KR940011410B1 - Preparation of thermoplastic resin composition - Google Patents

Preparation of thermoplastic resin composition Download PDF

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KR940011410B1
KR940011410B1 KR1019910000973A KR910000973A KR940011410B1 KR 940011410 B1 KR940011410 B1 KR 940011410B1 KR 1019910000973 A KR1019910000973 A KR 1019910000973A KR 910000973 A KR910000973 A KR 910000973A KR 940011410 B1 KR940011410 B1 KR 940011410B1
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thermoplastic resin
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KR920014871A (en
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이찬홍
김영민
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주식회사럭키
최근선
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
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Abstract

The thermoplastic resin is produced by blending at least 70 wt.pts. of a graft polymer resin, 5-25 wt.pts. of polybutylene terephthalate and at most 5 wt.pts. of a styrene-acrylonitrile copolymer resin, and dipping the blend into a solvent i.e. 95 % ethyl alcohol, gasoline or methylene chloride for 3 months. The graft polymer resin is produced by graft copolymerizing a mixt of 20-50 wt.pts. rubber latex having 0.25-0.35 of average particle size, 10-40 wt.pts. vinyl aromatic cpd., 30-60 wt.pts. vinyl cyane cpd., 2-6 wt.pts. acrylamide, 2-5 wt.pts. glycidyl(meth)acrylate, 0.2-0.5 wt.pt. polymerization initiator, 0.1 wt.pt. sodium phosphate, at most 3.0 wt.pts. emulsifier and 1.5-2.5 wt.pts. molecular wt. regulator.

Description

내화학성이 우수한 열가소성 수지 조성물의 제조방법Manufacturing method of thermoplastic resin composition excellent in chemical resistance

본 발명은 에틸알코올 및 가솔린등의 화학적 물질에 견디는 성질을 갖는 열가소성 수지 조성물의 제조방법에 관한 것이다.The present invention relates to a method for producing a thermoplastic resin composition having a property of withstanding chemical substances such as ethyl alcohol and gasoline.

일반적으로 ABS수지는 함유되어 있는 아크릴로니트릴로 인해 여러 솔벤트에 견디는 우수한 내화학성을 갖는다. 그러나 95%의 에틸알코올 및 가솔린, 메틸렌클로라이드와 접촉시 표면백화현상 및 팽윤현상이 나타난다. 본 발명자들은 이러한 단점을 해결하기 위해 연구를 거듭한 결과, 다음과 같은 그라프트 중합체를 이용해서 이를 해결했다.In general, ABS resin has excellent chemical resistance to various solvents due to the acrylonitrile contained. However, when it comes into contact with 95% of ethyl alcohol, gasoline, and methylene chloride, surface whitening and swelling occur. The present inventors have conducted research to solve these shortcomings, and solved this by using the following graft polymer.

즉, 본 발명의 요지는 겔 함량이 낮은 소구경 고무라텍스를 이용해서 응집시켜 대구경 고무입자로 비대화시켜 이 비대화된 대구경 고무입자와 소구경입자를 적절히 혼합하여 이 혼합라텍스 존재하에서 스티렌 α-메틸스티렌등의 비닐방향족 화합물 단량체,이것과 공중합 가능한 비닐시안 화합물, 아크릴아미드 또는 메타아크릴아마이드, 혹은 그 혼합 단량체, 에폭시링을 함유하는 글리시딜아크릴레이트 혹은 글리시딜 메타크릴레이트 등을 그라프트시켜 제조한 열가소성 수지와 나일론 혹은 폴리부틸렌 테레프탈레이트 수지와 혼련하여 메틸렌클로라이드등의 솔벤트에 견디는 내화학성이 우수한 열가소성 수지 조성물의 제조방법에 관한 것이다.That is, the gist of the present invention aggregates using a small-diameter rubber latex having a low gel content, enlarges it into large-diameter rubber particles, and appropriately mixes the enlarged large-diameter rubber particles and small-diameter particles, and in the presence of this mixed latex, such as styrene α-methylstyrene and the like. Prepared by grafting a vinylaromatic compound monomer, a vinylcyan compound copolymerizable with this, acrylamide or methacrylamide, a mixed monomer thereof, glycidyl acrylate or glycidyl methacrylate containing an epoxy ring, or the like. The present invention relates to a method for producing a thermoplastic resin composition excellent in chemical resistance that is kneaded with a thermoplastic resin and nylon or polybutylene terephthalate resin to withstand solvents such as methylene chloride.

