KR100461576B1 - Copolymer Polyester Resin - Google Patents

Copolymer Polyester Resin Download PDF

Info

Publication number
KR100461576B1
KR100461576B1 KR1019960065826A KR19960065826A KR100461576B1 KR 100461576 B1 KR100461576 B1 KR 100461576B1 KR 1019960065826 A KR1019960065826 A KR 1019960065826A KR 19960065826 A KR19960065826 A KR 19960065826A KR 100461576 B1 KR100461576 B1 KR 100461576B1
Authority
KR
South Korea
Prior art keywords
acid
polyester resin
mol
present
dicarboxylic acid
Prior art date
Application number
KR1019960065826A
Other languages
Korean (ko)
Other versions
KR19980047341A (en
Inventor
정종호
Original Assignee
에스케이케미칼주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 에스케이케미칼주식회사 filed Critical 에스케이케미칼주식회사
Priority to KR1019960065826A priority Critical patent/KR100461576B1/en
Publication of KR19980047341A publication Critical patent/KR19980047341A/en
Application granted granted Critical
Publication of KR100461576B1 publication Critical patent/KR100461576B1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
    • C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C08G63/21—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups in the presence of unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Landscapes

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

Abstract

본 발명은 도장강판용 도료에 유용한 공중합 폴리에스테르 수지에 관한 것으로서, 더욱 상세하게는 산 성분으로 2,6-나프탈렌 디카르복실산, 1,4-시클로헥산 디카르복실산, 그리고 트리말레인산 또는 무수트리말레인산을 함유하고, 다가알코올 성분으로 1,6-헥산디올을 함유하여, 프레스 가공후에 도막이 손상되지 않도록 고도의 가공성과 고경도를 실현시키며 이로써 가전, 건자재 및 자동차용 도장강판으로 유용한 공중합 폴리에스테르 수지에 관한 것이다.The present invention relates to a copolyester resin useful for coating steel coatings, and more particularly to 2,6-naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, and trimaleic acid or tri anhydride as acid components. Copolyester resin containing maleic acid and 1,6-hexanediol as polyhydric alcohol component to realize high workability and high hardness so as not to damage the coating film after press working, thereby making it useful as a coating steel sheet for home appliances, construction materials and automobiles It is about.

Description

공중합 폴리에스테르수지Copolymer Polyester Resin

본 발명은 도장강판용 도료에 유용한 공중합 폴리에스테르 수지에 관한 것으로서, 더욱 상세하게는 산 성분으로 2,6-나프탈렌 디카르복실산, 1,4-시클로헥산 디카르복실산, 그리고 트리말레인산 또는 무수트리말레인산을 함유하고, 다가알코올 성분으로 1,6-헥산디올을 함유하여, 프레스 가공후에 도막이 손상되지 않도록 고도의 가공성과 고경도를 실현시키며 이로써 가전, 건자재 및 자동차용 도장강판으로 유용한 공중합 폴리에스테르 수지에 관한 것이다.The present invention relates to a copolyester resin useful for coating steel coatings, and more particularly to 2,6-naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, and trimaleic acid or tri anhydride as acid components. Copolyester resin containing maleic acid and 1,6-hexanediol as polyhydric alcohol component to realize high workability and high hardness so as not to damage the coating film after press working, thereby making it useful as a coating steel sheet for home appliances, construction materials and automobiles It is about.

일반적인 도장강판의 제조에 있어서, 아크릴계 도료의 도막의 경우는 고경도이지만 가공성이 나쁘고, 고분자량 폴리에스테르계 도료의 도막의 경우는 가공성은 양호하나 경도가 낮은 문제가 있다. 또한 최근에는 분체도료를 이용한 도장강판도 시중에 판매되고 있으나, 도막표면에 요철이 심하고 생산성도 낮아 이를 개선하고자 하는 노력이 있어 왔다. 예컨대 일본공개특허공보 평 2-196876 호에서는 분체도료를 용제에 녹여서 도장함으로써 고경도, 고가공성 및 표면요철이 없는 양호한 도막을 형성한 바도 있으나 저장안정성이 불량하여 도장 작업성이 나쁜점이 지적되고 있다.In the production of a general coated steel sheet, in the case of a coating film of an acrylic paint, the hardness is high, but workability is poor. In the case of a coating film of a high molecular weight polyester paint, the workability is good but the hardness is low. In addition, recently, coated steel sheets using powder coatings have been sold on the market, but efforts have been made to improve the roughness of the coating surface and low productivity. For example, Japanese Unexamined Patent Publication No. 2-196876 discloses that a powder coating is dissolved and dissolved in a solvent to form a good coating film having high hardness, high processability, and no surface irregularities, but poor storage stability is pointed out due to poor storage stability. .

