JP2004002950A - Chromate-free treated metal strip having excellent corrosion resistance and alkali resistance - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、耐食性、耐アルカリ性に優れたクロメートフリー処理金属板に関する。
【０００２】
【従来の技術】
これまでに電気亜鉛系めっき鋼板や溶融亜鉛めっき系鋼板の表面処理鋼板が開発され、家電、建材、および自動車部品等の用途において幅広く利用されている。これらの鋼板の多くは、耐食性向上を目的として、一般にクロメート処理が用いられている。
このクロメート処理は、バリヤー性を有する３価クロムと、自己修復機能を有する６価クロムを含有し、優れた耐食性を有する処理であり、例として塗布型クロメート、電解型クロメートが挙げられる。
【０００３】
塗布型処理により形成されたクロメート皮膜は、６価クロムを多く含有し、特に加工部耐食性に優れている。しかしながら、６価クロムは発ガン性を有しており、６価クロムを多く含む塗布型クロメート処理は、製品として使用される際に人体への影響が問題とされている。電解処理により形成されたクロメート皮膜は、３価クロム主体であり、６価クロムの溶出は少ない。反面、耐食性は塗布型より劣り、特に加工時などで皮膜損傷が大きい場合、耐食性は低下する。
【０００４】
これらのクロメート処理の上層に更に、有機重合体を被覆すれば６価クロムの溶出は、かなり抑制されるものの十分ではない。また、特開平５−２３０６６６号公報に開示されているような一般に樹脂クロメートと呼ばれる方法では、６価クロムの溶出抑制に大幅な改善が認められるものの、微量の溶出は避けられない。また、上記クロメート処理は、何れも処理工程での廃液処理や作業者への安全性についての問題は、回避することができない。
【０００５】
上記のような問題から、近年、クロメート処理と同等な性能を有するクロメートフリー処理の検討が行われている。その代表的なものは、有機系樹脂で金属表面を被覆し、被覆皮膜の金属表面への吸着力の強化により耐食性を改善しようとする手法がある。例えば、特開平１１−５０６１公報、特開平１１−１５８６４７号公報があり、キレート形成基としてチオール基、チオケトン基など含硫黄基を含有する高分子キレート化処理剤が提案されている。これらは、基本的に皮膜損傷が大きい場合、加工時の損傷部に対する耐食性発現が乏しく、クロメート処理の耐食性に及ばず、クロメート処理と同等の耐食性を発現するには至っていない。
【０００６】
家電分野においては、塗装密着性や接着性を確保するための前処理として、油分や異物の除去を目的にアルカリ脱脂を行う場合がある。また、建材分野においては、プレス加工やロールフォーミング加工といった成形時にｐＨ７〜９程度の水溶性の加工油（クーラント）を用いる場合があり、これらの脱脂、加工時にクロメートフリー処理皮膜が溶出し、外観や耐食性が劣化する場合があった。そのため、脱脂、加工時での外観、耐食性が劣化しない耐アルカリ性に優れたクロメートフリー処理金属板が望まれていた。
【０００７】
以上に加えて自動車分野では、エンジン周りなどの熱が加わる条件でも優れた耐食性を有するクロメートフリー処理金属板が望まれていた。
【０００８】
【発明が解決しようとする課題】
本発明は、こうした状況に鑑みたものであり、その目的は、優れた耐食性、耐アルカリ性を有し、同時に６価クロムを含有しない環境適合性に優れたクロメートフリー処理金属板を提供することである。
【０００９】
【課題を解決するための手段】
本発明者らは、上記課題を解決するために鋭意検討した結果、金属またはめっき金属板の表面に、（ａ） チタニウム化合物をチタニウム換算で１０〜２００ｍｇ／ｍ２またはジルコニウム化合物をジルコニウム換算で１０〜２００ｍｇ／ｍ２、あるいはチタニウム化合物とジルコニウム化合物をそれぞれチタニウムとジルコニウム換算で合計１０〜２００ｍｇ／ｍ２の皮膜を有し、その皮膜中にさらに（ｂ）リン酸化合物と（ｃ）グアニジン化合物を含有させることで、耐食性、耐アルカリ性に優れたクロメートフリー処理金属板を得られることを見出した。
【００１０】
耐食性、耐アルカリ性の発現メカニズムは、明らかではないが、チタニウム化合物またはジルコニウム化合物を単独あるいは複合で含有し、更にリン酸化合物を含有する緻密な皮膜により、優れたバリヤー性が発現される。この皮膜が腐食環境下において、腐食因子（塩素イオンなど）の金属板表面への浸入を防ぎ腐食反応を抑制する。また、リン酸化合物とグアニジン化合物は、腐食環境下において、環境中に溶出した金属イオンをキレート化して、更に金属表面に吸着し、いわゆるインヒビター効果が期待でき、このインヒビター効果により、加工時、及びアルカリ溶液浸漬時に損傷した部分の腐食が抑制され、加工後耐食性、耐アルカリ性が向上しているものと考えられる。
【００１１】
即ち、本発明の要旨とするところは、
（１）金属またはめっき金属板の表面に、（ａ）チタニウム化合物をチタニウム換算で１０〜２００ｍｇ／ｍ２またはジルコニウム化合物をジルコニウム換算で１０〜２００ｍｇ／ｍ２、またはチタニウム化合物とジルコニウム化合物をそれぞれチタニウムとジルコニウム換算で合計１０〜２００ｍｇ／ｍ２の皮膜を有し、その皮膜中にさらに（ｂ）リン酸化合物と（ｃ）グアニジン化合物を含有することを特徴とする耐食性、耐アルカリ性に優れたクロメートフリー処理金属板、
（２）リン酸化合物含有量が、成分（ａ）１００質量部（換算値）に対して１０〜１５０質量部であることを特徴とする前記（１）に記載のクロメートフリー処理金属板、
（３）グアニジン化合物含有量が、成分（ａ）１００質量部（換算値）に対して１５〜１５０質量部であることを特徴とする前記（１）、（２）の何れかに記載のクロメートフリー処理金属板、
（４）皮膜中にマグネシウム、亜鉛、アルミニウム、ランタン、セリウム、ハフニウム、タンタル、ニオブ、タングステン、珪素、マンガン、コバルト、ニッケル化合物から選ばれる１種以上を、成分（ａ）の１００質量部（換算値）に対して５〜２００質量部含むことを特徴とする前記（１）〜（３）の何れかに記載のクロメートフリー処理金属板、
（５）皮膜中に１種以上の水溶性樹脂を、成分（ａ）の１００質量部（換算値）に対して０．５〜４０質量部含むことを特徴とする前記（１）〜（４）の何れかに記載のクロメートフリー処理金属板、