본 발명의 내용은 이해하기 쉽게 그 공정을 크게 나누어 보면, 다음과 같다.The contents of the present invention are as follows, if the process is largely divided into easy to understand.

① 고무라텍스 응집공정① Rubber Latex Coagulation Process

② 그라프트 중합공정② Graft polymerization process

③ 나일론 및 폴리부틸렌 테레프탈레이트와 혼련공정③ Kneading process with nylon and polybutylene terephthalate

이를 자세히 설명하면 다음과 같다.This will be described in detail as follows.

본 발명에서 이용되어지는 소구경 고무질 중합체 라텍스의 예로서는 폴리부타디엔, 부타디엔을 50중량% 이상 함유한 부타디엔과 다른 공중합성 단량체와의 공중합체 라텍스를 열거할 수 있다.As an example of the small diameter rubbery polymer latex used by this invention, the copolymer latex of butadiene containing 50 weight% or more of polybutadiene and butadiene, and another copolymerizable monomer can be mentioned.

부타디엔과 공중합성을 갖는 단량체의 구체적 예로서는 스티렌, α-메틸스티렌, 비닐톨루엔등의 비닐방향족 화합물, 아크릴로니트릴, 메타크릴로니트릴등의 비닐시안 화합물 등을 들 수 있다.Specific examples of the monomer having copolymerizability with butadiene include vinylaromatic compounds such as styrene, α-methylstyrene and vinyltoluene, and vinylcyan compounds such as acrylonitrile and methacrylonitrile.

그외에도 폴리이소프렌, 폴리클로로프렌, 에틸렌-프로필렌-비공액디엔 화합물의 3원 중합체도 사용할 수 있다. 이와 같은 고무질 중합체의 겔 함유량은 85∼90% 정도가 적절하며, 95% 이상일 때는 본 발명에서 의도하는 물성을 얻을 수 없다.In addition, ternary polymers of polyisoprene, polychloroprene and ethylene-propylene-non-conjugated diene compounds can also be used. As for the gel content of such a rubbery polymer, about 85 to 90% is suitable, and when it is 95% or more, the physical property intended by this invention cannot be obtained.

겔 함량의 측정은 고무라텍스를 응고하여 세척한 후, 40℃ 진공오븐에서 하루동안 건조한 후, 고무 1g을 톨루엔 100g에 놓고 48시간 동안 방치한 후, 용해된 부분과 용해되지 않은 부분의 함량을 측정한다.The gel content was measured by solidifying and washing the rubber latex, drying in a vacuum oven at 40 ° C. for one day, placing 1 g of rubber in 100 g of toluene and leaving it for 48 hours, and then measuring the content of dissolved and undissolved parts. do.

Figure kpo00001
Figure kpo00001

다음 상기의 소구경 고무라텍스를 이용하여 응집대구경 고무라텍스를 제조하였다.Next, agglomerated large-diameter rubber latex was prepared using the small-diameter rubber latex.

