JPH09239833A - Heat-shrinkable polyester film and production thereof - Google Patents
Heat-shrinkable polyester film and production thereofInfo
- Publication number
- JPH09239833A JPH09239833A JP7822596A JP7822596A JPH09239833A JP H09239833 A JPH09239833 A JP H09239833A JP 7822596 A JP7822596 A JP 7822596A JP 7822596 A JP7822596 A JP 7822596A JP H09239833 A JPH09239833 A JP H09239833A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- film
- shrinkage
- stretching
- 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]
【発明の属する技術分野】本発明は、熱収縮性ポリエス
テル系フィルムおよびその製造法に関し、さらに詳しく
は熱収縮性フイルムの収縮後にシワ、収縮斑、歪みの発
生が極めて少なく、かつ衝撃に対する耐破断性に優れ
た、ラベル用途に好適な熱収縮性ポリエステル系フィル
ムおよびその製造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 heat-shrinkable polyester film and a method for producing the same, and more specifically, it has very few wrinkles, shrinkage spots, and distortions after shrinking of the heat-shrinkable film, and has a resistance to rupture against impact. The present invention relates to a heat-shrinkable polyester film having excellent properties and suitable for label applications, and a method for producing the same.
【0002】[0002]
【従来の技術】熱収縮性フィルム、特にボトルの胴部の
ラベル用収縮フィルムの分野では、ポリ塩化ビニル、ポ
リエチレン等からなるフィルムが主として用いられてい
たが、近年、ポリ塩化ビニルについては廃棄時に焼却す
る際の塩素系ガス発生の問題、ポリエチレンについては
印刷が困難である問題等があり、さらにPETボトルの
回収にあたってはPET以外の樹脂ラベルを分別する必
要がある等の問題が加わり、熱収縮性ポリエステル系フ
ィルムが注目を集めている。ところが、熱収縮性ポリエ
ステル系フィルムは、急激に収縮するものが多く、収縮
後にシワ、収縮斑、歪みが残り、また収縮後に外部から
与えられた衝撃による破断が生じやすい等ラベル用収縮
フィルムとして満足されるものではなかった。かかる欠
点の一部を回避するため、特開平1−110931号公
報では主収縮方向と直交する方向の破断伸度を著しく小
さくすることによって収縮仕上がり性を改良する方法が
開示されている。2. Description of the Related Art In the field of heat-shrinkable films, particularly shrink films for labels on the body of bottles, films made of polyvinyl chloride, polyethylene, etc. have been mainly used. There is a problem of chlorine-based gas generation during incineration, there is a problem that printing is difficult for polyethylene, and there is also a problem that it is necessary to separate resin labels other than PET when collecting PET bottles. Polyester film has attracted attention. However, many heat-shrinkable polyester films shrink rapidly, and wrinkles, shrinkage spots, and distortions remain after shrinking, and breakage easily occurs due to an external shock after shrinking. It wasn't something that would be done. In order to avoid some of these drawbacks, Japanese Patent Application Laid-Open No. 1-110931 discloses a method of improving shrinkage finish by significantly reducing the breaking elongation in the direction orthogonal to the main shrinkage direction.
【0003】[0003]
【発明が解決しようとする課題】しかしながら、上記方
法で得られた収縮性フィルムにあっても、印刷、ラベリ
ング等の工程でテンションがかかると破断しやすいだけ
でなく、内容物を充填したボトルの胴部に環状に収縮し
て装着された状態でボトルをまとめて輸送を実施すれ
ば、相互にあるいは箱体と当たってラベル破れが起こり
やすくなり、やはりラベル用等の収縮フィルムとしての
実用性に乏しいフィルムであった。このように、熱収縮
性ポリエステル系フィルムでは、収縮仕上がり性と収縮
前あるいは後の耐破断性を両立させることが重要な課題
であった。本発明は、上記従来の熱収縮性ポリエステル
系フィルムの有する問題点を解決し、収縮後にシワ、収
縮斑、歪みの発生が極めて少なく、かつ衝撃に対する耐
破断性に優れた、ラベル用途に好適な熱収縮性ポリエス
テル系フィルムを提供することを目的とする。However, even the shrinkable film obtained by the above method is not only liable to break when tension is applied in the steps of printing, labeling, etc., but also of a bottle filled with contents. If the bottles are transported together in a state that they are contracted in a ring shape on the body, they are likely to be broken by colliding with each other or with the box, which also makes them useful as shrink films for labels. It was a poor film. As described above, in the heat-shrinkable polyester film, it has been an important issue to satisfy both shrink finish property and break resistance before or after shrinkage. The present invention solves the problems of the above conventional heat-shrinkable polyester film, wrinkles after shrinkage, shrinkage unevenness, occurrence of distortion is extremely small, and excellent in break resistance against impact, suitable for label applications. The object is to provide a heat-shrinkable polyester film.
【0004】[0004]
【課題を解決するための手段】上記目的を達成するた
め、本発明の熱収縮性ポリエステル系フィルムは、ジカ
ルボン酸成分中テレフタル酸成分が70モル%以上、ジ
オール成分中エチレングリコール成分が70モル%であ
るポリエステルからなる延伸されたフイルムであって、
90℃のエアーオーブン中で加熱開始から1分後までの
間に発現する主収縮方向の収縮応力の最大値(σmax)
が0.5〜1.2Kg/mm2、75℃温水中で10秒
間処理後の主収縮方向の熱収縮率が40%以下、95℃
温水中で10秒間処理後の主収縮方向の熱収縮率が50
%以上であることを特徴とする。In order to achieve the above object, the heat-shrinkable polyester film of the present invention has a terephthalic acid component of 70 mol% or more in the dicarboxylic acid component and an ethylene glycol component of 70 mol% in the diol component. A stretched film made of polyester which is
Maximum value of shrinkage stress (σmax) in the main shrinkage direction that develops from the start of heating in an air oven at 90 ° C for 1 minute
Of 0.5 to 1.2 Kg / mm 2 , heat shrinkage in the main shrinkage direction after treatment for 10 seconds in 75 ° C. warm water is 40% or less, 95 ° C.
The heat shrinkage in the main shrinkage direction after treatment in warm water for 10 seconds is 50
% Or more.
