JPH07109363A - Polyester film for metal lamination, laminated metal plate and metallic container - Google Patents
Polyester film for metal lamination, laminated metal plate and metallic containerInfo
- Publication number
- JPH07109363A JPH07109363A JP5257431A JP25743193A JPH07109363A JP H07109363 A JPH07109363 A JP H07109363A JP 5257431 A JP5257431 A JP 5257431A JP 25743193 A JP25743193 A JP 25743193A JP H07109363 A JPH07109363 A JP H07109363A
- Authority
- JP
- Japan
- Prior art keywords
- film
- polyester
- laminated
- metal plate
- metal
- 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)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、清涼飲料、ビール、缶
詰等の主として食料品容器用の金属材料に使用される金
属ラミネート用ポリエステル系フイルム、及び該フイル
ムがラミネートされたラミネート金属板、並びに該ラミ
ネート金属板を缶状に成形してなる金属容器に関するも
のである。さらに詳しくは、製缶工程でのフイルムの耐
スクラッチ性が優れており製缶の生産性が良好で、かつ
レトルト処理等食品充填後の加熱処理によるフイルムか
らのオリゴマーの溶出量が抑制された金属ラミネート用
フイルム、及び該フイルムがラミネートされたラミネー
ト金属板、並びに該ラミネート金属板を缶状に成形して
なる金属容器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 film for metal laminating, which is mainly used as a metal material for food containers such as soft drinks, beer and canned foods, and a laminated metal plate laminated with the film. The present invention relates to a metal container formed by forming the laminated metal plate into a can shape. More specifically, a metal having excellent scratch resistance of the film in the can making process and good can making productivity, and the amount of oligomers eluted from the film due to heat treatment after food filling such as retort treatment is suppressed. The present invention relates to a laminating film, a laminated metal plate laminated with the film, and a metal container formed by molding the laminated metal plate into a can shape.
【０００２】[0002]
【従来の技術】金属缶の内面および外面の腐食防止には
一般的には塗料が塗布され、その塗料としては熱硬化樹
脂が使用されている。2. Description of the Related Art A paint is generally applied to prevent corrosion of the inner and outer surfaces of a metal can, and a thermosetting resin is used as the paint.
【０００３】また腐食防止のために熱可塑性樹脂を用い
る方法がある。例えばポリオレフィンフイルムを加熱し
たティンフリースチールにラミネートしたり、あるいは
ポリプロピレン樹脂をラミネートすることが試みられて
いる。また、さらに耐熱性の良好なポリエステル系フイ
ルムを金属板にラミネートし、該ラミネート金属板を用
いて金属缶を成形することが検討されている。There is also a method of using a thermoplastic resin to prevent corrosion. For example, it has been attempted to laminate a polyolefin film on a heated tin-free steel or a polypropylene resin. Further, it has been studied to laminate a polyester film having better heat resistance on a metal plate and use the laminated metal plate to form a metal can.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、熱硬化
性樹脂塗料を塗装する方法は、該塗料の多くは溶剤型で
あり塗膜の形成には１５０〜２５０℃の高温での数分と
いう長時間加熱が必要であり、かつ焼き付け時に多量の
有機溶剤が飛散するので、工程の簡素化や公害防止等の
改良が嘱望されている。また、上記のような条件で塗布
しても少量の有機溶剤が塗膜中に残存し、食料品を充填
した場合に有機溶剤が食料品中に移行し食料品の味や臭
いに悪影響を及ぼす。また、塗料中に含まれる添加剤や
架橋反応の不完全さに起因する低分子量物質が食料品中
に移行し残存有機溶剤と同様の悪影響を及ぼす。However, in the method of coating a thermosetting resin coating, most of the coatings are solvent type and the coating film is formed at a high temperature of 150 to 250 ° C. for a long time of several minutes. Since heating is required and a large amount of organic solvent is scattered at the time of baking, improvements such as simplification of process and prevention of pollution are desired. In addition, a small amount of organic solvent remains in the coating film even when applied under the above conditions, and when a food product is filled, the organic solvent migrates into the food product and adversely affects the taste and smell of the food product. . In addition, additives contained in the paint and low molecular weight substances due to incomplete crosslinking reaction migrate into food products and have the same adverse effect as residual organic solvents.
【０００５】一方、熱可塑性樹脂フイルムを用いる方法
では、上記課題のうち工程の簡素化や公害防止等の課題
は解決される。しかしながら、熱可塑性樹脂フイルムと
して、例えばポリエチレンやポリプロピレン系のオレフ
ィン樹脂フイルムを用いた場合は、フイルムの耐熱性が
低くレトルト処理で白色化し剥離することがある。ま
た、オレフィン樹脂フイルムは柔らかいため耐スクラッ
チ性が劣るという問題を有している。フイルムの耐スク
ラッチ性が劣ると、例えば製缶工程でラミネート金属板
の毎葉を移送する時や巻締め加工等の加工工程でフイル
ム表面にスクラッチ傷が発生し、商品価値が落ちるとい
う問題がある。さらに、上記熱硬化性樹脂塗料における
残留溶剤の食料品中への移行という問題点は解決される
が、オレフィン樹脂フイルムでは、成膜時に発生した低
分子量物質や熱安定剤等の添加剤が食料品中へ移行する
ことによって食料品の味や臭いに悪影響を及ぼすという
問題がある。また、オレフィン樹脂フイルムは耐フレー
バー性に劣り、食料品中の香気成分が吸着するという問
題がある。On the other hand, the method using the thermoplastic resin film solves the above-mentioned problems such as the simplification of the process and the prevention of pollution. However, when a polyethylene or polypropylene-based olefin resin film is used as the thermoplastic resin film, the heat resistance of the film is low and the film may be whitened and peeled by the retort treatment. Further, since the olefin resin film is soft, it has a problem that scratch resistance is inferior. If the scratch resistance of the film is inferior, there is a problem that the scratches occur on the film surface during the transfer of laminated metal sheets in the can-making process, or during the processing such as the winding process, which lowers the product value. . Furthermore, the problem of migration of residual solvent into foodstuffs in the thermosetting resin coating is solved, but in the olefin resin film, additives such as low molecular weight substances and heat stabilizers generated during film formation are foodstuffs. There is a problem that the taste and smell of food products are adversely affected by the transfer into food products. Further, the olefin resin film is inferior in flavor resistance, and there is a problem that aroma components in foods are adsorbed.
