WO2006132426A2 - Surface treatment liquid and method of forming conversion layer - Google Patents
Surface treatment liquid and method of forming conversion layer Download PDFInfo
- Publication number
- WO2006132426A2 WO2006132426A2 PCT/JP2006/311888 JP2006311888W WO2006132426A2 WO 2006132426 A2 WO2006132426 A2 WO 2006132426A2 JP 2006311888 W JP2006311888 W JP 2006311888W WO 2006132426 A2 WO2006132426 A2 WO 2006132426A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- surface treatment
- conversion layer
- treatment liquid
- acid
- black
- Prior art date
Links
- 238000004381 surface treatment Methods 0.000 title claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 50
- 239000007788 liquid Substances 0.000 title abstract description 66
- 238000000034 method Methods 0.000 title description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011651 chromium Substances 0.000 claims abstract description 21
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011701 zinc Substances 0.000 claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- 238000004040 coloring Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 13
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 12
- 150000007524 organic acids Chemical class 0.000 claims abstract description 10
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000011282 treatment Methods 0.000 description 54
- 239000010410 layer Substances 0.000 description 46
- 238000005260 corrosion Methods 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 16
- 229910000831 Steel Inorganic materials 0.000 description 13
- 239000010959 steel Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 5
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 4
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 239000011636 chromium(III) chloride Substances 0.000 description 4
- 235000007831 chromium(III) chloride Nutrition 0.000 description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000004697 chelate complex Chemical class 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
- 239000003446 ligand Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-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
- 238000013019 agitation Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 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
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 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
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000010953 base metal Substances 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/46—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates
-
- 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
Definitions
- the present invention relates to a surface treatment liquid and a method of forming a conversion layer. More specifically, the invention relates to a surface treatment liquid to form a black conversion layer, and a method of forming the conversion layer using the liquid.
- Metal components are often plated with zinc or a zinc alloy for preventing corrosion of the metal.
- Corrosion of zinc or a zinc alloy may be suppressed by subjecting the plated metal components to chromate treatment, and corrosion of the metal component as a base metal may be largely retarded as compared with the metal component not subjected to the chromate treatment.
- a surface treatment liquid containing hexavalent chromium has been used for the chromate treatment.
- hexavalent chromium is a harmful substance, use thereof has been regulated.
- Jpn. Pat. Appln. KOKAI Publication No. 2000-509434 also describes use of dyes, pigments and coloring matter forming agents.
- the black conversion layer can be widely applied because it is excellent in decorative effects and serves for preventing workers from mistaking a component for a similar component. Accordingly, the chromate treatment disclosed- in Jpn. Pat. Appln. KOKAI Publication No. 2000-509434 is expected to be utilized for forming the black conversion layer as well as for forming colorless conversion layers.
- An object of the present invention is to enhance the stability of the hexavalent chromium-free surface treatment liquid for forming the black conversion layer.
- a hexavalent chromium-free surface treatment solution for forming a black conversion layer on zinc or zinc alloy comprising trivalent chromium, an organic acid, an inorganic acid, and a coloring material which makes the conversion layer black, wherein the coloring material contains metal whose concentration in the solution falls within a range of 0.01 g/L to 3 g/L, wherein a molar ratio of the sum of the metal in the coloring material and trivalent chromium with respect to carboxy group falls within a range of 0.1 to 0.3, and wherein a pH value of the solution is equal to or larger than 3 and smaller than- 6.
- a method of manufacturing a conversion layer comprising subjecting zinc or zinc alloy to a surface treatment using the surface treatment solution according to the first aspect. Best Mode for Carrying Out the Invention
- a surface treatment liquid according to the present embodiment is used for forming a black conversion layer on zinc or a zinc alloy.
- the surface treatment liquid contains no hexavalent chromium, and typically contains no phosphorous and no sulfur.
- the surface treatment liquid contains trivalent chromium, an organic acid, an inorganic acid, and a coloring material for coloring the conversion layer black.
- the surface treatment liquid typically contains water as a solvent.
- Trivalent chromium forms a complex, typically a chelate complex, having the organic acid as a ligand, and the chelate complex is dissolved in the solution.
- the surface treatment liquid may contain either one kind of a trivalent chromium complex, or at least two kinds of trivalent chromium complexes.
- the concentration of trivalent chromium is, for example, in the range of 1 g/L to 20 g/L, preferably 5 g/L to 10 g/L.
- concentration of trivalent chromium is low, the density of the black color of the black conversion layer obtained by using the surface treatment liquid may be insufficient.
