JP2005097712A - Surface-treated metallic material, method of surface treating therefor and resin-coated metallic material, metal can and can lid - Google Patents
Surface-treated metallic material, method of surface treating therefor and resin-coated metallic material, metal can and can lid Download PDFInfo
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- JP2005097712A JP2005097712A JP2003394779A JP2003394779A JP2005097712A JP 2005097712 A JP2005097712 A JP 2005097712A JP 2003394779 A JP2003394779 A JP 2003394779A JP 2003394779 A JP2003394779 A JP 2003394779A JP 2005097712 A JP2005097712 A JP 2005097712A
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- metal material
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- film
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Images
Landscapes
- Containers Having Bodies Formed In One Piece (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、表面処理金属材料及びその表面処理方法に関し、より詳細には、ノンクロムで環境性に優れていると共に、有機樹脂被膜との密着性、接着性、耐食性、耐デント性、耐磨耗性等に優れた表面処理金属材料、及びこのような表面処理金属材料の表面処理方法、また、かかる表面処理金属材料に樹脂被覆して成る樹脂被覆金属材料及びこれから成る金属缶及び缶蓋に関する。 The present invention relates to a surface-treated metal material and a surface treatment method thereof, and more specifically, it is non-chromium and has excellent environmental properties, and also has adhesion, adhesion, corrosion resistance, dent resistance, and wear resistance with an organic resin film. The present invention relates to a surface-treated metal material excellent in properties and the like, a surface treatment method for such a surface-treated metal material, a resin-coated metal material obtained by resin-coating such a surface-treated metal material, and a metal can and a can lid comprising the same.
鋼板、亜鉛系めっき鋼板、アルミニウム系めっき鋼板、亜鉛合金板、錫系めっき鋼板、アルミニウム箔、アルミニウム合金板、マグネシウム合金板等の金属材料と有機膜との密着性を向上させる処理として、また、接着剤を用いて金属材料を同種又は異種の金属材料と接合するための処理として、クロメート処理、リン酸塩処理、シランカップリング剤による処理、陽極酸化処理などが従来から知られている。
これらの処理を利用した金属材料は、家電製品や建材、車両、航空機、容器などの用途に広く利用されており、中でも、クロメート処理はその優れた耐食性と密着性から最も広く利用されてきた。
クロメート処理を処理方法から大別すると、化成型（反応型・塗布型）と電解型に分類でき、形成皮膜から大別すると、自己修復効果をより大きく利用するために最終製品中に微量の６価クロムが残存するタイプと最終製品中に６価クロムが残存しないタイプに分類できる。
As a treatment for improving the adhesion between a metal material such as a steel plate, a zinc-based plated steel plate, an aluminum-based plated steel plate, a zinc alloy plate, a tin-based plated steel plate, an aluminum foil, an aluminum alloy plate, and a magnesium alloy plate, and an organic film, As treatments for joining a metal material to the same or different metal materials using an adhesive, a chromate treatment, a phosphate treatment, a treatment with a silane coupling agent, an anodizing treatment, and the like are conventionally known.
Metal materials using these treatments are widely used for home appliances, building materials, vehicles, aircraft, containers, and the like, and among them, chromate treatment has been most widely used due to its excellent corrosion resistance and adhesion.
Chromate treatment can be broadly classified into treatment methods, and it can be classified into chemical molding (reaction type / coating type) and electrolytic type. It can be classified into a type in which hexavalent chromium remains and a type in which hexavalent chromium does not remain in the final product.
最終製品中に微量の６価クロムが残存するタイプについては、廃棄時に土壌等の環境に溶出する可能性が指摘されており、ヨーロッパを中心にクロメート処理の使用を撤廃する方向に進んでいる。また、何れのタイプのクロメート処理でも処理液中には有害物質である６価クロムを含んでいることから、環境上の種々の問題を有している。すなわち、６価クロム含有処理液の排水及び排気処理等を完全に行い、外部に排出させないことが必須であり、排水及び排気処理設備、廃棄処理費用等に多額の費用が必要になる。更に排水処理スラッジの移動や排気等についても規制が強くなっていることから、従来のクロメート処理に匹敵するノンクロム系の表面処理の開発が望まれている。 As for the type in which a small amount of hexavalent chromium remains in the final product, it has been pointed out that it may elute into the environment such as soil at the time of disposal, and the use of chromate treatment is proceeding mainly in Europe. In addition, any type of chromate treatment has various environmental problems because the treatment liquid contains hexavalent chromium which is a harmful substance. That is, it is essential to completely drain and exhaust the hexavalent chromium-containing treatment liquid and not to discharge it to the outside, and a large amount of cost is required for drainage and exhaust treatment equipment, disposal costs, and the like. Furthermore, since regulations on the movement and exhaust of wastewater treatment sludge are becoming stronger, it is desired to develop a non-chromium surface treatment comparable to conventional chromate treatment.
金属容器用の金属材料では、当然、最終製品には６価クロムが残存しないタイプのクロメート処理が利用されており、更にその上に有機樹脂等のコーティングが行われている。例えば、錫めっき鋼板を重クロム酸ソーダの水溶液中で陰極電解したり、鋼板をフッ化物含有無水クロム酸水溶液中で陰極電解処理したり、アルミニウム合金をリン酸クロメート処理し、その上に有機樹脂がコーティングされたものが用いられている。 As a matter of course, a metal material for a metal container uses a chromate treatment of a type in which hexavalent chromium does not remain in the final product, and is further coated with an organic resin or the like. For example, cathodic electrolysis of a tin-plated steel plate in an aqueous solution of sodium dichromate, cathodic electrolysis treatment of a steel plate in a fluoride-containing chromic anhydride aqueous solution, or treatment of an aluminum alloy with phosphoric acid chromate and an organic resin thereon The one coated with is used.
ノンクロム系表面処理としては、ジルコニウム、チタン、またはこれらの化合物と、リン酸塩およびフッ化物を含有し、約ｐＨ１．０〜４．０の酸性処理液を用いて、アルミニウム含有金属材料の表面上にジルコニウム及び／又はチタンの酸化物を主成分とする化成皮膜が形成したものが実際に利用されており、有機樹脂との相性によっては化成皮膜自体を無くしたものも実用されている(例えば特許文献１参照)。 As a non-chromium-based surface treatment, zirconium, titanium, or a compound thereof, a phosphate and a fluoride are used, and an acidic treatment solution having a pH of about 1.0 to 4.0 is used to treat the surface of the aluminum-containing metal material. In fact, a film formed with a chemical conversion film mainly composed of an oxide of zirconium and / or titanium is actually used, and depending on the compatibility with the organic resin, a film without the chemical conversion film itself is also in practical use (for example, patents). Reference 1).
近年、金属容器の衛生性や内容品のフレーバー保持性の観点から、ポリエステル樹脂を被覆したプレコート材料が広く利用されている。しかしながら、ポリエステル樹脂を利用した場合、従来広く用いられてきたエポキシフェノール系塗料やアクリルエポキシ系塗料に比較して透水性が高く、このことがプレコートであることと相俟って、クロメート処理を利用しなければ密着性や耐食性の点で内容品に制限を受ける場合があった。また、このようなポリエステル樹脂をアルミニウムに被覆したものをアルミニウム蓋材として用いた場合には、クロメート処理であっても、密着性が十分でないという問題があった。 In recent years, a precoat material coated with a polyester resin has been widely used from the viewpoint of hygiene of metal containers and flavor retention of contents. However, when polyester resin is used, it has higher water permeability compared to epoxy phenolic paints and acrylic epoxy paints that have been widely used in the past. Otherwise, the contents may be restricted in terms of adhesion and corrosion resistance. Further, when such a polyester resin coated with aluminum is used as an aluminum lid member, there is a problem that the adhesion is not sufficient even in the chromate treatment.
すなわち、プレコート材料の加工製品の例である、ポリエステル樹脂を被覆した缶では、プレコート金属材料を出発材料として利用できるという利点があるが、高加工部でのポリエステル樹脂の密着性低下や缶落下などの衝撃によって生じるポリエステル樹脂からのクラック部分からの腐食、またレトルト殺菌時における密着性の低下、更にはポリエステル被膜自体に欠陥がなくても内容品の成分によっては透過イオンによる腐食の誘発等といった、缶成形後に表面処理及び塗料をポストコートしていた従来の製法とは異なる問題点を有している。 In other words, a can coated with a polyester resin, which is an example of a pre-coated material processed product, has the advantage that a pre-coated metal material can be used as a starting material. Corrosion from the crack part from the polyester resin caused by the impact of, and the deterioration of the adhesion at the time of retort sterilization, and even if there is no defect in the polyester coating itself, depending on the components of the contents, induction of corrosion by permeated ions, etc. There is a problem different from the conventional manufacturing method in which the surface treatment and the post-coating of the paint are carried out after the can molding.
一方、缶蓋においては、従来より塗料をコイルコートして成形するプレコート材料を用いていたが、内容品のフレーバー保持性や衛生性の点から、ポリエステル樹脂を被覆したプレコート材料を利用する研究が盛んに行われている。ポリエステル樹脂を被覆したイージーオープン缶蓋では、ポリエステル樹脂との密着性低下によって、スコア開口部近傍において、樹脂と金属とが剥離するデラミネーションやそれによって誘発される開口部の樹脂の伸び、すなわちフェザリングという現象が起こりやすく、特にレトルト殺菌直後の缶蓋では、樹脂との密着性低下により開口不良が発生しやすいという問題点があった。 On the other hand, for can lids, a pre-coating material that has been conventionally formed by coil-coating a paint has been used, but from the viewpoint of flavor retention and hygiene of the contents, research has been conducted on the use of a pre-coating material coated with a polyester resin. It is actively done. In easy open can lids coated with polyester resin, due to a decrease in adhesion to the polyester resin, the delamination of the resin and metal in the vicinity of the score opening and the elongation of the resin in the opening induced by the delamination, that is, the feather A phenomenon called a ring is likely to occur, and particularly in a can lid immediately after retort sterilization, there is a problem in that an opening defect is likely to occur due to a decrease in adhesion to the resin.
このような観点から、カーボンを主成分とする有機化合物とリン化合物とジルコニウムあるいはチタニウム化合物を含む有機−無機複合皮膜を形成する方法(特許文献２)や、アルミニウム基体の表面に無機物を主体とする表面処理層、その上に水性フェノール樹脂を主体とする有機表面処理層を形成する方法が提案されている(特許文献３)。また、主に蓋材としての観点から陽極酸化処理の利用が提案されている(特許文献４及び５)。
またポリアクリル酸−ジルコニウム化合物によるアルミニウム材の処理についても提案されている（特許文献６及び非特許文献１参照）。
一方、ジルコニウム酸化膜を得る方法としては、ＺｒＯ２などをＰＶＤやＣＶＤなどによって、形成したり、湿式法により有機ジルコニウム化合物を塗布後加熱乾燥して酸化膜を得ることも試みられている。
更にまた、ジルコニウムイオンを含む水溶液中で陰極電解することにより、グラファイトやチタン基板上に酸化ジルコニウム粉や膜を形成する研究も行われている（非特許文献２及び３及び４参照）。
From this point of view, a method of forming an organic-inorganic composite film containing an organic compound containing carbon as a main component, a phosphorus compound, and a zirconium or titanium compound (Patent Document 2), or an inorganic substrate as a main component. A method for forming a surface treatment layer and an organic surface treatment layer mainly composed of an aqueous phenol resin on the surface treatment layer has been proposed (Patent Document 3). Also, the use of anodizing treatment has been proposed mainly from the viewpoint of a lid (
In addition, treatment of an aluminum material with a polyacrylic acid-zirconium compound has also been proposed (see Patent Document 6 and Non-Patent Document 1).
On the other hand, as a method for obtaining a zirconium oxide film, attempts have been made to form ZrO 2 or the like by PVD, CVD, or the like, or apply an organic zirconium compound by a wet method and then heat-dry to obtain an oxide film.
Furthermore, studies have been conducted to form zirconium oxide powder and films on graphite and titanium substrates by cathodic electrolysis in an aqueous solution containing zirconium ions (see Non-Patent
しかしながら、カーボンを主成分とする有機化合物とリン化合物とジルコニウムあるいはチタニウム化合物を含む有機−無機複合皮膜を形成する方法では、ある程度密着性は向上するが、耐食性が十分でなく、またアルミニウム基体の表面に無機物を主体とする表面処理層、その上に水性フェノール樹脂を主体とする有機表面処理層を形成する方法では、密着性、耐食性ともにある程度向上するが、工程数が増えるとともに、薬液使用後の廃液処理が煩雑化するという問題があった。
また、陽極酸化処理を利用した方法では、一次密着性は良好であるが、内容物充填後のレトルト殺菌処理により密着性が低下するという傾向にある他、処理設備にもコストがかかる上、処理に大電力を必要とするためコスト高となる問題があった。
更に、アルミニウム箔のような基材自身の厚みが薄い場合には、陽極酸化処理時の基材の溶解や加工性の乏しい陽極酸化膜の占める割合が高くなり、箔の柔軟性を低下させるという問題があった。
However, in the method of forming an organic-inorganic composite film containing an organic compound mainly composed of carbon, a phosphorus compound, and a zirconium or titanium compound, the adhesion is improved to some extent, but the corrosion resistance is not sufficient, and the surface of the aluminum substrate In the method of forming a surface treatment layer mainly composed of an inorganic substance and an organic surface treatment layer mainly composed of a water-based phenol resin on the surface treatment layer, adhesion and corrosion resistance are improved to some extent. There has been a problem that the waste liquid treatment becomes complicated.
In the method using anodizing treatment, the primary adhesion is good, but the retort sterilization treatment after filling the contents tends to reduce the adhesion, and the treatment equipment is also costly and the treatment However, there is a problem that the cost is high because large electric power is required.
Furthermore, when the thickness of the base material itself, such as an aluminum foil, is thin, the proportion of the anodized film having poor processability and dissolution of the base material during anodization increases, and the flexibility of the foil is reduced. There was a problem.
ポリアクリル酸−ジルコニウム化合物によるアルミニウム材の処理では、形成される皮膜は有機−無機複合皮膜であり、処理方法も基本的に塗布型処理であるため、高速処理時の金属材料基体との濡れ性や密着性の点で問題がある。
更に、上記従来技術の多くは、用いる金属材料がアルミニウム合金に限定されるものであり、金属材料全体の課題を解決できるものではない。
一方、金属材料の表面にＺｒＯ２などをＰＶＤやＣＶＤなどによって、形成することも公知であるが、真空を要するために、設備にコストがかかる上、高速処理は困難であり、結果的に更にコスト高となる。また、金属材料基体と処理膜との密着性や加工後の耐食性を確保することが難しい。
同様に、湿式法により有機ジルコニウム化合物を塗布後加熱乾燥して酸化膜を得る方法においても、金属材料基体と処理膜との密着性や加工後の耐食性を確保することが難しい。
更にまた、ジルコニウムイオンを含む水溶液中で陰極電解して酸化粉や酸化膜を形成する手段として、ｐＨ２．３の０．１モル／リットル−オキシ硝酸ジルコニウム水溶液中でグラファイトやチタン基板上に連続的に陰極電解を行う方法が提案されている。この方法によると、アルミ板や亜鉛めっき鋼板あるいはスズめっき鋼板などに用いるにはｐＨが低く基材の溶解が生じやすい、浴濃度が高く局部的な析出が起こりやすい、ゲル状の被膜として電解析出するので、電解後水洗時に被膜が脱落しやすいばかりでなく、処理液に流れがあるとゲル状物が浴中に脱落するため、必然的に浴が攪拌される帯状金属材料の連続高速処理は困難であるなどの問題点があった。また、電解直後に指でこすると析出物のほとんど全部が脱落してしまい、基材との密着性が弱く、特性面においても、高温多湿環境下での表面状態を保持することが難しく、耐食性や密着性などの諸特性に問題があった。
In the treatment of an aluminum material with a polyacrylic acid-zirconium compound, the formed film is an organic-inorganic composite film, and the treatment method is basically also a coating type treatment, so that wettability with a metal material substrate during high-speed treatment is achieved. There is a problem in terms of adhesion.
Furthermore, in many of the above prior arts, the metal material used is limited to an aluminum alloy, and cannot solve the problems of the entire metal material.
On the other hand, it is also well known that ZrO 2 or the like is formed on the surface of a metal material by PVD or CVD. However, since a vacuum is required, equipment is expensive and high-speed processing is difficult. Cost increases. In addition, it is difficult to ensure adhesion between the metal material substrate and the treatment film and corrosion resistance after processing.
Similarly, in a method of obtaining an oxide film by applying an organic zirconium compound by a wet method and then drying by heating, it is difficult to ensure adhesion between the metal material substrate and the treatment film and corrosion resistance after processing.
Furthermore, as means for forming an oxide powder or oxide film by cathodic electrolysis in an aqueous solution containing zirconium ions, it is continuously applied on a graphite or titanium substrate in a 0.1 mol / liter-zirconium oxynitrate aqueous solution at pH 2.3. A method of cathodic electrolysis has been proposed. According to this method, when used for aluminum plate, galvanized steel plate, tin-plated steel plate, etc., the pH is low, the base material is easily dissolved, the bath concentration is high, and local precipitation is likely to occur. Therefore, not only is the film easily removed during washing with water after electrolysis, but the gel-like material falls into the bath when there is a flow in the treatment liquid, so the continuous high-speed treatment of the band-shaped metal material that inevitably stirs the bath There were problems such as being difficult. Also, if you rub your finger immediately after electrolysis, almost all of the precipitates will fall off, and the adhesion to the substrate will be weak, and it will be difficult to maintain the surface state in a high-temperature and high-humidity environment in terms of characteristics, and corrosion resistance There were problems with various properties such as adhesion.
従って本発明の目的は、ノンクロムの表面処理で環境性に優れていると共に、有機樹脂被膜との密着性、接着性、耐食性、耐デント性、耐傷性、耐磨耗性等の諸特性に優れた表面処理金属材料、及びこのような表面処理金属材料の表面処理方法を提供することである。
また本発明の他の目的は、水溶液からの高速処理により製造が容易で低コストの表面処理方法を提供することである。
本発明の更に他の目的は、上記表面処理金属材料に有機樹脂、中でも特にポリエステル樹脂を被覆して成る樹脂被覆金属材料から成る耐食性、耐デント性、耐傷性、耐磨耗性等に優れた金属缶及び開口性に優れた缶蓋を提供することである。
Accordingly, the object of the present invention is excellent in environmental properties due to the non-chromium surface treatment, and also in various properties such as adhesion to an organic resin film, adhesion, corrosion resistance, dent resistance, scratch resistance, and abrasion resistance. Another object of the present invention is to provide a surface-treated metal material and a surface treatment method for such a surface-treated metal material.
