JPH05245930A - Polyester heat-shrinkable film - Google Patents
Polyester heat-shrinkable filmInfo
- Publication number
- JPH05245930A JPH05245930A JP4096565A JP9656592A JPH05245930A JP H05245930 A JPH05245930 A JP H05245930A JP 4096565 A JP4096565 A JP 4096565A JP 9656592 A JP9656592 A JP 9656592A JP H05245930 A JPH05245930 A JP H05245930A
- Authority
- JP
- Japan
- Prior art keywords
- film
- heat
- temperature
- shrinkage
- heat treatment
- 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.)
- Pending
Links
Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Polyesters Or Polycarbonates (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリエステル系熱収縮
フイルムに関し、更に詳しくは、低温収縮性、均一収縮
性等に優れ、例えば各種容器用収縮ラベルに用いて好適
なポリエステル系熱収縮フイルムに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester-based heat-shrinkable film, and more particularly to a polyester-based heat-shrinkable film which is excellent in low-temperature shrinkability and uniform shrinkability and is suitable for use in shrinkable labels for various containers. It is a thing.
【０００２】[0002]
【従来の技術】従来、合成樹脂製の熱収縮性フイルム
は、再加熱によって収縮する性質を利用して、収縮包
装、収縮ラベル、キャップシール等の用途に広く用いら
れている。例えば、ポリエチレンテレフタレート（以下
「ＰＥＴ」という）製容器や、ガラス製容器等の各種容
器を対象とする収縮ラベルには、塩化ビニル系樹脂や、
発泡ポリスチレン系樹脂等の一軸延伸フイルムが用いら
れている。その中でも、塩化ビニル系樹脂の一軸延伸フ
イルムからなる熱収縮フイルムは、低温収縮性、印刷適
性が良好であるために汎用されている。2. Description of the Related Art Conventionally, a heat shrinkable film made of a synthetic resin has been widely used for shrink wrapping, shrink label, cap seal, etc. due to its property of shrinking by reheating. For example, a shrinkable label for various containers such as a container made of polyethylene terephthalate (hereinafter referred to as “PET”) and a container made of glass includes vinyl chloride resin,
A uniaxially stretched film such as expanded polystyrene resin is used. Among them, the heat-shrinkable film made of a uniaxially stretched film of vinyl chloride resin is widely used because of its good low-temperature shrinkability and printability.
【０００３】しかしながら、塩化ビニル系樹脂からなる
熱収縮フイルムは、耐熱性が低い上に、焼却時に有毒な
塩化水素ガスを発生するという衛生上の問題を抱えてお
り、更に、これを収縮ラベルとしてＰＥＴ容器に用いた
ものは、その収縮ラベルと一体になったＰＥＴ容器は、
溶融回収時に異種の樹脂が混在するので、それを回収し
て再利用することができないという問題もあった。However, the heat shrink film made of vinyl chloride resin has low heat resistance and has a hygienic problem that it produces toxic hydrogen chloride gas when incinerated. The one used for the PET container is a PET container that is integrated with the shrink label,
There is also a problem that different types of resins are mixed at the time of melting and recovery, so that it cannot be recovered and reused.
【０００４】一方、ＰＥＴ等のポリエステル系樹脂から
なる熱収縮性フイルムは、耐熱性に優れ、しかも焼却時
に塩化水素等の有毒ガスが発生しないという特性を備え
ているので、塩化ビニル系熱収縮フイルムに代わるもの
としてその利用が注目されるようになった。On the other hand, a heat-shrinkable film made of a polyester resin such as PET has excellent heat resistance and does not generate a toxic gas such as hydrogen chloride when incinerated. Its use has gained attention as an alternative to.
【０００５】ところが、エチレンテレフタレートを繰り
返し単位とするＰＥＴのようなホモポリエステル樹脂
は、耐衝撃性やヒートシール性に劣るばかりでなく、延
伸時に結晶化するために熱収縮フイルムの熱収縮開始温
度が比較的高く、しかも温度上昇に伴って収縮率が急激
に増大する傾向を示し、耐衝撃性やヒートシール性に劣
るので、収縮包装用フイルムとしては不適であった。そ
こで、もっぱら結晶化を抑制する方向で研究が進められ
た。即ち、共重合ポリエステルや、ホモポリエステルに
共重合ポリエステルをブレンドした組成物等を材料とし
て製膜し、延伸することが試みられ、今日迄に数多くの
提案がなされている。However, a homopolyester resin such as PET containing ethylene terephthalate as a repeating unit is not only inferior in impact resistance and heat sealability but also has a heat shrinkage starting temperature of the heat shrinkable film because it is crystallized during stretching. The shrinkage rate is relatively high, and the shrinkage rate tends to increase rapidly as the temperature rises, and the impact resistance and heat sealability are poor. Therefore, the shrinkage wrapping film is unsuitable. Therefore, research has been advanced exclusively in the direction of suppressing crystallization. That is, it has been attempted to form a film using a copolyester or a composition obtained by blending a homopolyester with a copolyester as a material and stretching the film, and many proposals have been made to date.
【０００６】例えば、特開昭５７−４２７２６号公報に
は、芳香族ジカルボン酸成分としてテレフタル酸、ジオ
ール成分としてエチレングリコール及び１，４−シクロ
ヘキサンジメタノールからなる共重合ポリエステル系収
縮包装用フイルムが開示されており、特開平２−１６０
３２号公報及び特開平２−１５５６３０号公報には、共
重合ポリエステル製の熱収縮フイルムであって、一定方
向の収縮率や収縮応力について、特定値のものを用いた
ときは、収縮むらの改善を図り得ることが開示されてお
り、また、特開平２−１５３９４１号公報には、特定の
ジカルボン酸成分とジオール成分とから合成され、且つ
ガラス転移温度の特定範囲のものについては、低温収縮
性に優れ、且つ自然収縮性が少ないものが得られること
を開示している。For example, Japanese Patent Application Laid-Open No. 57-42726 discloses a copolyester type shrink wrapping film comprising terephthalic acid as an aromatic dicarboxylic acid component, ethylene glycol as a diol component, and 1,4-cyclohexanedimethanol. Japanese Patent Laid-Open No. 2-160
No. 32 and Japanese Patent Laid-Open No. 2-155630 disclose a heat shrink film made of a copolyester, which has improved shrinkage unevenness when a specific value is used for the shrinkage ratio and shrinkage stress in a certain direction. It is disclosed in Japanese Patent Laid-Open No. 2-153941 that a compound having a specific dicarboxylic acid component and a diol component and having a glass transition temperature in a specific range has low temperature shrinkability. It is disclosed that a material having excellent heat resistance and low natural shrinkability can be obtained.
