JP3952198B2 - Metal surface treatment method and galvanized steel sheet - Google Patents
Metal surface treatment method and galvanized steel sheet Download PDFInfo
- Publication number
- JP3952198B2 JP3952198B2 JP2003200654A JP2003200654A JP3952198B2 JP 3952198 B2 JP3952198 B2 JP 3952198B2 JP 2003200654 A JP2003200654 A JP 2003200654A JP 2003200654 A JP2003200654 A JP 2003200654A JP 3952198 B2 JP3952198 B2 JP 3952198B2
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- JP
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- Prior art keywords
- surface treatment
- metal surface
- treatment composition
- compound
- steel sheet
- 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.)
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- 238000004381 surface treatment Methods 0.000 title claims description 80
- 229910052751 metal Inorganic materials 0.000 title claims description 70
- 239000002184 metal Substances 0.000 title claims description 70
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims description 29
- 239000008397 galvanized steel Substances 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 28
- 239000000203 mixture Substances 0.000 claims description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 51
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 36
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 150000003682 vanadium compounds Chemical class 0.000 claims description 15
- 150000003755 zirconium compounds Chemical class 0.000 claims description 15
- 150000003609 titanium compounds Chemical class 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 28
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- 229910052759 nickel Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QBHQQYMEDGADCQ-UHFFFAOYSA-N oxozirconium(2+);dinitrate;dihydrate Chemical compound O.O.[Zr+2]=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBHQQYMEDGADCQ-UHFFFAOYSA-N 0.000 description 1
- DUSYNUCUMASASA-UHFFFAOYSA-N oxygen(2-);vanadium(4+) Chemical compound [O-2].[O-2].[V+4] DUSYNUCUMASASA-UHFFFAOYSA-N 0.000 description 1
- SGNLDVYVSFANHW-UHFFFAOYSA-N pentane-2,4-dione;zirconium Chemical compound [Zr].CC(=O)CC(C)=O SGNLDVYVSFANHW-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- BFDQRLXGNLZULX-UHFFFAOYSA-N titanium hydrofluoride Chemical compound F.[Ti] BFDQRLXGNLZULX-UHFFFAOYSA-N 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- BLSRSXLJVJVBIK-UHFFFAOYSA-N vanadium(2+) Chemical class [V+2] BLSRSXLJVJVBIK-UHFFFAOYSA-N 0.000 description 1
- PSDQQCXQSWHCRN-UHFFFAOYSA-N vanadium(4+) Chemical class [V+4] PSDQQCXQSWHCRN-UHFFFAOYSA-N 0.000 description 1
- DIMMBYOINZRKMD-UHFFFAOYSA-N vanadium(5+) Chemical class [V+5] DIMMBYOINZRKMD-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Description
【０００１】
【発明の属する技術分野】
本発明は、金属表面処理方法及び亜鉛めっき鋼板に関する。
【０００２】
【従来の技術】
耐食性に優れた鋼材として亜鉛めっき、亜鉛合金めっき等を施した亜鉛めっき鋼板が使用されている。このような亜鉛めっき鋼板は、亜鉛めっき層が空気と接触することによって酸化されて白錆が発生する。このため、表面処理を施すことによって酸化を防止することが必要とされる。また、用途によっては、亜鉛めっき鋼板を加工した後、塗装を行うことなく使用する場合もある。このような場合には、未塗装状態での防錆性能を有することが重要である。
【０００３】
このような処理として、クロム化合物を使用するクロメート処理が知られている。クロメート処理を施した場合は、白錆の発生が防止され、非常に良好な亜鉛めっき鋼板を得ることができる。しかし、クロム化合物を含む廃液は、廃棄処分に多大な負担を要するものであることから、クロムを使用しないノンクロメート処理によって化成処理を行う方法が検討されている。
【０００４】
特開平９−２４１８５６号公報、特開２００１−１７２７７１号公報及び特開２００１−２４７９７７号公報には、金属塩化合物を含有する亜鉛めっき鋼板用の金属表面処理剤が記載されている。しかし、このような処理剤による表面処理を行った亜鉛めっき鋼板は、防錆性、塗膜密着性等の性質が充分ではなかった。
【０００５】
特開２００２−１０５６５９号公報には、モリブデン、バナジウム、タングステン、ニオブ、タンタルから選ばれた金属の酸素酸塩、マンガン化合物、チタン化合物及びリン酸又はリン酸塩を含む亜鉛めっき鋼板用化成処理液が記載されている。しかし、このような亜鉛めっき鋼板用化成処理液では、マンガン化合物を使用することが必要である。マンガン化合物も、廃液の廃棄処分には多大な負担を要するものであるから、使用しないことが好ましいものである。
【０００６】
また、金属の表面処理組成物に使用する防錆成分としては、水分散性シリカが使用されている。しかし、水分散性シリカを単独で使用した場合には、防錆性が充分ではなく、このような亜鉛めっき鋼板に対して防錆性能を与える上で充分な防錆性を得ることはできなかった。
