KR19990031831A - Employee Copolymer Polyester Resin and Molded Product Using the Same - Google Patents
Employee Copolymer Polyester Resin and Molded Product Using the Same Download PDFInfo
- Publication number
- KR19990031831A KR19990031831A KR1019970052693A KR19970052693A KR19990031831A KR 19990031831 A KR19990031831 A KR 19990031831A KR 1019970052693 A KR1019970052693 A KR 1019970052693A KR 19970052693 A KR19970052693 A KR 19970052693A KR 19990031831 A KR19990031831 A KR 19990031831A
- Authority
- KR
- South Korea
- Prior art keywords
- polyester resin
- copolymerized polyester
- resin composition
- copolymer polyester
- acid
- Prior art date
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
- C08G63/19—Hydroxy compounds containing aromatic rings
- C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
- C08G63/195—Bisphenol A
-
- 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
-
- 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
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
본 발명은 투명성이 우수한 사원 공중합 폴리에스터 수지 조성물 및 이로부터 제조되는 투명 쉬트와 보틀에 관한 것으로, 수지조성물은 극한 점도 0.5∼1.4 인 공중합 폴리에스터 수지에 있어서 테레프탈산과 아이소프탈산, 에틸렌 글리콜 및 비스페놀 A를 직접 에스터와 반응시킨 후, 중축합 반응 촉매로 다단계 화합물을 공중합 폴리에스터 대비 200∼3,000 ppm을 투입하여 얻는 것을 특징으로 하며, 투명 쉬트와 보틀은 상기의 공중합 폴리에스터 수지를 용융압출 및 직접블로잉(Direct Blowing)하여 제조되는 것을 특징으로 한다.The present invention relates to an intrinsic copolymerized polyester resin composition having excellent transparency, and a transparent sheet and a bottle prepared therefrom, wherein the resin composition is a terephthalic acid, isophthalic acid, ethylene glycol and bisphenol A in a copolymer polyester resin having an intrinsic viscosity of 0.5 to 1.4. After the reaction with the ester directly, the polycondensation reaction catalyst to obtain a multi-stage compound 200 to 3,000 ppm compared to the copolymer polyester, characterized in that the transparent sheet and the bottle melt extrusion and direct blowing of the copolymer polyester resin It is characterized in that it is produced by (Direct Blowing).
Description
본 발명은 투명성이 우수한 사원 공중합 폴리에스터 수지 및 이로부터 제조되는 투명 용기의 제조방법에 관한 것으로, 특히 4 종이상의 공중합 모노머를 사용하여 공중합하여 성형시 결정화가 일어나지 않아 물이나 냉풍에 의한 급냉 등의 처리를 거치지 않고도 높은 투명성을 갖는 공중합 폴리에스터 수지 및 이를 압출, 블로잉하여 제조되는 두께 2∼10 mm 의 쉬트 및 두께 0.5∼3mm의 보틀의 제조방법에 관한 것이다.The present invention relates to a method for producing an intrinsic copolymerized polyester resin having excellent transparency and a transparent container manufactured therefrom. Particularly, crystallization does not occur during molding by copolymerization using four types of copolymer monomers, such as rapid cooling due to water or cold wind. The present invention relates to a copolymer polyester resin having a high transparency without undergoing treatment, and a sheet having a thickness of 2 to 10 mm and a bottle having a thickness of 0.5 to 3 mm produced by extrusion and blowing the same.
일반적으로 수지의 투명성은 수지 내에 존재하는 결정에 의해 좌우되는 데 성형시 제품내에 결정화가 생겨 투명성이 떨어지게 된다. 또한 수지의 결정화 속도가 냉각속도에 비해 빠를 경우 두껍게 성형되는 것이다. 이러한 것을 방지하기 위하여 성형시 급냉을 시키거나 새로운 공중합 모노머를 첨가하여 결정화를 억제시키는 방법이 있다.In general, the transparency of the resin depends on the crystals present in the resin, but crystallization occurs in the product during molding, resulting in poor transparency. In addition, when the crystallization rate of the resin is faster than the cooling rate is formed thick. In order to prevent this, there is a method of suppressing crystallization by quenching during molding or adding a new copolymerization monomer.
