KR100384383B1 - Manufacturing method of thermoplastic resin - Google Patents
Manufacturing method of thermoplastic resin Download PDFInfo
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- KR100384383B1 KR100384383B1 KR10-1998-0020635A KR19980020635A KR100384383B1 KR 100384383 B1 KR100384383 B1 KR 100384383B1 KR 19980020635 A KR19980020635 A KR 19980020635A KR 100384383 B1 KR100384383 B1 KR 100384383B1
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- C—CHEMISTRY; METALLURGY
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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
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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Abstract
본 발명은 내후성 수지에 저온 내 충격성을 향상시키기 위해서 대구경 아크릴레이트 고무를 갖는 ASA 수지를 제조하고 여기에 저온 내 충격성이 우수한 부타디엔 고무를 갖는 그라프트 ABS 수지를 제조한 후, 서로 혼련시켜 저온 내 충격성이 우수한 내후성 수지를 제조하는 방법을 제공한다.The present invention prepares ASA resins having a large diameter acrylate rubber in order to improve the impact resistance at low temperature to weather resistance resins, and to produce a graft ABS resin having a butadiene rubber excellent impact resistance at low temperatures, and then kneading with each other to low temperature impact resistance Provided is a method for producing this excellent weather resistant resin.
Description
본 발명은 열 가소성 수지를 제조하는 방법에 관한 것으로 더욱 상세하게는 저온 내 충격성이 우수한 내후성 수지 제조 방법에 관한 것이다.The present invention relates to a method for producing a thermoplastic resin, and more particularly, to a method for producing a weather resistant resin having excellent low temperature impact resistance.
ASA(Acrylate-Styrene-Acrylonitrile) 수지는 내후성, 내약품성, 열 안정성이 우수하여 옥외에 사용되는 전기·전자 부품과 건축용 자재, 스포츠 용품 등에 많이 사용되고 있지만 ASA 수지 제조시 사용되는 아크릴 고무의 유리 전이 온도 특성(유리 전이 온도 : -50 ℃)으로 인하여 저온 내 충격성이 부족하므로 추운 지방과 겨울철에 사용이 제한되고 있다.ASA (Acrylate-Styrene-Acrylonitrile) resin is widely used in outdoor electrical and electronic parts, construction materials, and sporting goods due to its excellent weather resistance, chemical resistance, and thermal stability, but the glass transition temperature of acrylic rubber used in the manufacture of ASA resin Due to its characteristics (glass transition temperature: -50 ℃), the impact resistance at low temperatures is insufficient, so its use in cold regions and in winter is limited.
내후성 ASA 수지를 제조하는 선행 문헌으로는 미국 특허 제3,426,101호, 일본 특허 공개 공보 평4-180949호, 평5-202264호, 평7-316243호, 서독 특허 제1260135호 등에 제조 방법이 알려져 있는데 이들 선행 특허는 내후성과, 내 충격성, 착색성 등을 향상 시키는 제조 방법을 제시하고 있지만 저온 내 충격성을 향상시키는 방법은 제시하지 못하고 있다.Prior arts for producing weatherable ASA resins are known in the United States Patent No. 3,426,101, Japanese Patent Application Laid-Open No. Hei 4-180949, Hei 5-202264, Hei 7-316243, West German Patent No. 1260135, and the like. Prior art has proposed a manufacturing method for improving weather resistance, impact resistance, colorability, etc., but does not provide a method for improving low temperature impact resistance.
또한 내후성 수지의 저온 내 충격성을 향상시키기 위해 아크릴레이트 고무 대신에 코어(Core:내부층)에 부타디엔 고무를, 셸(Shell:외부층)에 부틸아크릴레이트 고무를 가지는 고무질 공중합체를 도입하는 방법이 제시되고 있는데, 이 방법은 중합 방법이 힘들고 반응의 제어가 어렵다는 문제가 있다. 또 다른 방법으로는 저온내 충격성이 우수한 ABS 수지에 내후성을 보강하기 위해서 혼련시 자외선 흡수제를 다량 사용하는 방법이 가능할 수 있으나 이 방법은 ABS 수지의 노화 방지를 하는데 한계를 가지고 있을 뿐만 아니라 고가의 자외선 흡수제 사용으로 인한 원가 부담으로 내후성 수지 제조에 바람직하지 않은 방법이다.In addition, in order to improve the low temperature impact resistance of the weather resistant resin, a rubber copolymer having butadiene rubber in the core (inner layer) and butyl acrylate rubber in the shell (inner layer) instead of acrylate rubber is introduced. It is proposed that this method has a problem that the polymerization method is difficult and the control of the reaction is difficult. As another method, it may be possible to use a large amount of ultraviolet absorbents when kneading to reinforce weather resistance to the ABS resin having excellent low temperature impact resistance, but this method has a limitation in preventing aging of the ABS resin and expensive ultraviolet rays. Cost burden due to the use of absorbents is an undesirable method for producing weatherable resins.