【０００７】
【発明が解決しようとする課題】
本発明は、上記現状に鑑み、廃液の処理に負担を要することがなく、亜鉛めっき鋼板に良好な化成処理を行うことができる化成処理剤及び化成処理方法、並びに、このような化成方法によって得られた防錆性、密着性に優れた亜鉛めっき鋼板を提供することを目的とするものである。
【０００８】
【課題を解決するための手段】
本発明は、金属表面処理組成物で亜鉛めっき鋼板を表面処理し、皮膜を形成することを特徴とする金属表面処理方法であって、上記金属表面処理組成物が、酸化ニオブコロイド粒子を含むことを特徴とする金属表面処理方法である。
上記金属表面処理組成物は、更に、水分散性シリカを含むことが好ましい。
上記金属表面処理組成物は、更に、バナジウム化合物、ジルコニウム化合物及びチタニウム化合物からなる群より選択される少なくとも１種の化合物を含むことが好ましい。
上記金属表面処理組成物は、更に、水性樹脂を含むことが好ましい。
【００１０】
本発明は、上記金属表面処理方法によって得られる被覆された亜鉛めっき鋼板でもある。
以下に、本発明を詳細に説明する。
【００１１】
本発明の金属表面処理組成物は、酸化ニオブコロイド粒子を水性媒体中に分散させたものである。上記酸化ニオブコロイド粒子は、平均粒子径が小さい方がより安定して緻密な酸化ニオブの処理皮膜が形成されるため、被処理物に対して安定して防錆性を付与することができ、より好ましい。また、クロム、マンガン等のような、廃液の廃棄処分に負担を要する成分を含有する必要もない。
【００１２】
本発明で使用する酸化ニオブコロイド粒子は、ニオブの酸化物が水中に微粒子状態で分散しているものをいい、例えば、厳密には酸化ニオブが形成されず、水酸化ニオブと酸化ニオブの中間状態でアモルファス状態になっているものであってもよい。
【００１３】
本発明の金属表面処理組成物は、公知の方法によって製造された酸化ニオブゾルを使用することによって調製することができる。上記酸化ニオブゾルとしては特に限定されず、例えば、特開平６−３２１５４３号公報、特開平８−１４３３１４号公報、特開平８−３２５０１８号公報等に記載された公知の方法によって製造されたもの等を挙げることができる。また、多木化学株式会社によって市販されている酸化ニオブゾルを使用することもできる。
【００１４】
上記公知の酸化ニオブゾルの製造方法は、例えば、酸化ニオブをフッ化水素酸に溶解し、アンモニア水に添加した後、ろ過、洗浄を行い、水酸化ニオブのスラリーを得た後、しゅう酸二水和物を添加し、次いで水を添加し、攪拌しながら還流条件下で反応を進行させ、均一な酸化ニオブコロイド粒子溶液を得る方法等である。反応の終結、つまり、均一な酸化ニオブコロイド粒子溶液が得られたかどうかはスラリー液の色で判断することが可能であり、青色を帯びると均一な状態であると判断することができる。
本発明の金属表面処理組成物は、必要に応じて上記酸化ニオブゾルを必要な濃度に希釈したり、他の成分を混合したりすることによって調製することができる。
【００１５】
本発明の金属表面処理組成物に含まれる酸化ニオブコロイド粒子は、平均粒子径が１０００ｎｍ以下であることが好ましい。上記平均粒子径は、２〜６００ｎｍであることがより好ましく、２〜１００ｎｍであることが更に好ましい。上記平均粒子径は小さい方が、より安定して緻密な酸化ニオブの処理皮膜が形成されるため、被処理物に対して安定して防錆性を付与することが出来、より好ましい。上記酸化ニオブコロイド粒子の平均粒子径は、動的散乱光による粒度分布測定装置、例えば、ＮＩＣＯＭＰ Ｍｏｄｅｌ−３７０型（ＰＡＣＩＦＩＣ ＳＣＩＥＮＴＩＦＩＣ社製）等を用いて測定することができる。
【００１６】
本発明の金属表面処理組成物は、酸化ニオブコロイド粒子が、該コロイド粒子中のＮｂをＮｂ２Ｏ５として換算した場合、金属表面処理組成物の全固形分に対する含有率が、１質量％以上であることが好ましい。上記含有率が１質量％未満であると充分な防錆性が得られず、好ましくない。なお、上記数値は酸化ニオブコロイド粒子のＮｂをＮｂ２Ｏ５として換算した場合、金属表面処理組成物の全固形分に対する含有率である。上記含有率は、２〜３０質量％であることがより好ましい。
【００１７】
本発明の金属表面処理組成物は、表面処理膜の防錆性を向上させるために、更に、水分散性シリカを含有することが好ましい。水分散性シリカは、単独で使用した場合には、充分な防錆性能を得ることができないが、上記酸化ニオブコロイド粒子と併用することによって、相乗的に防錆性能を向上させることができるものである。
【００１８】
上記水分散性シリカとしては特に限定されず、例えば、ナトリウム等の不純物が少ない、球状シリカ、鎖状シリカ、アルミ修飾シリカ等を挙げることができる。上記球状シリカとしては特に限定されず、例えば、「スノーテックスＮ」、「スノーテックスＯ」、「スノーテックスＯＸＳ」、「スノーテックスＵＰ」（いずれも日産化学工業株式会社製）等のコロイダルシリカや、「アエロジル」（日本アエロジル株式会社製）等のヒュームドシリカ等を挙げることができる。上記鎖状シリカとしては特に限定されず、例えば、「スノーテックスＰＳ−Ｍ」、「スノーテックスＰＳ−ＭＯ」（いずれも日産化学工業株式会社製）等のシリカゲル等を挙げることができる。上記アルミ修飾シリカとしては、「アデライトＡＴ−２０Ａ」（旭電化工業株式会社製）等の市販のシリカゲル等を挙げることができる。
【００１９】
本発明の金属表面処理方法は、使用する表面処理組成物が上記水分散性シリカを含有する場合、表面処理組成物中のＳｉＯ２含有率は、表面処理組成物の全固形分に対して８０質量％以下であることが好ましい。８０質量％を超えると、皮膜が脆くなり防錆性が低下するという問題がある。上記上限は、６０質量％であることがより好ましく、３０質量％であることが更に好ましい。
【００２０】
本発明の金属表面処理組成物が上記水分散性シリカを含有する場合、表面処理組成物の全固形物に対するＮｂ２Ｏ５／ＳｉＯ２比率は、１／９９〜９９／１の範囲内であることが好ましい。Ｎｂ２Ｏ５の含有率が１／９９未満となるような比率であると、Ｎｂ２Ｏ５による防錆性が充分に発揮されない点で好ましくない。上記比率は、２／９８〜３０／７０であることがより好ましい。
【００２１】
本発明の金属表面処理組成物は、表面処理膜の防錆性を向上させるために、更に、バナジウム化合物、ジルコニウム化合物及びチタニウム化合物からなる群より選択される少なくとも１種の化合物を含むことが好ましい。上記バナジウム化合物、ジルコニウム化合物及びチタニウム化合物からなる群より選択される少なくとも１種の化合物を酸化ニオブコロイド粒子と併用することによって、更に防錆性能を向上させることができる。ニオブコロイド粒子、上記水分散性シリカ及び上記バナジウム化合物、ジルコニウム化合物及びチタニウム化合物からなる群より選択される少なくとも１種の化合物の三成分ないし四成分又は五成分を併用することが更に好ましい。
【００２２】
上記バナジウム化合物としては特に限定されず、例えば、バナジル化合物、５酸化バナジウム、バナジン酸塩、バナジン酸の焼成縮合物、バナジン酸のヘテロ縮合体及びそれらの混合物等を挙げることができる。具体例としては、例えば、酸化バナジウム（ＩＩ）、水酸化バナジウム（ＩＩ）等のバナジウム（ＩＩ）化合物；酸化バナジウム（ＩＩＩ）（Ｖ２Ｏ３）等のバナジウム（ＩＩＩ）化合物；酸化バナジウム（ＩＶ）（Ｖ２Ｏ４）、ハロゲン化バナジル（ＶＯＸ２）等のバナジウム（ＩＶ）化合物；酸化バナジウム（Ｖ）（Ｖ２Ｏ５）等のバナジウム（Ｖ）化合物；種々のオルトバナジン酸塩、メタバナジン酸塩又はピロバナジン酸塩等のバナジン酸塩、ハロゲン化バナジル（ＶＯＸ３）；又はこれらの混合物等を挙げることができる。バナジン酸塩としては特に限定されず、例えば、アンモニウム塩、アルカリ金属塩、アルカリ土類金属塩（例えば、マグネシウム、カルシウム）、その他の典型元素の金属塩（例えば、アルミニウム、スズ等）及び遷移金属塩（例えば、マンガン、コバルト、鉄、ニッケル）等を挙げることができる。なかでもアルカリ土類金属塩、亜鉛塩、マンガン塩、コバルト塩が好ましい。これらはバナジウムの酸化物と種々の金属の酸化物、水酸化物、炭酸塩等とを６００℃以上に焼成して得られたものであっても良い。
【００２３】
