JP3850253B2 - Aluminum substrate treatment material with excellent coating adhesion and corrosion resistance - Google Patents
Aluminum substrate treatment material with excellent coating adhesion and corrosion resistance Download PDFInfo
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- JP3850253B2 JP3850253B2 JP2001316776A JP2001316776A JP3850253B2 JP 3850253 B2 JP3850253 B2 JP 3850253B2 JP 2001316776 A JP2001316776 A JP 2001316776A JP 2001316776 A JP2001316776 A JP 2001316776A JP 3850253 B2 JP3850253 B2 JP 3850253B2
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
Description
【０００１】
【発明が属する技術分野】
本発明は、飲料缶や食缶の缶蓋用アルミニウム塗装下地処理材および缶蓋用アルミニウム塗装材に関する。特に、クロメート皮膜、ジルコニウム皮膜等の化成下地処理を行わずに樹脂皮膜を塗装した缶蓋用アルミニウム塗装材に関する。
【０００２】
【従来の技術】
アルミニウム材は軽量で、適度な機械的特性を有し、かつ美感、成形加工性、耐食性等に優れた特徴を有しているため、各種容器類等に広く使われている。例えば、食品のアルミニウム等容器は、アルミニウムの優れた成形加工性を利用して、樹脂塗装を行った後絞り加工する方法等により成形されている。
その場合、成形加工を受けてもアルミニウム表面と樹脂塗装との間の密着性を優れたものとするために、アルミニウム表面に密着性向上効果の大きい下地皮膜を予め施しておくことが一般的に行われている。
このため従来は、リン酸、クロム酸およびフッ酸を主成分とする化成処理液でアルミニウム材を処理する「クロメート処理」が施されてきた。例えば特開平３−１７７５８０号には下地皮膜としてクロム付着量を７〜２５ｍｇ／ｍ2としたリン酸クロメート皮膜層を設けた樹脂塗装材が提案されている。このようなクロメート処理は、製造工程管理が容易でコストが安く、しかも性能が安定するため、広く用いられてきた。
【０００３】
【発明が解決しようとする課題】
しかし近年、環境汚染、環境破壊、健康に対する安全性、エネルギー需給等への関心が急激に高まっている。
リン酸クロメート皮膜自体から有害な６価クロム等が溶出することは無く、リン酸クロメート皮膜自体が環境汚染や健康被害をまねくことは無いとされている。しかし、その製造工程では、無水クロム酸等の有害な６価クロムを含有する化成液を使っており、化成液廃液およびリンス工程で発生する６価クロムを含有する排水等を処理し、無害化しなければならない。このような処理には多大な人力およびエネルギー、高価な廃液処理設備等を必要とするため、製品のコストアップが避けられない。近年は規制が益々強化される方向にあり、廃液処理によるコストは従来以上に高まる傾向にある。
【０００４】
このような課題を克服するために、クロム等の有害な金属イオンを含まない化成処理液を塗布またはスプレー等でアルミニウム材表面に付着させた、いわゆるノンクロメート皮膜と言われる下地処理アルミニウム材が提案されている。
特開平１０−３１７１６２号にはリン酸またはその塩、ジルコニウム塩、フッ化物、亜リン酸またはその塩、硝酸またはその塩を含む表面処理浴で処理する方法、また特公平７−８４６６５号にはリン酸イオン、アルミニウムキレート化剤および界面活性剤を含むアルカリ脱脂剤で洗浄処理後、ジルコニウムイオン、リン酸イオンおよびフッ素イオンを含む化成処理剤で処理し、ジルコニウムを含む下地処理皮膜を形成する方法、あるいはさらにバナジウムイオンを含む化成処理液で処理して、ジルコニウムおよびバナジウムを含む下地処理皮膜を形成する方法、特開平７−３１０１８９号にはリン酸イオン、ジルコニウム化合物、フッ化物および酸化剤を含む処理液で処理する方法等が開示されている。
これらの処理液は有害な６価クロムを含まないことから、環境汚染や健康被害といった問題が著しく軽減されている。しかし、これらの皮膜は成形加工後の塗膜密着性やレトルト処理といった苛酷な条件下での耐食性に問題を残しており、リン酸クロメート皮膜の性能レベルに達していない。
【０００５】
このような性能上の問題を解決するために、特開平７−３３１２７６号にはリン酸イオン、ジルコニウム化合物またはチタン化合物、フッ化物および水溶性ポリアミドを含有する処理液で処理する方法、特開平１１−１１５０９８にはリン酸イオン、縮合リン酸イオンおよびフェノール系水溶性重合体からなる表面被覆層を設ける方法等、いわゆる有機−無機複合タイプの化成処理剤が、特開平１０−４６１０１号にはフェノール、ナフトールまたはビスフェノール−ホルムアルデヒド樹脂からなる被覆層を設けるといった有機皮膜タイプの下地処理層を設ける方法が開示されている。
