KR960022577A - Method for preparing emulsion polymer of core-cell structure by two-step emulsion polymerization method and coating composition containing same - Google Patents

Method for preparing emulsion polymer of core-cell structure by two-step emulsion polymerization method and coating composition containing same Download PDF

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KR960022577A
KR960022577A KR1019940037418A KR19940037418A KR960022577A KR 960022577 A KR960022577 A KR 960022577A KR 1019940037418 A KR1019940037418 A KR 1019940037418A KR 19940037418 A KR19940037418 A KR 19940037418A KR 960022577 A KR960022577 A KR 960022577A
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오정권
박종명
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김충세
고려화학 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof

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  • Medicinal Chemistry (AREA)
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  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)

Abstract

본 발명은 최소량의 유화제가 함유된 코아-셀 구조를 갖는 2단계 유화 중합체의 제조방법 및 그 유화 중합체가 함유되어 있는 도료 조성물에 관한 것으로서, 좀 더 상세하게는 기존의 유화중합법에 의해 제조된 카르복실산기를 충분히 하유한 코아 에멀젼을 중화제로 중화시켜서 이렇게 중화된 1단계 코아 에멀젼을 폴리머 분산제로 이용하여 외부의 저분자량 유화제의 첨가없이도 안정한 2단계 셀 에멀젼을 제조하며, 궁극적으로는 최소량의 저분자량 유화제가 함유된 코아-셀 구조의 안정한 유화 중합체를 제조하는 방법 및 이러한 유화 중합체가 함유된 도료 조성물에 관한 것이다.The present invention relates to a method for preparing a two-stage emulsion polymer having a core-cell structure containing a minimum amount of an emulsifier and a coating composition containing the emulsion polymer, and more particularly, to a coating composition containing the emulsion polymer. The neutralized core emulsion containing sufficient carboxylic acid groups is neutralized with a neutralizing agent, so that the neutralized one-stage core emulsion is used as a polymer dispersant to produce a stable two-stage cell emulsion without the addition of an external low molecular weight emulsifier. A method for producing a stable emulsion polymer having a core-cell structure containing a molecular weight emulsifier and a coating composition containing such an emulsion polymer.

본 발명에 따르면, 도료 건조 도막의 내수성, 내 알칼리성, 방청성, 및 부착력이 향상되고, 미려한 외관 및 고광택을 얻게 된다.According to the present invention, the water resistance, alkali resistance, rust resistance, and adhesion of the paint dried coating film are improved, and a beautiful appearance and high gloss are obtained.

Description

2단계 유화 중합법에 의한 코아-셀 구조의 유화 중합체의 제조방법 및 이를 함유하는 도료 조성물Method for preparing emulsion polymer of core-cell structure by two-step emulsion polymerization method and coating composition containing same

본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음As this is a public information case, the full text was not included.

Claims (24)

