JP2000043191A - Resin coated metal plate and production thereof - Google Patents
Resin coated metal plate and production thereofInfo
- Publication number
- JP2000043191A JP2000043191A JP10219009A JP21900998A JP2000043191A JP 2000043191 A JP2000043191 A JP 2000043191A JP 10219009 A JP10219009 A JP 10219009A JP 21900998 A JP21900998 A JP 21900998A JP 2000043191 A JP2000043191 A JP 2000043191A
- Authority
- JP
- Japan
- Prior art keywords
- metal plate
- polyester resin
- resin layer
- resin
- coated 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
- Laminated Bodies (AREA)
- Polyesters Or Polycarbonates (AREA)
- Rigid Containers With Two Or More Constituent Elements (AREA)
- Wrappers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリエステル樹脂
が被覆された成形加工用金属板に関する。詳しくは、絞
り加工や絞りしごき加工を施しても欠陥ができず、また
沸騰水に浸けても白化しにくい樹脂層が被覆された金属
板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal sheet for forming which is coated with a polyester resin. More specifically, the present invention relates to a metal plate coated with a resin layer that is free from defects even when subjected to drawing or drawing and ironing, and that is not easily whitened when immersed in boiling water.
【０００２】[0002]
【従来の技術・発明が解決しようとする課題】金属の成
形方法には、絞り法（ＤＲ法）、絞りしごき法（ＤＩ
法）などがあり、これらの金属成形体には防食の目的で
塗料を被覆するのが一般である。近年、成形してから塗
装する従来の方法に代わり、成形する前に金属板に予
め、塗料をコ−ティングするプレコート技術やフィルム
をラミネートするプレラミネート技術が開発されつつあ
る。2. Description of the Related Art Metal forming methods include a drawing method (DR method) and a drawing and ironing method (DI method).
Method), and these metal molded bodies are generally coated with a paint for the purpose of corrosion prevention. In recent years, instead of the conventional method of molding and then painting, a precoating technique of coating a paint on a metal plate before molding and a prelaminating technique of laminating a film have been developed.
【０００３】しかしこれらの技術によれば、コートある
いはラミネートされた樹脂層が、金属板成形工程で過酷
な変形や熱履歴を受けるので、成形後の樹脂層に欠陥が
生じ、十分な耐食性を発揮させるのが困難である場合が
多かった。[0003] However, according to these techniques, the coated or laminated resin layer is subjected to severe deformation and heat history in the metal plate forming process, so that a defect occurs in the formed resin layer and sufficient corrosion resistance is exhibited. It was often difficult to get them to do so.
【０００４】プレラミネート技術に適用するフィルムと
しては衛生性や保香性が優れていることから、ポリエチ
レンテレフタレートを中心としたポリエステル系フィル
ムが検討されている。しかしここで使用されるポリエス
テル系フィルムが予め延伸配向されていると、金属板成
形時の変形に追従できないため、フィルム層に亀裂が入
り、耐食性が悪化するとともに得られる成形体の外観も
悪いものとなる。As a film applied to the prelaminating technique, a polyester film mainly made of polyethylene terephthalate has been studied because of its excellent hygiene and fragrance retention properties. However, if the polyester-based film used here is stretched in advance, it cannot follow deformation during metal plate molding, so that the film layer is cracked, the corrosion resistance is deteriorated, and the appearance of the obtained molded product is poor. Becomes
【０００５】一方、非晶質のポリエステル系フィルム
は、成形時の変形に追従しやすく、成形後もフィルムに
亀裂ができず良好な耐食性が得られやすい。しかし該フ
ィルムは熱水に接すると樹脂が白化し外観が悪くなる問
題がある。一般に成形された缶の場合は、外面に印刷が
され、さらに表面の耐擦傷性を上げるために熱硬化性の
トップクリア塗料が焼き付け塗装される。また、内容物
によっては熱水処理やレトルト処理が行われる。こうし
た製缶後の熱履歴によってポリエステル樹脂層は脆化
し、衝撃が加わった場合樹脂層に亀裂が入りやすくな
る。非晶質無配向のポリエステル樹脂は、熱履歴による
脆化が著しく、缶に落下衝撃が加わった場合、亀裂が入
りやすくなるのが一般であった。このため該ポリエステ
ル系フィルムの面配向度や結晶化度を低めにコントロー
ルする方法が検討されている。この低い面配向度のフィ
ルムは変形の少ない成形加工ではあまり問題がなく、か
つ熱水による白化は少なくすることができる。しかし、
大きな変形を伴う成形加工を行うとフィルムに亀裂が発
生してしまう。[0005] On the other hand, an amorphous polyester film easily follows the deformation at the time of molding, and the film is not cracked even after molding, so that good corrosion resistance is easily obtained. However, the film has a problem that when exposed to hot water, the resin becomes white and its appearance deteriorates. Generally, in the case of a molded can, the outer surface is printed, and a thermosetting top clear paint is baked to further improve the scratch resistance of the surface. Further, depending on the contents, a hot water treatment or a retort treatment is performed. The polyester resin layer is embrittled by such heat history after can making, and the resin layer is easily cracked when an impact is applied. Amorphous non-oriented polyester resin is remarkably embrittled by heat history, and generally cracks easily when a drop impact is applied to the can. For this reason, methods for controlling the degree of plane orientation and crystallinity of the polyester-based film to be low have been studied. This film having a low degree of plane orientation has few problems in molding processing with little deformation, and whitening due to hot water can be reduced. But,
When a forming process involving large deformation is performed, cracks occur in the film.