これらによれば加工後の密着性は高まり、酸性の液に対する耐食性も向上するなど性能上の向上が認められる場合がある。しかし、下地処理皮膜中に樹脂を含むため、下地処理皮膜上に塗布する樹脂の種類によっては相性が悪い場合が生じ、塗工時にハジキを生じたり、所定の性能が出ない等の不具合が起こることがある。その上、廃液処理の際に、一旦金属成分と有機物とを予め分離することが必要で、さらに分離した有機物をＢＯＤ処理等で別途処理しなければならないため、工程が増し、廃液処理コストが増加する。
特開平４−２３１１２０号には１００〜２０００Åのリン酸または硫酸陽極酸化皮膜を設けた下地処理材が提案されている。しかし、この方法では電力を必要とするために設備のイニシャルコストおよびランニングコストが高いので、製品に求められている低コスト要求に応えられない。
【０００６】
ところで、アルミニウム板表面には圧延油等の有機物が付着している。そのため、上記の各種下地処理を施す際には、前処理として、アルカリ性液体による脱脂・エッチング工程、さらには酸洗等も付加して表面の汚れを除去する操作を行う。この前処理が不十分または不適切であると、アルミニウム板表面に多量の有機物層が残留したまま下地処理を施すことになる。
このような下地では、ときに有機物層が下地最表面に濃縮するため、近年急速に普及してきた水性塗料を塗装する場合、塗工時のハジキおよび密着性不良をまねく危険性が高い。
こうした事実から、水性塗料を用いる際は表面の有機物を極力減らすのが良い、との認識は公知であった。しかし一方で、工業的なスケールにおいて有機物層を完全に除去することは、コスト面で不可能であるため、有機物残存量の実際的な妥協点を見出す必要があった。
【０００７】
以上のような事情から、Ｃｒ等の有害重金属を含まず、塗料の塗膜密着性、耐食性および耐ハジキ性に優れ、なおかつ低コストで製造できる飲料缶または食缶用のアルミニウム蓋材が強く求められていた。
【０００８】
【課題を解決するための手段】
発明者らは上記課題を解決すべく、クロメート皮膜、ジルコニウム皮膜等の化成下地処理を行わず、アルミニウム酸化皮膜に直接塗装する方法の検討を続けた。その結果、アルミニウム酸化皮膜の厚みおよび構成成分を的確に制御し、かつその最表面を管理することによって、必ずしも重金属を含む化成皮膜を付与しなくとも、優れた材料を提供できることを突きとめた。
すなわち、表面に厚さ＝１〜２００ｎｍで、かつ最表面〜酸化皮膜／アルミ界面までの深さ方向での最大濃度がＭｇで５ｍａｓｓ％以下かつＨで１０ｍａｓｓ％以下である、ＡｌおよびＯを主成分とする酸化皮膜を設けることにより、優れた表面処理材が得られることを見出した。
請求項２の発明は、さらに最表面の炭素濃度を規定したものである。
請求項３の発明は、これらの上に樹脂皮膜を設けたものである。
請求項４、５は請求項１、２に関する製造方法である。
より具体的には、請求項１の発明は表面に厚さ＝１〜２００ｎｍで、かつ最表面から酸化皮膜／アルミ界面までの深さ方向での最大濃度がＭｇ：５ｍａｓｓ％以下、Ｈ：１０ｍａｓｓ％以下のＡｌおよびＯを主成分とする酸化皮膜を設けたことを特徴とする塗膜密着性および耐食性に優れた缶蓋用アルミニウム下地処理材である。
また請求項２の発明は、表面に厚さ＝１〜２００ｎｍで、かつ最表面から酸化皮膜／アルミ界面までの深さ方向での最大濃度がＭｇ：５ｍａｓｓ％以下、Ｈ：１０ｍａｓｓ％以下、かつ最表面のＣ濃度が５０ｍａｓｓ％以下のＡｌおよびＯを主成分とする酸化皮膜を設けたことを特徴とする水性塗料の塗膜密着性、耐食性および耐ハジキ性に優れた缶蓋用アルミニウム下地処理材である。
さらに請求項３の発明は、請求項１または２のアルミニウム下地処理材の表面に、エポキシ、ポリエステル、塩化ビニルの少なくとも１種を含む樹脂皮膜を設けたことを特徴とする塗膜密着性および耐食性に優れた缶蓋用アルミニウム塗装材である。
また請求項４の発明は、アルミニウム材に対し、エッチング量が５０〜２００ｍｇ／ｍ2のアルカリ脱脂を行った後、ｐＨが４．０以下かつＡｌイオン濃度、Ｍｇイオン濃度がそれぞれ１ｍａｓｓ％以下の酸で酸洗浄を行うことを特徴とする請求項１のアルミニウム下地処理材の製造方法である。
また請求項５の発明は、アルミニウム材に対し、エッチング量が５０〜２００ｍｇ／ｍ2かつ脱脂浴の油分が３ｍａｓｓ％以下のアルカリ脱脂を行った後、ｐＨが４．０以下かつＡｌイオン濃度，Ｍｇイオン濃度がそれぞれ１ｍａｓｓ％以下，油分が３ｍａｓｓ％以下の酸洗浴で酸洗浄を行うことを特徴とする請求項２のアルミニウム下地処理材の製造方法である。
【０００９】
【発明の実施の形態】
缶用塗装材の母材には、機械的強度、加工性を満足させるために２〜５ｍａｓｓ％程度のＭｇを添加したアルミニウム合金（ＪＩＳ−５０２１、５０５２、５０８２、５１８２等）が使われており、これらの材料は、加熱−圧延時にアルミニウム材マトリクス中のＭｇが表面に偏析濃化することが知られている。そして従来、その酸化皮膜構造は、最表面にＭｇ酸化物層があり、その下にアルミニウム酸化物層があるという２層構造モデルで示されていた。そして、Ｃ（炭素）の分布状態に関する考察はほとんどなされてこなかった。
発明者らはＧＤＳ（グロー放電発光スペクトル）、オージェといった解析機器を用い、酸化皮膜の深さ方向の元素分布、いわゆるデプスプロファイルを詳細に調査した。その結果、各元素は酸化皮膜全体に均一に存在するのではなく、また明確な二層を形成しているのでもなく、各元素ごとの濃度分布が異なることを確認した。
なお、測定対象とした元素は、Ｈ，Ｃ，Ｏ，Ｍｇ，Ａｌ，Ｍｎ，Ｓｉ，Ｆｅ，Ｚｎ，ＣｒおよびＺｒであり、以後、各元素のｍａｓｓ％は、この１１元素を母集団として議論するが、これらはアルミニウム材表面のほとんど全てを網羅していると考えられるため、議論の一般性を何ら損なうものではない。また、その深さ方向の測定精度は１ｎｍの精度が十分に保証されるものである。
