TWI440740B - 用於塗覆金屬基材之預處理組合物及方法 - Google Patents
用於塗覆金屬基材之預處理組合物及方法 Download PDFInfo
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- TWI440740B TWI440740B TW097129375A TW97129375A TWI440740B TW I440740 B TWI440740 B TW I440740B TW 097129375 A TW097129375 A TW 097129375A TW 97129375 A TW97129375 A TW 97129375A TW I440740 B TWI440740 B TW I440740B
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- 239000000203 mixture Substances 0.000 title claims description 179
- 229910052751 metal Inorganic materials 0.000 title claims description 123
- 239000002184 metal Substances 0.000 title claims description 123
- 239000000758 substrate Substances 0.000 title claims description 57
- 238000000034 method Methods 0.000 title claims description 39
- 238000000576 coating method Methods 0.000 title description 22
- 239000011248 coating agent Substances 0.000 title description 20
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- 239000011347 resin Substances 0.000 claims description 68
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 38
- 239000011737 fluorine Substances 0.000 claims description 28
- 229910052731 fluorine Inorganic materials 0.000 claims description 28
- 150000004673 fluoride salts Chemical class 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 20
- 238000004070 electrodeposition Methods 0.000 claims description 18
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- 239000008199 coating composition Substances 0.000 claims description 16
- 239000010960 cold rolled steel Substances 0.000 claims description 16
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 16
- 239000010959 steel Substances 0.000 claims description 16
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- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 7
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- 239000000243 solution Substances 0.000 description 31
- -1 i.e. Chemical compound 0.000 description 25
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- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 5
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
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- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 4
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
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- 238000004132 cross linking Methods 0.000 description 3
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- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 3
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- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
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- 206010073306 Exposure to radiation Diseases 0.000 description 2
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- 150000008064 anhydrides Chemical class 0.000 description 2
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- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 229960001759 cerium oxalate Drugs 0.000 description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 2
- RFEFPOFKDIOFQW-UHFFFAOYSA-K cerium(3+);2-hydroxypropanoate Chemical compound [Ce+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O RFEFPOFKDIOFQW-UHFFFAOYSA-K 0.000 description 2
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 2
- UADULFIZHZKEOP-UHFFFAOYSA-K cerium(3+);triformate Chemical compound [Ce+3].[O-]C=O.[O-]C=O.[O-]C=O UADULFIZHZKEOP-UHFFFAOYSA-K 0.000 description 2
- KQJQGYQIHVYKTF-UHFFFAOYSA-N cerium(3+);trinitrate;hydrate Chemical compound O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KQJQGYQIHVYKTF-UHFFFAOYSA-N 0.000 description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 2
