KR910001573B1 - Process for the production of a poly-epsilon caproamid film - Google Patents
Process for the production of a poly-epsilon caproamid film Download PDFInfo
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- KR910001573B1 KR910001573B1 KR1019880005208A KR880005208A KR910001573B1 KR 910001573 B1 KR910001573 B1 KR 910001573B1 KR 1019880005208 A KR1019880005208 A KR 1019880005208A KR 880005208 A KR880005208 A KR 880005208A KR 910001573 B1 KR910001573 B1 KR 910001573B1
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- 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
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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
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- 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
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- 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
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
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- 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
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/915—Cooling of flat articles, e.g. using specially adapted supporting means with means for improving the adhesion to the supporting means
- B29C48/9165—Electrostatic pinning
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- 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
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
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- 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
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
- B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
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- 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
- B29C55/30—Drawing through a die
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
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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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
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Abstract
Description
제1도는 축차 이축 연신방법에 필름의 제조공정도.1 is a manufacturing process diagram of a film in a sequential biaxial stretching method.
제2도는 본 발명 정전밀착법에 의한 미연신 시트의 냉각 공정도.2 is a cooling process diagram of an unstretched sheet by the electrostatic adhesion method of the present invention.
* 도면의 주요 부분에 대한 부호의 설명* Explanation of symbols for the main parts of the drawings
1 : 티다이 2 : 냉각체1: Tidai 2: Cooling body
3 : 종연신기 4 : 횡연신기3: longitudinal drawing machine 4: transverse drawing machine
5 : 전극 S : 시트5: electrode S: sheet
F : 필름F: Film
본 발명은 ε-카프로락탐의 단독 중합체를 사용한 호모성 폴리아미드계인 폴리-ε-카프로아미드 필름의 제조방법에 관한 것으로서 특히, 두께의 균일성, 우수한 투명성, 낮은 결정화도 및 결정화도 편차가 적은 상대점도 3.0 이상의 폴리-ε-카프로아미드 중합체 시트를 4.0K 이상의 고전압, 저전류로 인가한 전극과 톨상 회전식 냉각체면 사이에서 밀착, 냉각시키고 이를 우선 종방향으로 연신하고 다음에 횡방향으로 연신하는 축차이축 연신에 의한 상기 필름의 제조방법인 것이다. 열가소성 플라스틱 필름은 미배향 시트를 종, 횡 서로 직각방향으로 이축연신함으로써 가스차단성 내핀홀성, 내충격성, 파단강도, 투명성등의 물리적 성질이 향상된다. 따라서 미배향 필름의 이축 연신법으로 여러가지 방법이 제안되고 있으나 이들은 동시 이축연신법과 축차이축연신법으로 대별된다.The present invention relates to a method for producing a poly-ε-caproamide film, which is a homopolyamide based homopolymer of ε-caprolactam, and in particular, a relative viscosity 3.0 having low thickness uniformity, excellent transparency, low crystallinity and low degree of crystallinity variation. The above poly-ε-caproamide polymer sheet is brought into close contact with and cooled between an electrode applied with a high voltage and a low current of 4.0 K or higher and a toll-like rotary cooling body surface, followed by stretching in the longitudinal direction first, and then in the transverse direction. It is a manufacturing method of the said film by. The thermoplastic film biaxially stretches the unoriented sheet in the direction perpendicular to each other vertically and horizontally to improve physical properties such as gas barrier resistance pinhole resistance, impact resistance, breaking strength and transparency. Therefore, various methods have been proposed for biaxial stretching of unoriented films, but they are roughly classified into simultaneous biaxial stretching and sequential biaxial stretching.
동시 이축 연신법은 텐터내에서 종방향과 횡방향으로 동시에 이축연신하기 때문에 텐터크립의 파지기구가 매우 복잡하고 그 장치의 일반화가 되어 있지 않아서 고가이며 연신비 변환이 어려워 연신비 변환에 따른 생산성이 저하된다.Simultaneous biaxial stretching is biaxially stretched in both the longitudinal and the lateral directions in the tenter, so the gripping mechanism of the tenter creeps is very complicated and the device is not generalized, which makes it expensive and difficult to convert the draw ratio. .