【０００６】また、熱可塑性樹脂フイルムとしてポリエ
ステル系フイルムを用いた場合は、ポリオレフィン樹脂
フイルムの上記問題点が改良され、これまでのところ最
も好ましい方法である。すなわち、ポリエステル系フイ
ルムは、オレフィン樹脂フイルムに比べ耐スクラッチ性
が良好である。さらに、耐熱性が優れているため熱安定
剤等の添加剤が不要であり、かつ、耐熱性が良好であり
低分子量物質の生成も少なく、ポリオレフィン樹脂フイ
ルムに比べ添加剤や低分子量物質の移行による食料品の
味や臭いの問題は大幅に改良される。しかしながら、通
常のポリエステルフイルムでは耐スクラッチ性のレベル
が尚充分でなく、その改良が嘱望されていた。このた
め、ポリエステルフイルムの耐スクラッチ性を改良する
方法として、ポリエステルフイルムの表面に潤滑性や耐
スクラッチ性に優れた有機被膜をコーティング法で形成
するコーティング被膜法が提案されている。確かに、該
コーティング被膜法で耐スクラッチ性は改良されるが、
コーティング過程で有機溶剤を使用する必要があり、そ
の溶剤の極く一部が被膜層に残存し、食料品を充填した
場合に該有機溶剤が食品の味や臭いに悪影響を及ぼすと
いう問題がある。また、有機被膜層から低分子物質が溶
出し、残存有機溶剤と同様の悪影響を及ぼすという問題
もある。Further, when a polyester film is used as the thermoplastic resin film, the above problems of the polyolefin resin film are improved, and it is the most preferable method so far. That is, the polyester film has better scratch resistance than the olefin resin film. Furthermore, because it has excellent heat resistance, additives such as heat stabilizers are not necessary, and it has good heat resistance and produces less low molecular weight substances, and it is possible to transfer additives and low molecular weight substances compared to polyolefin resin films. The food taste and smell problems caused by are greatly improved. However, the level of scratch resistance of ordinary polyester films is still insufficient, and improvement thereof has been desired. Therefore, as a method for improving the scratch resistance of the polyester film, a coating film method has been proposed in which an organic film having excellent lubricity and scratch resistance is formed on the surface of the polyester film by a coating method. Although the scratch resistance is improved by the coating film method,
It is necessary to use an organic solvent in the coating process, and only a small part of the solvent remains in the coating layer, and there is a problem that when a food product is filled, the organic solvent adversely affects the taste and smell of food. . Further, there is also a problem that a low molecular weight substance is eluted from the organic coating layer and has the same adverse effect as the residual organic solvent.
【０００７】本発明の目的は、上記従来技術の諸問題を
解決し、耐スクラッチ性、耐熱性に優れ、製缶の生産性
が良好である金属ラミネート用フイルム、及び該フイル
ムがラミネートされたラミネート金属板、並びに該ラミ
ネート金属板を缶状に成形してなる金属容器を提供する
ことにある。The object of the present invention is to solve the above-mentioned problems of the prior art, to provide a film for metal laminating which is excellent in scratch resistance and heat resistance and has good can productivity, and a laminate in which the film is laminated. It is intended to provide a metal plate and a metal container formed by molding the laminated metal plate into a can shape.
【０００８】[0008]
【課題を解決するための手段】本発明の金属ラミネート
用ポリエステル系フイルムは、ポリエステルには非相溶
性の熱可塑性樹脂０．３〜１０重量％を含むポリエステ
ルよりなることを特徴とするものである。The polyester film for metal laminating of the present invention is characterized in that the polyester comprises a polyester containing 0.3 to 10% by weight of an incompatible thermoplastic resin. .
【０００９】また、本発明のラミネート金属板は、金属
板の少なくとも片面に、前記ポリエステル系フイルムが
ラミネートされたものである。さらに、本発明の金属容
器は、前記ラミネート金属板を成形してなるものであ
る。Further, the laminated metal plate of the present invention is one in which the polyester film is laminated on at least one surface of the metal plate. Furthermore, the metal container of the present invention is formed by molding the laminated metal plate.
【００１０】以下、本発明について詳しく説明する。The present invention will be described in detail below.
【００１１】本発明で用いられるポリエステルは、ポリ
エチレンテレフタレートまたはエチレンテレフタレート
構成単位を７０モル％以上含む共重合体であることが好
ましい。エチレンテレフタレート単位が７０モル％未満
では、耐熱性が低下し、例えば金属缶材にラミネートす
る場合の加工時にフイルムが伸びたり、熱収縮による幅
縮小、皺の発生等が起るため、ラミネート条件のマイル
ド化が必要となり加工の生産性が低下したり、ポリエス
テルの原料費が高くなり経済的に不利になる等の問題が
起り好ましくない。The polyester used in the present invention is preferably a copolymer containing polyethylene terephthalate or ethylene terephthalate constituent units in an amount of 70 mol% or more. When the ethylene terephthalate unit is less than 70 mol%, the heat resistance is lowered and, for example, when the film is laminated on a metal can material, the film may be stretched, the width may be reduced due to heat shrinkage, and wrinkles may occur. It is not preferable because mildness is required, processing productivity is reduced, and the cost of raw materials for polyester is increased, which is economically disadvantageous.
【００１２】テレフタル酸以外の共重合に用いられるジ
カルボン酸成分としては、イソフタル酸、フタル酸、ナ
フタレンジカルボン酸、ジフェニールジカルボン酸等の
芳香酸ジカルボン酸、アジピン酸、アゼライン酸、セバ
シン酸、デカンジカルボン酸、ドデカンジカルボン酸、
ダイマー酸等の脂肪族ジカルボン酸、シクロヘキサンジ
カルボン酸等の脂環族ジカルボン酸等が例示できる。こ
れら共重合成分の中で、耐フレーバー性の低下が少ない
点より、イソフタル酸やナフタレンジカルボン酸等の芳
香族ジカルボン酸の使用が好ましい。Dicarboxylic acid components used for copolymerization other than terephthalic acid include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, naphthalene dicarboxylic acid and diphenyl dicarboxylic acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid. Acid, dodecanedicarboxylic acid,
Examples thereof include aliphatic dicarboxylic acids such as dimer acid and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Among these copolymerization components, the use of aromatic dicarboxylic acids such as isophthalic acid and naphthalenedicarboxylic acid is preferable from the viewpoint of less deterioration in flavor resistance.