- MOOUSOJAOQPDEH-UHFFFAOYSA-K cerium(iii) bromide Chemical compound [Br-].[Br-].[Br-].[Ce+3] MOOUSOJAOQPDEH-UHFFFAOYSA-K 0.000 description 2
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- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 2
- 150000004699 copper complex Chemical class 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
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- WMYBXRITVYIFCO-UHFFFAOYSA-N copper;2-hydroxybutanedioic acid Chemical compound [Cu].OC(=O)C(O)CC(O)=O WMYBXRITVYIFCO-UHFFFAOYSA-N 0.000 description 1
- DYROSKSLMAPFBZ-UHFFFAOYSA-L copper;2-hydroxypropanoate Chemical compound [Cu+2].CC(O)C([O-])=O.CC(O)C([O-])=O DYROSKSLMAPFBZ-UHFFFAOYSA-L 0.000 description 1
- PUHAKHQMSBQAKT-UHFFFAOYSA-L copper;butanoate Chemical compound [Cu+2].CCCC([O-])=O.CCCC([O-])=O PUHAKHQMSBQAKT-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- LLVVIWYEOKVOFV-UHFFFAOYSA-L copper;diiodate Chemical compound [Cu+2].[O-]I(=O)=O.[O-]I(=O)=O LLVVIWYEOKVOFV-UHFFFAOYSA-L 0.000 description 1
- BQVVSSAWECGTRN-UHFFFAOYSA-L copper;dithiocyanate Chemical compound [Cu+2].[S-]C#N.[S-]C#N BQVVSSAWECGTRN-UHFFFAOYSA-L 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- PJBGIAVUDLSOKX-UHFFFAOYSA-N copper;propanedioic acid Chemical compound [Cu].OC(=O)CC(O)=O PJBGIAVUDLSOKX-UHFFFAOYSA-N 0.000 description 1
- LZJJVTQGPPWQFS-UHFFFAOYSA-L copper;propanoate Chemical compound [Cu+2].CCC([O-])=O.CCC([O-])=O LZJJVTQGPPWQFS-UHFFFAOYSA-L 0.000 description 1
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- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
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- 239000003599 detergent Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- KTFWVPPPATXYEG-UHFFFAOYSA-N diaminomethylidenesulfamic acid Chemical compound NC(=N)NS(O)(=O)=O KTFWVPPPATXYEG-UHFFFAOYSA-N 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
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- 239000003085 diluting agent Substances 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
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- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
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- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- BSZKBMAGLBURDO-UHFFFAOYSA-J hydrogen carbonate;zirconium(4+) Chemical compound [Zr+4].OC([O-])=O.OC([O-])=O.OC([O-])=O.OC([O-])=O BSZKBMAGLBURDO-UHFFFAOYSA-J 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
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- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
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- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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- 239000002244 precipitate Substances 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 150000004060 quinone imines Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006009 resin backbone Polymers 0.000 description 1
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- 230000000284 resting effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical class [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003442 suberic acids Chemical class 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
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- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 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