【０００７】[0007]
【本発明が解決しようとする課題】しかしながら，これ
らの従来技術では、未だ満足できる収縮特性を持つポリ
エステル系熱収縮フイルムを得るに至っていない。なぜ
ならば、上記の各従来技術で開示されているポリエステ
ル系熱収縮フイルムであっても、収縮を開始してから収
縮が完了するまでの加熱されたフイルム自体の温度差、
即ち収縮温度範囲は、なお２０℃以下であり、このよう
に極めて狭い収縮温度範囲しかないフイルムの場合は、
加熱されると、大きな収縮率で急激に収縮することにな
り、シュリンクトンネルを高速で通過させ５〜２０秒間
の短時間で収縮を完了させようとすると、収縮むらや皺
が依然として発生するという問題が残されているのであ
る。However, these prior art techniques have not yet yielded a polyester-based heat-shrinkable film having satisfactory shrinkage characteristics. Because, even in the polyester-based heat-shrinkable film disclosed in each of the above-mentioned prior art, the temperature difference of the heated film itself from the start of shrinkage to the completion of shrinkage,
That is, the shrinking temperature range is still 20 ° C. or less, and in the case of a film having such an extremely narrow shrinking temperature range,
When heated, it shrinks rapidly with a large shrinkage ratio, and when trying to complete shrinkage in a short time of 5 to 20 seconds by passing through a shrink tunnel at high speed, uneven shrinkage and wrinkles still occur. Is left.
【０００８】この辺の事情を更に詳述すると、被包装物
品が、シュリンクトンネルを通過する際、トンネル入り
口付近では、被包装物の前面と後面とでフイルムに温度
差が生じる。またトンネル内では、フイルムが被包装物
に接している部分と、接していない部分にも温度差が生
ずる。この温度差は、トンネル通過速度が大きいほど温
度差も大きくなる。このようなシュリンク包装機におい
て、収縮開始後急激に収縮率が増大するようなフイルム
を使用すると、フイルムの温度差に起因する収縮むらが
非常に大きくなり、予めフイルムに施された印刷の歪み
や皺が発生する。このような大きな歪みや皺は、シュリ
ンクトンネルの出口付近で仮にフイルム温度が均一にな
ったとしても、もはや修復されず最後まで残るのであ
る。Explaining the situation on this side in more detail, when the article to be packaged passes through the shrink tunnel, a temperature difference occurs between the front and rear surfaces of the article to be packaged near the entrance of the tunnel. Further, in the tunnel, a temperature difference occurs between the part where the film is in contact with the object to be packaged and the part where it is not in contact. This temperature difference increases as the tunnel passage speed increases. In such a shrink wrapping machine, if a film whose shrinkage rate increases rapidly after the start of shrinkage is used, the unevenness of shrinkage caused by the temperature difference of the film becomes very large, and the distortion of the printing applied to the film in advance or Wrinkles occur. Even if the film temperature becomes uniform near the exit of the shrink tunnel, such large distortions and wrinkles are not repaired and remain until the end.
【０００９】そこで、上述のような従来技術の欠点を解
消し、シュリンクトンネルを高速で通過させ、５〜２０
秒の短時間で収縮を完了させても、収縮むらや皺の発生
がなく均一な収縮が達成できるポリエステル系熱収縮フ
イルムを得る為に、本発明者等は鋭意研究を進めた結
果、所期のフイルムを得る為には、第一にフイルムを構
成する樹脂の成分を更に厳選すること、第二に延伸され
たフイルムをそのまま使用するのではなく、或る特定の
温度範囲及び時間をかけて熱処理する必要があることを
知見し、本発明を完成するに至ったのである。Therefore, the drawbacks of the prior art as described above are eliminated, and the shrink tunnel is passed at a high speed to obtain 5 to 20.
In order to obtain a polyester-based heat-shrinkable film capable of achieving uniform shrinkage without the occurrence of shrinkage unevenness and wrinkles even when shrinking is completed in a short time of seconds, the present inventors have conducted extensive research and as a result, In order to obtain the film of No. 1, first, the components of the resin that make up the film are further carefully selected, and secondly, the stretched film is not used as it is, but it takes a certain temperature range and time. They found that heat treatment was necessary, and completed the present invention.
【００１０】[0010]
【課題を解決する為の手段】本発明は、「テレフタル酸
を主体とするジカルボン酸成分と、エチレングリコール
を主体とするジオール成分と、炭素数が３〜１０の脂肪
族ジカルボン酸、炭素数が３〜１０の脂肪族ジオール、
炭素数が２〜１０の脂肪族ジオールの多量体、シクロヘ
キサンジメタノール、シクロヘキサンジオールの群中か
ら選ばれる１種もしくは２種以上の共重合成分とから得
られる共重合ポリエステル系樹脂を材料とした延伸フイ
ルムが、延伸温度〜延伸温度＋１００℃の温度条件下で
５〜３００秒の時間をかけて熱処理されてなることを特
徴とするポリエステル系熱収縮フイルム」をその要旨と
するものである。The present invention provides a "dicarboxylic acid component mainly containing terephthalic acid, a diol component mainly containing ethylene glycol, an aliphatic dicarboxylic acid having 3 to 10 carbon atoms, and 3-10 aliphatic diols,
Stretching using a copolymerized polyester resin obtained from a multimer of an aliphatic diol having 2 to 10 carbon atoms, and one or more copolymerization components selected from the group of cyclohexanedimethanol and cyclohexanediol A polyester-based heat-shrinkable film characterized in that the film is heat-treated under a temperature condition of stretching temperature to stretching temperature + 100 ° C. for a time of 5 to 300 seconds.
【００１１】本発明のポリエステル系熱収縮フイルムの
材料となる共重合ポリエステル系樹脂においては、共重
合成分として、炭素数が３〜１０の脂肪族ジカルボン
酸、炭素数が３〜１０の脂肪族ジオール、炭素数が２〜
１０の脂肪族ジオールの多量体、シクロヘキサンジメタ
ノール、シクロヘキサンジオールの群中から選ばれる１
種もしくは２種以上のものを用いて重合したものである
ことが、重要なポイントの一つであり、何れも柔軟な分
子鎖を有する成分である。In the copolymerized polyester resin used as the material for the polyester heat shrinkable film of the present invention, an aliphatic dicarboxylic acid having 3 to 10 carbon atoms and an aliphatic diol having 3 to 10 carbon atoms are used as a copolymerization component. , Carbon number 2
1 selected from the group of 10 aliphatic diol multimers, cyclohexanedimethanol, cyclohexanediol
One of the important points is that it is polymerized by using one kind or two or more kinds, and each is a component having a flexible molecular chain.
