JPH08323859A - Heat-shrinkable polyester film and production thereof - Google Patents
Heat-shrinkable polyester film and production thereofInfo
- Publication number
- JPH08323859A JPH08323859A JP13532995A JP13532995A JPH08323859A JP H08323859 A JPH08323859 A JP H08323859A JP 13532995 A JP13532995 A JP 13532995A JP 13532995 A JP13532995 A JP 13532995A JP H08323859 A JPH08323859 A JP H08323859A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- film
- shrinkage
- polyester film
- shrinkable polyester
- 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
Links
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、熱収縮性ポリエステル
フィルムに関し、より詳しくは、容器類の被覆用あるい
は結束用、集積物の包装用等に使用される熱収縮性ポリ
エステルフィルムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-shrinkable polyester film, and more particularly to a heat-shrinkable polyester film used for covering or bundling containers, wrapping integrated products and the like.
【０００２】[0002]
【従来の技術】熱収縮性プラスチックフィルムを素材と
して形成されるチューブ状体は、従来より、例えば容
器、瓶（プラスチックボトルを含む）、缶棒状物（パイ
プ、棒、木材、各種棒状体）等（以下、容器類と略す）
の被服用あるいは結束用として、表示、保護、結束、商
品価値向上等を目的として、特にこれらの容器のキャッ
プ、肩部、胴部等の全面または一部の被覆のほか、箱、
板、瓶、棒、ノート等の集積物の包装、或いはスキンパ
ックのように被覆状物を密着させて包装する分野等にお
いて広く利用されている。このような熱収縮性プラスチ
ックフィルムは、収縮性および収縮応力を利用した用途
展開が期待されている。上記の用途には、従来より、ポ
リ塩化ビニル、ポリスチレン、ポリエチレン、塩酸ゴム
等の熱収縮性プラスチックのフィルムが使用され、この
フィルムをチューブ状体に成形し、これを容器類を被覆
または集積物を包装した後、フィルムを熱収縮させてい
た。これらのフィルムは、食品、飲料等の包装用として
用いる場合には、通常ボイル処理、レトルト処理等の加
熱殺菌が施される。2. Description of the Related Art Conventionally, tubular bodies formed of a heat-shrinkable plastic film are, for example, containers, bottles (including plastic bottles), can rods (pipes, rods, wood, various rods), etc. (Hereafter, abbreviated as containers)
For the purpose of clothing, binding, labeling, protection, bundling, improving the commercial value, etc., in particular, in addition to covering all or part of the cap, shoulder, body, etc. of these containers, boxes,
It is widely used in the field of packaging a stack of plates, bottles, sticks, notebooks, or the like, or in the field of closely packing a covering material such as a skin pack. Such a heat-shrinkable plastic film is expected to be used for applications utilizing shrinkage and shrinkage stress. Films of heat-shrinkable plastics such as polyvinyl chloride, polystyrene, polyethylene, and hydrochloric acid rubber have been conventionally used for the above-mentioned applications. The film is formed into a tubular body, which is then coated with a container or an integrated product. After packaging, the film was heat-shrinked. When these films are used for packaging foods, beverages, etc., they are usually subjected to heat sterilization such as boiling treatment and retort treatment.
【０００３】[0003]
【発明が解決しようとする課題】しかし、上記のフィル
ムは耐熱性が悪いため、上記の加熱処理を行うと、フィ
ルムが溶融または破裂してフィルム状体を維持すること
ができないという問題があった。また上記フィルムは接
着性が悪いため、フィッシュアイ（フィルム内の添加剤
やポリマーのゲル状物等の小球状の固まり）が存在する
フィルムを印刷すると、インクが転移不良となって印刷
ピンホール（微小凹凸）が発生する。たとえ良好に印刷
できても、上記フィルムは耐薬品性が悪いため、印刷後
にフィルムが常温で収縮して印刷ピッチに寸法変化をも
たらすという問題があった。However, since the above-mentioned film is poor in heat resistance, there is a problem that the above-mentioned heat treatment causes the film to melt or rupture and the film-like body cannot be maintained. . Further, since the above-mentioned film has poor adhesiveness, when a film having fish eyes (small spherical lumps such as additives in the film and polymer gel-like substances) is printed, the ink does not transfer well and print pinholes ( Minute irregularities) occur. Even if good printing is possible, there is a problem that the film has poor chemical resistance, so that the film shrinks at room temperature after printing and causes a dimensional change in the printing pitch.
【０００４】一方、上記の欠点が大幅に改良されたポリ
エステル系熱収縮フィルムは、最近大いに注目されてい
る。しかし、通常、熱収縮はボトル等の容器に熱収縮性
フィルムを装着し、これを熱収縮させて固定させる工程
（以下、熱収縮トンネルと略す）により行われるが、熱
収縮トンネル自体の温度ムラおよび容器表面の温度ムラ
があるために、熱収縮フィルムに収縮ムラが発生する。
さらにポリエステル系熱収縮フィルムは、上記のポリ塩
化ビニル、ポリスチレン、ポリエチレン、塩酸ゴム等の
熱収縮性プラスチックフィルムと比べて熱収縮速度が大
きいという問題がある。熱収縮速度が大きいとフィルム
の収縮ムラが生じて商品価値が大幅に低くなる。例え
ば、このフィルムを瓶用のシュリングラベルとして用い
た場合、熱収縮速度が大きすぎると収縮率が最も高くな
る肩部に収縮ムラが集中し、かつラベル内部からの空気
の逃げがスムーズに進行せずに気泡が溜まる等の問題が
生じる。このような収縮ムラのあるラベルを使用すると
印刷時の濃度ムラにつながり、製品の美観が著しく悪く
なる。また、ポリエステル系熱収縮フィルムは、上記の
ポリ塩化ビニル、ポリスチレン、ポリエチレン、塩酸ゴ
ム等の熱収縮性プラスチックフィルムと比べて耐熱性が
良好であり、製品をボイル処理あるいはレトルト処理し
てもフィルムの溶融または破裂がないが、これらの処理
により収縮応力がなくなって２次たるみが生じ、商品価
値が低くなるという問題があった。本発明は、上記の欠
点を解決しようとするもので、その目的は、適度な収縮
速度を有して収縮ムラがなく、耐熱性が良好で、ボイル
処理やレトルト処理を施しても２次たるみのなく、印刷
性も良好な熱収縮ポリエステルフィルムを提供するもの
である。On the other hand, a polyester-based heat-shrinkable film, in which the above-mentioned drawbacks have been greatly improved, has recently received much attention. However, heat shrinkage is usually performed by mounting a heat shrinkable film on a container such as a bottle and then shrinking and fixing it (hereinafter abbreviated as heat shrink tunnel). Also, since there is temperature unevenness on the container surface, shrinkage unevenness occurs in the heat shrinkable film.
