KR20020039855A - Method for preparing latex having superior stability - Google Patents

Method for preparing latex having superior stability Download PDF

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KR20020039855A
KR20020039855A KR1020000069676A KR20000069676A KR20020039855A KR 20020039855 A KR20020039855 A KR 20020039855A KR 1020000069676 A KR1020000069676 A KR 1020000069676A KR 20000069676 A KR20000069676 A KR 20000069676A KR 20020039855 A KR20020039855 A KR 20020039855A
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weight
parts
rubber latex
iii
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KR100409073B1 (en
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김건수
박동진
김은경
이준태
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성재갑
주식회사 엘지씨아이
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/10Latex
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/16Aqueous medium
    • C08F2/22Emulsion polymerisation
    • C08F2/24Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26Emulsion polymerisation with the aid of emulsifying agents anionic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/16Aqueous medium
    • C08F2/22Emulsion polymerisation
    • C08F2/24Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/30Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00Macromolecular 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
    • C08F279/02Macromolecular 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
    • C08F279/04Vinyl aromatic monomers and nitriles as the only monomers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/10Transparent films; Clear coatings; Transparent materials

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

PURPOSE: Provided is a process for producing a rubber latex excellent in stability, the rubber latex can produce an acrylonitrile-butadiene-styrene resin excellent in high impact property and high transparency. CONSTITUTION: The process contains the step of emulsion-polymerizing 100pts.wt. of conjugated diene compound monomers and 0.01-3.0pts.wt. of a reactive emulsifier, wherein the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene, isoprene, and chloroprene, and the reactive emulsifier is at least one selected from the group consisting of an anionic emulsifier having an allyl group of a sulfate salt of polyoxyethylene allyl glycidic nonyl phenyl ether, a neutral emulsifier having a polyoxyethylene allyl glycidyl nonyl phenyl ether-based allyl group, an anionic emulsifier having a (meth)acryloyl group, and etc.

Description

안정성이 우수한 고무라텍스의 제조방법 {METHOD FOR PREPARING LATEX HAVING SUPERIOR STABILITY}Manufacturing method of rubber latex with excellent stability {METHOD FOR PREPARING LATEX HAVING SUPERIOR STABILITY}

[산업상 이용 분야][Industrial use]

본 발명은 안정성이 우수한 고무라텍스의 제조방법에 관한 것으로, 특히 고무라텍스의 제조에 있어서 반응형 유화제를 사용하여 안정성이 우수한 고무라텍스를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing a rubber latex having excellent stability, and more particularly to a method for producing a rubber latex having excellent stability using a reactive emulsifier in the production of the rubber latex.

[종래 기술][Prior art]

투명 아크릴로니트릴-부타디엔-스티렌(ABS : acrylonitrile-butadiene-styrene) 수지의 제조에 있어서, 투명도는 굴절율이 적절하게 조절되었을 때 분산되어진 고무질 중합체의 입자경 크기와 입자 분포, 및 후공정에서 생성된 응고물 등에 크게 영향을 받는다.In the preparation of transparent acrylonitrile-butadiene-styrene (ABS) resins, the transparency is determined by the particle size and particle distribution of the rubbery polymer dispersed when the refractive index is properly controlled, and the coagulation produced in the subsequent process. It is greatly affected by water.

내충격성과 투명성이 우수한 아크릴로니트릴-부타디엔-스티렌 수지를 얻기 위해서는 대구경 고무라텍스가 필요한데, 이를 제조하기 위한 종래의 방법으로는 하기와 같은 방법들이 알려져 있다.In order to obtain an acrylonitrile-butadiene-styrene resin having excellent impact resistance and transparency, a large diameter rubber latex is required. As a conventional method for preparing the same, the following methods are known.

ⅰ) 소구경 고무라텍스를 제조하여 초산, 인산 등과 같은 무기산성물 또는고분자 응집제와 같은 유기산성물질을 첨가하여 pH를 낮추고 입자를 융 착시켜서 대구경 고무라텍스를 제조하는 방법;Iii) preparing small-diameter rubber latex, adding inorganic acids such as acetic acid, phosphoric acid, or organic acidic substances such as polymer flocculant to lower pH and fusion particles to produce large-diameter rubber latex;

ⅱ) 소구경 고무라텍스를 냉동시켜 대구경 입자를 제조하는 방법;Ii) a method for producing large-diameter particles by freezing small-diameter rubber latex;

ⅲ) 중합 도중 아크릴레이트계 공중합체 라텍스를 첨가하거나 또는 다가금속 의 전해질을 첨가하여 대구경 고무라텍스를 제조하는 방법;Iii) a method for preparing a large diameter rubber latex by adding an acrylate copolymer latex or adding a polyvalent metal electrolyte during the polymerization;

ⅳ) 소구경 고무라텍스에 전단력을 가하여 대구경 고무라텍스를 제조하는 방 법;Iii) a method for producing large diameter rubber latex by applying shear force to small diameter rubber latex;

ⅴ) 아크릴로니트릴 단량체를 공단량체로 소량 도입하는 방법Iii) a small amount of acrylonitrile monomer introduced into the comonomer

ⅵ) 유화제의 양과 이온의 세기를 적절하게 조절하여 대구경 고무라텍스를 제조하는 방법.Iii) A method for producing large diameter rubber latex by appropriately adjusting the amount of emulsifier and the ionic strength.

상기 ⅰ) 내지 ⅳ)의 방법은 단시간내에 대구경 고무라텍스의 제조가 가능하다는 장점이 있으나, 응고물이 많이 생성되고 중합의 재현성이 부족하며 적절한 크기로 조절하기 힘들다는 문제가 있다. 따라서 응고물을 거르는 장치, 및 과정이 필요하지만, 상기 과정 중에 생성된 원치 않는 크기의 응고물이 첨가되는 문제점이 발생하고, 이는 투명도를 크게 저하시키는 원인이 된다. 또한 ⅴ)의 방법은 고무라텍스 중합 후 미반응 단량체를 제거해야 하는 문제점이 있고, 특히 저온충격강도에서 순수한 디엔계 고무라텍스를 사용하는 경우보다 투명도가 떨어지는 단점이 있다. 또한 ⅵ)의 방법은 반응시간이 오래 걸리고 유화제 농도가 낮아야 하므로, 응고물이 많이 생성되고 교반시 반응열을 제거하기 어렵다는 문제점이 있다.The method of iii) to iii) has the advantage that it is possible to manufacture large diameter rubber latex within a short time, but there is a problem that a lot of coagulum is produced and the reproducibility of polymerization is insufficient and it is difficult to control to an appropriate size. Therefore, a device for filtering the coagulum and a process are required, but a problem arises in that an unwanted coagulum produced during the process is added, which causes a significant decrease in transparency. In addition, the method of iii) has a problem in that unreacted monomers have to be removed after rubber latex polymerization, and in particular, transparency is lower than that of pure diene rubber latex at low temperature impact strength. In addition, the method of iii) requires a long reaction time and a low concentration of the emulsifier, so that a large amount of coagulum is generated and it is difficult to remove the reaction heat during stirring.

