JP2023155377A - Metal surface treatment method - Google Patents
Metal surface treatment method Download PDFInfo
- Publication number
- JP2023155377A JP2023155377A JP2023139242A JP2023139242A JP2023155377A JP 2023155377 A JP2023155377 A JP 2023155377A JP 2023139242 A JP2023139242 A JP 2023139242A JP 2023139242 A JP2023139242 A JP 2023139242A JP 2023155377 A JP2023155377 A JP 2023155377A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- metal surface
- surface treatment
- salt
- treatment method
- 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.)
- Pending
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 202
- 239000002184 metal Substances 0.000 title claims abstract description 202
- 238000004381 surface treatment Methods 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 33
- 150000003839 salts Chemical class 0.000 claims abstract description 102
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 20
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000003498 tellurium compounds Chemical class 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 11
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 21
- 238000004040 coloring Methods 0.000 claims description 19
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 17
- 150000004715 keto acids Chemical class 0.000 claims description 14
- 150000007522 mineralic acids Chemical class 0.000 claims description 14
- -1 inorganic acid salt Chemical class 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- YMUZFVVKDBZHGP-UHFFFAOYSA-N dimethyl telluride Chemical compound C[Te]C YMUZFVVKDBZHGP-UHFFFAOYSA-N 0.000 claims description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 7
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- OFDISMSWWNOGFW-UHFFFAOYSA-N 1-(4-ethoxy-3-fluorophenyl)ethanamine Chemical compound CCOC1=CC=C(C(C)N)C=C1F OFDISMSWWNOGFW-UHFFFAOYSA-N 0.000 claims description 4
- DLLMHEDYJQACRM-UHFFFAOYSA-N 2-(carboxymethyldisulfanyl)acetic acid Chemical compound OC(=O)CSSCC(O)=O DLLMHEDYJQACRM-UHFFFAOYSA-N 0.000 claims description 4
- DIZBQMTZXOUFTD-UHFFFAOYSA-N 2-(furan-2-yl)-3h-benzimidazole-5-carboxylic acid Chemical compound N1C2=CC(C(=O)O)=CC=C2N=C1C1=CC=CO1 DIZBQMTZXOUFTD-UHFFFAOYSA-N 0.000 claims description 4
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 4
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 4
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 4
- 229940005991 chloric acid Drugs 0.000 claims description 4
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 4
- 229940077239 chlorous acid Drugs 0.000 claims description 4
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 4
- 235000018417 cysteine Nutrition 0.000 claims description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- 229930182817 methionine Natural products 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 claims description 4
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims description 4
- QGMWCJPYHVWVRR-UHFFFAOYSA-N tellurium monoxide Chemical compound [Te]=O QGMWCJPYHVWVRR-UHFFFAOYSA-N 0.000 claims description 4
- IIXQANVWKBCLEB-UHFFFAOYSA-N tellurium trioxide Chemical compound O=[Te](=O)=O IIXQANVWKBCLEB-UHFFFAOYSA-N 0.000 claims description 4
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 claims description 4
- 229950006389 thiodiglycol Drugs 0.000 claims description 4
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000000174 gluconic acid Substances 0.000 claims description 3
- 235000012208 gluconic acid Nutrition 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 229940107700 pyruvic acid Drugs 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- SITVSCPRJNYAGV-UHFFFAOYSA-N tellurous acid Chemical compound O[Te](O)=O SITVSCPRJNYAGV-UHFFFAOYSA-N 0.000 claims description 3
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 claims 2
- 239000007788 liquid Substances 0.000 abstract description 74
- 238000012360 testing method Methods 0.000 description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000012736 aqueous medium Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 9
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- 229910052742 iron Inorganic materials 0.000 description 8
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- 229910000640 Fe alloy Inorganic materials 0.000 description 6
- 235000019646 color tone Nutrition 0.000 description 6
- 229910000861 Mg alloy Inorganic materials 0.000 description 5
- 229910000990 Ni alloy Inorganic materials 0.000 description 5
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
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- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
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- 238000005246 galvanizing Methods 0.000 description 1
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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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
-
- 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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 8
- C23C22/66—Treatment of aluminium or alloys based thereon
-
- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
-
- 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
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- C23C22/53—Treatment of zinc or alloys based thereon
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- 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
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- 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
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Abstract
Description
本発明は、金属表面処理方法に関する。 The present invention relates to a metal surface treatment method.
従来、種々の金属、特にアルミニウム又はアルミニウム合金の着色において、灰色系の色調を得るには陽極酸化や陽極酸化皮膜に染料を吸着させる方法が一般的である。 Conventionally, in coloring various metals, particularly aluminum or aluminum alloys, anodic oxidation or a method of adsorbing a dye to an anodic oxide film has been commonly used to obtain a gray tone.
例えば、特許文献１には、アルミニウム又はアルミニウム合金の素地表面に形成した電解発色又は自然発色による発色被膜を、電解着色可能な皮膜構造とした後、電解着色を行って、色を重ね合わせて新たな色調の皮膜を得ることを特徴とするアルミニウム及びアルミニウム合金の電解着色方法が開示されている。そして、このような構成によれば、従来の電解着色方法では得られない様々な中間色を含む種々の色調を得ることができる電解着色方法を提供することができる、と記載されている。 For example, in Patent Document 1, a colored film formed on the surface of an aluminum or aluminum alloy base material by electrolytic coloring or natural coloring is made into a film structure that can be electrolytically colored, and then electrolytically colored is applied to superimpose the colors to create a new color. A method for electrolytically coloring aluminum and aluminum alloys is disclosed, which is characterized by obtaining a film with a unique color tone. The document also states that with such a configuration, it is possible to provide an electrolytic coloring method that can obtain various color tones including various intermediate colors that cannot be obtained with conventional electrolytic coloring methods.
しかしながら、従来、金属表面を灰色系の色調に着色するには、例えば、アルミニウム又はアルミニウム合金であればアルマイトを利用する必要があった。すなわち、金属表面を灰色系の色調に着色するには、酸化膜を表面に有する金属を利用する必要があり、処理工程が多く、処理効率の改善が望まれている。 However, conventionally, in order to color a metal surface in a gray tone, it has been necessary to use alumite, for example, in the case of aluminum or an aluminum alloy. That is, in order to color the metal surface in a gray tone, it is necessary to use a metal having an oxide film on the surface, which requires many processing steps, and it is desired to improve the processing efficiency.
本発明は、このような問題に鑑み、良好な処理効率で金属表面を灰色系の色調に着色することが可能な金属表面処理方法を提供することを目的とする。 In view of these problems, an object of the present invention is to provide a metal surface treatment method that can color a metal surface in a gray tone with good treatment efficiency.
本発明者らは上記課題を解決するために鋭意検討した結果、テルル若しくはテルル化合物、又はこれらの塩を含む金属表面処理液により処理を行うことで、良好な処理効率で金属表面を灰色系の色調に着色することが可能となることを見出した。 As a result of intensive studies to solve the above problems, the present inventors have found that by treating metal surfaces with a metal surface treatment solution containing tellurium, tellurium compounds, or salts thereof, metal surfaces can be treated with a grayish color with good treatment efficiency. It has been found that it is possible to color the material in different colors.
以上の知見を基礎として完成した本発明は一側面において、テルル若しくはテルル化合物、又はこれらの塩を含む金属表面処理液である。 One aspect of the present invention, which was completed based on the above findings, is a metal surface treatment liquid containing tellurium, a tellurium compound, or a salt thereof.