Further, the polyester-based heat-shrinkable film has a problem that the heat-shrinkable rate is higher than that of the heat-shrinkable plastic film such as polyvinyl chloride, polystyrene, polyethylene, and hydrochloric acid rubber. If the heat shrinkage rate is high, uneven shrinkage of the film will occur and the commercial value will be significantly reduced. For example, when this film is used as a shrink label for bottles, the shrinkage rate becomes the highest if the heat shrinkage rate is too high. Shrinkage unevenness concentrates on the shoulder and air escapes smoothly from inside the label. Without this, problems such as air bubbles accumulating occur. The use of such a label having shrinkage unevenness leads to density unevenness at the time of printing, and the aesthetic appearance of the product is significantly deteriorated. Further, the polyester-based heat-shrinkable film has better heat resistance than the heat-shrinkable plastic film such as the above polyvinyl chloride, polystyrene, polyethylene, and hydrochloric acid rubber, so that even if the product is boiled or retorted, Although there is no melting or bursting, there is a problem that the shrinkage stress disappears and secondary sagging occurs due to these treatments, and the commercial value decreases. The present invention is intended to solve the above-mentioned drawbacks, and its purpose is to have an appropriate shrinkage rate, no shrinkage unevenness, good heat resistance, and a secondary sag even after boil treatment or retort treatment. And a heat-shrinkable polyester film having good printability.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記目的
を達成するために鋭意検討した結果、本発明に到達し
た。すなわち、本発明の熱収縮性ポリエステルフィルム
は、少なくとも一方向の熱収縮率が３０％以上であり、
かつ少なくとも当該方向の７０〜１２０℃の温度範囲に
おける平均熱収縮速度係数が０．１〜０．５％／秒・℃
の範囲である。好適な実施態様は、上記の熱収縮性ポリ
エステルフィルムは、当該方向と直角方向の熱収縮率が
１０％以下である。また本発明の熱収縮性ポリエステル
フィルムの製造方法は、未延伸ポリエステルフィルム
を、ポリエステルの平均ガラス転移点（Ｔｇ）以上の温
度で、かつ当該方向に２．５〜７．０倍の範囲、当該方
向と直角方向に１．０〜２．０倍の範囲で延伸する工程
を包含する。好適な実施態様は、上記の製造方法は、延
伸が、少なくとも当該方向に数段階に分けて温度を順次
上昇せしめて行われる。好適な実施態様は、上記の製造
方法は、延伸が、少なくとも当該方向に平均ガラス転移
点より高い温度より始めて３段階以上に温度を順次上昇
せしめて行われ、かつ各段階間の温度差が各々２〜８℃
である。The present inventors have arrived at the present invention as a result of extensive studies to achieve the above object. That is, the heat-shrinkable polyester film of the present invention has a heat shrinkage rate of 30% or more in at least one direction,
And at least the average heat shrinkage rate coefficient in the temperature range of 70 to 120 ° C. in the direction is 0.1 to 0.5% / sec · ° C.
Range. In a preferred embodiment, the heat shrinkable polyester film has a heat shrinkage rate of 10% or less in a direction perpendicular to the direction. Moreover, the manufacturing method of the heat-shrinkable polyester film of this invention WHEREIN: The temperature of the average glass transition point (Tg) of polyester or more, and the range of 2.5-7.0 times in the said direction. The step of stretching in the range of 1.0 to 2.0 times in the direction perpendicular to the direction is included. In a preferred embodiment, in the above-mentioned manufacturing method, the stretching is performed by at least gradually increasing the temperature in several steps in the direction. In a preferred embodiment, in the above-mentioned production method, the stretching is performed by starting at a temperature higher than the average glass transition point in at least the direction and gradually increasing the temperature in three or more steps, and the temperature difference between each step is different. 2-8 ° C
Is.
【０００６】以下に本発明を詳細に説明する。本発明の
熱収縮性ポリエステルフィルムは、少なくとも一方向
（以下、主収縮方向と記す）の熱収縮率が３０％以上、
好ましくは４０％以上、特に好ましくは５０％以上であ
る。主収縮方向の熱収縮率が３０％未満の場合には、熱
収縮率が悪いため、熱収縮性フィルムとしての機能を果
たさない。また、主収縮方向と直角方向の熱収縮率は、
好ましくは１５％以下、より好ましくは９％以下、特に
好ましくは７％以下である。この方向の熱収縮率が１５
％を超える場合には、熱収縮が大きくなりすぎて熱収縮
後のフィルムの仕上がりが波うち状となる場合がある。The present invention will be described in detail below. The heat-shrinkable polyester film of the present invention has a heat shrinkage rate of at least 30% in at least one direction (hereinafter referred to as the main shrinkage direction),
It is preferably at least 40%, particularly preferably at least 50%. When the heat shrinkage in the main shrinkage direction is less than 30%, the heat shrinkage is poor and the film does not function as a heat shrinkable film. Also, the heat shrinkage in the direction perpendicular to the main shrinkage direction is
It is preferably 15% or less, more preferably 9% or less, particularly preferably 7% or less. The heat shrinkage in this direction is 15
If it exceeds%, the heat shrinkage may be too large and the finished film after heat shrink may be wavy.