본 발명은 상기 종래 기술의 문제점을 고려하여, 안정성이 우수한 고무라텍스의 제조방법을 제공하는 것을 목적으로 한다.In view of the problems of the prior art, it is an object of the present invention to provide a method for producing a rubber latex having excellent stability.

본 발명의 다른 목적은 안정성을 증가시켜 응고물 생성을 줄이고, 고무 입경 분포가 좁은 고무라텍스를 제조할 수 있을 뿐만 아니라, 고충격성, 및 고투명성이 우수한 투명 아크릴로니트릴-부타디엔-스티렌 수지를 제조할 수 있는 안정성이 우수한 고무라텍스를 제공하는 것이다.Another object of the present invention is to increase the stability, to reduce the formation of coagulum, to produce a rubber latex having a narrow rubber particle size distribution, as well as to prepare a transparent acrylonitrile-butadiene-styrene resin having excellent high impact and high transparency. It is to provide a rubber latex with excellent stability.

[과제를 해결하기 위한 수단][Means for solving the problem]

본 발명은 상기 목적을 달성하기 위하여, 안정성이 우수한 고무라텍스의 제조방법에 있어서,In order to achieve the above object, the present invention provides a rubber latex manufacturing method excellent in stability,

ⅰ) 공액디엔 화합물 단량체Iii) conjugated diene compound monomer

에 ⅱ) 반응형 유화제를 가하여 유화중합하는 단계를 포함하는 안정성이 우수한 고무라텍스의 제조방법을 제공한다.Ii) adding a reactive emulsifier to provide a method for producing a rubber latex having excellent stability including the step of emulsion polymerization.

이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

[작용][Action]

본 발명은 공액디엔 화합물 단량체에 반응형 유화제를 가하여 유화중합함으로써 안정성을 증가시켜 응고물 생성을 줄이고, 고무 입경 분포가 좁은 고무라텍스를 제조할 수 있을 뿐만 아니라, 고충격성, 및 고투명성이 우수한 투명 아크릴로니트릴-부타디엔-스티렌 수지를 제조할 수 있는 안정성이 우수한 고무라텍스를 제조하는 것이다.The present invention increases the stability by adding a reactive emulsifier to the conjugated diene compound monomer to increase the stability to reduce the formation of coagulum, and to prepare a rubber latex with a narrow rubber particle size distribution, as well as high impact and high transparency It is to prepare a rubber latex having excellent stability capable of producing acrylonitrile-butadiene-styrene resin.

본 발명은 이를 위하여, 상기 고무라텍스는The present invention for this purpose, the rubber latex is

ⅰ) 공액디엔 화합물 단량체 100 중량부;Iii) 100 parts by weight of the conjugated diene compound monomer;

에 ⅱ) 반응형 유화제 0.01 내지 3.0 중량부를 가하여 유화중합으로 중합한다.Ii) 0.01 to 3.0 parts by weight of a reactive emulsifier is added to polymerize by emulsion polymerization.

더욱 구체적으로는,More specifically,

a) 반응기에a) in the reactor

ⅰ) 공액디엔 화합물 단량체 50 내지 100 중량부;Iii) 50 to 100 parts by weight of the conjugated diene compound monomer;

ⅱ) 반응형 유화제 0.5 중량부 이하;Ii) 0.5 parts by weight or less of a reactive emulsifier;

ⅲ) 비반응형 유화제 1 내지 4 중량부;V) 1 to 4 parts by weight of a non-reactive emulsifier;

ⅳ) 중합개시제 0.2 내지 1.5 중량부;Iii) 0.2 to 1.5 parts by weight of a polymerization initiator;

ⅴ) 전해질 0.5 내지 2 중량부;V) 0.5 to 2 parts by weight of electrolyte;

ⅵ) 분자량 조절제 0.1 내지 0.5 중량부; 및Iii) 0.1 to 0.5 parts by weight of a molecular weight modifier; And

ⅶ) 이온교환수 75 내지 100 중량부Viii) 75 to 100 parts by weight of ion-exchanged water

를 일괄투여하여 65∼75 ℃에서 4∼15 시간 동안 반응시키는 단계;Dosing in a batch to react at 65 to 75 ° C. for 4 to 15 hours;

b) 상기 a) 단계의 반응물에b) reactants of step a)

ⅰ) 나머지 공액디엔 화합물 단량체 50 중량부 이하; 및V) 50 parts by weight or less of the remaining conjugated diene compound monomers; And

ⅵ) 분자량 조절제 0.1 내지 0.5 중량부Iii) 0.1 to 0.5 parts by weight of molecular weight regulator

를 일괄투여 또는 연속투여하여 70∼85 ℃에서 10∼20 시간 동안 반응시키는To batch or continuous dosing and reacted at 70 to 85 ° C. for 10 to 20 hours.

단계; 및step; And

c) 상기 b) 단계의 반응물의 중합전환율이 총 화합물의 30∼70 %가 되면c) the polymerization conversion rate of the reactant of step b) is 30-70% of the total compound

ⅱ) 반응형 유화제 0.01 내지 3.0 중량부Ii) 0.01 to 3.0 parts by weight of a reactive emulsifier

를 가하는 단계Steps to apply

를 포함하는 방법으로 제조되는 것이 바람직하다.It is preferable to be prepared by a method comprising a.

상기 ⅰ) 공액디엔 화합물 단량체는 총 100 중량부 중 중합개시전 50 내지 100 중량부를 일괄투여하여 반응시킨 후, 나머지 공액디엔 화합물 단량체를 일괄투여, 또는 연속투여하여 반응시킨다.(Iii) The conjugated diene compound monomers are reacted by collectively administering 50 to 100 parts by weight of the total conjugated diene compound monomers before the start of polymerization, and then the remaining conjugated diene compound monomers are collectively administered or continuously administered.

또한 ⅰ) 공액디엔 화합물 단량체는 공액디엔 화합물을 단독, 또는 스티렌, α-메틸스티렌 등의 방향족 비닐 화합물, 및 아크릴로니트릴 등과 같은 비닐시안 화합물과 혼합하여 사용할 수 있고, 총 단량체 혼합물 중 15 중량부 이내로 사용하는 것이 바람직하다.Iii) The conjugated diene compound monomers may be used alone or in combination with aromatic vinyl compounds such as styrene and α-methylstyrene, and vinyl cyan compounds such as acrylonitrile, and 15 parts by weight of the total monomer mixture. It is preferable to use within.

상기 ⅰ) 공액디엔 화합물은 1,3-부타디엔, 이소프렌, 클로로프렌, 및 피레리덴으로 이루어진 군으로부터 1 종 이상 선택되어 사용할 수 있다.(Iii) The conjugated diene compound may be selected from one or more selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and pyreriden.