이러한 방법으로는 다른 공중합 모노머와의 공중합으로 결정 생성 및 성장을 억제하여 비결정성인 플리머를 얻는 방법이 시도되어지고 있다. 이러한 공중합 모노머로 많이 이용되어지는 것으로는 디에시드로서 아이소프탈산, 1,4-사이클로 헥산 디카르복실산, 프탈산, 2,5-, 2,6- 혹은 2,7-나프탈렌 디카르복실산, 쑥신산, 세바크산, 아디프산, 아젤라산, 수베르산, 피멜산, 굴르타르산이나 이들의 디알킬 에스터화물이 이용되어지고 다음성분으로서는 디에틸렌 글리콜, 1,2-, 1,3-프로판디올, 1,4-부탄디올, 네오펜틸글리콜, 1,6-헥산디올, 1,4-사이클로헥산디올, 1,4-사이클로헥산 디메탄올, 비스페놀A, 폴리에틸렌 글리콜, 폴리프로필렌 글리콜, 폴리테트라 메틸렌 에테르 글리콜 등이 이용되어 진다.As such a method, there has been attempted a method of obtaining an amorphous plymer by suppressing crystal formation and growth by copolymerization with another copolymerizing monomer. Examples of the copolymerized monomer include isophthalic acid, 1,4-cyclohexane dicarboxylic acid, phthalic acid, 2,5-, 2,6- or 2,7-naphthalene dicarboxylic acid, mugwort as dieside. Xinic acid, sebacic acid, adipic acid, azelaic acid, suberic acid, pimelic acid, guartaric acid or dialkyl esters thereof are used and the following components are diethylene glycol, 1,2-, 1,3- Propanediol, 1,4-butanediol, neopentylglycol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexane dimethanol, bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene Ether glycol and the like are used.
유럽 특허 제 143640 호 에서는 아이소프탈산(70∼90몰%), 1,3-디하이드록시에톡시벤젠(1,3-Dihydroxyethoxy benzene 혹은 Dihydroxyethoxy resorcinol, 0∼50몰%) 및 파라하이드록시 벤조산(2∼25몰%)을 공중합하였으며, 일본 특개평 2-187449 에서는 아이소프탈산(20∼80몰%), 1,3-디하이드록시에톡시 레소시놀(50∼90몰%)를 공중합한 예가 있다. 하지만 이 경우 아이소프탈산 이외의 공중합 모노머가 고가이며 또한 수급에 문제가 있어 상업적 생산에는 문제가 따른다.European Patent No. 143640 discloses isophthalic acid (70-90 mole%), 1,3-dihydroxyethoxy benzene (1,3-Dihydroxyethoxy benzene or Dihydroxyethoxy resorcinol, 0-50 mole%) and parahydroxy benzoic acid (2 -25 mol%), and Japanese Patent Laid-Open No. 2-187449 has an example in which isophthalic acid (20 to 80 mol%) and 1,3-dihydroxyethoxy resorcinol (50 to 90 mol%) are copolymerized. . However, in this case, copolymerization monomers other than isophthalic acid are expensive and there is a problem in supply and demand, and thus, commercial production is problematic.
일본 특개소 58-142914에서는 비스페놀A(아이소프로필리덴 디페놀, 2,2-디페녹시프로판, 2∼20몰%)를 이용하여 공중합하였으며 특개소 58-157818에서는 분자량 300∼8000범위의 비스페놀A의 에틸렌옥사이드 부가물(0.1∼30몰%)을 공중합하였다. 하지만 이 방법으로는 수지 제조단가가 높아지는 단점이 있거나 공중합 모노머의 수급이 어려운 문제가 있으며 테레프탈산에 의한 직접 에스터화 반응으로는 제조하기 어려운 문제가 있다.In Japanese Patent Laid-Open No. 58-142914, copolymerization was performed using bisphenol A (isopropylidene diphenol, 2,2-diphenoxypropane, 2-20 mol%), and in Japanese Patent Laid-Open 58-157818, bisphenol A having a molecular weight of 300-8000 Ethylene oxide adducts (0.1-30 mol%) were copolymerized. However, this method has a disadvantage in that the manufacturing cost of the resin increases, or there is a problem in that supply of copolymerization monomers is difficult, and there is a problem in that it is difficult to manufacture by direct esterification by terephthalic acid.
본 발명은 상기한 바와 같은 문제점을 해결하여 생산원가가 저렴하고 수급이 원활한 공중합 모노머를 사용하여 결정화가 되지 않고, 압출 혹은 블로잉 등의 성형성이 우수한 공중합 폴리에스터 수지 및 이로부터 제조되는 투명성이 우수한 쉬트 및 보틀을 제공하는 것을 목적으로 한다.The present invention solves the problems as described above, the production cost is low and the supply and demand is not easy to crystallize using a copolymer monomer, excellent copolymerization polyester resin excellent in moldability such as extrusion or blowing, and excellent transparency prepared therefrom It is an object to provide a sheet and a bottle.