上記ジルコニウム化合物としては特に限定されず、例えば、ジルコンフッ化水素酸（Ｈ２ＺｒＦ６）；ジルコンフッ化水素酸のアンモニウム、リチウム、ナトリウム、カリウム等のジルコンフッ化水素酸の塩；オキシ炭酸ジルコニウム酸アンモニウム（（ＮＨ４）２ＺｒＯ（ＣＯ３）２）；水酸化ジルコニウム、炭酸ジルコニウム、ホウ酸ジルコニウム、蓚酸ジルコニウム、硫酸ジルコニウム、硝酸ジルコニウム、硝酸ジルコニル、フッ化ジルコニウム等のジルコニウム塩化合物；ジブチルジルコニウムジラウリレート、ジブチルジルコニウムジオクテート、ナフテン酸ジルコニウム、オクチル酸ジルコニウム、アセチルアセトンジルコニウム等の有機ジルコニウム化合物；又はこれらの混合物等を挙げることができる。
【００２４】
上記チタニウム化合物としては特に限定されず、例えば、チタンフッ化水素酸、チタンフッ化アンモニウム、チタンフッ化ナトリウム、チタンフッ化カリウム、フルオロチタネート酸、アルカリ金属フルオロチタネート、フッ化チタン等の、フッ素−チタン化合物；シュウ酸チタンカリウム、チタンイソプロポキシド、チタン酸イソプロピル、チタンエトキシド、チタン２−エチル１−ヘキサノラート、チタン酸テトライソプロピル、チタン酸テトラｎ−ブチル、ブチルチタネートダイマー、チタンラクテート、チタントリエタノールアミネート等のチタン有機化合物；又はこれらの混合物等を挙げることができる。
【００２５】
本発明の金属表面処理組成物が上記バナジウム化合物、ジルコニウム化合物及びチタニウム化合物からなる群より選択される少なくとも１種の化合物を含む場合は、上記化合物は、Ｖ，Ｚｒ，Ｔｉ金属換算で表面処理組成物の全固形分に対して３０質量％以下であることが好ましい。３０質量％を超えると、添加効果が飽和して不経済となるため好ましくない。また、上記バナジウム化合物、ジルコニウム化合物、チタニウム化合物は、Ｖ，Ｚｒ，Ｔｉ金属換算で表面処理組成物の全固形分に対して０．５質量％以上であることが好ましい。上記バナジウム化合物、ジルコニウム化合物、チタニウム化合物が０．５質量％未満であると、防錆性が低下する場合があるため、好ましくない。上記下限は、１質量％であることがより好ましく、２．５質量％であることが更に好ましい。上記上限は、１５質量％であることがより好ましく、７．５質量％であることが更に好ましい。
【００２６】
更に、本発明の金属表面処理組成物は、水性樹脂を含有することが好ましい。ここでいう水性樹脂とは、水溶性樹脂及び水分散性樹脂を含むものである。上記水性樹脂としては特に限定されず、例えば、アクリル系樹脂、ポリオレフィン系樹脂、ポリウレタン系樹脂、エポキシ系樹脂、エチレンアクリル酸共重合体樹脂、フェノール系樹脂、ポリエステル系樹脂、アルキッド系樹脂、メラミン系樹脂、ポリカーボネート系樹脂及びポリアクリル酸、その他の熱架橋タイプ及び熱可塑タイプの樹脂等を挙げることができる。
【００２７】
これらの水性樹脂は単独で使用してもよいし、２種以上を併用してもよいし、又は、共重合して使用してもよい。また水性樹脂を用いる時には、その造膜性を向上させ、より均一で平滑な塗膜を形成するためにレベリング剤、濡れ性向上剤、消泡剤を用いてもよい。
【００２８】
本発明の金属表面処理組成物が上記水性樹脂を含有するものである場合は、水性樹脂は、表面処理組成物の全固形分に対して９０質量％以下であることが好ましい。９０質量％を超えると、添加効果が飽和して不経済となるため好ましくない。また、上記水性樹脂は、全固形分に対して５質量％以上であることが好ましい。上記水性樹脂が５質量％未満であると、防錆性が低下する場合があるため、好ましくない。上記下限は、１０質量％であることがより好ましく、２０質量％であることが更に好ましい。上記上限は、８０質量％であることがより好ましく、７０質量％であることが更に好ましい。
【００２９】
本発明の金属表面処理組成物は、リン酸化合物を含有することが好ましい。本発明の金属表面処理組成物に含まれるリン酸化合物は、被処理材である金属を溶出し、被処理材の表面にリン酸金属塩を形成することによって、表面処理膜の防錆性を更に向上させる働きがある。
【００３０】
上記リン酸化合物としては、水中においてリン酸イオンを形成することができる化合物であれば特に限定されず、例えば、リン酸；Ｎａ３ＰＯ４、Ｎａ２ＨＰＯ４及びＮａＨ２ＰＯ４等のリン酸塩類；縮合リン酸、ポリリン酸、メタリン酸、ピロリン酸、及び、ウルトラリン酸等の縮合リン酸又はそれらの塩類等が挙げられる。
【００３１】
本発明の金属表面処理組成物が上記リン酸化合物を含有する場合、表面処理組成物中のリン酸化合物含有率は、表面処理組成物の全固形物に対して、下限０．１質量％、上限２０質量％の範囲内であることが好ましい。含有率が０．１質量％未満であると耐食性の改善効果が充分でない場合があり、２０質量％を超えると亜鉛系めっき鋼板に過剰なエッチングを起こしたり、水性樹脂を含む組成物のゲル化を引き起こしたりする場合があるので好ましくない。上記下限は、より好ましくは、０．５質量％であり、上記上限は、より好ましくは、１０質量％である。
【００３２】
本発明の金属表面処理組成物は、更にシランカップリング剤を含有するものであることが好ましい。シランカップリング剤を含有することによって、皮膜の金属表面に対する密着性を改善することができ、さらに水性樹脂の架橋剤としての作用を有し、耐食性が向上するという点で好ましい。上記シランカップリング剤としては特に制限されず、例えば、ビニルメトキシシラン、ビニルトリメトキシシラン、ビニルエトキシシラン、ビニルトリエトキシシラン、３−アミノプロピルトリエトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メルカプトプロピルトリメトキシシラン、Ｎ−（１，３−ジメチルブチリデン）−３−（トリエトキシシリル）−１−プロパンアミン、Ｎ，Ｎ'−ビス〔３−（トリメトキシシリル）プロピル〕エチレンジアミン、Ｎ−（β−アミノエチル）−γ−アミノプロピルメチルジメトキシシラン、Ｎ−（β−アミノエチル）−γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、Ｎ−〔２−（ビニルベンジルアミノ）エチル〕−３−アミノプロピルトリメトキシシラン等を挙げることができる。
【００３３】
なかでも、特に好ましいシランカップリング剤としては、ビニルメトキシシラン、ビニルエトキシシラン、３−アミノプロピルトリエトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メルカプトプロピルトリメトキシシラン、Ｎ−（１，３−ジメチルブチリデン）−３−（トリエトキシシリル）−１−プロパンアミン、Ｎ，Ｎ'−ビス〔３−（トリメトキシシリル）プロピル〕エチレンジアミンを挙げることができる。上記シランカップリング剤は１種類を単独で使用するものであっても、２種類以上を併用して使用するものであってもよい。
【００３４】
本発明の表面処理組成物が上記シランカップリング剤を含有する場合、表面処理組成物中のシランカップリング剤は、表面処理組成物の全固形分に対して下限０．５質量％、上限３０質量％の範囲内で含有することが好ましい。シランカップリング剤の含有率が０．５質量％未満になると耐食性、ノンクロム防錆コーティング剤との密着性向上効果が不足する場合があり、３０質量％を越えると添加効果が飽和し不経済となる場合がある。上記下限は、１質量％であることがより好ましく、上記上限は、２０質量％であることがより好ましい。
【００３５】
本発明の表面処理組成物は、組成物の全固形分が固形分質量で、下限３質量％、上限５０質量％の範囲内で含有することが好ましい。固形分質量が３％未満になると表面処理組成物を塗布する際、防錆性能を維持するための十分な膜厚が得られないことがあり、５０質量％を超えると組成物のゲル化を引き起こしたりする場合があるので好ましくない。上記下限は、１０質量％がより好ましく、上気上限は、３０質量％であることがより好ましい。
【００３６】
上記各成分からなる本発明の金属表面処理組成物は、安定性においても優れるため、安定して亜鉛めっき鋼板の表面処理を行うことができる。
【００３７】
本発明の金属表面処理組成物の製造方法としては特に限定されず、例えば、酸化ニオブコロイド粒子、水分散性シリカ、バナジウム化合物，ジルコニウム化合物及びチタニウム化合物からなる群より選択される少なくとも１種の化合物、水性樹脂の順に容器に投入し、均一になるように攪拌することによって得ることができる。
【００３８】