【０００６】このほかにシクロヘキサンジメタノール成
分を共重合したポリエチレンテレフタレートフィルムを
積層するなど、ポリエステル樹脂を改質する方法なども
提案されているが、上記問題を解決するには至っていな
いのが現状である。In addition, a method of modifying a polyester resin, such as laminating a polyethylene terephthalate film copolymerized with a cyclohexane dimethanol component, has been proposed, but the above problem has not yet been solved. is there.
【０００７】本発明の目的は、良好な成形性を有し、か
つ沸騰水に浸けても白化しにくく、あるいはレトルト処
理にも耐えうる樹脂層が被覆された金属板を提供するこ
とである。本発明の他の目的は、上記した樹脂被覆金属
板を製造する方法を提供することである。An object of the present invention is to provide a metal plate coated with a resin layer which has good moldability, is hardly whitened even when immersed in boiling water, or can withstand retort treatment. Another object of the present invention is to provide a method for manufacturing the above-mentioned resin-coated metal sheet.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記目的
を達成するため鋭意検討した結果、特定のポリエチレン
テレフタレート系樹脂を金属板に押出しラミネート法で
被覆した非晶質のポリエステル樹脂層を有する金属板
が、絞り加工、絞りしごき加工しても欠陥ができず、沸
騰水に浸けても白化しないことを見出し、本発明を完成
した。また上記樹脂被覆金属板は、押出しラミネート法
で樹脂を金属板に積層した後、得られた樹脂層を再溶融
し、さらに急冷固化することによって得られることを見
出し、本発明を完成した。Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and as a result, extruded a specific polyethylene terephthalate-based resin onto a metal plate to form an amorphous polyester resin layer. The present inventors have found that the metal plate has no defect even when drawn or drawn and ironed, and does not become white even when immersed in boiling water, and thus completed the present invention. Further, they have found that the resin-coated metal plate can be obtained by laminating a resin on the metal plate by an extrusion laminating method, re-melting the obtained resin layer, and further rapidly cooling and solidifying the resin layer, thereby completing the present invention.
【０００９】すなわち、本発明は、金属板の少なくとも
片面に、押出しラミネートによって積層された、エチレ
ンテレフタレート単位を少なくとも９０モル％含み、還
元粘度が０．８０〜１．１ｄｌ／ｇで、結晶化度が６０
％以下のポリエステル樹脂層を有する樹脂被覆金属板に
関する。上記構成からなる樹脂被覆金属板は、絞り加工
や絞りしごき加工を行っても樹脂層に欠陥ができず、か
つ沸騰水に浸けても白化しない。That is, according to the present invention, at least one side of a metal plate is laminated by extrusion lamination, contains at least 90 mol% of ethylene terephthalate units, has a reduced viscosity of 0.80 to 1.1 dl / g, and has a crystallinity of Is 60
% Of a resin-coated metal plate having a polyester resin layer of not more than 0.1%. The resin-coated metal plate having the above-described configuration does not have any defect in the resin layer even when drawing or drawing and ironing is performed, and does not whiten when immersed in boiling water.
【００１０】また本発明は、金属板の少なくとも片面に
エチレンテレフタレート単位を少なくとも９０モル％含
むポリエステル樹脂を押出しラミネート法で積層した
後、該ポリエステル樹脂層を再溶融し、次いで急冷固化
することを含む、還元粘度が０．８０〜１．１ｄｌ／ｇ
で、結晶化度が６０％以下のポリエステル樹脂層を有す
る樹脂被覆金属板の製造方法に関する。上記構成からな
る本発明の樹脂被覆金属板の製造方法によって、絞り加
工や絞りしごき加工を行っても樹脂層に欠陥ができず、
かつ沸騰水に漬けても白化しない樹脂層が被覆された金
属板が容易に得られる。上記製造方法の好適な実施態様
として、ポリエステル樹脂層の再溶融を不活性ガス雰囲
気中で行うことが挙げられる。The present invention also includes extruding and laminating a polyester resin containing at least 90 mol% of ethylene terephthalate units on at least one surface of a metal plate by an extrusion laminating method, remelting the polyester resin layer, and then rapidly cooling and solidifying. 0.80 to 1.1 dl / g reduced viscosity
And a method for producing a resin-coated metal plate having a polyester resin layer having a crystallinity of 60% or less. By the method for manufacturing a resin-coated metal plate of the present invention having the above configuration, even if drawing or drawing and ironing is performed, a defect cannot be formed in the resin layer,
Further, a metal plate coated with a resin layer that does not whiten even when immersed in boiling water can be easily obtained. As a preferred embodiment of the above production method, re-melting of the polyester resin layer is performed in an inert gas atmosphere.
【００１１】[0011]
【発明の実施の形態】以下、本発明の樹脂被覆金属板及
びその製造方法の実施の形態を説明する。本発明で使用
される金属板としては、鉄、鋼、ブリキ、ティンフリー
スチール、黄銅、銅、アルミニウム、アルミニウム合金
などが挙げられる。これらは表面処理が施されていても
よい。表面処理としては、電気化学的処理、無機化学的
処理、有機化学的処理などがあり、クロメート処理、リ
ン酸クロメート処理、ジンククロメート処理、アルマイ
ト処理などが含まれる。金属板の厚さは特に限定されな
いが、通常０．０５〜３０ｍｍである。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the resin-coated metal plate of the present invention and a method for manufacturing the same will be described. Examples of the metal plate used in the present invention include iron, steel, tinplate, tin-free steel, brass, copper, aluminum, and aluminum alloy. These may be subjected to a surface treatment. The surface treatment includes an electrochemical treatment, an inorganic chemical treatment, an organic chemical treatment, and the like, and includes a chromate treatment, a phosphoric acid chromate treatment, a zinc chromate treatment, an alumite treatment, and the like. The thickness of the metal plate is not particularly limited, but is usually 0.05 to 30 mm.