- 238000005809 transesterification reaction Methods 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229940105963 yttrium fluoride Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- C23C22/34—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 fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
-
- 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
- C23C22/34—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 fluorides or complex fluorides
- C23C22/36—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 fluorides or complex fluorides containing also phosphates
- C23C22/361—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 fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
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- C—CHEMISTRY; METALLURGY
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Description
本發明係關於用於塗覆金屬基材之預處理組合物及方法,該等金屬基材包括含鐵基材,例如,冷軋鋼及電鍍鋅鋼。本發明亦係關於經塗覆金屬基材。
經常在金屬基材上使用保護塗層以改良耐腐蝕性及上漆能力(paint adhesion)。用於塗覆此等基材之習用技術包括涉及使用磷酸鹽轉化塗料及含鉻沖洗劑預處理金屬基材之技術。然而,此等磷酸鹽及/或含鉻酸鹽組合物之使用會造成環境及健康問題。
因此,已研發出不含鉻酸鹽及/或不含磷酸鹽之預處理組合物。此等組合物通常係基於以某種方式與基材表面反應並與之黏合以形成保護層之化學混合物。舉例而言,基於IIIB族或IVB族金屬化合物之預處理組合物最近變得愈加普遍。此等組合物經常含有游離氟來源,即,與結合至另一元素(例如,IIIB族或IVB族金屬)之氟相反,在該預處理組合物中得以分離之氟。游離氟可蝕刻金屬基材表面,進而促進含IIIB族或IVB族金屬之塗料沈積。然而,此等預處理組合物之耐腐蝕性能力通常明顯不及習用含有磷酸鹽及/或鉻之預處理物。
因此,人們可能期望提供可克服先前技術之至少某些上述弊端(包括與鉻酸鹽及/或磷酸鹽使用相關之環境弊端)的用於處理金屬基材之方法。進而言之,人們可能期望提供
如下用於處理金屬基材之方法:其在至少某些情況下可賦予相當於或甚至優於藉由使用磷酸鹽轉化塗料而賦予的耐腐蝕性之耐腐蝕性。人們亦可能期望提供相關經塗覆金屬基材。
在某些方面,本發明係關於用於處理金屬基材之組合物。此等組合物包括:(a)IIIB族及/或IVB族金屬;(b)正電性金屬;(c)0.1至300百萬分數("ppm")之游離氟;(d)金屬氟化物鹽,其係自可形成具有至少11之pKsp
之氟化物鹽的金屬形成;及(e)水。在某些實施例中,該組合物實質上不含重金屬磷酸鹽(例如,磷酸鋅)及鉻酸鹽。
在另一些方面,本發明係關於用於處理金屬基材之方法,其包括使該基材與預處理組合物接觸,該預處理組合物包括:(a)IIIB族及/或IVB族金屬;(b)正電性金屬;(c)游離氟;(d)金屬氟化物鹽,其係自可形成具有至少11之pKsp
之氟化物鹽的金屬形成;及(e)水,其中該可形成具有至少11之pKsp
之金屬氟化物鹽的金屬係以足以將游離氟在該組合物中之含量維持在不少於0.1 ppm且不大於300 ppm之量提供。
在又一些方面,本發明係關於用於處理金屬基材之組合物,其包括:(a)IIIB族及/或IVB族金屬;(b)0.1至300 ppm之游離氟;(c)金屬氟化物鹽,其係自可形成具有至少11之pKsp
之氟化物鹽的金屬形成;及(d)水。此等本發明組合物實質上不含磷酸根離子及鉻酸鹽。
本發明亦係關於經該組合物處理之基材。
基於下列詳細說明之目的,應理解本發明可採取各種替代變更形式及步驟順序,但其中明確說明相反之情況除外。而且,除在任何操作實例中或其中另有說明以外,在說明書及申請專利範圍中所表述之所有數值(例如,所用成份之數量)在所有情況下均應理解為由術語"約"修飾。因此,除非說明相反,否則,下列說明書及隨附申請專利範圍中所列示之數值參數均為可隨本發明尋求達成之期望性質而變化的近似值。無論如何,且並非試圖限制申請專利範圍之等效項之原則的應用,每一數字參數應至少根據所報導有效位的數量且藉由使用普通舍入技術來解釋。
儘管闡述本發明廣泛範圍之數字範圍及參數係近似值,但盡可能精確地報導具體實例中所述數值。然而,任何數值固有包含必然由其各自測試量測中存在之標準偏差引起的必然誤差。
而且,應理解本文所述任一數值範圍均意欲包括其中所包含全部子範圍。舉例而言,一"1至10"之範圍意欲包含介於(且包含)所述最小值1與所述最大值10間之全部子範圍,即,該等子範圍具有等於或大於1之最小值及等於或小於10之最大值。
在本申請案中,除非另有特別說明,否則所用單數包括複數且複數涵蓋單數。此外,除非另有特別說明,否則在該申請案中所用"或"意指"及/或",即使在某些情況下可明
確使用"及/或"。
如先前所述,本發明之某些實施例係關於用於處理金屬基材之方法。用於本發明之適宜金屬基材包括彼等經常用於汽車車身組件、汽車零部件及其他物件(例如,小的金屬零部件,包括緊固件,即,螺母、螺栓、螺桿、插針、釘子、夾子、按鈕及諸如此類)者。適宜金屬基材之具體實例包括但不限於冷軋鋼、熱軋鋼、塗覆有鋅金屬、鋅化合物或鋅合金之鋼(例如,電鍍鋅鋼、熱浸鍍鋅鋼、鋅鐵合金鋼(galvanealed steel))及鍍有鋅合金之鋼。亦可使用鍍有鋁合金、鋁之鋼及鍍有鋁合金之鋼基材。其他適宜非鐵金屬包括銅及鎂以及此等材料之合金。進而言之,藉由本發明方法塗覆之金屬基材可為以其他方式處理及/或其其餘表面經塗覆之基材的切割邊緣。按照本發明之方法經塗覆之金屬基材可呈(例如)金屬薄板或加工零件形式。
首先可清潔擬按照本發明之方法處理之基材以去除油脂、污垢及其他異物。此經常藉由採用溫和或強鹼清潔劑(例如,市售及常用於金屬預處理製程之清潔劑)來實施。適用於本發明之鹼性清潔劑的實例包括Chemkleen 163、Chemkleen 177及Chemkleen 490MX,該等各自均可自PPG Industries公司購得。通常在使用此等清潔劑之後及/或之前用水沖洗。
如先前所述,本發明之某些實施例係關於處理金屬基材之方法,其包括使該金屬基材與包含IIIB族及/或IVB族金屬之預處理組合物接觸。如本文所用術語"預處理組合物"
係指在與基材接觸時,與基材表面反應並以化學方式改變該基材表面且與其黏合以形成保護層之組合物。
經常地,該預處理組合物包括載劑(經常為水性介質)以使該組合物呈IIIB族或IVB族金屬化合物存於載劑中之溶液或分散液形式。在此等實施例中,可藉由諸如下列等各種已知技術中之任一種使該溶液或分散液與該基材接觸:浸塗或浸漬、噴塗、間歇噴塗、浸塗繼而噴塗、噴塗繼而浸塗、刷塗或滾塗。在某些實施例中,在施用於金屬基材時,該溶液或懸浮液係在介於60℉至150℉(15℃至65℃)間之溫度下。該接觸時間經常為自10秒至5分鐘,例如,30秒至2分鐘。
如本文所用術語"IIIB族及/或IVB族金屬"係指屬於CAS元素週期表之IIIB族或IVB族之元素,如在(例如)Handbook of Chemistry and Physics,第63版(1983)中所述。適用時,可使用金屬自身。在某些實施例中,使用IIIB族及/或IVB族金屬化合物。如本文所用術語"IIIB族及/或IVB族金屬化合物"係指包括至少一種屬於CAS元素週期表之IIIB族或IVB族之元素的化合物。
