KR19990009001A - Low temperature fusion polyester resin and its manufacturing method - Google Patents
Low temperature fusion polyester resin and its manufacturing method Download PDFInfo
- Publication number
- KR19990009001A KR19990009001A KR1019970031244A KR19970031244A KR19990009001A KR 19990009001 A KR19990009001 A KR 19990009001A KR 1019970031244 A KR1019970031244 A KR 1019970031244A KR 19970031244 A KR19970031244 A KR 19970031244A KR 19990009001 A KR19990009001 A KR 19990009001A
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- parts
- compound
- polyester resin
- formula
- 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
-
- 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
- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
- C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
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)
Abstract
본 발명은 주성분으로서 방향족 디에시드 또는 그 에스테르 유도체와 지방족 디올의 1:2 몰비 혼합물과 개질성분으로서 상기 방향족 디에시드 또는 그 에스테르 유도체 100중량부에 대하여 화학식 1의 화합물 5∼30중량부, 화학식 2의 화합물 40중량부 및 1,2,4-벤젠트리카르복실산 0.1∼0.5중량부가 배합되어 개질된 저온융착성 폴리에스테르 수지에 관한 것으로, 이러한 폴리에스테르 수지는 기존의 열융착성 폴리에스테르에 비하여 현저하게 낮은 연화점, 짧은 반응시간 및 높은 접착력을 나타낸다.The present invention relates to a 1: 2 molar ratio mixture of an aromatic dieside or an ester derivative thereof and an aliphatic diol as a main component and 5 to 30 parts by weight of the compound of formula 1 based on 100 parts by weight of the aromatic dieside or an ester derivative thereof as a modifying component. 40 parts by weight of the compound and 0.1 to 0.5 parts by weight of 1,2,4-benzenetricarboxylic acid are formulated in a modified low temperature fusion polyester resin, such a polyester resin compared to conventional heat fusion polyester It has a markedly low softening point, short reaction time and high adhesion.
위식에서 서로 같거나 다른 기로서 R1은 -COOCH3 In the above formula, R 1 is -COOCH 3
위식에서 서로 같거나 다른 기로서 R2는 -CH2CH2-O-CH2CH2- 또는Are each independently from gastroesophageal or a different group R 2 is -CH 2 CH 2 -O-CH 2 CH 2 - or
Description
본 발명은 폴리에스테르 수지에 관한 것으로, 더욱 상세하게는 주성분으로서 지방족 디올 및 방향족 디에시드 또는 그 에스테르 유도체와 개질성분으로서 결정성 억제제 화합물 및 반응촉진·접착력향상제 화합물로 이루어진, 반응시간이 짧고 접착력이 우수한 저온융착성 폴리에스테르 수지 및 그 제조방법에 관한 것이다.The present invention relates to a polyester resin, and more particularly, an aliphatic diol and an aromatic dieside or an ester derivative thereof as a main component and a crystalline inhibitor compound and a reaction promoting / adhesive enhancer compound as a modifying component, the reaction time is short and the adhesion is An excellent low temperature fusion polyester resin and a method of manufacturing the same.
일반적으로 열융착성 폴리에스테르 수지는 그 고유 특성 때문에 자동차의 시트카바, 침구류, 여성용 브래지어의 패드, 컴퓨터마우스의 패드, 신발류, 차의 티백 등의 부직포 소재로 널리 사용되고 있다. 이와 같은 부직포는 고온에서 열융착가능한 폴리에스테르 만으로는 제조하기 곤란한 점이 있어, 보다 낮은 온도에서 열융착가능한 폴리에스테르에 대한 요구가 증대되어 왔다.In general, heat-sealing polyester resins are widely used as nonwoven materials such as seat covers of cars, bedding, women's bra pads, computer mouse pads, footwear, and tea bags. Such nonwoven fabrics are difficult to manufacture with only polyester heat-sealable at high temperatures, and there is an increasing demand for polyesters heat-sealable at lower temperatures.
종래, 폴리에스테르에 저온융착성을 부여하기 위한 개질방법으로 잘 알려진 방법으로는 다음과 같은 두가지 방법이 있다.Conventionally, there are two methods well known as a modification method for imparting low temperature fusion to polyester.