유화중합법에 의해 제조된 카르복실산기를 충분히 함유한 코아 1단계 에멀션을 중화제로 중화시키고, 이렇게 중화된 1단계 코아 에멀젼을 폴리머 분산제로 이용하여 외부의 저분자량 유화제의 첨가없이도 안정한 2차 셀 에멀젼을 제조하는 것을 특징으로 하는 최소량의 유화제가 함유된 코아-셀 구조의 2단계 유화 중합체의 제조방법.Neutralize the core one-step emulsion containing a sufficient amount of carboxylic acid groups prepared by the emulsion polymerization method with a neutralizing agent, and use this neutralized one-step core emulsion as a polymer dispersant to stabilize the secondary cell emulsion without adding an external low molecular weight emulsifier. Method for producing a two-stage emulsion polymer of a core-cell structure containing a minimum amount of emulsifier, characterized in that to prepare a. 제1항에 있어서, 상기 카르복실산기를 포함하는 단량체는 중합 2단계인 셀 에멀젼 제조 단계에서 폴리머 분산안정제 역활을 하기에 충분하도록 염기로 이루어진 중화제로 중화시키며, 그 단량체의 양은 코아 폴리머 단량체 총 100중량부에 대해 10~40중량부로 함유되는 것을 특징으로 하는 코아-셀 구조를 갖는 2단계 유화중합체의 제조방법.The method of claim 1, wherein the monomer containing a carboxylic acid group is neutralized with a neutralizing agent consisting of a base sufficient to serve as a polymer dispersion stabilizer in the cell emulsion preparation step of the polymerization step 2, the amount of the monomers total 100 Method for producing a two-stage emulsion polymer having a core-cell structure, characterized in that contained in 10 to 40 parts by weight with respect to parts by weight. 제1항에 있어서, 상기 카르복실산을 포함하는 단량체는 단일 카르복실산을 포함하는 아크릴산, 메타크릴산, 비닐 벤젠산 및 이소펜틸 벤젠산 및 2개의 카르복실산을 포함하는 크로톤산, 이타콘산, 말레인산, 프말산과 그의 산무수물로 이루어진 그룹으로부터 하나 혹은 2개 이상을 혼합 사용하는 것을 특징으로 하는 코아-셀구조를 갖는 2단계 유화 중합체의 제조방법.The method of claim 1, wherein the monomer comprising carboxylic acid is acrylic acid, methacrylic acid, vinyl benzene acid and isopentyl benzene acid and single carboxylic acid and crotonic acid, itaconic acid and two carboxylic acids. A method for producing a two-stage emulsion polymer having a core-cell structure, characterized in that one or two or more are mixed and used from the group consisting of maleic acid, fmaric acid and acid anhydrides thereof. 제1항에 있어서, 상기 1단계 코아 폴리머의 단량체 조성이 단량체 총 100중량부에 대해 탄소수 1 내지 18개의 알킬 혹은 시클로 알킬 아크릴산 혹은 메타크릴산 에스테르 0~50중량부, 알콕시 알킬 아크릴산 혹은 메타크릴산 에스테르 0~5중량부, 탄소수가 2 내지 8개의 히드록시 알킬 아크릴산 혹은 메타크릴산 에스테르 0~10중량부, 비닐 아로마틱 화합물 0~90중량부, 탄소수 4내지 9개의 콘쥬게이트 디엔 0~5중량부, 아크릴로니트릴, 메타크릴로니트릴 0~30중량부 및 카르복실산을 포함하는 단량체 10∼40중량부로 이루어짐을 특징으로 하는 코아-셀 구조를 갖는 2단계 유화 중합체의 제조방법.The monomer composition of the first stage core polymer is 0 to 50 parts by weight of alkyl or cycloalkyl acrylic acid or methacrylic acid ester having 1 to 18 carbon atoms, alkoxy alkyl acrylic acid or methacrylic acid based on 100 parts by weight of the total monomers. 0 to 5 parts by weight of ester, 0 to 10 parts by weight of hydroxy alkyl acrylic acid or methacrylic acid ester having 2 to 8 carbon atoms, 0 to 90 parts by weight of vinyl aromatic compound, and 0 to 5 parts by weight of 4 to 9 conjugated dienes , Acrylonitrile, methacrylonitrile 0 to 30 parts by weight and a monomer comprising a carboxylic acid 10 to 40 parts by weight of the method of producing a two-stage emulsion polymer having a core-cell structure. 