【０００７】さらに本発明の熱収縮性ポリエステルフィ
ルムは、少なくとも主収縮方向の７０〜１２０℃の温度
範囲における平均熱収縮速度係数が０．１〜０．５％／
秒・℃の範囲であり、好ましくは０．１〜０．４％／秒
・℃、特に好ましくは０．１〜０．３５％／秒・℃の範
囲である。上述したように熱収縮トンネル自体の温度ム
ラおよび容器表面の温度ムラがあるため、この平均熱収
縮速度係数は、７０℃、８０℃、９０℃、１００℃、１
１０℃および１２０℃の各々の温度の熱風オーブン中に
おける平均収縮速度（％／秒）を求め、これと熱風オー
ブン温度（℃）との関係より算出される。主収縮方向の
平均熱収縮速度係数が０．１％／秒・℃未満の場合、熱
収縮時に収縮量が不足し、一方、この平均熱収縮速度係
数が０．５％／秒・℃を超える場合、熱収縮時に収縮ム
ラが発生する。また、主収縮方向と直角方向の７０〜１
２０℃の温度範囲における平均熱収縮速度係数は、好ま
しくは０．１％／秒・℃以下である。この方向の平均熱
収縮速度係数が０．１％／秒・℃を超える場合には、ポ
リエステルフィルムの仕上がりの寸法性が悪くなる場合
がある。Furthermore, the heat-shrinkable polyester film of the present invention has an average heat-shrinkage rate coefficient of 0.1 to 0.5% / at least in the temperature range of 70 to 120 ° C. in the main shrinkage direction.
The range is sec. ° C., preferably 0.1 to 0.4% / sec. ° C., and particularly preferably 0.1 to 0.35% / sec. ° C. As described above, since there is temperature unevenness of the heat shrink tunnel itself and temperature unevenness of the container surface, the average heat shrinkage rate coefficient is 70 ° C, 80 ° C, 90 ° C, 100 ° C, 1 ° C.
The average shrinkage rate (% / sec) in the hot air oven at each temperature of 10 ° C. and 120 ° C. is determined, and calculated from the relationship between this and the hot air oven temperature (° C.). When the average coefficient of thermal shrinkage in the main shrinkage direction is less than 0.1% / sec. ° C, the shrinkage amount is insufficient during thermal shrinkage, while the average coefficient of thermal shrinkage exceeds 0.5% / sec. ° C. In this case, shrinkage unevenness occurs during heat shrinkage. Also, 70 to 1 in the direction perpendicular to the main contraction direction
The average heat shrinkage rate coefficient in the temperature range of 20 ° C. is preferably 0.1% / sec · ° C. or less. If the average coefficient of heat shrinkage in this direction exceeds 0.1% / sec · ° C., the finished dimensional properties of the polyester film may deteriorate.
【０００８】本発明の熱収縮ポリエステルフィルムに使
用されるポリエステルは、主としてエチレンテレフタレ
ート繰り返し単位から構成されたポリエステルであり、
テレフタル酸またはその誘導体とエチレングリコールと
の重合反応により製造される。このポリエステルは、好
ましくはエチレンテレフタレート繰り返し単位を５０モ
ル％以上含む熱可塑性ポリエステルである。すなわち、
このポリステルは、ポリエチレンテレフタレートのホモ
ポリマー、あるいはテレフタル酸以外のジカルボン酸成
分、および／またはエチレングリコール以外のジオール
成分、および／またはオキシカルボン酸を含んで構成さ
れた共重合体であり、これらの共重合成分は特に限定さ
れない。また、上記のポリエステルは、単独で使用して
もよく、２種以上を混合して用いてもよい。２種以上を
併用する場合には、ポリエチレンテレフタレートと、テ
レフタル酸および／またはエチレングリコール以外の成
分を含むポリエステルとの組み合わせでも、このポリエ
ステルどうしの組み合わせであってもよい。さらに、こ
れらのポリエステルと、ポリブチレンテレフタレート、
ポリエチレン−２，６−ナフタレート、ポリシクロヘキ
サンジメチルテレフタレート等のホモポリエステルとの
組み合わせであってもよい。２種以上のポリエステルを
併用する場合には、多様な特性を有するフィルムが得ら
れるので好ましい。上記のポリエステルは、常法によ
り、溶融重合させることにより製造されるが、この方法
に限定されるものではなく、その他の重合法を採用して
もよい。このポリエステルの固有粘度は０．３〜１．２
ｄｌ／ｇのものが好ましい。さらに、必要に応じて、上
記のポリエステルに、二酸化チタン、微粒子シリカ、カ
オリン、炭酸カルシウム等の滑剤を配合してもよく、さ
らに、帯電防止剤、劣化防止剤、紫外線防止剤、染料等
の着色剤等を配合してもよい。The polyester used in the heat-shrinkable polyester film of the present invention is a polyester mainly composed of ethylene terephthalate repeating units,
It is produced by a polymerization reaction of terephthalic acid or its derivative and ethylene glycol. This polyester is preferably a thermoplastic polyester containing 50 mol% or more of ethylene terephthalate repeating units. That is,
This polyester is a homopolymer of polyethylene terephthalate or a copolymer composed of a dicarboxylic acid component other than terephthalic acid and / or a diol component other than ethylene glycol, and / or an oxycarboxylic acid. The polymerization component is not particularly limited. The above polyesters may be used alone or in combination of two or more. When two or more kinds are used in combination, polyethylene terephthalate may be combined with polyester containing a component other than terephthalic acid and / or ethylene glycol, or may be a combination of these polyesters. Furthermore, these polyesters, polybutylene terephthalate,
It may be a combination with a homopolyester such as polyethylene-2,6-naphthalate or polycyclohexanedimethyl terephthalate. When two or more polyesters are used in combination, a film having various properties can be obtained, which is preferable. The above polyester is produced by melt polymerization by a conventional method, but it is not limited to this method, and other polymerization methods may be adopted. The intrinsic viscosity of this polyester is 0.3 to 1.2.
Those of dl / g are preferred. Further, if necessary, the above polyester may be blended with a lubricant such as titanium dioxide, fine particle silica, kaolin, calcium carbonate, and the like, and further coloring such as an antistatic agent, an anti-degradation agent, an anti-UV agent, a dye, etc. You may mix agents and the like.