在某些實施例中,在預處理組合物中所用IIIIB族及/或IVB族金屬化合物係鋯、鈦、鉿、釔、鈰、或其混合物之化合物。適宜鋯化合物包括但不限於六氟鋯酸、其鹼金屬及銨鹽、碳酸鋯銨、硝酸氧鋯、羧酸鋯及羥基羧酸鋯(例如,氫氟鋯酸/乙酸鋯、草酸鋯、乙醇酸鋯銨、乳酸鋯銨、檸檬酸鋯銨及其混合物。適宜鈦化合物包括但不限於
氟鈦酸及其鹽。適宜鉿化合物包括但不限於硝酸鉿。適宜釔化合物包括但不限於硝酸釔。適宜鈰化合物包括但不限於硝酸鈰。
在某些實施例中,IIIB族及/或IVB族金屬化合物係以至少10 ppm金屬(例如,至少100 ppm金屬)或(在某些情況下)至少150 ppm金屬(以元素金屬量得)存於預處理組合物中。在某些實施例中,IIIB族及/或IVB族金屬化合物係以不大於5000 ppm金屬(例如,不大於300 ppm金屬)或(在某些情況下)不大於250 ppm金屬(以元素金屬量得)之量存於預處理組合物中。IIIB族及/或IVB族金屬在預處理組合物中之量可介於所述數值之任一組合之間,包含所述數值。
在某些實施例中,該預處理組合物亦包含正電性金屬。如本文所用術語"正電性金屬"係指具有較金屬基材為高之正電性的金屬。基於本發明之目的,此意指術語"正電性金屬"涵蓋與所處理金屬基材之金屬相比不易氧化之金屬。如彼等熟習此項技術者所理解,金屬氧化之趨勢稱為氧化電位,以伏特表示,且相對於標準氫電極加以量測,將該標準氫電極任意指定為零氧化電位。若干元素之氧化電位陳述於下表中。在下表中,倘若一元素具有較與其相比之元素為大之電壓值E*
,則該元素與另一元素相比不易被氧化。
因此,應理解,當該金屬基材包括諸如冷軋鋼、熱軋鋼、塗覆有鋅金屬、鋅化合物或鋅合金之鋼、熱浸鍍鋅鋼、鋅鐵合金鋼、鍍有鋅合金、鋁合金之鋼、鍍有鋁之鋼、鍍有鋁合金、鎂及鎂合金之鋼等先前所列示的一種材料時,用於納入該預處理組合物中之適宜正電性金屬包括(例如)鎳、銅、銀及金以及其混合物。
在某些實施例中,該預處理組合物中之正電性金屬的來源係水溶性金屬鹽。在本發明之某些實施例中,該水溶性金屬鹽係水溶性銅化合物。適用於本發明之水溶性銅化合物之具體實例包括但不限於氰化銅、氰化銅鉀、硫酸銅、硝酸銅、焦磷酸銅、硫氰酸銅、乙二胺四乙酸二鈉銅四水合物、溴化銅、氧化銅、氫氧化銅、氯化銅、氟化銅、葡萄糖酸銅、檸檬酸銅、月桂醯肌胺酸銅、甲酸銅、乙酸銅、丙酸銅、丁酸銅、乳酸銅、草酸銅、肌醇六磷酸銅、酒石酸銅、蘋果酸銅、琥珀酸銅、丙二酸銅、馬來酸銅、
苯甲酸銅、水楊酸銅、天冬胺酸銅、麩胺酸銅、富馬酸銅、甘油磷酸銅、葉綠素鈉銅、氟矽酸銅、氟硼酸銅及碘酸銅以及甲酸至癸酸之同系列羧酸的銅鹽、草酸至辛二酸系列之多元酸的銅鹽及羥基羧酸(包括乙醇酸、乳酸、酒石酸、蘋果酸及檸檬酸)之銅鹽。
當由此水溶性銅化合物提供之銅離子作為雜質以硫酸銅、氧化銅等形式沈澱時,較佳可添加可抑制銅離子沈澱之錯合劑,藉此使該等銅離子作為銅錯合物在該溶液中穩定。
在某些實施例中,該銅化合物可以諸如K3
Cu(CN)4
或Cu-EDTA等銅錯合物鹽形式添加,其自身可穩定地存於該組合物中,但藉由組合錯合劑與自身難容之化合物形成可穩定地存於該組合物中之銅錯合物亦為可能。其實例包括藉由CuCN與KCN之組合或CuSCN與KSCN或KCN之組合形成之氰化銅錯合物以及藉由CuSO4
與EDTA-2Na之組合形成之Cu-EDTA錯合物。
關於錯合劑,可使用可與銅離子形成錯合物之化合物;其實例包括諸如氰化物化合物及硫氰酸鹽化合物等無機化合物及多聚羧酸,且其具體實例包括乙二胺四乙酸、乙二胺四乙酸之鹽(例如,乙二胺四乙酸二氫二鈉二水合物)、胺基羧酸(例如,次氮基三乙酸及亞胺基二乙酸)、羥基羧酸(例如,檸檬酸及酒石酸)、琥珀酸、草酸、乙二胺四亞甲基膦酸及甘胺酸。
在某些實施例中,將諸如銅等正電性金屬以佔金屬總量
(以元素金屬量得)之至少1 ppm(例如,至少5 ppm)或(在某些情況下)至少10 ppm之量納入預處理組合物中。在某些實施例中,將正電性金屬以佔金屬總量(以元素金屬量得的)之不大於500 ppm(例如,不大於100 ppm)或(在某些情況下)不大於50 ppm之量納入此等預處理組合物中。正電性金屬在預處理組合物中之量可介於所述數值之任一組合之間,包含所述數值。
本發明之預處理組合物亦包含游離氟。應理解,在本發明預處理組合物中之游離氟的來源可有所變化。舉例而言,在某些情況下,該游離氟可源自用於預處理組合物之IIIB族及/或IVB族金屬化合物,例如,六氟鋯酸。由於IIIB族及/或IVB族金屬在預處理製程中會沈積於金屬基材上,因此六氟鋯酸中之氟會變成游離氟且應理解,倘若不加以抑制,則該預處理組合物中游離氟之含量在用本發明之預處理組合物預處理金屬時會隨時間增加。
另外,本發明預處理組合物之游離氟來源可包括除IIIB族及/或IVB族金屬化合物外之化合物。此等來源之非限制性實例包括HF、NH4
F、NH4
HF2
、NaF及NaHF2
。
如本文所用術語"游離氟"係指分離的氟離子且其在本發明預處理組合物中之濃度可藉由使用具有氟離子電極之計量儀量測預處理組合物來測定。本文實例闡明用於測定游離氟在用於本發明目的之組合物中之濃度的適宜方法。
本發明之預處理組合物亦包括金屬氟化物鹽,其係自可形成具有至少11(在某些情況下,至少15或在又一些情況
下,至少20)之pKsp
之氟化物鹽的金屬形成。應理解,pKsp
係指化合物之溶度積常數的反對數。在本發明中,提供一種含有金屬之化合物,其中應選擇該金屬以使其形成具有至少11之pKsp
的氟化物鹽。基於本發明之目的,金屬氟化物鹽之pKsp
數值係指在Lange's Handbook of Chemistry,第15版,McGraw-Hill,1999,表8.6中所報導pKsp
數值。在本發明之某些實施例中,形成具有至少11之pKsp
之氟化物鹽的金屬係選自鈰(CeF3
之pKsp
係15.1)、鑭(LaF3
之pKsp
係16.2)、鈧(ScF3
之pKsp
係23.24)、釔(YF3
之pKsp
係20.06)或其混合物。
進而言之,在本發明之組合物中,對提供用以可形成具有至少11之pKsp
之氟化物鹽的含金屬化合物之量應加以選擇以使游離氟在組合物中之含量不少於0.1 ppm(在某些情況下,不少於20 ppm)且不大於300 ppm(在某些情況下,不大於100 ppm)。應理解且如先前所述,游離氟在本發明預處理組合物中之含量在用本發明預處理組合物預處理金屬時會隨時間增加。在本發明中,按照需要對該預處理組合物提供如上文所述含金屬化合物以將游離氟之含量維持在佔該預處理組合物之不少於0.1 ppm且不大於300 ppm。
按照本發明,自可形成具有至少11之pKsp
之氟化物鹽的金屬形成的金屬氟化物鹽可在氟化物鹽形成後立刻自本發明組合物去除或者(倘若可選擇)可使該氟化物鹽保留在該組合物中一段時間。基於本發明之目的,重要的是此氟化物鹽形成並存在於該組合物中,即使僅有短暫時間。
因此,在本發明之某些實施例中,對預處理組合物提供含有釔之化合物。具體而言,於本發明預處理組合物中所添加之釔來源可藉由與組合物之游離氟反應形成氟化釔化合物(例如,YF3
)。在某些實施例中,預處理組合物之釔來源係水溶性釔鹽,例如,乙酸釔、氯化釔、甲酸釔、碳酸釔、胺基磺酸釔、乳酸釔及硝酸釔。當擬於該預處理組合物中添加釔之水性溶液時,硝酸釔(一種容易購得之釔化合物)係適宜釔來源。適用於本發明預處理組合物之其他釔化合物係有機及無機釔化合物,例如,氧化釔、溴化釔、氫氧化釔、鉬酸釔、硫酸釔、矽酸釔及草酸釔。亦可使用有機釔錯合物及釔金屬。適宜鈰化合物包括但不限於硝酸鈰六水合物。適宜鑭化合物包括但不限於硝酸鑭水合物。
已經發現,與使用包含可形成pKsp
小於11之金屬氟化物鹽之金屬之含金屬化合物的情況相比,藉由選擇包含可形成pKsp
至少為11之金屬氟化物鹽之金屬的含金屬化合物可使該含金屬化合物更有效地自組合物去除游離氟,藉此更容易地控制游離氟在組合物中之含量。另外,例如,使用含釔化合物之本發明實施例,所得含有金屬氟化物鹽(YF3
)之泥渣被視為對環境無害,此乃因不認為釔係重金屬。因此,本發明之組合物可避免某些先前技術金屬預處理組合物中所存在之環境弊端。
在某些實施例中,預處理組合物之pH係介於2.0至7.0之間,例如,3.5至5.5。按照需要可使用(例如)任一酸或鹼
調節預處理組合物之pH。在某些實施例中,藉由納入鹼性材料維持溶液之pH,該鹼性材料包括水溶性及/或水分散性鹼,例如,氫氧化鈉、碳酸鈉、氫氧化鉀、氫氧化銨、氨及/或胺(例如,三乙胺、甲基乙基胺)或其混合物。
