JP2004183015A - Metal surface treating agent, metal surface treating method and surface treated metallic material - Google Patents
Metal surface treating agent, metal surface treating method and surface treated metallic material Download PDFInfo
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- JP2004183015A JP2004183015A JP2002348715A JP2002348715A JP2004183015A JP 2004183015 A JP2004183015 A JP 2004183015A JP 2002348715 A JP2002348715 A JP 2002348715A JP 2002348715 A JP2002348715 A JP 2002348715A JP 2004183015 A JP2004183015 A JP 2004183015A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C22/40—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 molybdates, tungstates or vanadates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/42—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 molybdates, tungstates or vanadates containing also phosphates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、金属を素材としたシートコイル、成形品の表面に優れた耐食性及び耐アルカリ性を付与し、さらには塗装又はラミネートにより形成した樹脂層及び金属素材との層間密着性に優れ、かつクロムを含まない皮膜を形成させるために用いる金属表面処理剤、金属表面処理方法、表面処理された金属材料に関する。
さらに詳しくは、本発明は、鋼、亜鉛系メッキ鋼、アルミ系メッキ鋼などの鋼材、更にはアルミニウム、マグネシウム、銅、及びそれら合金などの非鉄金属材を素材とする自動車ボディー、自動車部品、建材、家電用部品等の成形加工品、鋳造品、シートコイル等に優れた耐食性及び耐アルカリ性を付与し、さらに層間密着性に優れ、かつクロムを含まない皮膜を形成させるために用いる表面処理剤、表面処理方法、表面処理された金属材料に関する。
【０００２】
【従来の技術】
鋼、亜鉛系メッキ鋼、アルミ系メッキ鋼などの鋼材、更にはアルミニウム、マグネシウム、銅、及びそれら合金などの非鉄金属材料は、大気中の酸素、水分、水分中に含まれるイオン等によって酸化され腐食する。これらの腐食を防止する方法として、従来より、クロム酸クロメート、リン酸クロメート等のクロムを含有する処理液に金属材料表面を接触させてクロメート皮膜を形成させる方法がある。
これらのクロメート処理を用いて形成された皮膜は、優れた耐食性、塗装密着性を有しているが、その処理液中に有害な６価クロムを含んでおり、廃水処理に手間やコストがかかる他、処理によって形成された皮膜中にも６価クロムを含有されているので環境面、安全面から敬遠される傾向にある。
【０００３】
クロムを含まないノンクロメート処理液を用いる方法としては、特許文献１に、少なくとも１個の窒素原子を有するエポキシ樹脂、アクリル樹脂、ウレタン樹脂等の有機高分子と特定の多価アニオンを含有する金属表面処理剤が開示されている。ここで、特定した多価アニオンの中にバナジン酸が記載されているが、５価のバナジウムの酸素酸であるバナジン酸は耐水性、耐アルカリ性が劣るため、処理された金属材料を、特にアルカリなどで洗浄した際、皮膜から脱落し耐食性が極端に低下するという不具合があった。また、処理後、水洗し乾燥することが記載されており、クロム廃水の問題はないが、有機物によるＣＯＤ等の廃水の問題を有している。
【０００４】
また、特許文献２に、バナジウム化合物と、ジルコニウム、チタニウム、モリブデン、タングステン、マンガン及びセリウムから選ばれる少なくとも１種の金属を含む金属化合物とを含有する金属表面処理剤が挙げられている。
特許文献２に記載された金属表面処理においては、処理液が６価クロムを含有しない利点があり、形成された皮膜も耐食性及び耐アルカリ性においてかなり改善されている。
【０００５】
【特許文献１】特開平１０−１７８９号公報（請求項１〜３）
【特許文献２】特開２００２−３０４６０号公報（請求項１）
【０００６】
【発明が解決しようとする課題】
特許文献２記載の金属表面処理では良好な耐食性及び耐アルカリ性を有する皮膜が得られるが、クロメート皮膜と比較するとそれでも十分とは言えず、これらの性能のさらなる向上が求められていた。
本発明は前記従来技術の抱える問題を解決するために成されたものであって、金属材料に優れた耐食性及び耐アルカリ性を付与すると共に、優れた層間密着性をも付与する、クロムを含まない金属表面処理剤、金属表面処理方法及び表面処理金属材料を提供することを目的とする。
【０００７】
【課題を解決するための手段】
本発明者は、前記課題を解決する手段について、鋭意研究を重ねた結果、特定の組成からなる表面処理剤を用いて金属材料表面を処理することにより、優れた耐食性、耐アルカリ性及び層間密着性を有する皮膜を得ることができることを見い出し、本発明を完成するに至った。
すなわち本発明は、少なくとも１種のバナジウム化合物（Ａ）と、コバルト、ニッケル、亜鉛、マグネシウム、アルミニウム、カルシウム、ストロンチウム、バリウム及びリチウムからなる群から選ばれる少なくとも１種の金属を含む金属化合物（Ｂ）とを含有することを特徴とする金属表面処理剤に関する。
【０００８】
なお、本発明において、層間密着性とは、本発明の金属表面処理剤のような金属表面処理剤を用いて得られる皮膜とその上に通常施される樹脂膜との密着性と該皮膜と金属表面との密着性との両方を意味する。ただし、実際的には、本発明の金属表面処理剤のような金属表面処理剤を用いて得られる皮膜は本来金属表面との密着性が良好な化成皮膜であり、したがって本発明の場合、層間密着性は、通常、樹脂膜との密着性を意味する。ただし、かかる皮膜自体に樹脂成分を含有させることもでき、かかる場合には、層間密着性は金属表面との密着性を意味する。
【０００９】
上記本発明においては、前記表面処理剤に、さらに、ジルコニウム、チタニウム、モリブデン、タングステン、マンガン及びセリウムよりなる群から選ばれる少なくとも１種の金属を含む金属化合物（Ｃ）を含有させることが、耐アルカリ性及び樹層間密着性を向上させるために好ましい。
また、前記バナジウム化合物（Ａ）において、酸化数５価のバナジウムイオンの全バナジウムに対する割合Ｖ５＋／Ｖが０〜０．６の範囲にあることが、処理剤中でのバナジウム化合物の安定性、形成皮膜の耐食性、耐アルカリ性及び層間密着性の向上の点から、好ましい。
また、前記金属表面処理剤に、さらに、水酸基、カルボニル基、カルボキシル基、１〜３級アミノ基、アミド基、リン酸基及びホスホン酸基よりなる群から選ばれる少なくとも１種の官能基を有する有機化合物（Ｄ）を含有させることが、５価のバナジウム化合物を用いる場合にはこれを４価〜２価に還元し、及び／又は本発明の処理液中のバナジウム化合物の安定性を向上させるために好ましい。
【００１０】
また、前記金属表面処理剤に、さらに、無機酸、有機酸、無機酸もしくは有機酸の塩、及びフッ素化合物より選ばれる少なくとも１種のエッチング剤（Ｅ）を含有させることが、形成させる皮膜と金属表面との密着性を向上させるために好ましい。
また、前記金属表面処理剤に、さらに、水溶性高分子又は／及び水系エマルション樹脂（Ｆ）を含有させることが、形成させる皮膜の耐食性、耐指紋性、耐溶剤性及び表面潤滑性の向上のために好ましい。
【００１１】
本発明は、また、金属材料表面を、前記したいずれかの金属表面処理剤に接触させた後、前記材料の温度が３０〜２５０℃になるように加熱乾燥して、少なくとも金属材料表面の片側に、厚さ０．００１〜２μｍの乾燥皮膜を形成させることを特徴とする金属材料の表面処理方法、及び前記表面処理方法を用いて形成された皮膜を有する表面処理金属材料に関する。さらに、金属材料が、亜鉛系メッキ鋼材、アルミニウム系メッキ鋼材、アルミニウム・亜鉛系合金メッキ鋼材、アルミニウム材、アルミニウム合金材、マグネシウム合金材及び銅合金材よりなる群から選ばれることが好ましい。
【００１２】
【発明の実施の形態】
本発明の金属表面処理剤中に含有させるバナジウム化合物（Ａ）は、バナジウムの酸化数が５価、４価、３価又は２価のバナジウム化合物、例えば五酸化バナジウム（Ｖ２Ｏ５）、メタバナジン酸（ＨＶＯ３）、メタバナジン酸アンモニウム、メタバナジン酸ナトリウム、オキシ三塩化バナジウム（ＶＯＣｌ３）等の酸化数５価のバナジウム化合物、三酸化バナジウム（Ｖ２Ｏ３）、二酸化バナジウム（ＶＯ２）、オキシ硫酸バナジウム（ＶＯＳＯ４）、バナジウムオキシアセチルアセトネート［ＶＯ（ＯＣ（ＣＨ３）＝ＣＨＣＯＣＨ３）２］、バナジウムアセチルアセトネート［Ｖ（ＯＣ（ＣＨ３）＝ＣＨＣＯＣＨ３）３］、三塩化バナジウム（ＶＣｌ３）、リンバナドモリブデン酸｛Ｈ１５−Ｘ［ＰＶ１２−ｘＭｏｘＯ４０］・ｎＨ２Ｏ（６＜ｘ＜１２，ｎ＜３０）｝、硫酸バナジウム（ＶＳＯ４・７Ｈ２Ｏ）、ニ塩化バナジウム（ＶＣｌ２）、酸化バナジウム（ＶＯ）等の酸化数４〜２価のバナジウム化合物等から選ばれる少なくとも１種である。
【００１３】
本処理剤がバナジウム化合物（Ａ）として酸化数４価以下（通常４〜２価）のバナジウム化合物を含有していることが好ましい。すなわち、酸化数５価のバナジウムイオンの全バナジウムに対する割合Ｖ５＋／Ｖ（式中、Ｖ５＋及びＶはそれぞれ酸化数５価のバナジウム質量及び全バナジウム質量を表す）が０〜０．６の範囲にあることが好ましく、０〜０．４の範囲にあることがより好ましく、０〜０．２の範囲にあることがより一層好ましく、０〜０．１の範囲にあることが最も好ましい。
上記割合が０．６を超える場合には、処理剤中でのバナジウム化合物の安定性が一般に悪くなる他、形成される皮膜の耐食性、耐アルカリ性及び層間密着性が低下してくる。
【００１４】
本処理剤中に４〜２価のバナジウム化合物を含有させる方法としては、前記したような４〜２価のバナジウム化合物を用いる他、５価のバナジウム化合物を予め還元剤を用いて４〜２価に還元したものを用いることができる。用いる還元剤は無機系、有機系いずれでも良いが、有機系が好ましく、前記有機化合物（Ｄ）を用いることが特に好ましい。
【００１５】
