KR940000966B1 - Process for preparing polyester film having a low shrink characteristics - Google Patents
Process for preparing polyester film having a low shrink characteristics Download PDFInfo
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- KR940000966B1 KR940000966B1 KR1019910005513A KR910005513A KR940000966B1 KR 940000966 B1 KR940000966 B1 KR 940000966B1 KR 1019910005513 A KR1019910005513 A KR 1019910005513A KR 910005513 A KR910005513 A KR 910005513A KR 940000966 B1 KR940000966 B1 KR 940000966B1
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- film
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- polyester film
- shrinkage
- polybutylene terephthalate
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- 229920006267 polyester film Polymers 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 27
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 12
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000002040 relaxant effect Effects 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 238000009998 heat setting Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008602 contraction Effects 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/91—Heating, e.g. for cross linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
본 발명은 저 수축성 폴리에스테르 필름, 특히 열수축율을 개선함으로써 고품질의 필름용으로 적합한 저 수축축성 폴리에스테르 필름을 제조하는 방법에 관한 것이다.The present invention relates to a process for producing a low shrinkage polyester film, in particular a low shrinkage polyester film suitable for high quality films by improving thermal shrinkage.
폴리에스테르 필름 원료의 주종을 이루는 폴리에틸렌테레프탈이트(PET)는 그 기계적 특성 및 투명성, 치수 안정성등이 우수하여 각종 필름 용도로 널리 쓰이고 있다. 그러나 고급 사진용 필름, 핫 스탬핑 호일(Hot Stamping Foil), 가요성 인쇄회로기판 (Flexible Printed Circuit Board)등은 기술의 발전에 따라 그 안정도 및 정밀도가 점점 더 요구되는 추세에 있으며, 이러한 고급화 되는 용도에 맞추어 필름 품질을 개량하는 것이 시급한 과제로 대두되고 있는 실정이다. 현재 고급품에 사용되고 있는 폴리에틸렌테레프탈이트 이축연시 필름은 가공될 때 또는 제품으로 사용되는 경우에 고온의 열이력을 받게되며, 이때 열수축율이 작은 것이 요구된다. 열수축을 작게하기 위한 종래의 제막기술로는 기재 필름(base film)의 폭방향에 대해서, 제조 공정중에, 이축연신후 열고정하고 제한된 수축을 허용하여 이완 열처리 함으로써 열수축을 작게 하는 것이 가능하다. 이러한 종래의 열처리만으로는 상기 용도에 만족할 정도로 열수축율이 작은 필름을 제조할 수 없다. 즉, 열수축율을 만족할 정도로 작게 하기 위해서는 이완 열처리를 충분히 해주어야 하는데, 이완율 6% 정도로 열처리를 심하게 하는 경우 길이 방향의 골 및 주름이 발생하여 평면성이 악화되는 문제가 있다. 이 외의 방법으로는 위와 같은 열처리된 필름을 취출부(take off)에서 다시 열처리하는 방법도 있는데, 이것도 이중으로 작업하게 되는 문제점이 있어 경제적인 방법이 될 수 없다.Polyethylene terephthalate (PET), which is a major component of polyester film raw materials, is widely used in various film applications due to its excellent mechanical properties, transparency, and dimensional stability. However, advanced photographic films, hot stamping foils, and flexible printed circuit boards are increasingly required for their stability and precision as technology advances. In order to meet these demands, improving film quality is an urgent task. Polyethylene terephthalate biaxially wound film, which is currently used in high-end products, is subjected to high temperature heat history when processed or used as a product, and it is required to have a low heat shrinkage rate. As a conventional film forming technique for reducing thermal shrinkage, it is possible to reduce heat shrinkage by relaxing heat treatment after biaxially stretching and allowing limited shrinkage in the width direction of a base film during the manufacturing process. Such a conventional heat treatment alone cannot produce a film having a low thermal shrinkage enough to satisfy the use. In other words, in order to reduce the heat shrinkage rate to a sufficient degree, the relaxation heat treatment should be sufficiently performed. However, when the heat treatment is severely performed at a relaxation rate of about 6%, there is a problem in that flatness and wrinkles occur in the longitudinal direction. As another method, there is also a method of heat-treating the heat-treated film as above at the take-off part, which also has a problem of working in duplicate, and thus cannot be an economical method.