【００１０】
Ｍｇは酸化皮膜全体に均一に存在するわけではなく、また従来の２層構造モデルで示されるような明確な層を形成しておらず、最表面よりやや深い部位が最も濃化した濃度勾配を有して分布している。
この時、最表面〜酸化皮膜／アルミ界面までの深さ方向でのＭｇの最大濃度が５ｍａｓｓ％以下となるよう調製した酸化皮膜は、缶用塗料の塗膜とアルミニウム材の塗膜密着性、特に、板厚減少を伴う強加工後の塗膜密着性が十分高いのに対し、最大濃度が５ｍａｓｓ％を超えていると、加工後の塗膜密着性が著しく低下することを見出した。
その理由として、Ｍｇ化合物は純粋なアルミ酸化膜との親和性に乏しく、Ｍｇ化合物／アルミ酸化膜の界面から塗膜剥離しやすいためと考えられる。また、Ｍｇ化合物は水への溶解度が高いので、多量に存在すると耐食性をも低下させる。そしてそれらの悪影響は、深さ方向でのＭｇの最大濃度が５ｍａｓｓ％を超えた時に顕著に現れる。
【００１１】
また、主に水酸化物に由来するＨ（水素）も、Ｍｇと同様に深さ方向に傾斜構造を有していた。そして、最表面〜酸化皮膜／アルミ界面までの深さ方向での最大濃度が１０ｍａｓｓ％以下となるよう調製した時、塗料の塗膜とアルミニウム材の加工後の塗膜密着性が十分高いのに対し、最大濃度が１０ｍａｓｓ％を超えていると、加工後の塗膜密着性が低下することを見出した。
その理由として、Ｈを含む化合物（水酸化Ａｌ，水酸化Ｍｇ，他）はもろいので、缶蓋のような強加工を行うと、Ｈを含む化合物を起点にして酸化皮膜が破壊されるためと考えられる。そしてその悪影響は、Ｈの最大濃度が１０ｍａｓｓ％を超えた時に顕著に現れる。
なお、上記のＭｇとＨの効果はどちらも大きいので、その最大濃度は同時に規定されるべきであり、どちらか片方を規定しただけでは十分な塗膜密着性を発揮することはできない。
【００１２】
これらに加え、有機物に由来するＣの検討を行った。発明者らの発見によれば、上記の酸化皮膜におけるＣは、例外なく皮膜最表面において最大値を示したのであるが、このＣ濃度が５０ｍａｓｓ％以下であれば、水性塗料に対し良好な耐ハジキ性および塗膜密着性が発揮される。一方、皮膜最表面のＣ濃度が５０ｍａｓｓ％を超えると、表面有機物が水性塗料をはじいてしまったり、仮に塗布できたとしても塗膜密着性を急激に低下させてしまう。
これは、ＭｇおよびＨを規定した酸化皮膜の好影響と、表面残存有機物の悪影響が相殺し合う領域が、Ｃ濃度に換算して５０ｍａｓｓ％であるためと考えられる。
【００１３】
以上のように、ＭｇおよびＨ濃度をそれぞれ規定した酸化皮膜をアルミニウム材表面に形成することにより、ＣｒやＺｒといった重金属を含む下地処理皮膜を付与しなくとも、優れた塗膜密着性および耐食性が得られる。
また、水性塗料等の耐ハジキ性が要求される場合は、さらにＣ濃度を規制することにより良好な性能が得られる。
【００１４】
なお、この酸化皮膜全体の厚みは１〜２００ｎｍが良い。１ｎｍ未満では酸化皮膜が少量のため、むき出しのアルミニウム表面が出現するなどで、塗膜密着性および耐食性が十分に発揮されない。一方、２００ｎｍを超えると、酸化皮膜が多量のためもろくなり、コイル巻取りなどの材料変形や蓋加工などの強い加工に耐えられず、酸化皮膜自身の微小なひび割れ（マイクロクラック）を引き起こし、やはり塗膜密着性が低下する。
【００１５】
これらの発明の範囲を図示すると、図１のとおりである。
【００１６】
ところで、請求項１を満たす酸化皮膜を得るには、一例として、エッチング量が５０〜２００ｍｇ／ｍ2のアルカリ脱脂を行った後、ｐＨが４．０以下かつＡｌ，Ｍｇイオン濃度がそれぞれ１ｍａｓｓ％以下の酸（コスト面から希硫酸が使いやすい）にて酸洗浄を行う方法を挙げることができる。
アルカリ脱脂によるエッチング量が５０ｍｇ／ｍ2では均質な酸化皮膜が形成されず、２００ｍｇ／ｍ2を超えるとアルミニウム板厚の精度に悪影響を及ぼす。また、酸洗がＭｇの低減に寄与することは、主に自動車用アルミニウム材の分野において公知であるが、ｐＨが４．０を超えるとその効果が半減する。さらに本発明の特徴である酸化皮膜中のＭｇおよびＨ濃度の規定にあたって、酸洗浴中のＡｌイオン濃度が１ｍａｓｓ％を超えると表面に水酸化Ａｌ等が残存するのでＨが、Ｍｇイオン濃度が１ｍａｓｓ％を超えると表面にＭｇ化合物が析出するのでＭｇが、それぞれ酸化皮膜中に濃縮するので好ましくない。
【００１７】
加えて、請求項２を満足させるためには、さらにアルカリ脱脂浴および酸洗浴の油分を３ｍａｓｓ％以下に制御すればよい。これは、いずれの浴の油分も表面に残存しやすく、酸化皮膜最表面のＣに影響を及ぼすためであり、油分が３ｍａｓｓ％を超えると、Ｃが急激に増加するため好ましくない。
【００１８】
もちろん、これ以外の方法で得られた酸化皮膜でも、請求項１または２さえ満たしていれば、本発明の好ましい効果を享受できるのは当然である。
この酸化皮膜の上に、エポキシ、ポリエステル、塩ビの少なくとも１種を含む樹脂皮膜を上塗りすると、その優れた塗膜密着性により高い耐食性を有し、さらに塗装ハジキによる品質不良を低減させた飲料缶または食缶用のアルミニウム蓋材を低コストで得ることができる。
【００１９】
【実施例】
以下、実験例に基づいて、本発明の好適な実施の形態を具体的に説明する。
表１に示した各合金を常法によりアルカリ脱脂（エッチング量＝約１００ｍｇ／ｍ2）した後、表１に示す成分からなる５０℃の１％硫酸酸洗浴に５秒間浸漬し、常温の純水にて５秒間洗浄し、表１に示す乾燥条件で乾燥させ、直ちに塗料を塗布・焼付した。酸洗浴は操業状態を再現するため、１％硫酸にＡｌ−Ｍｇ系アルミニウム板を多数回浸漬して浴中の各イオン濃度を調整し、また圧延油を添加して油分の調整した。
