, two or more substituted phosphorus plasticizers may be used as a mixture.                     

본 발명의 인계 가소제는 분자들 사이에 분자간력을 완화하여 고분자 물질의 경도와 점도를 바꾸는 등 그 물질의 성상을 용도에 따라 개선시킨다. 가소제의 첨가로 인해 고분자의 운동성이 증가되므로 용융온도가 저하되어 플라스틱의 유동성과 가공의 작업성을 증가시킨다. 특히 본 발명의 인계 가소제는 난연성과 내휘발성을 증대시키며, 전체 수지조성물 중에 0.2~5.0 중량%로 첨가된다. 인계 가소제의 함유량이 0.2% 중량 미만이면 흐름성이 개선되지 않는 반면, 5.0 중량%를 초과하면 성형품의 강도가 약해질 수가 있다.Phosphorus-based plasticizer of the present invention to improve the properties of the material, such as by changing the hardness and viscosity of the polymer material by relaxing the intermolecular force between the molecules. Due to the addition of plasticizers, the mobility of the polymer is increased, thereby lowering the melting temperature, thereby increasing the flowability of plastics and the workability of processing. In particular, the phosphorus-based plasticizer of the present invention increases flame retardancy and volatility, and is added in an amount of 0.2 to 5.0 wt% in the total resin composition. If the content of the phosphorus-based plasticizer is less than 0.2% by weight, the flowability is not improved, while if the content of the phosphorus plasticizer is more than 5.0% by weight, the strength of the molded article may be weakened.

본 발명의 아크릴 고무계 충격보강제는 플라스틱의 충격강도를 향상시켜 가공성을 촉진시키기 위한 것으로, 알킬 구조의 탄소수가 1∼6개인 알킬 아크릴레이트 고무를 성분으로 하며, 바람직하게는 탄소수가 4개인 부틸 구조의 부틸 아크릴레이트 고무를 사용한다. 충격보강제는 플라스틱의 압축 및 휨에 대한 저항력을 증진시켜 치수안정성을 높이는 첨가제로, 특히 본 발명에서 사용하는 아크릴 고무계 충격보강제는 내후성 및 내충격성을 증진시킨다. 본 발명의 아크릴 고무계 충격보강제는 전체 수지조성물 중에 1.0~10 중량%가 함유된다. 함유량이 1.0 중량% 미만의 경우 내충격성의 개선이 나타나지 않고, 10 중량%을 초과하면 강도가 저하될 수 있다. Acrylic rubber-based impact modifier of the present invention is to improve the impact strength of the plastic to promote workability, the alkyl acrylate rubber having 1 to 6 carbon atoms of the alkyl structure as a component, preferably of the butyl structure having 4 carbon atoms Butyl acrylate rubber is used. Impact reinforcing agent is an additive that increases the dimensional stability by increasing the resistance to compression and bending of plastics, in particular the acrylic rubber-based impact reinforcing agent used in the present invention improves weather resistance and impact resistance. The acrylic rubber impact modifier of the present invention contains 1.0 to 10% by weight in the total resin composition. If the content is less than 1.0% by weight, the impact resistance is not improved, and if the content is more than 10% by weight, the strength may be lowered.

본 발명의 열안정제는 가공 과정과 완성된 제품의 사용기간 중 수지의 물리적, 화학적 성질을 유지하도록 도와주는 화합물로, 하기 화학식 2의 구조를 가진다. The heat stabilizer of the present invention is a compound that helps to maintain the physical and chemical properties of the resin during the processing and the service life of the finished product, and has a structure of formula (2).                     

Figure 112001014560359-pat00002
Figure 112001014560359-pat00002

플라스틱의 혼합 및 제조 등의 조작은 고온에서 이루어지기 때문에 열안정제 없이는 심하게 분해된다. 본 발명의 열안정제는 전체 수지조성물 중에 0.1~0.5 중량%로 함유되며, 함유량이 0.1 중량% 미만이면 열안정 효과를 기대할 수 없고, 0.5 중량%를 초과하면 더 이상의 향상이 없게 된다. Since operations such as mixing and manufacturing of plastics are performed at high temperature, they are severely decomposed without a heat stabilizer. The heat stabilizer of the present invention is contained in 0.1 to 0.5% by weight in the total resin composition, if the content is less than 0.1% by weight can not be expected thermal stability effect, if it exceeds 0.5% by weight there is no further improvement.

이외에도 본 발명의 폴리카보네이트 수지 조성물에는 조색제, 윤활제, 자외선 안정제, 난연제 또는 산화 방지제 등을 추가로 첨가하여 다양한 용도로 응용할 수 있다.In addition to the polycarbonate resin composition of the present invention, a colorant, a lubricant, an ultraviolet stabilizer, a flame retardant, an antioxidant, or the like may be further added, which may be applied to various applications.

이하 본 발명은 실시예에 의거하여 더욱 상세히 설명하며, 본 발명이 실시예에 의해 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to Examples, and the present invention is not limited by Examples.

