JP2004533542A - Corrosion resistant treatment method for metal surface - Google Patents
Corrosion resistant treatment method for metal surface Download PDFInfo
- Publication number
- JP2004533542A JP2004533542A JP2003508743A JP2003508743A JP2004533542A JP 2004533542 A JP2004533542 A JP 2004533542A JP 2003508743 A JP2003508743 A JP 2003508743A JP 2003508743 A JP2003508743 A JP 2003508743A JP 2004533542 A JP2004533542 A JP 2004533542A
- Authority
- JP
- Japan
- Prior art keywords
- treatment
- metal surface
- acid
- solution
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
Abstract
Description
【技術分野】
【０００１】
本発明は、金属表面の耐食処理の分野に関するものである。本発明の一様相は、非被覆金属表面上に、耐食層を沈着させることを含むものである。本発明の他の様相は、前記金属表面上に既に沈着された耐食層の耐食作用を強化することを含むものである。本発明の特徴事項は、クロム又はニッケルのような、有毒重金属が全く用いられていないことである。
【背景技術】
【０００２】
耐食性を増強するために非被覆金属表面上に耐食層を沈着すること及び既に被覆されている金属表面をリンスすることに関連する広範囲にわたる先行技術がある。これら先行技術文献のいくつかを例示すると、アルミニウム表面を、クロムなし処理について具体的に記載したものがある。これに関連して用いられている用語「化成処理」は、処理溶液の成分が、金属表面に化学的に反応してその結果、前記処理溶液の成分と、金属表面からの金属原子との両方が合体して含まれる耐食層が形成されることを示すものである。
【０００３】
アルミニウム表面に、ほう素、硅素、チタン又はジルコニウムのフルオライドのそれぞれ、又はそれと有機重合体との組み合わせにより、非クロム含有化成処理を施して、永久耐食性を得ること、及び、それに引続く被覆のための基体を作製することは、原理的に既知である。
【０００４】
ＵＳ−Ａ−５１２９９６７（特許文献１）は、アルミニウムのリンスなし処理（以下これを、「即時乾燥された化成被覆」と記す。）用の処理浴を開示しており、この処理浴は、
ａ）１０〜１６ｇ／リットルのポリアクリル酸又はその単一重合体、
ｂ）１２〜１９ｇ／リットルのヘキサフルオロジルコン酸、
ｃ）０．１７〜０．３ｇ／リットルのフッ化水素酸、及び
ｄ）０．６ｇ／リットル以下のヘキサフルオロチタン酸、
を含むものである。
【０００５】
ＥＰ−Ｂ−８９４２（特許文献２）は、好ましくはアルミニウム缶に用いられる処理溶液を開示しており、この処理溶液は
ａ）０．５〜１０ｇ／リットルの、ポリアクリル酸又はそのエステル、及び
ｂ）０．２〜８ｇ／リットルの、Ｈ2ＺｒＦ6，Ｈ2ＴｉＦ6及びＨ2ＳｉＦ6から選ばれた少なくとも１成分
を含み、この溶液のpHは、３．５未満であり、かつ、前記処理液の補充用水性濃厚液は、
ａ）２５〜１００ｇ／リットルの、ポリアクリル酸又はそのエステル、
ｂ）２５〜１００ｇ／リットルの、Ｈ2ＺｒＦ6，Ｈ2ＴｉＦ6及びＨ2ＳｉＦ6から選ばれた少なくとも１成分、及び、
ｃ）７〜１２０ｇ／リットルの遊離フルオライドを生成するための遊離フッ化物源
を含むものである。
【０００６】
ＤＥ−Ｃ−１９３３０１３（特許文献３）は、３．５より高いpHを有する処理浴を開示しており、この処理浴は、金属量に換算して、０．１〜１５ｇ／リットルの、ほう素、チタン又はジルコニウムの錯フルオライドの他に、０．５〜３０ｇ／リットルの酸化剤、特に、メタニトロベンゼンスルホン酸ナトリウムを、含むものである。
【０００７】
ＤＥ−Ｃ−２４３３７０４には、特にアルミニウムへの被覆密着性及び永久耐食保護の向上のための処理浴についての記載があり、これらの処理浴はポリアクリル酸又はその塩又はエステルを０．１〜５ｇ／リットルと、フルオロジルコン酸アンモニウムを、ＺｒＯ2換算で０．１〜３．５ｇ／リットルを含むことがあるものである。これらの処理浴のpHは、広い範囲にわたって変動することができる。一般に、pHが６〜８の範囲内にあるとき最良の結果が得られる。
【０００８】
ＵＳ−Ａ−４９９２１１６には、アルミニウムの化成処理のための処理浴が記載されており、この処理浴は、約２．５〜５のpHを有し、少なくとも下記３成分を含むものである。
ａ）１．１×１０-5乃至５．３×１０-3モル／リットルの範囲内の濃度のりん酸イオン、上記濃度は１〜５００mg／リットルに相当する。
ｂ）１．１×１０-5〜１．３×１０-3モル／リットルの、Ｚｒ，Ｔｉ，Ｈｆ及びＳｉから選ばれた１元素のフッ素酸（上記濃度は、元素の種類に応じて、１．６〜３８０mg／リットルに相当する）、及び
ｃ）０．２６〜２０ｇ／リットルのポリフェノール化合物、この化合物はポリ（ビニルフェノール）と、アルデヒド及び有機アミンとの反応により得ることができる。
この場合、前記フッ素酸の前記りん酸塩に対するモル比は、約２．５：１から１：１０までの範囲内に保護されるべきものである。
【０００９】
ＤＥ−Ａ−２７１５２９２には、アルミニウム缶のクロムを含まない予備処理用の処理浴が開示されている。これらの処理浴は、少なくとも１０ppmのチタン及び／又はジルコニウム、１０〜１０００ppmのりん酸塩と、及び、存在するチタン及び／又はジルコニウムの錯フルオライドを形成するのに十分な量の、但し、少なくとも１３ppmの、フルオライドとを含み、かつ１．５〜４の範囲内のpHを有するものである。
【００１０】
ＷＯ９２／０７９７３は、アルミニウムに対する、クロムを用いない処理方法を開示しており、この処理方法は、酸性水性溶液中に不可欠成分として含まれた０．０１〜約１８重量％のＨ2ＺｒＦ6及び０．０１〜約１０重量％の３−（Ｎ−Ｃ1-4−アルキル−Ｎ−２−ヒドロキシエチルアミノメチル）−４−ヒドロキシスチレンポリマーを用いるものである。必要により使用される成分は、０．０５〜１０重量％のＳｉＯ2分散体、０．０６〜０．６重量％のポリマー可溶化剤、並びに界面活性剤である。
【００１１】
前記広範囲にわたる先行技術（その一部のみがこゝに報告されている）にも拘らず、金属表面の耐食保護処理のためのさらに処理剤及び処理方法の改善が必要とされている。
【００１２】
未公開のドイツ特許出願ＤＥ１０００５１１３は、ビニルピロリドンの単一重合体又は共重合体が、優れた腐食防止作用を有していることを見出したことに基くものである。この発明は、その第１の様相において、金属表面の耐食保護処理方法に関するものであって、この方法は金属表面を、ビニルピロリドンの単一重合体又は共重合体と接触させることを特徴とするものである。この場合、この発明の第１の態様において、前記金属表面は、先ず最初に先行技術による化成処理、例えば、亜鉛又は鉄を用いるりん酸塩、化成処理、金属、例えばチタン、ジルコニウム、又はハフニウム、或は場合によりほう素又は硅素、のフッ素酸を用いる化成処理、或は、ビニルピロリドン単位を含まない有機重合体の溶液又は懸濁液を用いる処理に供される。前記重合体の例は、前記特許出願明細書の導入部に引用された文献中に記載されている。
【００１３】
前記引用された発明のその他の態様は、前記金属表面を、ビニルピロリドンの単一重合体、又は共重合体と接触させ、それと同時に、前記金属表面を、化成処理に供することを含むものである。従って、この場合、前記単一重合体又は共重合体は、処理溶液中に含まれ、この手段により、化成層が、前記金属表面上に形成される。化成層形成用処理溶液は、例えば、りん酸又はそのアニオンを含んでいてもよい。亜鉛及び／又はマンガンなどの２価のカチオンも前記処理溶液中に含まれていてもよい。前記化成層形成用処理溶液の具体的例はりん酸亜鉛化成処理溶液であり、この溶液は、前記金属表面上に、亜鉛を含む金属りん酸塩の結晶層を形成する。しかしながら、この処理溶液は、りん酸及び／又はそのアニオンも含んでいてもよいが、しかし、２価の金属は含まないものである。その一例は、りん酸鉄溶液であり、これは、金属表面上に、具体的には、鉄含有表面上に、りん酸金属塩及び／又は、金属酸化物の実質的に非結晶質の層を形成する。このような処理浴液中のビニルピロリドンの単一重合体又は共重合体の存在は、この化成層により得られる耐食保護効果を改善する。このことは、若し前記処理溶液が、ビニルピロリドンの単一重合体又は共重合体に加えて、化成層を形成するための成分として、フッ酸及び／又は、金属及びセミ金属、例えばほう素、硅素、チタン、ジルコニウム及び／又はハフニウム、の錯フルオライドを、含む場合にも適用される。