本発明の金属表面処理液は一実施形態において、前記テルル若しくはテルル化合物、又はこれらの塩が、一酸化テルル、二酸化テルル、三酸化テルル、亜テルル酸、テルル酸、四塩化テルル、テルル化ジメチル、若しくはこれらの塩、又はこれらの組み合わせである。 In one embodiment of the metal surface treatment liquid of the present invention, the tellurium or tellurium compound, or a salt thereof is tellurium monoxide, tellurium dioxide, tellurium trioxide, tellurous acid, telluric acid, tellurium tetrachloride, dimethyl telluride. , or a salt thereof, or a combination thereof.
本発明の金属表面処理液は別の一実施形態において、前記テルル若しくはテルル化合物、又はこれらの塩の合計含有量が、０．５～１００ｇ／Ｌである。 In another embodiment of the metal surface treatment liquid of the present invention, the total content of the tellurium, tellurium compound, or salt thereof is 0.5 to 100 g/L.
本発明の金属表面処理液は更に別の一実施形態において、更に、無機酸若しくはその塩を含む。 In yet another embodiment, the metal surface treatment liquid of the present invention further contains an inorganic acid or a salt thereof.
本発明の金属表面処理液は更に別の一実施形態において、前記無機酸若しくはその塩が、硫酸、硝酸、塩酸、リン酸、若しくはこれらの塩、又はこれらの組み合わせである。 In yet another embodiment of the metal surface treatment liquid of the present invention, the inorganic acid or its salt is sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, a salt thereof, or a combination thereof.
本発明の金属表面処理液は更に別の一実施形態において、前記無機酸若しくはその塩の合計含有量が、１～２００ｇ／Ｌである。 In yet another embodiment of the metal surface treatment liquid of the present invention, the total content of the inorganic acid or its salt is 1 to 200 g/L.
本発明の金属表面処理液は更に別の一実施形態において、更に、有機硫黄化合物若しくはその塩を含む。 In yet another embodiment, the metal surface treatment liquid of the present invention further contains an organic sulfur compound or a salt thereof.
本発明の金属表面処理液は更に別の一実施形態において、前記有機硫黄化合物若しくはその塩が、チオ尿素、二酸化チオ尿素、チオジグリコール、ジメチルチオ尿素、チオリンゴ酸、ジチオジグリコール酸、ジメチルスルホキシド、メタンスルホン酸、ｐ－トルエンスルホン酸、ｐ－フェノールスルホン酸、チオシアン酸、システイン、メチオニン、若しくはこれらの塩、又はこれらの組み合わせである。 In yet another embodiment of the metal surface treatment liquid of the present invention, the organic sulfur compound or its salt is thiourea, thiourea dioxide, thiodiglycol, dimethylthiourea, thiomalic acid, dithiodiglycolic acid, dimethyl sulfoxide, Methanesulfonic acid, p-toluenesulfonic acid, p-phenolsulfonic acid, thiocyanic acid, cysteine, methionine, salts thereof, or combinations thereof.
本発明の金属表面処理液は更に別の一実施形態において、前記有機硫黄化合物若しくはその塩の合計含有量が、０．１～５０ｇ／Ｌである。 In yet another embodiment of the metal surface treatment liquid of the present invention, the total content of the organic sulfur compound or its salt is 0.1 to 50 g/L.
本発明の金属表面処理液は更に別の一実施形態において、更に、カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩を含む。 In yet another embodiment, the metal surface treatment liquid of the present invention further contains a carboxylic acid, a hydroxycarboxylic acid, or a salt thereof.
本発明の金属表面処理液は更に別の一実施形態において、前記カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩が、ギ酸、酢酸、プロピオン酸、乳酸、リンゴ酸、クエン酸、シュウ酸、グルコン酸、マロン酸、コハク酸、安息香酸、ピルビン酸、グリオキシル酸、ニトリロ三酢酸、エチレンジアミン四酢酸、若しくはこれらの塩、又はこれらの組み合わせである。 In yet another embodiment of the metal surface treatment liquid of the present invention, the carboxylic acid or hydroxycarboxylic acid, or a salt thereof, is formic acid, acetic acid, propionic acid, lactic acid, malic acid, citric acid, oxalic acid, gluconic acid. , malonic acid, succinic acid, benzoic acid, pyruvic acid, glyoxylic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, or a salt thereof, or a combination thereof.
本発明の金属表面処理液は更に別の一実施形態において、前記カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩の合計含有量が、０．５～１００ｇ／Ｌである。 In yet another embodiment of the metal surface treatment liquid of the present invention, the total content of the carboxylic acid, hydroxycarboxylic acid, or salt thereof is 0.5 to 100 g/L.
本発明の金属表面処理液は更に別の一実施形態において、更に、オキソ酸若しくはその塩を含む。 In yet another embodiment, the metal surface treatment liquid of the present invention further contains an oxoacid or a salt thereof.
本発明の金属表面処理液は更に別の一実施形態において、前記オキソ酸若しくはその塩が、過塩素酸、塩素酸、亜塩素酸、次亜塩素酸、臭素酸、炭酸、ホウ酸、若しくはこれらの塩、又はこれらの組み合わせである。 In yet another embodiment of the metal surface treatment liquid of the present invention, the oxo acid or its salt is perchloric acid, chloric acid, chlorous acid, hypochlorous acid, bromic acid, carbonic acid, boric acid, or any of these. salt, or a combination thereof.
本発明の金属表面処理液は更に別の一実施形態において、前記オキソ酸若しくはその塩の合計含有量が、０．５～１００ｇ／Ｌである。 In yet another embodiment of the metal surface treatment liquid of the present invention, the total content of the oxoacid or its salt is 0.5 to 100 g/L.
本発明の金属表面処理液は更に別の一実施形態において、処理対象の金属が、アルミニウム、アルミニウム合金、銅、銅合金、鉄、鉄合金、亜鉛、亜鉛合金、ニッケル、ニッケル合金、マグネシウム、及びマグネシウム合金からなる群から選択される少なくとも１種である。 In yet another embodiment of the metal surface treatment liquid of the present invention, the metal to be treated is aluminum, aluminum alloy, copper, copper alloy, iron, iron alloy, zinc, zinc alloy, nickel, nickel alloy, magnesium, and At least one member selected from the group consisting of magnesium alloys.
本発明は別の一側面において、本発明の金属表面処理液を使用して、金属に対して着色を行う工程を含む金属表面処理方法である。 In another aspect, the present invention is a metal surface treatment method including a step of coloring a metal using the metal surface treatment liquid of the present invention.
本発明の金属表面処理方法は一実施形態において、前記金属に対して着色を行う工程において、前記金属を前記金属表面処理液に１０℃～８０℃で１０秒～２０分間浸漬することで前記金属を着色する。 In one embodiment of the metal surface treatment method of the present invention, in the step of coloring the metal, the metal is immersed in the metal surface treatment solution at 10° C. to 80° C. for 10 seconds to 20 minutes. Color.
本発明によれば、良好な処理効率で金属表面を灰色系の色調に着色することが可能な金属表面処理方法を提供することができる。 According to the present invention, it is possible to provide a metal surface treatment method capable of coloring a metal surface in a gray tone with good treatment efficiency.