在某些實施例中,該預處理組合物包含樹脂黏合劑。適宜樹脂包括一種或多種烷醇胺與含有至少兩個環氧基之環氧官能基材料(例如,彼等揭示於美國專利第5,653,823號中者)的反應產物。在某些情況下,此等樹脂含有藉由在製備該樹脂中使用二羥甲基丙酸、鄰苯二甲醯亞胺或巰基甘油作為額外反應物納入的β羥基酯、醯亞胺或硫化物官能團。或者,該反應產物係雙酚A(可以EPON 880自Shell Chemical公司購得)之二縮水甘油基醚、二羥甲基丙酸與二乙醇胺(莫耳比例為0.6至5.0:0.05至5.5:1)之產物。其他適宜樹脂黏合劑包括揭示於美國專利第3,912,548號及第5,328,525號中之水溶性及水分散性聚丙烯酸;在美國專利第5,662,746號中所述酚甲醛樹脂;水溶性聚醯胺,例如,彼等揭示於WO 95/33869中者;馬來酸或丙烯酸與烯丙基醚之共聚物,如在加拿大專利申請案2,087,352中所述;及水溶性和分散性樹脂,包括環氧樹脂、胺基塑料、酚甲醛樹脂、鞣質(tannins)及聚乙烯基酚,如在美國專利第5,449,415號中所述。
在本發明之此等實施例中,該樹脂黏合劑係以佔組合物成份總重量之0.005重量%至30重量%(例如,0.5重量%至3重量%)之量存於該預處理組合物中。
然而,在其他實施例中,該預處理組合物實質上不含或(在某些情況下)完全不含任一樹脂黏合劑。如本文所用術語"實質上不含"在用於指示該預處理組合物中不存在樹脂黏合劑時意指任一樹脂黏合劑係以少於0.005重量%之量存於預處理組合物中。如本文所用術語"完全不含"意指該樹脂黏合劑根本不存於該預處理組合物中。
該預處理組合物視情況可含有其他材料,例如,經常用於預處理技術之非離子型表面活性劑及輔助劑。在水性介質中,可存在水分散性有機溶劑,例如,具有高達約8個碳原子之醇,例如,甲醇、異丙醇及諸如此類;或諸如乙二醇、二乙二醇或丙二醇及諸如此類之單烷基醚等二醇醚。當存在時,水分散性有機溶劑通常以佔水性介質總體積之高達約10體積%之量使用。
其他可選材料包括用作消泡劑或基材潤濕劑之表面活性劑。
在某些實施例中,預處理組合物亦包括反應加速劑,例如,亞硝酸根離子、硝酸根離子、含有硝基之化合物、硫酸羥胺、過硫酸根離子、亞硫酸根離子、連二亞硫酸根離子、過氧化物、鐵(III)離子、檸檬酸離子化合物、溴酸根離子、高氯酸根離子、氯酸根離子、亞氯酸根離子以及抗壞血酸、檸檬酸、酒石酸、丙二酸、琥珀酸及其鹽。適宜材料及其數量之具體實例闡述於美國專利公開申請案第2004/0163736 A1號之[0032]至[0041]中,其所述部分以引用方式併入本文中。
在某些實施例中,該預處理組合物亦包含填料,例如,矽質填料。適宜填料之非限制性實例包括矽石、雲母、蒙脫石、高嶺石、石棉、滑石粉、矽藻土、蛭石、天然及合成沸石、水泥、矽酸鈣、矽酸鋁、矽酸鈉鋁、聚矽酸鋁、礬土、矽膠及玻璃顆粒。除矽質填料外,亦可採用實質上不溶於水之填料的其他精細顆粒。此等可選填料之實例包括炭黑、活性炭、石墨、氧化鈦、氧化鐵、氧化銅、氧化鋅、氧化銻、氧化鋯、氧化鎂、礬土、二硫化鉬、硫化鋅、硫酸鋇、硫酸鍶、碳酸鈣及碳酸鎂。
在某些實施例中,該預處理組合物包括磷酸根離子。在某些實施例中,磷酸根離子係以10至500 ppm磷酸根離子(例如,25至200 ppm磷酸根離子)之量存在。磷酸根離子之例示性來源包括H3
PO4
、NaH2
PO4
、及/或(NH4
)H2
PO4
。然而,在某些實施例中,本發明之預處理組合物實質上或(在某些情況下)完全不含磷酸根離子。如本文所用術語"實質上不含"在用於指示預處理組合物中不存在磷酸根離子時意指磷酸根離子係以少於10 ppm之量存於該組合物中。如本文所用術語"完全不含"當用於指示不存在磷酸根離子時意指該組合物根本不具有磷酸根離子。
在某些實施例中,該預處理組合物實質上或(在某些情況下)完全不含鉻酸鹽及/或重金屬磷酸鹽,例如,磷酸鋅。如本文所用術語"實質上不含"在用於指示預處理組合物中不存在鉻酸鹽及/或重金屬磷酸鹽時意指此等物質以不會對環境造成負擔之量存於該組合物中。即,實質上不
使用該等物質且可消除在使用基於磷酸鋅之處理劑時所形成泥渣(例如,磷酸鋅)。如本文所用術語"完全不含"在用於指示不存在重金屬磷酸鹽及/或鉻酸鹽時意指該組合物根本不具有重金屬磷酸鹽及/或鉻酸鹽。
進而言之,在某些實施例中,該預處理組合物實質上不含或(在某些情況下)完全不含任一有機材料。如本文所用術語"實質上不含"在用於指示該組合物不存在有機材料時意指任何有機材料(倘若有)作為附帶雜質存於組合物中。換言之,任何有機材料之存在不影響該組合物之特性。如本文所用術語"完全不含"在用於指示不存在有機材料時意指該組合物根本不具有有機材料。
在某些實施例中,預處理塗料組合物之殘留物的覆膜率通常介於1至1000毫克每平方米(mg/m2
)(例如,10至400 mg/m2
)之間。預處理塗層之厚度可有所變化但其通常十分薄,經常具有小於1微米之厚度,在某些情況下,該厚度係自1至500奈米且在又一些情況下,其係自10至300奈米。
在與預處理溶液接觸後,基材可用水沖洗並乾燥。
在本發明方法之某些實施例中,在基材與預處理組合物接觸後,其隨後與包含成膜樹脂之塗料組合物接觸。可使用任一適宜技術以使該基材與此塗料組合物接觸,包括(例如)刷塗、浸塗、澆塗、噴塗及諸如此類。然而,在某些實施例中,如下文更具體地所述,此接觸包括電塗步驟,其中藉由電沈積將可電沈積組合物沈積於金屬基材
上。
如本文所用術語"成膜樹脂"係指在去除存於組合物中之任何稀釋劑或載劑後或在環境溫度或高溫下固化後可於至少基材之水平面上形成自撐式連續膜之樹脂。可使用的習知成膜樹脂尤其包括但不限於彼等常用於汽車OEM塗料組合物、汽車重塗塗料組合物、工業塗料組合物、建築塗料組合物、線圈塗料組合物及航空塗料組合物者。
在某些實施例中,該塗料組合物包含熱固性成膜樹脂。如本文所用術語"熱固性"係指在固化或交聯後不可逆轉地"固定"之樹脂,其中聚合組份之聚合鏈係藉由共價鍵連接在一起。該特性通常與經常由(例如)加熱或輻射誘發的組合物組成之交聯反應有關。固化或交聯反應亦可在環境條件下實施。一旦固化或交聯,熱固性樹脂在施加熱時將不會熔化且不溶於溶劑中。在其他實施例中,該塗料組合物包含熱塑性成膜樹脂。如本文所用術語"熱塑性"係指包括不藉由共價鍵連接且從而在加熱時可經受液體流動並溶於溶劑中之聚合組份的樹脂。
如先前所述,在某些實施例中,藉由電塗步驟使該基材與包含成膜樹脂之塗料組合物接觸,其中藉由電沈積使可電沈積組合物沈積於該金屬基材上。在電沈積製程中,使所處理金屬基材(用作一電極)及導電反電極與離子型可電沈積組合物接觸。在該電極與反電極之間有電流通過同時該等電極與可電沈積組合物接觸時,將以實質連續方式在該金屬基材上沈積可電沈積組合物之黏附性薄膜。
電沈積通常在介於1伏特至數千伏特之間(通常介於50伏特與500伏特之間)之恆定電壓下實施。電流密度通常介於1.0安培與15安培每平方英尺之間(10.8至161.5安培每平方米之間)且在電沈積過程中往往會迅速降低,表明形成連續的自絕緣膜。
在本發明之某些實施例中所用可電沈積組合物經常包含分散於水性介質中之樹脂相,其中該樹脂相包含:(a)含有活性氫基團之離子型可電沈積樹脂,及(b)具有與(a)之活性氫基團反應之官能團的固化劑。
在某些實施例中,在本發明之某些實施例中所用可電沈積組合物含有含活性氫之離子型(經常為陽離子型)可電沈積樹脂作為主要成膜聚合物。已知多種可電沈積成膜樹脂且其可用於本發明,只要該等聚合物具有"水分散性",即,適合溶於、分散於或乳化於水中。該水分散性聚合物本質上為離子型,即,該聚合物可含有陰離子型官能團以產生負電荷或(經常較佳地)陽離子官能團以產生正電荷。
適用於陰離子型可電沈積組合物之成膜樹脂的實例係鹼溶性含羧酸聚合物,例如,乾燥油或半乾燥脂肪酸酯與二羧酸或酐之反應產物或加合物;脂肪酸酯、不飽和酸或酐與可進一步與多元醇反應之任何額外不飽和修飾材料的反應產物。不飽和羧酸之羥基-烷基酯、不飽和羧酸與至少一種其他乙烯系不飽和單體的至少部分經中和之互聚物亦為適宜的。另一適宜可電沈積成膜樹脂包括烷基-胺基塑料媒介物,即,含有烷基樹脂及胺-醛樹脂之媒介物。又