【００１３】エチレングリコール以外の共重合に用いら
れるグリコール成分としては、ジエチレングリコール、
トリエチレングリコール、プロパンジオール、ブタンジ
オール、ヘキサンジオール、ドデカンメチレングリコー
ル、ネオペンチルグリコール等の脂肪族ジオール、シク
ロヘキサンジメタノール等の脂環族ジオール、ビスフェ
ノール誘導体のエチレンオキサイド付加体等の芳香族ジ
オール類等が例示できる。As the glycol component used for copolymerization other than ethylene glycol, diethylene glycol,
Aliphatic diols such as triethylene glycol, propanediol, butanediol, hexanediol, dodecanemethylene glycol, neopentyl glycol, alicyclic diols such as cyclohexanedimethanol, aromatic diols such as ethylene oxide adducts of bisphenol derivatives, etc. Can be illustrated.
【００１４】本発明において、ポリエステルは、極限粘
度が０．５以上のものであることが好ましい。In the present invention, the polyester preferably has an intrinsic viscosity of 0.5 or more.
【００１５】本発明で用いられるポリエステルには非相
溶の熱可塑性樹脂としては、ポリオレフィン系樹脂、ポ
リスチレン系樹脂、ポリアクリル系樹脂、ポリカーボネ
ート系樹脂、ポリアミド系樹脂、ポリスルホン酸系樹
脂、全芳香族ポリエステル系樹脂等が挙げられる。これ
ら熱可塑性樹脂は単独で用いてもよいし、二種以上を併
用してもよい。The thermoplastic resin which is incompatible with the polyester used in the present invention includes polyolefin resins, polystyrene resins, polyacrylic resins, polycarbonate resins, polyamide resins, polysulfonic acid resins, wholly aromatic resins. Examples include polyester resins. These thermoplastic resins may be used alone or in combination of two or more.
【００１６】本発明において、上記熱可塑性樹脂のポリ
エステルへの添加量は０．３〜１０重量％であるが、
０．５〜５重量％が好ましい。０．３重量％未満では、
高温でのフイルムと金属との滑り性の向上効果が小さ
く、耐スクラッチ性の改良効果が発現しない。逆に５重
量％を越えると、高温でのフイルムと金属との滑り性の
向上効果が飽和し、かつ、フイルムの製膜性が低下す
る。熱可塑性樹脂のポリエステルへの添加量を０．３〜
１０重量％とすることにより、８０℃でのフイルムと金
属との動摩擦係数が０．４５以下となり、耐スクラッチ
性が実用レベルとなる。In the present invention, the amount of the thermoplastic resin added to the polyester is 0.3 to 10% by weight.
0.5 to 5% by weight is preferable. Below 0.3% by weight,
The effect of improving the slip property between the film and the metal at high temperature is small, and the effect of improving scratch resistance is not exhibited. On the other hand, when it exceeds 5% by weight, the effect of improving the slipperiness between the film and the metal at high temperature is saturated, and the film forming property of the film is deteriorated. Addition amount of thermoplastic resin to polyester is 0.3 to
By setting the content to 10% by weight, the coefficient of dynamic friction between the film and the metal at 80 ° C. becomes 0.45 or less, and the scratch resistance becomes a practical level.
【００１７】上記熱可塑性樹脂のポリエステルフイルム
への添加は、ポリエステルの製造工程で行ってもよい
し、ポリエステル樹脂と上記熱可塑性樹脂とを溶融混練
法で行なってもよい。また、ポリエステルフイルムの製
造時に、高濃度の上記熱可塑性樹脂を含むマスターバッ
チを添加することにより行ってもよい。このような方法
により、本発明の金属ラミネート用ポリエステル系フイ
ルムを得ることができる。The addition of the thermoplastic resin to the polyester film may be carried out in the polyester production step, or the polyester resin and the thermoplastic resin may be melt-kneaded. Further, it may be carried out by adding a masterbatch containing a high concentration of the above-mentioned thermoplastic resin at the time of producing the polyester film. By such a method, the polyester film for metal laminate of the present invention can be obtained.
【００１８】また、本発明のポリエステル系フイルムに
おいては、上記熱可塑性樹脂と、無機微粒子や架橋高分
子粒子とを併用することも好ましい。この場合、無機微
粒子や架橋高分子粒子の添加量は、一般に０．０５〜２
重量％である。In the polyester film of the present invention, it is also preferable to use the thermoplastic resin in combination with inorganic fine particles or crosslinked polymer particles. In this case, the addition amount of the inorganic fine particles and the crosslinked polymer particles is generally 0.05 to 2
% By weight.
【００１９】また、ポリエステルには、必要に応じて、
酸化防止剤、熱安定剤、紫外線吸収剤、可塑剤、顔料、
帯電防止剤、潤滑剤、結晶核剤等を配合することもでき
る。Further, the polyester may contain, if necessary.
Antioxidant, heat stabilizer, UV absorber, plasticizer, pigment,
An antistatic agent, a lubricant, a crystal nucleating agent, etc. can also be added.
【００２０】本発明のポリエステル系フイルムは、フイ
ルム中のエチレンテレフタレート環状三量体の含有量が
０．７重量％以下であることが好ましい。この含有量
は、０．６重量％以下がより好ましく、０．５重量％以
下が特に好ましい。エチレンテレフタレート環状三量体
の含有量が０．７重量％を越えると、レトルト処理等の
食料品充填後の加熱処理によりフイルムからオリゴマー
の溶出が多くなり、缶内面ラミネートフイルムの場合
は、食料品にオリゴマーが移行し食品の味に対して悪影
響を及ぼすので好ましくない。また、缶外面ラミネート
フイルムの場合は、フイルム表面にオリゴマーが析出し
外観の美観が損われるので好ましくない。ここでいうオ
リゴマーとは、エチレンテレフタレート環状三量体を主
成分とするものである。In the polyester film of the present invention, the content of the ethylene terephthalate cyclic trimer in the film is preferably 0.7% by weight or less. The content is more preferably 0.6% by weight or less, particularly preferably 0.5% by weight or less. When the content of the ethylene terephthalate cyclic trimer exceeds 0.7% by weight, the amount of oligomers eluted from the film increases due to the heat treatment after filling food products such as retort treatment. It is not preferable because the oligomers migrate to and adversely affect the taste of food. Further, in the case of a can outer surface laminated film, oligomers are deposited on the surface of the film and the appearance is impaired, which is not preferable. The oligomer as used herein has an ethylene terephthalate cyclic trimer as a main component.
