JP4865139B2 - Method for forming chromium-free corrosion-resistant film on Sn-Zn alloy plating - Google Patents
Method for forming chromium-free corrosion-resistant film on Sn-Zn alloy plating Download PDFInfo
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- JP4865139B2 JP4865139B2 JP2001061459A JP2001061459A JP4865139B2 JP 4865139 B2 JP4865139 B2 JP 4865139B2 JP 2001061459 A JP2001061459 A JP 2001061459A JP 2001061459 A JP2001061459 A JP 2001061459A JP 4865139 B2 JP4865139 B2 JP 4865139B2
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- Prior art keywords
- alloy plating
- acid
- chromium
- film
- free
- 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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- 229910045601 alloy Inorganic materials 0.000 title claims description 30
- 239000000956 alloy Substances 0.000 title claims description 30
- 238000007747 plating Methods 0.000 title claims description 29
- 229910020994 Sn-Zn Inorganic materials 0.000 title claims description 26
- 229910009069 Sn—Zn Inorganic materials 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 11
- 238000005260 corrosion Methods 0.000 title description 15
- 230000007797 corrosion Effects 0.000 title description 15
- 150000003839 salts Chemical class 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- -1 inorganic acid ion Chemical class 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
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- 150000007513 acids Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- 239000011734 sodium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
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- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- 235000015165 citric acid Nutrition 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
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- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- 235000011090 malic acid Nutrition 0.000 description 1
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- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
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- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、Ｓｎ−Ｚｎ合金めっき皮膜上にクロムフリー耐食性皮膜を形成する方法及びそのために用いるクロムフリー皮膜形成用水溶液に関するものである。
【従来の技術】
近年、亜鉛めっきの耐食性を改良する目的で亜鉛と異種金属との合金めっきがいろいろ検討され実用化に至っている。この中でもＳｎ−Ｚｎ合金めっきは、耐食性、耐塩水性、二次加工性及びハンダ付け性に優れているため、自動車部品、電子部品等に用いる工業用めっきとして広く使用されてきている。
このＳｎ−Ｚｎ合金めっき単独では耐食性が十分ではなく、めっき後クロム酸処理、いわゆるクロメート処理が産業界で広範囲に採用されている。しかしながら、近年、六価クロムが人体や環境に悪い影響を与えることが指摘され、六価クロムの使用を規制する動きが、活発になってきている
【０００２】
【発明が解決しようとする課題】
本発明は、Ｓｎ−Ｚｎ合金めっきに、人体や環境に影響を与えるクロムを用いない化成処理を施しかつ従来のクロメートと同等な耐食性を有する皮膜を形成させることができる方法を提供することを目的とする。
本発明は、又、この方法に用いるクロムフリー皮膜形成用水溶液を提供することを目的とする。
