JPH09220761A - Production of multilayered stretched film - Google Patents
Production of multilayered stretched filmInfo
- Publication number
- JPH09220761A JPH09220761A JP2892296A JP2892296A JPH09220761A JP H09220761 A JPH09220761 A JP H09220761A JP 2892296 A JP2892296 A JP 2892296A JP 2892296 A JP2892296 A JP 2892296A JP H09220761 A JPH09220761 A JP H09220761A
- Authority
- JP
- Japan
- Prior art keywords
- evoh
- heat treatment
- stretched film
- temperature
- temp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は、ガスバリヤー性と
熱水処理耐性に優れた多層延伸フィルムの製造法に関す
るものである。TECHNICAL FIELD The present invention relates to a method for producing a multilayer stretched film having excellent gas barrier properties and hot water treatment resistance.
【０００２】[0002]
【従来の技術】ＥＶＯＨは優れたガスバリヤー性を有す
るが、吸湿性が高いという欠点がある。そこで、ＥＶＯ
Ｈのガスバリヤー性を生かしながら、吸湿性を改良し、
さらに、強度や耐熱性を向上させるために、ＥＶＯＨと
ポリアミド、ポリエステル、ポリオレフィンなどからな
る多層フィルムが食品包装用途などに使用されている。
しかしながら、ＥＶＯＨ層を多層包装フィルムの一層と
して用いた包材では、内容物の熱水処理により水分がＥ
ＶＯＨ層へ侵入し、ＥＶＯＨ層が白濁したり、波状のし
わや模様などの外観不良が発生するという問題があっ
た。EVOH has an excellent gas barrier property, but has a drawback that it has a high hygroscopic property. So EVO
Improves hygroscopicity while making full use of the gas barrier property of H,
Furthermore, in order to improve strength and heat resistance, a multilayer film composed of EVOH and polyamide, polyester, polyolefin or the like is used for food packaging and the like.
However, in the packaging material using the EVOH layer as one layer of the multi-layer packaging film, the water content of the EVOH layer becomes E due to the hot water treatment of the content.
There has been a problem that the EVOH layer penetrates into the VOH layer and becomes cloudy, and appearance defects such as wavy wrinkles and patterns occur.
【０００３】このような熱水処理による外観不良を防止
するために、ＥＶＯＨとポリアミド、ポリオレフィン、
ポリエステル、あるいはポリカーボネートのような熱可
塑性樹脂をブレンドする方法（特開平１−253442号公
報、特開平１− 22890号公報、特開平５−214186号公報
など）が提案されている。In order to prevent the appearance failure due to such hot water treatment, EVOH, polyamide, polyolefin,
A method of blending a thermoplastic resin such as polyester or polycarbonate (JP-A-1-253442, JP-A-1-22890, JP-A-5-214186, etc.) has been proposed.
【０００４】しかしながら、ＥＶＯＨと他の熱可塑性樹
脂との混合物は、溶融押出時に架橋反応によりゲル化
し、長時間の連続押出が困難となり操業性が低下した
り、ＥＶＯＨの特長であるガスバリヤー性が低下するな
どの問題があった。また、ＥＶＯＨに無機フィラーを添
加し、熱水処理耐性を付与する方法が提案されている
（特開平５−140344号公報）が、製膜前にＥＶＯＨと無
機フィラーをあらかじめ溶融混合する必要があるため、
熱履歴が長くなり樹脂が劣化したり、また、フィルムの
透明性が損なわれて商品価値が損なわれるなどの問題が
あった。However, a mixture of EVOH and another thermoplastic resin is gelated by a cross-linking reaction during melt extrusion, which makes continuous extrusion for a long time difficult and lowers operability, and EVOH has a characteristic gas barrier property. There was a problem such as a drop. Further, a method has been proposed in which an inorganic filler is added to EVOH to impart resistance to hot water treatment (JP-A-5-140344), but it is necessary to melt-mix the EVOH and the inorganic filler in advance before film formation. For,
There are problems that the heat history becomes long and the resin deteriorates, and that the transparency of the film is impaired and the commercial value is impaired.