제1도와 같이 압출기로부터 티 다이(1)를 통해서 용융압출되는 미배향 시트를 톨상 회전식 냉각체(2)등의 이동 냉각체면에서 냉각 고화한 후 톨식 종연신기(3)와 텐터식 횡연신기(4)를 차례로 이용하는 축차 이축연신법이 일반적으로 행해지고 있으나 이 방법은 용융상태의 미연신 시트와 이동냉각체와의 사이에 박층의 공기가 혼입되기 때문에 연전도가 나쁘게 되고 용융시트는 고화되어 결정화가 빠르게 진행되기 때문에 결정화도가 높고 투명도가 좋지않은 시트가 얻어지며 이 미연신 시트의 연신성이 나쁘고 또 연신 필름의 투명성도 나쁘다. 만일 용융상태의 중합체 미연신 시트가 공기의 박층을 형성시키지 않고 직접 이동하여 냉각체상에 밀착, 냉각된다면 그 결정화 속도가 떨어지고 연신성이 좋은 폴리-ε-카프로아미드 중합체 시트가 얻어진다. 이와 같이 압출된 용융시트가 냉각체면에서의 밀착상태를 확실하게 하기 위한 목적으로 본 발명에서는 티다이와 냉각체사이, 가능한한 냉각체면과의 가까이에 나이프 엣지상, 와이어상 또는 다침상의 전극(5)을 사용하여 전극과 냉각체면에 고전압, 저전류를 인가하고 그 사이로 미연신 시트를 통과케 함으로써 해당 시트물질을 냉각체면에 밀착·냉각시키는 정전인가 장치를 사용하였으며 바람직하게는 고가의 설비를 요하는 다침상 및 나이프 엣지상보다는 와이어상의 정전인가 장치를 사용한다.As shown in FIG. 1, the unoriented sheet melt-extruded from the extruder through the tee die 1 is cooled and solidified on the surface of a mobile cooling body such as a tall
한편, 원료인 폴리아미드수지의 중합도는 상대점도가 3.0 이상 바람직하게는 3.0∼4.5 범위의 고중합도가 요구된다. 상대점도가 3.0 이하의 낮은 중합도를 갖는 호모성 폴리아미드계인 폴리-ε-카프로아미드 수지는 온도에 쉽게 열화되므로 필름제조공정에서 올리고머에 의한 장치의 오염 및 이축연신 필름의 안정된 제몰성치를 내지 못한다. 그리고 중합도가 4.5보다 크면 제조공정에서 부하가 많이 걸려 연신성의 곤란등 필름제조가 어렵다. 따라서 본 발명은 상대점도가 3.0∼4.5 범위의 호모성 폴리아미드계인 폴리-ε-카프로아미드를 사용하고 상기한 정전인가 장치로써 균일한 두께, 우수한 투명성, 낮은 결정화도, 결정화도 편차가 적은 폴리-ε-카프로아미드 이축연신 필름을 고효율적으로 생산가능하게 한다.On the other hand, the polymerization degree of the polyamide resin which is a raw material is required to have a high degree of polymerization of a relative viscosity of 3.0 or more, preferably in the range of 3.0 to 4.5. The poly-ε-caproamide resin, which is a homopolyamide having a low degree of polymerization of 3.0 or less, is easily deteriorated with temperature, thus preventing the contamination of the device by the oligomer in the film production process and the stable property of the biaxially stretched film. In addition, when the degree of polymerization is greater than 4.5, it is difficult to produce films such as difficulty in drawing due to high load in the manufacturing process. Therefore, the present invention uses poly-ε-caproamide, which is a homopolyamide having a relative viscosity in the range of 3.0 to 4.5, and uses the above-mentioned electrostatic application device to achieve uniform thickness, excellent transparency, low crystallinity, and low crystallinity poly-ε-. Caproamide biaxially oriented films can be produced with high efficiency.
본 발명에 사용되는 원료로서는 일반적으로 나일론 6이라고 불리는 ε-카프로락탐의 단독 중합체를 사용하였으며 중합체 연신필름의 활성, 내블럭킹성, 연신성, 내열성, 제전성등을 향상시키기 위하여 해당 중합반응에 활재, 산화방지제, 자외선흡수제, 정전방지제등의 첨가제가 필름성질에 악 영향을 주지않는 범위에서 배합되어도 좋다.As a raw material used in the present invention, a homopolymer of ε-caprolactam generally called nylon 6 was used. In order to improve the activity, blocking resistance, stretchability, heat resistance, antistatic properties, etc. of the polymer stretched film, it was used in the polymerization reaction. And additives such as antioxidants, ultraviolet absorbers, and antistatic agents may be blended within a range that does not adversely affect film properties.