【0005】上記の構成からなる本発明の熱収縮性ポリ
エステル系フィルムは、安定した熱収縮性を有し、かつ
収縮後にシワ、収縮斑、歪みの発生が極めて少なく、か
つ衝撃に対する耐破断性に優れた、ラベル用途に好適な
熱収縮性フィルムである。The heat-shrinkable polyester film of the present invention having the above-mentioned constitution has stable heat-shrinkability, has very few wrinkles, shrinkage spots, and distortion after shrinkage, and has a high resistance to impact damage. It is an excellent heat-shrinkable film suitable for label use.
【0006】また、本発明の熱収縮性ポリエステル系フ
ィルムの製造法は、ジカルボン酸成分中テレフタル酸成
分が70モル%以上、ジオール成分中エチレングリコー
ル成分が70モル%であるポリエステル未延伸フイルム
を主収縮方向となる方向に延伸するにあたり、全延伸倍
率を3.0倍以上、全延伸倍率の40〜60%を延伸す
る前段の延伸温度をTg(ガラス転移点)+10〜Tg
+40℃、その後の、全延伸倍率の60〜40%を延伸
する後段の延伸温度をTg−15〜Tg+10℃で且つ
前段の延伸温度より低い温度で延伸することを特徴とす
る。Further, the heat shrinkable polyester film production method of the present invention is mainly a polyester unstretched film in which the terephthalic acid component in the dicarboxylic acid component is 70 mol% or more and the ethylene glycol component in the diol component is 70 mol%. When stretching in the shrinking direction, the total stretching ratio is 3.0 times or more, and the stretching temperature in the preceding stage for stretching 40 to 60% of the total stretching ratio is Tg (glass transition point) + 10 to Tg.
It is characterized in that the stretching temperature at the subsequent stage of stretching at + 40 ° C. and 60 to 40% of the total stretching ratio is Tg-15 to Tg + 10 ° C. and lower than the stretching temperature at the preceding stage.
【0007】上記の構成からなる本発明の熱収縮性ポリ
エステル系フィルムの製造法は、安定した熱収縮性を有
し、かつ収縮後にシワ、収縮斑、歪みの発生が極めて少
なく、かつ衝撃に対する耐破断性に優れた、ラベル用途
に好適な熱収縮性フィルムを製造する方法であって、延
伸条件を選んで収縮特性を一定範囲にすれば、収縮仕上
がり性と耐破断性が両立した熱収縮性ポリエステル系フ
ィルムが得られるのである。本発明方法の基本的な考え
方は主収縮方向の延伸の前段を高温に保持することによ
り収縮仕上がり性を良化させ、主収縮方向の延伸の後段
を低温に保持することにより耐破断性を良化させること
である。また、本発明では主収縮方向をフイルム製造時
の巾方向(横方向)とすることが熱収縮性フイルムの使
用時の利便性から考えて好ましい。The method for producing a heat-shrinkable polyester film of the present invention having the above-mentioned constitution has a stable heat-shrinkability, has very few wrinkles, shrinkage spots, and distortion after shrinkage, and is resistant to impact. A method of producing a heat-shrinkable film suitable for label use, which is excellent in rupture properties. If the shrinkage properties are set within a certain range by selecting the stretching conditions, the heat shrinkability that achieves both shrink finish and rupture resistance is achieved. Thus, a polyester film can be obtained. The basic idea of the method of the present invention is to improve the shrink finish by maintaining the temperature of the former stage of stretching in the main shrinking direction at high temperature, and to improve the puncture resistance by keeping the latter stage of stretching in the main shrinking direction at low temperature. It is to make it. Further, in the present invention, it is preferable that the main shrinking direction is the width direction (transverse direction) at the time of manufacturing the film in consideration of convenience when using the heat shrinkable film.
【0008】[0008]
【発明の実施の形態】以下本発明の実施の形態を具体的
に説明する。本発明で用いるポリエステルは、ジカルボ
ン酸成分中テレフタル酸成分が70モル%以上、ジオー
ル成分中エチレングリコール成分が70モル%であるポ
リエステルであって、より具体的にはテレフタル酸以外
のジカルボン酸成分として、シュウ酸、マロン酸、コハ
ク酸、アジピン酸、アゼライン酸、セバシン酸、フタル
酸、イソフタル酸、ナフタレンジカルボン酸等の公知の
ジカルボン酸の1種または2種以上を示すことができ
る。また、エチレングリコール以外のグリコール成分と
してプロピレングリコール、ネオペンチルグリコール、
テトラメチレングリコール、ヘキサメチレングリコー
ル、トリメチレングリコール、ジエチレングリコール、
ポリアルキレングリコール、1,4−シクロヘキサンジ
メタノール等の公知のジオールの1種または2種以上を
示すことができる。また、収縮仕上がり性が特に優れた
熱収縮性ポリエステルフィルムとするためには、ネオペ
ンチルグリコールがグリコール成分の残りの成分である
ポリエステルを使用することが好ましい。なお、本発明
において用いるジカルボン酸成分中テレフタル酸成分が
70モル%以上、ジオール成分中エチレングリコール成
分が70モル%以上であるポリエステルとは、2種以上
のポリエステルを混合して用いる場合、混合後にエステ
ル交換がなされているかどうかに関わらずポリエステル
全体の中のジカルボン酸成分中に占めるテレフタル酸の
割合い、グリコール成分中に占めるエチレングリコール
の割合いをそれぞれ示す。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be specifically described below. The polyester used in the present invention is a polyester having a terephthalic acid component of 70 mol% or more in the dicarboxylic acid component and an ethylene glycol component of 70 mol% in the diol component, and more specifically, as a dicarboxylic acid component other than terephthalic acid. , Oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and the like, may be used alone or in combination. Further, as a glycol component other than ethylene glycol, propylene glycol, neopentyl glycol,
Tetramethylene glycol, hexamethylene glycol, trimethylene glycol, diethylene glycol,
One or more known diols such as polyalkylene glycol and 1,4-cyclohexanedimethanol can be used. Further, in order to obtain a heat-shrinkable polyester film having particularly excellent shrink finish, it is preferable to use polyester in which neopentyl glycol is the remaining component of the glycol component. The polyester having a terephthalic acid component of 70 mol% or more in the dicarboxylic acid component and an ethylene glycol component of 70 mol% or more in the diol component used in the present invention means that when two or more polyesters are mixed and used, The proportions of terephthalic acid in the dicarboxylic acid component and the proportion of ethylene glycol in the glycol component in the whole polyester are shown regardless of whether or not transesterification is performed.