【００１２】具体的には、炭素数が３〜１０の脂肪族ジ
カルボン酸としては、例えばマロン酸、琥珀酸、アジピ
ン酸、アゼライン酸、マレイン酸、フマル酸等が挙げら
れ、炭素数が３〜１０の脂肪族ジオールとしては、１，
２─プロパンジオール、１，３─プロパンジオール、プ
ロピレングリコール、トリメチレングリコール、１，４
−ブタンジオール、１，６−ヘキサンジオール等が挙げ
られ、炭素数が２〜１０の脂肪族ジオールの多量体とし
ては、ジエチレングリコール、ポリエチレングリコー
ル、ポリプロピレングリコール、ポリ（トリメチレンオ
キシド）グリコール、ポリ（テトラメチレンオキシド）
グリコール等が挙げられる。Specific examples of the aliphatic dicarboxylic acid having 3 to 10 carbon atoms include malonic acid, succinic acid, adipic acid, azelaic acid, maleic acid and fumaric acid, which have 3 to 10 carbon atoms. As the aliphatic diol of 10, 1,
2-propanediol, 1,3-propanediol, propylene glycol, trimethylene glycol, 1,4
-Butanediol, 1,6-hexanediol and the like are mentioned, and as the multimers of the aliphatic diol having 2 to 10 carbon atoms, diethylene glycol, polyethylene glycol, polypropylene glycol, poly (trimethylene oxide) glycol, poly (tetra Methylene oxide)
Examples thereof include glycol.
【００１３】そして、２種以上のものを用いる場合は、
ジカルボン酸、脂肪族ジオール、脂肪族ジオールの多量
体、シクロヘキサンジメタノール、シクロヘキサンジオ
ールの何れか一つのグループから選択してもよいし、複
数のグループから選択してもよい。When two or more kinds are used,
It may be selected from any one group of dicarboxylic acids, aliphatic diols, multimers of aliphatic diols, cyclohexanedimethanol and cyclohexanediol, or may be selected from a plurality of groups.
【００１４】これらのジカルボン酸成分及びジオール成
分では、炭素数が３〜１０のものでなければならず、ま
た、脂肪族ジオールの多量体では、炭素数が２〜１０の
ものでなければならない。これらの炭素数に満たない場
合は広い温度範囲にわたって、徐々に収縮率が増加する
特性が得られず、また、これらの炭素数を超えると、結
晶化度が大となって収縮率が低下する傾向にある。The dicarboxylic acid component and the diol component must have 3 to 10 carbon atoms, and the aliphatic diol multimer must have 2 to 10 carbon atoms. If the number of carbon atoms is less than these, it is not possible to obtain the characteristic that the shrinkage rate gradually increases over a wide temperature range. If the number of carbon atoms is exceeded, the crystallinity becomes large and the shrinkage rate decreases. There is a tendency.
【００１５】本発明者等の実験によれば、このような共
重合成分を含むポリエステル樹脂は、柔軟な分子鎖を有
するものであるから、例えば、ガラス転移温度〜ガラス
転移温度＋１０℃の温度で１．５〜６倍に延伸し、得ら
れたフイルムを熱収縮させると、収縮開始後急激に収縮
率が増大する。ところが、本発明者等が更に研究を進め
た結果、延伸後、例えば延伸温度よりも５℃より高い温
度で１５秒以上熱処理して得られるフイルムを熱収縮さ
せると、収縮開始後、広い温度範囲（３０℃以上の幅）
にわたって収縮率が徐々に増加することが認められた。
この理由は次のように考察される。According to experiments conducted by the present inventors, the polyester resin containing such a copolymer component has a flexible molecular chain, and therefore, for example, at a temperature of glass transition temperature to glass transition temperature + 10 ° C. When the film obtained is stretched 1.5 to 6 times and the resulting film is heat-shrinked, the shrinkage rate rapidly increases after the start of shrinkage. However, as a result of further research conducted by the present inventors, when a film obtained by heat treatment after stretching, for example, at a temperature higher than 5 ° C. for 15 seconds or more is heat-shrinked, a wide temperature range after shrinkage is started. (Width above 30 ° C)
It was observed that the shrinkage rate gradually increased over the period.
The reason for this is considered as follows.
【００１６】一般に熱収縮フイルムは、その延伸加工の
段階で分子鎖に歪みが生じ、これを拘束したまま急冷す
ることにより歪みが凍結され、熱収縮性フイルムが得ら
れるのであり、使用に際してこのフイルムを再加熱する
と、ガラス転移温度付近の温度で分子鎖が動き始め、分
子鎖に残された歪みが解消することによって、フイルム
が収縮するのである。ところで、延伸の温度条件として
は、一般にガラス転移温度〜ガラス転移温度＋１０℃の
温度で延伸するのであるが、生じた分子鎖の歪みは、熱
収縮時にガラス転移温度〜ガラス転移温度＋１０℃の温
度範囲ですべて解消してしまうために、収縮開始後急激
に収縮率が増大するという収縮特性を持つのである。In general, a heat-shrinkable film is distorted in its molecular chain at the stage of its stretching process, and the strain is frozen by quenching while restraining it to obtain a heat-shrinkable film. When is reheated, the molecular chain starts to move at a temperature near the glass transition temperature, and the strain left in the molecular chain is eliminated, whereby the film shrinks. By the way, as the temperature condition for stretching, the glass is generally stretched at a temperature of glass transition temperature to glass transition temperature + 10 ° C, but the strain of the generated molecular chain is the temperature of glass transition temperature to glass transition temperature + 10 ° C during heat shrinkage. Since all of them are eliminated within the range, it has a contraction characteristic that the contraction rate rapidly increases after the start of contraction.
【００１７】一方、このように延伸後に急冷せずに熱処
理工程にかけると、分子鎖の動きが活発化し、歪みの緩
和と移動が起こる。この時、本発明のように柔軟な分子
鎖が存在すると、歪みの形態が様々に変化する。なかで
も、１，４−シクロヘキサンジメタノールは、シス・ト
ランス型異性体が存在し、このような分子構造をとるも
のは、その傾向が強いのである。そしてこのように歪み
の形態が種々変化したものは、得られたフイルムの収縮
温度も様々である（但しガラス転移温度よりは高温）。On the other hand, when the film is subjected to a heat treatment step without being rapidly cooled after being stretched as described above, the movement of the molecular chain is activated, and the strain is relaxed and transferred. At this time, if a flexible molecular chain is present as in the present invention, the form of strain changes variously. Among them, 1,4-cyclohexanedimethanol has cis / trans isomers, and those having such a molecular structure have a strong tendency. The film having various strains thus obtained has various shrinking temperatures of the obtained film (however, the temperature is higher than the glass transition temperature).