본 발명은 상기 중합방법으로 제조한 폴리-ε-카프로아미드 중합체를 압출기에 의하여 융점 이상으로 가열, 압출하고 4.0KV∼10.0KV의 고전압, 저전류로 인가한 와이어 단선식 정전밀착법으로 톨상 회전식 냉각체면에 정전밀착시켜 냉각, 고화하여 실질적인 무정형의 배향하지 않은 미연신 시트를 만든다. 이때 전압이 10.0KV보다 높으면 스파크 발생과 함께 와이어가 단선되어 정전인가 되기 어렵다. 또한 4.0KV 보다 낮으면 정전인가력이 낮아 이축연신 폴리아미드 필름의 생산성에 미치지 못한다. (폴리아미드 이축연신 필름의 경우 생산성을 위해서는 미연신 시트의 인취속도가 20m/분 이상이어야 한다. ) 이러한 정전밀착법에 의하여 제조된 미연신 시트는 5% 이하의 결정화도가 바람직하며 후의 연신공정에 용이하게 종, 횡 이축방향으로 연신되도록 이용된다.The present invention is a toll-phase rotary cooling by heating and extruding the poly-ε-caproamide polymer prepared by the polymerization method above the melting point by an extruder and applying a high voltage, low current of 4.0KV to 10.0KV. Electrostatic adhesion to the body surface causes cooling and solidification to produce a substantially amorphous, unoriented sheet. At this time, if the voltage is higher than 10.0KV, the wire is disconnected with the spark generation and it is difficult to apply the power failure. In addition, when lower than 4.0KV, the electrostatic force is low, which does not reach the productivity of the biaxially stretched polyamide film. (In the case of polyamide biaxially oriented film, the draw rate of the unstretched sheet should be 20 m / min or more for productivity.) The unstretched sheet produced by the electrostatic bonding method has a crystallinity of 5% or less, and is suitable for the subsequent stretching process. It is used to stretch in the longitudinal and transverse biaxial directions easily.
상기 정전인가 장치는 제2도와 같다. 즉 톨상 회전식 냉각체(2)의 면과 가깝게 와이어상 단선식 전극(5)을 설치하고 이 전극(5)에 접지로된 냉각체(2) 사이에 4.0KV∼10.0KV 범위의 고전압, 저전류를 인가한다. 그러면 전극과 냉각체면 사이에 정전기력이 생기게 되므로 이 사이로 진입되는 용융압출물은 냉각체면에 양호한 상태로 밀착되는 것이다. 이렇게 정전밀착법에 의하여 얻은 미연신시트(S)를 제1도의 톨식 종연신기(3)에 종연신비2.0 이상으로 종연신하고 텐터식 횡연신기(4)에서 횡연신비2.0이상으로 횡연신하고 열고정부(6)로 열고정하여 일정한 폭으로 인취되게 한 다음 그 양측 가장자리를 슬리이팅하여 완성된 필름(F)를 권취한다.The electrostatic application device is shown in FIG. That is, the wire-like
이와 같이하여 얻어진 폴리-ε-카프로아미드 이축연신 필름(F)은 그대로도 양호한 성질을 나타내나 특정방향의 물리적 성질을 향상시키기 위하여는 더욱 종연신 또는 횡연신을 하여도 좋다.The poly-ε-caproamide biaxially oriented film (F) thus obtained shows good properties as it is, but may be further longitudinally or laterally stretched in order to improve the physical properties in a specific direction.
본 발명에서 얻은 필름(F)에 대하여 그 특성치의 측정방법은 다음과 같다.The measuring method of the characteristic value about the film F obtained by this invention is as follows.
(B상대점도 : 수지를 96.3% 진한 황산에 1.0gr/100ml 농도로 용해해서 20℃ 항온조중에서 오스트발드 점도계를 사용 측정하였다.(B relative viscosity: The resin was dissolved in 96.3% concentrated sulfuric acid at a concentration of 1.0gr / 100ml and measured using an Ostwald viscometer in a 20 ° C incubator.