본 발명자들은 내후성 수지에 저온 내 충격성을 향상시키기 위해서 대구경 아크릴레이트 고무를 갖는 ASA 수지를 제조하고 여기에 저온 내 충격성이 우수한 부타디엔 고무를 갖는 그라프트 ABS 수지를 제조한 후, 서로 혼련시켜 저온 내 충격성이 우수한 내후성 수지를 제조하게 되어 본 발명을 완성하게 되었다.The present inventors prepared the ASA resin having a large diameter acrylate rubber in order to improve the impact resistance at low temperature to the weather resistant resin, and prepared a graft ABS resin having a butadiene rubber having excellent impact resistance at low temperature, and then kneading with each other to effect low temperature impact resistance This excellent weather resistant resin was produced to complete the present invention.
본 발명을 상세히 설명하면 다음과 같다.The present invention is described in detail as follows.
1) 내후성 ASA 수지 제조 방법1) Weathering ASA Resin Manufacturing Method
내후성 ASA 수지를 제조하기 위하여 3단계 유화 중합 방법을 사용하는데, 1단계 중합에서는 유화제를 사용하지 않고 아크릴레이트 단량체와 에틸렌글리콜디메타크릴레이트 가교제를 사용하여 가교된 대구경 아크릴레이트 고무를 먼저 만들고, 2단계 중합에서는 1단계 중합에서 만들어진 고무를 시이드(seed)로 사용하여 여기에 단량체인 부틸아크릴레이트와 가교제, 그라프팅제를 넣어 아크릴레이트 고무 입자를 더 크게 만들어 대구경 아크릴레이트 고무를 제조한다. 3단계 중합에서는 2단계에서 만들어진 대구경 아크릴레이트 고무에 스티렌과 아크릴로니트릴 단량체를 그라프트시켜 내후성 ASA 수지를 제조한다.To prepare weatherable ASA resin, a three-step emulsion polymerization method is used. In one-step polymerization, a cross-linked large-diameter acrylate rubber is first made by using an acrylate monomer and an ethylene glycol dimethacrylate crosslinking agent without using an emulsifier. In the step polymerization, the rubber produced in the first step polymerization is used as a seed, and butyl acrylate, a crosslinking agent, and a grafting agent are added thereto to make the acrylate rubber particles larger, thereby preparing a large diameter acrylate rubber. In the three-step polymerization, weather-resistant ASA resins are prepared by grafting styrene and acrylonitrile monomers to the large-diameter acrylate rubbers produced in step 2.
상기 각 중합 단계를 더욱 상세하게 설명하면 다음과 같다.Each of the above polymerization steps will be described in more detail as follows.