제1항에 있어서, 라디칼에 의해 부가중합될 수 있는 비닐기를 가진 단량체는 탄소수 1 내지 18개의 알킬 혹은 시클로 알킬 아크릴산 혹은 메타크릴산 에스테르와, 알콕시 알킬 아크릴산 혹은 메타크릴산 에스테르, 탄소수 2 내지 8개의 히드록시 알킬 아크릴산 흑은 메타크릴산 에스테르, 비닐 아로마틱 화합물, 탄소수 4 내지 9개의 콘쥬게이트 디엔, 아크릴로니트릴, 및 메타크릴로니트릴로 이루어진 그룹으로부터 선택되는 것을 특징으로 하는 코아-셀 구조를 갖는 2단계 유화 중합체의 제조방법.The monomer according to claim 1, wherein the monomer having a vinyl group that can be polymerized by a radical includes alkyl or cycloalkyl acrylic acid or methacrylic ester having 1 to 18 carbon atoms, alkoxy alkyl acrylic acid or methacrylic acid ester, and having 2 to 8 carbon atoms. Hydroxy alkyl acrylic acid black has a core-cell structure, characterized in that it is selected from the group consisting of methacrylic acid esters, vinyl aromatic compounds, conjugated dienes having 4 to 9 carbon atoms, acrylonitrile, and methacrylonitrile. Process for preparing a step emulsion polymer. 제1항에 있어서, 코아 폴리머의 분자량을 조절하기 위해 쇄전환제를 코아 단량체 100중량부에 대해 0.1~0.5중량부 사용하는 것을 특징으로 하는 코아-셀 구조를 갖는 2단계 유화 중합체의 제조방법.The method according to claim 1, wherein the chain conversion agent is used in an amount of 0.1 to 0.5 parts by weight based on 100 parts by weight of the core monomer to adjust the molecular weight of the core polymer. 제1항에 있어서, 라디칼 중합 개시제는 높은 온도에서 열해리에 의해 라디칼이 생성되는 암모늄, 칼륨, 나트륨 퍼설페이트, 시클로헥실 하이드로퍼옥시드, 큐멘 하이드로퍼옥시드, n-옥틸 하이드로퍼옥시드, t-부틸 하이드로퍼옥시드, sec-부틸 하이드로퍼옥시드, 1-페닐-2-메틸프로필 1-하이드로퍼옥시드와 같은 수용성 열해리 개시제를 코아 단량체 100중량부에 대해 0.2~1.5중량부 사용하는 것을 특징으로 하는 코아-셀구조를 갖는 2단계 유화 중합체의 제조방법.The radical polymerization initiator according to claim 1, wherein the radical polymerization initiator is ammonium, potassium, sodium persulfate, cyclohexyl hydroperoxide, cumene hydroperoxide, n-octyl hydroperoxide, t generated by thermal dissociation at high temperature. 0.2 to 1.5 parts by weight of a water-soluble thermal dissociation initiator such as -butyl hydroperoxide, sec-butyl hydroperoxide and 1-phenyl-2-methylpropyl 1-hydroperoxide based on 100 parts by weight of the core monomer A process for producing a two-stage emulsion polymer having a core-cell structure. 제1항에 있어서, 중합속도를 촉진시키고 코아 에멀젼의 안정성을 부여하기 위해 음이온 혹은 비이온 유화제를 단독 혹은 서로 혼합하여 사용하며, 그 양은 음이온의 경우 단량체 100중량부에 대해 0.2~2.0중량부를,비이온의 경우 0~1.0중량부 사용함을 특징으로 하는 코아-셀 구조를 갖는 2단계 유화 중합체의 제조방법.According to claim 1, In order to accelerate the polymerization rate and impart stability of the core emulsion, anionic or nonionic emulsifiers are used alone or mixed with each other, the amount is 0.2 to 2.0 parts by weight based on 100 parts by weight of monomer in the case of anion, Method for producing a two-stage emulsion polymer having a core-cell structure, characterized in that 0 to 1.0 parts by weight of non-ionic. 제1항에 있어서, 코아 에멀젼 중합 방법은 연속상의 물과 유화제를 초기 사입하고 개시제와 단량체를 사입하는 프로세스에 따르며 반응온도는 75-85℃인 것을 특징으로 하는 코아-셀 구조를 갖는 2단계 유화 중합체의 제조방법.The method of claim 1, wherein the core emulsion polymerization method is followed by a process of initially adding water and an emulsifier in a continuous phase and an initiator and a monomer, and a reaction temperature of 75-85 ° C. Method of Making Polymers. 