KR960004393A - Manufacturing method of modified polyester resin having excellent weather resistance and coating composition containing same - Google Patents

Manufacturing method of modified polyester resin having excellent weather resistance and coating composition containing same Download PDF

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Publication number
KR960004393A
KR960004393A KR1019940018915A KR19940018915A KR960004393A KR 960004393 A KR960004393 A KR 960004393A KR 1019940018915 A KR1019940018915 A KR 1019940018915A KR 19940018915 A KR19940018915 A KR 19940018915A KR 960004393 A KR960004393 A KR 960004393A
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South Korea
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weight
acrylic
resin
modified polyester
urethane
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KR1019940018915A
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Korean (ko)
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KR0149695B1 (en
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김형호
김봉진
김상식
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김충세
고려화학 주식회사
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/62Polymers of compounds having carbon-to-carbon double bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/06Polyurethanes from polyesters

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

본 발명은 내후성이 우수한 변성 폴리에스테르 수지의 제조방법 및 이를 함유하는 도료조성물에 관한 것이다.The present invention relates to a method for producing a modified polyester resin excellent in weatherability and to a coating composition containing the same.

본 발명의 아크릴 및 우레탄 변성 폴리에스테르 수지는 2가 이상의 알코올 혼합물과 2가 이상의 산 혼합물을 에스테르 촉매 존재하에서 반응시켜 수산기 말단의 폴리에스테르 수지를 제조한 다음, 개시제 존재하에서 하이드록실 말단 아크릴 수지를 제조한 후, 상기 폴리에스테르 수지와 아크릴 수지를 지방족 또는 지환족 디이소시아네이트로 변성, 합성하므로써 제조된다. 또한 본 발명의 도료 조성물은 상기 아크릴 및 우레탄 변성 폴리에스테르 수지와 경화제로 이루어져 있다.The acrylic and urethane-modified polyester resins of the present invention react a divalent or more alcohol mixture with a divalent or more acid mixture in the presence of an ester catalyst to produce a polyester resin at the hydroxyl end, and then produce a hydroxyl terminated acrylic resin in the presence of an initiator. After that, the polyester resin and the acrylic resin are produced by modifying and synthesizing with an aliphatic or alicyclic diisocyanate. In addition, the coating composition of the present invention consists of the acrylic and urethane-modified polyester resin and a curing agent.

본 발명에서는 아크릴 수지를 첨가하여 내후성 및 도료화시 도막의 경도를 향상시키고, 또한 우레탄 결합을 형성시켜주므로써 도막의 물리적 성질, 즉 부착성, 내충격성, 내마모성 등을 향상시키고, 화학적 성질, 즉 내약품성, 내용제성, 내수성 또한 향상시키며, 아울러 도막의 광택 및 전기 절연성도 향상시키게 된다.In the present invention, by adding an acrylic resin to improve the weather resistance and hardness of the coating film during coating, and also to form a urethane bond to improve the physical properties of the coating film, that is, adhesion, impact resistance, wear resistance, etc. It also improves chemical resistance, solvent resistance and water resistance, and also improves gloss and electrical insulation of the coating film.

Description

내후성이 우수한 변성 폴리에스테르 수지의 제조방법 및 이를 함유하는 도료조성물.A method for producing a modified polyester resin having excellent weather resistance and a coating composition containing the same.

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

Claims (10)