- concentration of trivalent chromium is high, on the other hand, stability of the surface treatment liquid may be insufficient.
- the coloring material contains a metal such as iron, cobalt, nickel or copper.
- the metal forms a complex, typically a chelate complex, having an organic acid as a ligand, and the complex is dissolved in the solution.
- the surface treatment liquid may contain one kind of the complex, or at least two kind of the complexes .
- the concentration of the metal contained in the coloring material in the surface treatment liquid is in the range of 0.01 g/L to 3 g/L, preferably in the range of 0.1 g/L to 1.0 g/L, and more preferably in the range of 0.3 g/L to 1.0 g/L.
- the density of the black color of the black conversion layer obtained may be insufficient when the concentration of the metal is low, while stability of the surface treatment liquid may be insufficient when the concentration of the metal is high.
- the organic acid includes monocarboxylic acids, polycarboxylic acids or a mixture thereof, typically dicarboxylic acids used for chelating ligands.
- examples of the organic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, phthalic acid, terephthalic acid, tartaric acid, citric acid, malic acid and ascorbic acid, and a mixture thereof.
- a molar ratio of a sum of the metal contained in the coloring material and trivalent chromium to carboxylic groups is in the range of 0.1 to 0.3, preferably in the range of 0.15 to 0.25. Stability of the surface treatment liquid may be insufficient when the ratio is small. On the other hand, the density of the black color of the black conversion layer obtained by using the surface treatment liquid may be insufficient when the molar ratio is large.
- the inorganic acid is, for example, hydrochloric acid or nitric acid, or a mixture thereof.
- Phosphoric acid or sulfuric acid may be 'also used as the inorganic acid.
- phosphoric acid imposes a great burden on effluent treatment.
- the concentration of the inorganic acid in the surface treatment liquid is adjusted so that pH of the treatment liquid falls within a range of 3 or more and less than 6, preferably within the range of 3.5 to 5. Stability of the surface treatment liquid may be insufficient while the density of the black color of the black conversion layer is insufficient, when the pH is small or large.
- the surface treatment liquid may further contain other components.
- the surface treatment liquid may further contain a filler such as colloidal silica, a surfactant and a corrosion inhibitor.
- a conversion layer can be formed on zinc or a zinc alloy by the following method using the surface treatment liquid.
- a metal component made of zinc or zinc alloy is prepared at first.
- a metal component made of iron or steel is prepared and is plated with zinc or zinc alloy.
- the kind of a plating bath used herein is not particularly restricted.
- a chloride bath, cyanide-free bath or cyanide bath may be used.
- the metal component is immersed in the surface treatment liquid.
- the temperature of the surface treatment liquid is about 40°C or more and typically 70°C or less.
- the immersion time may be in the range of 30 seconds to 120 seconds.
- the bath may be agitated by, for example, shaking agitation or air agitation while the metal component is immersed in the surface treatment liquid.
- a conversion layer can be formed on zinc or zinc alloy as described above. Conventionally used treatment methods using a rack, barrel or cage may be used for the surface treatment.
- An overcoat layer containing an organic or inorganic substance may be formed on the conversion layer, or an electrodeposition coating layer may be formed. The overcoat layer and electrodeposition coating layer may be used for modifying the appearance, for further improving corrosion resistance and for adjusting a torque of the metal component.
- the activated steel components were subjected to surface treatments using treatment liquids IA to IG, respectively, in which trivalent chromium and cobalt were dissolved as respective complexes.
- the treatment liquids IA to IG were prepared using chromium (III) chloride, cobalt chloride hexahydrate, oxalic acid dihydrate and sodium nitrate.
- the complexes contained in the treatment liquids IA to IG were produced by heating at a temperature of 80°C or more.
- the treatment temperature was set at 60°C and the immersion time was 45 seconds in each surface treatment using the treatment liquids IA to IG.
- the pH of each of the treatment liquids IA to IG was adjusted in the range of 4.5 to 5.0 using sodium hydroxide, sodium hydrogen carbonate, sodium carbonate and/or hydrochloric acid.
- Table 1 The composition of each of the treatment liquids IA to IG is shown in Table 1 below.
- the ratio (M Cr +M Co ) /M C0 0H shows the molar ratio of the sum of trivalent chromium and cobalt to the carboxylic group.
- Treatment liquids 2A to 2H in which trivalent chromium and cobalt are dissolved as complexes were prepared using chromium (III) chloride, cobalt chloride hexahydrate, oxalic acid dihydrate and sodium nitrate. These complexes were produced by heating at a temperature of 8 O 0 C or more.
