JP3256093B2 - Resin-coated metal sheet with excellent retort resistance and heat resistance - Google Patents
Resin-coated metal sheet with excellent retort resistance and heat resistanceInfo
- Publication number
- JP3256093B2 JP3256093B2 JP21645394A JP21645394A JP3256093B2 JP 3256093 B2 JP3256093 B2 JP 3256093B2 JP 21645394 A JP21645394 A JP 21645394A JP 21645394 A JP21645394 A JP 21645394A JP 3256093 B2 JP3256093 B2 JP 3256093B2
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- JP
- Japan
- Prior art keywords
- resin
- film
- layer
- melting point
- metal plate
- 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.)
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、食品缶詰、飲料缶その
他容器材料として使用される耐レトルト処理性と耐熱性
に優れた樹脂被覆金属板に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin-coated metal sheet excellent in retort treatment resistance and heat resistance used as a material for cans of foods, beverage cans and other containers.
【０００２】[0002]
【従来の技術】従来、製缶用材料としては、ぶりき、電
解クロム酸処理鋼板、その他の表面処理鋼板、或いはア
ルミニウムに有機塗装、印刷を施した素材が使用されて
きた。しかし、これらの有機塗装、印刷工程は、大規模
な塗装焼付け炉が必要であり、長い焼付け時間が必要で
あるばかりでなく、塗膜形成時に多量の有機溶剤を排出
する為に、環境対策の面より、排出ガス処理が必要であ
るという、問題点を有していた。近年、これらの欠点を
克服する方法として、熱可塑性樹脂フィルムを被覆した
金属板が開発されている。一例としては、ポリエステル
フィルムを接着剤を用いずに金属板にラミネートしたも
のとしては、特開平１−１９２５４６号公報、特開平４
−１０５９３１号公報が開示されている。2. Description of the Related Art Conventionally, as a material for cans, tinplate, electrolytic chromic acid-treated steel sheet, other surface-treated steel sheet, or a material obtained by applying organic coating and printing to aluminum has been used. However, these organic coating and printing processes require a large-scale paint baking furnace, which not only requires a long baking time, but also discharges a large amount of organic solvent during coating film formation. In view of this, there is a problem that exhaust gas treatment is required. In recent years, a metal plate coated with a thermoplastic resin film has been developed as a method for overcoming these drawbacks. As an example, a film obtained by laminating a polyester film on a metal plate without using an adhesive is disclosed in Japanese Patent Application Laid-Open Nos.
No. 105931 is disclosed.
【０００３】しかしながら、これらの熱可塑性樹脂フィ
ルム被覆金属板は、絞り成形加工、内容物充填後に、内
容物の殺菌処理を施す事を目的として、１２０℃、２５
分間程度のレトルト処理を施されるのが通常であり、そ
の際に樹脂皮膜に水滴状の模様が発生し外観の劣化を引
き起こしやすいという難点を有していた。本発明は特
に、このレトルト処理工程を受けても樹脂皮膜に水滴状
模様の発生の起こらない樹脂被覆金属板に関するもので
ある。[0003] However, these thermoplastic resin film-coated metal sheets are drawn at 120 ° C and 25 ° C for the purpose of subjecting the contents to sterilization after drawing and filling.
The retort treatment is usually performed for about a minute, and at that time, there is a problem that a water-drop-like pattern is generated on the resin film and the appearance is easily deteriorated. The present invention particularly relates to a resin-coated metal plate that does not cause a water-drop pattern on a resin film even after the retort treatment step.
【０００４】[0004]
【発明が解決しようとする課題】上記特開平１−１９２
５４６号公報は「２軸配向ポリエチレンテレフタレート
樹脂を上層（表層）とし、その熱固定温度より１０〜４
０℃結晶融解温度の低い無配向ポリエステル樹脂皮膜層
を下層（接着層）に有する事を特徴とする２層皮膜構造
のラミネート鋼板」であり、特開平４−１０５９３１号
公報は「上層（表層）が配向結晶構造を有する融点が２
００℃以上のポリエステル樹脂で、下層（接着層）が融
点１６０℃〜２２０℃のポリエステル樹脂である事を特
徴とする２層皮膜構造のラミネート鋼板」である。これ
らの樹脂被覆金属板は、接着剤を用いずにポリエステル
フィルムを金属板にラミネートするものであり、下層
（接着層）ポリエステル樹脂の融点程度に加熱された金
属板に熱接着する為に、その熱影響により金属板近傍の
樹脂層には、無定形ポリエステル層が生成しており、こ
の層によって密着性を確保している。SUMMARY OF THE INVENTION The above-mentioned Japanese Patent Laid-Open Publication No. 1-192-1991.
No. 546 discloses that a biaxially oriented polyethylene terephthalate resin is used as an upper layer (surface layer) and its heat setting temperature is 10 to 4 times.
A laminated steel sheet having a two-layer film structure characterized by having an unoriented polyester resin film layer having a low crystal melting temperature of 0 ° C. in the lower layer (adhesive layer) ”, and JP-A-4-1055931 describes“ upper layer (surface layer) ”. Has an oriented crystal structure and a melting point of 2
A laminated steel sheet having a two-layer film structure, wherein the lower layer (adhesive layer) is a polyester resin having a melting point of 160 ° C to 220 ° C. These resin-coated metal plates are made by laminating a polyester film to a metal plate without using an adhesive, and are thermally bonded to a metal plate heated to about the melting point of the lower (adhesive layer) polyester resin. An amorphous polyester layer is formed on the resin layer near the metal plate due to the thermal effect, and this layer ensures adhesion.
【０００５】しかし、かかるポリエステル樹脂被覆金属
板は、１００〜１３５℃、約２５分間のレトルト殺菌処
理を受けると、生成した無定形ポリエステル層樹脂の結
晶化が不均一に進行し、樹脂皮膜に水滴状の模様が発生
し、外観劣化を引き起こしやすいという難点を有してい
た。この無定形ポリエステル層の厚みを薄くし、水滴模
様を目立ち難くする方法も考えられ、熱接着時の熱影響
を最小とする為に、フィルム圧着温度を下層樹脂の融点
よりも低めとする方法も考えられたが、高速製造時に、
充分な密着性を安定して確保する事が困難であるという
問題点を有していた。However, when such a polyester resin-coated metal plate is subjected to a retort sterilization treatment at 100 to 135 ° C. for about 25 minutes, the crystallization of the formed amorphous polyester layer resin proceeds unevenly, and water droplets are formed on the resin film. This has the drawback that a pattern in the shape of a letter is generated and the appearance is likely to be deteriorated. A method of reducing the thickness of the amorphous polyester layer to make the water droplet pattern less conspicuous is also conceivable.In order to minimize the thermal effect at the time of thermal bonding, a method of lowering the film compression temperature below the melting point of the lower resin is also available. As thought, during high-speed manufacturing,
There is a problem that it is difficult to stably secure sufficient adhesion.