【０００５】さらに、ＥＶＯＨに架橋剤、架橋助剤を添
加して製膜した後に電子線を照射し、ＥＶＯＨを架橋さ
せることにより熱水処理耐性を付与する方法（特開平５
−271498号公報）も提案されているが、高価な電子線照
射設備が必要なため工業的に有利な方法とはいえなかっ
た。このように、ＥＶＯＨ層を一層として用いた多層包
装フィルムに熱水処理耐性を付与するための工業的に有
利な方法はなかった。Further, a method of imparting resistance to hot water treatment by adding a crosslinking agent and a crosslinking aid to EVOH to form a film, and then irradiating with an electron beam to crosslink the EVOH (Japanese Patent Laid-Open No. Hei 5)
No. 271498) has been proposed, but it cannot be said to be an industrially advantageous method because expensive electron beam irradiation equipment is required. Thus, there has been no industrially advantageous method for imparting resistance to hot water treatment to a multilayer packaging film using an EVOH layer as one layer.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、ＥＶＯＨの
優れたガスバリヤー性、透明性を損なわずに、工業的に
有利な方法で熱水処理耐性を付与することのできる多層
延伸フィルムの製造法を提供しようとするものである。DISCLOSURE OF THE INVENTION The present invention provides a multilayer stretched film capable of imparting resistance to hot water treatment by an industrially advantageous method without impairing the excellent gas barrier property and transparency of EVOH. It is an attempt to provide the law.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、溶融した
ＥＶＯＨが固化し、さらに結晶化するときの熱処理条件
について検討した結果、ＥＶＯＨの結晶構造を制御する
ことにより、熱水処理によるＥＶＯＨ層の白濁やしわの
発生などの外観不良を改良す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 The present inventors have examined the heat treatment conditions when the molten EVOH is solidified and further crystallized. As a result, by controlling the crystal structure of EVOH, the EVOH by hot water treatment is controlled. The present inventors have found that it is possible to improve appearance defects such as cloudiness and wrinkles in the layer, and arrived at the present invention.
【０００８】すなわち、本発明の要旨は次のようであ
る。ＥＶＯＨからなる層と、融点がＥＶＯＨよりも高い
熱可塑性樹脂（Ｐ）からなる層の少なくとも２層からな
る多層延伸フィルムに、ＥＶＯＨの融点以上、Ｐの融点
未満の温度で熱処理（ａ）を行った後に、下記式
（１）、（２）を満足する条件で熱処理（ｂ）を行うこ
とを特徴とする多層延伸フィルムの製造法。 ｔ≧ 0.00889（Ｔｃ−Ｔ）2 − 0.373（Ｔｃ−Ｔ）＋ 5.1 （１） −19≦Ｔｃ−Ｔ≦ 61 （２） ただし、Ｔは熱処理（ｂ）の温度（℃）、ｔは処理時間
（秒）、Ｔｃは示差走査熱量計で10℃／分の速度で降温
した場合のＥＶＯＨの結晶化ピーク温度（℃）を示す。That is, the gist of the present invention is as follows. Heat treatment (a) is performed on a multilayer stretched film consisting of at least two layers of a layer made of EVOH and a layer made of a thermoplastic resin (P) having a melting point higher than that of EVOH at a temperature not lower than the melting point of EVOH and lower than the melting point of P. After that, the method for producing a multilayer stretched film is characterized in that the heat treatment (b) is performed under conditions satisfying the following formulas (1) and (2). t ≥ 0.00889 (Tc-T) 2 -0.373 (Tc-T) + 5.1 (1) -19 ≤ Tc-T ≤ 61 (2) where T is the temperature of the heat treatment (b) (° C) and t is the treatment time. (Sec), Tc represents the peak crystallization temperature (° C.) of EVOH when the temperature was lowered with a differential scanning calorimeter at a rate of 10 ° C./min.