응집방법으로는 고압 호모지나이저(미국, 가울린사제품)를 이용하여 입경분포가 약 0.25∼0.35μ에 드는 응집대구경 고무라텍스를 얻었다. 이 응집 고무라텍스 20∼50중량부에 비닐방향족 화합물 10∼40중량부, 비닐시안 화합물 30∼60중량부, 아크릴아마이드 2∼6중량부 글리시딜아크릴레이트 혹은 글리시딜메타크릴레이트 2∼5중량부와 개시제 0.2∼0.5중량부, 인산나트륨 0.1중량부, 유화제 3.0중량부 이하, 분자량 조절제 1.5∼2.5중량부를 이용하여 그라프트 공중합을 행한다. 그라프트 중합의 방법은 총 단량체중 1/3가량은 일괄 투여하고 나머지 단량체는 연속적 투여방법을 채택하여 전환율이 80% 정도에 달하면 비닐방향족 화합물 5중량부 이하를 추가로 투여하고 전환율이 약 95% 이상일 때 반응을 종료시킨다. 이 그라프트 중합의 핵심부분은 총 그라프트 되어지는 단량체중 비닐시안 화합물이 차지하는 분율이 약 60%∼75% 정도이며 이 높은 비닐시안 화합물의 분율로 인해 내화학성이 증진되는 것이다. 그라프트 되어지는 분자사슬에 비닐시안 화합물의 양을 증진시키려면 유화제도 지방산염, 로진산염 보다는 낮은 pH에서도 안정성이 우수한 알킬아릴술폰산염이 적절하다. 다음, 여기서 얻어진 라텍스를 염화칼슘으로 응고시키고 세척, 건조하여 분말의 형태로 제조한다. 다음 나일론 6(LAPCO사 CAPRON 8202C) 5∼25중량부와 혼련하거나, 폴리부틸렌 테레프탈레이트(럭키 : UNPOX GP1000) 5∼25중량부와 혼련하여 압출 및 사출하여 10cm×10cm, 두께 3mm의 시편으로 제작하여 95% 에틸알코올, 가솔린에 3개월동안 침적시킨 후 중량변화를 측정했을 때, 1.0% 미만인 열가소성 수지를 제조하는 방법이다.As a coagulation method, a cohesive large-diameter rubber latex having a particle size distribution of about 0.25 to 0.35 mu was obtained by using a high pressure homogenizer (manufactured by Gaulin, USA). 20 to 50 parts by weight of this agglomerated rubber latex, 10 to 40 parts by weight of a vinyl aromatic compound, 30 to 60 parts by weight of a vinyl cyan compound, 2 to 6 parts by weight of acrylamide glycidyl acrylate or glycidyl methacrylate 2 to 5 Graft copolymerization is performed using a weight part, 0.2-0.5 weight part of initiators, 0.1 weight part of sodium phosphates, 3.0 weight part or less of emulsifiers, and 1.5-2.5 weight part of molecular weight modifiers. In the graft polymerization method, about 1/3 of the total monomers are administered in a batch and the remaining monomers are adopted in a continuous manner. When the conversion rate reaches 80%, 5 parts by weight or less of the vinylaromatic compound is additionally administered and the conversion rate is about 95%. When abnormal, the reaction is terminated. The key part of the graft polymerization is that the fraction of vinyl cyanide compounds in the total grafted monomers is about 60% to 75% and the chemical resistance is enhanced by the high fraction of vinyl cyanide compounds. In order to increase the amount of vinyl cyan compounds in the grafted molecular chain, an alkyl aryl sulfonate having an excellent stability even at a lower pH than a fatty acid salt or a rosin salt is suitable. The latex obtained here is then coagulated with calcium chloride, washed and dried to form a powder. Next, nylon 6 (LAPCO CAPRON 8202C) is kneaded with 5 to 25 parts by weight, or polybutylene terephthalate (Lucky: UNPOX GP1000) is kneaded with 5 to 25 parts by weight to extrude and inject into 10 cm x 10 cm, 3 mm thick specimens. After manufacturing and immersing in 95% ethyl alcohol, gasoline for 3 months, and measuring the weight change, it is a method for producing a thermoplastic resin less than 1.0%.

이하 실시예로 설명하면 다음과 같다.When described in the following examples.

[실시예 1]Example 1

① 응집대구경 제조 및 그라프트 중합① Agglomeration large diameter manufacturing and graft polymerization

겔 함량이 85∼90% 정도이고, 입경이 0.09∼0.12μ인 소구경 폴리부타디엔 고무라텍스를 가울린사의 고압 호모지나이제로 약 5,000psig에서 통과시켜 평균입경이 0.3μ인 응집대구경 고무라텍스를 제조한다.A small-diameter polybutadiene rubber latex with a gel content of about 85 to 90% and a particle size of 0.09 to 0.12 μ was passed through a high-pressure homogenizer from Gaulin at about 5,000 psig to produce a cohesive large-diameter rubber latex with an average particle diameter of 0.3 μ. do.