【０００６】[0006]
【課題を解決するための手段】そこで、本発明では、上
記の問題点を解決すべく、種々検討した結果、従来の２
層構造をもった熱可塑性樹脂被覆金属板では樹脂の熱特
性の内、融点のみを規定していた為に上記の問題点が発
生していた事を解明し、下層樹脂の結晶化温度を規定す
る事により、レトルト処理性に優れた２層構造樹脂被覆
金属板を提供するものである。すなわち、本発明の要旨
は、金属板の少なくとも片面上に、融点（Ｔｍ1 ）が１
９０℃≦Ｔｍ1 ≦２５０℃、かつ結晶化温度（Ｔｃ）１
００℃≦Ｔｃ≦１３０℃、かつ面配向係数が０〜０．１
００のポリエステル樹脂を被覆して下層樹脂層を形成
し、その上に融点（Ｔｍ2 ）が（Ｔｍ1 ＋１０℃）≦Ｔ
ｍ2 ≦２６０℃、かつ面配向係数が０．１００〜０．１
６９のポリエステル樹脂を被覆して上層樹脂層を形成し
たことを特徴とする耐レトルト処理性と耐熱性に優れた
樹脂被覆金属板である。Therefore, in the present invention, as a result of various investigations to solve the above-mentioned problems, as a result, the conventional 2
In the thermoplastic resin coated metal plate with a layer structure, it was clarified that the above-mentioned problem occurred because only the melting point was specified among the thermal characteristics of the resin, and the crystallization temperature of the lower layer resin was specified. Accordingly, the present invention provides a two-layer resin-coated metal sheet having excellent retort processing properties. That is, the gist of the present invention is that at least one surface of a metal plate has a melting point (Tm 1 ) of 1
90 ° C. ≦ Tm 1 ≦ 250 ° C. and crystallization temperature (Tc) 1
00 ° C ≦ Tc ≦ 130 ° C and the plane orientation coefficient is 0 to 0.1
To form a lower resin layer having a melting point (Tm 2 ) of (Tm 1 + 10 ° C.) ≦ T
m 2 ≦ 260 ° C. and a plane orientation coefficient of 0.100 to 0.1
69 is a resin-coated metal plate excellent in retort resistance and heat resistance, characterized in that an upper resin layer is formed by coating a polyester resin of No. 69.
【０００７】以下、本発明の内容について詳細に説明す
る。金属板の片面または両面に、２層構造の２軸配向ポ
リエステルフィルムを被覆する。使用される２軸配向フ
ィルム用ポリエステル樹脂は、上層下層とも同様の樹脂
でよく、分子鎖中に二重結合を含まない飽和ポリエステ
ル樹脂で、周知の様に飽和多価カルボン酸と飽和多価ア
ルコールとの重合体である。飽和多価カルボン酸として
は、テレフタル酸、フタル酸、イソフタル酸、コハク
酸、アゼライン酸、アジピン酸、セバチン酸、ドデカン
ジオン酸、ジフェニルカルボン酸、２，６ナフタレンジ
カルボン酸、１，４シクロヘキサンジカルボン酸、無水
トリメット酸等があげられる。Hereinafter, the contents of the present invention will be described in detail. One or both sides of a metal plate are coated with a biaxially oriented polyester film having a two-layer structure. The polyester resin for the biaxially oriented film to be used may be the same resin for the upper layer and the lower layer, and is a saturated polyester resin containing no double bond in the molecular chain. And a polymer of Examples of the saturated polycarboxylic acid include terephthalic acid, phthalic acid, isophthalic acid, succinic acid, azelaic acid, adipic acid, sebacic acid, dodecandionic acid, diphenylcarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid And trimetic anhydride.
【０００８】また飽和多価アルコールとしては、エチレ
ングリコール、１，４ブタンジオール、１，５ペンタン
ジオール、１，６ヘキサンジオール、プロピレングリコ
ール、ポリテトラメチレングリコール、トリメチレング
リコール、トリエチレングリコール、ネオペンチルグリ
コール、１，４シクロヘキサンジメタノール、トリメチ
ロールプロパン、ペンタエリスリトール等があげられ
る。これら成分について、これらのホモポリマー、コポ
リマーの単体、及びブレンドされたポリエステル樹脂が
適用される。[0008] Saturated polyhydric alcohols include ethylene glycol, 1,4 butanediol, 1,5 pentanediol, 1,6 hexanediol, propylene glycol, polytetramethylene glycol, trimethylene glycol, triethylene glycol, neopentyl. Glycol, 1,4 cyclohexane dimethanol, trimethylolpropane, pentaerythritol and the like. For these components, simple substances of these homopolymers and copolymers, and blended polyester resins are applied.
【０００９】また、上記ポリエステル樹脂に衝撃強度等
の改善を目的に、ポリアルキレングリコール誘導体等を
添加したものも適用できる。また潤滑性の変更、表面外
観の変更、耐指紋性の変更を目的に、フィルム表面粗度
を変更する事なども差し支えない。かかるフィルムに
は、必要に応じて、酸化防止剤、熱安定剤、紫外線吸収
剤、帯電防止剤、着色剤などを添加する事も差し支えな
い。Also, a polyester resin to which a polyalkylene glycol derivative or the like is added for the purpose of improving impact strength or the like can be applied. Further, the film surface roughness may be changed for the purpose of changing the lubricity, the surface appearance, and the fingerprint resistance. If necessary, an antioxidant, a heat stabilizer, an ultraviolet absorber, an antistatic agent, a colorant, and the like may be added to such a film.
【００１０】かかるポリエステル樹脂を、公知の共押し
出し装置により２層フィルムに成形し、フィルム成形
後、縦、横２方向に延伸した後、機械的強度や寸法安定
性を確保するための熱固定工程を適用する事により、均
質な２軸配向ポリエステルフィルムを得る事ができる。
２軸配向フィルムの分子鎖軸は、フィルム面に平行であ
るが、面内では無配向である。２軸配向フィルムは未延
伸フィルムに比して、一般に、寸法精度や機械的強度が
極端に向上する。２層構造ポリエステル樹脂フィルムの
厚みとしては、特に制限するものではないが、全体の厚
みが１０μｍ〜６０μｍのものが使用され、接着層（鋼
板と接着される下層）厚みは、最低１μｍ以上、できれ
ば３μｍ以上が望ましい。全体厚みが１０μｍ未満で
は、フィルムのピンホールが多数存在する様になり、耐
内容物性が劣り、６０μｍを越えると、フィルムコスト
が高くなり、容器用素材としては、商業的には適さな
い。[0010] The polyester resin is formed into a two-layer film by a known co-extrusion apparatus. After the film is formed, the film is stretched in two longitudinal and transverse directions, and then subjected to a heat fixing step for securing mechanical strength and dimensional stability. By applying the above, a homogeneous biaxially oriented polyester film can be obtained.
The molecular chain axis of the biaxially oriented film is parallel to the film plane, but is non-oriented in the plane. In general, a biaxially oriented film has extremely improved dimensional accuracy and mechanical strength as compared with an unstretched film. Although the thickness of the two-layer polyester resin film is not particularly limited, a total thickness of 10 μm to 60 μm is used, and the thickness of the adhesive layer (the lower layer bonded to the steel plate) is at least 1 μm, if possible. 3 μm or more is desirable. If the total thickness is less than 10 μm, many pinholes of the film will be present and the content resistance will be poor. If it exceeds 60 μm, the film cost will be high and it will not be commercially suitable as a container material.
