JPS60120050A - 熱収縮性筒状積層フイルム - Google Patents

熱収縮性筒状積層フイルム

Info

Publication number
JPS60120050A
JPS60120050A JP58228116A JP22811683A JPS60120050A JP S60120050 A JPS60120050 A JP S60120050A JP 58228116 A JP58228116 A JP 58228116A JP 22811683 A JP22811683 A JP 22811683A JP S60120050 A JPS60120050 A JP S60120050A
Authority
JP
Japan
Prior art keywords
layer
laminated film
heat
melting point
film
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.)
Granted
Application number
JP58228116A
Other languages
English (en)
Other versions
JPS6410183B2 (ja
Inventor
大屋　正樹
西本　由治
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kureha Corp
Original Assignee
Kureha Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=16871450&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=JPS60120050(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Kureha Corp filed Critical Kureha Corp
Priority to JP58228116A priority Critical patent/JPS60120050A/ja
Priority to US06/675,307 priority patent/US4732795A/en
Priority to EP84308302A priority patent/EP0149321B1/en
Priority to DE8484308302T priority patent/DE3472655D1/de
Publication of JPS60120050A publication Critical patent/JPS60120050A/ja
Priority to US07/130,528 priority patent/US4883693A/en
Publication of JPS6410183B2 publication Critical patent/JPS6410183B2/ja
Granted legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • 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
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
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    • B29C48/14—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration
    • B29C48/147—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration after the die nozzle
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Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。