[실시예 1∼6]EXAMPLES 1-6
상대점도가 2.0∼4.5 이상인 호모성 폴리아미드계인 폴리-ε-카프로아미드 수지를 각각 회전식 진공건조기로 110℃에서 진공건조하여 수분율을 0.1wt%로 조정한 다음 티다이(1)를 장착한 직경 90mm 압출기를 사용하여 260℃에서 가열용융 시킨뒤 용융중합체 수지를 25℃로 냉각된 톨상 회전식 냉각체(2)와, 이톨 접지로 하고 5.0KV의 고전압 저전류를 인가한 와이어 단선식전극(5)과의 사이로 진입시켜 두께 약 150μm, 폭1m의 무정형인 미연신 시트(S)를 얻었다. 이 미연신 시트(S)를 통상의 종연신기(3)에서 3.0배의 종연신비로 종연신하고, 역시 통상의 텐터식 횡연신기 3.5배의 횡연신비로 횡연신하고 열고정하여 두께 15μm의 이축연신필름(F)을 권취하였다. 표 1은 상기 실시예 1∼6에 의하여 정전인가 장치의 전압을 5.0KV로, 톨상 회전식 냉각체의 인취속도를 20 또는 40m/분으로 각각 일정하게 고정시키고, 상대점도치에 따른 각 제조 필름의 연신성과 연신필름의 두께 편차율을 각각 작성하였다. 이 경우 상대점도가 3.0∼4.5인 것이 연신성이 양호하고 연신된 필름의 두께 편차율도 10% 이하로 대체로 양호했다.The poly-ε-caproamide resin, a homopolyamide having a relative viscosity of 2.0 to 4.5 or more, was vacuum-dried at 110 DEG C with a rotary vacuum dryer, respectively, to adjust the water content to 0.1 wt%, and then to the diameter of 90 mm equipped with a Ti-die (1). After heating and melting at 260 DEG C using an extruder, the molten polymer resin was cooled to 25 DEG C., a toll-like
[표 1]TABLE 1
[실시예 7∼13]EXAMPLES 7-13
건조 및 정전인가, 연신장치의 조건이 상기 실시예 1∼6과 같고 상대점도 3.5인 호모성 폴리아미드계인 폴리-ε-카프로아미드 수지에 대하여 인가전압 3.0∼10.0KV, 톨상 회전식 냉각체의 인취속도 5∼70m/분으로 하여 미연신 시트와 연신필름을 제조하고 각각에 대하여 용융중합체 시트의 톨상회전식 냉각체면으로의 밀착상태에 따라 미연신 시트의 두께 편차율, 연신성, 연신 필름의 두께 편차율을 표 2에 작성하였다. 그 결과 인가전압 4.0∼10.0KV 범위에서 20m/분 이상의 미연신 시트에 대한 인취속도를 나타냈으며 또한 양호한 연신성, 10% 이하의 연신필름 두께 편차율을 나타내었다.The take-up speed of the toll-like rotary cooling body with an applied voltage of 3.0 to 10.0 KV for a poly-ε-caproamide resin, which is the same as those of Examples 1 to 6 and has a relative viscosity of 3.5, relative to that of drying and electrostatic application. The unstretched sheet and the stretched film were prepared at 5 to 70 m / min, and the thickness variation ratio of the unstretched sheet, the stretchability, and the thickness variation ratio of the stretched film according to the adhesion state of the molten polymer sheet to the toll-phase rotary cooling body surface. Was prepared in Table 2. As a result, the pulling speed of the unstretched sheet of 20 m / min or more in the applied voltage range of 4.0 to 10.0 KV was shown, and also the good stretchability and the variation ratio of the stretched film thickness of 10% or less were shown.
[표 2]TABLE 2
이상에서와 같이 본 발명은 ε-카프로락탐의 단독 중합체를 사용한 호모성 폴리아미드계인 폴리-ε-카프로아미드 시트를 상대점도 3.0이상 바람직하게는 3.0∼4.5 범위로 선정하고 특히 이러한 고중합도를 선정하되 톨상 회전식 냉각체면과 와이어 단선식 전극사이에 4.0KV∼10.0KV의 고전압 저전류를 인가하는 정전밀착법으로써 균일한 두께, 우수한 투명성, 낮은 결정화도, 결정화도 편차가 적은 폴리-ε-카프로아미드 이축 연신필름의 제조가 가능함과 아울러 경제성과 고효율적으로 생산 가능하게된 매우 효과적인 발명이다.As described above, the present invention selects a poly-ε-caproamide sheet, which is a homopolyamide based homopolymer of ε-caprolactam, in a relative viscosity of 3.0 or more, preferably in the range of 3.0 to 4.5, and particularly, selects such a high polymerization degree. Poly-ε-caproamide biaxially oriented film with uniform thickness, excellent transparency, low crystallinity and low degree of crystallinity, with electrostatic adhesion method applying high voltage and low current of 4.0KV ~ 10.0KV between the toll-shaped rotary cooling body surface and the wire disconnection electrode. It is a very effective invention that can be manufactured and economically and efficiently produced.