- the pH of each of the treatment liquids 2A to 2H was adjusted in the range of 4.0 to 4.5 using sodium hydroxide, sodium hydrogen carbonate, sodium carbonate and/or hydrochloric acid.
- the composition of each of the treatment liquids 2A to 2H is shown in Table 3.
- the surfaces of steel components subjected to zinc plating and activation treatment by the same method as in Example 1 were treated with the treatment liquids 2A to 2H, respectively.
- the treatment condition was the same as in Example 1.
- the appearance of the conversion layer thus obtained was evaluated by the same method as in Example 1.
- Stability of each of the treatment liquids 2A to 2H was also evaluated by the same method as in Example 1. The results of evaluation are summarized in Table 3 below.
- Treatment liquids 3A to 3G in which trivalent chromium and cobalt are dissolved as complexes were prepared using chromium (III) chloride, cobalt chloride hexahydrate, oxalic acid dihydrate and sodium nitrate. These complexes were produced by heating at a temperature of 8 O 0 C or more.
- the pH of each of the treatment liquids 3A to 3G was adjusted in the range of 4.5 to 5.0 using sodium hydroxide, sodium hydrogen carbonate, sodium carbonate and/or hydrochloric acid.
- the composition of each of the treatment liquids 3A to 3G is shown in Table 4 below.
- the surfaces of steel components subjected to zinc plating and activation treatment were treated with the surface treatment liquids 3A to 3G, respectively, by the same method as in Example 1.
- the treatment condition was the same as in Example 1.
- the appearance of the conversion layer thus obtained was evaluated by the same method as in Example 1. • Stability of each of the treatment liquids 3A to 3G was also evaluated by the same method as in Example 1. The results of evaluation are summarized in Table 4.
- Treatment liquids 4A to 41 in which trivalent chromium and cobalt were dissolved as complexes were prepared using chromium (III) chloride, cobalt chloride hexahydrate, oxalic acid dihydrate and sodium nitrate. These complexes were produced by heating at a temperature of 80°C or more.
- the pH of each of the treatment liquids 4A to 41 were adjusted using sodium hydroxide, sodium hydrogen carbonate, sodium carbonate and/or hydrochloric acid.
- the composition of each of the treatment liquids 4A to 41 is shown in Table 5 below.
- Corrosion resistance of the steel component after the surface treatment was evaluated according to a method of salt spray testing prescribed in JIS Z2371 (2000). Area ratios of white rust appeared on the steel component to the total area of the component (referred to as white rusting ratio) were measured when the salt spray testing was continued for 100 hours and 200 hours, respectively. Corrosion resistance is usually judged to be sufficient for the black conversion layer when the white rusting ratio after a continuous salt spray testing for 96 hours is less than 10%.
- the appearance of the conversion layer was improved by increasing the treatment time.
- the corrosion resistance of the conversion layer was improved by prolonging the treatment time, while it was deteriorated by further prolonging the treatment time.
Abstract
An object of the present invention is to enhance the stability of a hexavalent chromium-free surface treatment liquid for forming a black conversion layer. According to the present invention, there is provided a hexavalent chromium-free surface treatment solution for forming a black conversion layer on zinc or zinc alloy, containing trivalent chromium, an organic acid, an inorganic acid, and a coloring material which makes the conversion layer black, wherein the coloring material contains metal whose concentration in the solution falls within a range of 0.01 g/L to 3 g/L, wherein a molar ratio of the sum of the metal in the coloring material and trivalent chromium with respect to carboxy group falls within a range of 0.1 to 0.3, and wherein a pH value of the solution is equal to or larger than 3 and smaller than 6.
Description
D E S C R I P T I O N
SURFACE TREATMENT LIQUID AND METHOD OF FORMING CONVERSION LAYER
Technical Field
The present invention relates to a surface treatment liquid and a method of forming a conversion layer. More specifically, the invention relates to a surface treatment liquid to form a black conversion layer, and a method of forming the conversion layer using the liquid.
Background Art
Metal components are often plated with zinc or a zinc alloy for preventing corrosion of the metal.
Corrosion of zinc or a zinc alloy may be suppressed by subjecting the plated metal components to chromate treatment, and corrosion of the metal component as a base metal may be largely retarded as compared with the metal component not subjected to the chromate treatment.
A surface treatment liquid containing hexavalent chromium has been used for the chromate treatment. However, since hexavalent chromium is a harmful substance, use thereof has been regulated.