【０００９】[0009]
【発明の実施の形態】本発明におけるＥＶＯＨとして
は、エチレン成分の含有率が20〜50モル％、好ましくは
27〜44モル％、酢酸ビニル成分のけん化度が96モル％以
上、好ましくは99モル％以上のものがガスバリヤー性や
強度が優れ、また、メルトインデックス（210 ℃，2160
g ）の値が、0.2 〜60g/10分のものが加工性が良く好ま
しい。BEST MODE FOR CARRYING OUT THE INVENTION The EVOH of the present invention has an ethylene content of 20 to 50 mol%, preferably
27 to 44 mol% and vinyl acetate having a saponification degree of 96 mol% or more, preferably 99 mol% or more have excellent gas barrier properties and strength, and also have a melt index (210 ℃, 2160
It is preferable that the value of g) is 0.2 to 60 g / 10 minutes because of good workability.
【００１０】また、ＥＶＯＨには、その特性を損なわな
い限り、ＥＶＯＨと親和性のある樹脂、酸化防止剤、可
塑剤、帯電防止剤、滑剤、着色剤、充填剤などを添加す
ることができる。Further, EVOH may be added with a resin having an affinity for EVOH, an antioxidant, a plasticizer, an antistatic agent, a lubricant, a colorant, a filler, etc., as long as the characteristics thereof are not impaired.
【００１１】本発明におけるＰとしては、ＥＶＯＨより
も高い融点を有する樹脂であり、フィルムの破断などの
現象が起こりにくく、安定した生産性が得られる点から
は、ＥＶＯＨよりも５〜 100℃程度高い融点（非晶性樹
脂の場合は軟化点）を有する樹脂が好ましい。P in the present invention is a resin having a melting point higher than that of EVOH, and from the viewpoint that a phenomenon such as film breakage is unlikely to occur and stable productivity is obtained, it is about 5 to 100 ° C. as compared with EVOH. A resin having a high melting point (softening point in the case of an amorphous resin) is preferable.
【００１２】Ｐの好適な樹脂としては、ポリ−ε−カプ
ラミド（ナイロン６）、ポリヘキサメチレンアジパミド
（ナイロン66）、ポリヘキサメチレンセバカミド（ナイ
ロン610）、ポリラウリルアミド（ナイロン12）、ポリ
メタキシリレンアジパミドなどのポリアミド樹脂、ポリ
エチレンテレフタレート、ポリエチレンナフタレート、
ポリブチレンテレフタレート、ポリアリレート、ポリカ
ーボネートなどを挙げることができる。また、Ｐとして
は、上記のポリマーの混合物や共重合体を用いることも
できる。ナイロン６は、ＥＶＯＨとの接着性、強度、靭
性、透明性、耐ピンホール性に優れており、本発明にお
ける樹脂Ｐとして最も好適である。Suitable resins for P include poly-ε-capramide (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), polylauryl amide (nylon 12). Polyamide resin such as polymeta-xylylene adipamide, polyethylene terephthalate, polyethylene naphthalate,
Examples thereof include polybutylene terephthalate, polyarylate, and polycarbonate. Further, as P, a mixture or copolymer of the above polymers can be used. Nylon 6 is excellent in adhesiveness with EVOH, strength, toughness, transparency, and pinhole resistance, and is most suitable as the resin P in the present invention.
【００１３】本発明における多層延伸フィルムの構成
は、（Ａ）層と（Ｂ）層が含まれていれば特に制限はな
く、他の樹脂層として、たとえば、ＥＶＯＨよりも低い
融点を有する樹脂層を含んでいてもよいし、また、ＥＶ
ＯＨ層は一層でも複数層であってもよいが、包材構成と
してはＥＶＯＨの吸水性によるトラブルを防止するた
め、ＥＶＯＨ層は外部表面層としない構成にする方が望
ましい。The structure of the multilayer stretched film in the present invention is not particularly limited as long as it includes the layer (A) and the layer (B), and as another resin layer, for example, a resin layer having a melting point lower than EVOH. May be included, and EV
Although the OH layer may be a single layer or a plurality of layers, it is desirable that the EVOH layer is not the outer surface layer in order to prevent troubles due to water absorption of EVOH.