（６）皮膜中に潤滑成分を、成分（ａ）の１００質量部（換算値）に対して０．５〜１５質量部含むことを特徴とする前記（１）〜（５）の何れかに記載のクロメートフリー処理金属板、
（７）めっき金属板のめっき層が、Ｍｇ：１〜１０質量％、Ａｌ：２〜１９質量％、Ｓｉ：０．０１〜２質量％含有し、かつ、ＭｇとＡｌが下式
Ｍｇ（質量％）＋Ａｌ（質量％）≦２０（質量％）
を満たし、残部がＺｎ及び不可避的不純物よりなるＺｎ合金めっき層であることを特徴とする前記（１）〜（６）の何れかに記載のクロメートフリー処理金属板、
（８）めっき金属板のめっき層が
Ａｌ：５０〜９５質量％、Ｓｉ：０．５〜１２質量％含有し、残部が不可避的不純物もしくはＺｎ及び不可避的不純物よりなるＡｌ合金めっき層であることを特徴とする前記（１）〜（６）の何れかに記載のクロメートフリー処理金属板、である。
【００１２】
【発明実施の形態】
以下、本発明を詳述する。
本発明における皮膜の形成方法としては、チタニウム化合物、または、ジルコニウム化合物を単独あるいは複合で混合したものをベースとし、リン酸化合物、グアニジン化合物を含有させた処理液を使用する。
【００１３】
チタニウム化合物、ジルコニウム化合物を単体もしくは複合で使用することで、造膜性、バリヤー性、耐水性をもたせることができる。更にリン酸化合物を含有させることで、インヒビター効果が得られ、更に造膜性、耐水性が向上し、優れたバリヤー性が発現される。さらには、グアニジン化合物を含有させることで、グアニジン化合物のインヒビター効果を得ることができる。これらの成分の相乗効果で、優れた耐食性、耐アルカリ性（浸漬後の耐食性）を有する皮膜を形成することができる。
以上の技術により、従来にはない優れた耐食性と耐アルカリ性に優れたクロメートフリー処理金属板の開発に成功した。
【００１４】
以下、本発明である耐食性と耐アルカリ性に優れたクロメートフリー処理金属板の製造方法を詳述する。
【００１５】
本発明において適用可能な金属あるいはめっき金属板としては、鋼板およびその上層にめっきを施した亜鉛めっき金属板、亜鉛−ニッケルめっき金属板、亜鉛−鉄めっき金属板、亜鉛−クロムめっき金属板、亜鉛−アルミニウムめっき金属板、亜鉛−チタンめっき金属板、亜鉛−マグネシウムめっき金属板、亜鉛−マンガンめっき金属板等の亜鉛系の電気めっき、溶融めっき、蒸着めっき、アルミニウムまたはアルミニウム合金めっき金属板、鉛または鉛合金めっき金属板、錫または錫合金めっき金属板、さらにはこれらのめっき層に少量の異種金属元素あるいは不純物としてコバルト、モリブデン、ニッケル、チタン、クロム、アルミニウム、マンガン、鉄、マグネシウム、鉛、ビスマス、アンチモン、錫、銅、カドミウム、ヒ素等を含有したもの、または／およびシリカ、アルミナ、チタニア等の無機物を分散させたものが含まれる。さらには、以上のめっきと他のめっき、例えば鉄めっき、鉄−りんめっき等と組み合わせた複層めっきにも適用可能である。
各めっき金属板におけるめっき付着量は、片面１ｇ／ｍ２以上とすることが好ましく、これを下回ると耐食性が低下する。
【００１６】
本発明で用いるチタニウム化合物としては、例えば、チタンフッ化水素酸、チタンフッ化アンモニウム、シュウ酸チタンカリウム、硫酸チタン、塩化チタン、チタンイソプロポキシド、チタン酸イソプロピル、チタンエトキシド、チタン２−エチル−１−ヘキサノラート、チタン酸テトライソプロピル、チタン酸テトラ−ｎ−ブチル、チタンフッ化カリウム、チタンフッ化ナトリウム等が挙げられ、あるいはそれらの混合物を用いることも可能である。
【００１７】
また、ジルコニウム化合物としては、例えば、炭酸ジルコニルアンモニウム、ジルコンフッ化水素酸、ジルコンフッ化アンモニウム、ジルコンフッ化カリウム、ジルコンフッ化ナトリウム、ジルコニウムアセチルアセトナート、ジルコニウムブトキシド−１−ブタノール溶液、ジルコニウム−ｎ−プロポキシド、硝酸ジルコニル、塩化ジルコニウム、カルボン酸ジルコニウム等が挙げられ、あるいはそれらの混合物を用いることも可能である。
【００１８】
成分（ａ）の付着量としては、チタニウム化合物をチタニウム換算で１０〜２００ｍｇ／ｍ２、またはジルコニウム化合物をジルコニウム換算で１０〜２００ｍｇ／ｍ２、またはチタニウム化合物とジルコニウム化合物をそれぞれチタニウムとジルコニウム換算の合計として１０〜２００ｍｇ／ｍ２とするのが好ましい。付着量が、１０ｍｇ／ｍ２未満の場合、十分なバリヤー効果が得られず、耐食性が劣り、２００ｍｇ／ｍ２を超える場合、耐食性向上効果が飽和するため不経済である。また、皮膜が白く着色し外観上好ましくない。
【００１９】
本発明で用いるリン酸化合物としては、例えば、オルトリン酸およびオルトリン酸塩、ポリリン酸、メタリン酸、ピロリン酸、ウルトラリン酸等の縮合リン酸またはそれらの塩類が挙げられ、あるいはそれらの混合物を用いることも可能である。
リン酸化合物の付着量としては、成分（ｂ）のリン酸化合物を、成分（ａ）のチタニウム、及びジルコニウム化合物の１００質量部（換算値）に対して１０〜１５０質量部とするのが好ましい。リン酸化合物の付着量が、成分（ａ）の１０質量部未満であると、十分なインヒビター効果が得られず、耐食性が劣化する。１５０質量部を超える場合、耐食性向上効果が飽和するため不経済である。
【００２０】
本発明で用いるグアニジン化合物としては、例えば、塩酸グアニジン、硝酸グアニジン、炭酸グアニジン、ロダングアニジン、重炭酸アミノグアニジン、塩酸アミノグアニジン、リン酸グアニジン、スルファミン酸グアニジンなどが挙げられ、これらを単独で使用しても２種以上を併用しても良い。
グアニジン化合物の付着量としては、成分（ｃ）のグアニジン化合物を、成分（ａ）の１００質量部（換算値）に対して１５〜１５０質量部とするのが好ましい。グアニジン化合物の付着量が１５質量部未満であると、皮膜の損傷部の腐食を抑制するインヒビター効果が小さく、十分な耐食性が得られない。１５０質量部を超える場合、耐食性向上効果が飽和して不経済である。また、処理液の安定性が低下するため生産上好ましくない。
【００２１】
皮膜中に、更にマグネシウム、亜鉛、アルミニウム、ランタン、セリウム、ハフニウム、タンタル、ニオブ、タングステン、珪素、マンガン、コバルト、ニッケルの酸化物、水酸化物、錯フッ化物、硝酸塩、硫酸塩、リン酸塩などから選ばれる１種以上の金属化合物を、成分（ａ）の１００質量部（換算値）に対して５〜２００質量部含むことにより更に耐食性、耐アルカリ性の向上を図ることができる。