【００１２】本発明の金属板の少なくとも片面とは、製
缶後の缶内面側または缶外面側または内外両面いずれで
あってもかまわない。At least one surface of the metal plate of the present invention may be either the inner surface of the can, the outer surface of the can, or both the inner and outer surfaces after the can is made.
【００１３】本発明の被覆層を構成するポリエステル樹
脂は、ポリエチレンテレフタレート単位をポリエステル
樹脂全体に対して少なくとも９０モル％以上含むことを
必須とする。ポリエチレンテレフタレート単位が９０モ
ル％未満の場合は、沸騰水や熱水に浸けたり、レトルト
処理を行うと樹脂層が白化してしまう。好ましいポリエ
チレンテレフタレート含有率は、ポリエステル樹脂全体
に対して９２〜９７モル％である。The polyester resin constituting the coating layer of the present invention must contain at least 90 mol% of polyethylene terephthalate units based on the entire polyester resin. If the polyethylene terephthalate unit is less than 90 mol%, the resin layer will be whitened if immersed in boiling water or hot water or subjected to retort treatment. The preferred polyethylene terephthalate content is 92 to 97 mol% based on the entire polyester resin.
【００１４】ポリエステル樹脂層と金属板との密着性を
よくするために、ポリエステル樹脂は、樹脂全体に対し
て３モル％以上の共重合成分を含有することが好まし
い。上限は１０モル％が好ましく、特に４〜９モル％の
範囲が好ましい。共重合成分としてはジカルボン酸成
分、ジオール成分、オキシカルボン酸成分、トリカルボ
ン酸成分、トリオール成分などが挙げられ、これらが本
発明の目的を達する範囲で共重合されていてもかまわな
い。In order to improve the adhesion between the polyester resin layer and the metal plate, the polyester resin preferably contains 3 mol% or more of a copolymer component based on the whole resin. The upper limit is preferably 10 mol%, and particularly preferably in the range of 4 to 9 mol%. Examples of the copolymerization component include a dicarboxylic acid component, a diol component, an oxycarboxylic acid component, a tricarboxylic acid component, and a triol component, and these may be copolymerized as long as the object of the present invention is achieved.
【００１５】ジカルボン酸成分としては、シュウ酸、コ
ハク酸、アジピン酸、セバシン酸、マレイン酸、ダイマ
−酸、インダンジカルボン酸、イソフタル酸、ジフェニ
ルジカルボン酸、スルホイソフタル酸金属塩など、ジオ
ール成分としては、プロパンジオール、ブタンジオー
ル、ペンタンジオール、ネオペンチルグリコール、ヘキ
サンジオール、シクロヘキサンジメタノール、ビスフェ
ノールＡのエチレンオキサイド付加物、ビスフェノール
Ｓのエチレンオキサイド付加物、ポリエチレングリコー
ル、ポリテトラメチレングリコールなど、オキシカルボ
ン酸成分としてはオキシ安息香酸など、トリカルボン酸
成分としてはトリメリット酸、トリオール成分としては
トリメチロールプロパンなどが挙げられる。これらの成
分のポリエチレンテレフタレートへの共重合は、重合初
期、重合途中、重合後の押出機中など、どの段階で行っ
てももよい。共重合されたポリエステル樹脂は、本発明
の非晶質無配向の樹脂層を作るのに好適である。Examples of the dicarboxylic acid component include oxalic acid, succinic acid, adipic acid, sebacic acid, maleic acid, dimer acid, indandicarboxylic acid, isophthalic acid, diphenyldicarboxylic acid, and metal salts of sulfoisophthalic acid. Oxycarboxylic acid components such as, propanediol, butanediol, pentanediol, neopentyl glycol, hexanediol, cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol S, polyethylene glycol and polytetramethylene glycol As the tricarboxylic acid component, trimellitic acid can be used, and as the triol component, trimethylolpropane can be used. The copolymerization of these components with polyethylene terephthalate may be performed at any stage, such as at the beginning of polymerization, during polymerization, or in an extruder after polymerization. The copolymerized polyester resin is suitable for forming the amorphous non-oriented resin layer of the present invention.
【００１６】本発明で使用されるポリエステル樹脂の分
子量に関しては、金属板に積層された製品状態でのポリ
エステル樹脂の還元粘度が０．８０〜１．１ｄｌ／ｇで
ある必要がある。還元粘度が０．８０ｄｌ／ｇ未満の場
合は、沸騰水や熱水に浸けると樹脂層が白化してしま
い、外観が悪くなるとともに耐衝撃性も悪くなる。更に
還元粘度が０．５０ｄｌ／ｇ未満の場合は、耐屈曲性も
悪くなり成形加工を行う時に亀裂が発生しやすくなる。
また、還元粘度が１．１ｄｌ／ｇを越える場合は、重合
工程や押出し工程において経済的でない。還元粘度は、
フェノール／テトラクロルエタンの重量比６／４の混合
溶媒を用い、溶液濃度が０．４ｇ／ｄｌ、温度３０℃で
測定した値である。With respect to the molecular weight of the polyester resin used in the present invention, the reduced viscosity of the polyester resin in the state of a product laminated on a metal plate needs to be 0.80 to 1.1 dl / g. When the reduced viscosity is less than 0.80 dl / g, the resin layer is whitened when immersed in boiling water or hot water, resulting in poor appearance and poor impact resistance. Further, when the reduced viscosity is less than 0.50 dl / g, the bending resistance is deteriorated, and cracks are likely to occur during the forming process.