【００１４】本発明における多層延伸フィルムの製法に
おいては、ＥＶＯＨの融点以上、Ｐの融点未満の温度で
熱処理（ａ）を行った後に、前記式（１）及び（２）を
満足する熱処理（ｂ）を行うことが必要である。本発明
において、熱処理（ａ）の温度がＥＶＯＨの融点未満の
場合、得られる多層延伸フィルムの熱水処理耐性を改良
することができず、Ｐの融点以上の場合はフィルムが破
断しやすくなる。熱処理（ａ）は、通常、１〜10秒、好
ましくは２〜５秒行われる。In the method for producing a multilayer stretched film according to the present invention, after the heat treatment (a) is performed at a temperature higher than the melting point of EVOH and lower than the melting point of P, the heat treatment (b) satisfying the above formulas (1) and (2) is performed. ) Is necessary. In the present invention, when the temperature of the heat treatment (a) is lower than the melting point of EVOH, the resistance to hot water treatment of the obtained multilayer stretched film cannot be improved, and when the temperature is higher than the melting point of P, the film is easily broken. The heat treatment (a) is usually performed for 1 to 10 seconds, preferably 2 to 5 seconds.
【００１５】式（１）における処理時間ｔは、ＥＶＯＨ
の劣化を抑え、また経済的な観点から、最小時間＋60秒
を超えないようにするのがより好ましい。なお、式
（１）より、Ｔｃ−Ｔ＝21（℃）のときに処理時間ｔが
最小値（1.2 秒）となる。The processing time t in the equation (1) is EVOH.
It is more preferable not to exceed the minimum time +60 seconds from the viewpoint of suppressing the deterioration of the above and economically. From the formula (1), the processing time t becomes the minimum value (1.2 seconds) when Tc-T = 21 (° C).
【００１６】また、本発明の目的を達成するためのＥＶ
ＯＨの結晶構造を最適化するためには、−19≦Ｔｃ−Ｔ
≦61（℃）とすることが必要であり、１≦Ｔｃ−Ｔ≦41
（℃）がさらに好ましい。Further, an EV for achieving the object of the present invention
In order to optimize the crystal structure of OH, −19 ≦ Tc−T
≤61 (° C) is required, 1≤Tc-T≤41
(° C) is more preferable.
【００１７】本発明においては、熱処理（ａ）の後、速
やかに式（１）、（２）を満足する条件で熱処理（ｂ）
を行うことが好ましく、あらかじめ所定の温度に調節さ
れた熱処理炉内にフィルムを移送することが好ましい。In the present invention, after the heat treatment (a), the heat treatment (b) is immediately performed under the condition that the expressions (1) and (2) are satisfied.
It is preferable to carry out the above, and it is preferable to transfer the film into a heat treatment furnace adjusted to a predetermined temperature in advance.
【００１８】フィルムの製造方法としては、公知の任意
の方法を利用することができる。すなわち、各層を構成
する数種の樹脂を別々の押出機中で溶融し、フィードブ
ロック法により多層構造に重ね合わせた後、ダイスより
押し出す方法や、溶融した数種の樹脂をマルチマニホー
ルドダイス中で多層構造に重ね合わせて押し出す方法、
各層を構成する数種の樹脂層をラミネートして貼り合わ
せる方法などが挙げられる。Any known method can be used as the method for producing the film. That is, several kinds of resins constituting each layer are melted in separate extruders, and after superposing in a multi-layer structure by a feed block method, a method of extruding from a die or several kinds of melted resins in a multi-manifold die. A method of extruding by stacking on a multilayer structure,
Examples include a method of laminating and bonding several types of resin layers forming each layer.
【００１９】延伸方法としては、テンター式同時二軸延
伸法、テンター式逐次二軸延伸法、チューブラー式同時
二軸延伸法を用いることができる。As the stretching method, a tenter simultaneous biaxial stretching method, a tenter sequential biaxial stretching method, and a tubular simultaneous biaxial stretching method can be used.
【００２０】延伸後の熱処理方法としては、熱風をフィ
ルムに吹き付ける方法、赤外線をフィルムに照射する方
法、マイクロ波をフィルムに照射する方法、およびこれ
らの組合せを用いることができるが、熱風をフィルムに
吹き付ける方法が均一に精度良く加熱できるので最も好
ましい。As the heat treatment method after stretching, a method of blowing hot air to the film, a method of irradiating the film with infrared rays, a method of irradiating the film with microwaves, and a combination thereof can be used. The spraying method is the most preferable because it enables uniform and accurate heating.