하기의 가), 나) 및 다) 단계로 제조되는 것을 특징으로 하는 아크릴 및 우레탄 변성 폴리에스테르 수지의 제조 방법.Method for producing an acrylic and urethane-modified polyester resin, characterized in that prepared in the following steps a), b) and c). 가)2기 이상의 알코올 혼합물과 2가 이상의 산 혼합물을 촉매 존재하에서 반응시켜 수산기 말단의 폴리에스테르 수지를 제조; 나)개시제 존재하에서 하이드록실 말단 아크릴 수지를 제조; 다)상기 가), 나)의 수지를 지방족 또는 지환족 디이소시아네이트로 변성, 합성하여 아크릴 및 우레탄 변성 폴리에스테르 수지를 제조.A) reacting at least two alcohol mixtures with a divalent acid mixture in the presence of a catalyst to produce a polyester resin at the hydroxyl end; B) preparing a hydroxyl terminated acrylic resin in the presence of an initiator; C) Acrylic and urethane modified polyester resins are prepared by modifying and synthesizing the resins of the above a) and b) with aliphatic or alicyclic diisocyanates. 제1항에 있어서, 상기 가)단계에서의 알코올 혼합물은 다가알코올 솔리드 중량% 중 네오펜틸글리콜 20-90 중량%, 에틸렌글리콜 10-40중량%, 1,6-헥산디올 0-40중량%, 1,4-부탄디올 0-40중량%, 사이크로헥산디메탄디올 0-40%, 프로필렌글리콜 0-40중량%, 트리메티롤프로판 0-20중량%인 것을 특징으로 하는 아크릴 및 우레탄 변성 폴리에스테르 수지의 제조방법.According to claim 1, wherein the alcohol mixture in step a) is neopentylglycol 20-90% by weight, 10-40% by weight ethylene glycol, 0-40% by weight 1,6-hexanediol in the polyalcohol solid% by weight, 1,4-butanediol 0-40% by weight, cyclohexane dimethanediol 0-40%, propylene glycol 0-40% by weight, trimethyrolpropane 0-20% by weight of acrylic and urethane modified polyester Method for producing a resin. 제1항에 있어서, 상기 가)단계에서의 다가산 혼합물은 다가산 솔리드 중량%중 이소프탈산 20-60중량%, 테레프탈산 0-40중량%, 아디핀산 0-40중량%, 사이크로헥산디카르본산 0-60중량%, 메틸헥사이드로프탈산 0-40중량%인 것을 특징으로 하는 아크릴 및 우레탄 변성 폴리에스테르 수지의 제조방법.The polyacid mixture according to claim 1, wherein the polyacid mixture in step a) is 20-60 wt% of isophthalic acid, 0-40 wt% of terephthalic acid, 0-40 wt% of adipic acid, and cyclohexanedicare A method for producing acrylic and urethane-modified polyester resins, characterized in that 0-60% by weight of the main acid, 0-40% by weight of methyl hexedrophthalic acid. 제1항에 있어서, 상기 나)단계에서의 아크릴 수지는 하이드록실기를 함유하는 모노머를 5-35중량%, 메틸메타아크릴레이트 및 n-부틸메타아크릴레이트 각각 10-50중량%, 스티렌모노머 5-35중량%, 카르복실산기를 갖는 모노머를 0-20중량% 등을 사용하여 제조하는 것을 특징으로 하는 아크릴 및 우레탄 변성 폴리에스테르 수지의 제조방법.The method of claim 1, wherein the acrylic resin in step b) is 5-35% by weight of a monomer containing a hydroxyl group, 10-50% by weight of methyl methacrylate and n-butylmethacrylate, respectively, and styrene monomer 5 A method for producing an acrylic and urethane-modified polyester resin, characterized in that -35% by weight, a monomer having a carboxylic acid group, is produced using 0-20% by weight or the like. 제1항에 있어서, 상기 다)단계에서의 사용가능한 지환족 디이소시아네이트 모노머는 이소포론디이소시아네이트, 하이드로게네이트디페닐메탄디이소시아네이트, 사이크로헥실디이소시아네이트 등이 있고, 지방족 디이소시아네이트 모노머는 헥사메틸렌디이소시아네이트, 트리메틸헥사메틸렌디이소시아네이트 등으로서 이들 중 하나 이상을 선택해서 사용하는 것을 특징으로 하는 아크릴 및 우레탄 변성 폴리에스테르 수지의 제조방법.According to claim 1, wherein the alicyclic diisocyanate monomers usable in step c) are isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, cyclohexyl diisocyanate and the like, and the aliphatic diisocyanate monomer is hexamethylene. A method for producing an acrylic and urethane-modified polyester resin characterized in that at least one of these is selected and used as diisocyanate, trimethylhexamethylene diisocyanate and the like. 