これらの金属化合物の含有量を、５質量部以上とすることで、更なる耐食性向上効果が得られる。一方、２００質量部を超える場合、耐食性向上効果が飽和するため不経済であり、処理液の安定性も低下するため好ましくない。
【００２２】
皮膜中に、１種以上の水溶性樹脂を添加することにより、更に耐食性、耐アルカリ性の向上を図ることができる。水溶性樹脂としては、アクリル樹脂、ウレタン系樹脂、エポキシ系樹脂、エチレンアクリル共重合体、フェノール系樹脂、ポリエステル系樹脂、ポリオレフィン系樹脂、アルキド系樹脂、ポリカーボネート系樹脂等を単独で使用しても、２種以上を併用しても良い。
水溶性樹脂の付着量としては、成分（ａ）の１００質量部（換算値）に対して０．５〜４０質量部含むことが好ましい。付着量が０．５質量部未満では、耐食性、耐アルカリ性の向上効果が得られない。一方、４０質量部を超える場合、耐食性向上効果が飽和するので不経済あり、処理液の安定性が低下する。
【００２３】
尚、本発明においては皮膜中に潤滑成分として、二硫化モリブデン、グラファイト、二硫化タングステン、窒化ホウ素、フッ化黒鉛、フッ化セリウム、メラミンシアヌレート、フッ素樹脂系ワックス、ポリオレフィン系ワックスを添加することにより、加工性、耐疵付き性などを改善することができる。皮膜中に含まれる潤滑成分の含有量としては、成分（ａ）の１００質量部（換算値）に対して、０．５〜１５質量部含むことが好ましい。潤滑成分の含有量が、０．５質量部未満では、加工性、耐傷付き性の向上効果が乏しく、１５質量部を超えると加工性、耐傷付き性の向上効果が飽和するので不経済である。
【００２４】
また、本来の性能を損なわない範囲内で消泡剤やレベリング剤を皮膜中に添加しても良い。
【００２５】
本発明に用いるめっき金属板として、めっき層が、Ｍｇ：１〜１０質量％、Ａｌ：２〜１９質量％、Ｓｉ：０．０１〜２質量％含有し、かつ、ＭｇとＡｌが下式
Ｍｇ（質量％）＋Ａｌ（質量％）≦２０（質量％）
を満たし、残部がＺｎ及び不可避的不純物よりなる溶融亜鉛―アルミニウム合金めっき層とすることで更なる耐食性の向上を図ることができる。めっき層中のＡｌは耐食性向上のために添加される。２質量％未満では充分な耐食性の向上が得られず、１９質量％を超えると耐食性向上効果が飽和するとともに溶接性が大幅に低下するため、Ａｌ含有量は２〜１９質量％とするのが好ましい。Ｍｇの添加の目的も耐食性の向上である。１質量％未満では耐食性向上効果が不充分であり、１０質量％を超えるとめっき層が脆くなり密着性を低下させてしまうため、Ｍｇ含有量は１〜１０質量％とした。Ｓｉの添加目的は耐食性の向上とめっき層中のＡｌとＦｅの反応の抑制によるめっき密着性の向上である。０．０１質量％未満ではその添加効果が不充分であり、２質量％を超えるとめっき密着性向上効果が認められなくなる。尚、ＭｇとＡｌの含有量を式 Ｍｇ（質量％）＋Ａｌ（質量％）≦２０（質量％）に限定した理由は、めっき層中のＺｎ含有量が低くなると犠牲防食効果が低下し耐食性が低下するためである。
【００２６】
自動車のエンジン周りなどの熱の影響のある部分では、Ａｌ：５０〜９５質量％、Ｓｉ：０．５〜１２質量％を含有し、残部が不可避的不純物もしくはＺｎ及び不可避的不純物よりなるＡｌ合金めっき層を有する金属板を用いることで，耐熱性と耐食性の両方を高度に満足することができる。めっき層中のＡｌは耐食性と耐熱性の向上のために添加される。５０質量％未満では充分な耐熱性の向上が得られず、９５質量％を超えるとめっき密着性が低下するため，Ａｌ含有量は５０〜９５質量％とすることが好ましい。Ｓｉの添加目的は耐食性の向上とめっき層中のＡｌとＦｅの反応の抑制によるめっき密着性の向上である。０．５質量％未満ではその添加効果が不充分であり、１２質量％を超えるとめっき密着性向上効果が認められなくなるため、Ｓｉ含有量は０．５〜１２質量％とすることが望ましい。
【００２７】
また、めっき層中には上記の成分以外にＦｅ、Ｔｉ、Ｎｉ、Ｓｂ、Ｐｂ、Ｂ、Ｂｉ等の元素を単独あるいは複合で１質量％以内含有しても良い。
【００２８】
めっき付着量に関しては、特に限定するものではないが、耐食性の観点から１ｇ／ｍ２以上、また溶接性、加工性の観点からは３５０ ｇ／ｍ２以下であることが望ましい。
【００２９】
尚、溶融めっきの製造方法としては バッチ式のどぶづけめっき法、フラックス法、ゼンジミア法やＮｉ等のプレめっきを施して濡れ性を確保する方法等があるが、いずれでも構わない。また、めっき後の外観を変化させる目的で、水スプレー、気水スプレーを噴霧したり、リン酸ソーダ水溶液やＺｎ粉末、さらにはリン酸Ｚｎ粉末、リン酸水素Ｍｇ粉末もしくはそれらの水溶液を噴霧しても良い。
まためっき後、本発明の皮膜を形成する前にめっきの変色防止等のため硫酸Ｃｏ溶液や硫酸Ｎｉ溶液等による表面調整を施しても差し支えない。
【００３０】
本発明で皮膜を形成させるための塗布方式としては、スプレー、カーテン、フローコーター、ロールコーター、バーコーター、刷毛塗り、浸漬及び、エアーナイフ法等、いずれの方法を用いても良い。
【００３１】
また、焼き付け温度は、５０〜２５０℃とするのが望ましい。乾燥設備については特に制限するものではないが、熱風吹き付けによる方法や、ヒーターにより間接加熱方法、赤外線による方法、誘導加熱による方法、並びにこれらを併用する方法が採用できる。
【００３２】
【実施例】
以下、本発明を実施例及び比較例によって具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。
【００３３】
（１）薬剤の種類
実施例に用いた薬剤の一覧を表１に示す。
【００３４】
【表１】
（２）金属板の種類
金属板は、表２に示すものを用いた。板厚は何れも１．０ｍｍとした。
【００３６】
【表２】
（３）処理液の調製
表１に示すＴｉ／Ｚｒ化合物、リン酸化合物、グアニジン化合物、金属化合物、水溶性樹脂及び潤滑成分を表４， ５， ６， ７，８，９に示す比率で配合し、処理液を調製した。
【００３８】
（４）処理液の塗布・乾燥方法
無処理のめっき金属板に（３）で調製した処理液を乾燥質量として表４， ５， ６，７，８，９に示す値となるように塗布し、到達板温８０℃で乾燥して、評価用サンプルを作製した。また、処理皮膜の付着量の確認は、蛍光Ｘ線装置により皮膜中のＴｉ及びＺｒを測定しその指標とした。
【００３９】
（５）性能評価項目
（５）−１ 平板耐食性
（４）で作製した評価用サンプルを、ＪＩＳ Ｚ ２３７１に記載されている塩水噴霧試験方法に準じて、雰囲気温度３５℃で、５％のＮａＣｌ水溶液を試料に吹き付け、７２時間後の平板部白錆発生率を測定して評価した。以下の評価で、◎及び○を良好とした。