이에 본 발명에서는 공지의 고분자량 폴리에스테르계 도료의 도막에서 문제점으로 지적되어온 경도를 개선하면서도 고가공성을 유지할 수 있는 새로운 고분자량 폴리에스테르수지를 제조하기 위해선 신규한 원료사용과 분자구조의 개선이 해결책임을 알게 되었고, 그 결과 2,6-나프탈렌 디카르복실산 또는 그의 에스테르 유도체가 유리전이온도의 증가와 영(Young) 모듈러스의 증가로 고경도를 유지할 수 있으며, 1,4-시클로헥산 디카르복실산 또는 그의 에스테르 유도체가 고가공성 및 내화학성을 개선할 수 있으며, 그리고 1,6-헥산디올의 도입으로 고가공성을 실현할 수 있음을 알게됨으로써 본 발명을 완성하였다.Accordingly, in the present invention, in order to manufacture a new high molecular weight polyester resin which can maintain high processability while improving hardness, which has been pointed out as a problem in the coating film of a known high molecular weight polyester paint, new raw material use and improvement of molecular structure are solved. As a result, 2,6-naphthalene dicarboxylic acid or its ester derivatives can maintain high hardness by increasing glass transition temperature and increasing Young's modulus, and 1,4-cyclohexane dicar The present invention has been completed by knowing that an acid or an ester derivative thereof can improve high processability and chemical resistance, and can realize high processability by introducing 1,6-hexanediol.

따라서, 본 발명은 고경도, 고가공성 및 내오염성이 우수한 도장강판용 도료에 유용한 공중합 폴리에스테르수지를 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide a copolyester resin useful for paints for coating steel sheets excellent in high hardness, high workability and stain resistance.

본 발명은 산 성분으로 디카르복실산이 함유되어 있고 다가 알코올 성분으로 1,6-헥산디올이 함유되어 있는 공중합 폴리에스테르수지에 있어서, 상기 산 성분 중에는 2,6-나프탈렌 디카르복실산 또는 그의 에스테르 유도체 10 ∼ 40 몰%, 1,4-시클로헥산 디카르복실산 또는 그의 에스테르 유도체 5 ∼ 20 몰%, 그리고 트리말레인산 또는 무수 트리말레인산 0.2 ∼ 1.0 몰% 함유되어 있고, 상기 다가알코올 성분 중에는 1,6-헥산디올 3 ∼ 30 몰%가 함유되어 있는 공중합 폴리에스테르수지를 그 특징으로 한다.The present invention relates to a copolyester resin containing dicarboxylic acid as an acid component and 1,6-hexanediol as a polyhydric alcohol component, wherein 2,6-naphthalene dicarboxylic acid or ester thereof is included in the acid component. 10 to 40 mol% of derivatives, 5 to 20 mol% of 1,4-cyclohexanedicarboxylic acid or ester derivatives thereof, and 0.2 to 1.0 mol% of trimaleic acid or trimaleic anhydride, and the polyhydric alcohol component contains 1, It is characterized by the copolyester resin containing 3-30 mol% of 6-hexanediol.

이와같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.

