JPH1044230A - Preparation of biaxially oriented polyamide film - Google Patents
Preparation of biaxially oriented polyamide filmInfo
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- JPH1044230A JPH1044230A JP8201510A JP20151096A JPH1044230A JP H1044230 A JPH1044230 A JP H1044230A JP 8201510 A JP8201510 A JP 8201510A JP 20151096 A JP20151096 A JP 20151096A JP H1044230 A JPH1044230 A JP H1044230A
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- film
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- heat treatment
- stretching
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- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、テンター式延伸法
によるボーイング量が小さく、フィルム幅方向に均一な
熱収縮率を有し、かつ耐ピンホール性に優れた二軸延伸
ポリアミドフィルムの製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a biaxially stretched polyamide film having a small bowing amount by a tenter stretching method, a uniform heat shrinkage in the film width direction, and excellent pinhole resistance. It is about.
【０００２】[0002]
【従来の技術】二軸延伸ポリアミドフィルムは機械的特
性、光学的特性、ガスバリヤー性、耐衝撃性、耐ピンホ
ール性に優れているため、主に包装材料として幅広く使
用されている。2. Description of the Related Art Biaxially stretched polyamide films are widely used mainly as packaging materials because of their excellent mechanical properties, optical properties, gas barrier properties, impact resistance and pinhole resistance.
【０００３】二軸延伸ポリアミドフィルムをテンター式
延伸法で製造する場合、延伸部と熱処理部との境界部分
におけるフィルムに生じる応力の関係によってボーイン
グ現象が発生する。すなわち、フィルムは予熱部、延伸
部、熱処理部、リラックス部、冷却部を通過していく
が、延伸部の終端近辺、つまり設定延伸倍率に到達する
位置において延伸応力が最大となる。When a biaxially stretched polyamide film is produced by a tenter type stretching method, a bowing phenomenon occurs due to a stress generated in the film at a boundary between a stretched portion and a heat-treated portion. That is, the film passes through the preheating section, the stretching section, the heat treatment section, the relaxation section, and the cooling section. The stretching stress becomes maximum near the end of the stretching section, that is, at a position where the stretch ratio reaches the set stretching ratio.
【０００４】ところで、テンター内では、フィルムの両
端部はクリップで把持されているため、フィルム中央部
分は、延伸部の後の熱処理部から延伸部に向かって引き
寄せられるため、延伸機内に入る前のフィルムの進行方
向に直角に描いた線がフィルムの進行方向と逆の方向に
突き出た円弧を描くボーイング現象が発生する。この現
象の発生により、フィルムの進行方向に直角な方向の延
伸方向は、フィルム端部ほど相対的に斜め方向となる。
このようなフィルムを熱水や蒸気中におくと、カール現
象を起こすため、ボイル殺菌用途やレトルト殺菌用途の
ような包装用途に用いた場合には製袋性に問題が生じ
る。ボーイング現象の指標としては、熱水収縮率の斜め
差があり、この値が小さいほど好ましい。[0004] In the tenter, since both ends of the film are gripped by clips, the central portion of the film is drawn from the heat treatment section after the stretching section toward the stretching section. A bowing phenomenon occurs in which a line drawn at right angles to the traveling direction of the film draws an arc protruding in a direction opposite to the traveling direction of the film. Due to the occurrence of this phenomenon, the stretching direction in a direction perpendicular to the film traveling direction becomes relatively oblique toward the end of the film.
When such a film is placed in hot water or steam, it causes a curl phenomenon. Therefore, when the film is used for packaging such as boil sterilization and retort sterilization, there is a problem in bag making. As an index of the bowing phenomenon, there is an oblique difference in the hot water shrinkage, and the smaller the value, the more preferable.
【０００５】ボーイングを小さくするには、延伸時のフ
イルム温度を高くして延伸応力をできるだけ低くし、か
つ熱処理温度をできるだけ低くすることが望ましいが、
延伸温度を高くしすぎるとフィルムの強度が低下し、熱
処理温度を低くすると寸法安定性が低下するという問題
を有していた。In order to reduce bowing, it is desirable to raise the film temperature during stretching to lower the stretching stress as much as possible and to lower the heat treatment temperature as much as possible.