제1항에 있어서, 코아 폴리머를 중화시키기 위해 사용되는 중화제는 무기 염기인 암모니아, NaOH,KOH, LiOH 및 유기 염기인 디메틸에탄올아민, AMP 95(Angus사 제품) 및 트리틸 아민과 같은 1급, 2급,3급 아민 중에서 선택되는 것을 특징으로 하는 코아-셀 구조를 갖는 2단계 유화 중합체의 제조방법.The neutralizing agent according to claim 1, wherein the neutralizing agent used to neutralize the core polymer is a primary base such as inorganic base ammonia, NaOH, KOH, LiOH and organic base dimethylethanolamine, AMP 95 (manufactured by Angus) and trityl amine, A method for producing a two-stage emulsion polymer having a core-cell structure, characterized in that it is selected from secondary and tertiary amines. 제1항에 있어서, 2단계 에멀젼 중합의 안정성을 주기 위한 코아폴리머의 적정 중화도가 코아 폴리머의 카르복실산기의 총 양에 대해 5~75퍼센트이며, pH는 4.5~8.0임을 특징으로 하는 코아-셀 구조를 갖는 2단계 유화 중합체의 제조방법.The core of claim 1, wherein the appropriate degree of neutralization of the copolymer for the stability of the two-stage emulsion polymerization is 5 to 75 percent with respect to the total amount of carboxylic acid groups of the core polymer and the pH is 4.5 to 8.0. Method for producing a two-stage emulsion polymer having a cell structure. 제1항에 있어서, 2단계 셀 폴리머를 제조함에 있어서의 단량체는 카르복실산을 포함하는 단량체, 탄소수가 1 내지 18개인 알킬 혹은 시클로 알킬 아크릴산 혹은 메타크릴산 에스테르, 알콕시 알킬 아크릴산 혹은 메타크릴산 에스테르, 탄소수 2 내지 8개인 히드록시 알킬 아크릴산 혹은 메타크릴산 에스테르, 비닐 아로마틱화합물, 탄소수 4 내지 9개인 콘쥬게이트 디엔, 아크릴로니트릴 및 메타크릴로니트릴 중에서 하나 혹은 2개 이상을 선택하여 혼합 사용하며, 단량체 조성은 단량체 100중량부에 대해 0~8중량부의 카르복실산을 함유하는 단량체, 1~70중량부의 탄소수가 1에서 18개로 이루어진 알킬 혹은 시클로 알킬 아크릴산 혹은 메타크릴산 에스테르, 0~5중량부의 알콕시 알킬 아크릴산 혹은 메타크릴산 에스테르, 0~15중량부의 히드록시 알킬 아크릴산 혹은 메타크릴산 에스테르, 12~88중량부의 비닐 아로마틱 화합물, 0~5중량부의 탄소수 4 내지 9개인 콘쥬게이트 디엔 및 0~30중량부의 아크릴로니트릴 및 메타크릴로니트릴인 것을 특징으로 하는 코아-셀 구조를 갖는 2단계 유화 중합체의 제조방법.The method of claim 1, wherein the monomer in preparing the two-stage cell polymer is a monomer comprising carboxylic acid, alkyl or cycloalkyl acrylic acid or methacrylic acid ester having 1 to 18 carbon atoms, alkoxy alkyl acrylic acid or methacrylic acid ester Hydroxy alkyl acrylic acid or methacrylic acid ester having 2 to 8 carbon atoms, vinyl aromatic compound, conjugate diene having 4 to 9 carbon atoms, acrylonitrile and methacrylonitrile selected from one or two and mixed, The monomer composition is 0 to 8 parts by weight of a monomer containing 0 to 8 parts by weight of carboxylic acid, 1 to 70 parts by weight of alkyl or cycloalkyl acrylic acid or methacrylic acid ester having 1 to 18 carbon atoms, and 0 to 5 parts by weight. Alkoxy alkyl acrylic acid or methacrylic acid ester, 0-15 parts by weight of hydroxy alkyl acrylic acid Core-cell structure, characterized in that it is methacrylic acid ester, 12 to 88 parts by weight of vinyl aromatic compound, 0 to 5 parts by weight of conjugated diene having 4 to 9 carbon atoms and 0 to 30 parts by weight of acrylonitrile and methacrylonitrile Method for producing a two-stage emulsion polymer having a. 