本発明の金属表面処理方法は、亜鉛めっき鋼板を上記金属表面処理組成物によって処理する方法である。本発明の金属表面処理方法によって処理することができる亜鉛めっき鋼板としては特に限定されず、例えば、亜鉛めっき鋼板、亜鉛−ニッケルめっき鋼板、亜鉛−鉄めっき鋼板、亜鉛−クロムめっき鋼板、亜鉛−アルミニウムめっき鋼板、亜鉛−チタンめっき鋼板、亜鉛−マグネシウムめっき鋼板、亜鉛−マンガンめっき鋼板等の亜鉛系の電気めっき、溶融めっき、蒸着めっき鋼板等の亜鉛又は亜鉛系合金めっき鋼板を挙げることができる。
【００３９】
上記金属表面処理方法は、必要に応じて脱脂処理した上記亜鉛めっき鋼板に、上記金属表面処理組成物による処理を行う。上記金属表面処理組成物の処理を行う方法としては特に限定されず、例えば、一般に使用されるロールコート、シャワーコート、エアースプレー、エアレススプレー、カーテンフローコート、刷毛塗り、浸漬等を挙げることができる。
【００４０】
上記金属表面処理組成物によって処理を行った後は、加熱によって乾燥させることが好ましい。上記乾燥を行う温度は、下限５０℃、上限２５０℃の範囲が好ましい。５０℃未満であると、水分の蒸発速度が遅く、乾燥効率が悪化する場合がある。２５０℃を超えると、高温によって形成された皮膜中の成分が分解する場合がある。上記下限は、６０℃であることがより好ましく、上記上限は、１５０℃であることがより好ましい。また、乾燥時間は下限１秒、上限３００秒の範囲が好ましく、下限３秒、上限６０秒がより好ましい。
【００４１】
本発明の金属表面処理組成物は、塗布量が皮膜の固形分質量で、下限０．１ｇ／ｍ２、上限１０．０ｇ／ｍ２の範囲で塗布されることが好ましい。塗布量が０．１ｇ／ｍ２未満の場合は、厚みが不充分であるために加工性が低下したり、防錆性が充分に得られなかったりする場合がある。塗布量が１０．０ｇ／ｍ２を超えると、膜厚を増やしたことによる効果の向上が見られないため、経済的に不利であったり、厚みが増したことで巻き付け等が困難になったりする場合がある。上記下限は、０．２ｇ／ｍ２がより好ましく、０．３ｇ／ｍ２が更に好ましい。上記上限は、５．０ｇ／ｍ２がより好ましく、３．０ｇ／ｍ２が更に好ましい。
【００４２】
本発明は、上記金属表面処理方法によって得られた亜鉛めっき鋼板でもある。本発明の亜鉛めっき鋼板は、良好な表面処理皮膜が形成されてなるものであるため、防錆性能に優れ、白錆の発生等を生じることがない。
【００４３】
本発明の金属表面処理組成物は、酸化ニオブコロイド粒子を含む化成処理剤であり、これによって、廃液の処理に負担を要することがない成分によって、亜鉛めっき鋼板にクロメート処理と同等の良好な防錆性、密着性を与えるものである。これによって、亜鉛めっき鋼板に対して良好な金属表面処理を行うことができる金属表面処理方法を提供することができる。更に、本発明の金属表面処理方法によって防錆性、密着性に優れた亜鉛めっき鋼板を提供することができる。
【００４４】
【実施例】
以下に本発明を実施例により更に具体的に説明するが、本発明はこれら実施例のみに限定されるものではない。
【００４５】
実施例１〜８、比較例１〜３
酸化ニオブコロイド粒子、水分散性シリカ、バナジウム化合物、ジルコニウム化合物をこの順に攪拌しながら容器に投入し、水を加えて固形分濃度を１０〜１５％の範囲内で調製して表１に記載した表面処理組成物を得た。
【００４６】
実施例９〜２１、比較例４，５
酸化ニオブコロイド粒子、水分散性シリカ、バナジウム化合物、ジルコニウム化合物、チタニウム化合物、水性樹脂、リン酸化合物、シランカップリング剤をこの順に攪拌しながら容器に投入し、水を加えて固形分濃度を１５％調製して表２に記載した表面処理組成物を得た。
【００４７】
比較例６
市販の塗布型クロメート処理剤（日本ペイント株式会社製；サーフコートＳ−１００）をクロム付着量が２０ｍｇ／ｍ２となるように塗布した。
【００４８】
市販の亜鉛メッキ鋼板（日本テストパネル株式会社製、７０ｍｍ×１５０ｍｍ×０．４ｍｍ）を市販のアルカリ脱脂剤であるサーフクリーナー５３Ｓ（日本ペイント株式会社製）を用いて６０℃で２分間スプレー処理して脱脂し、水洗乾燥後に実施例１〜２１、比較例１〜５で使用した金属表面処理剤をバーコーターで乾燥付着量０．２〜１．０ｇ／ｍ２となるように塗布後、金属表面温度８０℃で乾燥させて試験板を得た。又、比較例６で使用した塗布型クロメート処理剤はバーコーターでクロム付着量２０ｍｇ／ｍ２となるように塗布後、同様に金属表面温度８０℃で乾燥させて試験板を得た。得られた試験板に対して、下記の方法によって評価を行った。結果を下記表１，２に示す。
【００４９】
なお、下記表１，２において使用した酸化ニオブコロイド粒子、水分散性シリカ、バナジウム化合物、ジルコニウム化合物、チタニウム化合物、水性樹脂、リン酸化合物、シランカップリング剤は次の通りである。
［酸化ニオブコロイド粒子］
Ａ；酸化ニオブゾル（Ｎｂ２Ｏ５；１０％、平均粒子径；５ｎｍ、多木化学株式会社製）
Ｂ；酸化ニオブコロイド粒子水分散体（Ｎｂ２Ｏ５；１０％、平均粒子径；２０００ｎｍ）
［水分散性シリカ］
Ａ；スノーテックスＯ（ＳｉＯ２；２０％、日産化学工業株式会社製）
Ｂ；アデライトＡＴ−２０Ａ（ＳｉＯ２；２０％、旭電化工業株式会社製）
Ｃ；スノーテックスＮ（ＳｉＯ２；２０％、日産化学工業株式会社製）
［バナジウム化合物］
Ａ；メタバナジン酸アンモニウム（Ｖ；４３．６％、試薬）
Ｂ；五酸化バナジウム（Ｖ；５６．０％、試薬）
Ｃ；硫酸バナジール（硫酸バナジル、Ｖ；２２．６％、新興化学工業株式会社）
［ジルコニウム化合物］
Ａ；ジルコゾールＡＣ−７（炭酸ジルコニウムアンモニウム、Ｚｒ；７４．０％；固形分換算値、；第一稀元素工業株式会社製）
Ｂ；ジルコニウム（IV）アセチルアセトナート（Ｚｒ；１８．７％、試薬）
Ｃ；硝酸ジルコニル二水和物（Ｚｒ；３３．０％、試薬）
［チタニウム化合物］
Ａ；オルガチックスＴＣ−４００（チタントリエタノールアミネート；Ｔｉ；１０．４％；固形分換算値、松本製薬株式会社製）
［水性樹脂］
Ａ；ＰＣ２２００（エチレンアクリル酸共重合体樹脂、固形分濃度；３０％、昭永化学株式会社製）
Ｂ；スーパーフレックス４２０（ポリウレタン樹脂、固形分濃度；３２％、第一工業製薬株式会社製）
Ｃ；ジュリマーＡＣ−１０Ｌ（ポリアクリル酸、固形分濃度；４０％、日本純薬株式会社製）
［リン酸化合物］
Ａ；リン酸水素二アンモニウム（固形分濃度；１００％、試薬）
［シランカップリング剤］
Ａ；サイラエースＳ−５１０（γ−グリシドキシプロピルトリメトキシシラン、固形分濃度；１００％、チッソ株式会社製）
Ｂ；サイラエースＳ−２１０（ビニルメトキシシラン、固形分濃度；１００％、チッソ株式会社製）
【００５０】
（評価方法）
＜耐食性＞
試験板の平面部及びエリクセンテスターで８ｍｍ押し出した加工部の端面部及び裏面部をテープシールし、５％の食塩水を３５℃で試験板の塗装面に噴霧し２４又は７２時間後の白錆発生面積率を下記の評価基準で評価した。
◎：白錆発生なし
○：白錆発生面積が１０％未満
〇△：同１０％以上３０％未満
△：同３０％以上５０％未満
×：同５０％以上
【００５１】
【表１】
【表２】
上記表１，２の結果より明らかなように、酸化ニオブコロイド粒子を含有する本発明の金属表面処理組成物は、防錆性に優れ、白錆の発生を抑制することができる。また、酸化ニオブコロイド粒子に加えて、更に、水分散性シリカ、水性樹脂、バナジウム化合物等を併用した金属表面処理組成物は、これらの成分を併用することによって、防錆性能がより向上する。これに対して、酸化ニオブコロイド粒子を含有しない金属表面処理組成物は、防錆性能に優れた化成皮膜を得ることができないため、良好な亜鉛めっき鋼板を得ることができない。また、本発明の金属処理組成物は、加工後の防錆性能にも優れるものである。
【００５４】
【発明の効果】
本発明の金属表面処理組成物は、上記酸化ニオブコロイド粒子からなるものであるため、防錆性、密着性に優れ、白錆の発生を抑制することができるものである。また、クロム化合物、マンガン化合物等を必須成分としないことから、廃液の処理に多大な負担を要することもない。[0001]
BACKGROUND OF THE INVENTION
The present invention ,Money The present invention relates to a genus surface treatment method and a galvanized steel sheet.