그 한가지 방법은 일반 폴리에스테르 수지에 비정형수지를 혼합하는 소위 물리적 블렌딩에 의한 방법으로, 그 대표적인 예는 고유점도가 0.620(㎗/g)인 일반 폴리에스테르 수지와 분자량 600∼20,000(g/㏖)정도의 폴리알킬렌글리콜 수지와의 블렌딩으로 블렌딩온도 270∼280℃의 고온에서 질소를 충진하면서 1시간 용융·혼합하여 제조하는 방법이 있다.One method is a so-called physical blending method in which an amorphous resin is mixed with a general polyester resin. A typical example thereof is a general polyester resin having an intrinsic viscosity of 0.620 (dl / g) and a molecular weight of 600 to 20,000 (g / mol). There is a method of melting and mixing for 1 hour while filling nitrogen at a high temperature of the blending temperature of 270 to 280 ° C. by blending with a polyalkylene glycol resin of a degree.
다른 한가지 방법은 중합단계에서부터 일반 폴리에스테르 수지의 결정성을 억제할 수 있는 제 2성분의 화합물을 첨가하는 방법이 있다. 여기서 제 2성분으로서 대두되는 화합물을 보면 방향족 디에시드 또는 이들의 에스테르 화합물 구조의 결정성을 깨뜨릴 수 있는 이들의 동족체로서 상기의 화학식 1과 같은 이소프탈산과 이들의 에스테르 화합물, 그리고 이소프탈산과 이들의 에스테르화합물을 들 수 있으며, 또한 대한민국 공개특허 제 95-18276호에 제시되는 바와 같이 상기 화학식 2와 같은 지방족 디올성분이 있다.Another method is to add the compound of the second component which can suppress the crystallinity of the general polyester resin from the polymerization step. Herein, the compounds that are raised as the second component are isophthalic acids and their ester compounds, and isophthalic acid and their compounds, as the homologues thereof that may break the crystallinity of the aromatic dieside or their ester compound structure. An ester compound may be mentioned, and as shown in Korean Patent Publication No. 95-18276, there is an aliphatic diol component such as Chemical Formula 2.
그러나, 후자의 방법에서 화학식 1의 결정화억제제 화합물을 사용하는 경우 저온에서의 열융착성을 부여하는데 한계가 있고 또한 화학식 1의 화합물이 고가이므로 이를 첨가하는데 따른 비용상승에 불가피한 문제점이 있으며, 화학식 2의 결정화억제제 화합물은 폴리에스테르의 연화점을 강하시키는 효과가 있고, 또한 저가이므로 경제성의 측면에서 유리한 것이나, 보다 낮은 온도에서 융착성을 갖도록 하기 위해서 다량으로 첨가하는 경우 반응시간이 길어지고 황변현상이 일어나며 접착력이 떨어지는 문제점이 있다.However, in the latter method, when the crystallization inhibitor compound of Formula 1 is used, there is a limit to imparting heat sealability at low temperature and the compound of Formula 1 is expensive, and thus there is an unavoidable problem in the cost of adding it. The crystallization inhibitor compound of has the effect of lowering the softening point of the polyester, and is inexpensive, which is advantageous in terms of economical efficiency, but when it is added in a large amount in order to have fusion at lower temperature, the reaction time becomes longer and yellowing occurs. There is a problem of poor adhesion.
본 발명은 상기한 바와 같은 선행기술의 문제점을 감안하여 저온에서 용융되고 접착성이 우수하며 반응시간이 짧은 저온융착성 폴리에스테르 수지 및 그 제조방법을 제공하는 것을 과제로 한다.The present invention has been made in view of the problems of the prior art as described above, to provide a low-temperature fusion polyester resin that melts at low temperatures, has excellent adhesion, and has a short reaction time, and a method of manufacturing the same.
상기한 과제를 해결하기 위한 본 발명자들의 연구에서 놀라웁게도 상기한 화학식 1 및 화학식 2의 결정화억제제 화합물과 1,2,4-벤젠트리카르복실산을 첨가하여 개질한 폴리에스테르가 연화점이 상당히 낮고 접착성이 우수하며 반응시간이 짧은 특성을 갖는다는 사실을 알게되어 본 발명을 완성하게 된 것이다.Surprisingly, in the study of the present inventors to solve the above problems, the softening point of the polyester modified by adding the crystallization inhibitor compounds of Formulas 1 and 2 and 1,2,4-benzenetricarboxylic acid is considerably low. It was found that the excellent adhesion and the short reaction time to complete the present invention.