【００１８】本発明において、共重合成分である、脂肪
族ジカルボン酸等の共重合成分の含有量は、共重合成分
が酸成分の場合は、酸成分中５〜５０モル％とし、ジオ
ール成分の場合は、ジオール成分中５〜５０モル％と
し、酸成分、ジオール成分どちらも含む場合は、その合
計が全モノマー中５〜５０モル％とするのがよい。な
お、共重合成分のジオール成分が脂肪族ジオールの多量
体のときは単量体換算のモル分率をいう。含有量は共重
合成分の含有量が５モル％未満の場合は、上記のような
様々な形態の歪みの発生する割合が小さく、収縮開始後
広い温度範囲にわたって収縮率が徐々に増加するという
本発明特有の収縮特性が得難い。また、共重合成分の含
有量が５０モル％を超えると、ポリエステル系樹脂が結
晶化し易くなるため、得られるフイルムの収縮率が低下
し、ヒートシール性も低下する。In the present invention, when the copolymerization component is an acid component, the content of the copolymerization component such as an aliphatic dicarboxylic acid is 5 to 50 mol% in the acid component, and the content of the diol component is In this case, the amount is 5 to 50 mol% in the diol component, and when both the acid component and the diol component are included, the total amount is preferably 5 to 50 mol% in all the monomers. In addition, when the diol component of the copolymerization component is a multimer of aliphatic diol, it means a mole fraction in terms of monomer. When the content of the copolymerization component is less than 5 mol%, the rate of occurrence of strains in various forms as described above is small, and the shrinkage rate gradually increases over a wide temperature range after the start of shrinkage. It is difficult to obtain shrinkage characteristics peculiar to the invention. Further, when the content of the copolymerization component exceeds 50 mol%, the polyester resin is likely to be crystallized, so that the shrinkage rate of the obtained film is lowered and the heat sealability is also lowered.
【００１９】叙上のようなポリエステル系樹脂を用い
て、本発明の熱収縮フイルムを成形するには、先ず、ポ
リエステル系樹脂を、押出機を用いて溶融混練し、Ｔダ
イ法、チューブラ法等によりシート状もしくはチューブ
状に押し出して未延伸フイルムを成形する。To mold the heat-shrinkable film of the present invention using the polyester resin as described above, first, the polyester resin is melt-kneaded using an extruder, and the T-die method, the tubular method, etc. Is extruded into a sheet or tube to form an unstretched film.
【００２０】次いで、この未延伸フイルムをロール延伸
法、テンター延伸法、チューブラ延伸法等の公知の延伸
方法を適宜選択して、少なくとも一軸方向に１．５〜６
倍程度延伸して延伸フイルムを成形するのである。延伸
工程における延伸温度は、ガラス転移温度〜ガラス転移
温度＋１０℃とするのがよい。延伸温度がガラス転移温
度に満たない場合はフイルムが切れ易く、ガラス転移温
度＋１０℃を超えると均一延伸が難しい。また、延伸倍
率は、１．５〜６倍とするのがよい。１．５倍より低い
と得られたフイルムが充分に収縮せず、６倍より高い場
合は延伸時にフイルムが切れ易くなり、生産性が低下す
る。Then, a known stretching method such as a roll stretching method, a tenter stretching method, or a tubular stretching method is appropriately selected for this unstretched film so that the unstretched film has a thickness of 1.5 to 6 in at least one axial direction.
The stretched film is formed by stretching the film about twice. The stretching temperature in the stretching step is preferably glass transition temperature to glass transition temperature + 10 ° C. If the stretching temperature is lower than the glass transition temperature, the film is easily broken, and if it exceeds the glass transition temperature + 10 ° C, uniform stretching is difficult. The draw ratio is preferably 1.5 to 6 times. If it is less than 1.5 times, the obtained film does not shrink sufficiently, and if it is more than 6 times, the film tends to be broken during stretching and productivity is lowered.
【００２１】そして、従来はこの後、適当な冷媒により
急冷してその延伸効果を保持させるのであるが、本発明
の場合は、延伸されたフイルムは急冷しないでそのまま
次工程の熱処理工程に送り込むのであり、本発明におけ
るもう一つの重要なポイントである。この熱処理を行う
とこのましい結果が得られるのは、延伸効果がある程度
抑制され、加熱収縮時の急激な収縮を防ぐことになるか
らである。Then, conventionally, after this, it is cooled rapidly by a suitable refrigerant to maintain its stretching effect. In the case of the present invention, however, the stretched film is sent to the next heat treatment step as it is without being rapidly cooled. Yes, this is another important point in the present invention. The reason why this desirable result is obtained by carrying out this heat treatment is that the stretching effect is suppressed to some extent and a rapid shrinkage during heat shrinkage is prevented.
【００２２】また、熱処理の方法としてはロール、テン
ター等公知の熱処理機を用いて熱処理することによって
得ることができる。この熱処理条件は、延伸温度〜延伸
温度＋１００℃の温度で５〜３００秒でなければなら
ず、好ましくは、延伸温度＋５℃〜延伸温度＋４０℃で
１５〜１２０秒とするのがよい。熱処理温度を低くする
場合は熱処理時間を長くし、熱処理温度を高くする場合
は、熱処理時間を短くすることにより好ましい熱処理効
果が得られる。そして、熱処理温度が延伸温度より低い
場合は充分な熱処理効果が得られないし、延伸温度＋１
００℃を超える高温で熱処理すると、収縮率の低下が大
きく、収縮フイルムとしての充分な収縮率が得られな
い。The heat treatment can be performed by using a known heat treatment machine such as a roll or a tenter. This heat treatment condition must be a stretching temperature to stretching temperature + 100 ° C for 5 to 300 seconds, and preferably a stretching temperature + 5 ° C to stretching temperature + 40 ° C for 15 to 120 seconds. When the heat treatment temperature is lowered, the heat treatment time is lengthened, and when the heat treatment temperature is raised, the heat treatment time is shortened to obtain a preferable heat treatment effect. If the heat treatment temperature is lower than the stretching temperature, a sufficient heat treatment effect cannot be obtained, and the stretching temperature +1
When the heat treatment is performed at a high temperature exceeding 00 ° C., the shrinkage rate is largely reduced, and a sufficient shrinkage rate as a shrinkable film cannot be obtained.
【００２３】また、熱処理時間が５秒未満の場合は、フ
イルム温度が不均一な状態で熱処理が終わってしまうた
め、熱処理効果にむらが生じ、収縮むらや皺の原因とな
る。一方、熱処理時間が３００秒を超える場合は、収縮
率の低下が大きく、また、設備的には、熱処理ロールを
使用する場合は、ロール径を大きくする必要があり、テ
ンターを使用する場合は、熱処理ゾーンを長くすること
が必要となる。なお、ラインスピードを遅くしても、熱
処理時間を長くすることができるが、生産性が低下する
ため、好ましくない。Further, if the heat treatment time is less than 5 seconds, the heat treatment ends with the film temperature being non-uniform, so that the heat treatment effect becomes uneven, causing shrinkage unevenness and wrinkles. On the other hand, when the heat treatment time exceeds 300 seconds, the shrinkage rate is largely reduced, and in terms of equipment, when the heat treatment roll is used, it is necessary to increase the roll diameter, and when the tenter is used, It is necessary to lengthen the heat treatment zone. Even if the line speed is slowed down, the heat treatment time can be lengthened, but this is not preferable because the productivity is lowered.