[0002]
[Prior art]
As a steel material having excellent corrosion resistance, a galvanized steel sheet subjected to galvanization, zinc alloy plating or the like is used. Such a galvanized steel sheet is oxidized and white rust is generated when the galvanized layer comes into contact with air. For this reason, it is necessary to prevent oxidation by applying a surface treatment. Moreover, depending on a use, after processing a galvanized steel plate, it may be used, without coating. In such a case, it is important to have rust prevention performance in an unpainted state.
[0003]
As such a treatment, a chromate treatment using a chromium compound is known. When the chromate treatment is performed, generation of white rust is prevented, and a very good galvanized steel sheet can be obtained. However, since the waste liquid containing a chromium compound requires a great burden on disposal, a method of performing chemical conversion treatment by non-chromate treatment without using chromium has been studied.
[0004]
Japanese Patent Application Laid-Open Nos. 9-241856, 2001-172777, and 2001-247777 describe metal surface treatment agents for galvanized steel sheets containing metal salt compounds. However, the properties of the galvanized steel sheet that has been surface-treated with such a treatment agent are not sufficient, such as rust prevention and coating film adhesion.
[0005]
JP 2002-105659 A discloses a chemical conversion treatment solution for a galvanized steel sheet containing an oxyacid salt, a manganese compound, a titanium compound, and phosphoric acid or phosphate of a metal selected from molybdenum, vanadium, tungsten, niobium, and tantalum. Is described. However, it is necessary to use a manganese compound in such a chemical conversion solution for galvanized steel sheet. Manganese compounds are also preferably not used because they require a large burden for disposal of the waste liquid.
[0006]
Moreover, water dispersible silica is used as a rust preventive component used in the metal surface treatment composition. However, when water-dispersible silica is used alone, the rust prevention is not sufficient, and sufficient rust prevention cannot be obtained for giving rust prevention performance to such a galvanized steel sheet. It was.
[0007]
[Problems to be solved by the invention]
In view of the above situation, the present invention provides a chemical conversion treatment agent and a chemical conversion treatment method capable of performing a good chemical conversion treatment on a galvanized steel sheet without burdening the treatment of waste liquid, and such a chemical conversion method. An object of the present invention is to provide a galvanized steel sheet having excellent rust prevention and adhesion.
[0008]
[Means for Solving the Problems]
The present invention is a metal surface treatment method characterized by surface-treating a galvanized steel sheet with a metal surface treatment composition to form a film, The metal surface treatment composition is Metal surface treatment characterized by containing niobium oxide colloidal particles Method It is.
The metal surface treatment composition preferably further contains water-dispersible silica.
The metal surface treatment composition is Furthermore, it is preferable to include at least one compound selected from the group consisting of a vanadium compound, a zirconium compound and a titanium compound.
The metal surface treatment composition preferably further contains an aqueous resin.
[0010]
The present invention is also a coated galvanized steel sheet obtained by the above metal surface treatment method.
The present invention is described in detail below.
[0011]
The metal surface treatment composition of the present invention is obtained by dispersing niobium oxide colloidal particles in an aqueous medium. The niobium oxide colloidal particles are more stable and dense niobium oxide treatment film is formed with a smaller average particle size, can stably impart rust prevention to the object to be treated, More preferred. Further, it is not necessary to contain a component such as chromium, manganese, etc., which requires a burden for disposal of the waste liquid.
[0012]
The niobium oxide colloidal particles used in the present invention are those in which niobium oxide is dispersed in water in the form of fine particles. For example, niobium oxide is not formed strictly, and an intermediate state between niobium hydroxide and niobium oxide is used. It may be in an amorphous state.
[0013]
The metal surface treatment composition of the present invention can be prepared by using a niobium oxide sol produced by a known method. The niobium oxide sol is not particularly limited, and examples thereof include those manufactured by known methods described in JP-A-6-321543, JP-A-8-143314, JP-A-8-325018, and the like. Can be mentioned. Moreover, niobium oxide sol marketed by Taki Chemical Co., Ltd. can also be used.
[0014]
The known niobium oxide sol manufacturing method is, for example, by dissolving niobium oxide in hydrofluoric acid and adding it to aqueous ammonia, followed by filtration and washing to obtain a niobium hydroxide slurry, and then dibasic oxalate dihydrate. A method of adding a hydrate, then adding water, and allowing the reaction to proceed under reflux conditions while stirring to obtain a uniform niobium oxide colloidal particle solution. The end of the reaction, that is, whether or not a uniform niobium oxide colloidal particle solution has been obtained can be determined by the color of the slurry, and when it is blue, it can be determined to be in a uniform state.
The metal surface treatment composition of the present invention can be prepared by diluting the niobium oxide sol to a required concentration as necessary, or mixing other components.
[0015]
The niobium oxide colloidal particles contained in the metal surface treatment composition of the present invention preferably have an average particle size of 1000 nm or less. The average particle diameter is more preferably 2 to 600 nm, and further preferably 2 to 100 nm. The smaller the average particle diameter, the more stable and dense the niobium oxide treatment film is formed, and therefore, it is possible to stably impart rust prevention to the object to be treated, which is more preferable. The average particle diameter of the niobium oxide colloidal particles can be measured using a particle size distribution measuring apparatus using dynamic scattered light, for example, NICOMP Model-370 type (manufactured by PACIFIC SCIENTIFIC).
[0016]
In the metal surface treatment composition of the present invention, the niobium oxide colloidal particles are formed by converting Nb in the colloidal particles to Nb. 2 O 5 When converted as, the content of the metal surface treatment composition with respect to the total solid content is preferably 1% by mass or more. If the content is less than 1% by mass, sufficient rust preventive properties cannot be obtained, which is not preferable. In addition, the above numerical values represent Nb of niobium oxide colloidal particles as Nb. 2 O 5 In terms of the total solid content of the metal surface treatment composition. The content is more preferably 2 to 30% by mass.
[0017]
The metal surface treatment composition of the present invention preferably further contains water-dispersible silica in order to improve the rust prevention property of the surface treatment film. Water dispersible silica, when used alone, cannot obtain sufficient rust prevention performance, but can be used in combination with the niobium oxide colloidal particles to improve rust prevention performance synergistically. It is.