제1항에 있어서, 2단계 셀 폴리머를 제조함에 있어서의 개시제는 알칼리 금속 혹은 암모늄 퍼설페이트로 이루어진 수용성 개시제와 유용성 개시제를 사용하며, 사용량은 2단계 중합에서 사용된 단량체 100중량부에 대해 0.1~1.5중량부임을 특징으로 하는 코아-셀 구조를 갖는 2단계 유화 중합체의 제조방법.The method of claim 1, wherein the initiator in preparing the two-stage cell polymer is a water-soluble initiator consisting of an alkali metal or ammonium persulfate and an oil-soluble initiator, the amount of the use is 0.1 to 100 parts by weight of the monomer used in the two-stage polymerization Method for producing a two-stage emulsion polymer having a core-cell structure, characterized in that 1.5 parts by weight. 제13항에 있어서, 유용성 개시제는 t-부틸 벤조퍼옥시드와 같은 디알킬 퍼옥시드와 2,2′-아조비스이소부티로 니트릴, 2,2′-아조비스메틸부티로니트릴, 1,1′-아조비스1-시클로헥산 카르보니트릴과 같은 아조화합물인 것을 특징으로 하는 코아-셀 구조를 갖는 2단계 유화 중합체의 제조방법.14. The oil-soluble initiator of claim 13, wherein the oil-soluble initiator is a dialkyl peroxide such as t-butyl benzoperoxide and 2,2'-azobisisobutyronitrile, 2,2'-azobismethylbutyronitrile, 1,1 ' A process for producing a two-stage emulsion polymer having a core-cell structure, characterized in that it is an azo compound such as azobis1-cyclohexane carbonitrile. 제1항에 있어서, 1단계 코아 폴리머와 2단계 중합 단량체의 비는 1:4~1:20이며, 1:10.5~1:15가 더욱 바람직한 것을 특징으로 하는 코아-셀 구조를 갖는 2단계 유화 중합체의 제조방법.The two-step emulsion having a core-cell structure according to claim 1, wherein the ratio of the first-stage core polymer and the two-stage polymerized monomer is 1: 4 to 1:20, and more preferably 1: 10.5 to 1:15. Method of Making Polymers. 제1항에 있어서, 2단계 에멀젼 중합법은 물과 중화된 코아 에멀젼을 초기 사입후 개시제와 단량체를 사입하는 프로세스에 따르되, 중합 온도는 75~84℃임을 특징으로 하는 코아-셀 구조를 갖는 2단계 유화 중합체의 제조방법.According to claim 1, The two-step emulsion polymerization method according to the process of injecting the initiator and monomer after the initial injection of water and neutralized core emulsion, 2, having a core-cell structure, characterized in that the polymerization temperature is 75 ~ 84 ℃ Process for preparing a step emulsion polymer. 제1항에 있어서, 반응상은 수상 단독이거나, 혹은 도료 응용시 도막 형성용 조용제로 사용되는 부틸셀로솔브, 에틸 셀로솔브 및 텍산올(이스트만사 제품)과 물의 혼용상을 사용하며, 조용제 양은 코아 에멀젼 100중량부에 대해 0~200중량부로 사용함을 특징으로 하는 코아-셀 구조를 갖는 2단계 유화 중합체의 제조방법.The reaction phase according to claim 1, wherein the reaction phase is a water phase alone or a mixed phase of butyl cellosolve, ethyl cellosolve and texanol (available from Eastman) and water used as a coating agent for coating film formation in coating applications. Method for producing a two-stage emulsion polymer having a core-cell structure, characterized in that used in 0 to 200 parts by weight based on 100 parts by weight of the emulsion. 제1항에 따른 최소량의 저분자량 유화제가 함유된 유화중합체가 도료 100중량부에 대해 수지 고형분 15~30중량부로 함유된 도료 조성물.The coating composition containing the resin solid content 15-30 weight part with respect to 100 weight part of paints the emulsion polymer containing the minimum amount of low molecular weight emulsifiers of Claim 1. 