KR100189393B1 - Process for manufacturing thermoplastic resins with high impact resistance and transparency - Google Patents
Process for manufacturing thermoplastic resins with high impact resistance and transparency Download PDFInfo
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- KR100189393B1 KR100189393B1 KR1019960064666A KR19960064666A KR100189393B1 KR 100189393 B1 KR100189393 B1 KR 100189393B1 KR 1019960064666 A KR1019960064666 A KR 1019960064666A KR 19960064666 A KR19960064666 A KR 19960064666A KR 100189393 B1 KR100189393 B1 KR 100189393B1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- C08F2/12—Polymerisation in non-solvents
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- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/44—Acrylonitrile
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- 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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Abstract
본 발명은 내충격성 및 투명성이 우수한 열가소성 수지의 제조방법에 관한 것으로, 좀더 자세하게는 메틸메타크릴레이트-아크릴로니트릴-부타디엔-스티렌공중합물의 제조방법에 관한 것이다.The present invention relates to a method for producing a thermoplastic resin excellent in impact resistance and transparency, and more particularly, to a method for producing a methyl methacrylate-acrylonitrile-butadiene-styrene copolymer.
본 발명의 목적은 투명성, 내충격성, 내약품성, 성형성 및 경제성이 우수한 메틸메타크릴레이트-아크릴로니트릴-부타디엔-스티렌 수지의 새로운 제조방법을 제공함에 있다.An object of the present invention is to provide a new method for preparing methyl methacrylate-acrylonitrile-butadiene-styrene resin having excellent transparency, impact resistance, chemical resistance, moldability and economical efficiency.
즉, 본 발명은 중량평균입경이 0.2∼0.5㎛이고 스티렌과 부타디엔의 함량이 각각 1∼30 중량 % 및 70∼99 중량%인 스티렌-부타디엔 고무 라텍스 40∼70 중량부에 메틸메타크릴레이트와 스티렌 및 아크릴로니트릴 단량체 혼합물 30∼60 중량부를 그라프트 중합시켜 얻은 라텍스와 메틸메타크릴레이트-스티렌-아크릴로니트릴 유화중합물 라텍스의 함량비가 각각 30∼50 중량% 및 50∼70 중량%가 되게 중합·성형하여 메틸메타크릴레이트-아크릴로니트릴-부타디엔-스티렌 수지를 제조함을 특징으로 한다.That is, the present invention is methyl methacrylate and styrene in the 40 to 70 parts by weight of styrene-butadiene rubber latex having a weight average particle diameter of 0.2 to 0.5㎛ and styrene and butadiene content of 1 to 30% by weight and 70 to 99% by weight, respectively. And polymerizing so that the content ratio of the latex obtained by graft polymerization of 30 to 60 parts by weight of the acrylonitrile monomer mixture and the methyl methacrylate-styrene-acrylonitrile emulsion latex is 30 to 50% by weight and 50 to 70% by weight, respectively. It is characterized by producing a methyl methacrylate-acrylonitrile-butadiene-styrene resin by molding.
본 발명에 의해 제조된 메틸메타크릴레이트-아크릴로니트릴-부타디엔-스티렌 공중합체 수지는 투명성, 내충격성, 내약품성, 성형성 및 경제성이 우수한 열가소성 수지로서, 화장품용기, 복사기 및 팩시밀리 부품, 가전제품 부품, 필기구 및 서류보관함 등의 사출성형용 수지로 범용적으로 사용될 수 있다.Methyl methacrylate-acrylonitrile-butadiene-styrene copolymer resin prepared by the present invention is a thermoplastic resin excellent in transparency, impact resistance, chemical resistance, moldability and economical efficiency, cosmetic containers, copiers and facsimile parts, home appliances It can be used universally as resin for injection molding of parts, writing instruments and filing cabinets.
Description
본 발명은 내충격성 및 투명성이 우수한 열가소성 수지의 제조방법에 관한 것으로, 좀더 상세하게는 메틸메타크릴레이트-아크릴로니트릴-부타디엔-스티렌 공중합물의 제조방법에 관한 것이다.The present invention relates to a method for producing a thermoplastic resin excellent in impact resistance and transparency, and more particularly, to a method for producing a methyl methacrylate-acrylonitrile-butadiene-styrene copolymer.
열가소성 투명 고분자의 발전단계는 크게 3단계로 나눌 수 있다. 제 1 단계의 수지는 폴리스티렌, 폴리염화비닐로서 투명성과 성형가공성은 우수하지만, 내충격성과 열안정성이 떨어지는 단점이 있다. 특히 폴리염화비닐은 최근 대두되는 환경보호 차원에서 사용에 많은 제약을 받고 있는 실정이다. 제 2단계 투명성 고분자는 스티렌-아크릴로니트릴 공중합물, 폴리메틸메타크릴레이트로서 투명성, 내열성, 내약품성은 우수하지만 내충격성이 떨어지는 단점이 있다. 제 3단계 투명 고분자로는 폴리카보네이트와 메틸메타크릴레이트-아크릴로니트릴-부타디엔-스티렌 공중합물이 있는데, 폴리카보네이트는 투명성, 기계적·열적 특성은 우수하지만 성형성이 떨어져 경제성에 문제가 있다.The development stage of the thermoplastic transparent polymer can be largely divided into three stages. The resin of the first step is polystyrene and polyvinyl chloride, which is excellent in transparency and moldability, but has a disadvantage in that impact resistance and thermal stability are poor. In particular, polyvinyl chloride is currently being restricted to use in view of environmental protection. The second stage of the transparent polymer is a styrene-acrylonitrile copolymer and polymethyl methacrylate, which is excellent in transparency, heat resistance, and chemical resistance, but is poor in impact resistance. The third transparent polymer is a polycarbonate and a methyl methacrylate-acrylonitrile-butadiene-styrene copolymer. Polycarbonate has excellent transparency, mechanical and thermal properties, but has poor moldability, which may cause economic problems.