1단계 중합에서 가교된 아크릴레이트 고무 제조시 주 단량체는 부틸아크릴레이트이며 그 사용량은 총 단량체 100 중량부 중 0.5 내지 5 중량부가 좋으며 가교제로서는 에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜디메타크릴레이트, 트리에틸렌글리콜디메타크릴레이트, 1,3-부탄디올디메타크릴레이트, 1,6-헥산디올메타크릴레이트, 네오펜틸글리콜디메타크릴레이트, 트리메틸롤 프로판트리메타크릴레이트, 트리메틸롤메탄크리아크릴레이트 등이 있으며 그 사용량은 총 단량체 100 중량부에 0.05 내지 0.3 중량부의 범위가 좋다. 전해질로는 NaHCO3, Na2S2O7, K2CO3등이 사용될 수 있으며 그 사용량은 총 단량체 100 중량부에 대하여 0.05 내지 0.4 중량부를 사용하는 것이 바람직하다. 개시제로는 무기 혹은 유기 과산화 화합물이 사용되며 수용성 개시제나 유용성 개시제 모두 사용 가능하다. 구체적으로 예를 들면 칼륨퍼설페이트, 나트륨퍼설페이트, 암모늄퍼설페이트와 같은 수용성 개시제와 큐멘하이드로 퍼옥사이드, 벤조일퍼옥사이드와 같은 유용성 개시제 등이 있다. 중합 개시제의 사용량은 단량체 100 중랑부에 대하여 0.05 내지 0.2 중량부가 좋다.In preparing the crosslinked acrylate rubber in the first stage polymerization, the main monomer is butyl acrylate, and the amount of the monomer is 0.5 to 5 parts by weight based on 100 parts by weight of the total monomers, and the crosslinking agent is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol methacrylate, neopentyl glycol dimethacrylate, trimethylol propane trimethacrylate, trimethylol methane acrylate And the amount thereof is preferably in the range of 0.05 to 0.3 parts by weight based on 100 parts by weight of the total monomers. As the electrolyte, NaHCO 3 , Na 2 S 2 O 7 , K 2 CO 3, and the like may be used, and the amount of use thereof is preferably 0.05 to 0.4 parts by weight based on 100 parts by weight of the total monomers. As an initiator, an inorganic or organic peroxide compound is used, and both a water-soluble initiator and an oil-soluble initiator can be used. Specific examples thereof include water-soluble initiators such as potassium persulfate, sodium persulfate and ammonium persulfate, and oil-soluble initiators such as cumene hydroperoxide and benzoyl peroxide. The amount of the polymerization initiator used is preferably 0.05 to 0.2 parts by weight based on 100 monomers of the monomer.
2단계 중합에서는 1단계에서 사용하는 중합된 고무 라텍스를 시이드로하여 대구경화 하기 위한 단계로서 사용하는 단량체는 부틸아크릴레이트로서 그 사용량은 총 단량체 100 중량부중 29 내지 49 중량부가 좋으며 유화제로서는 그 수용액의pH가 9 내지 13 정도로 C12내지 C20의 탄소수를 가진 지방산 금속염 또는 로진산금속염등 카르복실산 금속염의 유도체를 사용할 수 있다. 그라프팅제로는 아릴메타크릴레이트(AHA)나 트리아릴이소시아누레이트(TAIC), 트리아릴아민(TAA), 디아릴아민(DAA) 등이 사용 가능하며 그 사용량은 0.01 내지 0.07 중량부가 좋다. 중합후 가교된 대구경 아크릴레이트 고무 중합체 라텍스의 pH는 5 내지 9의 범위가 좋다. 또한 대구경 고무 중합체의 입경은 2500 내지 5000 Å 범위가 좋다.In the two-stage polymerization, the monomer used as a step for large-diameter curing using the polymerized rubber latex used in the first stage is butyl acrylate, and the amount of the monomer used is 29 to 49 parts by weight in 100 parts by weight of the total monomer. Derivatives of carboxylic acid metal salts such as fatty acid metal salts or rosin acid metal salts having a carbon number of C 12 to C 20 with a pH of 9 to 13 can be used. As the grafting agent, aryl methacrylate (AHA), triaryl isocyanurate (TAIC), triarylamine (TAA), diarylamine (DAA), or the like can be used, and the amount thereof is preferably 0.01 to 0.07 parts by weight. The pH of the crosslinked large diameter acrylate rubber polymer latex after polymerization is in the range of 5-9. In addition, the particle size of the large-diameter rubber polymer is preferably in the range of 2500 to 5000 mm 3.