以下、本発明の金属表面処理液及び金属表面処理方法の実施形態について説明するが、本発明は、これに限定されて解釈されるものではなく、本発明の範囲を逸脱しない限りにおいて、当業者の知識に基づいて、種々の変更、修正、改良を加え得るものである。 Embodiments of the metal surface treatment liquid and metal surface treatment method of the present invention will be described below, but the present invention is not to be construed as being limited thereto. Various changes, modifications, and improvements may be made based on the knowledge of
〔金属表面処理液〕
本発明の実施形態に係る金属表面処理液は、テルル若しくはテルル化合物、又はこれらの塩を含む。テルル若しくはテルル化合物、又はこれらの塩を含む金属表面処理液を用いることで、処理対象の金属を当該金属表面処理液に浸漬するだけで、金属表面に皮膜（着色皮膜）を形成することができ、これにより灰色系の色調に着色することができる。このため、金属表面を灰色系の色調に着色する際に、当該金属の表面に酸化膜を形成しておく必要もなく、電解によって着色する必要もなくなり、処理効率が良好となる。また、本発明の実施形態に係る金属表面処理液によれば、金属表面に形成する皮膜（着色皮膜）の密着性も良好となる。
[Metal surface treatment liquid]
The metal surface treatment liquid according to the embodiment of the present invention contains tellurium, a tellurium compound, or a salt thereof. By using a metal surface treatment solution containing tellurium, a tellurium compound, or a salt thereof, a film (colored film) can be formed on the metal surface simply by immersing the metal to be treated in the metal surface treatment solution. , This allows coloring to a gray tone. Therefore, when a metal surface is colored in a gray tone, there is no need to form an oxide film on the surface of the metal, and there is no need to color the metal surface by electrolysis, resulting in improved processing efficiency. Moreover, according to the metal surface treatment liquid according to the embodiment of the present invention, the adhesion of the film (colored film) formed on the metal surface is also improved.
（処理対象の金属）
本発明の実施形態に係る金属表面処理液で表面を着色する対象となる金属（処理対象の金属）としては、アルミニウム、アルミニウム合金、銅、銅合金、鉄、鉄合金、亜鉛、亜鉛合金、ニッケル、ニッケル合金、マグネシウム、及びマグネシウム合金からなる群から選択される少なくとも１種が挙げられる。処理対象の金属は、当該金属自体であってもよく、例えば、鉄系材料や鉄系部品などの金属基材の表面に形成された、当該金属のメッキであってもよい。
(Metal to be processed)
Metals whose surfaces are colored with the metal surface treatment solution according to the embodiment of the present invention (metals to be treated) include aluminum, aluminum alloys, copper, copper alloys, iron, iron alloys, zinc, zinc alloys, and nickel. , a nickel alloy, magnesium, and a magnesium alloy. The metal to be processed may be the metal itself, or may be, for example, plating of the metal formed on the surface of a metal base material such as an iron-based material or an iron-based component.
（テルル若しくはテルル化合物、又はこれらの塩）
テルル若しくはテルル化合物、又はこれらの塩は、一酸化テルル、二酸化テルル、三酸化テルル、亜テルル酸、テルル酸、四塩化テルル、テルル化ジメチル、若しくはこれらの塩、又はこれらの組み合わせであるのが好ましい。一酸化テルル、二酸化テルル、三酸化テルル、亜テルル酸、テルル酸、四塩化テルル、テルル化ジメチルの塩としては、これらの金属塩、又はアンモニウム塩などを用いることができる。
(Tellurium or tellurium compounds, or salts thereof)
Tellurium or a tellurium compound, or a salt thereof, is tellurium monoxide, tellurium dioxide, tellurium trioxide, tellurite acid, telluric acid, tellurium tetrachloride, dimethyl telluride, or a salt thereof, or a combination thereof. preferable. As the salts of tellurium monoxide, tellurium dioxide, tellurium trioxide, tellurous acid, telluric acid, tellurium tetrachloride, and dimethyl telluride, metal salts thereof, ammonium salts, and the like can be used.
本発明の実施形態に係る金属表面処理液におけるテルル若しくはテルル化合物、又はこれらの塩の合計含有量は、処理対象の金属の種類、及び、どの程度の灰色系の色調に着色するかによるが、例えば、テルル若しくはテルル化合物、又はこれらの塩の合計含有量は、０．５～１００ｇ／Ｌとすることができる。基本的には、テルル若しくはテルル化合物、又はこれらの塩の合計含有量が少ないほど、金属表面を薄い灰色系の色調に着色することができる。また、テルル若しくはテルル化合物、又はこれらの塩の合計含有量が多いほど、金属表面を濃い灰色系の色調に着色することができる。テルル若しくはテルル化合物、又はこれらの塩の合計含有量は、１～５０ｇ／Ｌであることがより好ましく、２～２０ｇ／Ｌであることがより好ましい。 The total content of tellurium, tellurium compounds, or salts thereof in the metal surface treatment solution according to the embodiment of the present invention depends on the type of metal to be treated and the gray tone to be colored. For example, the total content of tellurium or tellurium compounds, or salts thereof can be 0.5 to 100 g/L. Basically, the smaller the total content of tellurium, tellurium compounds, or salts thereof, the more the metal surface can be colored in a lighter gray tone. Furthermore, the higher the total content of tellurium, tellurium compounds, or salts thereof, the more the metal surface can be colored in a darker gray tone. The total content of tellurium or tellurium compounds, or salts thereof is more preferably 1 to 50 g/L, more preferably 2 to 20 g/L.
本発明の実施形態に係る金属表面処理液は、後述のように、無機酸若しくはその塩、有機硫黄化合物若しくはその塩、カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩、オキソ酸若しくはその塩等を含んでもよいが、これらの成分を含まない金属表面処理液の場合、特にアルミニウム、アルミニウム合金などの金属表面を、より美観に優れた灰色系の色調に着色することができる。 As described below, the metal surface treatment liquid according to the embodiment of the present invention contains an inorganic acid or its salt, an organic sulfur compound or its salt, a carboxylic acid or hydroxycarboxylic acid, or a salt thereof, an oxoacid or its salt, etc. However, in the case of a metal surface treatment liquid that does not contain these components, the surface of metals such as aluminum and aluminum alloys can be colored in a gray tone with a more aesthetically pleasing appearance.
（無機酸若しくはその塩）
本発明の実施形態に係る金属表面処理液は、更に、無機酸若しくはその塩を含んでもよい。本発明の実施形態に係る金属表面処理液は、無機酸若しくはその塩を含んでも、良好な処理効率で前述の処理対象の金属表面を灰色系の色調に着色することができる。また、本発明の実施形態に係る金属表面処理液は、無機酸若しくはその塩を含むことにより、金属溶解が促進し金属表面のｐＨが上昇することで着色皮膜が形成される反応が促進されるため、特に銅、銅合金、鉄、鉄合金、亜鉛、亜鉛合金、ニッケル、ニッケル合金、マグネシウム、マグネシウム合金などの金属の表面を、より美観に優れた灰色系の色調に着色することができる。
(Inorganic acid or its salt)
The metal surface treatment liquid according to the embodiment of the present invention may further contain an inorganic acid or a salt thereof. Even if the metal surface treatment liquid according to the embodiment of the present invention contains an inorganic acid or its salt, it can color the metal surface to be treated in a gray tone with good treatment efficiency. Furthermore, the metal surface treatment solution according to the embodiment of the present invention contains an inorganic acid or a salt thereof, thereby promoting metal dissolution and increasing the pH of the metal surface, thereby promoting a reaction in which a colored film is formed. Therefore, the surface of metals such as copper, copper alloys, iron, iron alloys, zinc, zinc alloys, nickel, nickel alloys, magnesium, and magnesium alloys can be particularly colored in gray tones that are more aesthetically pleasing.