【００２１】本発明における多層延伸フィルムの厚みは
特に制限はないが、フレキシブルな包材として使用する
場合、通常１〜50μm の厚みとされる。The thickness of the multilayer stretched film in the present invention is not particularly limited, but when it is used as a flexible packaging material, it is usually 1 to 50 μm.
【００２２】本発明における多層延伸フィルムを包装袋
用として使用する場合、ヒートシール性を付与したり、
ガスバリヤー性や機械的強度を高めるために、ポリプロ
ピレン、ポリエチレン、ポリビニルアルコールなどのプ
ラスチックフィルムや紙、アルミニウムなどと積層して
用いることができる。When the multilayer stretched film of the present invention is used for a packaging bag, it is endowed with heat sealability,
In order to enhance the gas barrier property and the mechanical strength, it can be used by being laminated with a plastic film such as polypropylene, polyethylene, polyvinyl alcohol or the like, paper, aluminum or the like.
【００２３】[0023]
【実施例】以下、実施例により本発明をさらに具体的に
説明する。なお、実施例及び比較例の評価に用いた原料
及び測定法は次のとおりである。EXAMPLES The present invention will be described in more detail below with reference to examples. In addition, the raw materials and the measuring methods used in the evaluation of the examples and comparative examples are as follows.
【００２４】（１）原料 ナイロン６：ユニチカ社製 A1030BRF を用いた。 ＥＶＯＨ：クラレ社製エバールを用いた。使用したＥＶ
ＯＨの銘柄と各々の性状を表１に示した。(1) Raw Material Nylon 6: A1030BRF manufactured by Unitika Ltd. was used. EVOH: Eval manufactured by Kuraray Co., Ltd. was used. EV used
The OH brands and their properties are shown in Table 1.
【００２５】[0025]
【表１】 [Table 1]
【００２６】（２）測定法 結晶化ピーク温度ＴC ：パーキンエルマー社製示差走査
熱量計（ DSC−７型）を用い、室温より昇温を始め、試
料の融点＋20℃まで10℃／分で昇温し、その温度で５分
間ホールドした後、10℃／分で降温し、現れた結晶化ピ
ークのピークトップから求めた。(2) Measuring method Crystallization peak temperature T C : Using a differential scanning calorimeter (DSC-7 type) manufactured by Perkin Elmer Co., Ltd., the temperature was started to rise from room temperature, and the sample melting point was + 20 ° C. at 10 ° C./min. The temperature was raised, the temperature was held for 5 minutes, the temperature was lowered at 10 ° C./min, and the peak top of the crystallization peak that appeared was determined.
【００２７】熱水処理耐性：多層延伸フィルムに、ドラ
イラミネート法により無延伸ポリプロピレンフィルム
（ＣＰＰ、東レ社製トレファンＺＫ−93Ｋ、厚み60μm
）をラミネートした。このラミネートフィルムのＣＰ
Ｐ面同士を重ね合わせた後、３方をヒートシールした袋
に水50mlを充填し、残る一方をヒートシールし、縦14cm
×横12cmの長方形の充填袋を製作した。次に、この充填
袋を 100℃×30分で熱水処理し、外観を観察し、以下の
ように評価し、評価ＡおよびＢを合格とし、評価Ｃを不
合格とした。 Ａ … 良好 Ｂ … 充填袋の表面積の５％以下に外観不良がみられ
る。 Ｃ … 充填袋の表面積の５％以上に外観不良がみられ
る。Resistance to hot water treatment: A non-stretched polypropylene film (CPP, Trefan ZK-93K manufactured by Toray Industries, Inc., thickness 60 μm) on a multilayer stretched film by a dry lamination method.
) Was laminated. CP of this laminated film
After overlapping the P sides, 50 ml of water was filled in a bag that was heat-sealed on three sides, and the remaining one was heat-sealed to a height of 14 cm.