本発明の金属表面処理剤中に含有させる、コバルト、ニッケル、亜鉛、マグネシウム、アルミニウム、カルシウム、ストロンチウム、バリウム及びリチウムよりなる群から選ばれる少なくとも１種の金属を含む金属化合物（Ｂ）は、前記金属の酸化物、水酸化物、錯化合物、無機酸もしくは有機酸との塩等である。かかる金属化合物（Ｂ）としては、例えば、コバルト（ＩＩ）アセチルアセトネート［Ｃｏ（ＯＣ（ＣＨ３）＝ＣＨＣＯＣＨ３）２］、コバルト（ＩＩＩ）アセチルアセチルアセトネート［Ｃｏ（ＯＣ（ＣＨ３）＝ＣＨＣＯＣＨ３）３］、硝酸コバルト（ＩＩ）、硫酸コバルト（ＩＩ）、酢酸コバルト（ＩＩ）、シュウ酸コバルト（ＩＩ）、シュウ酸コバルト（ＩＩＩ）、酸化コバルト（ＩＩ）、酸化コバルト（ＩＩＩ）、酸化コバルト（ＩＶ）、硝酸ニッケル（ＩＩ）、酢酸ニッケル（ＩＩ）、酢酸ニッケル（ＩＩＩ）、シュウ酸ニッケル（ＩＩ）、酸化ニッケル（ＩＩ）、ニッケル（ＩＩ）アセチルアセトネート［Ｎｉ（ＯＣ（ＣＨ３）＝ＣＨＣＯＣＨ３）２］、アミド硫酸ニッケル、塩基性炭酸ニッケル［ＮｉＣＯ３・２Ｎｉ（ＯＨ）３］、水酸化ニッケル（ＩＩ）、フッ化亜鉛、硫酸亜鉛、硝酸亜鉛、酢酸亜鉛、酸化亜鉛、亜鉛（ＩＩ）アセチルアセトネート［Ｚｎ（ＯＣ（ＣＨ３）＝ＣＨＣＯＣＨ３）２］、塩基性炭酸亜鉛［２ＺｎＣＯ３・３Ｚｎ（ＯＨ）２］、硝酸マグネシウム、硫酸マグネシウム、酢酸マグネシウム、フッ化マグネシウム、水酸化マグネシウム、シュウ酸マグネシウム、酸化マグネシウム、塩基性炭酸マグネシウム［（ＭｇＣＯ３）４・Ｍｇ（ＯＨ）２］、硝酸アルミニウム、硫酸アルミニウム、酸化アルミニウム、水酸化アルミニウム、フッ化アルミニウム、酢酸アルミニウム、酢酸カルシウム、フッ化カルシウム、ホスフィン酸カルシウム［Ｃａ（ＰＨ２Ｏ２）２］、硝酸カルシウム、水酸化カルシウム、シュウ酸カルシウム、酸化カルシウム、酢酸カルシウム、硝酸ストロンチウム、酢酸ストロンチム、炭酸ストロンチウム、硝酸バリウム、炭酸バリウム、酸化バリウム、硝酸リチウム、リン酸リチウム、フッ化リチウム、水酸化リチウム、硫酸リチウム、炭酸リチウム、シュウ酸二リチウム、酸化リチウム等が挙げられる。
これらの金属化合物（Ｂ）中、コバルト、ニッケル、亜鉛及びマグネシウムよりなる群から選ばれる少なくとも１種の金属を含む金属化合物が好ましい。
【００１６】
本発明の金属表面処理剤中に、任意成分として含有させる、ジルコニウム、チタン、モリブデン、タングステン、マンガン及びセリウムよりなる群から選ばれる少なくとも１種の金属を含む金属化合物（Ｃ）は、前記金属の酸化物、水酸化物、錯化合物、無機酸もしくは有機酸との塩等である。かかる金属化合物（Ｃ）としては、例えば、硝酸ジルコニル（ＺｒＯ（ＮＯ３）２）、酢酸ジルコニル、硫酸ジルコニル、炭酸ジルコニルアンモニウム｛（ＮＨ４）２［Ｚｒ（ＣＯ３）２（ＯＨ）２｝、ジルコニウムアセテート、硫酸チタニル（ＴｉＯＳＯ４）、チタンラクテート、ジイソプロポキシチタニウムビスアセチルアセトン｛（Ｃ５Ｈ７Ｏ２）２Ｔｉ［ＯＣＨ（ＣＨ３）２］２｝、乳酸とチタニウムアルコキシドとの反応物、モリブデン酸（Ｈ２ＭｏＯ４）、モリブデン酸アンモニウム、モリブデン酸ナトリウム、モリブドリン酸化合物（例えば、モリブドリン酸アンモニウム｛（ＮＨ４）３［ＰＯ４Ｍｏ１２Ｏ３６］・３Ｈ２Ｏ｝、モリブドリン酸ナトリウム｛Ｎａ３［ＰＯ４・１２ＭｏＯ３］・ｎＨ２Ｏ｝）、メタタングステン酸｛Ｈ６［Ｈ２Ｗ１２Ｏ４０］｝、メタタングステン酸アンモニウム｛（ＮＨ４）６［Ｈ２Ｗ１２Ｏ４０］｝、メタタングステン酸ナトリウム、パラタングステン酸｛Ｈ１０［Ｗ１２Ｏ４６Ｈ１０］｝、パラタングステン酸アンモニウム、パラタングステン酸ナトリウム、過マンガン酸（ＨＭｎＯ４）、過マンガン酸カリウム、過マンガン酸ナトリウム、リン酸二水素マンガン［Ｍｎ（Ｈ２ＰＯ４）２］、硝酸マンガン［Ｍｎ（ＮＯ３）２］、硫酸マンガン、フッ化マンガン、炭酸マンガン（ＭｎＣＯ３）、酢酸マンガン、酢酸セリウム［Ｃｅ（ＣＨ３ＣＯ２）３］、硝酸セリウム、塩化セリウム等が挙げられる。
これらの金属化合物（Ｃ）中、ジルコニウム及び／又はチタンを含む金属化合物が好ましい。
【００１７】
金属化合物（Ａ）、（Ｂ）及び（Ｃ）の好適な組合せとしては、バナジウム化合物（Ａ）と金属化合物（Ｂ）としてのコバルト及び／又はニッケルを含む金属化合物と金属化合物（Ｃ）としてのジルコニウムを含む金属化合物との組合せが、本発明で使用するすべての金属材料に、もっとも優れた耐食性、耐アルカリ性及び層間密着性を与える。また、バナジウム化合物（Ａ）と金属化合物（Ｂ）としての亜鉛及び／又はマグネシウムを含む金属化合物と金属化合物（Ｃ）としてのチタンを含む金属化合物との組合せが、アルミニウム含有金属材料に、上記の組合せと同様に優れた耐食性、耐アルカリ性及び層間密着性を与える。
【００１８】
本発明の金属表面処理剤中に、必要に応じ、含有させる有機化合物（Ｄ）は、水酸基、カルボニル基、カルボキシル基、１〜３級アミノ基、アミド基、リン酸基及びホスホン酸基よりなる群から選ばれる少なくとも１種の官能基を有する有機化合物である。
かかる有機化合物（Ｄ）としては、メタノール、エタノール、イソプロパノール、エチレングリコール等のアルコール類、ホルムアルデヒド、アセトアルデヒド、フルフラール、アセチルアセトン、アセト酢酸エチル、グリオキザール、ジピバロイルメタン、３−メチルペンタンジオン等のカルボニル化合物、ギ酸、酢酸、プロピオン酸、酒石酸、アスコルビン酸、グルコン酸、クエン酸、リンゴ酸、グリオキシル酸等の有機酸、トリエチルアミン、トリエタノールアミン、エチレンジアミン、ピリジン、イミダゾール、ピロール、モルホリン、ピペラジン等のアミン化合物、ホルムアミド、アセトアミド、プロピオンアミド、Ｎ−メチルプロピオンアミド等の酸アミド化合物、グリシン、アラニン、プロリン、グルタミン酸等のアミノ酸類、アミノトリ（メチレンホスホン酸）、１−ヒドロキシエチリデン−１，１´−ジホスホン酸、エチレンジアミンテトラ（メチレンホスホン酸）、フィチン酸等の有機リン酸、グルコース、マンノース、ガラクトース等の単糖類、麦芽糖、ショ糖等のオリゴ糖類、デンプン、セルロース等の天然多糖類、タンニン酸、フミン酸、リグニンスルホン酸、ポリフェノール等の芳香族化合物、ポリビニルアルコール、ポリエチレングリコール、ポリアクリル酸、ポリアクリルアミド、ポリエチレンイミン、水溶性ナイロン等の合成高分子等が挙げられる。
【００１９】
これらの有機化合物（Ｄ）の中で、、前記官能基から選ばれる少なくとも１種を１分子内に２個以上含む有機化合物が好ましく、さらには前記官能基として水酸基、カルボニル基、カルボキシル基、リン酸基及びホスホン酸基から選べばれる少なくとも１種を１分子内に２個以上含む有機化合物がより好ましい。
【００２０】
これらの有機化合物（Ｄ）は、５価のバナジウム化合物を用いる場合にはこれを４価、３価又は２価に還元し、及び／又は本発明の処理液中のバナジウム化合物の安定性を向上させるために好ましい。
【００２１】
これらの有機化合物（Ｄ）は、予めバナジウム化合物と混合し加熱（例えば、４０〜１００℃で５〜１２０分）するなどして十分に還元反応、安定化反応を進行させた混合物として表面処理剤に配合することができるが、単純に混合した表面処理剤として金属表面に塗布した後、加熱乾燥時に還元を進行させることも可能である。
【００２２】
本発明の金属表面処理剤中に、必要に応じ、含有させるエッチング剤（Ｅ）は、無機酸、有機酸、無機酸もしくは有機酸の塩、及びフッ素化合物より選ばれる少なくとも１種の化合物である。本発明の表面処理剤中に、必要に応じ、含有させるエッチング剤（Ｅ）は、無機酸、有機酸、無機酸もしくは有機酸の塩（特に、アンモニウム塩やナトリウム塩、カリウム塩等のアルカリ金属塩）、及びフッ素化合物より選ばれる少なくとも１種の化合物であり、処理剤塗布時又は加熱乾燥時に素材金属をエッチングするのに用いる。かかるエッチング剤（Ｅ）としては、リン酸、硝酸、硫酸等の無機酸もしくはその塩（特に、アンモニウム塩、ナトリウム塩、カリウム塩）、ギ酸、酢酸等の有機酸もしくはその塩（特に、アンモニウム塩、ナトリウム塩、カリウム塩）、フッ化水素酸、ホウフッ化水素酸（ＨＢＦ４）、ケイフッ化水素酸（Ｈ２ＳｉＦ６）、ジルコニウムフッ化水素酸（Ｈ２ＺｒＦ６）、チタンフッ化水素酸（Ｈ２ＴｉＦ６）、フッ化錫（Ｉ）（ＳｎＦ２）、フッ化錫（ＩＩ）（ＳｎＦ４）、フッ化第一鉄、フッ化第二鉄等のフッ素化合物を用いることができる。
エッチング剤（Ｅ）の使用は金属素材への反応性を高め、形成させる皮膜と金属素材との密着性を向上させるために好ましい。
【００２３】
本発明の処理剤における各構成成分の量については、バナジウム化合物（Ａ）はバナジウム換算で０．１〜１００ｇ／Ｌが好ましく、１〜７０ｇ／Ｌがより好ましい。金属化合物（Ｂ）は金属換算で０．０１〜５０ｇ／Ｌが好ましく、０．１〜２０ｇ／Ｌがより好ましい。金属化合物（Ｃ）は金属換算で０．１〜１００ｇ／Ｌが好ましく、１．０〜７０ｇ／Ｌがより好ましい。
バナジウム化合物（Ａ）、金属化合物（Ｂ）及び金属化合物（Ｃ）の質量比は、金属換算で、Ｖ／金属化合物（Ｃ）に占める金属換算質量＝１／２００〜９／１で、かつ金属化合物（Ｂ）に占める金属換算質量／（Ｖ＋金属化合物（Ｃ）に占める金属換算質量）＝１／１０００〜１／５であることが好ましく、Ｖ／金属化合物（Ｃ）に占める金属換算質量＝１／１００〜８／２で、かつ金属化合物（Ｂ）に占める金属換算質量／（Ｖ＋金属化合物（Ｃ）に占める金属換算質量）＝１／２００〜１／１０であることがより好ましい。
有機化合物（Ｄ）はバナジウム化合物中の酸化数５価のバナジウムの質量を１としたとき、０．０５〜１０が好ましく、０．１〜５がより好ましい。還元に必要な量より過剰に添加する方が、還元体の処理液中での安定性を向上させるためより好ましい。
エッチング剤（Ｅ）は０．０１〜１００ｇ／Ｌが好ましく、０．１〜７０ｇ／Ｌがより好ましい。
【００２４】
本発明の処理剤において、耐食性、耐指紋性、耐溶剤性及び表面潤滑性の向上を目的として、水溶性高分子又は／及び水系エマルション樹脂（Ｆ）、例えばポリアクリル酸、ポリアクリルアミド、ポリビニルアルコール、ポリエチレングリコール等の水溶性高分子、水に分散した形態のアクリル樹脂、ウレタン樹脂、エポキシ樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリオレフィン樹脂、エチレン−アクリル酸共重合体樹脂、ポリアセタール樹脂、ポリブチラール樹脂等の水系エマルション樹脂を添加することができる。これらは各単独でもしくは２種以上組み合わせて用いることができる。なお、水系エマルション樹脂（Ｆ）中の樹脂は液状で分散していても固体状で分散していてもよい。水溶性高分子又は／及び水系エマルション樹脂（Ｆ）の添加量は、全不揮発成分の５〜９５質量％が好ましく、１０〜９０質量％がより好ましい。
【００２５】
本発明の処理剤において、水に分散した形態のシリカゾル、及び／又はアルミナゾル、ジルコニアゾル等の金属ゾルを加えることができる。これらを加えるこちにより耐食性、耐水性、耐指紋性が向上する。この場合、添加する量は、全不揮発成分の２〜８０％質量％が好ましく、５〜６０％がより好ましい。