투명 메틸메타크릴레이트-아크릴로니트릴-부타디엔-스티렌 공중합물 제조를 위해서는 연속상과 불연속상의 굴절률 차이가 0.004에서 0.006 사이가 되도록 조절하며, 고무입자의 크기는 가능한 작게 하여야 하는데, 이 경우의 문제점으로는 굴절률의 조절이 넓은 온도 범위에 대해 정확성을 얻을 수 없을 뿐만 아니라, 분산상 크기의 감소는 내충격성을 저하시키며, 가공온도에 따라 투명도의 변화가 발생한다는 것 등을 들 수 있다.In order to prepare a transparent methyl methacrylate-acrylonitrile-butadiene-styrene copolymer, the refractive index difference between the continuous phase and the discontinuous phase is controlled to be 0.004 to 0.006, and the size of the rubber particles should be as small as possible. Not only does the control of the refractive index not achieve accuracy over a wide temperature range, but the decrease in the size of the dispersed phase lowers the impact resistance, and the change in transparency occurs depending on the processing temperature.
반면에, 투명 메틸메타크릴레이트-아크릴로니트릴-부타디엔-스티렌 공중합물은 투명성, 내충격성, 내약품성, 성형성, 경제성이 우수하다는 장점을 지닌다.On the other hand, the transparent methyl methacrylate-acrylonitrile-butadiene-styrene copolymer has the advantage of excellent transparency, impact resistance, chemical resistance, moldability, and economy.
본 발명자 들은 상기한 메틸메타크릴레이트-아크릴로니트릴-부타디엔스티렌 공중합물의 단점을 최소화하면서 장점을 극대화시킬 수 있는 방법을 찾아 내기 위하여 연구를 수행하던 중, 연속상과 불연속상의 굴절률의 조절 및 투명도의 변화에 적당한 온도, 스티렌-부타디엔 고무 라텍스의 중량평균입경 및 각 공정단계에서의 조성비 및 분자량의 최적조건을 알아내고 본발명을 완성하였다.The inventors of the present invention, while conducting research to find a method that can maximize the advantages while minimizing the disadvantages of the methyl methacrylate-acrylonitrile-butadiene styrene copolymer described above, the control of the refractive index and the transparency of the continuous and discontinuous phase The present invention was completed by finding the optimum temperature, the weight average particle diameter of the styrene-butadiene rubber latex and the composition ratio and molecular weight at each process step.
따라서, 본 발명의 목적은 투명성, 내충격성, 내약품성, 성형성 및 경제성이 우수한 메틸메타크릴레이트-아크릴로니트릴-부타디엔-스티렌 수지의 새로운 제조 방법을 제공함에 있다.Accordingly, an object of the present invention is to provide a novel method for preparing methyl methacrylate-acrylonitrile-butadiene-styrene resin having excellent transparency, impact resistance, chemical resistance, moldability, and economy.
즉, 본 발명은 중량평균입경이 0.2∼0.5㎛이고 스티렌과 부타디엔의 함량이 각각 1∼30 중량% 및 70∼99 중량%인 스티렌-부타디엔 고무 라텍스 40∼70 중량부에 메틸메타크릴레이트와 스티렌 및 아크릴로니트릴 단량체 혼합물 30∼60 중량부를 그라프트 중합시켜 얻은 라텍스와 메틸메타크릴레이트-스티렌-아크릴로니트릴 유화중합물 라텍스의 함량비가 각각 30∼50 중량% 및 50∼70 중량%가 되게 중합·성형하여 메틸메타크릴레이트-아크릴로니트릴-부타디엔-스티렌수지를 제조함을 특징으로 한다.That is, in the present invention, methyl methacrylate and styrene are present in 40 to 70 parts by weight of styrene-butadiene rubber latex having a weight average particle diameter of 0.2 to 0.5 µm and styrene and butadiene contents of 1 to 30% by weight and 70 to 99% by weight, respectively. And polymerizing so that the content ratio of the latex obtained by graft polymerization of 30 to 60 parts by weight of the acrylonitrile monomer mixture and the methyl methacrylate-styrene-acrylonitrile emulsion latex is 30 to 50% by weight and 50 to 70% by weight, respectively. It is characterized in that the methyl methacrylate-acrylonitrile-butadiene-styrene resin is produced by molding.
단량체, 이온교환수, 1차유화제, 개시제, 분자량조절제, 가교제를 넣어 내부온도 30℃∼60℃로 승온하여 유화중합을 개시한 후 6∼8시간 경과 후 반응전환율이 25∼30%일 때 2차 유화제로 투입하여 중합을 계속 진행한다. 14시간동안 중합을 하면 반응 전환율이 98%이상이며 라텍스가 안정된 0.1∼0.2㎛ 크기의 고무입자를 갖는 메틸메타크릴레이트-아크릴로니트릴-부타디엔-스티렌 공중합물용의 고무 라텍스가 제조가능하다. 이때 얻어진 고무 라텍스의 겔함량은 80∼90 중량%가 되도록 한다. 고무입자가 0.2㎛ 이상의 크기를 갖으면 충격강도는 높으나 투명성이 떨어지며, 반대로 0.1㎛ 이하이면 투명성은 좋으나 충격강도가 낮아지는 결점이 있다.When monomer, ion-exchanged water, primary emulsifier, initiator, molecular weight regulator, and crosslinking agent were added, the temperature was raised to 30 ° C to 60 ° C and the emulsion conversion was started after 6-8 hours. The polymerization is continued by adding a secondary emulsifier. When the polymerization is carried out for 14 hours, a rubber latex for methyl methacrylate-acrylonitrile-butadiene-styrene copolymer having a rubber particle having a reaction conversion of 98% or more and having a stable latex size of 0.1 to 0.2 µm can be produced. The gel content of the rubber latex thus obtained is 80 to 90% by weight. If the rubber particles have a size of 0.2 μm or more, the impact strength is high, but the transparency is low.
입자비대화제로 사용하는 고분자공중합체는 수용성인 아크릴산, 메타크릴산, 아크릴아마이드, 메틸아크릴아미드등 1종 혹은 2종이상 혼합물 1∼30 중량부와 고무계 단량체인 부틸아크릴레이트, 에틸아크릴레이트, 1,3-부타디엔등의 1종 혹은 2종이상 혼합물 70∼99 중량부로 구성되며 라텍스의 pH는 2∼4이며 점도는 30cps 이하인 것을 특징으로 한다.The polymer copolymer used as the particle thickening agent is 1 to 30 parts by weight of one or two or more mixtures of water-soluble acrylic acid, methacrylic acid, acrylamide, methylacrylamide and butyl acrylate, ethyl acrylate, 1, It is composed of 70 to 99 parts by weight of one kind or a mixture of two or more kinds of 3-butadiene, etc. The pH of the latex is characterized in that the viscosity is 30cps or less.