なお、従来例は現在広く用いられているリン酸クロメート処理の例で、アルカリ脱脂した後に常法によりリン酸クロメート処理（Ｃｒ付着量＝２０ｍｇ／ｍ2）したものである。
また塗料は、エポキシ樹脂を主成分とする水性塗料を塗布量＝７ｇ／ｍ2、乾燥温度２５０℃で塗布・焼付［水性］、または塩化ビニル樹脂を主成分とする溶剤塗料を塗布量＝７ｇ／ｍ2、乾燥温度２６０℃で塗布・焼付［塩ビ］した。
また、塗装前の表面をＧＤＳで測定した結果を表２に示す。
【００２０】
【表１】
【表２】
これらのサンプルに対し、以下のような評価試験を実施した。
[塗料ハジキ] 塗料焼付後、塗料ハジキに由来する塗装ヌケの個数を計数した。
[塗装まま密着性試験] 試験片に対し、ＪＩＳ−Ｋ５４００に準拠した１ｍｍ角碁盤目試験を行った。
[レトルト密着性試験] 加圧滅菌装置により、試験片を水道水中にて１２５℃×３０分保持した後、ＪＩＳ−Ｋ５４００に準拠した１ｍｍ角碁盤目試験を行った。
[３０％圧延密着性試験] 圧延機により、３０％の板厚減少となるまで圧延加工した後、ＪＩＳ−Ｋ５４００に準拠した１ｍｍ角碁盤目試験を行った。
[モデルジュース耐食性試験] 試験片に×型の切り込み（各辺の長さ４０ｍｍ）を入れ、１．０ｍａｓｓ％クエン酸一水和物＋０．５ｍａｓｓ％塩化ナトリウムの水溶液に７０℃×７２時間浸漬し、腐食の発生度合いを評価した。（◎：腐食なし，○：切り込みの一部に１ｍｍ以下の腐食，△：切り込みの一部に１〜２ｍｍの腐食，△×：切り込み全面に１〜２ｍｍの腐食，×：切り込み全面に２ｍｍ以上の腐食）
【００２３】
【表３】
表３から明らかなように、本発明条件を満足する発明例１は塗料のハジキがなく耐ハジキ性に優れ、また塗装後だけでなくレトルト処理を施しても圧延加工を施しても塗膜の剥離が皆無であり優れた塗膜密着性を示すとともに耐食性でも従来のクロメート処理材と同等以上の良好な性能を示しており、各評価試験とも優秀な結果となっている。
また、発明例２は発明例１の合金を代えたもの、発明例３は洗浄後の乾燥温度を低くして、常温の強風にて３秒間行ったもの、発明例４は洗浄後の乾燥温度を高くして、３５０℃の熱風で１分間乾燥させたものであるが、これらの板表面は表２にしめすように本発明条件を満たすもので、いずれも優秀な評価結果となっている。
これに対して、比較例１はアルカリ脱脂後に酸洗を行わずに、常温の純水にて５秒間洗浄したもの、比較例２はＡｌ％，Ｍｇ％が本願発明の範囲を超えた酸洗浴を用いたもの、比較例３は洗浄後の乾燥を３５０℃の熱風で６０分間の高温長時間条件で乾燥させたものであるが、これらは請求項１を満たさず、いずれも塗装したままでは剥離は無いものの、レトルト処理を行ったり、加工を施した場合には剥離が生じており、塗膜密着性および耐食性が劣る結果となっている。
また、発明例５は酸洗浴に圧延油１ｍａｓｓ％を追加して油分の多い浴を用いたもの、発明例６は酸洗浴に圧延油５ｍａｓｓ％を追加して、油分のさらに高い浴を用いたもの、比較例４は乾燥までは発明例６と同じ条件だが、塩ビ系塗料の代わりに水性塗料を用いたものである。発明例５は請求項２の条件を満たし、水性塗料でも良好な結果となっているが、発明例６および比較例４は同じ酸化皮膜であるが、塩ビ系塗料では良好な結果となるが請求項２の条件を満たさないため水性塗料に対してはやや劣る結果となっている。従って水性塗料を用いる場合には請求項２の条件を満たすようにすると良い。
なお、従来例は現在広く用いられているリン酸クロメート処理の例で、アルカリ脱脂した後に常法によりリン酸クロメート処理（Ｃｒ付着量＝２０ｍｇ／ｍ2）し、その上にエポキシ樹脂を主成分とする水性塗料を塗布・焼付したものである。
発明例１〜６は３０％圧延密着性試験において従来例を上回り、本発明の効果の高さが証明された。また、発明例１〜６は当然Ｃｒを使用しておらず、環境破壊や健康被害の観点からも優位性は明確である。
【００２５】
【発明の効果】
以上のように、本発明によれば従来行われてきたクロメート処理を行う必要がなく、現行の化成クロメートと同等以上の塗膜密着性、耐食性および耐ハジキ性を持ち、Ｃｒ等の有害重金属を含まない飲料缶・食缶用のアルミニウム蓋材を提供することができる。
【図面の簡単な説明】
【図１】本発明の元素の分布を示す模式図である。
【符号の説明】
Ｍｇ マグネシウム濃度
Ｈ 水素濃度
Ｃ 炭素濃度[0001]
[Technical field to which the invention belongs]
The present invention relates to an aluminum coating surface treatment material for can lids of beverage cans and food cans and an aluminum coating material for can lids. In particular, the present invention relates to an aluminum coating material for a can lid in which a resin film is coated without performing a chemical conversion base treatment such as a chromate film or a zirconium film.