[0018]
The water-dispersible silica is not particularly limited, and examples thereof include spherical silica, chain silica, and aluminum-modified silica that are low in impurities such as sodium. The spherical silica is not particularly limited. For example, colloidal silica such as “Snowtex N”, “Snowtex O”, “Snowtex OXS”, “Snowtex UP” (all manufactured by Nissan Chemical Industries, Ltd.) And fumed silica such as “Aerosil” (manufactured by Nippon Aerosil Co., Ltd.). The chain silica is not particularly limited, and examples thereof include silica gel such as “Snowtex PS-M” and “Snowtex PS-MO” (all manufactured by Nissan Chemical Industries, Ltd.). Examples of the aluminum-modified silica include commercially available silica gel such as “Adelite AT-20A” (manufactured by Asahi Denka Kogyo Co., Ltd.).
[0019]
In the metal surface treatment method of the present invention, when the surface treatment composition to be used contains the above water-dispersible silica, SiO in the surface treatment composition is used. 2 The content is preferably 80% by mass or less with respect to the total solid content of the surface treatment composition. When it exceeds 80 mass%, there exists a problem that a membrane | film | coat becomes weak and rust prevention property falls. The upper limit is more preferably 60% by mass and even more preferably 30% by mass.
[0020]
When the metal surface treatment composition of the present invention contains the water-dispersible silica, Nb based on the total solids of the surface treatment composition 2 O 5 / SiO 2 The ratio is preferably in the range of 1/99 to 99/1. Nb 2 O 5 When the content ratio is less than 1/99, Nb 2 O 5 It is not preferable in that the rust preventive property due to is not sufficiently exhibited. The ratio is more preferably 2/98 to 30/70.
[0021]
The metal surface treatment composition of the present invention preferably further contains at least one compound selected from the group consisting of a vanadium compound, a zirconium compound and a titanium compound in order to improve the rust prevention property of the surface treatment film. . By using at least one compound selected from the group consisting of the vanadium compound, zirconium compound and titanium compound in combination with the niobium oxide colloidal particles, the rust prevention performance can be further improved. It is more preferable to use in combination three or four or five components of at least one compound selected from the group consisting of niobium colloidal particles, the water-dispersible silica and the vanadium compound, zirconium compound and titanium compound.
[0022]
The vanadium compound is not particularly limited, and examples thereof include a vanadyl compound, vanadium pentoxide, vanadate, a burned condensate of vanadic acid, a heterocondensate of vanadic acid, and a mixture thereof. Specific examples include vanadium (II) compounds such as vanadium oxide (II) and vanadium hydroxide (II); vanadium oxide (III) (V 2 O 3 ) And the like; vanadium (IV) oxide (V 2 O 4 ), Vanadyl halide (VOX) 2 Vanadium (IV) compounds such as Vanadium oxide (V) (V 2 O 5 Vanadium (V) compounds such as), various vanadates such as orthovanadate, metavanadate or pyrovanadate, vanadyl halide (VOX) 3 ); Or a mixture thereof. The vanadate is not particularly limited, and examples thereof include ammonium salts, alkali metal salts, alkaline earth metal salts (eg, magnesium, calcium), metal salts of other typical elements (eg, aluminum, tin, etc.), and transition metals. A salt (for example, manganese, cobalt, iron, nickel) etc. can be mentioned. Of these, alkaline earth metal salts, zinc salts, manganese salts, and cobalt salts are preferred. These may be obtained by baking oxides of vanadium and various metal oxides, hydroxides, carbonates and the like at 600 ° C. or higher.
[0023]
The zirconium compound is not particularly limited. For example, zircon hydrofluoric acid (H 2 ZrF 6 ); Zircon hydrofluoric acid ammonium salts such as ammonium, lithium, sodium, potassium, etc .; ammonium oxycarbonate zirconate ((NH 4 ) 2 ZrO (CO 3 ) 2 ); Zirconium salt compounds such as zirconium hydroxide, zirconium carbonate, zirconium borate, zirconium oxalate, zirconium sulfate, zirconium nitrate, zirconyl nitrate, zirconium fluoride; dibutylzirconium dilaurate, dibutylzirconium dioctate, zirconium naphthenate, And organic zirconium compounds such as zirconium octylate and zirconium acetylacetone; or a mixture thereof.
[0024]
The titanium compound is not particularly limited, and examples thereof include fluorine-titanium compounds such as titanium hydrofluoric acid, titanium ammonium fluoride, sodium titanium fluoride, titanium titanium fluoride, fluorotitanate acid, alkali metal fluorotitanate, and titanium fluoride; Potassium titanate, titanium isopropoxide, isopropyl titanate, titanium ethoxide, titanium 2-ethyl 1-hexanolate, tetraisopropyl titanate, tetra n-butyl titanate, butyl titanate dimer, titanium lactate, titanium triethanolamate, etc. Or a mixture thereof.
[0025]
When the metal surface treatment composition of the present invention contains at least one compound selected from the group consisting of the vanadium compound, zirconium compound and titanium compound, the compound is a surface treatment composition in terms of V, Zr, Ti metal. It is preferable that it is 30 mass% or less with respect to the total solid of a thing. If it exceeds 30% by mass, the effect of addition becomes saturated and uneconomical. Moreover, it is preferable that the said vanadium compound, a zirconium compound, and a titanium compound is 0.5 mass% or more with respect to the total solid of a surface treatment composition in conversion of V, Zr, and Ti metal. If the vanadium compound, zirconium compound, or titanium compound is less than 0.5% by mass, the rust prevention property may be lowered, which is not preferable. The lower limit is more preferably 1% by mass and even more preferably 2.5% by mass. The upper limit is more preferably 15% by mass, and still more preferably 7.5% by mass.
[0026]
Furthermore, the metal surface treatment composition of the present invention preferably contains an aqueous resin. The aqueous resin here includes a water-soluble resin and a water-dispersible resin. The aqueous resin is not particularly limited. For example, acrylic resin, polyolefin resin, polyurethane resin, epoxy resin, ethylene acrylic acid copolymer resin, phenol resin, polyester resin, alkyd resin, melamine Examples thereof include resins, polycarbonate resins and polyacrylic acid, and other thermal crosslinking type and thermoplastic type resins.
[0027]
These aqueous resins may be used alone, in combination of two or more, or may be used after copolymerization. When using an aqueous resin, a leveling agent, a wettability improver, and an antifoaming agent may be used to improve the film forming property and form a more uniform and smooth coating film.
[0028]
When the metal surface treatment composition of this invention contains the said aqueous resin, it is preferable that an aqueous resin is 90 mass% or less with respect to the total solid of a surface treatment composition. If it exceeds 90% by mass, the effect of addition becomes saturated and uneconomical. Moreover, it is preferable that the said aqueous resin is 5 mass% or more with respect to the total solid. If the water-based resin is less than 5% by mass, the rust prevention property may be lowered, which is not preferable. The lower limit is more preferably 10% by mass, and still more preferably 20% by mass. The upper limit is more preferably 80% by mass, and still more preferably 70% by mass.
[0029]
The metal surface treatment composition of the present invention preferably contains a phosphoric acid compound. The phosphoric acid compound contained in the metal surface treatment composition of the present invention elutes the metal that is the material to be treated, and forms a metal phosphate on the surface of the material to be treated. There is a work to further improve.
[0030]
The phosphate compound is not particularly limited as long as it is a compound capable of forming phosphate ions in water. For example, phosphoric acid; Na 3 PO 4 , Na 2 HPO 4 And NaH 2 PO 4 Phosphates such as condensed phosphoric acid, polyphosphoric acid, metaphosphoric acid, pyrophosphoric acid, and condensed phosphoric acid such as ultraphosphoric acid or salts thereof.