無機酸若しくはその塩が、硫酸、硝酸、塩酸、リン酸、若しくはこれらの塩、又はこれらの組み合わせであるのが好ましい。硫酸、硝酸、塩酸、リン酸の塩としては、これらの金属塩、又はアンモニウム塩などを用いることができる。 Preferably, the inorganic acid or salt thereof is sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, or a salt thereof, or a combination thereof. As the salts of sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid, metal salts or ammonium salts thereof can be used.
本発明の実施形態に係る金属表面処理液における無機酸若しくはその塩の合計含有量は、１～２００ｇ／Ｌとすることができる。基本的には、無機酸若しくはその塩の合計含有量が少ないほど、金属表面を薄い灰色系の色調に着色することができる。また、無機酸若しくはその塩の合計含有量が多いほど、金属表面を濃い灰色系の色調に着色することができる。無機酸若しくはその塩の合計含有量は、１０～１５０ｇ／Ｌであることがより好ましく、７０～１２０ｇ／Ｌであることがより好ましい。 The total content of inorganic acids or salts thereof in the metal surface treatment liquid according to the embodiment of the present invention can be 1 to 200 g/L. Basically, the smaller the total content of inorganic acids or salts thereof, the more the metal surface can be colored in a lighter gray tone. Moreover, the larger the total content of the inorganic acid or its salt, the more the metal surface can be colored in a dark gray tone. The total content of inorganic acids or salts thereof is more preferably 10 to 150 g/L, more preferably 70 to 120 g/L.
（有機硫黄化合物若しくはその塩）
本発明の実施形態に係る金属表面処理液は、更に、有機硫黄化合物若しくはその塩を含んでもよい。本発明の実施形態に係る金属表面処理液は、有機硫黄化合物若しくはその塩を含んでも、良好な処理効率で前述の処理対象の金属表面を灰色系の色調に着色することができる。また、本発明の実施形態に係る金属表面処理液は、有機硫黄化合物若しくはその塩を含むことにより、有機硫黄化合物によって金属溶解が促進し金属表面のｐＨが上昇することで着色皮膜が形成される反応が促進される。このため、特に銅、銅合金、ニッケル、ニッケル合金などの金属の表面を、より美観に優れた灰色系の色調に着色することができる。
(Organic sulfur compound or its salt)
The metal surface treatment liquid according to the embodiment of the present invention may further contain an organic sulfur compound or a salt thereof. Even if the metal surface treatment liquid according to the embodiment of the present invention contains an organic sulfur compound or its salt, it can color the metal surface to be treated in a gray tone with good treatment efficiency. Furthermore, since the metal surface treatment liquid according to the embodiment of the present invention contains an organic sulfur compound or a salt thereof, the organic sulfur compound promotes metal dissolution and increases the pH of the metal surface, thereby forming a colored film. The reaction is accelerated. Therefore, the surface of metals such as copper, copper alloys, nickel, and nickel alloys can be colored in a gray tone with a more aesthetically pleasing appearance.
有機硫黄化合物若しくはその塩が、チオ尿素、二酸化チオ尿素、チオジグリコール、ジメチルチオ尿素、チオリンゴ酸、ジチオジグリコール酸、ジメチルスルホキシド、メタンスルホン酸、ｐ－トルエンスルホン酸、ｐ－フェノールスルホン酸、チオシアン酸、システイン、メチオニン、若しくはこれらの塩、又はこれらの組み合わせであるのが好ましい。チオ尿素、二酸化チオ尿素、チオジグリコール、ジメチルチオ尿素、チオリンゴ酸、ジチオジグリコール酸、ジメチルスルホキシド、メタンスルホン酸、ｐ－トルエンスルホン酸、ｐ－フェノールスルホン酸、チオシアン酸、システイン、メチオニンの塩としては、これらの金属塩、又はアンモニウム塩などを用いることができる。 The organic sulfur compound or its salt is thiourea, thiourea dioxide, thiodiglycol, dimethylthiourea, thiomalic acid, dithiodiglycolic acid, dimethylsulfoxide, methanesulfonic acid, p-toluenesulfonic acid, p-phenolsulfonic acid, thiocyanide. Preferably, it is an acid, cysteine, methionine, or a salt thereof, or a combination thereof. As salts of thiourea, thiourea dioxide, thiodiglycol, dimethylthiourea, thiomalic acid, dithiodiglycolic acid, dimethylsulfoxide, methanesulfonic acid, p-toluenesulfonic acid, p-phenolsulfonic acid, thiocyanic acid, cysteine, and methionine. These metal salts or ammonium salts can be used.
本発明の実施形態に係る金属表面処理液における有機硫黄化合物若しくはその塩の合計含有量は、０．１～５０ｇ／Ｌとすることができる。基本的には、有機硫黄化合物若しくはその塩の合計含有量が少ないほど、金属表面を薄い灰色系の色調に着色することができる。また、有機硫黄化合物若しくはその塩の合計含有量が多いほど、金属表面を濃い灰色系の色調に着色することができる。有機硫黄化合物若しくはその塩の合計含有量は、１～３０ｇ／Ｌであることがより好ましく、５～１５ｇ／Ｌであることがより好ましい。 The total content of organic sulfur compounds or salts thereof in the metal surface treatment liquid according to the embodiment of the present invention can be 0.1 to 50 g/L. Basically, the smaller the total content of organic sulfur compounds or their salts, the more the metal surface can be colored in a lighter gray tone. Moreover, the larger the total content of the organic sulfur compound or its salt, the more the metal surface can be colored in a dark gray tone. The total content of organic sulfur compounds or salts thereof is more preferably 1 to 30 g/L, more preferably 5 to 15 g/L.
（カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩）
本発明の実施形態に係る金属表面処理液は、更に、カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩を含んでもよい。本発明の実施形態に係る金属表面処理液は、カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩を含んでも、良好な処理効率で前述の処理対象の金属表面を灰色系の色調に着色することができる。また、本発明の実施形態に係る金属表面処理液は、カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩を含むことにより、カルボン酸若しくはヒドロキシカルボン酸がテルルとキレートすることで着色反応が抑制され緻密な皮膜が形成されやすくなる。このため、特に銅、銅合金、鉄、鉄合金、亜鉛、亜鉛合金などの金属の表面を、より美観に優れた灰色系の色調に着色することができる。
(Carboxylic acid or hydroxycarboxylic acid, or salt thereof)
The metal surface treatment liquid according to the embodiment of the present invention may further contain a carboxylic acid, a hydroxycarboxylic acid, or a salt thereof. Even if the metal surface treatment liquid according to the embodiment of the present invention contains a carboxylic acid, a hydroxycarboxylic acid, or a salt thereof, it is possible to color the metal surface to be treated in a gray tone with good treatment efficiency. can. Furthermore, since the metal surface treatment liquid according to the embodiment of the present invention contains a carboxylic acid, a hydroxycarboxylic acid, or a salt thereof, the carboxylic acid or hydroxycarboxylic acid chelates with tellurium, thereby suppressing a coloring reaction and creating a dense structure. A film is more likely to form. Therefore, the surface of metals such as copper, copper alloys, iron, iron alloys, zinc, and zinc alloys can be colored in a gray tone with a more aesthetically pleasing appearance.
カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩が、ギ酸、酢酸、プロピオン酸、乳酸、リンゴ酸、クエン酸、シュウ酸、グルコン酸、マロン酸、コハク酸、安息香酸、ピルビン酸、グリオキシル酸、ニトリロ三酢酸、エチレンジアミン四酢酸、若しくはこれらの塩、又はこれらの組み合わせであるのが好ましい。ギ酸、酢酸、プロピオン酸、乳酸、リンゴ酸、クエン酸、シュウ酸、グルコン酸、マロン酸、コハク酸、安息香酸、ピルビン酸、グリオキシル酸、ニトリロ三酢酸、エチレンジアミン四酢酸の塩としては、これらの金属塩、又はアンモニウム塩などを用いることができる。 Carboxylic acids or hydroxycarboxylic acids, or salts thereof, are Preferably, it is triacetic acid, ethylenediaminetetraacetic acid, or a salt thereof, or a combination thereof. The salts of formic acid, acetic acid, propionic acid, lactic acid, malic acid, citric acid, oxalic acid, gluconic acid, malonic acid, succinic acid, benzoic acid, pyruvic acid, glyoxylic acid, nitrilotriacetic acid, and ethylenediaminetetraacetic acid include Metal salts, ammonium salts, etc. can be used.
本発明の実施形態に係る金属表面処理液におけるカルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩の合計含有量は、０．５～１００ｇ／Ｌとすることができる。基本的には、カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩の合計含有量が少ないほど、金属表面を濃い灰色系の色調に着色することができる。また、カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩の合計含有量が多いほど、金属表面を薄い灰色系の色調に着色することができる。カルボン酸若しくはヒドロキシカルボン酸、又はこれらの塩の合計含有量は、１～５０ｇ／Ｌであることがより好ましく、１０～３０ｇ／Ｌであることがより好ましい。 The total content of carboxylic acids, hydroxycarboxylic acids, or salts thereof in the metal surface treatment liquid according to the embodiment of the present invention can be 0.5 to 100 g/L. Basically, the smaller the total content of carboxylic acids, hydroxycarboxylic acids, or salts thereof, the more the metal surface can be colored in a darker gray tone. Furthermore, the greater the total content of carboxylic acids, hydroxycarboxylic acids, or salts thereof, the more the metal surface can be colored in a lighter gray tone. The total content of carboxylic acids, hydroxycarboxylic acids, or salts thereof is more preferably 1 to 50 g/L, more preferably 10 to 30 g/L.
（オキソ酸若しくはその塩）
本発明の実施形態に係る金属表面処理液は、更に、オキソ酸若しくはその塩を含んでもよい。本発明の実施形態に係る金属表面処理液は、オキソ酸若しくはその塩を含んでも、良好な処理効率で前述の処理対象の金属表面を灰色系の色調に着色することができる。また、本発明の実施形態に係る金属表面処理液は、オキソ酸若しくはその塩を含むことにより、特に銅、銅合金、鉄、鉄合金、亜鉛、亜鉛合金などの金属の表面を、より美観に優れた灰色系の色調に着色することができる。
(Oxoacid or its salt)
The metal surface treatment liquid according to the embodiment of the present invention may further contain an oxoacid or a salt thereof. Even if the metal surface treatment liquid according to the embodiment of the present invention contains an oxoacid or its salt, it can color the metal surface to be treated in a gray tone with good treatment efficiency. In addition, the metal surface treatment liquid according to the embodiment of the present invention contains an oxoacid or a salt thereof, thereby making the surface of metals such as copper, copper alloys, iron, iron alloys, zinc, and zinc alloys more aesthetically pleasing. Can be colored to a nice gray tone.
オキソ酸若しくはその塩が、過塩素酸、塩素酸、亜塩素酸、次亜塩素酸、臭素酸、炭酸、ホウ酸、若しくはこれらの塩、又はこれらの組み合わせであるのが好ましい。過塩素酸、塩素酸、亜塩素酸、次亜塩素酸、臭素酸、炭酸、ホウ酸の塩としては、これらの金属塩、又はアンモニウム塩などを用いることができる。 Preferably, the oxoacid or salt thereof is perchloric acid, chloric acid, chlorous acid, hypochlorous acid, bromic acid, carbonic acid, boric acid, or a salt thereof, or a combination thereof. As the salts of perchloric acid, chloric acid, chlorous acid, hypochlorous acid, bromic acid, carbonic acid, and boric acid, metal salts or ammonium salts thereof can be used.
本発明の実施形態に係る金属表面処理液におけるオキソ酸若しくはその塩の合計含有量は、０．５～１００ｇ／Ｌとすることができる。基本的には、オキソ酸若しくはその塩の合計含有量が少ないほど、金属表面を薄い灰色系の色調に着色することができる。また、オキソ酸若しくはその塩の合計含有量が多いほど、金属表面を濃い灰色系の色調に着色することができる。オキソ酸若しくはその塩の合計含有量は、１～５０ｇ／Ｌであることがより好ましく、１０～３０ｇ／Ｌであることがより好ましい。 The total content of oxoacid or its salt in the metal surface treatment liquid according to the embodiment of the present invention can be 0.5 to 100 g/L. Basically, the smaller the total content of oxoacid or its salt, the more the metal surface can be colored in a lighter gray tone. Moreover, the larger the total content of oxoacid or its salt is, the more the metal surface can be colored in a dark gray tone. The total content of oxo acids or salts thereof is more preferably 1 to 50 g/L, more preferably 10 to 30 g/L.
（水性媒体）
本発明の実施形態に係る金属表面処理液は、前述の各種成分に、水性媒体を混合したものであってもよい。水性媒体は、水を主成分とする媒体を示す。水性媒体としては、例えば、水を主成分とし、水と混和可能なアルコール等の有機溶媒を含む媒体が挙げられる。水性媒体は、本発明の実施形態に係る金属表面処理液の調製の際、金属表面処理液の保存の際、又は金属表面を着色した後において、当該金属の着色表面の何らかの特性向上のために有利に作用する各種の成分、又は本発明の効果を実質的に阻害しない各種成分を、必要に応じて含むことができる。例えばｐＨ調整剤、保存安定剤等は、そのような成分の具体例である。
(aqueous medium)
The metal surface treatment liquid according to the embodiment of the present invention may be a mixture of the various components described above and an aqueous medium. The aqueous medium refers to a medium containing water as a main component. Examples of the aqueous medium include a medium containing water as a main component and an organic solvent such as alcohol that is miscible with water. The aqueous medium is used to improve some characteristics of the colored surface of the metal during preparation of the metal surface treatment solution according to the embodiment of the present invention, during storage of the metal surface treatment solution, or after the metal surface is colored. Various components that have an advantageous effect or that do not substantially inhibit the effects of the present invention can be included as necessary. For example, pH adjusters, storage stabilizers, etc. are specific examples of such components.