【００２１】本発明において、ポリエステルは公知の方
法により製造することができる。すなわち、エステル交
換法、直接重合法、あるいは分子量を高めるために固相
重合法等により製造することができる。これらのうち、
固相重合法が、エチレンテレフタレート環状三量体の含
有量を低くする意味で好ましい方法である。In the present invention, the polyester can be produced by a known method. That is, it can be produced by a transesterification method, a direct polymerization method, or a solid phase polymerization method for increasing the molecular weight. Of these,
The solid phase polymerization method is a preferable method in the sense that the content of the ethylene terephthalate cyclic trimer is reduced.
【００２２】本発明において、エチレンテレフタレート
環状三量体の含有量を０．７重量％以下にする方法は特
に制限はなく、製膜後のフイルムから水や有機溶剤でエ
チレンテレフタレート環状三量体を抽出除去することで
達成してもよいし、エチレンテレフタレート環状三量体
含有量の少ないポリエステルを原料を用いることにより
達成してもよい。後者の方法を採用するのが経済的であ
り推奨される。エチレンテレフタレート環状三量体の少
ないポリエステル原料を製造する方法も何ら制限はな
く、減圧加熱処理法、固相重合法、水や有機溶剤による
抽出法およびこれらの方法を組合せた方法等を挙げるこ
とができる。特に固相重合法でエチレンテレフタレート
環状三量体量を低減させた後、水抽出により更に該環状
三量体量低減させる方法は、原料ポリエステル中のエチ
レンテレフタレート環状三量体含有量が少なく、かつ、
製膜工程でのエチレンテレフタレート環状三量体の生成
量が抑えられるので最も好ましい方法である。In the present invention, the method for adjusting the content of the ethylene terephthalate cyclic trimer to 0.7% by weight or less is not particularly limited, and the ethylene terephthalate cyclic trimer can be prepared from the film after film formation with water or an organic solvent. It may be achieved by extraction and removal, or may be achieved by using a raw material of polyester having a low content of ethylene terephthalate cyclic trimer. It is economical and recommended to use the latter method. There is no limitation on the method for producing a polyester raw material having a small amount of ethylene terephthalate cyclic trimer, and examples thereof include a reduced pressure heat treatment method, a solid phase polymerization method, an extraction method with water or an organic solvent, and a method combining these methods. it can. Particularly, after reducing the amount of the ethylene terephthalate cyclic trimer by the solid-phase polymerization method, the method of further reducing the amount of the cyclic trimer by water extraction is such that the content of the ethylene terephthalate cyclic trimer in the raw material polyester is small, and ,
This is the most preferable method because the production amount of the ethylene terephthalate cyclic trimer in the film forming step can be suppressed.
【００２３】本発明のポリエステルフイルムは未延伸フ
イルムであっても、延伸フイルムであってもよい。延伸
フイルムの場合は１軸延伸および２軸延伸のいずれでも
よいが、等方性より２軸延伸フイルムが特に好ましい。
該フイルムの製造法も何ら制限を受けない。例えば、延
伸フイルムの場合は、Ｔダイ法、チューブラー法のいず
れの方法も適用できる。また、該ポリエステルフイルム
は単層であっても、複層であってもよい。The polyester film of the present invention may be an unstretched film or a stretched film. The stretched film may be either uniaxially stretched or biaxially stretched, but a biaxially stretched film is particularly preferable because of its isotropic property.
The manufacturing method of the film is not limited. For example, in the case of a stretched film, either the T-die method or the tubular method can be applied. Further, the polyester film may be a single layer or multiple layers.
【００２４】上記ポリエステル系フイルムを、金属板の
片面あるいは両面にラミネートすることにより、本発明
のラミネート金属板を得ることができる。上記ポリエス
テルフイルムの金属板へのラミネート法は特に限定はな
く、例えばドライラミネート法やサーマルラミネート法
等を採用することができる。接着剤層の具体例として
は、エポキシ樹脂、ポリウレタン系樹脂、ポリエステル
系樹脂、ポリエステルポリウレタン系樹脂、イソシアネ
ート系樹脂等、あるいはこれらの各種変性樹脂を挙げる
ことができる。ポリエステルフイルムの上層に低融点の
ポリエステル樹脂層を積層した多層フイルムを共押出し
法で製造し、金属板の通電加熱によりサーマルラミネー
トする方法が推奨される。また、ポリエステルフイルム
に接着剤層を積層した後、金属板とラミネートする方法
では、部分硬化状態で接着剤層フイルム上に形成してお
き、金属板にラミネートした状態で完全に硬化させるよ
うにする方法が推奨される。硬化方法としては熱、光お
よび電子線等による方法が推奨される。また、両面ラミ
ネートの場合は、同時に両面ラミネートしてもよいし、
逐次でラミネートしてもよい。The laminated metal plate of the present invention can be obtained by laminating the above polyester film on one side or both sides of the metal plate. The method for laminating the polyester film on the metal plate is not particularly limited, and for example, a dry laminating method or a thermal laminating method can be adopted. Specific examples of the adhesive layer include epoxy resin, polyurethane resin, polyester resin, polyester polyurethane resin, isocyanate resin, and various modified resins thereof. A method in which a multilayer film in which a polyester resin layer having a low melting point is laminated on an upper layer of a polyester film is produced by a co-extrusion method, and a metal plate is thermally laminated by electrically heating is recommended. In the method of laminating an adhesive layer on a polyester film and then laminating it on a metal plate, it is formed on the adhesive layer film in a partially cured state so that it is completely cured in a laminated state on the metal plate. Method is recommended. As a curing method, a method using heat, light, an electron beam or the like is recommended. In the case of double-sided laminating, both sides may be simultaneously laminated,
You may laminate sequentially.
【００２５】上記ラミネート金属板を成形することによ
り、本発明の金属容器を得ることができる。ラミネート
金属板の金属容器への成形法も何ら制限を受けないが、
天地蓋を巻締めて内容物を充填する、いわゆるピース缶
として用いるのが特に推奨される。By molding the above laminated metal plate, the metal container of the present invention can be obtained. There is no restriction on the method of forming a laminated metal plate into a metal container,
It is especially recommended to use it as a so-called piece can in which the top and bottom are wound and the contents are filled.
【００２６】[0026]
【実施例】次に実施例を挙げて本発明をより具体的に説
明する。EXAMPLES Next, the present invention will be described more specifically with reference to examples.