상기 고분자라텍스를 제조함에 있어서 극성기를 함유한 수용성의 아크릴산, 메타크릴산, 아크릴아미드, 메타아크릴아미드등의 단량체가 고무계 단량체인 부틸아크릴레이트, 에틸아크릴레이트, 1,3-부타디엔 표면에 편재되어 소입경의 합성 고무라텍스입자의 안정성저하로 인한 응집물이 발생하지 않은 상태에서 부착시키는 역할을 하고 있다. 이때 고분자라텍스를 제조함에 있어서 유화제는 알킬벤젠소다계로 도데실벤젠설포네이트, 라우릴벤젠설포네이트, 리니어 알킬설포네이트 등의 1종이상 혼합물의 수용액으로 제조하여 사용하는 것이 바람직하며, 첨가 유화제량은 0.5∼2.0 중량부를 첨가하며 이 범위의 첨가량으로 저점도의 라텍스를 얻을 수 있다. 또한 제조된 라텍스의 pH가 2∼4일 때 입자비대화시킬 고무라텍스의 준화학적 안정상태로 떨어뜨리는 역할을 하고 있다. 수용성 단량체가 1중량부 이하이면 고무입자의 서로간의 부착효과가 떨어지므로 입자비대화제 공중합체의 첨가량을 많이 투입하여야 하는 문제점이 있으며, 30중량부이상을 첨가하면 입자부착효과는 높아지나 라텍스의 점도 상승 및 중합율저하가 발생하며 특히 입자비대화시 응집물발생이 쉬우며 소기의 원하는 입자경분포를 갖는 입자를 얻기 어렵다.In preparing the polymer latex, monomers such as water-soluble acrylic acid, methacrylic acid, acrylamide and methacrylamide containing polar groups are localized on the surface of butyl acrylate, ethyl acrylate and 1,3-butadiene, which are rubber monomers. It acts to attach in a state in which aggregates do not occur due to the deterioration in stability of the particle size of the synthetic rubber latex particles. At this time, in preparing the polymer latex, the emulsifier is preferably used as an aqueous solution of at least one mixture of dodecylbenzenesulfonate, laurylbenzenesulfonate, linear alkylsulfonate and the like, based on alkylbenzene soda. 0.5 to 2.0 parts by weight can be added, and a low viscosity latex can be obtained with the addition amount in this range. In addition, when the pH of the prepared latex is 2-4, it plays a role of dropping the semi-chemically stable state of the rubber latex to enlarge the particles. If the water-soluble monomer is less than 1 part by weight, the adhesion effect of the rubber particles is reduced, so there is a problem that a large amount of the particle thickener copolymer is added. If more than 30 parts by weight is added, the particle adhesion effect is increased but the viscosity of the latex is increased. A rise and a decrease in the polymerization rate occur, especially when aggregates are apt to generate aggregates, and it is difficult to obtain particles having a desired particle size distribution.
입자비대화 방법은 입경이 0.15㎛ 이하이며 겔함량이 50∼90 중량%인 고무질중합체 라텍스 100 중량부에 알킬벤젠소다계로 도데실벤젠설포네이트, 라우릴벤젠설포네이트, 리니어 알킬설포네이트 등의 1종 이상 혼합물의 0.05∼0.50 중량부를 순수에 고형분이 10∼20%로 희석하여 제조된 유화용액을 첨가한 후 입자비대화제인 공중합체라텍스를 0.8∼2.5 중량부를 서서히 첨가하여 입자비대화된 고무의 크기가 90 중량% 이상이 0.2∼0.5㎛ 범위 안에 있는 고무질중합체를 얻으며 수산화 칼륨, 수산화나트륨 등 알카리 0.5∼1.0 중량부를 순수로 희석된 고형분이 5∼20% (w/v)인 알칼리수용액을 첨가하여 재차안정화를 시키는 절차를 거치는 입자비대화방법이다.Particle enlargement method is one kind of dodecylbenzenesulfonate, laurylbenzenesulfonate, linear alkylsulfonate, etc. based on alkylbenzene soda in 100 parts by weight of a rubbery polymer latex having a particle size of 0.15 탆 or less and a gel content of 50 to 90% by weight. After adding 0.05 ~ 0.50 parts by weight of the above mixture to the pure water, an emulsion solution prepared by diluting the solid content by 10-20% was added, followed by gradually adding 0.8 ~ 2.5 parts by weight of copolymer latex, which is a particle thickening agent, to increase the size of the rubber. It is stabilized again by adding an alkaline aqueous solution containing 5-20% (w / v) of solid content diluted with pure water to obtain rubbery polymer having a weight percentage of 0.2 to 0.5 µm or more and alkali hydroxides such as potassium hydroxide and sodium hydroxide. It is a method of particle enlargement through the procedure of.
본 발명에서 스태렌-부타디엔 고무 라텍스 중합에 사용되는 유화제는 통상적인 유화중합에 사용되는 유화제로서 나트륨도데실설페이트, 나트륨도데실벤젠설페이트, 나트륨올레익설페이트, 칼륨도데실설페이트, 칼륨스테아레이트, 나트륨스테아레이트, 나트륨올레이트, 로진지방산염등을 들 수 있으며 그 양은 1∼3 중량부가 사용된다.In the present invention, the emulsifiers used in the polymerization of the styrene-butadiene rubber latex are sodium dodecyl sulfate, sodium dodecylbenzene sulfate, sodium oleic sulfate, potassium dodecyl sulfate, potassium stearate, sodium as an emulsifier used in conventional emulsion polymerization. Stearate, sodium oleate, rosin fatty acid salt, etc., and the amount is used in an amount of 1 to 3 parts by weight.
