JP3584937B1 - 6価クロムフリー黒色防錆皮膜と表面処理液および処理方法 - Google Patents
6価クロムフリー黒色防錆皮膜と表面処理液および処理方法 Download PDFInfo
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- 238000004381 surface treatment Methods 0.000 title claims abstract description 60
- 238000011282 treatment Methods 0.000 title claims abstract description 60
- 238000000576 coating method Methods 0.000 title claims description 30
- 239000011248 coating agent Substances 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 25
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 74
- 239000011701 zinc Substances 0.000 claims abstract description 74
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000000243 solution Substances 0.000 claims abstract description 64
- 239000000463 material Substances 0.000 claims abstract description 60
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 51
- 239000010959 steel Substances 0.000 claims abstract description 51
- 238000007747 plating Methods 0.000 claims abstract description 49
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 25
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 25
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 22
- 230000003449 preventive effect Effects 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011651 chromium Substances 0.000 claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 16
- -1 nitrate ions Chemical class 0.000 claims abstract description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 9
- 238000007654 immersion Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 24
- 230000002378 acidificating effect Effects 0.000 claims description 14
- 229910052804 chromium Inorganic materials 0.000 claims description 13
- 150000007524 organic acids Chemical class 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 239000013522 chelant Substances 0.000 claims description 6
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 abstract description 36
- 230000007797 corrosion Effects 0.000 abstract description 36
- 229910001335 Galvanized steel Inorganic materials 0.000 abstract description 25
- 239000008397 galvanized steel Substances 0.000 abstract description 25
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract description 22
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 abstract description 19
- 239000002253 acid Substances 0.000 abstract description 6
- 229940085991 phosphate ion Drugs 0.000 abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 abstract description 5
- 239000010452 phosphate Substances 0.000 abstract description 4
- 229910000423 chromium oxide Inorganic materials 0.000 abstract description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 abstract description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 31
- 239000000047 product Substances 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910001430 chromium ion Inorganic materials 0.000 description 4
- 229910001429 cobalt ion Inorganic materials 0.000 description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 3