【００１４】
前記に引用したＤＥ１０００５１１３によれば、金属表面処理用の即席使用溶液は、０．０５〜２００ｇ／リットルのビニルピロリドンの単一重合体又は共重合体を含むことが好ましい。
【発明の開示】
【発明が解決しようとする課題】
【００１５】
本発明が解決しようとする課題は、前記ＤＥ１０００５１１３の課題手段を、使用される薬剤の効果に関して、更に改良することにある。
【課題を解決するための手段】
【００１６】
本発明は、金属表面を処理するための処理剤に関するものであり、この処理剤はりん酸及び／又はＺｒ，Ｔｉ，Ｈｆ及びＳｉから選ばれた１種以上の元素の少なくとも１種のフッ素酸或はそれぞれの対応アニオン、及び、ビニルピロリドンの単一重合体又は共重合体を含み、それが、使用のための即席使用溶液の形状にあって、
ａ）０．０２〜２０ｇ／リットルのりん酸及び／又はＺｒ，Ｔｉ，Ｈｆ及びＳｉから選ばれた１種以上の元素の少なくとも１種のフルオロ酸或はそれぞれのアニオンと、及び
ｂ）１０〜４９．９mg／リットルのビニルピロリドンの単一重合体又は共重合体
を含むことを特徴にするものである。
【発明を実施するための最良の形態】
【００１７】
りん酸が存在する場合、金属表面処理用処理剤は、りん酸塩化成処理溶液である。この溶液が、２価の金属、すなわち、亜鉛及び／又はマンガン、のイオンを含まない場合には、この溶液は“皮膜非形成性”りん酸塩化成溶液と称され、これは、例えば、りん酸鉄化成溶液の形状にあってもよい。亜鉛及び／又はマンガンを含むりん酸塩化成処理溶液（これは、例えば、０．３〜２ｇ／リットルの亜鉛イオンと、必要により、それに加えて、或はその代りに、ほぼ、前記と同一濃度のマンガンイオンを含む）は、化成処理分野においては、“皮膜形成性“りん酸塩化成処理液と称されている。この処理溶液は、りん酸とともに、或はその代りに、Ｚｒ，Ｔｉ，Ｈｆ及びＳｉから選ばれた１種以上の元素の１種以上のフッ素酸を含んでいてもよい。この溶液の設定されたpHに応じて、前記りん酸及び前記フッ素酸の両者は、部分的に、負の１価に、又は複数価に帯電したアニオンの形状に部分的に存在する。酸のアニオンの非解離酸に対する比は、各酸のプロトリシス定数（protolysis constant）及び実際に設定されたpHに応じて定まる。この現象は、一般に、酸−塩基平衡として知られている、上記の不可欠成分に加えて、本発明の処理剤は、水を含み、かつ必要により、pHを規定するための、耐食作用を増進するための、使用の容易性を改良するための、及び、他の目的のために有効な、他の活性成分或は、補助物質を含むものである。
【００１８】
本発明の処理剤が、ビニルピロリドンの共重合体を含む場合には、これらの共重合体は、ビニルピロリドンに加えて、１種以上の他のモノマーを含んでいてもよい。よって、これら共重合体は、例えば、２成分を含む共重合体、或は、３成分を含む共重合体（三元共重合体）である。単一重合体と二成分共重合体との混合物、単一重合体と三元共重合体との混合物、或は、二成分共重合体と三元共重合体との混合物もまた使用することができる。
【００１９】
即席使用処理剤は、濃厚液を希釈することにより得ることができる。これは、未公開ドイツ特許出願ＤＥ１０００５１１３の主題である。具体的組成に応じて、既にすべての活性成分を含む濃厚液は、長期間にわたる貯蔵において、十分に安定ではないことがある。このような場合には、この濃厚液を、少なくとも２つの成分に分け、各成分が、即席使用耐食処理剤の選択された成分を含むようにすることが好ましい。例えば、前記濃厚液の一成分が、少なくとも主に、処理剤の無機構成成分を含み、濃厚液の他の少なくとも１成分が、有機重合体を含むことが、適切であると思われる。また、濃厚液の２成分は、互に異るpH値を有していてもよく、それによって、濃厚液成分の貯蔵中の安定性を向上させることができる。即席使用の形状にある処理剤を調製するため、或は、補充するために、当該濃厚液の成分を各個に、水で、希釈して、活性成分が、所望の濃度範囲内にあるようにする。このとき、酸或は苛性アルカリ溶液を添加して、pHを、所要の範囲内に規定することが必要と思われる。
【００２０】
処理液中の活性成分ａ）及びｂ）の好ましい濃度範囲は、りん酸又は、りん酸塩イオンの場合は、５〜２０ｇ／リットル、特に８〜１０ｇ／リットルのりん酸塩イオンであり、フッ素酸の場合には、それに含まれるＺｒ，Ｔｉ，Ｈｆ及び／又はＳｉの量が、２０〜１０００mg／リットル、特に、５０〜４００mg／リットルである。処理液中のビニルピロリドンの単一重合体又は共重合体の濃度は、２０〜４５mg／リットルの範囲内にあることが好ましい。
好適なビニルピロリドンの単一重合体又は共重合体は、例えば、下記表１に記載のポリマー又は、表１中に記載のモノマーの重合体である。
【００２１】
【表１】
耐食保護効果を向上させるために、本発明の処理剤は、前記の他に、元素亜鉛、マンガン、セリウム又はバナジウムのイオンのような遷移金属イオン、及び、フッ化水素酸又は遊離フルオライド類を含んでいてもよい。また、クロムイオン又はニッケルイオンの存在は、原理的には有利である。しかし、工業的安全及び環境保護の理由により、クロムイオン又はニッケルイオンの添加を避けることが好ましい。従って、本発明の好ましい態様においては、処理剤はニッケル及びクロムを含まないものである。このことは、これらの金属又はその化合物は、処理剤に意識的には添加されないことを意味する。しかし、鋼合金などのタンクの原材料、又は、その処理されるべき表面から生起したニッケル及び／又はクロムのイオンが、処理剤（処理溶液）中に低濃度で混入する可能性は、否定できない。しかし、実際においては、即席使用の処理溶液中のニッケル及び／又はクロムの濃度は、約１０ppmより多量にはならないものと予想される。
【００２３】
本発明に係る即席使用処理剤は、１〜６の範囲内の、特に２〜５．５の範囲内のpHを有することが好ましい。このことは、元素Ｚｒ，Ｔｉ，Ｈｆ又はＳｉのフッ素酸類は、pH及びプロトリシス定数に応じて、部分的に、遊離酸の形状にあり、かつ部分的にその酸性アニオンの形状にあることを意味する。従って、これらのフッ素酸類が、そのまゝの形状で用いられるか、又は塩の形状で、用いられるかのいずれかについては関係がない。更に、Ｚｒ，Ｔｉ，Ｈｆ又はＳｉの酸可溶性化合物、及びフッ化水素酸又は可溶性フルオライド類を別々に添加してもよく、これは、上記元素のフルオロアニオン類がこれらから形成され得るからである。使用方法に応じて、pHを、上記の元素の遊離フッ素酸或は場合により、フッ化水素酸、硫酸、硝酸、又はりん酸のような酸の添加により、或は、アルカリ金属の炭酸塩の溶液、アルカリ金属の水酸化物の溶液又はアンモニアの添加により、所望の範囲内に規定するべきである。
【００２４】
カプロラクタム基を含むビニルピロリドンの単一重合体又は共重合体が、特に良好な抗腐食作用を有しているという理由により、本発明の具体的一態様において、本発明の処理剤は、カプロラクタム基を含むビニルピロリドンの単一重合体又は共重合体を含んでいる。
【００２５】
本発明の他の様相は、金属表面を処理する方法であり、この方法において、金属表面（これは、所望により耐食性層を既に担持していてもよい）を、前記の処理剤に接触させる。前記金属表面は、例えば、鋼、亜鉛めっき鋼（電気めっき又は、溶融浸漬めっきされたもの）、亜鉛合金により被覆された鋼、或はアルミニウム又はマグネシウムから形成された表面から選択されてもよい。この場合、金属アルミニウム及びマグネシウムは、一般に純粋物の形状にはなく、他の元素、例えばリチウム、亜鉛、銅、硅素、マグネシウム（アルミニウム合金の場合）又はアルミニウム（マグネシウム合金の場合）のような他の元素との合金の形状にある。本発明方法は、特に、車輌の構成、家庭用具工業、或は、建築又は調度の分野において使用される前記金属からなる表面の処理に有用なものである。