【０００９】上記のポリエステルは、押出し法やカレン
ダー法等の任意の方法によりフィルムに成形した後、延
伸される。延伸方法は特に制限されず、ロール延伸、長
間隙延伸、テンダー延伸、等の遠心方法が採用される。
またその形状面はフラット状、チューブ状のいずれの形
状でもよい。さらに延伸は逐次２軸延伸が有効であり、
その順序はどちらが先でもよい。延伸におけるヒートセ
ットは目的に応じて実施されるが、夏期高温下の寸法変
化を防止するためには、３０〜１５０℃の加熱ゾーンを
約１秒〜３０秒間通すことが好ましい。また延伸処理の
前後に主収縮方向と主収縮方向と直角方向のどちらか一
方向または両方向に最高７０％までの伸長をかけてもよ
い。特に主収縮方向に伸長し、主収縮方向と直角方向に
伸長せずに緩和させるのがよい。この時の延伸倍率は、
主収縮方向では、２．５〜７．０倍、好ましくは３．０
〜６．０倍、特に好ましくは４．０〜５．０倍の範囲で
ある。主収縮方向と直角方向では、１．０〜２．０倍、
好ましくは１．０〜１．８倍、特に好ましくは１．２〜
１．６倍の範囲である。主収縮方向の延伸倍率が２．５
倍未満の場合、熱収縮時に熱収縮量が不足し、一方この
延伸倍率が７．０倍を超える場合、フィルムの製膜時に
フィルムの破断が多くなる。また主収縮方向と直角方向
の延伸倍率が２．０倍を超える場合、主収縮方向と直角
方向の熱収縮が多くなりすぎ、フィルムの仕上がりが波
うち状となる。The above polyester is formed into a film by an arbitrary method such as an extrusion method or a calendar method, and then stretched. The stretching method is not particularly limited, and a centrifugal method such as roll stretching, long gap stretching, tender stretching, or the like is adopted.
The shape surface may be either flat or tubular. Further, sequential biaxial stretching is effective for stretching,
Either order may come first. Although the heat setting in the stretching is carried out according to the purpose, it is preferable to pass a heating zone of 30 to 150 ° C for about 1 to 30 seconds in order to prevent dimensional change under high temperature in summer. Further, before and after the stretching treatment, stretching may be performed up to 70% in either one of the main shrinkage direction and the direction perpendicular to the main shrinkage direction or both directions. In particular, it is preferable to stretch in the main shrinkage direction and relax without stretching in the direction perpendicular to the main shrinkage direction. The draw ratio at this time is
In the main contraction direction, 2.5 to 7.0 times, preferably 3.0
˜6.0 times, particularly preferably 4.0 to 5.0 times. 1.0 to 2.0 times in the direction perpendicular to the main contraction direction,
Preferably 1.0 to 1.8 times, particularly preferably 1.2 to
The range is 1.6 times. Stretch ratio in the main shrinkage direction is 2.5
If it is less than double, the amount of heat shrinkage is insufficient at the time of heat shrinkage. On the other hand, if the stretching ratio is more than 7.0 times, the film is often broken at the time of film formation. When the stretching ratio in the direction perpendicular to the main shrinking direction is more than 2.0 times, the heat shrinkage in the direction perpendicular to the main shrinking direction becomes too large, and the finished film becomes wavy.
【００１０】さらに、ポリエステルフィルムは、ポリエ
ステルの平均ガラス転移点（Ｔｇ）以上の温度で、好ま
しくは少なくとも主収縮方向は、数段階、好ましくは３
段階以上に分けて温度を順次上昇せしめて延伸される。
その際、最初の延伸時の温度はＴｇ＋７〜１３℃、好ま
しくはＴｇ＋９〜１１℃、就中Ｔｇ＋１０℃程度である
ことが適当である。各段階間の温度差は、通常各々２〜
８℃、好ましくは各々４〜６℃、就中各々５℃程度であ
る。例えば、３段階以上に分けて温度を順次上昇せしめ
て延伸される場合には、好ましくはＴｇ＋１０℃程度、
Ｔｇ＋１５℃程度、Ｔｇ＋２０℃程度の温度で順次行わ
れる。好ましくは、主収縮方向は、Ｔｇ＋２０℃〜Ｔｇ
＋５０℃の範囲にて予熱される。このような条件で延伸
することにより、平均熱収縮速度係数が０．１〜０．５
％／秒・℃の範囲である熱収縮性ポリエステルフィルム
を得ることができる。上記の延伸処理後、この延伸特性
を良好に安定させるために、伸長あるいは緊張状態を保
ってフィルムにストレスをかけながら冷却するか、又は
更に引き続いて冷却することが好ましい。Further, the polyester film has a temperature of not less than the average glass transition point (Tg) of polyester, preferably at least in the main shrinkage direction, in several stages, preferably 3
It is stretched by gradually increasing the temperature in stages or more.
At that time, the temperature during the first stretching is Tg + 7 to 13 ° C., preferably Tg + 9 to 11 ° C., and especially Tg + 10 ° C. The temperature difference between each stage is usually 2 to
It is 8 ° C., preferably 4 to 6 ° C., especially about 5 ° C. For example, when the temperature is sequentially raised in three or more stages and stretched, preferably Tg + 10 ° C.,
It is sequentially performed at a temperature of about Tg + 15 ° C. and about Tg + 20 ° C. Preferably, the main shrinkage direction is Tg + 20 ° C. to Tg
Preheated in the range of + 50 ° C. By stretching under such conditions, the average heat shrinkage rate coefficient is 0.1 to 0.5.
It is possible to obtain a heat-shrinkable polyester film in the range of% / sec · ° C. After the above stretching treatment, in order to stabilize this stretching property well, it is preferable to cool the film while keeping the stretched or tensioned state while applying stress, or further to cool it.