Another object of the present invention is to provide a low-cost surface treatment method that is easy to manufacture by high-speed treatment from an aqueous solution.
Still another object of the present invention is excellent in corrosion resistance, dent resistance, scratch resistance, abrasion resistance, and the like made of a resin-coated metal material obtained by coating the surface-treated metal material with an organic resin, particularly a polyester resin. The object is to provide a metal can and a can lid excellent in openability.
本発明によれば、金属材料表面に無機表面処理層が形成されている表面処理金属材料であって、前記無機表面処理層が少なくともＺｒ，Ｏ，Ｆを主成分とすると共に、リン酸イオンを含有しないことを特徴とする表面処理金属材料が提供される。
更に、本発明によれば、金属表面に無機成分を主体とする表面処理層が形成されている表面処理金属材料であって、前記無機表面処理層が少なくともＺｒ，Ｏ，Ｆを主成分とすると共に、前記無機表面処理層の最表面に含有されるＰとＺｒの原子比が、０≦Ｐ／Ｚｒ＜０．６であることを特徴とする表面処理金属材料が提供される。
本発明の表面処理金属材料においては、
１．無機表面処理層の最表面に含有されるＯとＺｒの原子比が、１＜Ｏ／Ｚｒ＜１０であること、
２．無機表面処理層の最表面に含有されるＦとＺｒの原子比が、０．１＜Ｆ／Ｚｒ＜２．５であること、
３．無機表面処理層の膜厚がＺｒの重量膜厚で５〜３００ｍｇ／ｍ2であること、
４．表面の少なくとも一部に１０乃至１００ｎｍのＺｒを含有する微粒子が存在していること、
が好ましい。
According to the present invention, there is provided a surface-treated metal material having an inorganic surface treatment layer formed on the surface of the metal material, wherein the inorganic surface treatment layer contains at least Zr, O, and F as main components and phosphate ions. There is provided a surface-treated metal material characterized by not containing it.
Furthermore, according to the present invention, there is provided a surface-treated metal material in which a surface treatment layer mainly composed of an inorganic component is formed on a metal surface, wherein the inorganic surface treatment layer contains at least Zr, O, and F as main components. In addition, a surface-treated metal material is provided in which the atomic ratio of P and Zr contained in the outermost surface of the inorganic surface treatment layer is 0 ≦ P / Zr <0.6.
In the surface-treated metal material of the present invention,
1. The atomic ratio of O and Zr contained in the outermost surface of the inorganic surface treatment layer is 1 <O / Zr <10;
2. The atomic ratio of F and Zr contained in the outermost surface of the inorganic surface treatment layer is 0.1 <F / Zr <2.5,
3. The film thickness of the inorganic surface treatment layer is 5 to 300 mg / m 2 by weight of Zr,
4). The presence of fine particles containing 10 to 100 nm of Zr on at least part of the surface;
Is preferred.
本発明によればまた、上記表面処理金属材料の少なくとも片面上に有機樹脂、中でも特にポリエステル樹脂が被覆されて成ることを特徴とする樹脂被覆金属材料、及びかかる樹脂被覆金属材料から成る金属缶及び缶蓋が提供される。 According to the present invention, at least one surface of the surface-treated metal material is coated with an organic resin, in particular, a polyester resin, a resin-coated metal material, and a metal can made of the resin-coated metal material and A can lid is provided.
本発明によれば更にまた、ＺｒとＦを含有しリン酸イオン濃度が、ＰＯ４として０．００３モル／リットル未満である水溶液中で陰極電解処理することにより金属板表面に無機皮膜を形成することを特徴とする金属板の表面処理方法が提供される。
上記金属材料の表面処理方法によれば、陰極電解処理を断続的に実施すること、及び水溶液中に、Ｚｒとして０．０１０〜０．０５０モル／リットルの範囲にあるＺｒイオンを含有すること、Ｆとして０．０３〜０．３５モル／リットルの範囲にあるＦイオンを含有することが好ましい。
Furthermore, according to the present invention, an inorganic coating is formed on the surface of the metal plate by cathodic electrolysis in an aqueous solution containing Zr and F and having a phosphate ion concentration of less than 0.003 mol / liter as PO 4. A surface treatment method for a metal plate is provided.
According to the surface treatment method of the metal material, the cathode electrolytic treatment is intermittently performed, and the aqueous solution contains Zr ions in the range of 0.010 to 0.050 mol / liter as Zr. It is preferable to contain F ions in the range of 0.03 to 0.35 mol / liter as F.
本発明によれば、金属の表面に、少なくともＺｒ，Ｏ，Ｆを主成分とすると共に、リン酸イオンを含有しない無機表面処理層を陰極電解によって形成することにより、あるいはまた、金属表面に少なくともＺｒ，Ｏ，Ｆを主成分とすると共に、最表面に含有されるＰとＺｒの原子比が、０≦Ｐ／Ｚｒ＜０．６である無機表面処理層を陰極電解によって形成することにより、高速生産性、環境保全性、耐傷性、接着性、加工性、密着性に優れた表面処理金属材料を低コストで提供することが可能であり、この表面処理金属材料に有機樹脂、中でも特にポリエステル樹脂被覆を行った金属材料から金属缶を形成することにより、高度の加工部においても、優れた密着性と耐食性とが得られ、また、この表面処理金属材料に有機樹脂、中でも特にポリエステル樹脂被覆を行った金属材料から缶蓋を形成することにより、加熱殺菌後においても優れた開口性が得られる。
本発明の表面処理金属材料及び樹脂被覆金属材料においては、特に金属缶及び缶蓋に有効に使用できるが、これ以外にも自動車、家電製品、建材等の用途にも有効に使用することができる。
According to the present invention, an inorganic surface treatment layer containing at least Zr, O, F as a main component and not containing phosphate ions is formed on the metal surface by cathodic electrolysis, or at least on the metal surface. By forming an inorganic surface treatment layer containing Zr, O, and F as main components and having an atomic ratio of P and Zr contained in the outermost surface of 0 ≦ P / Zr <0.6 by cathodic electrolysis, It is possible to provide a surface-treated metal material excellent in high-speed productivity, environmental protection, scratch resistance, adhesiveness, workability, and adhesion at low cost. By forming a metal can from a metal material coated with resin, excellent adhesion and corrosion resistance can be obtained even in highly processed parts. By forming the can lid of a metal material subjected to ester resin coating, excellent openability even after heat sterilization can be obtained.
The surface-treated metal material and resin-coated metal material of the present invention can be used effectively for metal cans and can lids, but can also be used effectively for applications such as automobiles, home appliances, and building materials. .
本発明の表面処理金属材料においては、金属材料表面に形成された無機表面処理層が、少なくともＺｒ，Ｏ，Ｆを主成分とすると共に、リン酸イオンを含有しない、あるいは、Ｚrに対するＰの比率を極力抑制することが重要な特徴である。
従来の金属材料の表面処理方法である、化成処理や陽極酸化処理では、皮膜形成機構上、硫酸イオンやリン酸イオンが膜中に含まれやすく、化成処理では構成成分となっている。これら膜中のアニオン、特にリン酸イオンのように、イオン半径の大きいアニオンは、レトルト殺菌処理などの高温多湿下で溶出しやすいことがわかっており、処理皮膜からこのようなアニオンが溶出すると、表面処理金属材料上に設けられた樹脂被膜の密着性や接着性が低下することになる。
本発明においては、無機表面処理層のアニオン量、特にリン酸イオンまたはＰ／Ｚｒを制御することにより、レトルト殺菌や高温多湿条件下での経時保管などに付された場合にも、処理皮膜中からのアニオンの溶出が有効に抑制されているため、樹脂被膜の密着性又は接着性が低下することが有効に防止されているのである。
In the surface-treated metal material of the present invention, the inorganic surface-treated layer formed on the surface of the metal material contains at least Zr, O, and F as main components and does not contain phosphate ions, or the ratio of P to Zr It is an important feature to suppress as much as possible.
In chemical conversion treatment and anodizing treatment, which are conventional surface treatment methods for metal materials, sulfate ions and phosphate ions are easily contained in the film due to the film formation mechanism, and are components in chemical conversion treatment. It is known that anions with large ionic radii, such as phosphate anions in these membranes, in particular, are likely to elute under high temperature and high humidity such as retort sterilization treatment. The adhesiveness and adhesiveness of the resin film provided on the surface-treated metal material will be reduced.
In the present invention, by controlling the amount of anions of the inorganic surface treatment layer, particularly phosphate ions or P / Zr, even when subjected to retort sterilization or storage over time under high temperature and high humidity conditions, Since the elution of the anion from is effectively suppressed, it is effectively prevented that the adhesiveness or adhesiveness of the resin film is lowered.
また本発明の表面処理金属材料においては、無機表面処理層が、Ｚｒ，Ｏ，Ｆを主構成成分とすることにより、高温多湿環境下においても処理層の最表面の状態を保持して安定な表面を維持することが可能であり、結果として耐食性の保持、及び樹脂被膜の密着性または接着性の低下を抑制することが可能となるのである。
すなわち、無機表面処理層が、Ｚｒ，Ｏを主構成成分とし、Ｆを含まない場合には、処理膜の構造は、ＺｒＯＸ（ＯＨ）Ｙの様な構造になっていると予想される。
しかし、水酸基は、高温多湿環境下において、水和して処理層の構造変化を誘起し諸特性に悪影響を及ぼす可能性がある。適量のＦを含む事によって、水酸基の少なくとも一部をＦで置換して、ＺｒＯＸ（ＯＨ）Ｙ−ＺＦＺの様な安定化構造をとることにより、高温多湿環境下での処理層の構造変化を抑制し、より一層安定な表面を保持することが可能となるのである。
Further, in the surface-treated metal material of the present invention, the inorganic surface-treated layer contains Zr, O, and F as main components, so that the state of the outermost surface of the treated layer is maintained and stable even in a high-temperature and high-humidity environment. It is possible to maintain the surface, and as a result, it is possible to maintain the corrosion resistance and suppress the decrease in the adhesion or adhesiveness of the resin film.
That is, when the inorganic surface treatment layer contains Zr, O as main components and does not contain F, the structure of the treatment film is expected to be a structure like ZrO X (OH) Y.
However, the hydroxyl group may be hydrated in a high-temperature and high-humidity environment to induce structural changes in the treatment layer and adversely affect various properties. By including a suitable amount of F, at least part of the hydroxyl groups substituted with F, by taking such stabilizing structure of ZrO X (OH) Y-Z F Z, the processing layer under high temperature and high humidity environment It is possible to suppress structural changes and maintain a more stable surface.
本発明の表面処理金属材料及びこの表面処理金属材料に有機樹脂、中でも特にポリエステル樹脂を被覆して成る樹脂被覆金属材料から作成した金属缶又は缶蓋においては、密着性及び耐食性に優れた上記樹脂被覆金属材料を利用していることから、高加工部でのポリエステル樹脂被膜の密着性や、衝撃によって生じるポリエステル樹脂被膜のクラック部分からの耐食性（耐デント性）、更にレトルト殺菌時での密着性を改善することができると共に、透過イオン量による腐食が抑制され、イージーオープン缶蓋の開口性等も改善することが可能となる。 In the metal can or can lid prepared from the surface-treated metal material of the present invention and a resin-coated metal material obtained by coating the surface-treated metal material with an organic resin, in particular, a polyester resin, the resin having excellent adhesion and corrosion resistance. Because it uses a coated metal material, the adhesion of the polyester resin film at high-processing parts, the corrosion resistance (dent resistance) from cracks in the polyester resin film caused by impact, and the adhesion during retort sterilization In addition, the corrosion due to the amount of permeated ions can be suppressed, and the openability of the easy open can lid can be improved.
更に、本発明の金属材料の表面処理方法においては、ＺｒとＦを含有しリン酸イオン濃度が、ＰＯ４として０．００３モル／リットル未満、より好ましくはリン酸イオンを含有しない水溶液中で陰極電解処理することが重要な特徴である。
陰極電解処理によれば、従来の化成処理皮膜と比較して、単位時間あたりのＺｒ重量膜厚の制御範囲を大幅に広げることができ、用途に応じた皮膜生成が可能となるのである。
一方、従来の化成処理においては、処理液組成による化学反応に依存していることから皮膜形成速度が限定されており、このため高速処理では膜厚が制限されるのに対して、陰極電解処理では、電解反応を利用するため、皮膜形成の高速処理が可能になるのである。また化成処理や陽極酸化処理では、皮膜形成機構上、硫酸イオンやリン酸イオンが膜中に含まれやすく、化成処理では構成成分になってしまうため、上述したようなアニオン量の制御が困難である。これに対して、陰極電解処理によれば、フッ化物の水溶液を用いるため、硫酸イオンやリン酸イオンのような大きなイオン半径を持つアニオンの量が制御された皮膜を形成することが可能になるのである。
更に、本発明の金属材料の表面処理方法においては、陰極電解処理を断続的に実施することが好ましい。すなわち、電解を連続的に行うのではなく、電解途中に停止時間を設けることにより、表面処理層のＯ／Ｚｒ比をコントロールし、かつ、連続電解時より析出効率を高めることができ、結果として高品質で高速な処理が可能となるのである。
Further, in the surface treatment method for a metal material according to the present invention, the cathode is contained in an aqueous solution containing Zr and F and having a phosphate ion concentration of less than 0.003 mol / liter as PO 4 , more preferably no phosphate ion. Electrolytic treatment is an important feature.
According to the cathodic electrolysis treatment, the control range of the Zr weight film thickness per unit time can be greatly expanded as compared with the conventional chemical conversion treatment film, and the film can be generated according to the application.
On the other hand, in the conventional chemical conversion treatment, the film formation rate is limited because it depends on the chemical reaction depending on the composition of the treatment solution. For this reason, the film thickness is limited in the high-speed treatment, whereas the cathode electrolytic treatment. Then, since an electrolytic reaction is used, high-speed processing of film formation becomes possible. In addition, in the chemical conversion treatment and anodizing treatment, sulfate ions and phosphate ions are easily contained in the film due to the film formation mechanism, and the chemical conversion treatment becomes a constituent component, so it is difficult to control the amount of anion as described above. is there. On the other hand, according to the cathodic electrolysis treatment, since an aqueous solution of fluoride is used, it is possible to form a film in which the amount of anion having a large ionic radius such as sulfate ion or phosphate ion is controlled. It is.
Furthermore, in the metal material surface treatment method of the present invention, it is preferable that the cathodic electrolytic treatment is intermittently performed. That is, instead of continuously performing electrolysis, by providing a stop time in the middle of electrolysis, the O / Zr ratio of the surface treatment layer can be controlled, and the deposition efficiency can be increased more than during continuous electrolysis. High-quality and high-speed processing becomes possible.
(表面処理金属材料)
本発明の表面処理金属材料においては、上述した通り、表面処理金属材料の無機表面処理層が、リン酸を含有していないことが一つの重要な特徴であるが、このことは以下の解析結果から明らかである。
すなわち、図１にリン酸イオンを含有する表面処理膜の代表例であるリン酸ジルコニウム化成処理１と、本発明によるリン酸イオンを含有しないＺｒ，Ｏ，Ｆを含む無機表面処理２において、Ｘ線光電子分光装置（以下、ＸＰＳという）により、Ｐ2pのピークを測定し比較した例を示した。化成処理表面１では、処理液中にリン酸を含有しているため、Ｐ2pのピークがはっきりと認められるのに対して、本発明による無機表面処理２においてはＰ2pのピークが認められないことは図１から明らかである。
(Surface-treated metal material)
In the surface-treated metal material of the present invention, as described above, it is one important feature that the inorganic surface-treated layer of the surface-treated metal material does not contain phosphoric acid. It is clear from
That is, in FIG. 1, a zirconium phosphate chemical conversion treatment 1, which is a representative example of a surface treatment film containing phosphate ions, and an
一方、図２及び図３は、上記リン酸ジルコニウム化成処理１と本発明の無機表面処理２について表面からスパッタリングを併用した深さ方向分析を行ったＯ1sピークを示す図である。図２及び図３中、最表面から得られたピークが最も下に位置し、表面から離れて金属基板に近いピークほど上側に示した。図２及び図３より、最表面では、表面汚染に由来したＯが存在するため、エネルギー位置からは判断できないが、深さ方向分析を行なうことにより、リン酸イオンに由来するＯ1sピークを持つ化成処理１のＯ1sピークの束縛エネルギー位置１１は、本発明によるリン酸イオンを含有しないＺｒ，Ｏ，Ｆを含む無機表面処理膜２のＯ1sピークの束縛エネルギー位置２１に比較して高エネルギー側に現れている。このことから、本発明の表面処理金属材料においては、表面処理層がリン酸を含有していないことが明らかである。
On the other hand, FIG.2 and FIG.3 is a figure which shows the O1s peak which performed the depth direction analysis which used sputtering together from the surface about the said zirconium phosphate chemical conversion treatment 1 and the
更に、本発明の表面処理金属材料においては、表面処理金属材料の無機表面処理層の最表面に含有されるＰとＺｒの原子比が、０≦Ｐ／Ｚｒ＜０．６の範囲、より好ましくは０≦Ｐ／Ｚｒ＜０．１の範囲にあることが重要な特徴である。Ｐ／Ｚｒが上記範囲よりも大きい場合には、皮膜中にリン酸または、不純物成分としてのＰが多く存在しており、十分な密着性が得られないからである。
また本発明の表面処理金属材料の無機表面処理層はＺｒ、Ｏ、Ｆを主構成成分として含有し、特にその最表面層は、Ｏ／Ｚｒの値が原子比で１〜１０の範囲、特に１〜５の範囲にあることが望ましい。Ｏ／Ｚｒが上記範囲よりも小さい場合には、皮膜作成が困難であり、一方Ｏ／Ｚｒが上記範囲よりも大きい場合には、十分な密着性が得られないからである。
更に、本発明の表面処理金属材料においては、表面処理金属材料の無機表面処理層の最表面に含有されるＦ／Ｚｒの値が原子比で０．１〜２．５の範囲、特に０．５〜２．０の範囲にあることが望ましい。Ｆ／Ｚｒが上記範囲より小さい場合には、前述したＺｒＯＸ（ＯＨ）Ｙ−ＺＦＺのような安定化構造をとれずに、高温多湿環境下での密着性が低下しやすく、一方Ｆ／Ｚｒが上記範囲よりも大きい場合にも、イオン半径が小さいとはいえ、Ｚｒに対するアニオン量が過多となり、やはり密着性が低下する。
Furthermore, in the surface-treated metal material of the present invention, the atomic ratio of P and Zr contained in the outermost surface of the inorganic surface-treated layer of the surface-treated metal material is more preferably in the range of 0 ≦ P / Zr <0.6. Is an important feature in the range of 0 ≦ P / Zr <0.1. This is because when P / Zr is larger than the above range, a large amount of phosphoric acid or P as an impurity component is present in the film, and sufficient adhesion cannot be obtained.