一陰離子型可電沈積樹脂組合物包括樹脂多元醇之混合酯,例如,闡述於美國專利第3,749,657號,第9行,第1至75列及第10行,第1至13列中者,該所述部分以引用方式併入本文中。亦可使用其他酸官能基聚合物,例如,彼等熟習此項技術者熟知的磷化聚環氧化物或磷化丙烯酸聚合物。
如上文所述,經常期望含有活性氫之離子型可電沈積樹脂(a)為陽離子型且能夠沈積在陰極上。此等陽離子型成膜樹脂之實例包括含有胺鹽基團之樹脂,例如,聚環氧化物與一級或二級胺之酸溶性反應產物,例如,彼等闡述於美國專利第3,663,389號、第3,984,299號、第3,947,338號及第3,947,339號中者。經常地,此等含有胺鹽基團之樹脂與封閉型異氰酸酯固化劑組合使用。該異氰酸酯可為完全封閉型,如在美國專利第3,984,299號中所述,或者該異氰酸酯可為部分封閉型並與樹脂骨架反應,例如,在美國專利第3,947,338號中所述。如在美國專利第4,134,866號及德國專利案第DE-OS 2,707,405號中所述單一組份組合物亦可用作成膜樹脂。除環氧-胺反應產物外,成膜樹脂亦可選自陽離子型丙烯酸樹脂,例如,彼等闡述於美國專利第3,455,806號及第3,928,157號中者。
除含有胺鹽基團之樹脂外,亦可採用含有四級銨鹽基團之樹脂,例如,彼等自有機聚環氧化物與三級胺鹽反應形成者,如在美國專利第3,962,165號、第3,975,346號及第4,001,101號中所述。其他陽離子樹脂之實例係含有三級鋶
鹽基團之樹脂及含有四級鏻鹽基團之樹脂,例如,彼等分別闡述於美國專利第3,793,278號及第3,984,922號中者。而且,可使用可藉由轉酯化反應固化之成膜樹脂,例如,闡述於歐洲申請案第12463號中者。進而言之,可使用自曼尼西鹼製備的陽離子組合物,例如,闡述於美國專利第4,134,932號中者。
在某些實施例中,存於可電沈積組合物中之樹脂係含有一級及/或二級胺基團之帶正電荷樹脂,例如,闡述於美國專利第3,663,389號、第3,947,339號及第4,116,900號中者。在美國專利第3,947,339號中,聚胺(例如,二伸乙基三胺或三伸乙基四胺)之聚酮亞胺衍生物與聚環氧化物反應。當該反應產物用酸中和並分散於水中時,產生游離一級胺基團。而且,當聚環氧化物與過量聚胺(例如,二伸乙基三胺及三伸乙基四胺)反應並在真空下自該反應混合物除去過量聚胺時形成等效產物,如在美國專利第3,663,389號及第4,116,900號中所述。
在某些實施例中,含有活性氫之離子型可電沈積樹脂係以佔電沈積浴總重量之1重量%至60重量%(例如,5重量%至25重量%)之量存於該可電沈積組合物中。
如所述,該可電沈積組合物之樹脂相經常進一步包含適合與該離子型可電沈積樹脂之活性氫基團反應之固化劑。舉例而言,封閉型有機聚異氰酸酯及胺基塑料固化劑二者均適用於本發明,但對於陰極電沈積而言,封閉型異氰酸酯經常為較佳。
經常為陰離子型電沈積之較佳固化劑的胺基塑料樹脂係胺或醯胺與醛之縮合產物。適宜胺或醯胺之實例係三聚氰胺、苯胍胺、脲及類似化合物。一般而言,所用醛係甲醛,但可自諸如乙醛及糠醛等其他醛製造產物。該等縮合產物含有羥甲基基團或類似羥烷基基團,視所採用特定醛而定。經常地,此等羥甲基基團藉由與諸如含有1個至4個碳原子之一元醇(例如,甲醇、乙醇、異丙醇及正-丁醇)等醇反應來醚化。胺基塑料樹脂可以商標CYMEL自American Cyanamid公司購得及以商標RESIMENE自Monsanto Chemical公司購得。
該等胺基塑料固化劑經常以介於5重量%至60重量%(例如,20重量%至40重量%)之量聯合含有活性氫之陰離子型可電沈積樹脂使用,該等百分比係基於該可電沈積組合物之樹脂固體總重量。
如所述,封閉型有機聚異氰酸酯經常用作陰極電沈積組合物之固化劑。該等聚異氰酸酯可為完全封閉型,如在美國專利第3,984,299號,第1行,第1至68列,第2行及第3行,第1至15列中所述;或為部分封閉型並與聚合物骨架反應,如在美國專利第3,947,338號,第2行,第65至68列,第3行及第4行,第1至30列中所述,該所述部分以引用方式併入本文中。"封閉型"意指該異氰酸酯基團與化合物反應以便所得封閉型異氰酸酯基團在環境溫度下對活性氫穩定但在高溫(通常介於90℃與200℃之間)下與成膜聚合物之活性氫反應。
適宜聚異氰酸酯包括芳香族及脂肪族聚異氰酸酯,包括環脂族聚異氰酸酯且代表性實例包括二苯基甲烷-4,4'-二異氰酸酯(MD1)、2,4-或2,6-甲苯二異氰酸酯(TD1)-包括其混合物-對-苯二異氰酸酯、四亞甲基二異氰酸酯及六亞甲基二異氰酸酯、二環己基甲烷-4,4'-二異氰酸酯、異佛爾酮二異氰酸酯、苯基甲烷-4,4'-二異氰酸酯與聚亞甲基聚苯基異氰酸酯之混合物。可使用諸如三異氰酸酯等之高級聚異氰酸酯。實例可包括三苯基甲烷-4,4',4"-三異氰酸酯。亦可使用異氰酸酯與諸如新戊二醇及三羥甲基丙烷等多元醇以及諸如聚己內酯二醇及三醇等聚合多元醇之預聚物(NCO/OH當量比率大於1)。
該等聚異氰酸酯固化劑經常以介於5重量%至60重量%(例如,20重量%至50重量%)之量聯合含有活性氫之陰離子型可電沈積樹脂使用,該等百分比係基於該可電沈積組合物之樹脂固體總重量。
在某些實施例中,包含成膜樹脂之塗料組合物亦包含釔。在某些實施例中,釔係以佔釔總量(以元素釔量得)之自10至10,000 ppm(例如,不大於5,000 ppm且在某些情況下,不大於1,000 ppm)之量存於此等組合物中。
可溶性及不溶性釔化合物均可用作釔來源。適用於不含鉛之可電沈積塗料組合物之釔來源的實例係可溶性有機及無機釔鹽,例如,乙酸釔、氯化釔、甲酸釔、碳酸釔、胺基磺酸釔、乳酸釔及硝酸釔。當意欲於電塗覆浴中添加釔之水溶液時,硝酸釔(一種易於購得之釔化合物)係較佳釔
來源。適用於可電沈積組合物之其他釔化合物係有機及無機釔化合物,例如,氧化釔、溴化釔、氫氧化釔、鉬酸釔、硫酸釔、矽酸釔及草酸釔。亦可使用有機釔錯合物及釔金屬。當擬於電塗覆浴中納入作為顏料糊組份之釔時,氧化釔經常為較佳釔來源。
本文所述可電沈積組合物係呈水性分散液形式。據信,術語"分散液"係兩相透明、半透明或不透明樹脂系統,其中該樹脂係在分散相中且水係在連續相中。樹脂相之平均粒徑通常為小於1.0且時常小於0.5微米,經常小於0.15微米。
樹脂相在水性介質中之濃度經常佔水性分散液總重量之至少1重量%,例如,自2重量%至60重量%。當此等組合物係呈樹脂濃縮物形式時,其通常具有佔該水性分散液重量之20重量%至60重量%之樹脂固體含量。
本文所述可電沈積組合物經常以兩種組份形式提供:(1)透明樹脂進料,其通常包括含有活性氫之離子型可電沈積樹脂,即,主要成膜聚合物、固化劑及任何額外的水分散性無顏料組份;及(2)顏料糊,其通常包含一種或多種著色劑(下文所述)、可與主要成膜聚合物相同或不同之水分散性研磨樹脂及(視情況)諸如潤濕或分散助劑等添加劑。將電沈積浴組份(1)及(2)分散於包含水及(時常)聚結溶劑之水性介質中。
如上文所述,除水外,該水性介質可含有聚結溶劑。有用的聚結溶劑經常為烴、醇、酯、醚及酮。較佳聚結溶劑
經常為醇、多元醇及酮。具體聚結溶劑包括異丙醇、丁醇、2-乙基己醇、異佛爾酮、2-甲氧基戊酮、乙二醇及丙二醇以及乙二醇之單乙基單丁基及單己基醚。聚結溶劑之量通常係佔水性介質總重量之介於0.01%與25%之間,例如,自0.05重量%至5重量%。
另外,可在包含成膜樹脂之塗料組合物中納入著色劑及(倘若需要)諸如界面活性劑、潤濕劑或觸媒等各種添加劑。本文所用術語"著色劑"意指將顏色及/或其他不透明性及/或其他視覺效果賦予組合物之任何物質。可以任何適宜形式將著色劑添加至組合物中,例如,離散顆粒、分散液、溶液及/或薄片。可使用單一著色劑或兩種或更多種著色劑之混合物。
實例性著色劑包括顏料、染料及色彩(例如,彼等用於塗劑工業中及/或列於Dry Color Manufacturers Association (DCMA)中者)以及特殊效果的組合物。著色劑可包含(例如)在使用條件下不能溶解但可潤濕之微細固體粉末。著色劑可為有機物或無機物且可聚結或不可聚結。可藉由使用諸如丙烯酸研磨媒介物等研磨媒介物納入著色劑,該媒介物之使用為一名熟習此項技術者所熟知。
實例性顏料及/或顏料組合物包括但不限於咔唑二噁嗪粗製顏料、偶氮、單偶氮、雙偶氮、萘酚AS、鹽型(色澱)、苯并咪唑酮、縮合類、金屬錯合物、異吲哚啉酮、異吲哚啉及多環酞菁、喹吖啶酮、苝、哌瑞酮、二酮基吡咯并吡咯、硫靛、蒽醌、陰丹士林、蒽嘧啶、黃烷士酮、