On the other hand, when the reduced viscosity exceeds 1.1 dl / g, it is not economical in the polymerization step and the extrusion step. The reduced viscosity is
Using a mixed solvent of phenol / tetrachloroethane in a weight ratio of 6/4, the value was measured at a solution concentration of 0.4 g / dl and a temperature of 30 ° C.
【００１７】金属板に積層された製品状態のポリエステ
ル樹脂の還元粘度を０．８０〜１．１ｄｌ／ｇに調整す
るためには、溶融押出しする前の原料ポリエステル樹脂
の還元粘度を０．８０ｄｌ／ｇ以上にする必要がある。
好ましくは０．９０ｄｌ／ｇ以上に調整する。上限は特
に制限はないが１．３ｄｌ／ｇ程度が好ましい。また後
述するように、ポリエステル樹脂層は押出ラミネートさ
れた後、再溶融されるので、熱安定性が改良されたポリ
エステル樹脂を原料として使用するのが好ましい。In order to adjust the reduced viscosity of the polyester resin in the product state laminated on the metal plate to 0.80 to 1.1 dl / g, the reduced viscosity of the raw polyester resin before melt extrusion is 0.80 dl / g. g or more.
Preferably, it is adjusted to 0.90 dl / g or more. The upper limit is not particularly limited, but is preferably about 1.3 dl / g. As will be described later, since the polyester resin layer is re-melted after extrusion lamination, it is preferable to use a polyester resin having improved thermal stability as a raw material.
【００１８】金属板に積層されたポリエステル樹脂は、
成形加工前の製品状態で結晶化度が６０％以下であるこ
とが必要である。ポリエステル樹脂の結晶化度は、ポリ
エステル樹脂の冷結晶化の発熱量および融解の吸熱量
を、示差走査型熱量計（ＤＳＣ）を用いて後述する方法
で測定し、次式で計算した値である。ただしこの値は相
対的な結晶化度の大小を表すもので、絶対量の割合を示
すものではない。The polyester resin laminated on the metal plate is
It is necessary that the degree of crystallinity be 60% or less in a product state before molding. The crystallinity of the polyester resin is a value obtained by measuring a calorific value of cold crystallization and an endothermic amount of melting of the polyester resin by a method described later using a differential scanning calorimeter (DSC) and calculating by the following equation. . However, this value indicates the relative degree of crystallinity, and does not indicate the ratio of the absolute amount.
【００１９】[0019]
【数１】 (Equation 1)
【００２０】ポリエステル樹脂層の上記結晶化度が６０
％より大きい場合、金属板を成形加工した時に樹脂層に
剥離やクラックができ問題である。好ましい結晶化度の
範囲は１０〜３０％である。The above crystallinity of the polyester resin layer is 60
%, There is a problem that the resin layer may peel or crack when the metal plate is formed. A preferred range of crystallinity is 10 to 30%.
【００２１】本発明のポリエステル樹脂には、公知の添
加剤を必要に応じて含有させることができる。例えば、
滑剤、ブロッキング防止剤、熱安定剤、酸化防止剤、帯
電防止剤、耐光剤、耐衝撃性改良剤などを含有させても
よい。また、酸化チタンなどの白色顔料、アントラキノ
ン系化合物、フタロシアニン系化合物、カーボンブラッ
クなどの着色剤を含有させて樹脂層を着色し、意匠性を
高めることもできる。The polyester resin of the present invention may contain known additives as necessary. For example,
A lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, an antistatic agent, a lightfast agent, an impact resistance improver, and the like may be contained. Further, the resin layer may be colored by adding a colorant such as a white pigment such as titanium oxide, an anthraquinone-based compound, a phthalocyanine-based compound, or carbon black to enhance the design.
【００２２】本発明の樹脂被覆金属板の好ましい製造方
法として、以下の方法が挙げられる。まずポリエステル
樹脂を金属板へ積層する方法としては、押出しラミネー
ト方式で直接金属板に樹脂を融着する方法が適用され
る。ポリエステル樹脂の還元粘度の低下を抑制するため
に、なるべく低い温度と短い時間で溶融し、また真空ベ
ント式の押出機で溶融押出しを行い、再溶融前の樹脂の
還元粘度を維持するのが好ましい。A preferred method for producing the resin-coated metal sheet of the present invention is as follows. First, as a method of laminating a polyester resin on a metal plate, a method of directly fusing the resin to the metal plate by an extrusion lamination method is applied. In order to suppress the reduction of the reduced viscosity of the polyester resin, it is preferable to melt at a temperature as low as possible and for a short time, and also perform melt extrusion with a vacuum vent type extruder to maintain the reduced viscosity of the resin before re-melting. .