The inorganic surface-treated layer of the surface-treated metal material of the present invention contains Zr, O, and F as main components, and particularly the outermost surface layer has an O / Zr value in the range of 1 to 10, particularly in the atomic ratio. It is desirable to be in the range of 1-5. This is because when O / Zr is smaller than the above range, film formation is difficult, whereas when O / Zr is larger than the above range, sufficient adhesion cannot be obtained.
Furthermore, in the surface-treated metal material of the present invention, the value of F / Zr contained in the outermost surface of the inorganic surface-treated layer of the surface-treated metal material is in the range of 0.1 to 2.5 in terms of atomic ratio. It is desirable to be in the range of 5 to 2.0. When F / Zr is smaller than the above range, the adhesive structure in a high-temperature and high-humidity environment tends to be lowered without taking the stabilizing structure like ZrO X (OH) YZ F Z described above, while F Even when / Zr is larger than the above range, although the ionic radius is small, the amount of anion with respect to Zr becomes excessive, and the adhesion is also lowered.
Ｐ／Ｚｒ，Ｏ／ＺｒおよびＦ／Ｚｒの原子比の測定方法としては、ＸＰＳにより、Ｐ2p，Ｏ1s，Ｆ1s，Ｚｒ3dのピークをそれぞれ測定し、解析ソフトにより原子濃度を求めた値から求めることができる。測定に用いる表面処理金属材料の状態としては、清浄な状態であれば、そのまま表面を解析する。有機樹脂が接着や融着された後であれば煮沸した過酸化水素水などに数分間浸漬してまず有機樹脂層を除去する必要がある。
清浄でないサンプルや前述の有機樹脂被覆層を除去後のサンプルは、有機物由来によるＣ層をＣ，Ｏ，Ｆ，Ｚｒ，基材金属元素などの主要元素の和を１００％とした時に対して、Ｃが原子濃度で１０％以下となるまでＡｒスパッタリングにより汚染層を軽く除去した時点でのＰ／Ｚｒ，Ｏ／ＺｒおよびＦ／Ｚｒ比を求めることができる。また、定法により、Ｐ，Ｏ，ＦおよびＺｒの各元素についてバックグランド除去後のピーク面積を求めてから、測定装置の相対感度係数を用いて各元素の原子濃度を求め、Ｐ／Ｚｒ，Ｏ／ＺｒおよびＦ／Ｚｒ比を計算により求めてもよい。
図４にＺｒ3dピーク３の例を示す。バックグランドの基準線４とピーク３に囲まれる範囲がピーク面積５となる。尚、当然ではあるが、バックグランドの引き方によって、原子比が変動するので、バックグランドの引き方には注意が必要である。
また、Ｐ2pのピークは、Ａｌ2sのプラズモンロスピークと混同しやすいので、注意が必要である。特に、深さ方向にスパッタリングするにつれて、Ｐ2pと考えられるピークがＡｌ2sピークとともに単調に増加するような場合には、表面皮膜単離後特性Ｘ線分析するなど他の方法でＰ元素の存在を確認する必要がある。
As a method for measuring the atomic ratio of P / Zr, O / Zr and F / Zr, the peak of P2p, O1s, F1s and Zr3d is measured by XPS, and the atomic concentration is obtained from the value obtained by analysis software. it can. If the surface-treated metal material used for the measurement is in a clean state, the surface is analyzed as it is. After the organic resin is bonded or fused, it is necessary to first remove the organic resin layer by immersing it in a boiled hydrogen peroxide solution for several minutes.
Samples that are not clean and samples after removal of the organic resin coating layer described above, when the sum of major elements such as C, O, F, Zr, and base metal elements is 100% in the C layer derived from organic matter, The P / Zr, O / Zr, and F / Zr ratios at the time when the contaminated layer is lightly removed by Ar sputtering until C becomes 10% or less in atomic concentration can be obtained. Also, after obtaining the peak area after background removal for each element of P, O, F, and Zr by a regular method, the atomic concentration of each element is obtained using the relative sensitivity coefficient of the measuring device, and P / Zr, O The / Zr and F / Zr ratios may be determined by calculation.
FIG. 4 shows an example of the
In addition, the peak of P2p is easily confused with the plasmon loss peak of Al2s, so care must be taken. In particular, when the peak considered to be P2p increases monotonously with the Al2s peak as sputtering is performed in the depth direction, the presence of P element is confirmed by other methods such as characteristic X-ray analysis after surface coating isolation. There is a need to.
また、膜厚としては、Ｚｒの重量膜厚で、５〜３００ｍｇ／ｍ２の間にあることが好ましく、５ｍｇ／ｍ２未満では皮膜の均一な生成が困難であり被覆率が充分でなく、３００ｍｇ／ｍ２を越えると、加工により密着性が低下するので好ましくない。
Ｚｒ膜厚の測定方法としては、市販の蛍光Ｘ線分析装置により定量する。まず、Ｚｒ重量膜厚既知の複数のサンプルからＺｒ膜厚とＺｒのＸ線強度の関係を示す検量線を作成し、ついで、未知試料を用いて測定したＺｒのＸ線強度を、検量線に基づき重量膜厚に換算する。
As the film thickness, the weight film thickness of Zr, is preferably between the 5 to 300 mg / m 2, not sufficient homogeneous product is difficult coverage of the film is less than 5 mg / m 2, If it exceeds 300 mg / m 2 , the adhesiveness is lowered by processing, which is not preferable.
As a measuring method of Zr film thickness, it quantifies with a commercially available fluorescent X-ray analyzer. First, a calibration curve indicating the relationship between the Zr film thickness and the X-ray intensity of Zr is created from a plurality of samples with known Zr weight film thickness, and then the X-ray intensity of Zr measured using an unknown sample is used as the calibration curve. Based on the weight film thickness.
また本発明の表面処理金属材料においては、被処理材となる金属材料基体がアルミニウム合金またはアルミニウム被覆鋼板など傷付きやすい金属からなる場合には、表面に粒径１０〜１００ｎｍの微粒子を析出させ、金属材料表面を被覆することができる。これは、Ｚｒを主体とする酸化物微粒子と考えられ、特殊な前処理を行うことなく、陰極電解によってアルミ表面を改質し、耐傷性や耐摩耗性などを改善する効果が得られる。 Further, in the surface-treated metal material of the present invention, when the metal material substrate to be treated is made of an easily damaged metal such as an aluminum alloy or an aluminum-coated steel plate, fine particles having a particle size of 10 to 100 nm are precipitated on the surface, The metal material surface can be coated. This is considered to be oxide fine particles mainly composed of Zr, and the effect of improving the scratch resistance, wear resistance, etc. is obtained by modifying the aluminum surface by cathodic electrolysis without performing a special pretreatment.
図５乃至図７は、本発明の表面処理金属材料の一例をそれぞれ示す断面図である。図５に示す表面処理金属材料３１は、金属材料基体３２、基体表面に設けられた、Ｚｒ，Ｏ，Ｆを主構成成分とする無機表面処理層３３を有している。図６の例では、無機表面処理層３３の中に粒径１０ｎｍ〜１００ｎｍのＺｒを含有する微粒子３４が存在している。
図７に示す表面処理金属材料３１は、Ｚｒ，Ｏ，Ｆを主構成成分とする無機表面処理層３３を有している点は図５と同じであるが、金属材料基体３２が金属材料３２ａと金属メッキ層３２ｂにより構成されている。基体３２の大部分を占める金属材料３２ａに被覆される金属メッキ層３２ｂは、後述するように、金属材料３２ａの耐食性を高める役割を持つものが使用される。
5 to 7 are cross-sectional views showing examples of the surface-treated metal material of the present invention. A surface-treated
The surface-treated
（金属材料基体）
本発明に用いる金属材料基体としては、各種表面処理鋼板やアルミニウム等の軽金属材料などが使用される。表面処理鋼板としては、冷圧延鋼板を焼鈍した後二次冷間圧延し、亜鉛メッキ、錫メッキ、ニッケルメッキ、アルミニウムメッキ等の表面処理の一種または二種以上行ったものを用いることができ、他にアルミニウムクラッド鋼板なども用いることができる。金属材料基体の表面側にメッキまたはクラッドなどにより形成される金属は、中心側に位置する金属の耐食性や耐摩耗性、通電性などの様々な性質を改善する目的で付けられているが、一般的には、耐食性を改善する目的で付与されている場合がほとんどである。また、軽金属材料としては、いわゆる純アルミニウムの他にアルミニウム合金が使用される。金属材料の元厚は、特に限定はなく、金属の種類、容器の用途或いはサイズによっても相違するが、金属板としては一般に０．１０乃至０．５０ｍｍの厚みを有するのがよく、この中でも表面処理鋼板の場合には０．１０乃至０．３０ｍｍの厚み、軽金属板の場合は０．１５乃至０．４０ｍｍの厚みを有するのがよい。
(Metal material substrate)
As the metal material substrate used in the present invention, various surface-treated steel plates and light metal materials such as aluminum are used. As the surface-treated steel sheet, a cold-rolled steel sheet is annealed and then secondary cold-rolled, and galvanized, tin-plated, nickel-plated, aluminum-plated, or the like can be used as a surface-treated steel sheet. In addition, an aluminum clad steel plate or the like can also be used. Metal formed by plating or cladding on the surface side of a metal material base is attached for the purpose of improving various properties such as corrosion resistance, wear resistance, and current carrying properties of the metal located on the center side. Specifically, it is almost always given for the purpose of improving the corrosion resistance. In addition to so-called pure aluminum, an aluminum alloy is used as the light metal material. The original thickness of the metal material is not particularly limited and varies depending on the type of metal and the use or size of the container. However, the metal plate generally has a thickness of 0.10 to 0.50 mm, and among these, the surface In the case of a treated steel plate, the thickness may be 0.10 to 0.30 mm, and in the case of a light metal plate, the thickness may be 0.15 to 0.40 mm.
(表面処理方法)
本発明の金属材料の表面処理方法においては、ＺｒとＦを含有しリン酸イオン濃度が、ＰＯ４として０．００３モル／リットル未満、より好ましくはリン酸を含有しない水溶液中で陰極電解処理することが重要な特徴である。
前述した通り、陰極電解処理によれば、従来の化成処理皮膜と比較して、単位時間あたりのＺｒ重量膜厚の制御範囲を大幅に広げることができ、用途に応じた皮膜生成が可能となる。
(Surface treatment method)
In the surface treatment method for a metal material of the present invention, cathodic electrolysis is performed in an aqueous solution containing Zr and F and having a phosphate ion concentration of less than 0.003 mol / liter as PO 4 , and more preferably not containing phosphoric acid. This is an important feature.
As described above, according to the cathodic electrolysis treatment, the control range of the Zr weight film thickness per unit time can be greatly expanded as compared with the conventional chemical conversion treatment film, and the film can be generated according to the application. .
また、本発明の表面処理方法においては、陰極電解処理を断続的に実施すること、すなわち電解途中に停止時間を設けて、攪拌した水溶液中で通電と停止のサイクルを複数回繰り返して電解を行う断続電解を行うことが好ましい。図８は、通電時間と停止時間の総和であるトータル電解時間とＺｒ重量膜厚の関係を示すものであり、図８から明らかなように、連続的に陰極電解を行った場合よりも断続的に陰極電解を行った場合のほうが、Ｚｒ重量膜厚の形成速度が速いことが理解される。
これは、連続的に電解していると陰極近傍で濃度分極を生じ、析出が阻害されるのに対し、断続的に電解することにより、電解停止の間に攪拌効果により、陰極近傍へＺｒ，Ｏ，ＯＨ，Ｆなどのイオンが供給されると共に、陰極に生成したルーズな膜、すなわち、Ｏ／Ｚｒ比の大きい膜を取り去り、結果としてＺｒ重量膜厚の形成速度が速く、かつ、より高品質な膜を提供することになる。
通電と停止のサイクルは、これに限定されるものではないが、通電時間が０．１乃至０．８秒、停止時間が０．３乃至１．５秒の範囲で、２乃至１０サイクル行うことが好ましい。
Further, in the surface treatment method of the present invention, the cathodic electrolysis is intermittently performed, that is, the electrolysis is performed by repeating the energization and deactivation cycle a plurality of times in the stirred aqueous solution by providing a stop time during the electrolysis. It is preferable to perform intermittent electrolysis. FIG. 8 shows the relationship between the total electrolysis time, which is the sum of the energization time and the stop time, and the Zr weight film thickness. As is clear from FIG. 8, it is more intermittent than when the cathode electrolysis is performed continuously. It is understood that the rate of formation of the Zr heavy film thickness is faster when cathodic electrolysis is performed.
This is because, when electrolysis is performed continuously, concentration polarization occurs in the vicinity of the cathode and precipitation is inhibited. On the other hand, by intermittent electrolysis, Zr, Ions such as O, OH, and F are supplied, and a loose film formed on the cathode, that is, a film having a large O / Zr ratio is removed. As a result, the formation rate of the Zr weight film thickness is high and higher. It will provide a quality film.
The energization and stop cycle is not limited to this, but the energization time is 0.1 to 0.8 seconds and the stop time is 0.3 to 1.5 seconds. Is preferred.
本発明の表面処理方法に用いる水溶液は、浴濃度が、Ｚｒとして０．０１０〜０．０５０モル／リットル、特に０．０１５〜０．０３５モル／リットルの範囲にあることが好ましい。陰極電解処理では、表面に緻密な酸化膜が形成されている金属板への処理は局所的な電解集中が生じることから均一な皮膜形成が困難であり、特殊な前処理が必要とされることが多いが、本発明においては、特殊な前処理を行うことなく、できるだけ均一な表面処理膜を生成するために、低濃度浴で電解処理を行うこととしている。すなわち、上記範囲よりも浴濃度が高いと、核生成が局所的に生じ、その部分に電解が優先的に集中するため、結果的に不均一な皮膜が形成され、一方上記範囲よりも浴濃度が低い場合には、浴の電気伝導度が低く、処理に要する電力上昇を招くので好ましくない。 The aqueous solution used in the surface treatment method of the present invention preferably has a bath concentration in the range of 0.010 to 0.050 mol / liter, particularly 0.015 to 0.035 mol / liter as Zr. In the cathodic electrolysis treatment, it is difficult to form a uniform film on the metal plate with a dense oxide film formed on the surface, so that a uniform film formation is difficult and a special pretreatment is required. However, in the present invention, electrolytic treatment is performed in a low-concentration bath in order to produce a surface treatment film that is as uniform as possible without performing any special pretreatment. That is, if the bath concentration is higher than the above range, nucleation occurs locally, and electrolysis concentrates preferentially in that portion, resulting in the formation of a non-uniform film, while the bath concentration is higher than the above range. Is low, the electric conductivity of the bath is low, which causes an increase in power required for the treatment, which is not preferable.
表面処理に用いる水溶液は、ｐＨ３．０〜８．０、より好ましくはｐＨ３．５〜６．５の水溶液であることが好ましく、処理液に用いるＺｒ薬剤としてはフッ化ジルコニウムカリウムＫＺｒＦ６やフッ化ジルコニウムアンモニウム（ＮＨ４）２ＺｒＦ６、炭酸ジルコニウムアンモニウム溶液（ＮＨ４）２ＺｒＯ（ＣＯ３）２などを用いることができる。また、ジルコニウムイオンとフッ素イオンを別々の薬剤より供給することもでき、Ｚｒ薬剤としてオキシ硝酸ジルコニウムＺｒＯ（ＮＯ３）２、オキシ酢酸ジルコニウムＺｒＯ（ＣＨ３ＣＯＯ）２など、Ｆ薬剤としてフッ化ナトリウムＮａＦ、フッ化カリウムＫＦ、フッ化アンモニウムＮＨ４Ｆなどを用いることができる。
浴中のＦイオンの浴濃度としては、Ｆとして、０．０３モル／リットル〜０．３５モル／リットルの範囲にある事が好ましい。上記範囲よりもフッ素イオン濃度が低いと、陰極である金属表面上にゲル状物質が生成し、連続生産時のハンドリング性を阻害するとともに、特性面でも高温多湿環境下で経時的に不安定な表面となるので好ましくなく、上記範囲よりも浴濃度が高いと析出効率を阻害する傾向があるとともに、浴中に沈殿物を生じやすいので好ましくない。
The aqueous solution used for the surface treatment is preferably an aqueous solution having a pH of 3.0 to 8.0, more preferably a pH of 3.5 to 6.5. Examples of the Zr agent used for the treatment liquid include potassium zirconium fluoride KZrF 6 and fluoride. Zirconium ammonium (NH 4 ) 2 ZrF 6 , zirconium ammonium carbonate solution (NH 4 ) 2 ZrO (CO 3 ) 2 and the like can be used. Zirconium ions and fluorine ions can also be supplied from separate agents, such as zirconium oxynitrate ZrO (NO 3 ) 2 and zirconium oxyacetate ZrO (CH 3 COO) 2 as Zr agents, and sodium fluoride NaF as F agents. , Potassium fluoride KF, ammonium fluoride NH 4 F, or the like can be used.
The F concentration in the bath is preferably in the range of 0.03 mol / liter to 0.35 mol / liter as F. If the fluorine ion concentration is lower than the above range, a gel-like substance is formed on the metal surface that is the cathode, which hinders handling during continuous production and is unstable over time in a high-temperature and high-humidity environment. Since it becomes a surface, it is not preferable, and when the bath concentration is higher than the above range, precipitation efficiency tends to be inhibited, and a precipitate is easily generated in the bath, which is not preferable.