3단계 중합은 2단계에서 중합된 대구경 아크릴레이트 고무에 방향족비닐 화합물과 비닐시안화 화합물을 사용하여 그라프팅시키는 단계로서 그 사용량은 총 단량체 100 중량부중 30 내지 60 중량부의 방향족 비닐 화합물과 10 내지 20 중량부의 비닐시안화 화합물을 사용하는 것이 좋고 필요에 따라 (메타)아크릴산 에스테르 화합물이나 기능성 단량체를 그라프팅 공중합시키는 것도 가능하다. 분자량 조절제는 3급 도데실 메르캅탄이 사용될 수 있다. 중합 종료후 중합 전환율은 95 % 이상이고 이 라텍스에 열 안정제를 투여하여 90 ℃ 이상의 온도에서 염화 칼슘 수용액으로 응집시킨 후 탈수 및 건조시켜 분말을 얻었다.Three-step polymerization is a step of grafting the large-diameter acrylate rubber polymerized in step 2 by using an aromatic vinyl compound and a vinyl cyanide compound, and the amount thereof is used in an amount of 30 to 60 parts by weight of an aromatic vinyl compound and 10 to 20 parts by weight of 100 parts by weight of the total monomers. It is preferable to use a negative vinyl cyanide compound and it is also possible to graft copolymerize a (meth) acrylic acid ester compound and a functional monomer as needed. As the molecular weight modifier, tertiary dodecyl mercaptan may be used. After the completion of the polymerization, the polymerization conversion was 95% or more, and a thermal stabilizer was added to the latex to coagulate with an aqueous calcium chloride solution at a temperature of 90 ° C or higher, followed by dehydration and drying to obtain a powder.
상기에서 제조한 내후성 ASA 중합체의 라텍스 안정성 여부는 다음과 같이 고형 응고분(%)을 측정하여 판단하였고 그라프트율과 라텍스 입자경은 하기와 같은 식과 방법으로 측정하였다.The latex stability of the weathering ASA polymer prepared above was determined by measuring solid coagulation (%) as follows. The graft rate and latex particle diameter were measured by the following formula and method.
고형응고분(%) = {반응조내의 생성 응고물 무게(g) /투여된 총 단량체의 무게} * 100Solid coagulation (%) = {weight of product coagulum in the reactor (g) / weight of total monomers administered} * 100
그라프트율(%) = {그라프트된 단량체 무게 / 고무질 무게} * 100Graft Rate (%) = {grafted monomer weight / rubber weight} * 100
입자경 : 다이나믹 레이져라이트 스케터링법으로 Nicomp(모델명 : 370 HPL)을 이용하여 측정하였다.Particle diameter: measured using Nicomp (model name: 370 HPL) by the dynamic laser light scattering method.
2) 저온 내 충격성이 우수한 그라프트 ABS 수지 제조 방법2) Manufacturing method of graft ABS resin excellent in low temperature impact resistance
입경이 2600 Å 내지 5000 Å되는 폴리부타디엔 고무 라텍스에 방향족 비닐 화합물, 비닐시안화 화합물 등을 이용하여 그라프트 공중합시켜 그라프트 ABS 수지를 얻는다. 그라프트 공중합시 각 성분의 첨가 방법으로는 각 성분을 전량 일괄 투여하는 방법과 다단계 분할 투여하는 방법, 연속 투여하는 방법이 가능하나 응고물 생성을 최소화 하기 위해서는 다단계 분할 투여나 연속 투여하는 방법이 바람직하다. 개시제로는 큐멘하이드로퍼옥사이드(CHP), 디이소프로필벤젠하이드로퍼옥사이드(DIPHP), 과황산염 등과 같은 과산화물과 소디움포름알데히드 술폭실레이트, 소디움에틸렌디아민 테트라아세테이트, 황산 제 1철, 덱스트로즈, 피롤린산나트륨, 아황산나트륨 등과 같은 환원제와의 혼합물로 된 산화-환원계 촉매를 사용할 수 있다. 분자량 조절제로는 3급 도데실 메르캅탄이 사용되며 유화제로는 로진산칼륨, 로진산나트륨 등의 로진산염이나 올레인산칼륨, 올레인산나트륨, 스테아린산나트륨 등의 지방산염 및 알킬아릴술폰산염 등을 사용한다. 중합 종료 후 수득된 라텍스의 중합 전환율은 96 % 이상이고 이 라텍스에 산화 방지제 및 안정제를 투여하여 90 ℃ 이상의 온도에서 황산 수용액으로 응집시킨 후 탈수 및 건조시켜 분말을 얻었다.A graft ABS resin is obtained by graft copolymerization of polybutadiene rubber latex having a particle diameter of 2600 mm to 5000 mm using an aromatic vinyl compound, a vinyl cyanide compound, or the like. In the graft copolymerization, each component may be added in a batch, multistage divided doses, or continuous doses. However, in order to minimize coagulation, multistage divided doses or continuous doses are preferable. Do. Initiators include peroxides such as cumene hydroperoxide (CHP), diisopropylbenzene hydroperoxide (DIPHP), persulfate, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, Oxidation-reduction catalysts in mixture with a reducing agent such as sodium pyrrolate, sodium sulfite and the like can be used. As the molecular weight regulator, tertiary dodecyl mercaptan is used, and as the emulsifier, rosin salts such as potassium rosinate and sodium rosinate, fatty acid salts such as potassium oleate, sodium oleate and sodium stearate, and alkylaryl sulfonate salts are used. The polymerization conversion rate of the latex obtained after the completion of the polymerization was 96% or more, and an antioxidant and a stabilizer were administered to the latex to coagulate with an aqueous sulfuric acid solution at a temperature of 90 ° C. or higher, followed by dehydration and drying to obtain a powder.