〔金属表面処理方法〕
次に、本発明の実施形態に係る金属表面処理方法について詳述する。まず、本発明の実施形態に係る金属表面処理液が入った浴槽を準備する。次に、浴槽中の金属表面処理液の温度を制御しながら、処理対象の金属を金属表面処理液に浸漬する。所定時間経過後、浴槽から処理対象の金属を引き上げることで、金属表面が灰色系の色調に着色された金属を得る。このように、本発明の実施形態に係る金属表面処理方法によれば、処理対象の金属を金属表面処理液に浸漬するだけで、灰色系の色調に着色することができる。このため、金属表面を灰色系の色調に着色する際に、当該金属の表面に酸化膜を形成しておく必要もなく、電解によって着色する必要もなくなり、処理効率が良好となる。
[Metal surface treatment method]
Next, a metal surface treatment method according to an embodiment of the present invention will be described in detail. First, a bath containing a metal surface treatment liquid according to an embodiment of the present invention is prepared. Next, the metal to be treated is immersed in the metal surface treatment liquid while controlling the temperature of the metal surface treatment liquid in the bath. After a predetermined period of time has elapsed, the metal to be treated is pulled up from the bathtub to obtain a metal whose surface is colored in a gray tone. As described above, according to the metal surface treatment method according to the embodiment of the present invention, the metal to be treated can be colored in a gray tone simply by immersing the metal in the metal surface treatment liquid. Therefore, when a metal surface is colored in a gray tone, there is no need to form an oxide film on the surface of the metal, and there is no need to color the metal surface by electrolysis, resulting in improved processing efficiency.
また、本発明の実施形態に係る金属表面処理方法において、処理対象の金属を金属表面処理液に浸漬する以外に、例えば、金属表面処理液を用いた吹き付け工程によって、処理対象の金属の表面に金属表面処理液を接触させて、処理対象の金属の表面を着色してもよい。 In addition, in the metal surface treatment method according to the embodiment of the present invention, in addition to immersing the metal to be treated in the metal surface treatment liquid, for example, the surface of the metal to be treated is coated by a spraying process using the metal surface treatment liquid. The surface of the metal to be treated may be colored by contacting it with a metal surface treatment liquid.
金属表面処理液による処理温度は、１０～８０℃の範囲が好ましく、１０～６０℃の範囲がより好ましく、３０～６０℃の範囲が更により好ましい。処理温度が１０℃以上であると表面処理の反応速度が増し、８０℃以下であると蒸発による金属表面処理液の液面の低下を抑制することができる。 The treatment temperature with the metal surface treatment liquid is preferably in the range of 10 to 80°C, more preferably in the range of 10 to 60°C, and even more preferably in the range of 30 to 60°C. When the treatment temperature is 10° C. or higher, the reaction rate of the surface treatment increases, and when the treatment temperature is 80° C. or lower, it is possible to suppress a drop in the liquid level of the metal surface treatment liquid due to evaporation.
金属表面処理液による処理時間は、１０秒～２０分間の範囲が好ましく、３０秒～２０分間の範囲がより好ましく、１分～１０分間の範囲が更により好ましい。基本的には、処理時間が短いほど、金属表面を薄い灰色系の色調に着色することができる。また、処理時間が長いほど、金属表面を濃い灰色系の色調に着色することができる。 The treatment time with the metal surface treatment liquid is preferably in the range of 10 seconds to 20 minutes, more preferably in the range of 30 seconds to 20 minutes, and even more preferably in the range of 1 minute to 10 minutes. Basically, the shorter the treatment time, the more the metal surface can be colored in a lighter gray tone. Furthermore, the longer the treatment time, the more the metal surface can be colored in a darker gray tone.
金属表面処理を行う際、あらかじめ処理対象の金属の脱脂、活性化、表面調整を行うことで、処理対象の金属の外観、耐食性及び金属表面処理液との反応性を向上させることが可能である。 When performing metal surface treatment, by degreasing, activating, and surface conditioning the metal to be treated in advance, it is possible to improve the appearance, corrosion resistance, and reactivity of the metal to be treated with the metal surface treatment solution. .
金属表面処理後に、ケイ素、樹脂及びワックスからなる群のうちの１種以上を含有するコーティング剤にて後処理を行っても良い。所望の金属表面の色調に影響を与えない範囲において、これらコーティング剤に特に限定はなく、アクリル樹脂、オレフィン樹脂、アルキド樹脂、尿素樹脂、エポキシ樹脂、メラミン樹脂、フッ素樹脂、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、フェノール樹脂、ポリエステル樹脂、ポリウレタン、ポリアミド、ポリカーボネート等の樹脂類やケイ酸塩、コロイダルシリカ等を成分とするコーティング剤を用いても良い。これらの樹脂濃度は、０．０１～８００ｇ／Ｌが好ましいが、適切な濃度は樹脂の種類により異なる。コーティング剤としては、具体的には、コスマーコート（商品名、関西ペイント（株））、ハイシール２７２（商品名、日本表面化学（株））、ストロンＪＳコート（商品名、日本表面化学（株））、トライナーＴＲ－１７０（商品名、日本表面化学（株））、フィニガード（商品名、Coventya社）等が挙げられる。アクリル樹脂としては、具体的には、ヒロタイト（商品名、日立化成（株））、アロセット（商品名、（株）日本触媒）等があり、オレフィン樹脂については、フローセン（商品名、住友精化（株））、ＰＥＳ（商品名、日本ユニカー（株））、ケミパール（商品名、三井化学（株））、サンファイン（商品名、旭化成（株））等が挙げられる。 After the metal surface treatment, a post-treatment may be performed using a coating agent containing one or more of the group consisting of silicon, resin, and wax. These coating agents are not particularly limited as long as they do not affect the desired color tone of the metal surface, and include acrylic resins, olefin resins, alkyd resins, urea resins, epoxy resins, melamine resins, fluororesins, polyethylene, polyvinyl chloride, A coating agent containing resins such as polystyrene, polypropylene, methacrylic resin, phenol resin, polyester resin, polyurethane, polyamide, polycarbonate, silicate, colloidal silica, etc. may be used. The concentration of these resins is preferably 0.01 to 800 g/L, but the appropriate concentration varies depending on the type of resin. Specific examples of coating agents include Cosmer Coat (product name, Kansai Paint Co., Ltd.), HiSeal 272 (product name, Nippon Surface Chemical Co., Ltd.), and Stron JS Coat (product name, Nippon Surface Chemical Co., Ltd.). ), Trinar TR-170 (trade name, Nippon Kaimen Kagaku Co., Ltd.), Finigard (trade name, Coventya Co., Ltd.), and the like. Specific examples of acrylic resins include Hilotite (trade name, Hitachi Chemical Co., Ltd.) and Alloset (trade name, Nippon Shokubai Co., Ltd.), and olefin resins include Frocene (trade name, Sumitomo Seika Chemical Co., Ltd.). Co., Ltd.), PES (trade name, Nippon Unicar Co., Ltd.), Chemipearl (trade name, Mitsui Chemicals Co., Ltd.), and Sunfine (trade name, Asahi Kasei Co., Ltd.).
本発明の実施形態に係る金属表面処理液は、金属表面を、所望の色に着色させる、所望の美観を付与する、又は識別性を付与する等の目的で使用することができる。このような処理対象の金属の形態としては、あらゆるものを用いることができ、特に限定されないが、例えば、装飾品、ボタンやファスナー等のファスニング部材、車載用部品等を用いることができる。また、当該処理対象の金属の形状についても限定されず、あらゆる形状のものを用いることができる。 The metal surface treatment liquid according to the embodiment of the present invention can be used for the purpose of coloring a metal surface in a desired color, imparting a desired aesthetic appearance, or imparting distinctiveness to the metal surface. Any form of metal to be treated can be used, and is not particularly limited; for example, ornaments, fastening members such as buttons and zippers, automotive parts, etc. can be used. Further, the shape of the metal to be treated is not limited either, and any shape can be used.
以下、本発明の実施例を示すが、これらは本発明をより良く理解するために提供するものであり、本発明が限定されることを意図するものではない。 Examples of the present invention will be shown below, but these are provided for better understanding of the present invention, and are not intended to limit the present invention.