【００２３】次いで、該ポリエステル樹脂層を再溶融し
て樹脂の配向をなくす。樹脂層を完全に再溶融するため
の加熱方法としては、熱風加熱、ロール加熱、通電加
熱、誘電加熱、高周波加熱などがある。例えば、熱風加
熱の場合、通常、樹脂の融点〜融点＋４０℃の熱風で、
３０〜１２０秒間加熱される。再溶融はポリエステル樹
脂の還元粘度の低下を抑制する必要があり、そのために
は、なるべく低い温度と短い時間で溶融し、再溶融時の
加熱雰囲気は、酸素や水分、特に酸素をなるだけ少なく
するのが好ましく、該雰囲気を窒素などの不活性ガスで
置換して酸化分解や加水分解を防ぐことが特に望まし
い。また再溶融させる直前のポリエステル樹脂層は熱風
などで乾燥させておくことが好ましい。Next, the polyester resin layer is melted again to eliminate the orientation of the resin. As a heating method for completely remelting the resin layer, there are hot air heating, roll heating, electric heating, dielectric heating, high frequency heating, and the like. For example, in the case of hot-air heating, usually, hot air of the melting point of the resin to the melting point + 40 ° C,
Heat for 30-120 seconds. It is necessary to suppress the reduction of the reduced viscosity of the polyester resin for remelting, and for that purpose, it is melted at a temperature as low as possible and for a short time, and the heating atmosphere at the time of remelting is to reduce oxygen and moisture, particularly oxygen as much as possible. It is particularly preferable to replace the atmosphere with an inert gas such as nitrogen to prevent oxidative decomposition and hydrolysis. It is preferable that the polyester resin layer immediately before remelting is dried with hot air or the like.
【００２４】再溶融された樹脂層は、次いで急冷固化す
るのが好ましい。その方法としては、水中浸せき、冷風
吹き付けなどが挙げられる。ここで急冷とは、溶融樹脂
が固化する際に結晶が生成するのを抑制するのに充分な
冷却速度をもつ冷却操作であり、通常１０℃／秒以上、
好ましくは５０℃／秒以上の冷却速度で樹脂のガラス転
移温度以下まで冷却する。The remelted resin layer is preferably quenched and solidified. Examples of the method include immersion in water and spraying with cold air. Here, quenching is a cooling operation having a cooling rate sufficient to suppress the generation of crystals when the molten resin is solidified.
Preferably, the resin is cooled to a temperature not higher than the glass transition temperature of the resin at a cooling rate of 50 ° C./second or more.
【００２５】樹脂の再溶融、次いで急冷固化することに
よって、ポリエステル樹脂が非晶質となり、さらに金属
板と樹脂層との密着力を高められる。By re-melting the resin and then rapidly solidifying it, the polyester resin becomes amorphous, and the adhesion between the metal plate and the resin layer can be enhanced.
【００２６】本発明のポリエステル樹脂層は、製造工程
において共押出法やコーティング法によって複層化され
ていてもよいが、主ポリエステル樹脂層は本特許の範囲
内のポリエステルである。本特許の積層されたポリエス
テル樹脂層の厚さは、５〜５０μｍ、特に８〜２０μｍ
が好ましい。The polyester resin layer of the present invention may be multi-layered by a co-extrusion method or a coating method in the production process, but the main polyester resin layer is a polyester within the scope of the present patent. The thickness of the laminated polyester resin layer of the present patent is 5 to 50 μm, particularly 8 to 20 μm.
Is preferred.
【００２７】ポリエステル樹脂層の表面は、用途によっ
ては接着性や濡れ性を良くするためにコロナ処理やコー
ティング処理や火炎処理を施してもよい。The surface of the polyester resin layer may be subjected to a corona treatment, a coating treatment or a flame treatment in order to improve the adhesiveness and wettability depending on the use.
【００２８】本発明の樹脂被覆金属板は、絞り加工、絞
り再絞り加工、絞り引っ張り曲げ伸ばし加工、絞りしご
き加工、曲げ加工などの加工方法で成形されて飲料缶な
ど容器やそれらの蓋や瓶のキャップ、カラー金属板とし
て電気製品の外装材料や建築用材料に使用される。特
に、飲料缶や飲料瓶のキャップに使用した際、温水や沸
騰水と接触したり、レトルト処理されたりしても白化し
て外観や耐衝撃性が悪くなることがないので好適であ
る。The resin-coated metal sheet of the present invention is formed by a processing method such as drawing, drawing re-drawing, drawing / bending / stretching, drawing / ironing, bending, and the like. It is used as a cap and a color metal plate for exterior materials and building materials of electrical products. In particular, when used for a cap of a beverage can or a beverage bottle, it is preferable because it does not whiten and deteriorate appearance and impact resistance even when it comes into contact with hot water or boiling water or is subjected to retort treatment.
【００２９】[0029]
【実施例】以下、本発明を実施例によってさらに詳細に
説明するが、本発明はその要旨を逸脱しない限り以下の
実施例に限定されるものではない。なお、以下の実施
例、比較例における物性の評価方法は以下の通りであ
る。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples without departing from the gist thereof. The methods for evaluating physical properties in the following examples and comparative examples are as follows.
【００３０】（評価方法） （１）還元粘度 還元粘度は、ウベローデ型粘度管でフェノール／テトラ
クロルエタンの重量比６／４の混合溶媒に、樹脂被覆金
属板から剥がしたポリエステル樹脂を溶液濃度０．４ｇ
／ｄｌで溶解し、温度３０℃で測定した。 （２）結晶化度 樹脂被覆金属板から剥がしたポリエステル樹脂に関し、
理学電機社製外熱型示差走査型熱量計（ＤＳＣ）を用い
て、７０℃から２００℃に現れる発熱ピークから冷結晶
化の発熱量を求め、１５０℃から２８０℃に現れる吸熱
ピークから融解の吸熱量を求め、下式で結晶化度を計算
した。サンプルは１０ｍｇ、昇温速度は２０℃／分であ
った。(Evaluation Method) (1) Reduced Viscosity The reduced viscosity was determined by using a Ubbelohde type viscosity tube in a mixed solvent of phenol / tetrachloroethane at a weight ratio of 6/4, and removing the polyester resin peeled from the resin-coated metal plate with a solution concentration of 0%. 0.4g
/ Dl and measured at a temperature of 30 ° C. (2) Crystallinity Regarding the polyester resin peeled from the resin-coated metal plate,
Using an external heat type differential scanning calorimeter (DSC) manufactured by Rigaku Denki, the calorific value of cold crystallization was determined from the exothermic peak appearing at 70 ° C to 200 ° C, and the melting endothermic peak was found at 150 ° C to 280 ° C. The amount of endotherm was determined, and the crystallinity was calculated by the following equation. The sample was 10 mg, and the heating rate was 20 ° C./min.