제1항에 있어서, 상기 가)단계에서의 폴리에스테르 수지는 수산기가 20-150, 카르복실가 15이하이며, 수평균 분자량은 500-4,000인 것을 특징으로 하는 아크릴 및 우레탄 변성 폴리에스테르 수지의 제조방법.The method of claim 1, wherein the polyester resin in step a) has a hydroxyl value of 20-150, a carboxyl value of 15 or less, and a number average molecular weight of 500-4,000. . 제1항에 있어서, 상기 나)단계에서의 아크릴 수지는 수산기가 5-150, 카르복실가 50이하이며, 수평균 분자량은 1,000-5,000인 것을 특징으로 하는 아크릴 및 우레탄 변성 폴리에스테르 수지의 제조방법.The method of claim 1, wherein the acrylic resin in step b) has a hydroxyl group of 5-150, a carboxyl number of 50 or less, and a number average molecular weight of 1,000-5,000. 제1항에 있어서, 상기 다)단계에서의 최종 아크릴 및 우레탄 변성 폴리에스테르 수지는 수산기가 10-100, 카르복실가 20이하이며, 수평균 분자량은 1,000-5,000인 것을 특징으로 하는 아크릴 및 우레탄 변성 폴리에스테르 수지의 제조방법.The acrylic and urethane-modified polyester of claim 1, wherein the final acrylic and urethane-modified polyester resin in step c) has a hydroxyl value of 10-100 and a carboxyl value of 20 or less, and a number average molecular weight of 1,000-5,000. Method for producing ester resin. 제1항에 있어서, 상기 가),나),다)단계에서 최종 수지의 솔리드 중량%중 가)단계의 폴리에스테르 수지와 나)단계의 아크릴 수지는 각각 10-80중량%, 다)단계의 디이소시아네이트는 1-25중량%인 것을 특징으로 하는 아크릴 및 우레탄 변성 폴리에스테르 수지의 제조방법.The method according to claim 1, wherein the polyester resin of step a) and acrylic resin of step b) of the solid weight% of the final resin in steps a), b) and c) are each 10-80% by weight, c) Diisocyanate is 1-25% by weight of the acrylic and urethane modified polyester resin production method. 제1항 내지 제9항 중 어느 한 항에 따른 아크릴 및 우레탄 변성 폴리에스테르 수지 조성물 60-90중량%와 경화제인 포름알데히드와 반응된 요소, 멜라민, 벤조구아민 수지 또는 블록이소시아네이트를 포함하는 폴리이소시아네이트 수지 10-40중량%로 이루어진 것을 특징으로 하는 도료 조성물.Polyisocyanate comprising 60-90% by weight of the acrylic and urethane-modified polyester resin composition according to any one of claims 1 to 9 and urea, melamine, benzoguamine resin or block isocyanate reacted with formaldehyde as a curing agent. Coating composition, characterized in that consisting of 10-40% by weight of the resin. ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.※ Note: The disclosure is based on the initial application.
KR1019940018915A 1994-07-30 1994-07-30 Process for preparing modified polyester resin having excellent weather-resistance and paint composition having it KR0149695B1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100394099B1 (en) * 1996-03-07 2004-01-24 에스케이케미칼주식회사 Urethane-modified copolymeric polyester resin for paint
KR100458717B1 (en) * 2001-12-28 2004-12-03 주식회사 금강고려화학 Resin composition of copolymerized polyester having high weather resistance and its preparation method
KR100470429B1 (en) * 1996-12-30 2005-10-21 고려화학 주식회사 Process for preparing acrylic-urethane-acrylic block copolymer water dispersion resin and water-soluble paint composition containing the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100394099B1 (en) * 1996-03-07 2004-01-24 에스케이케미칼주식회사 Urethane-modified copolymeric polyester resin for paint
KR100470429B1 (en) * 1996-12-30 2005-10-21 고려화학 주식회사 Process for preparing acrylic-urethane-acrylic block copolymer water dispersion resin and water-soluble paint composition containing the same
KR100458717B1 (en) * 2001-12-28 2004-12-03 주식회사 금강고려화학 Resin composition of copolymerized polyester having high weather resistance and its preparation method

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