また、本発明の処理剤において、アミノシラン、エポキシシラン、メルカプトシラン等のシランカップリング剤を加えることができる。これらを加えることにより層間密着性、耐食性が向上する。この場合、添加する量は、全不揮発成分の５〜４０質量％が好ましく、１０〜３０質量％がより好ましい。
【００２６】
また、本発明の処理剤において、ポリエチレンワックス、ポリプロピレンワックス、マイクロクリスタリンワックス、カルナウバワックス、ポリテトラフルオロエチレン等の潤滑剤を加えることができる。これらを加えることにより滑り性、成形加工性、キズ付き防止性を付与することができる。この場合、添加する量は、全不揮発成分の１〜４０質量％が好ましく、５〜３０質量％がより好ましい。
なお本発明において全不揮発成分とは表面処理剤を１１０℃で２時間加熱乾燥した後に残存する成分をいうものとする。
【００２７】
本発明の表面処理剤で用いる溶媒は水を主体とするが、皮膜の乾燥性の改善など必要に応じてアルコール、ケトン、セロソルブ系の水溶性有機溶剤の併用を妨げるものではない。
この他に、界面活性剤、消泡剤、レベリング剤、防菌防ばい剤、着色剤などを本発明の趣旨や皮膜性能を損なわない範囲で添加し得る。
【００２８】
次に本発明の表面処理方法について述べる。
本処理の前工程については特に制限はないが、通常は、本処理を行う前に素材に付着した油分、汚れを取り除くためにアルカリ脱脂剤、又は酸性脱脂剤で洗浄するか、湯洗、溶剤洗浄等を行う。その後、必要に応じて酸、アルカリなどによる表面調整を行う。素材表面の洗浄においては、洗浄剤が素材表面になるべく残留しないように洗浄後に水洗することが好ましい。
【００２９】
本処理方法については、本発明の表面処理剤を金属素材の表面に塗布した後、加熱乾燥できれば良く、塗布方法、乾燥方法などについては特に制限はない。
通常は素材表面に処理剤をロール転写させて塗り付けるロールコート法、或いはシャワーリンガー等によって流し掛けた後ロールで絞る方法、処理剤に素材を浸漬する方法、素材に処理剤をスプレーする方法が用いられる。処理液の温度は、特に限定するものではないが、本処理剤の溶媒は水が主体であるため、処理温度は０〜６０℃が好ましく、５〜４０℃がより好ましい。
【００３０】
乾燥工程は、必ずしも熱を必要とせず風乾、もしくはエアーブロー等の物理的除去でも構わないが、皮膜形成性、層間密着性を向上させるために加熱乾燥しても良い。その場合の温度は、３０〜２５０℃が好ましく、６０〜２２０℃がより好ましい。
【００３１】
形成される皮膜の付着量は乾燥皮膜量で０．００１〜２μｍが好ましく、０．００５〜１μｍがより好ましい。０．００１μｍ未満では十分な耐食性、耐アルカリ性及び層間密着性が得られず、２μｍを超えると皮膜自体がクラックなどが生じ、金属素材との密着性が低下する恐れがある。
【００３２】
本発明の表面処理剤から形成される皮膜上に、乾燥皮膜厚が０．３〜５０μｍになるように樹脂層を設けることにより、被処理金属材料の耐食性及び耐アルカリ性が向上する他、耐指紋性、耐溶剤性及び表面潤滑性を付与することができる。
【００３３】
このような樹脂層を設ける方法としては、樹脂をあらかじめ溶解又は分散した溶剤系塗料や水系塗料を、本発明の表面処理剤から形成される皮膜上に、塗布して０〜２００℃で乾燥する方法、又フィルム状の樹脂を、該皮膜上に、ラミネートする方法が挙げられる。該皮膜との層間密着性を有する樹脂としては、ポリエステル樹脂、塩化ビニル樹脂、アクリル樹脂、エポキシ樹脂、ポリイミド樹脂、ポリオレフィン系樹脂、ポリアミド樹脂、フェノール樹脂等が挙げられる。
また、特に、耐指紋性、耐溶剤性及び表面潤滑性を付与するよう樹脂層を設ける方法としては、水溶性又は水分散性の樹脂を主成分とする水系塗料（Ｚ）を、本発明の表面処理剤から形成される皮膜上に、塗布し、素材の到達温度が５０〜２５０℃で加熱乾燥する方法が望ましい。水系塗料（Ｚ）に用いる水溶性又は水分散性の樹脂は、付加重合性不飽和モノマーを重合して得られるアクリル系樹脂、ポリオレフィン系樹脂、縮合反応によって得られるエポキシ系樹脂、ウレタン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、フェノール系樹脂等であり、前記樹脂のガラス転移点は０〜１２０℃であることが好ましく、１０〜１００℃であることがより好ましい。ガラス転移点が０℃未満では皮膜の強度、硬度が乏しく、１２０℃を超えると造膜性が劣り密着性が劣る。
【００３４】
前記水系塗料（Ｚ）は、これらの樹脂から選ばれる少なくとも１種を含有し、その他、皮膜の強靭性や耐指紋性を向上させるために、水分散性シリカを含有させることが望ましく、さらに潤滑性を向上させるために水系ワックスを添加することが望ましい。これらの成分の含有量は、全不揮発分を１００質量部としたとき、不揮発分で、樹脂を５０〜１００質量部、水分散性シリカを０〜４０質量部、水系ワックスを０〜３０質量部が好ましい。また、樹脂を架橋し得る架橋剤を含有させることができる。
【００３５】
【作用】
本発明の表面処理剤は、素材金属に塗布され、加熱乾燥される際に、素材金属表面と反応し、緻密な不動態皮膜を形成する。
本発明の表面処理剤によって形成された皮膜が優れた耐食性を示すのは、皮膜の持つ酸素、水分、イオンの透過を遮るバリヤー効果の他、腐食電子を非局在化する効果（電位の平滑化）によるものと考えられる。本発明で特定したバナジウム化合物（Ａ）において、５価のバナジウム化合物は酸素と結合した多価アニオンとして存在し、耐水性、耐アルカリ性が劣るため、十分な性能を得ることができないが、還元された４価のバナジウム化合物、３価のバナジウム化合物及び２価のバナジウム化合物の少なくとも１種を含有する処理剤を用いて形成させた皮膜は、耐水性、耐アルカリ性及び層間密着性が向上すると考えられる。また、用いる金属化合物（Ｂ）は、金属素材表面に対する犠牲防食作用の発現、前記腐食電子の局在化を促進する作用、又は金属素材の皮膜内に拡散するイオンと難溶性塩を徐々に形成する作用により、皮膜自体を不溶化し、さらには金属素材を不活性化する効果があると考えられる。また、用いる金属化合物（Ｃ）は形成する皮膜に存在するバナジウム化合物（Ａ）を固定化して、前記バリアー効果をさらに高めると考えられる。
また、用いる有機化合物（Ｄ）は、５価バナジウム化合物を還元すると同時に水溶液中で還元された４価、３価及び２価の少なくとも１種の原子価のバナジウムを水溶液中でキレート安定化する作用があると考えられる。
本発明の皮膜上に、更に塗装又はラミネートにより樹脂を主体とした層を形成させると、樹脂層のバリヤー効果との相乗効果により耐食性が一層高くなる。
【００３６】
【実施例】
次に実施例及び比較例によって本発明を説明するが、本実施例は単なる一例に過ぎず、本発明を限定するものではない。実施例、比較例において作製した処理板試料についての評価方法は次の通りである。
１．素材
ａ：電気亜鉛メッキ鋼板（板厚：０．８ｍｍ）
ｂ：溶融亜鉛メッキ鋼板（板厚：０．８ｍｍ）
ｃ：５５％アルミ亜鉛メッキ鋼板（板厚：０．５ｍｍ）
ｄ：マグネシウム合金アルミニム板、Ａ５１８２（板厚：０．３ｍｍ）
【００３７】
２．本発明処理液
（１）処理液成分
使用したバナジウム化合物（Ａ）を以下に記す。
Ａ１：メタバナジン酸アンモニウム
Ａ２：五酸化バナジウム
Ａ３：三酸化バナジウム
Ａ４：バナジウムオキシアセチルアセトネート
使用した金属化合物（Ｂ）を以下に記す。
Ｂ１：塩基性炭酸ニッケル
Ｂ２：硝酸コバルト
Ｂ３：硝酸マグネネシウム
Ｂ４：酸化亜鉛
Ｂ５：水酸化リチウム
【００３８】
使用した金属化合物（Ｃ）を以下に記す。
Ｃ１：モリブデン酸アンモニウム
Ｃ２：メタタングステン酸アンモニウム
Ｃ３：炭酸ジルコニウムアンモニウム
Ｃ４：フルオロチタン酸
Ｃ５：炭酸マンガン
【００３９】
使用した有機化合物（Ｄ）を以下に記す。
Ｄ１：Ｌ−アスコルビン酸
Ｄ２：Ｄ−グルコース
Ｄ３：グリオキザール
使用したエッチング剤（Ｅ）を以下に記す。
Ｅ１：ＨＦ
Ｅ２：Ｈ２ＺｒＦ６
Ｅ３：ＣＨ３ＣＯＯＨ
Ｅ４：Ｈ２ＳｉＦ６
Ｅ５：（ＨＨ４）２ＨＰＯ４
【００４０】
使用した水溶性高分子又は／及び水系エマルション樹脂（Ｆ）を以下に示す。
Ｆ１：水系ポリウレタン樹脂（第一工業製薬（株）製、スーパーフレックス１００）
Ｆ２：水系エチレン−アクリル酸共重合体樹脂（エチレン／アクリル酸＝８０／２０＊、平均分子量約２万）
Ｆ３：水系エポキシ樹脂（旭電化工業（株）製、アデカレジンＥＰＥＡ−０４３４）
Ｆ４：水系アクリル樹脂（ブチルアクリレート／メチルメタクリレート／２−ヒドロキシエチルメタクリレート／アクリル酸／グリシジルメタクリレート／スチレン＝５０／２０／５／８／２／１５）＊
＊数値はモル％
【００４１】
（２）処理液の調製
実施例１〜１１、比較例１〜３の場合
バナジウム化合物（Ａ）と金属化合物（Ｂ）と金属化合物（Ｃ）とエッチング剤（Ｅ）と脱イオン水とを混合し、５０℃で１時間加温した。
実施例１２〜２１、比較例４の場合
有機化合物（Ｄ）の５％水溶液にバナジウム化合物（Ａ）を混合した後、８０〜１００℃で３０分加温し、室温まで冷却し、金属化合物（Ｂ）と金属化合物（Ｃ）、つづいてエッチング剤（Ｅ）を加え、最後に脱イオン水を加えて所定の濃度に調整した。
【００４２】
３．樹脂層を形成するための塗料、フィルム
樹脂層を形成させるために使用した上塗り塗料（Ｘ）を記す。
Ｘ：溶剤系塗料（デリコン７００、大日本塗料（株）製）
樹脂層を形成させるために使用したラミネートフィルム（Ｙ）を記す。
Ｙ：ポリエステルフィルム（ルミラーＳ１０、ＴＯＲＡＹ Ｉｎｄｕｓｔｏｒｉｅｓ．Ｉｎｃ．）
樹脂層を形成させるために使用した水系塗料（Ｚ）と処理方法を記す。水系塗料（Ｚ）としては、次に示すＺ１又はＺ２を使用した。
Ｚ１：水系ポリウレタン（第一工業製薬（株）製、スーパーフレックス１００）を固形分で１００質量部、水系シリカ（日産化学（株）製、スノーテックスＣ）をシリカ換算で２０質量部、水系ワックス（三井化学（株）製、ケミパールＷ９００）を固形分で１０質量部からなる不揮発分１０％の水系処理液。
Ｚ２：エチレン−アクリル酸共重合物（エチレン／アクリル酸＝８０／２０、平均分子量約２万）のアンモニア中和水系ポリマーを、固形分換
算で１００質量部、水分散性シリカをシリカ換算で１０質量部からなる不揮発性分２０％の水系処理液。
【００４３】
４．処理方法
（１）脱脂
日本パーカライジング（株）製アルカリ脱脂剤パルクリーン３６４Ｓ
（２０ｇ／Ｌ建浴、６０℃、１０秒スプレー、スプレー圧５０ｋＰａ）で素材を脱脂した後、スプレー水洗を１０秒行った。
（２）本発明処理液の塗布及び乾燥
Ｉ：処理液をバーコーター＃３で塗布し、熱風循環型オーブンを用いて板温８０℃で乾燥した。
ＩＩ：処理液をバーコーター＃３で塗布し、熱風循環型オーブンを用いて板温１５０℃で乾燥した。
【００４４】
（３）樹脂層の形成条件
本発明の処理剤、処理方法を用いて形成された表面処理金属材料の皮膜上に、次の方法により樹脂層を形成させた。
Ｘ：溶剤系塗料