Description

【発明の詳細な説明】 本発明は、塩化ビニリデン系樹脂層をバリヤ一層とし、
特定の厚みのポリアミドもしくは熱可囮性ポリエステル
層を少くとも一層含む適度な剛性と良好な延伸性を有す
る熱収縮性筒状積層フィルムに関する。
形状が不揃いで、かつ不規則な食品の包装には、一般に
熱収縮包装が用いられる。又これらの包装には長時間の
保存期間がめられる為、ガスバリヤ−性を必要とする。
ガスバリヤ−性のある熱収縮性フィルムとしては周知の
如く塩化ビニリデン系樹脂（ＰＶＤＣ）単独フィルムが
用いられてきた。しかしＰＶＤＣ単独フイルムは低温時
の機械的強度が小なため、ＰＶＤＣとポリオレフィン樹
脂の積層フィルムの開発が行なわれてきた。このような
フィルムとして、例えば特開昭５８−１２８８２１号は
特定のエチレン−酢酸ビニル共重合体（以後ＥＶＡと略
称する）からなる外層を有するＰＶＤＣの複合フィルム
であって、これらの問題を解決したものではあったが、
フィルムの剛性かや一不足するため食品包装時などの作
業性は必らずしも満足し得るものではなかった。
本発明者等は更にこれらの点を改良すべく鋭意検討を重
ねた結果、ポリアミドもしくは熱可塑性ポリエステルを
層構成に加えることによりこの目的を達成した。すなわ
ち、本発明による筒状積層フィルムはガスバリヤ一層が
６μ以上で全層の厚みに対して３０％以下のＰＶＤＣ，
両外層がオレフィン系樹脂からなり、内層に全層の厚み
に対して５〜４０チの厚みをもつ少くとも１層の結晶融
点が２４０℃以下を有するポリアミドもしくは熱可塑性
ポリエステルを有し、且つ夫々の眉間に接着剤層を有す
るものである。
本発明の熱収縮性筒状フィルムは、ガスバリヤ一層であ
るＰＶＤＣ層が比較的厚いので製造時ダイ流路内での滞
留時間が短かく、熱分解が起り難いという製造上の長所
がある。更に外層のオレフィン系樹脂とＰＶＤＣ層の間
に少くとも１層の特定厚みのポリアミド層もしくは熱可
塑性ポリエステル層を含むので適当な剛性を有し、包装
時に内容物によりフィルムが伸びる等の作業性の困難性
が克服されしかも特開昭５８−１２８８２１号に比し均
一性のよい延伸性を得ることができた。又、勿論、ガス
バリヤ−性にも優れている。
本発明でバリヤ一層として使用されるＰ’ＶＤＣは６５
〜９５重量％の塩化ビニリデン及びこれと共重合可能な
不飽和単量体の少なくとも１種の５〜３５重量％からな
る共重合体である。共重合可能な単量体としては、例え
ば塩化ビニル、アクリロニトリル、アクリル酸アルキル
エステル（アルキル基炭素数１〜１８個）等が包含され
る。これらの白基化ビニリデンー塩化ビニル共重合体が
一般的である。このＰＶＤＣ中には必要に応じて、少量
の可塑剤、安定剤を含有させてもよい。これらの添加剤
は当業者には公知であり、ジオクチル・アジペート、エ
ポキシ化大豆油等が代表的なものである。
ＰＶＤＣ層の厚みは６μ以上で全層の厚みに対して３０
％以下であることが必要である。６μ未満ではダイ内で
ポリアミドもしくは熱可塑性ポリエステルと積層して押
出す際ダイ流路内での滞留時間が長くなってＰＶＤＣが
熱分解し共押出が困難になる。又、全層厚みの３０チを
越えると積層フィルムの低温時の衝撃強度が低下する。
両外層を構成するオレフィン系樹脂としては例えば高密
度、中密度、低密度の各ポリエチレン、アイオノマー、
ＥＶＡ、エチレンとアクリル酸エステルの共重合体、エ
チレン−プロピレン共重合体、ポリプロピレン、エチレ
ンとαφオレフィンの共重合体であるいわゆる低密度線
状ポリエチレン（ＬＬＤＰＥ）ポリブテン等が単独もし
くは混合して用いられる。これらのオレフィン系樹脂の
うち、すぐれた延伸性の点から好ましい態様は下記の通
りである。
１）ＥＶＡ（結晶融点８０〜１０３℃のもの）を両外層
もしくは外層のうち１層に使用する。
（１）外層の１層が１）のＢＶＡであり、他の、外層が
ＬＬＤＰＩ　（結晶融点１１０〜１３０℃のもの）であ
る。
１１１）外層の１層力月）のＢＶＡであり他の外層が上
述（７）　ＬＬＤＰＢ　４　Ｇ　重量９６以下ト１）ｙ
）Ｆｉｖ人６０重量慢以上からなる混合物である。
１Ｖ）両外層の各々が上述のＬＬＤＰＦ！４０重量％以
下とｌ′）０）Ｅ　ＶＡ　６０重量％以上からなる混合
物である。
このうちｌ）　、　ＩＩ）　、　ｉｉＤが透明性耐衝撃
性の点から特に好ましい。
本願の特色はポリアミドもしくは熱可塑性ポリエステル
を内層に少くとも１層使用することにあり、この適度な
剛性と延伸性を有する層を備えることによりオレフィン
系樹脂とＰＶＤＣからなる積層フィルムの延伸性及びフ
ィルム剛性が改良される。
ポリアミドとしては結晶融点が２４０℃以下好ましくは
２２０℃を有するものが用いられ、例えばナイロン６−
６６（６，６６の共重合体χナイロン６１０（ポリへキ
サメチレンセバケート）、ナイロン６１２（ポリへキサ
メチレンラウレート）、ナイロン１１（１１−アミノウ
ンデカン酸縮合体）、ナイロン１２（ラウロラクタムの
開環重合体）、ナイロン６（ポリカプラミド）等が使用
される。熱可塑性ポリエステルとしては同様に結晶融点
が２４０℃以下好ましくは２２０℃もしくは融点の存在
しないものであり、酸成分の芳香族２塩基酸の１種以上
と脂肪族２塩基酸の１糧以上の残基からなり、グリコー
ル成分が脂肪族グリコール、脂環族グリコール又は芳香
族グリコールから選ばれたグリコール残基からなる共重
合ポリエステルが望ましく使用される。これらのエステ
ルとしては例えば商品名バイロン、ペルプレン〔東洋紡
■製品〕、ハイチル〔グツドイヤー■製品〕、ＰＥＴ−
Ｇ〔イーストマンコダック■製品〕等があげられる。
尚、本発明において結晶融点は差動走査型熱量計（パー
キンエルマー社ＪＩＩＢ型）を用い、サンプル８■、昇
温速度８℃／分で測定して得られた融解曲線の最大値を
示す温度である。ポリアミドもしくは熱可塑性ポリエス
テルは結晶融点が２４０℃を越えると共押出温度が高（