Accordingly, chromate treatment without using any hexavalent chromium as disclosed, for example, in Jpn. Pat. Appln. KOKAI Publication No. 2000-509434 has been
noticed.
Jpn. Pat. Appln. KOKAI Publication No. 2000-509434 also describes use of dyes, pigments and coloring matter forming agents. Among the colored conversion layers, the black conversion layer can be widely applied because it is excellent in decorative effects and serves for preventing workers from mistaking a component for a similar component. Accordingly, the chromate treatment disclosed- in Jpn. Pat. Appln. KOKAI Publication No. 2000-509434 is expected to be utilized for forming the black conversion layer as well as for forming colorless conversion layers.
However, the present inventors have found the following fact in the course of achieving the present invention. Precipitates are produced in the liquid when the treatment liquid according to Jpn. Pat. Appln. KOKAI Publication No. 2000-509434, which is prepared for forming the black conversion layer, is used for treating a metal component followed by using the liquid for treating another metal component on the next day. Consequently, the properties of the conversion layer, for example the density of the black color and corrosion resistance of the film, may be sometimes insufficient. This means that the treatment liquid still has room for improvement with respect to stability.
Disclosure of Invention
An object of the present invention is to enhance the stability of the hexavalent chromium-free surface treatment liquid for forming the black conversion layer.
According to a first aspect of the present invention, there is provided a hexavalent chromium-free surface treatment solution for forming a black conversion layer on zinc or zinc alloy, comprising trivalent chromium, an organic acid, an inorganic acid, and a coloring material which makes the conversion layer black, wherein the coloring material contains metal whose concentration in the solution falls within a range of 0.01 g/L to 3 g/L, wherein a molar ratio of the sum of the metal in the coloring material and trivalent chromium with respect to carboxy group falls within a range of 0.1 to 0.3, and wherein a pH value of the solution is equal to or larger than 3 and smaller than- 6. According to a second aspect of the present invention, there is provided a method of manufacturing a conversion layer, comprising subjecting zinc or zinc alloy to a surface treatment using the surface treatment solution according to the first aspect. Best Mode for Carrying Out the Invention
An embodiment of the present invention will be described below.
A surface treatment liquid according to the present embodiment is used for forming a black conversion layer on zinc or a zinc alloy. The surface treatment liquid contains no hexavalent chromium, and typically contains no phosphorous and no sulfur.
The surface treatment liquid contains trivalent chromium, an organic acid, an inorganic acid, and a coloring material for coloring the conversion layer black. The surface treatment liquid typically contains water as a solvent.
Trivalent chromium forms a complex, typically a chelate complex, having the organic acid as a ligand, and the chelate complex is dissolved in the solution. The surface treatment liquid may contain either one kind of a trivalent chromium complex, or at least two kinds of trivalent chromium complexes.
The concentration of trivalent chromium is, for example, in the range of 1 g/L to 20 g/L, preferably 5 g/L to 10 g/L. When the concentration of trivalent chromium is low, the density of the black color of the black conversion layer obtained by using the surface treatment liquid may be insufficient. When the concentration of trivalent chromium is high, on the other hand, stability of the surface treatment liquid may be insufficient.
The coloring material contains a metal such as iron, cobalt, nickel or copper. The metal forms a
complex, typically a chelate complex, having an organic acid as a ligand, and the complex is dissolved in the solution. The surface treatment liquid may contain one kind of the complex, or at least two kind of the complexes .
The concentration of the metal contained in the coloring material in the surface treatment liquid is in the range of 0.01 g/L to 3 g/L, preferably in the range of 0.1 g/L to 1.0 g/L, and more preferably in the range of 0.3 g/L to 1.0 g/L. The density of the black color of the black conversion layer obtained may be insufficient when the concentration of the metal is low, while stability of the surface treatment liquid may be insufficient when the concentration of the metal is high.
The organic acid includes monocarboxylic acids, polycarboxylic acids or a mixture thereof, typically dicarboxylic acids used for chelating ligands. Examples of the organic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, phthalic acid, terephthalic acid, tartaric acid, citric acid, malic acid and ascorbic acid, and a mixture thereof. A molar ratio of a sum of the metal contained in the coloring material and trivalent chromium to carboxylic groups is in the range of 0.1 to 0.3,
preferably in the range of 0.15 to 0.25. Stability of the surface treatment liquid may be insufficient when the ratio is small. On the other hand, the density of the black color of the black conversion layer obtained by using the surface treatment liquid may be insufficient when the molar ratio is large.