更に、表面処理に用いる水溶液には必要に応じて硝酸イオン、過酸化物、および錯化剤を添加してもよい。硝酸イオンは、長期にわたって電解する際に、析出状態の安定性を保つ効果があり、硝酸、硝酸ナトリウム、硝酸カリウム、硝酸アンモニウムなどをイオン源として用いる事ができる。過酸化物は、水溶液中で酸素を発生し、陰極表面近傍の濃度分極を抑制する効果があり、浴の攪拌が乏しい時に特に有用である。過酸化物としては、例えば、過酸化水素、ペルオキソ二硫酸アンモニウム、ペルオキソ二硫酸カリウム、ペルオキソホウ酸ナトリウム、ペルオキソ炭酸ナトリウム、ペルオキソ二硫酸ナトリウムなどを用いる事ができる。さらに、錯化剤は、浴中に沈殿物が生成するのを抑える働きがあり、エチレンジアミン四酢酸、エチレンジアミン四酢酸ナトリウム、クエン酸、クエン酸ナトリウム、ホウ酸、ニトリロ三酢酸、ニトリロ三酢酸ナトリウム、シクロヘキサンジアミン四酢酸、グリシンなどを用いる事ができる。硝酸イオン、過酸化物、および錯化剤の添加濃度は、高濃度すぎると析出効率を阻害する傾向があり、硝酸イオン、過酸化物、錯化剤のそれぞれの濃度は０．２モル／リットル以下である事が好ましい。
金属材料基体の前処理としては、定法により、脱脂、水洗、必要に応じて、酸洗、水洗を行い、表面を清浄化し、上記水溶液を３０〜６５℃の温度において、攪拌しながら、電流密度が０．５〜１００Ａ／ｄｍ２で、通電と停止のサイクルを繰り返す断続電解方式により、トータル電解時間が０．３〜２０秒間陰極電解し、最後に水洗することにより、好適な表面構造を得ることができる。
陽極側に相当する対極板には、酸化イリジウム被覆したチタン板が好適に用いられる。対極板の条件としては、電解中に対極材料が処理液中に溶解せず、酸素過電圧の小さい不溶性陽極であることが望ましい。
Furthermore, nitrate ions, peroxides, and complexing agents may be added to the aqueous solution used for the surface treatment as necessary. Nitrate ions have the effect of maintaining the stability of the deposited state during electrolysis over a long period of time, and nitric acid, sodium nitrate, potassium nitrate, ammonium nitrate, and the like can be used as an ion source. The peroxide has an effect of generating oxygen in an aqueous solution and suppressing concentration polarization near the cathode surface, and is particularly useful when the bath is poorly stirred. As the peroxide, for example, hydrogen peroxide, ammonium peroxodisulfate, potassium peroxodisulfate, sodium peroxoborate, sodium peroxocarbonate, sodium peroxodisulfate and the like can be used. Furthermore, the complexing agent has a function of suppressing the formation of precipitates in the bath, such as ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid sodium, citric acid, sodium citrate, boric acid, nitrilotriacetic acid, nitrilotriacetic acid sodium, Cyclohexanediaminetetraacetic acid, glycine, or the like can be used. If the concentration of nitrate ion, peroxide, and complexing agent is too high, the precipitation efficiency tends to be inhibited. The concentration of nitrate ion, peroxide, and complexing agent is 0.2 mol / liter. The following is preferable.
As the pretreatment of the metal material substrate, degreasing, washing with water, and if necessary, pickling and washing with water to clean the surface, stirring the aqueous solution at a temperature of 30 to 65 ° C. while stirring the current density Is 0.5 to 100 A / dm 2 , and a cathodic electrolysis with a total electrolysis time of 0.3 to 20 seconds by a discontinuous electrolysis method in which a cycle of energization and stop is repeated, and finally, a suitable surface structure is obtained by washing with water. be able to.
As the counter electrode plate corresponding to the anode side, a titanium plate coated with iridium oxide is preferably used. As a condition of the counter electrode plate, it is desirable that the counter electrode material is an insoluble anode having a small oxygen overvoltage without being dissolved in the treatment liquid during electrolysis.
(樹脂被覆金属材料)
本発明の樹脂被覆金属材料は、上記表面処理金属材料の少なくとも片面に有機樹脂、中でも特にポリエステル樹脂から成る層を被覆して成るものであり、上述した表面処理金属材料を用いることから、樹脂被覆の密着性及び接着性に優れており、このため優れた耐食性、耐デント性を有している。
本発明の樹脂被覆金属材料の一例の断面図を示す図９において、この樹脂被覆金属材料４１は、容器としたときの内面側（図において右側）で見て、金属材料基体４２、基体表面に設けられた、Ｚｒ，Ｏ，Ｆを主構成成分とする表面処理層４３、及びその上に設けられたポリエステル樹脂被覆層４４の多層構造を有している。図９の例では、容器としたときの外面側（図において左側）において、前記無機表面処理層３を介して外面樹脂保護層４５を備えているが、外面樹脂保護層４５は、前記ポリエステル樹脂被覆層４４と同一のポリエステル樹脂であっても、或いはこれと異なるポリエステル樹脂からなっていてもよく、また異なる樹脂からなっていてもよい。
(Resin-coated metal material)
The resin-coated metal material of the present invention is formed by coating at least one surface of the surface-treated metal material with a layer made of an organic resin, particularly a polyester resin. Therefore, it has excellent corrosion resistance and dent resistance.
In FIG. 9 which shows sectional drawing of an example of the resin-coated metal material of the present invention, this resin-coated
また、樹脂被覆金属材料の他の例を示す図１０において、この樹脂被覆金属材料４１は、Ｚｒ、Ｏ、Ｆを主構成成分とする表面処理層４３、基体４２の容器内面となる側に施されたポリエステル樹脂層４４及び外面となる側に施された外面樹脂保護層４５を備えている点では、図９のものと同様であるが、基体２が金属材料４２ａと金属メッキ層４２ｂにより構成されており、更に、ポリエステル樹脂層４４がポリエステル樹脂表層４４ａとポリエステル樹脂下層４ｂとの積層構造となっている。基体４２の大部分を占める金属材料４２ａに被覆される金属メッキ層４２ｂは、金属材料４２ａの耐食性を高める役割を持つものが使用されることは既に述べたとおりである。また、ポリエステル樹脂下層４４ｂとしては金属基体との接着性に優れたものが使用され、一方ポリエステル樹脂表層４４ａとしては耐内容物性に優れたものが使用されることは既に述べたとおりである。
Further, in FIG. 10 showing another example of the resin-coated metal material, this resin-coated
（有機樹脂被覆層）
本発明の樹脂被覆金属材料において、金属材料上に設ける有機樹脂としては、特に限定はなく、各種熱可塑性樹脂や熱硬化性乃至熱可塑性樹脂を挙げることができる。
有機樹脂としては、ポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、エチレン−酢酸ビニル共重合体、エチレン−アクリルエステル共重合体、アイオノンマー等のオレフィン系樹脂フィルム、またはポリブチレンテレフタレート等のポリエステルフィルム、もしくはナイロン６、ナイロン６，６、ナイロン１１、ナイロン１２等のポリアミドフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム等の熱可塑性樹脂フィルムの未延伸または二軸延伸したものであってもよい。積層の際に接着剤を用いる場合は、ウレタン系接着剤、エポキシ系接着剤、酸変性オレフィン樹脂系接着剤、コポリアミド系接着剤、コポリエステル系接着剤（厚さ：０．１〜５．０μｍ）等が好ましく用いられる。さらに熱硬化性塗料を、厚み０．０５〜２μｍの範囲で表面処理金属板側、あるいはフィルム側に塗布し、これを接着剤としてもよい。
(Organic resin coating layer)
In the resin-coated metal material of the present invention, the organic resin provided on the metal material is not particularly limited, and examples thereof include various thermoplastic resins and thermosetting or thermoplastic resins.
As the organic resin, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, olefin resin film such as ionomer, or polyester film such as polybutylene terephthalate, or A non-stretched or biaxially stretched thermoplastic resin film such as a nylon film such as nylon 6, nylon 6, 6,
さらに有機樹脂としては、フェノールエポキシ、アミノ−エポキシ等の変性エポキシ塗料、塩化ビニル−酢酸ビニル共重合体、塩化ビニル−酢酸ビニル共重合体けん化物、塩化ビニル−酢酸ビニル−無水マレイン酸共重合体、エポキシ変性−、エポキシアミノ変性−、エポキシフェノール変性−ビニル塗料または変性ビニル塗料、アクリル塗料、スチレン−ブタジェン系共重合体等の合成ゴム系塗料等の熱可塑性または熱硬化性塗料の単独または２種以上の組合わせであってもよい。
これらの中でも、容器用素材としてポリエステル樹脂が最も好適に用いられる。ポリエステル樹脂としては、エチレングリコールやブチレングリコールを主体とするアルコール成分と、芳香族二塩基酸、例えばテレフタル酸、イソフタル酸、ナフタレンジカルボン酸等の酸成分とから誘導される熱可塑性ポリエステルが挙げられる。
ポリエステルとしては、ポリエチレンテレフタレートそのものも勿論使用可能であるが、フィルムの到達し得る最高結晶化度を下げることが耐衝撃性や加工性の点で望ましく、この目的のためにポリエステル中にエチレンテレフタレート以外の共重合エステル単位を導入するのがよい。エチレンテレフタレート単位或いはブチレンテレフタレート単位を主体とし、他のエステル単位の少量を含む融点が２１０乃至２５２℃の共重合ポリエステルを用いることが特に好ましい。尚、ホモポリエチレンテレフタレートの融点は一般に２５５〜２６５℃である。
Further, as organic resins, modified epoxy paints such as phenol epoxy and amino-epoxy, vinyl chloride-vinyl acetate copolymer, saponified vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer , Epoxy-modified-, epoxy-amino-modified, epoxy-phenol-modified-vinyl paint or modified vinyl paint, acrylic paint, thermoplastic or thermosetting paint such as synthetic rubber paint such as styrene-butadiene copolymer alone or 2 It may be a combination of more than one species.
Among these, a polyester resin is most preferably used as a container material. Examples of the polyester resin include thermoplastic polyesters derived from an alcohol component mainly composed of ethylene glycol or butylene glycol and an acid component such as an aromatic dibasic acid such as terephthalic acid, isophthalic acid, or naphthalenedicarboxylic acid.
Of course, polyethylene terephthalate itself can be used as the polyester, but lowering the maximum crystallinity that the film can reach is desirable in terms of impact resistance and workability. For this purpose, other than ethylene terephthalate is included in the polyester. It is preferable to introduce the copolymerized ester unit. It is particularly preferable to use a copolyester having a melting point of 210 to 252 ° C. mainly composed of ethylene terephthalate units or butylene terephthalate units and containing a small amount of other ester units. The melting point of homopolyethylene terephthalate is generally 255 to 265 ° C.
一般に共重合ポリエステル中の二塩基酸成分の７０モル％以上、特に７５モル％以上がテレフタル酸成分から成り、ジオール成分の７０モル％以上、特に７５モル％以上がエチレングリコールまたはブチレングリコールから成り、二塩基酸成分の１乃至３０モル％、特に５乃至２５モル％がテレフタル酸以外の二塩基酸成分から成ることが好ましい。
テレフタル酸以外の二塩基酸としては、イソフタル酸、フタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸：シクロヘキサンジカルボン酸等の脂環族ジカルボン酸：コハク酸、アジピン酸、セバチン酸、ドデカンジオン酸等の脂肪族ジカルボン酸：の１種又は２種以上の組合せが挙げられ、エチレングリコールまたはブチレングリコール以外のジオール成分としては、プロピレングリコール、ジエチレングリコール、１，６−ヘキシレングリコール、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等の１種又は２種以上が挙げられる。勿論、これらのコモノマーの組合せは、共重合ポリエステルの融点を前記範囲とするのが好ましい。
In general, 70 mol% or more, particularly 75 mol% or more of the dibasic acid component in the copolyester is composed of a terephthalic acid component, and 70 mol% or more, particularly 75 mol% or more of the diol component is composed of ethylene glycol or butylene glycol, It is preferable that 1 to 30 mol%, particularly 5 to 25 mol% of the dibasic acid component is composed of a dibasic acid component other than terephthalic acid.
Dibasic acids other than terephthalic acid include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid and naphthalenedicarboxylic acid: alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid: succinic acid, adipic acid, sebacic acid, dodecanedioic acid, etc. Or a combination of two or more of the aliphatic dicarboxylic acids: As the diol component other than ethylene glycol or butylene glycol, propylene glycol, diethylene glycol, 1,6-hexylene glycol, cyclohexane dimethanol, bisphenol A 1 type, or 2 or more types, such as an ethylene oxide adduct. Of course, the combination of these comonomers is preferably such that the melting point of the copolyester falls within the above range.
また、このポリエステルは、成形時の溶融流動特性を改善するために、三官能以上の多塩基酸及び多価アルコールから成る群より選択された少なくとも１種の分岐乃至架橋成分を含有することができる。これらの分岐乃至架橋成分は、３．０モル％以下、好適には０．０５乃至３．０モル％の範囲にあるのがよい。
三官能以上の多塩基酸及び多価アルコールとしては、トリメリット酸、ピロメリット酸、ヘミメリット酸、１，１，２，２−エタンテトラカルボン酸、１，１，２−エタントリカルボン酸、１，３，５−ペンタントリカルボン酸、１，２，３，４−シクロペンタンテトラカルボン酸、ビフェニル−３，４，３’，４’−テトラカルボン酸等の多塩基酸や、ペンタエリスリトール、グリセロール、トリメチロールプロパン、１，２，６−ヘキサントリオール、ソルビトール、１，１，４，４−テトラキス（ヒドロキシメチル）シクロヘキサン等の多価アルコールが挙げられる。
Further, the polyester may contain at least one branching or crosslinking component selected from the group consisting of a tribasic or higher polybasic acid and a polyhydric alcohol in order to improve the melt flow characteristics during molding. . These branching or crosslinking components should be in the range of 3.0 mol% or less, preferably 0.05 to 3.0 mol%.
Examples of the trifunctional or higher polybasic acid and polyhydric alcohol include trimellitic acid, pyromellitic acid, hemimellitic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,1,2-ethanetricarboxylic acid, 1 , 3,5-pentanetricarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, polybasic acids such as biphenyl-3,4,3 ′, 4′-tetracarboxylic acid, pentaerythritol, glycerol, Examples include polyhydric alcohols such as trimethylolpropane, 1,2,6-hexanetriol, sorbitol, 1,1,4,4-tetrakis (hydroxymethyl) cyclohexane.
本発明の樹脂被覆金属材料において、製缶用または製蓋用素材に利用できる特に好適なポリエステル樹脂として、イソフタル酸成分を５乃至２５モル％含有するポリエチレンテレフタレート／イソフタレート、シクロヘキサンジメタノール成分を１乃至１０モル％含有するポリエチレン／シクロへキシレンジメチレンテレフタレート等が挙げられる。
ホモポリエステル或いは共重合ポリエステルは、フィルム形成範囲の分子量を有するべきであり、溶媒として、フェノール／テトラクロロエタン混合溶媒を用いて測定した固有粘度〔η〕は０．５乃至１．５、特に０．６乃至１．５の範囲にあるのがよい。
In the resin-coated metal material of the present invention, polyethylene terephthalate / isophthalate containing 5 to 25 mol% of isophthalic acid component and 1 cyclohexanedimethanol component are particularly suitable as a polyester resin that can be used for a can-making or lid-making material. Examples thereof include polyethylene / cyclohexylene dimethylene terephthalate containing 10 to 10 mol%.
The homopolyester or copolyester should have a molecular weight in the film forming range, and the intrinsic viscosity [η] measured using a phenol / tetrachloroethane mixed solvent as the solvent is 0.5 to 1.5, especially 0. It may be in the range of 6 to 1.5.
本発明に用いるポリエステル樹脂層は、上述したポリエステル或いはコポリエステル単独から形成されていても、或いはポリエステル或いはコポリエステルの２種以上のブレンド物、或いはポリエステル或いはコポリエステルと他の熱可塑性樹脂とのブレンド物から形成されていてもよい。ポリエステル或いはコポリエステルの２種以上のブレンド物としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンテレフタレート／イソフタレート、ポリエチレン／シクロへキシレンジメチレンテレフタレートの２種以上の組合せなどが挙げられるが、勿論この例に限定されない。 The polyester resin layer used in the present invention may be formed from the above-described polyester or copolyester alone, or a blend of two or more of polyester or copolyester, or a blend of polyester or copolyester and another thermoplastic resin. It may be formed from an object. Examples of blends of two or more of polyester or copolyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate, and combinations of two or more of polyethylene / cyclohexylene dimethylene terephthalate. It is not limited to.
ポリエステル中に配合できる他の熱可塑性樹脂としては、エチレン系重合体、熱可塑性エラストマー、ポリアリレート、ポリカーボネート等を挙げることができる。これらの改質樹脂成分の少なくとも１種を更に含有させ、耐高温湿熱性や耐衝撃性を更に向上させることができる。この改質樹脂成分は、一般にポリエステル１００重量部当たり５０重量部迄の量、特に好適には５乃至３５重量部の量で用いるのが望ましい。
エチレン系重合体として、例えば低−、中−或いは高−密度のポリエチレン、線状低密度ポリエチレン、線状超低密度ポリエチレン、エチレン−プロピレン共重合体、エチレン−ブテン−１共重合体、エチレン−プロピレン−ブテン−１共重合体、エチレン−酢酸ビニル共重合体、イオン架橋オレフィン共重合体（アイオノマー）、エチレン−アクリル酸エステル共重合体等が挙げられる。これらの内でも、アイオノマーが好適なものであり、アイオノマーのベースポリマーとしては、エチレン−（メタ）アクリル酸共重合体やエチレン−（メタ）アクリル酸エステル−（メタ）アクリル酸共重合体、イオン種としては、Ｎａ、Ｋ、Ｚｎ等のものが使用される。熱可塑性エラストマーとしては、例えばスチレン−ブタジエン−スチレンブロック共重合体、スチレン−イソプレン−スチレンブロック共重合体、水素化スチレン−ブタジエン−スチレンブロック共重合体、水素化スチレン−イソプレン−スチレンブロック共重合体等が使用される。
Examples of other thermoplastic resins that can be blended in the polyester include ethylene polymers, thermoplastic elastomers, polyarylate, and polycarbonate. At least one of these modified resin components can be further contained to further improve high-temperature wet heat resistance and impact resistance. This modified resin component is generally used in an amount of up to 50 parts by weight, particularly preferably 5 to 35 parts by weight, per 100 parts by weight of polyester.
Examples of the ethylene polymer include low-, medium- or high-density polyethylene, linear low density polyethylene, linear ultra-low density polyethylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene- Examples include propylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ion-crosslinked olefin copolymer (ionomer), and ethylene-acrylic acid ester copolymer. Among these, ionomers are preferable, and as the base polymer of ionomer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester- (meth) acrylic acid copolymer, ion As the seed, Na, K, Zn or the like is used. Examples of thermoplastic elastomers include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, hydrogenated styrene-butadiene-styrene block copolymers, and hydrogenated styrene-isoprene-styrene block copolymers. Etc. are used.