【００２７】実施例で用いた測定方法は次の通りであ
る。The measuring method used in the examples is as follows.
【００２８】(1) 高温摩擦係数 ５０ｍｍ×７０ｍｍの接触面積を有する重量１．５ｋｇ
の滑走子にフイルムサンプルをセットし、８０℃のティ
ンフリースチル板を速度２５０ｍｍ／分で滑走した時の
動摩擦係数を測定した。(1) High temperature friction coefficient 1.5 kg with a contact area of 50 mm × 70 mm
The film sample was set on the runner of No. 1 and the dynamic friction coefficient was measured when the Tin Free Still plate at 80 ° C. was slid at a speed of 250 mm / min.
【００２９】(2) 耐スクラッチ性 東洋精機（株）製の染色堅牢度摩擦試験機にて、フイル
ムサンプルをセットした荷重４００ｇの摩擦子を、８０
℃のティンフリースチル板を１００ｍｍの往復距離で３
０往復／分の条件で１分間摩擦処理した後のフイルム表
面の傷を肉眼観察で評価した。 ○：傷がほとんど認められない。 △：部分的に傷が認められる。 ×：全面に傷が認められる。 △以上は実用性がある。(2) Scratch resistance With a dyeing fastness friction tester manufactured by Toyo Seiki Co., Ltd., a rubbing element having a load of 400 g and having a film sample set thereon was
3 degrees with a free-fall distance of 100mm
The scratches on the film surface after rubbing for 1 minute under the condition of 0 reciprocations / minute were evaluated by visual observation. ◯: Almost no scratch is observed. Δ: Some scratches are recognized. X: A scratch is recognized on the entire surface. Δ or more is practical.
【００３０】(3) ポリエステルフイルム中のエチレンテ
レフタレート環状三量体の定量法 ポリエステルフイルムをヘキサフルオロアルコール／ク
ロロホルム＝２／３（Ｖ／Ｖ）に溶解し、メタノールで
ポリエステルを沈殿させ、沈殿物を濾別する。濾液を蒸
発乾固し、該蒸発乾固物をジメチルホルムアミドに溶解
する。該溶液を液体クロマトグラフィー法で展開し、エ
チレンテレフタレート環状三量体量を定量した。(3) Quantitative determination method of ethylene terephthalate cyclic trimer in polyester film A polyester film is dissolved in hexafluoroalcohol / chloroform = 2/3 (V / V), and the polyester is precipitated with methanol to obtain a precipitate. Filter off. The filtrate is evaporated to dryness and the evaporated dry matter is dissolved in dimethylformamide. The solution was developed by a liquid chromatography method to quantify the amount of ethylene terephthalate cyclic trimer.
【００３１】 (4) 金属板ラミネートフイルムのオリゴマー溶出量 １０ｃｍ角の金属板ラミネートフイルムを５００ｃｃの
蒸留水とともに、１２０℃で３０分間レトルト処理す
る。処理後の金属板ラミネートフイルムを風乾し、フイ
ルム表面の状態をルーペで観察しオリゴマー溶出の有無
を判定した。(4) Elution amount of oligomer of metal plate laminate film A metal plate laminate film of 10 cm square is subjected to retort treatment with 500 cc of distilled water at 120 ° C. for 30 minutes. The treated metal plate laminate film was air-dried, and the state of the film surface was observed with a loupe to determine the presence or absence of oligomer elution.
【００３２】［実施例１］平均粒径１．５μｍの凝集タ
イプのシリカ０．１重量％と、ポリスチレン樹脂１重量
％とを含み、抽出法で低オリゴマー化した極限粘度が
０．７０で、エチレンテレフタレート環状三量体含有量
が０．３３重量％のポリエチレンテレフタレート９７重
量部と、ポリエチレンテレフタレート−ポリテトラメチ
レングリコールエーテルブロック共重合体３重量部との
混合物を、Ｔダイ法で溶融押出し無定形シートとした
後、縦方向に９０℃で３．５倍、横方向に３．５倍延伸
し、２００℃で熱固定をし、厚さ１２μｍのフイルムを
得た。該ポリエステルフイルムの片面に接着剤（東洋イ
ンク社製のポリウレタン系接着剤「アドコート」および
硬化剤の混合物）を固形分換算で４ｇ／ｍ2 コーティン
グし、乾燥し４０℃で２４時間エージングして、ラミネ
ート用フイルムを得た。Example 1 0.1% by weight of agglomerate type silica having an average particle size of 1.5 μm and 1% by weight of polystyrene resin were used, and the intrinsic viscosity after oligomerization by the extraction method was 0.70. A mixture of 97 parts by weight of polyethylene terephthalate having an ethylene terephthalate cyclic trimer content of 0.33% by weight and 3 parts by weight of polyethylene terephthalate-polytetramethylene glycol ether block copolymer was melt-extruded by the T-die method to give an amorphous form. After being made into a sheet, it was stretched 3.5 times in the longitudinal direction at 90 ° C. and 3.5 times in the transverse direction and heat-set at 200 ° C. to obtain a film having a thickness of 12 μm. One side of the polyester film was coated with an adhesive (a mixture of a polyurethane adhesive "Adcoat" manufactured by Toyo Ink Co., Ltd. and a curing agent) at 4 g / m 2 in terms of solid content, dried and aged at 40 ° C. for 24 hours, A film for lamination was obtained.
【００３３】得られたラミネート用フイルムを脱脂処理
した冷延伸鋼板の両面にサーマルラミネート法によって
ラミネートし、両面ラミネート鋼板を得た。The obtained laminating film was laminated on both sides of a degreased cold-stretched steel sheet by a thermal lamination method to obtain a double-sided laminated steel sheet.
【００３４】得られたラミネート用フイルムおよびラミ
ネート鋼板の特性を表１に示す。The characteristics of the laminating film and laminated steel sheet thus obtained are shown in Table 1.
【００３５】本実施例で得られたフイルムおよびラミネ
ート鋼板は、高温でのフイルムと金属との滑り性が良好
で耐スクラッチ性が優れており、かつ、オリゴマーの溶
出量も少なく、金属ラミネート用フイルムおよびラミネ
ート鋼板として高品質であった。The film and laminated steel sheet obtained in this example have good slipperiness between the film and metal at high temperature and excellent scratch resistance, and have a small amount of oligomer elution, and a film for metal lamination. It was of high quality as a laminated steel sheet.