The inorganic acid is, for example, hydrochloric acid or nitric acid, or a mixture thereof. Phosphoric acid or sulfuric acid may be 'also used as the inorganic acid. However, phosphoric acid imposes a great burden on effluent treatment. On the other hand, since treatment of a solution containing sulfur discharges strong odor, a quite expensive plant investment is required for a good workability. The concentration of the inorganic acid in the surface treatment liquid is adjusted so that pH of the treatment liquid falls within a range of 3 or more and less than 6, preferably within the range of 3.5 to 5. Stability of the surface treatment liquid may be insufficient while the density of the black color of the black conversion layer is insufficient, when the pH is small or large.
The surface treatment liquid may further contain other components. For example, the surface treatment liquid may further contain a filler such as colloidal silica, a surfactant and a corrosion inhibitor.
A conversion layer can be formed on zinc or a zinc
alloy by the following method using the surface treatment liquid.
A metal component made of zinc or zinc alloy is prepared at first. Alternatively, a metal component made of iron or steel is prepared and is plated with zinc or zinc alloy. The kind of a plating bath used herein is not particularly restricted. For example, a chloride bath, cyanide-free bath or cyanide bath may be used. Then, the metal component is immersed in the surface treatment liquid. The temperature of the surface treatment liquid is about 40°C or more and typically 70°C or less. The immersion time may be in the range of 30 seconds to 120 seconds. The bath may be agitated by, for example, shaking agitation or air agitation while the metal component is immersed in the surface treatment liquid.
After pulling up the metal component from the surface treatment liquid, it is optionally washed with water, and is dried. A conversion layer can be formed on zinc or zinc alloy as described above. Conventionally used treatment methods using a rack, barrel or cage may be used for the surface treatment. An overcoat layer containing an organic or inorganic substance may be formed on the conversion layer, or an electrodeposition coating layer may be formed. The overcoat layer and electrodeposition
coating layer may be used for modifying the appearance, for further improving corrosion resistance and for adjusting a torque of the metal component.
Examples of the invention will be described below. (Example 1)
In this example, effects of the concentration of an organic acid in a surface treatment liquid on the color of a conversion layer and stability of the treatment liquid were investigated. A plurality of steel components was plated with zinc. The thickness of each plating layer was 10 μm or more. Then, the plated components were thoroughly washed with water before subjecting to an activation treatment. In this activation treatment, the steel component was immersed in an aqueous of nitric acid.
After thoroughly washed with water, the activated steel components were subjected to surface treatments using treatment liquids IA to IG, respectively, in which trivalent chromium and cobalt were dissolved as respective complexes.
The treatment liquids IA to IG were prepared using chromium (III) chloride, cobalt chloride hexahydrate, oxalic acid dihydrate and sodium nitrate. The complexes contained in the treatment liquids IA to IG were produced by heating at a temperature of 80°C or more. The treatment temperature was set at 60°C and the immersion time was 45 seconds in each surface
treatment using the treatment liquids IA to IG. The pH of each of the treatment liquids IA to IG was adjusted in the range of 4.5 to 5.0 using sodium hydroxide, sodium hydrogen carbonate, sodium carbonate and/or hydrochloric acid. The composition of each of the treatment liquids IA to IG is shown in Table 1 below.
Table 1
In Table 1, the ratio (MCr+MCo) /MC00H shows the molar ratio of the sum of trivalent chromium and cobalt to the carboxylic group.
The appearance, specifically the color, of the conversion layer thus obtained was visually evaluated. In this evaluation, as shown in Table 2 below, the surface showing a deep black color without any interference colors was evaluated as "A", the surface showing a deep- black color with some interference colors was evaluated as "B", the surface showing a pale black color was evaluated as "C", the surface showing a gray color (partially a cloudy black color) was evaluated as "D", and the surface showing a clear silver-white color was evaluated as "E". The results of evaluation are summarized in Table 1 above.
IV)
As shown in Table 1, the appearance of the conversion layer was poor when the ratio (MCr+MCo) /MCOOH was large. On the other hand, the stability of the surface treatment liquid was improved as the ratio (MCX-H-MQ0) /McooH was increased. (Example 2)
In this example, effects of the concentration of cobalt in a surface treatment liquid on the color of a conversion layer and stability of the treatment liquid were investigated.