ポリアリレートは、二価フェノールと二塩基酸とから誘導されたポリエステルとして定義され、二価フェノールとしては、ビスフェノール類として、２，２’−ビス（４−ヒドロキシフェニル）プロパン（ビスフェノールＡ）、２，２’−ビス（４−ヒドロキシフェニル）ブタン（ビスフェノールＢ）、１，１’−ビス（４−ヒドロキシフェニル）エタン、ビス（４−ヒドロキシフェニル）メタン（ビスフェノールＦ）、４−ヒドロキシフェニルエーテル、ｐ−（４−ヒドロキシ）フェノール等が使用されるが、ビスフェノールＡ及びビスフェノールＢが好適である。二塩基酸としては、テレフタル酸、イソフタル酸、２,２−（４−カルボキシフェニル）プロパン、４, ４’−ジカルボキシジフェニルエーテル、４, ４’−ジカルボキシベンゾフェノン等が使用される。ポリアリレートは、上記単量体成分から誘導されたホモ重合体でもよく、また共重合体でもよい。
また、その本質を損なわない範囲で、脂肪族グリコールと二塩基酸とから誘導されたエステル単位との共重合体であってもよい。これらのポリアリレートは、ユニチカ社のＵポリマーのＵシリーズ或いはＡＸシリーズ、ＵＣＣ社のＡｒｄｅｌＤ−１００、Ｂａｙｅｒ社のＡＰＥ、Ｈｏｅｃｈｓｔ社のＤｕｒｅｌ、ＤｕＰｏｎｔ社のＡｒｙｌｏｎ、鐘淵化学社のＮＡＰ樹脂等として入手できる。
Polyarylate is defined as a polyester derived from a dihydric phenol and a dibasic acid. As the dihydric phenol, 2,2′-bis (4-hydroxyphenyl) propane (bisphenol A), 2 , 2′-bis (4-hydroxyphenyl) butane (bisphenol B), 1,1′-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane (bisphenol F), 4-hydroxyphenyl ether, p- (4-hydroxy) phenol or the like is used, and bisphenol A and bisphenol B are preferred. As the dibasic acid, terephthalic acid, isophthalic acid, 2,2- (4-carboxyphenyl) propane, 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxybenzophenone, or the like is used. The polyarylate may be a homopolymer derived from the monomer component or a copolymer.
Further, it may be a copolymer of ester units derived from an aliphatic glycol and a dibasic acid as long as the essence is not impaired. These polyarylates are available as Unitika's U polymer U series or AX series, UCC Ardel D-100, Bayer APE, Hoechst Durel, DuPont Arylon, Kaneka Chemical NAP resin, etc. it can.
ポリカーボネートは、二環二価フェノール類とホスゲンとから誘導される炭酸エステル樹脂であり、高いガラス転移点と耐熱性とを有することが特徴である。ポリカーボネートとしては、ビスフェノール類、例えば、２，２’−ビス（４−ヒドロキシフェニル）プロパン（ビスフェノールＡ）、２，２’−ビス（４−ヒドロキシフェニル）ブタン（ビスフェノールＢ）、１，１’−ビス（４−ヒドロキシフェニル）エタン、ビス（４−ヒドロキシフェニル）メタン（ビスフェノールＦ）、１,１−ビス（４−ヒドロキシフェニル）シクロヘキサン、１,１−ビス（４−ヒドロキシフェニル）シクロペンタン、１,１−ビス（４−ヒドロキシフェニル）−１−フェニルメタン、１,１−ビス（４−ヒドロキシフェニル）−１−フェニルエタン、１,２−ビス（４−ヒドロキシフェニル）エタン等から誘導されたポリカーボネートが好適である。 Polycarbonate is a carbonate resin derived from bicyclic dihydric phenols and phosgene, and is characterized by having a high glass transition point and heat resistance. Examples of the polycarbonate include bisphenols such as 2,2′-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2′-bis (4-hydroxyphenyl) butane (bisphenol B), 1,1′- Bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane (bisphenol F), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, , 1-bis (4-hydroxyphenyl) -1-phenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,2-bis (4-hydroxyphenyl) ethane, etc. Polycarbonate is preferred.
本発明に用いるポリエステル樹脂層は、単層の樹脂層であってもよく、また同時押出などによる多層の樹脂層であってもよい。多層のポリエステル樹脂層を用いると、下地層、即ち表面処理金属材料側に接着性に優れた組成のポリエステル樹脂を選択し、表層に耐内容物性、即ち耐抽出性やフレーバー成分の非吸着性に優れた組成のポリエステル樹脂を選択できるので有利である。
多層ポリエステル樹脂層の例を示すと、表層／下層として表示して、ポリエチレンテレフタレート／ポリエチレンテレフタレート・イソフタレート、ポリエチレンテレフタレート／ポリエチレン・シクロへキシレンジメチレン・テレフタレート、イソフタレート含有量の少ないポリエチレンテレフタレート・イソフタレート／イソフタレート含有量の多いポリエチレンテレフタレート・イソフタレート、ポリエチレンテレフタレート・イソフタレート／［ポリエチレンテレフタレート・イソフタレートとポリブチレンテレフタレート・アジペートとのブレンド物］等であるが、勿論上記の例に限定されない。表層：下層の厚み比は、５：９５乃至９５：５の範囲にあるのが望ましい。
The polyester resin layer used in the present invention may be a single resin layer or a multilayer resin layer formed by coextrusion or the like. When a multilayer polyester resin layer is used, a polyester resin having a composition with excellent adhesion is selected for the base layer, that is, the surface-treated metal material side, and the surface layer is resistant to contents, that is, extraction resistance and non-adsorption of flavor components. This is advantageous because a polyester resin having an excellent composition can be selected.
Examples of multilayer polyester resin layers are shown as surface layer / lower layer, polyethylene terephthalate / polyethylene terephthalate / isophthalate, polyethylene terephthalate / polyethylene / cyclohexylene dimethylene / terephthalate, polyethylene terephthalate / isolated with low isophthalate content. Polyethylene terephthalate / isophthalate having a high phthalate / isophthalate content, polyethylene terephthalate / isophthalate / [blend of polyethylene terephthalate / isophthalate and polybutylene terephthalate / adipate] and the like are of course not limited thereto. The thickness ratio of the surface layer to the lower layer is preferably in the range of 5:95 to 95: 5.
上記ポリエステル樹脂層には、それ自体公知の樹脂用配合剤、例えば非晶質シリカ等のアンチブロッキング剤、無機フィラー、各種帯電防止剤、滑剤、酸化防止剤、紫外線吸収剤等を公知の処方に従って配合することができる。
中でも、トコフェロール（ビタミンＥ）を用いることが好ましい。トコフェロールは、従来より酸化防止剤としてポリエステル樹脂の熱処理時における減成による分子量低下を防止して耐デント性を向上させるものであることが知られているが、特にポリエステル樹脂に前述したエチレン系重合体を改質樹脂成分として配合したポリエステル組成物にこのトコフェロールを配合すると、耐デント性のみならず、レトルト殺菌やホットベンダー等の過酷な条件に付され皮膜にクラックが生じたような場合でも、クラックから腐食が進むことが防止され、耐食性が著しく向上するという効果を得ることができる。
トコフェロールは、０．０５乃至３重量％、特に０．１乃至２重量％の量で配合することが好ましい。
In the polyester resin layer, known compounding agents for resins, for example, antiblocking agents such as amorphous silica, inorganic fillers, various antistatic agents, lubricants, antioxidants, ultraviolet absorbers, etc., according to known formulations Can be blended.
Of these, tocopherol (vitamin E) is preferably used. Tocopherol is conventionally known as an antioxidant that prevents molecular weight reduction due to degradation during heat treatment of a polyester resin and improves dent resistance. When this tocopherol is blended with the polyester composition blended as a modified resin component, not only the dent resistance, but also when the film is cracked due to severe conditions such as retort sterilization and hot bender, It is possible to prevent the corrosion from proceeding from the crack and to obtain the effect that the corrosion resistance is remarkably improved.
Tocopherol is preferably blended in an amount of 0.05 to 3% by weight, particularly 0.1 to 2% by weight.
本発明において、有機樹脂層の厚みは、一般に３乃至５０μｍ、特に５乃至４０μｍの範囲にあることが望ましい。即ち、厚みが上記範囲を下回ると、耐腐食性が不十分となり、厚みが上記範囲を上回ると加工性の点で問題を生じやすい。 In the present invention, the thickness of the organic resin layer is generally in the range of 3 to 50 μm, particularly 5 to 40 μm. That is, when the thickness is less than the above range, the corrosion resistance becomes insufficient, and when the thickness exceeds the above range, a problem is likely to occur in terms of workability.
（樹脂被覆金属材料の製造）
本発明において、表面処理金属材料へのポリエステル被覆層の形成は任意の手段で行うことができ、例えば、押出コート法、キャストフィルム熱接着法、二軸延伸フィルム熱接着法等により行うことができる。押出コート法の場合、表面処理金属材料の上にポリエステル樹脂を溶融状態で押出コートして、熱接着させることにより製造することができる。即ち、ポリエステル樹脂を押出機で溶融混練した後、Ｔ−ダイから薄膜状に押し出し、押し出された溶融樹脂膜を表面処理金属材料と共に一対のラミネートロール間に通して冷却下に押圧一体化させ、次いで急冷する。多層のポリエステル樹脂層を押出コートする場合には、表層樹脂用の押出機及び下層樹脂用の押出機を使用し、各押出機からの樹脂流を多重多層ダイ内で合流させ、以後は単層樹脂の場合と同様に押出コートを行えばよい。また、一対のラミネートロール間に垂直に表面処理金属材料を通し、その両側に溶融樹脂ウエッブを供給することにより、前記基体両面にポリエステル樹脂の被覆層を形成させることができる。
(Manufacture of resin-coated metal materials)
In the present invention, the polyester coating layer can be formed on the surface-treated metal material by any means, for example, by an extrusion coating method, a cast film thermal bonding method, a biaxially stretched film thermal bonding method, or the like. . In the case of the extrusion coating method, it can be manufactured by extrusion coating a polyester resin in a molten state on a surface-treated metal material and thermally bonding it. That is, after melt-kneading the polyester resin with an extruder, it is extruded from a T-die into a thin film, and the extruded molten resin film is passed through a pair of laminating rolls together with a surface-treated metal material and is pressed and integrated under cooling. Then quench rapidly. When extrusion coating a multilayer polyester resin layer, an extruder for surface layer resin and an extruder for lower layer resin are used, and the resin flow from each extruder is merged in a multiple multilayer die, and thereafter a single layer Extrusion coating may be performed as in the case of resin. Further, by passing a surface-treated metal material vertically between a pair of laminate rolls and supplying a molten resin web on both sides thereof, a polyester resin coating layer can be formed on both sides of the substrate.
樹脂被覆金属材料の押出コート法による製造は具体的には次のように行われる。表面処理金属材料（以下単に金属材料とも呼ぶことがある）を必要により加熱装置により予備加熱し、一対のラミネートロール間のニップ位置に供給する。一方、ポリエステル樹脂は、押出機のダイヘッドを通して薄膜の形に押し出し、ラミネートロールと金属材料との間に供給され、ラミネートロールにより金属材料に圧着される。ラミネートロールは、一定の温度に保持されており、金属材料にポリエステル等の熱可塑性樹脂から成る薄膜を圧着して両者を熱接着させると共に両側から冷却して樹脂被覆金属材料を得る。一般に、形成される樹脂被覆金属材料を更に冷却用水槽等に導いて、熱結晶化を防止するため、急冷を行う。 The production of the resin-coated metal material by the extrusion coating method is specifically performed as follows. A surface-treated metal material (hereinafter sometimes simply referred to as a metal material) is preheated by a heating device as necessary, and supplied to a nip position between a pair of laminate rolls. On the other hand, the polyester resin is extruded in the form of a thin film through a die head of an extruder, supplied between the laminate roll and the metal material, and pressed onto the metal material by the laminate roll. The laminating roll is maintained at a constant temperature, and a thin film made of a thermoplastic resin such as polyester is pressure-bonded to the metal material to thermally bond both of them and cooled from both sides to obtain a resin-coated metal material. In general, the formed resin-coated metal material is further quenched into a cooling water tank or the like to prevent thermal crystallization.
この押出コート法では、樹脂組成の選択とロールや冷却槽による急冷とにより、ポリエステル樹脂層は、結晶化度が低いレベル、非晶密度との差が０．０５ｇ／ｃｍ３以下に抑制されているため、ついで行う製缶加工や蓋加工等に対する十分な加工性が保証される。勿論、急冷操作は上記例に限定されるものではなく、形成される樹脂被覆金属材料に冷却水を噴霧して、ラミネート板を急冷することもできる。 In this extrusion coating method, the polyester resin layer has a low crystallinity level and a difference from the amorphous density of 0.05 g / cm 3 or less due to selection of the resin composition and rapid cooling with a roll or a cooling bath. Therefore, sufficient workability is ensured for the subsequent can manufacturing, lid processing and the like. Of course, the rapid cooling operation is not limited to the above example, and the laminate plate can be rapidly cooled by spraying cooling water onto the resin-coated metal material to be formed.
金属材料に対するポリエステル樹脂の熱接着は、溶融樹脂層が有する熱量と、金属材料が有する熱量とにより行われる。金属材料の加熱温度（Ｔ１）は、一般に９０℃乃至２９０℃、特に１００℃乃至２８０℃の温度が適当であり、一方ラミネートロールの温度は１０℃乃至１５０℃の範囲が適当である。
また、本発明の樹脂被覆金属材料は、Ｔ−ダイ法やインフレーション製膜法で予め製膜されたポリエステル樹脂フィルムを金属材料に熱接着させることによっても製造することができる。フィルムとしては、押し出したフィルムを急冷した、キャスト成形法による未延伸フィルムを用いることもでき、また、このフィルムを延伸温度で、逐次或いは同時二軸延伸し、延伸後のフィルムを熱固定することにより製造された二軸延伸フィルムを用いることもできる。
The thermal adhesion of the polyester resin to the metal material is performed by the amount of heat that the molten resin layer has and the amount of heat that the metal material has. The heating temperature (T 1 ) of the metal material is generally 90 ° C. to 290 ° C., particularly 100 ° C. to 280 ° C., while the laminating roll temperature is suitably 10 ° C. to 150 ° C.
The resin-coated metal material of the present invention can also be produced by thermally bonding a polyester resin film previously formed by a T-die method or an inflation film formation method to the metal material. As the film, an unstretched film formed by a cast molding method in which the extruded film is rapidly cooled can be used, and this film is biaxially stretched sequentially or simultaneously at the stretching temperature, and the stretched film is heat-set. It is also possible to use a biaxially stretched film produced by the above method.
本発明においては、上記層構成以外にも種々の構成を採用することができ、表面処理金属材料とポリエステル層の間に、従来公知の接着用プライマーを設けることも可能である。この接着プライマーは、金属素材とフィルムとの両方に優れた接着性を示すものである。密着性と耐腐食性とに優れたプライマー塗料としては、種々のフェノールとホルムアルデヒドから誘導されるレゾール型フェノールアルデヒド樹脂と、ビスフェノール型エポキシ樹脂とから成るフェノールエポキシ系塗料であり、特にフェノール樹脂とエポキシ樹脂を５０：５０乃至１：９９の重量比、特に４０：６０乃至５：９５の重量比で含有する塗料である。接着プライマー層は一般に０．０１乃至１０μｍの厚みに設けるのがよい。接着プライマー層は予め金属素材上に設けてもよく、或いはポリエステルフィルムに設けてもよい。 In the present invention, various configurations other than the above-described layer configuration can be adopted, and a conventionally known adhesion primer can be provided between the surface-treated metal material and the polyester layer. This adhesion primer exhibits excellent adhesion to both the metal material and the film. As a primer paint excellent in adhesion and corrosion resistance, it is a phenol epoxy paint composed of a resol type phenol aldehyde resin derived from various phenols and formaldehyde and a bisphenol type epoxy resin. It is a paint containing a resin in a weight ratio of 50:50 to 1:99, in particular 40:60 to 5:95. The adhesive primer layer is generally preferably provided with a thickness of 0.01 to 10 μm. The adhesion primer layer may be provided in advance on a metal material, or may be provided on a polyester film.
（金属缶及びその製法）
本発明の金属缶は、前述した樹脂被覆金属材料から形成されている限り、任意の製缶法によるものでよい。この金属缶は、側面継ぎ目を有するスリーピース缶であることもできるが、一般にシームレス缶（ツーピース缶）であることが好ましい。このシームレス缶は、表面処理金属材料のポリエステル樹脂の被覆面が缶内面側となるように、絞り・再しぼり加工、絞り・再絞りによる曲げ伸ばし加工（ストレッチ加工）、絞り・再絞りによる曲げ伸ばし・しごき加工或いは絞り・しごき加工等の従来公知の手段に付すことによって製造される。
(Metal can and its manufacturing method)
As long as the metal can of the present invention is formed from the above-mentioned resin-coated metal material, any can manufacturing method may be used. The metal can can be a three-piece can having a side seam, but is generally preferably a seamless can (two-piece can). This seamless can is drawn and re-squeezed, bent and stretched by drawing and re-drawing (stretching), and bent and drawn by drawing and re-drawing so that the coated surface of the surface-treated metal material polyester resin faces the inner surface of the can. -It is manufactured by attaching to a conventionally known means such as ironing or drawing / ironing.
本発明の金属缶の一例であるシームレス缶を示す図１１において、このシームレス缶５１は、前述した樹脂被覆金属材料の絞り・しごき成形で形成されており、底部５２と胴部５３とを備えている。底部５２と胴部５３とは継ぎ目なしに接続されている。底部５２は、その中心部において、用いた樹脂被覆金属材料と実質上同一の厚み構成を有しているが、胴部５３の少なくとも一部は元板厚の３０％〜７０％まで薄肉化加工されている。胴部５３の上部には、一段或いは多段のネック部５４を介して、缶蓋との巻締用のフランジ部１５が形成されている。
In FIG. 11 which shows the seamless can which is an example of the metal can of this invention, this
このシームレス缶の製造は、既に述べたとおり、絞り加工としごき加工とにより行われるが、この方法としては、絞り加工としごき加工とは、ワンストロークで同時に行ってもよいし、また別のストロークで別に行ってもよい。
例えば、シームレス缶の好適な製造法では、樹脂被覆金属材料を円形にせん断し、これを絞りダイスと絞りポンチの組み合わせを用いて、絞り加工により浅絞りカップを作り、ついで同一金型中で絞りながらしごきを行う同時絞りしごき加工を複数回繰り返して径が小さくハイトの大きいカップに成形する。この成形法では、薄肉化のための変形が、缶軸方向（高さ方向）の荷重による変形（曲げ伸ばし）と缶厚み方向の荷重による変形（しごき）との組み合わせでしかもこの順序に行われ、これにより、缶軸方向への分子配向が有効に付与されるという利点がある。その後、ドーミング成形、加工により生じる被覆樹脂の残留歪みの除去を目的とした熱処理、続いて開口端部のトリミング加工、曲面印刷、ネックイン加工、フランジ加工を行って缶を作成する。
勿論、本発明の金属缶の製造には、公知の製缶法を適用することができ、例えば特開平４−２３１１２０号公報に記載された絞り・しごき成形法や、特開平９−２５３７７２号公報に記載された同時絞り・しごき成形法を適用することができる。
As described above, the manufacture of this seamless can is performed by drawing and ironing. However, as this method, the drawing and ironing may be performed simultaneously with one stroke or another stroke. You can do it separately.