【００２４】以上により、得られたポリエステル系熱収
縮フイルムは、シュリンクトンネルを高速で通過させ、
５〜２０秒の短時間で収縮を完了させても、収縮むらや
皺の無い均一な収縮が達成できる。The polyester heat shrink film thus obtained is passed through a shrink tunnel at high speed,
Even if the shrinkage is completed in a short time of 5 to 20 seconds, uniform shrinkage without uneven shrinkage and wrinkles can be achieved.
【００２５】なお、本発明で得られるポリエステル系熱
収縮フイルムの厚みは、特に限定はないが、もし収縮ラ
ベルに用いる場合は、上記の加熱収縮における各種条件
からみて、１０〜１２０μｍ、好ましくは３０〜７０μ
ｍとするのがよい。The thickness of the polyester heat-shrinkable film obtained in the present invention is not particularly limited, but when it is used for a shrinkable label, it is 10 to 120 μm, preferably 30 μm in view of various conditions in the above heat shrinkage. ~ 70μ
It is better to set m.
【００２６】[0026]
【作用】本発明ポリエステル系熱収縮フイルムは、テレ
フタル酸を主体とするジカルボン酸成分と、エチレング
リコールを主体とするジオール成分と、炭素数が３〜１
０の脂肪族ジカルボン酸、炭素数が３〜１０の脂肪族ジ
オール、炭素数が２〜１０の脂肪族ジオールの多量体、
シクロヘキサンジメタノール、シクロヘキサンジオール
の群中から選ばれる１種もしくは２種以上の共重合成分
とから得られる共重合ポリエステル系樹脂を材料とした
延伸フイルムを、急冷することなく特定の温度条件下で
特定の時間をかけて熱処理を施して得られたものである
から、様々の形態の歪みが形成され、熱収縮時に収縮開
始後広い温度範囲にわたって収縮率が徐々に増加すると
いう収縮特性が具備されている。The polyester heat-shrinkable film of the present invention has a dicarboxylic acid component mainly containing terephthalic acid, a diol component mainly containing ethylene glycol, and a carbon number of 3 to 1.
0 aliphatic dicarboxylic acid, aliphatic diol having 3 to 10 carbon atoms, multimer of aliphatic diol having 2 to 10 carbon atoms,
A stretched film made of a copolyester resin obtained from one or more copolymerization components selected from the group of cyclohexanedimethanol and cyclohexanediol is specified under specific temperature conditions without being rapidly cooled. Since it was obtained by performing heat treatment over a period of time, various types of strains are formed, and it has shrinkage characteristics that the shrinkage rate gradually increases over a wide temperature range after the start of shrinkage during thermal shrinkage. There is.
【００２７】[0027]
【実施例】以下、実施例について詳細に説明する。実施例１ ジカルボン酸成分が、テレフタル酸１００モル％よりな
り、ジオール成分が、エチレングリコール７０モル％と
１，４−シクロヘキサンジメタノール３０モル％よりな
る共重合ポリエステル樹脂を押出機を用いてシート状に
押し出し、厚さ１２０μｍの未延伸フイルムを得た。こ
の未延伸フイルムを、テンター延伸機を用い、８５℃で
横方向に３．０倍に延伸した後、同じくテンター延伸機
で横方向を保持したまま熱処理温度が１００℃、処理時
間１２０秒で熱処理し、厚さ４０μｍの熱収縮性フイル
ムを得、このフイルムのガラス転移温度を測定した。測
定には示差走査熱量計（ＤＳＣ）を使用した。EXAMPLES Examples will be described in detail below. Example 1 A copolymerized polyester resin in which a dicarboxylic acid component was 100 mol% terephthalic acid and a diol component was 70 mol% ethylene glycol and 30 mol% 1,4-cyclohexanedimethanol was used in a sheet form using an extruder. It was extruded to obtain an unstretched film having a thickness of 120 μm. This unstretched film was stretched 3.0 times in the transverse direction at 85 ° C. using a tenter stretching machine, and then heat treated at a temperature of 100 ° C. for a treatment time of 120 seconds while the transverse direction was also held by the tenter stretching machine. Then, a heat-shrinkable film having a thickness of 40 μm was obtained, and the glass transition temperature of this film was measured. A differential scanning calorimeter (DSC) was used for the measurement.
【００２８】次に、この熱収縮性フイルムについて、６
０〜１１０℃の温度域の、１０℃毎における延伸方向の
各熱収縮率を測定した。収縮率の測定は、サンプルとし
て、長さ（延伸方向）１００ｍｍ、幅１０ｍｍに切断し
たものを用い、測定温度に設定した熱風中で、５分間収
縮させて、その収縮率を測定した。Next, regarding this heat-shrinkable film, 6
Each heat shrinkage ratio in the stretching direction in the temperature range of 0 to 110 ° C. at every 10 ° C. was measured. The shrinkage rate was measured by using a sample cut into a length (stretching direction) of 100 mm and a width of 10 mm, shrinking it in hot air set to the measurement temperature for 5 minutes, and measuring the shrinkage rate.
【００２９】更に、この熱収縮性フイルムに格子状の模
様を印刷し、延伸方向に巻いてヒートシールにより接合
し、チューブ状にして熱収縮性ラベルとした。このラベ
ルをＰＥＴ製ボトルにかぶせ、シュリンクトンネルを通
過させ、収縮させた後、ラベルの印刷の歪みや皺の発生
の有無についての外観を観察し評価した。また、シュリ
ンクトンネルは２ゾーンからなり、第１ゾーンの熱風温
度を１００℃、第２ゾーンの熱風温度を２００℃に設定
した。Further, a grid-like pattern was printed on the heat-shrinkable film, wound in the stretching direction and bonded by heat sealing, and formed into a tube to obtain a heat-shrinkable label. This label was put on a PET bottle, passed through a shrink tunnel, and contracted, and then the appearance of the print distortion of the label and the presence or absence of wrinkles was observed and evaluated. The shrink tunnel was composed of two zones, and the hot air temperature in the first zone was set to 100 ° C and the hot air temperature in the second zone was set to 200 ° C.
【００３０】実施例２ ジカルボン酸成分が、テレフタル酸９５モル％とイソフ
タル酸５モル％よりなり、ジオール成分が、エチレング
リコール７５モル％と１，４−シクロヘキサンジメタノ
ール１５モル％とジエチレングリコール１０モル％より
なる共重合ポリエステル樹脂を用いたこと以外は、実施
例１と同様にして厚さ１６０μｍの未延伸フイルムを得
た。 Example 2 The dicarboxylic acid component was 95 mol% terephthalic acid and 5 mol% isophthalic acid, and the diol component was 75 mol% ethylene glycol, 15 mol% 1,4-cyclohexanedimethanol and 10 mol% diethylene glycol. An unstretched film having a thickness of 160 μm was obtained in the same manner as in Example 1 except that the copolyester resin was used.