본 발명에서 스티렌-부타디엔 고무 라텍스 중합에 사용되는 단량체는 디엔계 단량체와 방향족단량체 및 탄소수 1∼8의 아크릴산에스테르, 탄소수 1∼8의 메타크릴산알킬에스테르, 비닐시아닌계에서 선택한 1종 또는 2종 이상의 혼합단량체의 혼합물로서 구체적으로는 1,3-부타디엔, 이소프렌, 부틸아크릴레이트, 스티렌, 알파메틸스티렌, 메틸메타크릴레이트, 에틸아크릴레이트, 부틸메타크릴레이트 등을 들 수 있는데 그 첨가량은 디엔계 단량체 100∼70 중량부와 방향족 단량체 및 탄소수 1∼8의 아크릴산에스테르, 탄소수 1∼8의 메타크릴산알킬에스테르, 비닐시아닌계에서 선택한 1종 또는 2종 이상의 혼합단량체 0∼30 중량부로 구성되는데, 디엔계 단량체가 70 중량부이하이면 저온충격성이 낮다. 본 발명에 사용되는 가교제는 1,3-부탄디올디아크릴레이트, 1,3-부탄디올메타크리레이트, 디비닐벤젠, 에틸렌글리콜디아크릴레이트, 부틸렌글리콜 디아크릴레이트, 부틸렌글리콜디메타크릴레이트 등을 들 수 있으며 그 양은 0.2∼3.0 중량부이다.In the present invention, the monomers used for the styrene-butadiene rubber latex polymerization are selected from diene monomers and aromatic monomers, acrylic esters of 1 to 8 carbon atoms, alkyl esters of methacrylic acid of 1 to 8 carbons, and vinyl cyanine. Specific examples of the mixture of mixed monomers of more than one species include 1,3-butadiene, isoprene, butyl acrylate, styrene, alphamethyl styrene, methyl methacrylate, ethyl acrylate, butyl methacrylate, and the like. 100 to 70 parts by weight of a monomer, an aromatic monomer, acrylic acid ester of 1 to 8 carbon atoms, alkyl ester of methacrylic acid of 1 to 8 carbon atoms, and 0 to 30 parts by weight of one or more mixed monomers selected from vinylcyanine. If the diene monomer is 70 parts by weight or less, the low temperature impact properties are low. The crosslinking agent used in the present invention is 1,3-butanediol diacrylate, 1,3-butanediol methacrylate, divinylbenzene, ethylene glycol diacrylate, butylene glycol diacrylate, butylene glycol dimethacrylate, and the like. The amount is 0.2 to 3.0 parts by weight.
본 발명에서 스티렌-부타디엔 고무 라텍스 중합에 사용되는 중합개시제로는 하이드로겐퍼옥사이드, 디이소프로필벤젠퍼옥사이드, 큐멘하드로퍼옥사이드, 칼륨퍼셀페이트, 암모늄퍼설페이트, 라우릴퍼옥사이드, 메틸에틸케톤퍼옥사이드, 터셔리부틸하이드로퍼옥사이드 등을 들 수 있는데 그 양으로는 0.1∼1.0 중량부가 사용된다.In the present invention, the polymerization initiator used for the styrene-butadiene rubber latex polymerization is hydrogen peroxide, diisopropylbenzene peroxide, cumene hydroperoxide, potassium percellate, ammonium persulfate, lauryl peroxide, methyl ethyl ketone peroxide And tertiary butyl hydroperoxide; 0.1 to 1.0 parts by weight is used as the amount.
본 발명에서 스티렌-부타디엔 고무 라텍스 중합에 사용된 전해질로서는 황산마그네슘, 염화칼슘, 초산, 황산나트륨, 단독 또는 2가지이상의 혼합물을 이온교환수에 첨가하여 사용하는것으로써 상기 전해질 0.1∼0.4 중량부를 이온교화수에 첨가한다. 전해질첨가량이 0.4 중량부 이상이면 고무입자는 커지나 중합계가 불안정하여 응집물이 많이 발생하기 쉽다. 또한 0.1 중량부 이하이면 중합계는 안정하나 고무입경을 증대시키는 효과가 감소하며 중합시간이 길어진다.In the present invention, the electrolyte used for the polymerization of styrene-butadiene rubber latex is magnesium sulfate, calcium chloride, acetic acid, sodium sulfate, alone or a mixture of two or more thereof. Add. When the amount of the electrolyte added is 0.4 parts by weight or more, the rubber particles become large, but the polymerization system is unstable, and agglomerates are likely to be generated. In addition, if the content is 0.1 parts by weight or less, the polymerization system is stable, but the effect of increasing the rubber particle size is reduced, and the polymerization time becomes long.
그라프트중합시에 상기방법으로 제조된 고무질중합체 라텍스 고형분으로 40∼70 중량부 존재하에 이온교환수, 개시제, 분자량조절제, 가교제를 넣고 내부온도 50℃∼80℃로 승온하여 교반하면서 중합을 개시한다. 메틸메타크릴레이트 30∼70 중량부, 스티렌 30∼70 중량부, 아크릴로니트릴 0.01∼10 중량부 (합계 30∼60중량부)를 유화제, 가교제와 함께 2단 그라프트중합을 실시하며 전환율이 85∼98%가 되었을 때 열안정제를 0.01∼2.0 중량부를 첨가하여 중합이 얻어진다. 여기에서 첨가되는 개시제, 가교제, 유화제는 유화중합에 통상적으로 사용되는 것을 사용하여도 되며 그 첨가량과 종류는 고무질중합체에 사용된 것과 동일하다.In the graft polymerization, ion-exchanged water, an initiator, a molecular weight regulator, and a crosslinking agent are added to the rubbery polymer latex solid prepared by the above method in the presence of 40 to 70 parts by weight, and the polymerization is initiated while the temperature is raised to 50 ° C to 80 ° C and stirred. . 30 to 70 parts by weight of methyl methacrylate, 30 to 70 parts by weight of styrene, and 0.01 to 10 parts by weight of acrylonitrile (30 to 60 parts by weight in total) are subjected to two-stage graft polymerization together with an emulsifier and a crosslinking agent with a conversion ratio of 85 When it becomes -98%, 0.01-2.0 weight part of heat stabilizers are added and superposition | polymerization is obtained. Initiators, crosslinking agents, and emulsifiers added herein may be those used in emulsion polymerization, and the amounts and types of additions are the same as those used for the rubbery polymer.
그라프트중합에서의 단량체의 2단첨가법이란 고무질중합체에 첨가되는 총단량체량을 50 중량%씩 나누어 2단첨가하며 1단첨가시 전체 메틸메타크릴레이트의 첨가량의 60∼90 중량%를 포함하여 스티렌의 10∼40 중량%를 사입하며 2단 첨가시 메틸메타크릴레이트 10∼40 중량% 및 스티렌 60∼90 중량% 및 아크릴로니트릴 전량을 사입함을 특징으로 하며 첨가방법은 사입량 전량을 한번에 첨가하거나 정량적으로 연속적으로 첨가할 수 있다. 가능하면 연속으로 첨가하는 것이 좋다.The two-stage addition of monomers in graft polymerization is performed by dividing the total amount of monomers added to the rubbery polymer by 50% by weight in two-stages, including 60 to 90% by weight of the total amount of methyl methacrylate added in one stage. 10 to 40% by weight of styrene is injected, and when two steps are added, 10 to 40% by weight of methyl methacrylate, 60 to 90% by weight of styrene and the entire amount of acrylonitrile are added. It can be added or continuously added quantitatively. If possible, it is recommended to add it continuously.
