KR100461576B1 - Copolymer Polyester Resin - Google Patents
Copolymer Polyester Resin Download PDFInfo
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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.
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.
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.
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.
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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 |
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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 |
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