제18항에 있어서, 밀베이스에 안료, 부동액, 소포제, pH 조절제, 조용제, 분산제 등의 첨가제가 배합되는 것을 특징으로 하는 도료 조성물.The coating composition according to claim 18, wherein an additive such as a pigment, an antifreeze, an antifoaming agent, a pH adjusting agent, a co-solvent, a dispersing agent, and the like are blended into the mill base. 제19항에 있어서, 안료는 백색 도료인 경우 이산화티탄의 각종 그레이드를 단독 사용하며, 유색도료인 경우는 적색 산화철, 황색 산화철 단독 혹은 이산화티탄과 유기 안료를 혼합하여 사용하며, 백색 도료의 경우 안료의 양은 안료 부피 퍼세트(PVC)가 10~30이 되도록 사용함을 특징으로 하는 도료 조성물.The method of claim 19, wherein the pigment is used in the white paint of various grades of titanium dioxide alone, in the case of a colored paint red iron oxide, yellow iron oxide alone or a mixture of titanium dioxide and an organic pigment, in the case of a white paint pigment The amount of the coating composition, characterized in that the use of the pigment volume putter (PVC) is 10-30. 제19항에 있어서, 소포제는 실록산류의 소포제를 밀베이스와 마감단계에서 동량으로 분할하여 투입하되 총량은 도료 100중량부에 대해 0.05-0.5중량부를 사용함을 특징으로 하는 도료 조성물.The antifoaming agent according to claim 19, wherein the antifoaming agent of siloxane is divided into the same amount at the mill base and the finishing step, but the total amount is 0.05-0.5 parts by weight based on 100 parts by weight of paint. 제19항에 있어서, pH조절제는 AMP 95(Angus사 제품), 암모니아, 디메티에탄올아민을 사용하며 도료 100중량부에 대해 0.1~0.2중량부를 사용함을 특징으로 하는 도료 조성물.The coating composition according to claim 19, wherein the pH adjusting agent uses AMP 95 (manufactured by Angus), ammonia, dimethethanolamine, and 0.1 to 0.2 parts by weight based on 100 parts by weight of the paint. 제19항에 있어서, 도료 조성물의 흐름을 방지하고 도장을 원활하게 하기 위해 비이온성 폴리우레탄계 이소시에이티브 증점제를 단독 사용하거나, ASE계 중점제와 혼용 사용하며, 사용량은 폴리우레탄계 중점제를 단독 사용할 경우는 도료 100중량부에 대해 0.5~2.5중량부를 사용하며, ASE계와 혼용 사용함 경우는 도료 100중량부에 대해 폴리우레탄계는 0.2~1.0중량부, ASE계는 0.5~1.0중량부를 사용함을 특징으로 하는 도료조성물.20. The method of claim 19, in order to prevent the flow of the coating composition and smooth coating, a nonionic polyurethane-based isocyanate thickener is used alone or in combination with an ASE-based thickener, and the amount of the polyurethane-based thickener is used alone. In the case of 0.5 to 2.5 parts by weight based on 100 parts by weight of paint, and when used in combination with ASE system, polyurethane based 0.2 to 1.0 parts by weight, 0.5 to 1.0 parts by weight of ASE based on 100 parts by weight of paint Paint composition. 제19항에 있어서, 도말 형성용 조용제는 고비점 용제를 사용하며, 그 양은 사용되는 수지 고형분 100 중량부에 대해 5~10 중량부를 사용함을 특징으로 하는 도료 조성물.The coating composition according to claim 19, wherein the coating agent for forming a smear uses a high boiling point solvent, and the amount thereof is used in an amount of 5 to 10 parts by weight based on 100 parts by weight of the resin solids used. ※ 참고사항:최초출원 내용에 의하여 공개하는 것임.※ Note: The disclosure is based on the initial application.
KR1019940037418A 1994-12-27 1994-12-27 Method for preparing emulsion polymers having core-shell structure by two-step emulsion polymerization and paint composition containing the same KR0149696B1 (en)

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