이에 본 발명자들은 열수축율이 작은 폴리에스테르 필름을 제조하기 위해 연구를 거듭한 결과, 종래의 이축연신 필름 제조방법과는 상이한 방법으로, 우선 원료수지의 물성을 심한 이완 열처리에서도 견딜 수 있도록 개량한 후 열고정 온도를 일정범위로 최대 이완율 6%로 열처리 함으로써 필름의 평면성에 결함을 주지않고 고급 용도에 적합한 필름을 생산할 수 있는 제조 방법을 발견하고 본 발명을 완성하기에 이르렀다.Accordingly, the present inventors have repeatedly studied to produce a polyester film having a low thermal contraction rate, and as a result, a method different from the conventional biaxially oriented film production method, first, after improving the physical properties of the raw material resin to withstand severe heat treatment By heat-treating the heat setting temperature in a range of up to 6% of relaxation rate, the present inventors have found a manufacturing method capable of producing a film suitable for high-end applications without impairing the planarity of the film and completing the present invention.
이하 본 발명 방법을 상세 설명한다. 우선, 폴리에틸렌테레이트수지에 대하여 폴리부틸렌테레프탈레이트 수지 0.1 내지 20%를 배합한 후 이를 용융 압출하고 20℃ 이하로 급냉하여 무정형 미연신 쉬트를 제조한다. 이어서 95℃에서 쉬트를 연신율 3배로 하여 이축연신한 후 열처리를 행하였다. 열처리는 폴리부틸렌테레프탈레이트의 용점(약 225∼230℃)과 폴리에틸린테레프탈레이트의 융점(약 250∼260℃)사이에 드는 230℃∼240℃로 열고정한 후 이완율 6% 이하로 열처리하여 고온에서도 열수축율이 작은 폴리에스테르 이축연신 필름을 제조하였다. 이렇게 제조된 본 발명 이축연신 필름은 제조시의 심한 이완 열처리에도 불구하고 그 표면에 골 및 주름의 발명이 없을뿐 아니라 고급제품 용도에 적합한 낮은 열수축율을 갖는다. 이러한 본 발명의 작용효과가 어떤 메카니즘에 의한 것인지 명확하게 체계화된 바는 없으나, 열처리 과정에서 폴리부틸테레프탈이트수지 성분은 제용융 혹은 그에 가까운 변환가 생겨서 연신에 의한 배향 상태가 소실 또는 완화되고 폴리에틸테레프탈레이트수지 성분은 배향 상태가 결정으로 굳어지게 되며, 그 결과 열처리 후의 필름에는 배향 상태가 결정적으로열고정 되어 있는 고용점 폴리에틸렌테레이트의 조직속에 저융점 폴리부틸렌테레프탈레이트가 무배향 상태로 섞여 있는 메트릭스 구조가 형성되는 것으로 해석된다.The method of the present invention is described in detail below. First, 0.1 to 20% of a polybutylene terephthalate resin is blended with respect to a polyethylene terate resin, followed by melt extrusion and quenching to 20 ° C. or less to prepare an amorphous unstretched sheet. Subsequently, the sheet was biaxially stretched at an elongation of 3 times the elongation at 95 ° C and then heat treated. The heat treatment is heat-fixed at 230 ° C. to 240 ° C., which falls between the melting point of the polybutylene terephthalate (about 225 to 230 ° C.) and the melting point of the polyethylene terephthalate (about 250 to 260 ° C.), and then heats it to a relaxation rate of 6% or less. To produce a polyester biaxially oriented film having a low thermal contraction rate even at high temperatures. The biaxially stretched film of the present invention thus produced not only has no invention of bones and wrinkles on its surface in spite of severe relaxation heat treatment at the time of manufacture but also has a low heat shrinkage ratio suitable for high-end product use. It is not clearly formulated the mechanism by which the effect of the present invention is caused, but in the heat treatment process, the polybutyl terephthalate resin component is melt-melted or near-converted so that the orientation state due to stretching is lost or relaxed, and As for the terephthalate resin component, the orientation state is hardened by crystal, and as a result, the film after heat treatment is mixed with the low melting point polybutylene terephthalate in an unoriented state in the tissue of the solid solution polyethylene terate in which the orientation state is thermally fixed. It is interpreted that a matrix structure is formed.
배향 성분은 필름의 강도를 나타내지만, 열수축을 일으키는 원인이 되기도 하는데, 무배향 성분은 열수축을 일으킬 수 있는 연신응력이 이미 해소된 상태여서 열수축 작용의 저항체로 작용할 수 있게 되는 것이다.Although the orientation component shows the strength of the film, it may also cause thermal contraction, but the unoriented component may act as a resistor of thermal contraction action because the stretching stress that may cause thermal contraction is already solved.