본 발명은 고경도, 고가공성 및 내오염성이 양호한 도료용 공중합 폴리에스테르수지에 관한 것으로서, 본 발명에 사용되는 산 성분으로는 지방족 카르복실산, 방향족 카르복실산, 지환족 카르복실산 또는 이들의 무수물이 투입되는데, 본 발명에서 목적으로 하는 고경도, 고가공성 및 내오염성을 개선시키기 위해서는 산 성분중에 2,6-나프탈렌 디카르복실산이나 그의 에스테르 유도체, 1,4-시클로헥산 디카르복실산이나 그의 에스테르 유도체, 그리고 3관능성 산인 트리말레인산 또는 무수 트리말레인산이 함께 함유되어야만 한다.The present invention relates to a copolyester resin for paints having good hardness, high processability and pollution resistance, wherein the acid component used in the present invention is aliphatic carboxylic acid, aromatic carboxylic acid, alicyclic carboxylic acid or the like. Anhydrides are added, but in order to improve the high hardness, high processability and fouling resistance aimed at in the present invention, 2,6-naphthalene dicarboxylic acid or ester derivatives thereof and 1,4-cyclohexane dicarboxylic acid are included in the acid component. Or ester derivatives thereof and trimaleic acid or trimaleic anhydride as trifunctional acids.

만약 2,6-나프탈렌 디카르복실산 또는 그의 에스테르 유도체가 본 발명의 전체 산성분 중에 10 몰% 미만 함유되면 본 발명에서 목적으로 하는 경도를 개선시킬 수 없고, 40 몰%를 초과하여 함유되면 용해력이 약해진다. 또한 1,4-시클로헥산 디카르복실산 또는 그의 에스테르 유도체가 전체 산 성분중에 5 몰% 미만 함유되면 내화학성이 개선되지 않으며, 20 몰%를 초과하여 함유되면 경도가 떨어진다. 그리고 3관능성 산으로서 트리말레인산 또는 무수 트리말레인산이 0.2 몰% 미만 함유되면 내오염성이 향상되지 않으며, 1.0 몰% 초과하면 가공성이 불량해진다.If less than 10 mol% of 2,6-naphthalene dicarboxylic acid or its ester derivative is contained in the total acid component of the present invention, the hardness desired in the present invention cannot be improved, and if it is contained more than 40 mol%, solubility This weakens. In addition, when less than 5 mol% of 1,4-cyclohexane dicarboxylic acid or its ester derivative is contained in the total acid component, chemical resistance does not improve, and when it exceeds 20 mol%, hardness falls. If the trifunctional acid contains less than 0.2 mol% of trim maleic acid or trimellitic anhydride, fouling resistance does not improve. If it exceeds 1.0 mol%, workability is poor.

또한 본 발명에 따른 공중합 폴리에스테르수지 제조시 상기에서 언급한 상기 필수 산 성분이외에도 아디프산, 아젤라산, 세바스산 등과 같은 지방족 카르복실산 및 그의 에스테르 유도체, 테레프탈산, 이소프탈산, 나트륨 황화이소프탈산 등과 같은 방향족 카르복실산 및 그의 에스테르 유도체, 그리고 무수프탈산, 무수말레인산, 사염화 무수프탈산과 같은 무수화합물 중에서 선택된 산 성분을 함께 사용할 수도 있다.In addition to the above-mentioned essential acid components in the preparation of the copolymerized polyester resin according to the present invention, aliphatic carboxylic acids and ester derivatives thereof, such as adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, sodium isophthalic acid, etc. The same aromatic carboxylic acid and its ester derivatives and acid components selected from anhydrides such as phthalic anhydride, maleic anhydride and phthalic anhydride can also be used together.

또한 본 발명에 따른 공중합 폴리에스테르수지는 다가알코올의 필수성분으로서 1,6-헥산디올을 3 ∼ 30 몰% 함유시키는 바, 1,6-헥산디올이 전체 다가알코올 성분중에 3 몰% 미만으로 함유되면 프레스 가공성이 불량해지고, 30 몰%를 초과하면 내오염성이 저하된다. 상기 다가알코올의 필수성분 이외에도 에틸렌 글리콜, 프로필렌 글리콜, 네오펜틸 글리콜, 부탄디올, 트리메틸올 프로판, 디에틸렌 글리콜, 1,4-시클로헥산 디메탄올 및 폴리에틸렌 글리콜 중에서 선택된 단독 화합물 또는 하나 이상의 혼합물을 함께 사용할 수도 있다.In addition, the copolymerized polyester resin according to the present invention contains 3 to 30 mol% of 1,6-hexanediol as an essential component of the polyhydric alcohol, and therefore, 1,6-hexanediol is contained less than 3 mol% in the total polyhydric alcohol components. Press workability becomes poor, and when it exceeds 30 mol%, pollution resistance falls. In addition to the essential components of the polyhydric alcohol, a single compound or a mixture of one or more selected from ethylene glycol, propylene glycol, neopentyl glycol, butanediol, trimethylol propane, diethylene glycol, 1,4-cyclohexane dimethanol and polyethylene glycol may be used together. have.