◎：白錆発生なし
○：白錆発生面積 １０％未満
△：同 １０％以上５０％未満
×：同５０％以上
【００４０】
（５）−２ 加工部耐食性
（４）で作製した評価用サンプルを、試験片に６ｍｍのエリクセン加工を施し、ＪＩＳ Ｚ ２３７１に記載されている塩水噴霧試験に準じて、雰囲気温度３５℃で、５％のＮａＣｌ水溶液を試料に吹き付け、４８時間後の加工部おける白錆発生率を測定して評価した。以下の評価で、◎及び○を良好と判定した。
◎：白錆発生なし
○：白錆発生面積 １０％未満
△：同 １０％以上５０％未満
×：同 ５０％以上
【００４１】
（５）−３ 耐アルカリ性
（４）で作製した評価用サンプルを、水溶性加工油（佐藤特殊製油製ＳＴゾールＦ５）濃度 ３％水溶液に５分間浸漬後風乾し、ＪＩＳ Ｚ ２３７１に記載されている塩水噴霧試験方法に準じて、雰囲気温度３５℃で、５％のＮａＣｌ水溶液を試料に吹き付け、４８時間後の白錆発生率を測定して評価した。以下の評価で、◎及び○を良好とした。
◎：白錆発生面積 １０％未満
○：白錆発生面積 ３０％未満
△：同３０％以上５０％未満
×：同５０％以上
【００４２】
（５）−４加工性試験
（４）で作製した評価用サンプルにて、バウデン試験（荷重５００ｇ、圧子１０ｍｍφＳＵＪ−２、摺動距離５０ｍｍ、摺動速度５０ｍｍ／秒）を行い、摺動回数１０回目の摩擦係数を測定し評価した。
○：摩擦係数０．２未満
△：摩擦係数０．２〜０．４
×：摩擦係数０．４超
【００４３】
（５）−５ 連続溶接性
（４）で作製した評価用サンプルについて表３に示す条件で連続スポット溶接試験を行い。安定してナゲット径が４．５ｍｍφ以上形成できる打点数を求めた。
【００４４】
【表３】
以下の評価で◎及び○を良好と判定した。
◎：打点数 ２，０００点以上
○：１，０００点以上２，０００点未満
△：１，０００点未満
×：５００点未満
【００４６】
（５）−６ 耐熱耐食性試験
耐熱耐食性試験は、（４）で作製した評価用サンプルを３５０℃で８時間加熱後、ＪＡＳＯ Ｍ６０９に準拠したサイクル腐食試験（５％ＮａＣｌ水溶液噴霧（３５℃）→乾燥（６０℃，２０〜３０％ＲＨ）→湿潤（５０℃，９８％ＲＨ以上））を１５サイクル行い、白錆発生率を測定した。以下の評価で、◎及び○を良好とした。
◎：白錆発生面積 １０％未満
○：白錆発生面積 ３０％未満
△：同３０％以上５０％未満
×：同５０％以上
【００４７】
以上の評価結果を表４， ５， ６， ７，８，９に示す。表４， ５， ６， ７，８，９より、本発明のクロメートフリー処理金属板が、いずれの場合においても平板耐食性、加工部耐食性、耐アルカリ性、耐熱耐食性のみならず、溶接性に優れることは明らかである。
【００４８】
【表４】
【表５】
【表６】
【表７】
【表８】
【表９】
【発明の効果】
本発明のクロメートフリー処理金属板は、良好な耐食性と耐アルカリ性を有し、且つ６価クロムを全く使用していないため環境負荷を低減した金属板として、家電製品の筐体、自動車の外板、内板、エンジン周り、柱、梁、接合金物等の建築用に好適に用いることができる。よって、本発明により、良好な耐食性と耐アルカリ性を有するクロメートフリー処理金属板を市場に提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a chromate-free treated metal sheet having excellent corrosion resistance and alkali resistance.
[0002]
[Prior art]
Until now, electro-galvanized steel sheets and hot-dip galvanized steel sheet-treated steel sheets have been developed and widely used in applications such as home appliances, building materials, and automobile parts. Many of these steel sheets are generally subjected to a chromate treatment for the purpose of improving corrosion resistance.
This chromate treatment is a treatment containing trivalent chromium having a barrier property and hexavalent chromium having a self-healing function and having excellent corrosion resistance, and examples thereof include a coating type chromate and an electrolytic type chromate.
[0003]
The chromate film formed by the coating process contains a large amount of hexavalent chromium and is particularly excellent in the corrosion resistance of the processed portion. However, hexavalent chromium has carcinogenicity, and there is a problem that the coating type chromate treatment containing a large amount of hexavalent chromium has an effect on the human body when used as a product. The chromate film formed by the electrolytic treatment is mainly composed of trivalent chromium, and the elution of hexavalent chromium is small. On the other hand, the corrosion resistance is inferior to that of the coating type.