なりＰＶＤＣと共押出しが困難となる。又、ポリアミド
もしくは熱可塑性ポリエステル層が２層以上あるときは
相互に同種のものであっても文具ったものであってもよ
い。この層は全層の厚みに対し５〜４０チより好ましく
は５〜２０チの厚みをもつことが必要である。２層以上
ある時はその総計の厚みが５〜４０チになる。層厚みが
５％未満では延伸性、フィルム剛性に寄与し得ないし、
４０％を越えるとＰＶＤＣとの共押出が困難となる。Ｐ
ＶＤＣとの共押出性からより好ましくは２０１以下が望
ましい。
接着層を形成する材料としては酢酸ビニル含量１３〜２
８％のＥＶＡ、アクリル酸エステル含量１３〜２８チの
エチレン−アクリル酸エステル樹脂を含有するＦｉＶＡ
、エチレンアクリル酸エステル樹脂の不飽和カルボン酸
変性物、もしくは該酸変性物の金属変性物等が好ましく
使用される。更に好ましくは該エチレン−アクリル酸エ
ステル樹脂の不飽和カルボン酸変性物もしくは該変性物
の金属変性物である。これらの接着層はＰＶＤＣ層、オ
レフィン系樹脂層、ポリアミドもしくは熱可塑性ポリエ
ステル層のそれぞれの層間に設けられる。
接着層の厚みは０．５〜３μ、全層の厚みは２０〜１２
０μであるととが好ましい。
本発明の筒状積層フィルムは積層数に応じた押出機を用
いて環状ダイスを使用して筒状に押出される。本発明で
使用される環状ダイスの１例として第１図に全層の会合
部分を示す模式図を示す。第１図で７は複合流であり、
例えば１はオレフィン系樹脂、２はＰＶＤＣｌ　４はポ
リアミドもしくは熱可塑性ポリエステル、６はオレフィ
ン系樹脂８は接着性樹脂の各樹脂の流路を示す。第１図
のようにポリアミドもしくは熱可塑性ポリエステルの流
路の両側に断熱空間３゜５を設けることが好ましく、こ
の断熱空間を設けることによりポリアミド、熱可塑性ポ
リエステルが高温に押出されてもＰＶＤＣ層などに直接
温度が伝達されることを防ぐことができ、ＰＶＤＣ層な
ど比較的熱分解し易い樹脂と共押出することか可能とな
る。平板状（Ｔ−グイ）フィルムでは、このようなポリ
アミド層もしくは熱可塑性ポリエステル層と共押出する
と両端部分でＰＶＤＣが分解し易いので適当でない。積
層順はオレフィン系樹脂が間外層にある限り任意である
が、筒状の最外層から最内層ヘオレフィン系樹脂、接着
剤、ＰＶＤＣ，接着剤、ポリアミドもしくは熱可塑性ポ
リエステル、接着剤、オレフィン系樹脂の順であること
が熱分解せず連続運転できる点で望ましい。
このようにして押出された筒状の積層物は一般常法に従
い２軸延伸インフレーシヨン法により各々延伸され所望
の熱収縮フィルムが得られる。
本発明で得られた熱収縮性積層フィルムはガスバリヤ−
性及び適度な剛性をもつため、食品の包ｉｔこ特に好適
に使用される。以下実施例につき説明するが、本発明は
本発明特許請求の範囲内である限り本実施例により限定
されるものではない。
実施例 第１表記載のＰＶＤＣ，接着剤樹脂、ポリアミド、熱可
塑性ポリエステル、オレフィン系樹脂を複数の押出機で
別々に押出し、・溶融された材料を共押出し、実施例１
〜５は第１図にあるような断熱空間を有する環状ダイス
（但し比較例１〜３は第１図のような断熱空間のない通
常の環状ダイス）に流入しここで積層物とする。該ダイ
スから流出した積層物の筒状体は１５〜２５℃の冷却槽
で冷却され扁平幅１２０　Ｍ、厚さ５４０μの筒状とす
る。冷却槽中の筒状体の中には、内面同志密着防止のた
め、大豆油を封入しである。次に第３表に示された延伸
温度となる様に、調節された熱水槽中を、前記筒状体を
２０　ｍ　７分の速度で送りながら、約１２秒加熱しｓ
　２０　ｍ　７分の回転速度の第１ニツプローラーを通
過させる。筒状体は常温で冷却されながら、６０ｍ／分
で回転する第２のニップローラーを通過する迄に、長手
方向に３倍延伸されながら、筒状体内に送られる空気に
より、筒状体の直径に対し、３倍に膨張され、横方向に
延伸された。得られた２軸延伸フイルムの折り径は約３
５０１ｍ１厚さ約６０μであった。
第１表に実施例、比較例で使用した重合体の物性、第２
表にフィルムの物性試験方法、第３表に積層フィルムの
層構成及びフィルムの物性試験結果を示す。
肴、塩化ビニリデン／塩化ビニル＝７０／３０（重量比
）、エポキシ化大豆油ＩＰＨＲ 餐、エチレン−アクリル酸エステル樹脂の不飽和カルボ
ン酸変性物日本石油化学■製品 第　２　表 延伸性　○；特によくフィルム厚みむら３０％未満 Δ；延伸はできるが、フィルム厚みむ ら３０〜５０％ ×：延伸はできるが安定性がない、フ ィルム厚みむら５０％を越える フィル５：包装時に内容物によりフィルムが伸びるなど
の作業性不良が生じ難 い。
Δ；作業性不良となる場合もある Ｘ：作業性不良となり易い 共押出性○；共押出が連続１０時間以上可能であった。
Δ；共押出の連続時間が１０時間未満 であった。
Ｘ；共押出が連続１時間以内しかでき なかった。
第３表の実施例１〜５から明らかなように本発明の熱収
縮性フィルムは延伸性にすぐれ、共押出性もよいので製
造が容易であり、しかも得られたフィルムは適度なフィ
ルム剛性を有するため包装時の作業性が優れている。比
較例１は共押出性はよいがポリアミドもしくは熱可塑性
ポリエステルを含まないため、フィルム剛性が劣り作業
性が不良となる。又比較例２はポリアミドを内層に有し
ているもののＰＶＤＣ層があまりに薄いため共押出時に
ＰＶＤＣの分解を生じ積層フィルムを得ることができな
い。更に比較例３は熱可塑性ポリエステル層が全層の厚
みに対し４５チと厚いため共押出性が劣りＰＶＤＣが分
解気味となり延伸性も不良で良好な積層フィルムを得る
ことができない。
【図面の簡単な説明】
第１図は環状ダイスの模式図で全層の会合部分を示した
説明図である。 １．６．、・オレフィン樹脂流路、２・・・ＰＶＤＣ流
路、４ポリアミド又は熱可塑性ポリエステル流路、７・
・・複合流、３，５・・・断熱空間。 ＋１ｊ、邦人弁理出合　村　フＩ 第１図