본 발명에서, 원료 폴리에틸렌테레프탈레이트수지중의 폴리부틸렌틸테레프탈레이트수지의 배합량 20wt/%이하로 해야하는데 상기 비율을 유지하므로써 두 성분이 2개의 상(相)으로 분리되지 않고 균일하게 배합되어 1개의 상으로 상온에서 존재할 수 있게 하는 최대의혼합비율이다. 이 비율이상으로 폴리부틸렌테레프탈레이드수지를 폴리에틸렌태레프탈레이트 수지에 배합할 경우는 혼합 상태가 불균일 하게 되고 이로 인한 연신의 불균일, 필름 표면의 불균일이 수반되며 또, 폴리부틸렌테레프탈레이트수지의 빠른 결정화에 따른 연신의 어려움도 발생하게된다. 또한 폴리부틸렌테레프탈레이트수지를 0.1wt% 이하로 할 경우는 메트릭스 구조의 형성이 불가능하다. 또 열고정 온도를 230℃ 이하로 하는 경우 폴리부틸렌테레탈레프탈레이트의 융점 (약 225∼230℃)에 못미치는 관계로 폴리부틸렌테레프탈레이트의 재용융, 무배향화가 효과적으로 발생하지 않아서 열수축율의 개선 효과가 적으며, 240℃ 이상인 경우는 폴리에틸렌테레이트의 융점(약 250∼260℃)에 가까워지므로 열처리 열화가 일어나서 필름의 강도가 저하되는 문제가 있다.In the present invention, the blending amount of the polybutylene-yl terephthalate resin in the raw material polyethylene terephthalate resin should be 20wt /% or less, but by maintaining the above ratio, the two components are uniformly blended without being separated into two phases and thus one phase It is the maximum mixing ratio that can exist at room temperature. When the polybutylene terephthalate resin is blended with polyethylene terephthalate resin at a ratio higher than this ratio, the mixed state becomes uneven, resulting in uneven stretching and film surface unevenness, and rapid crystallization of polybutylene terephthalate resin. The difficulty of stretching will also occur. When the polybutylene terephthalate resin is made 0.1 wt% or less, it is impossible to form a matrix structure. In addition, when the heat setting temperature is lower than 230 ° C, the re-melting and non-orientation of the polybutylene terephthalate does not occur effectively because the polybutylene terephthalate falls short of the melting point (about 225 to 230 ° C). If the improvement effect is small, 240 ℃ or more is close to the melting point (about 250 ~ 260 ℃) of the polyethylene terate, there is a problem that the heat treatment deterioration occurs to reduce the strength of the film.
이하 본 발명을 실시예에 따라 상세히 설명한다. 본 실시예에 의거 제조된 본 발명품은 아래 방법에 따라 그 물성을 측정하고 결과를 표 Ⅰ에 기재하였다.Hereinafter, the present invention will be described in detail with reference to Examples. The present invention manufactured according to the present Example measured the physical properties according to the following method and the results are shown in Table I.
(1) 열수축의 측정 : 열풍순환식 오픈을 사용하되 시료는 필름을 폭 20cm, 길이 20cm 되게 절제하여 시료편으로 하였으며 장력 2.5kg 하중을 190℃에서 1분간 하방으로 작용시켜 폭 방향의 수축 길이를 측정하여 수축율을 계산하였다.(1) Measurement of heat shrinkage: Use hot air circulation type, but the sample was cut into 20cm wide and 20cm long to make the sample piece.The tension length of 2.5kg was applied downward at 190 ℃ for 1 minute to reduce the shrinkage length in the width direction. The shrinkage was calculated by measuring.
(2) 인장강도, 신장율, F-5치(F-5 value at 5% strain)측정 : 인스트론(Instron)을 사용하여 ASTMD882 시험법에 의거 측정하였다. 시료는 폭 15mm, 길이 150mm 필름을 시험편으로 하였으며 인스트론 게지 길이 50mm, 시험 스피드 500mm/분으로 하여 시험하였다.(2) Tensile strength, elongation rate, F-5 value (F-5 value at 5% strain) measurement: It was measured according to ASTMD882 test method using Instron. Samples were 15 mm wide and 150 mm long films as test pieces, and were tested with an Instron gauge length of 50 mm and a test speed of 500 mm / minute.
(3) 평면 평활성 관찰 : 제품의 외관을 육안 관찰하여 평가하였다.(3) Planar smoothness observation: The appearance of the product was visually observed and evaluated.
[실시예 1]Example 1
폴리에틸렌테레프탈레이트수지 950g에 폴리부틸렌테레프탈이트수지 50g를 배합하여 용융압출하고 20℃ 이하로 급냉시켜 미연신 필름을 제조하였다. 다음 95℃에서 종방향, 횡방향으로 각각 4배, 3.8배 이축연신을 행한 후 이축연신된 필름을 235℃에서 열고정하고 210℃에서 이완율6%로 이완열처리를 행하여 두께 12㎛의 필름을 제조하였다.50 g of polybutylene terephthalate resin was blended with 950 g of polyethylene terephthalate resin, melt-extruded, and rapidly cooled to 20 ° C. or lower to prepare an unstretched film. Next, biaxially stretched 4 times and 3.8 times in the longitudinal and transverse directions at 95 ° C., respectively, and the biaxially stretched film was heat-set at 235 ° C., and subjected to relaxation heat treatment at 210 ° C. with a 6% relaxation rate to produce a film having a thickness of 12 μm. It was.