본 발명의 고무라텍스의 제조방법에 사용되는 상기 ⅱ) 반응형 유화제는 알릴기, (메타)아크릴로일기, 및 프로페닐기를 가지는 음이온계 유화제, 또는 중성계 유화제 등이 사용될 수 있다.The ii) reactive emulsifier used in the rubber latex manufacturing method of the present invention may be an anionic emulsifier having an allyl group, a (meth) acryloyl group, and a propenyl group, or a neutral emulsifier.

상기 알릴기를 가지는 음이온 유화제로는 폴리옥시에틸렌 알릴그리시딜 노닐페닐 에테르의 설페이트염을 대표적으로 들 수 있으며, 시장에서 유용한 것으로는 ADEKARIA SOAP SE 계열(Asahi Denka 사의 제품) 등이 있으며, 알릴기를 가지는 중성계 유화제로는 폴리옥시에틸렌 알릴그리시딜 노닐페닐 에테르 계열이 있으며, 시장에서 유용한 것으로는 ADEKARIA SOAP NE 계열(Asahi Denka 사의 제품) 등이 있다. (메타)아크릴로일기를 가지는 음이온계 유화제로 시장에서 유용한 것은 ELEMINOL RS 계열(Sanyo Kasei 사의 제품)이 있고, 중성계 유화제로는 RMA-560 계열(Nippon Surfactant 사의 제품)이 있다. 프로펜기를 가지는 음이온계 유화제로는 폴리옥시에틸렌 알릴그리시딜 노닐 프로페닐 페닐 에테르의 암모늄설페이트염을 대표적으로 들 수 있으며, 시장에서 유용한 것으로는 AQUARON HS 계열이 있으며, 중성계 유화제로는 AQUARON BC(Daiichi Kogyo Seyaku 사의 제품) 계열이 있다. 이러한 반응형 유화제는 단독, 또는 2 종 이상의 혼합물로 사용할 수 있으며, 비반응형 유화제와 혼합하여 사용할 수 있다.Anionic emulsifiers having an allyl group may include sulfate salts of polyoxyethylene allylglycidyl nonylphenyl ether. Examples of useful anionic emulsifiers include ADEKARIA SOAP SE series (manufactured by Asahi Denka), and neutral allyl groups. Systemic emulsifiers include polyoxyethylene allylglycidyl nonylphenyl ether series, and useful ones on the market include the ADEKARIA SOAP NE series (product of Asahi Denka). The anionic emulsifier having a (meth) acryloyl group is useful in the market as the ELEMINOL RS series (manufactured by Sanyo Kasei), and the neutral emulsifier is the RMA-560 series (manufactured by Nippon Surfactant). Anionic emulsifiers having a propene group include ammonium sulfate salts of polyoxyethylene allylglycidyl nonyl propenyl phenyl ether, and useful in the market include AQUARON HS series, and neutral emulsifiers include AQUARON BC ( Daiichi Kogyo Seyaku's products) series. These reactive emulsifiers may be used alone or as a mixture of two or more thereof, and may be used by mixing with a non-reactive emulsifier.

또한 상기 ⅱ) 반응형 유화제는 유화중합시 0.01 내지 3.0 중량부를 첨가하는 것이 바람직하며, 바람직하게는 3.0 이하로 사용하는 것이 바람직하다. 3.0 이상이면 아크릴로니트릴-부타디엔-스티렌 중합 후의 응집 공정에서 라텍스의 모액이 잘 분리되지 않아 응집이 저조할 수 있다.In addition, the ii) reactive emulsifier is preferably added 0.01 to 3.0 parts by weight during the emulsion polymerization, it is preferable to use less than 3.0. If it is 3.0 or more, the mother liquor of latex may not be isolate | separated well in the aggregation process after acrylonitrile butadiene-styrene polymerization, and aggregation may be low.

상기 ⅲ) 비반응 유화제는 알킬 아릴 설포네이트, 알카리메틸 알킬 설페이트, 설포네이트화된 알킬에스테르, 지방산의 비누, 및 로진산의 알카리염으로 이루어지는 군으로부터 1 종 이상 선택되어 사용할 수 있다.(Iii) The non-reacting emulsifier may be selected from one or more selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, and alkali salts of rosin acid.

본 발명의 제조방법은 통상적인 유화중합에서 사용되는 분자량 조절제, 및 중합개시제를 첨가하여 고무라텍스를 제조할 수 있다.In the production method of the present invention, a rubber latex can be prepared by adding a molecular weight regulator and a polymerization initiator used in conventional emulsion polymerization.

상세하게는, 상기 ⅳ) 중합개시제는 나트륨 퍼설페이트, 또는 칼륨 퍼설페이트의 수용성 퍼설페이트; 큐멘하이드로 퍼옥사이드, 디이소프로필 벤젠 하이드로퍼옥사이드, 아조비스 이소부틸로니트릴, 3급 부틸 하이드로퍼옥사이드, 파라메탄 하이드로퍼옥사이드, 또는 벤조일퍼옥사이드의 지용성 중합개시제; 및 산화-환원계 중합계시제로 이루어진 군으로부터 1 종 이상 선택되어 사용할 수 있다.Specifically, the iii) polymerization initiator is a water-soluble persulfate of sodium persulfate, or potassium persulfate; Fat-soluble polymerization initiators of cumenehydro peroxide, diisopropyl benzene hydroperoxide, azobis isobutylonitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide, or benzoyl peroxide; And an oxidation-reduction type polymerization initiator can be used by selecting at least one type.

또한 ⅴ) 전해질은 KCl, NaCl, KHCO3, NaHCO3, Na2CO3, K2CO3, KHSO3, NaHSO3, K4P2O7, Na4P2O7, K3PO4, Na3PO4, Na2HPO4, 및 Na2HPO4로 이루어진 군으로부터 1 종 이상 선택하여 사용할 수 있다.And iii) KCl, NaCl, KHCO 3 , NaHCO 3 , Na 2 CO 3 , K 2 CO 3 , KHSO 3 , NaHSO 3 , K 4 P 2 O 7 , Na 4 P 2 O 7 , K 3 PO 4 , At least one selected from the group consisting of Na 3 PO 4 , Na 2 HPO 4 , and Na 2 HPO 4 can be used.

상기 ⅵ) 분자량조절제는 머캅탄류가 바람직하며, 그 예로는 n-옥틸머캅탄(NOM: n-octylmercaptane), n-도데실머캅탄(DDM: n-dodecylmercaptane ), 및 t-도데실머캅탄(TDDM: t-dodecyl mercaptane)으로 이루어지는 군으로부터 1 종 이상 선택하여 사용할 수 있다.(Iii) Preferably, the molecular weight regulators are mercaptans, for example n-octylmercaptane (NOM: n-octylmercaptane), n-dodecylmercaptane (DDM: n-dodecylmercaptane), and t-dodecylmercaptan (TDDM: t-dodecyl mercaptane) can be used by selecting one or more kinds.