皮蒽酮、蒽嵌蒽醌、二噁嗪、三芳基正碳離子、喹酞酮顏料、二酮基吡咯并吡咯紅("PPBO紅")、二氧化鈦、碳黑及其混合物。術語"顏料"及"經著色填料"可互換使用。
實例性染料包括但不限於為溶液及/或水基之彼等,例如,酞菁綠或酞菁藍、氧化鐵、釩酸鉍、蒽醌、苝、鋁及喹吖啶酮。
實例性色彩包括(但不限於)分散於水基或水可混溶性載劑中之顏料,例如,可自Degussa公司購得之AQUA-CHEM 896、可自Eastman Chemical公司之Accurate Dispersions分公司購得之CHARISMA COLORANTS及MAXITONER INDUSTRIAL COLORANTS。
如上所述,該著色劑可呈包含(但不限於)奈米顆粒分散體之分散體形式。奈米顆粒分散液可包括一種或多種高度分散之奈米顆粒著色劑及/或著色劑顆粒,其可產生期望可見色彩及/或不透明度及/或視覺效果。奈米顆粒分散體可包含著色劑,例如,具有小於150 nm(例如,小於70 nm、或小於30 nm)之粒徑的顏料或染料。可藉由用具有小於0.5 mm粒徑之研磨介質研磨儲備有機或無機顏料來製造奈米顆粒。實例性奈米顆粒分散體及其製備方法闡述於美國專利第6,875,800 B2號中,該案以引用方式併入本文中。奈米顆粒分散體亦可藉由結晶、沈澱、氣相冷凝及化學磨損(即,部分溶解)來產生。為了最大程度減少奈米顆粒在塗料中再次聚結,可使用經樹脂塗覆之奈米顆粒的分散體。本文所用"經樹脂塗覆之奈米顆粒的分散體"係指於
其中分散包括奈米顆粒及塗覆在該奈米顆粒上之樹脂的離散"複合微粒"的連續相。經樹脂塗覆之奈米顆粒的實例性分散體及其製備方法闡述於2004年6月24日申請之美國專利申請公開案第2005-0287348 A1號、2003年6月24日申請之美國臨時申請案第60/482,167號、及2006年1月20日申請之美國專利申請案第11/337,062號中,該案件亦以引用方式併入本文中。
可使用的實例性特殊效果組合物包括顏料及/或可產生一種或多種外觀效果之組合物,例如,產生反射、珠光、金屬光澤、磷光、螢光、光致變色、光敏性、熱致變色、光角變色及/或變色等效果。額外特殊效果組合物可提供其他可察覺特性,例如,不透明性或紋理。在某些實施例中,特殊效果組合物可產生色偏,使得在以不同角度觀察塗料時塗料顏色可改變。實例性顏色效果組合物闡述於美國專利第6,894,086號中,該案件以引用方式併入本文中。額外顏色效果組合物可包括透明經塗覆雲母及/或合成雲母、經塗覆矽石、經塗覆氧化鋁、透明液態晶體顏料、液態晶體塗料、及/或其中由材料內折射率差異而非材料表面與空氣間之折射率差異導致干涉之任何組合物。
在某些實施例中,可使用在暴露於一種或多種光源時可以可逆方式改變其顏色之光敏性組合物及/或光致變色組合物。光致變色及/或光敏性組合物可藉由暴露於特定波長之輻照來激活。當該組合物受到激發時,分子結構發生變化且變化結構呈現不同於該組合物初始顏色之新穎顏
色。當停止暴露於輻照時,該光致變色及/或光敏性組合物可回至靜息狀態,其中該組合物返回初始顏色。在某些實施例中,該光致變色及/或光敏性組合物在未激發狀態可為無色的且在激發狀態呈現顏色。完全顏色變化可在若干毫秒至數分鐘(例如,自20秒至60秒)內出現。實例性光致變色及/或光敏性組合物包括光致變色染料。
在某些實施例中,該光敏性組合物及/或光致變色組合物可締合及/或至少部分地黏合(例如,藉由共價鍵結)至聚合物及/或可聚合組份之聚合材料。與其中光敏性組合物可遷移出塗料並在該基材中結晶之某些塗料相反,本發明某些實施例之締合至及/或至少部分地黏合至聚合物及/或可聚合組份之光敏性組合物及/或光致變色組合物可最小程度地遷移出塗層。實例性光敏性組合物及/或光致變色組合物及其製備方法示於在2004年7月16日提出申請之美國專利申請案第10/892,919號中,該案以引用方式併入本文中。
一般而言,該著色劑可以足以賦予期望視覺及/或顏色效果之任一量存於塗料組合物中。該著色劑可佔1-65重量%,例如,3-40重量%或5-35重量%,其中重量百分比係以組合物總重量計。
在沈積後,經常加熱塗層以固化沈積組合物。該加熱或固化作業經常在介於120℃至250℃間(例如,自120℃至190℃)之溫度下實施介於10分鐘至60分鐘間之時間。在某些實施例中,所得膜之厚度係自10微米至50微米。
如根據上文所述可理解,本發明係關於用於處理金屬基材之組合物。此等組合物包括:(a)IIIB族及/或IVB族金屬;(b)正電性金屬;(c)0.1至300百萬分數("ppm")之游離氟;(d)金屬氟化物鹽,其自可形成具有至少11之pKsp
之氟化物鹽的金屬形成;及(e)水。在某些實施例中,該組合物實質上不含重金屬磷酸鹽(例如,磷酸鋅)及鉻酸鹽。
在又一些方面,本發明係關於用於處理金屬基材之組合物,其包含:(a)IIIB族及/或IVB族金屬;(b)0.1至300 ppm之游離氟;(c)金屬氟化物鹽,其係自可形成具有至少11之pKsp
之氟化物鹽的金屬形成;及(d)水。此等本發明組合物實質上不含磷酸根離子及鉻酸鹽。
如根據上述說明可知,本發明之方法及塗覆基材(在某些實施例中)並不包括沈積諸如磷酸鋅等結晶磷酸鹽或鉻酸鹽。因此,可避免與此等材料相關之環境弊端。然而,與其中使用此等材料之方法相比,本發明之方法已顯示可提供在至少某些情況下以相當、在某些情況下以甚至更佳程度抵抗腐蝕之經塗覆基材。此係本發明之令人感到吃驚且意外之發現並滿足了此項技術之長期需求。
下列實例闡述本發明,而不可將其視為將本發明限制於其細節。除非另有說明,否則在該等實例以及整個說明書中所有份數及百分數均以重量計。
氟化物離子濃度(包括游離及總的氟化物)可使用各種彼等熟習此項技術者熟知的方法來量測。經常地,氟化物離
子濃度可使用諸如由VWR International提供之sympHonyFluoride Ion Selective Combination Electrode等離子選擇性電極("ISE")或類似電極來量測。藉由將該電極浸沒於已知氟化物濃度之溶液中並記錄讀數(以毫伏計);隨後將此等毫伏讀數繪製成對數圖來標準化氟化物ISE。隨後將未知試樣之毫伏讀數與此校準圖比較並測定氟化物濃度。或者,該氟化物ISE可與可實施內在校準計算之計量儀一起使用且因此,在校準後,可直接讀取未知試樣之濃度。
氟化物離子係具有高電荷密度之小負離子,因此,在水性溶液中,其經常與具有高正電荷密度之金屬離子(例如,鋯或鈦)或與氫離子錯合。使用氟化物ISE不能量測由此錯合的氟化物離子,除非含有該等氟化物離子之溶液與可自此等錯合物中釋放氟化物離子之離子強度調節緩衝液混合。此時,可藉由氟化物ISE量測該等氟化物離子,且量測值稱作"總的氟化物"。在不使用此試劑時所得氟化物量測值稱作"游離氟化物",此乃因其僅為未黏合氫離子或在金屬錯合物中受到黏合之氟離子。
基於下列實例之目的,按照下列量測氟化物:藉由於50 mL包含存於去離子水之10重量%檸檬酸鈉二水合物(可自Aldrich Chemical,Milwaukee,WI購得)的離子強度調節緩衝液中添加2 mL各標準溶液(分別含有100 ppm、300 ppm及1000 ppm氟化物離子)來製備該等校準標樣。此等標樣各自之毫伏讀數隨後使用氟化物1SE量測且用於構建如上文所述校準曲線。對於總氟化物數值,將2 mL未知溶液與
50 mL檸檬酸鈉緩衝液混合並比較此溶液氟化物ISE之毫伏讀數與所產生校準曲線以測定總的氟化物。藉由直接讀取試樣溶液之毫伏數並與校準曲線比較且隨後將此數除以26(該除分係必須的,此乃因該等標樣因離子強度調節緩衝液而被稀釋26倍而游離氟化物試樣沒有)來測定游離氟化物。
按照下列製備12 L鋯預處理浴。將10.5 g 45%六氟鋯酸(可自Honeywell Specialty Chemicals,Morristown,NT購得)及17.57 g 5% w/w硝酸銅二倍半水合物溶液(可自Fisher Scientific,Fair Lawn,NJ購得)添加至大約12公升自來水中。用Chemfil Buffer(一種可自PPG Industries,Euclid,OH購得之溫和鹼性緩衝劑)將該溶液中和至pH 4.5。使用如上文所述ISE量測游離氟化物並獲得22 ppm數值之游離氟化物。
在適度混合時,在此溶液中於80℉下將經清潔冷軋鋼(CRS)板處理2分鐘。該板具有銅質表觀及某些藍色虹彩並使用便攜式X-射線螢光儀器(XRF)在大約43 nm下量測塗層厚度。