본 발명의 수지조성물은 테레프탈산 및 아이소프탈산, 에틸렌글리콜, 비스페놀A를 직접 에스터화 반응시키고 이를 공중합 폴리에스터 수지 대비 200∼3000ppm 의 티탄계 화합물을 중축합 촉매로 사용하여 제조되는 것을 특징으로 하며, 본 발명의 투명 쉬트성형물은 이로부터 압출성형되어 제조되는 것을 특징으로 하며, 본 발명의 보틀은 이로부터 블로잉 성형되어 제조되는 것을 특징으로 한다.The resin composition of the present invention is characterized in that it is prepared by directly esterifying terephthalic acid, isophthalic acid, ethylene glycol, and bisphenol A and using 200-3000 ppm titanium compound as a polycondensation catalyst as compared to the copolymerized polyester resin. The transparent sheet molding of the present invention is characterized in that it is produced by extrusion molding, and the bottle of the present invention is characterized by being blow molded from it.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
슬러리 제조시 투입되는 아이소프탈산의 양은 전체 디에시드(PPA + IPA) 외 5∼95몰%이다. 그리고 투입되는 비스페놀A의 양은 디올의 5∼50몰%이다. 비스페놀A의 양이 이보다 적게 투입되면 투명성 개선의 효과가 작은 문제점이 있고, 이보다 커지면 비스페놀 A를 에틸렌글리콜에 녹여 슬러리 제조하기가 어려운 문제점이 있다. 에틸렌 글리콜과 비스페놀A의 전체 디올을 테레프탈산과 아이소프탈산의 전체 디에시드의 100∼140몰%를 투입하여 슬러리를 제조한다. 디올의 양이 이보다 작으면 에스터화 반응율이 낮아져 최종 수지 제품의 품질이 열악해지며 이보다 크면 생산원가가 높아지는 문제가 있다.The amount of isophthalic acid added during slurry production is 5 to 95 mole% other than the total dieside (PPA + IPA). The amount of bisphenol A added is 5 to 50 mol% of the diol. If the amount of bisphenol A is less than this, there is a problem in that the effect of improving transparency is small, and if it is larger than this, there is a problem in that bisphenol A is dissolved in ethylene glycol and it is difficult to prepare a slurry. 100-140 mol% of all the diacids of terephthalic acid and isophthalic acid are prepared for the whole diol of ethylene glycol and bisphenol A, and a slurry is prepared. If the amount of diol is smaller than this, the esterification reaction rate is lowered, resulting in poor quality of the final resin product.
첨가제로는 인계와 페놀계를 사용하며, 인계로는 트리메틸포스페이트(Trimethyl phosphate)와 트리페닐포스페이트(Triphenyl phosphate)를 사용하는 것이 바람직하다. 페놀계로는 시바가이기(Ciba-Geigy)사의 이가녹스 1010(Iganox 1010)과 이가녹스 1098(Iganox 1090), 이가포스 168(Igafos 168)등을 사용하는 것이 바람직하다. 인계는 에틸렌글리콜에 균일하게 녹여 슬러리에 투입하며 페놀계의 안정제는 분말상을 슬러리에 그대로 투입한다.Phosphorus and phenols are used as the additive, and trimethyl phosphate and triphenyl phosphate are preferably used as the phosphorus. As a phenol type, it is preferable to use Iganox 1010, Iganox 1090, Igafos 168, etc. of Ciba-Geigy. Phosphorus is uniformly dissolved in ethylene glycol and added to the slurry. Phenolic stabilizer is added to the slurry as it is.
직접 에스터화 반응은 반응조내에 공중합 폴리에스터 수지의 올리고머가 들어있는 상태에서 슬러리를 서서히 투입하여 촉매없이 반응을 진행시키고 중축합반응은 티탄계 화합물을 에틸렌글리콜에 녹여 고진공이 시작되기 전에 투입한다. 그외의 반응과정은 테레프탈산을 이용한 직접 에스터화 반응에 의해 폴리에틸렌 테레프탈레이트를 제조하는 방법과 동일하다.In the direct esterification reaction, the slurry is gradually added while the oligomer of the copolymerized polyester resin is contained in the reaction tank to proceed the reaction without the catalyst. The polycondensation reaction is carried out before the high vacuum starts by dissolving the titanium compound in ethylene glycol. Other reaction processes are the same as those for preparing polyethylene terephthalate by direct esterification using terephthalic acid.
본 발명의 실시예는 다음과 같다.Embodiments of the present invention are as follows.
본 발명에서의 물성측정방법은 다음과 같다.The physical property measuring method in the present invention is as follows.