× A rectangular filling bag with a width of 12 cm was manufactured. Next, this filled bag was subjected to hot water treatment at 100 ° C. for 30 minutes, the appearance was observed, and the following evaluations were made. Evaluations A and B were passed, and evaluation C was not passed. A ... Good B ... Poor appearance is observed in 5% or less of the surface area of the filling bag. C ... 5% or more of the surface area of the filling bag has a poor appearance.
【００２８】実施例１ ３層共押出Ｔダイを用いて、第１押出機よりＥＶＯＨ
（クラレ社製EP−F101BZ）を 210℃で押し出し、第２押
出機よりナイロン６を 265℃で押し出し、ナイロン６／
ＥＶＯＨ／ナイロン６の構成の多層未延伸シートをダイ
スより押し出し、表面温度18℃に温調した冷却ドラム上
に密着させて急冷し、厚さ 150μm の未延伸シートを得
た。得られたシートの端部をテンター式同時二軸延伸機
のクリップで把持し、温度70℃で、延伸倍率が、縦 3.0
倍、横 3.3倍で同時二軸延伸した。次に、210 ℃で 4.0
秒間の熱処理〔熱処理（ａ）〕を施した後、直ちに、 1
70℃の雰囲気下で10.2秒間の熱処理〔熱処理（ｂ）〕を
行い、90℃で 2.0秒間フィルムを冷却した後、巻取機で
巻取り、ナイロン６／ＥＶＯＨ／ナイロン６＝ 5.0／5.
0 ／5.0 μm の厚みの多層延伸フィルムを得た。得られ
た多層延伸フィルムの評価結果を表２に示した。Example 1 A three-layer coextrusion T-die was used to produce EVOH from the first extruder.
(Kuraray EP-F101BZ) was extruded at 210 ° C, and nylon 6 was extruded from the second extruder at 265 ° C.
A multi-layer unstretched sheet of EVOH / nylon 6 was extruded from a die, brought into close contact with a cooling drum whose surface temperature was adjusted to 18 ° C., and rapidly cooled to obtain an unstretched sheet having a thickness of 150 μm. Hold the edge of the obtained sheet with a clip of a tenter type simultaneous biaxial stretching machine, and at a temperature of 70 ° C, the stretching ratio is 3.0
Simultaneously biaxially stretched at 3 times and laterally 3.3 times. Then 4.0 at 210 ° C
Immediately after 1 second heat treatment [heat treatment (a)], 1
Heat treatment [heat treatment (b)] for 10.2 seconds in an atmosphere of 70 ° C, cool the film at 90 ° C for 2.0 seconds, and wind with a winder, nylon 6 / EVOH / nylon 6 = 5.0 / 5.
A multilayer stretched film having a thickness of 0 / 5.0 μm was obtained. Table 2 shows the evaluation results of the obtained multilayer stretched film.
【００２９】実施例２〜５、比較例１〜４ 熱処理温度Ｔと処理時間ｔを表２に示す値に変更した外
は、実施例１と同様の方法で多層延伸フィルムを得た。
得られた多層延伸フィルムの評価結果を表２に示した。Examples 2 to 5 and Comparative Examples 1 to 4 Multilayer stretched films were obtained in the same manner as in Example 1 except that the heat treatment temperature T and the treatment time t were changed to the values shown in Table 2.
Table 2 shows the evaluation results of the obtained multilayer stretched film.
【００３０】比較例５ 熱処理（ａ）の温度を表２に示す値とした外は、実施例
２と同様の方法で多層延伸フィルムを得た。得られた多
層延伸フィルムの評価結果を表２に示した。Comparative Example 5 A multilayer stretched film was obtained in the same manner as in Example 2 except that the temperature of the heat treatment (a) was changed to the values shown in Table 2. Table 2 shows the evaluation results of the obtained multilayer stretched film.
【００３１】実施例６〜８、比較例６〜８ ＥＶＯＨの銘柄、熱処理温度Ｔ、及び処理時間ｔを表２
に示すとおりに変更した外は、実施例１と同様の方法で
多層延伸フィルムを得た。得られた多層延伸フィルムの
評価結果を表２に示した。Examples 6 to 8 and Comparative Examples 6 to 8 Table 2 shows the brands of EVOH, the heat treatment temperature T, and the treatment time t.