【課題を解決するための手段】
本発明は、基体上にＳｎ−Ｚｎ合金めっきを析出させた後、特定の組成の処理液を用いて化成処理を行うと、上記課題を効率的に解決できるとの知見に基づいてなされたのである。
すなわち、本発明は、基体上に５〜９５質量％のＺｎを含有するＳｎ−Ｚｎ合金めっき皮膜を有する基体を、(1)Ｔｉ、Ｖ、Ｍｎ、Ｚｒ、Ｍｏ、Ｗ及びＳｉからなる群から選ばれる少なくとも１種の金属の塩または酸素酸塩及び(2)無機酸イオンを含有する水溶液に接触させることを特徴とするＳｎ−Ｚｎ合金めっき皮膜上にクロムフリー皮膜を形成させる方法を提供する。
本発明は、又、(1)Ｔｉ、Ｖ、Ｍｎ、Ｚｒ、Ｍｏ、Ｗ及びＳｉからなる群から選ばれる少なくとも１種の金属の塩または酸素酸塩及び(2)及び無機酸イオンを含有するすることを特徴とする、Ｓｎ−Ｚｎ合金めっき皮膜上にクロムフリー皮膜形成用水溶液を提供する。
【０００３】
【発明の実施の形態】
本発明で用いる基体としては、鉄、ニッケル、銅などの各種金属、及びこれらの合金、あるいは亜鉛置換処理を施したアルミニウムなどの金属や合金の板状物、直方体、円柱、円筒、球状物などの種々の形状のものがあげられる。
本発明では、先ず基体上に、常法により５〜９５質量％（以下、％と略称する）、好ましくは５〜８０％のＺｎを含有するＳｎ−Ｚｎ合金めっきを析出させる。この範囲でＺｎを含有するＳｎ−Ｚｎ合金めっき皮膜を形成させると、最終製品に高耐食性を付与することができるので好ましい。
基体上にＳｎ−Ｚｎ合金めっきを析出させるには、具体的には、特開昭５１−７５６３２号公報などに記載の方法により行うのが好ましい。基体上に析出するＳｎ−Ｚｎ合金めっきの厚みは任意とすることができるが、１μｍ以上、好ましくは５〜２０μｍ厚とするのがよい。
【０００４】
本発明では、このようにして基体上にＳｎ−Ｚｎ合金めっきを析出させた後、例えば、水洗し、(1)Ｔｉ、Ｖ、Ｍｎ、Ｚｒ、Ｍｏ、Ｗ及びＳｉからなる群から選ばれる少なくとも１種の金属の塩または酸素酸塩及び(2)無機酸イオン、例えば、塩酸、硫酸、硝酸、リン酸或いはこれらの塩のうち1種または2種以上含有する水溶液に接触、例えば、この水溶液を用いて浸漬処理を行う。
ここで(1)Ｔｉ、Ｖ、Ｍｎ、Ｚｒ、Ｍｏ、Ｗ及びＳｉからなる群から選ばれる少なくとも１種の金属の塩または酸素酸塩としては、Ｔｉに関して、塩化チタンや硫酸チタン等、Ｖに関して、バナジン酸塩等、Ｍｎに関して、塩化マンガン、硫酸マンガンや過マンガン酸塩等、Ｚｒに関してジルコン酸塩等、Ｍｏに関してモリブデン酸塩等、Ｗに関して、タングステン酸塩等、Ｓｉについてはケイ酸塩やコロイダルシリカ（コロイド状酸化ケイ素）などがあげられる。各種金属濃度としては、0.001〜5モル/リットルであるのが好ましく、より好ましくは、0.005〜0.5モル/リットルである。本発明においてこの濃度範囲で成分(1)を用いると、連続的に安定な化成皮膜が形成でき、すぐれた耐食性が得られる。
又、無機酸イオン濃度は、水溶液中0.5〜100ｇ/リットルであるのが好ましく、より好ましくは、１〜50ｇ/リットルである。
本発明では、上記処理液中に、更に有機酸を含有させることができる。有機酸を含有させると、より均一で強固なクロムフリー皮膜が生成されるので好ましい。
使用できる有機酸としては、例えば、蟻酸、酢酸、プロピオン酸、酪酸、吉草酸、安息香酸等の炭素数１〜１０のモノカルボン酸、シュウ酸、マロン酸、マレイン酸、コハク酸、アジピン酸、グルタル酸、フタル酸等の炭素数２〜１０のジカルボン酸、乳酸、グリコール酸、グリセリン酸、グルコン酸、β−オキシ酪酸、サリチル酸等の炭素数３〜１０のオキシモノカルボン酸等が特に効果が高いので好ましい。
【０００５】
上記有機酸の他に、クエン酸、酒石酸、リンゴ酸等のオキシ多価カルボン酸、トリカルバリル酸等の多価カルボン酸も有効である。
ここで、有機酸としては前記の酸、あるいはそれらの塩（例えばナトリウム、カリウム、アンモニウム等の塩）の一種または二種以上を使用することができ、有機酸あるいはそれらの塩を合計１〜１００ｇ／リットル含有させるのが好ましく、より好ましくは５〜８０ｇ／リットルである。
なお、化成処理液のｐＨを0.5〜7.0にするのが好ましい。この範囲にｐＨを調整するために、前記無機酸及び/又は有機酸を用いてもよく、又水酸化アルカリ、アンモニア水などのアルカリ剤を用いてもよい。
本発明で用いる化成処理液における上記必須成分の残分は水であるが、メチルアミン、エチレンジアミン、ジエチレントリアミン等のアミン類等を加えることができる。
【０００６】
本発明のＳｎ−Ｚｎ合金めっきクロムフリー皮膜形成のための処理方法としては、上記水溶液に合金めっき物を浸漬するのが一般的である。例えば10〜50℃の液温で5〜600秒浸漬するのが好ましく、より好ましくは15〜120秒浸漬し、例えば、厚さ0.01〜3μｍ、好ましくは0.05〜1μｍのクロムフリー皮膜を形成させるのが良い。
なお、亜鉛めっきではクロメート皮膜の光沢を増すために、通常、クロメート処理前に被処理物を希硝酸溶液に浸漬させることが行われるが、本発明ではこのような前処理を用いなくともよい。
上記以外の条件や処理操作は、従来のクロメート処理方法に準じて行うことができる。
【０００７】
また、本発明のクロムフリー皮膜上にオーバーコート処理を施すことにより、更に耐食性を向上させることが出来、より耐食性を持たせるには、大変有効な手段である。例えば、まず、Ｓｎ−Ｚｎ合金めっき上に上記クロメートフリー化成皮膜処理を行い、水洗後オーバーコート処理液に浸漬、乾燥するする。また、クロメートフリー化成皮膜処理乾燥後、新たにオーバーコート処理液に浸漬、乾燥することも出来る。ここで、オーバーコートとは、珪酸塩、リン酸塩等の無機皮膜は勿論の事、ポリエチレン、ポリ塩化ビニル、ポリスチレン、ポリプロピレン、メタクリル樹脂、ポリカーボネート、ポリアミド、ポリアセタール、フッ素樹脂、尿素樹脂、フェノール樹脂、不飽和ポリエステル樹脂、ポリウレタン、アルキド樹脂、エポキシ樹脂、メラミン樹脂等の有機皮膜も有効である。