[0031]
When the metal surface treatment composition of the present invention contains the phosphoric acid compound, the phosphoric acid compound content in the surface treatment composition is a lower limit of 0.1% by mass relative to the total solids of the surface treatment composition, The upper limit is preferably in the range of 20% by mass. If the content is less than 0.1% by mass, the effect of improving the corrosion resistance may not be sufficient. If the content exceeds 20% by mass, the zinc-based plated steel sheet is excessively etched, or the composition containing the aqueous resin is gelled. It is not preferable because it may cause The lower limit is more preferably 0.5% by mass, and the upper limit is more preferably 10% by mass.
[0032]
The metal surface treatment composition of the present invention preferably further contains a silane coupling agent. By containing the silane coupling agent, the adhesion of the film to the metal surface can be improved, and further, it has an action as a crosslinking agent for the aqueous resin and is preferred in terms of improving the corrosion resistance. The silane coupling agent is not particularly limited, and examples thereof include vinyl methoxy silane, vinyl trimethoxy silane, vinyl ethoxy silane, vinyl triethoxy silane, 3-aminopropyl triethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N, N′-bis [3 -(Trimethoxysilyl) propyl] ethylenediamine, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxy Silane, γ-aminopropyltrieth Xysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-methacrylic Roxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxy A silane etc. can be mentioned.
[0033]
Among these, particularly preferable silane coupling agents include vinyl methoxy silane, vinyl ethoxy silane, 3-aminopropyl triethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-methacryloxy propyl trimethoxy silane, 3-mercapto. Mention of propyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine Can do. The silane coupling agent may be used alone or in combination of two or more.
[0034]
When the surface treatment composition of the present invention contains the silane coupling agent, the lower limit of the silane coupling agent in the surface treatment composition is 0.5% by mass and the upper limit is 30 with respect to the total solid content of the surface treatment composition. It is preferable to contain within the range of mass%. When the content of the silane coupling agent is less than 0.5% by mass, the effect of improving the corrosion resistance and adhesion with the non-chromium anticorrosive coating agent may be insufficient. When the content exceeds 30% by mass, the addition effect is saturated and uneconomical. There is a case. The lower limit is more preferably 1% by mass, and the upper limit is more preferably 20% by mass.
[0035]
In the surface treatment composition of the present invention, the total solid content of the composition is preferably a solid mass, and is contained within a range of a lower limit of 3 mass% and an upper limit of 50 mass%. When the solid content is less than 3%, when applying the surface treatment composition, a sufficient film thickness for maintaining the rust prevention performance may not be obtained. It is not preferable because it may cause it. The lower limit is more preferably 10% by mass, and the upper upper limit is more preferably 30% by mass.
[0036]
Since the metal surface treatment composition of the present invention comprising the above components is excellent in stability, the surface treatment of the galvanized steel sheet can be performed stably.
[0037]
The method for producing the metal surface treatment composition of the present invention is not particularly limited. For example, at least one compound selected from the group consisting of niobium oxide colloidal particles, water-dispersible silica, vanadium compounds, zirconium compounds, and titanium compounds. The aqueous resin can be put in the container in this order and stirred to be uniform.
[0038]
The metal surface treatment method of the present invention is a method of treating a galvanized steel sheet with the metal surface treatment composition. The galvanized steel sheet that can be treated by the metal surface treatment method of the present invention is not particularly limited. For example, galvanized steel sheet, zinc-nickel plated steel sheet, zinc-iron plated steel sheet, zinc-chromium plated steel sheet, zinc-aluminum Examples thereof include zinc-based electroplating such as plated steel sheet, zinc-titanium-plated steel sheet, zinc-magnesium-plated steel sheet, and zinc-manganese-plated steel sheet, and zinc or zinc-based alloy-plated steel sheet such as hot dipped and vapor-deposited steel sheet.
[0039]
In the metal surface treatment method, the galvanized steel sheet that has been degreased as necessary is treated with the metal surface treatment composition. The method for treating the metal surface treatment composition is not particularly limited, and examples thereof include generally used roll coat, shower coat, air spray, airless spray, curtain flow coat, brush coating, and dipping. .
[0040]
After the treatment with the metal surface treatment composition, it is preferably dried by heating. The drying temperature is preferably in the range of a lower limit of 50 ° C. and an upper limit of 250 ° C. If it is lower than 50 ° C., the evaporation rate of moisture is slow, and the drying efficiency may be deteriorated. When it exceeds 250 ° C., components in the film formed by high temperature may be decomposed. The lower limit is more preferably 60 ° C., and the upper limit is more preferably 150 ° C. The drying time is preferably in the range of a lower limit of 1 second and an upper limit of 300 seconds, more preferably a lower limit of 3 seconds and an upper limit of 60 seconds.
[0041]
In the metal surface treatment composition of the present invention, the coating amount is the solid content mass of the film, and the lower limit is 0.1 g / m. 2 Upper limit 10.0 g / m 2 It is preferable to apply in the range. Application amount is 0.1 g / m 2 If it is less than 1, the thickness may be insufficient, so that the workability may be lowered or the rust prevention property may not be sufficiently obtained. The coating amount is 10.0 g / m 2 If the thickness exceeds the range, the effect of increasing the film thickness is not improved, which may be economically disadvantageous, or may increase the thickness and make winding difficult. The lower limit is 0.2 g / m. 2 Is more preferable, 0.3 g / m 2 Is more preferable. The upper limit is 5.0 g / m 2 Is more preferable, 3.0 g / m 2 Is more preferable.
[0042]
The present invention is also a galvanized steel sheet obtained by the above metal surface treatment method. Since the galvanized steel sheet of the present invention is formed with a good surface treatment film, it is excellent in rust prevention performance and does not generate white rust.
[0043]
The metal surface treatment composition of the present invention is a chemical conversion treatment agent containing niobium oxide colloidal particles, and thereby a good anti-corrosion treatment equivalent to chromate treatment on a galvanized steel sheet due to a component that does not require a burden on the treatment of waste liquid. It gives rust and adhesion. Thereby, the metal surface treatment method which can perform favorable metal surface treatment with respect to a galvanized steel plate can be provided. Furthermore, a galvanized steel sheet excellent in rust prevention and adhesion can be provided by the metal surface treatment method of the present invention.
[0044]
【Example】
Examples The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
[0045]
Examples 1-8, Comparative Examples 1-3
Niobium oxide colloidal particles, water-dispersible silica, vanadium compound, and zirconium compound were put into a container with stirring in this order, and water was added to prepare a solid content concentration within a range of 10 to 15%, which is shown in Table 1. A surface treatment composition was obtained.
[0046]
Examples 9 to 21, Comparative Examples 4 and 5
Niobium oxide colloidal particles, water-dispersible silica, vanadium compound, zirconium compound, titanium compound, aqueous resin, phosphoric acid compound, and silane coupling agent are put into a container while stirring in this order, and water is added to obtain a solid content concentration of 15 % To obtain the surface treatment composition described in Table 2.
[0047]
Comparative Example 6
A commercially available coating-type chromate treatment agent (manufactured by Nippon Paint Co., Ltd .; Surfcoat S-100) has a chromium adhesion amount of 20 mg / m. 2 It applied so that it might become.
[0048]
A commercially available galvanized steel sheet (Nihon Test Panel Co., Ltd., 70 mm x 150 mm x 0.4 mm) was sprayed for 2 minutes at 60 ° C using Surf Cleaner 53S (Nihon Paint Co., Ltd.), a commercial alkaline degreasing agent. After degreasing and washing and drying with water, the metal surface treatment agent used in Examples 1 to 21 and Comparative Examples 1 to 5 was dried with a bar coater, and the adhesion amount was 0.2 to 1.0 g / m. 2 After application, a test plate was obtained by drying at a metal surface temperature of 80 ° C. The coating type chromate treatment agent used in Comparative Example 6 was a bar coater with a chromium adhesion amount of 20 mg / m. 2 After application, the test plate was obtained by similarly drying at a metal surface temperature of 80 ° C. The obtained test plate was evaluated by the following method. The results are shown in Tables 1 and 2 below.