[0004]
If an organic polymer is further coated on the upper layer of these chromate treatments, the elution of hexavalent chromium is considerably suppressed but not sufficient. Further, in the method generally referred to as resin chromate as disclosed in Japanese Patent Application Laid-Open No. 5-230666, although a significant improvement in the suppression of hexavalent chromium elution is recognized, a slight amount of elution is inevitable. In addition, in any of the above chromate treatments, the problem of waste liquid treatment in the treatment process and the problem of safety for workers cannot be avoided.
[0005]
Due to the above-mentioned problems, a chromate-free treatment having the same performance as the chromate treatment has been studied in recent years. As a typical example, there is a method of coating a metal surface with an organic resin and improving the corrosion resistance by enhancing the adsorbing force of the coating film on the metal surface. For example, JP-A-11-5061 and JP-A-11-158647 propose a polymer chelating agent containing a sulfur-containing group such as a thiol group or a thioketone group as a chelating group. Basically, when the film damage is large, the corrosion resistance to the damaged portion at the time of processing is poor, and it does not reach the corrosion resistance of the chromate treatment, and has not yet achieved the same corrosion resistance as the chromate treatment.
[0006]
In the field of home appliances, alkali degreasing may be performed for the purpose of removing oil and foreign matters as a pretreatment for ensuring coating adhesion and adhesion. In the building materials field, a water-soluble processing oil (coolant) having a pH of about 7 to 9 may be used at the time of molding such as press working or roll forming. And the corrosion resistance was sometimes deteriorated. Therefore, there has been a demand for a chromate-free treated metal plate having excellent alkali resistance without deteriorating the appearance and corrosion resistance during degreasing and processing.
[0007]
In addition to the above, in the field of automobiles, a chromate-free treated metal plate having excellent corrosion resistance even under heat-applied conditions such as around an engine has been desired.
[0008]
[Problems to be solved by the invention]
The present invention has been made in view of such circumstances, and an object of the present invention is to provide a chromate-free treated metal plate having excellent corrosion resistance and alkali resistance, and at the same time, containing no hexavalent chromium and having excellent environmental compatibility. is there.
[0009]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, (a) 10 to 200 mg / m 2 of titanium compound or 10 to zirconium compound of zirconium compound on the surface of a metal or plated metal plate. to 200 mg / m 2, or have a total 10 to 200 mg / m 2 of coating titanium compound and a zirconium compound at respective titanium and zirconium terms, in the film in addition (b) a phosphoric acid compound (c) guanidine compound It has been found that by containing the same, a chromate-free treated metal plate excellent in corrosion resistance and alkali resistance can be obtained.
[0010]
Although the mechanism of the development of corrosion resistance and alkali resistance is not clear, excellent barrier properties are exhibited by a dense film containing a titanium compound or a zirconium compound alone or in combination, and further containing a phosphoric acid compound. In a corrosive environment, this film prevents corrosion factors (such as chlorine ions) from penetrating into the metal plate surface and suppresses the corrosion reaction. Further, in a corrosive environment, the phosphate compound and the guanidine compound can chelate metal ions eluted into the environment, and further adsorb the metal ions, so that a so-called inhibitor effect can be expected. It is considered that the corrosion of the part damaged at the time of immersion in the alkali solution was suppressed, and the corrosion resistance and alkali resistance after processing were improved.
[0011]
That is, the gist of the present invention is:
(1) metal or the surface of the plated metal plate, (a) 10 to 200 mg / m 2 titanium compound of titanium in terms of the 10 to 200 mg / m 2 or zirconium compound in terms of zirconium or titanium compound and a zirconium compound, respectively titanium And a zirconium-equivalent total of 10 to 200 mg / m 2 , wherein the coating further contains (b) a phosphate compound and (c) a guanidine compound, and is excellent in corrosion resistance and alkali resistance. Free treated metal plate,
(2) The chromate-free treated metal plate according to (1), wherein the content of the phosphoric acid compound is 10 to 150 parts by mass with respect to 100 parts by mass (converted value) of the component (a).
(3) The chromate as described in any of (1) and (2) above, wherein the guanidine compound content is 15 to 150 parts by mass with respect to 100 parts by mass (converted value) of the component (a). Free treated metal plate,
(4) One or more kinds selected from magnesium, zinc, aluminum, lanthanum, cerium, hafnium, tantalum, niobium, tungsten, silicon, manganese, cobalt, and nickel compound in the film, 100 parts by mass of the component (a) (converted) The chromate-free treated metal plate according to any one of the above (1) to (3),
(5) The film according to (1) to (4), wherein the film contains one or more water-soluble resins in an amount of 0.5 to 40 parts by mass with respect to 100 parts by mass (converted value) of the component (a). A) a chromate-free treated metal plate according to any of
(6) The coating according to any one of (1) to (5), wherein the coating contains 0.5 to 15 parts by mass of a lubricating component based on 100 parts by mass (converted value) of the component (a). Chromate-free treated metal plate described,
(7) The plating layer of the plated metal plate contains Mg: 1 to 10% by mass, Al: 2 to 19% by mass, Si: 0.01 to 2% by mass, and Mg and Al are represented by the following formula Mg (mass) %) + Al (% by mass) ≦ 20 (% by mass)
The chromate-free treated metal plate according to any one of (1) to (6) above, wherein the balance is a Zn alloy plating layer composed of Zn and unavoidable impurities.
(8) The plating layer of the plated metal plate contains 50 to 95% by mass of Al and 0.5 to 12% by mass of Si, and the balance is an Al alloy plating layer composed of unavoidable impurities or Zn and unavoidable impurities. The chromate-free treated metal plate according to any one of the above (1) to (6).
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
As a method for forming a film in the present invention, a treatment solution containing a phosphate compound and a guanidine compound based on a titanium compound or a mixture of zirconium compounds alone or in combination is used.
[0013]
By using a titanium compound or a zirconium compound alone or in combination, it is possible to impart film forming properties, barrier properties, and water resistance. By further containing a phosphoric acid compound, an inhibitory effect can be obtained, and further, the film-forming property and water resistance are improved, and excellent barrier properties are exhibited. Furthermore, by containing a guanidine compound, an inhibitor effect of the guanidine compound can be obtained. By the synergistic effect of these components, a film having excellent corrosion resistance and alkali resistance (corrosion resistance after immersion) can be formed.