If the stretching temperature is too high, the strength of the film decreases, and if the heat treatment temperature is lowered, the dimensional stability decreases.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、寸法安定性
に優れ、かつ、製袋時のカールの原因となるボーイング
を低減させるのできる二軸延伸ポリアミドフイルムの製
造方法を提供しようとするものである。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a biaxially stretched polyamide film which has excellent dimensional stability and can reduce bowing which causes curling during bag making. It is.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、このよう
な問題を解決するために鋭意検討した結果、延伸部から
熱処理部へ移行する部分において、フィルムの幅方向に
温度勾配をつけたゾーンを設けることによりボーイング
量を低減させることができることを見出し本発明に到達
した。Means for Solving the Problems As a result of intensive studies to solve such a problem, the present inventors have found that a temperature gradient is applied in the width direction of the film at a portion where a transition is made from a stretching portion to a heat treatment portion. The present inventors have found that the bowing amount can be reduced by providing the zone, and have reached the present invention.
【０００８】すなわち、本発明の要旨は、次のとおりで
ある。テンター式延伸方法により、二軸延伸ポリアミド
フィルムを製造する方法において、延伸部と熱処理部と
の間に、下記式（１）、（２）を満足するように温度調
節された移行部を設けることを特徴とする二軸延伸ポリ
アミドフィルムの製造方法。 ２≦Te−Tc≦７ （１） Tm−20≦Te≦Tm−５ （２） ただし、Te（℃）はフィルムの幅方向の中央から、両側
に20〜45％（フィルムの全幅を 100％とする）の範囲の
部分の炉内の平均温度、Tc（℃）は中央から両側に20％
以内の部分の炉内の平均温度、Tm（℃）はポリアミド樹
脂の融点である。That is, the gist of the present invention is as follows. In a method for producing a biaxially stretched polyamide film by a tenter stretching method, a transition part whose temperature is controlled so as to satisfy the following equations (1) and (2) is provided between a stretching part and a heat treatment part. A method for producing a biaxially stretched polyamide film, characterized in that: 2 ≦ Te−Tc ≦ 7 (1) Tm−20 ≦ Te ≦ Tm−5 (2) However, Te (° C) is 20 to 45% on both sides from the center in the width direction of the film (100% of the total width of the film is The average temperature inside the furnace in the range of Tc (° C) is 20% on both sides from the center
The average temperature in the furnace, Tm (° C.), is the melting point of the polyamide resin.
【０００９】[0009]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明において用いられるポリアミドとしては、ナイロ
ン６、ナイロン66及びこれらを主体とするポリアミド等
が挙げられるが、コストパーフォーマンスの点で特にナ
イロン６が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Examples of the polyamide used in the present invention include nylon 6, nylon 66, and polyamides based on these. Nylon 6 is particularly preferred in terms of cost performance.
【００１０】ポリアミドには公知の添加剤、たとえば安
定剤、酸化防止剤、充填剤、滑剤、帯電防止剤、ブロッ
キング防止剤、着色剤などを含有させてもよい。The polyamide may contain known additives such as a stabilizer, an antioxidant, a filler, a lubricant, an antistatic agent, an antiblocking agent and a coloring agent.
【００１１】本発明の方法を実施するに当たっては、ま
ず、ポリアミドを常法によってＴダイ法で製膜して実質
的に無定形の未延伸フイルムを得る。次いで、この未延
伸フイルムに吸湿処理を施した後、予熱ゾーンで短時間
予熱処理し、引き続いて、縦方向、横方向に同時または
逐次二軸延伸し、さらに熱処理、リラックス処理、冷却
処理を行うことによって二軸延伸ポリアミドフィルムを
得る。In carrying out the method of the present invention, first, a polyamide is formed into a film by a T-die method by a conventional method to obtain a substantially amorphous unstretched film. Next, after performing the moisture absorption treatment on the unstretched film, the film is preheat-treated for a short time in the preheating zone, and subsequently, simultaneously or sequentially biaxially stretched in the machine direction and the transverse direction, and further heat-treated, relaxed, and cooled. Thereby, a biaxially stretched polyamide film is obtained.
【００１２】本発明においては、延伸部と熱処理部の間
の移行部において、フィルムの巾方向に温度差を設け、
フィルム中央部の温度をフィルム端部の温度よりも若干
低くなるように温度勾配をつけることより、フィルムの
巾方向の延伸応力の均一化が図られ、ボーイング現象が
低減される。In the present invention, a temperature difference is provided in the width direction of the film at the transition between the stretching section and the heat treatment section,
By applying a temperature gradient so that the temperature at the center of the film is slightly lower than the temperature at the edge of the film, the stretching stress in the width direction of the film is made uniform, and the bowing phenomenon is reduced.