For example, in a preferred method for manufacturing a seamless can, a resin-coated metal material is sheared into a circle, and a shallow drawn cup is formed by drawing using a combination of a drawing die and a drawing punch, and then drawn in the same mold. Simultaneously squeezing and ironing while repeating ironing is repeated several times to form a cup with a small diameter and a large height. In this molding method, deformation for thinning is performed in this order by a combination of deformation due to a load in the can axis direction (height direction) (bending and stretching) and deformation due to a load in the can thickness direction (squeezing). This has the advantage that the molecular orientation in the can axis direction is effectively imparted. After that, a can is produced by performing doming molding, heat treatment for the purpose of removing residual distortion of the coating resin generated by processing, and subsequently performing trimming processing of the end of the opening, curved surface printing, neck-in processing, and flange processing.
Of course, a known can-making method can be applied to the production of the metal can of the present invention. For example, the drawing and ironing method described in JP-A-4-231120, or JP-A-9-253772. It is possible to apply the simultaneous drawing and ironing method described in the above.
（缶蓋及びその製法）
本発明の缶蓋は、上述した樹脂被覆金属材料から形成されている限り、従来公知の任意の製蓋法によるものでよい。一般には、ステイ・オン・タブタイプのイージーオープン缶蓋やフルオープンタイプのイージーオープン缶蓋に適用することができる。
本発明のイージーオープン缶蓋の上面を示す図１２及び断面を拡大して示す図１３において、この蓋６０は、前述した樹脂被覆金属材料から形成されており、缶胴側面内面に嵌合されるべき環状リム部（カウンターシンク）６１を介して外周側に密封用溝６２を備えており、この環状リム部６１の内側には開口すべき部分６３を区画する全周にわたり形成されたスコア６４が設けられている。この開口すべき部分６３の内部には、大略中央部を押入して形成した略半円状の凹部パネル６５と凹部パネル６５の周囲に蓋材を突出させて形成したディンプル６６と蓋材を缶蓋外面側に突出させて形成したリベット６７とが形成され、開口用タブ６８がこのリベット６７のリベット打ちにより固定されている。開口用タブ６８は、一端に押し裂きによる開口用先端６９及び他端に保持用リング７０を有している。リベット６７の近傍において、スコア６４と反対側には、スコア６４とは不連続に並設された破断開始用スコア７１が形成されている。
(Can lid and its manufacturing method)
As long as the can lid of the present invention is formed of the above-described resin-coated metal material, any conventional lid-making method may be used. In general, the present invention can be applied to a stay-on-tab type easy open can lid and a full open type easy open can lid.
In FIG. 12 showing the upper surface of the easy open can lid of the present invention and FIG. 13 showing an enlarged cross section, the
開口に際しては、開口用タブ６８のリング７０を保持して、これを上方に持上げる。これにより破断開始用スコア７１が破断されて、開口用タブ６８の開口用先端６９が比較的大きく下方に押込まれ、スコア６４の一部が剪断開始される。
次いで、リング７０を上方に引張ることにより、スコア６４の残留部が全周にわたり破断されて開口が容易に行われる。
上記具体例の蓋は、いわゆるフルオープンタイプであるが、勿論、ステイ・オン・タブタイプのイージーオープン蓋にも適用可能である。
イージーオープン缶蓋の好適な製造方法では、樹脂被覆金属材料をプレス成形工程で円形に打抜くと共に蓋の形にし、密封用溝へのコンパウンドのライニング及び乾燥によるライニング工程を経て、スコア刻設工程で蓋の外面側から金属素材の途中に達するようにスコアの刻設を行い、ついでリベット形成、リベットにタブを取付け後、リベットを鋲打することによるタブ取付けを行い、イージーオープン缶蓋を作成する。イージーオープン缶蓋の適当な例は、例えば特開２０００−１２８１６８号公報に記載されている。
When opening, the
Next, by pulling the
The lid of the above specific example is a so-called full open type, but it can of course be applied to a stay-on-tab type easy open lid.
In a preferred manufacturing method of an easy open can lid, a resin-coated metal material is punched into a circular shape by a press molding process and formed into a lid shape, followed by a lining process by compound lining and drying in a sealing groove, and a score engraving process Create an easy open can lid by engraving the score so that it reaches the middle of the metal material from the outer surface side of the lid, then forming the rivet, attaching the tab to the rivet, then attaching the tab by hitting the rivet To do. A suitable example of an easy open can lid is described in, for example, Japanese Patent Application Laid-Open No. 2000-128168.
次に実施例と比較例とを示して本発明を具体的に説明し、効果を明らかにする。
金属容器は、表面処理金属材料又は樹脂被覆金属材料の加工性、耐食性の点で最も厳しい環境下におかれているので、実施例は金属缶および缶蓋で示すが、もちろん、本発明はこれらの実施例のみに限定されるものではない。
Next, an Example and a comparative example are shown, this invention is demonstrated concretely, and an effect is clarified.
Since the metal container is placed in the most severe environment in terms of workability and corrosion resistance of the surface-treated metal material or resin-coated metal material, the examples are shown as metal cans and can lids. However, the present invention is not limited to the examples.
ジルコニウムイオンおよびフッ素イオンの濃度がそれぞれ、ＺｒおよびＦとして表１に示すモル濃度で、リン酸イオンを含有しない水溶液となるよう調整し、処理浴とした。但し、ジルコニウム薬剤として、処理浴Ａ，Ｂ，Ｃ，Ｅにはフッ化ジルコニウムカリウム、処理浴Ｄにはフッ化ジルコニウムアンモニウム、処理浴Ｆ，Ｇにはオキシ硝酸ジルコニウムを用いた。また、処理浴Ａ，Ｆには所定の濃度となるようフッ化ナトリウムを添加して調整した。 The concentration of zirconium ions and fluorine ions was adjusted to be an aqueous solution containing no phosphate ions at the molar concentrations shown in Table 1 as Zr and F, respectively, to obtain a treatment bath. However, zirconium zirconium fluoride was used for the treatment baths A, B, C, and E, zirconium ammonium fluoride was used for the treatment bath D, and zirconium oxynitrate was used for the treatment baths F and G. The treatment baths A and F were adjusted by adding sodium fluoride so as to have a predetermined concentration.
[ポリエステルフィルムの作製]
２台の押出機から２層Ｔダイを介して表２に示す組成のエチレンテレフタレート単位を主体とするポリエステル樹脂を溶融押出し後、冷却ロールにて冷却して得られたフィルムを巻き取り、表３に示す構成のキャストフィルムａ，ｂ，ｃ，ｄ，ｅを得た。
[Production of polyester film]
A polyester resin mainly composed of ethylene terephthalate units having the composition shown in Table 2 is melt-extruded through a two-layer T die from two extruders, and then the film obtained by cooling with a cooling roll is wound up. Table 3 The cast films a, b, c, d, and e having the structure shown in FIG.
［表面原子比の測定］
表面処理後の金属材料をＸ線光電子分光装置（ＸＰＳ）により下記条件で、Ｐ2p，Ｏ1s，Ｆ1s，Ｚｒ3dのピークをそれぞれ測定し、解析ソフトにより求めた原子濃度からＰ／Ｚｒ，Ｏ／Ｚｒ，Ｆ／Ｚｒの原子比を計算により求めた。
装 置 ＰＨＩ社製 Quantum 2000
励起Ｘ線源 Ａｌモノクロメーター７５Ｗ−１７ｋＶ
測定径 φ１００μｍ
光電子取り出し角 ９０°（試料の法線に対し０°）
解析ソフト；ＭｕｌｔｉＰａｋ
[Measurement of surface atomic ratio]
The metal material after the surface treatment was measured for the P2p, O1s, F1s, and Zr3d peaks using an X-ray photoelectron spectrometer (XPS) under the following conditions, and P / Zr, O / Zr, The atomic ratio of F / Zr was obtained by calculation.
Excitation X-ray source Al monochromator 75W-17kV
Measurement diameter φ100μm
Photoelectron extraction angle 90 ° (0 ° with respect to sample normal)
Analysis software; MultiPak
[接着性評価]
表面処理金属材料を５ｍｍ幅で８０ｍｍ長さに短冊状に切断し、表３のｃに示すキャストフィルムを５ｍｍ幅で８０ｍｍ長さに短冊状に切段した。得られた２枚の表面処理短冊切片間に上記ポリエステルフィルム切片を挟み、２．０ｋｇ／ｃｍ２の圧力下で２５０℃３秒間加熱してＴピール試験片とした。その後、１１０℃６０分間のレトルト処理を行い、終了後すぐに水中に浸漬し、引張試験機による測定直前に水中から引き上げて、引張速度１０ｍｍ／分で接着強度を測定した。
[Adhesion evaluation]
The surface-treated metal material was cut into strips having a width of 5 mm and a length of 80 mm, and the cast film shown in c of Table 3 was cut into strips having a width of 5 mm and a length of 80 mm. The polyester film section was sandwiched between the two obtained surface-treated strip sections and heated at 250 ° C. for 3 seconds under a pressure of 2.0 kg / cm 2 to obtain a T peel test piece. Thereafter, a retort treatment was performed at 110 ° C. for 60 minutes, and the film was immersed in water immediately after the completion, pulled up from the water just before measurement by a tensile tester, and measured for adhesive strength at a tensile speed of 10 mm / min.
（実施例１）
１．表面処理金属板の作成
金属板として厚み０．２５ｍｍのＪＩＳ５０２１Ｈ１８アルミ合金板を用い、脱脂剤３２２Ｎ８（日本ペイント社製）を用いて、定法により、７０℃の浴中で１０秒間処理し、水洗後、４０℃の１％硫酸中に５秒間浸漬し、水洗、純水洗し、前処理を行った。ついで、浴温４５℃の表１のＡに示す処理浴中で、攪拌を行いながら、極間距離３０ｍｍの位置に配置した酸化イリジウム被覆チタン板を陽極として、電流密度１０Ａ／ｄｍ２で、０．４秒通電−０．６秒停止を４回繰り返して断続的に陰極電解を行い、その後すぐに、流水による水洗、純水洗、乾燥の後処理を行って表面処理アルミニウム板を得た。
(Example 1)
1. Preparation of surface-treated metal plate JIS5021H18 aluminum alloy plate with a thickness of 0.25 mm was used as the metal plate, and the degreasing agent 322N8 (manufactured by Nippon Paint Co., Ltd.) was used for 10 seconds in a 70 ° C. bath by a conventional method. The sample was immersed in 1% sulfuric acid at 40 ° C. for 5 seconds, washed with water and washed with pure water, and pretreated. Subsequently, in a treatment bath shown in A of Table 1 at a bath temperature of 45 ° C., with stirring, an iridium oxide-coated titanium plate disposed at a position of a distance of 30 mm between the anodes was used as an anode at a current density of 10 A / dm 2 . Cathodic electrolysis was performed by repeating 4 seconds of energization for 4 seconds and stopping for 0.6 seconds four times, and immediately thereafter, washing with running water, washing with pure water, and drying were performed to obtain a surface-treated aluminum plate.
２．樹脂被覆金属板の作成
得られた表面処理金属板を用いて、以下の方法で製蓋用の樹脂被覆金属板を作成した。
まず、予め板温度２５０℃に加熱しておいた表面処理金属板の蓋内面側となる片面上に、表３のｂのキャストフィルムの下層側が接するようにラミネートロールを介して熱圧着後、直ちに水冷することにより、片面にフィルムをラミネートとした。
次に、蓋外面側となる、金属板のもう一方の片面にエポキシアクリル系塗料をロールコートにより塗装し、１８５℃１０分間加熱の焼付け処理を行った。
2. Production of Resin-Coated Metal Plate Using the obtained surface-treated metal plate, a resin-coated metal plate for lid making was produced by the following method.
First, immediately after thermocompression bonding through a laminating roll so that the lower layer side of the cast film b in Table 3 is in contact with one side which is the lid inner surface side of the surface-treated metal plate heated to a plate temperature of 250 ° C. in advance. The film was laminated on one side by water cooling.
Next, an epoxy acrylic paint was applied on the other side of the metal plate, which is the outer surface side of the lid, by roll coating, and baked at 185 ° C. for 10 minutes.
３．表面処理金属板の評価
得られた表面処理金属板の一部は、Ｚr膜厚測定、表面原子比測定の測定、接着性評価に供した。結果を表４に示した。
表中、接着性の評価は、引張試験機により試験片を１０ｍｍ以上剥離した後の最大引張強度が、０．６ｋｇ／５ｍｍ以上のものを◎、０．３ｋｇ／５ｍｍ以上０．６ｋｇ／５ｍｍ未満のものを○、０．３ｋｇ／５ｍｍ未満のものを×とした。
3. Evaluation of surface-treated metal plate A part of the obtained surface-treated metal plate was subjected to Zr film thickness measurement, surface atomic ratio measurement, and adhesion evaluation. The results are shown in Table 4.
In the table, the evaluation of adhesiveness is that the maximum tensile strength after peeling the test piece by 10 mm or more with a tensile testing machine is 0.6 kg / 5 mm or more, ◎, 0.3 kg / 5 mm or more and less than 0.6 kg / 5 mm The sample was marked with ◯, and the sample with less than 0.3 kg / 5 mm was marked with ×.
４．缶蓋の開口性評価
得られた樹脂被覆金属板を用いて、定法により３０１径のフルオープン缶蓋を作製後、アルミ製の絞り−しごき加工による３５０ｇシームレス缶胴に水を充填して巻締めた後、１１０℃６０分のレトルト殺菌処理を行い、冷却後直ちに開口してスコア部周辺開口部の樹脂剥離状態を観察し、缶蓋の開口性評価を行った。結果を表４に示した。
表中、缶蓋の開口性評価は、開口部周辺のフェザリングを観察し、フェザリングが０．５ｍｍ未満で樹脂の剥離がないものを○、フェザリングが０．５ｍｍ以上のものを×とした。
4). Opening evaluation of can lid Using the obtained resin-coated metal plate, a 301-diameter full-open can lid was prepared by a regular method, and then 350g seamless can body was filled with water by aluminum drawing and ironing and tightened. After that, a retort sterilization treatment at 110 ° C. for 60 minutes was performed, and the resin was peeled off immediately after cooling to observe the resin peeling state of the opening around the score part, and the openability of the can lid was evaluated. The results are shown in Table 4.
In the table, for the evaluation of the opening of the can lid, the feathering around the opening was observed, and when the feathering was less than 0.5 mm and the resin was not peeled, ○, and when the feathering was 0.5 mm or more, x did.
（実施例２）
処理浴として表１のＢに示す浴を用いて電流密度を３Ａ／ｄｍ２とした以外は、実施例１と同様に、表面処理、樹脂被覆、製蓋および評価を行った。
(Example 2)
Surface treatment, resin coating, lid making and evaluation were performed in the same manner as in Example 1 except that the bath shown in B of Table 1 was used as the treatment bath and the current density was 3 A / dm 2 .
（実施例３）
処理浴として表１のＢに示す浴を用いて電流密度を５Ａ／ｄｍ２とした以外は、実施例１と同様に、表面処理、樹脂被覆、製蓋および評価を行った。
(Example 3)
Surface treatment, resin coating, lid making and evaluation were performed in the same manner as in Example 1 except that the bath shown in B of Table 1 was used as the treatment bath and the current density was 5 A / dm 2 .
（実施例４）
処理浴として表１のＣに示す浴を用いた以外は、実施例１と同様に、表面処理、樹脂被覆、製蓋および評価を行った。
Example 4
Surface treatment, resin coating, lid making, and evaluation were performed in the same manner as in Example 1 except that the bath shown in C of Table 1 was used as the treatment bath.
（実施例５）
処理浴として表１のＤに示す浴を用いた以外は、実施例１と同様に、表面処理、樹脂被覆、製蓋および評価を行った。
(Example 5)
Surface treatment, resin coating, lid making and evaluation were performed in the same manner as in Example 1 except that the bath shown in D of Table 1 was used as the treatment bath.
（実施例６）
処理浴として表１のＥに示す浴を用いて電解時間を０．４秒間の連続電解１回のみとした以外は、実施例１と同様に、表面処理、樹脂被覆、製蓋および評価を行った。
(Example 6)
Surface treatment, resin coating, lid making and evaluation were performed in the same manner as in Example 1 except that the bath shown in E of Table 1 was used as the treatment bath, and the electrolysis time was changed to only one continuous electrolysis for 0.4 seconds. It was.
（実施例７）
処理浴として表１のＢに示す浴にリン酸二水素カリウムを０．００１モル／リットル添加し、０．６秒通電−０．４秒停止を４回繰り返して陰極電解した以外は実施例１と同様に、表面処理、樹脂被覆、製蓋および評価を行った。
(Example 7)
Example 1 except that 0.001 mol / liter of potassium dihydrogen phosphate was added to the bath shown in B of Table 1 as a treatment bath, and cathodic electrolysis was performed by repeating 0.6 second energization-0.4 second stop four times. In the same manner, surface treatment, resin coating, lid making and evaluation were performed.
（実施例８）
処理浴として表１のＢに示す浴にリン酸二水素カリウムを０．００２モル／リットル添加し、０．６秒通電−０．４秒停止を８回繰り返して陰極電解した以外は実施例１と同様に、表面処理、樹脂被覆、製蓋および評価を行った。
(Example 8)
Example 1 except that 0.002 mol / liter of potassium dihydrogen phosphate was added to the bath shown in Table 1B as a treatment bath, and cathodic electrolysis was performed by repeating 0.6 second energization-0.4 second stop eight times. In the same manner, surface treatment, resin coating, lid making and evaluation were performed.
（実施例９）
処理浴として表１のＦに示す浴を用いて陰極電解した以外は実施例１と同様に、表面処理、樹脂被覆、製蓋および評価を行った。
Example 9
Surface treatment, resin coating, lid making, and evaluation were performed in the same manner as in Example 1 except that cathodic electrolysis was performed using the bath shown in Table 1 F as the treatment bath.