【００１１】樹脂の熱特性としては、下層（接着層）に
ついては、融点Ｔｍ1 が１９０℃〜２５０℃、かつ結晶
化温度が１００〜１３０℃であり、上層樹脂の融点Ｔｍ
2 は、下層樹脂の融点Ｔｍ1 ＋１０℃〜２６０℃である
事が必要である。ここでいう、樹脂の融点とは、測定対
象となる樹脂を一旦溶融した後に急速水冷し無定形状態
としたものを、示差走査熱量計（ＤＳＣ７、パーキンエ
ルマー社製）にて昇温速度１０℃／分にて測定した際
の、結晶融解時の吸熱ピークのピーク温度をいい、また
結晶化温度とは、同様にして測定した際に、樹脂の熱結
晶化が発生する時の発熱ピークのピーク温度をいう。Regarding the thermal characteristics of the resin, the lower layer (adhesive layer) has a melting point Tm 1 of 190 ° C. to 250 ° C., a crystallization temperature of 100 ° C. to 130 ° C., and a melting point Tm of the upper layer resin.
2, it is necessary that the melting point Tm 1 + 10 ℃ ~260 ℃ of the lower layer resin. As used herein, the melting point of the resin refers to a resin to be measured, which is once melted and then rapidly cooled with water to form an amorphous state, and the temperature is raised at a rate of 10 ° C. by a differential scanning calorimeter (DSC7, manufactured by PerkinElmer). / Min refers to the peak temperature of the endothermic peak at the time of crystal melting, and the crystallization temperature is the peak of the exothermic peak when thermal crystallization of the resin occurs when measured in the same manner. Refers to temperature.
【００１２】下層（接着層）の融点が１９０℃未満で
は、樹脂の特性から、同結晶融解開始温度が１８０℃未
満となり、製缶時の乾燥・加熱工程にて下層樹脂の融解
が発生し、フィルムの剥離が発生し、製缶性の低下を引
き起こし、２５０℃を越えると樹脂の結晶性が増大する
為、安定した無定型構造が存在できず、製缶時の熱処理
工程等で熱結晶化が進行し、密着力が不十分となる。下
層の結晶化温度は１００℃〜１３０℃である事が必要で
ある。１００℃未満だと、耐衝撃性が不十分となりやす
く、又１３０℃超では水滴模様の発生が顕著となる。When the melting point of the lower layer (adhesive layer) is lower than 190 ° C., the melting start temperature of the crystal becomes lower than 180 ° C. due to the characteristics of the resin, and the lower layer resin melts in the drying / heating step during can-making. Exfoliation of the film causes the deterioration of the can-making property. If the temperature exceeds 250 ° C, the crystallinity of the resin increases, so that a stable amorphous structure cannot be present. Progresses, and the adhesion becomes insufficient. The crystallization temperature of the lower layer needs to be 100 ° C to 130 ° C. If the temperature is lower than 100 ° C., the impact resistance tends to be insufficient, and if it is higher than 130 ° C., the generation of water droplet patterns becomes remarkable.
【００１３】なお、下層樹脂の結晶化温度と水玉模様の
発現との関係については、以下のように考えられる。レ
トルト処理では、下層樹脂の無定型構造が水を含む雰囲
気中での加熱処理によって、結晶化を起こす。下層樹脂
の結晶化温度がレトルト温度よりも高い場合には、結晶
化の速度が遅く、生成する結晶の数も少ないため生成し
た結晶は大きな結晶へと成長する、この大きな結晶が水
玉模様として発現すると推測される。一方、結晶化温度
が低い場合には、結晶化の速度が早く、生成する結晶の
数も多いため結晶はお互いの相互作用のために、大きな
結晶へは成長できず、水玉模様が発現しないものと推測
される。なお、樹脂の耐衝撃性及び水玉模様の発現性の
安定性から、出来れば、下層樹脂の結晶化温度は１０５
℃〜１２５℃である事が望ましい。The relationship between the crystallization temperature of the lower resin and the appearance of a polka dot pattern is considered as follows. In the retort treatment, the amorphous structure of the lower resin is crystallized by heat treatment in an atmosphere containing water. When the crystallization temperature of the lower resin is higher than the retort temperature, the crystallization speed is slow and the number of generated crystals is small, so the generated crystals grow into large crystals.These large crystals appear as polka dots It is guessed. On the other hand, when the crystallization temperature is low, the crystallization speed is high, and the number of generated crystals is large, so that the crystals cannot grow into a large crystal due to the interaction between them, and the polka dot pattern does not appear. It is presumed. In addition, if possible, the crystallization temperature of the lower resin should be 105 from the stability of the impact resistance of the resin and the development of the polka dot pattern.
It is desirable that the temperature be in the range of 125C to 125C.
【００１４】上層の融点が、下層樹脂の融点＋１０℃未
満の温度では、ポリエステルフィルムを下層樹脂の融点
程度に加熱した金属板に圧着する際に、上層の２軸配向
結晶構造を破壊する事なく、下層のみに均一な無定型ポ
リエステル層を生成させる事が困難となると同時に、圧
着ロールへの上層樹脂の粘着による表面仕上がり劣化を
防止する事が困難となる。また、上層の融点が、２６０
℃超ではポリエステル樹脂自体が非常に剛直となり加工
性が極端に悪くなる。When the melting point of the upper layer is lower than the melting point of the lower layer resin + 10 ° C., when the polyester film is pressed against a metal plate heated to about the melting point of the lower layer resin without destroying the biaxially oriented crystal structure of the upper layer. In addition, it is difficult to form a uniform amorphous polyester layer only in the lower layer, and at the same time, it is difficult to prevent deterioration of the surface finish due to adhesion of the upper layer resin to the pressure roll. The melting point of the upper layer is 260
If the temperature exceeds ℃, the polyester resin itself becomes very rigid and the workability becomes extremely poor.
【００１５】次に、上層樹脂層の配向性は面配向係数と
して０．１００〜０．１６９であり、下層樹脂層の面配
向係数は０〜０．１００である事が重要である。ここで
いう、面配向係数は、ポリエステル樹脂被覆金属板を塩
酸に浸漬し、金属板表面を溶解させ、樹脂皮膜のみを剥
離し、そのフィルムの上層側、下層側の縦方向、横方
向、厚み方向の屈折率をアッベの屈折率計によりもと
め、（縦方向屈折率＋横方向屈折率）／２−厚み方向屈
折率で定義される式により求められるものとする。上層
樹脂層の面配向係数が０．１６９を越えると、ポリエス
テル樹脂は剛直となり、加工性が低下してくる。また
０．１００未満になると、耐衝撃性が低下し、衝撃を受
けた際にクラックが発生しやすくなる。下層樹脂層の面
配向係数が０．１００を越えると金属板との密着性が著
しく低下し、加工時に剥離しやすくなる。Next, it is important that the orientation of the upper resin layer is 0.100 to 0.169 as a plane orientation coefficient, and the plane orientation coefficient of the lower resin layer is 0 to 0.100. As used herein, the plane orientation coefficient is such that a polyester resin-coated metal plate is immersed in hydrochloric acid, the surface of the metal plate is dissolved, only the resin film is peeled off, and the upper, lower, vertical, lateral, and thickness of the film are removed. The refractive index in the direction is determined by an Abbe refractometer, and is determined by an equation defined by (refraction index in the vertical direction + refractive index in the horizontal direction) / 2−refractive index in the thickness direction. If the plane orientation coefficient of the upper resin layer exceeds 0.169, the polyester resin becomes rigid, and the workability decreases. On the other hand, if it is less than 0.100, impact resistance is reduced, and cracks are likely to occur when subjected to impact. If the plane orientation coefficient of the lower resin layer exceeds 0.100, the adhesion to the metal plate is significantly reduced, and the lower resin layer is easily peeled off during processing.