前記溶剤系塗料（Ｘ）を乾燥膜厚が約２５μｍになるようにバーコート塗布し、市販のバッチ式乾燥炉内に置き、１４０℃で３０分加熱乾燥した。
Ｙ：ポリエステルフィルム
本発明の表面処理金属材料を加熱炉で到達板温が２４０℃になるまで昇温させ、あらかじめ１００℃に加温した前記ポリエステルフィルム（Ｙ）を加圧ラミネートして貼り合わせた。
Ｚ：水系塗料
本発明の処理液、処理方法を用いて形成された皮膜上に、前記水系塗料（Ｚ）を乾燥膜厚が約１μｍになるようにバーコート塗布し、板温１００℃で加熱乾燥した。
【００４５】
５．評価方法
（１）耐食性
塩水噴霧試験法ＪＩＳ−Ｚ−２３７１に基づき塩水噴霧１２０時間後、２４０時間後の白錆発生面積を求め評価した。
処理板に、日本パーカライジング（株）製アルカリ脱脂剤パルクリーン３６４Ｓを２０ｇ／Ｌに建浴し６０℃に調整した脱脂剤水溶液を３０秒間スプレーし、水洗した後、８０℃で乾燥した。この板について、上記（１）に記載した条件、評価法で耐食性を評価した。
【００４６】
（３）層間密着性
溶剤系塗料（Ｘ）又はポリエステルフィルム（Ｙ）を用いて樹脂層を形成させた後、１ｍｍ、１００マスの碁盤目試験を行い、更にその部位を７ｍｍ押し出しでエリクセン加工を施した。加工後、沸騰水中に５時間浸漬し、処理板を取り出して室温雰囲気下で３０分間、自然乾燥した。つづいて、テープ剥離試験を実施し、樹脂層の残存数を求めて次の評価基準により判定した。
（４）耐指紋性
処理板表面に指を押し付け、指紋の痕跡状態を肉眼で観察し評価した。
エタノールをしみ込ませたガーゼをシリコンゴム製の立方体（１ｃｍ角）に巻いて、試験面を５０，０００ｋＰａで３０往復ラビングした。
実施例及び比較例の処理液内容及び処理方法を表１及び表２及び表３に、処理板の評価結果を表４及び表５に示した。
表４より特定のバナジウム化合物（Ａ）と特定の金属化合物（Ｂ）とを含有する本発明の処理剤（実施例１〜２１）から形成された皮膜は、耐食性、耐アルカリ性、更には樹脂層（Ｘ又はＹ）及び各種金属材料との層間密着性において総合的に優れた結果を示すことが分かる。これに比べ、バナジウム化合物（Ａ）又は金属化合物（Ｂ）を含まない比較例１〜４では耐食性、耐アルカリ性、及び層間密着性の全ての性能を満足するものはなかった。
表５より、水溶性高分子又は水系エマルション樹脂（Ｆ）を含有する実施例２２〜２７は、さらに上層に樹脂層を設けていない１層処理となっているが、耐食性及び耐アルカリ性に優れており、また耐指紋性、耐溶剤性も優れていることが分かる。実施例２８〜４２は、水溶性高分子又は水系エマルション樹脂（Ｆ）を本発明処理剤中には含有していないが、実施例１〜１５の皮膜上にさらに樹脂層（Ｚ１又はＺ２）を施した２層処理となっている。これら実施例２８〜４２についても、耐食性及び耐アルカリ性に優れており、また耐指紋性、耐溶剤性も優れていることが分かる。これに比べ、バナジウム化合物（Ａ）又は金属化合物（Ｂ）を含まない比較例５（皮膜自体に樹脂成分を含有させたもの）及び比較例６〜９（比較例１〜４の皮膜上に樹脂層（Ｚ）を施したもの）では耐食性、耐アルカリ性及び耐溶剤性の全ての性能を満足するものはなかった。
【００４９】
【表１】
【表２】
【表３】
実施例２８ 実施例１で形成した皮膜上に上塗り処理剤Ｚ１による処理を行った。
実施例２９ 実施例２で形成した皮膜上に上塗り処理剤Ｚ２による処理を行った。
実施例３０ 実施例３で形成した皮膜上に上塗り処理剤Ｚ１による処理を行った。
実施例３１ 実施例４で形成した皮膜上に上塗り処理剤Ｚ２による処理を行った。
実施例３２ 実施例５で形成した皮膜上に上塗り処理剤Ｚ２による処理を行った。
実施例３３ 実施例６で形成した皮膜上に上塗り処理剤Ｚ２による処理を行った。
実施例３４ 実施例７で形成した皮膜上に上塗り処理剤Ｚ１による処理を行った。
実施例３５ 実施例８で形成した皮膜上に上塗り処理剤Ｚ２による処理を行った。
【００５３】
実施例３６ 実施例９で形成した皮膜上に上塗り処理剤Ｚ２による処理を行った。
実施例３７ 実施例１０で形成した皮膜上に上塗り処理剤Ｚ２による処理を行った。
実施例３８ 実施例１１で形成した皮膜上に上塗り処理剤Ｚ１による処理を行った。
実施例３９ 実施例１２で形成した皮膜上に上塗り処理剤Ｚ２による処理を行った。
実施例４０ 実施例１３で形成した皮膜上に上塗り処理剤Ｚ２による処理を行った。
実施例４１ 実施例１４で形成した皮膜上に上塗り処理剤Ｚ２による処理を行った。
実施例４２ 実施例１５で形成した皮膜上に上塗り処理剤Ｚ２による処理を行った。
【００５４】
比較例６ 比較例１で形成した皮膜上に上塗り処理剤Ｚ２による処理を行った。
比較例７ 比較例２で形成した皮膜上に上塗り処理剤Ｚ２による処理を行った。
比較例８ 比較例３で形成した皮膜上に上塗り処理剤Ｚ２による処理を行った。
比較例９ 比較例４で形成した皮膜上に上塗り処理剤Ｚ２による処理を行った。
【００５５】
【表４】
【表５】
【発明の効果】
本発明の金属表面処理剤は有害なクロム化合物を含まないノンクロメートタイプであり、本表面処理剤から形成される皮膜は、従来のクロメート皮膜と同等又はそれ以上の耐食性を有しており、本発明の表面処理剤、表面処理方法及び表面処理金属材料は産業上の利用価値が極めて大きいものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention provides a sheet coil made of a metal as a material, imparts excellent corrosion resistance and alkali resistance to the surface of a molded product, and further has excellent interlayer adhesion with a resin layer and a metal material formed by painting or lamination, and chromium. The present invention relates to a metal surface treatment agent, a metal surface treatment method, and a surface-treated metal material used for forming a film containing no metal.
More specifically, the present invention relates to an automobile body, an automobile part, and a building material made of a steel material such as steel, galvanized steel, or aluminum-plated steel, and a nonferrous metal material such as aluminum, magnesium, copper, or an alloy thereof. , Surface treatment agents used to impart excellent corrosion resistance and alkali resistance to molded products such as home appliance parts, cast products, sheet coils, etc., and to form a film having excellent interlayer adhesion and containing no chromium, The present invention relates to a surface treatment method and a surface-treated metal material.
[0002]
[Prior art]
Steel materials such as steel, zinc-plated steel, and aluminum-plated steel, as well as non-ferrous metal materials such as aluminum, magnesium, copper, and their alloys are oxidized by oxygen, moisture, ions contained in the moisture, etc. in the atmosphere. Corrodes. As a method of preventing such corrosion, there has been a method of forming a chromate film by bringing the surface of a metal material into contact with a treatment solution containing chromium such as chromate chromate and phosphate chromate.
Coatings formed using these chromate treatments have excellent corrosion resistance and coating adhesion, but contain harmful hexavalent chromium in the treatment liquid, and wastewater treatment requires labor and cost. In addition, since the hexavalent chromium is also contained in the film formed by the treatment, it tends to be avoided from the viewpoint of environment and safety.
[0003]
As a method using a non-chromate treatment solution containing no chromium, Patent Document 1 discloses an organic polymer such as an epoxy resin, an acrylic resin, or a urethane resin having at least one nitrogen atom and a metal containing a specific polyvalent anion. A surface treatment agent is disclosed. Here, vanadic acid is described in the specified polyvalent anions, but vanadic acid, which is an oxygen acid of pentavalent vanadium, has poor water resistance and alkali resistance. For example, there was a problem that when the substrate was washed by the method described above, it fell off from the film and the corrosion resistance was extremely reduced. In addition, it describes that after treatment, washing and drying are performed, and there is no problem of chromium wastewater, but there is a problem of wastewater such as COD due to organic substances.