이 응집 고무라텍스의 입경분포는 0.2μ 이하가 전체 입자 중량부중 약 20%를 차지하며 0.2μ 이상 0.5μ 이하가 70%이다. 이렇게 제조된 고무라텍스 25중량부를 일괄 반응조에 투여한다. 다시 이온교환수 200중량부, 소디움도데실벤젠술포네이트 1.0중량부, 아크릴로니트릴 15중량부, 스티렌 6중량부, 인산나트륨 0.1중량부, 터샤리도데실메르캅탄 1.1중량부, 피롤린산 나트륨 0.16중량부, 덱스트로즈 0.20중량부, 황산제일철 0.01중량부, 큐멘하이드로퍼옥사이드 0.09중량부, 아크릴아마이드 2중량부, 글리시딜아크릴레이트 1.0중량부를 일괄 투여하고 반응초기 온도를 45℃로 하고 1시간에 걸쳐 75℃로 승온한다. 다음 온도가 75℃에 도달하면 아크릴로니트릴 30중량부, 스티렌 13중량부, 아크릴아미드 3중량부, 글리시딜아크릴레이트 2.0중량부, 소디움도데실벤젠술포네이트 1.5중량부, 큐멘하이드로퍼옥사이드 0.2중량부, 이온교환수 150중량부, 터샤리도데실메르캅탄 1.0중량부를 서로 혼합하여 유화액으로 만든 다음, 약 4시간에 걸쳐 연속적 투여를 한다. 투입이 끝난 후, 온도를 다시 80℃로 승온하고 스티렌 3중량부, 이온교환수 4중량부, 피롤린산나트륨 0.07중량부, 소디움도데실벤젠술포네이트 0.4중량부, 덱스트로즈 0.08중량부, 황산제일철 0.0013중량부, 큐멘하이드로퍼옥사이드 0.05중량부를 일괄 투여한 후, 1시간동안 반응시키고 반응을 종료시킨다. 이 중합이 끝난 후, 전환율을 측정한 결과 96%였다. 이것은 <표1>의 G1에 도시하였다. G2는 G1의 중합방법과 동일하며 초기 고무라텍스 중량부가 20중량부이고 단량체의 양만 서로 다른 것이다. G3는 응집시 호모지나이저 압력을 4,300psig로 하여 0.25μ의 입자경을 갖는 고무라텍스를 얻고 이것을 그라프트 중합시 40중량부 이용하였다. 그리고 아크릴레이트 양을 G2에 비해 1.0중량부 중랑하였다. G4는 아크릴로니트릴의 함량이 총 그라프트 되어질 단량체 함량의 50중량% 미만인 경우를 나타낸 것이며, G5는 응집 고무라텍스의 평균입경이 0.4μ으로 아주 큰 경우를 나타낸 것이다. G6는 총 단량체중 아크릴로니트릴의 함량이 75중량% 이상인 경우를 나타낸 것이다. G7은 아크릴아미드나 글리시딜아크릴레이트를 전혀 사용치 않은 경우이다.In the particle size distribution of the cohesive rubber latex, 0.2 µm or less occupies about 20% of the total weight of the particles, and 0.2 µm or more and 0.5 µm or less is 70%. 25 parts by weight of the rubber latex thus prepared are administered to a batch reactor. 200 parts by weight of ion-exchanged water, 1.0 part by weight of sodium dodecylbenzenesulfonate, 15 parts by weight of acrylonitrile, 6 parts by weight of styrene, 0.1 part by weight of sodium phosphate, 1.1 part by weight of tersaridodecyl mercaptan, and 0.16 parts of sodium pyrrolate 1 part by weight, dextrose 0.20 part by weight, ferrous sulfate 0.01 part by weight, cumene hydroperoxide 0.09 part by weight, acrylamide 2 part by weight, glycidyl acrylate 1.0 part by weight, and the initial reaction temperature was 45 ° C. It heats up at 75 degreeC over time. When the next temperature reaches 75 ℃, 30 parts by weight of acrylonitrile, 13 parts by weight of styrene, 3 parts by weight of acrylamide, 2.0 parts by weight of glycidyl acrylate, 1.5 parts by weight of sodium dodecylbenzenesulfonate, cumene hydroperoxide 0.2 By weight, 150 parts by weight of ion-exchanged water, 1.0 part by weight of tersaridodecyl mercaptan are mixed with each other to form an emulsion, followed by continuous administration over about 4 hours. After the addition was completed, the temperature was again raised to 80 ° C., and 3 parts by weight of styrene, 4 parts by weight of ion-exchanged water, 0.07 part by weight of sodium pyrrolate, 0.4 part by weight of sodium dodecylbenzenesulfonate, 0.08 part by weight of dextrose, and sulfuric acid 0.0013 parts by weight of ferrous iron and 0.05 parts by weight of cumene hydroperoxide were collectively administered, followed by reaction for 1 hour, and the reaction was terminated. After the completion of this polymerization, the conversion was measured and found to be 96%. This is shown in G1 of Table 1. G2 is the same as the polymerization method of G1, the initial rubber latex parts by weight 20 parts by weight and the amount of monomers are different. G3 had a homogenizer pressure of 4,300 psig at the time of aggregation to obtain a rubber latex having a particle diameter of 0.25 µm, and 40 parts by weight of the graft polymerization was used. And the amount of acrylate was weighted 1.0 weight part compared with G2. G4 represents the case where the content of acrylonitrile is less than 50% by weight of the total monomer content to be grafted, and G5 represents the case where the average particle diameter of the agglomerated rubber latex is very large, 0.4 mu. G6 represents a case where the content of acrylonitrile in the total monomers is 75% by weight or more. G7 is a case where no acrylamide or glycidyl acrylate is used.