【００１１】このような構成の本発明の熱収縮ポリエス
テルフィルムは、以下の優れた特性を有する。 (1)一方向収縮性 収縮フィルムの役割の一つは被包装物の破壊や荷崩れ等
を防止する点にあるが、そのためには高い耐衝撃性を有
し、かつ主収縮方向に大きい収縮率を得ることが必要で
ある。本発明の熱収縮ポリエステルフィルムは、主収縮
方向の熱収縮率が３０％以上と高くかつ耐衝撃性が良好
であるため、美しい包装が得られ、しかも被包装物の保
護という面で優れた耐久性を示す。この傾向は落下テス
ト（収縮フィルムを装着したＰＥＴボトルを１．５ｍの
高さからコンクリートに落下させる）によって証明され
る。また一方向収縮性によって収縮包装後の仕上がり寸
法安定性がよい。 (2)耐熱性 従来のフィルムはいずれも耐熱性が悪いため、高温ボイ
ル処理やレトルト処理には耐えうることができず殺菌処
理に不適当なフィルムであり、処理中に破壊し、機能が
失われるが、本発明の熱収縮性ポリエステルフィルム
は、ポリエステルを原料としているので耐熱性が良好で
あり、ボイル処理やレトルト処理ができ優れた有用性を
示す。 (3)印刷性 従来のフィルムは、インクとの接着性が悪く、ハーフト
ーン印刷によりピンホールが発生するが、本発明の熱収
縮性ポリエステルフィルムは、ポリエステルを原料とし
ているので耐薬品性が良好であり、またテレフタル酸お
よび／またはエチレングリコール以外の酸成分および／
またはジオール成分を含むポリエステルを原料とするこ
とにより、インクとの接着性が向上して印刷性は改善さ
れる。 (4)産業廃棄物の問題 近年、プラスチックボトルの利用が急速に広まってい
る。このようなボトルの回収を考えた場合は同物質で形
成されることが好ましく、本発明の熱収縮性ポリエステ
ルフィルムをポリエステル系ボトルの包装に適用するこ
とはこの点有利である。 (5)収縮ムラ 本発明のフィルムは高い収縮率と高い収縮応力を有し、
また平均収縮速度係数が低いことから収縮ムラの発生は
ない。The heat-shrinkable polyester film of the present invention having such a constitution has the following excellent properties. (1) One-way shrinkability One of the roles of the shrink film is to prevent the package from being broken or the load collapsed.To that end, it has high impact resistance and large shrinkage in the main shrink direction. It is necessary to get a rate. The heat-shrinkable polyester film of the present invention has a high heat-shrinkage rate of 30% or more in the main shrinkage direction and has good impact resistance, so that beautiful packaging can be obtained and, in addition, it has excellent durability in terms of protection of the packaged object. Shows sex. This tendency is proved by a drop test (a PET bottle equipped with a shrink film is dropped onto concrete from a height of 1.5 m). In addition, unidirectional shrinkability provides good finished dimensional stability after shrink wrapping. (2) Heat resistance Since all conventional films have poor heat resistance, they cannot withstand high-temperature boil treatment or retort treatment and are unsuitable for sterilization treatment. However, since the heat-shrinkable polyester film of the present invention is made of polyester as a raw material, it has good heat resistance and can be boiled or retorted, thus showing excellent usefulness. (3) Printability Conventional films have poor adhesiveness to ink and pinholes are generated by halftone printing, but the heat-shrinkable polyester film of the present invention has good chemical resistance because it is made of polyester. And an acid component other than terephthalic acid and / or ethylene glycol and / or
Alternatively, by using a polyester containing a diol component as a raw material, the adhesiveness with ink is improved and the printability is improved. (4) Industrial waste problem In recent years, the use of plastic bottles has been rapidly spreading. When considering the recovery of such a bottle, it is preferable to form the same material, and it is advantageous to apply the heat-shrinkable polyester film of the present invention to packaging of a polyester bottle. (5) Shrinkage unevenness The film of the present invention has a high shrinkage ratio and high shrinkage stress,
Further, since the average shrinkage speed coefficient is low, no shrinkage unevenness occurs.
【００１２】[0012]
【実施例】以下、本発明を実施例を示して詳細に説明す
るが、本発明は、その要旨を超えない限りこれらの実施
例に何ら制約されない。本発明で用いた測定方法を以下
に示す。本実施例において、横方向とは、フィルムの成
形方向であり、主収縮方向である。また縦方向とは、フ
ィルムの成形方向と直角方向であり、主収縮方向と直角
方向である。 (1)平均収縮速度係数 加熱可能なテンシロン（島津製作所（株）製オートグラ
フＨＧ−３０００）を使用し、幅２０ｍｍ、長さ１５０
ｍｍの資料片を採取し、そのフィルムに１００ｍｍの標
線を記し６０ｍｍに設定した上下チャックに正確に１０
０ｍｍの標線を合わせて装着し、７０℃、８０℃、９０
℃、１００℃、１１０℃および１２０℃の熱風中（風速
１０ｍ／秒）でそれぞれ処理し、収縮応力の発生するま
での時間（ｔ）により以下の式でまずフィルムの横方向
の平均収縮速度を求めた。 平均収縮速度 ＝ （１００−６０）／（ｔ） （％／秒） 横軸に熱風温度、縦軸に平均収縮速度をとり、回帰式に
より回帰線直線を引きフィルムの横方向の平均収縮速度
係数（％／秒・℃）を求めた。 (2)収縮仕上がり性 ガラス瓶（３００ｍｌ）に印刷を施した熱収縮性フィル
ムを装着し、１３０℃の熱風（風速１０ｍ／秒）の熱収
縮トンネルを通し、仕上がり性を目視にて判定した。な
お、仕上がり性のランクについては、 ○：収縮ムラなし △：一部収縮ムラあり（２ヵ所以内） ×：収縮ムラあり（３ヵ所以上） として、○のみを合格とした。 (3)熱収縮率 サンプル標線間を２００ｍｍ（横方向）にとり、フィル
ムを幅１５０ｍｍに切断して１００℃の熱風を用いて１
分間加熱し、標線間長さを測定して横方向の熱収縮率を
求めた。 (4)熱収縮応力 平均収縮速度係数で用いたテンシロンを使用し、幅２０
ｍｍ、長さ１５０ｍｍの試料片を採取し、そのフィルム
に１００ｍｍの標線を記し１００ｍｍに設定した上下チ
ャックに試料片を装着して、１００℃の熱風中処理し、
その間の最大収縮応力を求め、次式に従って横方向の収
縮応力を算出した。 熱収縮応力 ＝ 最大収縮応力／断面積（ｋｇ／ｍｍ2 ） (5)ヘイズ 積分球式Ｈ．Ｔ．Ｒメーター（日本精密科学製）を用い
て入射光量、装置と試験片による散乱光量を測定し算出
した。EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. The measuring method used in the present invention is shown below. In this embodiment, the lateral direction is the film forming direction and the main shrinking direction. The longitudinal direction is a direction perpendicular to the film forming direction, and is a direction perpendicular to the main shrinkage direction. (1) Average shrinkage rate coefficient Using a heatable Tensilon (Autograph HG-3000 manufactured by Shimadzu Corporation), width 20 mm, length 150
Take a 10 mm piece of data, mark the film with a 100 mm mark, and add 10 mm to the upper and lower chucks set to 60 mm.