【００３６】本実施例で得たフイルムを缶胴内面および
底蓋の内面および外面用として用い、３ピース缶として
製缶したところ、製缶過程で該フイルムの表面にスクラ
ッチ傷が入ることなく高速度で製缶できた。さらに、該
成形缶にコーヒーを充填しレトルト処理をしたが、フイ
ルムからのオリゴマーや有機溶剤のコーヒー中への移行
がなく味覚の変化が無く商品価値の高いものであった。
また、レトルト処理をしても底蓋外面にオリゴマーの析
出は認められなかった。The film obtained in this example was used for the inner surface of the body of the can and the inner and outer surfaces of the bottom lid to make a three-piece can. When the can was made, scratches were not formed on the surface of the film and the film was highly scratched. I was able to make a can at speed. Further, the molded cans were filled with coffee and subjected to retort treatment, but there was no migration of oligomers or organic solvents from the film into the coffee and there was no change in taste, and the product value was high.
In addition, no oligomer was deposited on the outer surface of the bottom lid even after the retort treatment.
【００３７】［比較例１］実施例１においてポリスチレ
ン樹脂を用いなかった以外は、実施例１と同様の方法で
ラミネート用フイルムおよびラミネート鋼板を得た。こ
れらラミネート用フイルムおよびラミネート鋼板の特性
を表１に示す。Comparative Example 1 A laminating film and a laminated steel sheet were obtained in the same manner as in Example 1 except that polystyrene resin was not used in Example 1. Table 1 shows the properties of the laminating film and the laminated steel sheet.
【００３８】本比較例で得られたフイルムおよびラミネ
ート鋼板は、高温でのフイルムと金属との滑り性が悪
く、耐スクラッチ性に劣るものであり、金属ラミネート
用フイルムおよびラミネート鋼板として低品質であっ
た。The film and laminated steel sheet obtained in this comparative example have poor slip resistance between the film and metal at high temperature and are inferior in scratch resistance, and are of low quality as the film and laminated steel sheet for metal laminating. It was
【００３９】本比較例で得たフイルムを用い実施例１と
同様にして３ピース缶として製缶したが、製缶過程で該
フイルムの表面にスクラッチ傷が入り商品価値の低いも
のしか得られなかった。Using the film obtained in this Comparative Example, a 3-piece can was made in the same manner as in Example 1. However, scratches were formed on the surface of the film during the can making process, and only a product of low commercial value was obtained. It was
【００４０】［比較例２］実施例１においてポリスチレ
ン樹脂の添加量を１５重量％とした以外は、実施例１と
同様の方法で製膜したが、製膜時のフイルムの破断が多
く実用上問題があった。[Comparative Example 2] A film was formed in the same manner as in Example 1 except that the addition amount of the polystyrene resin was changed to 15% by weight in Example 1, but the film was often broken during film formation and was practically used. There was a problem.
【００４１】［比較例３］平均粒径１．５μｍの凝集タ
イプのシリカ０．１重量％を含み、溶融重合法で製造し
た極限粘度が０．６５で、エチレンテレフタレート環状
三量体含有量が１．０重量％のポリエチレンテレフタレ
ートを用いた以外は、実施例１と同様の方法でラミネー
ト用フイルムおよびラミネート鋼板を得た。これらラミ
ネート用フイルムおよびラミネート鋼板の特性を表１に
示す。COMPARATIVE EXAMPLE 3 0.1% by weight of agglomerate type silica having an average particle size of 1.5 μm, an intrinsic viscosity of 0.65 produced by a melt polymerization method and an ethylene terephthalate cyclic trimer content of A film for lamination and a laminated steel plate were obtained in the same manner as in Example 1 except that 1.0% by weight of polyethylene terephthalate was used. Table 1 shows the properties of the laminating film and the laminated steel sheet.
【００４２】本比較例で得られたフイルムおよびラミネ
ート鋼板は、高温でのフイルムと金属との滑り性が悪
く、耐スクラッチ性に劣り、かつ、オリゴマー含有量が
高くオリゴマー溶出量が多く、金属ラミネート用フイル
ムおよびラミネート鋼板として低品質であった。The film and laminated steel sheet obtained in this comparative example have a poor slip property between the film and the metal at a high temperature, are inferior in scratch resistance, and have a high oligomer content and a high oligomer elution amount, and thus a metal laminate. The film and the laminated steel sheet were of poor quality.
【００４３】本比較例で得たフイルムを用い実施例１と
同様にして３ピース缶として製缶し、コーヒーを充填し
たが、製缶工程で該フイルムの表面にスクラッチ傷が入
り、かつ、レトルト処理により底蓋外面にオリゴマー析
出があり、商品価値の低いものであった。Using the film obtained in this Comparative Example, a three-piece can was made in the same manner as in Example 1 and filled with coffee, but scratches were formed on the surface of the film in the can making process, and the retort was used. Due to the treatment, oligomers were deposited on the outer surface of the bottom lid, and the product value was low.
【００４４】［実施例２］無機粒子として平均粒径１．
５μｍの凝集タイプのシリカ０．３重量％と、低密度ポ
リエチレン１．０重量％とを含むポリエチレンエチレン
テレフタレートを用いた以外は、実施例１と同様の方法
でラミネート用フイルムおよびラミネート鋼板を得た。
これらラミネート用フイルムおよびラミネート鋼板の特
性を表１に示す。Example 2 As an inorganic particle, an average particle size of 1.
A film for lamination and a laminated steel sheet were obtained in the same manner as in Example 1 except that polyethylene ethylene terephthalate containing 0.3% by weight of 5 μm agglomerate type silica and 1.0% by weight of low density polyethylene was used. .
Table 1 shows the properties of the laminating film and the laminated steel sheet.
【００４５】本実施例で得られたフイルムおよびラミネ
ート鋼板は、高温でのフイルムと金属との滑り性が良好
で耐スクラッチ性も優れており、かつ、オリゴマー溶出
量も少なく金属ラミネート用フイルムとして高品質であ
った。The film and laminated steel sheet obtained in this example have good slipperiness between the film and metal at high temperature and excellent scratch resistance, and also have a small amount of oligomer elution and are excellent as a film for metal laminating. It was quality.
【００４６】本実施例で得たフイルムを用い実施例１と
同様にして３ピース缶として製缶し、コーヒーを充填し
たが、実施例１と同様に商品価値の高いものであった。Using the film obtained in this example, a three-piece can was made in the same manner as in Example 1 and filled with coffee, but it had a high commercial value as in Example 1.