【００１６】本発明に使用されるポリエステルフィルム
の一例としては、上下層樹脂ともカルボン酸としてはテ
レフタル酸とイソフタル酸、アルコールとしてはエチレ
ングリコールと１，４ブタンジオールを用いた重合体
で、熱特性が上層の融点が２４８℃、下層の融点が２３
０℃、下層結晶化温度が１２２℃であり、上層厚み２２
μｍ、下層厚み３μｍ、フィルム面配向係数０．１５、
極限粘度０．６５のものが上げられる。One example of the polyester film used in the present invention is a polymer using terephthalic acid and isophthalic acid as the carboxylic acid and ethylene glycol and 1,4-butanediol as the alcohol for both the upper and lower resins. Has a melting point of 248 ° C. in the upper layer and 23 in the lower layer.
0 ° C., the lower layer crystallization temperature is 122 ° C., and the upper layer thickness 22
μm, lower layer thickness 3 μm, film plane orientation coefficient 0.15,
Those having an intrinsic viscosity of 0.65 can be raised.
【００１７】本発明に於いて適用される金属板は、特に
限定するものではなく、Ｓｎメッキ、Ｎｉメッキ、Ｓｎ
／Ｎｉメッキのそれぞれのメッキ層の上に、化成処理を
施したメッキ鋼板及び、電解クロム酸処理鋼板、化成処
理を施したアルミ板も使用される。電解クロム酸処理鋼
板は通称ティン・フリー・スティール（ＴＦＳ）と呼ば
れているクロム・クロメート処理鋼板で、付着量は金属
クロムが３０〜１５０ｍｇ／ｍ2 、水酸化クロムは金属
クロム換算で５〜２５ｍｇ／ｍ2 が好ましい。The metal plate applied in the present invention is not particularly limited, and may be Sn plating, Ni plating, Sn plating, or the like.
On each plating layer of / Ni plating, a plated steel sheet subjected to a chemical conversion treatment, an electrolytic chromic acid-treated steel sheet, and an aluminum plate subjected to a chemical conversion treatment are also used. The electrolytic chromic acid-treated steel sheet is a chromium chromate-treated steel sheet commonly called Tin Free Steel (TFS), and has a coating amount of 30 to 150 mg / m 2 of chromium metal and a chromium hydroxide of 5 to 5 chromium hydroxide equivalent. 25 mg / m 2 is preferred.
【００１８】製造方法としては、下層樹脂の融点近傍に
加熱された金属板に、２層構造ポリエステルフィルムを
圧着して製造される。一例としては、前記の一例として
掲げたフィルム（厚み２５μｍ）を、２３０℃に加熱さ
れたＴＦＳ（厚み０．２２ｍｍ）にゴムロールで圧着
し、水中に浸漬急冷する方法が上げられる。As a production method, a two-layered polyester film is pressure-bonded to a metal plate heated near the melting point of the lower resin. As an example, there is a method in which the film (thickness: 25 μm) cited as an example above is pressure-bonded to TFS (thickness: 0.22 mm) heated to 230 ° C. by a rubber roll, and immersed and quenched in water.
【００１９】以下、本発明の実施例を示す。Hereinafter, embodiments of the present invention will be described.
実施例１ Ｔ−ダイ押出し後２軸延伸することにより、テレフタル
酸、イソフタル酸およびエチレングリコールを原料主成
分とするポリエステル系２層フィルムを作成した。この
２層フィルム（厚み１５．０μ）は、下層（厚み５．０
μ）の融点１９５℃、結晶化温度が１０５℃で、上層
（厚み１０．０μ）の融点２１０℃となるようイソフタ
ル酸共重合量が調整された。このフィルムを下層融点に
加熱したブリキ板（厚み０．２４ｍｍ，硬度６２（Ｈ
R30-T ）、錫付着量２．８ｇ／ｍ2 ）の片面にゴムロー
ルで圧着し、水中に浸漬急冷する方法により樹脂被覆金
属板を作成した。作成した樹脂被覆金属板を塩酸に浸漬
し、剥離された皮膜の面配向係数は上層０．１１２、下
層０．００６であった。樹脂被覆金属板は２段絞り成形
により缶体作成された。１段目の絞り成形は、ブランク
径：１２０ｍｍ、絞り比１．５で成形し、２段目は、絞
り比１．３で成形し、トリミング、フランジ加工を行
い、缶径６１ｍｍ、高さ３５ｍｍの深絞り缶を作成し
た。なお、耐熱性の評価として、絞り成形後、印刷、焼
付け（２００℃、４分）を行ったが問題無かった。さら
に、成形缶は内容物が充填された缶蓋が巻締められた
後、１２５℃、２５分間のレトルト殺菌処理された。樹
脂皮膜は缶体の外面、内面のいずれに使用された場合に
も、製缶加工時やレトルト殺菌処理時に皮膜欠陥を生じ
たり剥離することもなく、また、水玉状の模様が現れる
ことも無かった。Example 1 A polyester-based two-layer film containing terephthalic acid, isophthalic acid, and ethylene glycol as main components was prepared by extruding a T-die and then biaxially stretching. This two-layer film (thickness of 15.0 μm) has a lower layer (thickness of 5.0 μm).
μ) was 195 ° C., the crystallization temperature was 105 ° C., and the copolymerization amount of isophthalic acid was adjusted so that the melting point of the upper layer (10.0 μm) was 210 ° C. A tin plate (thickness 0.24 mm, hardness 62 (H
R30-T ), and a tin-adhered amount of 2.8 g / m 2 ) were pressed against one surface with a rubber roll, and immersed and quenched in water to form a resin-coated metal plate. The prepared resin-coated metal plate was immersed in hydrochloric acid, and the peeled film had a surface orientation coefficient of 0.112 for the upper layer and 0.006 for the lower layer. The resin-coated metal plate was formed into a can by two-step drawing. The first-stage drawing is performed with a blank diameter of 120 mm and a drawing ratio of 1.5, and the second stage is formed with a drawing ratio of 1.3, trimming and flange processing, and a can diameter of 61 mm and a height of 35 mm. Made a deep drawn can. In addition, as the evaluation of heat resistance, printing and baking (200 ° C., 4 minutes) were performed after drawing, but there was no problem. Further, the molded can was subjected to a retort sterilization treatment at 125 ° C. for 25 minutes after the can lid filled with the contents was wound. When the resin film is used on either the outer surface or the inner surface of the can body, it does not cause film peeling or peeling during can making or retort sterilization, and it does not show polka dot patterns. Was.