【００１３】本発明において、Te−Tcが７℃より大きい
と、フィルムの幅方向の強度などの物性のバランスがく
ずれ、また、Te−Tcが２℃より小さいとボーイング低減
の効果がほとんどみられなくなる。本発明においてTe
（℃）はフィルムの幅方向の中央部から両側に20〜45％
（フィルムの全幅を 100％とする）の部分の炉内の平均
温度であり、Tc（℃）はフィルム中央部から両側に20％
以内の部分の炉内の平均温度である。In the present invention, if Te-Tc is higher than 7 ° C., the balance of physical properties such as strength in the width direction of the film is lost, and if Te-Tc is lower than 2 ° C., the effect of reducing bowing is hardly observed. Disappears. In the present invention,
(° C) is 20 to 45% on both sides from the center in the width direction of the film
(The total width of the film is 100%) This is the average temperature inside the furnace, and Tc (° C) is 20% from the center of the film to both sides.
The average temperature in the furnace of the part within.
【００１４】また、本発明においては、Teは下記の温度
範囲であることが必要である。 Tm−20≦Te≦Tm−５ ただし、Tm（℃）はポリアミド樹脂の融点である。Teが
（Tm−20）℃よりも低いと、フィルムの熱収縮率が大き
くなるため寸法安定性が悪くなり、（Tm−５）℃より高
いとフィルムが白化したり切断が発生するので好ましく
ない。In the present invention, Te needs to be in the following temperature range. Tm-20 ≦ Te ≦ Tm-5 where Tm (° C.) is the melting point of the polyamide resin. If Te is lower than (Tm-20) ° C, the thermal shrinkage of the film becomes large, resulting in poor dimensional stability. If it is higher than (Tm-5) ° C, the film is undesirably whitened or cut. .
【００１５】本発明におけるテンター延伸機内の加熱方
式としては、生産性において熱風加熱方式が好ましい。
また、フィルム端部と中央部の温度差をつけるには、フ
ィルム端部側の熱風吹出ノズルのスリット幅を広くする
ように、フィルム幅方向にノズルスリット幅の勾配をつ
ける方法や、フィルム端部側に赤外線ヒーターを設置し
て追加加熱する方法などを用いることができる。赤外線
ヒーターを設置して追加加熱する方法は、熱風吹出ノズ
ルのスリット幅を広くする方法に比べて、装置の変更が
容易であるという利点がある。The heating method in the tenter stretching machine in the present invention is preferably a hot air heating method in terms of productivity.
In order to make the temperature difference between the film edge and the center part, a method of giving a gradient of the nozzle slit width in the film width direction so as to widen the slit width of the hot air blowing nozzle on the film edge side, A method of additionally heating by installing an infrared heater on the side can be used. The method of additionally heating by installing an infrared heater has an advantage that the apparatus can be easily changed as compared with the method of widening the slit width of the hot air blowing nozzle.
【００１６】本発明において、式（１）及び（２）を満
たすように移行部内の温度分布をコントロールすること
により、Te規定部に相当するフィルム端部側の熱量はTc
規定部に相当するフィルム中央部の熱量に比べて、10〜
60％高くなる。In the present invention, by controlling the temperature distribution in the transition portion so as to satisfy the formulas (1) and (2), the calorific value on the film end side corresponding to the Te defining portion is Tc
Compared to the calorific value at the center of the film,
60% higher.
【００１７】また、本発明において、移行部の後の熱処
理工程における処理温度はTe〜Tmの範囲が好ましく、熱
処理部とリラックス部においてフィルムの寸法安定性が
付与される。In the present invention, the treatment temperature in the heat treatment step after the transition portion is preferably in the range of Te to Tm, and the dimensional stability of the film is imparted in the heat treatment portion and the relax portion.
【００１８】本発明におけるポリアミドフィルムの延伸
方法としては、テンター式同時二軸延伸法、ロール縦延
伸とテンター式横延伸を用いる逐次二軸延伸法のいずれ
の方法も用いることができる。As the stretching method of the polyamide film in the present invention, any of a tenter type simultaneous biaxial stretching method and a sequential biaxial stretching method using a roll longitudinal stretching and a tenter type transverse stretching can be used.