[0002]
[Prior art]
Aluminum materials are lightweight, have appropriate mechanical properties, and have excellent characteristics such as aesthetics, moldability, and corrosion resistance, and are therefore widely used in various containers. For example, food containers made of aluminum or the like are molded by a method of drawing after resin coating using the excellent moldability of aluminum.
In that case, in order to improve the adhesion between the aluminum surface and the resin coating even after being subjected to molding, it is generally applied in advance to the aluminum surface with a base film having a large effect of improving adhesion. Has been done.
For this reason, conventionally, “chromate treatment” in which an aluminum material is treated with a chemical conversion treatment liquid containing phosphoric acid, chromic acid and hydrofluoric acid as main components has been performed. For example, Japanese Patent Application Laid-Open No. 3-177580 proposes a resin coating material provided with a phosphate chromate film layer having a chromium adhesion amount of 7 to 25 mg / m 2 as a base film. Such chromate treatment has been widely used because manufacturing process management is easy, cost is low, and performance is stable.
[0003]
[Problems to be solved by the invention]
However, in recent years, interest in environmental pollution, environmental destruction, health safety, energy supply and demand, etc. has increased rapidly.
It is said that no harmful hexavalent chromium or the like is eluted from the phosphate chromate film itself, and the phosphate chromate film itself does not cause environmental pollution or health damage. However, in the manufacturing process, chemical conversion liquid containing harmful hexavalent chromium such as chromic anhydride is used, and wastewater containing hexavalent chromium generated in the chemical conversion liquid waste liquid and rinsing process is treated and rendered harmless. There must be. Such treatment requires a great deal of manpower and energy, expensive waste liquid treatment equipment, and the like, and thus the cost of the product cannot be avoided. In recent years, regulations are increasingly tightened, and the cost of waste liquid treatment tends to be higher than before.
[0004]
In order to overcome these problems, a so-called non-chromate coating called a non-chromate film is proposed, in which a chemical conversion treatment solution that does not contain harmful metal ions such as chromium is applied or sprayed to the surface of the aluminum material. Has been.
Japanese Patent Laid-Open No. 10-317162 discloses a method of treating with a surface treatment bath containing phosphoric acid or a salt thereof, zirconium salt, fluoride, phosphorous acid or a salt thereof, nitric acid or a salt thereof, and Japanese Patent Publication No. 7-84665. A method of forming an undercoat film containing zirconium after washing with an alkaline degreasing agent containing a phosphate ion, an aluminum chelating agent and a surfactant and then treating with a chemical conversion treatment agent containing zirconium ion, phosphate ion and fluorine ion Alternatively, a method of forming a base treatment film containing zirconium and vanadium by treatment with a chemical conversion treatment solution containing vanadium ions, JP-A-7-310189 contains phosphate ions, zirconium compounds, fluorides and oxidizing agents. A method of processing with a processing liquid is disclosed.
Since these treatment liquids do not contain harmful hexavalent chromium, problems such as environmental pollution and health damage are significantly reduced. However, these coatings still have problems in corrosion resistance under severe conditions such as coating adhesion after molding and retort treatment, and have not reached the performance level of phosphate chromate coatings.
[0005]
In order to solve such performance problems, Japanese Patent Application Laid-Open No. 7-33276 discloses a method of treating with a treatment liquid containing phosphate ions, zirconium compound or titanium compound, fluoride and water-soluble polyamide. No.-115098 discloses a so-called organic-inorganic composite type chemical conversion treatment agent such as a method of providing a surface coating layer comprising phosphate ions, condensed phosphate ions and a phenolic water-soluble polymer. A method of providing an organic film type ground treatment layer such as providing a coating layer made of naphthol or bisphenol-formaldehyde resin is disclosed.
According to these, there is a case where improvement in performance such as adhesion after processing is enhanced and corrosion resistance against an acidic liquid is improved. However, since the base treatment film contains a resin, depending on the type of resin applied on the base treatment film, the compatibility may be poor, causing problems such as repellency during coating or failure to achieve the prescribed performance. Sometimes. In addition, it is necessary to separate the metal component from the organic matter in advance during waste liquid treatment, and the separated organic matter must be separately treated by BOD treatment, etc., which increases the number of processes and waste liquid treatment costs. To do.
JP-A-4-231120 proposes a base treatment material provided with a phosphoric acid or sulfuric acid anodized film having a thickness of 100 to 2000 mm. However, since this method requires electric power, the initial cost and running cost of the equipment are high, so it cannot meet the low-cost requirements for products.
[0006]
By the way, organic matter such as rolling oil adheres to the aluminum plate surface. Therefore, when performing the above-mentioned various base treatments, as a pre-treatment, an operation of removing the dirt on the surface by adding a degreasing / etching step with an alkaline liquid and further pickling is performed. If this pretreatment is insufficient or inappropriate, the base treatment is performed with a large amount of organic material layer remaining on the surface of the aluminum plate.
