KR20000026954A - Thermoplastic resin composition - Google Patents

Thermoplastic resin composition Download PDF

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KR20000026954A
KR20000026954A KR1019980044719A KR19980044719A KR20000026954A KR 20000026954 A KR20000026954 A KR 20000026954A KR 1019980044719 A KR1019980044719 A KR 1019980044719A KR 19980044719 A KR19980044719 A KR 19980044719A KR 20000026954 A KR20000026954 A KR 20000026954A
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resin
weight
thermoplastic resin
polycarbonate resin
polycarbonate
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KR1019980044719A
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Korean (ko)
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KR100435519B1 (en
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양승관
류민영
권영도
방태훈
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김윤
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
    • C08K5/49—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
    • 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

PURPOSE: A thermoplastic resin composition comprising an acrylonitrile-butadiene-styrene resin and a polycarbonate resin as a main composition is provided which has improved fluidity as well as heat resistance and mechanical physical properties. CONSTITUTION: A thermoplastic resin composition comprises 20 to 80% by weight of a Carbonari-butadiene-styrene resin and 20 to 80% by weight of a polycarbonate resin containing 50 to 100% by weight of a branched polycarbonate having a viscosity-average molecular weight of 12,000 to 25,000 and a melt index ratio of above 13 as a main composition. The composition is useful as a use for a housing of electronic articles requested for thin thickness such as a hand-held mobile phone, a battery, a hand-held computer, and an electronic pocket notebook.

Description

열가소성 수지 조성물Thermoplastic resin composition

본 발명은 열가소성 수지 조성물에 관한 것으로서, 더욱 상세하게는 아크릴로니트릴-부타디엔-스티렌 수지와 폴리카보네이트 수지를 주성분으로 하되, 상기 폴리카보네이트 수지에는 점도평균분자량(Mv)이 12,000∼25,000 이고 용융토출량비(MIR, Melt Index Ratio)가 13 이상인 분지상 폴리카보네이트 수지가 50∼100 중량% 함유됨으로써 사출성형과 같은 높은 전단속도 영역에서 점도의 떨어짐 현상(shear thinning effect)을 극대화시켜 유동성이 크게 개선되고 내열성, 기계적 물성이 우수하여 박판 부품 성형에 유용한 열가소성 수지 조성물에 관한 것이다.The present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition comprising an acrylonitrile-butadiene-styrene resin and a polycarbonate resin as main components, wherein the polycarbonate resin has a viscosity average molecular weight (Mv) of 12,000 to 25,000 and a melt flow rate (MIR) of 13 or more is contained in an amount of 50 to 100% by weight, thereby maximizing the shear thinning effect at a high shear rate region such as injection molding, And a thermoplastic resin composition which is excellent in mechanical properties and is useful for forming a thin plate part.

일반적으로 폴리카보네이트 수지는 비스페놀 A와 포스겐을 반응시켜 제조하며, 유리전이온도(Tg)는 주로 155℃ 범위를 갖는다. 이러한 폴리카보네이트 수지는 높은 충격강도, 수지 안정성 및 광학적 특성을 나타내는 열안정성 고분자의 장점을 지니고 있어서 투명성이 요구되는 건축자재용 방음벽, 창문, 그리고 먼지 오염이 적게 요구되는 렌즈용으로 사용되고 있다.Generally, polycarbonate resin is prepared by reacting bisphenol A with phosgene, and its glass transition temperature (Tg) is mainly in the range of 155 ° C. These polycarbonate resins have the advantages of heat-stable polymers that exhibit high impact strength, resin stability and optical properties, and thus are used for building materials such as soundproof walls, windows, and dust-less lenses that require low transparency.

그러나 폴리카보네이트 수지는 상기한 바와 같은 우수한 물리적 성질을 가지고 있음에도 불구하고 유동성이 부족하여 전자 제품 등에 사용되는 박판 부품을 성형하는 데에는 많은 문제점을 가지고 있다.However, although the polycarbonate resin has excellent physical properties as described above, it lacks fluidity and has many problems in forming a thin plate component used in electronic products.