【００２６】
上記事項に関連して、耐食性層を有していない前記金属の表面を処理することができる。本発明に係る前記処理方法は、このような場合、耐食性被覆層を形成し、この被覆層は、同時に、ラッカーのような必要によりその上に塗布されるべき有機被覆層との密着性を改善する。しかしながら、既に耐食性層により被覆されている前記金属表面を、さらに本発明の方法により処理してもよい。この場合、既に被覆している耐食性層の抗腐食作用がさらに増進される。例えば、本発明方法は、Ｘ−線非晶質又は結晶質被覆層を有する金属表面の後処理に好適であり、前記Ｘ−線非結晶性又は結晶性被覆層とは、例えば非被膜層形成性、又は被膜層形成性りん酸塩化成処理、例えば被膜層形成性りん酸亜鉛化成処理により形成されたものである。このような前処理された金属表面を、本発明方法により処理すると、前記前処理の後に、得られた初期耐食性層中に残存している空孔が封鎖される。
【００２７】
本発明の処理方法において、金属表面に、処理溶液を、例えば、スプレーにより、又は浸漬により接触させることができる。この場合、前記接触時間の経過後、前記処理溶液を、水ですすぎ洗いする工程を設けることが好ましく、このすすぎ洗い時間は例えば３０秒〜５分間であってもよい。上記方法の代りに、処理溶液を、金属表面にすすぎ洗いを施さない方法で、接触させてもよい。この場合処理溶液は、金属表面上にスプレーされるか、或は、金属表面に、塗布ローラーにより塗布される。接触時間（これは例えば２〜２０秒間の範囲内にある）の経過後、処理溶液を、中間すすぎ洗いすることなしに、乾燥する。この乾燥は、例えば、加熱炉内において行われる。
【００２８】
本発明の処理方法において、処理溶液は、好ましくは、１〜６の範囲内のpHを有する。しかし、pHの範囲は、基体、塗布方法及び接触時間に応じて、より狭いことが、好ましい。例えば、非被覆金属表面の処理においては、pHを、２〜６の範囲内に規定することが好ましく、特にアルミニウム表面の処理のためには、pHは２〜４の範囲内にあることが好ましく、特に、鋼、亜鉛又は亜鉛めっき鋼の処理のためにはpHは３〜５の範囲内にあることが好ましい。既に前処理され、例えば、りん酸塩化成層を有する金属表面には、３．５〜５の範囲内のpHを有する処理液を接触させることが好ましい。本発明方法の実施における処理溶液の温度は、一般に、当該処理溶液の凍結温度と、沸騰温度の間にあり、室温以上の範囲内の温度が、実務上の理由により好ましい。例えば、処理溶液の温度は、１５〜６０℃の範囲内にあればよく、特に２０〜４５℃であればよい。
【００２９】
本発明の処理方法は、１工程であり、関連分野における他の工程と、従来の順序により連結される。例えば、処理すべき金属表面は、通常、本発明の処理の前に従来の清浄化溶液を用いて清浄化される。しかし、本発明の処理の直前に処理されるべき金属表面が被覆されたとき、例えば亜鉛めっきされるとき、或は、化成処理、例えばりん酸塩化成処理、に供されるときには、前記清浄化工程は省略されてもよい。本発明の処理工程の後に、得られた金属表面は、有機被覆層、例えば、ラッカー、により従来方法により被覆される。この被覆層は、例えば、供塗装層、或は、電着塗装、特にカチオン電着塗装による、電着塗装層であってもよい。
【００３０】
本発明方法を実施するときの特に好ましい方法は、金属表面を、化成処理層を形成するための前記処理剤と接触させる前に、すなわち、化成処理中において、酸の水溶液により処理する工程を含むものである。この挿入された加工工程は、化成処理前に金属表面を、酸の水溶液で処理することを含み、この工程は、当業界においては、“酸洗い（acid pickling）”又は“酸洗い不動態化（pickle passivation）”と称される。前記酸洗い又は酸洗い不動態化に従来用いられている酸を、本発明の方法の目的のために用いることができる。これらの酸の例は、りん酸である。
【００３１】
実施例 化成処理としての使用
【実施例１】
【００３２】
従来の酸洗い不動態化を伴う化成処理
基材：溶融浸漬めっきされた鋼材（ＨＤＧ）
電気めっきされた鋼材（ＥＧ）
アルミニウム（ＡＣ１２０）
冷圧延鋼（ＣＲＳ）
工程の順序（スプレー塗布）
１．清浄化：
Ｒｉｄｏｌｉｎｅ（登録商標）（リドリン）１５７０、３％、８２秒間、５５℃
Ｒｉｄｏｓｏｌ（登録商標）（リドソール）１２７０、０．３％、本件出願人製造の市販の金属清浄化剤
２．すすぎ洗い： 脱イオン水
３．酸洗い不動態化：りん酸、０．２３％、８２秒間
４．すすぎ洗い： 脱イオン水
５．化成処理： １０８秒間、３０秒間、
Ｈ2ＺｒＦ6酸（４５％、１．３８ｇ／リットル）、及び
ビニルピロリドン／ビニルカプララクタム重合体
固体含有量（３７mg／リットル）、
を含む水溶液を使用
６．すすぎ洗い： 脱イオン水
７．乾燥： 圧縮空気
８．被覆処理： 鉛を含まないカチオン電着塗装法による（ＢＡＳＦ ＣＧ ３１０）
被覆層の厚さ：２０〜２３μｍ
【実施例２】
【００３３】
上記と同一の工程順序による。但し、工程３及び４を省略した。
【００３４】
腐食試験
亜鉛めっき基体： 食塩水中に浸漬後に被覆層の密着性試験
アルミニウム： 銅促進食塩スプレー試験 ＣＡＳＳ
ＤＩＮ ５００２１、１０日間
鋼： 食塩スプレー試験 ＳＳ ＤＩＮ ５００２１、２１日間
結果： スクライブ（刻印）に沿う塗膜のクリープ度（片側膨れ幅）：Ｕ／２単位：mm；
被覆層の密着性に関する石衝撃試験の結果：（Ｋ値によるＫ＝１のとき、最良の被覆層密着度であり、Ｋ＝１０のとき、最悪の被覆層密着度とする）
【００３５】
【表２】
【００３６】
化成処理及びそれに続く共重合体混合物使用粉体塗装（亜鉛めっき鋼）
基体： ＣＲＳ，ＥＧ，ＨＤＧ
工程の順序（浸漬法を適用）
１．清浄化： Ｒｉｄｏｌｉｎｅ（登録商標）（リドリン）１５７０、２％、
Ｒｉｄｏｓｏｌ（登録商標）（リドソール）１２３７、０．３％、
５分間、５５℃（出願人より製造された市販金属清浄化剤）
２．すすぎ洗い： 脱イオン水
３．化成処理： １８０秒間、３０℃
下記組成の処理浴を使用
Ｈ2ＺｒＦ6酸（４５％、１．３８ｇ／リットル）と、
ビニルピロリドン／ビニルカプロラクタム共重合体（＝Ｐa ）と、
ビニルピロリドン／ビニルイミダソール共重合体（＝Ｐb ）との混合物
（固形分含有量３７mg／リットル）
４．すすぎ洗い： 脱イオン水
５．乾燥： 圧縮空気
６．被覆処理： ポリエステルＰＥＳ ５８０７／ＲＡＬ ５００９ＧＬ
（ＴＩＧＳを含まず、Ｈｅｒｂｅｒｔ製品）、約６０〜８０μｍ厚
【００３７】
腐食試験
中性食塩スプレー試験 ＤＩＮ ５００２１ ＳＳ、２１日間
結果： スクライブに沿う塗膜のクリープ度、片側膨れ幅
クロスカット塗装密着試験による被膜の密着度
【００３８】
【表３】
ポリマーの配合割合例えば単一重合体／重合体比を変化させることができる。
Ｐa ％＝１００％−Ｐb ％、Ｐa ＞０
【実施例４】
【００４０】
共重合体混合物を用いる化成処理（粉体塗装）
基材： ＣＲＳ
工程の順序（浸漬法を適用）
１．清浄化： Ｒｉｄｏｌｉｎｅ（登録商標）（リドリン）１５７０、２％、
Ｒｉｄｏｓｏｌ（登録商標）（リドソール）１２３７、０．３％、
５分間、５５℃
２．すすぎ洗い： 脱イオン水
３．化成処理： １８０秒間、３０℃
下記組成の処理浴を使用した。
Ｈ2ＺｒＦ6酸（４５％、１．３８ｇ／リットル）と、
ビニルピロリドン／ビニルカプロラクタム共重合体（＝Ｐb ）と、
ビニルピロリドン／ビニルイミダソール共重合体（＝Ｐa ）との混合物、
（固形分含有量２２mg／リットル）
４．すすぎ洗い： 脱イオン水
５．乾燥： 圧縮空気
６．被覆処理： ポリエステルＰＥＳ ５８０７／ＲＡＬ ５００９ＧＬ
（ＴＩＧＣを含まず、Ｈｅｒｂｅｒｔ社の製品）、
約６０〜８０μｍ厚
【００４１】
腐食試験
中性食塩スプレー試験 ＤＩＮ ５００２１ ＳＳ、２１日間
【００４２】
【表４】
[0001]
The present invention relates to the field of corrosion treatment of metal surfaces. One aspect of the present invention involves depositing a corrosion resistant layer on an uncoated metal surface. Another aspect of the present invention involves enhancing the corrosion resistance of a corrosion resistant layer already deposited on the metal surface. A feature of the present invention is that no toxic heavy metals, such as chromium or nickel, are used.