【0009】本発明の熱収縮性フイルムを構成するポリ
エステルは、ジカルボン酸成分中テレフタル酸成分が7
0モル%以上、ジオール成分中エチレングリコール成分
が70モル%であるポリエステルであるが、テレフタル
酸、エチレングリコールがそれぞれジカルボン酸成分、
ジオール成分中70モル未満の場合、得られた熱収縮性
フィルムの収縮後の耐破断性が低下する。In the polyester constituting the heat-shrinkable film of the present invention, the terephthalic acid component in the dicarboxylic acid component is 7
The polyester is 0 mol% or more and the ethylene glycol component in the diol component is 70 mol%, and terephthalic acid and ethylene glycol are dicarboxylic acid components,
When the amount is less than 70 mol in the diol component, the resulting heat-shrinkable film has reduced resistance to breakage after shrinkage.
【0010】本発明の熱収縮性フィルムは90℃のエア
ーオーブン中で加熱開始から1分後までの間に発現する
主収縮方向(最大の収縮率を有する方向)の収縮応力の
最大値(σmax)が0.5〜1.2Kg/mm2である特
性を有する。熱収縮性フィルムの収縮応力の最大値(σ
max)が1.2Kg/mm2を越える場合、ボトル等の被
包装体を包装して収縮トンネルを通過させる場合に収縮
斑、歪みが発生しやすい。逆に主収縮方向の収縮応力の
最大値(σmax)が0.5Kg/mm2未満の場合、収縮
トンネルでボトルの胴部に熱収縮性フィルムを収縮させ
たラベルを装着した後、このボトルに温かい内容物を充
填した際、内容物の熱で収縮後のフィルムに歪みが生
じ、ボトルの上部でラベルが花びら状にたるむという欠
点が生じやすい。The heat-shrinkable film of the present invention has the maximum value (σmax) of shrinkage stress in the main shrinkage direction (direction having the maximum shrinkage ratio) developed in the air oven at 90 ° C. for 1 minute after the start of heating. ) Is 0.5 to 1.2 Kg / mm 2 . Maximum shrinkage stress of heat shrinkable film (σ
When the (max) exceeds 1.2 Kg / mm 2 , shrinkage unevenness and distortion are likely to occur when a packaged object such as a bottle is packaged and passed through a shrink tunnel. On the contrary, when the maximum value of shrinkage stress (σmax) in the main shrinkage direction is less than 0.5 Kg / mm 2 , after attaching the label shrinking the heat shrinkable film to the body of the bottle in the shrinking tunnel, When filled with warm contents, the heat of the contents distorts the film after shrinking, and the label tends to sag in the shape of petals at the top of the bottle.
【0011】また、本発明の熱収縮性フィルムは主収縮
方向の熱収縮率が75℃温水中で10秒間処理後では4
0%以下であり、95℃温水中では10秒間処理後で5
0%以上あることが必要である。特に、ボトル等の被包
装体を包装して収縮トンネルを通過させる場合の収縮斑
を抑制するためには、75℃温水中で10秒間処理後の
主収縮方向の熱収縮率は35%以下であるのが好まし
い。75℃での主収縮方向の熱収縮率が40%を越える
場合、上記収縮トンネルでフィルムを収縮させた場合、
シワ、収縮斑、歪みが発生しやすい。また、95℃での
主収縮方向の熱収縮率が50%未満の場合、ボトルの上
部で円錐状の径が小さくなっている部分の収縮不足を生
じやすい。The heat-shrinkable film of the present invention has a heat shrinkage in the main shrinkage direction of 4 after being treated in 75 ° C. hot water for 10 seconds.
0% or less, and 5 hours after treatment for 10 seconds in warm water at 95 ° C
It should be 0% or more. In particular, in order to suppress shrinkage unevenness when packaging a packaged object such as a bottle and passing it through a shrinking tunnel, the heat shrinkage rate in the main shrinking direction after treatment for 10 seconds in hot water at 75 ° C. is 35% or less. Preferably. When the heat shrinkage in the main shrinkage direction at 75 ° C exceeds 40%, when the film is shrunk in the shrink tunnel,
Wrinkles, shrinkage spots, and distortion easily occur. Further, when the thermal shrinkage in the main shrinkage direction at 95 ° C. is less than 50%, insufficient shrinkage is likely to occur in the upper portion of the bottle where the conical diameter is small.
【0012】また、本発明の熱収縮性フィルムの製造法
は主収縮方向に延伸する際、全延伸倍率が3.0倍以上
であることが必要である。全延伸倍率が3.0倍未満の
場合、得られた熱収縮性フィルムの厚み分布が悪く均一
性に欠け、フィルム製造工程および熱収縮性フィルムへ
の印刷等、熱収縮性フィルムを加工する工程での操業性
が低下するため生産性が低くなり、また熱収縮性フィル
ムの商品価値も低下する。Further, in the method for producing the heat-shrinkable film of the present invention, it is necessary that the total stretching ratio is 3.0 times or more when stretching in the main shrinking direction. When the total draw ratio is less than 3.0 times, the thickness distribution of the obtained heat-shrinkable film is poor and lacks uniformity, and the film-making step and the step of processing the heat-shrinkable film such as printing on the heat-shrinkable film. The productivity of the heat-shrinkable film is also lowered because the operability of the heat-shrinkable film is lowered.
【0013】また、本発明方法では未延伸のフィルムを
主収縮方向への延伸の前段(全延伸倍率の40〜60
%)をTg+10〜Tg+40℃の温度で延伸すること
が必要である。主収縮方向への延伸の前段の延伸倍率が
全延伸倍率の40%未満の場合あるいは延伸温度がTg
+10℃未満の場合、得られた熱収縮性フィルムの主収
縮方向の収縮応力の最大値(σmax)が大きくなり、熱
収縮率と収縮応力を両立させることができない。逆に主
収縮方向への延伸の前段の延伸倍率が全延伸倍率の60
%を越える場合あるいは延伸温度がTg+40℃以上の
場合、主収縮方向の収縮応力の最大値(σmax)が小さ
くなり収縮応力をコントロールできないばかりでなく、
得られたフィルムの耐破断性が低下するため本発明の目
的物が得られず、さらに得られた熱収縮性フィルムの厚
み分布が悪くなるため商品価値が低下する。In the method of the present invention, the unstretched film is stretched in the main shrinking direction before the stretching (total stretching ratio of 40 to 60).