Wear with the marked line of 0mm, 70 ℃, 80 ℃, 90
C., 100.degree. C., 110.degree. C., and 120.degree. C. in hot air (wind speed 10 m / sec), respectively. I asked. Average shrinkage rate = (100-60) / (t) (% / sec) The horizontal axis represents the hot air temperature and the vertical axis represents the average shrinkage rate, and a regression line is drawn by a regression equation to determine the average shrinkage rate coefficient in the lateral direction of the film. (% / Sec. ° C.) was determined. (2) Shrinkage Finishability A printed heat-shrinkable film was attached to a glass bottle (300 ml), passed through a heat-shrink tunnel of 130 ° C. hot air (air velocity 10 m / sec), and the finishability was visually evaluated. Regarding the rank of finishability, ◯: No shrinkage unevenness Δ: Partial shrinkage unevenness (within 2 places) ×: Shrinkage unevenness (3 places or more), and only ◯ was accepted. (3) Heat shrinkage rate The distance between sample marked lines is set to 200 mm (horizontal direction), the film is cut into a width of 150 mm, and hot air at 100 ° C. is used for 1
After heating for a minute, the length between marked lines was measured to determine the heat shrinkage ratio in the lateral direction. (4) Thermal shrinkage stress Using the tensilon used for the average shrinkage rate coefficient, width 20
mm, 150 mm long sample pieces were collected, 100 mm marked lines were marked on the film, the sample pieces were attached to the upper and lower chucks set to 100 mm, and treated in hot air at 100 ° C.,
The maximum shrinkage stress during that time was obtained, and the shrinkage stress in the lateral direction was calculated according to the following formula. Thermal shrinkage stress = maximum shrinkage stress / cross-sectional area (kg / mm 2 ) (5) Haze Integrating sphere formula T. The amount of incident light and the amount of scattered light by the device and the test piece were measured and calculated using an R meter (manufactured by Japan Precision Science Co., Ltd.).
【００１３】実施例１ ステンレス製オートクレーブを使用し、二塩基酸成分と
してテレフタル酸１００モル％と、グリコール成分とし
てエチレングリコール１５０モル％（酸成分に対して）
とネオペンチルグリコール６０モル％（酸成分に対し
て）を用い、触媒として三酸化アンチモン０．０２５モ
ル％（酸成分に対して）を用いて直接エステル化法によ
り重縮合した。得られたポリエステルの固有粘度は０．
７０ｄｌ／ｇ、平均ガラス転移点（Ｔｇ）は６９℃であ
った。このポリエステルを２８０℃で溶融押出し、厚さ
１８０μｍの未延伸フィルムを得た。このフィルムを縦
方向に１．１倍延伸し、次いでこれを予熱１００℃で処
理後、横方向に８０℃、８５℃および９０℃の３段階の
温度ゾーンで合計４．１倍に順次延伸した。次いでこの
フィルムを８０℃で熱処理して厚さ４０μｍの熱収縮ポ
リエステルフィルムを得た。得られた熱収縮ポリエステ
ルフィルムの物性を表１に示す。Example 1 Using a stainless steel autoclave, 100 mol% of terephthalic acid as a dibasic acid component and 150 mol% of ethylene glycol as a glycol component (based on the acid component).
And 60 mol% of neopentyl glycol (based on the acid component) and 0.025 mol% of antimony trioxide (based on the acid component) as a catalyst were subjected to polycondensation by the direct esterification method. The intrinsic viscosity of the obtained polyester is 0.
70 dl / g, average glass transition point (Tg) was 69 ° C. This polyester was melt extruded at 280 ° C. to obtain an unstretched film having a thickness of 180 μm. The film was stretched 1.1 times in the machine direction, then preheated to 100 ° C., and then sequentially stretched in the transverse direction to a total of 4.1 times in three temperature zones of 80 ° C., 85 ° C. and 90 ° C. . Then, this film was heat-treated at 80 ° C. to obtain a heat-shrinkable polyester film having a thickness of 40 μm. Table 1 shows the physical properties of the resulting heat-shrinkable polyester film.
【００１４】実施例２ ステンレス製オートクレーブを使用し、二塩基酸成分と
してテレフタル酸６０モル％（酸成分中）と２，６−ナ
フタレンジカルボン酸４０モル％（酸成分中）を用い、
グリコール成分としてエチレングリコール２１０モル％
（酸成分に対して）を用い、触媒として三酸化アンチモ
ン０．０２５モル％（酸成分に対して）を用いて直接エ
ステル化法により重縮合した。得られたポリエステルの
固有粘度は０．７１ｄｌ／ｇ、平均ガラス転移点（Ｔ
ｇ）は９５℃であった。このポリエステルを２９０℃で
溶融押出し、厚さ１８０μｍの未延伸フィルムを得た。
このフィルムを縦方向に１．１倍延伸し、次いでこれを
予熱１２０℃で処理後、横方向に１０５℃、１１０℃お
よび１１０℃の３段階の温度ゾーンで合計４．１倍に順
次延伸した。次いでこのフィルムを１０５℃で熱処理し
て厚さ４０μｍの熱収縮ポリエステルフィルムを得た。
得られた熱収縮ポリエステルフィルムの物性を表１に示
す。Example 2 Using a stainless steel autoclave, 60 mol% of terephthalic acid (in the acid component) and 40 mol% of 2,6-naphthalenedicarboxylic acid (in the acid component) were used as dibasic acid components,
210 mol% ethylene glycol as a glycol component
Polycondensation was carried out by the direct esterification method using (based on the acid component) and 0.025 mol% of antimony trioxide (based on the acid component) as a catalyst. The obtained polyester has an intrinsic viscosity of 0.71 dl / g and an average glass transition point (T
g) was 95 ° C. This polyester was melt extruded at 290 ° C. to obtain an unstretched film having a thickness of 180 μm.