또한, 폴리카보네이트 수지의 유동성을 개선하기 위한 방법으로서 히드록실기로 반응 종결된 지방족 폴리카보네이트 수지를 일부 첨가하는 방법[미국특허 제4,826,918호]과 알킬페닐기로 반응 종결된 폴리카보네이트 수지를 사용하는 방법[미국특허 제4,515,921호]이 공지되어 있다.As a method for improving the flowability of a polycarbonate resin, there is a method of partially adding an aliphatic polycarbonate resin terminated with a hydroxyl group (US Pat. No. 4,826,918) and a method using a polycarbonate resin terminated by an alkylphenyl group [U.S. Patent No. 4,515,921] is known.

이에 본 발명자들은 열가소성 수지 조성물중에 아크릴로니트릴-부타디엔-스티렌 수지와 함께 주성분으로 함유되는 폴리카보네이트 수지의 유동성을 개선시키고자 노력하였다. 그 결과, 분자량 분포가 넓은 분지상 폴리카보네이트 수지를 사용하는 경우 사출성형과 같은 높은 전단속도 영역에서 점도의 떨어짐 현상(shear thinning effect)이 극대화되는 점을 이용하여 폴리카보네이트 수지의 유동성을 크게 증가시킬 수 있음을 알게 되었고, 또한 이러한 특성은 폴리카보네이트 수지의 조성에 의해 좌우되는 것임을 알게 됨으로써 본 발명을 완성하였다.Accordingly, the present inventors have made efforts to improve the fluidity of the polycarbonate resin as a main component together with the acrylonitrile-butadiene-styrene resin in the thermoplastic resin composition. As a result, when the branched polycarbonate resin having a wide molecular weight distribution is used, the flowability of the polycarbonate resin is greatly increased by maximizing the shear thinning effect at a high shear rate region such as injection molding And that these properties are dependent on the composition of the polycarbonate resin, thereby completing the present invention.

따라서, 본 발명에서는 아크릴로니트릴-부타디엔-스티렌 수지와 폴리카보네이트 수지를 주성분으로 하는 열가소성 수지 조성물에 있어, 특정 점도평균분자량(Mv)과 용융토출량비(MIR, Melt Index Ratio)를 가지는 분지상의 폴리카보네이트 수지를 배합 사용함으로써, 유동성이 크게 개선되어 박판 부품 성형에 특히 유용한 열가소성 수지 조성물을 제공하는데 그 목적이 있다.Accordingly, the present invention provides a thermoplastic resin composition comprising as a main component an acrylonitrile-butadiene-styrene resin and a polycarbonate resin, wherein the thermoplastic resin composition has a specific viscosity average molecular weight (Mv) and a melt flow rate ratio (MIR) It is an object of the present invention to provide a thermoplastic resin composition which is particularly useful for forming a thin plate component by greatly improving the fluidity by mixing and using a polycarbonate resin.

본 발명은 아크릴로니트릴-부타디엔-스티렌 수지와 폴리카보네이트 수지를 주성분으로 하는 열가소성 수지 조성물에 있어서, 아크릴로니트릴 부타디엔 스티렌 수지 20~80 중량%와 폴리카보네이트 수지 20∼80 중량%로 구성하되, 폴리카보네이트 수지에는 점도평균분자량(Mv)이 12,000∼25,000 이고 용융토출량비(MIR, Melt Index Ratio)가 13 이상인 분지상 폴리카보네이트 수지가 50∼100 중량% 포함된 열가소성 수지 조성물을 그 특징으로 한다.The present invention provides a thermoplastic resin composition comprising an acrylonitrile-butadiene-styrene resin and a polycarbonate resin as main components, wherein the thermoplastic resin composition comprises 20 to 80% by weight of an acrylonitrile butadiene styrene resin and 20 to 80% by weight of a polycarbonate resin, The carbonate resin includes a thermoplastic resin composition containing 50 to 100% by weight of a branched polycarbonate resin having a viscosity average molecular weight (Mv) of 12,000 to 25,000 and a melt index ratio (MIR) of 13 or more.

본 발명을 더욱 상세히 설명하면 다음과 같다.The present invention will be described in more detail as follows.

본 발명에 따른 열가소성 수지는 아크릴로니트릴-부타디엔-스티렌 수지와 분지상 폴리카보네이트 수지가 포함된 폴리카보네이트 수지를 주성분으로 함으로써 점도의 떨어짐 현상(shear thinning effect)을 극대화하여 유동성을 개선시키는데 특징이 있다.The thermoplastic resin according to the present invention is characterized by maximizing the shear thinning effect and improving the flowability by using a polycarbonate resin containing an acrylonitrile-butadiene-styrene resin and a branched polycarbonate resin as a main component .