[Background Art]
[0002]
There is an extensive prior art relating to depositing a corrosion resistant layer on uncoated metal surfaces to enhance corrosion resistance and rinsing already coated metal surfaces. To illustrate some of these prior art documents, there is a specific description of an aluminum surface for a chromium-free treatment. The term "chemical conversion treatment" used in this context means that the components of the treatment solution chemically react with the metal surface, so that both the components of the treatment solution and the metal atoms from the metal surface. Indicate that a corrosion-resistant layer is formed, which is included by combining the two.
[0003]
Aluminium surface is subjected to non-chromium-containing chemical conversion treatment with boron, silicon, titanium or zirconium fluoride or a combination thereof with an organic polymer to obtain permanent corrosion resistance, and for subsequent coating. It is known in principle to make substrates of
[0004]
U.S. Pat. No. 5,129,967 discloses a treatment bath for a non-rinse treatment of aluminum (hereinafter referred to as "immediately dried conversion coating"), which treatment bath comprises:
a) 10 to 16 g / l of polyacrylic acid or a homopolymer thereof,
b) 12-19 g / l hexafluorozirconic acid,
c) 0.17-0.3 g / l hydrofluoric acid, and d) 0.6 g / l or less of hexafluorotitanic acid,
Is included.
[0005]
EP-B-8942 discloses a treatment solution, preferably used for aluminum cans, comprising a) 0.5 to 10 g / l of polyacrylic acid or its esters, and b) the 0.2～8G / liter, comprising at least one component selected from H 2 ZrF 6, H 2 TiF 6 and H 2 SiF 6, pH of the solution is less than 3.5, and, The aqueous concentrate for replenishment of the treatment liquid,
a) 25-100 g / l of polyacrylic acid or its ester,
b) the 25～100G / liter, at least one component selected from H 2 ZrF 6, H 2 TiF 6 and H 2 SiF 6 and,
c) Contains a source of free fluoride to produce 7-120 g / liter of free fluoride.
[0006]
DE-C-193 33013 discloses a treatment bath having a pH higher than 3.5, which treatment bath has a pH of 0.1 to 15 g / l in terms of metal. In addition to complex fluorides of elemental, titanium or zirconium, they contain 0.5 to 30 g / l of an oxidizing agent, especially sodium metanitrobenzenesulfonate.
[0007]
DE-C-2433704 describes, in particular, treatment baths for improving the coating adhesion to aluminum and the protection of permanent corrosion resistance, these treatment baths containing polyacrylic acid or salts or esters thereof of 0.1 to 0.1%. and 5 g / l, the fluorozirconate ammonium, those which may include a 0.1～3.5G / liter in terms of ZrO 2. The pH of these treatment baths can vary over a wide range. Generally, best results are obtained when the pH is in the range of 6-8.
[0008]
U.S. Pat. No. 4,992,116 describes a treatment bath for the chemical conversion treatment of aluminum, which treatment bath has a pH of about 2.5 to 5 and contains at least the following three components.
a) Phosphate ions at a concentration in the range of 1.1 × 10 -5 to 5.3 × 10 -3 mol / l, said concentration corresponding to 1 to 500 mg / l.
b) 1.1 × 10 −5 to 1.3 × 10 −3 mol / liter of one element of fluoric acid selected from Zr, Ti, Hf and Si (the concentration depends on the type of element, 1.6 to 380 mg / l) and c) 0.26 to 20 g / l of a polyphenol compound, which can be obtained by reacting poly (vinylphenol) with aldehydes and organic amines.