본 발명의 그라프트중합에 사용되는 유화제는 통상적인 유화중합에 사용되는 유화제로서 나트륨도데실설페이트, 나트륨도데실벤젠설페이트, 나트륨올레익설페이트, 칼륨도데실설페이트, 칼륨스테아레이트, 나트륨스테아레이트, 나트륨올레이트, 로진지방산염등을 들 수 있으며, 그 양은 1∼3 중량부가 사용된다.Emulsifiers used in the graft polymerization of the present invention as the emulsifier used in conventional emulsion polymerization, sodium dodecyl sulfate, sodium dodecylbenzene sulfate, sodium oleic sulfate, potassium dodecyl sulfate, potassium stearate, sodium stearate, sodium Oleate, rosin fatty acid salt, etc., and the amount is 1-3 parts by weight.
본 발명의 그라프트중합에 사용되는 가교제는 1,3-부탄디올디아크릴레이트, 1,3-부탄디올메타크릴레이트디비닐벤젠, 에틸렌글리콜디아크릴레이트, 부틸렌글리콜디아크릴레이트, 부틸렌글리콜디메타크릴레이트 등을 들 수 있는데 그 사용량은 0.2∼3 중량부이다.The crosslinking agent used in the graft polymerization of the present invention is 1,3-butanediol diacrylate, 1,3-butanediol methacrylate divinylbenzene, ethylene glycol diacrylate, butylene glycol diacrylate, butylene glycol dimetha Acrylate and the like, but the amount is 0.2 to 3 parts by weight.
본 발명에 사용되는 중합개시제로는 하이드로겐퍼옥사이드, 디이소프로필벤젠퍼옥사이드, 큐멘하드로퍼옥사이드, 칼륨퍼설페이트, 암모늄퍼설페이트, 라우릴퍼옥사이드, 메틸에틸케톤퍼옥사이드, 터셔리부틸하이드로퍼옥사이드 등을 들 수 있는데 그 양으로는 0.1∼1.0 중량부가 사용된다.Polymerization initiators used in the present invention include hydrogen peroxide, diisopropylbenzene peroxide, cumene hydroperoxide, potassium persulfate, ammonium persulfate, lauryl peroxide, methyl ethyl ketone peroxide, tertiary butyl hydroperoxide Etc. Although 0.1-1.0 weight part is used as the quantity.
이하 본 발명을 방법을 실시예 및 비교예에 의해 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail by way of examples and comparative examples.
실시예 1Example 1
(제조예 1. 입자비대화제의 제조)(Manufacture example 1. Preparation of particle thickening agent)
순수 (pure water) 280 중량부를 중합조에 투입한 후 승온하여 35℃로 유지하면서 부틸아크릴레이트 90 중량부, 에틸렌글리콜아크릴레이트 3.0 중량부, 터셔리도데실메르캅탄 0.3 중량부 혼합물의 20 중량부를 먼저 투입하여 충분히 분산시킨 후, 과황산칼륨 0.8 중량부를 먼저 투입하고 30분 동안 교반한 다음 아황산나트륨 0.9 중량부를 투입하여 시드중합을 시켰다. 여기에 잔량의 혼합단량체와 수용성 단량체인 아크릴산 10 중량부의 혼합물과 라우릴황산나트륨 5% 수용액 90 중량부를 5시간에 걸쳐 연속투입시키고 전환율이 95% 이상이 되면 70℃로 승온 후 3시간 숙성시켜 후중합하여 입자비대화제인 공중합체 라텍스를 얻었다.280 parts by weight of pure water was added to the polymerization tank, followed by heating to maintain the temperature at 35 ° C., 90 parts by weight of butyl acrylate, 3.0 parts by weight of ethylene glycol acrylate, and 0.3 parts by weight of tertidodecyl mercaptan. After adding and dispersing sufficiently, 0.8 parts by weight of potassium persulfate was added first, stirred for 30 minutes, and 0.9 parts by weight of sodium sulfite was added to seed polymerization. Here, the remaining amount of the mixed monomer and the mixture of 10 parts by weight of acrylic acid, which is a water-soluble monomer, and 90 parts by weight of a 5% aqueous solution of sodium lauryl sulfate are continuously added over 5 hours, and when the conversion rate is 95% or more, the mixture is heated to 70 ° C. and aged for 3 hours and then polymerized The copolymer latex which is a particle thickening agent was obtained.
(제조예 2. 스티렌-부타디엔 고무 라텍스의 제조)Preparation Example 2 Preparation of Styrene-Butadiene Rubber Latex
35 L 내압중합조 내부를 질소가스로 치환한 후, 진공펌프를 이용하여 내부압력을 -730∼740mmHg까지 낮춘 다음 이온교환수 150 중량부, 1,3-부타디엔 72 중량부, 스티렌 28 중량부, 나트륨올레이트 1.0 중량부, 수산화나트륨 0.2 중량부를 투입하고 내부온도를 50℃까지 상승시켰다. 내부온도가 55℃에 도달하면 에틸렌글리콜아크릴레이트 1.0 중량부, 터셔리부틸하이드로퍼록사이드 0.4 중량부, 암모니움퍼설페이트 1.0 중량부를 사입하여 중합을 개시하였다. 중합을 6 시간 동안 진행시킨 후 샘플링하여 반응전환율을 측정한 결과 27.5%를 얻었으며 카프로익산 1.0 중량부, 수산화나트퓸 0.2 중량부, 이온교환수 1.0 중량부를 첨가하여 중합을 계속 진행하였다. 중합을 12 시간 계속 진행시킨 결과 반응전환율이 98%, 겔함량이 82 중량%, 고무의 중량평균입경이 0.085 ㎛인 스티렌-부타디엔 고무 라텍스를 얻었으며, 응집물량은 0.05 중량% 이었다.After replacing the inside of the 35 L pressure vessel with nitrogen gas, lower the internal pressure to -730 to 740 mmHg using a vacuum pump, and then 150 parts by weight of ion-exchanged water, 72 parts by weight of 1,3-butadiene, 28 parts by weight of styrene, 1.0 part by weight of sodium oleate and 0.2 part by weight of sodium hydroxide were added thereto, and the internal temperature was raised to 50 ° C. When internal temperature reached 55 degreeC, superposition | polymerization was started by inserting 1.0 weight part of ethylene glycol acrylate, 0.4 weight part of tertiary butyl hydroperoxides, and 1.0 weight part of ammonium persulfate. After the polymerization was performed for 6 hours, the reaction conversion was measured by sampling. As a result, 27.5% was obtained. The polymerization was continued by adding 1.0 parts by weight of caproic acid, 0.2 parts by weight of sodium hydroxide, and 1.0 parts by weight of ion-exchanged water. The polymerization was continued for 12 hours to obtain styrene-butadiene rubber latex having a reaction conversion rate of 98%, a gel content of 82% by weight, and a rubber weight average particle diameter of 0.085 µm, and an aggregate amount of 0.05% by weight.