중합온도는 고무라텍스의 겔함량 및 팽윤도를 조정하기에 매우 중요하며, 이때 중합개시제의 선정도 고려되어야 한다. 저온내충격성이 우수한 아크릴로니트릴 -부타디엔-스티렌 수지를 얻기 위해서 적절한 고무라텍스의 평균입경은 2600 Å 내지 5000 Å이 적당하고 입경 표준편차는 25 %가 적당하다. 또한 전체 겔함량은 60 내지 95 %가 적당하고 팽윤지수는 18 내지 40 정도가 적당하다. 이때 고무질중합체의 평균입경이 2600 Å 이하이면 저온내충격성이 저하되고, 5000 Å 이상이면 아크릴로니트릴-부타디엔-스티렌 수지에 적용할 때 중합체의 안정성이 저하되어 응고물이 다량생성된다.The polymerization temperature is very important for adjusting the gel content and swelling degree of the rubber latex, and the selection of the polymerization initiator should also be considered. In order to obtain an acrylonitrile-butadiene-styrene resin having excellent low temperature impact resistance, an average particle diameter of suitable rubber latex is preferably 2600 mm to 5000 mm and a standard deviation of particle size is 25%. In addition, the total gel content is suitably 60 to 95% and the swelling index is about 18 to 40. In this case, when the average particle diameter of the rubbery polymer is 2600 mm 3 or less, the low temperature impact resistance is lowered, and when the average particle diameter is 5000 mm 3 or more, the stability of the polymer decreases when applied to the acrylonitrile-butadiene-styrene resin, thereby producing a large amount of coagulum.

이하의 실시예 및 비교예를 통하여 본 발명을 더욱 상세하게 설명한다. 단, 실시예는 본 발명을 예시하기 위한 것이지 이들만으로 한정하는 것은 아니다.The present invention will be described in more detail with reference to the following examples and comparative examples. However, an Example is for illustrating this invention and is not limited only to these.

[실시예]EXAMPLE

실시예 1Example 1

질소치환된 중합반응기(오토클레이브)에 이온교환수 75 중량부, 단량체로 1,3-부타디엔 100 중량부, 유화제로 로진산 칼륨염 2.0 중량부, 올레인산 칼륨염 0.4 중량부, 전해질로 탄산칼륨(K2CO3) 2.0 중량부, 분자량조절제로 3급 도데실머캅탄(TDDM) 0.3 중량부, 중합개시제로 과황산 칼륨 0.2 중량부를 일괄투여하고 반응온도 70 ℃에서 10 시간 동안 반응시켰다. 상기 반응물의 중합전환율이 50 %가 되면 반응유화제인 AQUARON HS-10 0.3 중량부를 일괄투여하고 온도를 75 ℃로 올려 20 시간 동안 더욱더 반응시킨 후, 중합전환율이 90 %가 되면 중합억제제를 투입하고 반응을 종결tlu 고무라텍스를 수득하였다.In a nitrogen-substituted polymerization reactor (autoclave) 75 parts by weight of ion-exchanged water, 100 parts by weight of 1,3-butadiene as monomer, 2.0 parts by weight of potassium rosin salt as emulsifier, 0.4 parts by weight of potassium oleate salt, potassium carbonate as electrolyte K 2 CO 3 ) 2.0 parts by weight, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, 0.2 parts by weight of potassium persulfate as a polymerization initiator were reacted at a reaction temperature of 70 ℃ for 10 hours. When the polymerization conversion rate of the reactants is 50%, 0.3 parts by weight of AQUARON HS-10, which is a reaction emulsifier, is added in a batch, and the temperature is increased to 75 ° C. for 20 hours. This terminated tlu rubber latex.

실시예 2Example 2

질소치환된 중합반응기에 이온교환수 75 중량부, 단량체로 1,3-부타디엔 100 중량부, 유화제로 로진산 칼륨염 2.0 중량부, 올레인산 칼륨염 0.4 중량부, 반응형 유화제로 AQUARON HS-10 0.1 중량부, 전해질로 탄산칼륨 2.0 중량부, 분자량조절제로 3급 도데실머캅탄 0.3 중량부, 중합개시제로 과황산 칼륨 0.2 중량부를 일괄투여하고 반응온도 70 ℃에서 10 시간 동안 반응시켜 중합전환율이 90 %가 되면 중합억제제를 투입하고 반응을 종결시켜 고무라텍스를 수득하였다.75 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 100 parts by weight of 1,3-butadiene as monomer, 2.0 parts by weight of potassium rosin salt as emulsifier, 0.4 parts by weight of potassium oleate salt, AQUARON HS-10 0.1 as reactive emulsifier Parts by weight, 2.0 parts by weight of potassium carbonate as electrolyte, 0.3 parts by weight of tertiary dodecylmercaptan as molecular weight regulator, 0.2 parts by weight of potassium persulfate as polymerization initiator and reacted for 10 hours at a reaction temperature of 70 ° C, resulting in 90% polymerization conversion. When the polymerization inhibitor was added to terminate the reaction to give a rubber latex.

실시예 3Example 3

질소치환된 중합반응기에 이온교환수 75 중량부, 단량체로 1,3-부타디엔 100중량부, 유화제로 로진산 칼륨염 2.0 중량부, 올레인산 칼륨염 0.4 중량부, 전해질로 탄산칼륨 2.0 중량부, 분자량조절제로 3급 도데실머캅탄 0.3 중량부, 중합개시제로 과황산 칼륨 0.2 중량부를 일괄투여하고 반응온도 70 ℃에서 10 시간 동안 반응시켰다. 상기 반응물의 중합전환율이 50 %가 되면 3급 도데실머캅탄 0.1 중량부, 로진산 칼륨 0.4 중량부, 반응유화제인 AQUARON HS-10 3 중량부를 연속투여하고 온도를 75 ℃로 올려 20 시간 동안 더욱더 반응시킨 후, 중합전환율이 90 %가 되면 중합억제제를 투입하고 반응을 종결시켜 고무라텍스를 수득하였다.75 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 100 parts by weight of 1,3-butadiene as monomer, 2.0 parts by weight of potassium rosin salt as emulsifier, 0.4 parts by weight of potassium oleate salt, 2.0 parts by weight of potassium carbonate as electrolyte, molecular weight 0.3 parts by weight of tertiary dodecyl mercaptan as a regulator and 0.2 parts by weight of potassium persulfate as a polymerization initiator were collectively administered and reacted at a reaction temperature of 70 ° C. for 10 hours. When the polymerization conversion rate of the reactants is 50%, 0.1 parts by weight of tertiary dodecylmercaptan, 0.4 parts by weight of potassium rosinate, and 3 parts by weight of AQUARON HS-10 which is a reaction emulsifier are continuously administered, and the temperature is raised to 75 ° C. for 20 hours. After the polymerization conversion was 90%, the polymerization inhibitor was added and the reaction was terminated to obtain a rubber latex.