（比較例１）
実施例１で用いた脱脂水洗後の金属板を、市販のジルコニウム系化成処理液（アロジン４０４、日本パーカライジング社製）を用いて定法により浴を作製し、液温４０℃で１５秒間スプレー処理し、その後すぐに、水洗、純水洗、乾燥の後処理を行い、表面処理アルミニウム板を得た以外は実施例１と同様に、樹脂被覆、製蓋および評価を行った。
(Comparative Example 1)
The metal plate after degreasing and washing used in Example 1 was prepared by a conventional method using a commercially available zirconium-based chemical conversion solution (Allodin 404, manufactured by Nihon Parkerizing Co., Ltd.), and sprayed at a liquid temperature of 40 ° C. for 15 seconds. Immediately thereafter, washing with water, washing with pure water, and post-treatment for drying were performed, and resin coating, lid making, and evaluation were performed in the same manner as in Example 1 except that a surface-treated aluminum plate was obtained.
（比較例２）
スプレー処理時間を１８秒間とした以外は、比較例１と同様に、表面処理、樹脂被覆、製蓋および評価を行った。
(Comparative Example 2)
Surface treatment, resin coating, lid making and evaluation were performed in the same manner as in Comparative Example 1 except that the spray treatment time was 18 seconds.
（比較例３）
処理浴として表１のＢに示す浴にリン酸二水素カリウムを０．００５モル／リットル添加し、０．６秒通電−０．４秒停止を４回繰り返して陰極電解した以外は実施例１と同様に表面処理、樹脂被覆、製蓋および評価を行った。
(Comparative Example 3)
Example 1 except that 0.005 mol / liter of potassium dihydrogen phosphate was added to the bath shown in B of Table 1 as a treatment bath, and cathodic electrolysis was repeated 4 times of 0.6 second energization-0.4 second stop. In the same manner as above, surface treatment, resin coating, lid making and evaluation were performed.
（比較例４）
処理浴として表１のＧに示す浴をアンモニアでｐＨ２．３に調整し、攪拌せずに陰極電解した以外は実施例１と同様に表面処理を行った。得られた皮膜を流水で洗浄すると皮膜が脱落するため、電解後は、溜まり水に静かに浸した後、乾燥した。樹脂被覆、製蓋および評価についても実施例１と同様に行った。
(Comparative Example 4)
Surface treatment was performed in the same manner as in Example 1 except that the bath indicated by G in Table 1 was adjusted to pH 2.3 with ammonia and subjected to cathodic electrolysis without stirring. When the obtained film was washed with running water, the film fell off. After electrolysis, the film was gently immersed in accumulated water and then dried. Resin coating, lid making and evaluation were performed in the same manner as in Example 1.
（比較例５）
攪拌しながら陰極電解した以外は比較例４と同様に表面処理を行った。得られた皮膜を流水で洗浄すると皮膜が脱落するため、電解後は、溜まり水に静かに浸した後、乾燥した。樹脂被覆、製蓋および評価についても比較例４と同様に行った。
(Comparative Example 5)
Surface treatment was performed in the same manner as in Comparative Example 4 except that the cathode electrolysis was performed while stirring. When the obtained film was washed with running water, the film fell off. After electrolysis, the film was gently immersed in accumulated water and then dried. Resin coating, lid making and evaluation were performed in the same manner as in Comparative Example 4.
（比較例６）
処理浴として表１のＧに示す浴を用いた。ｐＨ調整せずに陰極電解した以外は比較例４と同様に表面処理を行った。浴のｐＨは１．５３であった。得られた皮膜を流水で洗浄すると皮膜が脱落するため、電解後は、溜まり水に静かに浸した後、乾燥した。樹脂被覆、製蓋および評価についても比較例４と同様に行った。
(Comparative Example 6)
The bath indicated by G in Table 1 was used as the treatment bath. Surface treatment was performed in the same manner as in Comparative Example 4 except that cathodic electrolysis was performed without adjusting the pH. The bath pH was 1.53. When the obtained film was washed with running water, the film fell off. After electrolysis, the film was gently immersed in accumulated water and then dried. Resin coating, lid making and evaluation were performed in the same manner as in Comparative Example 4.
（比較例７）
攪拌しながら陰極電解した以外は比較例６と同様に表面処理を行った。得られた皮膜を流水で洗浄すると皮膜が脱落するため、電解後は、溜まり水に静かに浸した後、乾燥した。樹脂被覆、製蓋および評価についても比較例４と同様に行った。
(Comparative Example 7)
Surface treatment was performed in the same manner as in Comparative Example 6 except that the cathode electrolysis was performed while stirring. When the obtained film was washed with running water, the film fell off. After electrolysis, the film was gently immersed in accumulated water and then dried. Resin coating, lid making and evaluation were performed in the same manner as in Comparative Example 4.
（実施例１０）
１．表面処理金属板の作成
金属板として厚み０．２６ｍｍのＪＩＳ３００４Ｈ１９アルミ合金板を用いた以外は、実施例１と同様に表面処理を行った。
(Example 10)
1. Preparation of surface-treated metal plate Surface treatment was performed in the same manner as in Example 1 except that a JIS 3004H19 aluminum alloy plate having a thickness of 0.26 mm was used as the metal plate.
２．樹脂被覆金属板の作成
得られた表面処理金属板を、予め板温度２５０℃に加熱しておき、缶蓋内面側となる金属板の片面上に表３のｂのキャストフィルムの下層側が、缶外面側となるもう一方の片面上に表３のａのキャストフィルムが、接して被覆されるように、ラミネートロールを介して熱圧着後、直ちに水冷することにより、樹脂被覆金属板を得た。
2. Preparation of resin-coated metal plate The obtained surface-treated metal plate was heated in advance to a plate temperature of 250 ° C., and the lower layer side of the cast film b in Table 3 was placed on one side of the metal plate serving as the inner surface of the can lid. A resin-coated metal plate was obtained by immediately water-cooling after thermocompression bonding through a laminating roll so that the cast film a in Table 3 was in contact with and coated on the other surface on the outer surface side.
３．金属缶の作成
得られた樹脂被覆金属板の両面に、パラフィンワックスを両面に静電塗油後、直径１５４ｍｍの円形に打抜き、定法に従い浅絞りカップを作成した。ついでこの絞りカップを同時絞りしごき加工を２回繰り返して径が小さくハイトの大きいカップに成形した。この様にして得られたカップの諸特性は以下の通りであった。
カップ径 ６６ｍｍ、
カップ高さ １２８ｍｍ、
元板厚に対する缶壁部の厚み −６０％
このカップはドーミング成形後、樹脂フィルムの歪みをとるために２２０℃で６０秒間熱処理を行い、続いて開口端端部のトリミング加工、曲面印刷、２０６径へネックイン加工、フランジ加工を行って３５０ｇシームレス缶を作成した。
3. Preparation of Metal Can After both sides of the obtained resin-coated metal plate were electrostatically oiled with paraffin wax, they were punched into a circle with a diameter of 154 mm, and a shallow drawn cup was prepared according to a conventional method. Subsequently, the drawn cup was simultaneously drawn and ironed twice to form a cup having a small diameter and a large height. Various characteristics of the cup thus obtained were as follows.
Cup diameter 66mm,
Cup height 128mm,
The thickness of the can wall relative to the original plate thickness -60%
This cup is heat-treated at 220 ° C. for 60 seconds after doming to remove distortion of the resin film, followed by trimming of the end of the opening, curved surface printing, neck-in to 206 diameters, flange processing, and 350 g A seamless can was created.
４．表面処理金属板の評価
得られた表面処理金属板の一部は、実施例１と同様に、Ｚr膜厚測定、表面原子比測定の測定、接着性評価に供し、結果を表４に示した。
4). Evaluation of surface-treated metal plate A part of the obtained surface-treated metal plate was used for Zr film thickness measurement, surface atomic ratio measurement, and adhesion evaluation in the same manner as in Example 1. The results are shown in Table 4. .
５．金属缶のレトルト密着性評価
フランジ加工後の缶の開口端より５ｍｍ下部に缶内面側の全周に亘って素地に達する傷を入れ、空缶の状態で１２５℃の熱水蒸気中に３０分間保持し、缶内面側傷周辺部の被覆樹脂の剥離程度を観察し、レトルト密着性を評価した。結果を表４に示した。
表中、金属缶のレトルト密着性評価は、２０缶中一部でも剥離した缶が全くない時を○、２０缶中一部でも剥離した金属缶がある場合を×とした。
5). Evaluation of retort adhesion of metal cans Scratches reaching the substrate over the entire circumference of the inner surface of the can 5mm below the open end of the can after flange processing and kept in hot steam at 125 ° C for 30 minutes Then, the degree of peeling of the coating resin around the inner surface of the can inner surface was observed, and the retort adhesion was evaluated. The results are shown in Table 4.
In the table, the retort adhesion evaluation of the metal can was evaluated as ◯ when there was no peeled can even in a part of 20 cans, and x when there was a peeled metal can even in a part of 20 cans.
６．金属缶の耐食性評価
２５℃での缶内圧が３．５ｋｇ／ｃｍ２となるように炭酸水をパックした金属缶を３７℃で１週間貯蔵後、缶温を５℃に下げた後、金属缶を正立の状態から、水平方向に対し１５°傾斜した厚さ１０ｍｍの鋼板上に、５０ｃｍの高さから落下させボトムラジアス部を変形させた。その後、ボトムラジアス部を含む缶底部を円周方向に切り出し、０．１％塩化ナトリウム水溶液に５０℃で２週間経時後のボトムラジアス変形部周辺の腐食状態を観察し、耐食性を評価した。
結果を表４に示した。表中、金属缶の耐食性評価は、ボトムラジアスの変形部周辺を実体顕微鏡観察し、腐食が認められない場合を○、少しでも腐食している場合を×とした。
6). Corrosion resistance evaluation of metal cans After storing a metal can packed with carbonated water so that the internal pressure at 25 ° C is 3.5 kg / cm 2 at 37 ° C for one week, the can temperature is lowered to 5 ° C, then the metal can From an upright state, the bottom radius portion was deformed by dropping from a height of 50 cm onto a steel plate having a thickness of 10 mm inclined 15 ° with respect to the horizontal direction. Thereafter, the bottom of the can including the bottom radius portion was cut in the circumferential direction, and the corrosion state around the bottom radius deformed portion after aging for 2 weeks at 50 ° C. in a 0.1% sodium chloride aqueous solution was observed to evaluate the corrosion resistance.
The results are shown in Table 4. In the table, the corrosion resistance of metal cans was evaluated by observing the periphery of the deformed portion of the bottom radius with a stereomicroscope, and ◯ when no corrosion was observed and x when slightly corroded.
（実施例１１）
処理浴として表１のＢに示す浴を用いて電流密度を５Ａ／ｄｍ２とした以外は、実施例１０と同様に表面処理、樹脂被覆、製缶および評価を行った。
(Example 11)
Surface treatment, resin coating, canning and evaluation were performed in the same manner as in Example 10 except that the bath shown in B of Table 1 was used as the treatment bath and the current density was 5 A / dm 2 .
（実施例１２）
処理浴として表１のＣに示す浴を用いた以外は、実施例１０と同様に表面処理、樹脂被覆、製缶および評価を行った。
(Example 12)
Surface treatment, resin coating, canning, and evaluation were performed in the same manner as in Example 10 except that the bath shown in Table 1C was used as the treatment bath.
（比較例８）
金属板として厚み０．２６ｍｍのＪＩＳ３００４Ｈ１９アルミ合金板を用いた以外は、比較例１と同様に表面処理を行った。樹脂被覆、製缶および評価については実施例１０と同様に行った。
(Comparative Example 8)
Surface treatment was performed in the same manner as Comparative Example 1 except that a JIS3004H19 aluminum alloy plate having a thickness of 0.26 mm was used as the metal plate. Resin coating, can making and evaluation were carried out in the same manner as in Example 10.
（比較例９）
スプレー処理時間を１８秒間とした以外は、比較例８と同様に表面処理、樹脂被覆、製缶および評価を行った。
(Comparative Example 9)
Surface treatment, resin coating, canning and evaluation were performed in the same manner as in Comparative Example 8 except that the spray treatment time was 18 seconds.
（実施例１３）
１．表面処理金属板の作成
金属板として厚み０．２２ｍｍ、調質度ＤＲ８の冷延鋼板を電解脱脂、酸洗、水洗、純水洗し、前処理を行った。ついで、電流密度２．４Ａ／ｄｍ２とした以外は、実施例１と同様に、表１のＡの処理浴中で陰極電解処理を行って、表面処理金属板を得た。
(Example 13)
1. Preparation of surface-treated metal plate A cold-rolled steel plate having a thickness of 0.22 mm and a tempering degree DR8 was subjected to electrolytic degreasing, pickling, washing with water, and washing with pure water as a metal plate, followed by pretreatment. Next, a cathodic electrolysis treatment was performed in the treatment bath of A in Table 1 in the same manner as in Example 1 except that the current density was 2.4 A / dm 2 to obtain a surface-treated metal plate.
２．樹脂被覆金属板の作成
得られた表面処理金属板を予め板温度２５０℃に加熱しておき、内面側となる片面上に表３のｂのキャストフィルムの下層側が接して被覆され、外面側となるもう一方の片面上に表３のｄのキャストフィルムが被覆されるように、ラミネートロールを介して熱圧着後、直ちに水冷することにより、樹脂被覆金属板を得た。
2. Preparation of resin-coated metal plate The obtained surface-treated metal plate was previously heated to a plate temperature of 250 ° C., and the lower surface side of the cast film b in Table 3 was in contact with and coated on one surface which was the inner surface side. A resin-coated metal plate was obtained by immediately water-cooling after thermocompression bonding through a laminating roll so that the cast film of d in Table 3 was coated on the other side.
３．缶胴および缶蓋の作成
得られた樹脂被覆金属板に加工用潤滑剤を塗油後、再絞り加工（絞り比２．５）を行い、内径６５．３ｍｍの缶胴を作成した。続いて、樹脂フィルムの歪みをとるために２２０℃で６０秒間熱処理を行い、開口端端部のトリミング加工、フランジ加工を行って、高さ１０１．１ｍｍ深絞り缶を作成した。一方、得られた樹脂被覆金属板の一部を用いて、定法により、２１１径のフルオープン蓋に成形した。
3. Preparation of can body and can lid After applying a processing lubricant to the obtained resin-coated metal plate, redrawing (drawing ratio 2.5) was performed to prepare a can body having an inner diameter of 65.3 mm. Subsequently, in order to remove the distortion of the resin film, heat treatment was performed at 220 ° C. for 60 seconds, and the edge of the opening end was trimmed and flanged to produce a deep drawn can with a height of 101.1 mm. On the other hand, a part of the obtained resin-coated metal plate was molded into a 211-diameter full-open lid by a conventional method.
４．内容品充填試験
このようにして作成した缶胴および缶蓋を用いて、缶胴にミートソースを充填後、フルオープン蓋を２重巻締めし、１２０℃３０分のレトルト殺菌処理を行った。
4). Content Product Filling Test Using the can body and can lid prepared in this manner, the can body was filled with meat sauce, the full open lid was then double-wrapped, and a retort sterilization treatment at 120 ° C. for 30 minutes was performed.
５．表面処理金属板の評価
得られた表面処理金属板の一部は、実施例１と同様に、Ｚr膜厚測定、表面原子比の測定に供し、結果を表５に示した。
5). Evaluation of surface-treated metal plate A part of the obtained surface-treated metal plate was subjected to Zr film thickness measurement and surface atomic ratio measurement in the same manner as in Example 1, and the results are shown in Table 5.
６．容器評価
容器成形後の有機被膜の状態を調べ、剥離、穴あき等の以上がないかを観察した。また、内容物充填後、３７℃で６ヶ月貯蔵後開缶し、容器内面側の腐食や有機被膜の浮きなどが発生していないかを調べ、結果を表５に示した。
6). Container evaluation The state of the organic coating after container molding was examined and observed for peeling, perforation and the like. Further, after filling the contents, the container was opened after storage at 37 ° C. for 6 months, and it was examined whether corrosion on the inner surface side of the container or floating of the organic coating occurred, and the results are shown in Table 5.
（実施例１４）
１．表面処理金属板の作成
金属板として厚み０．１７ｍｍ、調質度ＤＲ８の冷延鋼板を、電解脱脂、酸洗、水洗、純水洗し、前処理を行い、片面あたりニッケルを０．３ｇ／ｍ２にめっきした後、片面あたりスズを０．６g／ｍ２にめっきし、リフロー処理を行って、ニッケル−スズ−鉄の合金層を形成した。続いて、実施例１３と同様に、表１のＡの処理浴中で陰極電解処理を行って表面処理金属板を得た。
(Example 14)
1. Preparation of surface-treated metal plate Cold-rolled steel sheet having a thickness of 0.17 mm and a tempering degree of DR8 as a metal plate is subjected to electrolytic degreasing, pickling, rinsing, pure water washing, pretreatment, and 0.3 g / m of nickel per side. After plating to 2 , tin was plated to 0.6 g / m 2 per side, and reflow treatment was performed to form a nickel-tin-iron alloy layer. Subsequently, as in Example 13, a cathodic electrolysis treatment was performed in the treatment bath A in Table 1 to obtain a surface-treated metal plate.
２．樹脂被覆金属板の作成
得られた表面処理金属板を、エポキシアクリル系水性塗料を用い、焼付け後の塗膜厚みが１０μｍになるように両面にロールコートし、２００℃１０分間の焼付け処理を行うことにより、樹脂被覆金属板を得た。
2. Preparation of resin-coated metal plate The obtained surface-treated metal plate is roll-coated on both sides using an epoxy acrylic water-based paint so that the coating thickness after baking is 10 μm and subjected to baking treatment at 200 ° C. for 10 minutes. Thus, a resin-coated metal plate was obtained.
３．缶胴および缶蓋の作成
得られた樹脂被覆金属板に加工用潤滑剤を塗油後、絞り加工（絞り比１．３）を行い、内径８３．３ｍｍの缶胴を作成した。続いて、開口端端部のトリミング加工、フランジ加工を行って、高さ４５．５ｍｍの絞り缶を作成した。一方、得られた樹脂被覆金属板の一部を用いて、定法により、３０７径のフルオープン蓋に成形した。
3. Preparation of can body and can lid The obtained resin-coated metal plate was coated with a processing lubricant and then subjected to drawing (drawing ratio 1.3) to prepare a can body having an inner diameter of 83.3 mm. Subsequently, trimming processing and flange processing of the end portion of the opening were performed, and a drawn can having a height of 45.5 mm was created. On the other hand, a part of the obtained resin-coated metal plate was molded into a 307-diameter full-open lid by a conventional method.