%) At a temperature of Tg + 10 to Tg + 40 ° C. If the draw ratio of the previous stage of drawing in the main shrinkage direction is less than 40% of the total draw ratio, or if the draw temperature is Tg.
When the temperature is less than + 10 ° C, the maximum value (σmax) of the shrinkage stress in the main shrinkage direction of the obtained heat-shrinkable film becomes large, and the heat shrinkage rate and the shrinkage stress cannot be made compatible with each other. On the contrary, the stretching ratio before the stretching in the main shrinkage direction is 60% of the total stretching ratio.
% Or the stretching temperature is Tg + 40 ° C. or higher, the maximum value (σmax) of the shrinkage stress in the main shrinkage direction becomes small and the shrinkage stress cannot be controlled.
Since the breaking resistance of the obtained film is lowered, the object of the present invention cannot be obtained, and the thickness distribution of the obtained heat-shrinkable film is deteriorated, so that the commercial value is lowered.
【0014】また、本発明方法では未延伸フィルムの主
収縮方向への延伸の後段(全延伸倍率の40%から60
%)をTg−15℃〜Tg+10℃の温度で且つ前段の
延伸温度より低い温度で延伸することが必要である。主
収縮方向への延伸の後段の倍率が全延伸倍率の40%未
満の場合あるいはTg+10℃を越える場合、得られた
熱収縮性フィルムを収縮させた後の衝撃力による耐破断
性が低下する。逆に主収縮方向への延伸の後段の延伸倍
率が60%を越える場合あるいは延伸温度がTg−15
℃未満の場合、延伸工程で破断を生じやすくなり、また
得られた熱収縮性フィルムは熱収縮後の透明性が悪くな
る傾向がある。In the method of the present invention, the unstretched film is stretched in the main shrinkage direction after the stretching (40% to 60% of the total stretching ratio).
%) At a temperature of Tg-15 ° C. to Tg + 10 ° C. and a temperature lower than the stretching temperature of the former stage. When the latter-stage draw ratio in the main shrinking direction is less than 40% of the total draw ratio or exceeds Tg + 10 ° C., the resulting heat-shrinkable film has reduced resistance to breakage due to impact force after shrinking. On the contrary, when the stretching ratio in the latter stage of stretching in the main shrinkage direction exceeds 60% or the stretching temperature is Tg-15.
When the temperature is lower than 0 ° C, breakage is likely to occur in the stretching step, and the heat-shrinkable film obtained tends to have poor transparency after heat-shrinking.
【0015】本発明の熱収縮性フイルムの厚みは特に限
定するものではないが、ラベル用収縮フィルムとして1
0〜200μmが好ましく、20〜100μmがさらに
好ましい。The thickness of the heat-shrinkable film of the present invention is not particularly limited.
0 to 200 μm is preferable, and 20 to 100 μm is more preferable.
【0016】また、本発明の熱収縮性フイルムの主収縮
方向と直交する方向の熱収縮率は特に限定するものでは
ないが、95℃温水中で10秒間処理後の熱収縮率が1
5%以下が好ましく、10%以下がさらに好ましい。The heat shrinkage rate of the heat shrinkable film of the present invention in the direction orthogonal to the main shrinkage direction is not particularly limited, but the heat shrinkage rate after treatment in hot water at 95 ° C. for 10 seconds is 1
It is preferably 5% or less, more preferably 10% or less.
【0017】次に本発明の熱収縮性フイルムの製造法を
より具体的に説明するが、下記製造法に限定されるもの
ではない。本発明に用いるポリエステル原料をホッパー
ドライヤー、パドルドライヤー等の乾燥機、または真空
乾燥機を用いて乾燥し、200〜300℃の温度でフイ
ルム状に押し出す。押し出しに際してはTダイ法、チュ
ーブラー法等、既存のどの方法を採用しても構わない。
押し出し後急冷して未延伸フィルムを得る。該未延伸フ
ィルムに対し延伸処理を行うが、本発明の目的を達成す
るには主収縮方向としては横方向が実用的であるので以
下主収縮方向が横方向である場合の製膜法の例を示す
が、主収縮方向を縦方向とする場合も下記方法における
延伸方向を90度変えるほか通常の操作に準じて製膜す
ることができる。Next, the method for producing the heat-shrinkable film of the present invention will be described in more detail, but the production method is not limited to the following. The polyester raw material used in the present invention is dried using a dryer such as a hopper dryer, a paddle dryer or the like, or a vacuum dryer, and extruded into a film at a temperature of 200 to 300 ° C. Any existing method such as a T-die method or a tubular method may be adopted for the extrusion.
After extrusion, it is rapidly cooled to obtain an unstretched film. The unstretched film is subjected to a stretching treatment, but in order to achieve the object of the present invention, the transverse direction is practical as the main shrinkage direction. Therefore, the following is an example of a film forming method in which the main shrinkage direction is the transverse direction. In the case where the main shrinkage direction is the longitudinal direction, the film can be formed according to the usual operation except that the stretching direction in the following method is changed by 90 degrees.
【0018】また、目的とする熱収縮性ポリエステル系
フィルムの厚み分布を均一化させることに着目すれば、
テンターを用いて横方向に延伸する際、延伸工程に先立
って実施される予備加熱工程では熱伝達係数を0.00
13カロリー/cm2・sec・℃以下の低風速で所定
のフィルム温度になるまで加熱を行うことが好ましい。
横方向の延伸は、その全延伸倍率を3.0倍以上、好ま
しくは3.5倍以上、さらに好ましくは4.0倍以上と
して延伸する。さらに、前段の延伸倍率を全延伸倍率の
40〜60%、好ましくは45〜55%とし、Tg+1
0〜Tg+40℃の温度、好ましくはTg+15〜Tg
+30℃の温度で延伸し、次いで後段の延伸倍率を全延
伸倍率の40〜60%好ましくは45〜55%とし、T
g−15〜Tg+10℃、好ましくはTg−10〜Tg
+5℃の温度で延伸する。また、後段の延伸温度は、前
段の延伸温度より低く、例えば1〜40℃の範囲で低い
温度が好ましい。しかる後必要により70〜100℃の
温度で熱処理して熱収縮性ポリエステル系フィルムを得
る。延伸に伴うフィルムの内部発熱を抑制し、巾方向の
フィルム温度斑を小さくする点に着目すれば、延伸工程
の熱伝達係数は0.0009カロリー/cm2・sec
・℃以上、好ましくは0.0011〜0.0017カロ
リー/cm2・sec・℃の条件がよい。延伸の方法
は、テンターでの横1軸延伸ばかりでなく、付加的に縦
方向を僅かに延伸することも可能である。このような2
軸延伸においては、逐次2軸延伸法、同時2軸延伸法の
いずれの方法によってもでもよく、さらに必要に応じて
縦方向または横方向に再延伸を行ってもよい。If attention is paid to making the thickness distribution of the desired heat-shrinkable polyester film uniform,
When the film is stretched in the transverse direction using a tenter, the heat transfer coefficient is 0.00 in the preheating step performed prior to the stretching step.