In this case, the molar ratio of the fluoric acid to the phosphate should be protected in the range of about 2.5: 1 to 1:10.
[0009]
DE-A 27 15 292 discloses a treatment bath for chromium-free pretreatment of aluminum cans. These treatment baths contain at least 10 ppm of titanium and / or zirconium, 10 to 1000 ppm of phosphate, and an amount sufficient to form complex fluorides of titanium and / or zirconium present, but at least 13 ppm. And fluoride and having a pH in the range of 1.5-4.
[0010]
WO92 / 07973 is to aluminum, discloses a processing method using no chromium, this treatment method, an acidic aqueous solution H 2 ZrF 6 and 0.01 to about 18 wt% was included as an integral component in the It employs 0.01 to about 10% by weight of a 3- (N-C 1-4 -alkyl-N-2-hydroxyethylaminomethyl) -4-hydroxystyrene polymer. Components used if necessary is, SiO 2 dispersion from 0.05 to 10% by weight, 0.06 to 0.6 wt% of the polymeric solubilizing agent, and a surfactant.
[0011]
Despite the widespread prior art (only some of which are reported here), there is still a need for further improvements in treating agents and treatment methods for corrosion protection of metal surfaces.
[0012]
The unpublished German patent application DE 10005113 is based on the finding that homopolymers or copolymers of vinylpyrrolidone have excellent corrosion protection. The present invention, in a first aspect thereof, relates to a method for treating a metal surface for corrosion protection, the method comprising contacting the metal surface with a vinylpyrrolidone homopolymer or copolymer. It is. In this case, in a first aspect of the invention, the metal surface is first treated with a chemical conversion treatment according to the prior art, for example a phosphate using zinc or iron, a chemical conversion treatment, a metal such as titanium, zirconium or hafnium, Alternatively, it may be subjected to a chemical conversion treatment of boron or silicon with fluorine acid or a treatment using a solution or suspension of an organic polymer containing no vinylpyrrolidone unit. Examples of such polymers are described in the literature cited in the introductory part of said patent application.
[0013]
Another aspect of the cited invention involves contacting the metal surface with a vinylpyrrolidone homopolymer or copolymer and, simultaneously, subjecting the metal surface to a chemical conversion treatment. Thus, in this case, the homopolymer or copolymer is included in the processing solution, and by this means a conversion layer is formed on the metal surface. The chemical conversion layer forming treatment solution may contain, for example, phosphoric acid or an anion thereof. Divalent cations such as zinc and / or manganese may also be included in the treatment solution. A specific example of the treatment solution for forming a chemical conversion layer is a zinc phosphate chemical conversion treatment solution, and this solution forms a crystal layer of a metal phosphate containing zinc on the metal surface. However, the treatment solution may also contain phosphate and / or its anions, but does not contain divalent metals. One example is an iron phosphate solution, which comprises a substantially amorphous layer of metal phosphate and / or metal oxide on a metal surface, in particular on an iron-containing surface. To form The presence of a homopolymer or copolymer of vinylpyrrolidone in such a treatment bath improves the corrosion protection provided by this conversion layer. This means that if the treatment solution is, in addition to the vinylpyrrolidone homopolymer or copolymer, hydrofluoric acid and / or a metal and semimetal, such as boron, The present invention is also applied to the case where a complex fluoride of silicon, titanium, zirconium and / or hafnium is included.
[0014]
According to DE 100 51 113 cited above, the ready-to-use solution for metal surface treatment preferably comprises 0.05 to 200 g / l of vinylpyrrolidone homopolymer or copolymer.
DISCLOSURE OF THE INVENTION
[Problems to be solved by the invention]
[0015]
The problem to be solved by the present invention is to further improve the above-mentioned means of DE 100 51 113 with respect to the effect of the drug used.
[Means for Solving the Problems]
[0016]
The present invention relates to a treating agent for treating a metal surface, the treating agent comprising phosphoric acid and / or at least one fluorine acid of at least one element selected from Zr, Ti, Hf and Si. Or the respective anion, and a homopolymer or copolymer of vinylpyrrolidone, which is in the form of a ready-to-use solution for use,
a) 0.02 to 20 g / l of phosphoric acid and / or at least one fluoroacid or at least one respective anion of one or more elements selected from Zr, Ti, Hf and Si; 49.9 mg / liter of a vinylpyrrolidone homopolymer or copolymer.
BEST MODE FOR CARRYING OUT THE INVENTION
[0017]
When phosphoric acid is present, the treating agent for metal surface treatment is a phosphate conversion treatment solution. If the solution does not contain ions of divalent metals, namely zinc and / or manganese, the solution is referred to as a "non-film-forming" phosphate conversion solution, which comprises, for example, phosphorus It may be in the form of a ferric acid chemical conversion solution. Phosphate conversion solution containing zinc and / or manganese (e.g., 0.3 to 2 g / l of zinc ions and, if necessary, additionally or alternatively, approximately the same concentration as above) In the chemical conversion treatment field, is referred to as a "film-forming" phosphate conversion treatment solution. The processing solution may include, or instead of, phosphoric acid, one or more fluoric acids of one or more elements selected from Zr, Ti, Hf, and Si. Depending on the set pH of the solution, both the phosphoric acid and the fluoric acid are partially present in the form of negatively charged monovalent or multiply charged anions. The ratio of acid anion to non-dissociated acid depends on the protolysis constant of each acid and the pH actually set. This phenomenon is due to the fact that, in addition to the above essential components, commonly known as the acid-base equilibrium, the treating agent of the present invention contains water and, if necessary, enhances the anti-corrosion action to regulate the pH. And other active ingredients or auxiliary substances which are useful for improving the ease of use and for other purposes.
[0018]
When the treating agent of the present invention contains copolymers of vinylpyrrolidone, these copolymers may contain one or more other monomers in addition to vinylpyrrolidone. Therefore, these copolymers are, for example, copolymers containing two components or copolymers containing three components (ternary copolymers). A mixture of a homopolymer and a binary copolymer, a mixture of a homopolymer and a terpolymer, or a mixture of a binary copolymer and a terpolymer can also be used. .
[0019]
The instant use treatment agent can be obtained by diluting the concentrated solution. This is the subject of the unpublished German patent application DE 10005113. Depending on the specific composition, concentrates already containing all active ingredients may not be sufficiently stable on long-term storage. In such a case, it is preferred that the concentrate be divided into at least two components, with each component including a selected component of the instant use anticorrosion agent. For example, it may be appropriate that one component of the concentrate comprises at least predominantly the inorganic constituents of the treating agent and at least one other component of the concentrate comprises an organic polymer. The two components of the concentrate may also have different pH values, thereby improving the stability of the concentrate during storage. To prepare or replenish the treatment in ready-to-use form, each of the components of the concentrate is diluted with water to provide the active ingredient within the desired concentration range. I do. At this time, it seems necessary to add an acid or caustic solution to regulate the pH within a required range.
[0020]
The preferred concentration range of the active ingredients a) and b) in the treatment liquid is 5 to 20 g / l, especially 8 to 10 g / l of phosphate ions in the case of phosphate or phosphate ions, and fluorine In the case of acids, the amount of Zr, Ti, Hf and / or Si contained therein is between 20 and 1000 mg / l, in particular between 50 and 400 mg / l. The concentration of the vinylpyrrolidone homopolymer or copolymer in the treatment liquid is preferably in the range of 20 to 45 mg / liter.
Suitable homopolymers or copolymers of vinylpyrrolidone are, for example, the polymers listed in Table 1 below or the polymers of the monomers listed in Table 1.