【００２０】実施例２ Ｔ−ダイ押出し後２軸延伸することにより、テレフタル
酸、イソフタル酸およびエチレングリコールを原料主成
分とするポリエステル系２層フィルムを作成した。この
２層フィルム（厚み４０．０μ）は、下層（厚み７．０
μ）の融点２４５℃、結晶化温度が１２５℃、上層（厚
み３３．０μ）の融点２６０℃となるようイソフタル酸
共重合量が調整された。このフィルムを下層融点に加熱
した化成処理を施したアルミ板（厚み０．２５ｍｍ）の
両面にゴムロールで圧着し、水中に浸漬急冷する方法に
より樹脂被覆金属板を作成した。作成した樹脂被覆金属
板を塩酸に浸漬し、剥離された皮膜の面配向係数は上層
０．１６０、下層０．０８１であった。樹脂被覆金属板
は２段絞り成形により缶体作成された。１段目の絞り成
形は、ブランク径：１２０ｍｍ、絞り比１．５で成形
し、２段目は、絞り比１．３で成形し、トリミング、フ
ランジ加工を行い、缶径６１ｍｍ、高さ３５ｍｍの深絞
り缶を作成した。なお、耐熱性の評価として、絞り成形
後、印刷、焼付け（２００℃、４分）を行ったが問題無
かった。さらに、成形缶は内容物が充填された缶蓋が巻
締められた後、１２５℃、２５分間のレトルト殺菌処理
された。樹脂皮膜は缶体の外面、内面のいずれでも、製
缶加工時やレトルト殺菌処理時に皮膜欠陥を生じたり剥
離することもなく、水玉状の模様が現れることも無かっ
た。Example 2 A two-layer polyester film containing terephthalic acid, isophthalic acid and ethylene glycol as main components was prepared by extruding a T-die and then biaxially stretching. This two-layer film (thickness 40.0 μm) has a lower layer (thickness 7.0).
μ), the crystallization temperature was 125 ° C., and the upper layer (thickness 33.0 μ) had a melting point of 260 ° C., so that the copolymerization amount of isophthalic acid was adjusted. This film was pressed with rubber rolls on both sides of a chemical conversion-treated aluminum plate (thickness 0.25 mm) heated to the lower layer melting point, and immersed and quenched in water to form a resin-coated metal plate. The prepared resin-coated metal plate was immersed in hydrochloric acid, and the peeled film had a surface orientation coefficient of 0.160 for the upper layer and 0.081 for the lower layer. The resin-coated metal plate was formed into a can by two-step drawing. The first-stage drawing is performed with a blank diameter of 120 mm and a drawing ratio of 1.5, and the second stage is formed with a drawing ratio of 1.3, trimming and flange processing, and a can diameter of 61 mm and a height of 35 mm. Made a deep drawn can. In addition, as the evaluation of heat resistance, printing and baking (200 ° C., 4 minutes) were performed after drawing, but there was no problem. Further, the molded can was subjected to a retort sterilization treatment at 125 ° C. for 25 minutes after the can lid filled with the contents was wound. The resin film did not cause any film defects or peeling during can making processing or retort sterilization treatment on either the outer surface or the inner surface of the can body, and no polka-dot pattern appeared.
【００２１】実施例３ Ｔ−ダイ押出し後２軸延伸することにより、テレフタル
酸、イソフタル酸およびエチレングリコールを原料主成
分とするポリエステル系２層フィルムを作成した。この
２層フィルム（厚み２５．０μ）は、下層（厚み５．０
μ）の融点２２５℃、結晶化温度が１２０℃、上層（厚
み２０．０μ）の融点２４５℃となるようイソフタル酸
共重合量が調整された。このフィルムを下層融点に加熱
したＴＦＳ（厚み０．１８ｍｍ、硬度７１
（ＨR30-T ）、金属クロム付着量：８０ｍｇ／ｍ2 、水
和酸化クロム［金属クロム換算］：１５ｍｇ／ｍ2 ）の
両面にゴムロールで圧着し、水中に浸漬急冷する方法に
より樹脂被覆金属板を作成した。作成した樹脂被覆金属
板を塩酸に浸漬し、剥離された皮膜の面配向係数は上層
０．１３０、下層０．０４４であった。樹脂被覆金属板
は２段絞り成形により缶体作成された。１段目の絞り成
形は、ブランク径：１２０ｍｍ、絞り比１．５で成形
し、２段目は、絞り比１．３で成形し、トリミング、フ
ランジ加工を行い、缶径６１ｍｍ、高さ３５ｍｍの深絞
り缶を作成した。なお、耐熱性の評価として、絞り成形
後、印刷、焼付け（２００℃、４分）を行ったが問題無
かった。さらに、成形缶は内容物が充填された缶蓋が巻
締められた後、１２５℃、２５分間のレトルト殺菌処理
された。樹脂皮膜は缶体の外面、内面のいずれでも、製
缶加工時やレトルト殺菌処理時に皮膜欠陥を生じたり剥
離することもなく、また、水玉状の模様が現れることも
無かった。Example 3 A polyester two-layer film mainly composed of terephthalic acid, isophthalic acid and ethylene glycol was prepared by extruding a T-die and then biaxially stretching it. This two-layer film (thickness 25.0 μm) is made of a lower layer (thickness 5.0).
μ), the crystallization temperature was 120 ° C., and the isophthalic acid copolymerization amount was adjusted so that the upper layer (thickness 20.0 μ) had a melting point of 245 ° C. This film was heated to the lower melting point of TFS (thickness 0.18 mm, hardness 71).
( HR30-T ), adhering amount of chromium metal: 80 mg / m 2 , hydrated chromium oxide (converted to chromium metal): 15 mg / m 2 ) A board was created. The prepared resin-coated metal plate was immersed in hydrochloric acid, and the peeled film had a surface orientation coefficient of 0.130 for the upper layer and 0.044 for the lower layer. The resin-coated metal plate was formed into a can by two-step drawing. The first-stage drawing is performed with a blank diameter of 120 mm and a drawing ratio of 1.5, and the second stage is formed with a drawing ratio of 1.3, trimming and flange processing, and a can diameter of 61 mm and a height of 35 mm. Made a deep drawn can. In addition, as the evaluation of heat resistance, printing and baking (200 ° C., 4 minutes) were performed after drawing, but there was no problem. Further, the molded can was subjected to a retort sterilization treatment at 125 ° C. for 25 minutes after the can lid filled with the contents was wound. The resin film did not cause any film defects or peeling during can making processing or retort sterilization treatment on either the outer surface or the inner surface of the can body, and no polka dot pattern appeared.
【００２２】実施例４ Ｔ−ダイ押出し後２軸延伸することにより、テレフタル
酸、イソフタル酸およびエチレングリコールを原料主成
分とするポリエステル系２層フィルムを作成した。この
２層フィルム（厚み１２．０μ）は、下層（厚み３．０
μ）の融点２００℃、結晶化温度が１１５℃で、上層
（厚み９．０μ）の融点２４５℃となるようイソフタル
酸共重合量が調整された。このフィルムを下層融点に加
熱したＳｎ／Ｎｉメッキ上に化成処理を施したメッキ鋼
板（厚み０．１９ｍｍ、硬度６１（ＨR30-T ）、ニッケ
ル付着量２５ｍｇ／ｍ2 、錫付着量１．２ｇ／ｍ2 ）の
両面にゴムロールで圧着し、水中に浸漬急冷する方法に
より樹脂被覆金属板を作成した。作成した樹脂被覆金属
板を塩酸に浸漬し、剥離された皮膜の面配向係数は上層
０．１４２、下層０．０３８であった。樹脂被覆金属板
は２段絞り成形により缶体作成された。１段目の絞り成
形は、ブランク径：１２０ｍｍ、絞り比１．５で成形
し、２段目は、絞り比１．３で成形し、トリミング、フ
ランジ加工を行い、缶径６１ｍｍ、高さ３５ｍｍの深絞
り缶を作成した。なお、耐熱性の評価として、絞り成形
後、印刷、焼付け（２００℃、４分）を行ったが問題無
かった。さらに、成形缶は内容物が充填され、缶蓋が巻
締められた後、１２５℃、２５分間のレトルト殺菌処理
された。樹脂皮膜は缶体の外面、内面のいずれでも、製
缶加工時やレトルト殺菌処理時に皮膜欠陥を生じたり剥
離することもなく、水玉状の模様が現れることも無かっ
た。Example 4 A polyester two-layer film mainly composed of terephthalic acid, isophthalic acid and ethylene glycol was prepared by extruding a T-die and then biaxially stretching it. This two-layer film (thickness 12.0 μm) has a lower layer (thickness 3.0).