このようなオーバーコートを施すためのオーバーコート処理液としては、例えば、ディップソール（株）製のディップコートＷなどを用いることができる。オーバーコート皮膜の厚みは任意とすることができるが、0.1〜20μｍとするのがよい。
【０００８】
【発明の効果】
本発明によれば、Ｓｎ−Ｚｎ合金めっき上に直接クロムフリー化成皮膜を生成することができる。この方法により得られためっき物は、Ｓｎ−Ｚｎ合金めっき自体の耐食性に加え、更にクロムフリー化成皮膜のもつ優れた耐食性を合わせもつ。従って、Ｓｎ−Ｚｎ合金めっき上に直接クロムフリー化成処理より得られる皮膜は、耐食性、耐塩水性及び耐熱性が従来の六価クロメートと同等で、また、Ｓｎ−Ｚｎ合金めっきのもつ延展性のために曲げ加工にも強いために、今後いろいろな分野で幅広く利用されることが期待できる。
次に、実施例および比較例を示して本発明を説明する。
【０００９】
【実施例】
実施例１
鋼板にＺｎ含有量を変えたＳｎ−Ｚｎ合金めっきを厚さ８μｍに施したものを、表１に示す化成処理液に浸漬した（浴温：２５℃−処理時間：３０秒）。
【表１】
表１
【００１０】
実施例２
実施例１Ｎｏ３のＴｉ化成皮膜処理後、オーバーコート処理を行った。オーバーコート処理条件を表２に示す。
【表２】
表２
比較例１
比較例として鋼板に８μｍＳｎ−Ｚｎ合金めっきを施したものに六価クロメート処理を行った。
六価クロメートはディップソール(株)製ＳＺ−２４８Ｓ（５０ml/l）を使用した。
実施例１、２及び比較例で得られたＳｎ−Ｚｎ合金めっきの外観及び塩水噴霧試験（ＪＩＳ−Ｚ−２３７１）結果をまとめて表３に示す。
表３に示されるように、実施例１Ｎｏ１〜１４の皮膜の場合でも比較例Ｎｏ１〜３の従来クロメート皮膜と比較し同等の耐食性が得られた。また、実施例２でオーバーコート処理した皮膜は、従来のクロメートより良い耐食性結果が得られた。
【００１２】
【表３】
表３
BACKGROUND OF THE INVENTION
The present invention relates to a method of forming a chromium-free corrosion-resistant coating on a Sn—Zn alloy plating coating and an aqueous solution for forming a chromium-free coating used therefor.
[Prior art]
In recent years, various alloy platings of zinc and dissimilar metals have been studied and put into practical use for the purpose of improving the corrosion resistance of galvanizing. Among these, Sn—Zn alloy plating is excellent in corrosion resistance, salt water resistance, secondary workability and solderability, and thus has been widely used as industrial plating used for automobile parts, electronic parts and the like.
This Sn—Zn alloy plating alone does not have sufficient corrosion resistance, and post-plating chromic acid treatment, so-called chromate treatment, is widely used in the industry. However, in recent years, it has been pointed out that hexavalent chromium has a bad influence on the human body and the environment, and the movement to regulate the use of hexavalent chromium has become active.
[Problems to be solved by the invention]
An object of the present invention is to provide a method capable of forming a film having a corrosion resistance equivalent to that of conventional chromate by subjecting Sn—Zn alloy plating to a chemical conversion treatment that does not use chromium that affects the human body and the environment. And
Another object of the present invention is to provide an aqueous solution for forming a chromium-free film used in this method.
[Means for Solving the Problems]
Since the present invention was made based on the knowledge that, after depositing Sn—Zn alloy plating on a substrate and then performing a chemical conversion treatment using a treatment liquid having a specific composition, the above problems can be solved efficiently. is there.