[0021]
[Table 1]
In order to improve the corrosion protection effect, the treating agent of the present invention contains, in addition to the above, transition metal ions such as ions of the elements zinc, manganese, cerium or vanadium, and hydrofluoric acid or free fluorides. You may go out. Also, the presence of chromium ions or nickel ions is advantageous in principle. However, for reasons of industrial safety and environmental protection, it is preferred to avoid adding chromium or nickel ions. Thus, in a preferred embodiment of the invention, the treating agent is free of nickel and chromium. This means that these metals or their compounds are not consciously added to the treatment. However, it is undeniable that raw materials for the tank such as a steel alloy or nickel and / or chromium ions generated from the surface to be treated may be mixed into the treatment agent (treatment solution) at a low concentration. However, in practice, the concentration of nickel and / or chromium in the ready-to-use processing solution is not expected to be greater than about 10 ppm.
[0023]
The instant treatment agent according to the invention preferably has a pH in the range from 1 to 6, especially in the range from 2 to 5.5. This means that the fluoric acids of the elements Zr, Ti, Hf or Si are, depending on the pH and the protolysis constant, partly in the form of the free acid and partly in the form of their acidic anions. I do. Thus, it does not matter whether these fluoroacids are used in their original form or in the form of a salt. Further, acid soluble compounds of Zr, Ti, Hf or Si, and hydrofluoric acid or soluble fluorides may be added separately, since fluoroanions of the above elements may be formed therefrom. . Depending on the method of use, the pH is raised by the addition of an acid such as free fluoric acid or optionally hydrofluoric acid, sulfuric acid, nitric acid or phosphoric acid of the above-mentioned elements, or the carbonate of an alkali metal. The solution, alkali metal hydroxide solution or addition of ammonia should define the desired range.
[0024]
In one specific embodiment of the present invention, the treating agent of the present invention comprises a caprolactam group because a homopolymer or copolymer of vinylpyrrolidone containing a caprolactam group has a particularly good anticorrosion effect. Including vinylpyrrolidone homopolymers or copolymers.
[0025]
Another aspect of the present invention is a method of treating a metal surface, in which a metal surface, which may optionally carry a corrosion resistant layer, if desired, is contacted with the treatment agent described above. The metal surface may be selected, for example, from steel, galvanized steel (electroplated or hot dip galvanized), steel coated with a zinc alloy, or a surface formed from aluminum or magnesium. In this case, the metallic aluminum and magnesium are generally not in pure form, but may be other elements such as lithium, zinc, copper, silicon, magnesium (for aluminum alloys) or other elements such as aluminum (for magnesium alloys). In the form of an alloy with the element. The method of the invention is particularly useful for treating surfaces made of such metals used in the field of vehicle construction, the household tool industry, or in the building or furniture sector.
[0026]
In connection with the above, the surface of the metal without the corrosion resistant layer can be treated. The treatment method according to the invention forms a corrosion-resistant coating in such a case, this coating simultaneously improving the adhesion with the organic coating to be applied thereon if necessary, such as a lacquer. I do. However, the metal surface already covered by the corrosion resistant layer may be further treated by the method of the present invention. In this case, the anti-corrosion effect of the already coated corrosion-resistant layer is further enhanced. For example, the method of the present invention is suitable for post-treatment of a metal surface having an X-ray amorphous or crystalline coating layer, and the X-ray amorphous or crystalline coating layer includes, for example, a non-coating layer formation. It is formed by a phosphate conversion treatment capable of forming a film or a coating layer, for example, a zinc phosphate conversion treatment forming a film layer. When such a pretreated metal surface is treated by the method of the present invention, pores remaining in the obtained initial corrosion resistant layer after the pretreatment are blocked.
[0027]
In the treatment method of the present invention, the treatment solution can be brought into contact with the metal surface by, for example, spraying or dipping. In this case, it is preferable to provide a step of rinsing the treatment solution with water after the elapse of the contact time, and the rinsing time may be, for example, 30 seconds to 5 minutes. As an alternative to the above method, the treatment solution may be brought into contact with the metal surface in such a way that it is not rinsed. In this case, the treatment solution is sprayed on the metal surface or applied to the metal surface by means of an application roller. After a contact time, which is, for example, in the range of 2 to 20 seconds, the treatment solution is dried without an intermediate rinse. This drying is performed, for example, in a heating furnace.
[0028]
In the treatment method of the present invention, the treatment solution preferably has a pH in the range of 1-6. However, it is preferred that the pH range be narrower, depending on the substrate, application method and contact time. For example, in the treatment of an uncoated metal surface, the pH is preferably defined in the range of 2 to 6, particularly for the treatment of an aluminum surface, the pH is preferably in the range of 2 to 4. Preferably, the pH is in the range from 3 to 5, especially for the treatment of steel, zinc or galvanized steel. It is preferable to contact a treatment liquid having a pH in the range of 3.5 to 5 to a metal surface which has already been pretreated and has a phosphate conversion layer, for example. The temperature of the processing solution in the practice of the method of the present invention is generally between the freezing and boiling temperatures of the processing solution, with temperatures in the range above room temperature being preferred for practical reasons. For example, the temperature of the processing solution may be in the range of 15 to 60 ° C, and in particular, may be in the range of 20 to 45 ° C.
[0029]
The processing method of the present invention is one step, and is connected to other steps in the related field in a conventional order. For example, the metal surface to be treated is typically cleaned using a conventional cleaning solution prior to the treatment of the present invention. However, when the metal surface to be treated is coated immediately before the treatment according to the invention, for example when it is galvanized, or when it is subjected to a chemical conversion treatment, for example a phosphate conversion treatment, the cleaning takes place. The steps may be omitted. After the treatment step of the present invention, the resulting metal surface is coated in a conventional manner with an organic coating layer, for example a lacquer. This coating layer may be, for example, a coating layer, or an electrodeposition coating layer by electrodeposition coating, especially cationic electrodeposition coating.
[0030]
A particularly preferred method of carrying out the method of the present invention includes a step of treating the metal surface with an aqueous acid before contacting the metal surface with the treating agent for forming the chemical conversion treatment layer, that is, during the chemical conversion treatment. It is a thing. This inserted processing step involves treating the metal surface with an aqueous solution of an acid prior to the conversion treatment, which is known in the art to be "acid pickling" or "pickling passivation." (Pickle passivation) ". Acids conventionally used for said pickling or pickling passivation can be used for the purposes of the method of the present invention. An example of these acids is phosphoric acid.
[0031]
Example Use as a chemical conversion treatment [Example 1]
[0032]
Conventional chemical conversion treatment with pickling passivation: Hot dip galvanized steel (HDG)
Electroplated steel (EG)
Aluminum (AC120)
Cold rolled steel (CRS)
Process order (spray application)
1. Purification:
Ridoline® (Ridolin) 1570, 3%, 82 seconds, 55 ° C.
1. Ridosol® (Lidosol) 1270, 0.3%, a commercially available metal cleaning agent manufactured by the applicant. Rinsing: Deionized water 3. 3. Pickling passivation: phosphoric acid, 0.23%, 82 seconds Rinsing: Deionized water5. Chemical conversion treatment: 108 seconds, 30 seconds,
H 2 ZrF 6 acid (45%, 1.38 g / l), and vinylpyrrolidone / vinyl coupler lactam polymer solids content (37 mg / l);
5. Use an aqueous solution containing Rinsing: Deionized water 7. Drying: compressed air8. Coating treatment: By lead-free cationic electrodeposition coating method (BASF CG 310)
Coating layer thickness: 20-23 μm
Embodiment 2
[0033]
According to the same process sequence as above. However, steps 3 and 4 were omitted.