얻어진 고무질중합체 라텍스 100 중량부에 알킬벤젠소다계로 라우릴벤젠설포네이트 0.20 중량부를 순수에 고형분이 20%(w/v)가 되게 희석하여 제조된 유화용액을 첨가한 후 입자비대화제인 공중합체라텍스를 0.8 중량부를 서서히 첨가하여 입자비대화된 고무의 중량평균 입경이 0.25㎛인 고무질중합체를 얻었으며 수산화 칼륨 0.7 중량부를 순수로 희석된 고형분이 10%(w/v)인 알칼리수용액을 첨가하여 재차 안정화시켰다.To 100 parts by weight of the obtained rubber latex, 0.20 parts by weight of laurylbenzenesulfonate in alkylbenzene soda was added to dilute the solids to 20% (w / v) in pure water, followed by addition of copolymer latex as a particle thickening agent. 0.8 parts by weight was gradually added to obtain a rubbery polymer having a weight average particle diameter of 0.25 µm, and 0.7 parts by weight of potassium hydroxide was further stabilized by adding an alkaline aqueous solution having a solid content of 10% (w / v) diluted with pure water. .
(제조예 3. 그라프트 메틸메타크릴레이트-아크릴로니트릴-부타디엔-스티렌 공중합물 제조)Preparation Example 3. Preparation of Graft Methyl Methacrylate-Acrylonitrile-Butadiene-Styrene Copolymer
10L 유리중합조에 상기 고무 라텍스 제조방법에 의해 제조된 고무 라텍스를 사용하여 이온 교환수 30 중량부, 고무라텍스 50 중량부(고형분환산), 터셔리부틸하이드로퍼옥사이드 0.4 중량부, 나트륨 올레이트 0.5 중량부, 나트륨 포름알데히드설폭시레이트 0.1 중량부, 황산 제일철 0.01중량부, 트리소디윰페닐포스페이트 0.3 중량부를 사입한 후 30 분동안에 반응온도를 65℃로 승온하였다.30 parts by weight of ion-exchanged water, 50 parts by weight of rubber latex (in terms of solids), 0.4 parts by weight of tertiary butyl hydroperoxide, and 0.5 parts by weight of sodium oleate using a rubber latex prepared by the rubber latex manufacturing method in a 10 L glass polymerization tank. After the addition of 0.1 part by weight of sodium formaldehyde sulfoxylate, 0.01 part by weight of ferrous sulfate, and 0.3 part by weight of trisodic phenyl phosphate, the reaction temperature was raised to 65 ° C for 30 minutes.
내부온도가 65℃에 도달하면 1단첨가 단량체로 스티렌 5.0 중량부, 메틸메타크릴레이트 20.0 중량부, 에틸렌글리콜아크릴레이트 0.5 중량부, 2단첨가 단량체로는 스티렌 15.0 중량부, 메틸메타크릴레이트 5.0 중량부, 아크릴로니트릴 5.0 중량부, 에틸렌글리콜아크릴레이트 0.5 중량부를 각각 3시간 동안 정량적으로 사입하여 중합을 진행한 후 75℃로 승온 후 3시간 동안 숙성시키면서 중합전환율이 98%일 때 나트륨올레이트 0.2 중량부 이온교환수 10 중량부 에틸렌디아민테트라나트륨초산염 1.0중량부를 첨가하여 중합을 종료하였다.When the internal temperature reaches 65 ° C., 5.0 parts by weight of styrene as a single monomer, 20.0 parts by weight of methyl methacrylate, 0.5 parts by weight of ethylene glycol acrylate, 15.0 parts by weight of styrene as a 2-stage monomer, and methyl methacrylate 5.0 Part by weight, 5.0 parts by weight of acrylonitrile and 0.5 parts by weight of ethylene glycol acrylate were added quantitatively for 3 hours, followed by polymerization, and then heated to 75 ° C. and aged for 3 hours. Sodium oleate when the polymerization conversion was 98%. 10 parts by weight of 0.2 parts by weight of ion-exchanged water and 1.0 parts by weight of ethylenediaminetetrasodium acetate were added to terminate the polymerization.
(제조예 4. 매트릭스 수지의 제조)Production Example 4. Production of Matrix Resin
순수 200 중량부를 중합조에 투입한 후 승온하여 35℃로 유지하면서 부틸아크릴레이트, 에틸렌글리콜아크릴레이트, 터셔리도데실메르캅탄의 혼합물의 20 중량%를 먼저 투입하여 충분히 분산시킨 후 과황산칼륨 0.8 중량부를 먼저 투입하고 30분 교반한 다음 아황산나트륨 0.9 중량부를 투입하여 시드중합을 시켰다. 여기에 메틸메타크릴레이트 45 중량부, 스티렌 45 중량부, 아크릴로니트릴 10 중량부, 터셔리도데실메르캅탄 0.3 중량부를 혼합물과 5 중량% 라우릴황산나트륨 수용액 90 중량부를 5시간에 걸쳐 연속투입시키고 전환율이 95% 이상이 되면 70℃로 승온 후 3시간 숙성시켜 후중합하여 메틸메타크릴레이트-스티렌-아크릴로니트릴 유화공중합물을 얻었다.200 parts by weight of pure water was added to the polymerization tank, and then the temperature was maintained at 35 ° C., while 20% by weight of a mixture of butyl acrylate, ethylene glycol acrylate, and tertiary dodecyl mercaptan was added first to disperse sufficiently, and then 0.8 weight of potassium persulfate. Part was added first and stirred for 30 minutes, and then 0.9 part by weight of sodium sulfite was seeded. 45 parts by weight of methyl methacrylate, 45 parts by weight of styrene, 10 parts by weight of acrylonitrile, and 0.3 parts by weight of tertiary dedecyl mercaptan were added to the mixture and 90 parts by weight of a 5% by weight aqueous solution of sodium lauryl sulfate over 5 hours. When the conversion was 95% or more, the mixture was heated at 70 ° C., aged for 3 hours, and then polymerized to obtain a methyl methacrylate-styrene-acrylonitrile emulsion copolymer.