The copolymerization amount of isophthalic acid was adjusted so that the melting point of (μ) was 200 ° C., the crystallization temperature was 115 ° C., and the melting point of the upper layer (9.0 μm) was 245 ° C. The film was heated to the lower layer melting point and plated on a Sn / Ni plated steel plate (thickness 0.19 mm, hardness 61 ( HR30-T ), nickel adhesion 25 mg / m 2 , tin adhesion 1.2 g) / M 2 ) were pressed with rubber rolls on both sides and immersed and quenched in water to form a resin-coated metal plate. The prepared resin-coated metal plate was immersed in hydrochloric acid, and the peeled film had a surface orientation coefficient of 0.142 for the upper layer and 0.038 for the lower layer. The resin-coated metal plate was formed into a can by two-step drawing. The first-stage drawing is performed with a blank diameter of 120 mm and a drawing ratio of 1.5, and the second stage is formed with a drawing ratio of 1.3, trimming and flange processing, and a can diameter of 61 mm and a height of 35 mm. Made a deep drawn can. In addition, as the evaluation of heat resistance, printing and baking (200 ° C., 4 minutes) were performed after drawing, but there was no problem. Further, the molded can was filled with the contents, and after the can lid was wrapped, it was subjected to a retort sterilization treatment at 125 ° C. for 25 minutes. The resin film did not cause any film defects or peeling during can making processing or retort sterilization treatment on either the outer surface or the inner surface of the can body, and no polka-dot pattern appeared.
【００２３】比較例１ Ｔ−ダイ押出し後２軸延伸することにより、テレフタル
酸、イソフタル酸およびエチレングリコールを原料主成
分とするポリエステル系２層フィルムを作成した。この
２層フィルム（厚み１５．０μ）は、下層（厚み５．０
μ）の融点１８５℃、結晶化温度が９５℃で、上層（厚
み１０．０μ）の融点２４０℃となるようイソフタル酸
共重合量が調整された。このフィルムを下層融点に加熱
したＴＦＳ（厚み０．２４ｍｍ、硬度６２
（ＨR30-T ）、金属クロム付着量：８０ｍｇ／ｍ2 、水
和酸化クロム［金属クロム換算］：１５ｍｇ／ｍ2 ）の
片面にゴムロールで圧着し、水中に浸漬急冷する方法に
より樹脂被覆金属板を作成した。作成した樹脂被覆金属
板を塩酸に浸漬し、剥離された皮膜の面配向係数は上層
０．１４２、下層０．００６であった。樹脂被覆金属板
は２段絞り成形により缶体作成された。１段目の絞り成
形は、ブランク径：１２０ｍｍ、絞り比１．５で成形
し、２段目は、絞り比１．３で成形し、トリミング、フ
ランジ加工を行い、缶径６１ｍｍ、高さ３５ｍｍの絞り
缶を作成した。なお、耐熱性の評価として、絞り成形
後、印刷、焼付け（２００℃、４分）を行ったが、缶体
の内外面いずれに適用した場合にも上層樹脂が１０ｍｍ
以上膜ずれを起こした。さらに、下層皮膜の衝撃加工性
不足のためか、缶底の衝撃加工部では皮膜が密着してい
ない部分が生じ、実用に耐えないものであった。また、
成形無しの樹脂被覆金属板（１００ｍｍ×１００ｍｍ）
を焼付け（２００℃、４分）処理を行ったところ、上層
樹脂が４ｍｍ膜ずれを起こし、熱処理を受ける用途で
は、実用に耐えないものであった。COMPARATIVE EXAMPLE 1 T-die extrusion was followed by biaxial stretching to produce a polyester-based two-layer film mainly composed of terephthalic acid, isophthalic acid and ethylene glycol. This two-layer film (thickness of 15.0 μm) has a lower layer (thickness of 5.0 μm).
μ), the crystallization temperature was 95 ° C., and the copolymerization amount of isophthalic acid was adjusted so that the melting point of the upper layer (10.0 μm) was 240 ° C. This film was heated to the lower melting point of TFS (thickness 0.24 mm, hardness 62
(H R30-T ), chromium metal adhesion: 80 mg / m 2 , hydrated chromium oxide [converted to chromium metal]: 15 mg / m 2 ). A board was created. The prepared resin-coated metal plate was immersed in hydrochloric acid, and the peeled film had a surface orientation coefficient of 0.142 for the upper layer and 0.006 for the lower layer. The resin-coated metal plate was formed into a can by two-step drawing. The first stage drawing was performed with a blank diameter of 120 mm and a drawing ratio of 1.5, and the second stage was formed with a drawing ratio of 1.3, trimming and flange processing, and a can diameter of 61 mm and a height of 35 mm. Squeezed cans. As the heat resistance evaluation, printing and baking (200 ° C., 4 minutes) were performed after drawing, but the upper layer resin was 10 mm even when applied to both the inner and outer surfaces of the can body.
As described above, film shift occurred. Furthermore, because of the lack of impact workability of the lower layer film, a portion where the film did not adhere to the impact-processed portion at the bottom of the can was generated, and was not practical. Also,
Resin coated metal plate without molding (100mm x 100mm)
Was subjected to a baking treatment (200 ° C., 4 minutes). As a result, the upper layer resin caused a film displacement of 4 mm, and was not practically usable in applications where it was subjected to heat treatment.
【００２４】比較例２ Ｔ−ダイ押出し後２軸延伸することにより、テレフタル
酸、イソフタル酸およびエチレングリコールを原料主成
分とするポリエステル系２層フィルムを作成した。この
２層フィルム（厚み２５．０μ）は、下層（厚み５．０
μ）の融点２５５℃、結晶化温度が１３５℃、上層（厚
み２０．０μ）の融点２６５℃となるようイソフタル酸
共重合量が調整された。このフィルムを下層融点に加熱
したＴＦＳ（厚み０．１８ｍｍ、硬度７１
（ＨR30-T ）、金属クロム付着量：８０ｍｇ／ｍ2 、水
和酸化クロム［金属クロム換算］：１５ｍｇ／ｍ2 ）の
両面にゴムロールで圧着し、水中に浸漬急冷する方法に
より樹脂被覆金属板を作成した。作成した樹脂被覆金属
板を塩酸に浸漬し、剥離された皮膜の面配向係数は上層
０．１５３、下層０．０８８であった。樹脂被覆金属板
は缶径２０６φの蓋に加工された。この蓋を用いて缶体
に内容物を充填し、１２５℃、２５分間のレトルト殺菌
処理された。樹脂皮膜は缶体の外面、内面のいずれで
も、製缶加工時やレトルト殺菌処理時に皮膜欠陥を生じ
たり剥離することは無かったが、蓋の外面側に水玉状の
模様が現れた。外観上、実用に耐えないものであった。COMPARATIVE EXAMPLE 2 T-die extrusion was followed by biaxial stretching to produce a polyester two-layer film containing terephthalic acid, isophthalic acid and ethylene glycol as main components. This two-layer film (thickness 25.0 μm) is made of a lower layer (thickness 5.0).