The film was stretched 1.1 times in the machine direction, preheated at 120 ° C., and then sequentially stretched in the transverse direction to a total of 4.1 times in three temperature zones of 105 ° C., 110 ° C. and 110 ° C. . Then, this film was heat-treated at 105 ° C. to obtain a heat-shrinkable polyester film having a thickness of 40 μm.
Table 1 shows the physical properties of the resulting heat-shrinkable polyester film.
【００１５】実施例３ 実施例１で製造したポリエステルに、ポリブチレンテレ
フタレートを８０：２０（重量比）で混合した。得られ
た混合物の固有粘度は０．７１ｄｌ／ｇ、平均ガラス転
移点（Ｔｇ）は６１℃であった。これを２７０℃で溶融
押出し、厚さ１８０μｍの未延伸フィルムを得た。この
フィルムを縦方向に１．２倍延伸し、次いでこれを予熱
１００℃で処理後、横方向に７０℃、７５℃および８０
℃の３段階の温度ゾーンで合計４．１倍に順次延伸し
た。次いでこのフィルムを７０℃で熱処理して厚さ４０
μｍの熱収縮ポリエステルフィルムを得た。得られた熱
収縮ポリエステルフィルムの物性を表１に示す。Example 3 Polybutylene terephthalate was mixed with the polyester prepared in Example 1 in a weight ratio of 80:20. The obtained mixture had an intrinsic viscosity of 0.71 dl / g and an average glass transition point (Tg) of 61 ° C. This was melt extruded at 270 ° C. to obtain an unstretched film having a thickness of 180 μm. The film was stretched 1.2 times in the machine direction and then preheated to 100 ° C before being machined in the transverse direction at 70 ° C, 75 ° C and 80 ° C.
The film was sequentially drawn in a total of 4.1 times in three temperature zones of 0 ° C. This film is then heat treated at 70 ° C to a thickness of 40
A μm heat-shrinkable polyester film was obtained. Table 1 shows the physical properties of the resulting heat-shrinkable polyester film.
【００１６】比較例１ 実施例１の未延伸フィルムを縦方向に１．１倍延伸し、
次いでこれを予熱９０℃で処理後、横方向に７５℃で
４．１倍に順次延伸した。次いでこのフィルムを７５℃
で熱処理して厚さ４０μｍの熱収縮ポリエステルフィル
ムを得た。得られた熱収縮ポリエステルフィルムの物性
を表１に示す。Comparative Example 1 The unstretched film of Example 1 was stretched 1.1 times in the machine direction,
Next, this was preheated at 90 ° C. and then sequentially stretched in the transverse direction at 75 ° C. by a factor of 4.1. This film is then placed at 75 ° C
Was heat-treated in order to obtain a heat-shrinkable polyester film having a thickness of 40 μm. Table 1 shows the physical properties of the resulting heat-shrinkable polyester film.
【００１７】比較例２ 実施例２の未延伸フィルムを縦方向に１．１倍延伸し、
次いでこれを予熱１１０℃で処理後、横方向に１００℃
で４．１倍に順次延伸した。次いでこのフィルムを１０
５℃で熱処理して厚さ４０μｍの熱収縮ポリエステルフ
ィルムを得た。得られた熱収縮ポリエステルフィルムの
物性を表１に示す。Comparative Example 2 The unstretched film of Example 2 was stretched 1.1 times in the machine direction,
Then, preheat it to 110 ℃, and then heat it to 100 ℃ in the transverse direction.
Then, the film was sequentially stretched to 4.1 times. This film is then
Heat treatment was performed at 5 ° C. to obtain a heat-shrinkable polyester film having a thickness of 40 μm. Table 1 shows the physical properties of the resulting heat-shrinkable polyester film.
【００１８】比較例３ 実施例１で得られたポリエステルを２８０℃で溶融押出
し、厚さ１００μｍの未延伸フィルムを得た。このフィ
ルムを縦方向に１．１倍延伸し、次いでこれを予熱１０
０℃で処理後、横方向に８０℃、８５℃および９０℃の
３段階の温度ゾーンで合計２．０倍に順次延伸した。次
いでこのフィルムを８０℃で熱処理して厚さ４０μｍの
熱収縮ポリエステルフィルムを得た。得られた熱収縮ポ
リエステルフィルムの物性を表１に示す。Comparative Example 3 The polyester obtained in Example 1 was melt extruded at 280 ° C. to obtain an unstretched film having a thickness of 100 μm. The film was stretched 1.1 times in the machine direction and then preheated 10
After the treatment at 0 ° C., it was sequentially stretched in the transverse direction in a total of 2.0 times in three temperature zones of 80 ° C., 85 ° C. and 90 ° C. Then, this film was heat-treated at 80 ° C. to obtain a heat-shrinkable polyester film having a thickness of 40 μm. Table 1 shows the physical properties of the resulting heat-shrinkable polyester film.
【００１９】[0019]
【表１】 [Table 1]
【００２０】表１より、実施例１〜３の熱収縮ポリエス
テルフィルムは、横方向の熱収縮率が３０％以上であ
り、かつ横方向の平均熱収縮速度係数が０．１〜０．５
％／秒であり、収縮ムラがなく収縮仕上がり性が良好で
あり、さらに横方向の収縮応力が高いことがわかる。一
方、比較例１および２の熱収縮ポリエステルフィルム
は、横方向の平均熱収縮速度係数が０．５％／秒を超
え、収縮ムラがあり収縮仕上がり性が悪いことがわか
る。From Table 1, the heat-shrinkable polyester films of Examples 1 to 3 have a heat shrinkage ratio of 30% or more in the transverse direction and an average heat shrinkage rate coefficient of 0.1 to 0.5 in the transverse direction.
% / Sec, there is no shrinkage unevenness, the shrinkage finish is good, and the shrinkage stress in the lateral direction is high. On the other hand, it can be seen that the heat-shrinkable polyester films of Comparative Examples 1 and 2 have an average heat-shrinkage rate coefficient in the transverse direction of more than 0.5% / sec, and have uneven shrinkage and poor shrink finish.