隨後於該鋯預處理溶液中,添加16.8 g Chemfos AFL(一種可自PPG Industries,Euclid,OH購得之不含氟化物之液體添加劑)。此添加會導致pH輕微下降至3.8。使用Chemfil Buffer將該溶液之pH調回至4.5。按照先前所述量測游離氟化物且發現為170 ppm。隨後藉由此浴以與先前
板等同之方式處理經清潔CRS板。此平板具有亮銅質表觀且藉由XRF量測的評定塗層厚度係20 nm。因此,較高含量之氟化物的存在可將塗層厚度減少大於50%。
此時,於該鋯預處理溶液中添加3.02 g硝酸釔六水合物(可自Acros Organics購得,一種Fisher Scientific之附屬物)。此造成pH輕微下降至pH 4.3。使用Chemfil Buffer將此調回至4.5。按照上文所述量測游離氟化物且測定為115 ppm。按照上文經處理之清潔CRS板具有適中的銅質色彩及藍色虹彩且藉由XRF測的塗層厚度係約31 nm。該預處理浴有些渾濁,據推測係氟化釔化合物沈澱。
於該鋯預處理浴中再添加3.06 g硝酸釔六水合物,此造成pH輕微降低至4.2。藉助添加Chemfil Buffer使pH返回至4.5。按照上文量測的游離氟化物係61 ppm且該預處理浴具有額外的沈澱。藉由預處理浴按照上文處理之清潔CRS板與先前板具有類似表觀。藉由XRF測定該塗層厚度,大約為45 nm。
於該鋯預處理浴中再添加2.98 g硝酸釔六水合物。該浴之pH輕微降低至4.2;添加足量Chemfil Buffer以使pH回至4.5。按照上文量測游離氟化物且發現為24 ppm,此接近初始數值。按照上文處理經清潔CRS板。該板外觀呈現藍色及某種虹彩。用XRF量測的塗層厚度係大約61 nm。
按照下列製備4公升鋯預處理浴:於大約4公升自來水中添加3.5 g 45%六氟鋯酸及5.84 g 5% w/w硝酸銅二倍半水
合物溶液以獲得具有175 ppm Zr及20 ppm Cu之溶液。使用Chemfil Buffer將此溶液中和至pH 4.5。在22 ppm下量測此溶液之游離氟化物。溶液溫度係82℉。取出2公升此溶液且用於預處理經清潔CRS板,2分鐘。該板表觀呈現適中的銅質色彩且發現使用便攜式XRF儀器測的塗層厚度係約28 nm。
於此2公升浴中添加6 g Chemfos AFL。該pH輕微降低至3.8。逐滴添加Chemfil Buffer以使該溶液回至pH 4.5。現在量測的游離氟化物為320 ppm。經由此浴處理2分鐘之經清潔CRS板實質上不具有可見預處理物;使用XRF量測得厚度為4 nm。
於此溶液中添加硝酸鑭水合物(可自Aldrich Chemical,Milwaukee,WI購得;32% La)。輕微渾濁之溶液此時立即變得十分渾濁。使用Chemfil Buffer將在添加硝酸鑭時降至3.3之pH調回至4.5。在31 ppm下量測游離氟化物。經由此浴處理2分鐘之經清潔CRS板具有銅質顏色及藍色虹彩並具有25 nm之塗層厚度,如藉由XRF所量測。
使用初始4 L浴之其餘2公升部分來將清潔CRS板處理2分鐘。此板具有適中的銅質顏色且量測的鋯預處理塗層為大約27 nm厚。於此浴中添加6 g Chemfos AFL。pH輕微降低至3.7且藉助逐滴添加Chemfil Buffer調回至4.5。現在在316 ppm下量測此浴之游離氟化物。經由此浴處理2分鐘之經清潔CRS板具有極少可見預處理物;使用XRF量測的厚
度為5 nm。
於此溶液中添加硝酸鈰六水合物(可自Alfa Aesar,Ward Hill,MA購得)。輕微渾濁之溶液此時立即變得十分渾濁。使用Chemfil Buffer將在添加硝酸鈰時降至3.3之pH調回至4.5。在28 ppm下量測游離氟化物。經由此浴處理2分鐘之清潔CRS板具有銅質顏色及藍色虹彩並具有29 nm之塗層厚度,如藉由XRF所量測。
彼等熟習此項技術者應瞭解,可對上述實施例做出改變而不背離其廣泛發明概念。因此應理解,本發明並不限於所揭示特定實施例,且其意欲涵蓋在隨附專利申請範圍所界定之本發明精神與範圍內之改良。
Claims (19)
- 一種用於處理金屬基材之預處理組合物,其包括:(a)IIIB族及/或IVB族金屬;(b)正電性金屬,其中該正電性金屬包含水溶性銅化合物;(c)0.1至300ppm游離氟;(d)金屬氟化物鹽,其係由包含釔、鑭、鈧及彼等之組合且可形成具有至少11之pKsp 之氟化物鹽的金屬形成,其中該可形成具有至少11之pKsp 之氟化物鹽的金屬係以可於該組合物中產生0.007ppm或更少的呈可溶性形式之金屬、且足以將游離氟在該組合物中之含量維持在不少於20ppm且不大於300ppm之量提供;及(e)水。
- 如請求項1之預處理組合物,其中該可形成具有至少11之pKsp 之金屬氟化物鹽的金屬係以足以將游離氟在該組合物中之含量維持在不少於20ppm且不大於100ppm之量提供。
- 如請求項1之預處理組合物,其中該IIIB族及/或IVB族金屬包括鋯。
- 如請求項1之預處理組合物,其中該IIIB族及/或IVB族金屬係以至少100ppm金屬之量存於該預處理組合物中。
- 如請求項1之預處理組合物,其中該正電性金屬係以佔以元素金屬量得的金屬總量之至少10ppm之量納於該等預處理組合物中。
- 如請求項1之預處理組合物,其中該預處理組合物實質上不含磷酸根離子。
- 如請求項1之預處理組合物,其中該組合物實質上不含磷酸根離子及鉻酸鹽。
- 一種用於處理金屬基材之方法,其包括使該基材與如請求項1之預處理組合物接觸。
- 如請求項8之方法,其中該金屬基材包括冷軋鋼、熱軋鋼、熱浸鍍鋅鋼、鋅鐵合金鋼及/或鍍有鋅合金之鋼。
- 如請求項8之方法,其中該IIIB族及/或IVB族金屬包括鋯。
- 如請求項8之方法,其中該IIIB族及/或IVB族金屬係以至少100ppm金屬之量存於該預處理組合物中。
- 如請求項8之方法,其中該正電性金屬進一步包括鎳、銀及/或金。
- 如請求項8之方法,其中該正電性金屬係以佔以元素金屬量得的金屬總量之至少10ppm之量納入該預處理組合物中。
- 如請求項8之方法,其中該游離氟係源自六氟鋯酸。
- 如請求項8之方法,其中自可形成具有至少11之pKsp 之氟化物鹽之金屬形成的金屬氟化物鹽包含釔。
- 如請求項8之方法,其中該可形成具有至少11之pKsp 之金屬氟化物鹽的金屬係以足以將游離氟在該組合物中之含量維持在不少於20ppm且不大於100ppm之量提供。
- 如請求項8之方法,其中該預處理組合物實質上不含磷 酸根離子。
- 如請求項8之方法,其中該預處理組合物實質上不含鉻酸鹽及/或磷酸鋅。
- 如請求項8之方法,其進一步包括使該基材與包括成膜樹脂之塗料組合物接觸,其中該接觸包括藉由電沈積將可電沈積組合物沈積在該金屬基材上之電塗步驟。
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US8673091B2 (en) | 2014-03-18 |
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WO2009020794A2 (en) | 2009-02-12 |
BRPI0813047A2 (pt) | 2014-12-16 |
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EP2188414A2 (en) | 2010-05-26 |
CN101796218B (zh) | 2013-01-30 |
HK1141841A1 (en) | 2010-11-19 |
CA2694515C (en) | 2015-06-23 |
AR067777A1 (es) | 2009-10-21 |
WO2009020794A3 (en) | 2009-03-26 |
KR20100050541A (ko) | 2010-05-13 |
RU2010107612A (ru) | 2011-09-10 |
ES2769262T3 (es) | 2020-06-25 |
UA100522C2 (ru) | 2013-01-10 |
CA2694515A1 (en) | 2009-02-12 |
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