- 극한 점도 측정Extreme viscosity measurement
제조한 공중합 폴리에스터 수지 칩을 페놀과 1,1,2,2-테트라클로로에탄(60/40 중량부) 용액에 녹여 25℃에서 우벨로데 점도계로 측정하였다.The prepared copolymerized polyester resin chip was dissolved in a solution of phenol and 1,1,2,2-tetrachloroethane (60/40 parts by weight) and measured at 25 ° C. with an ubelode viscometer.
- 열적 성질분석-Thermal property analysis
제조한 공중합 폴리에스터 수지 5∼10 mg을 Perkin Eimer DSC 7 으로 승온시 20℃/분, 강온시 -10℃/분으로 측정하였다.5 to 10 mg of the prepared copolymerized polyester resin was measured at 20 ° C./min when heated up and -10 ° C./minute when heated up with Perkin Eimer DSC 7.
- 투명도 측정-Transparency measurement
제조한 공중합 폴리에스터 수지를 티 다이를 이용하여 두께 2∼10 mm 의 쉬트와 오토 블로잉 머신을 사용하여 두께 0.5∼2 mm 의 보틀을 성형하여 UV/VIS 분광광도계로 측정하였다.The prepared copolyester resin was molded with a sheet of 2 to 10 mm in thickness using a tee die, and a bottle of 0.5 to 2 mm in thickness using an auto blowing machine, and measured by a UV / VIS spectrophotometer.
<실시예 1><Example 1>
테레프탈산과 에틸렌글리콜만으로 이루어진 올리고머 10 Kg 이 들어있는 반응기에 테레프탈산 1630g, 아이소프탈산 1650g, 에틸렌글리콜 3250g, 비스페놀 에이 1150g을 슬러리로 만들어 245∼265℃에서 약 3.5 시간 반응시켰다. 첨가제로는 트리메틸 포스페이트를 플리머 대비 500ppm 투입하였다. 이론양의 유출수가 나온 후 온도를 270∼290℃ 로 승온시킨 후 촉매로 테트라부틸 티탄에이트를 폴리머 대비 1000 ppm 투입 후 진공을 걸어주었다. 진공도는 0.5 mmHg 이하로 유지하여 약 4시간 동안 반응 시킨 후 배출하여 칩상으로 만들었다. 이 칩을 티 다이를 이용하여 쉬트를 제조하였고, 오토 블로잉 머신을 이용하여 보틀을 제조하였다. 이의 제반 물성은 표 1 에 나타내었다.In a reactor containing 10 Kg of oligomer consisting only of terephthalic acid and ethylene glycol, 1630 g of terephthalic acid, 1650 g of isophthalic acid, 3250 g of ethylene glycol, and 1150 g of bisphenol A were reacted at 245 to 265 ° C. for about 3.5 hours. As an additive, 500 ppm of trimethyl phosphate was added to the polymer. After the theoretical amount of effluent came out and the temperature was raised to 270 ~ 290 ℃, tetrabutyl titanate was added to the polymer 1000ppm as a catalyst and vacuum was applied. The degree of vacuum was maintained at 0.5 mmHg or less, reacted for about 4 hours, and then discharged into chips. This chip was used to make a sheet using a tee die, and a bottle was prepared using an auto blowing machine. Its general physical properties are shown in Table 1.
<비교예 1>Comparative Example 1
실시예 1에서 테레프탈산 5460g, 아이소프탈산 3440g, 에틸렌 글리콜 3850g으로 변경시킨 것 이외에는 동일하다.Except for changing to 5460 g of terephthalic acid, 3440 g of isophthalic acid and 3850 g of ethylene glycol in Example 1, it is the same.
<비교예 2>Comparative Example 2
실시예 1에서 테트라부틸 티탄에이트 대신에 삼산화 안티몬을 이용한 것 이외에는 동일하다.The same procedure as in Example 1 was performed except that antimony trioxide was used instead of tetrabutyl titaniumate.