〔試験例１：アルミニウム、アルミニウム合金の着色試験〕
（参考例１～３５、９２、９３）
試験片（処理対象の金属片）として、ＪＩＳ Ａ５０５２（アルミニウム－マグネシウム合金）、ＡＤＣ１２（アルミダイキャスト）を準備し、当該試験片の表面に、脱脂、水洗を順に行った。
次に、表１～３、８に示す液組成の金属表面処理液を入れた浴槽を準備した。金属表面処理液の水性媒体は純水を使用した。
次に、浴槽中の金属表面処理液を表１～３、８に示す温度に制御した状態で、試験片を浸漬した。表１～３、８に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。
[Test Example 1: Coloring test of aluminum and aluminum alloy]
(Reference examples 1 to 35, 92, 93)
JIS A5052 (aluminum-magnesium alloy) and ADC12 (aluminum die-cast) were prepared as test pieces (metal pieces to be treated), and the surfaces of the test pieces were sequentially degreased and washed with water.
Next, a bathtub containing a metal surface treatment liquid having the liquid composition shown in Tables 1 to 3 and 8 was prepared. Pure water was used as the aqueous medium of the metal surface treatment solution.
Next, the test pieces were immersed in the metal surface treatment liquid in the bathtub while the temperature was controlled as shown in Tables 1 to 3 and 8. After being immersed for the times shown in Tables 1 to 3 and 8, the test pieces were taken out. Next, the surface of the test piece was washed with water and then dried.
なお、参考例９２及び９３については、浸漬により皮膜（着色皮膜）を形成した後の試験片を水洗し、コーティング処理を行い、乾燥した。参考例９２のコーティング処理にはストロンＪＳコート（日本表面化学（株）製コーティング剤）、参考例９３のコーティング処理にはＴＲ－１７０（日本表面化学（株）製コーティング剤）を使用した。 In addition, for Reference Examples 92 and 93, the test pieces after forming a film (colored film) by immersion were washed with water, subjected to coating treatment, and dried. For the coating treatment of Reference Example 92, STRON JS Coat (coating agent manufactured by Nippon Surface Chemical Co., Ltd.) was used, and for the coating treatment of Reference Example 93, TR-170 (coating agent manufactured by Nippon Surface Chemical Co., Ltd.) was used.
〔試験例２：銅、銅合金の着色試験〕
（実施例３６～３８、４５、５１、参考例３９～４４、４６～５０、５２～５５）
試験片（処理対象の金属片）として、ＪＩＳ Ｃ２６００Ｐ（真鍮）、Ｃ１１００Ｐ（純銅）を準備し、当該試験片の表面に、脱脂、水洗を順に行った。
次に、表４～５に示す液組成の金属表面処理液を入れた浴槽を準備した。金属表面処理液の水性媒体は純水を使用した。
次に、浴槽中の金属表面処理液を表４～５に示す温度に制御した状態で、試験片を浸漬した。表４～５に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。
[Test Example 2: Coloring test of copper and copper alloy]
(Examples 36-38, 45, 51, Reference Examples 39-44, 46-50, 52-55)
JIS C2600P (brass) and C1100P (pure copper) were prepared as test pieces (metal pieces to be treated), and the surfaces of the test pieces were sequentially degreased and washed with water.
Next, a bathtub containing a metal surface treatment liquid having the liquid composition shown in Tables 4 and 5 was prepared. Pure water was used as the aqueous medium of the metal surface treatment solution.
Next, the test pieces were immersed in the metal surface treatment liquid in the bathtub, with the temperature controlled as shown in Tables 4 and 5. After being immersed for the time shown in Tables 4 and 5, the test pieces were taken out. Next, the surface of the test piece was washed with water and then dried.
〔試験例３：亜鉛、亜鉛合金の着色試験〕
（実施例５６～５９、６５、６９～７１、７５、参考例６０～６４、６６～６８、７２～７４）
試験片（処理対象の金属片）として、ＪＩＳ ＺＤＣ２（亜鉛ダイキャスト）及び亜鉛めっき材を準備し、当該試験片の表面に、脱脂、水洗を順に行った。当該亜鉛めっき材は、ＪＩＳで規定されるＪＩＳ ＳＰＣＣ（圧延鋼板）を基材として、膜厚８μｍのジンケート亜鉛メッキを施したものである。また、当該ジンケート亜鉛メッキの光沢剤として、日本表面化学株式会社製９０００ＡＢＳを使用した。
次に、表６～７に示す液組成の金属表面処理液を入れた浴槽を準備した。金属表面処理液の水性媒体は純水を使用した。
次に、浴槽中の金属表面処理液を表６～７に示す温度に制御した状態で、試験片を浸漬した。表６～７に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。
[Test Example 3: Coloring test of zinc and zinc alloy]
(Examples 56-59, 65, 69-71, 75, Reference Examples 60-64, 66-68, 72-74)
JIS ZDC2 (zinc die-cast) and galvanized material were prepared as test pieces (metal pieces to be treated), and the surfaces of the test pieces were degreased and washed with water in order. The galvanized material is made of JIS SPCC (rolled steel plate) specified by JIS as a base material, and is coated with zincate zinc plating with a film thickness of 8 μm. Furthermore, 9000ABS manufactured by Nippon Kaimen Kagaku Co., Ltd. was used as a brightener for the zincate galvanizing.
Next, a bathtub containing a metal surface treatment liquid having the liquid composition shown in Tables 6 and 7 was prepared. Pure water was used as the aqueous medium of the metal surface treatment solution.
Next, the test pieces were immersed in the metal surface treatment liquid in the bathtub, with the temperature controlled as shown in Tables 6 and 7. After being immersed for the time shown in Tables 6 and 7, the test pieces were taken out. Next, the surface of the test piece was washed with water and then dried.
〔試験例４：鉄、鉄合金の着色試験〕
（参考例７６～８０）
試験片（処理対象の金属片）として、ＪＩＳ ＳＰＣＣ（圧延鋼板）を準備し、当該試験片の表面に、脱脂、水洗を順に行った。
次に、表７に示す液組成の金属表面処理液を入れた浴槽を準備した。金属表面処理液の水性媒体は純水を使用した。
次に、浴槽中の金属表面処理液を表７に示す温度に制御した状態で、試験片を浸漬した。表７に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。
[Test Example 4: Coloring test for iron and iron alloys]
(Reference examples 76 to 80)
A JIS SPCC (rolled steel plate) was prepared as a test piece (metal piece to be treated), and the surface of the test piece was sequentially degreased and washed with water.
Next, a bathtub containing a metal surface treatment liquid having the liquid composition shown in Table 7 was prepared. Pure water was used as the aqueous medium of the metal surface treatment solution.
Next, the test pieces were immersed in the metal surface treatment liquid in the bathtub while the temperature was controlled to be as shown in Table 7. After being immersed for the time shown in Table 7, the test piece was taken out. Next, the surface of the test piece was washed with water and then dried.
〔試験例５：マグネシウム、マグネシウム合金の着色試験〕
（参考例８１～８６）
試験片（処理対象の金属片）として、ＪＩＳ ＡＺ３１及びＪＩＳ ＡＺ９１（マグネシウム－亜鉛合金）を準備し、当該試験片の表面に、脱脂、水洗を順に行った。
次に、表８に示す液組成の金属表面処理液を入れた浴槽を準備した。金属表面処理液の水性媒体は純水を使用した。
次に、浴槽中の金属表面処理液を表８に示す温度に制御した状態で、試験片を浸漬した。表８に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。
[Test Example 5: Coloring test of magnesium and magnesium alloy]
(Reference examples 81 to 86)
JIS AZ31 and JIS AZ91 (magnesium-zinc alloy) were prepared as test pieces (metal pieces to be treated), and the surfaces of the test pieces were sequentially degreased and washed with water.