[0004]
Patent Document 2 discloses a metal surface treating agent containing a vanadium compound and a metal compound containing at least one metal selected from zirconium, titanium, molybdenum, tungsten, manganese, and cerium.
The metal surface treatment described in Patent Literature 2 has the advantage that the treatment liquid does not contain hexavalent chromium, and the formed film is considerably improved in corrosion resistance and alkali resistance.
[0005]
[Patent Document 1] Japanese Patent Application Laid-Open No. 10-1789 (Claims 1 to 3)
[Patent Document 2] Japanese Patent Application Laid-Open No. 2002-30460 (Claim 1)
[0006]
[Problems to be solved by the invention]
The metal surface treatment described in Patent Literature 2 can provide a film having good corrosion resistance and alkali resistance, but it is still insufficient compared with a chromate film, and further improvement in these properties has been demanded.
The present invention has been made in order to solve the problems of the prior art, and provides excellent corrosion resistance and alkali resistance to a metal material, and also provides excellent interlayer adhesion, and does not contain chromium. It is an object to provide a metal surface treatment agent, a metal surface treatment method, and a surface treated metal material.
[0007]
[Means for Solving the Problems]
The present inventor has conducted extensive studies on means for solving the above-mentioned problems, and as a result of treating the metal material surface with a surface treating agent having a specific composition, excellent corrosion resistance, alkali resistance and interlayer adhesion have been achieved. Have been found to be able to obtain a film having the following formula:
That is, the present invention relates to a metal compound (B) containing at least one vanadium compound (A) and at least one metal selected from the group consisting of cobalt, nickel, zinc, magnesium, aluminum, calcium, strontium, barium and lithium. )).
[0008]
In the present invention, the interlayer adhesion refers to the adhesion between a film obtained by using a metal surface treating agent such as the metal surface treating agent of the present invention and a resin film usually applied thereon and the film. It means both adhesion to the metal surface. However, in practice, a film obtained by using a metal surface treating agent such as the metal surface treating agent of the present invention is originally a chemical conversion film having good adhesion to a metal surface. Adhesion usually means adhesion with a resin film. However, such a film itself may contain a resin component, and in such a case, the interlayer adhesion means the adhesion to the metal surface.
[0009]
In the present invention, the surface treatment agent may further contain a metal compound (C) containing at least one metal selected from the group consisting of zirconium, titanium, molybdenum, tungsten, manganese, and cerium. It is preferable for improving alkalinity and interlayer adhesion.
In the vanadium compound (A), the ratio V of vanadium ions having a valence of 5 to the total vanadium is V5+/ V is preferably in the range of 0 to 0.6 in view of the stability of the vanadium compound in the treatment agent, the corrosion resistance of the formed film, the alkali resistance, and the interlayer adhesion.
Further, the metal surface treatment agent further has at least one functional group selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, a primary to tertiary amino group, an amide group, a phosphoric acid group and a phosphonic acid group. When the pentavalent vanadium compound is used, the organic compound (D) is reduced to tetravalent to divalent, and / or improves the stability of the vanadium compound in the treatment liquid of the present invention. Preferred for.
[0010]
Further, the metal surface treatment agent may further contain at least one etching agent (E) selected from inorganic acids, organic acids, salts of inorganic acids or organic acids, and fluorine compounds. It is preferable to improve the adhesion to the metal surface.
Further, when the metal surface treating agent further contains a water-soluble polymer and / or an aqueous emulsion resin (F), the corrosion resistance, fingerprint resistance, solvent resistance and surface lubricity of the film to be formed are improved. Preferred for.