*1. 소성은 테레프탈산/아이소프탈산/에틸렌글리콜/비스페놀 에이의 몰비*One. Firing is molar ratio of terephthalic acid / isophthalic acid / ethylene glycol / bisphenol A
*2. DSC 상에 나타나지 않음*2. Does not appear on DSC
본 발명은 상기 실시예 및 비교예에 의하여 확인되는 바와 같이, 생산원가가 저렴하고 수급이 원활한 공중합 모노머를 사용하더라도 결정화가 되지 않고, 성형성이 우수한 공중합 폴리에스터 수지 및 이로부터 제조되는 투명성이 우수한 쉬트 및 보틀을 제공할 수 있다.The present invention, as confirmed by the above Examples and Comparative Examples, the production cost is low, even if using a smooth supply and demand of the copolymerization monomer is not crystallized, excellent in formability copolymer polyester resin and excellent transparency prepared therefrom Sheets and bottles can be provided.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019970052693A KR100507446B1 (en) | 1997-10-15 | 1997-10-15 | Employee Copolymer Polyester Resin and Molded Product Using the Same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019970052693A KR100507446B1 (en) | 1997-10-15 | 1997-10-15 | Employee Copolymer Polyester Resin and Molded Product Using the Same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR19990031831A true KR19990031831A (en) | 1999-05-06 |
| KR100507446B1 KR100507446B1 (en) | 2006-03-09 |
Family
ID=37179357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019970052693A KR100507446B1 (en) | 1997-10-15 | 1997-10-15 | Employee Copolymer Polyester Resin and Molded Product Using the Same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100507446B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010110813A (en) * | 2000-06-08 | 2001-12-15 | 조 정 래 | Manufacture of polyester |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4474918A (en) * | 1983-05-31 | 1984-10-02 | Eastman Kodak Company | Thermoplastic polyester compositions having improved barrier properties |
| JPH069765A (en) * | 1992-04-30 | 1994-01-18 | Mitsubishi Rayon Co Ltd | Heat-shrinkable polyester film |
| CA2139061C (en) * | 1993-12-28 | 1998-12-08 | Mitsui Chemicals, Inc. | Process for preparing polyester |
| JP2916665B2 (en) * | 1994-06-28 | 1999-07-05 | 三菱電線工業株式会社 | connector |
| KR960014204A (en) * | 1994-10-22 | 1996-05-22 | 박홍기 | Process for producing polyester copolymer |
-
1997
- 1997-10-15 KR KR1019970052693A patent/KR100507446B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010110813A (en) * | 2000-06-08 | 2001-12-15 | 조 정 래 | Manufacture of polyester |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100507446B1 (en) | 2006-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9676903B2 (en) | Polyester resin and method for preparing the same | |
| EP2870201B1 (en) | Ternary blends of terephthalate or isophthalate polyesters containing eg, chdm, and tmcd | |
| EP0684269B1 (en) | Process for the preparation of re-usable bottles starting from modified PET | |
| KR20140135752A (en) | Clear semi-crystalline articles with improved heat resistance | |
| JPS5964625A (en) | Polyisophthalate containing small quantity of cyclic dimer, copolymer of same and manufacture | |
| TW201731908A (en) | Polyester resin, preparation method thereof and resin article formed therefrom | |
| KR20170037588A (en) | Polyester resin copolymerized with isosorbide and 1,4- cyclohexane dimethanol and preparing method thereof | |
| JP5251790B2 (en) | Copolyester | |
| US20050261462A1 (en) | Methods of making titanium-catalyzed polyester resins | |
| JP2011068880A (en) | Molded article made of copolymerized polyester | |
| KR100507446B1 (en) | Employee Copolymer Polyester Resin and Molded Product Using the Same | |
| KR101121361B1 (en) | Blend of polyester copolymerized with 1,4-cyclohexanedimethanol having low oligomer content and polycarbonate, and preparing method thereof | |
| KR101883819B1 (en) | Polyester resin and preparation method thereof | |
| EP0119731B1 (en) | Copolyester of polyethylene terephthalate, process for making it and its use in producing molded articles | |
| JP3681493B2 (en) | Polyethylene naphthalate for bottles | |
| JPH02302432A (en) | Production of polyester | |
| KR101159850B1 (en) | Polyester resin copolymerized with neopentylglycol having low oligomer content and preparing method thereof | |
| JP2723141B2 (en) | Polyester resin composition and use thereof | |
| KR20010019041A (en) | Co-Polyester with high clarity and process for producing them | |
| JP2006188676A (en) | Polyester composition and polyester molded product composed of the same | |
| JPH11130851A (en) | Polyethylene-2,6-naphthalenedicarboxylate resin for bottle and molded product made therefrom | |
| KR101159840B1 (en) | Polyester resin copolymerized with 1,4-cyclohexanedimethanol having low oligomer content and preparing method thereof | |
| KR0143044B1 (en) | The process of preparation of polyester composition | |
| JP2003220642A (en) | Manufacturing method of hollow molded body of polyester resin | |
| JPH09208678A (en) | Molded polyester resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20110623 Year of fee payment: 7 |
|
| FPAY | Annual fee payment |
Payment date: 20120619 Year of fee payment: 8 |
|
| LAPS | Lapse due to unpaid annual fee |