With the technology described above, we succeeded in developing a chromate-free treated metal plate with excellent corrosion resistance and alkali resistance that has never existed before.
[0014]
Hereinafter, the method for producing a chromate-free treated metal sheet having excellent corrosion resistance and alkali resistance according to the present invention will be described in detail.
[0015]
Examples of the metal or plated metal plate applicable in the present invention include a steel plate and a zinc-plated metal plate having a plated upper layer, a zinc-nickel plated metal plate, a zinc-iron plated metal plate, a zinc-chromium plated metal plate, and zinc. -Zinc-based electroplating such as aluminum-plated metal plate, zinc-titanium-plated metal plate, zinc-magnesium-plated metal plate, zinc-manganese-plated metal plate, hot-dip plating, vapor deposition plating, aluminum or aluminum alloy-plated metal plate, lead or Lead alloy-plated metal sheets, tin or tin alloy-plated metal sheets, and a small amount of different metal elements or impurities such as cobalt, molybdenum, nickel, titanium, chromium, aluminum, manganese, iron, magnesium, lead, bismuth Contains antimony, tin, copper, cadmium, arsenic, etc. Ones, or / and silica, alumina, include those obtained by dispersing an inorganic material titania. Further, the present invention is also applicable to a multilayer plating in which the above plating is combined with another plating, for example, iron plating, iron-phosphorus plating, or the like.
The amount of plating applied to each plated metal plate is preferably 1 g / m 2 or more on one side, and if it is less than this, the corrosion resistance decreases.
[0016]
As the titanium compound used in the present invention, for example, titanium hydrofluoric acid, ammonium titanium fluoride, titanium potassium oxalate, titanium sulfate, titanium chloride, titanium isopropoxide, isopropyl titanate, titanium ethoxide, titanium 2-ethyl-1 -Hexanolate, tetraisopropyl titanate, tetra-n-butyl titanate, potassium titanium fluoride, sodium titanium fluoride and the like, or a mixture thereof can be used.
[0017]
Examples of zirconium compounds include zirconium ammonium carbonate, zircon hydrofluoric acid, zircon ammonium fluoride, potassium zircon fluoride, sodium zircon fluoride, zirconium acetylacetonate, zirconium butoxide-1-butanol solution, zirconium-n-propoxide, Examples include zirconyl nitrate, zirconium chloride, zirconium carboxylate, and the like, or a mixture thereof.
[0018]
Component The adhesion amount (a), the titanium compound in the titanium terms 10 to 200 mg / m 2 or zirconium compound in terms of zirconium 10 to 200 mg / m 2 or titanium compound and a zirconium compound of titanium and zirconium in terms respectively, It is preferable that the total amount be 10 to 200 mg / m 2 . When the amount is less than 10 mg / m 2 , a sufficient barrier effect cannot be obtained, and the corrosion resistance is poor. When the amount exceeds 200 mg / m 2 , the effect of improving the corrosion resistance is saturated, which is uneconomical. Further, the film is colored white, which is not preferable in appearance.
[0019]
Examples of the phosphoric acid compound used in the present invention include condensed phosphoric acids such as orthophosphoric acid and orthophosphate, polyphosphoric acid, metaphosphoric acid, pyrophosphoric acid, and ultraphosphoric acid, and salts thereof, or a mixture thereof. It is also possible.
The amount of the phosphoric acid compound to be attached is preferably 10 to 150 parts by mass with respect to 100 parts by mass (converted value) of the component (a) of the titanium compound and the zirconium compound. . When the attached amount of the phosphoric acid compound is less than 10 parts by mass of the component (a), a sufficient inhibitor effect cannot be obtained, and the corrosion resistance deteriorates. If the amount exceeds 150 parts by mass, the effect of improving corrosion resistance is saturated, which is uneconomical.
[0020]
The guanidine compound used in the present invention includes, for example, guanidine hydrochloride, guanidine nitrate, guanidine carbonate, rhodang anidine, aminoguanidine bicarbonate, aminoguanidine hydrochloride, guanidine phosphate, guanidine sulfamate, and the like. Or two or more of them may be used in combination.
The amount of the guanidine compound attached is preferably 15 to 150 parts by mass based on 100 parts by mass (converted value) of the guanidine compound as the component (c). If the amount of the guanidine compound is less than 15 parts by mass, the inhibitory effect of suppressing corrosion of the damaged portion of the film is small, and sufficient corrosion resistance cannot be obtained. If the amount exceeds 150 parts by mass, the effect of improving corrosion resistance is saturated, which is uneconomical. Further, the stability of the treatment liquid is lowered, which is not preferable in production.
[0021]
In the coating, magnesium, zinc, aluminum, lanthanum, cerium, hafnium, tantalum, niobium, tungsten, silicon, manganese, cobalt, nickel oxide, hydroxide, complex fluoride, nitrate, sulfate, phosphate The corrosion resistance and alkali resistance can be further improved by including 5 to 200 parts by mass of at least one metal compound selected from the above with respect to 100 parts by mass (converted value) of the component (a).
By setting the content of these metal compounds to 5 parts by mass or more, a further effect of improving corrosion resistance can be obtained. On the other hand, if it exceeds 200 parts by mass, the effect of improving the corrosion resistance is saturated, which is uneconomical, and the stability of the processing solution is undesirably reduced.
[0022]
By adding one or more water-soluble resins to the film, the corrosion resistance and alkali resistance can be further improved. As the water-soluble resin, acrylic resin, urethane resin, epoxy resin, ethylene acrylic copolymer, phenolic resin, polyester resin, polyolefin resin, alkyd resin, polycarbonate resin alone or the like Two or more kinds may be used in combination.
The amount of the water-soluble resin to be attached is preferably 0.5 to 40 parts by mass with respect to 100 parts by mass (converted value) of the component (a). If the amount is less than 0.5 parts by mass, the effect of improving corrosion resistance and alkali resistance cannot be obtained. On the other hand, when the amount exceeds 40 parts by mass, the effect of improving the corrosion resistance is saturated, which is uneconomical, and the stability of the treatment liquid is reduced.
[0023]
In the present invention, molybdenum disulfide, graphite, tungsten disulfide, boron nitride, graphite fluoride, cerium fluoride, melamine cyanurate, fluororesin-based wax, and polyolefin-based wax are added as lubricating components to the film. Thereby, workability, scratch resistance and the like can be improved. The content of the lubricating component contained in the coating is preferably 0.5 to 15 parts by mass with respect to 100 parts by mass (converted value) of the component (a). If the content of the lubricating component is less than 0.5 part by mass, the effect of improving workability and scratch resistance is poor, and if it exceeds 15 parts by mass, the effect of improving processability and scratch resistance is saturated, and it is uneconomical. .