That is, the present invention provides a substrate having a Sn—Zn alloy plating film containing 5 to 95% by mass of Zn on the substrate from the group consisting of (1) Ti, V, Mn, Zr, Mo, W and Si. Provided is a method for forming a chromium-free film on a Sn-Zn alloy plating film, which comprises contacting with an aqueous solution containing at least one selected metal salt or oxyacid salt and (2) an inorganic acid ion. .
The present invention also includes (1) at least one metal salt or oxyacid salt selected from the group consisting of Ti, V, Mn, Zr, Mo, W and Si, and (2) and an inorganic acid ion. An aqueous solution for forming a chromium-free film is provided on a Sn—Zn alloy plating film.
[0003]
DETAILED DESCRIPTION OF THE INVENTION
As the substrate used in the present invention, various metals such as iron, nickel, copper, and alloys thereof, or metal or alloys such as aluminum subjected to zinc substitution treatment, rectangular parallelepipeds, cylinders, cylinders, spherical objects, etc. These are various shapes.
In the present invention, Sn—Zn alloy plating containing 5 to 95% by mass (hereinafter abbreviated as “%”), preferably 5 to 80% Zn is first deposited on a substrate by a conventional method. It is preferable to form a Sn—Zn alloy plating film containing Zn within this range because high corrosion resistance can be imparted to the final product.
Specifically, the Sn—Zn alloy plating is preferably deposited on the substrate by the method described in JP-A-51-75632. The thickness of the Sn—Zn alloy plating deposited on the substrate can be arbitrary, but it is 1 μm or more, preferably 5 to 20 μm.
[0004]
In the present invention, after Sn—Zn alloy plating is deposited on the substrate in this way, for example, it is washed with water, and (1) at least selected from the group consisting of Ti, V, Mn, Zr, Mo, W and Si. Contact with an aqueous solution containing one or more of one metal salt or oxyacid salt and (2) inorganic acid ions such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or salts thereof, for example, this aqueous solution A dipping process is performed using
Here, (1) as at least one metal salt or oxyacid salt selected from the group consisting of Ti, V, Mn, Zr, Mo, W and Si, regarding Ti, titanium chloride, titanium sulfate, etc. , Vanadate, etc., Mn, manganese chloride, manganese sulfate, permanganate, etc., Zr, zirconate, etc., Mo, molybdate, etc., W, tungstate, etc. Examples thereof include colloidal silica (colloidal silicon oxide). The concentration of various metals is preferably 0.001 to 5 mol / liter, and more preferably 0.005 to 0.5 mol / liter. In the present invention, when component (1) is used in this concentration range, a stable chemical conversion film can be formed continuously, and excellent corrosion resistance can be obtained.
The inorganic acid ion concentration in the aqueous solution is preferably 0.5 to 100 g / liter, and more preferably 1 to 50 g / liter.
In the present invention, an organic acid can be further contained in the treatment liquid. The inclusion of an organic acid is preferable because a more uniform and strong chromium-free coating is produced.
Examples of organic acids that can be used include monocarboxylic acids having 1 to 10 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, oxalic acid, malonic acid, maleic acid, succinic acid, adipic acid, Particularly effective are dicarboxylic acids having 2 to 10 carbon atoms such as glutaric acid and phthalic acid, oxymonocarboxylic acids having 3 to 10 carbon atoms such as lactic acid, glycolic acid, glyceric acid, gluconic acid, β-oxybutyric acid and salicylic acid. It is preferable because it is high.
[0005]
Besides the above organic acids, oxypolycarboxylic acids such as citric acid, tartaric acid and malic acid, and polyvalent carboxylic acids such as tricarbaryl acid are also effective.
Here, as the organic acid, one or two or more of the above-mentioned acids or salts thereof (for example, salts of sodium, potassium, ammonium, etc.) can be used, and the total amount of organic acids or salts thereof is 1 to 100 g. / Liter is preferably contained, more preferably 5 to 80 g / liter.
In addition, it is preferable to make pH of a chemical conversion liquid into 0.5-7.0. In order to adjust the pH within this range, the inorganic acid and / or organic acid may be used, or an alkali agent such as alkali hydroxide or aqueous ammonia may be used.
The residue of the essential component in the chemical conversion treatment solution used in the present invention is water, but amines such as methylamine, ethylenediamine, and diethylenetriamine can be added.