[0011]
In the present invention, the metal material surface is contacted with any one of the metal surface treatment agents described above, and then heated and dried so that the temperature of the material is 30 to 250 ° C., and at least one side of the metal material surface And a method for surface-treating a metal material characterized by forming a dry film having a thickness of 0.001 to 2 μm, and a surface-treated metal material having a film formed using the surface treatment method. Further, it is preferable that the metal material is selected from the group consisting of a zinc-based plated steel, an aluminum-based plated steel, an aluminum / zinc-based alloy-plated steel, an aluminum, an aluminum alloy, a magnesium alloy, and a copper alloy.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
The vanadium compound (A) contained in the metal surface treatment agent of the present invention is a vanadium compound having a pentavalent, tetravalent, trivalent or divalent vanadium oxidation number, for example, vanadium pentoxide (V2O5), Metavanadic acid (HVO)3), Ammonium metavanadate, sodium metavanadate, vanadium oxytrichloride (VOCl3), Vanadium compounds having a valence of 5, and vanadium trioxide (V2O3), Vanadium dioxide (VO2), Vanadium oxysulfate (VOSO4), Vanadium oxyacetylacetonate [VO (OC (CH3) = CHCOCH3)2], Vanadium acetylacetonate [V (OC (CH3) = CHCOCH3)3], Vanadium trichloride (VCl3), Linvanado molybdic acid ｛HFifteen-X [PV12-XMoxO40] ・ NH2O (6 <x <12, n <30)}, vanadium sulfate (VSO4・ 7H2O), vanadium dichloride (VCl2), And at least one selected from vanadium compounds having an oxidation number of 4 to 2 such as vanadium oxide (VO).
[0013]
It is preferable that the present treating agent contains a vanadium compound having an oxidation number of 4 or less (usually 4 to 2) as the vanadium compound (A). That is, the ratio V of vanadium ions having a valence of 5 to the total vanadium V5+/ V (where V5+And V represent the mass of vanadium having a valence of 5 and the total mass of vanadium, respectively) are preferably in the range of 0 to 0.6, more preferably in the range of 0 to 0.4, and more preferably in the range of 0 to 0.4. More preferably, it is in the range of 2, more preferably in the range of 0 to 0.1.
If the above ratio exceeds 0.6, the stability of the vanadium compound in the treating agent generally deteriorates, and the corrosion resistance, alkali resistance and interlayer adhesion of the formed film decrease.
[0014]
As a method of including a 4- to 2-valent vanadium compound in the treatment agent, a 4- to 2-valent vanadium compound as described above may be used. Can be used. The reducing agent to be used may be either an inorganic type or an organic type, but is preferably an organic type, and particularly preferably uses the organic compound (D).
[0015]
The metal compound (B) containing at least one metal selected from the group consisting of cobalt, nickel, zinc, magnesium, aluminum, calcium, strontium, barium and lithium, contained in the metal surface treatment agent of the present invention, Metal oxides, hydroxides, complex compounds, salts with inorganic or organic acids, and the like. As such a metal compound (B), for example, cobalt (II) acetylacetonate [Co (OC (CH3) = CHCOCH3)2], Cobalt (III) acetylacetylacetonate [Co (OC (CH3) = CHCOCH3)3], Cobalt (II) nitrate, cobalt (II) sulfate, cobalt (II) acetate, cobalt (II) oxalate, cobalt (III) oxalate, cobalt (II) oxide, cobalt (III) oxide, cobalt (IV) oxide ), Nickel (II) nitrate, nickel (II) acetate, nickel (III) acetate, nickel (II) oxalate, nickel (II) oxide, nickel (II) acetylacetonate [Ni (OC (CH3) = CHCOCH3)2], Nickel amidosulfate, basic nickel carbonate [NiCO3・ 2Ni (OH)3], Nickel (II) hydroxide, zinc fluoride, zinc sulfate, zinc nitrate, zinc acetate, zinc oxide, zinc (II) acetylacetonate [Zn (OC (CH3) = CHCOCH3)2], Basic zinc carbonate [2ZnCO3・ 3Zn (OH)2], Magnesium nitrate, magnesium sulfate, magnesium acetate, magnesium fluoride, magnesium hydroxide, magnesium oxalate, magnesium oxide, basic magnesium carbonate [(MgCO3)4・ Mg (OH)2], Aluminum nitrate, aluminum sulfate, aluminum oxide, aluminum hydroxide, aluminum fluoride, aluminum acetate, calcium acetate, calcium fluoride, calcium phosphinate [Ca (PH2O2)2], Calcium nitrate, calcium hydroxide, calcium oxalate, calcium oxide, calcium acetate, strontium nitrate, strontium acetate, strontium carbonate, barium nitrate, barium carbonate, barium oxide, lithium nitrate, lithium phosphate, lithium fluoride, hydroxide Examples include lithium, lithium sulfate, lithium carbonate, dilithium oxalate, and lithium oxide.
Among these metal compounds (B), metal compounds containing at least one metal selected from the group consisting of cobalt, nickel, zinc and magnesium are preferred.
[0016]
The metal compound (C) containing at least one metal selected from the group consisting of zirconium, titanium, molybdenum, tungsten, manganese and cerium, which is contained as an optional component in the metal surface treatment agent of the present invention, Oxides, hydroxides, complex compounds, salts with inorganic or organic acids, and the like. As such a metal compound (C), for example, zirconyl nitrate (ZrO (NO3)2), Zirconyl acetate, zirconyl sulfate, ammonium zirconyl carbonate ｛(NH4)2[Zr (CO3)2(OH)2｝, Zirconium acetate, titanyl sulfate (TiOSO4), Titanium lactate, diisopropoxytitanium bisacetylacetone (C5H7O2)2Ti [OCH (CH3)2]2｝, A reaction product of lactic acid and titanium alkoxide, molybdic acid (H2MoO4), Ammonium molybdate, sodium molybdate, molybdophosphate compounds (eg, ammonium molybdate リ ブ (NH4)3[PO4Mo12O36] ・ 3H2O｝, sodium molybdophosphate ｛Na3[PO4・ 12MoO3] ・ NH2O｝), metatungstic acid ｛H6[H2W12O40], Ammonium metatungstate} (NH4)6[H2W12O40]｝, Sodium metatungstate, paratungstate ｛H10[W12O46H10]｝, Ammonium paratungstate, sodium paratungstate, permanganate (HMnO4), Potassium permanganate, sodium permanganate, manganese dihydrogen phosphate [Mn (H2PO4)2], Manganese nitrate [Mn (NO3)2], Manganese sulfate, manganese fluoride, manganese carbonate (MnCO3), Manganese acetate, cerium acetate [Ce (CH3CO2)3], Cerium nitrate, cerium chloride and the like.
Among these metal compounds (C), metal compounds containing zirconium and / or titanium are preferred.
[0017]
A preferred combination of the metal compounds (A), (B) and (C) is a metal compound containing vanadium compound (A) and cobalt and / or nickel as metal compound (B) and metal compound (C). The combination with the metal compound containing zirconium gives all the metallic materials used in the present invention the best corrosion resistance, alkali resistance and interlayer adhesion. Further, a combination of a vanadium compound (A), a metal compound containing zinc and / or magnesium as a metal compound (B), and a metal compound containing titanium as a metal compound (C) is added to the above-mentioned aluminum-containing metal material, Provides excellent corrosion resistance, alkali resistance and interlayer adhesion as well as the combination.
[0018]
If necessary, the organic compound (D) contained in the metal surface treating agent of the present invention comprises a hydroxyl group, a carbonyl group, a carboxyl group, a primary to tertiary amino group, an amide group, a phosphoric acid group and a phosphonic acid group. An organic compound having at least one functional group selected from the group.
Examples of the organic compound (D) include alcohols such as methanol, ethanol, isopropanol and ethylene glycol, carbonyl such as formaldehyde, acetaldehyde, furfural, acetylacetone, ethyl acetoacetate, glyoxal, dipivaloylmethane, and 3-methylpentanedione. Compounds, organic acids such as formic acid, acetic acid, propionic acid, tartaric acid, ascorbic acid, gluconic acid, citric acid, malic acid, and glyoxylic acid, and amines such as triethylamine, triethanolamine, ethylenediamine, pyridine, imidazole, pyrrole, morpholine, and piperazine Compounds, acid amide compounds such as formamide, acetamide, propionamide, N-methylpropionamide, and amino acids such as glycine, alanine, proline, and glutamic acid Aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1'-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), organic phosphoric acids such as phytic acid, monosaccharides such as glucose, mannose and galactose, maltose, sucrose Oligosaccharides such as starch, natural polysaccharides such as starch, cellulose, aromatic compounds such as tannic acid, humic acid, lignin sulfonic acid, polyphenol, polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide, polyethyleneimine, water-soluble nylon And the like.
[0019]
Among these organic compounds (D), organic compounds containing at least one selected from the above functional groups in one molecule are preferable, and a hydroxyl group, a carbonyl group, a carboxyl group, a phosphorus group, Organic compounds containing two or more in a molecule of at least one selected from an acid group and a phosphonic acid group are more preferred.
[0020]
When a pentavalent vanadium compound is used, these organic compounds (D) are reduced to tetravalent, trivalent or divalent and / or improve the stability of the vanadium compound in the treatment liquid of the present invention. Preferred for
[0021]
These organic compounds (D) are preliminarily mixed with a vanadium compound and heated (for example, at 40 to 100 ° C. for 5 to 120 minutes) to sufficiently reduce and stabilize the surface treatment agent. However, it is also possible to apply a simple mixed surface treatment agent to the metal surface and then promote the reduction during heating and drying.
[0022]
The etching agent (E) to be contained in the metal surface treating agent of the present invention, if necessary, is at least one compound selected from inorganic acids, organic acids, salts of inorganic acids or organic acids, and fluorine compounds. . The etching agent (E) to be contained in the surface treatment agent of the present invention, if necessary, may be an inorganic acid, an organic acid, or a salt of an inorganic acid or an organic acid (particularly, an alkali metal such as an ammonium salt, a sodium salt, or a potassium salt). Salt) and at least one compound selected from fluorine compounds. The compound is used for etching a material metal at the time of applying a treating agent or drying by heating. Examples of the etching agent (E) include inorganic acids such as phosphoric acid, nitric acid and sulfuric acid and salts thereof (particularly ammonium salts, sodium salts and potassium salts), and organic acids such as formic acid and acetic acid or salts thereof (particularly ammonium salts). , Sodium salts, potassium salts), hydrofluoric acid, borofluoric acid (HBF4), Hydrosilicofluoric acid (H2SiF6), Zirconium hydrofluoric acid (H2ZrF6), Titanium hydrofluoric acid (H2TiF6), Tin (I) fluoride (SnF)2), Tin (II) fluoride (SnF4), And fluorine compounds such as ferrous fluoride and ferric fluoride.