【００４７】［比較例４］平均粒径１．５μｍの凝集タ
イプのシリカに替えて低密度ポリエチレン０．２重量％
を用いた以外は、比較例３と同様の方法でラミネート用
フイルムおよびラミネート鋼板を得た。これらラミネー
ト用フイルムおよびラミネート鋼板の特性を表１に示
す。[Comparative Example 4] 0.2% by weight of low-density polyethylene was used in place of aggregate type silica having an average particle size of 1.5 μm.
A film for lamination and a laminated steel plate were obtained in the same manner as in Comparative Example 3 except that was used. Table 1 shows the properties of the laminating film and the laminated steel sheet.
【００４８】本比較例で得られたフイルムおよびラミネ
ート鋼板は、比較例３のフイルムと同様に低品質のもの
であった。The films and laminated steel sheets obtained in this Comparative Example were of low quality, like the film of Comparative Example 3.
【００４９】また、３ピース缶として製缶し、コーヒー
を充填したが、比較例３と同様に商品価値の低いもので
あった。Further, a can was made as a three-piece can and filled with coffee, but the product value was low as in Comparative Example 3.
【００５０】［実施例３］平均粒径２．４μｍの凝集タ
イプのシリカ０．２５重量％と、６ナイロン１．５重量
％とを含み、固相重合法で製造した極限粘度が０．７５
で、エチレンテレフタレート環状三量体含有量が０．４
重量％のポリエチレンテレフタレートを用いた以外は、
実施例１と同様の方法でラミネート用フイルムおよびラ
ミネート鋼板を得た。これらラミネート用フイルムおよ
びラミネート鋼板の特性を表１に示す。Example 3 0.25% by weight of agglomerate type silica having an average particle size of 2.4 μm and 1.5% by weight of 6 nylon were used, and the intrinsic viscosity produced by the solid phase polymerization method was 0.75.
And the ethylene terephthalate cyclic trimer content is 0.4
Other than using wt% polyethylene terephthalate,
A film for lamination and a laminated steel plate were obtained in the same manner as in Example 1. Table 1 shows the properties of the laminating film and the laminated steel sheet.
【００５１】本実施例で得られたフイルムおよびラミネ
ート鋼板は、実施例１と同様に高品質なものであった。
また、３ピース缶として製缶し、コーヒーを充填した
が、実施例１と同様に商品価値の高いものであった。The film and laminated steel sheet obtained in this example were of high quality as in Example 1.
Further, although it was made as a three-piece can and filled with coffee, it was of high commercial value as in Example 1.
【００５２】[0052]
【発明の効果】本発明の金属ラミネート用ポリエステル
系フイルムは、上述したように、高温でのフイルムと金
属との滑り性に優れており、製缶工程でのフイルム表面
の耐スクラッチ性が良好で高速で製缶ができ、かつ、レ
トルト処理等食品充填後の加熱処理においても、ラミネ
ート用フイルムからのオリゴマーの溶出が抑制されてい
るので、オリゴマーの食品中への移行や、フイルム表面
へのオリゴマーの析出による表面外観の低下が起らな
い。従って、本発明のフイルムは、金属板のラミネート
用フイルムとして極めて有用である。As described above, the polyester film for metal laminate of the present invention is excellent in the slipperiness between the film and the metal at a high temperature and has a good scratch resistance on the film surface in the can making process. Can be made at high speed, and the elution of oligomers from the laminating film is suppressed even during heat treatment such as retort treatment after food filling, so migration of oligomers into food and oligomers on the film surface are suppressed. The surface appearance does not deteriorate due to the precipitation of Therefore, the film of the present invention is extremely useful as a film for laminating metal plates.
【００５３】[0053]
【表１】 [Table 1]
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成５年１０月２６日[Submission date] October 26, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２５[Name of item to be corrected] 0025
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２５】上記ラミネート金属板を成形することによ
り、本発明の金属容器を得ることができる。ラミネート
金属板の金属容器への成形法も何ら制限を受けないが、
天地蓋を巻締めて内容物を充填する、いわゆる３ピース
缶として用いるのが特に推奨される。By molding the above laminated metal plate, the metal container of the present invention can be obtained. There is no restriction on the method of forming a laminated metal plate into a metal container,
It is particularly recommended to use it as a so-called three- piece can in which the top and bottom are wound and the contents are filled.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２８[Correction target item name] 0028
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２８】(1) 高温摩擦係数 ５０ｍｍ×７０ｍｍの接触面積を有する重量１．５ｋｇ
の滑走子にフイルムサンプルをセットし、８０℃のティ
ンフリースチル板上を速度２５０ｍｍ／分で滑走した時
の動摩擦係数を測定した。(1) High temperature friction coefficient 1.5 kg with a contact area of 50 mm × 70 mm
The film sample was set on the runner of No. 1, and the dynamic friction coefficient was measured when the film sample was slid on a Tin Free Steel plate at 80 ° C. at a speed of 250 mm / min.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２９[Name of item to be corrected] 0029
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２９】(2) 耐スクラッチ性 東洋精機（株）製の染色堅牢度摩擦試験機にて、フイル
ムサンプルをセットした荷重４００ｇの摩擦子を、８０
℃のティンフリースチル板上を１００ｍｍの往復距離で
３０往復／分の条件で１分間摩擦処理した後のフイルム
表面の傷を肉眼観察で評価した。 ○：傷がほとんど認められない。 △：部分的に傷が認められる。 ×：全面に傷が認められる。 △以上は実用性がある。(2) Scratch resistance With a dyeing fastness friction tester manufactured by Toyo Seiki Co., Ltd., a rubbing element having a load of 400 g and having a film sample set thereon was
The scratches on the film surface were evaluated by visual observation after rubbing for 1 minute at a reciprocating distance of 100 mm and a reciprocating distance of 100 mm on a timbre still plate at 0 ° C. ◯: Almost no scratch is observed. Δ: Some scratches are recognized. X: A scratch is recognized on the entire surface. Δ or more is practical.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 井坂 勤 大阪市北区堂島浜二丁目２番８号 東洋紡 績株式会社内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Tsutomu Isaka 2-8 Dojimahama, Kita-ku, Osaka Toyobo Co., Ltd.