실시예 4Example 4

질소치환된 중합반응기에 이온교환수 75 중량부, 단량체로 1,3-부타디엔 80 중량부, 유화제로 로진산 칼륨염 2.0 중량부, 올레인산 칼륨염 0.4 중량부, 전해질로 탄산칼륨 2.0 중량부, 분자량조절제로 3급 도데실머캅탄 0.3 중량부, 중합개시제로 과황산 칼륨 0.2 중량부를 일괄투여하고 반응온도 70 ℃에서 10 시간 동안 반응시켰다. 상기 반응물의 중합전환율이 50 %가 되면 1,3-부타디엔 20 중량부, 로진산 칼륨 0.4 중량부, 반응유화제인 AQUARON HS-10 0.2 중량부를 넣고 온도를 75 ℃로 올려 20 시간 동안 더욱더 반응시킨 후, 중합전환율이 90 %가 되면 중합억제제를 투입하고 반응을 종결시켜 고무라텍스를 수득하였다.75 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 80 parts by weight of 1,3-butadiene as monomer, 2.0 parts by weight of potassium rosin acid salt as emulsifier, 0.4 parts by weight of potassium oleate salt, 2.0 parts by weight of potassium carbonate as electrolyte, molecular weight 0.3 parts by weight of tertiary dodecyl mercaptan as a regulator and 0.2 parts by weight of potassium persulfate as a polymerization initiator were collectively administered and reacted at a reaction temperature of 70 ° C. for 10 hours. When the polymerization conversion rate of the reactant is 50%, 20 parts by weight of 1,3-butadiene, 0.4 parts by weight of potassium rosin acid, 0.2 parts by weight of AQUARON HS-10 which is a reaction emulsifier are added, and the temperature is raised to 75 ° C. for 20 hours. When the polymerization conversion rate was 90%, a polymerization inhibitor was added and the reaction was terminated to obtain a rubber latex.

비교예 1Comparative Example 1

질소치환된 중합반응기에 이온교환수 75 중량부, 단량체로 1,3-부타디엔 100 중량부, 유화제로 로진산 칼륨염 2.0 중량부, 올레인산 칼륨염 0.4 중량부, 전해질로 탄산칼륨 2.0 중량부, 분자량조절제로 3급 도데실머캅탄 0.3 중량부, 중합개시제로 과황산 칼륨 0.2 중량부를 일괄투여하고 반응온도 70 ℃에서 10 시간 동안 반응시킨 후, 중합전환율이 90 %가 되면 중합억제제를 투입하고 반응을 종결시켜 고무라텍스를 수득하였다.75 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 100 parts by weight of 1,3-butadiene as monomer, 2.0 parts by weight of potassium rosin salt as emulsifier, 0.4 parts by weight of potassium oleate salt, 2.0 parts by weight of potassium carbonate as electrolyte, molecular weight 0.3 parts by weight of tertiary dodecyl mercaptan as a control agent and 0.2 parts by weight of potassium persulfate as a polymerization initiator were reacted at a reaction temperature of 70 ° C. for 10 hours, and when the polymerization conversion rate reached 90%, a polymerization inhibitor was added to terminate the reaction. To give a rubber latex.

비교예 2Comparative Example 2

질소치환된 중합반응기에 이온교환수 75 중량부, 단량체로 1,3-부타디엔 80 중량부, 유화제로 로진산 칼륨염 2.0 중량부, 올레인산 칼륨염 0.4 중량부, 전해질로 탄산칼륨 2.0 중량부, 분자량조절제로 3급 도데실머캅탄 0.3 중량부, 중합개시제로 과황산 칼륨 0.2 중량부를 일괄투여하고 반응온도 70 ℃에서 10 시간 동안 반응시켰다. 상기 반응물의 중합전환율이 50 %가 되면 1,3-부타디엔 20 중량부, 로진산 칼륨 0.4 중량부를 넣고 온도를 75 ℃로 올려 20 시간 동안 더욱더 반응시킨 후, 중합전환율이 90 %가 되면 중합억제제를 투입하고 반응을 종결시켜 고무라텍스를 수득하였다.75 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor, 80 parts by weight of 1,3-butadiene as monomer, 2.0 parts by weight of potassium rosin acid salt as emulsifier, 0.4 parts by weight of potassium oleate salt, 2.0 parts by weight of potassium carbonate as electrolyte, molecular weight 0.3 parts by weight of tertiary dodecyl mercaptan as a regulator and 0.2 parts by weight of potassium persulfate as a polymerization initiator were collectively administered and reacted at a reaction temperature of 70 ° C. for 10 hours. When the polymerization conversion rate of the reactants is 50%, 20 parts by weight of 1,3-butadiene and 0.4 parts by weight of potassium rosinate are added and the temperature is increased to 75 ° C. for 20 hours, and the polymerization inhibitor is 90%. Charged and the reaction was terminated to give a rubber latex.

상기 실시예 1 내지 4, 및 비교예 1, 2에서 수득한 고무라텍스의 겔함량 및 팽윤지수, 입자경 및 입자경분포, 및 생성응고물을 하기와 같은 ㄱ), ㄴ), 및 ㄷ)의 방법으로 측정하였다.The gel content and swelling index, particle size and particle size distribution, and the resulting coagulum of the rubber latex obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were prepared by the following methods a), b), and c). Measured.

ㄱ) 겔함량 및 팽윤지수A) gel content and swelling index

고무질 중합체 라텍스를 묽은 산이나 금속염을 사용하여 응고시키고 세척하여 60 ℃의 진공오븐에서 24 시간 동안 건조하였다. 상기의 과정으로 수득한 고무덩어리를 잘게 자른 후, 1 g의 고무절편을 톨루엔 100 g에 넣고 48 시간 동안 실온의 암실에서 보관하였다. 이를 졸과 겔로 분리하고 하기의 수학식 1, 및 2에 따라겔함량 및 팽윤지수를 측정하여 그 결과를 표 1에 나타내었다.The rubbery polymer latex was coagulated with dilute acid or metal salt, washed and dried in a vacuum oven at 60 ° C. for 24 hours. After the rubber mass obtained by the above process was finely chopped, 1 g of rubber fragments were put in 100 g of toluene and stored in a dark room at room temperature for 48 hours. This was separated into a sol and a gel and the gel content and swelling index were measured according to the following Equations 1 and 2, and the results are shown in Table 1.

[수학식 1][Equation 1]

[수학식 2][Equation 2]

ㄴ) 입자경 및 입자경분포B) particle size and particle size distribution

다이나믹 레이져라이트 스케트링법으로 Nicomp 370HPL을 이용하여 측정하였다.It was measured using the Nicomp 370HPL by the dynamic laser light scattering method.

ㄷ) 생성응고물C) produced coagulum;

하기의 수학식 3에 의하여 측정하였다.It measured by the following formula (3).