본 발명의 열가소성 수지에 주성분으로 사용되는 아크릴로니트릴-부타디엔-스티렌 수지는 디엔계고무의 존재하에 시안화비닐 화합물과 방향족 비닐 화합물을 중합시켜 얻은 그라프트 공중합체이다. 아크릴로니트릴-부타디엔-스티렌 수지와 폴리카보네이트 수지의 조성비에 있어, 아크릴로니트릴-부타디엔-스티렌 수지의 함량이 20중량% 미만이면 저온 내충격성 및 가공성의 개선 효과가 미약하고, 80중량%를 초과하면 내열성 및 기계적 물성이 저하된다.The acrylonitrile-butadiene-styrene resin used as a main component in the thermoplastic resin of the present invention is a graft copolymer obtained by polymerizing a vinyl cyanide compound and an aromatic vinyl compound in the presence of a diene rubber. When the content of the acrylonitrile-butadiene-styrene resin is less than 20% by weight in the composition ratio of the acrylonitrile-butadiene-styrene resin and the polycarbonate resin, the effect of improving low-temperature impact resistance and workability is weak, The heat resistance and mechanical properties are lowered.

특히, 본 발명은 폴리카보네이트 수지의 조성에 가장 큰 특징이 있는 바, 점도평균분자량(Mv)이 12,000∼25,000 이고 용융토출량비(MIR, Melt Index Ratio)가 13 이상인 분지상 폴리카보네이트 수지는 전체 폴리카보네이트 수지중 50∼100 중량% 범위로 포함시키는 것이 바람직하다. 만약, 폴리카보네이트 수지중에 함유되는 분지상 폴리카보네이트 수지 함량이 50 중량% 미만이면 본 발명이 목적으로 하는 유동성 개선 효과를 얻을 수 없는 문제가 있다. 본 발명이 폴리카보네이트 수지에 포함시키는 분지상 폴리카보네이트 수지의 분자량 분포는 3∼5이며, 이러한 넓은 분자량 분포를 얻기 위해서 각각 다른 3종 이상의 분지상 폴리카보네이트 수지를 혼련 압출하는데 이때 분자량 3,000∼8,000의 폴리카보네이트 올리고머를 10 중량% 이하로 첨가하는 것이 바람직하다. 또한, 분지상 폴리카보네이트 수지의 점도평균분자량(Mv)이 12,000∼25,000 범위 미만이면 기계적·열적 물성이 극히 나쁘며, 상기 범위 이상이면 유동성이 저하되어 수지 가공에 문제가 발생한다.Particularly, the polycarbonate resin of the present invention has the most characteristic feature. The polycarbonate resin having a viscosity average molecular weight (Mv) of 12,000 to 25,000 and a melt index ratio (MIR) of 13 or more is a poly It is preferable that the amount is in the range of 50 to 100% by weight in the carbonate resin. If the content of the branched polycarbonate resin contained in the polycarbonate resin is less than 50% by weight, there is a problem that the aimed improvement of fluidity is not obtained. The branched polycarbonate resin included in the polycarbonate resin of the present invention has a molecular weight distribution of 3 to 5. To obtain such a broad molecular weight distribution, three or more different branched polycarbonate resins are kneaded and extruded. In this case, It is preferable to add polycarbonate oligomer in an amount of 10% by weight or less. If the viscosity average molecular weight (Mv) of the branched polycarbonate resin is less than the range of 12,000 to 25,000, the mechanical and thermal properties are extremely poor. If the viscosity average molecular weight (Mv) is in the above range, the flowability is lowered and problems occur in resin processing.

한편, 본 발명의 수지 조성물에는 산화방지제, 열안정제, 광안정제, 활제, 난연제, 가소제, 대전방지제, 항균제, 충격보강제, 착색제, 이형제, 소광제 등 일반적으로 사용되는 여러 유형의 첨가제들이 함께 사용될 수 있다.Meanwhile, various kinds of commonly used additives such as an antioxidant, a heat stabilizer, a light stabilizer, a lubricant, a flame retardant, a plasticizer, an antistatic agent, an antibacterial agent, an impact modifier, a colorant, a releasing agent and a quencher may be added to the resin composition of the present invention have.