[0049]
The niobium oxide colloidal particles, water-dispersible silica, vanadium compound, zirconium compound, titanium compound, aqueous resin, phosphoric acid compound, and silane coupling agent used in Tables 1 and 2 below are as follows.
[Niobium oxide colloidal particles]
A: Niobium oxide sol (Nb 2 O 5 10%, average particle size; 5 nm, manufactured by Taki Chemical Co., Ltd.)
B: Niobium oxide colloidal particle aqueous dispersion (Nb 2 O 5 10%, average particle size; 2000 nm)
[Water-dispersible silica]
A: Snowtex O (SiO 2 ; 20%, manufactured by Nissan Chemical Industries, Ltd.)
B: Adelite AT-20A (SiO 2 ; 20%, manufactured by Asahi Denka Kogyo Co., Ltd.)
C: Snowtex N (SiO 2 ; 20%, manufactured by Nissan Chemical Industries, Ltd.)
[Vanadium compounds]
A: Ammonium metavanadate (V; 43.6%, reagent)
B: Vanadium pentoxide (V; 56.0%, reagent)
C: vanadyl sulfate (vanadyl sulfate, V; 22.6%, Shinsei Chemical Co., Ltd.)
[Zirconium compound]
A: Zircosol AC-7 (ammonium zirconium carbonate, Zr; 74.0%; solid content conversion value; manufactured by Daiichi Rare Element Industrial Co., Ltd.)
B: Zirconium (IV) acetylacetonate (Zr; 18.7%, reagent)
C: Zirconyl nitrate dihydrate (Zr; 33.0%, reagent)
[Titanium compounds]
A: Olgatics TC-400 (titanium triethanolamate; Ti; 10.4%; solid content conversion value, manufactured by Matsumoto Pharmaceutical Co., Ltd.)
[Aqueous resin]
A: PC2200 (ethylene acrylic acid copolymer resin, solid content concentration: 30%, manufactured by Shoei Chemical Co., Ltd.)
B: Superflex 420 (polyurethane resin, solid content concentration: 32%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
C: Jurimer AC-10L (polyacrylic acid, solid content concentration: 40%, manufactured by Nippon Pure Chemical Co., Ltd.)
[Phosphate compound]
A: Diammonium hydrogen phosphate (solid content concentration: 100%, reagent)
[Silane coupling agent]
A: Silaace S-510 (γ-glycidoxypropyltrimethoxysilane, solid concentration: 100%, manufactured by Chisso Corporation)
B: Silaace S-210 (vinyl methoxysilane, solid content concentration: 100%, manufactured by Chisso Corporation)
[0050]
(Evaluation methods)
<Corrosion resistance>
The flat part of the test plate and the end face and back part of the processed part extruded 8 mm with an Erichcenten tester are tape-sealed, and 5% saline is sprayed on the painted surface of the test plate at 35 ° C, and white rust after 24 or 72 hours. The generation area ratio was evaluated according to the following evaluation criteria.
A: No white rust
○: White rust generation area is less than 10%
○ △: 10% or more and less than 30%
Δ: 30% or more and less than 50%
×: 50% or more
[0051]
[Table 1]
[Table 2]
As is clear from the results of Tables 1 and 2, the metal surface treatment composition of the present invention containing niobium oxide colloidal particles is excellent in rust prevention and can suppress the occurrence of white rust. Moreover, in addition to the niobium oxide colloidal particles, the metal surface treatment composition further using water-dispersible silica, aqueous resin, vanadium compound and the like further improves rust prevention performance by using these components in combination. In contrast, a metal surface treatment composition that does not contain niobium oxide colloidal particles cannot obtain a chemical conversion film excellent in rust prevention performance, and therefore cannot obtain a good galvanized steel sheet. Moreover, the metal treatment composition of this invention is excellent also in the antirust performance after a process.
[0054]
【The invention's effect】
Since the metal surface treatment composition of the present invention is composed of the above-mentioned niobium oxide colloidal particles, it is excellent in rust prevention and adhesion, and can suppress generation of white rust. Moreover, since a chromium compound, a manganese compound, or the like is not an essential component, a large burden is not required for the treatment of the waste liquid.
Claims (5)
前記金属表面処理組成物が、酸化ニオブコロイド粒子を含むことを特徴とする金属表面処理方法。A metal surface treatment method characterized by surface-treating a galvanized steel sheet with a metal surface treatment composition to form a film,
The metal surface treatment composition, metal surface treatment method which comprises the niobium oxide colloidal particles.
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|---|---|---|---|---|
| JP2007002330A (en) * | 2005-06-27 | 2007-01-11 | Baoshan Iron & Steel Co Ltd | Surface treatment agent for zinc or zinc alloy galvanized steel sheet, and surface treated zinc or zinc alloy galvanized steel sheet |
| JP4719662B2 (en) * | 2006-11-21 | 2011-07-06 | 日本パーカライジング株式会社 | Water-based surface treatment agent for environment-friendly precoat metal material, surface treatment metal material, and environment-friendly precoat metal material |
| JP5188090B2 (en) * | 2006-12-27 | 2013-04-24 | 朝日化学工業株式会社 | Coating liquid and clear coated steel plate |
| TWI394864B (en) * | 2007-12-27 | 2013-05-01 | Kansai Paint Co Ltd | Metal surface treatment composition, and surface-treated metal material with metal surface treatment film obtained from the metal surface treatment composition |
| CN101747841A (en) * | 2008-12-05 | 2010-06-23 | 安集微电子（上海）有限公司 | Chemical-mechanical polishing solution |
| CN101659175B (en) * | 2009-09-02 | 2012-11-21 | 苏州扬子江新型材料股份有限公司 | Scratching-resistant and wear-resistant color-coated steel sheet |
| JP2010031297A (en) * | 2009-11-16 | 2010-02-12 | Kansai Paint Co Ltd | Paint composition with excellent corrosion resistance |
| JP5528925B2 (en) * | 2010-07-09 | 2014-06-25 | 日本パーカライジング株式会社 | Metal surface treatment agent, surface treatment metal material, and metal surface treatment method |
| CN102746778B (en) * | 2012-06-29 | 2014-12-03 | 宝山钢铁股份有限公司 | Galvanizing steel strip with good conductivity, high corrosion resistance and fingerprint resistance, surface treatment agent and treatment method |
| BR112017011835A2 (en) | 2015-02-03 | 2017-12-26 | Nippon Steel & Sumitomo Metal Corp | fuel tank steel sheet |
| WO2016140146A1 (en) * | 2015-03-03 | 2016-09-09 | 株式会社スリーボンド | Anti-fogging agent composition |
| JP6674081B2 (en) * | 2016-07-14 | 2020-04-01 | ユケン工業株式会社 | Rust prevention coating solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1021705C (en) * | 1992-03-07 | 1993-07-28 | 冶金工业部钢铁研究总院 | Passivating liquid for surface of galvanized steel plate |
| CN1024815C (en) * | 1992-11-18 | 1994-06-01 | 冶金工业部钢铁研究总院 | Metal surface treating liquid |
| CN1250393C (en) * | 1999-10-08 | 2006-04-12 | 杰富意钢铁株式会社 | Surface treated zinc-based metal plated steel sheet |
| JP2001214283A (en) * | 1999-11-15 | 2001-08-07 | Kawasaki Steel Corp | Surface treated galvanized steel sheet |
| JP3779174B2 (en) * | 2000-11-13 | 2006-05-24 | Ｈｏｙａ株式会社 | Vapor deposition composition, method of forming antireflection film using the same, and optical member |
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| CN100363537C (en) | 2008-01-23 |
| CN1478921A (en) | 2004-03-03 |
| JP2004124254A (en) | 2004-04-22 |
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