[0024]
Further, an antifoaming agent or a leveling agent may be added to the film within a range not impairing the original performance.
[0025]
As the plated metal plate used in the present invention, the plating layer contains Mg: 1 to 10% by mass, Al: 2 to 19% by mass, Si: 0.01 to 2% by mass, and Mg and Al are represented by the following formula: (% By mass) + Al (% by mass) ≦ 20 (% by mass)
Is satisfied, and the balance is a molten zinc-aluminum alloy plating layer composed of Zn and unavoidable impurities, whereby the corrosion resistance can be further improved. Al in the plating layer is added for improving corrosion resistance. If it is less than 2% by mass, a sufficient improvement in corrosion resistance cannot be obtained, and if it exceeds 19% by mass, the effect of improving corrosion resistance is saturated and the weldability is greatly reduced. Therefore, the Al content is preferably 2 to 19% by mass. preferable. The purpose of adding Mg is also to improve corrosion resistance. If it is less than 1% by mass, the effect of improving the corrosion resistance is insufficient, and if it exceeds 10% by mass, the plating layer becomes brittle and the adhesion is reduced, so the Mg content was set to 1 to 10% by mass. The purpose of adding Si is to improve the corrosion resistance and the plating adhesion by suppressing the reaction between Al and Fe in the plating layer. If the amount is less than 0.01% by mass, the effect of the addition is insufficient. If the amount exceeds 2% by mass, the effect of improving the plating adhesion is not recognized. The reason why the contents of Mg and Al are limited to the formula Mg (% by mass) + Al (% by mass) ≦ 20 (% by mass) is that the lower the Zn content in the plating layer, the lower the sacrificial corrosion protection effect and the lower the corrosion resistance. It is because it decreases.
[0026]
A portion affected by heat, such as around an engine of an automobile, contains 50 to 95% by mass of Al and 0.5 to 12% by mass of Si, and the remainder is an unavoidable impurity or an Al alloy including Zn and unavoidable impurities. By using a metal plate having a plating layer, both heat resistance and corrosion resistance can be highly satisfied. Al in the plating layer is added for improving corrosion resistance and heat resistance. If the amount is less than 50% by mass, a sufficient improvement in heat resistance cannot be obtained, and if the amount exceeds 95% by mass, the plating adhesion is reduced. Therefore, the Al content is preferably set to 50 to 95% by mass. The purpose of adding Si is to improve the corrosion resistance and the plating adhesion by suppressing the reaction between Al and Fe in the plating layer. If the amount is less than 0.5% by mass, the effect of the addition is insufficient, and if the amount exceeds 12% by mass, the effect of improving the plating adhesion is not recognized. Therefore, the Si content is desirably 0.5 to 12% by mass.
[0027]
In addition, the plating layer may contain elements such as Fe, Ti, Ni, Sb, Pb, B, and Bi, alone or in combination, in an amount of 1% by mass or less in addition to the above components.
[0028]
The amount of plating is not particularly limited, but is preferably 1 g / m 2 or more from the viewpoint of corrosion resistance, and 350 g / m 2 or less from the viewpoint of weldability and workability.
[0029]
In addition, as a manufacturing method of the hot-dip plating, there are a batch-type dipping plating method, a flux method, a Sendzimir method, a method of applying a pre-plating of Ni or the like, and a method of ensuring wettability, but any method may be used. In addition, for the purpose of changing the appearance after plating, water spray, air-water spray, or a sodium phosphate aqueous solution or Zn powder, and further, a Zn phosphate powder, a Mg hydrogen phosphate powder or an aqueous solution thereof are sprayed. May be.
After plating, before forming the film of the present invention, the surface may be adjusted with a Co sulfate solution, a Ni sulfate solution, or the like to prevent discoloration of the plating.
[0030]
As a coating method for forming a film in the present invention, any method such as spraying, curtain, flow coater, roll coater, bar coater, brush coating, dipping, and air knife method may be used.
[0031]
The baking temperature is desirably 50 to 250 ° C. Although there is no particular limitation on the drying equipment, a method using hot air blowing, a method using indirect heating using a heater, a method using infrared rays, a method using induction heating, and a method using these in combination can be employed.
[0032]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
[0033]
(1) Kinds of drugs Table 1 shows a list of drugs used in the examples.
[0034]
[Table 1]
(2) Kind of metal plate The metal plate shown in Table 2 was used. The plate thickness was 1.0 mm in each case.
[0036]
[Table 2]
(3) Preparation of treatment liquid A Ti / Zr compound, a phosphoric acid compound, a guanidine compound, a metal compound, a water-soluble resin, and a lubricating component shown in Table 1 are blended in the ratios shown in Tables 4, 5, 6, 7, 8, and 9. Then, a treatment liquid was prepared.
[0038]
(4) Coating and drying method of treatment liquid The treatment liquid prepared in (3) is applied to an untreated plated metal plate so as to have a value shown in Tables 4, 5, 6, 7, 8, and 9 as a dry mass. Then, the sample was dried at a reaching plate temperature of 80 ° C. to prepare a sample for evaluation. The amount of the treated film deposited was confirmed by measuring Ti and Zr in the film with a fluorescent X-ray apparatus and using the measured values as indices.
[0039]
(5) Performance evaluation item (5) -1 A sample for evaluation prepared in flat plate corrosion resistance (4) was subjected to a salt spray test method described in JIS Z 2371 at an ambient temperature of 35 ° C and 5% NaCl. The aqueous solution was sprayed on the sample, and the white plate rust occurrence rate after 72 hours was measured and evaluated. In the following evaluations, ◎ and ○ were evaluated as good.
：: No white rust generated ○: White rust generated area less than 10% △: 10% or more and less than 50% ×: 50% or more
(5) -2 Processed part Corrosion resistance The test sample prepared in (4) was subjected to a 6 mm Erichsen process on a test piece, and subjected to a salt water spray test described in JIS Z 2371 at an ambient temperature of 35 ° C. A 5% aqueous solution of NaCl was sprayed on the sample, and the rate of occurrence of white rust in the processed portion after 48 hours was measured and evaluated. In the following evaluations, ◎ and ○ were judged to be good.
◎: No white rust generated ○: White rust generated area less than 10% △: 10% or more and less than 50% ×: 50% or more
(5) -3 The sample for evaluation produced in the alkali resistance (4) was immersed in a 3% aqueous solution of a water-soluble processing oil (ST Sole F5, manufactured by Satoh Oil Co., Ltd.) for 5 minutes, air-dried, and described in JIS Z 2371. A 5% aqueous solution of NaCl was sprayed on the sample at an ambient temperature of 35 ° C. according to the salt spray test method, and the white rust generation rate after 48 hours was measured and evaluated. In the following evaluations, ◎ and ○ were evaluated as good.