【００１９】[0019]
【実施例】次に、本発明を実施例によって具体的に説明
する。なお、実施例および比較例の評価に用いた測定方
法は次の通りである。Next, the present invention will be described specifically with reference to examples. In addition, the measuring method used for evaluation of an Example and a comparative example is as follows.
【００２０】１．ボーイング量 延伸機の入口でフィルムの進行方向に直角（フィルムの
幅方向）に、油性フェルトペンで直線を引く。延伸、熱
処理工程を経て、テンターより出てきたフィルムの中央
部の端部に対する前記直線の変形量（mm）を測定し、下
記式によりボーイング量を算出した。 ボーイング量（％）＝（フィルム中央部の変形量／フィ
ルム幅）× 1001. Boeing A straight line is drawn at right angles to the direction of film advance (the width direction of the film) at the entrance of the stretching machine using an oil-based felt pen. After the stretching and heat treatment steps, the amount of deformation (mm) of the straight line with respect to the center end of the film coming out of the tenter was measured, and the bowing amount was calculated by the following equation. Boeing amount (%) = (deformation amount at film center / film width) x 100
【００２１】２．熱水収縮率 フイルムの中央部、及び、中央から両側にそれぞれ幅方
向に40％離れた位置のフィルムを、幅方向に10mm、長さ
方向に 100mmの寸法にカットし、20℃×65％ＲＨの雰囲
気中で、標線間の寸法Ｌ0 を読取顕微鏡によって正確に
測定した後、沸騰水中に５分間浸漬し、沸騰水から引き
上げたフイルムを20℃、65％ＲＨの雰囲気中に放置して
平衡に達してから標線間の寸法Ｌ1 を測定し、次式より
求めた。 熱水収縮率 (％) ＝〔（Ｌ0 −Ｌ1 ）／Ｌ0 〕×1002. Hot water shrinkage The film at the center part of the film and at the position 40% apart in the width direction on both sides from the center are cut into 10mm in the width direction and 100mm in the length direction. in the atmosphere, after measuring precisely by microscope reading the dimension L 0 between the marked lines in boiling water and immersed for 5 minutes, the film of 20 ° C. was pulled up from the boiling water, allowed to stand in an atmosphere of RH 65% reached equilibrium by measuring the dimension L 1 between the marked line from was determined from the following equation. Hot water shrinkage (%) = [(L 0 −L 1 ) / L 0 ] × 100
【００２２】３．熱水収縮率の斜め差 20℃×65％ＲＨ雰囲気下で、フィルムの幅方向に対して
斜め45°と 135°の方向の熱水収縮率の差を測定した。
測定サンプルは、上記斜め方向に沿って、巾10mm×長さ
100mmの寸法にカットし、100 ℃熱水中で５分間ボイル
処理した後、20℃×65％ＲＨで２時間放置して寸法を測
定し、処理前の寸法に対する収縮率を求め、各方向の収
縮率の差の絶対値を熱水収縮率斜め差とした。なお、測
定サンプルは、フィルム中央部及びフィルム中央部から
幅方向にそれぞれ両側に40％離れた位置において、測定
サンプルの長さ方向の中点が前記の位置になるようにサ
ンプリングした。3. Oblique Difference in Hot Water Shrinkage Rate Under a 20 ° C. × 65% RH atmosphere, the difference between the hot water shrinkage rates in the directions of 45 ° and 135 ° oblique to the width direction of the film was measured.
The measurement sample is 10mm wide x length along the above diagonal direction.
Cut to 100mm size, boiled in hot water at 100 ° C for 5 minutes, then left at 20 ° C x 65% RH for 2 hours to measure the size, calculate the shrinkage relative to the size before processing, and The absolute value of the difference in the shrinkage was defined as the oblique difference in the hot water shrinkage. The measurement sample was sampled such that the middle point in the length direction of the measurement sample was at the above-described position at the film center and at positions 40% apart on both sides in the width direction from the film center.