본 발명에 의하면, 주성분으로서 방향족 디에시드 또는 그 에스테르 유도체와 지방족 디올의 1:2 몰비 혼합물과 개질성분으로서 상기 방향족 디에시드 또는 그 에스테르 유도체 100중량부에 대하여 화학식 1의 화합물 5∼30중량부, 화학식 2의 화합물 5∼40중량부 및 1,2,4-벤젠트리카르복실산 0.1∼0.5중량부가 배합되어 개질된 것을 특징으로 하는 저온융착성 폴리에스테르 수지가 제공된다.According to the present invention, 5 to 30 parts by weight of a compound of the formula (1) based on a 1: 2 molar ratio mixture of an aromatic dieside or an ester derivative thereof and an aliphatic diol as a main component and 100 parts by weight of the aromatic dieside or an ester derivative thereof as a modifying component, 5 to 40 parts by weight of the compound of the formula (2) and 0.1 to 0.5 parts by weight of 1,2,4-benzenetricarboxylic acid are combined to provide a low temperature fusion polyester resin characterized in that the modified.
이하 본 발명을 보다 상세하게 설명하기로 한다.Hereinafter, the present invention will be described in more detail.
본 발명의 저온융착성 폴리에스테르 수지는 다음과 같은 공정들을 포함하는 방법으로 제조될 수 있다:The low temperature fusion polyester resin of the present invention may be prepared by a method comprising the following processes:
(a) 산성분으로 방향족 디에시드 또는 이들의 에스테르 화합물과 디올성분으로 지방족 디올의 1:2몰비 혼합물을 촉매의 존재하에 에스테르화 또는 에스테르 교환 반응시키는 공정, 및(a) esterifying or transesterifying an aromatic dieside or its ester compound as an acid component with a 1: 2 molar ratio mixture of aliphatic diol as a diol component in the presence of a catalyst, and
(b) 상기 공정(a)에서 얻은 중간생성물에 상기 방향족 디에시드 또는 그 에스테르 유도체 100중량부에 대하여 결정화 억제제인 화학식 1 화합물 5∼30중량부 및 화학식 2의 화합물 5∼40중량부와 반응촉진 및 접착력향상제인 1,2,4-벤젠트리카르복실산 0.1∼0.5중량부를 배합하고 촉매의 존재하에 축중합시키는 공정.(b) Promoting reaction with 5 to 30 parts by weight of the compound of Formula 1 and 5 to 40 parts by weight of the compound of Formula 2 to 100 parts by weight of the aromatic dieside or its ester derivative in the intermediate obtained in step (a) And 0.1 to 0.5 parts by weight of 1,2,4-benzenetricarboxylic acid, which is an adhesion improving agent, and condensation polymerization in the presence of a catalyst.
본 발명에 있어서, 화학식 1의 화합물이 방향족 디에시드 또는 그 에스테르 유도체 100중량부에 대하여 5중량부 미만으로 배합되는 경우에는 개질효과가 미미하고, 30중량부를 초과하는 경우에는 더 이상의 저온 열융착성 향상을 기대하기 어려울 뿐만아니라 비용상승에 문제점이 있다. 화학식 2의 화합물이 방향족 디에시드 또는 그 에스테르 유도체 100중량부에 대하여 5중량부 미만인 경우에는 개질효과가 미미하고, 40중량부를 초과하는 경우에는 저온융착성이 떨어지고 황변현상이 일어날 수도 있다. 또한 1,2,4-벤젠트리카르복실산이 방향족 디에시드 또는 그 에스테르 유도체 100중량부에 대하여 0.1중량부 미만일 경우에는 접착력 향상효과가 없고, 0.5 중량부를 초과하는 경우에는 3차원 망목구조인 겔이 형성되어 방사공정시 문제가 된다.In the present invention, when the compound of Formula 1 is blended in less than 5 parts by weight with respect to 100 parts by weight of the aromatic dieside or its ester derivative, the modification effect is insignificant. Not only is it difficult to expect an improvement, but there are also problems with the cost. If the compound of Formula 2 is less than 5 parts by weight with respect to 100 parts by weight of the aromatic dieside or its ester derivative, the modification effect is insignificant, and if it exceeds 40 parts by weight, low temperature fusion property may occur and yellowing may occur. In addition, when 1,2,4-benzenetricarboxylic acid is less than 0.1 part by weight based on 100 parts by weight of aromatic dieside or its ester derivatives, there is no effect of improving adhesion, and when it exceeds 0.5 parts by weight, a gel having a three-dimensional network structure is obtained. It becomes a problem during the spinning process.
특별히 제한하기 위한 것은 아니지만, 상기 공정(a)에서는 촉매로서 칼슘아세테이트를 사용할 수 있으며, 상기 공정(b)에서는 촉매로서 안티몬트리아세테이트를 사용할 수 있다. 또한 상기 공정(a)에서는 코발트아세테이트와 같은 정색제와 포스포릭산과 같은 열안정제를 적정량 사용하는 것이 바람직하다.Although not particularly limited, calcium acetate may be used as the catalyst in the step (a), and antimontrea acetate may be used as the catalyst in the step (b). In the step (a), it is preferable to use an appropriate amount of a colorant such as cobalt acetate and a thermal stabilizer such as phosphoric acid.