【００３１】この未延伸フイルムを、テンター延伸機を
用い、７０℃で横方向に４．０倍に延伸した後、同じく
テンター延伸機で横方向を保持したまま熱処理温度が８
０℃、処理時間３０秒で熱処理し、厚さ４０μｍの熱収
縮性フイルムを得た。得られたフイルムについて、実施
例１と同様の測定及び評価を実施した。This unstretched film was stretched 4.0 times in the transverse direction at 70 ° C. using a tenter stretching machine, and then the heat treatment temperature was 8 while keeping the transverse direction in the same tenter stretching machine.
Heat treatment was performed at 0 ° C. for a treatment time of 30 seconds to obtain a heat-shrinkable film having a thickness of 40 μm. The obtained film was measured and evaluated in the same manner as in Example 1.
【００３２】実施例３ ジカルボン酸成分が、テレフタル酸９０モル％とアジピ
ン酸１０モル％よりなり、ジオール成分が、エチレング
リコール９０モル％と１，４−ブタンジオール１０モル
％よりなる共重合ポリエステル樹脂を用いたこと以外
は、実施例１と同様にして厚さ１６０μｍの未延伸フイ
ルムを得た。 Example 3 Copolyester resin in which the dicarboxylic acid component is 90 mol% terephthalic acid and 10 mol% adipic acid, and the diol component is 90 mol% ethylene glycol and 10 mol% 1,4-butanediol. An unstretched film having a thickness of 160 μm was obtained in the same manner as in Example 1 except that was used.
【００３３】この未延伸フイルムを、テンター延伸機を
用い、５５℃で横方向に４．０倍に延伸した後、同じく
テンター延伸機で横方向を保持したまま熱処理温度が７
０℃、処理時間２０秒で熱処理し、厚さ４０μｍの熱収
縮性フイルムを得た。得られたフイルムについて、実施
例１と同様の測定及び評価を実施した。This unstretched film was stretched 4.0 times in the transverse direction at 55 ° C. using a tenter stretching machine, and then the heat treatment temperature was adjusted to 7 while keeping the transverse direction in the same tenter stretching machine.
Heat treatment was performed at 0 ° C. for 20 seconds to obtain a heat-shrinkable film having a thickness of 40 μm. The obtained film was measured and evaluated in the same manner as in Example 1.
【００３４】実施例４ ジカルボン酸成分が、テレフタル酸８０モル％とイソフ
タル酸２０モル％よりなり、ジオール成分が、エチレン
グリコール９０モル％とポリエチレングリコール１０モ
ル％よりなる共重合ポリエステル樹脂を用いたこと以外
は、実施例１と同様にして厚さ２００μｍの未延伸フイ
ルムを得た。 Example 4 A copolyester resin was used in which the dicarboxylic acid component was 80 mol% terephthalic acid and 20 mol% isophthalic acid, and the diol component was 90 mol% ethylene glycol and 10 mol% polyethylene glycol. An unstretched film having a thickness of 200 μm was obtained in the same manner as in Example 1 except for the above.
【００３５】この未延伸フイルムをロール延伸機を用
い、６５℃で縦方向に５．０倍に延伸した後、熱処理温
度が８０℃、処理時間５秒で熱処理し、厚さ４０μｍの
熱収縮性フイルムを得た。得られたフイルムについて、
実施例１と同様の測定及び評価を実施した。This unstretched film was stretched 5.0 times in the machine direction at 65 ° C. using a roll stretching machine and then heat treated at a heat treatment temperature of 80 ° C. for a treatment time of 5 seconds to give a heat shrinkability of 40 μm. I got a film. About the obtained film,
The same measurement and evaluation as in Example 1 were performed.
【００３６】実施例５ ジカルボン酸成分が、テレフタル酸９０モル％とイソフ
タル酸１０モル％よりなり、ジオール成分が、エチレン
グリコール８０モル％と１，４─シクロヘキサンジオー
ル２０モル％よりなる共重合ポリエステル樹脂を用いた
こと以外は、実施例１と同様にして厚さ１４０μｍの未
延伸フイルムを得た。 Example 5 Copolymerized polyester resin in which the dicarboxylic acid component is 90 mol% terephthalic acid and 10 mol% isophthalic acid, and the diol component is 80 mol% ethylene glycol and 20 mol% 1,4-cyclohexanediol. An unstretched film having a thickness of 140 μm was obtained in the same manner as in Example 1 except that was used.
【００３７】この未延伸フイルムをテンター延伸機を用
い、８０℃で縦方向に３．５倍に延伸した後、同じくテ
ンター延伸機で横方向を保持したまま熱処理温度が９０
℃、処理時間３０秒で熱処理し、厚さ４０μｍの熱収縮
性フイルムを得た。得られたフイルムについて、実施例
１と同様の測定及び評価を実施した。This unstretched film was stretched 3.5 times in the longitudinal direction at 80 ° C. using a tenter stretching machine, and then the heat treatment temperature was 90 while keeping the transverse direction in the same tenter stretching machine.
Heat treatment was performed at 30 ° C. for 30 seconds to obtain a heat-shrinkable film having a thickness of 40 μm. The obtained film was measured and evaluated in the same manner as in Example 1.
【００３８】実施例６ ジカルボン酸成分が、テレフタル酸８０モル％とイソフ
タル酸２０モル％よりなり、ジオール成分が、エチレン
グリコール９５モル％とポリ（テトラメチレンオキシ
ド）グリコール５モル％よりなる共重合ポリエステル樹
脂を用いたこと以外は、実施例１と同様にして厚さ１６
０μｍの未延伸フイルムを得た。 Example 6 Copolyester having a dicarboxylic acid component of 80 mol% terephthalic acid and 20 mol% of isophthalic acid and a diol component of 95 mol% of ethylene glycol and 5 mol% of poly (tetramethylene oxide) glycol. A thickness of 16 was obtained in the same manner as in Example 1 except that a resin was used.
An unstretched film of 0 μm was obtained.
【００３９】この未延伸フイルムをテンター延伸機を用
い、７０℃で横方向に４．０倍に延伸した後、同じくテ
ンター延伸機で横方向を保持したまま熱処理温度が８０
℃、処理時間２０秒で熱処理し、厚さ４０μｍの熱収縮
性フイルムを得た。得られたフイルムについて、実施例
１と同様の測定及び評価を実施した。This unstretched film was stretched 4.0 times in the transverse direction at 70 ° C. using a tenter stretching machine, and then the heat treatment temperature was 80 while keeping the transverse direction in the same tenter stretching machine.