Next, a bathtub containing a metal surface treatment liquid having the liquid composition shown in Table 8 was prepared. Pure water was used as the aqueous medium of the metal surface treatment solution.
Next, the test pieces were immersed in the metal surface treatment liquid in the bathtub while the temperature was controlled as shown in Table 8. After being immersed for the time shown in Table 8, the test piece was taken out. Next, the surface of the test piece was washed with water and then dried.
〔試験例６：ニッケル、ニッケル合金の着色試験〕
（参考例８７～９１）
試験片（処理対象の金属片）として、ＪＩＳ Ｎｉ２００（純ニッケル）を準備し、当該試験片の表面に、脱脂、水洗を順に行った。
次に、表８に示す液組成の金属表面処理液を入れた浴槽を準備した。金属表面処理液の水性媒体は純水を使用した。
次に、浴槽中の金属表面処理液を表８に示す温度に制御した状態で、試験片を浸漬した。表８に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。
[Test Example 6: Coloring test of nickel and nickel alloy]
(Reference examples 87 to 91)
JIS Ni200 (pure nickel) was prepared as a test piece (metal piece to be treated), and the surface of the test piece was sequentially degreased and washed with water.
Next, a bathtub containing a metal surface treatment liquid having the liquid composition shown in Table 8 was prepared. Pure water was used as the aqueous medium of the metal surface treatment solution.
Next, the test pieces were immersed in the metal surface treatment liquid in the bathtub while the temperature was controlled as shown in Table 8. After being immersed for the time shown in Table 8, the test piece was taken out. Next, the surface of the test piece was washed with water and then dried.
〔試験例７〕
（比較例１～１０）
試験片（処理対象の金属片）として、表９に示す金属を準備し、当該試験片の表面に、脱脂、水洗を順に行った。
次に、表９に示す液組成の金属表面処理液を入れた浴槽を準備した。金属表面処理液の水性媒体は純水を使用した。
次に、浴槽中の金属表面処理液を表９に示す温度に制御した状態で、試験片を浸漬した。表９に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。
[Test Example 7]
(Comparative Examples 1 to 10)
The metals shown in Table 9 were prepared as test pieces (metal pieces to be treated), and the surfaces of the test pieces were sequentially degreased and washed with water.
Next, a bathtub containing a metal surface treatment liquid having the liquid composition shown in Table 9 was prepared. Pure water was used as the aqueous medium of the metal surface treatment solution.
Next, the test pieces were immersed in the metal surface treatment liquid in the bathtub while the temperature was controlled to be as shown in Table 9. After being immersed for the time shown in Table 9, the test piece was taken out. Next, the surface of the test piece was washed with water and then dried.
〔各種評価〕
実施例３６～３８、４５、５１、５６～５９、６５、６９～７１、７５、参考例１～３５、３９～４４、４６～５０、５２～５５、６０～６４、６６～６８、７２～７４、７６～９３及び比較例１～１０で作製した試験片について、色調評価及び密着性評価を以下の通り行った。
[Various evaluations]
Examples 36-38, 45, 51, 56-59, 65, 69-71, 75, Reference Examples 1-35, 39-44, 46-50, 52-55, 60-64, 66-68, 72- Color tone evaluation and adhesion evaluation were performed on the test pieces prepared in Comparative Examples 74, 76 to 93, and Comparative Examples 1 to 10 as follows.
（色調評価）
試験片の表面の色調は、目視により評価した。評価基準を以下に示す。
Ａ：均一で美観に優れた処理外観を有するアンティークグレー
Ｂ：均一で美観に優れた処理外観を有するＡよりも濃いアンティークグレー
Ｃ：均一で美観に優れた処理外観を有するＡよりも薄いアンティークグレー
Ｄ：着色せず
(color tone evaluation)
The color tone of the surface of the test piece was evaluated visually. The evaluation criteria are shown below.
A: Antique gray that has a uniform and aesthetically pleasing treated appearance B: Antique gray that is darker than A and has a uniform and aesthetically pleasing treated appearance C: Antique gray that is thinner than A and has a uniform and aesthetically pleasing treated appearance D: Not colored
（密着性評価）
試験片の表面に、カッターで１０×１０マス（合計１００マス）の切り込みを入れ、セロテープ（登録商標）を貼って剥がした際に、着色皮膜が剥がれなかったマス目の数をカウントした。１マス分のサイズは、縦×横＝１ｍｍ×１ｍｍであった。
各表には、（着色皮膜が剥がれなかったマス目の数）／１００で示しており、着色皮膜が剥がれなかったマス目の数が大きいほど着色皮膜の密着性が高いことを示している。
(Adhesion evaluation)
A cut of 10 x 10 squares (total 100 squares) was made on the surface of the test piece with a cutter, and when Cellotape (registered trademark) was applied and peeled off, the number of squares from which the colored film did not come off was counted. The size of one square was length x width = 1 mm x 1 mm.
In each table, the number of squares from which the colored film did not come off is expressed as /100, and the larger the number of squares from which the colored film did not come off, the higher the adhesion of the colored film.
実施例３６～３８、４５、５１、５６～５９、６５、６９～７１、７５、参考例１～３５、３９～４４、４６～５０、５２～５５、６０～６４、６６～６８、７２～７４、７６～９３及び比較例１～１０について、試験条件及び評価結果を表１～９に示す。
なお、表１～８における試験Ｎｏ．１～３５、３９～４４、４６～５０、５２～５５、６０～６４、６６～６８、７２～７４、７６～９３はそれぞれ参考例である。
Examples 36-38, 45, 51, 56-59, 65, 69-71, 75, Reference Examples 1-35, 39-44, 46-50, 52-55, 60-64, 66-68, 72- Test conditions and evaluation results for Tests 74, 76 to 93 and Comparative Examples 1 to 10 are shown in Tables 1 to 9.
In addition, test No. in Tables 1 to 8. 1 to 35, 39 to 44, 46 to 50, 52 to 55, 60 to 64, 66 to 68, 72 to 74, and 76 to 93 are reference examples, respectively.
以上の結果から、実施例３６～３８、４５、５１、５６～５９、６５、６９～７１、７５、参考例１～３５、３９～４４、４６～５０、５２～５５、６０～６４、６６～６８、７２～７４、７６～９３のように、テルル若しくはテルル化合物、又はこれらの塩を含む金属表面処理液によれば、良好な処理効率で金属表面を灰色系の色調に着色することができることが確認された。
一方、比較例１～１０のように、金属表面処理液がテルル若しくはテルル化合物、又はこれらの塩を含まないと、金属表面を灰色系の色調に着色することができないことが確認された。
From the above results, Examples 36-38, 45, 51, 56-59, 65, 69-71, 75, Reference Examples 1-35, 39-44, 46-50, 52-55, 60-64, 66 ~68, 72~74, 76~93, metal surface treatment liquids containing tellurium, tellurium compounds, or salts thereof can color metal surfaces in gray tones with good treatment efficiency. It was confirmed that it can be done.
On the other hand, as in Comparative Examples 1 to 10, it was confirmed that if the metal surface treatment solution did not contain tellurium, a tellurium compound, or a salt thereof, the metal surface could not be colored in a gray tone.
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