In such a base, the organic layer sometimes concentrates on the outermost surface of the base, and therefore, when applying a water-based paint that has been rapidly spreading in recent years, there is a high risk of causing repelling and poor adhesion during coating.
From these facts, it has been known that when using a water-based paint, it is better to reduce the surface organic matter as much as possible. However, on the other hand, since it is impossible in terms of cost to completely remove the organic layer on an industrial scale, it is necessary to find a practical compromise of the remaining amount of organic matter.
[0007]
For these reasons, there is a strong demand for aluminum cans for beverage cans or food cans that do not contain harmful heavy metals such as Cr, have excellent paint film adhesion, corrosion resistance, and repellency, and can be manufactured at low cost. It was done.
[0008]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the inventors have continued to study a method of directly coating an aluminum oxide film without performing a chemical conversion base treatment such as a chromate film or a zirconium film. As a result, it has been found that an excellent material can be provided by accurately controlling the thickness and components of the aluminum oxide film and managing its outermost surface without necessarily providing a chemical conversion film containing heavy metals.
That is, mainly Al and O having a thickness of 1 to 200 nm on the surface and a maximum concentration in the depth direction from the outermost surface to the oxide film / aluminum interface are 5 mass% or less for Mg and 10 mass% or less for H. It has been found that an excellent surface treatment material can be obtained by providing an oxide film as a component.
The invention of claim 2 further defines the carbon concentration on the outermost surface.
In the invention of claim 3, a resin film is provided on these.
Claims 4 and 5 are manufacturing methods according to claims 1 and 2.
More specifically, the invention of claim 1 has a thickness of 1 to 200 nm on the surface, and the maximum concentration in the depth direction from the outermost surface to the oxide film / aluminum interface is Mg: 5 mass% or less, H: 10 mass. It is an aluminum base treatment material for can lids excellent in coating film adhesion and corrosion resistance, characterized by providing an oxide film containing Al and O as a main component in an amount of 1% or less.
In the invention of claim 2, the thickness is 1 to 200 nm on the surface, and the maximum concentration in the depth direction from the outermost surface to the oxide film / aluminum interface is Mg: 5 mass% or less, H: 10 mass% or less, and Aluminum base treatment for can lids with excellent coating adhesion, corrosion resistance and repellency resistance of water-based paints, characterized by providing an oxide film mainly composed of Al and O having a C concentration of 50 mass% or less on the outermost surface It is a material.
Further, the invention according to claim 3 is characterized in that a coating film having at least one of epoxy, polyester, and vinyl chloride is provided on the surface of the aluminum base treatment material according to claim 1 or 2, and adhesion and corrosion resistance are provided. It is an excellent aluminum coating material for can lids.
According to the invention of claim 4, after alkaline degreasing with an etching amount of 50 to 200 mg / m 2 is performed on an aluminum material, the pH is 4.0 or less, and the Al ion concentration and the Mg ion concentration are each 1 mass% or less. 2. The method for producing an aluminum base treatment material according to claim 1, wherein acid cleaning is performed with an acid.
Further, the invention of claim 5 is that the aluminum material is subjected to alkali degreasing with an etching amount of 50 to 200 mg / m 2 and an oil content of the degreasing bath of 3 mass% or less, and then the pH is 4.0 or less and the Al ion concentration, The method for producing an aluminum base treatment material according to claim 2, wherein the acid cleaning is performed in a pickling bath having an Mg ion concentration of 1 mass% or less and an oil content of 3 mass% or less.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
As a base material for can coating materials, aluminum alloys (JIS-5021, 5052, 5082, 5182, etc.) added with Mg of about 2-5 mass% are used to satisfy mechanical strength and workability. These materials are known to cause segregation and concentration of Mg in the aluminum matrix on the surface during heating and rolling. Conventionally, the oxide film structure has been shown by a two-layer structure model in which an Mg oxide layer is present on the outermost surface and an aluminum oxide layer is present below the Mg oxide layer. And the consideration regarding the distribution state of C (carbon) has hardly been made.
The inventors investigated in detail the element distribution in the depth direction of the oxide film, so-called depth profile, using analytical equipment such as GDS (glow discharge emission spectrum) and Auger. As a result, it was confirmed that each element does not exist uniformly in the entire oxide film and does not form a clear two-layer, and the concentration distribution for each element is different.
The elements to be measured are H, C, O, Mg, Al, Mn, Si, Fe, Zn, Cr, and Zr. Hereinafter, the mass% of each element will be discussed based on the 11 elements as a population. However, these are considered to cover almost all the surface of the aluminum material, so that the generality of the discussion is not impaired. Further, the measurement accuracy in the depth direction is sufficiently guaranteed to be 1 nm.
[0010]
Mg does not exist uniformly throughout the oxide film, and does not form a clear layer as shown in the conventional two-layer structure model. Have distributed.
At this time, the oxide film prepared so that the maximum concentration of Mg in the depth direction from the outermost surface to the oxide film / aluminum interface is 5 mass% or less is the coating film adhesion of the paint for cans and the coating film of the aluminum material, In particular, it was found that the coating film adhesion after strong processing accompanied by a reduction in the plate thickness is sufficiently high, whereas if the maximum concentration exceeds 5 mass%, the coating film adhesion after processing is significantly reduced.
The reason is considered that the Mg compound has poor affinity with a pure aluminum oxide film, and the coating film is easily peeled off from the interface of the Mg compound / aluminum oxide film. Moreover, since the Mg compound has high solubility in water, if it is present in a large amount, the corrosion resistance is also lowered. These adverse effects are prominent when the maximum Mg concentration in the depth direction exceeds 5 mass%.