[표 1]TABLE 1

구분division 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 비교예 1Comparative Example 1 비교예 2Comparative Example 2 투여방법Dosing method 일괄투여Batch administration 이온교환수Ion exchange water 7575 7575 7575 7575 7575 7575 1,3-부타디엔1,3-butadiene 100100 100100 100100 8080 100100 8080 로진산 칼륨염Rosin acid potassium salt 2.02.0 2.02.0 2.02.0 2.02.0 2.02.0 2.02.0 올레인산 칼륨Potassium oleate 0.40.4 0.40.4 0.40.4 0.40.4 0.40.4 0.40.4 HS-10HS-10 -- 0.10.1 -- -- -- -- 탄산칼륨Potassium carbonate 2.02.0 2.02.0 2.02.0 2.02.0 2.02.0 2.02.0 3급 도데실머캅탄Class 3 dodecyl mercaptan 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 0.30.3 과황산칼륨Potassium persulfate 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 0.20.2 투여시기Dosing time 10 시간10 hours -- 10 시간10 hours 10 시간10 hours -- 10 시간10 hours 투여방법Dosing method 일괄투여Batch administration -- 연속투여Continuous administration 연속투여Continuous administration -- 연속투여Continuous administration 1,3-부타디엔1,3-butadiene -- -- -- 2020 -- 2020 3급 도데실머캅탄Class 3 dodecyl mercaptan -- -- 0.10.1 -- -- -- 로진산칼륨Potassium Rosinate -- -- 0.40.4 0.40.4 -- 0.40.4 HS-10HS-10 0.30.3 -- 33 0.20.2 -- -- 중합전환율 (%)Polymerization Conversion Rate (%) 9191 9090 9292 9191 9191 9090 겔함량 (%)Gel content (%) 6666 7575 6363 6868 6969 7575 팽윤지수Swelling index 2727 2424 2626 2323 2424 2323 입자경 (Å)Particle diameter 30003000 25002500 28002800 29002900 30003000 29002900 생성응고물 (%)Product coagulant (%) 0.0020.002 0.0020.002 0.0030.003 0.0020.002 0.0230.023 0.0120.012

상기 표 1에 나타낸 바와 같이, 반응형 유화제를 첨가한 실시예 1, 2, 3, 및 4의 경우 비교예 1, 및 2에 비하여 팽윤지수가 크고 응고물 생성이 적음을 확인할 수 있었다. 또한 단량체를 가하여 중합전환율이 총 화합물의 30∼70 %일 때 반응형 유화제를 가한 경우, 단량체와 반응형 유화제를 동시에 가한 경우보다 응고물 생성이 적음을 알 수 있었다.As shown in Table 1, in Examples 1, 2, 3, and 4 to which the reactive emulsifier was added, it was confirmed that the swelling index was larger than that of Comparative Examples 1 and 2, and the coagulation product was less produced. In addition, when the monomer was added and the polymerization conversion was 30 to 70% of the total compound, it was found that when the reactive emulsifier was added, coagulation was less produced than when the monomer and the reactive emulsifier were added simultaneously.

[사용예][Example]

사용예 1Example 1

질소치환된 중합반응기에 상기 실시예 1에서 수득한 고무라텍스 18 중량부를 투입하고 이온교환수 80 중량부, 올레인산나트륨 유화제 0.2 중량부, 메틸메타크릴레이트 14.38 중량부, 스티렌 5.62 중량부, 아크릴로니트릴 2.5 중량부, 3급 도데실머캅탄 0.2 중량부, 피로인산나트륨 0.048 중량부, 덱스트로즈 0.012 중량부, 황화제1철 0.001 중량부, 큐멘하이드로퍼옥사이드 0.04 중량부를 50 ℃에서 일괄투여하고 반응온도를 73 ℃까지 2 시간에 걸쳐 올리면서 반응시켰다. 여기에 이온교환수 70 중량부, 올레인산나트륨 0.4 중량부, 메틸메타크릴레이트 43.12 중량부, 스티렌 16.88 중량부, 아크릴로니트릴 7.5 중량부, 3급 도데실머캅탄 0.25 중량부, 필인산나트륨 0.048 중량부, 덱스트로즈 0.012 중량부, 황화제1철 0.001 중량부, 큐멘하이드로퍼옥사이드 0.10 중량부의 혼합 유화용액을 4 시간 동안 연속투여한 후, 다시 76 ℃로 승온하고 1 시간 동안 숙성시켜 반응을 종료하였다. 이 때 중합전환율은 99.5 %였고, 고형응고분은 0.05 %였다.18 parts by weight of the rubber latex obtained in Example 1 was added to a nitrogen-substituted polymerization reactor, 80 parts by weight of ion-exchanged water, 0.2 parts by weight of sodium oleate emulsifier, 14.38 parts by weight of methyl methacrylate, 5.62 parts by weight of styrene, and acrylonitrile. 2.5 parts by weight, tertiary dodecyl mercaptan 0.2 part by weight, sodium pyrophosphate 0.048 part by weight, dextrose 0.012 part by weight, ferrous sulfide 0.001 part by weight, cumene hydroperoxide 0.04 part by weight at 50 ℃ and the reaction temperature Reacted while raising to 73 degreeC over 2 hours. Here, 70 parts by weight of ion-exchanged water, 0.4 parts by weight of sodium oleate, 43.12 parts by weight of methyl methacrylate, 16.88 parts by weight of styrene, 7.5 parts by weight of acrylonitrile, 0.25 parts by weight of tertiary dodecyl mercaptan, and 0.048 parts by weight of sodium phosphate , 0.012 parts by weight of dextrose, 0.001 parts by weight of ferrous sulfide, and 0.10 parts by weight of cumene hydroperoxide were continuously administered for 4 hours, and then heated to 76 ° C. and aged for 1 hour to complete the reaction. . At this time, the polymerization conversion was 99.5% and the solid coagulum was 0.05%.

사용예 2Example 2

상기 사용예 1과 동일한 방법으로 하되, 실시예 2에서 수득한 고무라텍스를 사용하여 제조하였다.Was prepared in the same manner as in Example 1, using the rubber latex obtained in Example 2.

사용예 3Example 3

상기 사용예 1과 동일한 방법으로 하되, 실시예 3에서 수득한 고무라텍스를 사용하여 제조하였다.Was prepared in the same manner as in Example 1, using the rubber latex obtained in Example 3.

사용예 4Example 4

상기 사용예 1과 동일한 방법으로 하되, 실시예 4에서 수득한 고무라텍스를 사용하여 제조하였다.Was prepared in the same manner as in Example 1, using the rubber latex obtained in Example 4.

사용예 5Example 5

상기 사용예 1과 동일한 방법으로 하되, 비교예 1에서 수득한 고무라텍스를 사용하여 제조하였다.In the same manner as in Use Example 1, was prepared using the rubber latex obtained in Comparative Example 1.

사용예 6Use Example 6

상기 사용예 1과 동일한 방법으로 하되, 비교예 2에서 수득한 고무라텍스를 사용하여 제조하였다.Was prepared in the same manner as in Example 1, using the rubber latex obtained in Comparative Example 2.