3) 혼련 과정3) kneading process
상기 1) 방법으로 제조된 내후성 ASA 수지와 상기 2) 방법으로 제조된 그라프트 ABS 수지에 산화 방지제 및 광 안정제를 투입한 후 200 ℃ 내지 250 ℃에서 압출 혼련기를 이용하여 펠렛을 제조하고 이 펠렛을 다시 사출하여 물성을 측정하였다. 물성은 ASTM 방법으로 측정하였다.After the antioxidant and the light stabilizer were added to the weathering ASA resin prepared by the method 1) and the graft ABS resin prepared by the method 2), pellets were prepared using an extruder kneader at 200 ° C. to 250 ° C. Injection was carried out again to measure physical properties. Physical properties were measured by the ASTM method.
본 발명을 더욱 상세히 설명하고 예시하기 위하여 실시예를 들어 본 발명을 설명하지만, 본 발명이 실시예에 의하여 한정되는 것은 아니다.In order to explain and illustrate the present invention in more detail, the present invention will be described with reference to Examples, but the present invention is not limited to the Examples.
실시예 1Example 1
A) 내후성 ASA 수지 제조 공정A) Weathering ASA Resin Manufacturing Process
(1단계 중합 반응)(1 step polymerization reaction)
이온 교환수 70 중량부70 parts by weight of ion-exchanged water
부틸아크릴레이트 2 중량부2 parts by weight of butyl acrylate
에틸렌글리콜디메타크릴레이트(EDMA) 0.02 중량부0.02 part by weight of ethylene glycol dimethacrylate (EDMA)
탄산수소나트륨 0.1 중량부0.1 parts by weight of sodium bicarbonate
칼륨퍼설페이트(KPS) 0.04 중량부Potassium Persulfate (KPS) 0.04 parts by weight
상기 조성물을 질소치환된 중합 반응기에 넣고 70 ℃까지 승온한 후 1시간 동안 반응시킨다.The composition was placed in a nitrogen-substituted polymerization reactor and heated to 70 ° C. and reacted for 1 hour.
(2단계 중합 반응)(2-step polymerization reaction)
이온 교환수 45 중량부45 parts by weight of ion-exchanged water
디옥틸설포석시네이트 0.5 중량부0.5 parts by weight of dioctylsulfosuccinate
부틸메타아크릴레이트 38 중량부Butyl methacrylate 38 parts by weight
에틸렌글리콜디메타크릴레이트 0.12 중량부0.12 parts by weight of ethylene glycol dimethacrylate
아릴메타크릴레이트 0.04 중량부Aryl methacrylate 0.04 part by weight
탄산수소나트륨 0.1 중량부0.1 parts by weight of sodium bicarbonate
칼륨퍼설페이트 0.06 중량부0.06 parts by weight of potassium persulfate
상기 조성물에서 촉매인 칼륨퍼설페이트를 제외한 모든 조성물을 혼합물로 만든 후 1단계 중합 반응물에 만들어진 혼합물과 촉매를 70 ℃에서 4시간 동안 연속으로 각각 투입하면서 중합 반응을 실시했다.In the composition, all the compositions except for the potassium persulfate catalyst were made into a mixture, and then the mixture and the catalyst prepared in the first-stage polymerization reactant were continuously introduced at 70 ° C. for 4 hours, respectively.