It is preferable to heat at a low wind speed of 13 calories / cm 2 · sec · ° C. or lower until the film temperature reaches a predetermined value.
In the transverse stretching, the total stretching ratio is 3.0 times or more, preferably 3.5 times or more, and more preferably 4.0 times or more. Further, the stretching ratio of the former stage is 40 to 60%, preferably 45 to 55% of the total stretching ratio, and Tg + 1.
A temperature of 0 to Tg + 40 ° C., preferably Tg + 15 to Tg
Stretching is carried out at a temperature of + 30 ° C., and then the stretching ratio of the latter stage is 40 to 60%, preferably 45 to 55% of the total stretching ratio, and T
g-15 to Tg + 10 ° C., preferably Tg-10 to Tg
Stretch at a temperature of + 5 ° C. Further, the stretching temperature in the latter stage is lower than the stretching temperature in the former stage, and for example, a low temperature in the range of 1 to 40 ° C. is preferable. Then, if necessary, heat treatment is performed at a temperature of 70 to 100 ° C. to obtain a heat-shrinkable polyester film. The heat transfer coefficient in the stretching process is 0.0009 calories / cm 2 · sec, focusing on the point that the internal heat generation of the film during stretching is suppressed and the film temperature unevenness in the width direction is reduced.
-The temperature is not less than 0 ° C, preferably 0.0011 to 0.0017 calories / cm 2 · sec · ° C. As for the stretching method, not only transverse uniaxial stretching with a tenter but also a slight stretching in the longitudinal direction is possible. Such 2
The axial stretching may be performed by either a sequential biaxial stretching method or a simultaneous biaxial stretching method, and may be re-stretched in the machine direction or the transverse direction as required.
【0019】[0019]
【実施例】以下、実施例により本発明をさらに具体的に
説明するが、本発明はその要旨を越えない限り、これら
の実施例に限定されるものではない。なお、本発明にお
いて、フィルムの評価方法は下記の通りである。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. In the present invention, the film evaluation method is as follows.
【0020】(1)熱収縮率 フィルムを10cm×10cmの正方形に裁断し、所定
温度±0.5℃の温水中に無荷重状態で10秒間処理し
て熱収縮させた後、フィルムの縦および横方向の寸法を
測定し、下記(1)式に従い熱収縮率を求めた。該熱収縮
率の大きい方向を主収縮方向とした。 熱収縮率=(収縮前の長さ−収縮後の長さ/収縮前の長さ)×100(%) (1) 式(1) Heat Shrinkage The film was cut into a square of 10 cm × 10 cm, heat treated in unheated water for 10 seconds in warm water having a predetermined temperature of ± 0.5 ° C., and then the lengthwise and longitudinal directions of the film were measured. The dimension in the lateral direction was measured, and the heat shrinkage rate was calculated according to the following formula (1). The direction in which the heat shrinkage rate was large was defined as the main shrinkage direction. Thermal shrinkage = (length before shrinkage-length after shrinkage / length before shrinkage) x 100 (%) (1) Equation
【0021】(2)収縮応力の最大値 東洋精機(株)製のエアーオーブン付のテンシロン(型
式:UTM−4L)を用いてチャック間を50mm、サ
ンプル形状を主収縮方向:10cm、主収縮方向と直交
方向:2cmとし、90℃エアーオーブン中で1分間加
熱した際に発現する力をレコーダーに記録し、最大値を
読みとり、下記(2)式に従い収縮応力の最大値を求め
た。 収縮応力の最大値=(読み取り値/加熱前のサンプル断面積) (Kg/mm2) (2)式(2) Maximum value of shrinkage stress Using Tensilon (model: UTM-4L) with an air oven manufactured by Toyo Seiki Co., Ltd., 50 mm between chucks, sample shape main shrinkage direction: 10 cm, main shrinkage direction The orthogonal direction: 2 cm, the force developed when heated in an air oven at 90 ° C. for 1 minute was recorded on a recorder, the maximum value was read, and the maximum value of shrinkage stress was determined according to the following formula (2). Maximum shrinkage stress = (reading value / sample cross-section before heating) (Kg / mm 2 ) (2) Equation
【0022】(3)収縮仕上がり性 Fuji Astec INC製のスチームトンネル(型式:SH−1
500−L)を用い、通過時間10秒、1ゾーン温度/
2ゾーン温度:85℃/90℃に設定し、900ccの
角型PETボトル(高さ25.5cm、中央部断面の縦
7.1cm、横7.1cm)(市販のAGF(株)製の
ブレンディに使用されているボトル)を用いてテスト
(試料数=10)した。なお、熱収縮性フイルムには、
あらかじめ東洋インキ製造(株)の草・金・白のインキ
で3色印刷した。評価は目視で行い、基準は下記の通り
とした。 シワ・色斑・収縮不足とも未発生 → ○ 色斑が発生 → △ クレーター状のシワまたは収縮不足が発生 → ×(3) Shrinkage finish Steam tunnel made by Fuji Astec INC (model: SH-1
500-L), passage time 10 seconds, 1 zone temperature /
2-zone temperature: set to 85 ° C / 90 ° C, 900 cc square PET bottle (height 25.5 cm, central section cross section length 7.1 cm, width 7.1 cm) (commercially available AGF Co., Ltd. blendy The number of samples used was 10 (sample). In addition, the heat shrinkable film,
Three-color printing was performed in advance with grass, gold, and white ink from Toyo Ink Mfg. Co., Ltd. The evaluation was performed visually, and the criteria were as follows. No wrinkles, color spots, or insufficient shrinkage → ○ Color spots → △ Crater-like wrinkles or insufficient shrinkage → ×
【0023】(4)耐破断性 上記印刷フィルムを30℃・60%RH雰囲気下で15
日間保管した後、東洋精機(株)製のテンシロン(型
式:UTM−4L)を用いて、JIS C2318の方
法で引張試験を行い、主収縮方向と直角の方向(縦方
向)の伸度30%以下の発生数で評価(試料数=50)
した。(4) Breaking resistance The above-mentioned printing film is subjected to 15 at 30 ° C. and 60% RH atmosphere.