[표 1]TABLE 1

Figure kpo00002
Figure kpo00002

<연속투여><Continuous administration>

Figure kpo00003
Figure kpo00003

<일괄투여><Batch administration>

Figure kpo00004
Figure kpo00004

② 혼련공정② Kneading Process

상기 그라프트 중합체(G1) 80중량부를 염화칼슘으로 응고시키고, 세척 및 건조하여 분말의 형태로 제조한다. 다음 이 분말 나이론 6(LAPCO사(한국)의 Capron 8202C) 15중량부 SAN((주)럭키 80HF)(스티렌-아크릴로니트릴의 공중합체 수지) 5중량부를 이축 압축기를 이용하여 펠렛으로 제조하고 다시, 10cm×10cm, 두께 3mm의 시편으로 사출하여 이 시편을 95% 에틸알코올, 가솔린, 메틸렌클로라이드 용액에 3개월간 침적시킨 후, 그 중량변화를 측정하여 1.3% 미만인 경우 내화학성이 양호한 것으로 판정하였다. 그 내용을 표 2에 나타내었다.80 parts by weight of the graft polymer (G1) is solidified with calcium chloride, washed and dried to prepare a powder. Next, 5 parts by weight of 15 parts by weight of the powder nylon 6 (Capron 8202C manufactured by LAPCO (Korea)) SAN (Luck 80 Co., Ltd.) (copolymer resin of styrene-acrylonitrile) was manufactured into pellets using a twin screw compressor, and again. , 10cm × 10cm, 3mm thick specimen was injected into the specimen for 3 months in 95% ethyl alcohol, gasoline, methylene chloride solution, the weight change was measured and less than 1.3%, it was determined that the chemical resistance is good. The contents are shown in Table 2.

[실시예 2]Example 2

그라프트 중합체(G1) 70중량부, PBT수지((주)럭키의 LUPOX GP1000) 25중량부, SAN((주)럭키의 80HF) 5중량부 사용한 것을 제외하고는 실시예 1과 동일하게 사출하여 물성을 측정하였으며, 그 내용은 표 2에 나타내었다.Injected in the same manner as in Example 1 except that 70 parts by weight of the graft polymer (G1), 25 parts by weight of PBT resin (Lucky Co., Ltd.) and 5 parts by weight of SAN (Lucky Co., Ltd.) were used. Physical properties were measured, and the contents thereof are shown in Table 2.

[실시예 3]Example 3

그라프트 중합체(G1) 80중량부, PBT수지((주)럭키의 LUPOX GP1000) 20중량부 사용한 것을 제외하고는 실시예 1과 동일하게 사출하여 물성을 측정하였으며, 그 내용은 표 2에 나타내었다.Except for using 80 parts by weight of the graft polymer (G1) and 20 parts by weight of PBT resin (Lucky Co., Ltd. LUPOX GP1000), the physical properties of the graft polymer were measured in the same manner as in Example 1, and the contents thereof are shown in Table 2. .