[실시예 1~4 및 비교예 1~2][Examples 1-4 and Comparative Examples 1-2]

본 발명의 폴리카보네이트 수지 조성물에 대해 흐름성 및 내충격성이 향상되는지 확인하기 위해 표 1의 조성비에 따라 실시예와 비교예의 폴리카보네이트 수지 조성물을 제조하였다. 인계 가소제로 레소시놀 비스 디페닐 포스페이트(Resorcinol -bis (diphenyl phosphate))를, 아크릴 고무계 충격보강제로 부틸 아크릴레이트 고무를, 그리고 열안정제로 힌더드 페놀(hindered phenol)계 열안정제를 사용하였다. In order to confirm whether the flowability and impact resistance of the polycarbonate resin composition of the present invention is improved, the polycarbonate resin compositions of Examples and Comparative Examples were prepared according to the composition ratios of Table 1. Resorcinol-bis (diphenyl phosphate) was used as a phosphorus plasticizer, butyl acrylate rubber was used as an acrylic rubber impact modifier, and a hindered phenol type heat stabilizer was used as a heat stabilizer.                     

폴리카보네이트 (중량%)Polycarbonate (% by weight) 유리섬유 (중량%)Fiberglass (wt%) 레소시놀 비스 디페닐 포스페이트 (중량%)  Resorcinol Bis Diphenyl Phosphate (% by weight) 부틸 아크레 이트 고무 (중량%)Butyl Acreate Rubber (wt%) 힌더드 페놀계 열안정제 (중량%)Hindered phenolic heat stabilizer (wt%) 실시예 1 실시예 2 실시예 3 실시예 4Example 1 Example 2 Example 3 Example 4 84.7 74.7 64.7 54.784.7 74.7 64.7 54.7 10 20 30 4010 20 30 40 2.0 2.0 2.0 2.02.0 2.0 2.0 2.0 3.0 3.0 3.0 3.03.0 3.0 3.0 3.0 0.3 0.3 0.3 0.3     0.3 0.3 0.3 0.3 비교예 1 비교예 2Comparative Example 1 Comparative Example 2 66.7 67.766.7 67.7 30 3030 30 0 2.00 2.0 3.0 03.0 0 0.3 0.3     0.3 0.3

각 예에 있어 290℃에서 압출가공한 후, 300℃에서 사출성형하여 제작한 시편을 ASTM규격에 의거하여 물성을 측정하였다. 용융지수는 300 ℃에서 2.16 kg의 조건으로 측정하였으며, 제품의 외관의 양호정도는 육안으로 평가하였다. 측정한 물성 평가 결과는 표 2에 나타내었다. In each case, the physical properties of the specimens produced by extrusion molding at 290 ° C. and then injection molded at 300 ° C. were measured in accordance with ASTM standards. Melt index was measured under the condition of 2.16 kg at 300 ℃, and good appearance of the product was visually evaluated. The measured property evaluation results are shown in Table 2.

용융지수 (g/10min)Melt Index (g / 10min) 아이조드 충격강도 (㎏㎝/㎝)Izod impact strength (㎏㎝ / ㎝) 인장강도 (㎏/㎠)Tensile Strength (㎏ / ㎠) 굴곡강도 (㎏/㎠)Flexural Strength (㎏ / ㎠) 외관 Exterior 실시예 1 실시예 2 실시예 3 실시예 4Example 1 Example 2 Example 3 Example 4 9.0 8.0 7.0 6.09.0 8.0 7.0 6.0 14.0 15.0 16.0 15.814.0 15.0 16.0 15.8 950 1,150 1,300 1,500950 1,150 1,300 1,500 1,300 1,600 1,900 2,1501,300 1,600 1,900 2,150 양호 양호 양호 양호Good good good good 비교예 1 비교예 2Comparative Example 1 Comparative Example 2 2.5 7.52.5 7.5 12.0 8.012.0 8.0 1,100 1,2001,100 1,200 1,500 1,9501,500 1,950 불량 불량Bad bad

표 2에 나타난 바와 같이 실시예 1~4는 우수한 용융지수와 함께 아이조드 충격강도, 인장강도 및 굴곡강도 등의 기계적 강성이 모두 유지되는 것을 알 수 있었다. 이에 비하여 인계 가소제를 첨가하지 않은 비교예 1은 용융지수가 현저히 감소하였고, 인계 가소제를 사용하였으나 충격보강제를 사용하지 않은 비교예 2는 용융지수는 우수하지만 아이조드 충격강도가 현저히 감소하였다. As shown in Table 2, Examples 1 to 4 were found to maintain all of the mechanical stiffness such as Izod impact strength, tensile strength and flexural strength with excellent melt index. On the other hand, Comparative Example 1, in which no phosphorus-based plasticizer was added, significantly decreased the melt index, and Comparative Example 2, which used a phosphorus-based plasticizer but did not use an impact modifier, had a good melt index but significantly decreased the Izod impact strength.