[0034]
Corrosion test Galvanized substrate: Adhesion test of coating layer after dipping in saline solution Aluminum: Copper accelerated salt spray test CASS
DIN 50021, 10 days steel: salt spray test SS DIN 50021, 21 days Results: Degree of creep of the coating along the scribe (one-side blister): U / 2 units: mm;
Result of stone impact test on adhesion of coating layer: (K = 1 according to K value is the best coating layer adhesion degree, and K = 10 is the worst coating layer adhesion degree)
[0035]
[Table 2]
[0036]
Chemical conversion treatment followed by powder coating using a copolymer mixture (galvanized steel)
Base: CRS, EG, HDG
Process order (Immersion method applied)
1. Cleaning: Ridoline® (Ridolin) 1570, 2%,
Ridosol® (Lidosol) 1237, 0.3%,
5 minutes, 55 ° C (commercially available metal cleaning agent manufactured by the applicant)
2. Rinsing: Deionized water 3. Chemical conversion treatment: 180 seconds, 30 ° C
Using a treatment bath having the following composition: H 2 ZrF 6 acid (45%, 1.38 g / liter);
A vinylpyrrolidone / vinylcaprolactam copolymer (= P a );
Mixture with vinylpyrrolidone / vinylimidazole copolymer (= P b ) (solids content 37 mg / l)
4. Rinsing: Deionized water5. Drying: compressed air6. Coating treatment: polyester PES 5807 / RAL 5009GL
(Without TIGS, Herbert product), about 60-80 μm thick
Corrosion test Neutral salt spray test DIN 50021 SS, 21 days Result: Degree of creep of coating film along scribe, adhesion of coating film by one-side blister width cross-cut coating adhesion test
[Table 3]
The compounding ratio of the polymer, for example, the homopolymer / polymer ratio can be changed.
P a% = 100% -P b %, P a> 0
Embodiment 4
[0040]
Chemical conversion treatment using a copolymer mixture (powder coating)
Base material: CRS
Process order (Immersion method applied)
1. Cleaning: Ridoline® (Ridolin) 1570, 2%,
Ridosol® (Lidosol) 1237, 0.3%,
55 ° C for 5 minutes
2. Rinsing: Deionized water 3. Chemical conversion treatment: 180 seconds, 30 ° C
A treatment bath having the following composition was used.
H 2 ZrF 6 acid (45%, 1.38 g / l);
A vinylpyrrolidone / vinylcaprolactam copolymer (= P b );
A mixture with a vinylpyrrolidone / vinylimidazole copolymer (= P a ),
(Solid content 22mg / l)
4. Rinsing: Deionized water5. Drying: compressed air6. Coating treatment: polyester PES 5807 / RAL 5009GL
(Excluding TIGC, product of Herbert),
About 60-80 μm thick
Corrosion test Neutral salt spray test DIN 50021 SS, 21 days
[Table 4]
Claims (6)
それが、
ａ）０．０２〜２０ｇ／リットルのりん酸及び／又はＺｒ，Ｔｉ，Ｈｆ及びＳｉから選ばれた１種以上の元素の少なくとも１種のふっ素酸、或はそれらの各々のアニオン、並びに、
ｂ）１０〜４９．９mg／リットルの、ビニルピロリドンの単一重合体又は共重合体を含み、かつ即時使用可能な溶液の状態にあることを特徴とする金属表面処理剤。Phosphoric acid and / or at least one hydrofluoric acid of one or more elements selected from Zr, Ti, Hf and Si or an anion of each of them, and a metal containing a homopolymer or copolymer of vinylpyrrolidone A surface treatment agent,
that is,
a) 0.02 to 20 g / l of phosphoric acid and / or at least one hydrofluoric acid of one or more elements selected from Zr, Ti, Hf and Si, or an anion of each of them;
b) A metal surface treating agent containing 10 to 49.9 mg / liter of a vinylpyrrolidone homopolymer or copolymer and being in a ready-to-use solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10131723A DE10131723A1 (en) | 2001-06-30 | 2001-06-30 | Corrosion protection agents and corrosion protection processes for metal surfaces |
| PCT/EP2002/006888 WO2003002781A1 (en) | 2001-06-30 | 2002-06-21 | Corrosion protection agent and corrosion protection method for metal surfaces |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004533542A true JP2004533542A (en) | 2004-11-04 |
| JP2004533542A5 JP2004533542A5 (en) | 2005-10-06 |
Family
ID=7690132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003508743A Pending JP2004533542A (en) | 2001-06-30 | 2002-06-21 | Corrosion resistant treatment method for metal surface |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US20040151619A1 (en) |
| EP (1) | EP1402083B1 (en) |
| JP (1) | JP2004533542A (en) |
| KR (1) | KR20040043135A (en) |
| CN (1) | CN1527889A (en) |
| AT (1) | ATE294259T1 (en) |
| BR (1) | BR0210725A (en) |
| CA (1) | CA2453138A1 (en) |
| CZ (1) | CZ20033572A3 (en) |
| DE (2) | DE10131723A1 (en) |
| ES (1) | ES2240824T3 (en) |
| MX (1) | MXPA03011369A (en) |
| RU (1) | RU2004102694A (en) |
| SK (1) | SK16192003A3 (en) |
| WO (1) | WO2003002781A1 (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10310972A1 (en) | 2003-03-13 | 2004-09-23 | Basf Ag | Passivating layer on a metallic surface, prepared by precipitation of water-soluble, nitrogen-containing polymer at the metal surface upon addition of metal salt(s) at a pH of less than 7 |
| CN1768245A (en) * | 2003-03-31 | 2006-05-03 | 贝洱两合公司 | Heat exchanger and method for treating the surface of said heat exchanger |
| DE10339165A1 (en) | 2003-08-26 | 2005-03-24 | Henkel Kgaa | Colored conversion coatings on metal surfaces |
| DE10353149A1 (en) * | 2003-11-14 | 2005-06-16 | Henkel Kgaa | Supplementary corrosion protection for components made of pre-coated metal sheets |
| DE10358309A1 (en) * | 2003-12-11 | 2005-07-21 | Henkel Kgaa | Functionalized phenol-aldehyde resin and process for treating metal surfaces |
| DE10358310A1 (en) * | 2003-12-11 | 2005-07-21 | Henkel Kgaa | Two-stage conversion treatment |
| DE102004022565A1 (en) * | 2004-05-07 | 2005-12-22 | Henkel Kgaa | Colored conversion coatings on metal surfaces |
| US7351295B2 (en) * | 2006-03-23 | 2008-04-01 | Pp6 Industries Ohio, Inc. | Cleaning and polishing rusted iron-containing surfaces |
| DE102006039633A1 (en) * | 2006-08-24 | 2008-03-13 | Henkel Kgaa | Chrome-free, thermally curable corrosion inhibitor |
| DE102007005943A1 (en) | 2007-02-01 | 2008-08-07 | Henkel Ag & Co. Kgaa | Metal pretreatment with luminescent pigments |
| ES2391870T3 (en) * | 2007-02-12 | 2012-11-30 | Henkel Ag & Co. Kgaa | Procedure to treat metal surfaces |
| DE102007057185A1 (en) | 2007-11-26 | 2009-05-28 | Henkel Ag & Co. Kgaa | Zirconium phosphating of metallic components, in particular iron |
| CN101748002A (en) * | 2008-11-28 | 2010-06-23 | 安集微电子（上海）有限公司 | Fluorine-containing composition and application thereof |
| CN101928650B (en) * | 2009-06-23 | 2016-02-17 | 安集微电子（上海）有限公司 | A kind of fluoro-containing composition and application thereof |
| EP2405031A1 (en) * | 2010-07-07 | 2012-01-11 | Mattthias Koch | Method for coating shaped bodies and coated shaped body |
| KR101263086B1 (en) * | 2010-12-28 | 2013-05-09 | 주식회사 포스코 | Plate type zirconium phosphate and preparation method thereof |
| KR101645063B1 (en) * | 2013-03-27 | 2016-08-03 | 주식회사 포스코 | Plate type zirconium phosphate and preparation method thereof |