μ), the crystallization temperature was 135 ° C., and the upper layer (20.0 μm) had a melting point of 265 ° C., and the isophthalic acid copolymerization amount was adjusted. This film was heated to the lower melting point of TFS (thickness 0.18 mm, hardness 71).
( HR30-T ), adhering amount of chromium metal: 80 mg / m 2 , hydrated chromium oxide (converted to chromium metal): 15 mg / m 2 ) A board was created. The prepared resin-coated metal plate was immersed in hydrochloric acid, and the peeled film had a surface orientation coefficient of 0.153 for the upper layer and 0.088 for the lower layer. The resin-coated metal plate was processed into a lid having a can diameter of 206φ. The can was filled with the contents using the lid, and subjected to a retort sterilization treatment at 125 ° C. for 25 minutes. The resin film did not cause any film defects or peeling during the can-making process or the retort sterilization treatment on both the outer surface and the inner surface of the can body, but a polka dot pattern appeared on the outer surface side of the lid. The appearance was not practical.
【００２５】比較例３ Ｔ−ダイ押出し後２軸延伸することにより、テレフタル
酸、イソフタル酸およびエチレングリコールを原料主成
分とするポリエステル系２層フィルムを作成した。この
２層フィルム（厚み２５．０μ）は、下層（厚み５．０
μ）の融点２２０℃、結晶化温度が１２０℃、上層（厚
み２０．０μ）の融点２２５℃となるようイソフタル酸
共重合量が調整された。このフィルムを下層融点に加熱
したＴＦＳ（厚み０．１８ｍｍ、硬度７１
（ＨR30-T ）、金属クロム付着量：８０ｍｇ／ｍ2 、水
和酸化クロム［金属クロム換算］：１５ｍｇ／ｍ2 ）の
両面にゴムロールで圧着し、水中に浸漬急冷する方法に
より樹脂被覆金属板を作成したが、密着性、耐衝撃性、
表面仕上がりの良い樹脂被覆鋼板を安定して得ることが
できなかった。Comparative Example 3 T-die extrusion was followed by biaxial stretching to produce a polyester-based two-layer film mainly composed of terephthalic acid, isophthalic acid and ethylene glycol. This two-layer film (thickness 25.0 μm) is made of a lower layer (thickness 5.0).
μ), the isophthalic acid copolymerization amount was adjusted so that the melting point was 220 ° C., the crystallization temperature was 120 ° C., and the melting point of the upper layer (20.0 μm) was 225 ° C. This film was heated to the lower melting point of TFS (thickness 0.18 mm, hardness 71).
( HR30-T ), adhering amount of chromium metal: 80 mg / m 2 , hydrated chromium oxide (converted to chromium metal): 15 mg / m 2 ) The board was made, but the adhesion, impact resistance,
A stable resin-coated steel sheet with a good surface finish could not be obtained.
【００２６】比較例４ Ｔ−ダイ押出し後２軸延伸することにより、テレフタル
酸、イソフタル酸およびエチレングリコールを原料主成
分とするポリエステル系２層フィルムを作成した。この
２層フィルム（厚み２５．０μ）は、下層（厚み５．０
μ）の融点２２０℃、結晶化温度が１２０℃、上層（厚
み２０．０μ）の融点２４５℃となるようイソフタル酸
共重合量が調整された。このフィルムを下層融点に加熱
したＴＦＳ（厚み０．１８ｍｍ、硬度７１
（ＨR30-T ）、金属クロム付着量：８０ｍｇ／ｍ2 、水
和酸化クロム［金属クロム換算］：１５ｍｇ／ｍ2 ）の
両面にゴムロールで圧着し、水中に浸漬急冷する方法に
より樹脂被覆金属板を作成した。作成した樹脂被覆金属
板を塩酸に浸漬し、剥離された皮膜の面配向係数は上層
０．１７５、下層０．０８８であった。樹脂被覆金属板
は２段絞り成形により缶体作成された。１段目の絞り成
形は、ブランク径：１２０ｍｍ、絞り比１．５で成形
し、２段目は、絞り比１．３で成形し、トリミング、フ
ランジ加工を行い、缶径６１ｍｍ、高さ３５ｍｍの絞り
缶を作成した。加工時に缶体の内外面ともに皮膜剥離が
発生し、実用に耐えないものであった。Comparative Example 4 T-die extrusion was followed by biaxial stretching to produce a polyester-based two-layer film mainly composed of terephthalic acid, isophthalic acid and ethylene glycol. This two-layer film (thickness 25.0 μm) is made of a lower layer (thickness 5.0).
μ), the isophthalic acid copolymerization amount was adjusted so that the melting point was 220 ° C., the crystallization temperature was 120 ° C., and the melting point of the upper layer (20.0 μm) was 245 ° C. This film was heated to the lower melting point of TFS (thickness 0.18 mm, hardness 71).
( HR30-T ), adhering amount of chromium metal: 80 mg / m 2 , hydrated chromium oxide (converted to chromium metal): 15 mg / m 2 ) A board was created. The prepared resin-coated metal plate was immersed in hydrochloric acid, and the peeled film had a surface orientation coefficient of 0.175 for the upper layer and 0.088 for the lower layer. The resin-coated metal plate was formed into a can by two-step drawing. The first-stage drawing is performed with a blank diameter of 120 mm and a drawing ratio of 1.5, and the second stage is formed with a drawing ratio of 1.3, trimming and flange processing, and a can diameter of 61 mm and a height of 35 mm. Squeezed cans. At the time of processing, film peeling occurred on the inner and outer surfaces of the can body, which was not practical.
【００２７】比較例５ Ｔ−ダイ押出し後２軸延伸することにより、テレフタル
酸、イソフタル酸およびエチレングリコールを原料主成
分とするポリエステル系２層フィルムを作成した。この
２層フィルム（厚み２５．０μ）は、下層（厚み５．０
μ）の融点２２０℃、結晶化温度が１２０℃、上層（厚
み２０．０μ）の融点２４５℃となるようイソフタル酸
共重合量が調整された。このフィルムを下層融点に加熱
したＴＦＳ（厚み０．１８ｍｍ、硬度７１
（ＨR30-T ）、金属クロム付着量：８０ｍｇ／ｍ2 、水
和酸化クロム［金属クロム換算］：１５ｍｇ／ｍ2 ）の
両面にゴムロールで圧着し、水中に浸漬急冷する方法に
より樹脂被覆金属板を作成した。作成した樹脂被覆金属
板を塩酸に浸漬し、剥離された皮膜の面配向係数は上層
０．０８５、下層０．０４４であった。樹脂被覆金属板
は２段絞り成形により缶体作成された。１段目の絞り成
形は、ブランク径：１２０ｍｍ、絞り比１．５で成形
し、２段目は、絞り比１．３で成形し、トリミング、フ
ランジ加工を行い、缶径６１ｍｍ、高さ３５ｍｍの絞り
缶を作成した。缶体の衝撃加工部で皮膜が白化した。顕
微鏡で観察すると微小クラックが認められ、実用上問題
となった。Comparative Example 5 T-die extrusion and biaxial stretching were performed to prepare a polyester-based two-layer film mainly composed of terephthalic acid, isophthalic acid and ethylene glycol. This two-layer film (thickness 25.0 μm) is made of a lower layer (thickness 5.0).