한편, 본 발명에서 사용되는 에스테르화 촉매로는 Ca, Ce, Pb, Mn, Zn, Mg, Sb 등의 초산화물과 Sb2O3 또는 GeO2 중에서 선택된 것이 사용될 수 있고, 열안정제로는 인산화물을 사용할 수 있다.Meanwhile, the esterification catalyst used in the present invention may be selected from superoxides such as Ca, Ce, Pb, Mn, Zn, Mg, Sb, and Sb 2 O 3 or GeO 2 , and as a thermal stabilizer, phosphorus oxide Can be used.

이와같은 성분을 이용하여 본 발명의 공중합 폴리에스테르수지를 제조하는 경우, 산 성분과 다가알코올 성분을 넣고 에스테르화 촉매를 투입한 다음에는 상온에서 약 200 ∼ 250 ℃까지 서서히 승온시켜서 부산물인 물이나 에탄올이 유출완료되면 축중합 촉매와 열안정제를 투입시켜서 진공반응을 계속한다. 온도를 270 ∼ 300 ℃까지 승온시켜 수시간동안 공중합시키면 수평균 분자량이 5,000 ∼ 15,000인 공중합 폴리에스테르수지가 얻어진다. 이때 수산기가는 5 ∼ 30 KOH mg/g 범위가 되도록 하였다.In the case of preparing the copolyester resin of the present invention using such a component, the acid component and the polyhydric alcohol component are added, followed by the addition of an esterification catalyst, followed by gradually raising the temperature to about 200 to 250 ° C., by-product water or ethanol. When this outflow is completed, the vacuum reaction is continued by adding a polycondensation catalyst and a heat stabilizer. When the temperature is raised to 270 to 300 ° C. and copolymerized for several hours, a copolymer polyester resin having a number average molecular weight of 5,000 to 15,000 is obtained. At this time, the hydroxyl value was 5 to 30 KOH mg / g range.

본 발명에 따르면 공중합 폴리에스테르수지의 수평균 분자량이 5,000 보다 적으면 경화밀도가 높아져서 프레스 가공성이 불량해지고, 15,000 보다 크면 내오염성이 개선되지 않으며 도장 작업성도 불량해진다. 또한 수산기가가 5 미만이면 내오염성이 불량해지며 30을 초과하면 경화밀도가 높아서 가공성이 불량해진다.According to the present invention, when the number average molecular weight of the copolymerized polyester resin is less than 5,000, the curing density is increased, and the press workability is poor. If the hydroxyl value is less than 5, the fouling resistance is poor. If the hydroxyl value is more than 30, the curing density is high, resulting in poor workability.

본 발명에 따라 제조된 공중합 폴리에스테르 수지는 아미노 포름알데히드 또는 우레아 수지와 같은 열경화제와 소포제, 습윤제 등의 첨가제와 배합하여 도료화시킨다.The copolyester resin prepared according to the present invention is coated with a thermosetting agent such as amino formaldehyde or urea resin and additives such as an antifoaming agent and a wetting agent.

따라서, 이렇게 제조된 도료는 종래와는 프레스 가공성이 좋고 경도가 높아서 프레스 가공시 프레스에 의한 찰과상에 견디어 내는 바인더 수지로서 매우 유용하다.Therefore, the coating material thus prepared is very useful as a binder resin that withstands abrasion by presses during press work due to its good press formability and high hardness.