(제조예 5. 메틸메타크릴레이트-아크릴로니트릴-부타디엔-스티렌 수지의 제조 (콤파운딩))Preparation Example 5. Preparation of Methyl Methacrylate-Acrylonitrile-Butadiene-Styrene Resin (Compounding)
중합 후 얻어진 그라프트 중합체 라텍스 40 중량부와 매트릭스 수지 라텍스 60 중량부의 혼합물에 페놀계 항산화제 및 황계항산화제를 각각 0.2 중량부씩을 투입하고 충분히 교반시킨 후, 이온교환수 100 중량부를 첨가하여 온도를 90℃까지 승온, 교반을 시키면서 황산마그네슘 0.5 중량부를 첨가하여 입자를 얻었다. 이어서 원심분리기로 탈수, 세척하여 건조하여 분말상의 메틸메타크릴레이트-부타디엔-스티렌 수지를 제조하였다.To the mixture of 40 parts by weight of the graft polymer latex obtained after the polymerization and 60 parts by weight of the matrix resin latex, 0.2 parts by weight of a phenolic antioxidant and a sulfur based antioxidant were respectively added and stirred thoroughly, and then 100 parts by weight of ion-exchanged water was added to increase the temperature. 0.5 weight part of magnesium sulfate was added, heating up and stirring to 90 degreeC, and particle | grains were obtained. Subsequently, dehydration, washing and drying with a centrifuge gave a powdery methyl methacrylate-butadiene-styrene resin.
상기방법으로 제조된 메틸메타크릴레이트-부타디엔-스티렌 수지의 충격보강효과 및 고온열안정성 및 투명성을 평가하기 위하여 180℃에서 5 분간 믹싱롤러로 혼합을 시킨 후, 190℃, 5분동안 300Kg/cm2의 압력으로 프레스에서 3mm 두께의 시트로 가공한 후 ASTM 방법에 준하여 아이조드충격시편, 인장강도시편, 투명도시편을 제작하여 광투과율, HAZE, 충격강도 및 인장강도를 측정하였다. 고온 체류시 열안정성을 측정하기 위하여 220℃에서 5분동안 300Kg/cm2으로 프레스에서 3mm 두께의 시트로 가공한 후 아이조드 충격시편, 인장강도 시편, 투명도 시편을 제작하여 광투과율, HAZE, 충격강도 및 인장강도를 측정하였다. 그 측정결과를 다음의 표1에 나타내었다.In order to evaluate the impact reinforcing effect and high temperature thermal stability and transparency of the methyl methacrylate-butadiene-styrene resin prepared by the above method, the mixture was mixed with a mixing roller at 180 ° C. for 5 minutes, and then 300 kg / cm for 5 minutes at 190 ° C. After processing into a sheet of 3mm thickness in the press at a pressure of 2 , Izod impact specimens, tensile steel specimens, and transparent specimens were fabricated according to the ASTM method, and the light transmittance, HAZE, impact strength, and tensile strength were measured. In order to measure the thermal stability at high temperature, after processing for 3 minutes at 300Kg / cm 2 at 220 ℃ for 3 minutes, Izod impact specimen, tensile strength specimen and transparency specimen were fabricated to make light transmittance, HAZE, impact strength. And tensile strength. The measurement results are shown in Table 1 below.
실시예 2. - 실시예 8.Example 2-Example 8.
제조예 1에 대하여 부틸아크릴레이트와 아크릴산의 조성비, 제조예 2에 대하여 입자비대화제의 첨가량, 스티렌과 부타디엔의 조성비, 제조예 3에 대해 고무 라텍스의 양, 그라프트시키는 단량체의 조성비, 제조예 4에 대하여 매트릭스 수지의 단량체의 조성비 및 분자량, 제조예 5에 대하여 각 라텍스의 혼합비율을 조절하여 실시예 1과 동일한 방법으로 광투과율, HAZE, 충격강도 및 인장강도를 측정하였다. 각 실시예에 대해 조절인자와 물성결과를 표 1 및 표 2에 나타내었다.Composition ratio of butyl acrylate and acrylic acid with respect to Preparation Example 1, addition amount of particle thickening agent with respect to Preparation Example 2, composition ratio of styrene and butadiene, amount of rubber latex with respect to Preparation Example 3, composition ratio of monomer to be grafted, Preparation Example 4 The light transmittance, HAZE, impact strength and tensile strength were measured in the same manner as in Example 1 by adjusting the composition ratio and molecular weight of the monomer of the matrix resin, and the mixing ratio of each latex with respect to Preparation Example 5. The regulators and the physical property results for each Example are shown in Table 1 and Table 2.
비교예 1 - 비교예 4Comparative Example 1-Comparative Example 4
비교예 1에 대하여 입자비대화제의 첨가량 (제조예 2), 비교예 2에 대하여 고무라텍스의 양(제조예 3) 및 각 라텍스의 혼합비율(제조예 5), 비교예 3에 대하여 그라프트시키는 단량체의 조성비 (제조예 3) 및 매트릭스 수지의 단량체의 조성비 및 분자량 (제조예 4), 비교예 4에 대하여 각 라텍스의 혼합비율(제조예 5)를 조절하여 실시예 1과 동일한 방법으로 광투과율, HAZE, 충격강도 및 인장강도를 측정하였다. 각 비교예에 따른 조절인자와 물성결과를 표1 및 표2에 나타내었다.The amount of the particle thickening agent added to Comparative Example 1 (Preparation Example 2), the amount of rubber latex (Preparation Example 3), and the mixing ratio of each latex (Preparation Example 5) and Comparative Example 3 The light transmittance was adjusted in the same manner as in Example 1 by adjusting the composition ratio of the monomer (Preparation Example 3), the composition ratio of the monomer of the matrix resin and the molecular weight (Preparation Example 4), and the mixing ratio (Preparation Example 5) of each latex with respect to Comparative Example 4. , HAZE, impact strength and tensile strength were measured. The control factors and the physical properties according to the comparative examples are shown in Table 1 and Table 2.