The use of the etching agent (E) is preferable for increasing the reactivity to the metal material and improving the adhesion between the film to be formed and the metal material.
[0023]
The amount of each component in the treatment agent of the present invention is preferably from 0.1 to 100 g / L, more preferably from 1 to 70 g / L, in terms of vanadium compound (A). The metal compound (B) is preferably 0.01 to 50 g / L in terms of metal, more preferably 0.1 to 20 g / L. The metal compound (C) is preferably from 0.1 to 100 g / L, more preferably from 1.0 to 70 g / L, in terms of metal.
The mass ratio of the vanadium compound (A), the metal compound (B) and the metal compound (C) is V / metal compound mass = 1/200 to 9/1 in terms of metal, and The mass in terms of metal in the compound (B) / (V + the mass in terms of metal in the metal compound (C)) is preferably 1/1000 to 1/5, and V / the mass in terms of metal in the metal compound (C) = It is more preferable that the ratio is 1/100 to 8/2, and the mass in terms of metal in the metal compound (B) / (V + the mass in terms of metal in the metal compound (C)) = 1/200 to 1/10.
The organic compound (D) is preferably 0.05 to 10, and more preferably 0.1 to 5, when the mass of pentavalent vanadium in the vanadium compound is defined as 1. The addition in excess of the amount required for reduction is more preferable in order to improve the stability of the reduced form in the processing solution.
The amount of the etching agent (E) is preferably 0.01 to 100 g / L, more preferably 0.1 to 70 g / L.
[0024]
In the treating agent of the present invention, a water-soluble polymer and / or an aqueous emulsion resin (F) such as polyacrylic acid, polyacrylamide, and polyvinyl alcohol are used for the purpose of improving corrosion resistance, fingerprint resistance, solvent resistance, and surface lubricity. , Water-soluble polymers such as polyethylene glycol, water-dispersed acrylic resin, urethane resin, epoxy resin, polyester resin, polyamide resin, polyolefin resin, ethylene-acrylic acid copolymer resin, polyacetal resin, polybutyral resin, etc. Water-based emulsion resin can be added. These can be used alone or in combination of two or more. The resin in the aqueous emulsion resin (F) may be dispersed in a liquid state or a solid state. The addition amount of the water-soluble polymer and / or the aqueous emulsion resin (F) is preferably from 5 to 95% by mass, more preferably from 10 to 90% by mass of the total nonvolatile components.
[0025]
In the treating agent of the present invention, a silica sol dispersed in water and / or a metal sol such as an alumina sol or a zirconia sol can be added. By adding these, corrosion resistance, water resistance, and fingerprint resistance are improved. In this case, the amount to be added is preferably 2 to 80% by mass of the total nonvolatile components, and more preferably 5 to 60%.
Further, in the treatment agent of the present invention, a silane coupling agent such as aminosilane, epoxysilane, mercaptosilane and the like can be added. Addition of these improves interlayer adhesion and corrosion resistance. In this case, the amount to be added is preferably 5 to 40% by mass, more preferably 10 to 30% by mass of the total nonvolatile components.
[0026]
Further, in the treating agent of the present invention, a lubricant such as polyethylene wax, polypropylene wax, microcrystalline wax, carnauba wax, and polytetrafluoroethylene can be added. By adding these, slip properties, moldability, and scratch resistance can be imparted. In this case, the amount to be added is preferably 1 to 40% by mass, more preferably 5 to 30% by mass of the total nonvolatile components.
In the present invention, the term "all non-volatile components" means components remaining after the surface treatment agent is dried by heating at 110 ° C. for 2 hours.
[0027]
The solvent used in the surface treatment agent of the present invention is mainly water, but does not prevent the combined use of alcohol, ketone, and cellosolve-based water-soluble organic solvents as necessary, such as improvement of the drying property of the film.
In addition, a surfactant, an antifoaming agent, a leveling agent, a bactericidal / antibacterial agent, a coloring agent, and the like may be added as long as the purpose of the present invention and the film performance are not impaired.
[0028]
Next, the surface treatment method of the present invention will be described.
Although there is no particular limitation on the pre-process of this treatment, usually, before performing this treatment, the material is washed with an alkaline degreaser or an acidic degreaser to remove oil and dirt attached to the material, or washed with hot water, solvent. Perform cleaning, etc. Thereafter, if necessary, the surface is adjusted with an acid, an alkali or the like. In the cleaning of the material surface, it is preferable to wash with water after cleaning so that the cleaning agent does not remain on the material surface as much as possible.
[0029]
In the present treatment method, it is only necessary that the surface treatment agent of the present invention can be heated and dried after being applied to the surface of the metal material, and there is no particular limitation on the application method and the drying method.
Usually, a roll coating method in which the treatment agent is transferred to the surface of the material by roll transfer, or a method in which the treatment agent is squeezed with a roll after pouring with a shower ringer, a method in which the material is immersed in the treatment agent, and a method in which the treatment agent is sprayed on the material are used Can be Although the temperature of the treatment solution is not particularly limited, the treatment temperature is preferably 0 to 60 ° C, more preferably 5 to 40 ° C, since the solvent of the present treatment agent is mainly water.
[0030]
The drying step does not necessarily require heat, and may be air drying or physical removal such as air blowing, but may be performed by heating and drying in order to improve film forming properties and interlayer adhesion. The temperature in that case is preferably from 30 to 250C, more preferably from 60 to 220C.
[0031]
The adhesion amount of the formed film is preferably from 0.001 to 2 μm, more preferably from 0.005 to 1 μm in terms of the amount of the dried film. If the thickness is less than 0.001 μm, sufficient corrosion resistance, alkali resistance and interlayer adhesion cannot be obtained. If the thickness exceeds 2 μm, the coating itself may be cracked and the adhesion to a metal material may be reduced.
[0032]
By providing a resin layer on the film formed from the surface treatment agent of the present invention so that the dry film thickness becomes 0.3 to 50 μm, the corrosion resistance and alkali resistance of the metal material to be treated are improved, and the fingerprint resistance is also improved. Properties, solvent resistance and surface lubricity.
[0033]
As a method of providing such a resin layer, a solvent-based paint or a water-based paint in which a resin is dissolved or dispersed in advance is coated on a film formed from the surface treatment agent of the present invention, and dried at 0 to 200 ° C. And a method of laminating a film-like resin on the film. Examples of the resin having interlayer adhesion to the film include polyester resin, vinyl chloride resin, acrylic resin, epoxy resin, polyimide resin, polyolefin resin, polyamide resin, phenol resin and the like.
Particularly, as a method for providing a resin layer so as to impart fingerprint resistance, solvent resistance and surface lubricity, a water-based paint (Z) containing a water-soluble or water-dispersible resin as a main component may be used. It is desirable to apply the method on a film formed from a surface treatment agent, and to heat and dry the material at a temperature of 50 to 250 ° C. The water-soluble or water-dispersible resin used in the water-based paint (Z) includes acrylic resins, polyolefin resins, epoxy resins, urethane resins obtained by condensation reaction, obtained by polymerizing addition-polymerizable unsaturated monomers. It is a polyester-based resin, a polyamide-based resin, a phenol-based resin, or the like, and the glass transition point of the resin is preferably from 0 to 120 ° C, more preferably from 10 to 100 ° C. If the glass transition point is less than 0 ° C, the strength and hardness of the film are poor, and if it exceeds 120 ° C, the film-forming properties are poor and the adhesion is poor.
[0034]
The water-based paint (Z) preferably contains at least one kind selected from these resins, and further contains water-dispersible silica in order to improve the toughness and fingerprint resistance of the film. It is desirable to add an aqueous wax in order to improve the properties. The content of these components is, assuming that the total non-volatile components are 100 parts by mass, the non-volatile components are 50 to 100 parts by mass of the resin, 0 to 40 parts by mass of the water-dispersible silica, and 0 to 30 parts by mass of the aqueous wax. Is preferred. Further, a crosslinking agent capable of crosslinking the resin can be contained.
[0035]
[Action]
The surface treating agent of the present invention reacts with the surface of the base metal when applied to the base metal and dried by heating to form a dense passive film.
The film formed by the surface treatment agent of the present invention exhibits excellent corrosion resistance because of the barrier effect of blocking the oxygen, moisture and ion transmission of the film, as well as the effect of delocalizing corroded electrons (smoothing potential). ). In the vanadium compound (A) specified in the present invention, the pentavalent vanadium compound exists as a polyvalent anion bonded to oxygen and has poor water resistance and alkali resistance, so that sufficient performance cannot be obtained. A film formed using a treating agent containing at least one of a tetravalent vanadium compound, a trivalent vanadium compound, and a divalent vanadium compound is considered to have improved water resistance, alkali resistance, and interlayer adhesion. . Further, the metal compound (B) used exhibits a sacrificial anticorrosion effect on the surface of the metal material, an effect of promoting the localization of the corrosive electrons, or gradually forms a hardly soluble salt with ions diffusing into the film of the metal material. It is considered that the effect of insolubilizing the film itself and further inactivating the metal material due to the action of the film. Further, it is considered that the metal compound (C) used fixes the vanadium compound (A) present in the film to be formed, and further enhances the barrier effect.
Further, the organic compound (D) used reduces the pentavalent vanadium compound and simultaneously stabilizes at least one kind of tetravalent, trivalent or divalent vanadium reduced in the aqueous solution in an aqueous solution. It is thought that there is.
When a layer mainly composed of a resin is further formed on the film of the present invention by painting or laminating, the corrosion resistance is further enhanced by a synergistic effect with the barrier effect of the resin layer.
[0036]
【Example】
Next, the present invention will be described with reference to examples and comparative examples. However, the present examples are merely examples, and do not limit the present invention. The evaluation method for the processed plate samples produced in the examples and comparative examples is as follows.
1. Material
a: Electrogalvanized steel sheet (sheet thickness: 0.8mm)
b: Hot-dip galvanized steel sheet (sheet thickness: 0.8 mm)
c: 55% aluminum galvanized steel sheet (sheet thickness: 0.5 mm)
d: magnesium alloy aluminum plate, A5182 (plate thickness: 0.3 mm)
[0037]
2. Treatment liquid of the present invention
(1) Processing liquid components
The used vanadium compound (A) is described below.