[0011]
Moreover, H (hydrogen) mainly derived from hydroxide also has an inclined structure in the depth direction, similar to Mg. And when the maximum concentration in the depth direction from the outermost surface to the oxide film / aluminum interface is adjusted to 10 mass% or less, the coating film of the paint and the coating film after processing of the aluminum material are sufficiently high. On the other hand, when the maximum density exceeded 10 mass%, it discovered that the coating-film adhesiveness after a process fell.
The reason for this is that compounds containing H (Al hydroxide, Mg hydroxide, etc.) are fragile, and if the strong process such as can lid is performed, the oxide film is destroyed starting from the compound containing H. Conceivable. The adverse effect is prominent when the maximum concentration of H exceeds 10 mass%.
In addition, since the effect of said Mg and H is large both, the maximum density | concentration should be prescribed | regulated simultaneously, and sufficient coating-film adhesiveness cannot be exhibited only by specifying either one.
[0012]
In addition to these, C derived from organic substances was examined. According to the discovery of the inventors, C in the above oxide film showed the maximum value on the outermost surface of the film without exception, but if this C concentration is 50 mass% or less, it has good resistance to water-based paints. The repellency and coating film adhesion are exhibited. On the other hand, when the C concentration on the outermost surface of the film exceeds 50 mass%, the surface organic matter repels the water-based paint, or even if it can be applied, the coating film adhesion is drastically reduced.
This is presumably because the region where the positive effect of the oxide film defining Mg and H and the adverse effect of the remaining organic matter on the surface cancel each other is 50 mass% in terms of C concentration.
[0013]
As described above, by forming an oxide film that defines Mg and H concentrations on the surface of an aluminum material, excellent coating film adhesion and corrosion resistance can be obtained without providing a ground treatment film containing heavy metals such as Cr and Zr. can get.
Further, when repellency resistance such as water-based paint is required, good performance can be obtained by further regulating the C concentration.
[0014]
The total thickness of the oxide film is preferably 1 to 200 nm. If the thickness is less than 1 nm, the amount of the oxide film is small, so that a bare aluminum surface appears and the coating film adhesion and corrosion resistance are not sufficiently exhibited. On the other hand, when the thickness exceeds 200 nm, the oxide film becomes fragile due to its large amount, and cannot withstand strong deformation such as material deformation such as coil winding and lid processing, causing micro cracks in the oxide film itself. Coating film adhesion is reduced.
[0015]
The scope of these inventions is illustrated in FIG.
[0016]
By the way, in order to obtain an oxide film satisfying claim 1, as an example, after performing alkali degreasing with an etching amount of 50 to 200 mg / m 2 , the pH is 4.0 or less, and the Al and Mg ion concentrations are 1 mass%, respectively. Examples of the acid cleaning method include the following acids (dilute sulfuric acid is easy to use from the viewpoint of cost).
When the etching amount by alkali degreasing is 50 mg / m 2 , a uniform oxide film is not formed, and when it exceeds 200 mg / m 2 , the accuracy of the aluminum plate thickness is adversely affected. Further, it is known that pickling contributes to the reduction of Mg mainly in the field of aluminum materials for automobiles, but when the pH exceeds 4.0, the effect is halved. Further, in defining the Mg and H concentrations in the oxide film, which is a feature of the present invention, if Al ion concentration in the pickling bath exceeds 1 mass%, Al hydroxide and the like remain on the surface, so that H and Mg ion concentration are 1 mass. If it exceeds 50%, an Mg compound is deposited on the surface, so Mg is concentrated in the oxide film.
[0017]
In addition, in order to satisfy claim 2, the oil content of the alkaline degreasing bath and the pickling bath may be further controlled to 3 mass% or less. This is because the oil content of any bath tends to remain on the surface and affects C on the outermost surface of the oxide film. If the oil content exceeds 3 mass%, C increases rapidly, which is not preferable.
[0018]
Of course, even if an oxide film obtained by a method other than this is satisfied with claim 1 or 2, it is natural that the preferred effect of the present invention can be enjoyed.
When a resin film containing at least one of epoxy, polyester, and vinyl chloride is overcoated on this oxide film, it has high corrosion resistance due to its excellent coating film adhesion, and further reduced quality defects due to paint repelling Or the aluminum lid | cover material for food cans can be obtained at low cost.
[0019]
【Example】
Hereinafter, preferred embodiments of the present invention will be specifically described based on experimental examples.
Each alloy shown in Table 1 was degreased by alkali (etching amount = about 100 mg / m 2 ) by a conventional method, and then immersed in a 50% 1% sulfuric acid pickling bath composed of the components shown in Table 1 for 5 seconds. It was washed with water for 5 seconds, dried under the drying conditions shown in Table 1, and immediately applied and baked with paint. In order to reproduce the operating state of the pickling bath, the concentration of each ion in the bath was adjusted by immersing an Al—Mg-based aluminum plate in 1% sulfuric acid many times, and the oil content was adjusted by adding rolling oil.
The conventional example is a phosphoric acid chromate treatment that is widely used at present, and is an alkali degreased and then phosphoric acid chromate treatment (Cr adhesion amount = 20 mg / m 2 ) by a conventional method.
In addition, as for the paint, an aqueous paint mainly composed of epoxy resin is applied amount = 7 g / m 2 , applied and baked at a drying temperature of 250 ° C. [aqueous], or a solvent paint mainly composed of vinyl chloride resin is applied amount = 7 g. / M 2 , coating and baking [PVC] at a drying temperature of 260 ° C.
Table 2 shows the results of measuring the surface before coating with GDS.
[0020]
[Table 1]
[Table 2]
The following evaluation tests were performed on these samples.
[Paint repellency] After baking the paint, the number of coating spots derived from the paint repellency was counted.
[As-paint adhesion test] The test piece was subjected to a 1 mm square cross cut test based on JIS-K5400.