Treatment liquids 2A to 2H in which trivalent chromium and cobalt are dissolved as complexes were prepared using chromium (III) chloride, cobalt chloride hexahydrate, oxalic acid dihydrate and sodium nitrate. These complexes were produced by heating at a temperature of 8 O0C or more. The pH of each of the treatment liquids 2A to 2H was adjusted in the range of 4.0 to 4.5 using sodium hydroxide, sodium hydrogen carbonate, sodium carbonate and/or hydrochloric acid. The composition of each of the treatment liquids 2A to 2H is shown in Table 3.
The surfaces of steel components subjected to zinc plating and activation treatment by the same method as in Example 1 were treated with the treatment liquids 2A to 2H, respectively. The treatment condition was the same as in Example 1. The appearance of the conversion layer thus obtained was evaluated by the same method as
in Example 1. Stability of each of the treatment liquids 2A to 2H was also evaluated by the same method as in Example 1. The results of evaluation are summarized in Table 3 below.
Table 3
H-1 Oi
As shown in Table 3, the appearance of the conversion layer was improved as the concentration of cobalt was increased. On the other hand, the stability of the surface treatment liquid was decreased as the concentration of cobalt was increased. (Example 3)
In this example, effects of the concentration of chromium in a surface treatment liquid on the color of a conversion layer and stability of the treatment liquid were investigated by the following method.
Treatment liquids 3A to 3G in which trivalent chromium and cobalt are dissolved as complexes were prepared using chromium (III) chloride, cobalt chloride hexahydrate, oxalic acid dihydrate and sodium nitrate. These complexes were produced by heating at a temperature of 8 O0C or more. The pH of each of the treatment liquids 3A to 3G was adjusted in the range of 4.5 to 5.0 using sodium hydroxide, sodium hydrogen carbonate, sodium carbonate and/or hydrochloric acid. The composition of each of the treatment liquids 3A to 3G is shown in Table 4 below.
The surfaces of steel components subjected to zinc plating and activation treatment were treated with the surface treatment liquids 3A to 3G, respectively, by the same method as in Example 1. The treatment condition was the same as in Example 1. The appearance of the conversion layer thus obtained was evaluated by
the same method as in Example 1. • Stability of each of the treatment liquids 3A to 3G was also evaluated by the same method as in Example 1. The results of evaluation are summarized in Table 4.
Table 4
OO
As shown in Table 4, the appearance of the conversion layer was improved as the concentration of trivalent chromium was increased. On the other hand, the stability of the surface treatment liquid was decreased as the concentration of trivalent chromium was increased. (Example 4)
In this example, effects of pH value of a surface treatment liquid on the color and corrosion resistance, respectively, of a conversion layer were investigated by the following method.
Treatment liquids 4A to 41 in which trivalent chromium and cobalt were dissolved as complexes were prepared using chromium (III) chloride, cobalt chloride hexahydrate, oxalic acid dihydrate and sodium nitrate. These complexes were produced by heating at a temperature of 80°C or more. The pH of each of the treatment liquids 4A to 41 were adjusted using sodium hydroxide, sodium hydrogen carbonate, sodium carbonate and/or hydrochloric acid. The composition of each of the treatment liquids 4A to 41 is shown in Table 5 below.
Then, the surfaces of steel components subjected to zinc plating and activation treatment by the same method as in Example 1 were treated with treatment liquids 2A to 2H. The treatment condition was the same as in Example 1. The appearance of the conversion
layer thus obtained was evaluated by the same method as in Example 1. The results of evaluation are summarized in Table 5 below.
Corrosion resistance of the steel component after the surface treatment was evaluated according to a method of salt spray testing prescribed in JIS Z2371 (2000). Area ratios of white rust appeared on the steel component to the total area of the component (referred to as white rusting ratio) were measured when the salt spray testing was continued for 100 hours and 200 hours, respectively. Corrosion resistance is usually judged to be sufficient for the black conversion layer when the white rusting ratio after a continuous salt spray testing for 96 hours is less than 10%.
As shown in Table 6, the result is evaluated as "A" when no white rust appears after 200 hours' continuous test; as "B" when no white rust appears after 100 hours' continuous test but the white rusting ratio is more than 0% and less than 10% after
200 hours' continuous test; as "C" when no white rust appears after 100 hours' continuous test but the white rusting ratio is 10% or more after 200 hours' continuous test; as "D" when the white rusting ratio is more than 0% and less than 10% after 100 hours' continuous test and is 10% or more after 200 hours' continuous test; and as "E" when the white rusting
ratio is 10% or more after 100 hours' continuous test The results of evaluation are summarized in Table 5.