[0006]
As a processing method for forming the Sn—Zn alloy plating chromium-free film of the present invention, it is common to immerse the alloy plating in the aqueous solution. For example, it is preferable to immerse at a liquid temperature of 10 to 50 ° C. for 5 to 600 seconds, more preferably 15 to 120 seconds, for example, to form a chromium-free film having a thickness of 0.01 to 3 μm, preferably 0.05 to 1 μm. Is good.
In galvanization, in order to increase the gloss of the chromate film, the object to be treated is usually immersed in a dilute nitric acid solution before the chromate treatment. However, in the present invention, such a pretreatment may not be used.
Conditions and processing operations other than those described above can be performed in accordance with conventional chromate processing methods.
[0007]
Further, by applying an overcoat treatment on the chromium-free film of the present invention, the corrosion resistance can be further improved, and this is a very effective means for imparting more corrosion resistance. For example, first, the chromate-free chemical conversion film treatment is performed on the Sn—Zn alloy plating, and after being washed with water, it is immersed in an overcoat treatment liquid and dried. Moreover, after chromate-free chemical conversion film treatment drying, it can also be newly immersed in an overcoat treatment liquid and dried. Here, the overcoat is not only an inorganic film such as silicate and phosphate, but also polyethylene, polyvinyl chloride, polystyrene, polypropylene, methacrylic resin, polycarbonate, polyamide, polyacetal, fluorine resin, urea resin, phenol resin. Organic films such as unsaturated polyester resins, polyurethanes, alkyd resins, epoxy resins and melamine resins are also effective.
As an overcoat treatment liquid for applying such an overcoat, for example, Dipcoat W manufactured by Dipsol Co., Ltd. can be used. The thickness of the overcoat film can be arbitrarily set, but is preferably 0.1 to 20 μm.
[0008]
【Effect of the invention】
According to the present invention, a chromium-free chemical conversion film can be directly formed on the Sn—Zn alloy plating. The plated product obtained by this method has not only the corrosion resistance of the Sn—Zn alloy plating itself, but also the excellent corrosion resistance of the chromium-free chemical conversion film. Therefore, the film obtained by direct chromium-free chemical conversion treatment on the Sn—Zn alloy plating has the same corrosion resistance, salt water resistance and heat resistance as the conventional hexavalent chromate, and because of the extensibility of Sn—Zn alloy plating. Since it is also resistant to bending, it can be expected to be widely used in various fields in the future.
Next, an Example and a comparative example are shown and this invention is demonstrated.
[0009]
【Example】
Example 1
A steel sheet with Sn-Zn alloy plating with a Zn content changed to a thickness of 8 µm was immersed in a chemical conversion treatment solution shown in Table 1 (bath temperature: 25 ° C-treatment time: 30 seconds).
[Table 1]
Table 1
[0010]
Example 2
After the Ti chemical conversion film treatment of Example 1 No3, an overcoat treatment was performed. Table 2 shows the overcoat treatment conditions.
[Table 2]
Table 2
Comparative Example 1
As a comparative example, the steel plate was plated with 8 μm Sn—Zn alloy and subjected to hexavalent chromate treatment.
As the hexavalent chromate, SZ-248S (50 ml / l) manufactured by Dipsol Co., Ltd. was used.
Table 3 summarizes the appearance and salt spray test (JIS-Z-2371) results of the Sn—Zn alloy plating obtained in Examples 1 and 2 and the comparative example.
As shown in Table 3, even in the case of the films of Examples 1 No. 1 to 14, the same corrosion resistance was obtained as compared with the conventional chromate film of Comparative Examples No. 1 to No. 3. Further, the coating film overcoated in Example 2 gave better corrosion resistance results than the conventional chromate.
[0012]
[Table 3]
Table 3
Claims (4)
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| JP5594732B2 (en) * | 2008-12-05 | 2014-09-24 | ユケン工業株式会社 | Chemical conversion composition and method for producing member having antirust coating |
| EP3040385A4 (en) | 2013-08-28 | 2017-03-29 | Dipsol Chemicals Co., Ltd. | Friction modifier for top coating agent for trivalent chromium chemical conversion coating film or chromium-free chemical conversion coating film, and top coating agent including same |
| JP6216208B2 (en) * | 2013-10-22 | 2017-10-18 | 日本パーカライジング株式会社 | Non-phosphating agent for plastic working, treatment liquid, chemical film and metal material having chemical film |
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| JP3290791B2 (en) * | 1993-12-28 | 2002-06-10 | ディップソール株式会社 | Method for forming high corrosion resistant black film on Sn-Zn alloy plating |
| JPH1161432A (en) * | 1997-08-28 | 1999-03-05 | Nippon Steel Corp | Inorganic / organic composite surface treated metal plate |
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