이 때 얻어진 라텍스의 입경은 4000 Å, pH는 8, 중합 전환율은 98 %였다.The particle size of the latex obtained at this time was 4000 Pa, pH was 8, and the polymerization conversion rate was 98%.
(3단계 중합 반응)(3-step polymerization reaction)
이온 교환수 63 중량부63 parts by weight of ion-exchanged water
디옥틸설포석시네이트 0.5 중량부0.5 parts by weight of dioctylsulfosuccinate
스티렌(SM) 40 중량부Styrene (SM) 40 parts by weight
아크릴로니트릴(AN) 18 중량부Acrylonitrile (AN) 18 parts by weight
메틸메타아크릴레이트(MMA) 2 중량부Methyl methacrylate (MMA) 2 parts by weight
3급 도데실메르캅탄(TDDM) 0.05 중량부0.05 parts by weight of tertiary dodecyl mercaptan (TDDM)
칼륨퍼설페이트 0.1 중량부0.1 part by weight of potassium persulfate
상기 조성물에서 촉매인 칼륨퍼설페이트를 제외한 모든 조성물을 혼합물로 만든 후, 2단계 중합 반응물에 촉매와 혼합물을 각각 70 ℃에서 3시간 동안 연속으로 투입하면서 중합 반응을 실시한 후 중합 전환율을 높이기 위하여 80 ℃에서 1시간 동안 더 반응시킨 후 60 ℃까지 냉각시켰다.In the composition, all the compositions except for the potassium persulfate catalyst were made into a mixture, and then the catalyst and the mixture were continuously added to the two-stage polymerization reaction at 70 ° C. for 3 hours, followed by polymerization to increase the polymerization conversion at 80 ° C. After further reacting for 1 hour at, it was cooled to 60 ° C.
이 때 중합된 라텍스의 입경은 4800 Å이였으며 중합 전환율은 99 %, pH는 9.5, 그라프트율은 45 %였다.At this time, the particle size of the polymerized latex was 4800 mm 3, the polymerization conversion rate was 99%, the pH was 9.5, the graft rate was 45%.
수득된 라텍스를 염화 칼슘 수용액으로 90 ℃에서 응집한 후 탈수하고 건조하여 내후성 ASA 분말 입자를 수득하였다.The latex obtained was aggregated at 90 ° C. with an aqueous calcium chloride solution, dehydrated and dried to obtain weatherable ASA powder particles.
B) 저온 내 충격성이 우수한 그라프트 ABS 수지 제조 공정B) Manufacturing Process of Graft ABS Resin with Excellent Impact Resistance at Low Temperature
(1단계 중합반응)(1 step polymerization)
이온 교환수 65 중량부65 parts by weight of ion-exchanged water
폴리부타디엔 고무 라텍스(입경 : 3000 Å, 겔 함량 : 75 %) 50 중량부50 parts by weight of polybutadiene rubber latex (particle size: 3000 Å, gel content: 75%)
소디움에틸렌디아민테트라아세테이트 0.1 중량부Sodium Ethylenediaminetetraacetate0.1 parts by weight
황산 제 1철 0.005 중량부0.005 parts by weight of ferrous sulfate
포름알데히드소디움술폭실레이트 0.23 중량부0.23 part by weight of formaldehyde sodium sulfoxylate
로진산칼륨 0.35 중량부0.35 parts by weight of potassium rosin
상기 조성물을 질소 치환된 중합 반응기에 일괄 투여하여 1시간 동안 반응 온도를 70 ℃까지 올렸다.The composition was administered in a batch to a nitrogen-substituted polymerization reactor to raise the reaction temperature to 70 ° C. for 1 hour.