Claims (5)
脂０．３〜１０重量％を含むポリエステルよりなること
を特徴とする、金属ラミネート用ポリエステル系フイル
ム。1. A polyester film for metal laminating, wherein the polyester comprises a polyester containing 0.3 to 10% by weight of an incompatible thermoplastic resin.
レートまたはエチレンテレフタレート構成単位を７０モ
ル％以上含む共重合体であることを特徴とする、請求項
１記載のポリエステル系フイルム。2. The polyester film according to claim 1, wherein the polyester is a copolymer containing polyethylene terephthalate or ethylene terephthalate constituent units in an amount of 70 mol% or more.
状三量体の含有量が０．７重量％以下であることを特徴
とする、請求項２記載のポリエステル系フイルム。3. The polyester film according to claim 2, wherein the content of the ethylene terephthalate cyclic trimer in the film is 0.7% by weight or less.
３のいずれか１項記載のポリエステル系フイルムがラミ
ネートされたラミネート金属板。4. The method according to claim 1, which is provided on at least one surface of the metal plate.
4. A laminated metal plate on which the polyester film according to any one of 3 is laminated.
してなる金属容器。5. A metal container formed by molding the laminated metal plate according to claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25743193A JP3389651B2 (en) | 1993-10-15 | 1993-10-15 | Polyester film for metal lamination, laminated metal plate and metal container |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25743193A JP3389651B2 (en) | 1993-10-15 | 1993-10-15 | Polyester film for metal lamination, laminated metal plate and metal container |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07109363A true JPH07109363A (en) | 1995-04-25 |
| JP3389651B2 JP3389651B2 (en) | 2003-03-24 |
Family
ID=17306273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25743193A Expired - Lifetime JP3389651B2 (en) | 1993-10-15 | 1993-10-15 | Polyester film for metal lamination, laminated metal plate and metal container |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3389651B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002072346A1 (en) * | 2001-03-14 | 2002-09-19 | Jfe Steel Corporation | Film-laminated metal sheet for container |
| JP2005161707A (en) * | 2003-12-03 | 2005-06-23 | Jfe Steel Kk | Resin-coated metal sheet for container and its production method |
| JP2005187761A (en) * | 2003-12-26 | 2005-07-14 | Toyobo Co Ltd | Polyester unstretched film |
| JP2005280178A (en) * | 2004-03-30 | 2005-10-13 | Toyobo Co Ltd | Polyester film for coating metal sheet, method for manufacturing this polyester film and method for manufacturing polyester film-coated metal sheet |
| JP2005305701A (en) * | 2004-04-19 | 2005-11-04 | Daiwa Can Co Ltd | Polyester film-coated metal sheet, its manufacturing method and polyester film-coated metal can |
| JP2008155436A (en) * | 2006-12-22 | 2008-07-10 | Toyobo Co Ltd | Biaxially stretched resin film |
Citations (6)
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|---|---|---|---|---|
| JPH02277635A (en) * | 1989-04-19 | 1990-11-14 | Toppan Printing Co Ltd | Laminated material excellent in aroma retentivity and container using the same |
| JPH0332837A (en) * | 1989-06-29 | 1991-02-13 | Du Pont Mitsui Polychem Co Ltd | Multilayer packing material |
| JPH0386729A (en) * | 1989-08-30 | 1991-04-11 | Teijin Ltd | Polyester film for forming application |
| JPH04139221A (en) * | 1990-09-28 | 1992-05-13 | Mitsui Petrochem Ind Ltd | Polyethylene terephthalate molded article |
| JPH04183745A (en) * | 1990-11-16 | 1992-06-30 | Toray Ind Inc | Polyester composition for insulating film |
| JPH05186613A (en) * | 1992-01-16 | 1993-07-27 | Teijin Ltd | Metallic plate-laminating polyester film |
-
1993
- 1993-10-15 JP JP25743193A patent/JP3389651B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02277635A (en) * | 1989-04-19 | 1990-11-14 | Toppan Printing Co Ltd | Laminated material excellent in aroma retentivity and container using the same |
| JPH0332837A (en) * | 1989-06-29 | 1991-02-13 | Du Pont Mitsui Polychem Co Ltd | Multilayer packing material |
| JPH0386729A (en) * | 1989-08-30 | 1991-04-11 | Teijin Ltd | Polyester film for forming application |
| JPH04139221A (en) * | 1990-09-28 | 1992-05-13 | Mitsui Petrochem Ind Ltd | Polyethylene terephthalate molded article |
| JPH04183745A (en) * | 1990-11-16 | 1992-06-30 | Toray Ind Inc | Polyester composition for insulating film |
| JPH05186613A (en) * | 1992-01-16 | 1993-07-27 | Teijin Ltd | Metallic plate-laminating polyester film |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002072346A1 (en) * | 2001-03-14 | 2002-09-19 | Jfe Steel Corporation | Film-laminated metal sheet for container |
| US7198856B2 (en) | 2001-03-14 | 2007-04-03 | Jfe Steel Corporation | Film-laminated metal sheet for container |
| US7435465B2 (en) | 2001-03-14 | 2008-10-14 | Jfe Steel Corporation | Film-laminated metal sheet for container |
| JP2005161707A (en) * | 2003-12-03 | 2005-06-23 | Jfe Steel Kk | Resin-coated metal sheet for container and its production method |
| JP2005187761A (en) * | 2003-12-26 | 2005-07-14 | Toyobo Co Ltd | Polyester unstretched film |
| JP2005280178A (en) * | 2004-03-30 | 2005-10-13 | Toyobo Co Ltd | Polyester film for coating metal sheet, method for manufacturing this polyester film and method for manufacturing polyester film-coated metal sheet |
| JP4576142B2 (en) * | 2004-03-30 | 2010-11-04 | 東洋紡績株式会社 | Polyester film for metal plate coating, method for producing the same, and method for producing polyester film-coated metal plate |
| JP2005305701A (en) * | 2004-04-19 | 2005-11-04 | Daiwa Can Co Ltd | Polyester film-coated metal sheet, its manufacturing method and polyester film-coated metal can |
| JP4576147B2 (en) * | 2004-04-19 | 2010-11-04 | 大和製罐株式会社 | Polyester film-coated metal sheet, method for producing polyester film-coated metal sheet, and polyester film-coated metal can |
| JP2008155436A (en) * | 2006-12-22 | 2008-07-10 | Toyobo Co Ltd | Biaxially stretched resin film |
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| Publication number | Publication date |
|---|---|
| JP3389651B2 (en) | 2003-03-24 |
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