μ), the isophthalic acid copolymerization amount was adjusted so that the melting point was 220 ° C., the crystallization temperature was 120 ° C., and the melting point of the upper layer (20.0 μm) was 245 ° C. This film was heated to the lower melting point of TFS (thickness 0.18 mm, hardness 71).
( HR30-T ), adhering amount of chromium metal: 80 mg / m 2 , hydrated chromium oxide (converted to chromium metal): 15 mg / m 2 ) A board was created. The prepared resin-coated metal plate was immersed in hydrochloric acid, and the peeled film had a surface orientation coefficient of 0.085 for the upper layer and 0.044 for the lower layer. The resin-coated metal plate was formed into a can by two-step drawing. The first-stage drawing is performed with a blank diameter of 120 mm and a drawing ratio of 1.5, and the second stage is formed with a drawing ratio of 1.3, trimming and flange processing, and a can diameter of 61 mm and a height of 35 mm. Squeezed cans. The film became white at the impact-processed part of the can body. Observation with a microscope revealed minute cracks, which became a practical problem.
【００２８】比較例６ Ｔ−ダイ押出し後２軸延伸することにより、テレフタル
酸、イソフタル酸およびエチレングリコールを原料主成
分とするポリエステル系２層フィルムを作成した。この
２層フィルム（厚み２５．０μ）は、下層（厚み５．０
μ）の融点２２０℃、結晶化温度が１２０℃、上層（厚
み２０．０μ）の融点２４５℃となるようイソフタル酸
共重合量が調整された。このフィルムを下層融点に加熱
したＴＦＳ（厚み０．１８ｍｍ、硬度７１
（ＨR30-T ）、金属クロム付着量：８０ｍｇ／ｍ2 、水
和酸化クロム［金属クロム換算］：１５ｍｇ／ｍ2 ）の
両面にゴムロールで圧着し、水中に浸漬急冷する方法に
より樹脂被覆金属板を作成した。作成した樹脂被覆金属
板を塩酸に浸漬し、剥離された皮膜の面配向係数は上層
０．１４５、下層０．１２０であった。樹脂被覆金属板
は２段絞り成形により缶体作成された。１段目の絞り成
形は、ブランク径：１２０ｍｍ、絞り比１．５で成形
し、２段目は、絞り比１．３で成形し、トリミング、フ
ランジ加工を行い、缶径６１ｍｍ、高さ３５ｍｍの絞り
缶を作成した。加工時に缶体の内外面とも皮膜剥離が発
生し、実用に耐えないものであった。Comparative Example 6 T-die extrusion was followed by biaxial stretching to produce a polyester-based two-layer film containing terephthalic acid, isophthalic acid and ethylene glycol as main components. This two-layer film (thickness 25.0 μm) is made of a lower layer (thickness 5.0).
μ), the isophthalic acid copolymerization amount was adjusted so that the melting point was 220 ° C., the crystallization temperature was 120 ° C., and the melting point of the upper layer (20.0 μm) was 245 ° C. This film was heated to the lower melting point of TFS (thickness 0.18 mm, hardness 71).
( HR30-T ), adhering amount of chromium metal: 80 mg / m 2 , hydrated chromium oxide (converted to chromium metal): 15 mg / m 2 ) A board was created. The prepared resin-coated metal plate was immersed in hydrochloric acid, and the peeled film had a surface orientation coefficient of 0.145 for the upper layer and 0.120 for the lower layer. The resin-coated metal plate was formed into a can by two-step drawing. The first-stage drawing is performed with a blank diameter of 120 mm and a drawing ratio of 1.5, and the second stage is formed with a drawing ratio of 1.3, trimming and flange processing, and a can diameter of 61 mm and a height of 35 mm. Squeezed cans. At the time of processing, film peeling occurred on the inner and outer surfaces of the can body, which was not practical.
【００２９】[0029]
【発明の効果】以上述べたごとく、本発明による樹脂被
覆金属板から得られた、絞り缶体は加工性・耐レトルト
処理性・耐熱性に優れたものであり、絞り缶のみなら
ず、缶蓋（ＥＮＤ）・イージー・オープン・エンド（Ｅ
ＯＥ）・ストレッチ加工を伴う絞り再絞り缶（ＤＴＲ
缶）・５ｇａｌ缶・ペール缶等の容器用の樹脂被覆金属
板として使用できる。As described above, the drawn can body obtained from the resin-coated metal plate according to the present invention has excellent workability, retort treatment resistance, and heat resistance. Lid (END) Easy Open End (E
OE) ・ Drawing and redrawing can with stretch processing (DTR)
(Cans), 5 gal cans, pail cans, and other resin-coated metal plates.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平５−331302（ＪＰ，Ａ) 特開 平４−105931（ＪＰ，Ａ) 特開 平１−192546（ＪＰ，Ａ) 特開 平５−269858（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B32B 15/08 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-5-331302 (JP, A) JP-A-4-105931 (JP, A) JP-A-1-192546 (JP, A) JP-A-5-192546 269858 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) B32B 15/08
Claims (1)
ｍ1 ）が１９０℃≦Ｔｍ1 ≦２５０℃、かつ結晶化温度
（Ｔｃ）１００℃≦Ｔｃ≦１３０℃、かつ面配向係数が
０〜０．１００のポリエステル樹脂を被覆して下層樹脂
層を形成し、その上に融点（Ｔｍ2 ）が（Ｔｍ1 ＋１０
℃）≦Ｔｍ2 ≦２６０℃、かつ面配向係数が０．１００
〜０．１６９のポリエステル樹脂を被覆して上層樹脂層
を形成したことを特徴とする耐レトルト処理性と耐熱性
に優れた樹脂被覆金属板。At least one side of a metal plate has a melting point (T
m 1 ) is coated with a polyester resin having a temperature of 190 ° C. ≦ Tm 1 ≦ 250 ° C., a crystallization temperature (Tc) of 100 ° C. ≦ Tc ≦ 130 ° C., and a plane orientation coefficient of 0 to 0.100 to form a lower resin layer. And the melting point (Tm 2 ) is (Tm 1 +10
° C) ≦ Tm 2 ≦ 260 ° C. and the plane orientation coefficient is 0.100
A resin-coated metal plate excellent in retort resistance and heat resistance, wherein an upper resin layer is formed by coating a polyester resin of 0.169 to 0.169.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21645394A JP3256093B2 (en) | 1994-09-12 | 1994-09-12 | Resin-coated metal sheet with excellent retort resistance and heat resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21645394A JP3256093B2 (en) | 1994-09-12 | 1994-09-12 | Resin-coated metal sheet with excellent retort resistance and heat resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0880592A JPH0880592A (en) | 1996-03-26 |
| JP3256093B2 true JP3256093B2 (en) | 2002-02-12 |
Family
ID=16688753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21645394A Expired - Lifetime JP3256093B2 (en) | 1994-09-12 | 1994-09-12 | Resin-coated metal sheet with excellent retort resistance and heat resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3256093B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007276204A (en) * | 2006-04-04 | 2007-10-25 | Teijin Dupont Films Japan Ltd | Metal sheet laminate molding processing film |
| JP6426348B2 (en) * | 2014-01-30 | 2018-11-21 | 帝人フィルムソリューション株式会社 | Biaxially oriented polyester film for metal plate bonding and forming |
-
1994
- 1994-09-12 JP JP21645394A patent/JP3256093B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0880592A (en) | 1996-03-26 |
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