(2단계 중합 반응)(2-step polymerization reaction)
이온 교환수 50 중량부50 parts by weight of ion-exchanged water
로진산칼륨 0.65 중량부0.65 parts by weight of potassium rosin
스티렌(SM) 35 중량부Styrene (SM) 35 parts by weight
아크릴로니트릴(AN) 15 중량부15 parts by weight of acrylonitrile (AN)
3급 도데실메르캅탄(TDDM) 0.4 중량부Grade 3 dodecyl mercaptan (TDDM) 0.4 part by weight
디이소프로필렌벤젠하이드로퍼옥사이드 0.4 중량부0.4 part by weight of diisopropylene benzene hydroperoxide
상기 조성물을 혼합 유화물로 만든 후 1단계 중합 반응물에 70 ℃에서 3시간 동안 연속 투입한 후 다시 80 ℃로 승온 후 1시간 동안 숙성시키고 반응물을 종료시킨다. 이 때 중합 전환율은 96 %였고 그라프트율은 35 %, 고형 응고분은 0.2 %였다. 그리고 수득된 라텍스를 황산 수용액으로 응고시켜 세척한 다음 그라프트 ABS 수지 분말을 얻는다. 이 때 얻어진 중합체의 그라프트율은 35 % 정도였다.The composition was made into a mixed emulsion, and then continuously added to the first-stage polymerization reaction at 70 ° C. for 3 hours, then heated to 80 ° C. again, and aged for 1 hour to terminate the reaction. At this time, the polymerization conversion rate was 96%, the graft rate was 35%, and the solidified content was 0.2%. The latex obtained is coagulated with an aqueous sulfuric acid solution, washed, and then graft ABS resin powder is obtained. The graft ratio of the polymer obtained at this time was about 35%.
실시예 2Example 2
실시예 1의 A)에서 EDMA 대신에 TAIC를 사용한 것 외에는 실시예 1과 동일한 방법으로 실시하였다.In Example 1 A), the same method as in Example 1 was carried out except that TAIC was used instead of EDMA.
실시예 3Example 3
실시예 1의 A)에서 촉매로 KPS 대신 CHP를 쓴 것 외에는 동일한 방법으로 중합하였다.The polymerization was carried out in the same manner as in Example A) except that CHP was used instead of KPS as the catalyst.
실시예 4Example 4
실시예 1의 A)에서 촉매로 kPS 대신 DIPHP를 쓴 것 외에는 동일한 방법으로 중합하였다.Polymerization was carried out in the same manner as in Example 1 A) except that DIPHP was used instead of kPS as the catalyst.
실시예 5Example 5
실시예 1의 A)의 3단계 중합에서 유화제로 디옥틸설포네이트 대신 라우릴설페이트를 쓴 것 외에는 동일한 방법으로 중합을 하였다.In the three-step polymerization of A) of Example 1, polymerization was carried out in the same manner except that lauryl sulfate was used instead of dioctylsulfonate as an emulsifier.
비교예 1Comparative Example 1
실시예 1의 B)에서 사용되는 폴리부타디엔 고무 라텍스의 입경이 3000 Å 대신에 2500 Å를 쓴 것 외에는 동일한 방법으로 중합을 하였다. 이 때 얻어진 중합체의 그라프트율은 50 % 정도였다.The polymerization was carried out in the same manner, except that the particle diameter of the polybutadiene rubber latex used in B) of Example 1 used 2500 mm 3 instead of 3000 mm 3. The graft ratio of the polymer obtained at this time was about 50%.
비교예 2Comparative Example 2
실시예 1의 B)에서 사용되어지는 폴리부타디엔 고무 라텍스의 겔 함량이 75%인 대신에 95 %인 라텍스를 사용한 것 외에는 동일한 방법으로 중합을 하였다.The polymerization was carried out in the same manner except that the gel content of the polybutadiene rubber latex used in Example 1B) was 95% instead of 75%.
적용예 1Application example 1
상기 실시예 1 A)에서 제조한 ASA 수지 분말 40 중량부와 B)에서 제조한 그라프트 ABS 수지 분말 10 중량부, SAN(LG 화학 제품, 제품명 : 80 HF) 50 중량부에 활제 0.5 중량부, 산화 방지제 0.4 중량부, 자외선 안정제 0.6 중량부를 첨가한후 혼합하여 200 ℃ 내지 220 ℃의 실린더 온도에서 압출 혼련기를 사용하여 펠릿 형태로 제조하였다. 이 펠렛 형태로 제조하였다. 이 펠렛으로 사출하여 시편을 제조하고 물성을 측정하여 표 1에 나타내었다.40 parts by weight of the ASA resin powder prepared in Example 1 A) and 10 parts by weight of the graft ABS resin powder prepared in B), 0.5 part by weight of lubricant, 50 parts by weight of SAN (LG Chemical, product name: 80 HF), 0.4 parts by weight of antioxidant and 0.6 parts by weight of UV stabilizer were added and mixed to prepare pellets using an extrusion kneader at a cylinder temperature of 200 ° C to 220 ° C. Prepared in the form of pellets. The pellets were injected into the pellets to prepare specimens, and the physical properties thereof were shown in Table 1.