【００２３】４．引張強度 長さ 150mm×巾10mmの寸法のフィルムをサンプリング
し、20℃×65％ＲＨで２時間放置した後、島津製作所社
製オートグラフAG-100E 型を使用し、チャック間距離 1
00mm、引張速度 500mm／分で測定した。4. Tensile strength A film with dimensions of 150 mm length x 10 mm width was sampled and left at 20 ° C x 65% RH for 2 hours. Then, using an Autograph AG-100E manufactured by Shimadzu Corporation, the distance between chucks was 1
The measurement was performed at 00 mm and a pulling speed of 500 mm / min.
【００２４】実施例１ 相対粘度 3.0(25 ℃、95％濃硫酸中、1g/dl ）、融点 2
20℃のナイロン６（ユニチカ社製 A1030BRF ）を、90mm
φ押出機にて 260℃で、幅 630mmのＴダイよりシート状
に溶融押出した後、表面温度20℃の冷却ロールに密着さ
せて急冷し、厚さ 150μm の実質的に無定形で配向して
いない未延伸フィルムを得た。得られた未延伸フィルム
を50℃の温水中に浸漬し、フィルムの水分率を５％に調
整した後、195 ℃で縦方向（ＭＤ）に 3.0倍、横方向
（ＴＤ）に 3.3倍の倍率で同時二軸延伸し、続いて移行
部のTe規定部に相当する部分に、幅 1.5m の赤外線ヒー
ター（８kw）を設置して、移行部でのフィルム中央部の
温度（Tc）を 208℃、端部の温度（Te）を 210℃に設定
し、この移行部中を約１秒間フィルムを通過させた。つ
いで、温度 211℃で熱固定処理を行い、次に５％のリラ
ックス処理を行い、厚さ15μm 、幅1420mmの二軸延伸ポ
リアミドフィルムを得た。得られた二軸延伸ポリアミド
フィルムについて、ボーイング量、熱水収縮率、熱水収
縮率の斜め差、引張強度を測定した結果を表１に示し
た。ボーイング量及び熱水収縮率の斜め差が小さいフィ
ルムが得られた。EXAMPLE 1 Relative viscosity 3.0 (1 g / dl in 25 ° C., 95% concentrated sulfuric acid), melting point 2
Nylon 6 (A1030BRF manufactured by Unitika) at 20 ° C
After being extruded into a sheet from a 630 mm wide T-die at 260 ° C using a φ extruder, the sheet is closely cooled to a cooling roll with a surface temperature of 20 ° C, quenched, and oriented substantially amorphous with a thickness of 150 μm. No unstretched film was obtained. The obtained unstretched film was immersed in warm water at 50 ° C. to adjust the moisture content of the film to 5%, and then at 195 ° C., a magnification of 3.0 times in the machine direction (MD) and 3.3 times in the transverse direction (TD). At the same time, and an infrared heater (8 kw) with a width of 1.5 m was installed at the part corresponding to the Te defined part at the transition part, and the temperature (Tc) at the center of the film at the transition part was 208 ° C. The edge temperature (Te) was set at 210 ° C. and the film was passed through this transition for about 1 second. Subsequently, a heat-setting treatment was carried out at a temperature of 211 ° C., followed by a 5% relaxation treatment to obtain a biaxially stretched polyamide film having a thickness of 15 μm and a width of 1420 mm. With respect to the obtained biaxially stretched polyamide film, the results obtained by measuring the bowing amount, the hot water shrinkage, the oblique difference in the hot water shrinkage, and the tensile strength are shown in Table 1. A film having a small difference in the bowing amount and the hot water shrinkage was obtained.
【００２５】実施例２、比較例１〜４ Tc及びTeを表１に示した温度に変更した以外は、実施例
１と同様にして、二軸延伸ポリアミドフィルムを得た。
得られた二軸延伸ポリアミドフィルムについて、ボーイ
ング量、熱水収縮率、熱水収縮率の斜め差、引張強度を
測定した結果を表１に示した。比較例１のように、Tcと
Teの温度差を設けない場合には、ボーイング量が大きい
フィルムとなった。比較例２のようにTcとTeの温度差が
大きい場合、フィルムの中央の熱収縮率が大きくなり、
幅方向の熱収バランスの悪いフィルムとなった。比較例
３のようにTeが低いとフィルムの熱収縮率が大きくなっ
た。比較例４ではTeが高いため、フィルムが白化した
り、切断が発生した。Example 2, Comparative Examples 1 to 4 A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that Tc and Te were changed to the temperatures shown in Table 1.