Claims (3)

    【特許請求の範囲】
  1. （１）ガスバリヤ一層が６μ以上で全層の厚みに対して
    ３０チ以下の塩化ビニリデン系樹脂、両外層がオレフィ
    ン系樹脂からなり、内層釜こ全層の厚みに対して５〜４
    ０％の厚みをもつ少くとも１層の結晶融点が２４０℃以
    下を有するポリアミドもしくは熱可塑性ポリエステルを
    有し、且つ夫々の層間に接着剤層をもつことからなる熱
    収縮性筒状積層フィルム。
  2. （２）外層の少くとも１層が、８０〜１０３℃の結晶融
    点を有するエチレン−酢酸ビニル共重合体からなる特許
    請求の範囲第１項記載の熱収縮性筒状積層フィルム。
  3. （３）外層の１層が、結晶融点１１０〜１３０℃を有す
    る線状低密度ポリエチレン又は該線状低密度ポリエチレ
    ン４０重量−以下と８０〜１０３℃の結晶融点を有する
    エチレン−酢酸ビ斗ル共重合体６０重量係以上とからな
    る混合物である特許請求の範囲第２項記載の熱収縮性筒
    状積層フィルム。
JP58228116A 1983-12-02 1983-12-02 熱収縮性筒状積層フイルム Granted JPS60120050A (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP58228116A JPS60120050A (ja) 1983-12-02 1983-12-02 熱収縮性筒状積層フイルム
US06/675,307 US4732795A (en) 1983-12-02 1984-11-27 Heat-shrinkable laminate tubular film
EP84308302A EP0149321B1 (en) 1983-12-02 1984-11-29 Heat-shrinkable laminate tubular film and process for producing it
DE8484308302T DE3472655D1 (en) 1983-12-02 1984-11-29 Heat-shrinkable laminate tubular film and process for producing it
US07/130,528 US4883693A (en) 1983-12-02 1987-12-09 Heat-shrinkable laminate tubular film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58228116A JPS60120050A (ja) 1983-12-02 1983-12-02 熱収縮性筒状積層フイルム

Publications (2)

Publication Number Publication Date
JPS60120050A true JPS60120050A (ja) 1985-06-27
JPS6410183B2 JPS6410183B2 (ja) 1989-02-21

Family

ID=16871450

Family Applications (1)

Application Number Title Priority Date Filing Date
JP58228116A Granted JPS60120050A (ja) 1983-12-02 1983-12-02 熱収縮性筒状積層フイルム

Country Status (4)

Country Link
US (2) US4732795A (ja)
EP (1) EP0149321B1 (ja)
JP (1) JPS60120050A (ja)
DE (1) DE3472655D1 (ja)

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US4732795A (en) 1988-03-22
DE3472655D1 (en) 1988-08-18
JPS6410183B2 (ja) 1989-02-21
US4883693A (en) 1989-11-28
EP0149321A1 (en) 1985-07-24
EP0149321B1 (en) 1988-07-13

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