상기한 방법에 의해 얻어지는 개질 폴리에스테르는 연화점이 매우 낮고 접착력이 강한 저온융착성 폴리에스테르이다.The modified polyester obtained by the above method is a low temperature fusion polyester having a very low softening point and strong adhesion.
상기한 바와 같은 본발명의 특징 및 기타의 장점은 후술되는 실시예로부터 보다 명백하게 될 것이다. 단, 본발명은 하기 실시예에 제한되지 않는다.Features and other advantages of the present invention as described above will become more apparent from the embodiments described below. However, the present invention is not limited to the following examples.
〈실시예 1 내지 12〉<Examples 1 to 12>
에틸렌글리콜 634g과 디메틸테레프탈레이트 1000g의 1:2 몰비 혼합물에 촉매로서 칼슘아세테이트 400ppm, 정색제로서 코발트아세테이트 60ppm, 열안정제로 포스포릭산을 150ppm을 가하여 에스테르교환반응시켰다. 여기에 디메틸테레프탈레이트 100중량부 기준으로 결정화 억제제인 화학식 1의 디메틸이소프탈레이트 및 화학식 2의 1,4-사이클로헥산디메탄올과 반응성촉진 및 접착력향상제인 1,2,4-벤젠트리카르복실산을 하기 표 1에 제시되는 함량으로 첨가하고, 촉매로서 안티몬트리아세테이트를 400ppm정도 첨가하여 중합온도 285℃, 0.3㎜Hg의 고온·감압하에서 축중합시켰다. 제조된 중합체들의 평균 고유점도는 0.620(㎗/g)이며 평균 분자량 분포는 2.8이었다.To a 1: 2 molar ratio mixture of 634 g of ethylene glycol and 1000 g of dimethyl terephthalate, 400 ppm of calcium acetate as a catalyst, 60 ppm of cobalt acetate as a colorant, and 150 ppm of phosphoric acid as a heat stabilizer were added for transesterification. Herein, based on 100 parts by weight of dimethyl terephthalate, dimethylisophthalate of Formula 1, which is a crystallization inhibitor, and 1,4-cyclohexanedimethanol, of Formula 2, and 1,2,4-benzenetricarboxylic acid, which promotes reactivity and enhances adhesion, It was added in the content shown in Table 1 below, and about 400ppm of antimontriacetate was added as a catalyst, and then polycondensation was carried out under a high temperature and reduced pressure of a polymerization temperature of 285 ° C. and 0.3 mmHg. The average intrinsic viscosity of the prepared polymers was 0.620 (dl / g) and the average molecular weight distribution was 2.8.
〈비교예 1〉<Comparative Example 1>
화합물 1, 2 및 1,2,4-벤젠트리카르복실산을 투입하지 않은 것을 제외하고는 실시예 1과 동일한 절차를 반복하였다.The same procedure as in Example 1 was repeated except that Compounds 1, 2 and 1,2,4-benzenetricarboxylic acid were not added.
〈비교예 2〉<Comparative Example 2>
화합물 1을 30중량부 투입하고, 화합물 2 및 1,2,4-벤젠트리카르복실산을 투입하지 않은 것을 제외하고는 실시예 1과 동일한 절차를 반복하였다.The same procedure as in Example 1 was repeated except that 30 parts by weight of compound 1 was added and compound 2 and 1,2,4-benzenetricarboxylic acid were not added.
〈비교예 3〉<Comparative Example 3>
화합물 2를 40중량부 투입하고, 화합물 1 및 1,2,4-벤젠트리카르복실산을 투입하지 않은 것을 제외하고는 실시예 1과 동일한 절차를 반복하였다.40 parts by weight of Compound 2 was added, and the same procedure as in Example 1 was repeated except that Compound 1 and 1,2,4-benzenetricarboxylic acid were not added.
상기 실시예 및 비교예에 의거하여 얻은 수지의 연화점, 반응시간, 접착력을 측정하여 그 결과를 하기 표 1에 제시하였다.The softening point, reaction time, and adhesive force of the resin obtained based on the above Examples and Comparative Examples were measured, and the results are shown in Table 1 below.