상술한 바와같이, 본 발명은 종래와는 달리 산 성분과 다가알코올 성분 및 조성을 새롭게 구성한 공중합 폴리에스테르수지로서, 프레스 가공성, 내오염성, 고경도성 등의 제반물성이 우수하여 각종 도료용, 바인더 수지 등으로 사용하기에 매우 적합하다.As described above, the present invention is a copolymer polyester resin newly composed of an acid component, a polyalcohol component, and a composition, which is different from the conventional one, and is excellent in various physical properties such as press workability, stain resistance, high hardness, etc. Very suitable for use as

이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

실시예 1 ∼ 4 및 비교예 1 ∼ 4Examples 1-4 and Comparative Examples 1-4

500 ㎖ 3구 플라스크, 온도계, 냉각기, 맨틀, 교반기, 진공펌프를 미리 준비하고, 3구 플라스크에 다음 표 1과 같은 조성으로 산 성분과 다가알코올 성분을 넣은 다음 에스테르화 촉매로 Zn 초산화물을 투입한 후 상온에서 230 ℃까지 서서히 승온시켜 부산물인 물이나 에탄올이 이론 유출량까지 유출되면 축중합 촉매로서 삼산화 안티몬 0.2 g과 열안정제로서 트리메틸포스포릭산 0.3 g을 투입하여 수시간 동안 진공반응을 실시하고 온도 280 ℃까지 승온시켜 수평균 분자량이 5,000 ∼ 15,000의 범위에 들도록 반응시켰다. 제조된 공중합 폴리에스테르수지의 수평균 분자량 및 수산기가는 다음 표 1에 나타내었다.Prepare a 500 ml three-necked flask, thermometer, cooler, mantle, stirrer, and vacuum pump in advance, add acid and polyalcohol components with the composition shown in the following table 1, and add Zn superoxide as esterification catalyst. After gradually raising the temperature from room temperature to 230 ℃, when by-product water or ethanol flows out to the theoretical effluent, 0.2 g of antimony trioxide as a polycondensation catalyst and 0.3 g of trimethylphosphoric acid as a heat stabilizer are put in a vacuum reaction for several hours. It heated up to the temperature of 280 degreeC, and made it react so that a number average molecular weight might fall in the range of 5,000-15,000. The number average molecular weight and hydroxyl value of the prepared copolymerized polyester resin are shown in Table 1 below.

구 분division 실시예Example 비교예Comparative example 1One 22 33 44 1One 22 33 44 다가산(몰%)Polyacid (mol%) 테레프탈산Terephthalic acid 4040 5050 54.854.8 4040 3030 5050 -- 5555 이소프탈산Isophthalic acid 3030 1010 1919 2020 1010 32.532.5 88 2020 아디프산Adipic acid -- -- -- 44 -- 17.517.5 -- -- 세바스산Sebas 3.43.4 -- -- -- 12.112.1 -- -- 0.80.8 2,6-나프탈렌 디카르복실산2,6-naphthalene dicarboxylic acid 19.119.1 29.329.3 19.519.5 25.125.1 -- -- 68.968.9 17.517.5 1,4-시클로헥산 디카르복실산1,4-cyclohexane dicarboxylic acid 7.27.2 10.310.3 6.26.2 10.310.3 47.947.9 -- 22.722.7 9.39.3 무수트리말레인산Trimaleic anhydride 0.30.3 0.40.4 0.50.5 0.60.6 -- -- 0.40.4 0.40.4 다가알코올(몰%)Polyhydric alcohol (mol%) 에틸렌 글리콜Ethylene glycol 37.237.2 37.237.2 44.744.7 44.744.7 37.237.2 44.744.7 29.829.8 44.744.7 네오펜틸 글리콜Neopentyl glycol 41.241.2 43.743.7 43.743.7 37.537.5 43.743.7 55.355.3 50.050.0 37.537.5 1,3-프로판 디올1,3-propane diol 9.19.1 4.94.9 -- 7.97.9 4.94.9 -- 20.220.2 -- 1,6-헥산 디올1,6-hexane diol 12.512.5 14.214.2 11.611.6 9.99.9 14.214.2 -- -- 17.817.8 수지물성Resin properties 수평균 분자량(a) Number average molecular weight (a) 12,00012,000 8,0008,000 10,00010,000 7,0007,000 8,0008,000 10,00010,000 18,00018,000 3,0003,000 수산기가(b)(KOH mg/g)Hydroxyl value (b) (KOH mg / g) 1212 1919 1414 2121 2020 1515 44 5050 (주) (a) GPC법 : Milton Roy사 제품을 사용하였으며 분자량 3,600, 7,000, 9,200의 폴리스티렌으로 기준을 잡은 후 도료용 수지를 테트라하이 드로퓨란에 녹여서 측정함. (b) 수지 2 g을 아세틸화시약 10 ㎖에 넣고 100 ℃로 60분간 가열한 후, 순수 1 ㎖를 넣고 10분간 가열한 다음 상온까지 냉각한 후, 아 세톤을 적당량 투입하고 1N KOH 용액으로 적정하여 산출함.Note: (a) GPC method: Milton Roy's product was used, and after setting the standard with polystyrene having molecular weight of 3,600, 7,000, and 9,200, the coating resin was dissolved in tetra-hydrofuran and measured. (b) 2 g of resin was added to 10 ml of acetylated reagent, heated at 100 ° C. for 60 minutes, 1 ml of pure water was added thereto, heated for 10 minutes, cooled to room temperature, acetone was added in an appropriate amount, and titrated with 1N KOH solution. Calculated by