【００３１】[0031]
【数２】 (Equation 2)
【００３２】（３）絞り加工性 ａ）絞り缶（ＤＩ缶）の作製 樹脂被覆アルミニウム板を絞り比２．５で絞り加工して
直径３０ｍｍの絞り缶を作製した。 ｂ）絞り缶の外観 作製した絞り缶の外側側面を目視で観察し、樹脂層の剥
離や亀裂の有無を確認した。 良好：剥離や亀裂なし 不良：剥離や亀裂あり ｃ）絞り缶のＥＲＶ 作製したＤＩ缶に２５ｍｌの１重量％食塩水を満たし、
Ｇｏｏｄｗｉｌｌ Ｉｎｓｔｒｕｍｅｎｔ社製、型式Ｇ
ＰＳ−１８３０エナメルレータ−でＥＲＶ（エナメルレ
イティング値）を測定した。測定条件は、電圧が直流６
ボルト、缶底外側に金属露出部を作りそこを陽極に接続
した。通電開始３０秒後の電流値を測定した。電流がた
くさん流れるほど絶縁体であるフィルムに欠陥が存在
し、絞り缶内面の金属が露出していることを示してい
る。製缶直後のＥＲＶ値はｌｍＡ以下であることが望ま
しい。 （４）耐沸騰水性 絞り缶を沸騰水に２時間浸けた後、缶の樹脂層が白化し
ているか否かを目視で観測した。(3) Drawability a) Preparation of drawn can (DI can) A resin-coated aluminum plate was drawn at a drawing ratio of 2.5 to prepare a drawn can having a diameter of 30 mm. b) Appearance of the drawn can The outer side surface of the manufactured drawn can was visually observed to confirm the presence or absence of peeling or cracking of the resin layer. Good: No peeling or cracking Bad: Peeling or cracking c) ERV of drawn can Fill the prepared DI can with 25 ml of 1% by weight saline solution,
Goodwill Instrument, Model G
The ERV (enamel rating value) was measured with a PS-1830 enameler. The measurement conditions are as follows:
An exposed metal part was formed on the outside of the bolt and the bottom of the can, and this was connected to the anode. The current value was measured 30 seconds after the start of energization. The more current flows, the more defects are present in the insulator film, indicating that the metal on the inner surface of the draw can is exposed. It is desirable that the ERV value immediately after can production is 1 mA or less. (4) Boiling Water Resistance After the squeezing can was immersed in boiling water for 2 hours, it was visually observed whether or not the resin layer of the can was whitened.
【００３３】実施例１〜５および比較例１〜３ （ポリエステル樹脂の作製）直重法によって表１に示し
た共重合成分を表１に示したモル比で共重合した還元粘
度０．６８〜０．７０のポリエステルのチップを溶融重
縮合によって得た。次いで回転式真空熱処理機を用いて
還元粘度０．９０〜１．０５になるように固相重合を行
った。全てのポリエステルには平均粒径が１．８μｍの
シリカゲル微粉末をフィルム中に１重量％含有するよう
に添加し、分散させた。Examples 1 to 5 and Comparative Examples 1 to 3 (Preparation of polyester resin) Copolymerized components shown in Table 1 were copolymerized at a molar ratio shown in Table 1 with a reduced viscosity of 0.68 to Polyester chips of 0.70 were obtained by melt polycondensation. Next, solid-state polymerization was performed using a rotary vacuum heat treatment machine so that the reduced viscosity became 0.90 to 1.05. To all the polyesters, a silica gel fine powder having an average particle size of 1.8 μm was added and dispersed so as to contain 1% by weight in the film.
【００３４】（押出しラミネート金属板の作製）ダイス
幅４００ｍｍの押出しラミネート機に、厚み０．３ｍｍ
のリン酸クロメート処理されたアルミニウム板のロール
をセットし、作製したポリエステル樹脂のチップを真空
乾燥し、水分率０．０１重量％以下にした後、真空ベン
ト式の２軸押出機を使用して、Ｔダイより押出機で２７
０℃で溶融押出しで連続的にアルミニウム板に押出しラ
ミネートし、樹脂の被覆層厚みが約１５μｍになるよう
に引き取った。押出しラミネートされる直前のアルミニ
ウム板は、加熱金属ロールで２００℃に予備加熱し、樹
脂がラミネートされた後は２０℃の冷却用金属ロールと
シリコンゴムロールの間でプレスした。樹脂がラミネー
トされたアルミニウム板を窒素置換した熱風オープン中
で２００〜２７０℃で６０〜１２０秒間加熱し、樹脂を
完全に再溶融させた後、熱風オーブンより取り出し、５
秒以内に５℃の冷風を吹き付け、急冷固化した。(Preparation of Extruded Laminated Metal Sheet) A 0.3 mm thick extruded laminating machine having a die width of 400 mm was used.