With respect to the obtained biaxially stretched polyamide film, the results obtained by measuring the bowing amount, the hot water shrinkage, the oblique difference in the hot water shrinkage, and the tensile strength are shown in Table 1. As in Comparative Example 1, Tc
When the temperature difference of Te was not provided, a film having a large bowing amount was obtained. When the temperature difference between Tc and Te is large as in Comparative Example 2, the heat shrinkage at the center of the film becomes large,
The film had poor heat balance in the width direction. As in Comparative Example 3, when Te was low, the heat shrinkage of the film increased. In Comparative Example 4, since the content of Te was high, the film was whitened or cut.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【発明の効果】本発明によれば、機械的特性を低下させ
ることなく、製袋時のカールの原因となるボーイングを
低減でき、幅方向に均一な性能バランスを有する二軸延
伸ポリアミドフィルムを製造することが可能となる。ま
た、設備的にもコストがかからないため、その工業的価
値は大きい。According to the present invention, a biaxially stretched polyamide film having a uniform performance balance in the width direction can be produced without reducing the mechanical properties and reducing bowing which causes curling during bag making. It is possible to do. In addition, since the cost is not required in terms of equipment, its industrial value is great.
Claims (1)
リアミドフィルムを製造する方法において、延伸部と熱
処理部との間に、下記式（１）、（２）を満足するよう
に温度調節された移行部を設けることを特徴とする二軸
延伸ポリアミドフィルムの製造方法。 ２≦Te−Tc≦７ （１） Tm−20≦Te≦Tm−５ （２） ただし、Te（℃）はフィルムの幅方向の中央から、両側
に20〜45％（フィルムの全幅を 100％とする）の範囲の
部分の炉内の平均温度、Tc（℃）は中央から両側に20％
以内の部分の炉内の平均温度、Tm（℃）はポリアミド樹
脂の融点である。1. A method for producing a biaxially stretched polyamide film by a tenter-type stretching method, wherein the temperature is adjusted between a stretching portion and a heat treatment portion so as to satisfy the following formulas (1) and (2). A method for producing a biaxially stretched polyamide film, comprising providing a transition portion. 2 ≦ Te−Tc ≦ 7 (1) Tm−20 ≦ Te ≦ Tm−5 (2) However, Te (° C) is 20 to 45% on both sides from the center in the width direction of the film (100% of the total width of the film is The average temperature inside the furnace in the range of Tc (° C) is 20% on both sides from the center
The average temperature in the furnace, Tm (° C.), is the melting point of the polyamide resin.
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| JP20151096A JP3660063B2 (en) | 1996-07-31 | 1996-07-31 | Method for producing biaxially stretched polyamide film |
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| JP20151096A JP3660063B2 (en) | 1996-07-31 | 1996-07-31 | Method for producing biaxially stretched polyamide film |
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| JP3660063B2 JP3660063B2 (en) | 2005-06-15 |
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| JP2001055453A (en) * | 1999-08-17 | 2001-02-27 | Nippon Synthetic Chem Ind Co Ltd:The | Biaxially oriented film based on saponification product of ethylene-vinyl acetate copolymer and its production |
| JP2006015743A (en) * | 2004-06-02 | 2006-01-19 | Toyobo Co Ltd | Polyamide resin laminated film roll and its manufacturing method |
| JP2006015742A (en) * | 2004-06-02 | 2006-01-19 | Toyobo Co Ltd | Polyamide resin laminated film roll and its manufacturing method |
| JP2007130759A (en) * | 2004-06-02 | 2007-05-31 | Toyobo Co Ltd | Polyamide resin film roll and its manufacturing method |
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| JP2006015743A (en) * | 2004-06-02 | 2006-01-19 | Toyobo Co Ltd | Polyamide resin laminated film roll and its manufacturing method |
| JP2006015742A (en) * | 2004-06-02 | 2006-01-19 | Toyobo Co Ltd | Polyamide resin laminated film roll and its manufacturing method |
| JP2007130759A (en) * | 2004-06-02 | 2007-05-31 | Toyobo Co Ltd | Polyamide resin film roll and its manufacturing method |
| JP2010076109A (en) * | 2008-09-24 | 2010-04-08 | Fujifilm Corp | Film manufacturing method |
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| JP2018024102A (en) * | 2016-08-08 | 2018-02-15 | ユニチカ株式会社 | Polyamide film, laminate and packaging material using the same |
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