[실시예 2]Example 2
폴리에틸렌테레프탈레이트수지 900g에 폴리부틸렌테프탈이트수지 100g을 배합하는 외에는 실시예1과 동일한 방법으로 두께 12㎛의 필름을 제조하였다.A film having a thickness of 12 μm was prepared in the same manner as in Example 1, except that 100 g of polybutylenetephthalate resin was blended with 900 g of polyethylene terephthalate resin.
[실시예 3]Example 3
열고정 온도를 230℃로 하는 것 외에는 실시예 1과 동일한 방법으로 실시하여 두께 12㎛의 필름을 제조하였다.A film having a thickness of 12 µm was prepared in the same manner as in Example 1 except that the heat setting temperature was 230 ° C.
[실시예 4]Example 4
열고정 온도를 240℃로 하는 것 외에는 실시예 1과 동일한 방법으로 실시하여 두께 12㎛의 필름을 제조하였다.A film having a thickness of 12 µm was prepared in the same manner as in Example 1 except that the heat setting temperature was 240 ° C.
비교실시예1Comparative Example 1
폴리에틸렌테레프탈레이트수지 1000g에폴리부틸렌테프탈레이수지 1g을 첨가하는 외에는 실시예 1과 동일한 방법으로 두께 12㎛의 필름을 제조하였다.A film having a thickness of 12 μm was prepared in the same manner as in Example 1, except that 1 g of polybutylene terephthalate resin was added to 1000 g of polyethylene terephthalate resin.
비교실시예2Comparative Example 2
폴리에틸렌테레프탈레이트수지 750g에 폴리부틸렌테레이트수지 250g을 배합하는 외에는 실시예 1과 동일한 방법으로 두께 12㎛ 필름을 제조하였다.A 12 탆 thick film was prepared in the same manner as in Example 1 except that 250 g of polybutylene terate resin was added to 750 g of polyethylene terephthalate resin.
비교실시예3Comparative Example 3
열고정 온도를 220℃로 하는 것 외에는 실시예 1과 동일한 방법으로 실시하여 두께 12㎛의 필름을 제조하였다.A film having a thickness of 12 μm was prepared in the same manner as in Example 1 except that the heat setting temperature was 220 ° C.
비교실시예4Comparative Example 4
열고정 온도를 245℃로 하는 것 외에는 실시예 1과 동일한 방법으로 실시하는 두께 12㎛의 필름을 제조하였다.A film having a thickness of 12 µm was prepared in the same manner as in Example 1 except that the heat setting temperature was 245 ° C.
[표 1]TABLE 1
상기 표 Ⅰ 에에 나타난 바와 같이 본 발명품은 열수축율이 1.3∼1.7로 대조품의 2.0∼3.0에 비해 50%정도 낮은 열수축율을 보이고 있으며, 외관에 있어서도 대조품은 연신 불균일, 주름 및 후열처리 후 파단등이 발생 불량한 외판을 갖고 있으나 본 발명품은 평활한 평면을 갖고 있어 고급 필름 제품의 용도로 적합함을 알 수 있다.As shown in Table I, the present invention shows a heat shrinkage rate of about 1.3% to 1.7, which is about 50% lower than 2.0 to 3.0 of the control product. Although it has a poor appearance plate, the present invention has a smooth flat surface it can be seen that it is suitable for the use of high-quality film products.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019910005513A KR940000966B1 (en) | 1991-04-06 | 1991-04-06 | Process for preparing polyester film having a low shrink characteristics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019910005513A KR940000966B1 (en) | 1991-04-06 | 1991-04-06 | Process for preparing polyester film having a low shrink characteristics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR920019849A KR920019849A (en) | 1992-11-20 |
| KR940000966B1 true KR940000966B1 (en) | 1994-02-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019910005513A KR940000966B1 (en) | 1991-04-06 | 1991-04-06 | Process for preparing polyester film having a low shrink characteristics |
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| Country | Link |
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| KR (1) | KR940000966B1 (en) |
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| WO2010028052A1 (en) * | 2008-09-08 | 2010-03-11 | Saint-Gobain Performance Plastics Corporation | Sanitary coupling assembly |
| KR20170090921A (en) * | 2016-01-29 | 2017-08-08 | 주식회사 효성 | Preparing biaxially oriented polyester film |
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| KR920019849A (en) | 1992-11-20 |
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