A multilayer stretched film was obtained in the same manner as in Example 1 except that the changes were made as shown in. Table 2 shows the evaluation results of the obtained multilayer stretched film.
【００３２】[0032]
【表２】 [Table 2]
【００３１】[0031]
【発明の効果】本発明によれば、ＥＶＯＨの優れたガス
バリヤー性、透明性を損なわずに、熱水処理耐性を有す
る多層延伸フィルムを提供することができるので、各種
の包装用袋の材料として幅広い応用が可能である。EFFECTS OF THE INVENTION According to the present invention, since a multilayer stretched film having resistance to hot water treatment can be provided without impairing the excellent gas barrier property and transparency of EVOH, various packaging bag materials can be provided. As a wide range of applications are possible.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ２９Ｋ 55:00 77:00 Ｂ２９Ｌ 9:00 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location B29K 55:00 77:00 B29L 9:00
Claims (2)
（ＥＶＯＨ）からなる層と、融点がＥＶＯＨよりも高い
熱可塑性樹脂（Ｐ）からなる層の少なくとも２層からな
る多層延伸フィルムに、ＥＶＯＨの融点以上、Ｐの融点
未満の温度で熱処理（ａ）を行った後に、下記式
（１）、（２）を満足する条件で熱処理（ｂ）を行うこ
とを特徴とする多層延伸フィルムの製造法。 ｔ≧ 0.00889（Ｔｃ−Ｔ）2 − 0.373（Ｔｃ−Ｔ）＋ 5.1 （１） −19≦Ｔｃ−Ｔ≦ 61 （２） ただし、Ｔは熱処理（ｂ）の温度（℃）、ｔは処理時間
（秒）、Ｔｃは示差走査熱量計で10℃／分の速度で降温
した場合のＥＶＯＨの結晶化ピーク温度（℃）を示す。1. A multilayer stretched film comprising at least two layers, a layer made of a saponified ethylene-vinyl acetate copolymer (EVOH) and a layer made of a thermoplastic resin (P) having a melting point higher than that of EVOH. A method for producing a multilayer stretched film, which comprises performing heat treatment (a) at a temperature not lower than the melting point and lower than the melting point of P, and then performing heat treatment (b) under conditions satisfying the following formulas (1) and (2). . t ≥ 0.00889 (Tc-T) 2 -0.373 (Tc-T) + 5.1 (1) -19 ≤ Tc-T ≤ 61 (2) where T is the temperature of the heat treatment (b) (° C) and t is the treatment time. (Sec), Tc represents the peak crystallization temperature (° C.) of EVOH when the temperature was lowered with a differential scanning calorimeter at a rate of 10 ° C./min.
１記載の多層延伸フィルムの製造法。2. The method for producing a multilayer stretched film according to claim 1, wherein P is poly-ε-capramide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2892296A JP3650454B2 (en) | 1996-02-16 | 1996-02-16 | Manufacturing method of multilayer stretched film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2892296A JP3650454B2 (en) | 1996-02-16 | 1996-02-16 | Manufacturing method of multilayer stretched film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09220761A true JPH09220761A (en) | 1997-08-26 |
| JP3650454B2 JP3650454B2 (en) | 2005-05-18 |
Family
ID=12261905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2892296A Expired - Lifetime JP3650454B2 (en) | 1996-02-16 | 1996-02-16 | Manufacturing method of multilayer stretched film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3650454B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001341198A (en) * | 2000-06-02 | 2001-12-11 | Unitika Ltd | Biaxially stretched polyamide film and method for manufacturing the same |
| JP2007283570A (en) * | 2006-04-14 | 2007-11-01 | Kyoraku Co Ltd | Manufacturing process of biaxially stretched multilayer film |
-
1996
- 1996-02-16 JP JP2892296A patent/JP3650454B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001341198A (en) * | 2000-06-02 | 2001-12-11 | Unitika Ltd | Biaxially stretched polyamide film and method for manufacturing the same |
| JP2007283570A (en) * | 2006-04-14 | 2007-11-01 | Kyoraku Co Ltd | Manufacturing process of biaxially stretched multilayer film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3650454B2 (en) | 2005-05-18 |
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