After storage for a day, Tensilon (model: UTM-4L) manufactured by Toyo Seiki Co., Ltd. was used to perform a tensile test according to the method of JIS C2318, and the elongation was 30% in the direction perpendicular to the main shrinkage direction (longitudinal direction). Evaluation by the number of occurrences below (number of samples = 50)
did.
【0024】(5)Tg(ガラス転移点) セイコー電子工業(株)製のDSC(型式:DSC22
0)を用いて、未延伸フィルム10mgを−40℃から
120℃まで昇温速度20℃/分で昇温した際に得られ
た吸熱曲線に接線を引き、その交点をTg(ガラス転移
点)とした。(5) Tg (glass transition point) DSC manufactured by Seiko Instruments Inc. (model: DSC22)
0) was used to draw a tangent line to the endothermic curve obtained when 10 mg of an unstretched film was heated from -40 ° C to 120 ° C at a heating rate of 20 ° C / min, and the intersection was defined as Tg (glass transition point). And
【0025】(6)厚み分布 アンリツ(株)製の接触厚み計(型式:KG60/A)
を用いて、縦方向5cm・横方向50cmのサンプルの
厚みを測定(試料数=20)し、各々のサンプルについ
て、下記(3)式により厚みのバラツキを求めた。また、
該厚みのバラツキの平均値(n=50)を下記の基準に
従って評価した。 厚みのバラツキ=(最大厚み−最少厚み/平均厚み)×100(%) (3)式 平均値:6%以下 → ○ 平均値:6%より大きく10%未満 → △ 平均値:10%以上 → ×(6) Thickness distribution Contact thickness gauge manufactured by Anritsu Corporation (Model: KG60 / A)
The thickness of a sample of 5 cm in the lengthwise direction and 50 cm in the widthwise direction was measured using (sample number = 20), and the variation in the thickness of each sample was determined by the following equation (3). Also,
The average value of the thickness variations (n = 50) was evaluated according to the following criteria. Thickness variation = (maximum thickness-minimum thickness / average thickness) x 100 (%) (3) Formula Average value: 6% or less → ○ Average value: greater than 6% and less than 10% → △ Average value: 10% or more → ×
【0026】実施例に用いたポリエステルは以下の通り
である。 ポリエステルA:ポリエチレンテレフタレート ポリエステルB:エチレングリコール70モル%、ネオ
ペンチルグリコール30モル%とテレフタル酸とからな
るポリエステル ポリエステルC:ポリブチレンテレフタレート ポリエステルD:テレフタル酸65モル%、アジピン酸
10モル%、イソフタル酸25モル%とブタンジオール
とからなるポリエステルThe polyesters used in the examples are as follows. Polyester A: Polyethylene terephthalate Polyester B: Polyester consisting of 70 mol% ethylene glycol, 30 mol% neopentyl glycol and terephthalic acid Polyester C: Polybutylene terephthalate Polyester D: 65 mol% terephthalic acid, 10 mol% adipic acid, isophthalic acid Polyester consisting of 25 mol% and butanediol
【0027】(実施例1)ポリエステルAを35wt
%、ポリエステルBを55wt%、ポリエステルCを1
0wt%混合したポリエステルを280℃で押し出し・
急冷して、未延伸フィルムを得た(Tg:69℃)。該
未延伸フィルムを、熱伝達係数0.0008カロリー/
cm2・sec・℃の条件でフィルム温度が100℃に
なるまで予備加熱した後、テンターで横方向に88℃で
2.6倍、続けて同方向に70℃で2.2倍延伸した。
次いで80℃で20秒間熱処理し、厚み60μmの熱収
縮性ポリエステル系フィルムを得た。 (実施例2)ポリエステルAを35wt%、ポリエステ
ルBを55wt%、ポリエステルDを10wt%混合し
たポリエステルを280℃でTダイから押し出し、チル
ロールで急冷して、未延伸フィルムを得た(Tg67
℃)。該未延伸フィルムを実施例1の操作と同様に予備
加熱を行った後、テンターで横方向に85℃で2.6
倍、続けて同方向に70℃で2.2倍延伸した。次いで
80℃で20秒間熱処理し厚み60μmの熱収縮性ポリ
エステル系フィルムを得た。 (実施例3)未延伸フイルムを縦方向に75℃で1.1
倍延伸した後、横延伸に移った以外は実施例2に準じた
方法で製膜し、厚み60μmの熱収縮性ポリエステルフ
ィルムを得た。 (実施例4)実施例1の方法で得られた未延伸フィルム
を熱伝達係数0.0008カロリー/cm2・sec・
℃の条件でフィルム温度が91℃になるまで予備加熱し
た後、テンターで横方向に85℃で1.8倍、続けて同
方向に68℃で2.2倍延伸した。次いで80℃で20
秒間熱処理し厚み60μmの熱収縮性ポリエステル系フ
ィルムを得た。 (比較例1)ポリエステルAを15wt%、ポリエステ
ルBを75wt%、ポリエステルCを10wt%混合し
たポリエステルを用いた以外は実施例1に記載した条件
で製膜して厚み60μmの熱収縮性ポリエステル系フィ
ルムを得た。 (比較例2)実施例1の方法で得られた未延伸フィルム
を横方向に70℃で2.6倍、続けて同方向に70℃で
2.2倍延伸した(即ち、温度差をつけずに低温側だけ
で延伸した)以外は実施例1に記載した方法で製膜し、
厚み60μmの熱収縮性ポリエステル系フィルムを得
た。 (比較例3)実施例1の方法で得られた未延伸フィルム
を横方向に88℃で2.6倍、続けて同方向に88℃で
2.2倍延伸した(即ち、温度差をつけずに高温側だけ
で延伸した)以外は実施例1に記載した方法で製膜し、
厚み60μmの熱収縮性ポリエステル系フィルムを得
た。 (比較例4)横方向延伸の後段の延伸を50℃で2.2
倍とした以外は実施例1に記載した方法で製膜したが、
製膜不良(破断)のためフィルムが得られなかった。 (比較例5)横方向延伸を88℃で3.2倍、続けて同
方向に70℃で1.6倍とした以外は実施例1に記載し
た方法で製膜して厚み60μmの熱収縮性ポリエステル
系フィルムを得た。 (比較例6)横方向延伸を85℃で1.4倍、続けて同
方向に65℃で2.4倍とした以外は実施例4に記載し
た方法で製膜して厚み60μmの熱収縮性ポリエステル
系フィルムを得た。 (比較例7)熱伝達係数を0.0017カロリー/cm
2・sec・℃とし、延伸後の熱処理温度を70℃とし
た以外は実施例1に記載した方法で厚み60μmの熱収
縮性ポリエステル系フィルムを得た。 (比較例8)延伸後の熱処理温度を90℃とした以外は
実施例1に記載した方法でせいまくして、厚み60μm
の熱収縮性ポリエステル系フィルムを得た。(Example 1) 35 wt% of polyester A
%, Polyester B 55 wt%, polyester C 1
Extrude polyester mixed with 0 wt% at 280 ° C.