[Retort Adhesion Test] A test piece was held in tap water at 125 ° C. for 30 minutes with a pressure sterilization apparatus, and then a 1 mm square cross-cut test based on JIS-K5400 was performed.
[30% Rolling Adhesion Test] After rolling with a rolling mill until the plate thickness was reduced by 30%, a 1 mm square grid test in accordance with JIS-K5400 was performed.
[Model Juice Corrosion Resistance Test] X-shaped cuts (length of each side: 40 mm) were put into the test piece, and immersed in an aqueous solution of 1.0 mass% citric acid monohydrate +0.5 mass% sodium chloride at 70 ° C. for 72 hours. The degree of occurrence of corrosion was evaluated. (◎: No corrosion, ○: Corrosion of 1 mm or less in part of the cut, △: Corrosion of 1 to 2 mm in part of the cut, Δ ×: Corrosion of 1 to 2 mm in the entire cut, ×: 2 mm or more in the entire cut Corrosion)
[0023]
[Table 3]
As is apparent from Table 3, Invention Example 1 which satisfies the conditions of the present invention has no repellency of paint and excellent repellency, and after coating as well as retort treatment or rolling, There is no peeling and excellent coating film adhesion, and corrosion resistance is as good as or better than that of conventional chromate treatment materials, and each evaluation test is excellent.
Inventive Example 2 was obtained by replacing the alloy of Inventive Example 1, Inventive Example 3 was carried out for 3 seconds with a strong wind at room temperature after lowering the drying temperature after washing, and Inventive Example 4 was the drying temperature after washing. The plate surface was dried for 1 minute with hot air at 350 ° C., but these plate surfaces satisfy the conditions of the present invention as shown in Table 2, and both have excellent evaluation results.
In contrast, Comparative Example 1 was washed with pure water at room temperature for 5 seconds without performing acid pickling after alkaline degreasing, and Comparative Example 2 was a pickling bath in which Al% and Mg% exceeded the scope of the present invention. In Comparative Example 3, drying after washing was performed with hot air at 350 ° C. for 60 minutes at a high temperature for a long time, but these did not satisfy claim 1 and none of them were coated. Although there is no peeling, peeling occurs when retorting or processing is performed, resulting in poor coating adhesion and corrosion resistance.
Inventive Example 5 uses a bath containing a large amount of oil by adding 1% by mass of rolling oil to the pickling bath, and Inventive Example 6 uses a bath having a higher oil content by adding 5% by mass of rolling oil to the pickling bath. Comparative Example 4 was the same as Invention Example 6 until drying, but a water-based paint was used instead of the vinyl chloride paint. Invention Example 5 satisfies the conditions of Claim 2 and gives good results even with water-based paints, while Invention Example 6 and Comparative Example 4 have the same oxide film, but PVC paints give good results. Since the condition of Item 2 is not satisfied, the result is slightly inferior to the water-based paint. Therefore, when the water-based paint is used, the condition of claim 2 should be satisfied.
The conventional example is a phosphoric acid chromate treatment that is widely used at present. After alkaline degreasing, phosphoric acid chromate treatment (Cr adhesion amount = 20 mg / m 2 ) is carried out by an ordinary method, and an epoxy resin is a main component on the chromate treatment. The water-based paint is applied and baked.
Inventive Examples 1 to 6 exceeded the conventional example in the 30% rolling adhesion test, and the high effect of the present invention was proved. Inventive Examples 1 to 6 naturally do not use Cr, and the advantages are clear from the viewpoint of environmental destruction and health damage.
[0025]
【The invention's effect】
As described above, according to the present invention, it is not necessary to carry out the conventional chromate treatment, and it has coating adhesion, corrosion resistance, and repellency resistance equivalent to or better than the current chemical chromate, and is capable of removing harmful heavy metals such as Cr. An aluminum lid for beverage cans / food cans can be provided.
[Brief description of the drawings]
FIG. 1 is a schematic diagram showing the distribution of elements of the present invention.
[Explanation of symbols]
Mg Magnesium concentration H Hydrogen concentration C Carbon concentration
Claims (5)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006008201A (en) * | 2004-06-28 | 2006-01-12 | Furukawa Sky Kk | Aluminum alloy material for beverage container excellent in resistance to blackening by boiling water |
| JP2008127625A (en) * | 2006-11-21 | 2008-06-05 | Furukawa Sky Kk | Aluminum plate for forming cap having excellent resin adhesiveness after forming, and its manufacturing method |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006200007A (en) * | 2005-01-21 | 2006-08-03 | Furukawa Sky Kk | Aluminum alloy sheet for automobile body sheet having excellent water wettability after degreasing and adhesive property |
| JP5184173B2 (en) * | 2008-03-27 | 2013-04-17 | 古河スカイ株式会社 | Resin-coated aluminum material, resin-coated aluminum material, and production methods thereof |
| JP5580948B1 (en) | 2013-09-27 | 2014-08-27 | 日本ペイント株式会社 | Surface treatment method for aluminum cans |
| JP6773434B2 (en) * | 2016-03-31 | 2020-10-21 | 富士フイルム株式会社 | Metal foil, metal foil manufacturing method and current collector for power storage device |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006008201A (en) * | 2004-06-28 | 2006-01-12 | Furukawa Sky Kk | Aluminum alloy material for beverage container excellent in resistance to blackening by boiling water |
| JP4500115B2 (en) * | 2004-06-28 | 2010-07-14 | 古河スカイ株式会社 | Aluminum alloy material for beverage containers with excellent black water resistance against boiling water |
| JP2008127625A (en) * | 2006-11-21 | 2008-06-05 | Furukawa Sky Kk | Aluminum plate for forming cap having excellent resin adhesiveness after forming, and its manufacturing method |
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