실험예Experimental Example

본 발명의 성능을 평가하기 위해서 상기 실시예 1 ∼ 4 및 비교예 1 ∼ 4에서 합성한 공중합 폴리에스테르수지를 Solvesso #150/#200(Exxon사 제품) = 8/2인 용제로 50% 용액상으로 만들어서 다음 표 2와 같은 분산 배합상을 제조한 후에 다음 표 3과 같은 용해 배합을 실시하여 도료를 만들었다.In order to evaluate the performance of the present invention, the copolymerized polyester resins synthesized in Examples 1 to 4 and Comparative Examples 1 to 4 were dissolved in 50% solution with Solvesso # 150 / # 200 (manufactured by Exxon) = 8/2. After preparing a dispersed compound phase as shown in Table 2, and then to perform a dissolution compounding as shown in Table 3 to make a paint.

분산배합상Distributed compound phase TiO2 (Rutile형)50% 수지용액Solvesso #150습윤제* TiO 2 (Rutile type) 50% resin solution Solvesso # 150 Wetting agent * 60 g 30 g 10 g0.5 g 60 g 30 g 10 g0.5 g (주) * 미국 몬산토사 제품 "Modaflow"Co., Ltd. * Monsanto Products "Modaflow"

용해배합Melt blend 분산배합액50% 수지용액Cymel 303*n-부탄올p-톨루엔설폰산 10% 용액Dispersion solution 50% Resin solution Cymel 303 * n-butanol p-toluenesulfonic acid 10% solution 100.0 g60.0 g17.0 g10.0 g2.1 g100.0 g60.0 g17.0 g10.0 g2.1 g (주) * 미국 사이나미드사 제품Co., Ltd. * Products made by Cinnamid, USA

각 실시예 및 비교예에 따른 수지를 사용하여 상기와 같이 제조된 도료의 도막 물성을 각각 다음 표 4에 함께 나타내었다.The coating film properties of the paints prepared as described above using the resins according to the examples and the comparative examples are respectively shown in Table 4 below.