[실시예 4]Example 4

그라프트 중합체(G1) 90중량부, 나일론 6(Capron 8202C 한국의 LAPCO사) 10중량부 사용한 것을 제외하고는 실시예 1과 동일하게 사출하여 물성을 측정하였으며, 그 내용은 표 2에 나타내었다.The physical properties of the graft polymer (G1) were measured in the same manner as in Example 1 except that 90 parts by weight of graft polymer (G1) and 10 parts by weight of nylon 6 (Capron 8202C Korea, LAPCO Co., Ltd.) were used.

[실시예 5]Example 5

그라프트 중합체(G3) 70중량부, 나일론 6(Capron 8202C 한국의 LAPCO사) 25중량부, SAN((주)럭키의 80HF) 5중량부 사용한 것을 제외하고는 실시예 1과 동일하게 사출하여 물성을 측정하였으며, 그 내용은 표 2에 나타내었다.Extruded in the same manner as in Example 1 except that 70 parts by weight of graft polymer (G3), 25 parts by weight of nylon 6 (Capron 8202C Korea LAPCO Co., Ltd.), and 5 parts by weight of SAN (80HF, Lucky Co., Ltd.) were used. Was measured, and the contents thereof are shown in Table 2.

[비교예 1]Comparative Example 1

그라프트 중합체(G4) 80중량부, 나일론 6(Capron 8202C 한국의 LAPCO사) 20중량부 사용한 것을 제외하고는 실시예 1과 동일하게 사출하여 물성을 측정하였으며, 그 내용은 표 2에 나타내었다.Except for using 80 parts by weight of graft polymer (G4) and 20 parts by weight of nylon 6 (Capron 8202C Korea's LAPCO Co., Ltd.), the physical properties of the graft polymer were measured in the same manner as in Example 1, and the contents thereof are shown in Table 2.

[비교예 2]Comparative Example 2

그라프트 중합체(G5) 75중량부, PBT수지((주)럭키의 LUPOX GP1000) 25중량부 사용한 것을 제외하고는 실시예 1과 동일하게 사출하여 물성을 측정하였으며, 그 내용은 표 2에 나타내었다.Except 75 parts by weight of graft polymer (G5) and 25 parts by weight of PBT resin (Lucky Co., Ltd. LUPOX GP1000), the physical properties of the graft polymer were measured in the same manner as in Example 1, and the contents thereof are shown in Table 2. .

[비교예 3]Comparative Example 3

그라프트 중합체(G6) 80중량부, 나일론 6(Capron 8202C 한국의 LAPCO사) 20중량부 사용한 것을 제외하고는 실시예 1과 동일하게 사출하여 물성을 측정하였으며, 그 내용은 표 2에 나타내었다.Except for using 80 parts by weight of graft polymer (G6), 20 parts by weight of nylon 6 (Capron 8202C Korea's LAPCO Co., Ltd.) was injected in the same manner as in Example 1 to measure the physical properties, the contents are shown in Table 2.

[비교예 4][Comparative Example 4]

그라프트 중합체(G6) 80중량부, PBT수지((주)럭키의 LUPOX GP1000) 20중량부 사용한 것을 제외하고는 실시예 1과 동일하게 사출하여 물성을 측정하였으며, 그 내용은 표 2에 나타내었다.Except for using 80 parts by weight of the graft polymer (G6), 20 parts by weight of PBT resin (Lucky Co., Ltd. LUPOX GP1000), the physical properties were measured in the same manner as in Example 1, and the properties thereof are shown in Table 2. .

[비교예 5][Comparative Example 5]

그라프트 중합체(G7) 80중량부, 나일론 6(Capron 8202C 한국의 LAPCO사) 20중량부 사용한 것을 제외하고는 실시예 1과 동일하게 사출하여 물성을 측정하였으며, 그 내용은 표 2에 나타내었다.Except for using 80 parts by weight of graft polymer (G7), 20 parts by weight of nylon 6 (Capron 8202C Korea LAPCO Co., Ltd.) was injected and the physical properties were measured in the same manner as in Example 1, the contents are shown in Table 2.