A1: Ammonium metavanadate
A2: Vanadium pentoxide
A3: Vanadium trioxide
A4: Vanadium oxyacetylacetonate
The metal compound (B) used is described below.
B1: Basic nickel carbonate
B2: Cobalt nitrate
B3: Magnesium nitrate
B4: Zinc oxide
B5: Lithium hydroxide
[0038]
The metal compound (C) used is described below.
C1: ammonium molybdate
C2: ammonium metatungstate
C3: Zirconium ammonium carbonate
C4: Fluorotitanic acid
C5: Manganese carbonate
[0039]
The used organic compound (D) is described below.
D1: L-ascorbic acid
D2: D-glucose
D3: Glyoxal
The used etching agent (E) is described below.
E1: HF
E2: H2ZrF6
E3: CH3COOH
E4: H2SiF6
E5: (HH4)2HPO4
[0040]
The used water-soluble polymer and / or aqueous emulsion resin (F) is shown below.
F1: Water-based polyurethane resin (Daiichi Kogyo Seiyaku Co., Ltd., Superflex 100)
F2: water-based ethylene-acrylic acid copolymer resin (ethylene / acrylic acid = 80/20 *, average molecular weight about 20,000)
F3: water-based epoxy resin (Adeka Resin EPEA-0434 manufactured by Asahi Denka Kogyo KK)
F4: water-based acrylic resin (butyl acrylate / methyl methacrylate / 2-hydroxyethyl methacrylate / acrylic acid / glycidyl methacrylate / styrene = 50/20/5/8/2/15) *
* Value is mol%
[0041]
(2) Preparation of treatment solution
Examples 1 to 11 and Comparative Examples 1 to 3
The vanadium compound (A), the metal compound (B), the metal compound (C), the etching agent (E), and deionized water were mixed and heated at 50 ° C. for 1 hour.
Examples 12 to 21 and Comparative Example 4
After mixing the vanadium compound (A) with a 5% aqueous solution of the organic compound (D), the mixture is heated at 80 to 100 ° C. for 30 minutes, cooled to room temperature, and then mixed with the metal compound (B) and the metal compound (C). An etching agent (E) was added, and finally, deionized water was added to adjust the concentration to a predetermined value.
[0042]
3. Paints and films for forming resin layers
The top coat (X) used to form the resin layer is described.
X: Solvent-based paint (Delicon 700, manufactured by Dainippon Paint Co., Ltd.)
The laminate film (Y) used for forming the resin layer is described.
Y: Polyester film (Lumirror S10, TORAY Industries, Inc.)
The water-based paint (Z) used for forming the resin layer and the treatment method are described. Z1 or Z2 shown below was used as the water-based paint (Z).
Z1: 100 parts by mass of a water-based polyurethane (Superflex 100, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 20 parts by mass of water-based silica (Snowtex C, manufactured by Nissan Chemical Co., Ltd.) in terms of silica, water-based wax (Mitsui Chemicals Co., Ltd., Chemipearl W900), an aqueous treatment liquid having a solid content of 10 parts by mass and a nonvolatile content of 10%.
Z2: Solidification of ammonia-neutralized water-based polymer of ethylene-acrylic acid copolymer (ethylene / acrylic acid = 80/20, average molecular weight about 20,000)
An aqueous treatment liquid having a nonvolatile content of 20%, comprising 100 parts by mass in total and 10 parts by mass of water-dispersible silica in terms of silica.
[0043]
4. Processing method
(1) Degreasing
Nippon Parkerizing Co., Ltd. alkaline degreasing agent PALCLEAN 364S
(20 g / L bath, 60 ° C., spray for 10 seconds, spray pressure 50 kPa), degreased the material, and spray-washed for 10 seconds.
(2) Application and drying of the treatment liquid of the present invention
I: The treatment liquid was applied with a bar coater # 3, and dried at a plate temperature of 80 ° C. using a hot-air circulation type oven.
II: The treatment liquid was applied with a bar coater # 3 and dried at a plate temperature of 150 ° C. using a hot air circulation type oven.
[0044]
(3) Conditions for forming resin layer
A resin layer was formed on the surface-treated metal material film formed using the treatment agent and the treatment method of the present invention by the following method.
X: Solvent-based paint
The solvent-based paint (X) was applied by bar coating so that the dry film thickness became about 25 μm, placed in a commercially available batch-type drying furnace, and dried by heating at 140 ° C. for 30 minutes.
Y: Polyester film
The surface-treated metal material of the present invention was heated in a heating furnace until the reached plate temperature reached 240 ° C., and the polyester film (Y) previously heated to 100 ° C. was pressure-laminated and bonded.
Z: water-based paint
The water-based coating material (Z) was applied by bar coating to a film formed by using the processing solution and the processing method of the present invention so that the dry film thickness became about 1 μm, and was heated and dried at a plate temperature of 100 ° C.
[0045]
5. Evaluation method
(1) Corrosion resistance
Based on the salt spray test method JIS-Z-2371, the area of white rust occurrence after 120 hours and 240 hours after salt spray was determined and evaluated.
The treated plate was sprayed with an aqueous degreasing agent adjusted to 60 ° C. for 30 seconds after bathing with 20 g / L of an alkaline degreasing agent PALCLEAN 364S manufactured by Nippon Parkerizing Co., Ltd., washed with water, and then dried at 80 ° C. This plate was evaluated for corrosion resistance under the conditions and evaluation method described in (1) above.
[0046]
(3) Interlayer adhesion
After a resin layer was formed using the solvent-based paint (X) or the polyester film (Y), a grid test of 1 mm and 100 squares was performed, and the site was extruded by 7 mm and subjected to Erichsen processing. After processing, the plate was immersed in boiling water for 5 hours, and the treated plate was taken out and naturally dried at room temperature for 30 minutes. Subsequently, a tape peeling test was carried out, and the number of remaining resin layers was obtained and determined according to the following evaluation criteria.
(4) Fingerprint resistance
A finger was pressed against the surface of the processed plate, and the trace state of the fingerprint was visually observed and evaluated.
The gauze impregnated with ethanol was wound around a silicon rubber cube (1 cm square), and the test surface was rubbed 30 times at 50,000 kPa.
Tables 1, 2 and 3 show the treatment liquid contents and treatment methods of Examples and Comparative Examples, and Tables 4 and 5 show the evaluation results of the treated plates.
From Table 4, the film formed from the treating agent of the present invention (Examples 1 to 21) containing the specific vanadium compound (A) and the specific metal compound (B) has a corrosion resistance, an alkali resistance, and a resin layer. It can be seen that excellent results are obtained in the interlayer adhesion between (X or Y) and various metal materials. In contrast, none of Comparative Examples 1 to 4 containing the vanadium compound (A) or the metal compound (B) satisfied all of the corrosion resistance, alkali resistance, and interlayer adhesion.
As shown in Table 5, Examples 22 to 27 containing the water-soluble polymer or the aqueous emulsion resin (F) have a single-layer treatment in which no resin layer is provided as an upper layer, but have excellent corrosion resistance and alkali resistance. It can be seen that they also have excellent fingerprint resistance and solvent resistance. In Examples 28 to 42, although the water-soluble polymer or the aqueous emulsion resin (F) was not contained in the treating agent of the present invention, a resin layer (Z1 or Z2) was further formed on the coating of Examples 1 to 15. This is a two-layer process. It can be seen that these Examples 28 to 42 also have excellent corrosion resistance and alkali resistance, and also have excellent fingerprint resistance and solvent resistance. In comparison, Comparative Example 5 (containing a resin component in the film itself) and Comparative Examples 6 to 9 (containing no resin on the film of Comparative Examples 1 to 4) containing no vanadium compound (A) or metal compound (B) No layer (Z)) satisfies all the properties of corrosion resistance, alkali resistance and solvent resistance.
[0049]
[Table 1]
[Table 2]
[Table 3]
Example 28 The film formed in Example 1 was treated with the overcoat treatment agent Z1.
Example 29 The film formed in Example 2 was treated with an overcoat treatment agent Z2.
Example 30 The film formed in Example 3 was treated with an overcoat treatment agent Z1.
Example 31 The film formed in Example 4 was treated with an overcoat treatment agent Z2.
Example 32 The film formed in Example 5 was treated with an overcoat treatment agent Z2.
Example 33 The film formed in Example 6 was treated with an overcoat treatment agent Z2.
Example 34 The film formed in Example 7 was treated with an overcoat treatment agent Z1.
Example 35 The film formed in Example 8 was treated with the overcoat treatment agent Z2.
[0053]
Example 36 The film formed in Example 9 was treated with the overcoat treatment agent Z2.
Example 37 The film formed in Example 10 was treated with an overcoat treatment agent Z2.
Example 38 The film formed in Example 11 was treated with the overcoat treatment agent Z1.
Example 39 The film formed in Example 12 was treated with an overcoat treatment agent Z2.
Example 40 The film formed in Example 13 was treated with an overcoat treatment agent Z2.
Example 41 The film formed in Example 14 was treated with the overcoat treatment agent Z2.
Example 42 The film formed in Example 15 was treated with an overcoat treatment agent Z2.
[0054]
Comparative Example 6 The film formed in Comparative Example 1 was treated with an overcoat treatment agent Z2.
Comparative Example 7 The coating formed in Comparative Example 2 was treated with an overcoat treatment agent Z2.
Comparative Example 8 The film formed in Comparative Example 3 was treated with an overcoat treatment agent Z2.
Comparative Example 9 The film formed in Comparative Example 4 was treated with an overcoat treatment agent Z2.
[0055]
[Table 4]
[Table 5]
【The invention's effect】
The metal surface treatment agent of the present invention is a non-chromate type that does not contain harmful chromium compounds, and a film formed from the surface treatment agent has corrosion resistance equal to or higher than that of a conventional chromate film. The surface treatment agent, surface treatment method and surface treated metal material of the present invention have extremely high industrial utility value.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002348715A JP4167046B2 (en) | 2002-11-29 | 2002-11-29 | Metal surface treatment agent, metal surface treatment method and surface treatment metal material |
Applications Claiming Priority (1)
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