도막물성Coating property 구 분division 실 시 예Example 비 교 예Comparative Example 1One 22 33 44 1One 22 33 44 도막물성Coating property 연필경도(1) Pencil Hardness (1) 2H2H 3H3H 2H2H 2H2H BB HBHB 측불Side payment 2H2H 가공성(I.T)(2) Machinability (IT) (2) 55 55 55 55 44 55 측불Side payment 00 용해성(3) Solubility (3) 00 00 00 00 00 00 ×× 00 매직 내오염성(4) Magic Pollution Resistance (4) 흑Black 55 55 55 55 44 55 측불Side payment 55 적enemy 55 55 55 55 1One 44 측불Side payment 55 청blue 55 55 55 55 33 44 측불Side payment 55 (주) (1) 0.3 mm 두께의 아연도금 강판에 에스테르계 하도도료를 코팅하고 210 ℃ 에서 1분간 열풍건조기로 건조한 후 본 발명으로 배합된 도료를 건도막으 로 15 ∼ 25 μ이 되도록 코팅하여 230 ℃에서 1분간 열풍건조기로 건조 한 후 미쯔비시 연필로 도막경도를 측정하였다.(2) 상기 (1)과 같이 건조된 도장강판을 180 ℃로 구부려서 0.3 mm 두께의 강 판을 끼워넣은 후 완전히 굴곡시켰을 때 도막손상이 심한 것은 0점이고 양호한 것은 5점으로 하였다.(3) 용제 셀로솔브아세테이트/kocosol #100 = 1/1에 수지 40% 조건으로 용해 시켰을 때 수지가 투명하게 용해되면 0이고 용액이 흐려지거나 백탁현상 이 보이면 ×이다.(4) 상기 (1)과 같이 건조된 도장강판위에 흑, 적, 청의 매직잉크(모나미제) 를 도포시킨 후, 20 ℃에서 244시간 방치한 다음 에탄올로 닦았다. 5 : 잉크흔적이 없음 3 : 잉크흔적이 희미하게 남았음 1 : 잉크흔적이 명확히 남았음Co., Ltd. (1) Coating an ester-based paint on a 0.3 mm-thick galvanized steel sheet and dry it with a hot air dryer at 210 ° C. for 1 minute, and then coat the paint blended according to the present invention with a dry film to be 15 to 25 μ 230 After drying with a hot air dryer at 1 ° C. for 1 minute, the hardness of the coating was measured with a Mitsubishi pencil. (2) The coated steel sheet dried as described in (1) was bent at 180 ° C. and inserted into a 0.3 mm thick steel plate, thereby completely bending. (3) Solvent cellosolve acetate / kocosol # 100 = 1/1 When dissolving the resin at 40% condition, the resin was transparent and dissolved, and the solution became cloudy. (4) After applying black, red, and blue magic ink (made by Monami) on the coated steel sheet dried as in (1), it was left at 20 DEG C for 244 hours and then wiped with ethanol. 5: No ink trace 3: Ink traces remain faint 1: Ink traces remain clearly

따라서, 본 발명의 공중합 폴리에스테르수지는 고경도, 고가공성 및 내오염성이 우수하여 가전, 건자재 및 자동차용 도장강판으로 유용하다.Therefore, the copolyester resin of the present invention is excellent in high hardness, high processability and pollution resistance, and is useful as a coated steel sheet for home appliances, construction materials, and automobiles.

Claims (3)

산 성분으로 다가 산이 함유되어 있고 다가 알코올 성분으로 1,6-헥산디올이 함유되어 공중합되어 있는 폴리에스테르수지에 있어서, In a polyester resin copolymerized by containing polyhydric acid as an acid component and 1,6-hexanediol as a polyhydric alcohol component, 상기 산 성분 중에는 2,6-나프탈렌 디카르복실산 또는 그의 에스테르 유도체 10 ∼ 40 몰%, 1,4-시클로헥산 디카르복실산 또는 그의 에스테르 유도체 5 ∼ 20 몰%, 그리고 트리말레인산 또는 무수 트리말레인산 0.2 ∼ 1.0 몰% 함유되어 있고, 상기 다가 알코올 성분 중에는 1,6-헥산디올 3 ∼ 30 몰%가 함유되어 있는 것임을 특징으로 하는 공중합 폴리에스테르수지.Among the acid components, 10 to 40 mol% of 2,6-naphthalene dicarboxylic acid or ester derivatives thereof, 5 to 20 mol% of 1,4-cyclohexane dicarboxylic acid or ester derivatives thereof, and trimaleic acid or trimaleic anhydride Co-polyester resin characterized by containing 0.2-1.0 mol% and containing 3-30 mol% of 1, 6- hexanediol in the said polyhydric alcohol component. 제 1 항에 있어서, 상기 공중합 폴리에스테르수지의 수평균 분자량 5,000 ∼ 15,000 범위인 것임을 특징으로 하는 공중합 폴리에스테르수지.The copolymerized polyester resin according to claim 1, wherein the copolymerized polyester resin has a number average molecular weight of 5,000 to 15,000. 제 1 항에 있어서, 상기 공중합 폴리에스테르수지의 수산기가는 5 ∼ 30 KOH mg/g 범위인 것임을 특징으로 하는 공중합 폴리에스테르수지.The copolymerized polyester resin according to claim 1, wherein the hydroxyl value of the copolymerized polyester resin is in the range of 5 to 30 KOH mg / g.
KR1019960065826A 1996-12-14 1996-12-14 Copolymer Polyester Resin KR100461576B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1019960065826A KR100461576B1 (en) 1996-12-14 1996-12-14 Copolymer Polyester Resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1019960065826A KR100461576B1 (en) 1996-12-14 1996-12-14 Copolymer Polyester Resin