Table 5
ND
[V)
Table 6
IV) LO
As shown in Table 5, the appearance and corrosion resistance of the conversion layer were improved by increasing the pH value, while they were largely deteriorated by further increasing the pH value. (Example 5)
In this example, effects of a surface treatment temperature on the color and corrosion resistance of a conversion layer were investigated by the following method. The surfaces of steel components subjected to zinc plating and activation treatment by the same method as in Example 1 were treated with a treatment liquid 4E. The treatment condition was the same as in Example 1, except that the treatment temperature was changed as shown in Table 7 below. The appearance of the conversion layer thus obtained was evaluated by the same method as in Example 1. Subsequently, corrosion resistance of the steel component after the surface treatment was evaluated by the same method as in Example 4. The results of evaluation are summarized in Table 7.
Table 7
As shown in Table 1, the appearance and corrosion resistance of the conversion layer were improved by increasing the treatment temperature, while they were deteriorated by further increasing the temperature. (Example 6)
In this example, effects of a surface treatment time on the color and corrosion resistance of a conversion layer were investigated by the following method. The surfaces of steel components subjected to zinc plating and activation treatment by the same method as in Example 1 was treated with a treatment liquid 4E. The treatment condition was the same as in Example 1, except that the treatment time was changed as shown in Table 8 below. The appearance of the conversion layer thus obtained was evaluated by the same method as in Example 1. Subsequently, corrosion resistance of the steel component after the surface treatment was evaluated by the same method as in Example 4. The results of evaluation are summarized in Table 8.
Table 8
K)
As shown in Table 8, the appearance of the conversion layer was improved by increasing the treatment time. On the other hand, the corrosion resistance of the conversion layer was improved by prolonging the treatment time, while it was deteriorated by further prolonging the treatment time.
Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.
Claims
1. A hexavalent chromium-free surface treatment solution for forming a black conversion layer on zinc or zinc alloy, comprising: trivalent chromium, an organic acid, an inorganic acid, and a coloring material which makes the conversion layer black, wherein the coloring material contains metal whose concentration in the solution falls within a range of 0.01 g/L to 3 g/L, wherein a molar ratio of the sum of the metal in the coloring material and trivalent chromium with respect to carboxy group falls within a range of 0.1 to 0.3, and wherein a pH value of the solution is equal to or larger than 3 and smaller than 6.
2. The surface treatment solution according to claim 1, wherein a concentration of trivalent chromium in the solution falls within a range of 1 g/L to 20 g/L.
3. The surface treatment solution according to claim 1, wherein the organic acid includes a dicarboxylic acid.
4. The surface treatment solution according to claim 1, wherein the pH value falls within a range of
3.5 to 5.0.
5. A method of manufacturing a conversion layer,
comprising: subjecting zinc or zinc alloy to a surface treatment using the surface treatment solution according to claim 1.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2005167327A JP4429214B2 (en) | 2005-06-07 | 2005-06-07 | Surface treatment liquid and method for forming chemical conversion film |
| JP2005-167327 | 2005-06-07 |
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| WO2006132426A2 true WO2006132426A2 (en) | 2006-12-14 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008107039A1 (en) * | 2007-03-05 | 2008-09-12 | Atotech Deutschland Gmbh | Chromium(vi)-free black passivation of surfaces containing zinc |
| JP2009299179A (en) * | 2008-06-17 | 2009-12-24 | Pangang Group Research Inst Co Ltd | Composition containing silica sol, production method therefor, and self-lubricating galvanized metallic material using the composition |
| EP2735626A2 (en) * | 2007-08-03 | 2014-05-28 | Dipsol Chemicals Co., Ltd. | Corrosion-resistant trivalent-chromium chemical conversion coating and solution for trivalent-chromium chemical treatment |
| US10400338B2 (en) | 2017-05-12 | 2019-09-03 | Chemeon Surface Technology, Llc | pH stable trivalent chromium coating solutions |