４．内容品充填試験
このようにして作成した缶胴および缶蓋を用いて、缶胴にツナ油漬けを充填後、フルオープン蓋を２重巻締めし、１１５℃６０分のレトルト殺菌処理を行った。
4). Content filling test Using the can body and can lid prepared in this way, the can body was filled with tuna oil, then the full open lid was double-wrapped and retort sterilized at 115 ° C for 60 minutes. .
５．表面処理金属板の評価
実施例１３と同様に、Ｚr膜厚測定、表面原子比の測定を実施した。
5). Evaluation of surface-treated metal plate In the same manner as in Example 13, measurement of the Zr film thickness and measurement of the surface atomic ratio were performed.
６．容器評価
開缶後硫化変色の有無を調べた以外は、実施例１３と同様に容器評価を実施した。
6). Container evaluation Container evaluation was performed in the same manner as in Example 13 except that the presence or absence of sulfur discoloration was examined after opening the container.
（実施例１５）
１．表面処理金属板の作成
金属板として厚み０．２２ｍｍ、調質度Ｔ４の冷延鋼板を、電解脱脂、酸洗、水洗、純水洗し、前処理を行い、片面あたりスズを２．０ｇ／ｍ２にめっき後、リフロー処理を行い、続いて、電流密度を１．０Ａ／ｄｍ２とした以外は実施例１３と同様に、表１のＡの処理浴中で陰極電解処理を行って、缶胴用表面処理金属板を得た。
一方、０．２１ｍｍの調質度Ｔ４の冷延鋼板についても、上記と同様に処理し、缶蓋用表面処理金属板を得た。
(Example 15)
1. Preparation of surface-treated metal plate Cold rolled steel sheet having a thickness of 0.22 mm and a tempering degree T4 as a metal plate is subjected to electrolytic degreasing, acid washing, water washing, pure water washing, pretreatment, and 2.0 g / m tin per side. 2 after plating, followed by reflow treatment, followed by cathodic electrolysis in the treatment bath of A in Table 1 in the same manner as in Example 13 except that the current density was 1.0 A / dm 2. A surface-treated metal plate for a trunk was obtained.
On the other hand, a cold-rolled steel sheet having a tempering degree T4 of 0.21 mm was treated in the same manner as described above to obtain a surface-treated metal sheet for can lids.
２．樹脂被覆金属板、缶胴および缶蓋の作成
缶胴用表面処理金属板を用いて、エポキシアクリル系水性塗料を缶胴の継目部分にあたる場所を除いて、焼付け後の膜厚が内面側５μｍ、外面側３μｍになるようにマージン塗装し、２００℃の熱風乾燥炉中で１０分間焼付け硬化させて樹脂被覆金属板を得た。
作成した樹脂被覆金属板をブランク状に切断し、そのブランクを線電極を用いた市販の電気抵抗溶接機にて円筒状にて溶接し、次に、缶胴の溶接継ぎ目部の内外面側に溶剤型エポキシユリア系補修塗料を乾燥塗膜厚みが４０μｍになるようにスプレー塗装した後２５０℃の熱風乾燥炉中で３分間焼付け、継ぎ目部分を被覆して溶接缶胴（缶径６５．４ｍｍ、缶胴高さ１２２ｍｍ）を作成した。
一方、缶蓋用表面処理金属板に、エポキシアクリル系水性塗料を、焼付け後の塗膜厚みが１０μｍになるように両面にロールコートし、２００℃１０分間の焼付け処理を行った後、定法により、２０９径のシェル蓋に成形した。
缶胴の一方の開口端を、フランジ加工、ネックイン加工し、前記２０９径の蓋を巻締めた後、もう一方の開口端をトリプルネックイン、フランジ加工した。
2. Preparation of resin-coated metal plate, can barrel and can lid Using a surface-treated metal plate for can barrels, the film thickness after baking is 5 μm on the inner surface side, except where the epoxy acrylic water-based paint is applied to the seam portion of the can barrel. Margin coating was performed so that the outer surface side would be 3 μm, and baked and cured in a hot air drying oven at 200 ° C. for 10 minutes to obtain a resin-coated metal plate.
The prepared resin-coated metal plate is cut into a blank shape, and the blank is welded in a cylindrical shape with a commercially available electric resistance welder using a wire electrode. Next, on the inner and outer surfaces of the weld seam of the can body After spray-coating a solvent-type epoxy urea-based repair coating so that the dry coating thickness is 40 μm, it is baked for 3 minutes in a hot air drying oven at 250 ° C., and the seam portion is coated to form a welded can body (can diameter 65.4 mm A can body height of 122 mm) was created.
On the other hand, an epoxy acrylic water-based paint is roll-coated on both surfaces so that the coating thickness after baking is 10 μm on the surface-treated metal plate for can lids and subjected to baking treatment at 200 ° C. for 10 minutes. , 209 diameter shell lid.
One opening end of the can body was subjected to flange processing and neck-in processing. After the 209-diameter lid was wound, the other opening end was subjected to triple neck-in processing and flange processing.
３．内容品充填試験
５０℃でコーヒー飲料を充填した後、市販の２０６径アルミＳＯＴ蓋を２重巻締めし、１２５℃２５分のレトルト殺菌処理を行った。
3. Content product filling test After filling a coffee beverage at 50 ° C, a commercially available 206-diameter aluminum SOT lid was double-rolled and subjected to a retort sterilization treatment at 125 ° C for 25 minutes.
４．表面処理金属板の評価
実施例１３と同様に、Ｚr膜厚測定、表面原子比の測定を実施した。
4). Evaluation of surface-treated metal plate In the same manner as in Example 13, measurement of the Zr film thickness and measurement of the surface atomic ratio were performed.
５．容器評価
開缶後の鉄溶出量も測定した以外は、実施例１３と同様に容器評価を実施した。
5). Container evaluation Container evaluation was carried out in the same manner as in Example 13 except that the amount of iron elution after opening the can was also measured.
（実施例１６）
１．表面処理金属板の作成
金属板として厚み０．２２ｍｍ、調質度Ｔ４の冷延鋼板を、電解脱脂、酸洗、水洗、純水洗し、前処理を行い、片面あたりニッケルを０．０３ｇ／ｍ２にめっきした後、片面あたりスズを１．３g／ｍ２にめっき後、リフロー処理を行い、続いて、実施例１５と同様に、表１のＡの処理浴中で陰極電解処理を行って缶胴用表面処理金属板を得た。
一方、０．２１ｍｍの調質度Ｔ４の冷延鋼板についても、上記と同様に処理し、缶蓋用表面処理金属板を得た。
(Example 16)
1. Preparation of surface-treated metal plate Cold-rolled steel sheet having a thickness of 0.22 mm and a tempering degree T4 as a metal plate is subjected to electrolytic degreasing, pickling, water washing, pure water washing, pretreatment, and nickel per one side of 0.03 g / m. After plating to 2 , tin was plated to 1.3 g / m 2 on one side, followed by reflow treatment, and then, in the same manner as in Example 15, cathodic electrolysis was performed in the treatment bath of A in Table 1. A surface-treated metal plate for can bodies was obtained.
On the other hand, a cold-rolled steel sheet having a tempering degree T4 of 0.21 mm was treated in the same manner as described above to obtain a surface-treated metal sheet for can lids.
２．樹脂被覆金属板、缶胴および缶蓋の作成
缶胴用表面処理金属板を用いて、エポキシフェノール溶剤型塗料を缶胴の継目部分にあたる場所を除いて、焼付け後の膜厚が内面側５μｍ、外面側３μｍになるようにマージン塗装し、２００℃の熱風乾燥炉中で１０分間焼付け硬化させて樹脂被覆金属板を得た。
作成した樹脂被覆金属板をブランク状に切断し、そのブランクを線電極を用いた市販の電気抵抗溶接機にて円筒状にて溶接し、次に、缶胴の溶接継ぎ目部の内外面側に溶剤型エポキシユリア系補修塗料を乾燥塗膜厚みが４０μｍになるようにスプレー塗装した後２５０℃の熱風乾燥炉中で３分間焼付け、継ぎ目部分を被覆して溶接缶胴（缶径６５．４ｍｍ、缶胴高さ１２２ｍｍ）を作成した。
一方、缶蓋用表面処理金属板に、エポキシフェノール溶剤型塗料を、焼付け後の塗膜厚みが１０μｍになるように両面にロールコートし、２００℃１０分間の焼付け処理を行った後、定法により、２０９径のシェル蓋に成形した。
缶胴の一方の開口端を、フランジ加工、ネックイン加工し、前記２０９径の蓋を巻締めた後、もう一方の開口端をトリプルネックイン、フランジ加工した。
2. Preparation of resin-coated metal plate, can body and can lid Using a surface-treated metal plate for can body, the film thickness after baking is 5 μm on the inner surface side except for the place where the epoxy phenol solvent type paint is applied to the joint part of the can body. Margin coating was performed so that the outer surface side would be 3 μm, and baked and cured in a hot air drying oven at 200 ° C. for 10 minutes to obtain a resin-coated metal plate.
The prepared resin-coated metal plate is cut into a blank shape, and the blank is welded in a cylindrical shape with a commercially available electric resistance welder using a wire electrode. Next, on the inner and outer surfaces of the weld seam of the can body After spray-coating a solvent-type epoxy urea-based repair coating so that the dry coating thickness is 40 μm, it is baked for 3 minutes in a hot air drying oven at 250 ° C., and the seam portion is coated to form a welded can body (can diameter 65.4 mm A can body height of 122 mm) was created.
On the other hand, an epoxy phenol solvent type paint is roll-coated on both sides so that the coating thickness after baking is 10 μm on the surface-treated metal plate for can lid, and after baking treatment at 200 ° C. for 10 minutes, , 209 diameter shell lid.
One opening end of the can body was subjected to flange processing and neck-in processing. After the 209-diameter lid was wound, the other opening end was subjected to triple neck-in processing and flange processing.
３．内容品充填試験
９３℃でオレンジジュースをホットパックした後、２０６径アルミＳＯＴ蓋を２重巻締めて密封した。
3. Content Product Filling Test After hot-packing orange juice at 93 ° C., a 206-diameter aluminum SOT lid was double wrapped and sealed.
４．表面処理金属板の評価
実施例１３と同様に、Ｚr膜厚測定、表面原子比の測定を実施した。
4). Evaluation of surface-treated metal plate In the same manner as in Example 13, measurement of the Zr film thickness and measurement of the surface atomic ratio were performed.
５．容器評価
実施例１５と同様に容器評価を実施した。
5). Container evaluation Container evaluation was carried out in the same manner as in Example 15.
（実施例１７）
１．表面処理金属板の作成
金属板として厚み０．１９５ｍｍ、調質度Ｔ３の冷延鋼板を、電解脱脂、酸洗、水洗、純水洗し、前処理を行い、片面あたりスズを１．０ｇ／ｍ２にめっきした後、続いて、実施例１５と同様に、表１のＡの処理浴中で陰極電解処理を行って、缶胴用表面処理金属板を得た。
一方、金属板として厚み０．２８５ｍｍのＪＩＳ５１８２Ｈ１９アルミ合金板を用いた以外は、実施例１と同様に前処理および陰極電解処理を行って缶蓋用表面処理金属板を得た。
(Example 17)
1. Preparation of surface-treated metal plate Cold-rolled steel sheet having a thickness of 0.195 mm and a tempering degree T3 as a metal plate is subjected to electrolytic degreasing, acid washing, water washing, pure water washing, pretreatment, and 1.0 g / m tin per side. After plating on 2 , the cathode electrolytic treatment was then performed in the treatment bath of A in Table 1 in the same manner as in Example 15 to obtain a surface-treated metal plate for can bodies.
On the other hand, the surface treatment metal plate for can lids was obtained by carrying out pretreatment and cathodic electrolytic treatment in the same manner as in Example 1 except that a JIS5182H19 aluminum alloy plate having a thickness of 0.285 mm was used as the metal plate.
２．樹脂被覆金属板の作成
得られた缶胴用および缶蓋用表面処理金属板を予め板温度２５０℃に加熱しておき、片面上に表３のｅのキャストフィルムの下層側が接して被覆され、外面側となるもう一方の片面上に表３のｄのキャストフィルムが被覆されるように、ラミネートロールを介して熱圧着後、直ちに水冷することにより、樹脂被覆金属板を得た。
2. Preparation of resin-coated metal plate The surface-treated metal plate for can body and can lid obtained in advance was heated to a plate temperature of 250 ° C., and the lower layer side of the cast film of e in Table 3 was covered on one side and coated, A resin-coated metal plate was obtained by immediately water-cooling after thermocompression bonding through a laminating roll so that the cast film of d in Table 3 was coated on the other side of the outer surface side.
３．缶胴および缶蓋の作成
缶胴用樹脂被覆金属板の両面にパラフィンワックスを静電塗油後、直径１４０ｍｍの円形に打抜き、定法に従い浅絞りカップを作成した。ついでこの絞りカップを再絞り・しごき加工を２回繰り返して径が小さくハイトの大きい、絞りーしごきカップを得た。この様にして得られたカップの諸特性は以下の通りであった。
カップ径 ５２ｍｍ、
カップ高さ １３８ｍｍ、
元板厚に対する缶壁部の厚み −５０％
このカップはドーミング成形後、樹脂フィルムの歪みをとるために２２０℃で６０秒間熱処理を行い、続いて開口端端部のトリミング加工、曲面印刷、２００径へネックイン加工、フランジ加工を行って２５０ｇシームレス缶を作成した。
また、缶蓋用樹脂被覆金属板から定法に従い、２００径のＳＯＴ蓋を作成した。
3. Preparation of Can Cylinder and Can Lid Paraffin wax was electrostatically applied to both sides of the resin-coated metal plate for the can cylinder, and then punched into a circle having a diameter of 140 mm, and a shallow drawn cup was prepared according to a conventional method. Then, the drawn cup was redrawn and ironed twice to obtain a drawn and ironed cup having a small diameter and a large height. Various characteristics of the cup thus obtained were as follows.
Cup diameter 52mm,
Cup height 138mm,
-50% of can wall thickness with respect to original plate thickness
This cup is heat treated at 220 ° C. for 60 seconds after doming, and then trimmed at the end of the opening, curved surface printing, neck-in to 200 diameters, flanged, 250 g A seamless can was created.
In addition, a 200-diameter SOT lid was prepared from a resin-coated metal plate for can lids according to a conventional method.
４．内容品充填試験
前記２５０ｇ缶に５℃でコーラをコールドパックし、直ちに、前記ＳＯＴ蓋を２重巻締めして密封した。
4). Content product filling test Cola was cold packed in the 250 g can at 5 ° C., and the SOT lid was immediately wound twice and sealed.
５．表面処理金属板の評価
実施例１３と同様に、Ｚr膜厚測定、表面原子比の測定を実施した。
5). Evaluation of surface-treated metal plate In the same manner as in Example 13, measurement of the Zr film thickness and measurement of the surface atomic ratio were performed.
６．容器評価
実施例１５と同様に容器評価を実施した。
6). Container evaluation Container evaluation was carried out in the same manner as in Example 15.
（実施例１８）
１．表面処理金属板および樹脂被覆金属板の作成
缶胴用金属板として厚み０．２８ｍｍのＪＩＳ３００４Ｈ１９アルミ合金板を、缶蓋用金属板として厚み０．２５ｍｍのＪＩＳ５１８２Ｈ１９アルミ合金板を用いて、両面に表３のａのキャストフィルムを被覆した以外は、実施例１と同様にして、前処理、表面処理、樹脂被覆を行った。
得られた缶胴用樹脂被覆金属板の両面に、パラフィンワックスを両面に静電塗油後、直径１６６ｍｍの円形に打抜き、定法に従い、浅絞りカップを作成した。次いで、この浅絞りカップを、再絞り−しごき加工を行い、絞り−しごき加工により缶体を得た。この様にして得られた缶体の諸特性は以下の通りであった。
缶体径 ６６ｍｍ、
缶体高さ １２８ｍｍ、
元板厚に対する缶壁部の厚み −６３％
この缶体を、定法に従い、ドーミング成形後、樹脂フィルムの歪みをとるために２２０℃で６０秒間熱処理を行い、続いて開口端端部のトリミング加工、曲面印刷、２０６径へネックイン加工、フランジ加工を行って３５０ｇシームレス缶を作成した。
一方、缶蓋用樹脂被覆金属板から定法に従い、２０６径のＳＯＴ蓋を作成した。
(Example 18)
1. Preparation of surface-treated metal plate and resin-coated metal plate Using a JIS3004H19 aluminum alloy plate with a thickness of 0.28 mm as a metal plate for a can body and a JIS5182H19 aluminum alloy plate with a thickness of 0.25 mm as a metal plate for a can lid, Pretreatment, surface treatment, and resin coating were performed in the same manner as in Example 1 except that the cast film of 3a was coated.
A paraffin wax was electrostatically applied to both sides of the obtained resin-coated metal plate for can barrels, and then punched into a circular shape with a diameter of 166 mm, and a shallow drawn cup was prepared according to a conventional method. Subsequently, this shallow drawn cup was redrawn and ironed, and a can body was obtained by drawing and ironing. Various characteristics of the can thus obtained were as follows.
Can body diameter 66mm,
Can body height 128mm,
The thickness of the can wall relative to the original plate thickness -63%
This can body was subjected to heat treatment at 220 ° C. for 60 seconds in order to remove the distortion of the resin film after doming according to a conventional method, followed by trimming of the end of the opening, curved surface printing, neck-in to 206 diameters, flange Processing was performed to prepare a 350 g seamless can.
On the other hand, a 206-diameter SOT lid was prepared from a resin-coated metal plate for can lids according to a conventional method.
２．内容品充填試験
前記３５０ｇ缶に５℃でビールをコールドパック後、前記ＳＯＴ蓋を２重巻締めして密封した。
2. Content Product Filling Test After cold-packing beer into the 350 g can at 5 ° C., the SOT lid was double wrapped and sealed.
３．表面処理金属板の評価
実施例１３と同様に、Ｚr膜厚測定、表面原子比の測定を実施した。
3. Evaluation of surface-treated metal plate In the same manner as in Example 13, measurement of the Zr film thickness and measurement of the surface atomic ratio were performed.
４．容器評価
開缶後のアルミ溶出量も測定した以外は、実施例１３と同様に容器評価を実施した。
4). Container evaluation Container evaluation was carried out in the same manner as in Example 13 except that the aluminum elution amount after opening the can was also measured.
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