Publications (2)

Publication Number Publication Date
KR19980047341A KR19980047341A (en) 1998-09-15
KR100461576B1 true KR100461576B1 (en) 2005-09-26

Family

ID=37304866

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1019960065826A KR100461576B1 (en) 1996-12-14 1996-12-14 Copolymer Polyester Resin

Country Status (1)

Country Link
KR (1) KR100461576B1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100602280B1 (en) * 1998-12-31 2006-12-22 에스케이케미칼주식회사 Copolymerized Polyester Resin Composition for Coating

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR840000375A (en) * 1982-07-27 1984-02-22 요시자끼 고오조오 Method of manufacturing polyester resin coated metal sheet
US4973654A (en) * 1988-12-23 1990-11-27 Eastman Kodak Company Copolyesters from 4,4'-biphenyldicarboxylic acid, 1,6-hexanediol and ethylene glycol
US5321118A (en) * 1993-09-30 1994-06-14 Eastman Chemical Company 1-acetoacetamido-2,3-propane diol monomer and polyesters prerpared therefrom
KR960014204A (en) * 1994-10-22 1996-05-22 박홍기 Process for producing polyester copolymer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR840000375A (en) * 1982-07-27 1984-02-22 요시자끼 고오조오 Method of manufacturing polyester resin coated metal sheet
US4973654A (en) * 1988-12-23 1990-11-27 Eastman Kodak Company Copolyesters from 4,4'-biphenyldicarboxylic acid, 1,6-hexanediol and ethylene glycol
US5321118A (en) * 1993-09-30 1994-06-14 Eastman Chemical Company 1-acetoacetamido-2,3-propane diol monomer and polyesters prerpared therefrom
KR960014204A (en) * 1994-10-22 1996-05-22 박홍기 Process for producing polyester copolymer

Also Published As

Publication number Publication date
KR19980047341A (en) 1998-09-15

Similar Documents

Publication Publication Date Title
EP1453882B1 (en) Copolyester resin for solventborne coating and coating composition comprising the same
AU2002337165A1 (en) Copolyester resin for solventborne coating and coating composition comprising the same
EP0573687A1 (en) Resin composition for powder coatins
US3491066A (en) Process for preparing a linear polyester resin having pendant alcoholic hydroxy groups
JPS6324023B2 (en)
US3992346A (en) Production of highly flexible coatings
KR100461576B1 (en) Copolymer Polyester Resin
US4123404A (en) Water-based coatings
US4478994A (en) Use of unsaturated polyesters as additive binders improving adhesion in coating agents for coating of metals
JPS5911370A (en) Coating resin composition
JPH0569151B2 (en)
JPH0216327B2 (en)
JPH061945A (en) Coating composition for coated steel plate
KR100616182B1 (en) Copolyester resin and coating composition comprising it
JPH04227713A (en) Polyester resin composition for powder coating compound
JPS6317303B2 (en)
KR960006298B1 (en) Copolyester resin composite
JP3338853B2 (en) Resin composition for paint
KR950006717B1 (en) Polyester copolymer resin
JPH061841A (en) Block copolyester/amide resin and coating composition for coated steel sheet containing same
KR101467328B1 (en) Polyester resin and paint composition including the same
JPS6134754B2 (en)
JPH0557310B2 (en)
JPH02170876A (en) Resin composition for coating
CN116970329A (en) Coiled material finishing paint with high gloss and high distinctness of image and preparation method thereof

Legal Events

Date Code Title Description
A201 Request for examination
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20131122

Year of fee payment: 10

FPAY Annual fee payment

Payment date: 20141120

Year of fee payment: 11

FPAY Annual fee payment

Payment date: 20151120

Year of fee payment: 12

FPAY Annual fee payment

Payment date: 20161121

Year of fee payment: 13