Heat treatment was performed at a temperature of 20 ° C. for 20 seconds to obtain a heat-shrinkable film having a thickness of 40 μm. The obtained film was measured and evaluated in the same manner as in Example 1.
【００４０】比較例１ 延伸したフイルムを急冷し、熱処理を行わなかったこと
以外は、実施例１と同様にして厚さ４０μｍの熱収縮性
フイルムを得た。得られたフイルムについて、実施例１
と同様の測定及び評価を実施した。 Comparative Example 1 A heat-shrinkable film having a thickness of 40 μm was obtained in the same manner as in Example 1 except that the stretched film was rapidly cooled and no heat treatment was performed. About the obtained film, Example 1
Measurements and evaluations similar to the above were performed.
【００４１】比較例２ ジオール成分として、エチレングリコールのみを用いた
こと以外は、実施例４と同様にして厚さ１２０μｍの未
延伸フイルムを得た。 Comparative Example 2 An unstretched film having a thickness of 120 μm was obtained in the same manner as in Example 4, except that only ethylene glycol was used as the diol component.
【００４２】この未延伸フイルムをテンター延伸機を用
い、７５℃で横方向に３．０倍に延伸した後、急冷し熱
処理を行うことなく厚さ４０μｍの熱収縮性フイルムを
得た。得られたフイルムについて、実施例１と同様の測
定及び評価を実施した。This unstretched film was stretched 3.0 times in the transverse direction at 75 ° C. using a tenter stretching machine and then rapidly cooled to obtain a heat-shrinkable film having a thickness of 40 μm without heat treatment. The obtained film was measured and evaluated in the same manner as in Example 1.
【００４３】比較例３ ジオール成分として、エチレングリコールのみを用いた
こと以外は、実施例４と同様にして厚さ１２０μｍの未
延伸フイルムを得た。 Comparative Example 3 An unstretched film having a thickness of 120 μm was obtained in the same manner as in Example 4 except that only ethylene glycol was used as the diol component.
【００４４】この未延伸フイルムをテンター延伸機を用
い、７５℃で横方向に３．０倍に延伸した後、テンター
延伸機で横方向を保持したまま熱処理温度が８５℃、処
理時間３０秒で熱処理し、厚さ４０μｍの熱収縮性フイ
ルムを得た。得られたフイルムについて、実施例１と同
様の測定及び評価を実施した。This unstretched film was stretched 3.0 times in the transverse direction at 75 ° C. using a tenter stretching machine, and then the heat treatment temperature was 85 ° C. and the treatment time was 30 seconds while keeping the transverse direction in the tenter stretching machine. Heat treatment was performed to obtain a heat-shrinkable film having a thickness of 40 μm. The obtained film was measured and evaluated in the same manner as in Example 1.
【００４５】上記の各実施例及び比較例についての熱収
縮フイルムの樹脂を構成するモノマー組成、ガラス転移
温度、延伸条件及び熱処理条件については表１に、また
熱収縮率、シュリンクトンネルの条件及び外観評価結果
については表２にそれぞれ示した。The composition of the monomers constituting the resin of the heat shrink film, the glass transition temperature, the stretching conditions and the heat treatment conditions in each of the above Examples and Comparative Examples are shown in Table 1, and the heat shrinkage rate, the shrink tunnel conditions and the appearance. The evaluation results are shown in Table 2.
【００４６】[0046]
【表１】 [Table 1]
【００４７】[0047]
【表２】 [Table 2]
【００４８】[0048]
【発明の効果】本発明のポリエステル系熱収縮フイルム
は、テレフタル酸を主体とするジカルボン酸成分と、エ
チレングリコールを主体とするジオール成分と、炭素数
が３〜１０の脂肪族ジカルボン酸、炭素数が３〜１０の
脂肪族ジオール、炭素数が２〜１０の脂肪族ジオールの
多量体、シクロヘキサンジメタノール、シクロヘキサン
ジオールの群中から選ばれる１種もしくは２種以上の共
重合成分とから得られる共重合ポリエステル系樹脂を材
料とした延伸フイルムを、急冷することなく特定の温度
条件下で特定の時間をかけて熱処理を施して得られたも
のであるから、様々の形態の歪みが形成され、熱収縮時
に収縮開始後広い温度範囲にわたって収縮率が徐々に増
加するという収縮特性が具備されている。The polyester heat-shrinkable film of the present invention comprises a dicarboxylic acid component mainly containing terephthalic acid, a diol component mainly containing ethylene glycol, an aliphatic dicarboxylic acid having 3 to 10 carbon atoms, and a carbon number. A copolymer obtained from an aliphatic diol having 3 to 10 carbon atoms, a multimer of an aliphatic diol having 2 to 10 carbon atoms, and one or more copolymerization components selected from the group of cyclohexanedimethanol and cyclohexanediol. A stretched film made of a polymerized polyester resin is obtained by subjecting it to a heat treatment under a specific temperature condition for a specific time without being rapidly cooled, so that various forms of strain are formed, It has shrinkage characteristics such that the shrinkage rate gradually increases over a wide temperature range after the start of shrinkage during shrinkage.
【００４９】従って、本発明のポリエステル系熱収縮フ
イルムは、シュリンクトンネルを高速で通過させ、５〜
２０秒の短時間で収縮を完了させても、収縮むらや皺の
ない均一な収縮が達成できるため、収縮包装のみなら
ず、被包装物を一個一個包装するような個包装に使用し
ても、収縮工程の生産性を低下させることなく、美しい
仕上がりが得られ、例えば、ＰＥＴ容器等の各種容器用
収縮ラベルに用いて好適である。Therefore, the polyester heat-shrinkable film of the present invention passes through the shrink tunnel at a high speed,
Even when shrinking is completed in a short time of 20 seconds, uniform shrinkage without uneven shrinkage and wrinkles can be achieved, so it can be used not only for shrink wrapping but also for individual wrapping such as wrapping individual items. A beautiful finish can be obtained without lowering the productivity in the shrinking process, and is suitable for use in shrinkable labels for various containers such as PET containers.