A roll of an aluminum plate treated with phosphoric acid chromate is set, and the produced polyester resin chips are vacuum-dried to a moisture content of 0.01% by weight or less, and then, using a vacuum vent type twin screw extruder. , Extruder from T die 27
It was continuously extruded and laminated on an aluminum plate by melt extrusion at 0 ° C., and was taken out so that the thickness of the resin coating layer became about 15 μm. The aluminum plate immediately before extrusion lamination was preheated to 200 ° C. with a heated metal roll, and after the resin was laminated, pressed between a cooling metal roll at 20 ° C. and a silicon rubber roll. The resin-laminated aluminum plate was heated at 200 to 270 ° C. for 60 to 120 seconds in a hot air open with a nitrogen purge to completely re-melt the resin, and then removed from the hot air oven.
Within 5 seconds, cold air of 5 ° C. was blown to rapidly cool and solidify.
【００３５】比較例４および５ 実施例２および３においてアルミニウム板にラミネート
した樹脂層を再溶融させる際、窒素置換した熱風オーブ
ン中の代わりに窒素置換しないオーブン中で再溶融させ
た以外は実施例１と同様にして樹脂被覆アルミニウム板
を作製した。Comparative Examples 4 and 5 In Examples 2 and 3, except that the resin layer laminated on the aluminum plate was remelted in an oven without nitrogen replacement instead of a hot air oven with nitrogen replacement. In the same manner as in Example 1, a resin-coated aluminum plate was produced.
【００３６】比較例６ 実施例１においてアルミニウム板にラミネートした樹脂
層を再溶融させずに、そのまま評価した。Comparative Example 6 The resin layer laminated on the aluminum plate in Example 1 was evaluated without re-melting.
【００３７】比較例７ 実施例１においてアルミニウム板にラミネートした樹脂
層を再溶融させた後、冷風で冷却せずに放冷した以外は
実施例１と同様にして樹脂被覆アルミニウム板を作製し
た。Comparative Example 7 A resin-coated aluminum plate was produced in the same manner as in Example 1 except that the resin layer laminated on the aluminum plate in Example 1 was re-melted and then allowed to cool without cooling with cool air.
【００３８】アルミニウム板に被覆された樹脂の特性と
樹脂被覆アルミニウム板とそれを絞り加工した成形体の
評価結果を表１に示した。Table 1 shows the characteristics of the resin coated on the aluminum plate and the results of evaluation of the resin-coated aluminum plate and the molded product obtained by drawing the same.
【００３９】[0039]
【表１】 [Table 1]
【００４０】表１に示したとおり、本発明のフィルム被
覆金属板を絞り加工した缶は、外観が良好で欠陥も少な
く、かつ沸騰水に浸けてもアルミニウム板に被覆した樹
脂層が白化しなかった。一方、本発明の範囲外である共
重合比および還元粘度の樹脂が被覆された比較例１〜５
では、沸騰水に浸けたら、アルミニウム板に被覆した樹
脂層が白化して外観が悪くなった。比較例６および７で
はアルミニウム板に被覆したポリエステル樹脂の結晶化
度が本発明の範囲より大きかったため、絞り加工した缶
の外観が悪く、樹脂層に亀裂や剥離が観察された。ＥＲ
Ｖ値も高かった。As shown in Table 1, the cans obtained by drawing the film-coated metal plate of the present invention have good appearance and few defects, and the resin layer coated on the aluminum plate does not whiten even when immersed in boiling water. Was. On the other hand, Comparative Examples 1 to 5 coated with a resin having a copolymerization ratio and a reduced viscosity outside the range of the present invention.
Then, when immersed in boiling water, the resin layer coated on the aluminum plate was whitened and the appearance was poor. In Comparative Examples 6 and 7, since the crystallinity of the polyester resin coated on the aluminum plate was larger than the range of the present invention, the appearance of the drawn can was poor, and cracks and peeling were observed in the resin layer. ER
The V value was also high.
【００４１】[0041]
【発明の効果】本発明の樹脂被覆金属板のポリエステル
樹脂層は、絞り加工、絞りしごき加工を施しても欠陥が
ほとんどなく、かつ結晶化度が６０％以下であるにもか
かわらず、沸騰水に浸けてもほとんど白化しない。した
がって、特に熱水処理やレトルト処理などが必要な缶な
どに好適に使用される。The polyester resin layer of the resin-coated metal plate of the present invention has almost no defects even when subjected to drawing and drawing and ironing, and has a crystallinity of not more than 60%. Almost no whitening when immersed in Therefore, it is particularly suitably used for cans requiring hot water treatment, retort treatment, and the like.