[표 2]TABLE 2

Figure kpo00005
Figure kpo00005

Figure kpo00006
Figure kpo00006

Claims (5)

평균입자경이 0.25∼0.35μ인 응집대구경 고무입자 20∼50중량부에 비닐방향족 화합물 10∼40중량부, 비닐시안 화합물 30∼60중량부, 아크릴아마이드 혹은 메타크릴아마이드 2∼6중량부, 글리시딜아크릴레이트 혹은 글리시딜메타크릴레이트 2∼5중량부의 혼합단량체, 개시제, 연쇄이동제로 그라프트 중합하여 제조한 수지 70중량부 이상과 폴리부틸렌 테레프탈레이트 5∼25중량부, 스티렌-아크릴로니트릴의 공중합 수지 5중량부 이하의 혼련하여 95% 에탈알코올, 혹은 가솔린, 메틸렌클로라이드 등의 솔벤트에 3개월간 침적시 중량변화가 1.0% 미만인 내화학성이 우수한 열가소성 수지 조성 물의 제조방법.20 to 50 parts by weight of agglomerated large-diameter rubber particles having an average particle diameter of 0.25 to 0.35 μ, 10 to 40 parts by weight of a vinyl aromatic compound, 30 to 60 parts by weight of a vinyl cyan compound, 2 to 6 parts by weight of acrylamide or methacrylamide, and glyci 70 parts by weight or more of a resin prepared by graft polymerization with a diacrylate or glycidyl methacrylate mixed monomer, an initiator, a chain transfer agent, 5 to 25 parts by weight of polybutylene terephthalate, and styrene-acrylo A method for producing a thermoplastic resin composition having excellent chemical resistance when the mixture is mixed with 5 parts by weight or less of nitrile and immersed in a solvent such as 95% ethanol or gasoline or methylene chloride for 3 months. 제1항에 있어서, 고무의 겔 함량이 85∼90%임을 특징으로 하는 열가소성 수지 조성물의 제조방법.The method for producing a thermoplastic resin composition according to claim 1, wherein the gel content of the rubber is 85 to 90%. 제1항에 있어서, 고무입자의 성분이 1,3-부타디엔 단일중합체, 1,3-부타디엔-스티렌 공중합체, 1,3-부타디엔-아크릴로니트릴 공중합체로 유리전이온도가 -50℃ 미만인 것을 특징으로 하는 열가소성 수지 조성물의 제조방법.According to claim 1, wherein the rubber particles are 1,3-butadiene homopolymer, 1,3-butadiene-styrene copolymer, 1,3-butadiene-acrylonitrile copolymer, the glass transition temperature is less than -50 ℃ The manufacturing method of the thermoplastic resin composition characterized by the above-mentioned. 제1항에 있어서, 비닐방향족 화합물이 스티렌, α-메틸스티렌, 비닐톨루엔, 할로겐화 스티렌인 것을 특징으로 하는 열가소성 수지 조성물의 제조방법.The method for producing a thermoplastic resin composition according to claim 1, wherein the vinylaromatic compound is styrene, α-methylstyrene, vinyltoluene, or halogenated styrene. 제1항에 있어서, 그라프트 중합시 단량체의 첨가방법이 전체 단량체의 약 1/3가량만 일괄 투여하고 나머지는 연속 투입하여 그라프팅을 행하고 그라프팅이 끝난 후, 다시 80℃로 승온하고 1시간동안 숙성시켜 전환율이 95% 이상인 열가소성 수지 조성물의 제조방법.The method according to claim 1, wherein the method of adding the monomers during graft polymerization is performed in a batch of about 1/3 of the total monomers, and the rest is continuously added to perform grafting, and after completion of the grafting, the temperature is raised to 80 ° C. again for 1 hour. A method of producing a thermoplastic resin composition having a conversion rate of 95% or more by aging.
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Publication number Priority date Publication date Assignee Title
KR100708991B1 (en) * 2005-05-19 2007-04-18 주식회사 엘지화학 Method for preparing of acrylonitrile butadiene styrene latex

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100708991B1 (en) * 2005-05-19 2007-04-18 주식회사 엘지화학 Method for preparing of acrylonitrile butadiene styrene latex

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