【００５０】また、塩化ビニル系樹脂のように、焼却時
に塩化水素を発生することがないから衛生上問題がな
く、また、収縮ラベルとして、ＰＥＴ製容器に用いて
も、回収し、再使用することも可能であり経済的であ
る。Also, unlike vinyl chloride resin, hydrogen chloride is not generated during incineration, so there is no problem in hygiene, and even when it is used as a shrinkable label in a PET container, it is recovered and reused. It is also possible and economical.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ２９Ｋ 105:02 Ｂ２９Ｌ 7:00 4Ｆ Ｃ０８Ｌ 67:02 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location B29K 105: 02 B29L 7:00 4F C08L 67:02
Claims (1)
成分と、エチレングリコールを主体とするジオール成分
と、炭素数が３〜１０の脂肪族ジカルボン酸、炭素数が
３〜１０の脂肪族ジオール、炭素数が２〜１０の脂肪族
ジオールの多量体、シクロヘキサンジメタノール、シク
ロヘキサンジオールの群中から選ばれる１種もしくは２
種以上の共重合成分とから得られる共重合ポリエステル
系樹脂を材料とした延伸フイルムが、延伸温度〜延伸温
度＋１００℃の温度条件下で５〜３００秒の時間をかけ
て熱処理されてなることを特徴とするポリエステル系熱
収縮フイルム。1. A dicarboxylic acid component mainly containing terephthalic acid, a diol component mainly containing ethylene glycol, an aliphatic dicarboxylic acid having 3 to 10 carbon atoms, an aliphatic diol having 3 to 10 carbon atoms, and carbon. 1 or 2 selected from the group consisting of multimers of aliphatic diol having a number of 2 to 10, cyclohexanedimethanol and cyclohexanediol
A stretched film made of a copolymerized polyester resin obtained from one or more copolymerization components is heat-treated for 5 to 300 seconds under a temperature condition of stretching temperature to stretching temperature + 100 ° C. Characteristic polyester heat shrink film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3-344459 | 1991-12-26 | ||
| JP34445991 | 1991-12-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05245930A true JPH05245930A (en) | 1993-09-24 |
Family
ID=18369435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4096565A Pending JPH05245930A (en) | 1991-12-26 | 1992-04-16 | Polyester heat-shrinkable film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05245930A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001012697A1 (en) * | 1999-08-17 | 2001-02-22 | Eastman Chemical Company | Reactor grade copolyesters for shrink film applications |
| WO2003006229A1 (en) * | 2001-07-11 | 2003-01-23 | Toyo Boseki Kabushiki Kaisha | Heat-shrinkable polyester films and process for production thereof |
| WO2003011950A1 (en) * | 2001-08-01 | 2003-02-13 | Dupont Teijin Films U.S. Limited Partnership | Conformable copolyester film |
| WO2003039841A1 (en) * | 2001-08-01 | 2003-05-15 | Toyo Boseki Kabushiki Kaisha | Heat shrinking polyester film roll |
| JP2004509789A (en) * | 2000-09-29 | 2004-04-02 | デュポン テイジン フィルムズ ユー．エス．リミテッド パートナーシップ | Multilayer polymer film |
| JP2008115313A (en) * | 2006-11-07 | 2008-05-22 | Riken Technos Corp | Resin composition and calendered sheet |
| JP2008115312A (en) * | 2006-11-07 | 2008-05-22 | Riken Technos Corp | Resin composition and calendered sheet |
| JP2008115311A (en) * | 2006-11-07 | 2008-05-22 | Riken Technos Corp | Resin composition and calendered sheet |
| WO2009111058A1 (en) * | 2008-03-07 | 2009-09-11 | Eastman Chemical Company | Miscible polyester blends and shrinkable films prepared therefrom |
| JP2012036273A (en) * | 2010-08-05 | 2012-02-23 | Mitsubishi Plastics Inc | Thermally shrinkable polyester-based film |
| JP2012036272A (en) * | 2010-08-05 | 2012-02-23 | Tokan Kogyo Co Ltd | Heat-shrinkable polyester film, and insulated container using the same |
| US20120226014A1 (en) * | 2009-11-13 | 2012-09-06 | Roy Lee | Copolymerized polyester heat shrinkable film |
| US8986591B2 (en) | 2004-12-07 | 2015-03-24 | Eastman Chemical Company | Void-containing polyester shrink film with improved density retention |
| US10138338B2 (en) | 2012-12-12 | 2018-11-27 | Eastman Chemical Company | Copolyesters plasticized with polymeric plasticizer |
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|---|---|---|---|---|
| JP2012211346A (en) * | 1999-08-17 | 2012-11-01 | Eastman Chemical Co | Reactor grade copolyester for shrink film application |
| WO2001012697A1 (en) * | 1999-08-17 | 2001-02-22 | Eastman Chemical Company | Reactor grade copolyesters for shrink film applications |
| JP2004509789A (en) * | 2000-09-29 | 2004-04-02 | デュポン テイジン フィルムズ ユー．エス．リミテッド パートナーシップ | Multilayer polymer film |
| US8445085B2 (en) | 2000-09-29 | 2013-05-21 | Dupont Teijin Films U.S. Limited Partnership | Multi-layer polymeric film |
| US7749584B2 (en) | 2001-07-11 | 2010-07-06 | Toyo Boseki Kabushiki Kaisha | Heat-shrinkable polyester films |
| WO2003006229A1 (en) * | 2001-07-11 | 2003-01-23 | Toyo Boseki Kabushiki Kaisha | Heat-shrinkable polyester films and process for production thereof |
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| WO2003039841A1 (en) * | 2001-08-01 | 2003-05-15 | Toyo Boseki Kabushiki Kaisha | Heat shrinking polyester film roll |
| US8986591B2 (en) | 2004-12-07 | 2015-03-24 | Eastman Chemical Company | Void-containing polyester shrink film with improved density retention |
| JP2008115313A (en) * | 2006-11-07 | 2008-05-22 | Riken Technos Corp | Resin composition and calendered sheet |
| JP2008115312A (en) * | 2006-11-07 | 2008-05-22 | Riken Technos Corp | Resin composition and calendered sheet |
| JP2008115311A (en) * | 2006-11-07 | 2008-05-22 | Riken Technos Corp | Resin composition and calendered sheet |
| WO2009111058A1 (en) * | 2008-03-07 | 2009-09-11 | Eastman Chemical Company | Miscible polyester blends and shrinkable films prepared therefrom |
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| US20120226014A1 (en) * | 2009-11-13 | 2012-09-06 | Roy Lee | Copolymerized polyester heat shrinkable film |
| US9169365B2 (en) * | 2009-11-13 | 2015-10-27 | Sk Chemicals Co., Ltd. | Copolymerized polyester heat shrinkable film |
| JP2012036272A (en) * | 2010-08-05 | 2012-02-23 | Tokan Kogyo Co Ltd | Heat-shrinkable polyester film, and insulated container using the same |
| JP2012036273A (en) * | 2010-08-05 | 2012-02-23 | Mitsubishi Plastics Inc | Thermally shrinkable polyester-based film |
| US10138338B2 (en) | 2012-12-12 | 2018-11-27 | Eastman Chemical Company | Copolyesters plasticized with polymeric plasticizer |
| US10329393B2 (en) | 2012-12-12 | 2019-06-25 | Eastman Chemical Company | Copolysters plasticized with polymeric plasticizer for shrink film applications |
| US10329395B2 (en) | 2012-12-12 | 2019-06-25 | Eastman Chemical Company | Copolyesters plasticized with polymeric plasticizer for shrink film applications |
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