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 鈴木 慎司 滋賀県大津市堅田二丁目１番１号 東洋紡 績株式会社総合研究所内 (72)発明者 小長谷 重次 滋賀県大津市堅田二丁目１番１号 東洋紡 績株式会社総合研究所内 (72)発明者 前園 俊一郎 栃木県真岡市鬼怒ケ丘15番地 株式会社神 戸製鋼所真岡製造所内 (72)発明者 畑中 孝一 栃木県真岡市鬼怒ケ丘15番地 株式会社神 戸製鋼所真岡製造所内 (72)発明者 福井 正信 栃木県真岡市鬼怒ケ丘15番地 株式会社神 戸製鋼所真岡製造所内 (72)発明者 服部 伸郎 栃木県真岡市鬼怒ケ丘15番地 株式会社神 戸製鋼所真岡製造所内 Ｆターム(参考） 3E061 AA15 AB04 AC01 AD01 BA01 DA02 3E086 BA13 BA15 BB90 CA11 4F100 AB01A AK41B AK41C AK42B AK42C BA02 BA03 BA06 BA10B BA10C BA14 EH172 GB15 JA06B JA06C JL06 JL09 YY00B YY00C 4J029 AA03 AB07 AC02 AD01 AD08 AE03 BA02 BA03 BA04 BA05 BA10 BD03A BF25 BF26 CA01 CA02 CA04 CA06 CB05A CB06A CB10A CH02 CH06 CH07 DB02 EB04A FC05 FC36 GA13 GA22 HA01 HB01 JE182 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shinji Suzuki 2-1-1 Katata, Otsu-shi, Shiga Prefecture Inside Toyobo Co., Ltd. (72) Inventor Shigetsugu Konagaya 2-1-1 Katata, Otsu-shi, Shiga Prefecture No.Toyobo Ajinomoto Co., Ltd. (72) Inventor Shunichiro Maezono 15 Kinugaoka, Moka City, Tochigi Prefecture Kobe Steel Moka Works, Ltd. Inside the Kobe Steel Moka Works (72) Inventor Masanobu Fukui 15 Kinugaoka, Moka City, Tochigi Prefecture Inside the Kobe Steel Moka Works (72) Inventor Nobuo Hattori 15 Kinugaoka, Moka City, Tochigi Stock Kobe Steel Moka Works F-term (reference) 3E061 AA15 AB04 AC01 AD01 BA01 DA02 3E086 BA13 BA15 BB90 CA11 4F100 AB01A AK41B AK41C A K42B AK42C BA02 BA03 BA06 BA10B BA10C BA14 EH172 GB15 JA06B JA06C JL06 JL09 YY00B YY00C 4J029 AA03 AB07 AC02 AD01 AD08 AE03 BA02 BA03 BA04 BA05 BA10 BD03A BF25 BF26 CA01 CA02 CA04 CA02 CH06 FC02 FC06
Claims (3)
ネートによって積層された、エチレンテレフタレート単
位を少なくとも９０モル％含み、還元粘度が０．８０〜
１．１ｄｌ／ｇで、結晶化度が６０％以下のポリエステ
ル樹脂層を有する樹脂被覆金属板。1. A metal sheet, comprising at least 90 mol% of ethylene terephthalate units laminated by extrusion lamination on at least one side of a metal plate, having a reduced viscosity of 0.80 to 0.80.
A resin-coated metal plate having a polyester resin layer having a crystallinity of not more than 60% at 1.1 dl / g.
フタレート単位を少なくとも９０モル％含むポリエステ
ル樹脂を押出しラミネート法で積層した後、該ポリエス
テル樹脂層を再溶融し、次いで急冷固化することを含
む、還元粘度が０．８０〜１．１ｄｌ／ｇで、結晶化度
が６０％以下のポリエステル樹脂層を有する樹脂被覆金
属板の製造方法。2. A reduced viscosity method comprising extruding and laminating a polyester resin containing at least 90 mol% of ethylene terephthalate units on at least one surface of a metal plate by an extrusion laminating method, re-melting the polyester resin layer, and then rapidly cooling and solidifying. A method for producing a resin-coated metal sheet having a polyester resin layer having a ratio of 0.80 to 1.1 dl / g and a crystallinity of 60% or less.
ス雰囲気中で行う請求項２記載の樹脂被覆金属板の製造
方法。3. The method according to claim 2, wherein the remelting of the polyester resin layer is performed in an inert gas atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21900998A JP4144074B2 (en) | 1998-08-03 | 1998-08-03 | Resin-coated metal plate and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21900998A JP4144074B2 (en) | 1998-08-03 | 1998-08-03 | Resin-coated metal plate and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000043191A true JP2000043191A (en) | 2000-02-15 |
| JP4144074B2 JP4144074B2 (en) | 2008-09-03 |
Family
ID=16728839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21900998A Expired - Fee Related JP4144074B2 (en) | 1998-08-03 | 1998-08-03 | Resin-coated metal plate and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP4144074B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001233334A (en) * | 2000-02-18 | 2001-08-28 | Toyo Seikan Kaisha Ltd | Welded can drum and manufacturing method therefor |
| JP2002193256A (en) * | 2000-12-26 | 2002-07-10 | Daiwa Can Co Ltd | Double-sided film laminated can cover and its manufacturing method |
| JP2010012624A (en) * | 2008-07-01 | 2010-01-21 | Toyo Kohan Co Ltd | Method for manufacturing resin coated metal plate |
| JP2021154574A (en) * | 2020-03-26 | 2021-10-07 | マツダ株式会社 | Joint structure and joint method of metal member and resin member |
-
1998
- 1998-08-03 JP JP21900998A patent/JP4144074B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001233334A (en) * | 2000-02-18 | 2001-08-28 | Toyo Seikan Kaisha Ltd | Welded can drum and manufacturing method therefor |
| JP2002193256A (en) * | 2000-12-26 | 2002-07-10 | Daiwa Can Co Ltd | Double-sided film laminated can cover and its manufacturing method |
| JP4667595B2 (en) * | 2000-12-26 | 2011-04-13 | 大和製罐株式会社 | Double-sided film laminate can lid and method for producing the same |
| JP2010012624A (en) * | 2008-07-01 | 2010-01-21 | Toyo Kohan Co Ltd | Method for manufacturing resin coated metal plate |
| JP2021154574A (en) * | 2020-03-26 | 2021-10-07 | マツダ株式会社 | Joint structure and joint method of metal member and resin member |
| JP7376044B2 (en) | 2020-03-26 | 2023-11-08 | マツダ株式会社 | Bonding structure and bonding method between metal and resin components |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4144074B2 (en) | 2008-09-03 |
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