| DE102015206812A1 (en) | 2015-04-15 | 2016-10-20 | Henkel Ag & Co. Kgaa | Polymer-containing pre-rinse before a conversion treatment |
| EP3502311A1 (en) * | 2017-12-20 | 2019-06-26 | Henkel AG & Co. KGaA | Method for the corrosion protection and cleaning pretreatment of metallic components |
| MX2022010366A (en) * | 2020-02-25 | 2022-09-21 | Chemetall Gmbh | One-step pretreatment method of metallic substrates for metal cold forming. |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1933013C3 (en) * | 1969-06-28 | 1978-09-21 | Gerhard Collardin Gmbh, 5000 Koeln | Process for the production of protective layers on aluminum, iron and zinc by means of solutions containing complex fluorides |
| US3912548A (en) * | 1973-07-13 | 1975-10-14 | Amchem Prod | Method for treating metal surfaces with compositions comprising zirconium and a polymer |
| US4148670A (en) * | 1976-04-05 | 1979-04-10 | Amchem Products, Inc. | Coating solution for metal surface |
| JPS6267181A (en) * | 1985-09-19 | 1987-03-26 | Nippon Parkerizing Co Ltd | Aqueous solution for chemical conversion of titanium or alloy thereof |
| US5129967A (en) * | 1988-05-03 | 1992-07-14 | Betz Laboratories, Inc. | Composition and method for non-chromate coating of aluminum |
| US4992116A (en) * | 1989-04-21 | 1991-02-12 | Henkel Corporation | Method and composition for coating aluminum |
| US5239002A (en) * | 1990-08-16 | 1993-08-24 | Phillips Petroleum Company | Polymeric adhesive and anti-corrosion agents |
| EP0815295A1 (en) * | 1995-02-28 | 1998-01-07 | Henkel Corporation | Reducing or avoiding surface irregularities in electrophoretic painting of phosphated metal surfaces |
| DE19621184A1 (en) * | 1996-05-28 | 1997-12-04 | Henkel Kgaa | Zinc phosphating with integrated post-passivation |
| JPH10182916A (en) * | 1996-10-21 | 1998-07-07 | Nippon Paint Co Ltd | Metal surface-treating composition containing acrylic resin and containing n-heterocycle, treatment by using the same and treated metal material |
| EP1037719B1 (en) * | 1997-10-14 | 2005-08-24 | Henkel Kommanditgesellschaft auf Aktien | Composition and process for multi-purpose treatment of metal surfaces |
| DE10005113A1 (en) * | 2000-02-07 | 2001-08-09 | Henkel Kgaa | Corrosion inhibitor and corrosion protection method for metal surfaces |
| DE10010758A1 (en) * | 2000-03-04 | 2001-09-06 | Henkel Kgaa | Corrosion protection of zinc, aluminum and/or magnesium surfaces such as motor vehicle bodies, comprises passivation using complex fluorides of Ti, Zr, Hf, Si and/or B and organic polymers |
| DE10010355A1 (en) * | 2000-03-07 | 2001-09-13 | Chemetall Gmbh | Applying phosphate coatings to metallic surfaces comprises wetting with an aqueous acidic phosphatizing solution containing zinc ions, manganese ions and phosphate ions, and drying the solution |
| DE10030462A1 (en) * | 2000-06-21 | 2002-01-03 | Henkel Kgaa | Adhesion promoter in conversion solutions |
-
2001
- 2001-06-30 DE DE10131723A patent/DE10131723A1/en not_active Withdrawn
-
2002
- 2002-06-21 WO PCT/EP2002/006888 patent/WO2003002781A1/en active IP Right Grant
- 2002-06-21 CN CNA028132149A patent/CN1527889A/en active Pending
- 2002-06-21 DE DE50202924T patent/DE50202924D1/en not_active Expired - Fee Related
- 2002-06-21 JP JP2003508743A patent/JP2004533542A/en active Pending
- 2002-06-21 AT AT02780906T patent/ATE294259T1/en not_active IP Right Cessation
- 2002-06-21 MX MXPA03011369A patent/MXPA03011369A/en unknown
- 2002-06-21 CZ CZ20033572A patent/CZ20033572A3/en unknown
- 2002-06-21 SK SK1619-2003A patent/SK16192003A3/en unknown
- 2002-06-21 RU RU2004102694/02A patent/RU2004102694A/en not_active Application Discontinuation
- 2002-06-21 EP EP02780906A patent/EP1402083B1/en not_active Expired - Lifetime
- 2002-06-21 ES ES02780906T patent/ES2240824T3/en not_active Expired - Lifetime
- 2002-06-21 CA CA002453138A patent/CA2453138A1/en not_active Abandoned
- 2002-06-21 BR BR0210725-2A patent/BR0210725A/en not_active IP Right Cessation
- 2002-06-21 KR KR10-2003-7017270A patent/KR20040043135A/en not_active Application Discontinuation
-
2003
- 2003-12-11 US US10/734,815 patent/US20040151619A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| CA2453138A1 (en) | 2003-01-09 |
| ATE294259T1 (en) | 2005-05-15 |
| WO2003002781A1 (en) | 2003-01-09 |
| MXPA03011369A (en) | 2004-07-01 |
| ES2240824T3 (en) | 2005-10-16 |
| BR0210725A (en) | 2004-07-20 |
| DE10131723A1 (en) | 2003-01-16 |
| CN1527889A (en) | 2004-09-08 |
| US20040151619A1 (en) | 2004-08-05 |
| SK16192003A3 (en) | 2004-05-04 |
| RU2004102694A (en) | 2005-06-10 |
| CZ20033572A3 (en) | 2004-11-10 |
| DE50202924D1 (en) | 2005-06-02 |
| EP1402083B1 (en) | 2005-04-27 |
| EP1402083A1 (en) | 2004-03-31 |
| KR20040043135A (en) | 2004-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2004533542A (en) | Corrosion resistant treatment method for metal surface | |
| JP2004533542A5 (en) | ||
| US20030138567A1 (en) | Anti-corrosive agents and method for protecting metal surfaces against corrosion | |
| KR101596293B1 (en) | Optimized passivation on ti-/zr-basis for metal surfaces | |
| EP0315059B1 (en) | Process and composition for zinc phosphate coating | |
| US7776448B2 (en) | Conversion coatings including alkaline earth metal fluoride complexes | |
| JP5837885B2 (en) | Multi-step method for anti-corrosion pretreatment of metal parts | |
| EP0181377A1 (en) | Metal treatment | |
| WO2003018872A1 (en) | Non-chrome passivation process for zinc and zinc alloys | |
| JP3333611B2 (en) | Hexavalent chromium-free chemical conversion surface treatment agent for aluminum and aluminum alloys | |
| US6749694B2 (en) | Conversion coatings including alkaline earth metal fluoride complexes | |
| JPH02305972A (en) | Composition of phosphate treating liquid of metal and treatment thereof | |
| JP4975378B2 (en) | Metal surface treatment liquid, surface treatment method, surface treatment material | |
| JP2004501280A (en) | Binder added to chemical conversion solution | |
| CN107532305B (en) | Pre-rinse containing polymer prior to conversion treatment | |
| JP4258924B2 (en) | Phosphate conversion treatment method for galvanized steel sheet | |
| JP3847479B2 (en) | Chromate treatment solution for aluminum plated steel sheet | |
| JP3515925B2 (en) | Corrosion resistant film, corrosion resistant Al alloy material and method of forming corrosion resistant film | |
| JPH09151336A (en) | Surface-treating composition for metal and method for treating metal surface | |
| JPH0129871B2 (en) | ||
| MXPA00002319A (en) | Pretreatment before painting of composite metal structures containing aluminum portions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050620 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080617 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20081014 |