- ABXXWVKOBZHNNF-UHFFFAOYSA-N chromium(3+);dioxido(dioxo)chromium Chemical group [Cr+3].[Cr+3].[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Cr]([O-])(=O)=O ABXXWVKOBZHNNF-UHFFFAOYSA-N 0.000 description 3
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 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 3
- 150000002500 ions Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- UBFMILMLANTYEU-UHFFFAOYSA-H chromium(3+);oxalate Chemical compound [Cr+3].[Cr+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UBFMILMLANTYEU-UHFFFAOYSA-H 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002691 malonic acids Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002913 oxalic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium
Landscapes
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
【解決手段】3価クロム化合物、コバルト化合物、シュウ酸、リン酸、および硫酸を含有し、6価クロムと硝酸イオンを含有しない酸性水溶液からなり、水溶液中のリン酸イオン/硫酸イオンの質量比が1より大である表面処理液を用いて、亜鉛系めっき鋼材に反応型の浸漬処理を行うと、耐食性に優れた黒色防錆皮膜が形成される。この皮膜は、めっき表面との界面の亜鉛の低次酸化物を含んだ黒色層と、その上のリン酸塩層と、最上層の亜鉛を含有しないクロム/リンの酸化物層の3層からなる皮膜構造を有する。その上に、有機または無機オーバーコート層を形成してもよい。
Description
(1)亜鉛系めっき鋼材の表面に黒色防錆皮膜を形成するための酸性の表面処理液であって、3価クロム化合物、コバルト化合物、キレート形成能のある有機酸、リン酸、および硫酸を含有し、6価クロムと硝酸イオンを含有しない酸性水溶液からなり、水溶液中のリン酸イオン/硫酸イオンの質量比が1以上であることを特徴とする表面処理液。
(3)液のpHが2〜3の範囲である、上記(1) または(2) に記載の表面処理液。
(4)亜鉛系めっき鋼材を上記 (1)〜(3) のいずれかに記載の表面処理液中に浸漬した後、乾燥して、黒色防錆皮膜をめっき表面に形成することを特徴とする、亜鉛系めっき鋼材の黒色化処理方法。
(6)塩化浴を用いた電気亜鉛系めっき表面に、3価クロム化合物を含有し、6価クロムを含まない、L値が15未満の黒色防錆皮膜を有する、黒色化亜鉛系めっき鋼材。
本発明は、亜鉛系めっき鋼材に6価クロムフリーの黒色防錆皮膜を形成する技術に関する。
本発明の表面処理液は亜鉛系めっき鋼材の反応型化成処理に使用するものである。従って、所望の皮膜を形成するのに十分な時間、亜鉛系めっき鋼材を表面処理液に浸漬した後、乾燥することにより、表面処理を実施することができる。
比較例として、3価クロム化合物を含有し、6価クロム化合物を含有しないが、組成が本発明の範囲外である表面処理液を使用して黒色化処理を行った。具体的には、シュウ酸、リン酸、またはコバルト化合物のいずれかを含有しないか、またはリン酸イオン/硫酸イオンの質量比が1より小である表面処理液を使用した。処理液組成と処理条件を表2に示す。
上記のように表面処理した亜鉛系めっき材の外観(黒色度)と耐食性について、次のように評価した。それらの試験結果も、表1 (実施例) 、表2 (比較例) および表3 (従来例) に併記する。なお、亜鉛めっき材がボルトである場合、外観についてはボルト材により評価したが、明度と耐食性の評価は、鋼板に同じめっき浴とめっき条件で電気亜鉛系めっきおよび表面処理を行った試験片を用いて行った。
◎:黒色 (均一に真っ黒) 、
○:灰色 (一部が黒色だが不均一であるものを含む) 、
△:黒っぽい煤状物質が表面に付着している、
×:白色〜薄黄色。
◎:L値<15
○:15≦L値<20
×:L値≧20。
○:120 時間での白錆発生面積率が10%未満、
×:120 時間での白錆発生面積率が10%以上。
(1)この公報の実施例1〜6に従って、ジンケート浴で電気亜鉛めっきした亜鉛めっき鋼板を表面処理した場合、実施例4および6ではL値=15の黒色皮膜が形成されたが、その他の実施例でのL値は、1例でL値が18であったのを除いて、L値は20以上であった (シュウ酸が無水物である場合と2水和物である場合の両方を含めて) 。
Claims (8)
- 亜鉛系めっき鋼材の表面に黒色防錆皮膜を形成するための酸性の表面処理液であって、3価クロム化合物、コバルト化合物、キレート形成能のある有機酸、リン酸、および硫酸を含有し、6価クロムと硝酸イオンを含有しない酸性水溶液からなり、水溶液中のリン酸イオン/硫酸イオンの質量比が1以上であることを特徴とする表面処理液。
- 前記有機酸がシュウ酸である、請求項1に記載の表面処理液。
- 液のpHが2〜3の範囲である、請求項1または2に記載の表面処理液。
- 亜鉛系めっき鋼材を請求項1〜3のいずれかに記載の表面処理液中に浸漬した後、乾燥して、黒色防錆皮膜をめっき表面に形成することを特徴とする、亜鉛系めっき鋼材の黒色化処理方法。
- 形成された黒色防錆皮膜の上に有機または無機オーバーコート層を形成する、請求項4に記載の亜鉛系めっき鋼材の黒色化処理方法。
- 塩化浴を用いた電気亜鉛系めっき表面に、3価クロム化合物を含有し、6価クロムを含まない、明度指数(L*a*b* 表色系のL* の値)が15未満の黒色防錆皮膜を有する、黒色化亜鉛系めっき鋼材。
- 亜鉛系めっき表面に、請求項1〜3のいずれかに記載の表面処理液を用いた浸漬処理により形成された、6価クロムを含まず、3価クロムを含む、明度指数が15未満の黒色防錆皮膜を有する、黒色化亜鉛系めっき鋼材。
- 前記黒色防錆皮膜の上にさらに無色の無機または有機オーバーコート層を有する、請求項6または7に記載の黒色化亜鉛系めっき鋼材。
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JP2008232238A (ja) * | 2007-03-20 | 2008-10-02 | Calsonic Compressor Inc | 締結部材とそれを用いた気体圧縮機 |
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