본 발명의 폴리카보네이트 수지 조성물은 폴리카보네이트 수지에 인계 가소제 및 아크릴 고무계의 충격보강제를 혼합하여, 보강제로 첨가된 유리섬유에 의해 흐름성 및 내충격성이 떨어지는 것을 막고 성형 후 유리섬유에 의해 제품의 외관이 불량해지는 것을 방지하는 효과가 있다.The polycarbonate resin composition of the present invention is mixed with a polycarbonate resin and a phosphor-based plasticizer and an acrylic rubber impact modifier to prevent the flow and impact resistance of the glass fiber added as a reinforcing agent, and the appearance of the product by the glass fiber after molding There is an effect of preventing this defect.

그러므로 본 발명의 폴리카보네이트 수지 조성물을 사용할 때 기계적 강성이 더욱 강화되면서 동시에 다소 부족했던 흐름성이 우수해져 성형 가공성이 보완되는 효과를 기대할 수 있으며, 이러한 특성을 이용하여 전기 전자 제품 등의 외장재로 유용하게 사용할 수 있다. Therefore, when the polycarbonate resin composition of the present invention is used, the mechanical rigidity is further enhanced, and at the same time, the flowability which is somewhat lacked is excellent, and the molding workability can be expected to be effective. Can be used.

Claims (6)

폴리카보네이트 44.5~88.7 중량%, 유리섬유 10~40 중량%, 하기 화학식 1의 구조를 갖는 인계 가소제 0.2~5.0 중량%, 아크릴 고무계 충격보강제 1.0~10 중량% 및 하기 화학식 2의 구조를 갖는 열안정제 0.1~0.5 중량%로 이루어짐을 특징으로 하는 폴리카보네이트 수지 조성물;Polycarbonate 44.5 ~ 88.7 wt%, glass fiber 10-40 wt%, phosphorus plasticizer having the structure of formula (1) 0.2 ~ 5.0 wt%, acrylic rubber impact modifier 1.0-10 wt% and heat stabilizer having the structure of formula (2) Polycarbonate resin composition characterized in that consisting of 0.1 to 0.5% by weight; [화학식 1][Formula 1]
Figure 112007003738215-pat00007
Figure 112007003738215-pat00007
 상기 화학식에서 Ar1~Ar4는 크레실, 페닐, 자이렌, 프로필페닐 및 부틸페닐로 구성되는 군에서 선택된 하나이며, R은 아릴렌이고, n은 0~5의 정수이다.Ar 1 to Ar 4 in the above formula is one selected from the group consisting of cresyl, phenyl, xylene, propylphenyl and butylphenyl, R is arylene, n is an integer of 0-5. [화학식 2][Formula 2]
Figure 112007003738215-pat00008
Figure 112007003738215-pat00008
 삭제delete 제 1항에 있어서, 상기와 같이 치환된 인계 가소제를 두 가지 이상 혼합하여 사용하는 것을 특징으로 하는 폴리카보네이트 수지 조성물.The polycarbonate resin composition according to claim 1, wherein two or more substituted phosphorus-based plasticizers are mixed and used. 제 1항에 있어서, 아크릴 고무계 충격보강제는 알킬 구조의 탄소수가 1∼6개인 알킬 아크릴레이트 고무임을 특징으로 하는 폴리카보네이트 수지 조성물.The polycarbonate resin composition according to claim 1, wherein the acrylic rubber impact modifier is an alkyl acrylate rubber having 1 to 6 carbon atoms of an alkyl structure. 삭제delete 삭제delete
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Publication number Priority date Publication date Assignee Title
KR960001029A (en) * 1994-06-30 1996-01-25 유현식 Thermoplastic resin composition having flame retardancy
JPH0912858A (en) * 1995-07-05 1997-01-14 Mitsubishi Eng Plast Kk Glass-fiber-reinforced polycarbonate resin composition
JPH0948912A (en) * 1995-08-07 1997-02-18 Nippon G Ii Plast Kk Polycarbonate resin composition
KR19980044595A (en) * 1996-12-07 1998-09-05 유현식 High fluidity polycarbonate-based thermoplastic resin composition
KR20010009104A (en) * 1998-07-10 2001-02-05 유현식 Flame retardant thermoplastic resin composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR960001029A (en) * 1994-06-30 1996-01-25 유현식 Thermoplastic resin composition having flame retardancy
JPH0912858A (en) * 1995-07-05 1997-01-14 Mitsubishi Eng Plast Kk Glass-fiber-reinforced polycarbonate resin composition
JPH0948912A (en) * 1995-08-07 1997-02-18 Nippon G Ii Plast Kk Polycarbonate resin composition
KR19980044595A (en) * 1996-12-07 1998-09-05 유현식 High fluidity polycarbonate-based thermoplastic resin composition
KR20010009104A (en) * 1998-07-10 2001-02-05 유현식 Flame retardant thermoplastic resin composition

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