물성측정 결과Property measurement result
[표 1]TABLE 1
BA : 부틸아크릴레이트 단량체BA: Butylacrylate Monomer
AA : 아크릴산 단량체AA: Acrylic Acid Monomer
MMA : 메틸메타크릴레이트 단량체MMA: Methyl methacrylate monomer
St : 스티렌 단량체St: Styrene Monomer
AN : 아크릴로니트릴 단량체AN: Acrylonitrile Monomer
MABS : 메틸메타크릴레이트-아크릴로니트릴-부타디엔-스티렌 공중합물MABS: Methyl methacrylate-acrylonitrile-butadiene-styrene copolymer
MSAN : 메틸메타크릴레이트-스티렌-아크릴로니트릴 공중합물MSAN: Methyl methacrylate-styrene-acrylonitrile copolymer
물성측정결과Property measurement result
[표 2]TABLE 2
실시예 2와 비교예 1은 실시예 1에 대해 입자비대화제의 첨가량을 중량한 경우인데 입자비대화제의 첨가량이 증가할수록 그라프트중합 후 라텍스에서 응집물이 과다하게 생성되었으며 투명성도 떨어지는 것을 알 수 있었다. 실시예 3, 실시예 4, 비교예 2는 그라프트중합시 고무의 양과 단량체의 중량비율을 조절한 경우인데 고무함량이 매우 높을 때 최종 성형물의 충격강도가 떨어짐을 아 수 있었다.Example 2 and Comparative Example 1 is a case in which the amount of the particle thickening agent is added to the weight of Example 1, and as the amount of the particle thickening agent is increased, the aggregates are excessively formed in the latex after graft polymerization, and the transparency is also decreased. . In Example 3, Example 4, and Comparative Example 2, the amount of rubber and the weight ratio of the monomers were adjusted during graft polymerization, and the impact strength of the final molded product was lowered when the rubber content was very high.
표 2의 실시예 5와 비교예 3은 고무의 스티렌-부타디엔 조성비와 매트릭스 수지인 메닐메타크릴레이트-스티렌-아크릴로니트릴 공중합물의 조성비를 변화시킨 것으로, 비교예 3의 경우 투명성이 떨어지는 현상을 보였다. 실시예 6, 실시예 7, 실시예 8, 비교예 4는 그라프트 수지와 매트릭 수지의 조성비를 달리하여 전체 고무함량을 변화시킨 경우로서 고무의 함량이 증가할수록 투명성이 떨어지는 것을 알 수 있었다.In Example 5 and Comparative Example 3 of Table 2, the composition ratio of the styrene-butadiene composition ratio of rubber and the menyl methacrylate-styrene-acrylonitrile copolymer, which is a matrix resin, was changed. . In Example 6, Example 7, Example 8, and Comparative Example 4, the total rubber content was changed by changing the composition ratio of the graft resin and the matrix resin, and it was found that the transparency decreased as the rubber content increased.
본 발명에 의해 제조된 메틸메타크릴레이트-아크릴로니트릴-스티렌 공중합체수지는 투명성, 내충격성, 내약품성, 성형성 및 경제성이 우수한 열가소성 수지로서 화장품용기, 복사기 및 팩시밀리 부품, 가전제품 부품, 필기구 및 서류보관함 등의 사출성형용 수지로 범용적으로 사용될 수 있다.The methyl methacrylate-acrylonitrile-styrene copolymer resin prepared according to the present invention is a thermoplastic resin having excellent transparency, impact resistance, chemical resistance, moldability, and economy, and is a cosmetic container, a copier and a facsimile part, a home appliance part, a writing instrument. And it can be used universally as resin for injection molding, such as document storage.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100396402B1 (en) * | 2000-12-21 | 2003-09-02 | 제일모직주식회사 | Thermoplastic Resin Composition Having Excellent Chemical Resistance And Easy Vacuum Formability |
| KR100467780B1 (en) * | 2002-09-30 | 2005-01-24 | 주식회사 엘지화학 | Thermoplastic resin composition and method for preparing thereof |
| KR100519382B1 (en) * | 2002-12-10 | 2005-10-06 | 주식회사 엘지화학 | A method for preparing the themoplastic resin modifier having anti-stress impact and a method for preparing its intermediate |
| KR20160032668A (en) * | 2014-09-16 | 2016-03-24 | 주식회사 엘지화학 | Thermoplastic resin composition and thermoplastic resin molded article prepared by using the same |
| WO2016043424A1 (en) * | 2014-09-16 | 2016-03-24 | 주식회사 엘지화학 | Thermoplastic resin composition and thermoplastic resin molded article prepared therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101054693B1 (en) * | 2007-11-09 | 2011-08-08 | 제일모직주식회사 | Transparent thermoplastic resin and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100396402B1 (en) * | 2000-12-21 | 2003-09-02 | 제일모직주식회사 | Thermoplastic Resin Composition Having Excellent Chemical Resistance And Easy Vacuum Formability |
| KR100467780B1 (en) * | 2002-09-30 | 2005-01-24 | 주식회사 엘지화학 | Thermoplastic resin composition and method for preparing thereof |
| KR100519382B1 (en) * | 2002-12-10 | 2005-10-06 | 주식회사 엘지화학 | A method for preparing the themoplastic resin modifier having anti-stress impact and a method for preparing its intermediate |
| KR20160032668A (en) * | 2014-09-16 | 2016-03-24 | 주식회사 엘지화학 | Thermoplastic resin composition and thermoplastic resin molded article prepared by using the same |
| WO2016043424A1 (en) * | 2014-09-16 | 2016-03-24 | 주식회사 엘지화학 | Thermoplastic resin composition and thermoplastic resin molded article prepared therefrom |
| KR101644752B1 (en) * | 2014-09-16 | 2016-08-01 | 주식회사 엘지화학 | Thermoplastic resin composition and thermoplastic resin molded article prepared by using the same |
| US9834645B2 (en) | 2014-09-16 | 2017-12-05 | Lg Chem, Ltd. | Thermoplastic resin composition and thermoplastic resin molded article prepared therefrom |
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| KR19980046343A (en) | 1998-09-15 |
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