It cooled rapidly and the unstretched film was obtained (Tg: 69 degreeC). A heat transfer coefficient of 0.0008 calories /
The film was preheated to a temperature of 100 ° C. under the condition of cm 2 · sec · ° C., and then stretched by a tenter in the transverse direction at a draw ratio of 88 ° C. for 2.6 times and then in the same direction at a temperature of 70 ° C. for a draw ratio of 2.2 times.
Then, it was heat-treated at 80 ° C. for 20 seconds to obtain a heat-shrinkable polyester film having a thickness of 60 μm. (Example 2) A polyester in which 35 wt% of polyester A, 55 wt% of polyester B and 10 wt% of polyester D were mixed was extruded from a T die at 280 ° C and rapidly cooled by a chill roll to obtain an unstretched film (Tg67).
° C). The unstretched film was preheated in the same manner as in Example 1 and then 2.6 in a transverse direction at 85 ° C. with a tenter.
Then, the film was stretched 2.2 times in the same direction at 70 ° C. Then, it was heat-treated at 80 ° C. for 20 seconds to obtain a heat-shrinkable polyester film having a thickness of 60 μm. (Example 3) An unstretched film was stretched in the machine direction at 75 ° C for 1.1
After being double-stretched, a film was formed in the same manner as in Example 2 except that the transverse stretching was performed to obtain a heat-shrinkable polyester film having a thickness of 60 μm. (Example 4) The heat transfer coefficient of the unstretched film obtained by the method of Example 1 was 0.0008 calories / cm 2 · sec ·
The film was preheated to a temperature of 91 ° C under the condition of ° C, and then stretched by a tenter in the transverse direction at a draw ratio of 85 ° C for 1.8 times and then in the same direction at a temperature of 68 ° C for a draw ratio of 2.2 times. Then 20 at 80 ℃
It was heat-treated for a second to obtain a heat-shrinkable polyester film having a thickness of 60 μm. (Comparative Example 1) A heat-shrinkable polyester system having a thickness of 60 μm formed by the film formation under the conditions described in Example 1 except that the polyester obtained by mixing 15 wt% of polyester A, 75 wt% of polyester B and 10 wt% of polyester C was used. I got a film. (Comparative Example 2) The unstretched film obtained by the method of Example 1 was stretched 2.6 times in the transverse direction at 70 ° C and then 2.2 times in the same direction at 70 ° C (that is, with a temperature difference. Film was formed by the method described in Example 1 except that the film was stretched only on the low temperature side).
A heat-shrinkable polyester film having a thickness of 60 μm was obtained. (Comparative Example 3) The unstretched film obtained by the method of Example 1 was stretched in the transverse direction by a factor of 2.6 at 88 ° C and then in the same direction by a factor of 2.2 at 88 ° C (that is, with a temperature difference. Film was formed by the method described in Example 1 except that the film was stretched only on the high temperature side.
A heat-shrinkable polyester film having a thickness of 60 μm was obtained. (Comparative Example 4) Later stretching in the transverse direction was conducted at 50 ° C. for 2.2.
A film was formed by the method described in Example 1 except that the number was doubled.
A film could not be obtained due to poor film formation (breakage). (Comparative Example 5) A film was formed by the method described in Example 1 except that the transverse stretching was carried out 3.2 times at 88 ° C and then 1.6 times at 70 ° C in the same direction. A polyester film was obtained. (Comparative Example 6) A film was formed by the method described in Example 4 except that the transverse stretching was performed at 85 ° C by 1.4 times, and subsequently in the same direction at 65 ° C by 2.4 times. A polyester film was obtained. (Comparative Example 7) Heat transfer coefficient of 0.0017 calories / cm
A heat shrinkable polyester film having a thickness of 60 μm was obtained by the method described in Example 1 except that the heat treatment temperature after stretching was 2 sec / ° C. and the heat treatment temperature after stretching was 70 ° C. (Comparative Example 8) A thickness of 60 µm was obtained by the method described in Example 1 except that the heat treatment temperature after stretching was 90 ° C.
To obtain a heat-shrinkable polyester film.