：: White rust occurrence area less than 10% ：: White rust occurrence area less than 30% △: 30% or more and less than 50% ×: 50% or more
(5) -4 A Bowden test (load: 500 g, indenter: 10 mmφ SUJ-2, sliding distance: 50 mm, sliding speed: 50 mm / sec) was performed on the evaluation sample prepared in the workability test (4). The coefficient of friction at the second time was measured and evaluated.
：: coefficient of friction less than 0.2 △: coefficient of friction 0.2 to 0.4
×: Coefficient of friction exceeding 0.4
(5) -5 Continuous spot welding test was performed on the evaluation sample prepared in (4) under the conditions shown in Table 3. The number of hit points at which a nugget diameter of 4.5 mmφ or more can be formed stably was determined.
[0044]
[Table 3]
In the following evaluations, ◎ and ○ were judged to be good.
：: Number of hit points 2,000 or more ○: 1,000 to less than 2,000 points △: Less than 1,000 points ×: Less than 500 points
(5) -6 Heat and corrosion resistance test The heat and corrosion resistance test was conducted by heating the evaluation sample prepared in (4) at 350 ° C. for 8 hours, and then performing a cycle corrosion test (5% NaCl aqueous solution spray (35 ° C.) spraying according to JASO M609) → Drying (60 ° C., 20 to 30% RH) → wetting (50 ° C., 98% RH or more)) was performed for 15 cycles, and the white rust generation rate was measured. In the following evaluations, ◎ and ○ were evaluated as good.
：: White rust occurrence area less than 10% ：: White rust occurrence area less than 30% △: 30% or more and less than 50% ×: 50% or more
Tables 4, 5, 6, 7, 8, and 9 show the above evaluation results. According to Tables 4, 5, 6, 7, 8, and 9, the chromate-free treated metal sheet of the present invention is excellent not only in flat corrosion resistance, corrosion resistance in processed parts, alkali resistance and heat resistance corrosion resistance, but also in weldability in any case. Is clear.
[0048]
[Table 4]
[Table 5]
[Table 6]
[Table 7]
[Table 8]
[Table 9]
【The invention's effect】
INDUSTRIAL APPLICABILITY The chromate-free treated metal sheet of the present invention has good corrosion resistance and alkali resistance, and does not use any hexavalent chromium. , Inner plate, around engine, columns, beams, metal joints, etc. can be used suitably for construction. Therefore, according to the present invention, a chromate-free treated metal plate having good corrosion resistance and alkali resistance can be provided on the market.
Claims (8)
（ａ）チタニウム化合物をチタニウム換算で１０〜２００ｍｇ／ｍ２またはジルコニウム化合物をジルコニウム換算で１０〜２００ｍｇ／ｍ２、あるいはチタニウム化合物とジルコニウム化合物をそれぞれチタニウムとジルコニウム換算で合計１０〜２００ｍｇ／ｍ２の皮膜を有し、その皮膜中にさらに（ｂ）リン酸化合物と（ｃ）グアニジン化合物を含有することを特徴とする耐食性、耐アルカリ性に優れたクロメートフリー処理金属板。On the surface of metal or plated metal plate,
(A) titanium compound of titanium in terms of 10 to 200 mg / m 2 or zirconium compound in terms of zirconium in the 10 to 200 mg / m 2, or titanium compound and a zirconium compound of the total 10 to 200 mg / m 2 of titanium and zirconium in terms respectively A chromate-free treated metal plate having excellent corrosion resistance and alkali resistance, comprising a film and further containing (b) a phosphate compound and (c) a guanidine compound in the film.
Ｍｇ：１〜１０質量％、Ａｌ：２〜１９質量％、Ｓｉ：０．０１〜２質量％含有し、かつ、ＭｇとＡｌが下式
Ｍｇ（質量％）＋Ａｌ（質量％）≦２０（質量％）
を満たし、残部がＺｎ及び不可避的不純物よりなるＺｎ合金めっき層であることを特徴とする請求項１〜６の何れかに記載のクロメートフリー処理金属板。The plating layer of the plated metal plate contains Mg: 1 to 10% by mass, Al: 2 to 19% by mass, Si: 0.01 to 2% by mass, and Mg and Al are represented by the following formula: Mg (% by mass) + Al ( Mass%) ≦ 20 (mass%)
The chromate-free treated metal sheet according to any one of claims 1 to 6, wherein a zinc alloy plating layer comprising Zn and inevitable impurities is satisfied.
Ａｌ：５０〜９５質量％、Ｓｉ：０．５〜１２質量％含有し、残部が不可避的不純物もしくはＺｎ及び不可避的不純物よりなるＡｌ合金めっき層であることを特徴とする請求項１〜６の何れかに記載のクロメートフリー処理金属板。The plating layer of the plated metal plate contains 50 to 95% by mass of Al and 0.5 to 12% by mass of Si, and the balance is an Al alloy plating layer composed of unavoidable impurities or Zn and unavoidable impurities. The chromate-free treated metal plate according to claim 1.
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| JP2008285738A (en) * | 2007-05-21 | 2008-11-27 | Jfe Steel Kk | Surface-treated steel sheet |
| WO2009004684A1 (en) * | 2007-06-29 | 2009-01-08 | Nihon Parkerizing Co., Ltd. | Aqueous fluid for surface treatment of zinc-plated steel sheets and zinc-plated steel sheets |
| CN105051257A (en) * | 2013-03-15 | 2015-11-11 | 汉高股份有限及两合公司 | Improved trivalent chromium-containing composition for aluminum and aluminum alloys |
| JP2016089232A (en) * | 2014-11-06 | 2016-05-23 | 日新製鋼株式会社 | Method for surface-treating zinc-aluminum magnesium alloy plated steel sheet |
| WO2020129473A1 (en) | 2018-12-20 | 2020-06-25 | Ｊｆｅスチール株式会社 | Surface-treated steel sheet |
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| WO2020129473A1 (en) | 2018-12-20 | 2020-06-25 | Ｊｆｅスチール株式会社 | Surface-treated steel sheet |
| KR20210092258A (en) | 2018-12-20 | 2021-07-23 | 제이에프이 스틸 가부시키가이샤 | surface treatment steel plate |
| US11795526B2 (en) | 2018-12-20 | 2023-10-24 | Jfe Steel Corporation | Surface-treated steel sheet |
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