상기 사용예 1 내지 6에서 제조된 그라프트 공중합체를 염화칼슘 수용액 5.0 중량부로 응고시키고 세척하여 수득한 분말을 비교한 결과를 하기 표 2에 나타내었다.The graft copolymers prepared in Examples 1 to 6 were coagulated with 5.0 parts by weight of an aqueous calcium chloride solution, and the powders obtained by washing were shown in Table 2 below.

[표 2]TABLE 2

구분division 사용예 1Example 1 사용예 2Example 2 사용예 3Example 3 사용예 4Example 4 사용예 5Example 5 사용예 6Use Example 6 놋치 아이조드 충격강도ASTM, D-256Notch Izod Impact Strength ASTM, D-256 1818 1414 1616 1717 1818 1717 유동지수 ASTM, D-1238Flow Index ASTM, D-1238 2020 1616 1919 1919 2020 1818 헤이즈값 ASTM, D-1003Haze value ASTM, D-1003 2.52.5 1.51.5 2.32.3 2.42.4 4.04.0 3.83.8 중합 후의 생성응고물Product coagulation after polymerization 0.0230.023 0.0360.036 0.0130.013 0.0220.022 0.0530.053 0.0480.048 염화칼슘에서 라텍스 응집성Latex Cohesion in Calcium Chloride 좋음good 좋음good 나쁨Bad 좋음good 좋음good 좋음good

상기 표 2에 나타낸 바와 같이, 반응형 유화제를 첨가하여 제조한 고무라텍스를 사용하여 제조한 그라프트 공중합체인 사용예 1, 2, 3, 및 4의 경우, 반응형 유화제를 첨가하지 않은 사용예 5, 및 6보다 헤이즈값이 우수하고, 중합 후의 응고물 생성이 적음을 확인 할 수 있었다.As shown in Table 2, in Examples 1, 2, 3, and 4, which are graft copolymers prepared using a rubber latex prepared by adding a reactive emulsifier, use example 5 without a reactive emulsifier was added. It was confirmed that the haze value was superior to, and 6, and the formation of coagulum after polymerization was less.

본 발명의 제조방법은 안정성을 증가시켜 응고물 생성을 줄이고 고무 입경 분포가 좁은 고무라텍스를 제조할 수 있을 뿐만 아니라, 고충격성, 및 고투명성이 우수한 투명 아크릴로니트릴-부타디엔-스티렌 수지를 제조할 수 있는 안정성이 우수한 고무라텍스를 제공할 수 있다.The production method of the present invention can increase the stability to reduce the formation of coagulum and to produce a rubber latex having a narrow rubber particle size distribution, as well as to prepare a transparent acrylonitrile-butadiene-styrene resin excellent in high impact and high transparency. It is possible to provide a rubber latex with excellent stability.

Claims (13)