【0028】実施例1〜4および比較例1〜8で得られ
たフィルムの評価結果を表1に示す。表1から明らかな
ように、実施例1〜4で得られた熱収縮性フィルムはい
ずれも良好な収縮仕上がり(シワ・色斑・収縮不足等の
欠点がない)を示し、耐破断性に優れ、厚み分布も良好
であった。このように、本発明の熱収縮性ポリエステル
系フィルムは、高品質で実用性が高く、特に収縮ラベル
用として好適である。一方、比較例1で得られた熱収縮
性フィルムは耐破断性が劣り、比較例2で得られた熱収
縮性フィルムはシワ・色斑が生じ、比較例3および5で
得られた熱収縮性フィルムは厚み分布が悪くさらに耐破
断性が劣り、比較例6で得られた熱収縮性フィルムは色
斑が生じ、比較例7で得られた熱収縮性フィルムはシワ
が生じかつ厚み分布が悪く、比較例8で得られた熱収縮
性フィルムは収縮不足が起こりかつ耐破断性が劣ってい
た。このように、比較例で得られた熱収縮性ポリエステ
ル系フィルムはいずれも品質が劣り、実用性が低いもの
であった。Table 1 shows the evaluation results of the films obtained in Examples 1 to 4 and Comparative Examples 1 to 8. As is clear from Table 1, the heat-shrinkable films obtained in Examples 1 to 4 all showed a good shrink finish (no defects such as wrinkles, color spots, insufficient shrinkage, etc.) and excellent break resistance. The thickness distribution was also good. As described above, the heat-shrinkable polyester film of the present invention has high quality and high practicality, and is particularly suitable for shrink labels. On the other hand, the heat-shrinkable film obtained in Comparative Example 1 is inferior in break resistance, the heat-shrinkable film obtained in Comparative Example 2 has wrinkles and color spots, and the heat-shrinkable films obtained in Comparative Examples 3 and 5 The heat-shrinkable film obtained in Comparative Example 6 has color spots, and the heat-shrinkable film obtained in Comparative Example 7 has wrinkles and a thickness distribution. Poorly, the heat shrinkable film obtained in Comparative Example 8 suffered from insufficient shrinkage and was inferior in break resistance. As described above, the heat-shrinkable polyester films obtained in Comparative Examples were inferior in quality and were not practical.
【0029】[0029]
【表1】 [Table 1]
【0030】[0030]
【発明の効果】請求項1記載の本発明の熱収縮性ポリエ
ステル系フィルムは収縮後にシワ、収縮斑、歪みの発生
が極めて少なく、かつ衝撃に対する耐破断性に優れてい
る。また、請求項2記載の本発明の熱収縮性ポリエステ
ル系フィルムの製造法は、収縮後にシワ、収縮斑、歪み
の発生が極めて少なく、かつ衝撃に対する耐破断性に優
れている熱収縮性ポリエステルフイルムが容易に得られ
る。EFFECTS OF THE INVENTION The heat-shrinkable polyester film of the present invention according to claim 1 has very few wrinkles, shrinkage spots, and distortions after shrinkage, and is excellent in impact resistance rupture resistance. Further, the method for producing a heat-shrinkable polyester film of the present invention according to claim 2 is a heat-shrinkable polyester film in which wrinkles, shrinkage spots, and distortion are extremely small after shrinkage and which is excellent in break resistance against impact. Is easily obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 奥村 慎一郎 愛知県犬山市大字木津字前畑344番地 東 洋紡績株式会社犬山工場内 (72)発明者 江崎 浩明 愛知県犬山市大字木津字前畑344番地 東 洋紡績株式会社犬山工場内 (72)発明者 高林 清蔵 愛知県犬山市大字木津字前畑344番地 東 洋紡績株式会社犬山工場内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shinichiro Okumura 344 Maebata, Kizu, Inuyama City, Aichi Prefecture Inuyama Plant, Toyobo Co., Ltd. (72) Hiroaki Esaki 344 Maebata, Kizu, Inuyama City, Aichi Prefecture Toyobo Co., Ltd. Inuyama Factory (72) Inventor Kiyozo Takabayashi Inuyama City, Aichi Prefecture, Kyuzu, Majihata 344, Toyobo Co., Ltd. Inuyama Factory
Claims (2)
70モル%以上、ジオール成分中エチレングリコール成
分が70モル%であるポリエステルからなる延伸された
フイルムであって、90℃のエアーオーブン中で加熱開
始から1分後までの間に発現する主収縮方向の収縮応力
の最大値(σmax)が0.5〜1.2Kg/mm2、75
℃温水中で10秒間処理後の主収縮方向の熱収縮率が4
0%以下、95℃温水中で10秒間処理後の主収縮方向
の熱収縮率が50%以上であることを特徴とする熱収縮
性ポリエステル系フィルム。1. A stretched film comprising a polyester having a terephthalic acid component of 70 mol% or more in a dicarboxylic acid component and an ethylene glycol component of 70 mol% in a diol component, which is heated in an air oven at 90 ° C. The maximum value (σmax) of the contraction stress in the main contraction direction that occurs between 1 minute and 1 minute after is 0.5 to 1.2 kg / mm 2 , 75
The heat shrinkage in the main shrinkage direction after treatment for 10 seconds in warm water at 4 ℃ is 4
A heat-shrinkable polyester film having a heat-shrinkage rate of 0% or less and a main shrinkage direction of 50% or more after treatment in warm water of 95 ° C. for 10 seconds.
70モル%以上、ジオール成分中エチレングリコール成
分が70モル%であるポリエステル未延伸フイルムを主
収縮方向となる方向に延伸するにあたり、全延伸倍率を
3.0倍以上、全延伸倍率の40〜60%を延伸する前
段の延伸温度をTg+10〜Tg+40℃、その後の、
全延伸倍率の60〜40%を延伸する後段の延伸温度を
Tg−15〜Tg+10℃で且つ前段の延伸温度より低
い温度で延伸することを特徴とする熱収縮性ポリエステ
ル系フィルムの製造法。2. When stretching a polyester unstretched film having a terephthalic acid component in the dicarboxylic acid component of 70 mol% or more and an ethylene glycol component in the diol component of 70 mol% in the direction of the main shrinkage direction, the total stretching ratio is A stretching temperature of 3.0 g or more and Tg + 10 to Tg + 40 ° C. in the preceding stage for stretching 40 to 60% of the total stretching ratio, and thereafter,
A method for producing a heat-shrinkable polyester film, which comprises stretching at a stretching temperature of Tg-15 to Tg + 10 ° C. in the latter stage of stretching 60 to 40% of the total stretching ratio and a temperature lower than the stretching temperature of the former stage.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7822596A JP3829353B2 (en) | 1996-03-05 | 1996-03-05 | Heat-shrinkable polyester film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7822596A JP3829353B2 (en) | 1996-03-05 | 1996-03-05 | Heat-shrinkable polyester film |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH09239833A true JPH09239833A (en) | 1997-09-16 |
JP3829353B2 JP3829353B2 (en) | 2006-10-04 |
Family
ID=13656116
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7822596A Expired - Fee Related JP3829353B2 (en) | 1996-03-05 | 1996-03-05 | Heat-shrinkable polyester film |
Country Status (1)
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JP (1) | JP3829353B2 (en) |
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