Claims (1)
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019880005208A KR910001573B1 (en) | 1988-05-04 | 1988-05-04 | Process for the production of a poly-epsilon caproamid film |
NL8900189A NL8900189A (en) | 1988-05-04 | 1989-01-26 | METHOD FOR MANUFACTURING POLY-EPSILON-CAPROAMIDE FILM |
IT8919457A IT1229890B (en) | 1988-05-04 | 1989-02-16 | METHOD FOR THE PREPARATION OF POLY BETA CAPROAMIDE FILM |
DE3908690A DE3908690A1 (en) | 1988-05-04 | 1989-03-16 | Process for the production of a biaxially stretched poly- epsilon -caproamide film |
GB8906628A GB2218036A (en) | 1988-05-04 | 1989-03-22 | Biaxially stretched poly- epsilon -caproamide film |
JP1113543A JPH0257316A (en) | 1988-05-04 | 1989-05-02 | Method and device for manufacturing poly-epsilon-capron amide film |
CN89102928A CN1037479A (en) | 1988-05-04 | 1989-05-03 | The manufacture method of poly-epsilon-caproamide film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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KR1019880005208A KR910001573B1 (en) | 1988-05-04 | 1988-05-04 | Process for the production of a poly-epsilon caproamid film |
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KR890017069A KR890017069A (en) | 1989-12-15 |
KR910001573B1 true KR910001573B1 (en) | 1991-03-16 |
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KR1019880005208A KR910001573B1 (en) | 1988-05-04 | 1988-05-04 | Process for the production of a poly-epsilon caproamid film |
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JP (1) | JPH0257316A (en) |
KR (1) | KR910001573B1 (en) |
CN (1) | CN1037479A (en) |
DE (1) | DE3908690A1 (en) |
GB (1) | GB2218036A (en) |
IT (1) | IT1229890B (en) |
NL (1) | NL8900189A (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2503150B2 (en) * | 1991-04-16 | 1996-06-05 | 東芝機械株式会社 | Device for automatically rolling molten resin sheets |
JP4020283B2 (en) * | 1999-03-19 | 2007-12-12 | 富士フイルム株式会社 | Method for producing biaxially stretched polyester film |
KR20010002581A (en) * | 1999-06-16 | 2001-01-15 | 홍순달 | A method of manufacturing for nylon flat yarn |
JP4710103B2 (en) * | 2000-06-01 | 2011-06-29 | 東レ株式会社 | Method for removing deposits on roll surface and method for producing thermoplastic resin film |
US6623679B2 (en) | 2000-12-29 | 2003-09-23 | Eastman Kodak Company | Method of controlling width of polyester film support |
US20020132196A1 (en) * | 2000-12-29 | 2002-09-19 | Eastman Kodak Company | Method of controlling width of polyester film support |
KR20080003372A (en) * | 2005-04-28 | 2008-01-07 | 토요 보세키 가부시기가이샤 | Process for producing polyamide-based resin film roll |
WO2013084845A1 (en) * | 2011-12-05 | 2013-06-13 | 東洋紡株式会社 | Biaxially oriented polyamide-based resin film, and production method therefor |
CN103824648B (en) * | 2014-01-25 | 2016-10-19 | 陕西师范大学 | A kind of method of heat treatment transparent conductive film material |
HUE052138T2 (en) * | 2015-02-20 | 2021-04-28 | Toray Industries | Method for producing microporous plastic film |
HUE051622T2 (en) * | 2015-02-20 | 2021-03-01 | Toray Industries | Method for producing microporous plastic film |
KR102357542B1 (en) * | 2015-02-20 | 2022-02-03 | 도레이 카부시키가이샤 | Method for manufacturing microporous plastic film |
-
1988
- 1988-05-04 KR KR1019880005208A patent/KR910001573B1/en active Pre-grant Review Request
-
1989
- 1989-01-26 NL NL8900189A patent/NL8900189A/en not_active Application Discontinuation
- 1989-02-16 IT IT8919457A patent/IT1229890B/en active
- 1989-03-16 DE DE3908690A patent/DE3908690A1/en not_active Withdrawn
- 1989-03-22 GB GB8906628A patent/GB2218036A/en not_active Withdrawn
- 1989-05-02 JP JP1113543A patent/JPH0257316A/en active Pending
- 1989-05-03 CN CN89102928A patent/CN1037479A/en active Pending
Also Published As
Publication number | Publication date |
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IT8919457A0 (en) | 1989-02-16 |
GB8906628D0 (en) | 1989-05-10 |
KR890017069A (en) | 1989-12-15 |
CN1037479A (en) | 1989-11-29 |
JPH0257316A (en) | 1990-02-27 |
IT1229890B (en) | 1991-09-13 |
DE3908690A1 (en) | 1989-11-16 |
NL8900189A (en) | 1989-12-01 |
GB2218036A (en) | 1989-11-08 |
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