* 화합물 1 … 디메틸이소프탈레이트* Compound 1... Dimethylisophthalate
* 화합물 2 … 1,4-사이클로헥산디메탄올* Compound 2... 1,4-cyclohexanedimethanol
* 접착력 … 박리시험(폭 5㎜×길이 50㎜), 용융접착온도; 130℃(㎏/㎠)* Adhesive strength. Peeling test (width 5mm x length 50mm), melt bonding temperature; 130 ℃ (㎏ / ㎠)
* 황변도 … 칼로리메터(Colorimeter)에 의한 칼라 b치로서, +쪽으로 증가할수록 황변이 심해지고, -쪽으로 증가하면 청색을 띰.* Yellowness… Color b value by calorimeter (Colorimeter), yellowing increases with increasing to + side, blue when increasing with-side.
상기 표 1로부터, 본발명에 따라 개질된 실시예 1 내지 12의 폴리에스테르는 비교예 1 내지 3의 폴리에스테르에 비하여 현저하게 낮은 연화점, 짧은 반응시간 및 높은 접착력을 나타냄을 알 수 있다.From Table 1, it can be seen that the polyester of Examples 1 to 12 modified according to the present invention exhibits a significantly lower softening point, a shorter reaction time, and a higher adhesion than the polyesters of Comparative Examples 1 to 3.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019970031244A KR100225425B1 (en) | 1997-07-05 | 1997-07-05 | Low temperrature bondable polyester and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019970031244A KR100225425B1 (en) | 1997-07-05 | 1997-07-05 | Low temperrature bondable polyester and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR19990009001A true KR19990009001A (en) | 1999-02-05 |
| KR100225425B1 KR100225425B1 (en) | 1999-10-15 |
Family
ID=19513531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019970031244A KR100225425B1 (en) | 1997-07-05 | 1997-07-05 | Low temperrature bondable polyester and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100225425B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005103112A1 (en) * | 2004-04-27 | 2005-11-03 | Kolon Industries, Inc | A flame retardant polyester with excellent color tone, and a process of preparing the same |
-
1997
- 1997-07-05 KR KR1019970031244A patent/KR100225425B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005103112A1 (en) * | 2004-04-27 | 2005-11-03 | Kolon Industries, Inc | A flame retardant polyester with excellent color tone, and a process of preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100225425B1 (en) | 1999-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1114095B1 (en) | Nucleating agent for polyesters | |
| KR101372581B1 (en) | Hydrolysis resistant and biodegradable aliphatic/aromatic copolyester resin composition | |
| US4645802A (en) | Blends of bisphenol A polycarbonate with poly(ester-imides) and poly(ester-imide-amides) | |
| KR102061805B1 (en) | Thermal adhesive polyester composition, thermal adhesive polyester complex-fiber comprising the same, and non-woven fabric | |
| CN109651605A (en) | A kind of preparation method of biodegradable copolyester hot melt adhesive | |
| WO1997018253A1 (en) | Thermally stable polyesters formed utilizing antimony compounds as catalysts | |
| KR100225425B1 (en) | Low temperrature bondable polyester and preparation thereof | |
| CN101353562A (en) | Preparation of polyester hot-melt adhesive | |
| CN112280022A (en) | Preparation method and application of composition for heavy metal-free low-melting-point polyester | |
| US4990594A (en) | Producing a copolyester from a lower dialkyl ester of terephthalic acid, a glycol and a dicarboxylic acid | |
| KR100957951B1 (en) | Alipathic polyester resin with high intensity and method of preparing thereof | |
| KR100526490B1 (en) | Low Temperature Fusion Polyester Resin Composition_ | |
| US4581398A (en) | Hydrolysis-resistant thermoplastic molding composition comprising high molecular weight polybutylene terephthalatepolyester and a dicarboxylic acid salt | |
| JPH0563506B2 (en) | ||
| JP3376389B2 (en) | Polyester block copolymer and method for producing the same | |
| KR20010016861A (en) | Process for producing polyester hot melt adhesive composition for fabric | |
| JP2530649B2 (en) | Method for producing modified polyester | |
| JP3366918B2 (en) | Method for producing modified polyester | |
| KR100368533B1 (en) | Manufacturing method of biodegradable aliphatic polyester | |
| US5082731A (en) | Producing a copolyester from a lower dialkyl ester of terephthalic acid, a glycol and a dicarboxylic acid | |
| JP3251746B2 (en) | Polyester elastic body and method for producing the same | |
| KR960012437B1 (en) | Method for manufacturing high viscosity polyester | |
| KR100501468B1 (en) | High strength biodegradable polyester resin and its manufacturing method | |
| HU212446B (en) | Method of producing polyester | |
| KR100330379B1 (en) | Thermoplastic aliphatic polyester resin with excellent transparency and its manufacturing method |
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: 20040712 Year of fee payment: 6 |
|
| LAPS | Lapse due to unpaid annual fee |