【００２１】[0021]
【発明の効果】以上の説明で明らかなように、本発明に
よれば、収縮ムラがなく、収縮応力が高く、印刷性、耐
衝撃性および耐熱性が良好である熱収縮ポリエステルフ
ィルムを提供することができるので、このフィルムを使
用して包装すると破壊や荷崩れがなく美しくかつ仕上が
りの寸法安定性が良好な包装物が得られる。またこの包
装物にボイル処理やレトルト処理を行ってもフィルムの
溶融、破裂、２次たるみがない。さらにこの包装物の印
刷性も良好となる。従って、本発明の熱収縮ポリエステ
ルフィルムは、被覆用、結束用の包装材料として非常に
有用である。さらにまたリサイクルの点から、ポリエス
テル系ボトルの包装への適用が有利となる。As is apparent from the above description, according to the present invention, there is provided a heat-shrinkable polyester film having no shrinkage unevenness, high shrinkage stress, and good printability, impact resistance and heat resistance. Therefore, if this film is used for packaging, a packaged product which is free from breakage and collapse of load and has a good finished dimensional stability can be obtained. Even if the package is boiled or retorted, the film does not melt, burst, or have secondary sagging. Further, the printability of this package is also improved. Therefore, the heat shrinkable polyester film of the present invention is very useful as a packaging material for coating and binding. Furthermore, from the viewpoint of recycling, application to packaging of polyester bottles is advantageous.
───────────────────────────────────────────────────── 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 Ｂ２９Ｌ 7:00 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI technical display location B29L 7:00
Claims (5)
上であり、かつ少なくとも当該方向の７０〜１２０℃の
温度範囲における平均熱収縮速度係数が０．１〜０．５
％／秒・℃の範囲であることを特徴とする熱収縮性ポリ
エステルフィルム。1. A heat shrinkage ratio in at least one direction is 30% or more, and an average heat shrinkage rate coefficient in a temperature range of 70 to 120 ° C. in at least the direction is 0.1 to 0.5.
A heat-shrinkable polyester film characterized by being in the range of% / sec. ° C.
以下であることを特徴とする請求項１に記載の熱収縮性
ポリエステルフィルム。2. The heat shrinkage in the direction perpendicular to the said direction is 10%.
The heat-shrinkable polyester film according to claim 1, wherein:
ステルの平均ガラス転移点（Ｔｇ）以上の温度で、かつ
一方向に２．５〜７．０倍の範囲、当該方向と直角方向
に１．０〜２．０倍の範囲で延伸する工程を包含するこ
とを特徴とする請求項１に記載の熱収縮性ポリエステル
フィルムの製造方法。3. An unstretched polyester film, at a temperature not lower than the average glass transition point (Tg) of polyester, in a range of 2.5 to 7.0 times in one direction, and 1.0 to in a direction perpendicular to the direction. The method for producing a heat-shrinkable polyester film according to claim 1, comprising a step of stretching in a range of 2.0 times.
分けて温度を順次上昇せしめて行われることを特徴とす
る請求項３に記載の熱収縮性ポリエステルフィルムの製
造方法。4. The method for producing a heat-shrinkable polyester film according to claim 3, wherein the stretching is performed by raising the temperature in stages in at least the direction in several stages.
ス転移点より高い温度より始めて３段階以上に温度を順
次上昇せしめて行われ、かつ各段階間の温度差が各々２
〜８℃であることを特徴とする請求項４に記載の熱収縮
性ポリエステルフィルムの製造方法。5. Stretching is performed by starting at a temperature higher than the average glass transition point in at least that direction and gradually increasing the temperature in three or more steps, and the temperature difference between each step is 2 each.
It is -8 degreeC, The manufacturing method of the heat-shrinkable polyester film of Claim 4 characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13532995A JP3635717B2 (en) | 1995-06-01 | 1995-06-01 | Heat-shrinkable polyester film and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13532995A JP3635717B2 (en) | 1995-06-01 | 1995-06-01 | Heat-shrinkable polyester film and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08323859A true JPH08323859A (en) | 1996-12-10 |
| JP3635717B2 JP3635717B2 (en) | 2005-04-06 |
Family
ID=15149226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13532995A Expired - Fee Related JP3635717B2 (en) | 1995-06-01 | 1995-06-01 | Heat-shrinkable polyester film and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3635717B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999029490A1 (en) * | 1997-12-05 | 1999-06-17 | Gunze Limited | Low temperature heat shrinkable film for labels |
| US20110172386A1 (en) * | 2007-11-19 | 2011-07-14 | Kolon Industries, Inc. | Thermo-shrinkable polyester film |
| US9221573B2 (en) | 2010-01-28 | 2015-12-29 | Avery Dennison Corporation | Label applicator belt system |
| WO2018021212A1 (en) * | 2016-07-27 | 2018-02-01 | 東洋紡株式会社 | Heat-shrinkable film, heat shrink label, and packaging body |
-
1995
- 1995-06-01 JP JP13532995A patent/JP3635717B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999029490A1 (en) * | 1997-12-05 | 1999-06-17 | Gunze Limited | Low temperature heat shrinkable film for labels |
| US6270866B1 (en) | 1997-12-05 | 2001-08-07 | Gunze Limited | Low temperature heat shrinkable film for labels |
| US20110172386A1 (en) * | 2007-11-19 | 2011-07-14 | Kolon Industries, Inc. | Thermo-shrinkable polyester film |
| US9187637B2 (en) * | 2007-11-19 | 2015-11-17 | Kolon Industries, Inc. | Thermo-shrinkable polyester film |
| US9221573B2 (en) | 2010-01-28 | 2015-12-29 | Avery Dennison Corporation | Label applicator belt system |
| US9637264B2 (en) | 2010-01-28 | 2017-05-02 | Avery Dennison Corporation | Label applicator belt system |
| WO2018021212A1 (en) * | 2016-07-27 | 2018-02-01 | 東洋紡株式会社 | Heat-shrinkable film, heat shrink label, and packaging body |
| JPWO2018021212A1 (en) * | 2016-07-27 | 2019-05-09 | 東洋紡株式会社 | Heat shrinkable film, heat shrinkable label, and package |
| JP2022084685A (en) * | 2016-07-27 | 2022-06-07 | 東洋紡株式会社 | Heat-shrinkable film, heat-shrinkable label, and package |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3635717B2 (en) | 2005-04-06 |
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