안정성이 우수한 고무라텍스의 제조방법에 있어서,In the method for producing a rubber latex having excellent stability, ⅰ) 공액디엔 화합물 단량체Iii) conjugated diene compound monomer 에 ⅱ) 반응형 유화제를 가하여 유화중합하는 단계Ii) emulsion polymerization by adding a reactive emulsifier 를 포함하는 안정성이 우수한 고무라텍스의 제조방법.Method for producing a stable rubber latex comprising a. 제 1 항에 있어서,The method of claim 1, ⅰ) 공액디엔 화합물 단량체 100 중량부;Iii) 100 parts by weight of the conjugated diene compound monomer; 에 ⅱ) 반응형 유화제 0.01 내지 3.0 중량부를 가하여 유화중합으로 중합하Ii) adding 0.01 to 3.0 parts by weight of a reactive emulsifier to polymerize by emulsion polymerization. 는 단계Steps 를 포함하는 안정성이 우수한 고무라텍스의 제조방법.Method for producing a stable rubber latex comprising a. 제 1 항에 있어서,The method of claim 1, a) 반응기에a) in the reactor ⅰ) 공액디엔 화합물 단량체 50 내지 100 중량부;Iii) 50 to 100 parts by weight of the conjugated diene compound monomer; ⅱ) 반응형 유화제 0.5 중량부 이하;Ii) 0.5 parts by weight or less of a reactive emulsifier; ⅲ) 비반응형 유화제 1 내지 4 중량부;V) 1 to 4 parts by weight of a non-reactive emulsifier; ⅳ) 중합개시제 0.2 내지 1.5 중량부;Iii) 0.2 to 1.5 parts by weight of a polymerization initiator; ⅴ) 전해질 0.5 내지 2 중량부;V) 0.5 to 2 parts by weight of electrolyte; ⅵ) 분자량 조절제 0.1 내지 0.5 중량부; 및Iii) 0.1 to 0.5 parts by weight of a molecular weight modifier; And ⅶ) 이온교환수 75 내지 100 중량부Viii) 75 to 100 parts by weight of ion-exchanged water 를 일괄투여하여 65∼75 ℃에서 4∼15 시간 동안 반응시키는 단계;Dosing in a batch to react at 65 to 75 ° C. for 4 to 15 hours; b) 상기 a) 단계의 반응물에b) reactants of step a) ⅰ) 나머지 공액디엔 화합물 단량체 50 중량부 이하; 및V) 50 parts by weight or less of the remaining conjugated diene compound monomers; And ⅵ) 분자량 조절제 0.1 내지 0.5 중량부Iii) 0.1 to 0.5 parts by weight of molecular weight regulator 를 일괄투여 또는 연속투여하여 70∼85 ℃에서 10∼20 시간 동안 반응시키는To batch or continuous dosing and reacted at 70 to 85 ° C. for 10 to 20 hours. 단계; 및step; And c) 상기 b) 단계의 반응물의 중합전환율이 총 화합물의 30∼70 %가 되면c) the polymerization conversion rate of the reactant of step b) is 30-70% of the total compound ⅱ) 반응형 유화제 0.01 내지 3.0 중량부Ii) 0.01 to 3.0 parts by weight of a reactive emulsifier 를 가하는 단계Steps to apply 를 포함하는 안정성이 우수한 고무라텍스 제조방법.Excellent rubber latex manufacturing method comprising a. 제 1 항 내지 제 3 항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 3, 상기 ⅱ) 반응형 유화제가 폴리옥시에틸렌 알릴그리시딕 노닐페닐 에테르의 설페이트염의 알릴기를 가지는 음이온계 유화제; 폴리옥시에틸렌 알릴그리시딜 노닐페닐 에테르 계열의 알릴기를 가지는 중성계 유화제; (메타)아크릴로일기를 가지는 음이온계 유화제; (메타)아크릴로일기를 가지는 중성계 유화제; 폴리옥시에틸렌 알릴그리시딕 노닐 프로페닐 페닐 에테르의 알모늄설페이트염의 프로펜기를 가지는 음이온계 유화제; 중성계 유화제로 이루어진 군으로부터 1 종 이상 선택되는 아크릴로니트릴-부타디엔-스티렌 라텍스의 제조방법.Ii) an anionic emulsifier in which the reactive emulsifier has an allyl group of the sulfate salt of polyoxyethylene allyl glycidic nonylphenyl ether; Neutral emulsifiers having an allyl group of the polyoxyethylene allylglycidyl nonylphenyl ether series; Anionic emulsifier which has a (meth) acryloyl group; Neutral emulsifiers having a (meth) acryloyl group; Anionic emulsifiers having a propene group of an aluminum sulfate salt of polyoxyethylene allylglycidyl nonyl propenyl phenyl ether; A method for producing acrylonitrile-butadiene-styrene latex selected from the group consisting of neutral emulsifiers. 제 3 항에 있어서,The method of claim 3, wherein 상기 ⅲ) 비반응 유화제가 알킬 아릴 설포네이트, 알카리메틸 알킬 설페이트, 설포네이트화된 알킬에스테르, 지방산의 비누, 및 로진산의 알카리염으로 이루어지는 군으로부터 1 종 이상 선택되는 안정성이 우수한 고무라텍스의 제조방법.Iii) Preparation of rubber latex having excellent stability, wherein the unreacted emulsifier is selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, and alkali salts of rosin acid. Way. 제 1 항 내지 제 3 항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 3, 상기 ⅰ) 공액디엔 화합물 단량체가 공액디엔 화합물을 단독, 또는 스티렌, α-메틸스티렌 등의 방향족 비닐 화합물, 및 아크릴로니트릴 등과 같은 비닐시안 화합물과 혼합되어 총 단량체 혼합물 중 15 중량부 이내로 사용하는 안정성이 우수한 고무라텍스의 제조방법.(Iii) Stability of conjugated diene compound monomers used alone or in combination with aromatic vinyl compounds such as styrene and α-methylstyrene, and vinyl cyan compounds such as acrylonitrile and used within 15 parts by weight of the total monomer mixture. This excellent rubber latex manufacturing method. 제 1 항 내지 제 3 항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 3, 상기 ⅰ) 공액디엔 화합물이 1,3-부타디엔, 이소프렌, 클로로프렌, 및 피레리덴으로 이루어진 군으로부터 1 종 이상 선택되는 안정성이 우수한 고무라텍스의 제조방법.Iii) a method for producing a rubber latex having excellent stability wherein the conjugated diene compound is selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and pyreriden. 제 3 항에 있어서,The method of claim 3, wherein 상기 ⅲ) 비반응 유화제가 알킬 아릴 설포네이트, 알카리메틸 알킬 설페이트, 설포네이트화된 알킬에스테르, 지방산의 비누, 및 로진산의 알카리염으로 이루어지는 군으로부터 1 종 이상 선택되는 안정성이 우수한 고무라텍스의 제조방법.Iii) Preparation of rubber latex having excellent stability, wherein the unreacted emulsifier is selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, and alkali salts of rosin acid. Way. 제 3 항에 있어서,The method of claim 3, wherein 상기 ⅳ) 중합개시제가 나트륨 퍼설페이트, 또는 칼륨 퍼설페이트의 수용성 퍼설페이트; 큐멘하이드로 퍼옥사이드, 디이소프로필 벤젠 하이드로퍼옥사이드, 아조비스 이소부틸로니트릴, 3급 부틸 하이드로퍼옥사이드, 파라메탄 하이드로퍼옥사이드, 또는 벤조일퍼옥사이드의 지용성 중합개시제; 및 산화-환원계 중합계시제로 이루어진 군으로부터 1 종 이상 선택되는 안정성이 우수한 고무라텍스의 제조방법.Iii) the polymerization initiator is sodium persulfate or water-soluble persulfate of potassium persulfate; Fat-soluble polymerization initiators of cumenehydro peroxide, diisopropyl benzene hydroperoxide, azobis isobutylonitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide, or benzoyl peroxide; And an oxidation-reduction type polymerization initiator, and at least one selected from the group consisting of rubber latex having excellent stability. 제 3 항에 있어서,The method of claim 3, wherein 상기 ⅴ) 전해질이 KCl, NaCl, KHCO3, NaHCO3, Na2CO3, K2CO3, KHSO3, NaHSO3, K4P2O7, Na4P2O7, K3PO4, Na3PO4, Na2HPO4, 및 Na2HPO4로 이루어진 군으로부터 1 종 이상 선택되는 안정성이 우수한 고무라텍스의 제조방법.I) KCl, NaCl, KHCO 3 , NaHCO 3 , Na 2 CO 3 , K 2 CO 3 , KHSO 3 , NaHSO 3 , K 4 P 2 O 7 , Na 4 P 2 O 7 , K 3 PO 4 , A method for producing a rubber latex having excellent stability selected from the group consisting of Na 3 PO 4 , Na 2 HPO 4 , and Na 2 HPO 4 . 제 3 항에 있어서,The method of claim 3, wherein 상기 ⅵ) 분자량조절제가 n-옥틸머캅탄, n-도데실머캅탄, 및 t-도데실머캅탄으로 이루어지는 군으로부터 1 종 이상 선택되는 안정성이 우수한 고무라텍스의 제조방법.(Iii) A method for producing a rubber latex having excellent stability, wherein the molecular weight modifier is at least one selected from the group consisting of n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan. 제 1 항 내지 제 3 항 중 어느 한 항 기재의 제조방법으로 제조되는 평균입경 2600∼5000 Å, 입경 표준편차 25 %, 전체 겔함량 60∼95 중량%, 팽윤지수 18∼40의 고무라텍스.A rubber latex having an average particle diameter of 2600 to 5000 mm 3, a particle size standard deviation of 25%, a total gel content of 60 to 95% by weight, and an swelling index of 18 to 40, produced by the method according to any one of claims 1 to 3. 제 12 항 기재의 고무라텍스를 사용하여 제조되는 안정성이 우수한 아크릴로니트릴-부타디엔-스티렌 수지.The acrylonitrile-butadiene-styrene resin excellent in the stability manufactured using the rubber latex of Claim 12.
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US9920153B2 (en) 2013-06-28 2018-03-20 Lg Chem, Ltd. Method of preparing thermoplastic resin composition having superior surface clearness and gloss
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EP2759553A4 (en) * 2011-11-24 2015-06-24 Lg Chemical Ltd Production method for nitrile rubber
US9163096B2 (en) 2011-11-24 2015-10-20 Lg Chem, Ltd. Method for producing nitrile rubber
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US9920153B2 (en) 2013-06-28 2018-03-20 Lg Chem, Ltd. Method of preparing thermoplastic resin composition having superior surface clearness and gloss
KR20160073005A (en) * 2014-12-16 2016-06-24 주식회사 엘지화학 Preparation method of diene rubber polymer and acrylonitrile-butadiene-styrene graft copolymer comprising the same
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