본 발명에서는 상기와 같은 수지 조성물을 이용하여 상기 조성물을 210∼260℃의 온도에서 이축용융혼련압출기로 혼련압출하여 성형용 펠렛을 제조하고 이를 열풍건조한 후, 사출성형기로 성형하여 유동성이 매우 우수한 열가소성 수지를 제조한다.In the present invention, the above-mentioned resin composition is used to knead extrudate the above composition at a temperature of 210 to 260 DEG C by a twin-screw melt kneading extruder to produce a molding pellet, which is hot-air dried and molded by an injection molding machine, To prepare a resin.

상기한 바와 같이, 본 발명에 따른 열가소성 수지는 유동성이 매우 우수하면서도 내열성, 기계적물성이 우수하여 개인이동통신단말기, 배터리, 노트북PC, 전자수첩등 박판 부품 성형에 매우 유용하다.As described above, the thermoplastic resin according to the present invention has excellent fluidity and excellent heat resistance and mechanical properties, and is very useful for forming thin plate parts such as personal mobile communication terminals, batteries, notebook PCs, and electronic notebooks.

이와 같은 본 발명을 실시예에 의거하여 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 한정되는 것은 아니다.The present invention will now be described in detail with reference to the following examples, but it should not be construed as being limited thereto.

실시예 1 ∼ 2 및 비교예 1 ∼ 2Examples 1 to 2 and Comparative Examples 1 to 2

다음 표 1에 나타낸 조성물과 함량으로 210∼260℃의 온도에서 이축용융혼련압출기로 혼련압출하여 성형용 펠렛을 제조한 다음, 120℃에서 5시간동안 열풍건조한 후, 230∼260℃의 온도로 사출성형하여 시편을 제조하였다.Kneaded and extruded by a twin screw extruder at a temperature of 210 to 260 DEG C in the composition and contents shown in the following Table 1 to prepare molding pellets and then hot air dried at 120 DEG C for 5 hours and then extruded at 230 to 260 DEG C The specimens were molded.

실험예Experimental Example

상기 실시예 및 비교예에서는 제조한 시편에 대하여 내충격성, 아이조드충격강도, 인장강도, 굴곡강도, 내열성, 나선흐름길이를 측정하고 그 결과를 다음 표 1에 나타내었다. 내충격성은 ASTM D526에 의한 1/8인치 아이조드 시편의 충격강도로서, 기계적성질은 ASTM D638 및 D792에 의한 인장강도와 굴곡강도로서, 그리고 내열성은 ASTM D648에 의하되 18.6㎏의 하중을 적용하여 측정, 평가하였고, 또한 나선 흐름 길이(Spiral flow length)는 배럴온도 260℃, 금형온도 60℃에서 80㎏·f/㎠의 사출압력으로 사출했을 때 측정된 값이다.In the examples and comparative examples, impact resistance, Izod impact strength, tensile strength, flexural strength, heat resistance and spiral flow length were measured and the results are shown in Table 1 below. Impact resistance is the impact strength of 1/8-inch zzodo specimen according to ASTM D526. The mechanical properties are measured as tensile strength and flexural strength according to ASTM D638 and D792, and heat resistance is measured and evaluated by applying load of 18.6 kg according to ASTM D648 And the spiral flow length was a value measured at an injection pressure of 80 kgf / cm 2 at a barrel temperature of 260 ° C and a mold temperature of 60 ° C.

구 분 (중량%)Category (% by weight) 실시예1Example 1 실시예2Example 2 비교예1Comparative Example 1 비교예2Comparative Example 2 PC1) PC 1) 5050 6060 -- -- PC2) PC 2) 2020 -- 7070 -- PC3) PC 3) -- -- -- 6060 ABS 수지ABS resin 3030 4040 3030 4040 산화방지제Antioxidant 0.25phr0.25 phr 0.25phr0.25 phr 0.25phr0.25 phr 0.25phr0.25 phr Spiral flow length(㎝)Spiral flow length (cm) 2424 2626 1111 66 아이조드충격강도Izod impact strength 7878 7575 7575 8080 인장강도(㎏·f/㎠)Tensile strength (kg · f / cm 2) 600600 600600 605605 590590 굴곡강도(㎏·f/㎠)Flexural Strength (kgf / cm2) 800800 802802 809809 813813 굴곡탄성율(㎏·f/㎠)Flexural modulus (kg · f / cm 2) 21,90021,900 22,30022,300 21,72021,720 22,14022,140 열변형온도(℃)Heat deformation temperature (캜) 110110 108108 111111 114114 1) : 점도평균분자량 23,000, 분자량분포 2.2 인 선형 폴리카보네이트수지2) : 점도평균분자량 18,000, 용융토출량비 14, 분자량분포 4.5 인분지상 폴리카보네이트 수지3) : 점도평균분자량 29,000, 용융토출량비 14, 분자량분포 2.4 인분지상 폴리카보네이트 수지ABS수지 : (주)효성바스프, Teluran 967K산화방지제 : 일본 동도화성, YOSHINOX SR1): linear polycarbonate resin having a viscosity average molecular weight of 23,000 and a molecular weight distribution of 2.2 2) a viscosity-average molecular weight of 18,000, a melt flow rate ratio of 14, a molecular weight distribution of 4.5, a terpolymeric polycarbonate resin having a viscosity average molecular weight of 29,000, Molecular weight distribution 2.4 parts Terrestrial polycarbonate resin ABS resin: Hyosung BASF Co., Teluran 967K Antioxidant: Japan Dongdo Mars, YOSHINOX SR