| WO2020079215A1 (en) * | 2018-10-19 | 2020-04-23 | Atotech Deutschland Gmbh | A method for electrolytically passivating a surface of silver, silver alloy, gold, or gold alloy |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE502006003710D1 (en) * | 2006-01-31 | 2009-06-25 | Atotech Deutschland Gmbh | Aqueous reaction solution and process for the passivation of zinc and zinc alloys |
| JP5110505B2 (en) * | 2007-04-04 | 2012-12-26 | 奥野製薬工業株式会社 | Composition for overcoat for chemical conversion film formed on zinc or zinc alloy |
| JP5110504B2 (en) * | 2007-04-04 | 2012-12-26 | 奥野製薬工業株式会社 | Composition for forming black chemical conversion film |
| CN102011118B (en) * | 2010-12-24 | 2012-09-26 | 杭州东方表面技术有限公司 | Trivalent chromium passivating agent for zinc and zinc alloy coatings |
| JP6101921B2 (en) * | 2011-12-22 | 2017-03-29 | 日本表面化学株式会社 | Pretreatment liquid for coating and coating method |
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| US20040156999A1 (en) * | 2003-02-07 | 2004-08-12 | Pavco, Inc. | Black trivalent chromium chromate conversion coating |
| EP1484432A1 (en) * | 2002-03-14 | 2004-12-08 | Dipsol Chemicals Co., Ltd. | Treating solution for forming black hexavalent chromium-free chemical coating on zinc or zinc alloy plated substrate, and method for forming black hexavalent chromium-free chemical coating on zinc or zinc alloy plated substrate |
| JP2004346360A (en) * | 2003-05-21 | 2004-12-09 | Okuno Chem Ind Co Ltd | Composition for depositing black chemical conversion coating |
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- 2005-06-07 JP JP2005167327A patent/JP4429214B2/en not_active Expired - Fee Related
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| EP1484432A1 (en) * | 2002-03-14 | 2004-12-08 | Dipsol Chemicals Co., Ltd. | Treating solution for forming black hexavalent chromium-free chemical coating on zinc or zinc alloy plated substrate, and method for forming black hexavalent chromium-free chemical coating on zinc or zinc alloy plated substrate |
| US20040156999A1 (en) * | 2003-02-07 | 2004-08-12 | Pavco, Inc. | Black trivalent chromium chromate conversion coating |
| JP2004346360A (en) * | 2003-05-21 | 2004-12-09 | Okuno Chem Ind Co Ltd | Composition for depositing black chemical conversion coating |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008107039A1 (en) * | 2007-03-05 | 2008-09-12 | Atotech Deutschland Gmbh | Chromium(vi)-free black passivation of surfaces containing zinc |
| EP1970470A1 (en) * | 2007-03-05 | 2008-09-17 | Atotech Deutschland Gmbh | Chrome(VI)-free black passivates for surfaces containing zinc |
| US8460534B2 (en) | 2007-03-05 | 2013-06-11 | Atotech Deutschland Gmbh | Chromium(VI)-free black passivation of surfaces containing zinc |
| EP2735626A2 (en) * | 2007-08-03 | 2014-05-28 | Dipsol Chemicals Co., Ltd. | Corrosion-resistant trivalent-chromium chemical conversion coating and solution for trivalent-chromium chemical treatment |
| EP2735626A3 (en) * | 2007-08-03 | 2014-10-22 | Dipsol Chemicals Co., Ltd. | Corrosion-resistant trivalent-chromium chemical conversion coating and solution for trivalent-chromium chemical treatment |
| US11643732B2 (en) | 2007-08-03 | 2023-05-09 | Dipsol Chemicals Co., Ltd. | Corrosion-resistant trivalent-chromium chemical conversion coating and solution for trivalent-chromium chemical treatment |
| JP2009299179A (en) * | 2008-06-17 | 2009-12-24 | Pangang Group Research Inst Co Ltd | Composition containing silica sol, production method therefor, and self-lubricating galvanized metallic material using the composition |
| EP2138606A1 (en) | 2008-06-17 | 2009-12-30 | PanGang Group Research Institute Co., Ltd. | A composition containing silica sol, its preparation method, and galvanized self-lubricating metal material using the composition |
| US10400338B2 (en) | 2017-05-12 | 2019-09-03 | Chemeon Surface Technology, Llc | pH stable trivalent chromium coating solutions |
| WO2020079215A1 (en) * | 2018-10-19 | 2020-04-23 | Atotech Deutschland Gmbh | A method for electrolytically passivating a surface of silver, silver alloy, gold, or gold alloy |
| US11447884B2 (en) | 2018-10-19 | 2022-09-20 | Atotech Deutschland GmbH & Co. KG | Method for electrolytically passivating a surface of silver, silver alloy, gold, or gold alloy |
| US11851780B2 (en) | 2018-10-19 | 2023-12-26 | Atotech Deutschland GmbH & Co. KG | Method for electrolytically passivating a surface of silver, silver alloy, gold, or gold alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4429214B2 (en) | 2010-03-10 |
| WO2006132426A3 (en) | 2007-02-15 |
| JP2006342376A (en) | 2006-12-21 |
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