적용예 2Application example 2
적용예 1과 동일한 방법으로 적용하되 사용되어지는 그라프트 ABS 수지 분말을 실시예 1 B)의 제조 방법 대신에 비교예 1의 제조 방법으로 제조한 분말을 사용하였다.The graft ABS resin powder to be used in the same manner as in Application Example 1, but to be used in place of the production method of Example 1 B) was used to prepare a powder of the comparative method of Comparative Example 1.
적용예 3Application example 3
적용예 1과 동일한 방법으로 적용하되 사용되어지는 그라프트 ABS 수지 분말을 실시예 1 B) 제조 방법 대신에 1 비교예 2의 방법으로 제조한 분말을 사용하였다.The graft ABS resin powder to be applied in the same manner as in Application Example 1, but to be used in place of the production method of Example 1 B) was used a powder prepared in the method of Comparative Example 2.
본 발명에 의하면, 내후성은 있으나 저온 내 충격성이 부족한 ASA 수지의 문제점이 개선됨으로써, 저온 내 충격성 및 내후성이 우수한 수지를 제조할 수 있게 된다.According to the present invention, by improving the problem of the ASA resin having weather resistance but low temperature impact resistance, it is possible to produce a resin excellent in low temperature impact resistance and weather resistance.
또한 저온 내 충격성 및 내후성 수지 제조를 위한 기존 기술의 문제점인 복잡한 중합 방법, 반응 제어의 어려움, ABS 수지의 노화 방지의 한계 및 원가 부담을 해결할 수 있다.In addition, it is possible to solve the complex polymerization method, the difficulty of reaction control, the limitation of the anti-aging of ABS resin and the cost burden, which are problems of the existing technology for manufacturing low temperature impact resistance and weather resistance resin.
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| KR920009914A (en) * | 1990-11-02 | 1992-06-25 | 시바따 마쓰지로 | Thermoplastic resin composition |
| JPH0657154A (en) * | 1992-06-29 | 1994-03-01 | Basf Ag | Molding material based on impact-resistant modified thermoplastic resin |
| KR0141352B1 (en) * | 1993-12-30 | 1998-07-01 | 성재갑 | Thermoplastic resin composition for use of processable improvement maetrial |
-
1998
- 1998-06-03 KR KR10-1998-0020635A patent/KR100384383B1/en not_active IP Right Cessation
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57167308A (en) * | 1981-04-08 | 1982-10-15 | Hitachi Chem Co Ltd | Production of impact-resistant, weather-resistant thermoplastic resin |
| JPS58187411A (en) * | 1982-04-27 | 1983-11-01 | Hitachi Chem Co Ltd | Production of shock-resistant thermoplastic resin |
| JPS588716A (en) * | 1982-06-24 | 1983-01-18 | Asahi Chem Ind Co Ltd | Production of transparent thermoplastic resin |
| JPS6121152A (en) * | 1984-07-10 | 1986-01-29 | Asahi Chem Ind Co Ltd | Thermoplastic resin composition |
| US5116907A (en) * | 1988-03-31 | 1992-05-26 | Basf Aktiengesellschaft | Heat distortion resistant, thermoplastic molding material containing a copolymer, preparation of the molding material and its use |
| KR920009914A (en) * | 1990-11-02 | 1992-06-25 | 시바따 마쓰지로 | Thermoplastic resin composition |
| JPH0657154A (en) * | 1992-06-29 | 1994-03-01 | Basf Ag | Molding material based on impact-resistant modified thermoplastic resin |
| KR0141352B1 (en) * | 1993-12-30 | 1998-07-01 | 성재갑 | Thermoplastic resin composition for use of processable improvement maetrial |
Also Published As
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|---|---|
| KR20000000787A (en) | 2000-01-15 |
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