상술한 바와 같이 본 발명에 따른 열가소성 수지는 아크릴로니트릴-부타디엔-스티렌 수지와 폴리카보네이트 수지를 주성분으로 하되, 점도평균분자량(Mv)이 12,000 ∼ 25,000 이고, 용융토출량비(MIR, Melt Index Ratio)가 13 이상인 분지상 폴리카보네이트 수지를 혼합 사용함으로써, 유동성이 매우 우수하면서도 내열성, 기계적 물성이 우수하여 개인이동통신단말기, 배터리, 노트북PC, 전자수첩등 얇은 두께가 요구되어지는 전자제품 하우징 용도에 적합하다.As described above, the thermoplastic resin according to the present invention mainly comprises acrylonitrile-butadiene-styrene resin and polycarbonate resin, and has a viscosity average molecular weight (Mv) of 12,000 to 25,000, a melt index ratio (MIR) Is superior in fluidity and excellent in heat resistance and mechanical properties, and is suitable for use in an electronic product housing where a thin thickness is required such as a personal mobile communication terminal, a battery, a notebook PC, and an electronic notebook, by mixing a ground polycarbonate resin Do.

Claims (3)

아크릴로니트릴-부타디엔-스티렌 수지와 폴리카보네이트 수지를 주성분으로 하는 열가소성 수지에 있어서, 아크릴로니트릴-부타디엔-스티렌 수지 20∼80 중량%, 폴리카보네이트 수지 20∼80 중량%로 구성되며, 폴리카보네이트 수지에는 점도평균분자량(Mv)이 12,000∼25,000 이고 용융토출량비(MIR, Melt Index Ratio)가 13 이상인 분지상 폴리카보네이트 수지가 50∼100 중량% 함유됨을 특징으로 하는 열가소성 수지 조성물A thermoplastic resin consisting essentially of an acrylonitrile-butadiene-styrene resin and a polycarbonate resin, wherein the thermoplastic resin comprises 20 to 80% by weight of an acrylonitrile-butadiene-styrene resin and 20 to 80% by weight of a polycarbonate resin, (Mv) of 12,000 to 25,000 and a branched polycarbonate resin having a melt flow rate ratio (MIR) of 13 or more is contained in an amount of 50 to 100% by weight based on the total weight of the thermoplastic resin composition 제 1항에 있어서, 상기 분지상 폴리카보네이트 수지는 분자량 분포가 3∼5 인 것임을 특징으로 하는 열가소성 수지 조성물The thermoplastic resin composition according to claim 1, wherein the branched polycarbonate resin has a molecular weight distribution of 3 to 5 제 1항에 있어서, 상기 분지상 폴리카보네이트 수지는 분자량 3,000∼8,000의 폴리카보네이트 올리고머를 10 중량% 이하로 첨가하고 혼련압출하여 제조된 것임을 특징으로 하는 열가소성 수지 조성물The thermoplastic resin composition according to claim 1, wherein the branched polycarbonate resin is prepared by adding 10% by weight or less of a polycarbonate oligomer having a molecular weight of 3,000 to 8,000 and kneading and extruding the polycarbonate oligomer.
KR10-1998-0044719A 1998-10-24 1998-10-24 Thermoplastic resin composition KR100435519B1 (en)

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* Cited by examiner, † Cited by third party
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